Chem. Soc. Rev., 2020, 49, 180-232

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Voltage issue of aqueous rechargeable

metal-ion batteries
Cite this: Chem. Soc. Rev., 2020,
49, 180
Zhuoxin Liu,†ab Yan Huang,†c Yang Huang, †a Qi Yang,b Xinliang Li,b
Zhaodong Huangb and Chunyi Zhi *bd
Published on 29 November 2019. Downloaded on 8/10/2020 7:54:37 AM.
Over the past two decades, a series of aqueous rechargeable metal-ion batteries (ARMBs) have been
developed, aiming at improving safety, environmental friendliness and cost-efficiency in fields of
consumer electronics, electric vehicles and grid-scale energy storage. However, the notable gap
between ARMBs and their organic counterparts in energy density directly hinders their practical
applications, making it difficult to replace current widely-used organic lithium-ion batteries. Basically,
this huge gap in energy density originates from cell voltage, as the narrow electrochemical stability
window of aqueous electrolytes substantially confines the choice of electrode materials. This review
highlights various ARMBs with focuses on their voltage characteristics and strategies that can effectively
raise battery voltage. It begins with the discussion on the fundamental factor that limits the voltage of
ARMBs, i.e., electrochemical stability window of aqueous electrolytes, which decides the maximum-
allowed potential difference between cathode and anode. The following section introduces various
Received 10th August 2019 ARMB systems and compares their voltage characteristics in midpoint voltage and plateau voltage, in
DOI: 10.1039/c9cs00131j relation to respective electrode materials. Subsequently, various strategies paving the way to high-
voltage ARMBs are summarized, with corresponding advancements highlighted. The final section
rsc.li/chem-soc-rev presents potential directions for further improvements and future perspectives of this thriving field.
a
College of Materials Science and Engineering, Shenzhen University,
b
Shenzhen 518060, China 1. Introduction
Department of Materials Science and Engineering, City University of Hong Kong,
83 Tat Chee Avenue, Hong Kong 999077, China. E-mail: cy.zhi@cityu.edu.hk Human activities of economical production and consumption
c
State Key Laboratory of Advanced Welding and Joining,
require the use of energy, which affects the environment
Harbin Institute of Technology (Shenzhen), Shenzhen 518055, China
d
Shenzhen Research Institute, City University of Hong Kong, Shenzhen 518057,
in aspects of land use, water use, water/air pollution, harm
China to public health, endangerment to wildlife and loss of their
† These authors contributed equally. habitat, greenhouse gas emissions, etc.1,2 With our planet
Zhuoxin Liu received his PhD Yan Huang received her PhD
degree from City University of degree in University of Rochester
Hong Kong in 2019. Later, he in 2013. Then she moved to City
joined Collage of Materials Science University of Hong Kong as a post-
and Engineering, Shenzhen Univer- doctoral fellow, followed by a
sity as an assistant professor. His research fellow. She has been a
research mainly focuses on flexible professor in School of Materials
aqueous energy storage devices, Science and Engineering at Harbin
including supercapacitors and Institute of Technology, Shenzhen
aqueous metal-ion batteries. since September 2017. Her research
interests include flexible and
wearable electronic devices,
Zhuoxin Liu Yan Huang mainly energy storage (batteries,
supercapacitors) and conversion
(fuel cells).
180 | Chem. Soc. Rev., 2020, 49, 180--232 This journal is © The Royal Society of Chemistry 2020
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Review Article Chem Soc Rev
facing such energy and environmental challenges, there has Aqueous rechargeable metal-ion batteries (ARMBs) are
been a growing requirement for high-energy energy storage promising alternatives that can resolve the major challenges
systems (ESSs) in applications of consumer electronics and facing conventional LIBs, as water is an ideal electrolyte solvent
electrical vehicles where long-lasting power supply is needed, considering the following aspects: (i) the safety issue of flammable
as well as in connection with renewable power plants where organic electrolytes that cause fire and explosions can be funda-
clean and sustainable energy resources such as solar, wind, tide mentally avoided, (ii) the strict manufacturing requirements can
and geothermal heat can be penetrated for large-scale stationary be exempted, (iii) the cost of water and water-soluble electrolyte
energy storage.3–5 Electrochemical EESs, especially rechargeable salts is relatively low, (iv) the ionic conductivity of aqueous
batteries, possessing a variety of advantageous characteristics electrolytes can be 2 orders of magnitude higher than that of
including high round-trip efficiency, eco-friendly operation, organic electrolytes, resulting in better round-trip efficiency and
tunable power and energy output, and simple maintenance, rate capability, and (v) water solvent is totally non-toxic and
have been regarded as the most competitive candidates for environmentally benign.6,19,20 In these regards, the suitability of
power supply in terms of either portable or large-scale stationary ARMBs for portable/wearable applications and for large-scale grid-
applications.4,6,7 storage has been revisited.
Current market of rechargeable batteries is undoubtedly Dahn and colleagues first proposed an aqueous recharge-
dominated by lithium-ion batteries (LIBs), as they show relatively able lithium-ion battery (ARLB) where the flammable organic
high energy density, decent cycle stability and good energy solvent was replaced by water.21 Various ARLBs have been
efficiency among various battery systems,8 thus they have been thoroughly studied and substantial improvements in electro-
serving many applications ranging from small electronics to chemical performances have been achieved ever since, which
automotive vehicles. Despite the tremendous success in commer- has attracted considerable attention of more researchers to
cialization, conventional LIBs suffer from issues of cost and safety, aqueous energy storage systems.14,22–27 To date, a variety of
where the former mainly attributes to the scarcity of lithium aqueous rechargeable batteries based on many other metal ions
resources and the strict requirement of environment during including naturally-abundant alkali metal ions (Na+ and K+)
manufacturing, while the latter originates from the flammable and multivalent charge carriers (Zn2+, Mg2+, Al3+, etc.) has also
organic electrolyte and the thermal runaway induced by the been investigated.6,18,28–31 On one hand, the monovalent alkali
reactivity of electrodes with electrolytes.9–12 P. Rüetschi proposed metal ions of Na and K are more cost-effective in developing
the ‘‘three E’’ criteria for the development of battery system for low-cost energy storage systems regarding their abundant
sustainable applications,13 i.e., energy (high gravimetric and reserves in Earth’s crust. On the other hand, multivalent metal
volumetric energy density), economics (low cost, low maintenance cations can, theoretically, transfer more than one electron and
need, long service life), and environment (non-toxic, safe, reliable, thereby excel in achieving higher specific capacity and energy
recyclable). Apparently, conventional LIBs are no longer an ideal density. Basically, these ARMBs share similar electrochemistry
candidate for the blooming flexible and wearable electronics as with their counterparts based on organic electrolytes, where
the involvement of mechanical stresses and deformations during metal ions could intercalate from/into electrode hosts through
use arouse higher requirement for safety.14–17 Meanwhile, aqueous media.6,32 Besides, in contrast with traditional aqueous
temporally intermittent and spatially dispersed renewable lead acid (Pb–acid), nickel–cadmium (Ni–Cd) and nickel–metal
energy sources call for high reliability, absolute safety and cost hydride (Ni–MH) batteries, these intercalation-based ARMBs
efficiency, which makes conventional LIBs less feasible for the possess the merits of better cycle stability arising from reversible
corresponding large-scale energy storage.5,18 intercalation reactions, and higher power density originating
Yang Huang was awarded his Chunyi Zhi got his PhD degree in
PhD degree from City University physics from Institute of Physics,
of Hong Kong in 2016. He is Chinese Academy of Sciences.
currently an assistant professor After that, he started to work
in the College of Materials Science as a postdoctoral researcher in
and Engineering, Shenzhen Univer- National Institute for Materials
sity. His research mainly focuses on Science (NIMS) in Japan,
low-dimensional materials (e.g. followed by a research fellow in
transition metal carbides and International Center for Young
nitrides, known as MXenes), and Scientists in NIMS and a
their applications in advanced permanent position in NIMS
micro-/nano-electronic devices as a senior researcher. He is
Yang Huang (e.g. battery and supercapacitor). Chunyi Zhi currently an associate professor
in Department of Materials
Science and Engineering, City University of Hong Kong. His
research focuses on flexible/wearable energy storage devices, etc.
This journal is © The Royal Society of Chemistry 2020 Chem. Soc. Rev., 2020, 49, 180--232 | 181
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Chem Soc Rev Review Article

Fig. 2 Comparison of standard electrode potentials and theoretical capa-

Fig. 1 Energy comparison between typical ARMBs and conventional cities of various metal anodes.
organic LIBs.
from rapid ion-diffusion pathways offered by the intercalative shuttling metal ions.39,40 As for anodes, most pure metals
electrode structures, without the liability of memory effect, poor cannot be directly used. Fig. 2 compares different metal anodes
energy efficiency and environmental pollution.18,33 in terms of their standard electrode potentials and specific
However, the major obstacle that hampers the practical capacities. Obviously, although all these metals are light
applications of ARMBs is energy density. Fig. 1 compares the enough to deliver high capacity, the potentials of most metals
energy density between typical ARMBs and conventional LIBs. (except for zinc) are too low to allow reversible redox reactions
It is highly possible that ARMBs replace LIBs in many fields before hydrogen evolution, meaning alternative metal-ion inter-
if their energy density can be raised to a considerably high calative anodes are also needed for these ARMB systems.
level. There are two factors directly responsible for the energy Therefore, regarding cell voltage, the selection of suitable
density of a given battery system, i.e., specific capacity and cell cathodes and anodes together with electrolyte voltage window
voltage.34 Generally, specific capacity of most active materials are critical in determining battery energy density.
in aqueous electrolytes is almost the same as it in organic Currently, there are no reviews that have specifically focused
electrolytes,6,35 while cell voltage is absolutely confined by on, and comprehensively analysed and summarized, the vol-
electrochemical stability window of electrolytes, as the operat- tage issue of ARMBs under the purpose of attaining high energy
ing voltage of an ARMB cell is decided by the potential density. We consider it timely and necessary to present a review
difference of redox reactions between cathode and anode, on this research frontier, to provide recent advances and
which should lie within the electrochemical stability window potential guidance for improving the overall performances of
of aqueous electrolytes. Whereas, the stable voltage window of ARMBs. This review article first introduces the fundamental
aqueous electrolytes is much narrower than that of current basics of electrochemical stability window of aqueous electro-
organic electrolytes, which is only approximately 1.23 V. Beyond lytes, as well as how it can be further manipulated to benefit the
this window, decomposition (electrolysis) of water occurs voltage of ARMBs. The following section covers the develop-
with the evolution of H2 and O2, disabling the possibility ment of various ARMB systems and compares their voltage
of redox reactions of electrode materials. It should be noted characteristics in midpoint voltage and plateau voltage, in
that in practice this voltage window can be wider due to kinetic relation to respective electrode materials. Then, we go into
effects, including overpotentials for H2/O2 evolution at details of various strategies that pave the way to high-voltage
electrode surfaces and the interactions between ions and ARMBs, with corresponding advancements highlighted. The
solvents that increase the difficulty for water decomposition.36,37 final section discusses the challenges and perspectives of this
Therefore, the choice of electrode materials in aqueous electro- blooming field so that insights for future development of high-
lytes is substantially limited, especially when taking side energy ARMBs can be rendered.
reactions with water or/and oxygen, proton co-insertion,
and dissolution of electrode materials into account,6,35,38 thus
resulting in a relatively-low cell operating voltage and an 2. Electrochemical stability window of
inferior energy density. aqueous electrolytes
Albeit lower in energy density, various ARMB systems have
grown into a vigorous force in the field of energy storage due to In principle, most ARMBs discussed in this article share a
their irreplaceable characteristics. Normally, ARMBs employ ‘‘rocking chair’’ type of working mechanism, where metal ions
metal-ion intercalative cathodes and aqueous electrolytes with shuttle between cathode and anode via electrolyte. These metal
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ions (or together with hydrogen ions) can reversibly intercalate the redox mechanisms of some electrode materials are still
into/de-intercalate from cathode and anode, resulting in a under debate, meaning their category as intercalation-type
rechargeable energy storage system, as illustrated in Fig. 3a.18 or conversion-type electrode is not clearly identified yet.41–44
While zinc-ion battery is an exception, as Zn/Zn2+ electrode Several traditional alkaline battery systems are also involved
gives a standard electrode potential of E = 0.76 V, which for comparison.
allows its stripping/plating in many aqueous electrolytes To initiate intercalation/de-intercalation of metal ions, or
without significant hydrogen evolution. Therefore, another stripping/plating of metal anodes, the electrochemical stability
mechanism involving metal stripping/plating at anode side of solvent water should be carefully considered. When applied
and ion intercalation at cathode side is commonly seen for potential is lower than that of hydrogen evolution reaction
zinc-ion batteries (Fig. 3b).19,30,31 Moreover, due to the limited (HER), or higher than that of the oxygen evolution reaction
choice of electrode materials in aqueous electrolytes, some (OER), water molecules would be decomposed into hydrogen
representative battery systems employing conversion-type and oxygen, that’s what we call the electrolysis of water. Water
electrodes involving metal ion shuttling and conversion decomposition is an irreversible process, which can be depicted
reactions without metal ion intercalation/de-intercalation, by the following equation:
and polymer electrodes involving doping/de-doping or enolization/

H2O - H2 + 12O2
de-enolization, are also discussed. It should be also noted that
Fig. 3 (a) Illustration of the configuration of a battery using metal ion-intercalative cathode and anode. (b) Illustration of the configuration of a zinc-ion
battery with zinc stripping/plating at anode and zinc-ion intercalation at cathode. It should be noted that some conversion-type materials and organic
compounds have also been utilized to construct high-performance aqueous battery systems. (c) Pourbaix diagram showing the voltage window of
aqueous electrolytes. To initiate a reversible ARMB system, working potentials of electrode materials should locate within the window of OER and HER
potentials.
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In a battery system, this process is separated into two parts DGH, the corresponding overpotential to initiate HER is also
occurring at cathode and anode, respectively. At cathode side, large. Overpotentials that overcome intrinsic activation barriers
oxygen evolution reaction (OER) occurs: at cathode and anode, as well as solution resistance and contact
resistance, etc., vary with electrode materials, electrolytes and
2OH - H2O + 12O2 + 2e (neutral/alkaline)
pH values.6,37,49 Thus, the practical electrochemical stability of
water in terms of potential difference is described as:50
H2O - 2H+ + 12O2 + 2e (acidic)
DE = DE0 + Zc + Za + Zother
At anode side, hydrogen evolution reaction (HER) occurs:
where Zc is the cathodic overpotential, Za is the anodic over-
2H2O + 2e - H2 + 2OH (neutral/alkaline) potential, and Zother is overpotential from other resistances. The
final potential difference DE, i.e., the electrochemical stability
2H+ + 2e - H2 (acidic) window of water, is thus larger than 1.23 V.
Therefore, as illustrated in Fig. 3c, only electrode materials
The thermodynamic potential of water decomposition varies with working potentials located within the window of OER and
with temperature. The potential difference DE0 that triggers the HER potentials are useable in constructing a reversible ARMB
decomposition of water can be thermodynamically determined system. Electrode materials with working potentials beyond
by the following calculation: this window are not suitable in aqueous electrolytes, unless
special precautions are taken to prevent OER and/or HER,
DG = nFDE0
which will be discussed in Section 4. In addition, chemical
where DG is the change of Gibbs free energy, n is the trans- stability and solubility in water at certain pH values should also
ferred electron quantity, and F refers to the Faraday constant. be considered when screening electrode materials.6
According to this calculation, the potential difference DE0 Albeit wider than 1.23 V, the electrochemical stability
for water decomposition is around 1.23 V at 25 1C and window of water is still not comparable to that of organic
101.32 kPa, which is much narrower than that of most organic electrolytes (44 V),51 which substantially confines the choice
electrolytes.37,45 It should be noted that many researchers used of electrode materials. As mentioned before, two factors directly
HOMO (highest occupied molecular orbital) and LUMO (lowest decide the energy density of a battery system: specific capacity
unoccupied molecular orbital) to discuss the electrochemical and cell voltage. While the specific capacity of many electrode
stability of electrolytes in battery systems, which is improper materials changes little in aqueous electrolytes compared to it
and should be avoided. For the case of water that can be in organic electrolytes, it is of great significance to increase the
considered as an oxide with a band gap of 8.7–8.9 eV,46 its cell voltage of ARMBs if targeting at higher energy density for
thermodynamic potential window of 1.23 V is limited by HER at practical applications. Wider electrochemical stability window
4.02 eV and OER at 5.25 eV at the pH of 7.47 While if judged of water can enable electrode materials with higher or lower
by the HOMO–LUMO energy difference, its stable voltage working potentials, thus resulting in a larger cell voltage. In the
window should be wide enough to allow for the redox reactions following parts we will discuss the factors that influence the
of sodium metal anode. Therefore, there is no direct correlation voltage window of water, and how this window can be further
between the HOMO–LUMO energy gap and the Fermi levels for manipulated to benefit the voltage of ARMBs.
electrons to involve water decomposition, it is more correct to
examine OER and HER when talking about the electrochemical 2.1 pH of electrolytes and local pH change
stability window of water.48 As illustrated in Fig. 3c, OER and HER potentials are substan-
Water decomposition is pH-dependant, and the potentials tially affected by electrolyte pH, thus the voltage window can be
where OER and HER should occur as a function of pH value are manually adjusted to cover higher or lower working potentials
shown in the Pourbaix diagram (Fig. 3c). The practical electro- of electrode materials, allowing for wider cell voltage and more
chemical processes in aqueous electrolytes are very compli- stable charging/discharging. Literatures have reported the
cated, and actual water decomposition usually requires higher deliberate choosing of acidic or alkaline electrolytes for better
potential than theoretical values. The excess potential needed is battery performances. For example, OER easily occurs for
termed as overpotential (Z). Take HER as an example, which is LiMn2O4 cathode for aqueous lithium-ion batteries (ALIBs)
considered to involve three steps in acidic condition.45 The first when working at high pH values, because OER potential shifts
step is H+ + e - Hads, it is called Volmer step where a proton to lower potential in alkaline condition, thus leading to inferior
combines with an electron to yield a hydrogen atom absorbed cycle performance.52 LiNi1/3Co1/3Mn1/3O2 (NCM), known as a
at electrode surface. HER is subsequently facilitated by the promising high-voltage cathode for LIBs, should be used in
following reactions of Tafel step (2Hads - H2) or Heyrovsky acidic to mild alkaline aqueous electrolytes. If using at the pH
step (Hads + H+ + e - H2), or both. No matter what steps occur, of 13, OER occurs at a lower potential (0.75 V vs. SCE, saturated
Hads is always involved. The Gibbs free energy of the absorption calomel electrode) that overlaps with the working potential of
of hydrogen atom on electrode surface DGH should be over- NCM, leading to the insufficient utilization of NCM capacity of
come by applying excess potential, i.e., overpotential. If Hads lithium storage.53 Wang et al. suggested that the pH of electro-
is strongly bound to electrode, suggesting large and positive lytes for FePO42H2O anode in ALIBs should not be too low in
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order to fully utilize its capacity, otherwise HER cannot be 1 M concentration.55 Whereas, the discovered influences of salt
excluded during electrochemical processes.54 type on electrolyte voltage window is not significant so far, and
Regardless of the special purposes to adjust electrolyte pH, there’re no developed guidelines in determining the voltage
the widest voltage window of an aqueous electrolyte is usually window range of a given salt unless further experimental
achieved at a neutral pH. Yokayama et al. compared the voltage studies are conducted.
windows of 0.5 M H2SO4, 1.0 M HClO4, 0.33 M H3PO4 and Besides the type of electrolyte salt, one effective approach to
1.0 M NaOH solutions and found that all the acidic solutions expand electrochemical stability window of aqueous electro-
exhibited similar voltage windows except for NaOH, mainly due lytes is to increase the concentration of electrolyte salts. This
to the shifting of OER to a lower potential in alkaline solutions. approach can be divided into two strategies, one is to increase
Moreover, all these electrolytes yielded narrower voltage salt concentration but still keep water as the major constituent
windows compared to 1 M neutral electrolyte.55 Similarly, of electrolyte. Wessells et al. found that the concentration of
Wessells et al. reported the electrochemical stability window Li2SO4 and LiNO3 has similar influences on both cathodic and
of 1 M LiNO3 electrolyte gradually decreased with the increase anodic processes, leading to a wider full cell voltage with
of pH value, which reached the widest at a neutral pH.56 For the increasing salt concentration.56 A distinct correlation between
anode material of Na2V6O160.14H2O used in ALIBs, the pH of water concentration and electrolyte voltage window was also
Li2SO4 electrolyte was tuned by LiOH. As the pH increases observed for a series of aqueous electrolytes,55 of which voltage
from 7 to 12, the voltage window of electrolyte decreased windows were significantly expanded with the decrease of water
correspondingly.57 In addition, electrode materials may exhibit concentration (the increase of salt concentration), as reduced
different redox reactions that occur at different potentials water concentration would lead to reduced water activity,
depending on electrolyte pH. For example, the Co3O4 cathode resulting in positively-shifted/negatively-shifted potentials of
we developed for zinc-based battery underwent significantly OER/HER and correspondingly decreased reaction rate,
different reactions in mild electrolyte compared to it in alkaline although the influences on OER and HER are asymmetrical.
condition, which led to a much higher cut-off voltage of 2.2 V, Moreover, a saturated aqueous solution of sodium perchlorate
as well as largely enhanced cycle stability.58 Although Co3O4 is was reported to yield a remarkable voltage window as wide as
not a intercalative cathode for zinc ions, its pH-dependant beha- 3.2 V. The authors ascribed the wide voltage window to the
viour can be a good reference in developing high-voltage ARMBs. increased difficulty in water electrolysis,59 where the O–H bond
Generally, the pH of aqueous electrolytes adjacent to elec- of water was enhanced due to the loss of hydrogen bond in
trodes will change due to the ions generated or consumed concentrated electrolytes with increased ions. In addition,
during electrochemical processes. Thus, if cathode and anode concentrated electrolytes may affect the working voltage of
are well partitioned in anolyte and catholyte by a separator certain battery systems. In a study of Zhao and co-workers,60
(which is a commonly adopted configuration in battery devices), LiFePO4//LiV3O8 full cell with varied LiNO3 electrolyte concen-
the corresponding acidity and alkalinity are both expected to rise trations (2 M, 5 M and 9 M) showed different working voltages.
more than the case of free mixing of electrolyte without separa- The voltage plateau was raised with the increase of LiNO3
tion, which is ascribed to the increased concentration of H+ and concentration, despite the little change in electrode polariza-
OH in respective compartment. Such pH change only induces tion and voltage lag.
a slight change to the potential of OER and HER, however, if we The other strategy is to utilize ‘‘water-in-salt’’-like electro-
examine a rather small area that surrounds electrodes in lytes, which was developed by dissolving ultra-soluble salts into
neutral electrolytes, where the proton concentration is very water to obtain solutions containing more salt than water in
low (ca. 107 M at pH = 7), the local pH in the vicinity both volume and weight ratio. Due to the absence of free water
of electrodes would change drastically due to the produced molecules, ‘‘water-in-salt’’ electrolytes hinder the direct inter-
H+/OH by OER/HER. As a result, the voltage window of neutral action of water molecules with electrode materials. Besides, a
electrolytes is expanded via the shifting of OER and HER protective layer analogous to solid–electrolyte interphase (SEI)
occurring upon drastic local pH change. Such local pH in organic electrolytes could form at electrode surface due
change is effectively suppressed by the buffering of H+/OH to the reduction of salt anions. ‘‘Water-in-salt’’ electrolyte was
in acidic/alkaline electrolytes, therefore acidic/alkaline electro- first proposed by Suo et al., the 21 M LiTFSI electrolyte they
lytes usually exhibit narrower voltage window compared to developed enabled a stable voltage window as wide as 3.0 V,
neutral electrolytes.55 allowing for an ALIB with a cell voltage over 2.3 V.61 Having
inherited the foundation of ‘‘water-in-salt’’, hydrate-melt and
2.2 Electrolyte salts and concentration ‘‘water-in-bisalt’’ electrolytes were subsequently developed,62,63
At similar concentration and pH, the type of electrolyte salt has targeting at even higher voltage windows. This concept was
moderate influences on the electrochemical stability window of further extended to other types of ARMBs including sodium-ion
aqueous electrolytes. In the study of Wessells and co-workers, battery, potassium-ion battery, magnesium-ion battery, etc.64–67
albeit petty, the electrolytes of 1 M Li2SO4, 1 M LiNO3, 1 M Increasing the concentration of electrolytes could also
NaNO3, and 1 M Mg(NO3)2 exhibit varied voltage windows.56 extend the working temperature of batteries, as the freezing
Similar phenomenon was observed for NaClO4, NaNO3, LiNO3 point of electrolytes could be effectively depressed at high salt
and lithium bis(trifluorosulfonyl)imide (LiTFSI) solutions with concentration.68,69 However, lower temperature may decrease
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the solubility of electrolyte salts, resulting in salt deposition to exclude oxygen before electrochemical tests.60,78,80–82
and reduced concentration. Therefore, the solubility of electro- Chen et al. further demonstrated an ALIB with oxygen self-
lyte salts at low temperatures should be thoroughly considered. elimination capability, where the lithiated polyimide anode
It should also be noted that ionic conductivity of electrolytes could be oxidized by the generated oxygen to its pristine state.
usually increases with the increase of salt concentration and The sealed battery that overcharged to 2.2 V can still restore its
reaches its maximum value at optimum salt concentration initial capacity and high coulombic efficiency, showing remark-
(Kohlrausch law).70 When salt concentration continues rising, able stability.83 Nevertheless, the strategy of oxygen elimination
ionic conductivity will pass its peak value and gradually is only effective in aspect of preventing the shrinkage of voltage
decrease, affecting the overall battery performances. Thus, it window caused by oxygen-involved side reactions, instead of
is important to avoid unnecessary high salt concentration when expanding the intrinsic voltage window of a given electrolyte.
expanding electrolyte voltage window. Besides, data of long-term cycling test indicate that the removal
of dissolved oxygen does not completely address the issue of
2.3 Electrolyte additives electrochemical instability in aqueous electrolytes.80,84
It is well established that the decomposition of organic electro-
lyte components in conventional LIBs result in the formation of 2.5 Overpotentials

a passivation layer at electrode surface, which is called SEI.71–75 As aforementioned, overpotentials to overcome intrinsic activa-
This protective SEI extends the voltage window of organic tion barriers of water decomposition push OER and HER
electrolytes and allows for the stable cycling of LIBs over a potentials apart, resulting in wider voltage window of aqueous
broad voltage range. Whereas, aqueous electrolytes lack of such electrolytes. Overpotentials usually vary with a few factors
organic species essential to the formation of SEI, their voltage including pH values, electrolytes, electrode materials, etc.
window is thus restricted by the thermodynamic potentials of Generally, these factors work synergistically to affect over-
OER/HER. One possible method to stabilize and/or expand potentials. In neutral electrolytes, the overpotential of HER could
their voltage window is to use additives that are capable of readily reach 200 mV, and the overpotential for OER could extend
forming a SEI-like protective layer on electrode surface. For to over 1.8 V (vs. SHE, standard hydrogen electrode).85–87
example, vinylene carbonate (VC) that has been widely The electrocatalytic activity of electrode materials on water
employed in organic electrolytes to yield a stable SEI was proved decomposition is one major concern for constructing high-
to be an effective additive in aqueous electrolytes.76 The voltage ARMBs. To ensure high overpotentials, highly catalytic
protective film derived from VC to some extent prevented the electrode materials should be avoided. MoS2, for example, a
penetration of water molecules into electrode materials, thus material from the transition metal dichalcogenide family,
alleviating water decomposition and resulting in better cou- possesses high specific capacity.88,89 While the overpotential
lombic efficiency and battery cycle stability. It is also reported of MoS2 in acid electrolytes is only 40–50 mV, leading to a
that OER was effectively suppressed in the aqueous electrolyte narrow operational voltage window.90,91 When used in neutral
containing disodium propane-1,3-disulfonate (PDSS), leading or alkaline electrolytes, MoS2 could work at a higher operating
to a wide electrochemical stability window that was positively voltage as electrode for supercapacitors.92,93 Similar cases are IrO2
extended to 1.6 V (vs. Ag/AgCl).77 Although the mechanism and RuO2 electrodes.94 In the cathodes of ALIBs, de-lithiated
remains unclear, the authors suggested that the bulky anions of spinel LiMn2O4 and Li2MnP2O7 are proved to be catalytic
PDSS served as a barrier between electrolyte and electrode, on OER, meaning they facilitate oxygen evolution and lower
which played a similar role as SEI and increased the resistance upper voltage limit of electrolyte, thus deteriorating battery
of oxidative decomposition of water. Hou et al. further reported performances.95,96
that the addition of sodium dodecyl sulfate (SDS) into aqueous In practice, current collectors are essential components of
electrolyte resulted in the expanding of voltage window to electrodes, their electrochemical stability should also be thor-
around 2.5 V, as the hydrophobic layer formed via SDS being oughly considered. Among the various current collectors
electrostatically adsorbed onto electrode surface can effectively employed in ARMBs, stainless steel was found to be more
suppress OER/HER.78 electrochemically stable than carbon nanotubes (CNTs)-based
current collectors,97 and nickel mesh was demonstrated to yield
2.4 Dissolved oxygen a 2.8 V-wide voltage window.98 As the widely-adopted current
In a study of Xia and co-workers, dissolved oxygen in aqueous collectors for conventional LIB cathodes in industry is aluminium,
electrolytes was found to be a nonnegligible factor causing Kühnel et al. successfully applied aluminium current collectors in
electrochemical instability of ALIBs.79 Their investigations concentrated LiTFSI electrolyte, where the aluminium dissolu-
revealed that discharged state of ALIB anodes would react with tion in aqueous solution was substantially suppressed.99 The
water and oxygen, regardless of pH and electrolyte salt, leading high overpotential of aluminium with oxidized passivation
to capacity decay during cycling. Therefore, eliminating the layer promised a voltage window of 4.2 V, highlighting the
oxygen dissolved in electrolytes as well as sealing cells in the possibility of using a cost-effective and light-weight current
absence of oxygen can notably stabilize and widen voltage collector in ARMBs.
window of electrolytes. Many studies reported the improve- The above parts introduce the fundamental basics of water
ments in cycle stability by bubbling nitrogen or argon into cells decomposition, summarize and highlight the factors that affect
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the electrochemical stability window of aqueous electrolytes. electrode materials for ALIBs. In other words, the working
Put together, precise control of electrolyte pH, careful selecting potential of electrode materials should be located between
of electrolyte salt and tuning of its concentration, introducing OER and HER to avoid the electrolysis of H2O in electrolyte.100
of additives, elimination of dissolved oxygen, and considera- So far, a variety of electrode materials have been developed
tion of overpotentials are crucial for stabilizing and expanding for high-performance ALIBs. Representative cathode and anode
voltage window of aqueous electrolytes. Meanwhile, wide materials with the consideration of their redox potentials are
voltage window does not directly promise high-voltage ARMBs, discussed as follows.
it only offers a possibility for pairing more distant cathode and 3.1.1 Cathode materials for aqueous lithium-ion batteries.
anode regarding their redox potentials. Therefore, the choosing There are two basic requirements for selecting appropriate
of suitable cathode and anode is the final step that decides the cathode materials for ALIBs: (1) the capability to perform
operating voltage of a battery system. reversible Li+ intercalation/de-intercalation; (2) a lower potential
for Li+ intercalation/de-intercalation compared to the potential of
OER. Having met the above requirements, a variety of lithium
3. Marching of aqueous rechargeable intercalative compounds used in organic lithium batteries are
metal-ion batteries: performances, considered as the potential candidates for ALIBs, including oxides
voltage characteristics and comparison (LiMn2O4, LiCoO2, LiNi1/3Co1/3Mn1/3O2, etc.),98,101–107 polyanionic
compounds (LiFePO4, LiMnPO4, LiCoPO4, etc.)108–113 and
Holding the merits of intrinsic safety, cost efficiency and eco- Prussian blue analogues (PBAs).114
friendliness, various ARMBs have grown into a vigorous force in In order to maximize energy density, working potential of
the field of energy storage. Regarding cell voltage, some cathode materials should approach OER potential. Therefore,
claimed high voltage values actually refer to open circuit LiMn2O4 is one of the most promising cathode materials in
voltage, which cannot reflect the real working voltage of an consideration of its suitable Li+ intercalation potential. Typically,
ARMB. Besides, some ARMBs exhibit clear discharge plateau, it displays two redox pairs at around 0.75 V/0.89 V and
which extends from the initial voltage drop at the beginning of 0.86 V/1.05 V (vs. SCE), respectively (Fig. 4a), resulting in a
discharging to the knee of the discharging curve, while some midpoint voltage of 0.77 V (vs. SCE).115 Nanostructures have
only display capacitor-like sloping discharging profiles. More- been introduced to improve its electrochemical performances.
over, it is commonly seen that ARMBs are discharged to a low For example, Wu’s group reported a porous LiMn2O4 synthe-
cut-off voltage to struggle for more capacity, thereby their sized by utilizing polystyrene as sacrificial template (Fig. 4b).25
capacity/energy mainly comes from low-voltage zone, which It exhibited excellent rate performances, maintaining 95% of its
shows little practicability. To fully reveal voltage characteristics, initial capacity (118 mA h g1) at the high current density of
in this article, we employ the concepts of midpoint voltage and 10 A g1. Its capacity retention reached 93% after 10 000 charge/
plateau voltage to depict ARMBs. Midpoint voltage is defined as discharge cycles at 1.0 A g1, suggesting a lifetime usability
the battery voltage when 50% of the discharging capacity is without maintenance. The porous nanomorphology and high
delivered, and plateau voltage is defined as the voltage at the crystallinity should account for such high performances. They
midpoint of a discharge plateau. As discharge profiles vary with further developed LiMn2O4 nanotubes via a two-step method by
discharge rate, these two voltage parameters are both picked employing multiwall CNTs (MWCNTs) as template (Fig. 4c).116
from the lowest reported discharge rate for a certain study. In This LiMn2O4 nanotube cathode can be operated at ultrafast
this section, a series of ARMB systems are introduced in aspects second-level charge/discharge rates, and even retained 53.9% of
of their electrochemical properties (e.g. specific capacity, its capacity at 600C. As revealed by literatures, the long-term
cycling stability, energy and power densities, etc.), together cycling issue of LiMn2O4 cathode could be well addressed by
with a focus on their voltage characteristics (e.g. midpoint several effective strategies, including Al doping to suppress
voltage, plateau voltage, and open circuit voltage). Meanwhile, Jahn–Teller distortion and stabilize octahedral sites,117,118
upon a rational comparison within a certain ARMB system, designing porous structure to ensure high crystallinity and
proposed strategies including materials optimization and para- alleviate Jahn–Teller distortion strain,119 and introducing tubular
meter regulation to further improve their energy storage structure to buffer the strain and stress from Jahn–Teller
performances are discussed in detail. effects.120 In addition to LiMn2O4, layered lithium oxides, includ-
ing LiCoO2 and LiNi1/3Co1/3Mn1/3O2 (NCM), which are commonly
3.1 Aqueous lithium-ion batteries used in traditional organic LIBs, have also been investigated as
Aqueous rechargeable lithium-ion batteries (ALIBs) were first cathode materials for ALIBs due to their relatively high redox
launched in 1994, which could operate reversibly with a mid- potentials.70,98,121–125 However, H+ insertion occurs preferentially
point voltage of around 1.5 V and simultaneously provide an over Li+ insertion in this type of materials when using LiOH
energy density of 75 W h kg1 based on the mass of both active electrolyte.126,127 As indicated by later studies, reversible Li+
materials, comparable to both Pb–acid and Ni–Cd batteries.21 insertion into and extraction from LiCoO2 is possible in LiNO3
As pointed out in this conceptual and pioneering study, the and Li2SO4 electrolyte.70,98,121,122 It was found that the redox
potentials of hydrogen and oxygen evolution should be taken potential of LiCoO2 increased linearly with the electrolyte
into account as an important factor when selecting both of the concentration, suggesting reversible Li+ intercalation instead
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midpoint voltage of 0.65 V (vs. SCE). All the above-discussed

cathode materials exhibit tilting plateau upon discharging.
Another group of promising cathode material is polyanionic
compounds. LiFePO4 with olivine structure was reported as the
first polyanionic cathode for ALIBs.108 Though Li+ inter-
calation/de-intercalation in LiFePO4 was proved to be feasible
by electrochemical analysis and ex situ characterizations, the
capacity of LiFePO4 was far lower than its theoretical value
(70 mA h g1, corresponding to a utilization rate of 41%), and
faded rapidly after several charge/discharge cycles. The oxida-
tion of LiFePO4 to FePO4 was not fully reversible, and sub-
sequent reduction resulted in the mixture of LiFePO4 and Fe3O4
that led to poor cyclability.108 LiFePO4 showed a sharp redox
pair at 0.12 V/0.32 V (vs. Ag/AgCl), yielding a flat discharge
plateau at around 0.12 V (vs. Ag/AgCl) (Fig. 4e).131 It was found

out that O2 and OH in aqueous electrolytes significantly
deteriorated the cycling stability of LiFePO4.132 For example,
Fig. 4 (a) CV curves of LiMn2O4 cathode and LiV3O8 anode in 2 M Li2SO4 when using 0.5 M Li2SO4 (pH = 7) electrolyte in the presence of
aqueous electrolyte at 0.2 mV s1. Reproduced with permission from O2, obvious capacity degradation was observed during cycling.
ref. 115, Copyright 2007 Elsevier. (b) TEM image of the synthesized porous
Transmission electron microscopy (TEM) results further
LiMn2O4. Reproduced with permission from ref. 25, Copyright 2011
Royal Society of Chemistry. (c) TEM image of the synthesized LiMn2O4 revealed that floccules formed on the surface of LiFePO4 with
nanotubes. Reproduced with permission from ref. 116, Copyright 2013 the existence of O2, which were identified as Fe(OH)2 and
American Chemical Society. (d) CV curves of LiCoO2 cathode at 0.1 mV s1 Fe2O3. Whereas these impurities were not detected in the
in aqueous LiNO3 electrolytes with different concentrations. Reproduced absence of O2. Thus, side reactions originated from O2 and
with permission from ref. 121, Copyright 2009 Elsevier. (e) GCD curves of
OH should account for the cycling instability of LiFePO4. With
carbon coated LiFePO4 of different cycles. Reproduced with permission
from ref. 131, Copyright 2017 American Chemical Society. (f) TEM image a thin carbon coating (about 5 nm) on LiFePO4 (Fig. 4f), the
showing the coated carbon layer on LiFePO4. Reproduced with permission attack from dissolved O2 and OH could be eased and cycling
from ref. 132, Copyright 2011 Elsevier. (g) The unit cell of Prussian blue stability could thus be enhanced. Besides, metal ion doping
crystal structure. Each of the eight sub-cells within the unit cell contains an is an effective strategy to adjust working potentials and to
open ‘‘A site’’. (h) GCD curves of CuHCF as cathode for ALIB at various
improve the overall electrochemical performances of polyanionic
rates. (i) GCD curves of NiHCF as cathode for ALIB at various rates.
Reproduced with permission from ref. 114, Copyright 2011 The Electro- compounds, this includes Mn/Ni co-doping, Fe/Mn co-doping,
chemical Society. Ni/Co doping/co-doping, etc.112,113,133–135
PBAs that possess a structure of archetypal hexacyanometalate
framework are described in a general formula of AxPR(CN)6, in
of H+ insertion in high concentration electrolytes (Fig. 4d). As which nitrogen-coordinated transition metal cations (P) and
expected, LiCoO2 cathode can be cycled with relative low hexacyanometalate complexes (R(CN)6) form a face-centred cubic
polarization in a potential range of 0.55–1.15 V (vs. SHE) and framework with large interstitial A sites (Fig. 4g).136–140 The ionic
deliver a capacity of 105 mA h g1 in 5 M LiNO3 with a midpoint occupancy in A sites varies from 0 to 2 depending on valence
voltage of 0.93 V (vs. SHE).121 Raising upper potential limit to changes in one or both of the P and R species.141 These
1.4 V, LiCoO2 cathode yielded a capacity of 135 mA h g1 with a materials have been proposed as potential cathodes for
deteriorated coulombic efficiency of 98.5%.70 The decreased aqueous battery systems as they are able to accommodate a
reversibility of LiCoO2 above 1.3 V should be attributed to water variety of metal ions, including Li+, Na+, K+, and NH4+ in
electrolysis. Besides, with optimized morphology, nano-LiCoO2 aqueous solutions. In a representative work, copper hexacyano-
achieved a charge/discharge capacity of 147 mA h g1 at ferrate (CuHCF) and nickel hexacyanoferrate (NiHCF) were
1000 mA g1 (7C rate) in 0.5 M Li2SO4 electrolyte.128 As an prepared via a co-precipitation method and exhibited certain
alternative to LiCoO2 in organic LIBs, NCM has also been electrochemical activity in 1 M LiNO3 electrolyte (pH = 2).114
studied in aqueous electrolytes. Its electrochemical stability Both CuHCF and NiHCF were able to provide a specific capacity
was seriously affective by electrolyte pH, as its oxidation peak of around 56 mA h g1 at 0.83C, and retained 65% and 58%
shifted obviously to higher potentials in repeated cyclic voltam- of the capacity, respectively, at the high current density of
metry (CV) cycles at the pH of 7 and 9.123,124 Literatures have 2500 mA g1 (41.7C), as shown in Fig. 4h and i. However,
reported that NCM electrode has relatively low stability under cycling stability of CuHCF and NiHCF was poor, only 40% of
low-pH conditions due to H+ exchange/insertion, which could their initial capacities could be maintained. This was due to
be further stabilized by polypyrrole (PPy) coating and nano- the dissolution of active materials, which may result from the
structuring that favour Li+ intercalation/de-intercalation reversibility larger Stokes radius of Li+ (2.4 Å) compared with the radius of
and charge transfer kinetics.125,129,130 It could be operated in the connected channels between A sites (1.6 Å) in Prussian blue
potential range of 0–1.05 V (vs. SCE) in 0.5 M Li2SO4 with a structure.142,143 The cathodes of CuHCF and NiHCF were
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operated in the potential range of 0.4–1.3 V and 0.2–0.9 V, with

a midpoint voltage of 0.83 V and 0.59 V, respectively (vs. SHE).
3.1.2 Anode materials for aqueous lithium-ion batteries.
Along with the development of cathode materials, a number
of appropriate anode materials have been proposed for con-
structing ALIBs, including vanadium oxides (VO2(B), layered
g-LiV3O8, V2O5, etc.),144–152 polyanionic compounds (pyrophos-
phate TiP2O7 and Na superionic conductor (NASICON)-type
LiTi2(PO4)3),101,153–155 and organic polymer compounds (PPy
and polyimides).156,157 These anode materials meet the two basic
requirements similarly raised for cathodes: (1) the capability
allows for reversible Li+ intercalation/de-intercalation; (2) redox
potentials shouldn’t negatively exceed the potential of HER. In
early studies, severe capacity fading was commonly observed
for most anode materials, which are mainly attributed to the

following reasons: (1) dissolution of active materials;106,158,159
(2) irreversible structural transformation resulted from proton
insertion;160,161 (3) spontaneous de-intercalation of lithiated
materials accompanied by water decomposition.154,155,162
Several strategies have been introduced to improve electro-
chemical performances of anode materials, including control-
ling electrolyte pH, removing residual O2, etc.60,163 In this Fig. 5 (a) GCD curves of the VO2//LiVOPO4 full cell in the initial cycles at
50 mA g1. Reproduced with permission from ref. 166, Copyright 2019
section, some representative anode materials are discussed
Elsevier. (b) TEM image of an individual loose flowerlike VO2 sphere.
regarding their electrochemical properties in relation to voltage Reproduced with permission from ref. 146, Copyright 2009 American
characteristics. Meanwhile, obstacles in constructing high- Chemical Society. (c) GCD curves of the LiNi0.81Co0.19O2 cathode, the
performance ALIBs and effective solutions are presented. LiV3O8 anode, and the corresponding full cell in 1 M Li2SO4 aqueous
Monoclinic structured VO2(B) was used as anode material electrolyte. Reproduced with permission from ref. 167, Copyright 2000
Elsevier. (d) Schematic illustration of the PPy coating ontoLiV3O8 particles.
for the first proposed ALIB in 1994, as it possesses suitable
Reproduced with permission from ref. 169, Copyright 2018 Elsevier. (e) CV
tunnel structure that allows for the rapid intercalation/ curves of TiP2O7 at 0.2 mV s1 in 5 M LiNO3 aqueous electrolyte. (f) CV
de-intercalation of Li+,164 and its redox potential is moderately curves of LiTi2(PO4)3 at 0.2 mV s1 in 5 M LiNO3 aqueous electrolyte.
higher than that of HER in an alkaline electrolyte, excluding the Reproduced with permission from ref. 170, Copyright 2007 Elsevier. (g)
potential hydrogen insertion or the involvement of H+/OH Working mechanism of the ALIB with doping/de-doping anode and
intercalation/de-intercalation cathode. Reproduced with permission from
during electrochemical processes.144,165 Whereas, it was
ref. 156, Copyright 2008 Wiley-VCH. (h) The cell configuration based on
revealed that VO2(B) suffered from poor cycling stability in a polyimide anode with enolization redox mechanism and an inorganic
strong basic electrolyte (at the pH of 11.3) due to its sponta- intercalative cathode. (i) GCD curves of polyimide//LiCoO2 full cell in
neous dissolution. Though decreasing pH values from 11.3 5 M LiNO3 aqueous electrolyte at the current density of 100 mA g1.
to 6.2 can increase its discharge capacity and coulombic effi- Reproduced with permission from ref. 157, Copyright 2014 Elsevier.
ciency, HER occurs when pH goes below 7.165 In one study, it was
suggested that the highly concentrated LiTFSI aqueous electrolyte
could improve the electrochemical properties of monoclinic VO2, anode and LiNi0.81Co0.19O2 cathode showed sloping discharge
which resulted in an ALIB with a plateau voltage of around 1.35 V profiles, realizing a midpoint voltage of 0.87 V and a total
(Fig. 5a) and a good capacity retention of 84% after 1000 cycles at capacity of 45 mA h g1 (based on the mass of both active
100 mA g1 when coupling with LiVOPO4 cathode.166 Detailed materials), as shown in Fig. 5c. However, its cycling stability
discussion on concentrated LiTFSI electrolyte is given in Section was far from satisfactory. Further ex situ XRD analysis uncovered
4.4.2. Another method to enhance the electrochemical properties the distortion of crystal structure, the additional peaks emerged
of VO2(B) is morphological optimization. Through a hydrothermal after 100 cycles suggested the formation of new compounds
route using polyvinyl pyrrolidone as capping reagent, flowerlike including LiV2O5 and V2O5. Besides, the decreased (100) peak
VO2(B) assembled by singly-crystalline nanosheets was synthe- indicated a deteriorated layered structure of g-LiV3O8. These
sized (Fig. 5b), which was paired with a LiMn2O4 cathode to yield irreversible changes in crystal structure impeded Li+ intercalation
an ALIB operating in the voltage range of 0.5–1.65 V with a specific and accounted for the inferior cycling stability. By modifying
capacity of 74.9 mA h g1 at 60 mA g1.146 Its midpoint voltage morphology, electrochemical performances of g-LiV3O8 anode
was located at 1.10 V. The high aspect ratio and surface areas could be enhanced. For example, a macaroni-like Li1.2V3O8 nano-
derived from the flowerlike nanostructures favour Li+ migration, material with high discharge capacity was fabricated by a solution
leading to improved electrochemical kinetics. process using b-cyclodextrin as template.168 The cell based on this
g-LiV3O8 was fist investigated by Kohler et al. using 1 M nanostructured Li1.2V3O8 anode and a LiMn2O4 cathode could
Li2SO4 or LiCl electrolyte.167 The full cell based on g-LiV3O8 operate at a voltage range of 0.5–1.4 V in 1.0 M Li2SO4 aqueous
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electrolyte. It exhibited three-staged discharge profiles with a cathode could be operated reversibly within a voltage range of
midpoint voltage located at 1.0 V. Specific capacities were 189, 0–1.6 V in a saturated Li2SO4 aqueous electrolyte (pH = 7),
140 and 101 mA h g1 (based on the mass of anode material) at delivering a midpoint voltage of around 0.44 V.156 Different
0.1, 0.5, and 1.0C, respectively. Such increased capacities were from other anode materials, PPy realises energy storage through
attributed to the porous structure of Li1.2V3O8 anode that facili- a reversible doping and de-doping mechanism (Fig. 5g) at an
tated Li+ intercalation. In a more recent study from our group, PPy average redox potential of 0.27 V. Moreover, unlike many
coating was employed to improve the cycling stability of LiV3O8 vanadium-based anodes, PPy does not dissolve in aqueous
(Fig. 5d), which achieved a capacity retention of 73.2% after 100 solution, and its doping/de-doping mechanism is highly
cycles at 0.5 A g1, whereas the pristine uncoated LiV3O8 only reversible. Therefore, it should exhibit good stability during
retained 30.6% of its original capacity.169 It was also discovered repeated electrochemical processes. As revealed by Wang et al.,
that PPy coating suppressed the hydrogen evolution at LiV3O8 the PPy//LiCoO2 cell with a midpoint voltage of 0.80 V showed
side, as the conductive PPy layer facilitated ion and charge no obvious degradation after 120 charge/discharge cycles.171
transfer, enabling the predominant reaction of Li+ intercalation Another example of organic polymer anode material is polyimide
over HER. Literature has also shown that increasing electrolyte with conjugated carbonyl groups based on 1,4,5,8-naphthalene-
concentration and eliminating dissolved oxygen resulted in a teracarboxylic dianhydride moiety.157 Polyimide undergoes an
consistent capacity during 100 charge/discharge cycles for the enolization process to combine with Li+ and simultaneously
ALIB consisting of LiV3O8 anode and LiFePO4 cathode, which redistribute charges within the conjugated aromatic molecule
operated in the narrow voltage range of 0–0.8 V with a flat but low (Fig. 5h), which is significantly distinguished from Li+ inter-
plateau voltage at 0.23 V.60 The enhanced cycling stability should calation/de-intercalation mechanism or doping/de-doping
attribute to reduced electrochemical resistance and less polariza- mechanism. Polyimide anode could provide a high discharging/
tion of the optimized aqueous electrolyte. In general, LiV3O8 charging capacity of 192 mA h g1/160 mA h g1 with midpoint
can work as a reliable anode material for ALIBs when rational discharging/charging voltage of 0.50 V/0.39 V (vs. SCE).
precautions are taken to tackle its problematic instability. Assembled with a LiCoO2 cathode in 5 M LiNO3, the resultant
Similarly, V2O5 showed poor cyclability in aqueous media due ALIB exhibited a discharge capacity of 71 mA h g1 and a specific
to dissolution issue and crystal structure changes.107,151,160 energy of 80 W h kg1 at 100 mA g1 (based on the mass of both
To enhance its reversibility in aqueous electrolytes, polymer active materials), along with plateau voltage of 1.10 V (Fig. 5i). This
coatings of polyaniline (PANI) and PPy was introduced, result- ALIB also displayed a good cyclability by maintaining 80% of its
ing in full cells with notably improved cycling stability, deliver- original capacity after 200 charge/discharge cycles, which was
ing midpoint voltages of 0.80 V and 1.05 V when coupled with attributed to the unique Li+ diffusion-independent enolization
LiNi1/3Mn1/3Co1/3O2 and LiMn2O4, respectively.107,151 mechanism that avoided strains and structure distortions during
In addition to oxides, polyanionic compounds have been repeated electrochemical processes.
investigated as anode materials for ALIBs due to their flat For ALIBs, the options of anode materials from traditional
charge/discharge plateau and proper redox potentials. In organic LIBs are less compared to cathode materials, as most
2007, the redox potentials of two polyanionic compounds, anode materials used for traditional LIBs possess redox potentials
namely, pyrophosphate TiP2O7 and NASICON-type LiTi2(PO4)3, significantly lower than that of HER. Besides, many organic
were systematically investigated in 5 M LiNO3 aqueous solution.170 compounds used in traditional LIBs cannot be directly utilized
CV curves of TiP2O7 and LiTi2(PO4)3 clearly indicated that they as electrodes in ALIBs because of their instability in aqueous
could act as anode materials for ALIBs without obvious hydrogen electrolytes.172 Thereby, researchers have devoted tremendous
evolution, since their redox reactions occur at the potentials of efforts in developing anode materials with suitable redox poten-
approximately 0.35 and 0.45 V (vs. SHE), respectively, which tials for aqueous electrolytes. Redox potentials of representative
were moderately higher than that of HER (Fig. 5e and f). The cathode and anode materials for ALIBs are summarized and
resultant TiP2O7/LiMn2O4 and LiTi2(PO4)3//LiMn2O4 full cells compared in Fig. 6. The notably higher redox potential of
delivered specific capacities of around 42 and 45 mA h g1 (based LiMn2O4 makes it the most widely-adopted cathode for high-
on the mass of both active materials) with high midpoint voltages energy ALIBs. As for anode materials, attention should be paid
of 1.38 and 1.47 V, respectively. However, both batteries decayed to the low-potential NASICON-type LiTi2(PO4)3 and its fluoride
rapidly due to structural decomposition and morphological LiTi2(PO4)2.88F0.12. Although some vanadium oxides show low
changes.159 Several effective approaches have been proposed to redox potentials, their toxic synthesis and intrinsic instability in
further improve the electrochemical performances of these poly- water hinder their further applications. Besides electrochemical
anionic anodes, including porous structuring, carbon coating and potentials, extensive efforts are also needed to better address the
electrolyte optimization (pH adjust and oxygen elimination), issues of unsatisfactory cyclability and insufficient utilization of
which realized 80–90% capacity retention after several hundreds theoretical capacity of current electrode materials, as well as to
of charge/discharge cycles or even over 1000 cycles.101,153,163 explore new families of high-performance electrode materials.
Considering their redox potential position of 0.8 to 0.3 V
(vs. SHE) and the intrinsic deficiency of lithium ion, organic 3.2 Aqueous sodium-ion and potassium-ion batteries
polymer materials mainly serve as anodes for ALIBs. For Aqueous sodium-ion (ASIBs) and aqueous potassium-ion batteries
example, A cell consisting of a PPy anode and a spinel LiMn2O4 (AKIBs) with similar monovalent ion intercalation/de-intercalation
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Fig. 6 Comparison of redox potentials of representative electrode materials for ALIBs. Red-colour columns and blue-colour columns represent
cathodes and anodes, respectively.
mechanisms to ALIBs have been developed as promising alternative containing different alkali metal sulphates.177 Galvanostatic
energy storage systems due to the easy accessibility of sodium/ charge/discharge (GCD) curves exhibited an capacitor-like linear
potassium resources, which could be better choices for grid-scale relationship with time between the potential range of 0–1 V
energy storage that imposes higher requirement on cost. Their (vs. SCE) with midpoint voltages at around 0.4 V (vs. SCE), and
electrode materials are also quite limited considering the narrow the specific capacities for Li+, Na+, and K+ storage were 37, 43
electrochemical stability window of water, and they usually exhibit and 50 mA h g1, respectively. Their study revealed that the
lower energy density compared to ALIBs due to the higher atomic intercalation/de-intercalation of K+ into/from the interlayered
mass of sodium/potassium. In this section, the development of space of V2O50.6H2O was more facile compared to Li+ and Na+,
ASIBs and AKIBs will be discussed in terms of their electrochemical which may be attributed to the moderate charge density of K+.
performances and voltage characteristics based on cathode and Another attractive category of metal oxide for ASIBs and AKIBs
anode materials, which mainly include spinel-structured materials, is MxMnO2 (M = Na, K), which possesses various crystal
polyanionic compounds, PBAs, etc. structures and properties depending on sodium/potassium
3.2.1 Cathode materials for aqueous sodium-ion and ratio. Among them, Na0.44MnO2 with three-dimensionally inter-
potassium-ion batteries. Similar to ALIBs, the redox potentials connected S-shaped Na tunnels has been widely studied, and it
of electrodes for ASIBs and AKIBs should well locate between was found that Na+ ions could reversibly intercalate/de-intercalate
those of OER and HER to avoid water splitting. Various electrode into/from Na0.44MnO2 host at three redox potentials (0.05, 0.27,
materials have been developed in recent years, and representative and 0.50 V vs. SCE) in the composition range of Na0.44xMnO2
cathode materials can be categorized into four types, i.e., (0.25 o x o 0.44).178 Capacity and stability of Na0.44MnO2 can be
transition metal oxides, polyanionic compounds, PBAs, and further improved by heteroatom substitution, as reported by
organic polymers. Wang et al.179 The Ti-substituted Na0.44MnO2 cathode exhibited
Transition metal oxides can be readily synthesized with a reversible capacity of 76 mA h g1 at 2C and a high rate
controllable morphology and high electrochemical activity, performance up to 8C with 60 mA h g1 retained in a full cell
therefore have attracted tremendous attention in battery coupled with NaTi2(PO4)3/C anode, which was superior to pristine
research.173 As a representative, MnO2 has been demonstrated Na0.44MnO2 (30–40 mA h g1). This ASIB exhibited a good
the capability of hosting sodium ions.174 For example, an ASIB midpoint voltage of around 1.13 V. As for KxMnO2, Liu et al.
based on cubic spinel-type l-MnO2 cathode delivered a high discovered the charge storage mechanism involved K+ extraction
capacity up to 78 mA h g1 and a high midpoint voltage in the first charge process and reversible Na+ intercalation/
of 1.35 V when coupled with an activated carbon anode.175 de-intercalation in subsequent cycles.180 The full cell assembled
Minakshi et al. reported g-MnO2 as cathode for Na+ intercalation/ by coupling K0.27MnO2 cathode with NaTi2(PO4)3 anode delivered
de-intercalation in 7 M NaOH aqueous electrolyte.176 A high a specific capacity of 68.5 mA h g1 at 0.2 A g1 in the voltage
specific capacity of 225 mA h g1 was obtained accompanied range of 0–1.6 V with a midpoint voltage of 0.71 V (Fig. 7a–c).
with a midpoint voltage of 1.32 V (vs. Zn/Zn2+). They confirmed Such ASIB was further improved by designing a hollow nano-
the intercalation of sodium ions into MnO2 structure via XRD and structure for K0.27MnO2 to facilitate electron/ion transport, which
proton induced X-ray emission analysis. Qu et al. examined the increased the specific capacity to 84.9 mA h g1 at 150 mA g1
electrochemical behaviour of V2O50.6H2O in aqueous electrolytes and 56.6 mA h g1 at 600 mA g1 (Fig. 7d and e).181
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Fig. 7 (a) EDS elemental mapping images of K0.27MnO2. (b) Schematic

illustration of the electrochemical mechanisms of the layered K0.27MnO2
cathode. (c) GCD curves of the NaTi2(PO4)3//K0.27MnO2 full cell at 200 mA g1.
Reproduced with permission from ref. 180, Copyright 2014 Elsevier. (d)
Schematic illustration of the synthesis of the K0.27MnO2 with hollow nano-
structure. (e) Rate capacity of the NaTi2(PO4)3//K0.27MnO2 full cell at various

current densities. Reproduced with permission from ref. 181, Copyright 2016
American Chemical Society.
Polyanionic compounds contain a series of tetrahedron

Fig. 8 (a) Initial GCD curves of Na3V2(PO4)3 cathode at various rates.
anion units (XO4)n or their derivatives (XmO3m+1)n (X = S, P, Reproduced with permission from ref. 182, Copyright 2014 Wiley-VCH. (b)
Si, As, Mo, or W) with strong covalent-bonded MOx polyhedra CV curves of polyimide anode and NaVPO4F cathode in 5 M NaNO3
(M represents a transition metal). The (XO4)n unit not only aqueous electrolyte at 0.1 mV s1. Reproduced with permission from
allows fast conduction of alkali ions in an open framework, but ref. 157, Copyright 2014 Elsevier. (c) The illustrative structure of CuNiHCF
cell containing a framework of hexacyanoferrate groups linked by nitrogen
also stabilizes the redox potentials of transition metals. There-
coordinated P site transition-metal ions of Cu and Ni. (d) TEM image
fore, a series of polyanionic compounds including NASICON-type revealing the 20–50 nm particles of CuNiHCF. Reproduced with permis-
material, phosphate, pyrophosphate, fluorinated pyrophosphate, sion from ref. 186, Copyright 2012 American Chemical Society. (e) Rietveld
olivine-type material, etc., have been developed as cathode refinement patterns of X-ray diffraction data of K2FeIIFeII(CN)62H2O
materials for ASIBs. For example, the representative NASICON- nanocubes. (f) FESEM image of K2FeIIFeII(CN)62H2O nanocubes. (g) The
first discharge curves of K2FeIIFeII(CN)62H2O cathode at various current
type cathode Na3V2(PO4)3 (NVP) has large tunnels to accommodate
densities showing two flat plateaus. Reproduced with permission from ref. 66,
sodium ions. Song et al. investigated the electrochemical beha- Copyright 2017 American Chemical Society. (h) GCD curves of the NaTi2(PO)3/
viour of NVP cathode in aqueous solutions of 1 M Li2SO4, 1 M C anode, K2NiFe(CN)61.2H2O cathode and the corresponding full cell. Repro-
Na2SO4, and 1 M K2SO4, respectively. Its storage of Na+ was duced with permission from ref. 187, Copyright 2018 Wiley-VCH.
promising, which exhibited a capacity of around 50 mA h g1
(209 F g1) at 8.5C with a flat discharge plateau at around 0.4 V
(vs. SCE) (Fig. 8a), whereas its Li+ and K+ storage capability was and K+ storage.183 The utilization of PBA frameworks for
far from satisfactory.182 The intercalation of Li+ into NVP selective cation insertion could date back to 1970s–1980s, when
framework is irreversible due to the larger hydrated ionic radius a number of thin-film PBA frameworks (KM[Fe(CN)6], M = Co,
of Li+, and K+ tends to form electric double-layer capacitance on Ni, Cu, Cr, and Ti) were proved electrochemically active in
NVP surface rather than intercalate into the framework because aqueous electrolytes.184 In recent years, a series of high perfor-
of the weak solvation and high conductivity of K+. Qin et al. mance PBA cathodes for ASIBs and AKIBs were reported by
reported a fluoridised NASICON-type compound of NaVPO4F Cui’s group. They first proposed a NiHCF with a chemical
(NVPF) for ASIBs, which showed shifted potentials with two composition of K0.6Ni1.2Fe(CN)63.6H2O for reversible intercala-
pairs of redox peaks at 0.26 V/0.20 V and 0.79 V/0.77 V (vs. SCE) tion/de-intercalation of Na+ and K+ in mildly acidic NaNO3 or
in 5 M NaNO3 aqueous electrolyte, promising higher cell KNO3 electrolyte.137 Based on the redox couple of Fe(CN)64/
voltage compared to NVP (Fig. 8b).157 Another widely studied Fe(CN)63, the NiHCF cathode delivered a specific capacity of
NASICON-type compound is iron-based pyrophosphate, which around 60 mA h g1 at 0.83C with midpoint voltages at 0.59 V
includes Na2FeP2O7, LiFePO4, NaFePO4, etc. Their redox potentials and 0.69 V (vs. SHE) for Na+ and K+ intercalation, respectively.
approximately locate in the range of 0.45–0.72 V (vs. SCE), This cathode also exhibited an extremely stable cycle perfor-
suggesting a moderate full cell working voltage of 0.95–1.22 V if mance with charge/discharge cycles up to 5000 at 8.3C for both
coupling with a 0.5 V (vs. SCE) anode. Na+ and K+ storage, which benefited from the intrinsic rigid
As aforementioned, the ionic radii of Na+ and K+ are larger metal–organic framework. They also synthesized a low-cost PBA
than that of Li+, the choice of host materials for their reversible by replacing the nitrogen-coordinated Fe3+ with Cu2+ through a
intercalation/de-intercalation is thus more limited. Therefore, controlled co-precipitation method.185 The CuHCF delivered a
PBAs with open framework that are suitable to host Na+ and K+ similar capacity for K+ storage compared to NiHCF, but
are urgently needed. Their large ionic channels, compositional achieved a higher midpoint voltage at 0.95 V (vs. SHE). The
and electrochemical tenability are highly potential in both Na+ low-strain structure of CuHCF also contributed to an excellent
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cycling performance, which obtained 83% of the original based on the redox reaction of nitroxide radicals or conjugated
capacity after 40 000 deep discharge cycles. Furthermore, the structure, which does not involve Na+ intercalation/de-inter-
redox potential of PBA can be precisely tuned by adjusting calation, meaning that these polymers can readily be utilized
Cu/Ni ratio in the framework of a Cu–Ni alloyed PBA.186 As for other alkali metal-ion battery systems.
revealed, Cu and Ni could form a fully miscible solution at 3.2.2 Anode materials for aqueous sodium-ion and potassium-
particular sites in the framework without perturbing the struc- ion batteries. Representative anode materials for ASIBs and AKIBs
ture (Fig. 8c and d). The CuNiHCF integrated the high rate, long can be categorized into five types, which include carbon
cycle life of both NiHCF and CuHCF cathodes with controllable materials, transition metal oxides, phosphates, PBAs and
redox potentials. The highest midpoint voltages achieved for K+ organic compounds.
and Na+ storage was around 0.91 V and 0.88 V, respectively. In early works, low-cost activated carbon (AC) has been
However, the sodium-deficient nature of NiHCF and CuHCF utilized as anode material for ASIBs due to its excellent stability
may restrict their practical application due to the need for a in aqueous media.175 It was demonstrated that high surface
sodiated anode. Thus, a cathode of high K+-content potassium area activated carbons or surface modified carbons exhibited a
iron(II) hexacyanoferrate dihydrate (K2FeIIFeII(CN)62H2O) pseudocapacitive and possible hydrogen storage behaviours
nanocubes was synthesized for AKIBs (Fig. 8e and f).66 The between 1.0 and 0.3 V (vs. Hg/Hg2SO4). However, its specific
K2FeIIFeII(CN)62H2O cathode can provide two-electron transfer capacity was just around 50 mA h g1.
per molecular unit, thereby delivering remarkable capacities in The research of metal oxides as anode has been conducted
aqueous electrolytes (up to 120 mA h g1). It exhibited two by Wu’s group, where PPy-coated MoO3 nanobelts for sodium
discharge plateaus at 0.85 V and 0.20 V (vs. Ag/AgCl), respec- storage were developed.198 This anode showed two pairs of
tively (Fig. 8g). Another potassium-rich mesoporous nickel redox potentials located at 0.25 V/0.08 V and 0.49 V/
ferrocyanide(II) (K2NiFe(CN)61.2H2O) to host K+ was synthe- 0.34 V (vs. SCE) with a reversible capacity of 33 mA h g1.
sized recently, which realized impressive rate performances.187 When coupled with Na0.35MnO2, the full ASIB yielded sloping
Its single charge/discharge could be completed within 4.1 s, discharge profiles with a midpoint voltage of 0.6 V. While its
with a capacity of 42 mA h g1 delivered. A flat discharge capacity is still not satisfactory, which is much lower compared
plateau at 0.51 V could be observed, contributing to a plateau to many anodes of ALIBs, thus having urged researchers to
voltage of 1.35 V for the full cell coupled with NaTi2(PO)3/C anode pursue anodes with higher capacities for high-performance
(Fig. 8h). It should be mentioned that this PBA type cathode ASIBs and AKIBs. Deng et al. developed a 1D-nanostructured
was also capable of hosting bivalent magnesium and trivalent sodium vanadium oxide (Na2V6O16nH2O, NVO) through a
aluminium ions, showing high versatility. In addition, many other hydrothermal method (Fig. 9a).199 The layer-structured NVO
PBAs including FeHCF (with two discharge plateaus at 0.8 V and
0.1 V (vs. Ag/AgCl)),188 NaCoHCF (with two discharge plateaus at
0.90 V and 0.38 V (vs. Ag/AgCl)),189 NaMnHCF (with two redox
pairs at 0.58 V/0.39 V and 1.17–1.23 V/1.00 V (vs. Ag/AgCl)),190
VHCF (with a midpoint voltage of 0.84 V (vs. Ag/AgCl)),191 etc.,
have been investigated for sodium storage, showing high diversity
of this open-framework materials.
Compared with inorganic materials, polymers represent a
promising candidate as battery electrodes because of their
merits of metal-free nature, flexibility, light weight, and cost-
effectiveness. More importantly, their structural diversity and
capability of molecular functionalization enable subtle control
of their redox properties and thus providing many opportunities
in improving cell voltage and battery performances.192,193
Whereas, although organic polymer electrodes have been widely Fig. 9 (a) TEM image of the 1D nanostructured Na2V6O16nH2O. Repro-
investigated in ALIBs,194 their applications in ASIBs and AKIBs are duced with permission from ref. 199, Copyright 2014 Elsevier. (b) GCD
still lacking. Koshika et al. reported a poly(2,2,6,6-tetramethyl- curves of the NaTi2(PO4)3//Na cell in non-aqueous electrolyte and the
piperidinyloxy-4-yl vinylether) (PTVE) cathode for sodium storage NaTi2(PO4)3//Zn cell in aqueous electrolyte at 2.0 mA cm2. Inset shows
the cycle stability in aqueous electrolyte. Reproduced with permission
with one-electron reaction in 0.1 M NaCl aqueous solution.195
from ref. 201, Copyright 2011 The Electrochemical Society. (c) Working
The PTVE cathode exhibited a flat discharge plateau at 0.73 V mechanism of the MnII–NRC–MnIII/II//CuII–NRC–FeIII/II ASIB based on
(vs. Ag/AgCl) with a reversible capacity of 130 mA h g1 at 60C, Na+ intercalation/de-intercalation. The anode and the cathode have the
and maintained 75% of the initial capacity after 1000 cycles. same open framework crystal structure. (d) GCD curves of the MnII–
Besides, PPy-based cathodes were also discovered for ASIBs, NRC–MnIII/II//CuII–NRC–FeIII/II full cell at various C rates. Reproduced
with permission from ref. 139, Copyright 2014 Springer Nature. (e) The
whose redox potential was located between 0 and 0.8 V (vs.
reduction potentials of quinone electrodes measured by CV test vs.
Ag/AgCl), and maintained a high specific capacity of around electrolyte pH values. It can be seen that PPTO could be used as anode
110 mA h g1 for hundreds of cycles.196,197 It is worth mention- for various ARMB systems. Reproduced with permission from ref. 205,
ing that the energy storage mechanism of PTVE and PPy is Copyright 2017 Springer Nature.
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anode enabled Na+ intercalation/de-intercalation with a solid- to reversibly combine Na+. The polyimide anode showed
state diffusion coefficient of about 1014 cm S1. More impor- symmetric redox peaks at 0.34 V/0.52 V (vs. SCE) and
tantly, it delivered an initial specific capacity of 123 mA h g1 delivered a discharging capacity of 184 mA h g1 and a charging
with a midpoint voltage at 0.41 V (vs. SCE). The major draw- capacity of 165 mA h g1 in a 5 M NaNO3 aqueous solution.
back of this material is that its capacity faded quickly in When coupled with NaVPO4F cathode, the full ASIB exhibited a
subsequent charge/discharge cycles due to irreversible structural midpoint voltage of 0.90 V. Meanwhile, Deng et al. reported
change upon sodium intercalation/de-intercalation, which is a another redox-active and water-insoluble polyimides, namely,
common issue for vanadium oxides. poly-(naphthalene four formyl ethylenediamine) (PNFE).204 The
NASICON-type NaTi2(PO4)3 (NTP) is a representative phos- reversible Na+-association/dissociation with the carbonyl
phate anode material for ASIBs due to its open framework for groups occurred within the potential range of 1.0 to 0 V with
sodium storage.200 Park et al. studied the electrochemical a midpoint voltage of 0.58 V (vs. Ag/AgCl). This PNFE not only
behaviour of NTP in both organic and aqueous electrolyte.201 delivered a high capacity of 130 mA h g1, but also provided a
It delivered a specific capacity of 120 mA h g1 in organic superior rate capability as well as an excellent capacity reten-
electrolyte with a midpoint voltage of 2.1 V (vs. Na+/Na), and a tion of 91.2% over 1000 cycles. Besides, as a widely investigated
specific capacity of 123 mA h g1 in aqueous electrolyte with a organic compound in organic batteries, quinones have been
midpoint voltage of 0.77 V (vs. Ag/AgCl) (Fig. 9b), corres- demonstrated as suitable anode materials for aqueous batteries
ponding to the redox conversion between Ti3+ and Ti4+. The by Yao’s group. They discovered that prepared quinones were
cyclability of NTP anode was better in aqueous electrolyte, able to operate with different charge carrier species (including
whereas, it still faded quickly within 30 charge/discharge cycles, H+, Li+, Na+, K+, Mg2+) under different pH values (from 1 to 15),
which is similar to that of LiTi2(PO4)3. Xia’s group revealed that temperatures (35 to 25 1C) and atmospheres (with/without O2).205
the capacity fading of aqueous batteries should be ascribed By rationally selecting/designing quinone molecules with
to side reactions between discharged electrodes with water desired structure, they further developed three major systems
and/or oxygen in aqueous electrolytes.163 Eliminating dissolved coupling with various industrially-mature cathode materials,
oxygen, adjusting electrolyte pH and carbon coating are including PbO2 (in acidic condition), LiMn2O4 (in neutral
effective approaches to improve the cycling stability of NTP. condition), and Ni(OH)2 (in alkaline condition). Among these
For example, a microwave-assisted method was employed to quinone molecules, polymerized pyrene-4,5,9,10-tetraone (PPTO)
synthesize carbon-coated NTP, which exhibited an improved was especially versatile as anode for ARMBs (Fig. 9e). Besides the
capacity retention of 86% after 100 cycles at 1C in 1 M Na2SO4 capability to initiate ALIBs, it was also coupled with NVP cathode
aqueous electrolyte.202 Frogspawn-structured hierarchical por- in a neutral 5 M NaNO3 electrolyte, resulting an ASIB showing a
ous NTP/C arrays were also reported for ASIBs with a superior high specific capacity of 201 mA h g1 as well as a good cyclability
cycle life up to 2000 cycles at 20C.203 of 79% capacity retention over 80 charge/discharge cycles. The
As discussed in Section 3.2.1, PBAs have been used as full ASIB exhibited sloping discharge profiles with a midpoint
cathode materials for ASIBs due to their relatively high redox voltage of 0.65 V.
potentials of Fe and other N-coordinated metal ions. Such For ASIBs and AKIBs, representative cathode and anode
unique open framework-structured materials, however, have materials have been discussed in this section, unveiling their
seldom been reported as anode for sodium/potassium storage. inferior performances compared to ALIBs, which is mainly due
The first study of utilizing PBA as anode for ASIB was proposed to their larger ionic radius that imposes higher requirement on
by Pasta et al.139 Aiming to develop an anode with sufficiently host materials including larger intercalative framework and
low potential while avoiding triggering HER, they screened a better structural stability. Redox potentials of reprehensive
series of PBAs including CrII–NRC–MnII/I (0.312 V vs. SHE), cathode and anode materials for ASIBs and AKIBs are summarized
MnII–NRC–MnIII/II (0.052 V vs. SHE), FeII–NRC–MnIII/II and compared in Fig. 10. As revealed, NASICON-type materials
(0.075 V vs. SHE) and CrII–NRC–MnIII/II (0.352 vs. SHE), and exhibit desired potentials as either cathode or anode. Some
selected MnII–NRC–MnIII/II in consideration of stability and PBA-type materials are also preferential for ASIB and AKIB
crystallinity. The prepared MnHCF anode exhibited a specific cathode. It should be noted that except for the study employing
capacity of 57 mA h g1 at 50C and yielded a full cell midpoint a concentrated aqueous electrolyte (introduced in Section 4.4.2),
voltage of 0.88 V when paired with CuII–NRC–FeIII/II cathode no stable anode materials in normal aqueous electrolytes have
(Fig. 9c and d). This full ASIB showed negligible capacity loss been reported for AKIBs so far. To facilitate the development
over 1000 cycles in 10 M NaClO4 aqueous electrolyte saturated of ASIBs and AKIBs, more studies should be implemented
with Mn(ClO4)2 at pH = 6.4. to promote electrochemical kinetics and structural stability of
In addition, as carbonyl-based organic electrodes have been electrode materials.
widely investigated in organic rechargeable batteries, it is
feasible to borrow some effective strategies from these well- 3.3 Aqueous zinc-ion batteries
studied representatives to develop high-performance ASIBs and Traditional alkaline zinc-based batteries are either non-rechargeable
AKIBs. In 2014, Qin et al. proposed a 1,4,5,8-naphthalenetetra- or extremely poor in cycle stability. Zinc-ion batteries employing
carboxylic dianhydride (NTCDA)-derived polyimide as anode for neutral/mild aqueous electrolytes have shown great improvements
ASIB.157 It involved an enolization process during discharge/charge in reversibility and rate performance. Aside from the nature
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Fig. 10 Comparison of redox potentials of representative electrode materials for ASIBs and AKIBs. Red-colour columns and blue-colour columns
represent cathodes and anodes, respectively.
abundance and eco-friendliness, zinc metal is regarded as an result, the AZIB based on commercial a-MnO2 could only
ideal anode material for aqueous zinc-ion batteries (AZIBs) due provide a capacity of around 187 mA h g1 at 100 mA g1. To
to its high theoretical capacity (820 mA h g1), high electrical improve electrochemical properties, nanostructured MnO2 was
conductivity, relatively low redox potential, and high safety.206–209 further electrodeposited on carbon fibre paper (MnO2@CFP).43
Due to the feasibility of directly utilizing zinc metal as anode in The AZIB based on MnO2@CFP presented a long and flat
aqueous electrolytes, research efforts of AZIBs are mainly focused discharge plateau at 1.3 V accompanied with a tilting plateau
on developing suitable cathode materials. In this section, a variety at 1.4 V in mild acidic ZnSO4 + MnSO4 electrolyte (Fig. 11a),
of representative cathodes for AZIBs such as manganese-based which delivered a discharge capacity of 290 mA h g1 at 90 mA g1
materials, vanadium-based materials, organic materials, and and a cyclability of 10 000 cycles at 6.5C with a capacity decay rate of
other compounds including PBAs, two-dimensional (2D) materi- 0.007% per cycle. The improvement of working voltage of
als and nickel/cobalt oxides, are thoroughly discussed in terms of MnO2@CFP cathode arose from the highly-porous nanoflake struc-
their electrochemical performances and voltage characteristics. It ture and strong interfacial adhesion that favoured the reversible
should be noted that all the specific capacity values of reported insertion/extraction of H+ and Zn2+ ions during charge/discharge
AZIBs are based on the mass of cathode materials unless other- (Fig. 11b), which also ensured high cycling stability. Among the
wise specified. MnO2 polymorphs, b-MnO2 is considered to be the most thermo-
3.3.1 Manganese-based materials as cathode for aqueous dynamically stable one as it is composed of MnO6 octahedral unit
zinc-ion batteries. Manganese-based materials are considered single chains by forming a 1 1 tunnel along c axis. Although such
as one type of the most promising cathode materials for AZIBs narrow tunnel is not favourable for the diffusion of Zn2+,221 it was
due to their low cost, high operating potential (1.0–1.8 V vs. revealed in a recent study that the AZIB based on b-MnO2 nanorod
Zn/Zn2+) and high theoretical energy storage capability (e.g., cathode could deliver a high capacity of 270 mA h g1 at 100 mA g1
308 mA h g1 for MnO2).210 Benefiting from the rich diversity, with two tilting discharge plateaus at 1.40 V and 1.24 V, and retain
a number of manganese-based oxides can be readily used 75% of its original capacity after 200 charge/discharge cycles.222
in constructing AZIBs, such as MnO2 with different crystal Ex situ characterization technologies confirmed the storage of
structures,211–216 Mn2O3,217 Mn3O4,218 ZnMn2O4,219 etc. Zn2+ via the intercalating of Zn2+ into the b-MnO2, resulting in the
In the early stage, MnO2 was the most investigated cathode formation of Zn-intercalated phases and the precipitation of
material for AZIBs due to its tunnel or layered structure that ZnSO43Zn(OH)25H2O. g-MnO2 with randomly arranged 1 2
enables reversible intercalation/de-intercalation of zinc ions. and 1 1 tunnels has also demonstrated reversible zinc storage
MnO2 exhibits different crystallographic polymorphs including capability with a high discharge capacity of 285 mA h g1 at 0.05
a-, b-, g-, R-type (tunnel structures), d-type (layered structure), mA cm1 and similar discharge profiles to a-MnO2 with two
and l-type (spinel structure).220 The phase structure and tilting plateaus.223 In addition, d-MnO2 with typical layered struc-
morphology of MnO2 can play a significant role in the electro- ture was found to exhibit one discharge plateau at 1.23 V during
chemical properties and voltage characteristics of AZIBs. For its initial cycling, while two discharge plateaus at 1.38 V and
example, the commercial a-MnO2 with 2 2 tunnels shows two 1.23 V were observed in the subsequent cycling (vs. Zn/Zn2+).224
discharge plateaus at around 1.4 and 1.3 V (vs. Zn/Zn2+), Detailed investigations revealed that the intercalation of Zn2+
corresponding to H+ and Zn2+ ions insertion, both of which caused the phase transformation of layered d-MnO2 to spinel-
are very tilting owing to the large a-MnO2 particle size. As a type ZnMn2O4 and layered-type d-ZnxMnO2 with Mn(II) phase. In a
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an average width of 5 nm. It displayed a discharge capacity

of 382.2 mA h g1 at 0.3 A g1 and a superior cyclability of
3000 cycles with 94% capacity retention at 3.0 A g1.229 In
addition, doping metal ions (e.g. Al3+, Co2+, Ni2+) into MnO2
lattice could facilitate Zn2+ intercalation and enhance working
potential.230–232 Yang et al. studied the electronic structure of
Al-doped a-MnO2 via first-principle calculations, and found
that the substitution of Mn with Al atom caused redistribution
of charge density, which provided more electrons for a-MnO2,
thus contributing to an enhanced electronic conductivity.232
Another feasible approach is to engineer oxygen vacancy in
MnO2, which can improve electrical conductivity by regulating
surface chemistry. Owing to the presence of oxygen vacancy,
the Gibbs free energy of Zn2+ absorption on the MnO2 surface
can be reduced to thermoneutral value, indicating the highly

reversible adsorption/desorption process of Zn2+. Besides, more
electrons can be contributed into the delocalized electron cloud
of oxygen-deficient MnO2, since fewer electrons are required for
the formation of Zn–O bonding, which improves the attainable
capacity. As a result, the oxygen-deficient MnO2 cathode
achieved a high discharge capacities of 345 mA h g1 and a
remarkable stability of 84% capacity retention after 2000 cycles
at 5 A g1.233 In addition to intrinsically poor conductivity,
repeated insertion of hydrated cations during electrochemical
processes destroys the ordered structure of MnO2, leading to
inevitable capacity fading. Introducing a polymer (e.g. polyani-
Fig. 11 (a) GCD curves of the Zn//MnO2@CFP full cell at 0.3C in mild line) into MnO2 layers has been proposed to effectively con-
acidic ZnSO4 + MnSO4 aqueous electrolyte. (b) Discharge galvanostatic solidate the latter’s layered structure and avoid the phase
intermittent titration technique (GITT) curves of the Zn//MnO2@CFP full
transformation induced by hydrated H+/Zn2+ insertion, which
cell at 50 mA g1 for 2 min with 4 h rest. It is proposed that the region I
voltage plateau attributes to H+ insertion and the region II voltage plateau resulted in improved cycling stability and discharge capacity
attributes to Zn2+ insertion. Reproduced with permission from ref. 43, (Fig. 11d and e).234 Another novel approach incorporated
Copyright 2017 American Chemical Society. (c) Schematic illustration of crystal water into the layered host structure of MnO2 and
Zn2+ intercalation/de-intercalation in the 3D framework of ZnMn2O4 (left) shielded the electrostatic interactions between zinc ions and
and hypothesized Zn2+ diffusion passage in ZnMn2O4 without and with Mn
host materials, revealing promoted Zn2+ diffusion. Moreover,
vacancies (right). Reproduced with permission from ref. 219, Copyright
2016 American Chemical Society. (d) Schematic illustration of the synth- such interlayer crystal water molecules assisted the stabilization of
esis of PANI-intercalated MnO2 nanolayers. (e) Cycling test of the Zn// layered MnO2 framework by suppressing side reactions during
PANI-intercalated MnO2 full cell at 200 mA g1. Reproduced with permis- cycling. The as-assembled AZIB with a high open-circuit voltage of
sion from ref. 234, Copyright 2018 Springer Nature. 1.55 V delivered a high capacity of 350 mA h g1 at 100 mA g1
along with improved cycling stability and rate capability.235
later study, this ZnMn2O4 was turned into a viable zinc host 3.3.2 Vanadium-based materials as cathode for aqueous
material by introducing cation vacancies.219 The resultant AZIB zinc-ion batteries. Vanadium-based compounds usually show
with cation-defective spinel ZnMn2O4 cathode provided a specific lower midpoint voltages (o1.0 V vs. Zn/Zn2+) compared to
capacity of 150 mA h g1 at 50 mA g1 with a midpoint voltage of Mn-based materials, while they possess high discharge capacities
1.33 V. Facile charge transfer and Zn2+ intercalation in the robust (up to 400 mA h g1). Here, some representative vanadium-based
cation-defective spinel structure were revealed to account for its cathode materials that have been widely used in AZIBs are
good performances (Fig. 11c). introduced, including V2O5, MxV3O8 and vanadium-based phos-
Despite its advantages, MnO2 cathode suffers from intrinsic phates and sulphides, with corresponding discussions on their
poor electrical conductivity that hinders electrochemical full cell voltage characteristics, reaction mechanisms and
kinetics. One obvious symptom is that the charging/discharging strategies to improve overall electrochemical performances.
curves of pristine MnO2 display sloping voltage plateau and shorter V2O5 has been widely studied for AZIBs owing to its
duration period at high rates. So far, it is generally accepted that the extremely high theoretical capacity of 589 mA h g1 based on
combination of a conducting material (e.g. CNTs, graphene) with two-electron redox centres.236 Whereas, V2O5 for Zn2+ inter-
MnO2 is an effective strategy to improve its conductivity, thus calation generally exhibits poor cycling stability and low rate
bringing about better electrochemical properties.225–228 For capability because of its unstable layered structure during
example, Wu et al. attempted to increase the conductivity of electrochemical processes. Similar to the strategies used for
a-MnO2 nanowire by coating graphene scroll on its surface with MnO2, to promote performances, structural water and hetero
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metal ions can be introduced into layered V2O5 as pillars that It showed no obvious discharge plateau, and the midpoint
strengthen its interlayer structure.236,237 For example, Yan et al. voltage located at around 0.70 V.
fabricated a V2O5nH2O/graphene (VOG) composite via a liquid Bearing relative high oxidation states of V5+ and layered
phase method.238 The initial CV curve of VOG showed two pairs structure, MxV3O8 (M = Li, Na, H, etc.) composed of VO6
of redox peaks associating with Zn2+ intercalation/de-intercalation octahedra and V2O8 square pyramids have been studied as
located at 0.97 V/0.91 V and 0.63 V/0.54 V, respectively. Subse- cathode candidates for Zn2+ intercalation/de-intercalation. For
quent CV curves overlapped with the initial one, indicating the example, Wan et al. proposed a simple liquid–solid stirring
solid-solution reaction of Zn2+ intercalation/de-intercalation strategy to fabricate NaV3O81.5H2O (NVO) nanobelts for AZIBs.240
was highly reversible (Fig. 12a). The AZIB with VOG cathode CV profiles of the resultant AZIB exhibited two pairs of redox
delivered a high initial capacity of 381 mA h g1 at 60 mA g1 peaks located at 0.55 V/0.77 V and 0.85 V/1.06 v which were owing
and retained 71% of its initial capacity after 900 cycles. Its to the reversible redox reactions from NaZn0.1V3O81.5H2O to
discharge profiles showed no obvious plateau but a midpoint H2.14NaZn0.2V3O81.5H2O and then to H3.9NaZn0.5V3O81.5H2O,
voltage of 0.68 V. Ming et al. reported a layered Mg2+-intercalated corresponding to the valence changes of vanadium from V5+ to
V2O5 cathode with enhanced electrochemical activity for AZIBs V4+ and V4+ to V3+.241–243 The AZIB achieved a highly reversible
(Fig. 12b).239 Due to the larger radius of hydrated Mg2+ (4.3 Å), capacity of 380 mA h g1 at 0.05 A g1 along with a midpoint
the expanded interlayer spacing (13.4 Å) allowed for efficient Zn2+ voltage located 0.72 V (Fig. 12d). 1 M Na2SO4 as an additive was
intercalation/de-intercalation, resulting an AZIB with a wide added into the ZnSO4 electrolyte to suppress the dissolution of
working voltage range of 0.1–1.8 V (Fig. 12c). The AZIB based NVO and the growth of Zn dendrites, which notably improved the
on Mg0.34V2O5nH2O cathode delivered 353 mA h g1 and reversibility of Zn2+ intercalation/de-intercalation, resulting in a
264 mA h g1 at 100 mA g1 and 1.0 A g1, respectively, along high capacity retention of 82% after 1000 cycles at 4 A g1.
with a 97% capacity retention after 2000 cycles at 5.0 A g1. Zn3V2O7(OH)22H2O and Zn2V2O7 are another type of vanadium-
based cathode materials for AZIBs, which have porous crystal
framework and expanded interlayer space. A study showed that
an AZIB employing ultralong Zn3V2O7(OH)22H2O (ZVO) nano-
wires as cathode delivered a specific capacity of 213 mA h g1
at 50 mA g1 along with a midpoint voltage of 0.75 V (Fig. 12e
and f).244 Since the open-framework structure of ZVO cathode
allows fast immigration of Zn2+, the AZIB exhibited very good
rate capability, achieving 76 mA h g1 at a high current density
of 3000 mA g1. Besides, as an alternative to Zn3V2O7(OH)22H2O,
Zn2V2O7 nanowires were synthesized by one-step hydrothermal
method recently.245 AZIBs based on Zn2V2O7 cathode could be
operated in a voltage range of 0.4–1.4 V with a midpoint voltage
of 0.67 V. After fully activation, the battery delivered a specific
capacity of 197.4 mA h g1 at 300 mA g1. Benefitted from its
nanowire morphology and robust structure, the AZIB exhibited
high rate performance and long-term cyclability, achieving 85%
capacity retention (138 mA h g1) after 1000 cycles at 4000 mA g1.
Other vanadium-based cathodes include vanadium-based
phosphates and sulphides. For example, owing to the presence
of PO43 polyanions, NASICON-typed NVP cathode exhibited a
flat discharge plateau located at 1.10 V (vs. Zn/Zn2+), exceeding
the midpoint voltages of most vanadium oxides.209 But it
Fig. 12 (a) CV curves of the as-prepared VOG for the initial 3 cycles.
Reproduced with permission from ref. 238, Copyright 2018 Wiley-VCH. (b)
suffered serious capacity decay during long-term cycles. To
Crystal structure of the layered Mg2+-intercalated V2O5. (c) GCD curves of address this issue, Li et al. fabricated a Na3V2(PO4)2F3 cathode
the Mg2+-intercalated V2O5 cathode at various current densities. Repro- for AZIBs, the full cell displayed an even higher plateau voltage
duced with permission from ref. 239, Copyright 2018 American Chemical of 1.63 V, as well as a high energy density of 97.5 W h kg1
Society. (d) GCD curves of the Zn//NVO full cell at various current
and an excellent cyclability with 95% capacity retained after
densities. Reproduced with permission from ref. 240, Copyright 2018
Springer Nature. (e) TEM image of the ZVO nanowires. Inset shows its
4000 cycles.246 This good electrochemical performance was due
EDS mapping, revealing the existence of Zn, O and V. (f) GCD curves of the to the strong affinity of F atoms, which endowed Na3V2(PO4)2F3
ZVO cathode at 50 mA g1 for the initial 3 cycles. Reproduced with with more stable structure that led to ‘‘zero-strain’’ change
permission from ref. 244, Copyright 2018 Wiley-VCH. (g) TEM image of during Zn2+ intercalation/de-intercalation. In addition, the
the VOPO4 particle. (h) Comparison of the 2nd GCD curves between Zn//
introduction of extra anionic redox reaction is another effective
VOPO4 batteries in 21 M LiTFSI electrolyte and in 1 M Zn(Tr)2 electrolyte.
Reproduced with permission from ref. 247, Copyright 2019 Wiley-VCH. (i)
strategy to enhance the working voltage and energy density of
SEM–EDX of the as-prepared layered VS2. Reproduced with permission AZIBs, thus a high-performance AZIB with reversible oxygen
from ref. 248, Copyright 2017 Wiley-VCH. redox chemistry was developed based on layered VOPO4
View Article Online
cathode and ‘‘water-in-salt’’ electrolyte (Fig. 12g).247 Due to the Moreover, the p-chloranil delivered a high energy density of
contribution of oxygen redox reactions, the Zn//VOPO4 battery around 200 W h kg1, which is comparable with state-of-the-art
displayed an expanded working voltage range of 0.8–2.1 V, cathodes of AZIBs. For organic carbonyl compounds, carbonyl
which was much wider than the voltage range of 0.8–1.8 V groups are believed to be the active centres of electrochemistry, so
when merely relying on the redox reactions of vanadium increasing carbonyl groups in these compounds could be a
(Fig. 12h). This broadened voltage range notably benefited reliable approach to enhance overall electrochemical perfor-
battery capacity (from 109 mA h g1 to 139 mA h g1) and mances. According to Zhao et al., calix[4]quinone (C4Q) with eight
midpoint voltage (from 1.32 V to 1.44 V). Moreover, a sulphide carbonyls could serve as a high-performance cathode for AZIBs
of VS2 synthesized via a facile hydrothermal reaction (Fig. 12i) (Fig. 13c), which presented a discharge capacity of 337 mA h g1
was employed as cathode for AZIBs in 2017 for the first time, as well as a good cycling stability with 87% capacity retention after
the full cell exhibited a midpoint voltage of 0.63 V with two flat 1000 cycles.251 Moreover, this AZIB exhibited a flat discharge
discharge plateaus located at 0.69 V and 0.61 V.248 This battery plateau at 1.0 V with a low polarization of 70 mV, which
delivered a specific capacity of 190.3 mA h g1 at 0.05 A g1 and contributed to stable energy output and high energy efficiency
an energy density of 123 W h kg1 (the latter was based on the (Fig. 13d). Such remarkable Zn2+ storage capability was attributed
mass of both active materials). to the carbonyls on and under C4Q molecules that displayed
3.3.3 Organic materials as cathodes for aqueous zinc-ion lower electrostatic potential and thus enabling the nimble uptake
batteries. A variety of organic compounds have been proposed of Zn2+ during redox reactions. However, a Nafion separator was
as cathode materials for AZIBs, including organic carbonyl needed in this Zn//C4Q AZIB to prevent the crossover of
compounds and conducting polymers.249 According to Kundu discharging products originated from C4Q cathode. As an
et al., p-chloranil with soft crystal structure could realize reversible alternative, Guo et al. designed a pyrene-4,5,9,10-tetraone
and efficient Zn2+ storage, offering a large discharge capacity of (PTO) cathode for AZIBs,252 which was inherently insoluble
over 200 mA h g1 along with a flat discharge plateau at around and thus without requiring the expensive fluorine-containing
1.1 V and a small polarization of 50 mV (Fig. 13a and b).250 membrane as separator. The PTO exhibited two pairs of redox
peaks at 1.0 V/1.17 V and 0.63 V/0.85 V (vs. Zn/Zn2+) that
corresponded to the reversible coordination/incoordination of
Zn2+ on carbonyl group of PTO during charge/discharge. Due to
the efficient utilization of carbonyl groups in PTO, the Zn//PTO
battery showed a high capacity of 336 mA h g1 at 0.04 A g1
with a midpoint voltage of 0.75 V (Fig. 13e), contributing to a
high energy density of 186.7 W h kg1. Although carbonyl-
containing organic electrodes possess fast redox kinetics, they
generally exhibit poor rate performance due to their intrinsic
low electronic conductivity. Thus, further optimization is needed
for better excavating this type of organic carbonyl compounds.
Compared to metal oxides and organic carbonyl compounds,
conducting polymers with long-range p-conjugation system
possess higher electrical conductivity and structural stability.
Recently, two typical conducting polymers of PANI and PPy
have been investigated as cathode for AZIBs. Kim et al.
proposed a polyaniline-coated carbon fibre (PANI/CF) cathode
for flexible AZIBs.253 It was found that a thin (150 nm) and
highly porous PANI layer was immobilized on carbon fibres,
providing high surface area and enhanced electrical conductivity
for redox reactions.254 Such PANI/CF cathode could be operated at
a high rate of 600C within the voltage range of 0.7–1.7 V. In
another study, PANI nanorods were deposited on lens papers with
large voids that could effectively promote electrolyte infiltration
Fig. 13 (a) CV curves of the Zn anode (black line) and the p-chloranil
and ion diffusion.255 The resultant AZIB delivered a specific
cathode (red line) in 1 M Zn(OTf)2–H2O electrolyte at 5 mV s1 and 0.1 mV s1,
respectively. (b) Selected cycles of GCD curves of the p-chloranil cathode at
capacity of 142.3 mA g g1 at 0.2 A g1 over the voltage range of
C/5 rate. The numbers indicate cycle number. Reproduced with permission 0.7–1.7 V. One drawback of PANI cathode is its instability in acidic
from ref. 250, Copyright 2018 American Chemical Society. (c) Schematic electrolytes, where PANI undergoes deprotonation during
illustration of the synthesis of C4Q. (d) GCD curves of the Zn//C4Q full cell repeated charge/discharge, leading to severe degradation. To solve
at 20 mA g1. The upper X axis indicates the uptake number of zinc ions.
this problem, Shi et al. reported a sulfo-self-doped PANI electrode
Reproduced with permission from ref. 251, Copyright 2018 American Asso-
ciation for the Advancement of Science. (e) GCD curves of the Zn//PTO full
(PANI-S) where SO3 self-dopant acted as internal proton
cell at various current densities. Reproduced with permission from ref. 252, reservoir to maintain high local proton concentration on the
Copyright 2018 Wiley-VCH. polymer backbone and promoted reversible redox reactions
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during charge/discharge. AZIB employing such cathode was

operated in the voltage range of 0.5–1.6 V with a discharge
capacity of 184 mA h g1 at 0.2 A g1.256 All these PANI-based
AZIBs showed sloping discharge profiles with a midpoint
voltage at around 1.09 V. Similar to PANI, PPy can also imitate
reversible doping/de-doping when used as cathode for AZIBs.
As reported by Wang et al., the Zn//PPy battery provided a
capacity of 123 mA h g1 and a midpoint voltage of 0.55 V
within the voltage range of 0–1.2 V, retaining 41% and 38% of
its initial capacity after 100 and 200 cycles, respectively.252 Li
et al. further fabricated nanostructured PPy composite aerogels
that allowed easy electrolyte infiltration and ion diffusion.257
The obtained AZIB delivered a higher specific capacity of
150 mA h g1 and a higher midpoint voltage of 1.04 V within
the voltage range of 0.6–1.6 V, and retained 76.7% of its initial

capacity after 1000 charge/discharge cycles at 8 A g1. Fig. 14 (a) GCD curves of the FeHCF cathode after various cycles at the
3.3.4 Other cathode materials for aqueous zinc-ion batteries. current density of 1 A g1, showing increasing capacity. (b) A record-high
Up to now, a few PBAs with large open framework suitable for cycle stability of the Zn//FeHCF full cell with in-depth discharge/charge
zinc-ion intercalation have been investigated as cathode materials processes up to 10 000 cycles at 3 A g1. Reproduced with permission
from ref. 261, Copyright 2019 Wiley-VCH. (c) Schematic illustration of the
for AZIBs. Zn//ZnHCF battery was first reported in 2014 by Zhang fabrication of E-MoS2. (d) GCD curves of Zn/E-MoS2 full cell at various
et al., which delivered a capacity of 65.4 mA h g1 at 1C and a current densities. Reproduced with permission from ref. 264, Copyright
midpoint voltage of 1.72 V with a tilting discharge plateau.258 In a 2018 Elsevier. (e) Schematic illustration of the formed quasi-SEI layer
later study, another AZIB prototype was constructed based on between zinc metal anode and the solid-state PANa electrolyte. (f)
CuHCF cathode, yielding a midpoint voltage of around 1.7 V.259 It Comparison of capacity retention with the state-of-the-art aqueous alka-
line rechargeable batteries. Reproduced with permission from ref. 16,
can be seen that PBAs as cathode for AZIBs usually exhibit high Copyright 2018 Wiley-VCH.
operating voltages (with midpoint voltage 41.5 V), while their
discharge capacities are relatively low (o100 mA h g1), and their
cycle stability was not satisfactory. For example, the discharge zinc ion storage capability was attributed to the ultrathin
capacity of CuHCF was lower than 60 mA h g1, and it was just mesoporous arrays featuring high surface areas and single-
demonstrated to be charged/discharged for over 100 cycles. crystalline layered structure with 2D facile ion transport path-
To address such concerns, Kasiri et al. proposed to partially ways. Our group also demonstrated an AZIB utilizing a 2D
substitute Cu with Zn in CuHCF, and thus achieved an excellent layered material of MoS2 nanosheets with expanded interlayer
cycling stability of 85.54% capacity retention at 1C after spacing (E-MoS2) grown on carbon fibre cloth as zinc-ion
1000 cycles.260 More recently, our group utilized a high- intercalative cathode.264 The enlarged interlayer distance of
voltage scanning method up to 2.3 V to activate FeHCF, which E-MoS2 enable Zn2+ intercalation with fast reaction kinetics
remarkably improved its specific capacity, cycling stability.261 and low energy barrier. Thus, the Zn/E-MoS2 battery exhibited a
The resultant AZIB employing this activated FeHCF delivered high specific capacity (202.6 mA h g1 at 0.1 A g1) and an
an increased capacity of 76 mA h g1 (at 1 A g1) with a record outstanding long-term cycling stability (98.6% capacity retention
cycling stability that retained 82% and 73% of its initial capacity after 600 cycles). However, this AZIB showed sloping discharge
after 5000 and 10 000 charge/discharge cycles (at 3 A g1), profiles with a low midpoint voltage of 0.6 V, which impedes its
respectively (Fig. 14a and b). Kinetic analyses revealed that such energy density (Fig. 14c and d).
remarkable performances were attributed to the increased redox In addition, some high-performance AZIBs with conversion-
active sites and stable structure induced by the high-voltage type nickel/cobalt oxide cathodes have been developed. For
activation. Whereas, this AZIB exhibited a midpoint voltage of example, a flexible Zn/Ni battery operated within the voltage range
around 1.25 V, which is lower compared to the AZIBs using of 1.4–1.9 V was proposed by using a self-supported NiCo2O4
ZnHCF and CuHCF cathodes. cathode, which delivered a high capacity of 183.1 mA h g1 and
Besides, it is well-known that 2D materials with large inter- an energy density of 303.8 W h kg1.265 However, due to the
layer space could offer abundant active sites with reduced ion insufficient active sites and intrinsic poor conductivity (semi-
diffusion resistance, which is favourable for metal ion inter- conductor nature), the capacity and rate capability of NiCo2O4
calation/de-intercalation.262 Chao et al. reported the first AZIB cathodes are far from satisfactory. To tackle these issues,
utilizing a 2D Layered cathode of zinc orthovanadate array.263 ultrathin NiCo2O4 nanosheets (P-NiCo2O4x) were prepared
This AZIB exhibited a specific capacity of 204 mA h g1 and using a facile solvothermal method with the simultaneous
sloping discharge profiles with a midpoint voltage of 0.86 V introduction of oxygen vacancies and phosphate ions, which
at 0.5C. Its maximum energy and power densities reached exhibited improved electrochemical properties.266 It is found
115 W h kg1 and 5100 W kg1, respectively (based on the that oxygen vacancies not only acted as shallow donor to
mass of both electrodes including current collectors). The good improve electrical conductivity of NiCo2O4, but also provided
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sufficient active sites for Zn2+ insertion. Besides, phosphate ion of zinc and restricted the motion of deposition kinetics, hence
has a longer bond length and lower electronegativity compared preventing the runaway growth of large dendrites. Parker et al.
to O2 on the surface, leading to a decreased energy of electron initially proposed to suppress zinc dendrite growth by construct-
transport, thus improving surface activity and reaction kinetics. ing three-dimensional zinc anode.273 The three-dimensional zinc
As a result, the P-NiCo2O4x cathode presented a tilting high- sponge they demonstrated reached ca. 90% utilization (corres-
voltage plateau at 1.68 V, which was notably superior to pristine ponding to 728 mA h gZn1) when discharged in alkaline electro-
NiCo2O4 cathode. At the high current density of 3 A g1, the lyte, and it can be cycled in various cells without the formation of
P-NiCo2O4x cathode provided a high capacity of 361.3 mA h g1, macroscale dendrites. Another method proposed by Higashi et al.
which was ten times higher than that of pristine NiCo2O4 cathode. employed a backside-plating configuration, where the backside
It also achieved an outstanding energy density of 616.5 W h kg1 plating of zinc was achieved via coating an insulation layer on the
at a power density of 5.15 kW kg1. In a recent study, our group edges and the ‘‘front’’ side of a copper foil that faces zinc metal
has demonstrated for the first time that electrolyte played a counter electrode.274 In this way, zinc ions have to travel over the
unique and important role in improving cycle stability for AZIBs edge and deposit on the open back side of the copper foil,
based on NiCo-hydroxide cathode.16 The developed sodium poly- enabling long-term cycling of zinc batteries without shorting.
acrylate (PANa) hydrogel held a concentrated electrolyte solution, In neutral or mildly acidic aqueous electrolytes (which are
where water was well absorbed and retained, and zinc ions were adopted by most AZIBs), two main strategies have been devel-
immobilized to form a quasi-SEI on the PANa network (Fig. 14e), oped to effectively suppress zinc dendrites. One is to construct
thus facilitating ion transport and suppressing zinc dendrite artificial SEI. As revealed by Li et al., the Zn@C anode where
formation. The resultant battery exhibited a tilting discharge carbon coating layer served as an artificial SEI realized stable
plateau at 1.58 V and retained 73% and 65% of its initial capacity zinc stripping/plating and improved kinetics without obvious
after 10 000 and 16 000 charge/discharge cycles at 96C (Fig. 14f), zinc dendrite formation, which should be attributed to the even
respectively. Although possessing attractive performances, it current distribution and resultant homogeneous zinc deposition
should be noted that these reported zinc batteries based on facilitated by the porous carbon coating film.275 Nanosized metal–
conversion-type nickel/cobalt oxides usually adopt alkaline elec- organic frameworks and in situ reduced graphene oxide have also
trolytes for reversible cycling, which should be further optimized been utilized as artificial SEI layer to obtain dendrite-free zinc
in terms of corrosiveness and eco-friendliness. anode, which were claimed to be capable of regulating electro-
3.3.5 Suppression of zinc dendrites. Except for cathode lyte flux on anode surface, resulting in a homogeneous plating
materials, performances of AZIBs are also strongly affected by process.276,277 Another strategy is to construct unique anode
zinc stripping/plating at anode side. Zinc metal is a hostless structures. A free-standing, three-dimensional layered Ti3C2Tx
anode where the metal dissolves into electrolyte upon dis- MXene@Zn paper anode as an alternative to bulky zinc metal
charge and gets plated back upon charge, accompanied with was developed by Tian et al. via in situ electroplating.278 This
the redistribution of zinc on anode surface. Dendritic zinc is anode can provide rapid electron transport pathways, thereby
formed easily during these processes. These zinc dendrites are realizing uniform charge distribution and thus effectively
normally in needle shapes and grow continuously on anode suppressing the formation of dendrites. SEM images revealed
surface during battery usage. Eventually zinc dendrites will the smooth zinc surface on Ti3C2Tx MXene in aqueous electro-
penetrate to cathode and the battery will result in a sudden lyte with outstanding durability. In addition, microporous
short circuit or a sudden capacity drop. Even when short circuit zinc-based metal–organic framework ZIF-8 treated at 500 1C
is not reached, the growth of zinc dendrite will increase anode and flexible three-dimensional CNT framework were both
surface area and thereby accelerate the corrosion of anode and found to be attractive host matrix for zinc plating and stripping,
other surface dependent side reactions, leading to a faster and the resultant anodes with unique structures realized high
battery performance decay.267,268 Coulombic efficiency and dendrite-free plating attributing to
Therefore, the suppression of zinc dendrites is of vital decreased local current density, low zinc nucleation overpotential
importance in achieving and maintaining satisfactory AZIB as well as homogeneous electric field distribution.279,280
performances. A variety of studies on zinc dendrites have been In a study that investigates the fractal growth of zinc
conducted for alkaline zinc-based batteries (the cathodes of dendrites in alkaline electrolytes, the authors pointed out that
which are non-intercalative). For example, back to the 1990s, zinc dendrite growth patterns are affected by various factors,
Kan et al. reported Triton X-100 additive as an effective inhibitor including electrolyte concentration, electrolyte thickness,
on zinc dendrite growth, which can improve the dispersion and voltage variation, anion variation and solvent nature.281 Recently,
cathodic polarization of electrolyte, resulting in finer deposited our group studied the growth behaviour of zinc dendrites in
zinc particles that helped raise efficiency and prolong battery cycle neutral/mild aqueous electrolytes and found that dendrites
life.269 Later on, other additives such as nickel triflate,270 poly- growth is substantially affected by battery configuration,
ethylene glycol,271 benzyltrimethylammonium hydroxide,272 etc., applied current density and the mass loading of cathode
were reported effective in suppressing zinc dendrite growth in materials, which explained the diverse results of battery cycle
alkaline electrolytes. These additives resulted in the formation of life reported in literatures.282 Subsequently, we proposed an
an interphase layer originated from either molecular absorption electrohealing methodology to in situ eliminate the already-
or chemical reactions, which affected the nucleation and growth formed zinc dendrites by decreasing applied current density,
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Fig. 15 Comparison of redox potentials of representative electrode materials for AZIBs. Red-colour columns and green-colour column represent
cathodes and zinc metal anode, respectively. (Some conversion-type NiCo compounds are also included.).
aiming to prolong battery lifetime or to in situ rescue 3.4.1 Aqueous magnesium-ion batteries. Magnesium metal
in-service AZIBs. possesses a high theoretical volumetric capacity (3833 mA h cm3
Back to battery voltage characteristics, for AZIBs, major compared to the 2046 mA h cm3 of lithium metal) due to its
types of cathode materials have been discussed in this section, divalent charge carrier ions. Moreover, magnesium element is
with their redox potentials summarized and compared in earth abundant and its raw materials are cost effective. There-
Fig. 15. As revealed, PBA-type materials could provide high fore, aqueous magnesium-ion batteries (AMIBs) have recently
redox potentials, while vanadium oxides, sulphides and polymers attracted increasing attention. However, only a few crystal
show relatively low redox potentials. However, discharge capa- phases have been served as cathode materials for AMIBs to
cities of high-potential PBAs are rather small (o80 mA h g1) date, which is mainly due to the aforementioned reason that
compared to other materials (200–300 mA h g1). Cathodes divalent Mg2+could cause strong electrostatic interaction with
with simultaneous high redox potentials and high specific anions in electrode hosts, leading to sluggish kinetics or even
capacities are lacking. Due to the thick solvation sheath and inertness. Recently investigated crystal structures such as
large charge/radius ratio, the intercalation kinetics of zinc Chevrel phases (MgxMo6T8, T = S, Se)293,294 and dichalco-
ions are usually sluggish, and their high atomic mass and genides (MoS2, WSe2)295–297 demonstrate weak electrostatic
strong positive polarity lead to poor kinetics of ion transport interaction between Mg2+ and their anionic frameworks, which
and low solid-state solubility in bulky electrodes. Therefore, is attributed to the moderate polarity of the anions in those
in pursue of high-performance AZIBs, it is highly desired to structures and their large channel dimensions. Whereas, the
continue discovering new cathode materials that bear high moderate polarity leads to weak bonding strength between
capacity, high rate capability, stable cycle performance and transition metals and their surrounding anions, resulting
high redox potentials with flat and high-voltage discharge in relatively low redox potentials. For example, both redox
plateaus. potentials of Chevrel phases and dichalcogenides are below
2 V (vs. Mg/Mg2+), indicating that achieving high voltage while
3.4 Other aqueous multivalent metal-ion batteries maintaining fast kinetics simultaneously is challenging for
Aqueous multivalent metal-ion batteries are considered as promis- cathode materials of AMIBs. In addition, compared to mono-
ing alternatives to aqueous monovalent metal-ion battery systems. valent metal ions, the bivalency leads to stronger solvation
Besides the earth abundance of these metal elements, one major of magnesium ions in electrolytes,298 further inducing a
reason favours their high potential is that, multivalent metal cations larger energy penalty on de-solvation at electrolyte–electrode
can, theoretically, transfer more than one electron and thereby interfaces.299 In order to overcome the interdiffusion barrier
achieve higher specific capacity and energy density.283–289 However, associated with electrostatic attraction, Nam et al. adopted
multivalent cations with large charge densities diffuse much more a novel approach of engaging water into active cathode host
slowly in electrode materials than monovalent cations do due to (i.e., layered Birnessite manganese oxide (Mg-B)).300 The
their strong cation–cation repulsive and cation–anion attractive so-called crystal water in cathode host could effectively shield
forces.287–292 Therefore, current aqueous multivalent metal-ion the electrostatic interactions between Mg2+ and host anions and
batteries exhibit less ideal electrochemical performances, high- thereby improve electrochemical activity. Furthermore, hydration
performance aqueous multivalent metal-ion battery systems have of Mg2+ alleviated de-solvation energy penalty and Coulomb
been rarely reported so far. repulsion between Mg2+ and host surfaces.301 Based on these
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(OMS), has been frequently reported in the fields of energy

storage and catalysis due to its diverse tunnel structures.304–307
Zhang et al. studied Mg-OMS-1 with 3 3 tunnels, Mg-OMS-7
with 1 1 tunnels308 and Mg-OMS-2 with 2 2 and 1 1
tunnels309 in various aqueous electrolytes including 0.5 M
MgCl2, 0.5 M Mg(NO3)2 and 0.5 M MgSO4. These cathodes were
operated in the potential range of 0.6 to 0.8 V (vs. SCE) with
sloping discharge profiles. In fact, the capacity contribution in
the potential range of 0.6 to 0 V was quite small, which should
be exempted unless considerably low-potential anodes could
be identified to fully utilize this low discharge portion of
cathodes. Their specific capacities were roughly in the range
of 150–250 mA h g1, which are much higher compared to most
electrode materials employed in ALIBs. They can also be stably
cycled in various aqueous electrolytes for hundreds of charge/

Fig. 16 (a) GCD curves of the Mg-B cathode at various current densities. discharge cycles, showing high potential for high-performance
Reproduced with permission from ref. 300, Copyright 2015 American AMIBs. In addition, a-MnO2 nanosheets and commercial Mn3O4
Chemical Society. (b) GCD curves of MgMn2O4 at the current density of
have also been investigated as cathode for magnesium storage,310,311
50 mA g1. (c) GCD curves of MgMn2O4/rGO at the current density of
50 mA g1. Reproduced with permission from ref. 303, Copyright 2018 Royal which was operated in the potential range up to 1.50 V (vs. SCE)
Society of Chemistry. (d) CV curves of PBN cathode and polyimide anode at and 0.95 V (vs. Ag/AgCl) with discharge capacities of 145 mA h g1
1 mV s1. (e) GCD curves of the polyimide//PBN full cell at 1 A g1. Reproduced and 105 mA h g1 at low current densities, respectively.
with permission from ref. 328, Copyright 2017 American Chemical Society. Regarding anode, due to the negative redox potential of
(f) PXRD pattern of MgMn2O4 with an illustration of its crystal structure (right).
magnesium metal, it is irreversible to utilize it as anode in
(g) GCD curves of the MgMn2O4 cathode in 1 M ‘‘MgSO4 + ZnSO4’’ + 0.1 M
MnSO4 aqueous electrolyte at 500 mA g1. Reproduced with permission from aqueous or moisture-contaminated nonaqueous electrolytes.
ref. 322, Copyright 2018 American Chemical Society. Similar to coated/protected lithium metal anode for ALIBs,
the strategy of coating/protecting magnesium metal anode with
a thin membrane should be a feasible approach to initiate full
combined effects, the Mg-B host exhibited a high reversible cells.312–314 Still, most reported aqueous magnesium-ion electro-
capacity of 231 mA h g1 within the potential range of 0.3 to chemistry were only investigated in a half cell configuration
1.1 V (vs. Ag/AgCl) in an aqueous electrolyte of 0.5 M Mg(ClO4)2 due to the absence of proper electrochemical couples136,315 that
(Fig. 16a). Moreover, the Mg-B cathode possessed high cycle originates from limited Mg2+ host materials316–323 and the
stability in this aqueous electrolyte and maintained 62.5% of narrow voltage window of aqueous electrolytes.324,325 Examples
its initial capacity after 10 000 cycles at 2000 mA g1. The of full AMIBs are few. Zhang et al. reported the utilization of
reversible capacity of 88.6 mA h g1 is also remarkable as even FeVO4 as anode for AMIBs, which was operated in the potential
the well-known stable PBA electrodes just deliver capacities of range of 1.0 to 0 V (vs. SCE) with a specific capacity over
o80 mA h g1 for monovalent metal-ion batteries137,185 and 180 mA h g1 at 50 mA g1.326,327 However, when coupled with
o50 mA h g1 for divalent metal-ion batteries136 at similar Mg-OMS-1 cathode, the obtained AMIB exhibited sloping dis-
current densities in aqueous electrolytes. charge profiles, whose midpoint voltage was just over 0.4 V,
Other types of manganese oxides have also been widely- showing poor practicability. Chen et al. reported a full AMIB by
studied for AMIBs. Cabello et al. observed that magnesium employing a PBA type nickel hexacyanoferrate cathode (NiHCF)
could be reversibly extracted/inserted from/into MgMn2O4 coupled with a polyimide anode.328 Its working principle
during electrochemical processes in both aqueous and non- involved Mg2+ intercalation/de-intercalation at cathode side
aqueous electrolytes, although the cycling of MgMn2O4 in and reversible enolization at anode side. CV profiles indicated
aqueous electrolyte was not as stable as in the non-aqueous that magnesium ions can be extracted from PBN cathode
electrolyte based on carbonate solvent. This cathode exhibited successfully prior to oxygen evolution and be inserted into
sloping discharge profiles within the potential range of 0–1.3 V polyimide anode ahead of hydrogen evolution (Fig. 16d). The
(vs. Ag/AgCl).302 Actually the poor conductivity of MgMn2O4 AMIB delivered an initial capacity of 33 mA h g1 (based on the
seriously confines its electrochemical performances, therefore mass of both active materials) and achieved 60% capacity
reduced graphene oxide (rGO) was further introduced to retention after 5000 charge/discharge cycles within the voltage
enhance its electron transfer.303 The as-prepared MgMn2O4/ range of 0–1.55 V. It showed no obvious discharge plateau, and
rGO nanocomposite delivered a specific capacity of 140.1 mA h g1 the midpoint voltage was at around 0.75 V (Fig. 16e). Further-
at 1000 mA g1, which was 69% higher than that of pristine more, due to the shortage of AMIB anodes, Soundharrajan et al.
MgMn2O4. While it still didn’t exhibit obvious discharge plateau constructed a magnesium–zinc hybrid battery by using a Mg2+
when operated in the potential range of 0.45 to 0.9 V (vs. SCE) intercalative cathode of MgMn2O4 and a zinc metal anode,
(Fig. 16b and c). Besides, one unique category of manganese which benefited from the low redox potential of zinc stripping/
dioxide minerals, manganese oxide octahedral molecular sieves plating and thus exhibited a high midpoint voltage of 1.35 V
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with a tilting plateau at 1.32 V (Fig. 16f and g).322 Nevertheless,

to facilitate the development of high-performance AMIBs for
practical applications, more electrode materials with high
capacities and suitable redox potentials are to be explored.
3.4.2 Aqueous calcium-ion batteries. Similar to AMIBs,
aqueous calcium-ion batteries (ACIBs) are suggested as another
potential alternative to ALIBs. Cations of calcium feature biva-
lency and calcium is the fifth most abundant element on earth.
Therefore, low-cost ACIBs with large capacities are highly
expected regarding commercial feasibility.
It has been demonstrated that aqueous electrolytes could
promote Ca2+ diffusion in electrodes, as calcium ions are hydrated
by water molecules, the shielding effect of water weakens their
charge density and thus enables their fast diffusion.28,329–331 Large
channels allowing for Ca2+ diffusion are also necessary for elec-
trode materials. Several research groups including Cui’s group
have demonstrated that calcium ions could rapidly diffuse
into a PBA type electrode of NiHCF that possesses large open
interstitial sites and channels within the cyano-bridged per-
Fig. 17 (a) Cycle test of the CuHCF cathode in 8.37 M Ca(NO3)2 aqueous
ovskite framework.136,329 This PBA cathode exhibited a tilting electrolyte at 2C. Reproduced with permission from ref. 333, Copyright
discharge plateau at 0.62 V (vs. SCE). However, its relatively low 2016 The Chemical Society of Japan. (b) GCD curves of the CuHCF
capacity (around 50 mA h g1) and cycle instability during cathode in 8.4 M Ca(NO3)2 aqueous electrolyte at 0.2C. Reproduced with
initial cycles inhibited its practical applications. The PBA permission from ref. 334, Copyright 2018 Elsevier. (c) Illustration of the
possible electrochemical redox reactions of PNDIE anode. (d) CV curves of
cathode of K2BaFe(CN)6 was also investigated in 1 M Ca(NO3)2
PNDIE anode and Ca0.3CuHCF cathode in 2.5 M Ca(NO3)2 aqueous
aqueous electrolyte, although showing a flat plateau, its redox electrolyte at 1 mV s1. (e) GCD curves of the PNDIE//Ca0.3CuHCF full
potential was located at around 0.15 V (vs. Ag/AgCl), which was too cell at 1C rate (450 mA g1, according to the total mass of active materials).
low for a cathode material.332 Lee et al. studied the effect of the Reproduced with permission from ref. 335, Copyright 2017 Wiley-VCH.
concentration of aqueous electrolytes on electrochemical perfor-
mances of CuHCF cathode for AMIBs. They found that super-
concentrated electrolyte could enhance the electrochemical in Fig. 17c, each reduction step to form radical anion and
performances by reducing the hydration number and radius of dianion was associated with Ca2+ coordination to the enolate
hydrated calcium ionms.333,334 The capacity was ca. 13% higher groups of PNDIE with neglect change and damage to its frame-
than that in dilute electrolyte. Besides, as shown in Fig. 17a, work, as charges were redistributed within the conjugated
ca. 97% of the initial capacity could be maintained after 150 cycles aromatic molecule.336 Typical CVs of the two electrodes are
in the super-concentrated electrolyte. In contrast, only ca. 58% of displayed in Fig. 17d, clearly showing redox potentials of both
the initial capacity was retained in the dilute electrolyte. This may cathode and anode located within the electrochemical stability
be attributed to the suppressed structural collapse of CuHCF window of the 2.5 M Ca(NO3)2 aqueous electrolyte. The redox
electrode in super-concentrated electrolyte.333 In addition, cyclability peaks of PNDIE anode were at 0.44 V/0.19 V and 0.65 V/
gradually improved with the rise of electrolyte concentration.334 The 0.45 V (vs. Ag/AgCl), indicating a two-step electron transfer
capacity retention after 1000 cycles in 1 M Ca(NO3)2 electrolyte during calciation/de-calciation. The redox peak of Ca0.3CuHCF
was only 49%, whereas 89% was realized after 5000 cycles in cathode was also well-defined at 0.83 V/0.80 V (vs. Ag/AgCl),
8.4 M Ca(NO3)2 electrolyte. Compared to the previous reported resulting in a full ACIB with a midpoint voltage of 1.13 V that
PBA cathodes,136,329 this was a huge improvement. The authors showed no obvious discharge plateau (Fig. 17e). Another aqueous
proposed two potential reasons for the well maintenance of CuHCF full ACIB was fabricated by using barium hexacyanoferrate
structure in the 8.4 M electrolyte: (1) the dissolution of transition (BaHCF), meso-carbon micro beads (MCMB) and 1 M Ca(ClO4)2
metal ions from CuHCF into electrolyte was suppressed by the as cathode, anode and electrolyte, respectively.337 The BaHCF
highly concentrated Ca2+, and (2) the repetitive hydrated Ca2+ cathode exhibited a reduction peak at 0.28 V and an oxidation
intercalation/de-intercalation-induced structural stress in the CuHCF peak at 0.34 V (vs. Ag/AgCl), and the MCMB anode showed
electrode was relatively weak as Ca2+ have a smaller hydration radius broad redox peaks at 0.6 V and 0.4 V (vs. Ag/AgCl). Conse-
in the 8.4 M electrolyte than in 1 M electrolyte. Whereas, the tilting quently, the full battery delivered nearly 40 mA h g1 capacity
discharge plateau of CuHCF became less obvious with the increase (based on the mass of cathode material) within the voltage
of electrolyte concentration. The midpoint voltage was at around range of 0–2.0 V, while it showed no discharge plateau and
0.51 V (vs. SCE) in 8.4 M Ca(NO3)2 electrolyte (Fig. 17b). its midpoint voltage was just around 0.6 V. Like the case of
A low-cost aqueous full ACIB was fabricated based on a AMIBs, the limited choices of electrode materials, especially
Ca0.3CuHCF cathode and a poly[N,N 0 -(ethane-1,2-diyl)-1,4,5,8- anode materials, substantially restrict the advancing of high-
naphthalenetetracarboxiimide] (PNDIE) anode.335 As depicted performance ACIBs. Further simulations and experiments are
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needed to discover new electrode materials with desired electro-

chemical characteristics.
3.4.3 Aqueous aluminium-ion batteries. Aqueous aluminium-
ion batteries (AAIBs) emerge as a competitive alternative to ALIBs
due to the large volumetric capacity of aluminium and the smaller
radius of Al3+ that favours intercalative chemistry.338–346 The high
abundancy and easy accessibility of aluminium raw materials
further make AAIBs appealing for large-scale energy storage.345,346
Currently, aluminium metal cannot be directly employed as
anode in aqueous electrolytes as its electrochemical plating/
stripping potentials are far beyond the stable voltage window of
water. Anatase TiO2 with good chemical stability and nontoxicity
has been widely studied in lithium storage,347 and its feasibility
in aluminium storage has also been validated. Liu et al. first
demonstrated the reversible intercalation/de-intercalation of Al3+

into/from anatase TiO2 nanotubes in 1 M AlCl3 aqueous
electrolyte.348 Typically, a large redox pair can be observed at
around 1.26 V/0.84 V (vs. SCE) (Fig. 18a). Al3+ intercalation/
de-intercalation occurred prior to HER (1.43 V vs. SCE)
because the strong solvation of aluminium ions in aqueous
electrolytes resulted in a high overpotential for hydrogen
evolution.349 Based on the analysis of electrochemical kinetics, Fig. 18 (a) CV curves of the anatase TiO2 nanotubes in 1 M AlCl3, MgCl2
it was found that solid phase diffusion during Al3+ intercalation/ and LiCl aqueous electrolytes at 20 mV s1. Reproduced with permission
de-intercalation was dominant for the anatase TiO2 nanotube from ref. 348, Copyright 2012 Royal Society of Chemistry. (b) Low
arrays. The electrode delivered a capacity of 75 mA h g1 under magnification TEM image of the black anatase TiO2 nano-leaves. Inset is
a photograph of willow leaves. (c) Comparison of CV profiles of the black
the current density of 4 mA cm2. Besides, single-crystal black
anatase TiO2 nano-leaves and commercial white anatase TiO2 at 1 mV s1.
anatase TiO2 nano-leaves were subsequently prepared via a (d) Comparison of rate performance of (I) commercial white anatase TiO2
solution plasma processing technique by He et al.350 Fig. 18b and (II) black anatase TiO2 nano-leaves. Reproduced with permission from
shows a low-magnification image of the as-prepared 2D willow ref. 350, Copyright 2014 Royal Society of Chemistry. (e) GCD curves of the
leaf-like TiO2 nanostructure. These TiO2 nano-leaves demon- NVP cathode in aqueous AlCl3 electrolyte of the initial several cycles at
10 mA g1. Reproduced with permission from ref. 356, Copyright 2018
strated better Al3+ storage performance than commercial white
Elsevier. (f) CV curve of the CuHCF cathode in aqueous Al2(SO4)3 electrolyte
anatase TiO2 as the nano-leaves exhibited a more negative with a schematic illustration showing the positions of Al3+ in CuHCF frame-
potential for Al3+ de-intercalation and a more positive potential work. (g) GCD curves of the CuHCF cathode in aqueous Al2(SO4)3 electrolyte
for Al3+ intercalation (Fig. 18c), indicating that the electrochemical at various current densities. Reproduced with permission from ref. 357,
processes were more reversible. CV curves and electrolyte pH Copyright 2015 Royal Society of Chemistry. (h) Synthesis route of the ultrathin
graphite nanosheet cathode. (i) GCD curves of the Zn//graphite nanosheet
values remained almost unchanged after cycling, demonstrating
full cell at various current densities. Reproduced with permission from
that the electrochemical reactions were stable and reversible, and ref. 359, Copyright 2016 American Chemical Society. (j) Schematic illustration
HER was successfully avoided. Fig. 18d reveals that the capacities of the structure of AlxMnO2nH2O. (k) GCD curves of the Al//AlxMnO2nH2O
of the TiO2 nano-leaves were 259.7 and 141.3 mA h g1 at 0.1 A g1 full cell at 30 mA g1 of the initial 5 cycles. Reproduced with permission from
and 2 A g1, respectively, significantly higher than commercial ref. 360, Copyright 2019 Springer Nature.
TiO2 electrodes. Such remarkable difference arose from the fast

electron transport and Al3+ diffusion in TiO2 nano-leaves due a redox pair at around 0.08 V/0.28 V (vs. mercury–mercurous
to their short diffusion path. In addition, it is reported that sulfate electrode, MSE) with a discharge capacity of 250 mA h g1
electrically conductive agents such as CNTs and graphene are at the current density of 20 mA g1 in 1 M LiCl aqueous
essential in facilitating Al3+ intercalation/de-intercalation in electrolyte. While this capacity rapidly decayed to 130 mA h g1
TiO2 electrode.351,352 Study estimated that graphene could at the 5th cycle, showing poor cycle stability. Nacimiento et al.
remarkably enhance Al3+ ion diffusion coefficient in TiO2 by reported a NASICON-type NVP as cathode for AAIBs using AlCl3
672 times.353 dissolved in oxygen-free water as aqueous electrolyte.356 The NVP
Not many stable cathode materials have been discovered for cathode showed a 47 mA h g1 specific capacity at the current
AAIBs so far. Orthorhombic vanadium pentoxide (V2O5) with a density of 10 mA g1 with a flat discharge plateau at around 0.37 V
layered structure built up from VO5 square pyramids could (vs. SCE) (Fig. 18e). They proposed a mechanism wherein NVP
serve as cathode for ALIBs and AZIBs, and its xerogel (xero-V2O5) loses Na+ during the first charging cycle, and subsequent
consisting of V2O5 bilayers with water in between intrigues discharging leads to both bulk intercalation and surface
significant changes in electrochemistry.354 The intercalation of storage of Al3+, both of which contribute to the resultant capacity.
aluminium ions into V2O5 xerogel in aqueous electrolytes was Multiple characterization techniques have clearly demonstrated
initially investigated by González et al.355 This xero-V2O5 exhibited the successful Al3+ intercalation/de-intercalation, despite the poor
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cycle stability that needs further optimization. Moreover, although could open a new way to explore high-voltage and high-energy
monovalent and divalent cations can readily insert into PBAs reversible ARMB configurations.
framework as demonstrated in many battery systems, the inter- On top of that, the type of electrolyte has a prominent effect
calation chemistry of trivalent cations that would carry more on Al3+ intercalation behaviour. For example, it was difficult
charges to PBAs has rarely been studied. Liu et al. investigated for Al3+ to intercalate into TiO2 nanotube arrays in aqueous
CuHCF as cathode material for AAIBs for the first time, achieving Al2(SO4)3 electrolyte.361 The same phenomenon was observed in
a specific capacity of 64 mA h g1 at 50 mA g1 with a midpoint an aprotic electrolyte system: no redox peaks were shown in the
voltage of 0.52 V (vs. SCE) in 0.5 M Al2(SO4)3 aqueous solution electrolyte of Al triflate in PC/THF from 0.75 V to 4.2 V, while
(Fig. 18f and g).357 Broadened CV peaks for Al3+ intercalation were an obvious redox pair was detected in the electrolyte of AlCl3
observed in CuHCF, suggesting complex mechanisms and in [EMIm]Cl.340 It is also revealed that Al3+ intercalation/
poor insertion kinetics.329,357 This CuHCF cathode sustained de-intercalation in MoO3 is favoured in specific types of aqueous
1000 charge/discharge cycles, which is far superior to the above- electrolyte. Compared with Al2(SO4)3 and Al(NO3)3, AlCl3 electro-
introduced cathode materials. While the capacity retention of lyte provides higher Al3+ storage capacity, superior long-term
54.9% is still not satisfactory compared to relatively mature stability and less polarization. In detail, the Al3+ storage capacity
ALIBs and AZIBs. of MoO3 in the first discharge cycle was found to be 680 mA h g1
A full AAIB coupling CuHCF cathode and TiO2 anode was in AlCl3 electrolyte, which is the highest reported value so far for
fabricated by Holland et al., showing a relatively high tilting AAIBs.362 Therefore, it is anticipated that Cl played a significant
discharge plateau at 1.45 V.358 While its specific capacity based role in facilitating the reversible and effective Al3+ intercalation/
on both cathodes was merely 10.6 mA h g1, making the good de-intercalation,361 which could shed light on the research of Al3+
capacity retention of 70% over 1750 charge/discharge cycles storage in other transition metal electrodes (e.g., TiO2, V2O5, etc.).
almost meaningless. The authors stated that the slight shift in This section discusses aqueous multivalent metal-ion batteries
neutron diffraction parameters was not sufficient to verify the including AMIBs, ACIBs and AAIBs. Redox potentials of their
major mechanism of charge storage for TiO2 anode, which electrode materials are summarized and compared. As shown in
should be via either Al3+ intercalation or surface adsorption. To Fig. 19, not many electrode materials have been developed so far,
achieve higher capacity, an aqueous rechargeable Al3+–Zn2+ the studies of AMIBs, ACIBs and AAIBs are still in their infancy.
dual-ion hybrid battery was developed based on zinc metal The multivalence of their metal ions usually induces strong
anode and ultrathin graphite nanosheet cathode (Fig. 18h) in electrostatic interaction with anions in electrode hosts, resulting
aqueous Al2(SO4)3–Zn(CH3COO)2 electrolyte.359 The stripping/ in sluggish kinetics or even inertness. It should be noted that
plating of zinc metal anode and the Al3+ intercalation/ PBA-type materials are extremely versatile in ARMBs, as they
de-intercalation into/from the outer graphene layers of graphite show excellent capability to host various metal ions including
cathode led to a discharge capacity of 94 mA h g1 for the not only Li+, Na+, K+, and Zn2+, but also Mg2+, Ca2+, and Al3+.
hybrid Zn//graphite battery with a midpoint voltage of 1.0 V In-depth studies on PBAs may help facilitate the advancement
(Fig. 18i). Besides, this hybrid battery could be rapidly charged of AMIBs, ACIBs and AAIBs.
within 2 min while maintaining a high capacity and demon- We further compare the voltage characteristics including
strated a good cycle stability with 94% capacity retention after midpoint voltage and plateau voltage of various ARMB systems
200 cycles. More recently, Wu et al. fabricated an AAIB by in Fig. 20. As revealed, most reported ARMBs exhibit a mid-
successfully utilizing an aluminium metal anode in 4 M alumi- point voltage less than 1.5 V. The majority of the ARMBs do not
nium trifluoromethanesulfonate (Al(OTF)3) aqueous electrolyte.360 yield a flat discharge plateau, especially for AMIBs, ACIBs
In this electrolyte, passivation occurred on aluminium metal that and AAIBs, all of which just show sloping discharge profiles.
effectively suppressed hydrogen evolution, pushing its onset Generally speaking, the midpoint voltages of AMIBs, ACIBs and
potential from 1.1 V to 0.3 V (vs. Al3+/Al), allowing for the AAIBs are lower than those of ALIBs, ASIBs, AKIBs and AZIBs,
reversible stripping/plating of aluminium metal. An AlxMnO2nH2O except for the cell utilizing TiO2 anode, as TiO2 could provide a
cathode was synthesized via incorporating water and Al3+ into significant low redox potential (Fig. 19). The difference in
spinel Mn3O4 structure through in situ electrochemical trans- midpoint voltage is small among all these ARMBs, which is
formations (Fig. 18j). It was found that the aqueous electrolyte mainly due to the narrow voltage window of aqueous electro-
and crystal water in this cathode could screen the electrostatic lytes that substantially confines cell voltage. In the following
interaction between aluminium ions and cathode frameworks, sections, we will focus on the strategies that can effectively raise
thus enabling reversible electrochemical trivalent processes. cell voltage.
The resultant Al//AlxMnO2nH2O full cell in 4 M Al(OTF)3
yielded an open circuit voltage over 1.6 V with a midpoint
voltage at 1.05 V. Although its working voltage is not the highest 4. Towards high-voltage ARMBs:
among all AAIBs, it exhibited a remarkable discharge capacity strategies and advancements
of 467 mA h g1 at 30 mA g1, leading to a record high energy
density of 481 W h kg1 (Fig. 18k). The strategy of enabling Regarding the constrained cell voltage of ARMBs in aqueous electro-
passivation of aluminium metal in aqueous electrolyte and lytes, in this section, we discuss five major categories of strategies
tailoring polarity between metal ions and host frameworks that have been demonstrated effective in raising cell voltage.
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Fig. 19 Comparison of redox potentials of representative electrode materials for AMIBs, ACIBs and AAIBs. Red-colour columns and blue-colour
columns represent cathodes and anodes, respectively.
Fig. 20 Voltage comparison among various ARMB systems. Solid circles represent midpoint voltages, and hollow stars at the same x-axis position
represent corresponding plateau voltages (the voltage of the first discharge plateau is adopted if a battery yields more than one plateau). Some sodium–
potassium hybrid batteries are also included.
These strategies involve the screening of suitable electrode materials

to fully utilize the electrochemical stability window of normal 4.1 Fully exploit electrolyte voltage window
aqueous electrolytes, the isolating of water or the avoiding of Electrode materials play a vital role in determining cell voltage,
electrode-water contact, and the broadening of electrolyte voltage and the voltage window of electrolytes decides the feasibility of
window. Generally, type of electrode material, electrolyte pH, electro- pairing up electrodes. Thus, with a given electrolyte, the voltage
lyte concentration, etc., all have a significant influence on the of a battery can be regulated by carefully selecting electrodes
parasitic gas evolution at electrode–electrolyte interface. By adopting whose redox potentials are well within the electrolyte voltage
effective strategies and cautiously tuning parameters, ARMBs with window. By pairing a cathode with a more positive redox
higher operating voltage that even exceeds 2 V could thus be realized. potential, with an anode with a more negative redox potential,
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the battery voltage can be considerably raised in conventional LIBs and SIBs in recent years.364–366 They exhibit relatively high
aqueous electrolytes. Besides, in terms of electrode materials, operating voltage due to inductive effect of the polyanion as
the core of suppressing hydrogen and oxygen evolution is to well as structural stability with an open framework allowing
utilize anode with high hydrogen evolution overpotential and metal ion diffusion. In 2015, a Na3V2O2x(PO4)2F32x/CNTs
cathode with high oxygen evolution overpotential. This section cathode with excellent cyclability was reported to operate in
highlights the studies on achieving high-voltage ARMBs with aqueous electrolytes with high redox potentials at 0.73 V/0.68 V
conventional aqueous electrolytes via examining the redox (vs. SCE) (Fig. 21b).367 Consequently, a flat high-voltage discharge
potentials as well as the overpotentials of both cathodes and plateau of 1.42 V for the NaTi2(PO4)3//Na3V2O2x(PO4)2F32x/
anodes. MWCNT full ASIB was obtained. Although the ASIB could be
4.1.1 Electrode materials with desired redox potentials. stably charged/discharged for 400 cycles, its maximum capacity
Clustered molybdenum sulfide (Mo6S8), previously known as was just around 40 mA h g1, which was inferior to its
an intercalation host for many metal ions in organic electro- performance in organic electrolytes (4100 mA h g1). Such
lytes, was discovered to be an ultrafast anode for ALIBs.363 It low capacity value should be attributed to the intercalative
showed a sufficiently-low redox pair at around 0.74 V/0.78 V reversibility of just one sodium ion in an aqueous solution
(vs. SCE), contributing to a plateau voltage of 1.68 V when within the limited voltage range.
coupled with LiMn2O4 cathode (Fig. 21a). This ASIB could It is most favourable to combine two electrodes with distant
deliver a specific capacity of 74.7 mA h g1 (based on the mass redox potentials that are still well within electrolyte voltage
of both active materials) at an extraordinary high rate of 60C. window, so that the cell voltage could be maximized. Xue et al.
Although its long-term cycle stability was not examined, prepared 3D hierarchy LiCoO2 nanorod arrays as cathode and
such high discharge plateau surpassed most reported ALIBs coupled it with LiTi2(PO4)3 anode. The former exhibited redox
whose midpoint voltages were less than 1.5 V. Similarly, cathode potentials at around 0.8 V and the latter exhibited redox
materials with higher redox potentials are also developed potentials at around 0.7 V, leading to a tilting discharge
for high-voltage ARMBs. Polyanion compounds have been plateau of 1.51 V for the resultant ALIB (Fig. 21c).368 Liu et al.
extensively explored as alternatives to metal oxides in both utilized the high redox potential of LiMn2O4 cathode and the
low redox potential of TiO2, constructed an ALIB showing a
high midpoint voltage of around 2.06 V with two discharge
plateaus at 2.24 V and 1.90 V.369 In this ALIB, HER was
effectively suppressed in the mixed 3.5 M LiCl/0.25 M Li2SO4
electrolyte due to the high anodic hydrogen evolution over-
potential, enabling the reversible lithium-ion intercalation/
de-intercalation at TiO2 anode side. As the commonly employed
anode for AZIBs is zinc metal, the selection of electrode
materials to realize high-voltage AZIBs depends on the select
of cathode materials. Compared to the widely studied MnO2
cathode, PBA cathodes are inferior in terms of specific capacity,
while they offer attractive redox potentials that are usually
higher than 1.5 V (vs. Zn/Zn2+). For example, Zhang et al. fabricated
ZnHCF for AZIBs, and the resultant full battery exhibited a tilting
discharge plateau of around 1.72 V, much higher than the
1.38 V and 1.2 V of Zn//MnO2 battery (Fig. 21d and e).258
Moreover, Shan et al. synthesized surface hydroxylated Mn5O8
electrodes to construct a symmetrical ASIB (Fig. 21f and g).370
Fig. 21 (a) GCD curves of the Mo6S8//LiMn2O4 full cell in 2 M Li2SO4
This Mn5O8 electrode showed a wide potential window in a
electrolyte for consecutive 50 cycles at 0.5 mA. Cycle numbers are
indicated. Reproduced with permission from ref. 363, Copyright 2012
0.1 M Na2SO4 electrolyte between 1.7 V (with an overpotential
Springer Nature. (b) CV curves of the Na3V2O2x(PO4)2F32x/CNTs cathode of 0.64 V towards HER) and 0.8 V (with an overpotential of
at 0.2 mV s1 in aqueous electrolyte. Reproduced with permission from 0.63 V towards OER), which originated from sluggish HER and
ref. 367, Copyright 2015 Royal Society of Chemistry. (c) GCD curves of OER kinetics that were verified by TAFEL plots. The interaction
individual electrode and the corresponding LiTi2(PO4)3/C//LiCoO2 full cell
between hydroxylated interphase on the surface and the unique
in aqueous Li2SO4 electrolyte. Reproduced with permission from ref. 368,
Copyright 2019 Elsevier. (d) A schematic of the Zn//ZnHCF battery. (e)
bivalence structure of Mn5O8 accounted for the suppression of
Discharge curves of the Zn//ZnHCF battery at various rates. Reproduced HER and OER, and a two-electron charge transfer mechanism
with permission from ref. 258, Copyright 2015 Wiley-VCH. (f) Illustration of via Mn2+/Mn4+ was identified, providing facile pathway for
the lattice structure of Mn5O8. Purple represents Mn4+, blue represents Na+ diffusion. The as-assembled symmetrical ASIB could be
Mn2+, red represents O, and white indicates the possible unoccupied sites.
charged to 3.0 V and exhibited remarkable rate capability.
(g) TEM image of the Mn5O8 particles. (h) GCD curves of the Mn5O8
symmetric cell at 5 A g1. Inset shows its energy efficiency and coulombic
While its charge/discharge profiles were sloping, resulted in a
efficiency. Reproduced with permission from ref. 370, Copyright 2016 midpoint voltage of around 1.0 V, which is relatively low
Springer Nature. compared to its upper cut-off voltage of 3.0 V (Fig. 21h).
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4.1.2 Electrode materials to form hybrid battery systems.

Constructing hybrid battery systems with different metal-ion
reactions at cathode and anode expands the choice range of
electrode materials. Specifically, due to the relatively low redox
potential and large capacity of zinc metal, utilizing zinc metal
as anode and another metal-ion intercalative material as
cathode has become a preferential strategy to fabricate high-
voltage ARMBs. The above-mentioned Na3V2O2x(PO4)2F32x/
CNTs cathode for ASIBs was thus employed to pair with zinc
metal anode, initiating a hybrid battery with a flat discharge
plateau of 1.65 V, notably higher than the 1.42 V of its ASIB
counterpart.367 In Section 3.4.1, we discussed that due to the
shortage of proper anode materials for AMIBs, a magnesium–
zinc hybrid battery where Mg2+ intercalation/de-intercalation
occur at MgMn2O4 cathode and zinc stripping/plating occur at

anode was developed, displaying a tilting plateau at 1.32 V.322
Besides, partial substitution of element in electrode materials
has been demonstrated to be effective in increasing cell voltage
Fig. 22 (a) CV curves of the Zn/LiMn0.8Fe0.2PO4 hybrid battery at 0.1 mV s1
in a hybrid battery system. In detail, olivine-based phosphate in the aqueous electrolyte of 21 M LiTFSI + 0.5 M ZnSO4. (b) GCD curves of
LiFePO4 exhibits fast kinetic behaviour and reversible high the Zn/LiMn0.8Fe0.2PO4 hybrid battery at various rates. Reproduced with
capacity, and the similar compound of LiMnPO4 possesses a permission from ref. 376, Copyright 2016 Elsevier. (c–e) GCD curves
higher redox potential of 4.1 V (vs. Li/Li+) compared to that of of aqueous mixed-ion batteries of CuHCF/Li+ + Na+/TiP2O7, CuHCF/Li+ +
K+/TiP2O7 and CuHCF/Na+ + K+/NaTi2(PO4)3 and their individual electrodes
LiFePO4 (3.4 V vs. Li/Li+).371,372 Therefore, the partial substitu-
at the rate of 1.5C. Reproduced with permission from ref. 377, Copyright 2017
tion of Fe2+ by Mn2+ integrated both merits of high redox Royal Society of Chemistry. (f) Illustration of the working mechanism of the
potential and excellent rate capability.373–375 Coupled with a K–Na hybrid aqueous battery system. (g) GCD curves of the K–Na hybrid
zinc metal anode, the CV curve of the resulted hybrid battery aqueous battery and their individual electrodes (vs. SCE) at 1C rate. (h) CV
revealed that 80% of its total capacity arose from the Mn2+/Mn3+ curves of the K–Na hybrid aqueous battery at 1 mV s1. Reproduced with
permission from ref. 378, Copyright 2018 Wiley-VCH.
region. This hybrid battery exhibited a flat discharge plateau at 1.8 V
(Fig. 22a and b), approaching an energy density of 183 W h kg1
(based on the mass of both active materials), which has exceeded density of 69.6 W h kg1 (based on the mass of both active
most rechargeable aqueous batteries.376 materials) is superior to that of traditional lead–acid, Ni–Cd and
Moreover, high-voltage hybrid batteries with dual-intercalative Ni–MH batteries.
electrodes have also been designed. In a work of Jiang et al., a
variety of high-voltage hybrid batteries have been demonstrated 4.2 Regulate electrolyte pH
with CuHCF as cathode and TiP2O7 or NaTi2(PO4)3 as anode.377 It As the potentials of OER and HER vary with pH values,
was found that the intercalation voltage for the ion-selective theoretically, the electrochemical stability window of aqueous
CuHCF cathode followed the sequence of K+ 4 Na+ 4 Li+. As a electrolytes can be deliberately adjusted to accommodate electrode
result, a series of high-voltage batteries based on ‘‘M+/N+-dual materials with even more positive or negative redox potentials
shuttles’’ including CuHCF/Li+ + Na+/TiP2O7, CuHCF/Li+ + K+/ by regulating electrolyte pH. Moreover, electrode materials may
TiP2O7 and CuHCF/Na+ + K+/NaTi2(PO4)3 were obtained with exhibit different electrochemical behaviours that occur at
midpoint voltages at 1.36 V, 1.42 V and 1.55 V, respectively different potentials depending on electrolyte pH. In this
(Fig. 22c–e). These hybrid batteries relied on two electrochemical section, studies employing aqueous electrolytes with regulated
processes: co-intercalation/de-intercalation of M+ (small ionic pH values for achieving more stable cycle performance and/or
radius) and N+ (large ionic radius) at CuHCF cathode, and higher cell voltage are discussed. This section is divided into
release/storage of M+ at the ion-selective TiP2O7 or NaTi2(PO4)3 two parts, focusing on regulating the general pH and designing
anode. Similarly, Liu et al. constructed a high-voltage potassium– multiple electrolytes with varied pH values, respectively. Although
sodium hybrid battery based on a K-FeHCF cathode and a carbon- these strategies were majorly adopted in supercapacitors, alkaline
coated NaTi2(PO4)3 (NTP/C) anode.378 Utilizing the unique cation batteries and metal-ion batteries with conversion-type electrodes,
selectivity of both electrodes, the resultant hybrid battery using their potential in ARMBs should not be neglected.
mixed-ion electrolyte (containing both Na+ and K+) involved the 4.2.1 Regulate general pH of electrolytes. It is comprehen-
K+ intercalation/de-intercalation at K-FeHCF cathode and Na+ sible that simply regulating general pH does not always expand
intercalation/de-intercalation at NTP/C anode (Fig. 22f), which electrolyte voltage window, as the potential difference of OER
exhibited two-stage discharge profiles with two flat plateaus at and HER would not be correspondingly increased. As discussed
1.70 V and 0.98 V, respectively (Fig. 22g and h). It delivered a high in Section 2.1, the widest voltage window of an aqueous electrolyte
capacity of 160 mA h g1 at a 0.5C and retained 94.3% of its initial is usually achieved at a neutral pH value. Whereas, besides using
capacity after 1000 charge/discharge cycles at 60C. Its high energy neutral electrolytes to obtain a wider voltage window, regulating
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general pH of electrolytes can also benefit cell voltage in the intercalative FePO4, it has long been used as a cathode for
following aspects. conventional LIBs due to its potential of 3.4 V vs. (Li+/Li).380 By
First, redox reactions of some electrodes that beyond elec- properly tuning electrolyte pH and pairing with a suitable
trolyte voltage window at neutral pH can be reversibly initiated cathode, Wang and co-workers successfully utilized olivine
under certain pH conditions. For example, Liu et al. fabricated FePO4 and amorphous FePO42H2O as anodes for ALIBs.54
vertically oriented anatase TiO2 nanotube arrays as lithium-ion Although these anodes are stable in a broad pH range, accord-
intercalative anode to pair with H+ insertive a-NiOH cathode.379 ing to calculation, electrolyte pH should not be too low, which
CV curve of this anatase TiO2 in a mixed alkaline LiOH/KOH was optimized at pH = 5. Otherwise full capacity of anodes
aqueous electrolyte revealed redox peaks at 1.39 V and cannot be utilized due to severe HER at lower pH values. The
1.11 V (vs. Hg/HgO) attributing to lithium-ion intercalation/ authors further pointed out that many common cathodes of LIBs
de-intercalation, and the HER peak was notably shifted to a are confined to alkaline conditions because of the instability of
more negative potential of 1.53 V (vs. Hg/HgO), suggesting anodes in acidic conditions. If paired with a stable anode and
that HER was substantially suppressed in this alkaline electrolyte, put in acidic an electrolyte, cathodes such as LiFePO4 and
allowing for the prior occurrence of lithium-ion intercalation/ LiCoO2 should exhibit more stable performances as OER would
de-intercalation in TiO2 anode. As a result, the assembled battery be effectively suppressed.

yielded a flat high-voltage plateau at 1.74 V. Third, it is possible that the change of electrolyte pH value
Second, the better utilization of electrode materials with leads to the change of redox potential of electrode materials.
distant potentials by regulating general pH can result in more Although no intercalative electrode materials of ARMBs have
stable performances. Pei et al. first investigated the spinel been reported to manifest such feature, experiences can be
LiMn2O4 cathode in aqueous electrolytes with different pH values. borrowed from other conversion-type electrodes. One example
In their studies, OER occurred more easily with increasing pH is the Zn//Co3O4 battery developed by our group.58 2 M ZnSO4 +
values (Fig. 23a), which is in accordance with the Pourbaix 0.2 M CoSO4 mild electrolyte was used to replace traditional
diagram shown in Fig. 3c. Therefore, the battery employing a alkaline electrolyte for the first time, and the OER potential for
LiMn2O4 cathode and a zinc foil anode displayed better cycle Co(III) rich-Co3O4 cathode was found shifted to a significantly
stability at pH = 2 than at pH = 5.52 For the lithium-ion higher position of 2.26 V, compared to 1.93 V in alkaline
electrolyte (vs. Zn/Zn2+). Obviously, such broadened voltage
window is ascribed to the lower pH value of electrolyte, as
revealed in Fig. 3c. Furthermore, we found that the redox
reaction of Co3O4 in mild electrolyte was notably different from
that in alkaline electrolyte, which was a highly reversible conversion
reaction that yielded a higher cell voltage (Fig. 23b). The
as-fabricated Zn//Co3O4 battery in mild electrolyte exhibited a
high discharge voltage plateau of 1.9 V, as well as an exceptional
cycling stability (92% capacity retention after 5000 cycles at 4 A g1).
4.2.2 Design multiple electrolytes with varied pH values.
The core of this strategy is to construct an energy storage cell
with more than one electrolyte, the pH values of which are
different. It should be noted that this strategy has not been
reported for ARMBs with intercalative electrodes, but its appli-
cation in conversion-type electrodes and other energy storage
systems has received considerable attention, which can be good
experiences for developing high-voltage ARMBs.
For electrodes of alkaline batteries, their redox potentials
may shift with pH variation according to the Nernst equation.
By utilizing this, Li et al. developed a battery with three
electrolytes.381 PbO2 cathode was placed in acidic H2SO4 electro-
Fig. 23 (a) CV curves of LiMn2O4 in electrolytes with varied pH values. lyte, and NiMHx anode was placed in alkaline KOH electrolyte.
Reproduced with permission from ref. 52, Copyright 1996 Elsevier. (b)
To avoid self-neutralization, an additional neutral K2SO4 electro-
GCD curves of the Zn//Co3O4 battery in alkaline and mild electrolytes.
Reproduced with permission from ref. 58, Copyright 2018 Royal Society of
lyte separated by cation exchange membrane from acidic electro-
Chemistry. (c) Illustration of the configuration of the Zn//KMnO4 battery lyte and anion exchange membrane from alkaline electrolyte was
using an acidic–alkaline dual-electrolyte. Reproduced with permission used in between instead of applying a bipolar membrane, which
from ref. 382, Copyright 2013 Royal Society of Chemistry. (d) Illustrative was expensive and vulnerable to large current density. Due to the
concept of the cell with KOH and Na2SO4 as catholyte and anolyte,
positive shift of PbO2 potential and negative shift of NiMHx
respectively. (e) Electrode potential limits vs. voltage measured at 40 mA g1;
(f) CV curves of the cell for various voltage windows up to 1.6 V measured
potential, a battery with an open circuit voltage up to 2.64 V was
at 0.4 mV s1. Reproduced with permission from ref. 383, Copyright 2018 obtained, which was remarkable compared to 1.92 V of conven-
Wiley-VCH. tional lead–acid battery in acidic electrolyte and 1.40 V of Ni–MH
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battery in alkaline electrolyte. The battery delivered a flat high-

voltage discharge plateau at around 2.12 V.
OER and HER also vary with pH. If the high OER potential in
acidic condition and the low HER potential in alkaline condi-
tion can be combined, the overall voltage window of electrolytes
can be substantially expanded. To realize this, a thin film of
ceramic lithium super-ionic conductor (LATSP) was employed
to partition acidic and alkaline electrolytes while lithium ions
can still pass through, resulting an acidic-alkaline dual-electrolyte
(Fig. 23c).382 To exploit the expanded voltage window, KMnO4
with a high working potential of 1.5 V (vs. SHE) was chosen to pair
with Zn anode, giving a battery with a high open circuit voltage of
2.8 V and a midpoint voltage of 2.2 V, whose theoretical energy
density may be comparable to conventional LIBs. Similar studies
were conducted on supercapacitors.383–385 For example, Ratajczak

and co-worker experimentally verified the concept of using two
aqueous electrolytes of different pH values separated by a cationic Fig. 24 (a) Characteristics and configurations of traditional Li-ion battery,
exchange membrane to enable a high-voltage electrochemical Ni–MH battery, and the proposed Ni–Li battery. (b) GCD curves of the
Ni–Li battery between 3.0 and 3.75 V. The battery was discharged at 0.1,
cell based on carbon materials (Fig. 23d).383 According to
0.2, 0.5, and 1.0 A g1, respectively. Reproduced with permission from
calculations employing the Nernst equation, the cell using ref. 386, Copyright 2009 American Chemical Society. (c) Illustration of the
0.5 M KOH (pH = 13.2) catholyte and 1.0 M Na2SO4 (pH = 6.6) as-fabricated Li–Ni battery with hybrid electrolyte separated by a LATP
anolyte were able to operate up to 1.62 V without water decom- film. (d) GCD curves of the Li–Ni battery to 30th cycle at 50 mA g1.
position (Fig. 23e and f). Reproduced with permission from ref. 387, Copyright 2017 Wiley-VCH.
Given the above facts, there is still plenty of room for

facilitating the strategy of designing multiple electrolytes to high- cathode is placed in the aqueous part, is highly feasible in
voltage electrochemical cells, especially to high-voltage ARMBs. achieving high cell voltage. In this concept, the organic part of
As more cathodes and anodes are being discovered, electrolytes electrolyte serves as a thick interphase layer that isolates anode
with varied pH values that yield wider voltage window could from aqueous solution. A rechargeable Ni–Li battery system
better accommodate their working potentials, which is promis- was designed by following this concept, where two reversible
ing in developing low-cost and high-energy AMRBs. electrode processes were integrated in an aqueous and a non-
aqueous electrolyte, respectively.386 As illustrated in Fig. 24a,
4.3 Construct artificial interphase layers it was fabricated by using 1 M LiClO4 in EC/DMC (ethylene
Solid–electrolyte interphase (SEI) in non-aqueous LIBs in situ carbonate/dimethyl carbonate) as organic electrolyte for metallic
forms from the decomposition of organic electrolyte species, lithium anode, and 1 M LiOH + 1 M KOH as aqueous electrolyte
which can significantly alleviate parasitic reactions and stabilize/ for Ni(OH)2 cathode. The organic part and aqueous part of
expand electrochemical stability windows. Whereas, such protec- electrolyte was separated by a lithium ion-conductive thin
tive interphase layer cannot form spontaneously in conventional film of LISICON (lithium super ionic conductor). On one
aqueous electrolytes. This section introduces the strategy of hand, the organic part of electrolyte prevented lithium metal
constructing artificial interphase layers to enable high-voltage from reacting with water. On the other hand, it enabled a wider
ARMBs. Generally, two specific methods can be conceived. One potential range for the stripping/plating of lithium metal. As a
is to employ organic–aqueous hybrid electrolyte, where the organic result, the proposed battery exhibited a high plateau voltage of
part serves as a thick interphase layer to isolate anodes from the 3.47 V, as well as a high specific capacity of 268 mA h g1
aqueous part of electrolyte, enabling the reversible utilizing of (Fig. 24b), promising an ultrahigh energy density of 935 W h kg1
anodes with low working potentials in organic electrolyte. The other based on the mass of active materials. Another battery based on
is to construct a thin SEI-like layer directly on electrode surfaces, a conversion-type cathode was also reported by Zhang et al.387 It
blocking the contact with water molecules, thus suppressing water employed a NiO/CNT cathode and a metallic lithium anode
decomposition and extending voltage window. with an organic–aqueous hybrid electrolyte separated by a
4.3.1 Design organic–aqueous hybrid electrolyte. The lower lithium ion-conductive LATP film (Li1+x+yAlxTi2xSiyP3yO12)
cell voltage of ARMBs compared to their organic counterparts is (Fig. 24c). The resultant battery exhibited a stable discharge
usually directly associated with the high working potential of plateau of 3.38 V, although further studies are needed to improve
anodes, as many desired anodes with low working potential its cycle stability (Fig. 24d). Both of the above-mentioned studies
cannot be directly utilized in aqueous solutions due to hydrogen employed conversion-type cathodes, however, if replace them with
evolution. If placed in organic electrolyte, the reversible usability intercalative cathodes such as LiMn2O4, LiCoO2, LiFePO4, etc.,
of these anodes can then be initiated. Therefore, designing an high-voltage ALIBs could be readily fabricated.
organic–aqueous hybrid electrolyte for energy storage systems, 4.3.2 Artificial SEI to block water molecules. If a thin and
where anode is placed in the organic part of electrolyte and dense protective interphase layer is coated onto electrode
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surface, it can be regarded as an imitation of SEI, i.e., an 164 mA h g1 at 0.1C. However, its rate performance was still
artificial SEI. An artificial SEI should meet the following not comparable to conventional ALIBs, the issue of low ionic
requirements: (1) it should be capable of preventing water conductivity of artificial SEI awaits to be properly addressed.
penetration, thus, water molecules cannot pass through, other- Besides, the realization of artificial SEI onto lithium metal surface
wise HER would be triggered; (2) it should be ionic conductive, usually requires an extra layer to prevent the direct contact between
so that the electrochemical processes can be proceeded. This lithium metal and the ionically conductive isolation layer (LISICON,
concept has been widely implemented on ALIB systems. For A-LLTO, LATP, etc.), otherwise the latter would be reduced by
example, Wang et al. introduced a LISICON film onto lithium lithium metal due to their chemical instability.386,391 The widely-
metal anode (Fig. 25a). In this study, LISICON served as a applied extra layer could be gel polymer electrolyte, which is a thin
separator as well as a solid electrolyte, whose ionic conductivity polymer layer (PVDF/PMMA/PVDF, PEO, etc.) saturated with organic
at room temperature was around 0.1 mS cm2. With LiMn2O4 electrolyte (1 M LiClO4 in EC/DMC).388–390,392
as cathode and 0.5 M Li2SO4 as electrolyte, lithium ions at An artificial SEI was further designed for aluminium anode
cathode side can transport in the aqueous electrolyte, pass to enable its consistent usability in aqueous electrolytes.393 It is
through the LISICON coating layer, and reach the lithium metal known that Al readily forms a high-bandgap passivation layer of
anode. Benefiting from the low potential of lithium metal Al2O3, which turns Al to be inert in electrochemical processes.
stripping/plating (Fig. 25b), the operating voltage of the resultant Particularly, if used in aqueous electrolytes, higher potential is
ALIB could thus extend to over 4 V with two flat plateaus located at needed to drive ion transport through the passivation layer,
4.06 V and 3.85 V, respectively.388 A similar ALIB based on leading to severe hydrogen evolution. It was found that immersing
LISICON-coated lithium metal anode and LiCoO2 cathode was Al in the acidic ionic liquid (IL) electrolyte of AlCl3-[EMIm]Cl for
also developed, exhibiting a midpoint voltage of 3.70 V.389 more than one day could induce a tightly bound, IL-enriched
Whereas, the ionic conductivity of LISICON is not satisfactory, interphase on Al surface (Fig. 25c and d), which erodes the
which could be a bottleneck in achieving high specific capacity passivation coating of Al2O3 and prevents its subsequent for-
and rate performance. Le and co-workers developed a perovskite- mation. Moreover, this interphase is permanent and favourable
structured aluminium-substituted lithium lanthanum titanate for aluminium ion transport. By utilizing this artificial SEI, a
(A-LLTO), the ionic conductivity of which was enhanced to battery based on Al anode and MnO2 cathode was constructed,
0.317 mS cm2 with optimized fabrication conditions, much higher which can be reversibly cycled in aqueous Al(CF3SO3)3 electro-
than the 0.1 mS cm2 of LISICON.390 By applying the A-LLTO lyte without notable hydrogen evolution, delivering an energy
as an artificial SEI for lithium metal anode and pairing with density up to 500 W h kg1 due to its high specific capacity and
LiCoO2 cathode, the resultant ALIB exhibited an open circuit high cell voltage (with a midpoint voltage of 1.37 V and a
voltage of nearly 4.2 V, and a notably larger specific capacity of plateau voltage of 1.40 V) (Fig. 25e).
Based on the above discussion, it is understood that con-
structing artificial interphase layers usually involves the addition of
organic electrolyte, meaning the cost and safety concerns of
conventional organic battery systems cannot be completely
erased. Although some approaches have been proposed to
construct artificial SEI on cathode or anode without the using
of organic electrolyte, they just managed to stabilize electrode
and achieve better cycle performance, rather than raise cell
voltage.394,395 Therefore, the direct and effective strategy of
constructing artificial interphase layers still needs further
optimization.
4.4 Concentrated aqueous electrolytes

Studies have shown that concentrated aqueous electrolytes
have profound influences on electrochemical stability window
as well as on potentials of electrode materials. This section
divides these studies into three categories with thorough dis-
Fig. 25 (a) The schematic illustration of the LISICON film-coated lithium
cussion. The first category involves electrolytes with increased
metal. GPE represents a gel polymer electrolyte containing organic lithium
salt solution. (b) CV curve of the LISICON film-coated lithium metal at
concentration of conventional salts, which alters OER/HER
0.1 mV s1 in 0.5 M Li2SO4 aqueous electrolyte. Reproduced with permission potentials and suppresses water decomposition rate. The
from ref. 388, Copyright 2013 Springer Nature. (c) SEM image of pristine Al second category refers to the ‘‘water-in-salt’’/‘‘water-in-bisalt’’
metal. (d) SEM image of Al metal after treatment with AlCl3-IL electrolyte. systems where the absence of free water molecules and the
Insets of (c and d) are digital photos of Al metals. (e) GCD curves of the
formation of anodic SEI originating from salt anions jointly
aqueous Al-ion battery employing treated Al metal in 2 M Al(CF3SO3)3
electrolyte at 100 mA g1 (current density was based on the mass of MnO2
prevents the direct interaction between water and electrode
cathode). Reproduced with permission from ref. 393, Copyright 2018 surfaces. The third category is about hydrate-melt electrolytes,
American Association for the Advancement of Science. where no free water molecule exists, and all water molecules
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participate in ion hydration, resulting in unique physicochem-

ical behaviours. All the three categories of concentrated aqu-
eous electrolytes feature a wider electrochemical stability
window and help realize a higher battery voltage.
4.4.1 Conventional aqueous electrolytes with increased
concentration. It is first studied by Wessells et al. that the
increase of Li2SO4 and LiNO3 concentration in aqueous electro-
lytes led to larger potential difference between OER and HER,
suggesting wider electrochemical stability window.56 While they
didn’t go further to explore the corresponding mechanisms, and
the concentration of Li2SO4 and LiNO3 they investigated only went
up to 2 M and 5 M, respectively.
Tomiyasu et al. proposed a novel mechanism that accounts
for the concentration-dependent voltage window of electrolytes.59
In their study, they focused on hydrogen bond in aqueous

electrolytes, which is a bonding between a hydrogen and an
adjacent oxygen within 0.3 nm. It’s like the tug-of-war, i.e., the
weaker the intermolecular hydrogen bonding, the tougher
the intramolecular O–H bonding, and the more difficult
the occurrence of water decomposition. Therefore, by using
extremely soluble sodium perchlorate (219.6 g can be dissolved
in 100 g water at 25 1C), the authors obtained a saturated
aqueous solution where the ratio of water molecules to sodium
perchlorate molecules was only 3.3. It is comprehensible that
the addition of salt disturbs hydrogen bonding between water
molecules, as the electronegative oxygen atoms would be more
attracted to cations and the electron poor hydrogen atoms Fig. 26 (a) Estimated structure of a supercapacitor based on saturated
would be more attracted to anions. In saturated sodium per- sodium perchlorate electrolyte. At least one water molecule should be
chlorate solution, the hydrogen bonding may be eliminated strongly hydrated to NaClO4, and the hydrogen bonding between water
because of the absence of neighbouring water molecules as well molecules would be weakened. (b) Electrochemical stability windows of
saturated sodium perchlorate electrolyte, 1 M H2SO4, and 1 M NaOH
as their intense hydration to salt ions (Fig. 26a). Consequently,
aqueous electrolytes using a glassy carbon as working electrode measured
the voltage window of this solution was expanded to 3.2 V due from 30 mV s1 to 200 mV s1 at 25 1C. Reproduced with permission from
to the loss of hydrogen bonding and the resultant enhancement ref. 59, Copyright 2017 Springer Nature. (c) Spin–spin relaxation time of
of O–H bonding (Fig. 26b). various electrolytes with various water concentrations. (d) Width of voltage
In a study of Yokoyama et al. seeking the origin of electro- window versus water concentration according to various electrolytes.
Reproduced with permission from ref. 55, Copyright 2018 The Electro-
chemical stability of aqueous electrolytes, the authors demon-
chemical Society. (e) Linear sweep voltammograms of Ti current collectors
strated that water concentration was a universal feature that (dashed lines) and CV curves of Na2Mn[Fe(CN)6] and KMn[Cr(CN)6] elec-
determines the voltage windows of aqueous electrolytes, as a trodes in 17 M NaClO4 electrolyte. (f) GCD curves of Na2Mn[Fe(CN)6] and
clear correlation between water concentration and voltage KMn[Cr(CN)6] electrodes in 17 M NaClO4 electrolyte. Reproduced with
window could be observed regardless the type of electrolyte permission from ref. 396, Copyright 2018 Wiley-VCH.
salt (Fig. 26c and d).55 In the case of concentrated electrolytes,
water activity can no longer be approximated to unity. According
to Nernst equation, potentials of OER (EOER) and HER (EHER) can involving water activity or water concentration is not included
be thus expressed as below, in the equation for HER, therefore, the authors concluded that
the influence of water concentration on potentials of OER
0 RT RT
EOER ¼ EH 2 O=O2
2:303 pH lnðaH2 O Þ2 and HER is asymmetrical. The widest voltage window achieved
F 4F
for conventional electrolyte salt in their study was around
RT RT 2.45 V (33 mol dm3 NaClO4 solution) when measured at the
0
EOER ¼ EH 2 =H2 O
2:303 pH ln K current density of 0.1 mA cm2.
F 2F
Nakamoto et al. demonstrated that the practical voltage
0 0
where EH 2 O=O2
and EH 2 =H2 O
are the standard potentials of OER window of a highly concentrated electrolyte of 17 M NaClO4
and HER, respectively. R is the gas constant, T is temperature, F is aqueous solution can be extended to 2.8 V.396 Based on this
the Faraday constant, and K is the equilibrium constant of water highly concentrated electrolyte, Na2Mn[Fe(CN)6] (NMHCF) cathode
ionization aH2O represents water activity. Reduced water concen- exhibited two redox pairs at 0.6 V and 1.0 V (vs. Ag/AgCl), while
tration (increased salt concentration) of electrolytes decreases KMn[Cr(CN)6] (KMHCC) anode exhibited a redox pair at around
water activity, thus increasing OER potential. However, the term 1.1 V (vs. Ag/AgCl), reflecting the intercalation/de-intercalation of
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sodium ions into/from the open frameworks attributing to

Fe2+/Fe3+ and Mn2+/Mn3+ in NMHCF and Cr3+/Cr2+ in KMHCC,
respectively (Fig. 26e and f). An ASIB that can be charged to 2.6 V
with a discharge midpoint voltage of 1.61 V was thus obtained.
Despite the high voltage, the specific capacity of the battery based
on the mass of both active materials was less than 40 mA h g1,
which was mainly restricted by the intrinsically low sodium ion-
accommodation capacity of KMHCC (which is only around
70 mA h g1). Thus, the resultant energy density of this battery
was just around 58 W h kg1, much less than conventional
LIBs. Moreover, its cycle stability (80% capacity retention after
100 cycles at 30C rate) also needs further improvement.
It should be noted that to obtain highly concentrated
aqueous electrolytes, the electrolyte salt should be highly
soluble in water. In these concentrated electrolytes enabled by

conventional inorganic salts, water is still the major constituent,
which differs from the categories of ‘‘water-in-salt’’ electrolytes
and hydrate-melt electrolytes.
4.4.2 ‘‘Water-in-salt’’/‘‘water-in-bisalt’’ electrolytes. The concept Fig. 27 (a) Electrochemical stability window of LiTFSI–H2O electrolytes
with various concentrations measured on nonactive electrodes at 10 mV s1.
of ‘‘water-in-salt’’ electrolyte was first proposed by Suo et al. in 2015, (b) GCD curves of the Mo6S8//LiMn2O4 full cell in 21 M LiTFSI ‘‘water-in-salt’’
where salt outnumbered solvent in terms of both weight and electrolyte at 0.15C. (c) TEM images of initial Mo6S8 (left) and cycled Mo6S8
volume, which is the reverse of conventional ‘‘salt-in-water’’.61 (right), showing the formation of the protective SEI. (d) Illustration of the
LiTFSI was employed as electrolyte salt due to its high solubility evolution of Li+ primary solvation sheath in diluted and ‘‘water-in-salt’’
at room temperature and good stability against hydrolysis. It’s electrolytes. Reproduced with permission from ref. 61, Copyright 2015
American Association for the Advancement of Science. (e) GCD curves of
claimed that the concept of ‘‘water-in-salt’’ applies when the the LiMn2O4//C-TiO2 full cell in ‘‘water-in-bisalt’’ electrolyte at the 2nd,
concentration of LiTFSI reaches 5 M, and an electrochemical 5th and 100th cycles. Reproduced with permission from ref. 63, Copyright
stability window of 3.0 V could be achieved at the concentration 2016 Wiley-VCH.
of 21 M (Fig. 27a). An ALIB using LiMn2O4 cathode and Mo6S8
anode was assembled to testify the feasibility of 21 M ‘‘water-in-
salt’’ electrolyte. It is noticeable that the electrochemical beha- unhydrated salt with similar chemical structures to form a dual-
viours of these electrode materials also changed, although no salt mixture, resulting in an even higher salt ion/water ratio.63 The
electrochemical studies have been offered in this research to developed ‘‘water-in-bisalt’’ electrolyte consisted of 21 M LiTFSI
further understand such phenomenon. By expanding electrolyte and 7 M LiOTf (lithium trifluoromethane sulfonate), thereby its
voltage window, the ALIB can be operated up to 2.3 V, yielding lithium ion concentration reached 28 M, and the corresponding
a midpoint voltage of 1.83 V with two flat plateaus at 1.94 V ratio of water molecules to salt ions was approximately 2.
and 1.52 V, respectively, notably higher than ALIBs based on Benefited from the higher salt concentration, a denser SEI layer
normal electrolytes (Fig. 27b). The expanding of voltage window could be promoted and water activity could be further decreased,
originated from two aspects (Fig. 27c and d). On one hand, allowing a wider electrochemical stability window of around 3.1 V.
lithium ions are well hydrated with sufficient free water molecules An ALIB with an open circuit voltage up to 2.5 V (showing a flat
at dilute concentrations, and the water molecules become insuffi- plateau at 2.07 V) was fabricated and reversibly cycled by
cient with the increase of salt concentration, leading to drastic coupling of LiMn2O4 cathode and TiO2 anode, delivering an
change in the solvation sheath of lithium ions. Particularly, the energy density of 100 W h kg1 (based on the mass of both
ratio of free water molecules to lithium ions is only 2.6 at the active materials) (Fig. 27e).
concentration of 21 M, meaning that the electrostatic field Since the voltage window of ‘‘water-in-salt’’/‘‘water-in-bisalt’’
originated from the formal charge on lithium ions can no longer electrolytes exceeds 3.0 V, ARMBs based on such electrolytes
be neutralized. As a result, TFSI enters the solvation sheath of Li+ could further raise their operating voltage by employing suitable
and an interphasial chemistry is thus enabled on anode surface electrodes with redox potentials sitting at the edge of electrolyte
before water decomposition, leading to the formation of a dense voltage window. For example, commercial spinel P4332 structured
layer of protective SEI. On the other hand, the short of free water LiNi0.5Mn1.5O4 cathode has a considerably high potential, while
molecules due to the high concentration deceases water activity, the positive shift of its potential in ‘‘water-in-salt’’ electrolytes
contributing to both cathodic and anodic electrochemical hinders its utilization.398 Wang et al. studied the Fd3% m type
stability. Synergistically, the voltage window of electrolyte is LiNi0.5Mn1.5O4 cathode, which bears two redox pairs at 4.6 V
significantly expanded.397 (Ni2+/Ni3+) and 4.8 V(Ni3+/Ni4+).399 The former can be fully utilized
Inherited from ‘‘water-in-salt’’ electrolytes, a ‘‘water-in-bisalt’’ as it is completely within the voltage window of 21 M LiTFSI
electrolyte was subsequently developed based on the knowledge ‘‘water-in-salt’’ electrolyte even taking potential shift into account
that a saturated electrolyte could further accommodate another (Fig. 28a). An ALIB showing two flat discharge plateaus at 2.56 V
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Fig. 28 (a) The electrochemical stability window of ‘‘water-in-salt’’ elec-

trolyte measured on non-active current collectors at 10 mV s1. The
corresponding redox potentials of LiNi0.5Mn1.5O4 cathodes with different
crystal structures and Mo6S8 anode (inset) were measured at 0.1 mV s1.
(b) GCD curves of the Fd3m % LiNi0.5Mn1.5O4 cathode in ‘‘water-in-salt’’

electrolytes before and after pH adjustment. (c) GCD curves of the
LiNi0.5Mn1.5O4//Mo6S8 full cell in pH-adjusted ‘‘water-in-salt’’ electrolyte
at 0.5C. Reproduced with permission from ref. 399, Copyright 2017 Wiley-
VCH. (d) GCD curves of the symmetric LiVPO4F full cell at various C rates.
(e) Cycle stability of the symmetric LiVPO4F full cell at 20C. The specific
capacities were based on total electrode weight. Reproduced with per-
mission from ref. 400, Copyright 2017 Wiley-VCH. Fig. 29 (a) Ionic conductivity of NaFSI and LiTFSI electrolytes of various
concentrations at 20 1C. (b) Electrochemical stability window of various
‘‘water-in-salt’’ electrolytes measured on stainless steel at 0.1 mV s1.
and 2.10 V with a midpoint voltage of 2.50 V was thus obtained by Redox potentials of NaTi2(PO4)3 and Na3(VOPO4)2F electrodes in 35 M
NaFSI at 0.05 mV s1 were also shown. Reproduced with permission from
coupling Fd3% m LiNi0.5Mn1.5O4 cathode and Mo6S8 anode, deliver-
ref. 64, Copyright 2017 American Chemical Society. (c) Electrochemical
ing an energy density of 80 W h kg1 with a capacity decay of only stability windows of 1 M and 22 M KCF3SO3 electrolytes measured at
0.075% per charge/discharge cycle at 5C rate. Furthermore, by 1 mV s1, which are marked with red and black, respectively. Reproduced
adjusting electrolyte pH, the voltage window was positively shifted with permission from ref. 254, Copyright 2019 Springer Nature. (d) CV
by 0.1 V, allowing for the better utilization of cathode capacity. curves of KTi2(PO4)3 anode in 30 M KAc and nonaqueous electrolytes at
0.5 and 0.1 mV s1, respectively. Inset shows its charge–discharge profiles
The Fd3% m LiNi0.5Mn1.5O4 cathode at the pH of 5 could deliver a
in 30 M KAc at the current density of 200 mA g1. (e) Cycle stability of the
higher capacity of 125 mA h g1 when being charged to 5.05 V KTi2(PO4)3 anode in 30 M KAc electrolyte. Reproduced with permission
(vs. Li+/Li), almost having reached its full capacity, leading to a from ref. 65, Copyright 2018 American Chemical Society. (f) Visualization
126 W h kg1 energy density for the resultant LiNi0.5Mn1.5O4// of the equilibrium electrolytes of 1 M KOAc, 1 M LiOAc, 27 M KOAc, and
Mo6S8 ALIB with similar voltage profiles (Fig. 28b and c). Yang 32 M KOAc + 8 M LiOAc. Atom color: K, purple; Li, green; O, red; C, grey;
H, white. (g) CV curves of various electrodes in 32 M KOAc + 8 M LiOAc
and co-workers further applied ‘‘water-in-salt’’ as gel polymer
electrolyte at 0.2 mV s1. Reproduced with permission from ref. 405,
electrolyte (GPE) by dissolving 25 M LiTFSI into water at 90 1C Copyright 2018 Royal Society of Chemistry.
followed by adding PVA.400 The realization of the high concen-
tration of 25 M suggested the interaction between PVA chains with
LiTFSI, which must have facilitated the latter’s solubility. A compared to LiTFSI (Fig. 29a). This ‘‘water-in-salt’’ electrolyte of
symmetric ALIB employing LiVPO4F as both cathode and anode 35 M NaFSI gave a voltage window slightly wider than that of 21 M
based on this GPE exhibited a flat high-voltage discharge plateau LiTFSI (Fig. 29b), suggesting the feasibility of 2 V ASIBs and more
(2.44 V) (Fig. 28d), superior energy density (141 W h kg1 based stable cycling. Very recently, Jiang et al. extended the voltage
on the mass of both active materials) and remarkable cycle life window of aqueous potassium-ion electrolyte to 3.0 V by increasing
(4000 charge/discharge cycles) (Fig. 28e), which could be attributed the concentration of KCF3SO3 to 22 M (Fig. 29c).254 They synthesized
to the extremely high concentration that ensured its ultra-stable a Fe-substituted Mn-rich PBA cathode (KxFeyMn1y[Fe(CN)6]wzH2O)
reversibility. and an organic 3,4,9,10-perylenetetracarboxylic diimide (PTCDI)
Besides ALIBs, the concept of ‘‘water-in-salt’’ electrolyte has anode, resulting in an AKIB showing a midpoint voltage of 1.50 V
also been extended into other ARMB systems including with a flat but short discharge plateau at 1.78 V. It also achieved a
ASIBs,64,401–403 AKIBs,65 AMIBs,66 hybrid zinc batteries,67,275,404 high energy density of 80 W h kg1 and remarkable cycling stability
etc. For example, in the study of Kühnel and co-workers,64 sodium that retained 73% capacity after 2000 charge/discharge cycles at 4C.
bis(fluorosulfonyl)imide (NaFSI) was employed as electrolyte salt In addition, the large organic anion of electrolyte salt is not always
to construct ‘‘water-in-salt’’ electrolyte, as its melting point of necessary to achieve the effect of ‘‘water-in-salt’’. For example, Liu
106 1C is much lower than that NaTFSI (257 1C), suggesting et al. used a 17 M NaClO4 aqueous electrolyte to enable an ASIB with
weaker lattice energy and higher solubility. Experimental data an open circuit voltage of 1.92 V and a midpoint voltage of 1.50 V.403
revealed that its solubility at room temperature can be as high as Leonard et al. demonstrated a 3.2 V-wide electrochemical stability
35 M, while better ionic conductivity can be still maintained window spanning from 1.7 V to 1.5 V (vs. Ag/AgCl) by using a 30 M
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Their first application for aqueous energy storage systems was

introduced and termed as ‘‘hydrate-melt’’ by Yamada et al., who
carefully screened lithium salt anions and investigated their
optimized eutectic combinations with the purpose of expanding
the electrochemical stability window.62 Specifically, they explored
the eutectic composition of two lithium salts with organic imide
anions, LiN(SO2CF3)2 (LiTFSI) and LiN(SO2C2F5)2 (LiBETI), and
found that Li(TFSI)0.7(BETI)0.3 exhibited highest miscibility with
water, resulting in a stable and transparent solution with an ultra-
low water concentration (10.1 mol dm3). In this way, free water
molecules can be isolated from each other by the bulky TFSI/BETI
anions, and all water molecules can be involved in the hydration
shells of lithium ions (Fig. 30a and b).
Fig. 30 (a) Liquidus line of LiTFSI + LiBETI mixtures in water. The light blue
area above represents a stable liquid phase of fully miscible salts and water, It should be noted that ‘‘water-in-salt’’ type electrolytes differ
whereas the dark blue area underneath represents a partially miscible from hydrate-melt electrolytes as they still contain non-negligible
phase. (b) Stoichiometric amounts of salts and water used to prepare the amount of free water due to their off-eutectic design. For the solution
hydrate melt of Li(TFSI)0.7(BETI)0.32H2O, resulting a transparent liquid. (c) with the water/anion molar ratio of 2 (Li(TFSI)0.7(BETI)0.32H2O),
Snapshots of equilibrium trajectories obtained from first-principles DFT-
a stable state was discovered where all water molecules were
MD simulations of Li(TFSI)0.7(BETI)0.32H2O hydrate melt and dilute LiTFSI/
H2O. Atom color: C, dark grey; H, light grey; O, red; N, blue; S, yellow; F, coordinated with lithium ions and intramolecular hydrogen
green; Li, purple. (d) Equilibrium potential shift of lithium ion intercalation bonding was neglectable (Fig. 30c). The authors also investigated
versus Li+ molality of electrolytes. (e) Voltage windows of pure water, the equilibrium potential shift of intercalation/de-intercalation
conventional LiTFSI/H2O electrolyte, and the hydrate-melt electrolyte with reaction of lithium ions, which was commonly observed in
redox potentials of Li4Ti5O12, LiCoO2 and LiNi0.5Mn1.5O4 indicated. Repro-
‘‘water-in-salt’’ type electrolytes. The equilibrium potential shift
duced with permission from ref. 62, Copyright 2016 Springer Nature.
was measured to be 0.25 V in Li(TFSI)0.7(BETI)0.32H2O hydrate
melt, higher than that of 22 M LiTFSI (Fig. 30d). Anodic and
potassium acetate (KOAc) aqueous electrolyte, which allowed for the cathodic potential limits were further pushed due to a thermo-
reversible cycling of the low-potential KTi2(PO4)3 anode (1.4 V/ dynamic mechanism (lowered HOMO level) and a kinetic
1.0 V vs. Ag/AgCl) for AKIBs (Fig. 29d and e).65 The potential mechanism (anion-based passivation), respectively, resulting
hysteresis between K+ intercalation and de-intercalation was smaller in an ultra-wide voltage window of 3.8 V. Moreover, due to the
in 30 M KOAc (around 0.3 V) than in nonaqueous electrolyte positive shift of reactive potentials, this voltage window allows
(around 0.5 V), suggesting higher energy efficiency. Furthermore, for reversible cycling of Li4Ti5O12 anode, whose reaction potentials
Lukatskaya et al. constructed a ‘‘water-in-bisalt’’ electrolyte by mix- are completely located within the voltage window. High-voltage
ing inorganic salts of lithium acetate (LiOAc) and KOAc. According LiCoO2 and LiNi0.5Mn1.5O4 cathodes can also be utilized as their
to MD simulation results, the ionic hydration shells of the highly upward-shifted potentials are still within the voltage window
concentrated 32 M KOAc + 8 M LiOAc electrolytes exhibit (Fig. 30e). As a result, the Li4Ti5O12//LiCoO2 and the Li4Ti5O12//
significantly interpenetrated feature, where every water mole- LiNi0.5Mn1.5O4 full ALIBs exhibited high-voltage discharge
cule is involved in at least one hydration shell at any given time plateaus at 2.26 V and 3.10 V, respectively.
(Fig. 29f). Thus, it can be regarded as a typical ‘‘water-in-bisalt’’ So far, there are no other investigations employing hydrate-
electrolyte, where no free water exists, and the solvation sheath melt electrolytes for ARMBs, except that Wu et al. developed a
consists of solely shared water molecules. The molecular water- Li–O2 battery based on a hydrate-melt electrolyte, which was
to-salt ratio was pushed to an ultralow value of 1.3. Resultantly, organic solvent-free and thus was effectively exempted from
conventional LIB anode materials including Li4Ti5O12 and side reactions regarding solvent degradation and by-products
TiO2 exhibited reversible Li+ intercalation/de-intercalation formation.408 Therefore, more studies are needed to further
in the 32 M KOAc + 8 M LiOAc ‘‘water-in-bisalt’’ electrolyte evaluate and improve the practicability of this novel kind of
(Fig. 29g), and the corresponding TiO2//LiMn2O4 full ALIB electrolytes.
yielded a flat high-voltage discharge plateau of 2.10 V.405 These
organic component-free ‘‘water-in-salt’’/‘‘water-in-bisalt’’ electrolytes 4.5 Electrolyte additives with interphase-forming capability
are cheap and environmentally benign, and can be readily regulated Differing from artificial SEI, additives with interphase-forming
over a wide range, showing high adaptability and versatility. capability tend to in situ form an extra interphase between
4.4.3 Hydrate-melt electrolytes. The concept of hydrate electrode and electrolyte, via either polymerization, physical
melt is similar to ‘‘water-in-salt’’. In fact, the ‘‘water-in-bisalt’’ absorption, or chemical decomposition of additives during
electrolyte was inspired by the implementation of hydrate-melt electrochemical processes. This section highlights the studies
electrolyte. Hydrate-melt electrolyte is actually the extending involving electrolyte additives that benefit battery voltage.
of super-concentrated electrolyte into water solvent. Super- The in situ-formed, additive-originated interphases hinder the
concentrated electrolytes have been studied for conventional LIBs transport of water molecules to electrode surfaces, suppress the
to enable better stability and even higher cell voltage (44 V).406,407 evolution of hydrogen or oxygen, and thus result in stabilized
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cycling of high-voltage electrode materials or broadened voltage

windows.
In non-aqueous electrolytes, interphase-forming additives
have been reported to be utilized to enhance stability of
batteries, which is realized by their preferential reduction
before electrolyte components during electrochemical processes
that strengthens SEIs.409 The first report of the successful applica-
tion of an electrolyte additive into an aqueous energy storage
system was introduced by Stojković et al.76 In their work, the
addition of 1% VC (vinylene carbonate) in aqueous LiNO3 electro-
lyte greatly boosted the capacity of Li1.05Cr0.10Mn1.85O4 cathode,
with a notable increase in its coulombic efficiency and a signifi-
cant reduction of its capacity decay. It is claimed that the addition
of VC facilitated the formation of a thin interphase of polymeric
species onto electrode surface, resulting in a protective interphase

that can hinder the penetration of water molecules and alleviate
the harm it does to lithium ion intercalation.410–412
Electrolyte additives have been reported to be physically Fig. 31 (a) Linear sweep voltammograms of Pt electrodes in aqueous
absorbed onto electrode surfaces, serving as a barrier inter- electrolyte of 0.5 M LiNO3 + saturated PDSS buffered with 0.25 M Li–PO4
phase to isolate water molecules, thus raising the resistance to (pH = 7) showing the positive expanding of voltage window to 1.6 V (vs. Ag/
reductive/oxidative decomposition of electrolytes, resulting a AgCl). Reproduced with permission from ref. 77, Copyright 2016 Royal
wider voltage window. For example, Miyazaki and co-workers Society of Chemistry. (b) CV curves of the Na2MnFe(CN)6 cathode in the
pristine electrolyte at 5 mV s1. (c) CV curves of the Na2MnFe(CN)6
saturated 0.5 M LiNO3 electrolyte with disodium propane-1,3- cathode in the electrolyte containing SDS at 5 mV s1. Reproduced with
disulfonate (PDSS), enabling the utilization of the high-potential permission from ref. 78, Copyright 2017 Royal Society of Chemistry. (d) CV
LiNi0.5Mn1.5O4 cathode.77 The authors explained that the PDSS curves of graphite anode pre-coated with LiTFSI-HFE gel and LiVPO4F
anions were like bulky TFSI anions, which could effectively cover cathode in ‘‘water-in-bisalt’’ electrolyte coupled with lithium metal anode
the surface of LiNi0.5Mn1.5O4 cathode and repel water molecules pre-coated with LiTFSI-HFE gel measured at 0.5 mV s1. Insets illustrate
the cell configurations. (e) GCD curves of LiVPO4F cathode coupled with Li
during electrochemical processes. Compared to other highly metal anode at 0.3C. Reproduced with permission from ref. 413, Copyright
concentrated electrolytes, the addition of PDSS does not change 2017 Elsevier. (f) Illustration of the formation of SEI-like interphase on the
the concentration of electrolyte salt (i.e., lithium salt for this anode in HANE. (g) TEM image of fully lithiated Li4Ti5O12 anode. (h)
case), therefore, the potentials for lithium ion intercalation/ Electrochemical stability window of the HANE measured on pure current
de-intercalation would not be affected. In addition, the dissolution collectors and on active materials of Li4Ti5O12 and LiNi0.5Mn1.5O4. (i)
Discharge profiles of the Li4Ti5O12//LiNi0.5Mn1.5O4 full cell at various C
of the high-potential cathode material in low-pH condition was rates. Reproduced with permission from ref. 414, Copyright 2018 Elsevier.
suppressed by adding a phosphate buffer. Resultantly, a wide
voltage window positively extending to 1.6 V (vs. Ag/AgCl) was
obtained (Fig. 31a), allowing for the reversible redox reactions interphase through additive decomposition should meet the
of the high-potential LiNi0.5Mn1.5O4 cathode (two redox pairs at following requirements: (1) the additive should be chemically
1.45 V/1.49 V and 1.48 V/1.52 V (vs. Ag/AgCl), respectively). Similarly, stable in the given electrolyte solution. (2) It should be electro-
a hybrid aqueous battery system by coupling Na2MnFe(CN)6 chemically unstable so that decomposition can occur and
cathode and zinc anode showing two flat discharge plateaus at interphase ingredient can be released during electrochemical
1.75 V and 1.58 V was developed.78 It was confirmed that the processes. Yang et al. introduced a highly-fluorinated ether
second redox pair of Na2MnFe(CN)6 cathode located at around (HFE) as an electrolyte additive, which was mixed with 0.5 M
1.1 V (vs. SHE) could not be initiated in conventional 1 M Na2SO4 + LiTFSI and 10 wt% polyethylene oxide to form a transparent
1 M ZnSO4 electrolyte due to severe OER. With the addition of gel. This gel was extremely hydrophobic and exhibited com-
sodium dodecyl sulfate (SDS), OER was effectively suppressed plete inertness toward lithium metal. It also remained phase
and the second redox reaction of cathode could thus be separated from the 21 M LiTFSI + 7 M LiOTf ‘‘water-in-bisalt’’
reversed (Fig. 31b and c). The resultant battery delivered a high GPE. The pre-coating of LiTFSI-HFE gel onto graphite or
energy density of 170 W h kg1 (based on the mass of cathode lithium metal electrode initiated their reversible cycling in
material) as well as a good cycling stability. DFT calculations ‘‘water-in-bisalt’’ GPE (Fig. 31d), leading to the feasibility of a
further revealed the existence of a high-energy barrier that series of high-voltage ALIBs with discharge plateaus located at
blocks the transport of water molecules through the dense around 4.0 V and energy densities approaching conventional
hydrophobic interphase of SDS additives on electrode surface, state-of-the-art LIBs (Fig. 31e). It was discovered that the LiTFSI-
OER and HER potentials are thus increased, leading to the HFE gel were consumed to yield a solid interphase consisting of
expanding of voltage window. both organic fluorinated hydrocarbon and inorganic fluorides,
Decomposition of electrolyte additives can also in situ form a in accordance with previous reported organic electrolytes.413
protective, SEI-like interphase. The formation of a protective Moreover, in the hybrid aqueous/non-aqueous electrolyte
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(HANE) developed by Wang et al.,414 the non-aqueous compo- could be realized in organic electrolytes. However, such high
nent of dimethyl carbonate (DMC) served as an additive in capacity decays during cycling in aqueous electrolytes due to the
‘‘water-in-salt’’ electrolyte, which provided a secondary ingre- lack of protective SEI on cathode.121,416,417 Wang et al. introduced
dient of alkylcarbonate in addition to LiF originating from TFSI an additive of tris(trimethylsilyl) borate (TMSB) into ‘‘water-in-
reduction to strengthen the SEI-like interphase formed on salt’’ electrolyte, which was subsequently oxidized to form a
anode during electrochemical processes (Fig. 31f and g), protective interphase on LiCoO2 cathode (Fig. 32d and e).418 At
extending voltage window downward to 1.0 V (vs. Li/Li+) a high cut-off voltage, the interphase-protected LiCoO2 delivered a
(Fig. 31h). The electrochemical stability window of the HANE high capacity of 170 mA h g1 with remarkable cycling stability.
was around 4.1 V wide, enabling an ALIB with a flat discharge An ALIB coupling LiCoO2 cathode with Mo6S8 anode exhibited a
plateau at 3.2 V based on LiNi0.5Mn1.5O4 cathode and Li4Ti5O12 2.50 V open circuit voltage and a 1.95 V midpoint voltage
anode (Fig. 31i). This ALIB showed an energy density as high as (Fig. 32f), achieving an energy density as high as 120 W h kg1
165 W h kg1 and a cycle stability over 1000 charge/discharge cycles. and a low capacity decay rate of 0.013%/charge–discharge cycle, as
More recently, Wang’s group proposed a conversion-intercalation the protective interphase effectively suppressed OER and cobalt
chemistry of the cathode containing equimolar lithium halide salts dissolution from cathode to electrolyte.
(LiBr)0.5(LiCl)0.5–graphite (LBC–G) (Fig. 32a).415 In this study, ‘‘water- Voltage characteristics of high-voltage ARMBs employing the
in-bisalt’’ electrolyte was utilized to bind partially hydrated LiBr/LiCl above-mentioned various strategies are compared in Fig. 33. As
within the cathode host, and HFE gel was employed to coat graphite revealed, most of these ARMBs possess midpoint voltages
anode so that a protective interphase could be formed to higher than 1.5 V, and the majority of them exhibit a flat
initiate its electrochemical processes. This new cathode plateau upon discharge, showing high potential in providing
chemistry combined the high energy of the conversion reaction high-energy and consistent output. Midpoint voltages of the
and the good reversibility of intercalation process, resulting in ARMBs based on conventional aqueous electrolytes that fully
a full ALIB with a midpoint voltage of 3.98 V and an ultrahigh exploit voltage window (introduced in Section 4.1) are basically
energy density of 460 W h kg1 (based on the mass of both in the range of 1.2–2.0 V. By regulating electrolyte pH, midpoint
electrodes) (Fig. 32b and c). voltages can be raised to 1.8–2.3 V (ARMBs introduced in
In addition, an electrolyte additive has been reported to Section 4.2). Concentrated aqueous electrolytes including
stabilize high-voltage cathode material. Layered LiCoO2, when the novel ‘‘water-in-salt’’/‘‘water-in-bisalt’’ and hydrate-melt elec-
charged to 4.2 V (vs. Li/Li+), could deliver a specific capacity of trolytes further pushes midpoint voltages up to 2.5 V and above
140 mA h g1, corresponding to 50% Li extraction to Li0.5CoO2, (ARMBs introduced in Section 4.4). Impressively, protective inter-
which has been regarded as a relatively reliable cathode phase layers either artificially formed (ARMBs introduced in
material. If charged to 4.5 V (vs. Li/Li+), a higher specific Section 4.3) or in situ formed via electrolyte additives (ARMBs
capacity of 180 mA h g1 (corresponding to 70% Li extraction) introduced in Section 4.5) can ultimately realize ARMBs with
midpoint voltages over 4.0 V, which are even comparable to
traditional organic LIBs. Still, there is a long way to go before
they can be practically applied and commercialized, further
researches on cost cut-down, cell assembly and encapsulation
techniques are needed.
5. Future perspectives and concluding

remarks
Compared with conventional organic LIBs, ARMBs possess a
number of irreplaceable merits including low cost, high power,
intrinsic safety and environmental benignity, showing great
Fig. 32 (a) Schematic illustrations of the conversion–intercalation chem- potential in large-scale stationary energy storage as well as in
istry of the LBC–G cathode upon oxidation. The two-step reactions small electronics concerning wearable applications. The intro-
include the oxidation of Br (at 4.0 V) and Cl (at 4.2 V) and their ducing of aqueous electrolytes accounts for the superiority of
subsequent intercalation into the graphitic host. Discharge process is
ARMBs, which erases the usage of expensive, flammable and toxic
a reversal. (b) GCD curves of ALIBs based on LBC–G cathodes with
anhydrous LiBr/LiCl or LiBr/LiCl monohydrates and HFE–PEO gel coated
organic electrolytes. Whereas, aqueous electrolytes inevitably
graphite anodes at 0.2C. (c) Energy density of the graphite//LBC–G full cell bring the confinement of operating voltage for ARMBs due to
compared with other batteries (based on the mass of both electrodes). the narrow electrochemical stability window of water (B1.23 V).
Reproduced with permission from ref. 415, Copyright 2019 Springer Consequently, batteries with aqueous electrolytes normally exhibit
Nature. (d and e) TEM images of the LiCoO2 cathode after cycling in
lower energy density compared to their counterparts based on
21 M LiTFSI ‘‘water-in-salt’’ electrolyte containing 0.1 wt% TMSB additive.
A protective interphase can be clear observed. (f) GCD curves of the
organic electrolytes. To alleviate this problematic issue, effective
LiCoO2//Mo6S8 full cell at 0.5C. Inset shows its CV curves. Reproduced strategies have been proposed to broaden electrolyte voltage
with permission from ref. 418, Copyright 2016 Royal Society of Chemistry. window, resulting in ARMBs with higher operating voltages.
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Fig. 33 Voltage comparison among various high-voltage ARMB systems. Solid circles represent midpoint voltages, and hollow stars at the same x-axis
position represent corresponding plateau voltages (the voltage of the first discharge plateau is adopted if a battery yields more than one plateau).
Nevertheless, running high-voltage ARMBs far away from their large organic groups, which are extremely expensive, and the
intrinsic ‘‘safe zone’’ leads to other problems, including high concentration further pushes up their cost. As for electro-
jeopardized cycle stability originating from aggravated side lyte additives, their long-term influences on electrochemical
reactions, higher cost due to the use of expensive chemicals/ performances should be carefully observed, and their decom-
components, more complicated configurations, etc. position to form SEI-like interphase usually associate with
Reviewing representative ARMBs, it is delighted to see that the use of organic components and ‘‘water-in-salt’’/‘‘water-in-
some tough problems have been more or less addressed by bisalt’’ electrolytes.
applying a variety of ingenious solutions. However, ideal Therefore, to enable practicability, more cost-effective and
ARMBs prototypes possessing high energy and power density facile strategies should be envisioned and implemented. For
with simultaneous long-term cycling stability are rare, not to example, there are many experiences of constructing artificial
mention the concern about cost. As the ultimate goal of ARMBs SEIs for conventional LIBs,419–421 which can be translated to
is commercialization, it is an urgent need to upgrade their ARMBs with suitable adjustments. This kind of strategy should
practicability to a new level. According to the achievements that be carefully screened and optimized to cater for the original
have been made so far, potential directions for further improve- intentions of low cost and industrial simplicity. Besides, almost
ments of future ARMBs are proposed in the following aspects. all works based on ‘‘water-in-salt’’/‘‘water-in-bisalt’’ electrolytes
and hydrate-melt electrolytes are limited to several types of
5.1 Envision more cost-effective and facile strategies organic salts, there should be cheaper and more effective
Although effective, current strategies to obtain high-voltage options for constructing high-voltage ARMBs with reasonable
ARMBs are usually complex and/or costly. Specifically, the cost. Some ionic liquids (ILs) have been reported to be good
effect of regulating electrolyte pH is moderate, while it may supporting components for aqueous electrolytes, and their
be more demanding on cell configuration, or induce side mixture with water mitigates the disadvantages of high viscos-
reactions of electrode materials, or cause safety concerns ity and low ionic conductivity, which could also be a promising
of erosion. Constructing artificial interphase is even more research direction of expanding electrolyte voltage window.241,422–424
complicated in engineering, and it usually involves the use of Moreover, studies have shown that some gel polymer electrolytes
an extra layer of lithium-ion conductor and organic electrolyte (GPEs) have better tolerance for high voltages, which was
to initiate the utilization of low-potential lithium metal or ascribed to the mechanism of ‘‘molecular cages’’ where water
carbon anode, meaning the cost and safety concern are actually molecular are ‘‘locked’’ and more interacted with polymer
not much eased. The novel ‘‘water-in-salt’’/‘‘water-in-bisalt’’ chains,425 or a special ionic conduction mechanism of coopera-
electrolytes and hydrate-melt electrolytes are impressive in tive O - B coordination bonds in polymer.241 These gel
expanding voltage window, which makes the cycling of elec- polymers enabled high-voltage energy storage devices without
trode materials with higher/lower redox potentials in aqueous severe water electrolysis. Although more comprehensive investi-
solutions possible. Whereas, they generally employ salts with gations are needed to further reveal their in-depth mechanisms,
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it would be inspiring if GPEs with stronger capability to suppress

water electrolysis are discovered.
5.2 Discover new electrode materials for aqueous electrolytes

Comparative studies have demonstrated that the difference
of electrochemical performances of some existed electrode
materials in aqueous electrolytes and non-aqueous electrolytes
is not noticeable, which means traditional methods of material
optimization could be readily translated into ARMBs to
enhance battery performances. Besides, due to the narrower
voltage window of aqueous electrolytes, it is more important to
fully exploit the voltage window by utilizing electrode materials
with desired redox potentials sitting at the edge of the window.
In return, their redox potentials are affected by electrolyte pH,
electrolyte salt concentration, crystal orientation, etc.,58,60,61,399

which requires a more comprehensive and accurate control of Fig. 34 Relationship between exchange current for HER and metal–
the whole electrochemical system. Moreover, some reported hydrogen bond strength of various metal electrodes. Reproduced with
high voltage values for ARMBs actually refer to open circuit permission from ref. 432, Copyright 2019 Wiley-VCH.
voltage, while the corresponding batteries only yielded low
discharge plateau or no plateau but capacitor-like sloping
discharge profiles, which is not favourable to energy density solutions with different concentrations were compared, which
and stable energy output. Therefore, electrode materials with showed that the shift of voltages window at different LiTFSI
high redox potentials and simultaneously fast redox kinetics concentrations is highly dependent on the choice of metallic
are highly desired to construct ARMBs with high-voltage electrode.429 Lahan et al. demonstrated that current collector
discharge plateaus. In addition, the seeking of more suitable played a unique role in determining the electrochemical
electrode materials should not only be focused on redox performance of TiO2 anode for aluminium-ion batteries. The
potentials, materials with larger specific capacities are always employed graphene current collector significantly suppressed
preferential regarding to the promotion in energy density of HER on anode, allowing for reversible Al3+ intercalation/
ARMBs. For example, Kundu et al. reported a vanadium oxide de-intercalation.430 Fig. 34 gives the relationship between
bronze pillared by interlayer zinc ions and water as cathode hydrogen evolution from the interaction of water and the
material for AZIBs, although the average operating voltage of strength of adsorbed metal–hydrogen (M–H) bonds on current
the resultant cell was less than 1.0 V, the energy density reached collectors.431,432 It is clearly seen that the exchange current for
250 W h kg1 (based on the mass of cathode material) due to HER increases to a peak and then gradually decreases with the
the large specific capacity (220 mA h g1) at 15C-rate, meaning increasing of M–H bond strength. Consideration of the inter-
large specific capacity could help compensate low operating action energy between atomic hydrogen and surface metal
voltage in practical applications.426 However, when discovering atoms actually results in the divide of metals into two distinct
new electrode materials for ARMBs, their stability in aqueous groups. The peak of the curve should correspond to Dg0 = 0,
solutions should be thoroughly considered, especially at certain where Dg0 is the standard free energy of hydrogen adsorption.
pH values, as literatures have demonstrated the dissolution of Consequently, in the left rising part of the curve in Fig. 34 there
electrode materials or their intermediate compounds into water should be metals not-adsorbing hydrogen, while in the right
during electrochemical processes, which are mainly responsible descending part there should be metals adsorbing hydrogen. At
for battery capacity decay.27,57,132,427,428 low M–H bond strength, the trend for HER is low as hydrogen
bonds weakly with metal surface. At high M–H bond strength,
5.3 Systematic studies of current collectors and binders H–H recombination is decreased as the bonding between
Various current collectors have been employed in ARMBs, hydrogen and metal is so strong.433 Therefore, metals sit at
including nickel mesh, stainless steel sheet/grid, titanium foil, either extreme of this curve are preferred for current collectors
graphite foil, carbon fabric, carbon nanotube fabric, etc. How- in aqueous electrolytes as their overpotential for HER is high,
ever, detailed studies of the influences of current collectors contributing to wider electrochemical stability window.
on battery performances in aqueous electrolytes are absent. Besides, the corrosion of metallic current collectors is more
Conventional LIBs widely adopt aluminium as current collector severe in aqueous electrolytes.434 Platinum, titanium, and
because of its good electrical conductivity, light weight and cost nickel are demonstrated to be more resistant to corrosion,
efficiency. While for practical application of ARMBs, the select while they are more expensive than stainless steel, copper and
of current collectors should be conducted with extra cautiousness aluminium.435 To avoid corrosion and facilitate long-term
regarding the narrower voltage window and more complicated stability, the contact area between current collector and electrolyte
electrochemical processes. In a study of Coustan and coworkers, is suggested to be minimized. This can be achieved via fully
voltage windows of various metallic current collectors in LiTFSI coating current collectors with electrode material on both sides,
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and/or protecting the bare current collector area with inert Compared to the studies on electrode materials and liquid
coatings.436,437 Moreover, the choice of binder for ARMBs is quite electrolytes, very little work is directed toward characterizing,
limited. The widely-adopted polyvinylidene-di-fluoride (PVDF) evaluating and developing separators/solid-sate electrolytes for
binder suffers from high cost and toxicity, and the solvent of ARMBs. To score higher energy density and maintain consistent
N-methyl-pyrrolidone (NMP) used to dissolve PVDF has similar energy output, researchers should devote more into these areas.
disadvantages.438 The gradual dissolution of PVDF into aqueous Mechanical strength, chemical stability, thermal stability, perme-
electrolytes further required the seeking for safer, more cost- ability, porosity, wettability, electrolyte absorption and retention,
effective and more stable binders for ARMBs.439 Overall, the thickness, and dimensional stability should all be considered
choice of current collector and binder for ARMBs seems trivial, when enhancing separators/solid-sate electrolytes. It is worth
but it is crucial in terms of improving battery performances. bearing in mind that it is eventually the applications that decide
Therefore, systematic and in-depth studies in these aspects are what kind of separator/solid-sate electrolyte is most suitable for a
urgently needed. certain ARMB system, as no single separator/solid-sate electrolyte
satisfies all the needs. Thus, compromises need to be made. There
5.4 Enhancement of separators/solid-state electrolytes has always been a growing demand for thinner separators/solid-
A separator is usually in the form of a porous membrane sate electrolytes to push up battery energy density,445 and the
sandwiched between cathode and anode, permeable to electro- blooming field of wearable electronics call for highly flexible,
lyte ions but preventing electric contact of electrodes. It plays a highly mechanically-durable separators/solid-sate electrolytes
vital role in a battery system, and should meet the following to ensure both comfortable wearing and stable energy supply.
requirements: (1) electric insulation; (2) low ionic resistance; Researchers should work along with industrial manufacturers to
(3) chemical stability against electrolyte, electrode reactants create the next generation of ARMBs with enhanced separators/
and by-products; (4) mechanically strong and stable; (5) readily solid-sate electrolytes.
wettable by electrolyte.440 It should be clarified that currently
there is no single separator that can satisfy all batteries with 5.5 Thoroughly examine OER and HER behaviour in ARMBs
varied chemistries, configurations and geometries. Conven- As researches are mainly focused on directly enhancing battery
tional LIBs extensively adopt polyolefins (polyethylene and performances, the profound influences of OER and HER during
polypropylene) with microporous structures as separators, as the electrochemical processes of ARMBs have not been thor-
they possess good mechanical properties, chemical stability oughly investigated yet. For ARMBs, OER and HER together
and affordability. But these polyolefins are inherently non- decide the electrochemical stability window of their aqueous
wettable by aqueous solutions, so that aqueous electrolytes electrolytes, thus affecting the usability of electrode materials
cannot penetrate these membranes and ions migration cannot and resultant cell voltages. Besides, OER and HER themselves
occur. Recent researches of ARMBs tend to utilize cellulose- as well as associated parasitic reactions significantly deteriorate
based microporous nonwoven fabrics as separators, which are the long-term stability of ARMBs, attributing to either altera-
chemically stable and hydrophilic. Whereas, sufficient thick- tion in electrolyte concentration and/or accessibility due to
ness is needed for them to maintain satisfactory mechanical water consumption, or dissolution of intermediate by-products
strength. originated from electrode active materials. On top of that, even
To avoid liquid leakage and simplify battery configuration, minor gas evolution could disable the sealing of ARMBs, which
solid-state electrolytes that can serve simultaneously as battery impedes long-term durability, torturing the encapsulation for
separators have been accordingly developed. For conventional further commercialization. Therefore, it is of tremendous impor-
LIBs, commonly-adopted solid-state electrolytes are polymer tance to systematically study OER and HER during battery charge/
electrolytes, gel polymer electrolytes and inorganic solid-state discharge processes with respect to various battery components
electrolytes.441,442 Although attractive in operation safety and including electrode materials, electrolytes, binders, conductive
cell assembly, these solid-state electrolytes suffer either low additives, and current collectors. Due to the similarities in electro-
lithium-ion conductivity, low mechanical strength or poor chemistry, research methods and experiences can be borrowed
flexibility. For ARMBs, as water is the electrolyte solvent, it is from the studies of metal–air batteries446–449 for OER and the
feasible to utilize hydrogel as solid-state electrolyte. Hydrogels studies of electrocatalytic hydrogen production37,450–452 for
are typically swollen polymer networks with a large amount of HER. Moreover, real-time monitoring electrolyte local pH may
absorbed water, resulting in high ionic conductivity and stability help quantify OER and HER processes that involve hydrogen
against liquid leakage. Some hydrogel electrolytes such as poly(vinyl ions and hydroxides, and pH change could in return affect the
alcohol), sodium polyacrylate and gelatin are actually not advant- activity of OER and HER.453,454 Coulombic efficiency may also be
ageous in maintaining consistent battery performance, because they utilized as an effective indicator for examining OER and HER, and
would be easily affected or damaged upon high shearing force, literatures have already paid attention to its importance in galvano-
pressure, or sharp cut. But through careful design and modification, static charge/discharge cycling, self-discharge test and galvanostatic
we have demonstrated the successful applications of self-healing intermittent titration technique (GITT) test.63,399,400,455,456 With
hydrogel electrolyte and soft-yet-tough hydrogel electrolyte in various in-depth understanding of OER and HER behaviour in certain
aqueous battery systems, having achieved improved device-level ARMB configurations, effective and accurate strategies can thus
usability and durability.213,443,444 been envisioned to better enhance battery performances.
View Article Online
5.6 In-depth exploration of degradation mechanisms of emphasized on the co-insertion process of protons and zinc ions,
ARMBs where the cathode lattice contraction induced by zinc ion inter-
Degradation mechanisms of conventional LIBs have been calation and the expansion caused by hydronium intercalation
thoroughly investigated, which has helped address the cycle offset each other, favouring lattice integrity and battery long-term
life issue and achieve wide applications of LIBs. For ARMBs, stability.240,480
few studies have specially focused on their degradation Exploring degradation mechanisms is extremely important
mechanisms during cycling. Actually, the adoption of aqueous in terms of either commercialisation of ARMBs or achieving
solutions brings about more complicated chemical reactions high-voltage ARMBs. For instance, replacing oxide ion with
and thus should result in more diverse degradation processes. polyanions can expand charge voltage limited by the top of
Literatures have demonstrated that some vanadium-based the anion-p bands of cathodes, while it could result in structural
compounds can be utilized as promising cathodes for various instability and performance decay after cycling.481 Also, some
ARMB systems, while their fast dissolution into aqueous electrodes show electrochemical instability at high applied
electrolytes accounts for the rapid capacity fading of ARMBs.457 voltage.460 Currently, during the investigations of ARMB degrada-
Phase transformation of electrode materials is another major tion mechanisms, more attentions are devoted to electrode
factor that causes battery performance decay. For example, intrinsic properties, while their association with aqueous
MnO2 goes through irreversible phase transformation to spinel electrolytes has seldom been attended. Besides, the studies
ZnMn2O4. The latter possesses a high negative formation energy on the degradation of aqueous electrolyte and hydrogel electro-
(1293.3 kJ mol1) that can well stabilize this compound, leading lytes themselves are usually neglected. Therefore, researchers
to unfavourable zinc ion extraction during charging. Together are suggested to conduct more comprehensive and in-depth
with the loss of redox-active Mn element originating from Mn2+ exploration of the degradation mechanism of ARMBs.
dissolution, capacity fading of the Zn//MnO2 battery is thus
5.7 Employment of in situ characterization techniques
inevitable.44,432,458 Na2/3[Ni1/3Mn2/3]O2 for sodium intercalation
and LiNiO2 for lithium intercalation were also found to experience Electrochemical testing approaches such as cyclic voltammetry,
phase transformation upon cycling.459,460 Nayak et al. reported galvanostatic charge/discharge, electrochemical impedance
that the layered-to-spinel phase transformation of Li- and Mn-rich spectroscopy and rate performance test are widely-adopted
cathode Li1.2Ni0.16Mn0.56Co0.08O2 was responsible for its average methods to investigate the electrochemical mechanisms and
discharge voltage decay.461 Also, the migration of some transition evaluate the performances of ARMBs. While these methodol-
metal ions in electrode materials would cause concentration ogies are incapable of describing the detailed reaction mechan-
gradient in lattice, leading to the formation of structural recon- isms and microscopic variations of electrode chemical/physical
struction layer throughout the whole electrochemical process and state during electrochemical processes, hence ARMBs in opera-
the resultant performance decay.462 Besides, it is reported that tion are like a ‘‘black box’’. This ‘‘black box’’ can be unfolded
structural instability of high-voltage oxygen-containing cathodes via various ex situ characterization techniques. However, for
can result in the release of lattice oxygen. Extensive oxygen release ex situ measurements, the ongoing electrochemical processes
causes severe cathode performance decay and triggers thermal have to be stopped and the electrode/electrolyte components
runaway of conventional LIBs.463,464 In addition, other causes obtained from the disassembled cells need to be carefully
including irreversible electrochemical instabilities at electrode– handled prior to the tests. In this respect, ex situ techniques
electrolyte interfaces,465,466 induced microcracks within secondary cannot reveal the exact reaction routes happened in ARMBs.
particles of electrode materials,467 redox reactions between Instead, in situ characterization techniques can track the whole
electrode and binder,468 and non-uniform coatings of electrodes469 electrochemical processes without disturbing ARMBs, omitting
that would deteriorate battery long-term performance have also the influence and uncertainty brought by cell disassembly
been located. and electrode/electrolyte post-treatment, thereby providing
To deal with the suffering battery degradation issue, researchers systematic, accurate and profound information of structural
have proposed corresponding solutions. Polymer coating strategy evolutions and reaction mechanisms.
and addition of specific salt to change dissolution equilibrium Various in situ characterization techniques including X-ray,
were proved effective to suppress the dissolution of vanadium- electron, neutron, optical, and scanning probes have been
based compounds.27,240 Doping electrode materials with various applied to the studies of LIBs and lithium–sulfur batteries.482,483
valence groups can affect their structures and properties in Whereas, only in situ X-ray diffraction and Raman spectroscopy
various ways, which include acting as pillars to uphold electrode have been relatively widely-adopted for the studies of ARMBs. It
structural integrity,470 increasing lattice spacing for faster ion is suggested that researchers conduct more systematic in situ
intercalation,471 decreasing lattice distortion,472 increasing the characterizations with the cutting-edge techniques to detect
energy barrier for transition metal migration,461 and delaying ARMB electrode at different depths of discharge and states
oxygen release reaction,473 thus alleviating their structural trans- of charge, as well as the influences of aqueous electrolytes and
formations. Constructing core–shell structures via modification of the interfaces between electrolytes and electrodes, therefore
surface chemical composition without affecting bulk composition building up a bridge linking the macroscopic electrochemical
has also been proposed to enhance the structural stability of performances with the microscopic physical and chemical
electrodes.474–479 Moreover, for AZIBs, Wang et al. and Wan et al. variations of ARMB components. For example, in situ optical
View Article Online
spectroscopy characterizations such as Fourier transform infra- stable energy output and high energy efficiency, which can be
red spectroscopy and ultraviolet-visible absorption spectroscopy found in both organic and inorganic electrode materials among
can be combined with Raman spectroscopy to quantitatively or different ARMBs.120,251 Whereas sloping discharge profiles are
semi-quantitatively identify fingerprints of electrodes, electrolyte also commonly seen in some systems with slow electrochemical
and reaction products under different electrochemical operating kinetics. Therefore, by studying general strategies that can
stages.484 In situ transmission electron microscopy and scanning regulate discharge plateau or other voltage characteristics, it
electron microscopy can reveal the morphology evolution including is highly feasible to develop universal approaches to control the
expansion, extraction and crack formation of electrodes, and multi- electrochemical performance of various ARMBs. To achieve
dimensional information of electrodes can be obtained via trans- this, precise characterization technologies and convincing the-
mission X-ray microscopy together with X-ray absorption near-edge oretical calculations/simulations are indispensable.
structure.483 Nuclear magnetic resonance imaging has been Thorough studies have been made on ARMBs in the past two
reported to real-time monitor the microstructure growth of decades, while the attempts to achieve practically usable high-
lithium metal, suggesting its huge potential in the studies of voltage and high-energy ARMBs are preliminary and deficient.
zinc dendrites in AZIBs.485 Moreover, structure- and dynamic- Although ARMBs cannot compete with commercial LIBs yet,
function relations of energy materials can be unveiled by in situ recent investigations and the proposed perspectives have
neutron-based techniques, and identifying battery working provided insightful strategies and promising opportunities that
mechanism at molecular and/or atomic scale is thus feasible. can facilitate the practical development of high-voltage and
Specifically, in situ neutron powder diffraction can be applied high-energy ARMBs.
to help understand the complicated ion-intercalation and phase
transitions in electrode materials, and even modest dynamical
information can be probed from atomic displacement Conflicts of interest
parameters.486 Besides, in situ small-angle neutron scattering
There are no conflicts to declare.
that probes materials at larger length scales from 1 nanometre
up to several micrometres is particularly powerful for characteriza-
tion of structural evolution at nanometre scales.487 Driven by these Notes and references
cutting-edge in situ characterization techniques, energy material
optimization and battery cell design could be substantially 1 R. Iranpour, M. K. Stenstrom, G. Tchobanoglous, D. Miller,
promoted, thus advancing current ARMB technologies. J. Wright and M. Vossoughi, Science, 1999, 285, 706–711.
2 C. P. Grey and J. M. Tarascon, Nat. Mater., 2016, 16, 45–56.
5.8 More general theory and regulation strategies 3 M. Armand and J. M. Tarascon, Nature, 2008, 451, 652–657.
A profound understanding of energy storage mechanisms is 4 B. Dunn, H. Kamath and J. M. Tarascon, Science, 2011, 334,
the foundation for continuous evolution of ARMBs. To date, 928–935.
compared with the fast advancing of electrochemical perfor- 5 Z. Yang, J. Zhang, M. C. Kintner-Meyer, X. Lu, D. Choi,
mances (e.g. capacity), in-depth understanding of electrochemical J. P. Lemmon and J. Liu, Chem. Rev., 2011, 111, 3577–3613.
reaction mechanisms has not been correspondingly realized, and 6 H. Kim, J. Hong, K. Y. Park, H. Kim, S. W. Kim and
some explanations of electrochemical processes are still under K. Kang, Chem. Rev., 2014, 114, 11788–11827.
debate. For example, co-insertion of protons with guest ions play 7 D. Larcher and J. M. Tarascon, Nat. Chem., 2015, 7, 19–29.
entirely different roles in different ARMB systems, and in one 8 K. S. Kang, Y. S. Meng, J. Breger, C. P. Grey and G. Ceder,
case, they lead to poor cyclability,163 whereas in other case they Science, 2006, 311, 977–980.
result in increased capacity.43 Thus, it is important to establish a 9 J. M. Tarascon and M. Armand, Nature, 2001, 414, 359–367.
detailed theory that uncovers the relationship between electrode 10 O. Schmidt, A. Hawkes, A. Gambhir and I. Staffell, Nat.
composition/structure evolution and corresponding changes in Energy, 2017, 2, 17110.
electrochemical characteristics, providing convincing information 11 N. Alias and A. A. Mohamad, J. Power Sources, 2015, 274,
for tuning dominant physical and chemical properties to further 237–251.
improve electrochemical performances. Considering the variety of 12 B. Li, J. Zheng, H. Zhang, L. Jin, D. Yang, H. Lv, C. Shen,
ARMBs together with the large quantity of constituent electrode A. Shellikeri, Y. Zheng, R. Gong, J. P. Zheng and C. Zhang,
materials, it is a challenging task to summarize general rules and Adv. Mater., 2018, 30, 1705670.
subsequently build a versatile theory from traditional perspec- 13 F. Beck and P. Rüetschi, Electrochim. Acta, 2000, 45,
tives. Common mechanisms are few among various ARMBs 2467–2482.
despite the similarity of guest ions intercalation/de-intercalation. 14 Z. Liu, F. Mo, H. Li, M. Zhu, Z. Wang, G. Liang and C. Zhi,
This is the reason why most of the existing explanations or Small Methods, 2018, 2, 1800124.
mechanisms were made on a case-by-case basis. Here, starting 15 Z. Wang, H. Li, Z. Tang, Z. Liu, Z. Ruan, L. Ma, Q. Yang,
from voltage characteristics may provide a different perspective D. Wang and C. Zhi, Adv. Funct. Mater., 2018, 28, 1804560.
angle to construct a theory with high generality and practicability 16 Y. Huang, Z. Li, Z. Pei, Z. Liu, H. Li, M. Zhu, J. Fan, Q. Dai,
for electrochemical improvements disregarding battery and M. Zhang, L. Dai and C. Zhi, Adv. Energy Mater., 2018,
electrode types. For example, flat discharge plateau indicates 8, 1802288.
View Article Online
17 Q. Yang, Y. Wang, X. Li, H. Li, Z. Wang, Z. Tang, L. Ma, 42 D. C. Hannah, G. Sai Gautam, P. Canepa and G. Ceder, Adv.
F. Mo and C. Zhi, Energy Environ. Mater., 2018, 1, 183–195. Energy Mater., 2018, 8, 1800379.
18 Z. Xing, S. Wang, A. Yu and Z. Chen, Nano Energy, 2018, 50, 43 W. Sun, F. Wang, S. Hou, C. Yang, X. Fan, Z. Ma, T. Gao,
229–244. F. Han, R. Hu, M. Zhu and C. Wang, J. Am. Chem. Soc.,
19 G. Fang, J. Zhou, A. Pan and S. Liang, ACS Energy Lett., 2017, 139, 9775–9778.
2018, 3, 2480–2501. 44 H. Pan, Y. Shao, P. Yan, Y. Cheng, K. S. Han, Z. Nie,
20 W. Tang, Y. Zhu, Y. Hou, L. Liu, Y. Wu, K. P. Loh, H. Zhang C. Wang, J. Yang, X. Li, P. Bhattacharya, K. T. Mueller and
and K. Zhu, Energy Environ. Sci., 2013, 6, 2093–2104. J. Liu, Nat. Energy, 2016, 1, 16039.
21 W. Li, J. R. Dahn and D. S. Wainwright, Science, 1994, 264, 45 A. J. Bard and L. R. Faulkner, Electrochemical Methods -
1115–1118. Fundamentals and Applications, John Wiley & Sons, Inc.,
22 X. L. Dong, L. Chen, X. L. Su, Y. G. Wang and Y. Y. Xia, 2nd edn, 2001.
Angew. Chem., Int. Ed., 2016, 55, 7474–7477. 46 W. Chen, F. Ambrosio, G. Miceli and A. Pasquarello,
23 J. X. Zheng, Y. Y. Hou, Y. D. Duan, X. H. Song, Y. Wei, Phys. Rev. Lett., 2016, 117, 186401.
T. C. Liu, J. T. Hu, H. Guo, Z. Q. Zhuo, L. L. Liu, Z. Chang, 47 D. R. Lide, CRC Handbook of Chemistry and Physics, CRC
X. W. Wang, D. Zherebetskyy, Y. Y. Fang, Y. Lin, K. Xu, Press, Boca Raton, FL, 99th edn, 2018.
L. W. Wang, Y. P. Wu and F. Pan, Nano Lett., 2015, 15, 48 P. Peljo and H. H. Girault, Energy Environ. Sci., 2018, 11,
6102–6109. 2306–2309.
24 W. Tang, L. L. Liu, Y. S. Zhu, H. Sun, Y. P. Wu and K. Zhu, 49 X. Zang, C. Shen, M. Sanghadasa and L. Lin, ChemElectroChem,
Energy Environ. Sci., 2012, 5, 6909–6913. 2019, 6, 976–988.
25 Q. T. Qu, L. J. Fu, X. Y. Zhan, D. Samuelis, J. Maier, L. Li, 50 T. R. Cook, D. K. Dogutan, S. Y. Reece, Y. Surendranath,
S. Tian, Z. H. Li and Y. P. Wu, Energy Environ. Sci., 2011, 4, T. S. Teets and D. G. Nocera, Chem. Rev., 2010, 110,
3985–3990. 6474–6502.
26 Y. Zhao, Y. Zhang, H. Sun, X. L. Dong, J. Y. Cao, L. Wang, 51 R. Chen, R. Luo, Y. Huang, F. Wu and L. Li, Adv. Sci., 2016,
Y. F. Xu, J. Ren, Y. N. Hwang, I. H. Son, X. L. Huang, 3, 1600051.
Y. G. Wang and H. S. Peng, Angew. Chem., Int. Ed., 2016, 55, 52 W. Pei, Y. Hui and H. Q. Yang, J. Power Sources, 1996, 63,
14382–14386. 275–278.
27 Z. X. Liu, H. F. Li, M. S. Zhu, Y. Huang, Z. J. Tang, Z. X. Pei, 53 Y. G. Wang, J. Y. Lou, W. Wu, C. X. Wang and Y. Y. Xia,
Z. F. Wang, Z. C. Shi, J. Liu, Y. Huang and C. Y. Zhi, Nano J. Electrochem. Soc., 2007, 154, A228–A234.
Energy, 2018, 44, 164–173. 54 Y. Wang, S. Z. Yang, Y. You, Z. Feng, W. Zhu, V. Gariepy,
28 R. K. Guduru and J. C. Icaza, Nanomaterials, 2016, 6, 41. J. Xia, B. Commarieu, A. Darwiche, A. Guerfi and K. Zaghib,
29 T. Liu, X. Cheng, H. Yu, H. Zhu, N. Peng, R. Zheng, ACS Appl. Mater. Interfaces, 2018, 10, 7061–7068.
J. Zhang, M. Shui, Y. Cui and J. Shu, Energy Storage Mater., 55 Y. Yokoyama, T. Fukutsuka, K. Miyazaki and T. Abe,
2019, 18, 68–91. J. Electrochem. Soc., 2018, 165, A3299–A3303.
30 Y. Li, J. Fu, C. Zhong, T. Wu, Z. Chen, W. Hu, K. Amine and 56 C. Wessells, R. Ruffo, R. A. Huggins and Y. Cui, Electro-
J. Lu, Adv. Energy Mater., 2019, 9, 1802605. chem. Solid-State Lett., 2010, 13, A59–A61.
31 M. Song, H. Tan, D. Chao and H. Fan, Adv. Funct. Mater., 57 D. Zhou, S. Liu, H. Wang and G. Yan, J. Power Sources,
2018, 28, 1802564. 2013, 227, 111–117.
32 D. Bin, F. Wang, A. Tamirat, L. Suo, Y. Wang, C. Wang and 58 L. Ma, S. Chen, H. Li, Z. Ruan, Z. Tang, Z. Liu, Z. Wang,
Y. Xia, Adv. Energy Mater., 2018, 8, 1703008. Y. Huang, Z. Pei, J. A. Zapien and C. Zhi, Energy Environ.
33 J. O. G. Posada, A. J. R. Rennie, S. P. Villar, V. L. Martins, Sci., 2018, 11, 2521–2530.
J. Marinaccio, A. Barnes, C. F. Glover, D. A. Worsley and 59 H. Tomiyasu, H. Shikata, K. Takao, N. Asanuma, S. Taruta
P. J. Hall, Renewable Sustainable Energy Rev., 2017, 68, and Y. Y. Park, Sci. Rep., 2017, 7, 45048.
1174–1182. 60 M. Zhao, B. Zhang, G. Huang, H. Zhang and X. Song,
34 A. Eftekhari, Adv. Energy Mater., 2018, 8, 1801156. J. Power Sources, 2013, 232, 181–186.
35 J. Huang, Z. Guo, Y. Ma, D. Bin, Y. Wang and Y. Xia, 61 L. M. Suo, O. Borodin, T. Gao, M. Olguin, J. Ho, X. L. Fan,
Small Methods, 2019, 3, 1800272. C. Luo, C. S. Wang and K. Xu, Science, 2015, 350, 938–943.
36 E. Roduner, Catal. Today, 2018, 309, 263–268. 62 Y. Yamada, K. Usui, K. Sodeyama, S. Ko, Y. Tateyama and
37 X. Zou and Y. Zhang, Chem. Soc. Rev., 2015, 44, 5148–5180. A. Yamada, Nat. Energy, 2016, 1, 16129.
38 Y. Wang, J. Yi and Y. Xia, Adv. Energy Mater., 2012, 2, 63 L. Suo, O. Borodin, W. Sun, X. Fan, C. Yang, F. Wang,
830–840. T. Gao, Z. Ma, M. Schroeder, A. von Cresce, S. M. Russell,
39 S. Husmann and A. J. G. Zarbin, Electrochim. Acta, 2018, M. Armand, A. Angell, K. Xu and C. Wang, Angew. Chem.,
283, 1339–1350. Int. Ed., 2016, 55, 7136–7141.
40 W. Zuo, W. Zhu, D. Zhao, Y. Sun, Y. Li, J. Liu and 64 R.-S. Kühnel, D. Reber and C. Battaglia, ACS Energy Lett.,
X. W. Lou, Energy Environ. Sci., 2016, 9, 2881–2891. 2017, 2, 2005–2006.
41 S. H. Yu, X. Feng, N. Zhang, J. Seok and H. D. Abruna, Acc. 65 D. P. Leonard, Z. Wei, G. Chen, F. Du and X. Ji, ACS Energy
Chem. Res., 2018, 51, 273–281. Lett., 2018, 3, 373–374.
View Article Online
66 F. Wang, X. Fan, T. Gao, W. Sun, Z. Ma, C. Yang, F. Han, 90 W. Chen, J. Gu, Q. Liu, R. Luo, L. Yao, B. Sun, W. Zhang,
K. Xu and C. Wang, ACS Cent. Sci., 2017, 3, 1121–1128. H. Su, B. Chen, P. Liu and D. Zhang, ACS Nano, 2018, 12,
67 P. Hu, M. Yan, T. Zhu, X. Wang, X. Wei, J. Li, L. Zhou, Z. Li, 308–316.
L. Chen and L. Mai, ACS Appl. Mater. Interfaces, 2017, 9, 91 D. Kong, H. Wang, J. J. Cha, M. Pasta, K. J. Koski, J. Yao
42717–42722. and Y. Cui, Nano Lett., 2013, 13, 1341–1347.
68 P. W. Wilson and A. D. Haymet, Phys. Chem. Chem. Phys., 92 M. Salanne, B. Rotenberg, K. Naoi, K. Kaneko, P. L.
2009, 11, 2679–2682. Taberna, C. P. Grey, B. Dunn and P. Simon, Nat. Energy,
69 M. S. Wei, B. X. Li, X. N. Zang, W. S. Chen, Y. Chu, 2016, 1, 16070.
M. Sanghadasa and L. W. Lin, 2017 19th International 93 Y. Yang, H. Fei, G. Ruan, C. Xiang and J. M. Tour, Adv.
Conference on Solid-State Sensors, Actuators and Microsys- Mater., 2014, 26, 8163–8168.
tems (Transducers), 2017, 702–705. 94 J. Suntivich, K. J. May, H. A. Gasteiger, J. B. Goodenough
70 R. Ruffo, F. La Mantia, C. Wessells, R. A. Huggins and and Y. Shao-Horn, Science, 2011, 334, 1383–1385.
Y. Cui, Solid State Ionics, 2011, 192, 289–292. 95 D. M. Robinson, Y. B. Go, M. Greenblatt and G. C. Dismukes,
71 Z. Zhu, Y. Tang, Z. Lv, J. Wei, Y. Zhang, R. Wang, W. Zhang, J. Am. Chem. Soc., 2010, 132, 11467–11469.
H. Xia, M. Ge and X. Chen, Angew. Chem., Int. Ed., 2018, 57, 96 J. Park, H. Kim, K. Jin, B. J. Lee, Y. S. Park, H. Kim, I. Park,
3656–3660. K. D. Yang, H. Y. Jeong, J. Kim, K. T. Hong, H. W. Jang,
72 Y. Gao, Z. Yan, J. L. Gray, X. He, D. Wang, T. Chen, K. Kang and K. T. Nam, J. Am. Chem. Soc., 2014, 136,
Q. Huang, Y. C. Li, H. Wang, S. H. Kim, T. E. Mallouk 4201–4211.
and D. Wang, Nat. Mater., 2019, 18, 384–389. 97 J. Liu, L. Yi, L. Liu and P. Peng, Mater. Chem. Phys., 2015,
73 A. J. Louli, L. D. Ellis and J. R. Dahn, Joule, 2019, 3, 745–761. 161, 211–218.
74 W. J. Chang, S. H. Kim, J. Hwang, J. Chang, D. W. Yang, 98 G. J. Wang, N. H. Zhao, L. C. Yang, Y. P. Wu, H. Q. Wu and
S. S. Kwon, J. T. Kim, W. W. Lee, J. H. Lee, H. Park, T. Song, R. Holze, Electrochim. Acta, 2007, 52, 4911–4915.
I. H. Lee, D. Whang and W. Il Park, Nat. Commun., 2018, 99 R. S. Kühnel, D. Reber, A. Remhof, R. Figi, D. Bleiner and
9, 3461. C. Battaglia, Chem. Commun., 2016, 52, 10435–10438.
75 C. Cao, I. I. Abate, E. Sivonxay, B. Shyam, C. Jia, B. Moritz, 100 W. Li, W. R. Mckinnon and J. R. Dahn, J. Electrochem. Soc.,
T. P. Devereaux, K. A. Persson, H.-G. Steinrück and 1994, 141, 2310–2316.
M. F. Toney, Joule, 2019, 3, 762–781. 101 J.-Y. Luo and Y.-Y. Xia, Adv. Funct. Mater., 2007, 17,
76 I. B. Stojković, N. D. Cvjetićanin and S. V. Mentus, Electro- 3877–3884.
chem. Commun., 2010, 12, 371–373. 102 A. Eftekhari, Electrochim. Acta, 2001, 47, 495–499.
77 K. Miyazaki, T. Shimada, S. Ito, Y. Yokoyama, T. Fukutsuka 103 J.-W. Lee and S.-I. Pyun, Electrochim. Acta, 2004, 49,
and T. Abe, Chem. Commun., 2016, 52, 4979–4982. 753–761.
78 Z. Hou, X. Zhang, X. Li, Y. Zhu, J. Liang and Y. Qian, 104 R. L. Deutscher, T. M. Florence and R. Woods, J. Power
J. Mater. Chem. A, 2017, 5, 730–738. Sources, 1995, 55, 41–46.
79 J. Y. Luo, W. J. Cui, P. He and Y. Y. Xia, Nat. Chem., 2010, 2, 105 A. Yuan and Q. Zhang, Electrochem. Commun., 2006, 8,
760–765. 1173–1178.
80 Z. Guo, Y. Zhao, Y. Ding, X. Dong, L. Chen, J. Cao, C. Wang, 106 V. S. Nair, Y. L. Cheah and S. Madhavi, J. Electrochem. Soc.,
Y. Xia, H. Peng and Y. Wang, Chem, 2017, 3, 348–362. 2014, 161, A256–A263.
81 X. Zhang, Z. Hou, X. Li, J. Liang, Y. Zhu and Y. Qian, 107 H. Wang, K. Huang, Y. Zeng, F. Zhao and L. Chen, Electro-
J. Mater. Chem. A, 2016, 4, 856–860. chem. Solid-State Lett., 2007, 10, A199–A203.
82 K. Nakamoto, Y. Kano, A. Kitajou and S. Okada, J. Power 108 M. Manickam, P. Singh, S. Thurgate and K. Prince, J. Power
Sources, 2016, 327, 327–332. Sources, 2006, 158, 646–649.
83 L. Chen, W. Li, Z. Guo, Y. Wang, C. Wang, Y. Che and 109 F. Sauvage, L. Laffont, J. M. Tarascon and E. Baudrin,
Y. Xia, J. Electrochem. Soc., 2015, 162, A1972–A1977. J. Power Sources, 2008, 175, 495–501.
84 F. Yu, S. Zhang, C. Fang, Y. Liu, S. He, J. Xia, J. Yang and 110 H. Manjunatha, T. V. Venkatesha and G. S. Suresh, Electro-
N. Zhang, Ceram. Int., 2017, 43, 9960–9967. chim. Acta, 2011, 58, 247–257.
85 M. G. Walter, E. L. Warren, J. R. McKone, S. W. Boettcher, 111 M. Minakshi, Electrochim. Acta, 2010, 55, 9174–9178.
Q. X. Mi, E. A. Santori and N. S. Lewis, Chem. Rev., 2010, 112 M. Minakshi, P. Singh, N. Sharma, M. Blackford and
110, 6446–6473. M. Ionescu, Ind. Eng. Chem. Res., 2011, 50, 1899–1905.
86 J. K. Norskov, T. Bligaard, J. Rossmeisl and C. H. Christensen, 113 M. Minakshi, P. Singh, D. Appadoo and D. E. Martin,
Nat. Chem., 2009, 1, 37–46. Electrochim. Acta, 2011, 56, 4356–4360.
87 N. Batisse and E. Raymundo-Piñero, J. Power Sources, 2017, 114 C. D. Wessells, S. V. Peddada, M. T. McDowell, R. A. Huggins
348, 168–174. and Y. Cui, J. Electrochem. Soc., 2011, 159, A98–A103.
88 T. Stephenson, Z. Li, B. Olsen and D. Mitlin, Energy 115 G. J. Wang, H. P. Zhang, L. J. Fu, B. Wang and Y. P. Wu,
Environ. Sci., 2014, 7, 209–231. Electrochem. Commun., 2007, 9, 1873–1876.
89 X. Chia, A. Y. Eng, A. Ambrosi, S. M. Tan and M. Pumera, 116 W. Tang, Y. Hou, F. Wang, L. Liu, Y. Wu and K. Zhu, Nano
Chem. Rev., 2015, 115, 11941–11966. Lett., 2013, 13, 2036–2040.
View Article Online
117 A. Yuan, L. Tian, W. Xu and Y. Wang, J. Power Sources, 142 K. Itaya, T. Ataka and S. Toshima, J. Am. Chem. Soc., 1982,
2010, 195, 5032–5038. 104, 4767–4772.
118 W. Xu, A. Yuan, L. Tian and Y. Wang, J. Appl. Electrochem., 143 P. C. F. Pau, J. O. Berg and W. G. McMillan, J. Phys. Chem.,
2011, 41, 453–460. 1990, 94, 2671–2679.
119 Q. Qu, L. Fu, X. Zhan, D. Samuelis, J. Maier, L. Li, S. Tian, 144 W. Li, J. R. Dahn and D. S. Wainwright, Science, 1994, 264,
Z. Li and Y. Wu, Energy Environ. Sci., 2011, 4, 3985–3990. 1115–1118.
120 W. Tang, Y. Hou, F. Wang, L. Liu, Y. Wu and K. Zhu, Nano 145 W. Li, W. R. McKinnon and J. R. Dahn, J. Electrochem. Soc.,
Lett., 2013, 13, 2036–2040. 1994, 141, 2310–2316.
121 R. Ruffo, C. Wessells, R. A. Huggins and Y. Cui, Electrochem. 146 S. Zhang, Y. Li, C. Wu, F. Zheng and Y. Xie, J. Phys. Chem.
Commun., 2009, 11, 247–249. C, 2009, 113, 15058–15067.
122 G. J. Wang, Q. T. Qu, B. Wang, Y. Shi, S. Tian, Y. P. Wu and 147 J. Ni, W. Jiang, K. Yu, Y. Gao and Z. Zhu, Electrochim. Acta,
R. Holze, Electrochim. Acta, 2009, 54, 1199–1203. 2011, 56, 2122–2126.
123 Y.-g. Wang, J.-y. Luo, C.-x. Wang and Y.-y. Xia, 148 G. Wang, L. Fu, N. Zhao, L. Yang, Y. Wu and H. Wu, Angew.
J. Electrochem. Soc., 2006, 153, A1425–A1431. Chem., 2007, 119, 299–301.
124 Y.-g. Wang, J.-y. Lou, W. Wu, C.-x. Wang and Y.-y. Xia, 149 H. Heli, H. Yadegari and A. Jabbari, J. Phys. Chem. C, 2011,
J. Electrochem. Soc., 2007, 154, A228–A234. 115, 10889–10897.
125 R. B. Shivashankaraiah, H. Manjunatha, K. C. Mahesh, 150 H. Li, T. Zhai, P. He, Y. Wang, E. Hosono and H. Zhou,
G. S. Suresh and T. V. Venkatesha, J. Solid State Electro- J. Mater. Chem., 2011, 21, 1780–1787.
chem., 2012, 16, 1279–1290. 151 W. Tang, X. Gao, Y. Zhu, Y. Yue, Y. Shi, Y. Wu and K. Zhu,
126 M. Mohan Rao, M. Jayalakshmi, O. Schäf, H. Wulff, J. Mater. Chem., 2012, 22, 20143–20145.
U. Guth and F. Scholz, J. Solid State Electrochem., 2001, 5, 152 K. H. Reiman, K. M. Brace, T. J. Gordon-Smith,
50–56. I. Nandhakumar, G. S. Attard and J. R. Owen, Electrochem.
127 M. Mohan Rao, M. Jayalakshmi, O. Schäf, U. Guth, Commun., 2006, 8, 517–522.
H. Wulff and F. Scholz, J. Solid State Electrochem., 1999, 153 J.-Y. Luo, J.-L. Liu, P. He and Y.-Y. Xia, Electrochim. Acta,
4, 17–23. 2008, 53, 8128–8133.
128 W. Tang, L. L. Liu, S. Tian, L. Li, Y. B. Yue, Y. P. Wu, 154 C. Wessells, F. La Mantia, H. Deshazer, R. A. Huggins and
S. Y. Guan and K. Zhu, Electrochem. Commun., 2010, 12, Y. Cui, J. Electrochem. Soc., 2011, 158, A352–A355.
1524–1526. 155 C. Wessells, R. A. Huggins and Y. Cui, J. Power Sources,
129 L. Liu, F. Tian, X. Wang, Z. Yang, Q. Chen and X. Wang, 2011, 196, 2884–2888.
J. Solid State Electrochem., 2012, 16, 491–497. 156 G. Wang, Q. Qu, B. Wang, Y. Shi, S. Tian and Y. Wu,
130 F. Wang, S. Xiao, Z. Chang, Y. Yang and Y. Wu, Chem. ChemPhysChem, 2008, 9, 2299–2301.
Commun., 2013, 49, 9209–9211. 157 H. Qin, Z. P. Song, H. Zhan and Y. H. Zhou, J. Power
131 A. Tron, Y. N. Jo, S. H. Oh, Y. D. Park and J. Mun, ACS Appl. Sources, 2014, 249, 367–372.
Mater. Interfaces, 2017, 9, 12391–12399. 158 A. Caballero, J. Morales and O. A. Vargas, J. Power Sources,
132 P. He, J.-L. Liu, W.-J. Cui, J.-Y. Luo and Y.-Y. Xia, Electro- 2010, 195, 4318–4321.
chim. Acta, 2011, 56, 2351–2357. 159 K. Sun, D. A. Juarez, H. Huang, E. Jung and S. J. Dillon,
133 X.-H. Liu, T. Saito, T. Doi, S. Okada and J.-i. Yamaki, J. Power Sources, 2014, 248, 582–587.
J. Power Sources, 2009, 189, 706–710. 160 H. Wang, Y. Zeng, K. Huang, S. Liu and L. Chen, Electro-
134 M. Zhao, G. Huang, W. Zhang, H. Zhang and X. Song, chim. Acta, 2007, 52, 5102–5107.
Energy Fuels, 2013, 27, 1162–1167. 161 M. Manickam, P. Singh, T. B. Issa and S. Thurgate, J. Appl.
135 M. Minakshi, N. Sharma, D. Ralph, D. Appadoo and Electrochem., 2006, 36, 599–602.
K. Nallathamby, Electrochem. Solid-State Lett., 2011, 14, 162 W. Li and J. R. Dahn, J. Electrochem. Soc., 1995, 142, 1742–1746.
A86–A89. 163 J.-Y. Luo, W.-J. Cui, P. He and Y.-Y. Xia, Nat. Chem., 2010, 2, 760.
136 R. Y. Wang, C. D. Wessells, R. A. Huggins and Y. Cui, Nano 164 D. W. Murphy, P. A. Christian, F. J. DiSalvo, J. N. Carides and
Lett., 2013, 13, 5748–5752. J. V. Waszczak, J. Electrochem. Soc., 1981, 128, 2053–2060.
137 C. D. Wessells, S. V. Peddada, R. A. Huggins and Y. Cui, 165 M. Zhang and J. R. Dahn, J. Electrochem. Soc., 1996, 143,
Nano Lett., 2011, 11, 5421–5425. 2730–2735.
138 M. Pasta, C. D. Wessells, R. A. Huggins and Y. Cui, 166 M. Shao, J. Deng, F. Zhong, Y. Cao, X. Ai, J. Qian and
Nat. Commun., 2012, 3, 1149. H. Yang, Energy Storage Mater., 2019, 18, 92–99.
139 M. Pasta, C. D. Wessells, N. Liu, J. Nelson, M. T. McDowell, 167 J. Köhler, H. Makihara, H. Uegaito, H. Inoue and M. Toki,
R. A. Huggins, M. F. Toney and Y. Cui, Nat. Commun., 2014, Electrochim. Acta, 2000, 46, 59–65.
5, 3007. 168 C. Cheng, Z. H. Li, X. Y. Zhan, Q. Z. Xiao, G. T. Lei and
140 Z. Wu, J. Xie, Z. J. Xu, S. Zhang and Q. Zhang, J. Mater. X. D. Zhou, Electrochim. Acta, 2010, 55, 4627–4631.
Chem. A, 2019, 7, 4259–4290. 169 Z. Liu, H. Li, M. Zhu, Y. Huang, Z. Tang, Z. Pei, Z. Wang,
141 H. Kim, J. Hong, K.-Y. Park, H. Kim, S.-W. Kim and Z. Shi, J. Liu, Y. Huang and C. Zhi, Nano Energy, 2018, 44,
K. Kang, Chem. Rev., 2014, 114, 11788–11827. 164–173.
View Article Online
170 H. Wang, K. Huang, Y. Zeng, S. Yang and L. Chen, Electro- 199 C. Deng, S. Zhang, Z. Dong and Y. Shang, Nano Energy,
chim. Acta, 2007, 52, 3280–3285. 2014, 4, 49–55.
171 G. J. Wang, L. C. Yang, Q. T. Qu, B. Wang, Y. P. Wu and 200 Q. Yang, S. Cui, Y. Ge, Z. Tang, Z. Liu, H. Li, N. Li,
R. Holze, J. Solid State Electrochem., 2010, 14, 865–869. H. Zhang, J. Liang and C. Zhi, Nano Energy, 2018, 50,
172 J. Xie and Q. Zhang, J. Mater. Chem. A, 2016, 4, 7091–7106. 623–631.
173 S. Wang, C. Sun, N. Wang and Q. Zhang, J. Mater. Chem. A, 201 S. I. Park, I. Gocheva, S. Okada and J.-i. Yamaki,
2019, 7, 10138–10158. J. Electrochem. Soc., 2011, 158, A1067–A1070.
174 L. Athouël, F. Moser, R. Dugas, O. Crosnier, D. Bélanger 202 W. Wu, J. Yan, A. Wise, A. Rutt and J. F. Whitacre,
and T. Brousse, J. Phys. Chem. C, 2008, 112, 7270–7277. J. Electrochem. Soc., 2014, 161, A561–A567.
175 J. F. Whitacre, T. Wiley, S. Shanbhag, Y. Wenzhuo, 203 B. Zhao, B. Lin, S. Zhang and C. Deng, Nanoscale, 2015, 7,
A. Mohamed, S. E. Chun, E. Weber, D. Blackwood, 18552–18560.
E. Lynch-Bell, J. Gulakowski, C. Smith and D. Humphreys, 204 W. Deng, Y. Shen, J. Qian and H. Yang, Chem. Commun.,
J. Power Sources, 2012, 213, 255–264. 2015, 51, 5097–5099.
176 M. Minakshi, Mater. Sci. Eng., B, 2012, 177, 1788–1792. 205 Y. Liang, Y. Jing, S. Gheytani, K.-Y. Lee, P. Liu, A. Facchetti
177 Q. T. Qu, L. L. Liu, Y. P. Wu and R. Holze, Electrochim. Acta, and Y. Yao, Nat. Mater., 2017, 16, 841.
2013, 96, 8–12. 206 Y. Li and H. Dai, Chem. Soc. Rev., 2014, 43, 5257–5275.
178 F. Sauvage, E. Baudrin and J. M. Tarascon, Sens. Actuators, 207 H. Zhang, K. Ye, X. Huang, X. Wang, K. Cheng, X. Xiao,
B, 2007, 120, 638–644. G. Wang and D. Cao, J. Power Sources, 2017, 338, 136–144.
179 Y. Wang, L. Mu, J. Liu, Z. Yang, X. Yu, L. Gu, Y.-S. Hu, H. Li, 208 J. F. Parker, C. N. Chervin, I. R. Pala, M. Machler, M. F. Burz,
X.-Q. Yang, L. Chen and X. Huang, Adv. Energy Mater., J. W. Long and D. R. Rolison, Science, 2017, 356, 415–418.
2015, 5, 1501005. 209 G. Li, Z. Yang, Y. Jiang, C. Jin, W. Huang, X. Ding and
180 Y. Liu, Y. Qiao, W. Zhang, H. Xu, Z. Li, Y. Shen, L. Yuan, Y. Huang, Nano Energy, 2016, 25, 211–217.
X. Hu, X. Dai and Y. Huang, Nano Energy, 2014, 5, 97–104. 210 A. Konarov, N. Voronina, J. H. Jo, Z. Bakenov, Y.-K. Sun and
181 Y. Liu, Y. Qiao, X. Lou, X. Zhang, W. Zhang and Y. Huang, S.-T. Myung, ACS Energy Lett., 2018, 3, 2620–2640.
ACS Appl. Mater. Interfaces, 2016, 8, 14564–14571. 211 M. H. Alfaruqi, S. Islam, D. Y. Putro, V. Mathew, S. Kim,
182 W. Song, X. Ji, Y. Zhu, H. Zhu, F. Li, J. Chen, F. Lu, Y. Yao J. Jo, S. Kim, Y.-K. Sun, K. Kim and J. Kim, Electrochim.
and C. E. Banks, ChemElectroChem, 2014, 1, 871–876. Acta, 2018, 276, 1–11.
183 J. Qian, C. Wu, Y. Cao, Z. Ma, Y. Huang, X. Ai and H. Yang, 212 M. Chamoun, W. R. Brant, C.-W. Tai, G. Karlsson and
Adv. Energy Mater., 2018, 8, 1702619. D. Noréus, Energy Storage Mater., 2018, 15, 351–360.
184 V. D. Neff, J. Electrochem. Soc., 1978, 125, 886–887. 213 Z. Liu, D. Wang, Z. Tang, G. Liang, Q. Yang, H. Li, L. Ma,
185 C. D. Wessells, R. A. Huggins and Y. Cui, Nat. Commun., F. Mo and C. Zhi, Energy Storage Mater., 2019, 23, 636–645.
2011, 2, 550. 214 G. Wu, Y. Xue, L. Wang, X. Wang and G. Chen, J. Mater.
186 C. D. Wessells, M. T. McDowell, S. V. Peddada, M. Pasta, Chem. A, 2018, 6, 3376–3380.
R. A. Huggins and Y. Cui, ACS Nano, 2012, 6, 1688–1694. 215 M. Zhu, Z. Wang, H. Li, Y. Xiong, Z. Liu, Z. Tang, Y. Huang,
187 W. Ren, X. Chen and C. Zhao, Adv. Energy Mater., 2018, A. L. Rogach and C. Zhi, Energy Environ. Sci., 2018, 11,
8, 1801413. 2414–2422.
188 X. Wu, Y. Luo, M. Sun, J. Qian, Y. Cao, X. Ai and H. Yang, 216 I. Stosevski, A. Bonakdarpour, F. Cuadra and D. P. Wilkinson,
Nano Energy, 2015, 13, 117–123. Chem. Commun., 2019, 55, 2082–2085.
189 X. Wu, M. Sun, S. Guo, J. Qian, Y. Liu, Y. Cao, X. Ai and 217 B. Jiang, C. Xu, C. Wu, L. Dong, J. Li and F. Kang,
H. Yang, ChemNanoMat, 2015, 1, 188–193. Electrochim. Acta, 2017, 229, 422–428.
190 K. Nakamoto, R. Sakamoto, M. Ito, A. Kitajou and 218 C. Zhu, G. Fang, J. Zhou, J. Guo, Z. Wang, C. Wang, J. Li,
S. Okada, Electrochemistry, 2017, 85, 179–185. Y. Tang and S. Liang, J. Mater. Chem. A, 2018, 6, 9677–9683.
191 J.-H. Lee, G. Ali, D. H. Kim and K. Y. Chung, Adv. Energy 219 N. Zhang, F. Cheng, Y. Liu, Q. Zhao, K. Lei, C. Chen, X. Liu
Mater., 2017, 7, 1601491. and J. Chen, J. Am. Chem. Soc., 2016, 138, 12894–12901.
192 J. Xie, P. Gu and Q. Zhang, ACS Energy Lett., 2017, 2, 1985–1996. 220 M. Song, H. Tan, D. Chao and H. J. Fan, Adv. Funct. Mater.,
193 J. Xie, C. E. Zhao, Z. Q. Lin, P. Y. Gu and Q. Zhang, Chem. – 2018, 28, 1802564.
Asian J., 2016, 11, 1489–1511. 221 C. Wei, C. Xu, B. Li, H. Du and F. Kang, J. Phys. Chem.
194 Y. Xu, M. Zhou and Y. Lei, Mater. Today, 2018, 21, 60–78. Solids, 2012, 73, 1487–1491.
195 K. Koshika, N. Sano, K. Oyaizu and H. Nishide, Chem. 222 S. Islam, M. H. Alfaruqi, V. Mathew, J. Song, S. Kim, S. Kim,
Commun., 2009, 836–838, DOI: 10.1039/B818087C. J. Jo, J. P. Baboo, D. T. Pham, D. Y. Putro, Y.-K. Sun and
196 H. Long, W. Zeng, H. Wang, M. Qian, Y. Liang and J. Kim, J. Mater. Chem. A, 2017, 5, 23299–23309.
Z. Wang, Adv. Sci., 2018, 5, 1700634. 223 M. H. Alfaruqi, V. Mathew, J. Gim, S. Kim, J. Song, J. P. Baboo,
197 Y. Wei, Q. Hu, Y. Cao, D. Fang, W. Xu, M. Jiang, J. Huang, S. H. Choi and J. Kim, Chem. Mater., 2015, 27, 3609–3620.
H. Liu and X. Fan, Org. Electron., 2017, 46, 211–217. 224 M. H. Alfaruqi, J. Gim, S. Kim, J. Song, D. T. Pham, J. Jo,
198 Y. Liu, B. H. Zhang, S. Y. Xiao, L. L. Liu, Z. B. Wen and Z. Xiu, V. Mathew and J. Kim, Electrochem. Commun., 2015,
Y. P. Wu, Electrochim. Acta, 2014, 116, 512–517. 60, 121–125.
View Article Online
225 S. Luo, L. Xie, F. Han, W. Wei, Y. Huang, H. Zhang, M. Zhu, 249 J. Xie and Q. Zhang, Small, 2019, 15, 1805061.
O. G. Schmidt and L. Wang, Adv. Funct. Mater., 2019, 250 D. Kundu, P. Oberholzer, C. Glaros, A. Bouzid, E. Tervoort,
29, 1901336. A. Pasquarello and M. Niederberger, Chem. Mater., 2018,
226 D. Xu, B. Li, C. Wei, Y.-B. He, H. Du, X. Chu, X. Qin, 30, 3874–3881.
Q.-H. Yang and F. Kang, Electrochim. Acta, 2014, 133, 251 Q. Zhao, W. Huang, Z. Luo, L. Liu, Y. Lu, Y. Li, L. Li, J. Hu,
254–261. H. Ma and J. Chen, Sci. Adv., 2018, 4, eaao1761.
227 L. Chen, Z. Yang, H. Qin, X. Zeng and J. Meng, J. Power 252 Z. Guo, Y. Ma, X. Dong, J. Huang, Y. Wang and Y. Xia,
Sources, 2019, 425, 162–169. Angew. Chem., Int. Ed., 2018, 57, 11737–11741.
228 B. Li, J. Chai, X. Ge, T. An, P.-C. Lim, Z. Liu and Y. Zong, 253 C. Kim, B. Y. Ahn, T.-S. Wei, Y. Jo, S. Jeong, Y. Choi, I.-D.
ChemNanoMat, 2017, 3, 401–405. Kim and J. A. Lewis, ACS Nano, 2018, 12, 11838–11846.
229 B. Wu, G. Zhang, M. Yan, T. Xiong, P. He, L. He, X. Xu and 254 L. Jiang, Y. Lu, C. Zhao, L. Liu, J. Zhang, Q. Zhang, X. Shen,
L. Mai, Small, 2018, 14, 1703850. J. Zhao, X. Yu, H. Li, X. Huang, L. Chen and Y.-S. Hu,
230 C. Pan, R. Zhang, R. G. Nuzzo and A. A. Gewirth, Adv. Nat. Energy, 2019, 4, 495–503.
Energy Mater., 2018, 8, 1800589. 255 Y. Ma, X. Xie, R. Lv, B. Na, J. Ouyang and H. Liu,
231 C. Yuan, Y. Zhang, Y. Pan, X. Liu, G. Wang and D. Cao, ACS Sustainable Chem. Eng., 2018, 6, 8697–8703.
Electrochim. Acta, 2014, 116, 404–412. 256 H. Y. Shi, Y. J. Ye, K. Liu, Y. Song and X. Sun, Angew. Chem.,
232 Z. Yang, X. Wang and Y. Huang, Curr. Appl. Phys., 2015, 15, Int. Ed., 2018, 57, 16359–16363.
1556–1561. 257 X. Li, X. Xie, R. Lv, B. Na, B. Wang and Y. He, Energy
233 T. Xiong, Z. G. Yu, H. Wu, Y. Du, Q. Xie, J. Chen, Technol., 2019, 7, 1801092.
Y.-W. Zhang, S. J. Pennycook, W. S. V. Lee and J. Xue, 258 L. Zhang, L. Chen, X. Zhou and Z. Liu, Adv. Energy Mater.,
Adv. Energy Mater., 2019, 9, 1803815. 2015, 5, 1400930.
234 J. Huang, Z. Wang, M. Hou, X. Dong, Y. Liu, Y. Wang and 259 R. Trócoli and F. La Mantia, ChemSusChem, 2015, 8,
Y. Xia, Nat. Commun., 2018, 9, 2906. 481–485.
235 K. W. Nam, H. Kim, J. H. Choi and J. W. Choi, Energy 260 G. Kasiri, J. Glenneberg, A. Bani Hashemi, R. Kun and F. La
Environ. Sci., 2019, 12, 1999–2009. Mantia, Energy Storage Mater., 2019, 19, 360–369.
236 N. Zhang, Y. Dong, M. Jia, X. Bian, Y. Wang, M. Qiu, J. Xu, 261 Q. Yang, F. Mo, Z. Liu, L. Ma, X. Li, D. Fang, S. Chen,
Y. Liu, L. Jiao and F. Cheng, ACS Energy Lett., 2018, 3, S. Zhang and C. Zhi, Adv. Mater., 2019, 31, 1901521.
1366–1372. 262 X. Zhan, Z. Chen and Q. Zhang, J. Mater. Chem. A, 2017, 5,
237 J. Meng, Z. Liu, C. Niu, X. Xu, X. Liu, G. Zhang, X. Wang, 14463–14479.
M. Huang, Y. Yu and L. Mai, J. Mater. Chem. A, 2016, 4, 263 D. Chao, C. R. Zhu, M. Song, P. Liang, X. Zhang, N. H. Tiep,
4893–4899. H. Zhao, J. Wang, R. Wang, H. Zhang and H. J. Fan,
238 M. Yan, P. He, Y. Chen, S. Wang, Q. Wei, K. Zhao, X. Xu, Adv. Mater., 2018, 30, 1803181.
Q. An, Y. Shuang, Y. Shao, K. T. Mueller, L. Mai, J. Liu and 264 H. Li, Q. Yang, F. Mo, G. Liang, Z. Liu, Z. Tang, L. Ma,
J. Yang, Adv. Mater., 2018, 30, 1703725. J. Liu, Z. Shi and C. Zhi, Energy Storage Mater., 2019, 19,
239 F. Ming, H. Liang, Y. Lei, S. Kandambeth, M. Eddaoudi 94–101.
and H. N. Alshareef, ACS Energy Lett., 2018, 3, 2602–2609. 265 H. Zhang, X. Zhang, H. Li, Y. Zhang, Y. Zeng, Y. Tong,
240 F. Wan, L. Zhang, X. Dai, X. Wang, Z. Niu and J. Chen, Nat. P. Zhang and X. Lu, Green Energy Environ., 2018, 3, 56–62.
Commun., 2018, 9, 1656. 266 Y. Zeng, Z. Lai, Y. Han, H. Zhang, S. Xie and X. Lu,
241 M. Jiang, J. Zhu, C. Chen, Y. Lu, E. S. Pampal, L. Luo, P. Zhu Adv. Mater., 2018, 30, 1802396.
and X. Zhang, J. Mater. Chem. A, 2016, 4, 16588–16596. 267 F. R. Mclarnon and E. J. Cairns, J. Electrochem. Soc., 1991,
242 G. He, C. A. Bridges and A. Manthiram, Chem. Mater., 2015, 138, 645–664.
27, 6699–6707. 268 R. Y. Wang, D. W. Kirk and G. X. Zhang, J. Electrochem.
243 J.-H. Kim, A. Huq, M. Chi, N. P. W. Pieczonka, E. Lee, Soc., 2006, 153, C357–C364.
C. A. Bridges, M. M. Tessema, A. Manthiram, K. A. Persson 269 J. Q. Kan, H. G. Xue and S. L. Mu, J. Power Sources, 1998, 74,
and B. R. Powell, Chem. Mater., 2014, 26, 4377–4386. 113–116.
244 C. Xia, J. Guo, Y. Lei, H. Liang, C. Zhao and H. N. Alshareef, 270 Z. Liu, T. Cui, G. Pulletikurthi, A. Lahiri, T. Carstens,
Adv. Mater., 2018, 30, 1705580. M. Olschewski and F. Endres, Angew. Chem., Int. Ed., 2016,
245 B. Sambandam, V. Soundharrajan, S. Kim, M. H. Alfaruqi, 55, 2889–2893.
J. Jo, S. Kim, V. Mathew, Y.-k. Sun and J. Kim, J. Mater. 271 A. Mitha, A. Z. Yazdi, M. Ahmed and P. Chen, ChemElec-
Chem. A, 2018, 6, 3850–3856. troChem, 2018, 5, 2409–2418.
246 W. Li, K. Wang, S. Cheng and K. Jiang, Energy Storage 272 X. Liu, O. Bolton and R. Akolkar, J. Electrochem. Soc., 2019,
Mater., 2018, 15, 14–21. 166, D583–D588.
247 F. Wan, Y. Zhang, L. Zhang, D. Liu, C. Wang, L. Song, Z. Niu 273 J. F. Parker, C. N. Chervin, E. S. Nelson, D. R. Rolison and
and J. Chen, Angew. Chem., Int. Ed., 2019, 58, 7062–7067. J. W. Long, Energy Environ. Sci., 2014, 7, 1117–1124.
248 P. He, M. Yan, G. Zhang, R. Sun, L. Chen, Q. An and L. Mai, 274 S. Higashi, S. W. Lee, J. S. Lee, K. Takechi and Y. Cui,
Adv. Energy Mater., 2017, 7, 1601920. Nat. Commun., 2016, 7, 11801.
View Article Online
275 W. Li, K. Wang, M. Zhou, H. Zhan, S. Cheng and K. Jiang, 299 Y. Mizuno, M. Okubo, E. Hosono, T. Kudo, H. Zhou and
ACS Appl. Mater. Interfaces, 2018, 10, 22059–22066. K. Oh-ishi, J. Phys. Chem. C, 2013, 117, 10877–10882.
276 A. Xia, X. Pu, Y. Tao, H. Liu and Y. Wang, Appl. Surf. Sci., 300 K. W. Nam, S. Kim, S. Lee, M. Salama, I. Shterenberg,
2019, 481, 852–859. Y. Gofer, J.-S. Kim, E. Yang, C. S. Park, J.-S. Kim, S.-S. Lee,
277 M. Liu, L. Yang, H. Liu, A. Amine, Q. Zhao, Y. Song, J. Yang, W.-S. Chang, S.-G. Doo, Y. N. Jo, Y. Jung, D. Aurbach and
K. Wang and F. Pan, ACS Appl. Mater. Interfaces, 2019, 11, J. W. Choi, Nano Lett., 2015, 15, 4071–4079.
32046–32051. 301 Y. Mizuno, M. Okubo, E. Hosono, T. Kudo, K. Oh-ishi,
278 Y. Tian, Y. An, C. Wei, B. Xi, S. Xiong, J. Feng and Y. Qian, A. Okazawa, N. Kojima, R. Kurono, S.-i. Nishimura and
ACS Nano, 2019, 13, 11676–11685. A. Yamada, J. Mater. Chem. A, 2013, 1, 13055–13059.
279 Y. Zeng, X. Zhang, R. Qin, X. Liu, P. Fang, D. Zheng, 302 M. Cabello, R. Alcántara, F. Nacimiento, G. Ortiz, P. Lavela
Y. Tong and X. Lu, Adv. Mater., 2019, 31, 1903675. and J. L. Tirado, CrystEngComm, 2015, 17, 8728–8735.
280 Z. Wang, J. Huang, Z. Guo, X. Dong, Y. Liu, Y. Wang and 303 G. Liu, Q. Chi, Y. Zhang, Q. Chen, C. Zhang, K. Zhu and
Y. Xia, Joule, 2019, 3, 1289–1300. D. Cao, Chem. Commun., 2018, 54, 9474–9477.
281 S. Akbar, I. I. Naqvi, M. Muhammad and E. Zahir, Asian 304 C. K. King’ondu, N. Opembe, C.-h. Chen, K. Ngala,
J. Chem., 2009, 21, 4190–4198. H. Huang, A. Iyer, H. F. Garcés and S. L. Suib, Adv. Funct.
282 Q. Yang, G. Liang, Y. Guo, Z. Liu, B. Yan, D. Wang, Mater., 2011, 21, 312–323.
Z. Huang, X. Li, J. Fan and C. Zhi, Adv. Mater., 2019, 305 D. Liu, B. B. Garcia, Q. Zhang, Q. Guo, Y. Zhang, S. Sepehri
31, 1903778. and G. Cao, Adv. Funct. Mater., 2009, 19, 1015–1023.
283 R. E. Doe, R. Han, J. Hwang, A. J. Gmitter, I. Shterenberg, 306 V. V. Krishnan and S. L. Suib, J. Catal., 1999, 184, 305–315.
H. D. Yoo, N. Pour and D. Aurbach, Chem. Commun., 2014, 307 S. L. Suib, Acc. Chem. Res., 2008, 41, 479–487.
50, 243–245. 308 H. Zhang, K. Ye, R. Cang, K. Zhu, J. Yan, K. Cheng,
284 H. D. Yoo, I. Shterenberg, Y. Gofer, G. Gershinsky, N. Pour G. Wang and D. Cao, J. Electroanal. Chem., 2017, 807,
and D. Aurbach, Energy Environ. Sci., 2013, 6, 2265–2279. 37–44.
285 J. Muldoon, C. B. Bucur, A. G. Oliver, T. Sugimoto, 309 H. Zhang, K. Ye, K. Zhu, R. Cang, X. Wang, G. Wang and
M. Matsui, H. S. Kim, G. D. Allred, J. Zajicek and D. Cao, ACS Sustainable Chem. Eng., 2017, 5, 6727–6735.
Y. Kotani, Energy Environ. Sci., 2012, 5, 5941–5950. 310 X. Cao, L. Wang, J. Chen and J. Zheng, ChemElectroChem,
286 N. Wu, Z. Z. Yang, H. R. Yao, Y. X. Yin, L. Gu and Y. G. Guo, 2018, 5, 2789–2794.
Angew. Chem., Int. Ed., 2015, 54, 5757–5761. 311 Z. Jia, J. Hao, L. Liu, Y. Wang and T. Qi, Ionics, 2018, 24,
287 G. G. Amatucci, F. Badway, A. Singhal, B. Beaudoin, 3483–3491.
G. Skandan, T. Bowmer, I. Plitza, N. Pereira, T. Chapman 312 P. G. Bruce, S. A. Freunberger, L. J. Hardwick and
and R. Jaworski, J. Electrochem. Soc., 2001, 148, A940–A950. J.-M. Tarascon, Nat. Mater., 2012, 11, 19.
288 E. Levi, M. D. Levi, O. Chasid and D. Aurbach, J. Electroceram., 313 L. Li, X. Zhao, Y. Fu and A. Manthiram, Phys. Chem. Chem.
2009, 22, 13–19. Phys., 2012, 14, 12737–12740.
289 D. Aurbach, I. Weissman, Y. Gofer and E. Levi, Chem. Rec., 314 X. Wang, Y. Hou, Y. Zhu, Y. Wu and R. Holze, Sci. Rep.,
2003, 3, 61–73. 2013, 3, 1401.
290 E. Levi, Y. Gofer and D. Aurbach, Chem. Mater., 2010, 22, 315 K. A. See, K. W. Chapman, L. Zhu, K. M. Wiaderek,
860–868. O. J. Borkiewicz, C. J. Barile, P. J. Chupas and A. A. Gewirth,
291 S. K. Das, S. Mahapatra and H. Lahan, J. Mater. Chem. A, J. Am. Chem. Soc., 2015, 138, 328–337.
2017, 5, 6347–6367. 316 X. Sun, V. Duffort, B. L. Mehdi, N. D. Browning and
292 H. Tian, T. Gao, X. Li, X. Wang, C. Luo, X. Fan, C. Yang, L. F. Nazar, Chem. Mater., 2016, 28, 534–542.
L. Suo, Z. Ma, W. Han and C. Wang, Nat. Commun., 2017, 317 P. Shan, Y. Gu, L. Yang, T. Liu, J. Zheng and F. Pan, Inorg.
8, 14083. Chem., 2017, 56, 13411–13416.
293 D. Aurbach, Z. Lu, A. Schechter, Y. Gofer, H. Gizbar, 318 H. Zhang, K. Ye, X. Huang, X. Wang, K. Cheng, X. Xiao,
R. Turgeman, Y. Cohen, M. Moshkovich and E. Levi, G. Wang and D. Cao, J. Power Sources, 2017, 338, 136–144.
Nature, 2000, 407, 724. 319 H. Zhang, K. Ye, S. Shao, X. Wang, K. Cheng, X. Xiao,
294 D. Aurbach, G. S. Suresh, E. Levi, A. Mitelman, O. Mizrahi, G. Wang and D. Cao, Electrochim. Acta, 2017, 229, 371–379.
O. Chusid and M. Brunelli, Adv. Mater., 2007, 19, 4260–4267. 320 C. Drosos, C. Jia, S. Mathew, R. G. Palgrave, B. Moss,
295 Y. Liang, R. Feng, S. Yang, H. Ma, J. Liang and J. Chen, A. Kafizas and D. Vernardou, J. Power Sources, 2018, 384,
Adv. Mater., 2011, 23, 640–643. 355–359.
296 B. Liu, T. Luo, G. Mu, X. Wang, D. Chen and G. Shen, 321 Z. Jia, J. Hao, L. Liu, Y. Wang and T. Qi, Ionics, 2018, 24,
ACS Nano, 2013, 7, 8051–8058. 3483–3491.
297 Y. Liang, H. D. Yoo, Y. Li, J. Shuai, H. A. Calderon, 322 V. Soundharrajan, B. Sambandam, S. Kim, V. Mathew,
F. C. Robles Hernandez, L. C. Grabow and Y. Yao, Nano J. Jo, S. Kim, J. Lee, S. Islam, K. Kim, Y.-K. Sun and
Lett., 2015, 15, 2194–2202. J. Kim, ACS Energy Lett., 2018, 3, 1998–2004.
298 M. Okoshi, Y. Yamada, A. Yamada and H. Nakai, 323 J. Zhijun, H. Jiawei, L. Lujing, W. Yi and Q. Tao, Ionics,
J. Electrochem. Soc., 2013, 160, A2160–A2165. 2018, 24, 3483–3491.
View Article Online
324 L. Chen, J. Bao, X. Dong, D. Truhlar, Y. Wang, C. Wang and 351 M. Kazazi, Z. A. Zafar, M. Delshad, J. Cervenka and
Y. Xia, ACS Energy Lett., 2017, 2, 1115–1121. C. Chen, Solid State Ionics, 2018, 320, 64–69.
325 F. Wang, Y. Lin, L. Suo, X. Fan, T. Gao, C. Yang, F. Han, 352 H. Lahan and S. K. Das, Ionics, 2018, 24, 1855–1860.
Y. Qi, K. Xu and C. Wang, Energy Environ. Sci., 2016, 9, 353 H. Lahan, R. Boruah, A. Hazarika and S. K. Das, J. Phys.
3666–3673. Chem. C, 2017, 121, 26241–26249.
326 H. Zhang, K. Ye, K. Zhu, R. Cang, J. Yan, K. Cheng, 354 Y. Wang, H. M. Shang, T. Chou and G. Z. Cao, J. Phys.
G. Wang and D. Cao, Chem. – Eur. J., 2017, 23, 17118. Chem. B, 2005, 109, 11361–11366.
327 H. Zhang, K. Ye, K. Zhu, R. Cang, J. Yan, K. Cheng, 355 J. R. González, F. Nacimiento, M. Cabello, R. Alcántara,
G. Wang and D. Cao, Electrochim. Acta, 2017, 256, 357–364. P. Lavela and J. L. Tirado, RSC Adv., 2016, 6, 62157–62164.
328 L. Chen, J. L. Bao, X. Dong, D. G. Truhlar, Y. Wang, 356 F. Nacimiento, M. Cabello, R. Alcántara, P. Lavela and
C. Wang and Y. Xia, ACS Energy Lett., 2017, 2, 1115–1121. J. L. Tirado, Electrochim. Acta, 2018, 260, 798–804.
329 R. Y. Wang, B. Shyam, K. H. Stone, J. N. Weker, M. Pasta, 357 S. Liu, G. L. Pan, G. R. Li and X. P. Gao, J. Mater. Chem. A,
H. W. Lee, M. F. Toney and Y. Cui, Adv. Energy Mater., 2015, 2015, 3, 959–962.
5, 1401869. 358 A. Holland, R. D. McKerracher, A. Cruden and R. G. A.
330 N. A. Hewish, G. W. Neilson and J. E. Enderby, Nature, Wills, J. Appl. Electrochem., 2018, 48, 243–250.
1982, 297, 138–139. 359 F. Wang, F. Yu, X. Wang, Z. Chang, L. Fu, Y. Zhu, Z. Wen,
331 M. Smeu, M. S. Hossain, Z. Wang, V. Timoshevskii, Y. Wu and W. Huang, ACS Appl. Mater. Interfaces, 2016, 8,
K. H. Bevan and K. Zaghib, J. Power Sources, 2016, 306, 9022–9029.
431–436. 360 C. Wu, S. Gu, Q. Zhang, Y. Bai, M. Li, Y. Yuan, H. Wang,
332 P. Padigi, G. Goncher, D. Evans and R. Solanki, J. Power X. Liu, Y. Yuan, N. Zhu, F. Wu, H. Li, L. Gu and J. Lu, Nat.
Sources, 2015, 273, 460–464. Commun., 2019, 10, 73.
333 C. Lee and S. K. Jeong, Chem. Lett., 2016, 45, 1447–1449. 361 Y. Liu, S. Sang, Q. Wu, Z. Lu, K. Liu and H. Liu, Electrochim.
334 C. Lee and S. K. Jeong, Electrochim. Acta, 2018, 265, 430–436. Acta, 2014, 143, 340–346.
335 S. Gheytani, Y. L. Liang, F. L. Wu, Y. Jing, H. Dong, 362 H. Lahan and S. K. Das, J. Power Sources, 2019, 413,
K. K. Rao, X. W. Chi, F. Fang and Y. Yao, Adv. Sci., 2017, 134–138.
4, 1700465. 363 M. D. Levi, Y. Shilina, G. Salitra, D. Aurbach, E. Guyot,
336 Z. P. Song, H. Zhan and Y. H. Zhou, Angew. Chem., Int. Ed., S. Seghir, J. M. Lecuire and C. Boulanger, J. Solid State
2010, 49, 8444–8448. Electrochem., 2012, 16, 3443–3448.
337 M. Adil, P. K. Dutta and S. Mitra, ChemistrySelect, 2018, 3, 364 C. P. Grey and N. Dupre, Chem. Rev., 2004, 104, 4493–4512.
3687–3690. 365 C. Masquelier and L. Croguennec, Chem. Rev., 2013, 113,
338 X.-P. Gao and H.-X. Yang, Energy Environ. Sci., 2010, 3, 6552–6591.
174–189. 366 M. S. Whittingham, Chem. Rev., 2004, 104, 4271–4301.
339 C.-X. Zu and H. Li, Energy Environ. Sci., 2011, 4, 2614–2624. 367 P. R. Kumar, Y. H. Jung, C. H. Lim and D. K. Kim, J. Mater.
340 N. Jayaprakash, S. Das and L. Archer, Chem. Commun., Chem. A, 2015, 3, 6271–6275.
2011, 47, 12610–12612. 368 L. Xue, Q. Zhang, X. Zhu, L. Gu, J. Yue, Q. Xia,
341 J. Muldoon, C. B. Bucur and T. Gregory, Chem. Rev., 2014, T. Xing, T. Chen, Y. Yao and H. Xia, Nano Energy, 2019,
114, 11683–11720. 56, 463–472.
342 G. A. Elia, K. Marquardt, K. Hoeppner, S. Fantini, R. Lin, 369 S. Liu, S. H. Ye, C. Z. Li, G. L. Pan and X. P. Gao,
E. Knipping, W. Peters, J. F. Drillet, S. Passerini and J. Electrochem. Soc., 2011, 158, A1490–A1497.
R. Hahn, Adv. Mater., 2016, 28, 7564–7579. 370 X. Shan, D. S. Charles, Y. Lei, R. Qiao, G. Wang, W. Yang,
343 W. I. Al Sadat and L. A. Archer, Sci. Adv., 2016, 2, e1600968. M. Feygenson, D. Su and X. Teng, Nat. Commun., 2016,
344 S. Gu, H. Wang, C. Wu, Y. Bai, H. Li and F. Wu, Energy 7, 13370.
Storage Mater., 2017, 6, 9–17. 371 D. B. Ravnsbaek, K. Xiang, W. Xing, O. J. Borkiewicz,
345 G. A. Elia, K. Marquardt, K. Hoeppner, S. Fantini, R. Lin, K. M. Wiaderek, P. Gionet, K. W. Chapman, P. J. Chupas
E. Knipping, W. Peters, J.-F. Drillet, S. Passerini and and Y. M. Chiang, Nano Lett., 2014, 14, 1484–1491.
R. Hahn, Adv. Mater., 2016, 28, 7564–7579. 372 A. K. Padhi, K. S. Nanjundaswamy and J. B. Goodenough,
346 Y. Hu, D. Sun, B. Luo and L. Wang, Energy Technol., 2019, J. Electrochem. Soc., 1997, 144, 1188–1194.
7, 86–106. 373 A. Yamada, Y. Kudo and K. Y. Liu, J. Electrochem. Soc.,
347 S. Liu, S. Ye, C. Li, G. Pan and X. Gao, J. Electrochem. Soc., 2001, 148, A747–A754.
2011, 158, A1490–A1497. 374 S. K. Martha, J. Grinblat, O. Haik, E. Zinigrad, T. Drezen,
348 S. Liu, J. J. Hu, N. F. Yan, G. L. Pan, G. R. Li and X. P. Gao, J. H. Miners, I. Exnar, A. Kay, B. Markovsky and
Energy Environ. Sci., 2012, 5, 9743–9746. D. Aurbach, Angew. Chem., Int. Ed., 2009, 48, 8559–8563.
349 K. Fic, G. Lota, M. Meller and E. Frackowiak, Energy 375 M. S. Zhao, G. L. Huang, B. Zhang, F. Wang and X. P. Song,
Environ. Sci., 2012, 5, 5842–5850. J. Power Sources, 2012, 211, 202–207.
350 Y. J. He, J. F. Peng, W. Chu, Y. Z. Li and D. G. Tong, 376 J. W. Zhao, Y. Q. Li, X. Peng, S. M. Dong, J. Ma, G. L. Cui
J. Mater. Chem. A, 2014, 2, 1721–1731. and L. Q. Chen, Electrochem. Commun., 2016, 69, 6–10.
View Article Online
377 P. Jiang, H. Z. Shao, L. Chen, J. W. Feng and Z. P. Liu, 402 J. Han, H. Zhang, A. Varzi and S. Passerini, ChemSusChem,
J. Mater. Chem. A, 2017, 5, 16740–16747. 2018, 11, 3704–3707.
378 C. Liu, X. Wang, W. Deng, C. Li, J. Chen, M. Xue, R. Li and 403 S. Liu, L. Wang, J. Liu, M. Zhou, Q. Nian, Y. Feng, Z. Tao
F. Pan, Angew. Chem., Int. Ed., 2018, 57, 7046–7050. and L. Shao, J. Mater. Chem. A, 2019, 7, 248–256.
379 S. Liu, G. L. Pan, N. F. Yan and X. P. Gao, Energy Environ. 404 J. Zhao, Y. Li, X. Peng, S. Dong, J. Ma, G. Cui and L. Chen,
Sci., 2010, 3, 1732–1735. Electrochem. Commun., 2016, 69, 6–10.
380 H. Dou, P. Nie and D. R. MacFarlane, J. Mater. Chem. A, 405 M. R. Lukatskaya, J. I. Feldblyum, D. G. Mackanic,
2014, 2, 19536–19541. F. Lissel, D. L. Michels, Y. Cui and Z. Bao, Energy Environ.
381 H. Li, G. Weng, C. Y. V. Li and K.-Y. Chan, Electrochim. Sci., 2018, 11, 2876–2883.
Acta, 2011, 56, 9420–9425. 406 Y. Yamada and A. Yamada, J. Electrochem. Soc., 2015, 162,
382 L. Chen, Z. Guo, Y. Xia and Y. Wang, Chem. Commun., A2406–A2423.
2013, 49, 2204–2206. 407 J. Wang, Y. Yamada, K. Sodeyama, C. H. Chiang,
383 P. Ratajczak and F. Béguin, ChemElectroChem, 2018, 5, Y. Tateyama and A. Yamada, Nat. Commun., 2016, 7, 12032.
2518–2521. 408 S. Wu, Y. Qiao, S. Yang, J. Tang, P. He and H. Zhou, ACS
384 S. Sur, A. R. Kottaichamy, Z. Manzoor Bhat, M. C. Devendrachari, Catal., 2018, 8, 1082–1089.

R. Thimmappa and M. O. Thotiyl, Chem. Phys. Lett., 2018, 409 K. Xu, Chem. Rev., 2014, 114, 11503–11618.
712, 160–164. 410 H. Ota, K. Shima, M. Ue and J.-i. Yamaki, Electrochim. Acta,
385 C. Li, W. Wu, P. Wang, W. Zhou, J. Wang, Y. Chen, L. Fu, 2004, 49, 565–572.
Y. Zhu, Y. Wu and W. Huang, Adv. Sci., 2019, 6, 1801665. 411 L. El Ouatani, R. Dedryvere, C. Siret, P. Biensan,
386 H. Li, Y. Wang, H. Na, H. Liu and H. Zhou, J. Am. Chem. S. Reynaud, P. Iratcabal and D. Gonbeau, J. Electrochem.
Soc., 2009, 131, 15098–15099. Soc., 2009, 156, A103–A113.
387 M. Zhang, Z. Huang, Z. Shen, Y. Gong, B. Chi, J. Pu and 412 H. Ota, Y. Sakata, Y. Otake, K. Shima, M. Ue and J. Yamaki,
J. Li, Adv. Energy Mater., 2017, 7, 1700155. J. Electrochem. Soc., 2004, 151, A1778–A1788.
388 X. Wang, Y. Hou, Y. Zhu, Y. Wu and R. Holze, Sci. Rep., 413 C. Yang, J. Chen, T. Qing, X. Fan, W. Sun, A. von Cresce,
2013, 3, 1401. M. S. Ding, O. Borodin, J. Vatamanu, M. A. Schroeder,
389 X. Wang, Q. Qu, Y. Hou, F. Wang and Y. Wu, Chem. N. Eidson, C. Wang and K. Xu, Joule, 2017, 1, 122–132.
Commun., 2013, 49, 6179–6181. 414 F. Wang, O. Borodin, M. S. Ding, M. Gobet, J. Vatamanu,
390 H. T. T. Le, D. T. Ngo, Y.-J. Kim, C.-N. Park and C.-J. Park, X. Fan, T. Gao, N. Eidson, Y. Liang, W. Sun, S. Greenbaum,
Electrochim. Acta, 2017, 248, 232–242. K. Xu and C. Wang, Joule, 2018, 2, 927–937.
391 H. T. T. Le, R. S. Kalubarme, D. T. Ngo, H. S. Jadhav and 415 C. Yang, J. Chen, X. Ji, T. P. Pollard, X. Lu, C. J. Sun, S. Hou,
C.-J. Park, J. Mater. Chem. A, 2015, 3, 22421–22431. Q. Liu, C. Liu, T. Qing, Y. Wang, O. Borodin, Y. Ren, K. Xu
392 S. Makino, R. Yamamoto, S. Sugimoto and W. Sugimoto, and C. Wang, Nature, 2019, 569, 245–250.
J. Power Sources, 2016, 326, 711–716. 416 Z. Chen and J. R. Dahn, Electrochim. Acta, 2004, 49, 1079–1090.
393 Q. Zhao, M. J. Zachman, W. I. Al Sadat, J. X. Zheng, 417 A. Ramanujapuram, D. Gordon, A. Magasinski, B. Ward,
L. F. Kourkoutis and L. Archer, Sci. Adv., 2018, 4, eaau8131. N. Nitta, C. Huang and G. Yushin, Energy Environ. Sci.,
394 J. Zhi, A. Z. Yazdi, G. Valappil, J. Haime and P. Chen, Sci. 2016, 9, 1841–1848.
Adv., 2017, 3, e1701010. 418 F. Wang, Y. Lin, L. Suo, X. Fan, T. Gao, C. Yang, F. Han,
395 M. Ahmed, A. Z. Yazdi, A. Mitha and P. Chen, ACS Appl. Y. Qi, K. Xu and C. Wang, Energy Environ. Sci., 2016, 9,
Mater. Interfaces, 2018, 10, 30348–30356. 3666–3673.
396 K. Nakamoto, R. Sakamoto, Y. Sawada, M. Ito and 419 N. W. Li, Y. X. Yin, C. P. Yang and Y. G. Guo, Adv. Mater.,
S. Okada, Small Methods, 2019, 3, 1800220. 2016, 28, 1853–1858.
397 L. Suo, D. Oh, Y. Lin, Z. Zhuo, O. Borodin, T. Gao, F. Wang, 420 L. Ma, M. S. Kim and L. A. Archer, Chem. Mater., 2017, 29,
A. Kushima, Z. Wang, H. C. Kim, Y. Qi, W. Yang, F. Pan, 4181–4189.
J. Li, K. Xu and C. Wang, J. Am. Chem. Soc., 2017, 139, 421 M. S. Kim, J.-H. Ryu, Deepika, Y. R. Lim, I. W. Nah,
18670–18680. K.-R. Lee, L. A. Archer and W. Il Cho, Nat. Energy, 2018,
398 H. G. Jung, M. W. Jang, J. Hassoun, Y. K. Sun and 3, 889–898.
B. Scrosati, Nat. Commun., 2011, 2, 516. 422 Z. Liu, G. Pulletikurthi and F. Endres, ACS Appl. Mater.
399 F. Wang, L. Suo, Y. Liang, C. Yang, F. Han, T. Gao, W. Sun Interfaces, 2016, 8, 12158–12164.
and C. Wang, Adv. Energy Mater., 2017, 7, 1600922. 423 A. Tatlisu, Z. Huang and R. Chen, ChemSusChem, 2018, 11,
400 C. Yang, X. Ji, X. Fan, T. Gao, L. Suo, F. Wang, W. Sun, 3899–3904.
J. Chen, L. Chen, F. Han, L. Miao, K. Xu, K. Gerasopoulos 424 Y. Zhang, R. Ye, D. Henkensmeier, R. Hempelmann and
and C. Wang, Adv. Mater., 2017, 29, 1701972. R. Chen, Electrochim. Acta, 2018, 263, 47–52.
401 L. Suo, O. Borodin, Y. Wang, X. Rong, W. Sun, X. Fan, 425 J. Wei, J. Zhou, S. Su, J. Jiang, J. Feng and Q. Wang,
S. Xu, M. A. Schroeder, A. V. Cresce, F. Wang, C. Yang, ChemSusChem, 2018, 11, 3410–3415.
Y.-S. Hu, K. Xu and C. Wang, Adv. Energy Mater., 2017, 426 D. Kundu, B. D. Adams, V. Duffort, S. H. Vajargah and
7, 1701189. L. F. Nazar, Nat. Energy, 2016, 1, 16119.
View Article Online
427 R. Benedek, M. M. Thackeray, J. Low and T. Bučko, J. Phys. 457 J. Liu, C. Xu, Z. Chen, S. Ni and Z. X. Shen, Green Energy
Chem. C, 2012, 116, 4050–4059. Environ., 2018, 3, 20–41.
428 A. S. Arico, P. Bruce, B. Scrosati, J. M. Tarascon and W. Van 458 S. Zhao, B. Han, D. Zhang, Q. Huang, L. Xiao, L. Chen,
Schalkwijk, Nat. Mater., 2005, 4, 366–377. D. G. Ivey, Y. Deng and W. Wei, J. Mater. Chem. A, 2018, 6,
429 L. Coustan, G. Shul and D. Bélanger, Electrochem. Commun., 5733–5739.
2017, 77, 89–92. 459 Y. Liu, X. Fang, A. Zhang, C. Shen, Q. Liu, H. A. Enaya and
430 H. Lahan and S. K. Das, Ionics, 2018, 24, 2175–2180. C. Zhou, Nano Energy, 2016, 27, 27–34.
431 S. Trasatti, J. Electroanal. Chem., 1972, 39, 163–184. 460 J. Xu, E. Hu, D. Nordlund, A. Mehta, S. N. Ehrlich,
432 V. Verma, S. Kumar, W. Manalastas, R. Satish and X. Q. Yang and W. Tong, ACS Appl. Mater. Interfaces,
M. Srinivasan, Adv. Sustainable Syst., 2019, 3, 1800111. 2016, 8, 31677–31683.
433 J. K. Norskov, T. Bligaard, A. Logadottir, J. R. Kitchin, 461 P. K. Nayak, J. Grinblat, M. Levi, E. Levi, S. Kim, J. W. Choi
J. G. Chen, S. Pandelov and J. K. Norskov, J. Electrochem. and D. Aurbach, Adv. Energy Mater., 2016, 6, 1502398.
Soc., 2005, 152, J23–J26. 462 Q. Lin, W. Guan, J. Meng, W. Huang, X. Wei, Y. Zeng, J. Li
434 B. C. Church, D. T. Kaminski and J. Jiang, J. Mater. Sci., and Z. Zhang, Nano Energy, 2018, 54, 313–321.
2014, 49, 3234–3241. 463 S. Sharifi-Asl, J. Lu, K. Amine and R. Shahbazian-Yassar,

435 M. Pourbaix, Corros. Sci., 1974, 14, 25–82. Adv. Energy Mater., 2019, 9, 1900551.
436 S. Gheytani, Y. Liang, Y. Jing, J. Q. Xu and Y. Yao, J. Mater. 464 R. Jung, P. Strobl, F. Maglia, C. Stinner and H. A. Gasteiger,
Chem. A, 2016, 4, 395–399. J. Electrochem. Soc., 2018, 165, A2869–A2879.
437 S. Liu, J. J. Hu, N. F. Yan, G. L. Pan, G. R. Li and X. P. Gao, 465 W. Zhang, F. H. Richter, S. P. Culver, T. Leichtweiss,
Energy Environ. Sci., 2012, 5, 9743–9746. J. G. Lozano, C. Dietrich, P. G. Bruce, W. G. Zeier and
438 S. Hu, Y. Li, J. Yin, H. Wang, X. Yuan and Q. Li, Chem. Eng. J. Janek, ACS Appl. Mater. Interfaces, 2018, 10, 22226–22236.
J., 2014, 237, 497–502. 466 J. Cabana, B. J. Kwon and L. Hu, Acc. Chem. Res., 2018, 51,
439 S. Maazi, A. H. Navarchian, M. Khosravi and P. Chen, Solid 299–308.
State Ionics, 2018, 320, 84–91. 467 K.-J. Park, J.-Y. Hwang, H.-H. Ryu, F. Maglia, S.-J. Kim,
440 P. Arora and Z. M. Zhang, Chem. Rev., 2004, 104, 4419–4462. P. Lamp, C. S. Yoon and Y.-K. Sun, ACS Energy Lett., 2019,
441 T. Famprikis, P. Canepa, J. A. Dawson, M. S. Islam and 4, 1394–1400.
C. Masquelier, Nat. Mater., 2019, 18, 1278–1291. 468 X. Shi, J. Du, T. G. J. Jones, X. Wang and H. P. Liang, ACS
442 F. Zheng, M. Kotobuki, S. Song, M. O. Lai and L. Lu, Appl. Mater. Interfaces, 2018, 10, 29667–29674.
J. Power Sources, 2018, 389, 198–213. 469 L. David, R. E. Ruther, D. Mohanty, H. M. Meyer, Y. Sheng,
443 Y. Huang, J. Liu, J. Wang, M. Hu, F. Mo, G. Liang and S. Kalnaus, C. Daniel and D. L. Wood, Appl. Energy, 2018,
C. Zhi, Angew. Chem., Int. Ed., 2018, 57, 9810–9813. 231, 446–455.
444 D. Wang, L. Wang, G. Liang, H. Li, Z. Liu, Z. Tang, J. Liang 470 K. Hoang, Phys. Rev. Mater., 2017, 1, 075403.
and C. Zhi, ACS Nano, 2019, 13, 10643–10652. 471 W. Cho, S. Myeong, N. Kim, S. Lee, Y. Kim, M. Kim, S. J. Kang,
445 J. Xie, Z. Wang, Z. J. Xu and Q. Zhang, Adv. Energy Mater., N. Park, P. Oh and J. Cho, Adv. Mater., 2017, 29, 1605578.
2018, 8, 1703509. 472 R. Yu, X. Wang, Y. Fu, L. Wang, S. Cai, M. Liu, B. Lu,
446 F. Cheng and J. Chen, Chem. Soc. Rev., 2012, 41, 2172–2192. G. Wang, D. Wang, Q. Ren and X. Yang, J. Mater. Chem. A,
447 Z. L. Wang, D. Xu, J. J. Xu and X. B. Zhang, Chem. Soc. Rev., 2016, 4, 4941–4951.
2014, 43, 7746–7786. 473 E. Hu, S.-M. Bak, Y. Liu, J. Liu, X. Yu, Y.-N. Zhou, J. Zhou,
448 D. Aurbach, B. D. McCloskey, L. F. Nazar and P. G. Bruce, P. Khalifah, K. Ariyoshi, K.-W. Nam and X.-Q. Yang, Adv.
Nat. Energy, 2016, 1, 16128. Energy Mater., 2016, 6, 1501662.
449 J.-S. Lee, S. Tai Kim, R. Cao, N.-S. Choi, M. Liu, K. T. Lee 474 S. Kalluri, M. Yoon, M. Jo, H. K. Liu, S. X. Dou, J. Cho and
and J. Cho, Adv. Energy Mater., 2011, 1, 34–50. Z. Guo, Adv. Mater., 2017, 29, 1605807.
450 M. S. Faber and S. Jin, Energy Environ. Sci., 2014, 7, 3519–3542. 475 B. Qiu, M. Zhang, L. Wu, J. Wang, Y. Xia, D. Qian, H. Liu,
451 W. Liu, E. Hu, H. Jiang, Y. Xiang, Z. Weng, M. Li, Q. Fan, S. Hy, Y. Chen, K. An, Y. Zhu, Z. Liu and Y. S. Meng,
X. Yu, E. I. Altman and H. Wang, Nat. Commun., 2016, Nat. Commun., 2016, 7, 12108.
7, 10771. 476 Y. Cho, S. Lee, Y. Lee, T. Hong and J. Cho, Adv. Energy
452 Q. Ding, B. Song, P. Xu and S. Jin, Chem, 2016, 1, 699–726. Mater., 2011, 1, 821–828.
453 M. Macka, P. Andersson and P. R. Haddad, Anal. Chem., 477 X. D. Zhang, J. L. Shi, J. Y. Liang, Y. X. Yin, J. N. Zhang,
1998, 70, 743–749. X. Q. Yu and Y. G. Guo, Adv. Mater., 2018, 30, 1801751.
454 W. Sheng, Z. Zhuang, M. Gao, J. Zheng, J. G. Chen and 478 L. Hu, P. Brüner, T. Grehl, H. H. Brongersma and
Y. Yan, Nat. Commun., 2015, 6, 5848. J. Cabana, Chem. Mater., 2017, 29, 5896–5905.
455 L. Suo, F. Han, X. Fan, H. Liu, K. Xu and C. Wang, J. Mater. 479 J. Ahn, J. H. Kim, B. W. Cho, K. Y. Chung, S. Kim,
Chem. A, 2016, 4, 6639–6644. J. W. Choi and S. H. Oh, Nano Lett., 2017, 17, 7869–7877.
456 C. Yang, L. Suo, O. Borodin, F. Wang, W. Sun, T. Gao, 480 L. L. Wang, K. W. Huang, J. T. Chen and J. R. Zheng, Sci.
X. Fan, S. Hou, Z. Ma, K. Amine, K. Xu and C. Wang, Adv., 2019, 5, eaax4279.
Proc. Natl. Acad. Sci. U. S. A., 2017, 114, 6197–6202. 481 G. Venugopal, J. Power Sources, 2001, 101, 231–237.
View Article Online
482 J. H. Tian, T. Jiang, M. Wang, Z. Hu, X. Zhu, L. Zhang, 485 A. J. Ilott, M. Mohammadi, H. J. Chang, C. P. Grey and
T. Qian and C. Yan, Small Methods, 2019, 1900467, DOI: A. Jerschow, Proc. Natl. Acad. Sci. U. S. A., 2016, 113,
10.1002/smtd.201900467. 10779–10784.
483 D. Liu, Z. Shadike, R. Lin, K. Qian, H. Li, K. Li, S. Wang, 486 A. R. Armstrong, C. Arrouvel, V. Gentili, S. C. Parker,
Q. Yu, M. Liu, S. Ganapathy, X. Qin, Q. H. Yang, M. S. Islam and P. G. Bruce, Chem. Mater., 2010, 22,
M. Wagemaker, F. Kang, X. Q. Yang and B. Li, Adv. Mater., 6426–6432.
2019, 31, 1806620. 487 C. J. Jafta, X. G. Sun, G. M. Veith, G. V. Jensen, S. M.
484 L. Zhang, T. Qian, X. Zhu, Z. Hu, M. Wang, L. Zhang, T. Jiang, Mahurin, M. P. Paranthaman, S. Dai and C. A. Bridges,
J. H. Tian and C. Yan, Chem. Soc. Rev., 2019, 48, 5432–5453. Energy Environ. Sci., 2019, 12, 1866–1877.

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Voltage issue of aqueous rechargeable

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Fig. 2 Comparison of standard electrode potentials and theoretical capa-

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and polymer electrodes involving doping/de-doping or enolization/

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lyte components in conventional LIBs result in the formation of 2.5 Overpotentials

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midpoint voltage of 0.65 V (vs. SCE). All the above-discussed

plateau at around 0.12 V (vs. Ag/AgCl) (Fig. 4e).131 It was found

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operated in the potential range of 0.4–1.3 V and 0.2–0.9 V, with

for most anode materials, which are mainly attributed to the

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Fig. 7 (a) EDS elemental mapping images of K0.27MnO2. (b) Schematic

structure. (e) Rate capacity of the NaTi2(PO4)3//K0.27MnO2 full cell at various

Polyanionic compounds contain a series of tetrahedron

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an average width of 5 nm. It displayed a discharge capacity

can be reduced to thermoneutral value, indicating the highly

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during charge/discharge. AZIB employing such cathode was

the voltage range of 0.6–1.6 V, and retained 76.7% of its initial

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(OMS), has been frequently reported in the fields of energy

cycled in various aqueous electrolytes for hundreds of charge/

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with a tilting plateau at 1.32 V (Fig. 16f and g).322 Nevertheless,

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needed to discover new electrode materials with desired electro-

demonstrated the reversible intercalation/de-intercalation of Al3+

TiO2 electrodes. Such remarkable diﬀerence arose from the fast

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These strategies involve the screening of suitable electrode materials

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4.1.2 Electrode materials to form hybrid battery systems.

occur at MgMn2O4 cathode and zinc stripping/plating occur at

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de-intercalation in TiO2 anode. As a result, the assembled battery be eﬀectively suppressed.

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battery in alkaline electrolyte. The battery delivered a flat high-

were conducted on supercapacitors.383–385 For example, Ratajczak

Given the above facts, there is still plenty of room for