Author’s Accepted Manuscript

Solid electrolytes and interfaces in all-solid-state

sodium batteries: progress and perspective

Wenru Hou, Xianwei Guo, Xuyang Shen, Khali

Amine, Haijun Yu, Jun Lu

www.elsevier.com/locate/nanoenergy

PII: S2211-2855(18)30524-X
DOI: https://doi.org/10.1016/j.nanoen.2018.07.036
Reference: NANOEN2903
To appear in: Nano Energy
Received date: 18 June 2018
Revised date: 12 July 2018
Accepted date: 18 July 2018
Cite this article as: Wenru Hou, Xianwei Guo, Xuyang Shen, Khali Amine,
Haijun Yu and Jun Lu, Solid electrolytes and interfaces in all-solid-state sodium
batteries: progress and perspective, Nano Energy,
https://doi.org/10.1016/j.nanoen.2018.07.036
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 Solid electrolytes and interfaces in all-solid-state sodium
batteries: progress and perspective
Wenru Houa1, Xianwei Guoa1, Xuyang Shena, Khali Amineb, Haijun Yua*, Jun Lub*,

a
College of Materials Science and Engineering, Key Laboratory of Advanced
Functional Materials, Education Ministry of China, Beijing University of Technology,
Beijing, 100124, P.R. China
b
Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700,
South Cass Avenue, Lemont, Illinois 60439, United States
hj-yu@bjut.edu.cn,
junlu@anl.gov.

*Corresponding Authors

Abstract:
All-solid-state sodium batteries are promising candidates for the next generation of
energy storage with exceptional safety, reliability and stability. The solid
electrolytes are key components for enabling all-solid-state sodium batteries with high
electrochemical performances. This Review discusses the current developments on
inorganic and organic sodium ions solid electrolytes, including β/β’’-alumina,
NASICON, sulfides, polymers and others. In particular, the structures, ionic
conductivities and fabrications as well as electrochemical/chemical stabilities of solid
electrolytes are discussed. The effective approaches for forming intimate interfaces
between solid electrolytes and electrodes are also reviewed. And perspectives on
future developments in the field of solid electrolytes and possible directions to
improve interfacial contacts for future practical applications of all-solid-state sodium
batteries are included.

Graphical Abstract

1
W. H. and X. G. contributed equally to this paper.
1
 Cathode Anode

Interfaces Interfaces

Solid electrolyte Solid electrolyte Solid electrolyte

All-solid-state sodium batteries are the promising candidate for the next generation of

large-scale energy storage with exceptional safety, reliability and stability. The solid

electrolytes are the key components for enabling all-solid-state sodium batteries with

high electrochemical performances. The current developments of solid electrolytes

were reviewed in this article. In particular, the intrinsic properties of solid electrolytes

and the effective approaches for forming intimate interfaces between solid electrolytes

and electrodes are deeply discussed. Besides, several directions are also suggested for

developing the solid electrolytes and improving the interfacial contacts for future

practical applications of all-solid-state sodium batteries.

Keywords: Sodium ions, inorganic solid electrolytes, organic solid electrolytes,

all-solid-state batteries, interfaces
1. Introduction
As the effective energy storage and conversion technology for the integration of

renewable resources, the electrochemically secondary batteries have attracted great

attentions in the past few decades.[1-10] Among these, lithium-ion batteries (LIBs)

are very popular because of high energy density, high power output, and long cycling

lifetime, which have been widely applied in the modern life, such as portable

2
electronics and electric vehicles.[11-18] However, the low reserves of Li salts and

increase of cost with rising demands have been becoming the stringent problems.

Therefore, it’s imperative to develop alternative energy storage system for future

replacement of LIBs. After intensively studied in recent years, the sodium (Na)

batteries have been considered as one of most promising candidates because of highly

abundant Na resource, low cost, and comparative performances to that of LIBs.[5, 7,

19-26] However, the conventional Na batteries based on organic liquid electrolyte

are still suffered from safety issues, such as liquid leakage, weak thermal stability

with ignitability and explosiveness, which are similar to liquid electrolyte based LIBs.

Comparing to organic liquid electrolyte, the solid electrolyte own high thermal

stability, low flammability, no leakage and volatilization, no risk of fire and explosion,

which are beneficial for developing all-solid-state Na battery with high safety and

stability.[27-30] Furthermore, Na metal can be utilized in all-solid-state battery, in

which the energy density can be enhanced greatly, and formation of dendrites can be

restrained to prevent the internal short circuit.

As the critical component of all-solid-state Na battery, the solid electrolyte plays a key

role by acting as both ionic conductor and separator between cathode and anode

(Figure 1). However, the practical applications of all-solid-state Na batteries are

still hindered by some deficiencies of solid electrolytes, including low ionic

conductivity at room temperature, narrow electrochemical window, weak

chemical/electrochemical stability, and poor interfacial compatibility between

electrodes and electrolytes, especially the insufficient contact with limited ions

3
transport pathways during volume changes of electrodes for Na

insertions/extractions.[27-29, 31-40] Thus, there are two key points that urgent to be

solved for developing all-solid-state Na batteries: one is fabricating solid electrolyte

with high ionic conductivity at room temperature, the other is how to make an

intimate interface between solid electrolyte and electrode.

+
discharge e-

Cathode
(Composite) e-

discharge
Cathode/electrolyte interface
Composite cathode
Solid electrolyte
(Inorganic)
charge

Anode/electrolyte interface

charge
Na Anode Na Anode
e-

e-

Fig. 1 Schematic diagram of all-solid-state Na batteries based on (left) inorganic and (right)
polymer electrolyte.

In this Review, the widely studied Na-ions solid electrolytes with structures and ionic

conductivities as well as preparation methods and electrochemical/chemical stabilities

will be briefly summarized, which are classified into several parts, including

β/β’’-alumina, sodium super ionic conductor (NASICON), sulfides, polymers and

others. And then, based on typical solid electrolytes, several approaches for

improving the contacts between electrolytes and electrodes for configurations of

all-solid-state Na batteries will be discussed, which are beneficial for enhancing

electrochemical performances. Finally, a perspective on the future direction for

developing high-performance Na-ions solid electrolytes and making intimate

interfaces between electrolytes and electrodes for all-solid-state batteries will be

proposed. We hope this Review provide the guidance not only for materials design

4
of solid electrolytes, but also for forming interfaces in all-solid-state Na batteries with

favorable electrochemical performances for practical applications.

2. Na-ions solid electrolytes

The history of developing Na-ions solid electrolyte was much earlier than that of

Li-ions, and the layer structured β-alumina (Na2O·11Al2O3) as an ion conductor was

firstly prepared for sodium-sulphur (Na-S) batteries.[40-44] As the migration of Na

ions was restricted by two-dimensional (2D) planes of β-Al2O3, NASICON materials

with 3D framework for fast ions transport were introduced.[34, 37, 45-48]

Meanwhile, the sulfides are proposed to offer higher ionic conductivities.[32, 33, 35,

49-56] Besides inorganic solid electrolytes, the polymer electrolytes have been

developed for all-solid-state Na batteries.[31, 57-59] Until now, inorganic solid

electrolytes and polymer electrolytes are main aspects in Na-ions solid electrolytes for

improving the safety and electrochemical performance of all-solid-state batteries.

Since the primary role is ions transfer, the high ionic conductivity is a predominant

parameter for evaluating Na solid electrolyte.[27-29] In addition, the

chemical/electrochemical stability, compatibility to electrodes, and thermal stability

are also important for the application of solid electrolyte in all-solid-state Na battery.

5
 o
T ( C)
300 200 100 60 25
0
Na3.3La0.3Zr1.7Si2PO12 Glass-ceramic Plastic-crystal
c-Na3PS4 Succinonitrile (SN)-NaClO4
-1 1M NaTFSI/
Na--alumina
PC-EC-DMC

log[(S cm )] -2 Na3PSe4
-1

NASICON
-3 Na3Zr2Si2PO12

-4 Antiperovskite Glass
Na3OBr Na2S-P2S5

-5 Polymer Na2(BH)12-(BH)10
PEO-NaClO4 (5%TiO2)

-6
Polymer
PEO-NaPF6-
-7
1.5 2.0 2.5 3.0 3.5
-1 -1
1000 T (K )
Fig. 2 Temperature-dependent ionic conductivities of typical Na-ions solid electrolytes, including
organic liquid electrolytes, and solid electrolytes consisting of β’’-alumina, NASICON, sulfides,
polymers and others. The ionic conductivities are summarized from refs. [31, 32, 36, 37, 51,
60-65]

The ionic conductivities of typical Na-ion solid electrolytes, such as β-Al2O3,

NASICON, sulfides, and polymers, are presented in Fig. 2. It can be seen that

inorganic electrolytes such as sulfides (such as Na3PS4), NASICON, sodium

borohydride and Na-β”-alumina electrolytes have relatively high ionic conductivities

at room temperature. As ionic conductivities are closely determined by ions

transport mechanisms, the understanding of mechanisms is critical for materials

design of fast ions conductors. Similar to Li-ions solid electrolytes with analogous

framework in crystalline inorganic electrolyte materials, ionic transport generally

relies on concentrations of mobile ions and vacancies (non-mobile ions in the

framework), and relative sizes between them in crystal structures, which follows the

models of Schottky and Frenkel point defects that in connected conduction

6
pathways.[34, 45, 47, 66-71] The more mobile ions, connected vacancies in open

structure, and suitable size ratio of ions/vacancies are much beneficial for offering

higher ionic conductivities, which have been demonstrated in β-Al2O3 and NASICON.

In non-crystalline sulfides with short- and medium-range order amorphous structure,

the high concentration of mobile ion carrier species can effectively improve the ionic

conductivity. [72] Besides, the size increase of anion sublattice causes high

conductivity, which are generated by enlarged size of migration channel and reduced

interaction between mobile ions and structural cations.[32, 33, 35, 51, 53-56, 73]

Furthermore, in polymer electrolytes, the ion transports are related to segmental

motions of polymer chains, which create free volumes for the hopping of ions that

coordinate with polar groups.[31, 57, 61, 74-80] Depending on dissociation ability

of sodium salt in the polymer, the fast ions diffusions can be achieved by hopping

large number of free ions from one coordinating site to another, accompanying by

segmental motion of polymer chains, and then the long-distance transport can be

realized by continuous hopping under an electrical field. 51, 59-66 For PEO

electrolyte, the generally accepted view is that ionic conductivity caused by ion

migration in amorphous regions of polymer hosts, in which the molecular chains can

oscillate above its glass transition temperature (Tg).[81]

The electrochemical/chemical stabilities of solid electrolytes are also important

factors to be considered for all-solid-state Na batteries. Comparing to stable

electrolytes of β-Al2O3 and NASICON, the sulfides are easy to be decomposed to H2S

through hydrolysis in the air.[32, 53, 60, 73, 82, 83] It has been demonstrated that

7
the chemical stability of sulfide electrolytes can be improved by several effective

modifications, such as adding soft acid to form strong bonding with sulfur, adjusting

the composition to isolate PS43-, and adding metal oxides to absorb H2S.[84-86] The

electrochemical stabilities of batteries are involved into electrode/electrolyte

interfaces, electrochemical stable windows and electrolyte variations during long

cycling. Among these, the intimate contact interface with large surface area and

compatibility to electrode are most important factors to enhance battery performances.

2.1 β-Al2O3 and β’’-Al2O3

β-Al2O3 and β’’-Al2O3 are early developed Na-ions solid electrolytes for rechargeable

high-temperature Na-S batteries.[44] The β-Al2O3 with formula of

Na2O·(8-11)Al2O3 has a hexagonal structure (P63/mmc; a0= 0.559, c0= 2.261 nm),

while β’’-Al2O3 of Na2O·(5-7)Al2O3 has a rhombohedral structure (R3m; a0= 0.560,

c0= 3.395 nm).[44] As shown in Fig. 3, Na ions transport pathways in both β- and

β’’-Al2O3 are 2D planes, while the differences are chemical stoichiometry and

stacking sequence of oxygen ions in conduction layers.[43] The basic unit consists

of alternating layers with spinel block and conduction plane, in which the spinel block

is four layers stack of oxygen ions with Al ions, and the conduction planes consists of

packed oxygen and Na ions. As higher concentration of Na ions in conduction plane

with different oxygen stacking sequence, the β’’-Al2O3 has a higher ionic conductivity

than β-Al2O3.

For ionic conductivity of Na-β’’-Al2O3, the highest value of 100 mS cm-1 can be

obtained in single crystal at room temperature, while the commercial β’’-Al2O3

8
polycrystalline product only reaches 2 mS cm-1. [66, 67] Generally the ionic

conductivity can be increased with elevated temperature. So the ionic conductivity

of

(a) (b)
A A
B B
C C
A
A Conduction
Conduction
Plane
Plane

C-Axis
C
A A
C B
B C
A Conduction
Plane
B
C
O2- Na+ Al3+ A
B

Fig. 3 Schematic diagram of stacking sequence and ion conduction plane for (a) β-Al2O3 and (b)
β”-Al2O3.

β’’-Al2O3 at 300 oC increases to 1 S cm-1 for single crystal, which is much higher than

that of polycrystalline β’’-Al2O3 (0.24 S cm-1 at 300 oC).[2, 44] However, the

highest ionic conductivity for polycrystalline can be increased to 19 mS·cm-1 at room

temperature in solid electrolyte fabricated by spark plasma sintering (SPS).[87] It

has been demonstrated that the ionic conductivity of β’’-Al2O3 can be enhanced by

increasing the concentration of Na ions in conduction plane, and substituting Al ions

by doping of Mg2+, Nb5+, Zr4+ and Ti4+.[88-91] Furthermore, the optimization of

β-Al2O3 and β’’-Al2O3 proportions and adjustment of microstructure are also effective

ways to increase ionic conductivities.[92, 93]

The Na-β”-Al2O3 solid electrolytes can be prepared by solid-state reaction,

co-precipitation technique, sol-gel process, solution combustion way,

spray-freeze/freeze-drying method, microwave heating and mechanochemical

methods.[42, 88, 91, 94-97] For conventional solid-state reaction and solution-based

9
chemical methods, the uniform β”- Al2O3 with high ionic conductivity is not easy to

be obtained because of Na loss, grain growth, moisture sensitivity (caused by

byproduct of NaAlO2 along grain boundaries), and inhomogeneity mixed with

β-Al2O3 impurity. Recently the β”- Al2O3 ceramics with anisotropic ionic

conductivity were prepared by SPS, which is effective for rapid densification of pure

β”-Al2O3 with automatic c-axis orientation alignment and beneficial for enhancing the

ionic conductivity.[87] Further improvement is still required to develop favorable

methods for fabricating pure β”-Al2O3 with high yield of production, low cost and

well-controlled microstructure.

2.2 NASICON

Different from Na-ions migrations in 2D planes of layer-structured β’’-Al2O3, the

NASICON, like Na1+xZr2P3-xSixO12 (0≤x≤3) as solid solution of NaZr2P3O12 and

Na4Zr2Si3O12, was developed by Hong and Goodenough et al. to offer fast Na ions

conduction in 3D diffusion pathways.[45, 46] The composition of NASICON is

generally summarized as NaMM’P3O12, in which Na site can be substituted, vacant,

or filled in excess, while M and M’ sites are usually occupied by divalent (Mg2+, Cu2+,

Co2+, Zn2+, Mn2+, Fe2+,…), trivalent (Al3+, Cr3+, Sc3+, Y3+, La3+,…), tetravalent (Ti4+,

Ge4+, Sn4+, Nb4+,…), or pentavalent (V5+, Nb5+, Ta5+,…) metal ions to ensure the

charge balance.[98] For M and M’ substituted ions, the valences and ionic radius

should be carefully screened to enlarge ions channels and weaken the interaction

between mobile ions and skeleton atoms. The NASICON has a covalent framework

structure consisting of interconnected polyhedral, in which M(M’)O6 octahedra are

10
linked by corner-sharing PO4(SiO4) tetrahedra to form a skeleton structure and large

number of interstitial sites as 3D interconnected channels for Na ions migrations (Fig.

4). For widely investigated Na1+xZr2P3-xSixO12 (0≤x≤3) solid solution, the chemical

substitutions are variable in a wide range, resulting in low thermal expansion.

Therefore, the NASICON with covalent framework has a high thermal and chemical

stability that are beneficial for stable operation of solid-state Na batteries.

(a) (b)

ZrO6 octahedra

PO4/SiO4 tetrahedra

Na

Fig. 4 The crystal structure of NASICON. (a) Rhombohedral structure (b) Monoclinic structure.

The ionic conductivities of NASICON are in the range from 10-4 to 10-3 S cm-1 at

room temperature (Fig. 5). In order to increase the ionic conductivity for operation

of all-solid-state batteries at room temperature, both Na concentration and size of M

and M’ cations in AMM’P3O12 should be controlled at the optimum value

simultaneously: around 3.3 mol of Na per formula unit and the average size of M

cations should be close to 0.72 Å (i.e. the ionic radius of Zr).[68] Thus, the ionic

conductivity of NASICON is variable with different substitute ions at ambient

temperature. For example, Na1+xZr2P3-xSixO12 has highest ionic conductivity of

6.7×10-4 S cm-1 at room temperature for x=2, and 0.2 S cm-1 at 300 oC, respectively.

[46] And 90wt.% NASICON-10wt.% 60Na2O-10Nb2O5-30P2O5 glass-ceramic

11
composite electrolyte exhibits high ionic conductivity of 1.2×10-4 S cm-1 at room

temperature.[99] For Na3+xZr2-xLaxSi2PO12, the ionic conductivity can reach to

3.4×10-3 S cm-1 at room temperature when x=0.35.[36] And an optimum total

Na-ion conductivity of 4.0×10-3 S cm-1 at room temperature is achieved in

Na3.4Sc0.4Zr1.6(SiO4)2(PO4).[34] Accordingly, element doping is effective for

improving ionic conductivities, in which the dopants with low solid solubility can

result in improving grain boundary conductivity by forming a conducting secondary

phase, and the changes in Si:P ratio within bulk transformation from monoclinic to

rhombohedral NASICON.[47] Thus, further research needs to be focused on the

strategies to improve the conductivity of NASICON by preparing phase pure and high

density products, enhancing microstructure of grain size and boundary, and doping by

substituted ions.
0
Na3.4Sc0.4Zr1.6(SiO4)2(PO4)
-1

-2
log[(S cm )]
-1

Na3Zr2Si2PO12 Na3.3Zr0.7La0.3Si2PO12
-3

-4

-5 Na2.4V1.4Zr0.6(PO4)3

-6 Na1.4Al0.4Ti1.6(PO4)3

-7
1.5 2.0 2.5 3.0 3.5
-1 -1
1000T (K )
Fig. 5 Temperature-dependent ionic conductivities of NASICON materials. The ionic
conductivities are summarized from refs. [32, 34, 36, 100, 101]

The NASICON materials can be synthesized by conventional solid-state reaction,

sol-gel, hydrothermal, and spray-freeze/freeze-drying methods.[26, 36, 45-47, 102,

12
103] Among these, the products from sol-gel and hydrothermal are more uniform

and much easier to be controlled with low content of ZrO2 impurity than that of

solid-state reaction, and then high-density and high-purity NASICON pellets can be

easily generated. Besides, the fully dense ceramic pellet with high ionic

conductivity at room temperature was obtained by SPS.[104] Furthermore, a

solution-assisted solid-state reaction has been developed for the synthesis of

Sc-substituted NASICON, Na3+xScxZr2‑ x(SiO4)2(PO4) (0≤x≤0.6). [34] In most

recently, Na3+xZr2-xLaxSi2PO12 has been fabricated by in-situ compositing method with

introduction of larger La3+ cation, while a new Na3La(PO4)2 phase formed by

extracting charge carrier ions and anions from the starting material.[36] The new

phase plays a positive effect on ion conductivity by creating a concentration variation

of Na+ in frame structure, increasing the compact density of composite electrolyte,

and promoting ion transport along grain boundary. Besides, 90wt.% NASICON and

10wt.% 60Na2O-10Nb2O5-30P2O5 glass-ceramic composite electrolyte with low

electrical resistivity has been fabricated at low sintering temperature (900 °C) with

short time (10 min). [99]

2.3 Sulfides

The sulfides electrolytes have attracted much attentions because of high ionic

conductivities, excellent mechanical properties for intimate contact between electrode

and electrolyte, isotropic ionic conductions without grain boundary resistances,

simple manufacturing operations for processing into a film at low temperature, and

variable compositions in a wide range.[28] However, sulfides electrolytes have low

13
chemical stabilities in air because of the hydrolysis by water molecular with

generation of H2S gas, which should be handled in inert gas atmosphere.

Generally, sulfides electrolytes can be divided into glass and glass-ceramic. In detail,

glassy electrolytes with equivalent phase, like Na2S-GeS2, Na2S-SiS2 and

xNa2S-(100-x)P2S5, have amorphous structures with high disorders and high

concentrations of mobile ions in sublattice.[60, 105-107] The small

electronegativity of sulfur with weak binding ions and big ion radius are beneficial for

creating larger ions transport channels, which can meet the primary requirements for

fast Na ions migrations.

Glass-ceramic electrolytes that prepared by crystallization of glass precursor have

been extensively studied in recent years. For instance, Na3PS4 glass-ceramic

electrolyte has both cubic phase (I4̅3m; a0=6.9965 Å) and tetragonal phase (P421c;

a0= 6.9520 Å, c0= 7.0757 Å) (Fig. 6).[32] As can be seen in Fig. 6a, there are Na1

and Na2 sites in cubic Na3PS4, in which ionic conduction is closely related to many

aspects, such as Na disorder that induced by Na excess, 3D diffusion pathways along

Na1 and Na2 sites, and introduction of Na-vacancies.[52] In order to enhance ionic

conductivity, a Na3P1-xAsxS4 (partial substitution of P by As) was synthesized, in

which the improvement of conductivity stems from longer Na-S bond length in

unstable saddle point structure of transition state that regulated by duel effects of

alloying.[73] As Na3PS4 is unstable in the air that caused by high affinity between S

and O, a stable Na3SbS4 with tetragonal structure (P421c; a0=7.15270 Å, c0=7.2874 Å)

and 3D Na ions diffusion pathways was recently designed to address this issue (Fig.

14
6b).[33] The Na3SbS4 exhibits not only superior ionic conductivity at room

temperature, but also outstanding air stability and good compatibility to metallic Na

anode, which is considered as a promising candidate for all-solid-state Na metal

batteries.[53, 108] Most recently, a tetragonal Na4-xSn1-xSbxS4 (0.02≤x≤0.33,

space group I41/acd) with fast 3D ionic conduction pathways has been developed,

which is different from Na4SnS4 or Na3SbS4.[54] The new solid electrolytes showed

a high ionic conductivity (0.2-0.5 mS cm-1 at 30 °C), excellent dry-air stability, no

H2S evolution in contact with water, and reversible precipitation from homogeneously

dissolved aqueous solution. As ionic diffusions are effected greatly by size of

transfer channels and type of anion substitutions, the cubic Na3PSe4 (I43m;

a0=7.31359 Å) has been synthesized in order to provide a more appropriate

framework for diffusions of Na cations because of bigger atomic radius of Se than S.

[51] However, it’s more likely that the formation of Na vacancies in Na3PSe4 plays

a key role to achieve fast Na-ions diffusions, not the direct linkage with specific

polymorph or composition.[50, 83] Recently, Na10SnP2S12 and Na11Sn2PS12 have

been obtained, which showed higher ionic conductivity at room temperature and more

stable in battery applications than cubic Na3PS4.[35, 55, 56]

The sulfides electrolytes usually exhibit higher ionic conductivity than that of oxides

because the electronegativity of sulfur (with larger atomic radius) is smaller than that

of oxygen, which leads to a smaller electrostatic force between Na and S in

framework.[32, 49-51] Also the ionic conductivity can be enhanced by precipitation

of superionic conducting crystal from glass precursor, and low grain-boundary

15
resistance, in which crystal domains are filled with amorphous phases. Therefore,

the ionic conductivity of Na3PS4 (cubic structure) can achieve 2×10-4 S cm-1 at room

temperature with low activation energy of 27 kJ mol-1 in the temperature range of

27-270 oC (Fig. 7), which is higher than that of xNa2S-(100-x)P2S5 glass electrolyte

(10-5 S cm-1).[32, 105] The ionic conductivity of Na3PS4 can be increased

effectively by partial substitutions from anions (like Se2-, Cl-, Br- and I-) and cations

(including As3+, Ge4+,Ti4+, Si4+, and Sb4+ ).[109-111] Among these, the cubic

Na3PSe4 (Se-substitution of S in Na3PS4) has high ionic conductivity of 1.16×10-3 S

cm-1 at room

(a) (b)

PS4tetrahedrons

Na1

Na2

P/As/Sb

S/Se

Fig. 6 The crystal structures of different sulfides electrolytes with (a) cubic and (b) tetragonal
structures.

temperature and low activation energy of 0.21 eV.[51] Also the tetragonal

Na2.9375PS3.9375Cl0.0625 that generated by SPS process has ionic conductivity of

1.14×10-3 S cm-1 at room temperature, while xNaI(100-x)Na3PS4 showed an ionic

conductivity of ~1.0×10-4 S cm-1 with x=29.[82, 109] Furthermore, Na3P0.62As0.38S4

exhibits high ionic conductivity of 1.46×10-3 S cm-1 at room temperature.[73]

Moreover, the ionic conductivity of Na3PS4 has been improved to 7.4×10-3 S cm-1 at

16
room temperature by combining 6 mol% Na4SiS4.[112] The air stable Na3SbS4 has

ionic conductivity of 1.0×10-3 S cm-1 at room temperature with an active energy of

0.22 eV, and the ionic conductivity of tetragonal Na4-xSn1-xSbxS4 (0.02≤x≤0.33) is

0.2-0.5 mS cm-1 at 30 oC.[33, 54] For Na10SnP2S12 and Na11Sn2PS12, the ionic

conductivities are 0.4×10-3 and (1.4-4.0) ×10-3 S cm-1 at room temperature,

respectively.[35, 55, 56]

The typical preparation process of sulfides electrolyte is mechanical ball milling and

low-temperature heating treatment of precursors.[60, 106] As the instability of

sulfides electrolytes in air, all processes should be protected under inert atmosphere.

The glassy electrolytes can be obtained by heating crystalline materials above the
0

-1
c-Na3PS4 Na3P0.62As0.38S4
-2
log[(S cm )]

Na3SbS4
-1

-3

-4 t-Na3PS4
Na3PSe4
-5

-6 Na2S-P2S5

-7
1.5 2.0 2.5 3.0 3.5
-1 -1
1000T (K )
Fig. 7 Temperature-dependent ionic conductivities of typical sulfides electrolytes. The ionic
conductivities are summarized from refs. [32, 51, 53, 60, 73]

melting point and followed by quickly cooling to below Tg, which have chemically

distinct from mechanically deformed materials. For example, Na2S-GeS2 and

Na2S-P2S5 have been prepared by melt-quenching with mechanical milling followed

by alloying, respectively.[106, 107] Differently, glass-ceramic electrolyte needs to

17
be prepared by crystallization of glass precursor. For instance, the cubic and

tetragonal Na3PS4 can be fabricated by heating Na2S-P2S5 at 270 oC and 420 oC,

respectively.[32, 106] And Na3P1-xAsxS4 has been synthesized by ball milling of

Na2S, P2S5 and As2S5 powders, followed by heating the cold pressed pellet at 270 °C

for 2h.[73] Similarly, Na3SbS4 was fabricated by melting Na metal, Sb and S with

stoichiometric proportion for sequential solid-state reaction, in which the final product

was obtained by ball milling of resultant ingot.[33] Besides, the synthesis of

Na3PSe4 from well-mixed Na2Se, red phosphorus and Se powder with stoichiometric

ratio can be performed in a boron nitride tube at a synthesis temperature of 300 °C

under a continuous flow of dry argon gas.[51]

2.4 Polymers

Compared to inorganic solid electrolytes, the solid polymer electrolytes have several

advantages, such as mechanical flexibility, light weight, low cost, convenience of

fabrication process, and accommodation of volume changes of electrodes during

charging/discharging, which have been extensively studied for all-solid-state Na

batteries. The early Na-ions polymer electrolyte was started from dissolving Na salt

in polyethylene oxide (PEO) solvent to form cations and anions, in which Na cations

were solvated by polymer chains and became movable through the connected

chains.[113] The ions transportability within electrolyte has been significantly

affected by the number of free Na cations and their moving ability along polymer

chains. However, the high ionic conductivity at room temperature is still difficult to

be achieved for polymer electrolytes, as the sufficiently amorphous chain segments

18
for ion transport can only be obtained above Tg of polymers.[114] So most of

polymer electrolytes based solid-state batteries need to be operated at elevated

temperature of 60-80 oC, which is close to the melting temperature of Na metal (90 oC)

and may cause safety issues of solid-state Na metal batteries. So far, the PEO,

poly(vinyl pyrrolidone) (PVP), polyvinyl alcohol (PVA), polyacrylonitrile (PAN),

poly(trimethylene carbonate) (PTMC), poly(ethylene glycol) (PEG), and poly(ionic

liquid) have been explored as host solvent for dissolution of Na salt for polymer

electrolytes.[57, 74, 114-119] As gel polymer electrolytes are prepared by adsorbing

liquid electrolyte into polymer frameworks, which are not solid electrolytes and no

longer to be discussed here.

Besides single polymer as solvent, the composite electrolytes combining with other

organic polymers have been proposed to improve ionic conductivities and

electrochemical stabilities. For example, PEO electrolyte blended with

succinonitrile (SN), PVP and PANI have been employed as polymer composite

electrolytes.[77, 120-122] Besides, organic-inorganic composite electrolytes have

also been prepared by dispersing inorganic fillers into polymer matrix in proportion,

in which the fillers can be categorized into inert ceramic powders (AlCl3, BaTiO3,

CuO, SiO2, ZrO2, TiO2) and ionic conductors (NASICON).[61, 76, 78, 123-126] It

has been demonstrated that not only the ionic conductivity, but also the mechanical

property and interfacial stability between polymer electrolyte and electrode can be

improved greatly by synergistic effect of polymers and inorganic fillers in composite

electrolytes.[76] Furthermore, the enhancement of ionic conductivity should be

19
originated from the low crystallinity with decreased Tg of polymer electrolyte

(reduced by adding nanosized fillers), high ionic transfer number with decrease of

activation energy, and high interfacial ionic conductivity (increased by ions adsorb on

high surface of fillers).[31] Thus, the particle size, surface areas and content of

fillers are critical factors to increase the conductivity of composite electrolytes. The

mechanical property of composite electrolyte was mainly improved by fillers that

acting as a support matrix to retain solid structure, even at high temperatures.

Moreover, the electrochemical window and thermal stability of composite electrolytes,

and cycling stability of all-solid-state Na batteries can be increased simultaneously.[61,

127] However, there are several problems still need to be solved in composite

electrolytes, especially the agglomeration of fillers when the concentration exceeds a

critical value, and the reduced flexibility caused by interactions between fillers and

polymers.[76]

-1

-2 PEO12-NaFSI-40%Na3.4Zr1.8Mg0.2Si2PO12

PEG10-NaI PEO15-NaFNIFS
-3
log[(S cm )]

PEO-NaClO4-5%TiO2
-1

PAN-NaCF3SO3
-4
PVP-NaClO3
PTMC5-NaTFSI
-5

-6
PEO/PVP-NaF PEO8-NaPF6
-7
PVA-NaF
-8
2.4 2.6 2.8 3.0 3.2 3.4
-1 -1
1000T (K )
Fig. 8 Temperature-dependent ionic conductivities of polymer electrolytes and composite
electrolytes. The ionic conductivities are summarized from refs. [31, 57, 59, 61, 74, 116-118, 120,
126]

20
The Na-ions polymer electrolytes have ionic conductivities in the range of 10-5-10-7 S

cm-1 at room temperature, which are not sufficient for operating all-solid-state Na

batteries (Fig. 8). The earliest PEO-NaClO4 showed ionic conductivity of 3.1 × 10-6

S cm-1 at 60 °C with EO/Na+ molar ratio of 12:1.[115] Then PEO-NaPF6 has ionic

conductivity of 5 × 10-6 S cm-1 with EO/Na+16.[122] Afterwards, PEO electrolytes

with different Na salts, including NaCF3SO3, NaFeF4, NaLaF4, NaAsF6, NaTFSI, and

NaFSI have been proposed, while ionic conductivities were still at the low level.[31,

75, 79, 113, 128] Recently, Na[(FSO2)(n-C4F9SO2)N] (NaFNFSI)-PEO with

EO/Na+ = 15 exhibits a high ionic conductivity of 3.36 × 10-4 S cm-1 at 80 °C and can

be applied in all-solid-state Na batteries with sufficient thermal stability and wide

electrochemical window (≈ 4.87 V vs. Na+/Na).[59] Furthermore, a family of

fluorine-free Na salts, including sodium pentacyanopropenide (NaPCPI), sodium

2,3,4,5-tetracyanopirolate (NaTCP) and sodium 2,4,5-tricyanoimidazolate (NaTIM)

have been investigated, in which PEO-NaTCP shows highest ionic conductivity of

1.24×10-3 S cm-1 at 70 °C with high thermal stability and large electrochemical

stability window (up to 5 V vs. Na+/Na).[58]

It has been demonstrated that the ionic conductivities can be improved in composite

electrolytes. For example, a composite polymer electrolyte comprising of 50%wt

PEO-50%wt SN with sodium-triflate (NaCF3SO3) salt exhibits the ionic conductivity

of 1.1×10-4 S cm-1 at room temperature.[77] Furthermore, PEO-PVP with NaF and

PEO-PANI with NaClO4 show ionic conductivities of 1.2×10-7 and 2.0×10-5 S cm-1 at

room temperature, respectively.[120, 121] For organic-inorganic composite

21
electrolytes, PEO20-NaClO4-5wt.% TiO2 shows a higher ionic conductivity of

2.62×10-4 S cm-1 at 60 oC than that of pure PEO-NaClO4 with 1.34×10-5 S cm-1.[61]

Also PEO70-(NaHCO3)30-12wt.% SiO2 and PEO20-NaClO4-5% SiO2-70%

1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide (Emim FSI) composite

electrolytes have ionic conductivities of 2.04×10-5 and 8.0×10-4 S cm-1 at room

temperature, respectively.[129, 130] Furthermore, the high ionic conductivity of

6.96 ×10-5 S cm-1 for PEO25-NaClO4-5 wt.% ZrO2 nanoparticles (4.5 nm) is an order

of magnitude higher than pure PEO electrolyte at room temperature.[125] Recently,

a hybrid solid electrolyte of PVdF-HFP-Na3Zr2Si2PO12-liquid electrolyte has been

prepared with high ionic conductivity of 1.2×10-4 S cm-1 at 0 oC, and solvent-free

PEO12-NaFSI-Na3Zr2Si2PO12 and PEO12-NaFSI-Na3.4Zr1.8Mg0.2Si2PO12 composite

electrolytes using NASICON nanoparticles as fillers show highest value of 2.2×10-5 S

cm-1 and 4.4×10-5 S cm-1 at room temperature, respectively.[126, 127] Beside ionic

conductivity, the thermal stability, cation transference number, flexibility and

mechanical strength can also be enhanced in organic-inorganic composite electrolytes,

which are beneficial for operating all-solid-state Na battery at elevated temperature.

Besides PEO based electrolytes, other Na-ions polymer electrolytes with high ionic

conductivities have also been explored. For instance, the ion conductivity of

PAN-24 wt.% NaCF3SO3 can be up to 7.13×10-4 S cm-1 at room temperature with low

activation energy of 0.23 eV.[117] The PVA-30wt.% NaBr has ionic conductivity of

1.362×10-5 S cm-1 at 40 oC.[131] And for PVP polymer with different Na salts of

NaClO3 and NaClO4, the ionic conductivities at room temperature were not high as

22
that of other polymers.[74, 115] Recently, a hierarchical poly(ionic liquid)-based

polymer electrolyte that synthesized via in-situ polymerizing method has high ionic

conductivity of 1.1510-3 S cm-1 at room temperature.[119]

The polymer electrolytes are usually fabricated by solution-casting method, in which

polymer host and Na salt are dissolved in organic solutions and then poured in PTFE

molds for film formation.[31, 132] Also the solvent-free hot pressing technique is

effective to make polymer electrolyte film.[58] Furthermore, a cellulose blended

NaClO4/PEO polymer electrolyte has been synthesized by combining solution-casting

and hot-pressing method, which can improve mechanical properties without

hampering ionic conductivity and thermal stability.[133] For poly(ionic liquid)

based solid electrolyte, the flexible film has been prepared by in-situ polymerization

of precursor solution, which exhibits satisfied thermal and electrochemical stabilities,

inherent incombustibility, good mechanical strength and excellent flexibility.[119]

2.5 Others

As illustrated above, organic polymer electrolytes with high amorphous state can offer

high ionic conductivity. However, the crystalline organic solid electrolytes can also

be applied as fast Na-ions conductors. For one thing, a co-crystalline

NaClO4-(DMF)3 (dimethylformamide) organic electrolyte with hexagonal structure

_
(space group P62c) can offer linear channels of Na+ and ClO4- in crystallographic c

direction and exhibit high ionic conductivity of 3×10-4 S cm-1 at room temperature

with low activation barrier of 25 kJ mol-1 (Fig. 9), which was caused by fast ions

diffusions through bulk crystal as well as grain boundary.[134] Furthermore, the

23
co-crystalline electrolyte can be melted between 55~65 oC with no decomposition,

and reversibly returned to solid state after cooling, which are beneficial for

penetration of electrolyte into electrodes and improving battery performances, when

the battery was treated with liquid NaClO4(DMF)3 at melting state. For another, the

plastic crystal electrolytes are also developed by dissolving Na salt into a polar

organic molecular solid, which has ordered crystalline structure at low temperature,

and occurs solid-solid phase transitions at high temperature because of various

rotational/orientational motions and increase in entropy (the solid-state closer to

liquid-state with freedom and facile dynamics).[135] Thus, the plastic crystal solid

electrolyte has high ionic conductivity with high thermal and mechanical stabilities.

For example, plastic crystal electrolyte of uccinonitrile (N≡C(CH2)2CH2-C≡N, SN)

with 5 mol% NaPF6 and 5 mol% NaClO4 exhibit high ionic conductivity of 10-3 S

cm-1 at room temperature and high electrochemical window up to 4.8 V vs. Na+/Na,

respectively.[136] More recently, a new plastic crystal electrolyte of

N-methyl-N-methyl-pyrrolidinium dicyanamide [C1mpyr][N(CN)2]-Na[N(CN)2]

shows ionic conductivity of 10-4 S cm-1 at 80°C, and N-ethyl-N-methylpyrrolidinium

tetrafluoroborate [C2mpyr][BF4]/PVDF composite fiber prepared by

co-electrospinning has ionic conductivity of 10-6 S cm-1 at room temperature.[100,

135] Similarly, a series of trimethylisobutylphosphonium (P111i4) based plastic

crystal electrolyte with different Na salts, such as P1i444-NaNTf2 and P1i444-NaFSI

have been explored, in which P1i444-20 mol% NaFSI has a high ionic conductivity

near 10-3 S cm-1 at room temperature.[137]

24
 0
Na2B12H12 Na2(B12H12)0.5(B10H10)0.5
-1 Na2B10H10
SCN-NaPF6
-2
Na (BH4)0.5(NH2)0.5 DMF-NaClO4

log[(S cm )]
-3
-1
-4 (Na2B10H10)0.25(Na2B12H12)0.75
Na3OBr
-5
-6
-7 Pli444FSI-NaFSI

-8
1.5 2.0 2.5 3.0 3.5 4.0
-1 -1
1000T (K )
Fig. 9 Temperature-dependent ionic conductivities of crystalline organic solid electrolytes,
Na-rich anti-perovskites and Na-borohydrides solid electrolytes. Two lines for Na2B12H12 and
Na2B12H12 represent the heating-cooling processes. The ionic conductivities are summarized from
refs. [62, 64, 65, 134, 136-139]

Besides, other inorganic solid electrolytes, like Na-rich anti-perovskites and

Na-borohydrides have also been proposed (Fig. 9). The Na-rich anti-perovskites of

Na3OX (X=Cl, Br, I) have large structural tolerance, in which the ionic conductivity

can be improved by divalent alkali-earth metal doping, non-stoichiometric mixtures

and mismatch substitution, which can be up to 10-3 S cm-1 at about 200 oC.[62]

Furthermore, the uniform and high compact Na3OBr solid electrolyte has been

obtained by SPS, accompanying by lower amount of pores when compared to

cold-pressed sample.[140] Moreover, the interfacial impedance and activation

energy can also be reduced. However, the unreacted NaBr impurity still exist in

main phase of cubic Na3OBr and thus, the bulk conductivity of Na3OBr is low (10-7 S

cm-1 at 180 oC), which needs to be further improved.

The Na-borohydrides composed of Na+ as center and borohydrogen anions as

surrounds have also been demonstrated as Na-ions conductors.[141, 142] Based on

25
NaBH4 (Fm-3m; a0 = 0.61571 Å) and NaNH2 (Fddd; a0=0.89613Å, b0=1.0454Å,

c0=0.80727Å), Na(BH4)-Na(NH2)-NaI and Na(BH4)0.5(NH2)0.5 composite electrolytes

exhibit the ionic conductivity of 10-6 S cm-1 at room temperature, respectively,

originating from specific anti-perovskite structure with vacancies in Na site.[139]

And as structural transition from low-temperature monoclinic to high-temperature

cubic phase, the Na2B12H12 has fast Na+ diffusion with superior conductivity of 0.1 S

cm-1 around 250 oC (Fig. 9).[143, 144] Similarly, the disordered Na2B10H10 with fcc

phase above 80 oC exhibits a higher ionic conductivity than Na2B12H12 and a favorable

air-stability at room temperature.[138] Recently, the pseudobinary

(Na2B10H10)0.25-(Na2B12H12)0.75 composite electrolyte obtained by mechanically

ball-milling shows partial stability and high ions conductivity up to 1.0×10-4 S cm-1 at

room temperature.[64] Also Na2(B12H12)0.5(B10H10)0.5 composite electrolyte with

high ionic conductivity (close to 10-3 S cm-1 at room temperature) demonstrates highly

thermal stability, large electrochemical stability window and good compatibility to Na

metal anode.[64, 65]

3. Interfaces of electrolyte-electrode for all-solid-state Na batteries

As both ionic conductor and separator, the solid electrolyte layer is sandwiched

between compressed powder electrode layers (positive and negative electrode) to

fabricate bulk-type all-solid-state Na batteries (Fig. 1), in which electrode layers are

composed of active materials and solid electrolyte. Accordingly, Na ions diffuse

from active material to solid electrolyte by migration across the interface, and

electrons transfer from active material to collectors through conduction paths of

26
conductive additive (acetylene black in electrode layers). Based on various solid

electrolytes that discussed above, all-solid-state Na batteries can be classified as

inorganic solid-electrolyte batteries and organic solid electrolyte batteries. Although

inorganic solid electrolytes exhibit high ionic conductivity, wide electrochemical

window, and high safety and thermal stability, the corresponding all-solid-state

batteries still have several challenges: large interfacial resistance between electrode

and electrolyte, poor interfacial compatibility of electrode/electrolyte during volume

change of electrodes (caused by Na+ insertions/extractions), insufficient contact area

with limited ions transport pathways, and low ratio of active material in

electrolyte-electrode composite.[28] Differently, organic solid electrolyte batteries

have the advantages of favorable contact on the interface, high level of safety,

flexibility of shape and size, light weight and simple fabrication. However,

all-solid-state batteries are suffered by poor electrochemical performances at room

temperature with low ionic conductivity of electrolyte, instability of

electrode/electrolyte interface for long cycles, limited operating temperature, and

inferior mechanical stability. For composite solid electrolytes by dispersing

inorganic fillers into polymer electrolytes, the corresponding batteries can also be

seen as organic solid electrolyte batteries, in which the overall performances could be

enhanced by improving ionic conductivity, electrochemical window,

thermal/mechanical stability and interfacial stability between electrolyte and

electrode.[36, 126, 145] Therefore, for all-solid-state Na batteries, besides high

ionic conductivities of solid electrolytes, the intimate contact with large area for

27
sufficient ions conduction at electrode-electrolyte interface, and mechanical/structural

stability of interfaces are critical factors for improving the electrochemical

performances.

The cathode materials that used in all-solid-state Na batteries are similar to that of

liquid-electrolyte based batteries, such as sodium layered metal oxides (NaCoO2,

Na2/3[Fe1/2Mn1/2]O2, Na0.67Ni0.33Mn0.67O2, NaCu1/9Ni2/9Fe1/3Mn1/3O2),

NASICON-related phosphate (Na3V2(PO4)3, NaTi2(PO4)3) and sulfide (TiSx). The

most common anode materials are Na metal and Na alloy.[32, 40, 59, 63, 64, 126,

146-151] Thus, the interfaces in all-solid-state Na batteries are involved into

cathode/electrolyte interface and metal anode/electrolyte interface. In this section,

several approaches for forming interfaces and enhancing contact areas between

electrolyte and electrode are discussed, in which the architectures of all-solid-state

batteries as well as electrochemical performances are also demonstrated.

3.1 Cathode/electrolyte interface

As most of cathodes are composed of powder materials for bulk-type solid-state Na

batteries, the poor interfacial contact between electrolyte and cathode has negative

effect on the performances of solid-state batteries. So far, there are many strategies

for forming intimate interfaces, which can be classified into to following aspects.

Composite cathode from active material and electrolyte

The common approach to fabricate the interfacial contact is preparing composite

cathode that mixed by active material and electrolyte, which have been widely

adopted in both inorganic and organic solid electrolytes batteries (Fig. 10a). For

28
inorganic solid electrolyte, the nanocomposite can be obtained by mechanical milling

process. For example, the composite cathode consisting of Na3V2(PO4)3 (NVP) and

Na3Zr2Si2PO12 (NZSP) has been prepared by ball-milling, and the all-solid-state

symmetric NVP-NZSP/NZSP/NVP-NZSP batteries showed favorable discharge

capacity at room temperature and high reversibility at elevated temperature (200

o
C).[148] For sulfides electrolytes, the Na3PS4-Na2S-C composite cathode was

prepared by mechanical milling of Na3PS4, Na2S and acetylene black in a stainless

steel pot under an Ar atmosphere.[152] Using NaSn alloy as negative electrode, the

all-solid-state Na-S battery exhibited a high reversible capacity of 869.2 mAh g-1 with

an excellent cycling stability and rate capabilities at 60 oC. Also the solid-state

battery with well-mixed TiS2/Na3PS4 nano-powders as composite cathode and Na-Sn

alloy as anode showed an average discharge voltage of 1.6 V and reversible capacity

of 90 mAh g-1 for 10 cycles.[32] Moreover, the composite electrodes prepared for

(TiS2-Na3.75Sn0.75Sb0.25S4)/Na3.75Sn0.75Sb0.25S4/Na-Sn all-solid-state Na batteries

demonstrate high capacity of 201 mAh g-1 with excellent reversibility. Similar

process based on Na3PS4 have been achieved in all-solid-state

NaCrO2/Na3PS4/Na15Sn4 battery, which can retain about 60 mAh g-1 for 15 cycles at

room temperature.[153] Furthermore, the composite cathodes based on

94Na3PS4-6Na4SiS4, Na3-xPS4-xClx (x=6.25%) and Na3+xMxP1-xS4 (M =Ge4+, Sn4+)

(x=0, 0.1) solid electrolytes have also been explored for all-solid-sate Na-ion batteries,

demonstrating sulfide electrolytes have great merits for decreasing grain boundaries

and making favorable solid-solid contacts by cold pressing without hot treatment.[109,

29
111, 112] Even for Na-borohydrides electrolytes, the composite cathode can be

prepared by mixing TiS2 and Na2B10H10-Na2B12H12, and the corresponding

all-solid-state battery shows a high initial charge capacity (237 mAh g-1) with stable

cycling stability.[64]

For the fabrication of composite electrode, the heterogeneous inorganic solid

electrolyte powders and active material are firstly physically/mechanically mixed

(may cause the aggregation of each component), followed by cold-pressing, which is

not enough to form void-free dense composites with intimate contact, or not sufficient

for improving the electrochemical performances of all-solid-state batteries.

Fortunately, for organic solid electrolyte, the composite cathode can be prepared by

well mixing of active materials and polymer electrolytes in the solvent. For example,

by fabricating the cathode sheets with mixing of NaCu1/9Ni2/9Fe1/3Mn1/3O2 (65wt.%),

super P (10wt.%), NaFNFSI-PEO (EO/Na+=15) SPE (20wt.%), and PVDF (5wt.%) in

a quantitative acetonitrile under strong agitation, the composite

cathode/NaFNFSI-PEO/Na all-solid-state battery can afford high initial reversible

capacity (122.4 mAh g-1 at 0.1C), good cycling performance (capacity retention of 70%

after 150 cycles at 1C), and excellent rate capability.[59]

Wetting agent on the interface

Besides solid composite electrode, the organic liquid electrolyte and ionic liquid have

been applied as wetting agent to enhance the tight contact between cathode and solid

electrolyte (Fig. 10b). As liquid electrolyte is unstable at high temperature, the ionic

liquid is preferably to be adopted because of nonflammability, nonvolatility, high

30
thermal and electrochemical stability. For instance, a small amount of

N-methyl-N-propylpiperidinium-bis(fluorosulfonyl) imide (PP13FSI) ionic liquid has

been used at cathode side of Na3V2(PO4)3/IL/Na3+xZr2-xLaxSi2PO12/Na all-solid-state

battery, which has low interfacial resistance (close to the battery added with liquid

electrolyte) and exhibits an initial charge capacity of 116 mAh g-1 under a current of

0.2 C at room temperature, and high capacity of 90 mAh g-1 after 10 000 cycles at 10

C with full reversibility.[126] More recently, a toothpaste-like cathode by using

Na0.66Ni0.33Mn0.67O2 and N-Alkyl-N-methylpyrrolidinium-bis(fluorosulfonyl)imide

(PY14FSI) ionic liquid has been synthetized via non-sintered method for improving

the contact area (between cathode and Na-β’’-Al2O3 ceramic pellet) and ionic transfer

in all-solid-state Na batteries, which deliver a capacity of 80 mAh g-1 in voltage range

of 2.5-3.8 V at 0.1C, superior stability with capacity retention of 90% after 10 000

cycles at 6 C, and thermal stability with capacity of 79 mAh g-1 at 70 °C.[147]

Surface coating of active material by electrolyte

Another effective approach for forming intimate interface is surface coating of active

material particles by thin films of solid electrolytes (Fig. 10c). For example, the

solid-liquid interfaces can be achieved by heating glass electrolytes at around glass

transition temperature, followed by favorable contacts after cooled down to room

temperature. Furthermore, besides heating-cooling process, the solution-processed

solidified Na3SbS4 coating on NaCrO2 nanoparticles have been proposed as cathodes,

which provide intimate ionic contact for improving the utilization of active material in

all-solid-state batteries over conventional mixed electrodes.[33] With much more

31
uniform distributions of solid electrolytes with active materials, the solid-state battery

based on Na3SbS4-coated NaCrO2 shows discharge capacity of 108 mAh g-1, which is

almost the same value as that of liquid-electrolyte battery.

Interlayer/interphase between electrode and electrolyte

It has been demonstrated that the interfacial resistance can be reduced by making

interlayer/interphase for ions transports between solid electrolytes and cathodes. For

instance, a plastic-crystal electrolyte interphase consisting of SN and NaClO4 has

been introduced to enhance the interfacial contact between Na3Zr2(Si2PO12) pellet and

Na3V2(PO4)3 cathode.[63] As shown in Fig. 10d, like liquid electrolyte, all the

active

(a) (b) (c)

active material wetting agent solid electrolyte

(d) (e) (f)

interlayer/interphase composite electrolyte nanofiber film

Fig. 10 Strategies for the formation of interfaces between cathodes and solid electrolytes by (a)
composite cathode, (b) wetting agent, (c) coating by electrolyte, (d) adding interlayer, (e)
composite electrolyte, and (f) nanofiber film of cathode. The solid electrolytes that marked in
dash lines in (e) and (f) are not essential for fabrications of all-solid-state batteries.

particles of cathode can be surrounded by plastic-crystal electrolyte, in which the

32
stable contact can be kept between cathode and electrolyte, especially for volume

changes during Na ions insertions/extractions. Therefore, all-solid-state

Na3V2(PO4)3-Na3Zr2(Si2PO12)-NaClO4-SN/Na3Zr2(Si2PO12)/Na battery exhibited

charge capacity of 115 mAh g-1 and discharge capacity of 112 mAh g-1 with a slight

polarization of about 30 mV, and cycling stability for 100 cycles at 1 C with 98% of

initial capacity.

Composite electrolyte

Taking the advantage of both inorganic ceramics and organic polymers, the composite

electrolytes have been proposed to provide improved ionic conductivity with high

flexibility for reducing the interfacial resistances between solid electrolytes and

electrodes (Fig. 10e). For instance, using

Na3Zr2Si2PO12-PVdF-HFP-NaFSI-TEGDME hybrid solid electrolyte (HSE), the

NaFePO4/HSE/Na all-solid-state battery shows discharge capacity of 131 mAh g-1

and 2% irreversible charge capacity at initial cycle, and the NaFePO4/HSE/hard

carbon full battery has an average voltage of 2.6 V, a discharge capacity of 120 mAh

g-1 at 0.2 C and good capacity retention of 96% after 200 cycles.[127] Surprisingly,

for the solvent-free Na3Zr2Si2PO12 and Na3.4Zr1.8Mg0.2Si2PO12-PEO-NaFSI composite

polymer electrolyte (CPE), the Na3V2(PO4)3/CPE/Na all-solid-state battery delivers a

reversible capacity of 106 mAh g-1 with an initial coulombic efficiency of 94.0% at

0.1 C, and a superior cycling stability without obvious capacity loss after 120

cycles.[126]

Structural design of electrode and battery

33
The structural design of electrode and battery are also effective approaches for

making intimate interfaces of solid electrolytes and cathodes. For example, the

Na3V2(PO4)3 nanofibers with 3D network structure has been fabricated for offering

short diffusion pathways of fast ions transport, high surface area for interfacial contact

between electrode and electrolyte, structural stability to avoid the agglomeration, and

high packing density when compared to particle materials (Fig. 10f).[149] Thus the

Na3V2(PO4)3/PEO-NaClO4-Al2O3/Na all-solid-state battery shows a high reversible

capacity of 107 mAh g-1 at 0.2C and excellent cycling stability with 87.5% capacity

retained after 1000 cycles at 2C. Moreover, an amorphous TiS3 was applied to make

TiS3/Na3PS4/Na15Sn4 solid-state battery with high discharge capacity of 300 mAh g-1

because of the amorphous structural flexibility and no volume change during Na ions

insertions/extractions.[151]

3.2 Anode/electrolytes interfaces

For all-solid-state Na batteries, the anode/electrolyte interfaces are mainly focused on

the interfacial contact between Na metal/alloy and solid electrolytes with formation of

pathways for fast ions transports, and Na metal should be plated/stripped reversibly

without obvious dendrites. It has been demonstrated that the interfaces are more

stable and intimate between polymer electrolytes and Na anode than that of inorganic

solid electrolytes, where Na dendrite formation is unavoidable and followed by

penetrations of grain boundaries. Moreover, the interfacial contact will not intimate

after volume changes of Na anode thin film over charge/discharge cycles, which

causes the decay of cycling stability. Thus, the interfacial modifications between Na

34
anode and inorganic solid electrolyte are essential to reduce resistance and enhance

the performance of all-solid-state Na metal batteries.

Cold pressing for interfacial contact

For the assembling of all-solid-state Na batteries with electrolyte pellet, Na metal foil

was generally pressed on one side of solid electrolyte under a pressure to make

interfacial contact (Fig. 11a). However, following this cold pressing process, the

interfaces are not intimate and an interval appears between Na anode and solid

electrolytes, which are not favorable for keeping the electrochemical performances of

all-solid-state Na batteries. Furthermore, Na dendrite formation may be much easier

with point contact for interface, where grain boundaries of solid electrolyte pellets

will be penetrated easily and the interval will be enlarged. From a comparative

study on exploring the stability and viability of solid electrolytes against metallic Na

anode, the Na-β”-Al2O3 based battery showed much more stability and interfacial

property, while there was a continuously growing interphase between Na3PS4 and Na

metal, which should be caused by interfacial kinetics.[154]

Wetting by liquid electrolyte or melting Na

Similar to cathode/electrolyte interface, the organic liquid electrolyte can be used as

wetting agent to enhance interfacial contact between Na anode and solid electrolyte at

room temperature (Fig. 11b). The stability at high temperature is still need to be

improved. Besides, it is supposed that liquid Na metal could be an ideal electrode

for the complete connection with much lower polarization with solid electrolyte.

However, it was not real in the high temperature Na/β”-Al2O3/S system.[155]

35
Furthermore, the surface of inorganic electrolytes can also be wetted by liquid

metallic Na to decrease the interfacial resistance at high temperature, however, the

inhibition of dendrite formation during battery cycling are not improved. More

worse, the solid electrolytes, like NASICON-type ceramics, have a low stability and

element was easy to be reduced when in contact with molten Na.[156]

(a) (b)

Na metal Na metal

(c) (e)

Na metal Na metal

Fig. 11 Strategies for the formation of interfaces between Na anode and solid electrolytes by (a)
cold pressing, (b) wetting agent, (c) adding interlayer, and (d) surface coating.

Interlayer between anode and electrolyte

The interlayer can be added or formed for ions transports between Na anode and solid

electrolytes to reduce the interfacial resistance and enhance the contact (Fig. 11c).

The polymer electrolyte layer with sufficient ions transport pathways has been used to

improve solid-state battery performances. For example, a dry Na+ conductive

polymer layer of cross-linked poly(ethylene glycol) methyl ether acrylate (CPMEA)

has been added between Na metal and solid electrolyte, and all-solid-state

NaTi2(PO4)3/CPMEA/NASICON/CPMEA/Na battery shows high capacity of 102

mAh g-1 for 70 cycles at 0.2C at 65 °C with high coulombic efficiency, indicating that

interface interstitial layer has a good capability for dendrite suppression.[156]

36
Furthermore, another interface interstitial layer has been in-situ created by heating Na

metal at 380 oC on the surface of NASICON pellets (H-NASICON).[156] Although

the surface of NASICON was partially reduced, the in-situ formed black interlayer

was amorphous and can be used as Na+ conductive thin layer. Therefore, from better

wetting and adhesion across Na/H-NASICON interface, the resistance of

Na/H-NASICON/Na is obviously lowered from 4000 to 400  cm-2, and

all-solid-state NaTi2(PO4)3/H-NASICON/Na battery exhibited high capacity of 110

mAh g-1 at 0.2 C for first 25 cycles and 75 mAh g-1 at 1 C during following 35 cycles.

Besides ionic conductor, the electronic additive can also be used as buffer layer to

reduce the resistance between anode and solid electrolyte. With addition of

nano-carbon material AB to anode, the increase of resistance (caused by Na15Sn4)

after charge process can be restricted, and rate performance of solid-state

a-TiS3/Na3PS4/Na15Sn4 battery can be improved simultaneously.[157]

Surface coating

The surface coating is an effective approach to make intimate contact between

cathode and solid electrolyte, which can also be used for Na anode (Fig. 11d).

However, there is little report on this aspect in all-solid-state Na battery, which has

been applied in liquid-electrolyte batteries and solid-state Li batteries. For example,

a deposition of Al2O3 thin layer on Na metal via low-temperature plasma-enhanced

atomic layer deposition (PEALD) can effectively prevent further reaction of Na metal

with electrolyte and suppress dendrite growth, which are favorable for the

improvement of electrochemical performance in liquid electrolyte based Na

37
batteries.[158] Furthermore, the molecular layer deposition (MLD) for protection of

Na anode in carbonate-based electrolyte was developed to form an inorganic-organic

hybrid coating layer on anode surface, which is mechanically flexible and chemically

stable for repeated Na plating/stripping on surface of Na anode.[159] Thus, this

approach can be adopted for interfacial treatment by combining melting Na in

solid-state batteries, in which the electrochemical performances could be improved.

4. Conclusions and perspective

The rechargeable Na based batteries have been proposed as the promising alternative

of Li based batteries because of low cost and high abundance of Na resources in

Earth’s crust. And the all-solid-state Na batteries based on solid electrolytes are

more preferable for large-scale energy storage owing to high safety and stability better

than the liquid electrolyte with inflammability and explosive. So far, various

Na-ions solid electrolytes have been developed, including the β/β’’-Al2O3, NASICON,

sulfides, polymers, crystalline organic solid electrolytes, anti-perovskites and

borohydrides. Among these, the inorganic solid electrolytes such as

Na-β/β’’-Al2O3 and NASICON, show higher ionic conductivities and relative

stabilities at room temperature, but are still suffered by the poor compatibility to the

electrode materials. Although the sulfides exhibit high ionic conductivity and soft

interfaces with electrodes, the poor chemical stabilities in the air are not beneficial for

the battery performances. The polymer have the mechanical flexibility and good

interfacial compatibility, however, the long cycling stability of all-solid-state Na

batteries cannot be achieved as the low ionic conductivities at room temperature, and

38
the poor interfacial and electrochemical stabilities during charging/discharging.

Therefore, the applications of all-solid-state Na batteries are still hindered by

deficiencies of solid electrolytes and untight contacts with large interfacial resistances

between electrodes and solid electrolytes, which play crucial effect on the total battery

performances (Fig. 12).

The challenges of low ionic conductivity, weak electrochemical stability and poor

mechanical property of solid electrolytes can be overcome by several methods. For

one thing, the structural integration for the materials design as an effective way should

be firstly taken into attention. For inorganic solid electrolytes, the ionic

conductivities and electrochemical stabilities can be improved by substitution or

dopants. For example, the ionic conductivities of NASICON can be increased by

dual elements doping. Similarly, the ionic conductivities of sulfides can be

improved by substituting different anion species and adding Na oxides/sulphur, which

can increase the Na concentration and the decrease the activation energy for ions

transports. However, increasing the amount of network modifiers with Na

compounds may facilitate the crystallization of glass, which are not favorable for the

increase of ionic conductivity. Furthermore, the instability of sulfides electrolytes in

the air, that is, the H2S gas generation should be suppressed by partial substitution of

oxygen for sulfur in sulfides. For polymer electrolytes, the ionic conductivities at

room temperature can be increased by blending, copolymerization and cross-linking

with molecular chains. Besides, the composite polymer electrolytes by combining

organic polymer and inorganic fillers seem to be more effective to improve the ionic

39
conductivities and mechanical properties. For another, the fabricating process of

solid electrolytes should be optimized. It has been considered that for the inorganic

electrolytes, the SPS technique can make high density ceramic pellet with high ionic

conductivity at room temperature. However, mechanical properties of solid

electrolytes with low elastic modulus and high ductility to the electrodes are preferred

to be achieved by fabrication process. Thus the new technique for the synthesis of

solid electrolytes should be proposed in the future. And the in-situ polymerization

should be more adopted for preparing the polymer electrolytes, no matter the single or

composite electrolytes. Last but not least, the new solid electrolytes with proper

structures and superior properties should be designed by combining the theoretical

calculations, experimental investigations and advanced characterizations. Thus, not

only the intrinsic properties should be increased, but also the understanding of ions

transport mechanism should be further explored.

N-I-I: Na/ISE interface

N-O-I: Na/OSE interface

Na N-C-I: Na/CSE interface

C-I-I: Cathode/ISE interface

C-O-I: Cathode/OSE interface

C-C-I: Cathode/CSE interface

Fig. 12 Different solid electrolytes and the interfaces between electrodes and solid electrolytes in
all-solid-state Na batteries.

40
Another big challenge for developing all-solid-state Na batteries is the interfacial

issue, especially the large interfacial resistance and poor compatibility between

electrode and electrolyte (Fig. 12). Moreover, the electrodes suffer volume change

during Na+ insertions/extractions, which cause the insufficient contact area with

reduced ions transport pathways and poor cycling stabilities of batteries. The

interfacial stability is very important for the configurations and operations of

all-solid-state batteries. Thus, the intimate contact, sufficient/fast ions transport

pathways, and mechanical/structural stability at the electrode-electrolyte interface are

crucial for improving the battery performances. Several approaches are effective to

form the favorable interfaces of the cathode/electrolyte, like composite materials from

active material and electrolyte, wetting agent on the interface, surface coating by

electrolyte, interlayer/interphase, composite electrolyte and structural design of

electrode. As the contact is rigid between cathode and inorganic solid electrolytes, a

wetting agent and soft thin interlayer/interphase with high ions diffusions and

stabilities are preferable to offer high interfacial stability and fast diffuse rate of ions

across the interface, which are beneficial for improving the battery performances.

Besides, the solid electrolytes with low elastic modulus, the active materials with

small volume changes during charge/discharge, the nanosized particles with short ions

diffusion pathways are also instructive to improve the battery performances. For

the polymer electrolytes batteries, the interfacial issues are much easier to be solved.

In addition, for the interfaces between Na anode and electrolytes, the interlayer

between them are considered to be more effective to reduce the resistance. However,

41
the formation of Na dendrite are still not fully restrained or eliminated, and the anode

protection still needs to be achieved by suitable approaches. Thus, further research

is required to make intimate interfaces with high stabilities between electrodes and

solid electrolytes to construct the high performance all-solid-state Na batteries.

Besides the electrolytes and interfacial issues that fully discussed in this review,

some other aspects, like the fundamental understanding of the ions transports

mechanisms in both the interfaces and the bulk batteries during the charge/discharge,

and the battery constructions that consisting of composite cathodes, solid electrolytes

and Na metal anode, are need to be further explored for all-solid-state Na batteries.

The ions transports on the interfaces are much more critical for understanding the

interfacial process and enhancing the electrochemical performances of all-solid-state

Na batteries. And experimental and theoretical calculation approaches are preferred

to be combined for further development. The design of battery construction is also

important for optimizing the performances of all-solid-state Na batteries. Besides

the conventional techniques, the integration of composite cathodes by SPS and 3D

printer, are considered as the advanced fabrication methods to design optimum

microstructures for all-solid-state batteries. Thus, much more research on

all-solid-state batteries are still needed for the deeper understanding of fundamental

mechanism and accelerating its process of the practicality.

Notes

The authors declare no competing financial interest.

ACKNOWLEDGMENTS

42
We are grateful for the financial support of the Beijing Natural Science Foundation (B)

(KZ201610005003), National Natural Science Foundation of China (Grants 51622202,

U1507107, 21503009 and 21603009), the National Key R&D Program of China

(Grant No. 2018YFB0104302), Guangdong Science and technology project

(2016B010114001) and the Funding Projects for “Thousand Youth Talents Plan”.

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Wenru Hou is a M.S. candidate at Beijing University of Technology under the
supervision of Prof. Haijun Yu. Her research interests are synthesis and
characterization of the solid electrolytes for all-solid-state lithium and sodium
batteries.

Dr. Xianwei Guo received his Ph.D. from Institute of Physics, Chinese Academy of
Sciences in 2012. He carried out postdoctoral research at Tohoku University (Japan)
from 2012-2016. He is currently an Associate Professor in the College of Materials
Sciences and Engineering, Beijing University of Technology. His expertise and
interest are on high-energy-density Li-air batteries, all-solid-state batteries materials
and devices, and nanoporous materials for energy storage.

Xuyang Shen is a Bachelor candidate at Beijing University of Technology under the

supervision of Prof. Haijun Yu. His research interests are synthesis and
characterization of the solid electrolytes for all-solid-state lithium batteries.

49
Dr. Khalil Amine is a Distinguished Fellow and the Manager of the Advanced
Battery Technology programs at Argonne National Laboratory, where he is
responsible for directing the research and development of advanced materials and
battery systems for HEV, PHEV, EV, satellite, military and medical applications. Dr.
Amine currently serves a member of the U.S. National Research Consul on battery
related technologies. Among his many awards, Dr. Khalil is a 2003 recipient of
Scientific America's Top Worldwide Research 50 Research Award, a 2009 recipient of
the US Federal Laboratory Award for Excellence in Technology Transfer, and is the
five-time recipient of the R & D 100 Award, which is considered as the Oscar of
technology and innovation. In addition, he was recently awarded the ECS battery
technology award and the international battery association award. Dr. Amine holds or
has filed over 130 patents and patent applications and has over 280 publications. From
1998 to 2008, Dr. Amine was the most cited scientist in the world in the field of
battery technology.

Dr. Haijun Yu is a professor at College of Materials Science and Engineering,

Beijing University of Technology (BJUT). He received his Ph.D. in 2007 from
Northeastern University, and then did research work on advanced battery materials
and devices at General Research Institute for Non-ferrous Metals (GRINM) and
National Institute of Advanced Industrial Science and Technology (AIST). His current

50
research interests focus on the advanced electrode materials for
lithium/sodium/aluminum-ions batteries, all-solid-state batteries, novel devices for
energy storage and reaction mechanism.

Dr. Jun Lu is a chemist at Argonne National Laboratory. His research interests focus
on the electrochemical energy storage and conversion technology, with main focus on
beyond Li-ion battery technology. Dr. Lu earned his bachelor degree in Chemistry
Physics from University of Science and Technology of China (USTC) in 2000. He
completed his Ph.D. from the Department of Metallurgical Engineering at University
of Utah in 2009 with a major research on metal hydrides for reversible hydrogen
storage application. He is the awardee of the first DOE-EERE postdoctoral fellow
under Vehicles Technology Program from 2011 to 2013. He is also the first awardee of
IAOEES Award for Research Excellence in Electrochemistry Energy in 2016. He is
the associate editor of ACS Applied Materials and Interfaces. Dr. Lu has
authored/co-authored more than 170 peer-reviewed research articles, including Nature;
Nature Energy, Nature Nanotechnology; Chem. Rev.; Nature Commun.; JACS; etc,
and has filed over 20 patents and patent applications.

Highlights
 The overall picture and intrinsic properties about the present solid electrolytes
of all solid-state sodium batteries are reviewed;
 The effective approaches for forming intimate interfaces between solid
electrolytes and electrodes are emphasized.
 Several possible directions for developing solid electrolytes and improving the
interfacial contacts are suggested as well.

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