Er 3762

INTERNATIONAL JOURNAL OF ENERGY RESEARCH
Int. J. Energy Res. (2017)

Published online in Wiley Online Library (wileyonlinelibrary.com). DOI: 10.1002/er.3762
REVIEW PAPER
Degradation mechanisms in Li-ion batteries: a state-of-

the-art review
M. M. Kabir‡ and Dervis Emre Demirocak*,†
Frank H. Dotterweich College of Engineering, Texas A&M University-Kingsville, TX, USA
SUMMARY
One of the most prominent energy storage technologies which are under continuous development, especially for mobile
applications, is the Li-ion batteries due to their superior gravimetric and volumetric energy density. However, limited cycle
life of Li-ion batteries inhibits their extended use in stationary energy storage applications. To enable wider market
penetration of Li-ion batteries, detailed understanding of the degradation mechanisms is required. A typical Li-ion battery
comprised of an active material, binder, separator, current collector, and electrolyte, and the interaction between these
components plays a critical role in successful operation of such batteries. Degradation of Li-ion batteries can have both
chemical and mechanical origins and manifests itself by capacity loss, power fading or both. Mechanical degradation
mechanisms are associated with the volume changes and stress generated during repetitive intercalation of Li ions into
the active material, whereas chemical degradation mechanisms are associated with the parasitic side reactions such as solid
electrolyte interphase formation, electrolyte decomposition/reduction and active material dissolution. In this study, the main
degradation mechanisms in Li-ion batteries are reviewed. Copyright © 2017 John Wiley & Sons, Ltd.
KEY WORDS
Li-ion batteries; degradation mechanisms; chemical origin; mechanical origin; degradation causes; characterization techniques
Correspondence
*Dervis Emre Demirocak, Department of Mechanical & Industrial Engineering, Texas A&M University-Kingsville, 700 University Blvd
MSC 191, Kingsville, TX 78363 USA.
†
E-mail: dervis.demirocak@tamuk.edu
‡
Kabir.mehdi@gmail.com
Received 23 January 2017; Revised 2 April 2017; Accepted 2 April 2017
1. INTRODUCTION secondary battery technologies that are commercially

available, Li-ion batteries have the highest gravimetric
Recently, energy storage technologies have attracted and volumetric energy density as shown in Figure 1, and
increasing interest given the accelerated worldwide shift they are promising for the future of energy storage
to the renewable energy systems. The global warming and systems. Nevertheless, formidable challenges such as
environmental pollution due to excessive use of fossil fuels, limited cycle life, cost and poor performance in hot and
forthcoming exhaustion of fossil fuel sources and energy cold climates need to be tackled to further the role of
security concerns are the driving motivations behind this Li-ion batteries in energy storage technologies. To achieve
paradigm shift [1]. Energy storage is the key technology this advancement, a better understanding of the
for large-scale utilization of renewable energy sources due degradation mechanisms in Li-ion batteries is required.
to intermittent nature of these sources. The development The degradation in a Li-ion battery often manifests itself
of energy storage technologies is particularly challenging by capacity loss and power fade and can have both chemical
for mobile applications because high gravimetric and and mechanical origins. The interdependent nature of the
volumetric energy density are of paramount importance various degradation mechanisms in Li-ion batteries makes
due to space and weight limitations in mobile platforms. the study of the degradation mechanisms challenging and
Additionally, a novel energy storage technology should often requires the employment of novel in-situ and ex-situ
perform on par with fossil fuel (i.e., gas and diesel) based characterization techniques to elucidate the degradation
systems in terms of cost, cycle life and refueling time to mechanisms at the nanoscale. The most important
ensure widespread market penetration. characterization techniques for understanding the
One of the most important technologies for energy degradation mechanism in Li-ion batteries are in-situ and
storage in mobile applications is batteries. Among different ex-situ transmission electron microscopy (TEM) [4], in-situ
Copyright © 2017 John Wiley & Sons, Ltd.

Kabir M. M. and Demirocak D. E. Degradation Mechanisms in Li-ion Batteries: A State-of-the-Art Review
comparison with the other battery chemistries, because

of their high gravimetric and volumetric energy densities
as well as their low rate of self-discharge. Figure 1
demonstrates the gravimetric and volumetric energy
densities for different battery chemistries [3]. According
to Figure 1, both gravimetric and volumetric energy
densities for Li-ion batteries are nearly two times the
Ni-MH batteries. Given such striking features, Li-ion
batteries have been widely utilized in small portable
devices ranging from consumer electronics and
appliances to medical devices in the last two decades,
such as Bluetooth® headsets, GPS devices, cell phones,
laptops, cameras, hearing aids, and health monitoring
devices.
Figure 1. Comparison of gravimetric and volumetric energy
density for a variety of battery chemistries [2,3] [Colour figure
In addition to portable devices, Li-ion batteries are
can be viewed at wileyonlinelibrary.com] also extensively employed in mobile applications, for
instance: Segway personal transporters, electrical
scooters, electric bicycles, electric vehicles, and a
variety of military and commercial aircrafts to power
atomic force microscopy (AFM) [5], ex-situ X-ray diffraction several of their systems. Some of these large format
(XRD), Raman spectroscopy, X-ray photoelectron batteries are fabricated by means of typical commercial
spectroscopy (XPS), and scanning electron microscopy cells (e.g., Tesla Roadster battery pack). These designs
(SEM) [6,7]. The better understanding of the degradation comprise several parallel cells to construct blocks or
mechanism would lead to prolonged cycle life, development elements which are connected in series. The other kinds
of improved materials as well as help in identifying the of large packs are manufactured via ‘large format cells’,
optimal control strategies to limit degradation. having a capacity range from 10 to 100 Ah. Moreover,
From the foregoing discussion, it should be clear that Li-ion batteries have started to replace the other types of
more concentration and investigation on the degradation battery technologies in aerospace applications. Recently,
mechanisms of Li-ion batteries are required to ameliorate Li-ion battery has been utilized in the aviation industry
the performance and lifetime of such batteries. Hence, the to drive the auxiliary power units (APUs), emergency
principal objective of this study is to identify and delineate lighting system, flight control electronics, and flight
the causes of degradation as well as the degradation modes recorder as an independent power supply. Regarding
recognized to date for each of the main battery space applications, they are also being installed on the
components. In this way, we first provide basic manned mission power supplies, research probes, and
descriptions and fundamentals on Li-ion batteries, satellites [8].
including their application areas, brief comparisons Currently, transportation sector heavily relies on fossil
between Li-ion battery and the other commercial battery fuels, and hydrocarbon-fueled internal combustion engines
types on the basis of energy density and overall are one of the primary sources of greenhouse gas emissions
performance, their key components, and their working (i.e., CO2). Switching from fossil fuel-based vehicles to
principle. In the second section, degradation mechanisms hybrid electric vehicles (HEV), plug-in hybrid electric
will be classified and explained in detail. In the third vehicles (PHEV), and electric vehicles (EV) can help
section, we will give an overview of the Li-ion battery mitigating global warming and can reduce air pollution
degradation modes and discuss each of them in detail. In especially in metropolitan areas. Therefore,
Section 4, a summary of primary causes that can expedite electrochemical energy storage systems (EES), in
the whole-cell battery aging is introduced. Finally, a brief particular, Li-ion batteries can play a vital role in achieving
review on the main in-situ and ex-situ characterization this objective. The Ragone plot shown in Figure 2
techniques used for experimentally investigating Li-ion illustrates the trade-off governing the power density and
batteries will be presented. the energy density for several EESs such as
supercapacitors, fuel cells, and batteries. The specific
1.1. Li-ion batteries, applications, power and specific energy can be interpreted as the
comparison with other battery technologies acceleration and range of the vehicle, respectively [9,10].
According to Figure 2, Li-ion batteries exhibit the highest
A glance at the periodic table reveals that lithium is the power and energy density among other battery chemistries.
lightest solid element and thus highly electropositive. Currently available Li-ion battery chemistries can satisfy
Lithium’s ionic and atomic radii are rather small and the United States Advanced Battery Consortium (USABC)
can be employed to build electrochemical batteries targets for HEV and PHEVs, but achieving the targets for
accompanied with high voltage and high specific capacity EV requires further improvements in both specific energy
[2]. Indeed, Li-ion batteries are advantageous in and specific power of Li-ion batteries.
Int. J. Energy Res. (2017) © 2017 John Wiley & Sons, Ltd.
DOI: 10.1002/er
Degradation Mechanisms in Li-ion Batteries: A State-of-the-Art Review Kabir M. M. and Demirocak D. E.
Figure 2. Ragone plot, depicting the correlation of specific energy with specific power for EES devices, coupled with the goals
established by the USABC for HEVs, PHEVs, and EVs [9] [Colour figure can be viewed at wileyonlinelibrary.com]
Figure 3 shows the current performance of Li-ion 1.2. Working principle of Li-ion batteries
battery for PHEV application and compares it with the
goals. As illustrated in this plot, the life and cost of Li- A typical Li-ion battery is comprised of the following main
ion batteries need to be remarkably improved for the components: anode, cathode, separator, and electrolyte. Li-
successful use of this technology in vehicle electrification ion batteries include two electrodes (i.e., cathode and
[10,11]. anode) whose chemical potentials are different. This
In addition to the mobile applications, there is a difference in chemical potential specifies the cell’s open
considerable interest to apply Li-ion batteries to a variation circuit voltage. Separator is an inactive component of a
of grid-scale stationary storage applications, where a Li-ion battery that prevents the physical contact between
significant cycle life is required [8,12]. Hence, a solid the two electrodes. Electrolyte enables the Li-ion diffusion
understanding of the phenomena governing the between the electrodes during charging and discharging
degradation mechanisms of Li-ion batteries is necessary cycles. Once an external circuit electronically connects
to achieve desired improvements in the cycle life and the the two electrodes, electrons are transferred from anode
cost as well. (the negative electrode) to the cathode (the positive one)
Figure 3. Present-day performance of Li-ion batteries in comparison with the goals set by the US FreedomCAR in 2011 [11] [Colour
figure can be viewed at wileyonlinelibrary.com]
DOI: 10.1002/er
which causes the potential difference to be balanced. and undergo intercalation and de-intercalation process. The
Positive Li ions are also carried by the electrolyte in the additives are usually carbon materials to enhance the
same direction. The chemical energy stored in the cell is electronic conductivity within the composite electrode.
then converted to the electricity in the external circuit. This Binder’s main role is to keep the active materials in
process is reversible, implying that Li-ion cells can be physical contact with each other as well as in contact with
recharged whereby electrical energy is converted back to the current collector. The electrode materials should
chemical energy. Figure 4 illustrates the schematic of the possess the following key features [10]:
battery’s working principle.
The energy stored in a battery can be calculated by • The electrode materials should be capable of keeping a
multiplying the discharge power (in Watts) by the large amount of Li ions per material’s unit formula to
discharge time (in hours). Over time by cycling the cell, maximize the capacity of the cell.
the energy capacity of the battery gradually decreases • The cathode material should contain low Li chemical
depending on various parameters such as potential, while the anode material should pose a high Li
charge/discharge rate and operation temperature. The chemical potential to maximize the cell’s operating voltage.
respective cell voltage is dependent not only upon potential • The electrode materials are expected to show good
difference of the two electrodes, but also on the reaction structural integrity and low volumetric expansion upon
kinetics as well as the cell resistance. Rise in the cell Li intercalation/de-intercalation during cycling to
impedance contributes to the enhanced voltage plateaus maximize the cycle life.
within charging and the reduced voltage plateaus within • The electrode materials should possess appropriate
discharging, which brings about the power fade and the electronic and ionic conductivity to minimize losses of
decline in the efficiency of energy conversion. Thus, the polarization and to maximize the cell’s power capability.
life cycle of a battery is mostly designated by the • The electrode material’s redox voltages shall lie within
impedance rise and the capacity fade. the electrolyte’s stable operating voltages.
• The electrode materials require to be environmentally
benign, low-cost, and chemically and thermally stable
1.3. Main components of Li-ion batteries
for a desirable range of operating conditions.
The main components of a typical Li-ion battery are as
follows: anode, cathode, electrolyte, and separator. The
interaction of these components dictates the cell
1.3.1.1. Anode. The negative electrode (anode) of
performance, power and energy capacity, cycle life, safety
a Li-ion battery comprises a Li intercalation compound
behavior, and operating temperatures. The following
covered into a thin layer on the copper current collector.
sections introduce these components in a greater detail.
Uniform and thin coatings of the active materials are needed
for the cells utilizing organic electrolytes (almost all the
1.3.1. Electrodes commercial cells available at present). Therefore, the
The electrodes are composite structures consisting of process of anode materials mixing and coating is mostly
active materials, additives, and binders. The active proprietary because variations in manufacturing and
materials are typically metal oxides for cathodes and production process influence the final coating and may have
different types of carbons for anodes in modern Li-ion a severe impact on the rate capability, cell capacity, and, in
batteries. The main role of the active materials is to store general, on the cell aging behavior. Defects regarding the
Li safely for prolonged times. During battery operation, negative electrode coating can contribute to the cell thermal
Li ions shuttle back and forth between cathode and anode, runaway and the cell failure alike.
Figure 4. Working principle of Li-ion batteries [2] [Colour figure can be viewed at wileyonlinelibrary.com]
DOI: 10.1002/er
Lithium may be an ideal anode material for the Li-ion 1.3.2. Electrolyte
batteries; however, due to plating of Li within charge and With respect to the function of electrolyte, already
discharge, and the subsequent formation of dendrites, the risk explained in the Section 1.2, a suitable electrolyte is
of short-circuit for the cell exists. Hence, carbonaceous expected to possess the following major features:
materials are preferred for the Li-ion battery anodes [13].
The most widely used anode material is graphite, in the form • should have a good ionic conductivity and electronic
of powder, combined with binder material, but the carbon insulation to make ion transport better as well as to
nature can substantially vary by the graphite source minimize self-discharge.
(synthetic or natural), particle size, purity, particle shape, • should be electrochemically inert with oxidizing or
distribution of particle size, porosity of particles, carbon reducing electrode surface during the cell’s operating
crystalline phase, and compaction degree. The carbonaceous voltage window.
anodes, in general, exhibit a good rate of lithium • should not react with the other components of the
insertion/removal, therefore, improve the charge/discharge battery, for example, current collector and separator.
rate (C-rate) of the battery. However, the cell performance • should be environmentally benign.
is restricted because of the solid electrolyte interphase (SEI)
formation due to electrolyte decomposition during the cell Electrolyte is typically constituted of one or more liquid
cycling (it will be discussed in more detail in Section 3). solvents along with lithium salts. The most common salt
Anodes made up of silicon, titanate, and germanium used for electrolyte is lithium hexafluorophosphate
materials have been studied as well, but at the present (LiPF6). The most usual electrolytes being currently used
non-graphitic negative electrodes are scarcely in Li-ion batteries are non-aqueous. A combination of
implemented. linear and cyclic carbonate solvents, for instance, ethylene
carbonate (EC) and dimethyl carbonate (DMC), is often
used in the cell electrolyte as this mixture offers a low
1.3.1.2. Cathode. The usual cathode materials viscosity, high ionic conductivity, and SEI-forming ability.
include layered oxides such as LiMO2, LiM2O4 (i.e., While EC at ambient temperature is solid and has a low
spinels), and LiMPO4 (i.e., olivines) in which M is a viscosity, the mixture of EC:DMC is liquid for a range of
transition metal atom [14]. The most common material used their compositions. The ratio of EC:DMC mixture varies
for the cathode in commercial Li-ion cells is lithium cobalt depending on the properties required for different cell
oxide (LiCoO2). The cobalt-based materials have a pseudo applications. For instance, a cell for low-temperature
tetrahedral structure allowing two-dimensional diffusion of applications is likely to have an electrolyte with a lower
lithium ions. The cobalt-based cathodes are ideal given their viscosity compared to the one designed for room
high volumetric capacity, high theoretical specific heat temperature applications to facilitate the Li-ion diffusion
capacity, high discharge voltage, low self-discharge, and at low temperatures. Moreover, manufacturers usually use
appropriate cycling performance [15]. However, due to various additives to improve the cell performance [16].
expensive and toxic cobalt, the other cathode materials are The additives can facilitate the SEI formation on the
also developed. The most significant cathode materials other graphite, diminish the irreversible capacity loss due to
than LiCoO2 are spinels lithium manganese oxide SEI formation and during extended cycling, enable LiPF6
(LiMn2O4), lithium iron phosphate (LiFePO4), or mixed to have increased thermal stability against the organic
metal oxides which comprise of cobalt, nickel, aluminum, solvents, protect the positive materials against dissolution
and manganese oxides, for instance LiNi0.8Co0.15Al0.05O2 (specifically manganese-based materials), and ameliorate
(i.e., NCA) and LiMn0.5Ni0.5O2. The manganese-based the electrolyte properties involving: viscosity, ionic
cathodes develop a cubic crystal lattice system, allowing conductivity, and wettability of polyolefin separator.
for three-dimensional diffusion of lithium ions. Manganese-
based materials are attractive because manganese is cheaper 1.3.3. Separator
and less toxic compared to other materials used. Separator is basically a porous membrane which is
Nevertheless, they pose limitations as manganese tends to placed between the positive and negative electrodes. The
dissolve into the electrolyte during cycling, resulting in the separator’s main function is to physically separate cathode
cathode’s poor cycling stability and storage capabilities, and anode. At the same time, the separator pores allow
preventing it from the market penetration [15]. transport of lithium ions through diffusion during charge
The most recent cathode materials among those and discharge.
mentioned above have been olivine-structured ones such The key considerations influencing the separator
as LiFePO4. It operates at a lower voltage, nearly 3.3 V selection are as follows [17]:
vs Li/Li+, but exhibits higher power and energy density
coupled with proper structural stability. In addition, taking • Good electronic insulation
advantage of nano-sized particles can alleviate the lower • Minimal resistance in ion transport and high ability in
conductivity of LiFePO4 [10]. This cathode is also electrolyte absorption and retention
preferred by some automobile manufactures because of • Low Gurley value (air permeability), implying low
being low-cost and environmentally benign. electrical resistance and high porosity
DOI: 10.1002/er
• Appropriate dimensional and mechanical stability as on the capacity fading and impedance increase may be quite
well as adequate physical strength including: puncture sophisticated. An overview of major degradation
strength, mix penetration strength, and tensile strength mechanisms and their interactions has been represented in
• Uniformity in the thickness and tortuosity Figure 6, implying the complexity of degradation in Li-ion
• Chemical stability and resistance against degradation batteries. The interplay between different subcomponents,
caused by electrode reactants, electrolyte, and impurities for instance anode, cathode, binder, electrolyte, separator,
• Thermal stability and current collector, reveals the aging mechanism that can
• Readily and quickly wettable by typical electrolytes include both mechanical and chemical origins which are
• High ability in hindering migration of soluble species or closely interrelated [19]. Accordingly, the aging mechanism
particles between the cathode and anode can be classified into the following:
Until recently, very few studies have been conducted to

develop new separators in comparison with the other cell 2.1. Chemical degradation mechanisms
components. The most widely used separators in the non-
Chemical degradation mechanisms can mostly be traced to
aqueous Li-ion batteries are microporous polyolefins. They
the electrolyte decomposition and reduction, SEI
may be fabricated in the form of a single layer of
formation, binder decomposition, solvent co-intercalation,
polypropylene (PP), polyethylene (PE), or laminates of PP
active material dissolution, gas evolution, and loss of
and PE (see Figure 5). This figure illustrates the surface
lithium [19]. These mechanisms have broadly been
scanning electron micrograph (SEM) and the cross-sectional
investigated so that there is an extensive range of
SEM of Celgard 2325 separator. The surface SEM (part a)
publications focusing on the side reactions in different cell
only demonstrates the PP pores whereas the PE pores can
components. The electrolyte could be reduced through the
be seen in the cross-sectional SEM (part b). The thickness
lithiated negative electrode during low potential range and
of these films is around 20 μm. Slightly thicker separators
oxidized by the delithiated cathode in high potentials.
are typically used in EV/HEV applications for safety.
Electrolyte impurities can operate as catalyst for the side
reactions [20,21]. The kinetics of side reactions is strongly
dependent upon temperature and the cell voltage. As an
2. CLASSIFICATION OF illustration, degradation in most of materials is accelerated
DEGRADATION MECHANISMS IN at elevated temperatures. These side reactions bring about
LI-ION BATTERIES some changes in materials of the electrodes. The redox
reaction between the electrode and electrolyte contributes
Aging is defined as reduction in performance, lifespan, and to the interface layer formation resulting, by itself, in the
reliability of a system. Battery aging can contribute to either cell’s impedance increase and capacity fading. Thus, these
capacity fading or power fading, or both of them. Because effects often arise from several various processes and their
batteries are composed of a set of interconnected components interactions, and do not occur independently.
subject to the aging, a cell component’s aging and its Generally speaking, long-term chemical degradation of
subsequent performance deterioration affect operational battery hardware materials may negatively influence the
conditions of other components, which will, in turn, expedite electrical performance, the cell lifespan, and/or safety
the entire system aging. Hence, the governing mechanisms through (i) enhanced electrical resistance or even
Figure 5. Cross-sectional and surface SEMs of Celgard 2325 separator (a) uni-layer and (b) tri-layer microporous separator [17]
DOI: 10.1002/er
Figure 6. Degradation mechanisms in Li-ion batteries, adapted from [18] [Colour figure can be viewed at wileyonlinelibrary.com]
continuity loss, (ii) corrosion products attacking or 3.1. Anode degradation

passivating the active materials, (iii) exposure to the
contaminants reacting with active materials (given the loss 3.1.1. Solid electrolyte interphase (SEI) formation
of cell sealing), and (iv) the loss of electrolyte. Many researchers consider the dominant cause of anode
aging to be due to changes occurring at
electrolyte/electrode interface (see Figure 7), arising from
2.2. Mechanical degradation mechanisms reactions between the negative electrode and the electrolyte
[26]. The side reaction between the electrolyte surface and
Side reactions do not stand for the sole reason for battery
the anode in the Li-ion batteries results in the decomposition
degradation. Lithium insertion and extraction bring also
of the reductive electrolyte as well as the Li ion
about the volume expansion or shrinkage. This process
consumption [10]. The products of decomposition are then
takes often place inhomogeneously.
deposited onto the electrode surface, forming a film referred
Mechanical degradation mechanisms are mainly
to as SEI. The active lithium is consumed by the SEI layer,
concerned to the volume changes and subsequent stress
which increases the electrode impedance and thereby
generated in the active material particles of anode or
contributes to the cell’s capacity and power fading.
cathode within lithium de/-intercalation. As a consequence
Despite the fact that SEI layer may be formed at both the
of tensile stress, active particles may undergo cracks, loss
cathode and the anode, it is more prominent at the anode side
of contact between each other or from the current collector,
given the low potentials (vs. Li/Li+) within the cell charging.
and isolation as well [19,22,23]. Furthermore, stress
Because the SEI is constituted of the decomposition products
induced over cycling of a battery changes the structure of
of electrolyte, it can be perceived that the SEI layer’s
pores in the separator and leads to lower lithium ion
composition and characteristics depend upon the electrolyte
mobility [19,24]. Similar to the chemical degradation,
solvents as well as the anode surface. Several reactions
mechanical degradation is also enhanced by aging,
regarding the electrolyte decomposition can be found in the
compromising the cathode and anode structures as well
literature [20]. As the carbonate solvents are widely used in
as mechanical properties of the other battery components,
the Li-ion batteries, there is a range of studies associated with
for example, modulus of elasticity and hardness of the
the reduction reactions resulting in the SEI layer formation
cathode, or the crystallinity of poly-vinylidene fluoride
for solvents including: EC, propylene carbonate (PC), diethyl
(PVDF) binder [19]. Mechanical and chemical degradation
carbonate (DEC), and DMC [20,27,28].
modes will, in more detail, be discussed in the Section 3.
When SEI layer is initially formed, it restricts the
electrolyte’s further reduction and also the anode surface
corrosion; however, the SEI stabilization and growth occur
3. DEGRADATION MODES continuously during the cell’s lifetime albeit at a lower rate
compared to the initial stages [10] as the kinetics of
In this section, we are going to review different chemical decomposition reaction or the solvent molecule diffusion
and mechanical modes of degradation, which the main can limit the SEI growth rate [29]. Continuous growth
components of Li-ion batteries often undergo them, and deposition of the electrolyte decomposition products
adversely affecting the battery performance, or ultimately may affect pore size and structure, wettability of
leading to the cell failure. electrolyte, contact resistance of the negative and positive
DOI: 10.1002/er
Figure 7. Possible degradation mechanisms in the anode [25] [Colour figure can be viewed at wileyonlinelibrary.com]
electrodes, as well as the separator porosity [16]. The SEI 3.1.3. Changes of the active material
layer growth can generally be expedited at the lower anode Minor aging effects generally occur inside the bulk of
potentials and the elevated temperatures. the active material. The volume changes in graphite,
As a result, the SEI formation and its steady growth are caused by the insertion and extraction of lithium ions is
typically considered as the primary cause of Li-ion not expected to be significant (less than 10%, depending
battery’s performance deterioration in the forms of on the material) [25]. Structural changes may lead to the
increased internal resistance and capacity fade. In this mechanical stresses imposed on defects and also on
regard, some research has been undertaken to model the carbon–carbon bonds, resulting in the structural damages
cell capacity fading due to the SEI growth under various and cracking. Also, graphite particle cracking and graphite
operating conditions [30–32]. exfoliation caused by co-intercalation of solvents,
electrolyte reduction within graphite, and gas evolution
within graphite will contribute to the accelerated electrode
3.1.2. Lithium plating degradation [35]. The latter exhibits the strongest influence
Lithium plating is a well-recognized and inherently upon the active material changes that causes battery aging.
hazardous degradation mechanism in Li-ion batteries.
Lithium plating is described as the precipitation of the
lithium metal, which occurs at the surface of the anode 3.1.4. Changes in the anode structure
once the anode potential exceeds the threshold value of Loss of electrical or mechanical contact within the
0 V (vs. Li/Li+) [10,25,32]. In addition to the active lithium anode causes higher cell’s internal resistance, and thus
consumption leading to the capacity loss, the formation of contributes to aging. One of the unavoidable sources of
lithium dendrites during lithium plating can bring about the contact loss is the change in the volume of active anode
tearing of the separator, subsequent short circuit, and materials, leading to the mechanical disintegration
instant battery failure. throughout the anode structure. Contact loss may take
In the case of carbonaceous electrodes, the lithium place between (i) carbon particles, (ii) carbon and current
plating takes place when the intercalation rate of the lithium collector, (iii) carbon and binder, and (iv) current collector
ions into the carbonaceous electrode is too slow and/or the and binder [25]. The electrode porosity is considered to be
lithium ion transport to the electrode surface is very high. important to the good performance of anode, as it enables
Below the room temperature, the lithium ion diffusion into electrolyte to penetrate within bulk of anode. The active
the electrode is slow, needing overpotential to retain the material’s change in volume negatively affects the
given net current, which, in turn, causes the lithium plating. electrode porosity. In the literature, it is broadly
Furthermore, lithium plating can occur through cell acknowledged that the fluorine-containing polymers and
imbalance (e.g., excessive cathode material) [33], local copolymers employed to composite electrodes as binder
electrode polarization, and geometric misfits [10,25,29,34]. materials react with anode, forming LiF [36,37]. Such
DOI: 10.1002/er
interplay can lead to the degradation of mechanical 3.2. Cathode degradation

properties of anode in the long term. Furthermore, the
current collector may be corroded through reacting with 3.2.1. General aspects
electrolyte components, or when the anode potential The aging mechanisms and the measures to harness
reaches too much positive vs. Li/Li+. It resulted in the them regarding lithium metal oxide cathodes are still of
mechanical or electronic contact loss between current growing interest and not thoroughly understood at present.
collector and the other components of the electrode. On A couple of changes on cathode can impact the life span of
the other hand, corrosion products having poor electrical a Li-ion battery [25]:
conductivity bring about overpotentials, which in turn, set
the stage for potential distributions, inhomogeneous • active material aging
current, and therefore, lithium plating [25,38]. • changes or degradation of electrode components such as
binder, conducting agents, or current collector corrosion
• electrolyte component oxidation and subsequent
3.1.5. Conclusion on the anode aging formation of surface film
Table I gives an overview of the causes and effects of • aging product reaction with anode
the anode aging and also expresses the main factors
enhancing or alleviating the aging. As a conclusion, These reactions do not take place separately and may
with regard to the various aging mechanisms for the not be considered independently. They are susceptible to
carbonaceous anodes, already described and also briefly the electrode composition designed individually and are
represented in Table 1, aging effects can be primarily also affected by storage and cycling conditions. Capacity
traced to the changes in the electrolyte/electrode fading in positive active materials may be rooted in the
interface. following [25]:
Table I. Li-ion anode aging-causes, effects, and impacts [25].
Cause Effect Results in Alleviated by Elevated by
Electrolyte decomposition Impedance increase Power fade Stable SEI (additives) High state of charge
and SEI formation Lithium loss Capacity fade The passage of time High temperature
reduces the rate
Gas evolution, solvent Lithium loss Capacity fade Overcharge
co-intercalation, and Graphite exfoliation Carbon pre-treatment
particle cracking Additives
Reduced surface area Power fade Additives
arisen from SEI Impedance increase High state of charge
stabilization and growth High temperature
Porosity change arisen from Overpotentials Power fade
volume change of active Impedance increase Additives High state of charge
material particles, SEI External pressure High cycling rate
stabilization and growth
Contact loss caused by Active material loss External pressure
the change in volume Capacity fade High depth of
of active materials discharge
High cycling rate
Binder decomposition Capacity fade
Mechanical instability Appropriate binder High temperature
Lithium loss selection High state of charge
Impedance increase Power fade Appropriate choice Low state of charge
Current collector Inhomogeneous of current collector Overdischarge
corrosion current and potential
distribution
Overpotentials
Lithium plating and Lithium loss Capacity fade Narrow operating Cell imbalance
dendrite formation range of potential Geometric misfits
Low temperature
High cycling rate
Local polarization
of electrode
DOI: 10.1002/er
• structural changes within cycling Most recently, Demirocak and Bhushan [19] have
• modification of surface film probed the changes in mechanical properties of a LiFePO4
• chemical decomposition or dissolution reaction cathode by nanoindentation technique in a large format
prismatic cell. Their results indicate that mechanical
Analogous to the negative electrode, degradation in degradation increases by aging, so that both modulus of
positive active materials is dependent upon state of charge elasticity and hardness lessened. Moreover, implications
(SOC) and cycling conditions. The cathode materials of the degradation in mechanical properties on PVDF
involve the electrochemical reaction of Li ions insertion binder degradation were discussed in detail. As a
into the metal oxide, as follows: consequence represented in their study, degraded
mechanical properties revealed the reduced crystallinity
LiMO2 ⇔ Lix MO2 þ ð1-xÞLiþ þ ð1-xÞe of PVDF binder [19].
This insertion/extraction of Li ions results in changing 3.2.3. Active material dissolution

the materials’ molar volume that can generate mechanical Aging caused by the active material dissolution is
stresses and strains for positive active particles and, thus, mainly seen in the Mn-based cathodes [10]. Although this
for the electrode. Besides, phase transition may take place, aging mechanism has been observed in olivine structured
causing the crystal lattice distortion and subsequently more cathode and manganese layered oxide, it is of the greatest
mechanical stresses. Figures 8 and 9 illustrate a schematic significance to the spinel structured manganese cathode,
of aging mechanisms in the Li-ion cathode. specifically at elevated temperatures and charged states
[25]. The dissolution reaction is as follows:
3.2.2. Structural changes and mechanical stress
As mentioned previously, degradation mechanism can 2Mn3þ →Mn4þ þ Mn2þ
possess both chemical and mechanical origins [19,40].
Along the lines of the mechanical root, lithium de/- While Mn2+dissolves in the electrolyte, the Mn3+ ions
intercalation process causes the volume expansion or stay in solid structure. The Mn dissolution into electrolyte
shrinkage, which, in turn, induces mechanical stresses exhibits twice the effect on the cell aging. First, manganese
and strains to the active material particles over the cell dissolution contributes to the capacity fade concerned to
lifetime, and consequently compromises the electrode the active material loss. Second, the dissolved manganese
structure and mechanical properties of the other battery ions will migrate to the anode and will be deposited onto
components. As found in the literature, such a structural the electrode surface and/or compounded in the SEI layer.
change impacts the cathode performance more than a This intensifies the process of electrolyte decomposition
regular carbonaceous anode [10,25]. leading to the charge loss in lithiated carbon-based anode
During lithiation/delithiation process, some of the [47,48]. Vetter et al. [25] also stated the deposition of
cathode oxides may undergo the phase change, resulting manganese species, such as MnCO3, MnF2, and different
in the crystal lattice distortion as well as further mechanical oxides, on the cathode surface enhances the electrode
stresses [10]. The misfit strains at the boundaries of the impedance.
phase contribute to discontinuities, bringing about the
nanoparticles cracking [9]. There are several investigations 3.2.4. Active material isolation
which have attempted to model the crack formation and Isolation of the active particles is known as one of the
propagation arising from mechanical stress and strain major causes of battery degradation [25]. Three
imposed to the cathode nanoparticles [41–46]. explanations for this mechanism can be presented [19]:
Figure 8. Possible degradation mechanisms for the cathode [25] [Colour figure can be viewed at wileyonlinelibrary.com]
DOI: 10.1002/er
Figure 9. Causes and effects of degradation in the cathode [39]
(i) crack formation in the active materials and likely internal temperature up to around 130°C (e.g., given the
fragmentation (i.e., mechanical degradation), (ii) fracture high current draws brought about through a cell’s external
of binder, which interconnects active particles (i.e., short circuit) [8]. The separator shutdown property is
mechanical degradation), and (iii) binder adhesion determined by means of measuring the separator
property deterioration (i.e., chemical degradation). Hence, impedance while temperature increases linearly [17,50,51].
the active material isolation can include roots in Figure 11 reveals the shutdown behavior of a trilayer
mechanical degradation of the active material and binder, separator (PP/PE/PP), in which the escalation in
as well as chemical degradation of the binder. impedance relates to the collapse of pore structure caused
by the separator melting, forming a comparatively
3.3. Separator degradation nonporous film between the two electrodes. The
impedance increase took place at around the melting point
Separator degradation can be responsible for the power
fading and finally cell failure. The main causes regarding
separator degradation are typically traced to the lithium
dendrite growth caused by separator pores, attack through
the electrolyte, the blocking of passageways in the
separator over cycling, and structural degradation arising
from elevated temperature or high cycle number [49]. High
temperatures (often the range of 130 to 150°C) cause the
softening of separator’s films and the closing of their pores,
resulting in the stoppage of charge/discharge process
through hindering the ion transport between the electrodes.
Hence, these separators are usually called ‘shutdown’
separators. In case, a slight internal short takes place in
the battery (e.g., minor contaminants entering the
separator), local shutdown of the separator disables a small Figure 10. Micro-shorting location on the separator (with a
point through melting and then closes separator pores, diameter of almost 1 mm) where separator melted locally and
shown in Figure 10. The entire cell can also be shutdown [8] [Colour figure can be viewed at
permanently disabled when there is an abnormal rise in wileyonlinelibrary.com]
DOI: 10.1002/er
Figure 11. Internal impedance as a function of temperature for a multilayer separator (PP/PE/PP), Celgard 2325, at 1 kHz and heating
rate of 60°C/min [17] [Colour figure can be viewed at wileyonlinelibrary.com]
of PE (i.e., 130°C) and proceeded until the melting point separators. This is traced to the better properties of PP in
corresponding to PP (i.e., 165°C). the oxidation resistance when it is in contact with cathode.
Even though the materials used for separator are inert The resistance of separator to penetration, separator
and do not influence electrical output or energy storage, thickness, separator permeability, porosity, and toughness
their physical properties can substantially impact the cell may vary significantly by desirable cell characteristics
performance and safety. To attain good performance in and functions. As an illustration, one of the approaches to
Li-ion batteries, separators should exhibit uniformity in heightening cell capacity is to reduce the separator
their pore structure, low shrinkage, and a low amount of thickness as thinner separators present lower resistance.
resistance. The separators which have high resistance will However, this strategy generally poses a drawback, that
poorly perform within high discharge rate and will also is, thinner separators can contain less electrolyte, and
prolong charging time of the battery [17]. Low shrinkage consequently they do not exhibit good mechanical strength
is another prominent characteristic of separators, and may lead to the cell failures.
specifically regarded for higher capacity batteries, for Despite the prominent role of separator in the cell
example, high speed laptops experiencing higher degradation, there are a few studies conducted over it in
temperatures (nearly 75°C) in certain circumstances [52]. the literature. Norin et al. [24] represented that the
This can contribute to the separator shrinkage and separator at least is partially responsible for power fading
eventually high resistance of the cell as well as poor arisen from intrinsic increase in the separator ionic
cycling in the long term. Besides, the shrinkage in impedance. They demonstrated that the resistance rose
transverse direction (TD) may result in safety problems dramatically during aging or cycling at elevated
due to the internal short between cathode and anode. temperatures, so that separator stands for around 15% of
Larger pores in the separator pore structure can, by itself, the overall cell impedance increase. They later revealed
contribute to the shorts in the manufacturing process or that decline in separator ionic conductivity originated from
may fail during HiPot (high potential) testing. Bigger pores the clogging of separator pores caused by the electrolyte
will set the stage for more soft shorts and allow higher self- decomposition products (SEI layer formation), which was
discharge, particularly within high temperature storage, expedited at elevated temperatures [49]. The separators
whereas pores with very small size can result in the high having lower resistance can also help the cell performance
resistance and undesirable cycle life under cycling and under low-temperature conditions. The impedance of
storage with high temperatures [17]. Hence, this highlights electrolyte is very high at very low temperatures; hence,
the significance of optimization in separator’s pore size to a small contribution coming from the separator can, in
achieve appropriate strength and performance. turn, assist the cell to keep its overall impedance lower
The separators applied for Li-ion cells often encounter a [17].
severe oxidizing environment on the side of cathode and Atomic force microscopy (AFM) images taken by
also an intense reducing environment on the anode side. Nurin et al. [24] from separators whose cells aged by
Thus, the separators should be designed to be stable under 28 weeks revealed a persistent change in the surface
such harsh conditions over long-term high-temperature structure of separator from a uniformity in the layout of
cycling. Separators having poor oxidation resistance may perpendicular fibers showing pores to a plane of swollen
contribute to poor storage performance at elevated fibers blemished by means of crevices and electrode
temperatures and tenuous long-term cycling behavior particles imprints. The PP fibers in the aged separator were
alike. The oxidation resistance characteristics of multilayer covered by compact particles with a size of 10–200 nm. As
separators (PP/PE/PP) having PP at the outer layer and PE a result, increase in the fiber thickness and their subsequent
at the inner layer is premier as compared to the PE swollen appearance witnessed in the aged separators is
DOI: 10.1002/er
Figure 12. SEM images of separators derived from (a) unaged (fresh) cell and (b) aged cell stored for a 40-week period at 55°C [49]
believed to be due to the deposition of electrolyte Figure 13 gives an insight into the nature of deposit
decomposition products [49]. Scanning electron using thermo-gravimetric analysis/differential thermal
microscopy images of the aged separator shown in analysis (TGA/DTA) characterization. TGA curve of the
Figure 12 acknowledge the AFM data and exhibit unaged separator does not show appreciable changes when
considerable changes in relation to the separator heating up to 120°C, while the separator removed from an
morphology. On the other hand, the images with lower aged cell which was under operation for 40 weeks at 55°C
magnification demonstrate that the deposit distribution on shows a 1% mass loss at 47°C, and afterwards a steady
the separator is significantly uneven and displays a patchy mass loss with a slower slope by 120°C. The loss of
pattern. However, there remain some areas that represent
no or slight change in comparison with the separator’s
original morphology.
The particles depositing on the fibers substantially
diminish both the pore size and the separator
homogeneity, whereby increase the average path length
for the ions, and subsequently enhance the potential drop
across the cell separator. To clarify this effect and its
accompanying consequences on the separator
performance, Kostecki et al. [49] utilized impedance
spectroscopy to determine average ionic conductivity of
the separators. They also observed the loss of separator
porosity and uniformity with the aid of TEM, which was
directly responsible for impedance rise through decreasing
the amount of electrolyte lying inside the separator and/or
reducing the channel and pore size. Both of these effects Figure 13. TGA curves for the separator of unaged Celgard
can contribute to the considerable impediment of Li-ion 2300 (solid line) and aged separator taken from the cell held at
transport. 55°C for 40 weeks (dashed line) [49]
DOI: 10.1002/er
weight shown as a slight baseline shift in the DTA implies A brief review of corrosion behavior of the aluminum
an endothermic process concerned to the changes and copper current collectors used in Li-ion batteries is
observed in the TGA curve. The sharp decline in the presented in the succeeding section.
separator mass at T < 50°C can be attributed to the
evaporation of organic solvents trapped within the pores. 3.4.1. Aluminum corrosion
On the other hand, the steady mass loss observed at Some researchers have investigated electrochemical
elevated temperatures is associated with the process of behavior of aluminum in various compositions of organic
deposit decomposition. Kostecki et al. [49] applied electrolyte solutions [53–56]. The anodic properties of
fluorescence microscopy as a successful method to aluminum depend greatly upon the electrolyte solution
identify the composition of the deposit and reported that composition as well as the electrode metallurgy [54,56].
the separator samples removed from the aged cells emit The metallic aluminum in the air and neutral water
fluorescence across a wide range of excitation environment is usually stable given the protective surface
wavelengths (350–580 nm) and emission wavelengths layer made up of aluminum oxide (Al2O3) and aluminum
(350–660 nm). According to their investigation, this hydroxide (Al(OH)3). Likewise, this characteristic is
deposit originates from a two-stage decomposition process anticipated in organic electrolyte solutions including slight
of LiPF6 EC:EMC electrolyte, involving homogenous quantity of oxidants [56]. The commonly used electrolyte
decomposition and heterogeneous redox reactions solutions are the binary mixtures of alkyl carbonates and
occurring at special areas which are in contact with the dissolving inorganic lithium salts (LiBF4, LiPF6, etc.).
electrodes. These deposits comprise lithium Nonetheless, alternative salts to LiPF6 have broadly been
halophosphates, LiPOx:LiF, which are responsible for pursued due to its lack of thermal and chemical stability
the strong fluorescence emission mentioned above, and in organic medium comprising trace amounts of water.
are remarkably accelerated at high temperatures. The spectroscopic and electrochemical experiments reveal
It can be concluded from the literature [24,49] that the that the forming of surface film containing fluoride can
products of electrolyte decomposition, forming a film on play a prominent role in preventing aluminum anodic
the separator and thereby clogging the pores and impeding corrosion imposed by the organic electrolyte solutions
Li-ion transport, are partially responsible for the cell [55]. In another study, Braithwaite et al. [38] also applied
resistance increase and stand for almost 10% of the total two types of fluorocarbon-based coating to evaluate the
cell impedance rise. aluminum corrosion behavior. This coating is generally
regarded as a vehicle to boost the adhesion between active
3.4. Current collector degradation electrode materials and current collectors. As a
consequence, they reported an increase in aluminum
The most broadly used materials of current collectors for resistance to the pitting corrosion.
the positive and negative electrodes are thin foils of Braithwaite et al. [38] took advantage of XPS and
aluminum and copper, respectively. The current collector electrochemical impedance spectroscopy (EIS) analyses
function is to evenly transmit current throughout the as effective analytical techniques to identify corrosion
battery to active materials, supply mechanical support to behavior of the current collector materials in LiPF6
electrode active materials, and provide a mechanical link electrolytes with two different kinds of solvent, involving:
to the internal leads (which can be welded to bare parts EC:DMC and PC:DEC. According to their report, after 40
of the current collector) transferring the current into the electrical cycles in the PC:DEC solvent, some localized
battery. pitting corrosion had been triggered on the aluminum
The principal materials of current collectors being surface (as can be seen in Figure 14b as compared to
employed in Li-ion batteries have been shown to be Figure 14a). The continuation of cycling up to 690 cycles
vulnerable to the environmental degradation: copper to resulted in the increased density of the attack. Interestingly,
environmentally assisted cracking (EAC) and aluminum cycling in EC:DMC electrolyte led to an even greater
to the localized pit-like corrosion [38]. Localized pitting density, only by 150 cycles (Figure 15a). Additionally,
takes place at highly oxidizing potentials concerned to cross-sectional SEM image (Figure 15b) revealed what
the charge condition of the cathode. Nevertheless, the seems optically to be pits are mounds which have
pitting corrosion mechanism in the positive-electrode accumulated in pits. The later analysis of surface
current collector appears to be more complicated and also implemented by Auger and XPS techniques manifested
different as compared to that perceived typically from the that the mounds were composed of Al° and Al2O3 and
aqueous systems presumably due to the organic electrolyte were electrically isolated from aluminum foil.
as well as the electrical cycling imposed. Under such The principal outcomes extracted from electrochemical
circumstances, the pits and corroded sites are filled with a impedance spectroscopy (EIS) analysis undertaken by
mixture of metal-oxide products, shaping the nodules and [38] about the corrosion behavior of aluminum current
surface mounds. On the other hand, copper is susceptible collector can be concluded as follows:
to EAC nearly at the lithium potential in times of existence
of particular metallurgical conditions such as fairly large (i) The role of electrolyte composition on Al current
size of grains and work hardening. collector corrosion:
DOI: 10.1002/er
Figure 14. Aluminum current collector’s surface (a) before cycling and (b) after 40 cycles in the electrolyte of PC:DEC solvent [38]
[Colour figure can be viewed at wileyonlinelibrary.com]
EC:DMC electrolyte appeared to be more corrosive The enhanced charge potential reduced the resistance
(lower value of pitting resistance, Rpit) as compared to against aluminum corrosion. Higher anodic potential
the other electrolyte composed of PC:DEC solvent during leads to the greater corrosion current, the outcome which
several hundred cycles (Figure 16). The parameter of is compatible with a lower value of pitting resistance,
pitting resistance, Rpit, is considered as a reliable indicator represented by the Nyquist plot in Figure 17. The
for aluminum corrosion susceptibility so that the lower Nyquist plot has made a comparison between the
values of pitting resistance indicate the higher imaginary part of impedance and the real impedance
susceptibility of aluminum to corrosion. Another result component.
which can be perceived from Figure 16 is that the pitting
resistance tends to increase by cycling for both the (iii) The role of Al alloy on current collector corrosion:
electrolyte compositions. However, this observation
cannot denote that the process of pitting corrosion is self- The electrochemical behavior of aluminum was not
limiting and ceases in the electrolytes over time. shown to be an appreciable function of electrical cycling
(the number of cycles) and metallurgical purity (as
(ii) The role of applied anodic potential on Al current compared between two aluminum alloys 1100 and
collector corrosion: 1145).
Figure 15. (a) Photographs of aluminum surface in EC:DMC electrolyte and (b) cross-sectional SEM of aluminum foil in the EC:DMC
after 150 cycles [38]
DOI: 10.1002/er
in surfaces. Eventually, over-discharging can contribute

to the battery thermal runaway [8].
Unlike aluminum surface, copper, in general, is not
vulnerable to the localized pitting corrosion at the cell
cathodic potentials, implying that it covers an open circuit
voltage greater than 3 V vs. Li in such electrolytes, and
also the ‘applied’ potential of approximately 0–1.5 V vs.
Li on the electrode. Hence, this feature makes copper
cathodically protected.
To find out about the copper susceptibility to EAC,
Braithwaite et al. [38] investigated the effect of the
following factors: strain rate, work-hardening degree, grain
size, and applied voltage. Only under a certain
Figure 16. The impact of composition of electrolyte on the combination of environmental and metallurgical
corrosion behavior of aluminum alloy1100 (pitting resistance as circumstances including fairly large grain size and work-
a function of electrical cycling) [38] [Colour figure can be hardening coupled with the zero applied voltage (0 V vs.
viewed at wileyonlinelibrary.com] Li), copper was shown to be susceptible to the
intergranular EAC. As stated in their report, the exclusion
of each of these conditions could eliminate any
3.4.2. Copper corrosion susceptibility. Accordingly, it is perceptible that the copper
The potential of copper current collector at extremely susceptibility to EAC may be removed through appropriate
low voltages of the cell (around 1 V) rises to the point at attention to the metallurgy. Figures 18 and 19 demonstrate
which the copper will initiate to be oxidized and dissolved the susceptibility of copper to the EAC as well as the effect
in the form of copper ions within electrolyte. Then, of grain size with comparison of two different copper
dissolved copper ions during subsequent recharging plate samples accompanied with the corresponding SEM images
as copper metal onto the anode surface decrease the of fracture surfaces.
permeability and cause the cell to be vulnerable to the
lithium plating and the consequent capacity fade. Lithium
plating via corrosion with the electrolyte results directly 4. THE WHOLE-CELL BATTERY
in the capacity loss and may even contribute to the AGING
catastrophic failure through making an internal short
[26,57]. When a severe over-discharge takes place, cell Battery aging may contribute to either capacity fading or
degradation is usually accelerated as the anode gets power fading, or both of which, and can be enhanced by
damaged through copper plating; it will lose the capability high cycling rate, both low and high temperatures, both
of lithium uptake over the ‘normal’ charging rates. Under low and high SOC, both overcharge and over-discharge,
such circumstances, ‘normal’ charge cycles bring about high depth of discharge (DOD), and moisture. However,
the lithium plating, leading to a larger permeability loss we will only focus on those primary causes affecting the
whole-cell battery performance and cycle life and at the
same time do not arise from the electrical abuse. Thus,
the effect of the following factors is depicted in this
section: cycling rate (C-rate) and the cycle number,
temperature, SOC, and moisture.
4.1. Effect of cycling rate and cycle number
As vividly seen in the literature, aging is accelerated with

faster cycling rate resulting in more capacity fade, while
slower C-rates contribute to higher capacity (less capacity
fade) [58–61]. Likewise, the maximum storage capacity
declines gradually as a consequence of cycle aging, the
greater the number of cycles the reduced the battery
capacity. The irreversible capacity loss arisen from the
cycle aging can be traced to each or combination of the
following: electrolyte decomposition, SEI layer formation
on the surfaces of the electrodes and current collectors,
Figure 17. The influence of applied anodic potential on the dissolution of active materials, phase transitions in the
aluminum (alloy1100) electrochemical behavior with PC:DEC insertion electrode, and structural changes of the electrodes
solvent [38] [58].
DOI: 10.1002/er
Figure 18. Cross-sectional photographs of copper bar. Upper images do not show brittle behavior while lower ones demonstrate it: (a)
transverse and (b) longitudinal [38]
Figure 19. SEM images of copper surface: (a) brittle fracture in the work-hardened copper with coarse grains and (b) ductile fracture in
the work-hardened copper with fine grains [38]
DOI: 10.1002/er
Figure 20 illustrates the effect of C-rate on the battery

capacity fade and also reveals the proportion of different
attributes, ranging from kinetic hindrance (including:
polarization and the other Li ion transport problems) to
loss of lithium inventory and active material, in the
capacity fade of a {LiMn1/3Ni1/3Co1/3O2 + LiMn2O4}
composite positive electrode-based Li-ion cell as a
function of the number of cycle under 2C cycle aging
regime. This study’s authors [59] concluded that the cell
degradation takes place in two steps. In the first step, the
capacity fade is shown to be linear during the first
500 cycles (Figure 20). In this step, capacity fading arises
from the loss of lithium inventory caused in turn by
parasitic reactions, forming the SEI film on the electrode
Figure 21. The Ragone plot as a function of cycle aging [59]
surfaces. As a subsequent implication, less amounts of
[Colour figure can be viewed at wileyonlinelibrary.com]
Li+ come back to the negative electrode during charging
regime. In the second step, because the SEI layer proceeds
to grow on the electrode surfaces, it restrains interfacial Accordingly, an efficient thermal management system
kinetics causing active material loss in the electrodes is required for the battery (especially for those being used
which expedites the capacity fading. for high-power applications, such as electric and hybrid
The adverse effect of cycle aging on the battery electric vehicles) to attain effective operation and long life
performance can clearly be observed in the Ragone plot in all environmental conditions. In this regard, some
correlating specific energy with specific power at different battery thermal models and analyses to assess the battery
cycle numbers ranged from 10 to 950 cycles (Figure 21). thermal management system in electric vehicles under
different usage scenarios have recently been investigated,
which can be found in [63,64].
4.2. Effect of temperature Although several types of thermal management systems
are available, there remains a need to address various
Temperature can significantly affect the Li-ion battery issues like high power consumption, narrow optimum
safety, performance, and cycle life [8,25,60,61]. As temperature range, and operation in varying climates.
mentioned already, both high and low temperatures have Using phase-change materials can effectively contribute
detrimental impact on the cell performance, in particular, to resolving these issues. In this context, readers are
on the cell capacity. The impact of temperature and voltage referred to a helpful article, reviewing the use of phase-
on the battery failure tends to emerge promptly, whereas change materials as well as cooling strategies used in
their influence upon the cycle life is less visible. various thermal management systems for electric and
Figure 22 demonstrates that cycle life begins to decline hybrid electric vehicles [65].
gradually as a result of cell operation at temperatures lower In this study, we thus classify temperature effect based
than around 10°C, and upper than about 60°C; however, on the operating temperature range into the following:
the cell would encounter the thermal runaway threat at
nearly 70°C.
Figure 20. The cell capacity loss map under room temperature Figure 22. The general trend of cell cycle life under a wide
as a function of cycle aging at various C-rates [59] [Colour range of operating temperature [62] [Colour figure can be
figure can be viewed at wileyonlinelibrary.com] viewed at wileyonlinelibrary.com]
DOI: 10.1002/er
4.2.1. Low temperature operation battery through increasing the capacity as a result of the
According to the Arrhenius law, the rate of chemical increased reaction rate based on the Arrhenius effect.
reactions is in proportion to the temperature. The However, it also enhances the cell degradation rate (refer to
Arrhenius equation describes the correlation governing Figure 22). Higher currents cause greater heat dissipation
the rate of a chemical reaction being pursued and the according to RI2, resulting therefore in higher internal
temperature. It reveals that chemical reaction rate rises temperatures. Subsequently, the SEI film growth is
exponentially when temperature elevates. As an expedited at elevated temperatures and lower negative
illustration, a 10°C escalation in temperature can double electrode potentials as well [25,58,61,62]. The adverse
the rate of cell degradation. In contrast, the rate at which impact of SEI layer evolution and its how-to-work as a
the cell active materials react decreases as a result of degradation mechanism which leads to the irreversible
reduction in the operating temperature, which implies a fall capacity loss was explained in the previous sections.
in the cell power handling capacity during charge and Figure 23 represents the voltage against the cell
discharge. On the other hand, the decreased reaction rate discharge capacity (or the SOC) at various temperatures
and the electrode materials contraction caused by low ranging from subzero (20°C) to above room temperature
temperatures confine intercalation spaces required for the (45°C), in order to assess the effect of temperature, while
Li ions insertion, which can in turn lead to the anode the cells operated under a moderate discharge rate of 1C.
lithium plating and subsequent capacity fading [60,62]. As can vividly be seen in this figure, both the cell capacity
and voltage have taken a declining trend as the implication
of temperature decrease, specifically under subzero
4.2.2. High temperature operation ambient temperatures.
Taking a glance at Figure 23 shows that the more the
operating temperature, the greater the capacity. In general, 4.3. Effect of SOC
temperature temporarily improves performance of Li-ion
As mentioned already in the beginning of Section 4, both
low and high SOC can enhance battery aging in the form
of either capacity fade or power fade, or both. Voltage
restrictions are essential to elude over-charge/discharge
and their corresponding problems. Figure 24 illustrates
the SOC operating window for a typical Li-ion battery
and also obviously indicates the possible consequences of
operating outside the ideal window.
4.4. Effect of moisture
Contaminants, in particular water or moisture, have also

been shown to be responsible for the cell degradation.
The most broadly used salt for the electrolyte of Li-ion
batteries (i.e., LiPF6) is highly susceptible to moisture.
Figure 23. The effect of operating temperature at a moderate As a result of the exposure to moisture, LiPF6 salt will be
discharge rate of 1C; adapted from [60] [Colour figure can be decomposed into hydrofluoric acid (HF), which exhibits a
viewed at wileyonlinelibrary.com] very high reactivity causing to decay the electrolyte and
Figure 24. SOC operating window and the effects of improper operating range of SOC [62] [Colour figure can be viewed at
wileyonlinelibrary.com]
DOI: 10.1002/er
Table II. Some of the main in-situ characterization techniques used to study Li-ion batteries [71].
Characterization technique Main requirement(s) Remarks
Optical techniques Top cover transparent to visible light
Raman microscope Structural and chemical composition

at about 2-μm spatial resolution
Optical microscope Only exhibits microscale morphological
changes. Low resolution
Electron techniques High vacuum required, Nanoscale morphological changes
restricting electrolyte can be measured
selection. Window
transparent to incoming
electron beam
Solid-state Li-ion battery is used.

Transmission electron Ionic liquid as electrolyte is used,
microscope (TEM) having ultra-low vapor pressure.
Sample must be thin, less than
100-nm thickness (FIB required).
Cross-section observation can be made.
Scanning electron A lower vacuum in some SEM types

microscope (SEM) (<10 Torr) enables the use of electrolyte.
Battery cannot be cycled in SEM.
Cell assembly aided with nanomanipulator.
An ionic fluid is used, having low vapor pressure.
Atomic force microscope (AFM) A clear path providing the It can be utilized in ambient, however,
access with probe inert atmosphere required.
Either continuous electrolyte flow or
non-flowing electrolyte can be used
Neutron techniques Window transparent to It can quantify Li distribution and

energy particle transport in battery during operation
Neutron depth profiling (NDP) It can measure Li concentration

within the cell electrodes.
Neutron reflectivity (NR) It can measure neutron reflectivity intensity
as a function of momentum transfer.
Small angle neutron scattering Notable for measuring the structure variation in a
(SANS) sample through neutron scattering intensity.
Neutron imaging (NI)
Neutron diffraction Wound cathode, electrolyte, and anode stack
X-ray techniques Window transparent to X-ray It can monitor detailed structural changes.
X-ray absorption spectroscopic (XAS) Kapton X-ray window The completely sealed cell allows prolong
monitoring. XAS also provides detailed information
on electronic structure and ordering.
Transmission X-ray microscope Used for the study of structure and phase composition.
DOI: 10.1002/er
electrodes alike. The proposed reactions for decomposition involving electron microscopes (SEM and TEM), optical,
of LiPF6 salt are as follows [66]: X-ray, neutron, Raman and AFM techniques as well as
hybrids of these techniques such as AFM–Raman [71].
LiPF 6 ⇌LiF þ PF 5 To perform in-situ experiments, ‘custom-built
electrochemical cells’ operating inside the characterization
device should be exploited. Each of these experimental
PF 5 þ H 2 O→OPF 3 þ 2HF techniques poses its own challenges related to the
operating conditions. For example, in-situ TEM and SEM
Consequently, the prevention of moisture penetration to experiments require vacuum environment which renders
the cell is of a great significance during cell design and using a liquid electrolyte impossible during these
assembly process. experiments. Therefore, for in-situ experiments under
vacuum, usually solid electrolytes are used [71]. On the
other hand, in-situ AFM technique needs open cell design,
5. CHARACTERIZATION allowing access to cell electrodes which are being studied
TECHNIQUES MAINLY USED FOR [72,73]. Table II provides a breakdown of design
LI-ION BATTERIES requirements as well as remarks on various
electrochemical cells applied to the main characterization
During operation, Li-ion batteries are complex systems techniques for Li-ion batteries.
into which a set of electrical, chemical, and mechanical
processes occur, such as side reactions, phase
transformations, and volume changes. The main 6. CONCLUSIONS
characterization techniques for Li-ion batteries can be
classified into the in-situ and the ex-situ techniques. The While the operation mechanism of Li-ion batteries is well
Latin word of ‘in-situ’ literally denotes ‘in position’, and recognized, their degradation mechanisms still remain a
in the research field of batteries, it refers to the challenge. Battery aging may contribute to the cell
measurements taken on the materials located inside the cell impedance, capacity fading, and power fading, which are
at their original positions (i.e., without disassembling the mainly caused by storage and cycling conditions in such
battery) [67,68]. In-situ techniques allow direct monitoring a way that it can be enhanced by high cycling rate, both
of micro and nanoscale reactions and processes, therefore, low and high temperatures, both low and high SOC, both
provide the capability of directly linking these processes to overcharge and over-discharge, high depth of discharge
the battery’s electrochemical response. This enables (DOD), and moisture. However, these causes drive the
characterization to occur in more realistic circumstances, battery components degradation and adversely affect the
in contrast to ex-situ experiments. On the other hand, ex- cell life span through several complex and closely
situ characterization techniques (also known as post- interrelated mechanisms, having either chemical or
mortem analysis) are beneficial when there is a need for mechanical origin, or the both, which consist primarily of
higher resolution and sensitivity. Due to formidable electrolyte decomposition and reduction, SEI film
challenges in developing in-situ techniques and the need formation and evolution, binder decomposition, solvent
for specialized and expensive instruments, ex-situ co-intercalation, active material dissolution, gas evolution,
techniques are more frequently employed in battery loss of lithium, phase and structural changes of electrodes
material characterization studies. The sample preparation caused by lithium insertion and extraction, and change in
for ex-situ techniques may induce artifacts to the battery separator morphology.
material under study, hence may lead to wrong Accordingly, avoiding the extreme operating conditions
conclusions. Therefore, extreme caution should be mentioned above and following the operating windows
exercised in preparing samples for ex-situ techniques. In- would postpone the battery degradation and extend the
operando characterization demonstrates a particular case battery lifetime considerably. Nevertheless, one of the serious
of in-situ measurements, when the cell is being challenges needed to overcome in order to extend the use of
charged/discharged during characterization, enabling non- Li-ion batteries is to improve their cycle life as well as to
equilibrium state measurements which cannot be detected make modifications enabling them to operate under extreme
by ex-situ techniques. conditions. Hence, there is a considerable room to develop
Ex-situ characterization techniques comprise primarily new anode and cathode materials having higher specific
of AFM, SEM, TEM, Raman spectroscopy, and other capacity and, at the same time, good structural stability.
neutron and X-ray techniques [69,70]. The ex-situ studies Notwithstanding the great effort made in this study to
are often implemented by making comparisons between compile and delineate both degradation causes and
the aged and unaged electrode materials to understand degradation mechanisms available in the literature, further
electrical, structural, and morphological changes, taking investigations will be required to better appreciate
place over cycling. degradation mechanisms in Li-ion batteries in order to
Different in-situ characterization techniques have been achieve longer cycle life along with better performance.
employed so far to study degradation in Li-ion batteries, Finally, it is important to point out that the improved
DOI: 10.1002/er
understanding of degradation mechanisms plays a crucial formation. Journal of Power Sources 2001;
role in building more realistic aging model and therefore 97–98:58–66.
predicting the cell end of life more reliably, which is of a 14. Goodenough JB. Cathode materials: a personal
great significance to the certain applications such as perspective. Journal of Power Sources 2007; 174:996.
military and medical applications. 15. Nitta N, Wu F, Lee JT, Yushin G. Li-ion battery
materials: present and future. Materials Today 2015;
18:5.
REFERENCES 16. Hellqvist Kjell M, Performance of conventional and
structural lithium-ion batteries, Doctoral Thesis,
1. Newton DE. Fracking: A Reference Handbook Applied Electrochemistry, School of Chemical
(Contemporary World Issues). Publisher: ABC-CLIO- Science and Engineering, Kungliga Tekniska
LLC: California, 2015. ISBN:978-1-61069-691-3. Högskolan, Stockholm (2013).
2. Chen DD, Microscopic investigations of degradation 17. Arora P, Zhang Z. Battery separators. Chemical
in lithium-ion batteries, Doctoral Thesis, Karlsruher Reviews 2004; 104:4419–4462.
Institut für Technologie (KIT), June (2012). 18. http://epg.eng.ox.ac.uk/content/degradation-lithium-
3. Tarascon JM, Armand M. Issues and challenges facing ion-batteries, Christoph Birkl, Energy & Power Group
rechargeable lithium batteries. Nature 2001; (EPG), Department of Engineering Science, University
414:359–367. of Oxford, (2014).
4. Noh KW, Dillon SJ. Morphological changes in and 19. Demirocak DE, Bhushan B. Probing the aging effects
around Sn electrodes during Li ion cycling on nanomechanical properties of a LiFePO4 cathode
characterized by in situ environmental TEM. Scripta in a large format prismatic cell. Journal of Power
Materialia 2013; 69:658–661. Sources 2015; 280:256–262.
5. Shen C, Wang S, Jin Y, Han WQ. In situ AFM 20. Arora P, White RE, Doyle M. Capacity fade
imaging of solid electrolyte interfaces on HOPG with mechanisms and side reactions in lithium-ion batteries.
ethylene carbonate and fluoroethylene carbonate based Journal of the Electrochemical Society 1998;
electrolytes. ACS Applied Materials Interfaces 2015; 145:3647–3667.
7:25441–25447. 21. Broussely M, Biensan P, Bonhomme F, Blanchard P,
6. Huang Z et al. Preparation, characterization, and Herreyre S, Nechev K, Staniewicz RJ. Main aging
lithium intercalation behavior of LiVO3 cathode mechanisms in Li ion batteries. Journal of Power
material for lithium-ion batteries. Journal Physical Sources 2005; 146:90–96.
Chemistry C 2016; 120(6):3242–3249. 22. Mukhopadhyay A, Sheldon BW. Deformation and
7. Lyczko N et al. Characterization of LiFePO4/C stress in electrode materials for Li-ion batteries.
cathode for lithium ion batteries. Industrial and Progress in Materials Science 2014; 63:58–116.
Engineering Chemistry Research 2012; 51:292–300. 23. Ramdon S, Bhushan B. Nanomechanical
8. Mikolajczak C, Kahn M, White K, Thomas Long R, characterization and mechanical integrity of unaged
Lithium-ion batteries hazard and use assessment, Fire and aged Li-ion battery cathodes. Journal of Power
Protection Research Foundation, July (2011). Sources 2014; 246:219–224.
9. Srinivasan V, Batteries for vehicular applications. In: 24. Norin L, Kostecki R, McLarnon F. Study of membrane
AIP conference proceedings physics of sustainable degradation in high-power lithium-ion cells. Solid-
energy, Berkeley, CA, (2008), vol. 1044, pp. 283–296. State Letters 2002; 5:A67–A69.
10. Nagpure SC, Bhushan B, Babu SS. Multi-scale 25. Vetter J, Novak P, Wagner MR, Veit C, Moller KC,
characterization studies of aged Li-ion large format Besenhard JO, Winter M, Wohlfahrt-Mehrens M,
cells for improved performance: an overview. Journal Vogler C, Hammouche A. Aging mechanisms in
of Electrochemical Society 2013; 160(11): lithium-ion batteries. Journal of Power Sources 2005;
A2111–A2154. 147:269–281.
11. Howell D, Overview of battery R&D activities, US 26. Aurbach D, Zinigrad E, Cohen Y, Teller H. A short
Department of Energy, Annual Merit Review, (2012), review of failure mechanisms of lithium metal and
Washington, D.C. lithiated graphite anodes in liquid electrolyte solutions.
12. Dunn B, Kamath H, Tarascon JM. Electrical energy Solid State Ionics 2002; 148:405–416.
storage for the grid: a battery of choices. Science 27. Goers D, Spahr M, Leone A, Markle W, Novak P.
2011; 334:928–935. Electrochimica Acta 2011; 56:3799.
13. Kong F, Kostecki R, Nadeau G, Song X, Zaghib K, 28. Bedrov D, Smith G, Van Duin A. Journal Physical
Kinoshita K, McLarnon F. In-situ studies of SEI Chemical A 2012; 116:2978.
DOI: 10.1002/er
29. Marcicki J, “Modeling, parametrization, and Primary and Secondary Battery Technology and
diagnostic for lithium-ion batteries with automotive Applications; Fort Lauderdale, FL, Florida
application”. Doctoral Thesis, Ohio State University, Educational Seminars, Inc.: Fort Lauderdale, FL,
Columbus, OH, (2012). (1995).
30. Safari M, Morcrette M, Teyssot A, Delacourt C. 51. Roth EP, Doughty DH, Pile DL. Effects of separator
Journal of the Electrochemical Society 2009; 156:145. breakdown on abuse response of 18650 Li-ion cells.
31. Ning G, White R, Popov B. Electrochimica Acta 2006; Journal of Power Sources 2007; 174:579–583.
51:2012. 52. Maleki H, Shamsuri AK. Thermal analysis and
32. Broussely M, Herreyre S, Biensan P, Kasztejna P, modeling of a notebook computer battery, J. Power
Nechev K, Staniewicz R. Journal Power Sources Sources 2003; 115:131–136.
2001; 97:13. 53. Kawakita J, Kobayashi K. Journal of Power Sources
33. Ohzuku T, Ueda A, Yamamoto N, Iwakoshi Y. 2000; 90:182.
Journal Power Sources 1995; 54:99. 54. Yoshimoto N, Shibata T, Ishikawa M, Morita M,
34. Ratnakumar BV, Smart MC, Surampudi S. Journal Gijutu H. Journal of the Surface Finishing Society of
Power Sources 2001; 97–98:137. Japan 2001; 52:581.
35. Winter M, Moeller KC, Besenhard JO, Nazri GA, 55. Morita M, Shibata T, Yoshimoto N, Ishikawa M.
Pistoia G. Lithium Batteries Science and Technology. Electrochimica Acta 2002; 47:2787.
Kluwer Academic: Dordrecht, 2003. 56. Morita M et al. Anodic behavior of aluminum current
36. Du Pasquier A, Disma F, Bowmer T, Gozdz AS, collector in LiTFSI solutions with different solvent
Amatucci G, Tarascon JM. Journal of the compositions. Journal of Power Sources 2003;
Electrochemical Society 1998; 145:472–477. 119–121:784.
37. Spotnitz R, Franklin J. Jouranl of Power Sources 57. Cannarella J, Arnold CB. The effects of defects on
2003; 113:81–100. localized plating in lithium-ion batteries. Journal of
38. Braithwaite JW et al. Corrosion of lithium-ion battery the Electrochemical Society 2015; 162(7):
current collectors. Journal Electrochemical Society A1365–A1373.
1999; 146(2):448–456. 58. Ning G, Haran B, Popov BN. Journal of Power
39. Wohlfahrt-Mehrens M, Vogler C, Garche J. Journal Sources 2003; 117:160–169.
Power Sources 2004; 127:58–64. 59. Dubarry M et al. Evaluation of commercial lithium-ion
40. Demirocak DE, Bhushan B. Journal of Colloid and cells based on composite positive electrode for plug-in
Interface Science 2014; 423:151–157. hybrid electric vehicle applications. Part II:
41. Zhang X, Shyy W, Sastry AM. Journal of the Degradation mechanism under 2C cycle aging.
Electrochemical Society 2007; 154:A910–A916. Journal of Power Sources 2011; 196:10336–10343.
42. Christensen J, Newman J. Journal of Solid State 60. Ji Y, Zhang Y, Wang CY. Li-ion cell operation at low
Electrochemistry 2006; 10:293. temperatures. Journal of the Electrochemical Society
43. Renganathan S, Sikha G, Santhanagopalan S, White R. 2013; 160(4):A636–A649.
Journal Electrochemical Society 2010; 157:A155. 61. Leng F, Ming Tan C, Pecht M. Effect of temperature
44. Zhao K, Pharr M, Vlassak J, Suo Z. Journal of Applied on the aging rate of Li ion battery operating above
Physics 2010; 108:073517. room temperature. Scientific Reports 2015; 5:12967.
45. Deshpande R, Cheng Y, Verbrugge M, Timmons A. https://doi.org/10.1038/srep12967.
Journal of the Electrochemical Society 2011; 158:A718. 62. www.electropaedia.com, copyright by Woodbank
46. Nagpure SC, Dinwiddie R, Babu SS, Rizzoni G, Communications Ltd (2005).
Bhushan B, Frech T. Journal of Power Sources 63. Samadani E et al. Li-ion battery performance and
2010; 195:872. degradation in electric vehicles under different usage
47. Du Pasquier A, Blyr A, Cressent A, Lenain C, scenarios. Intenatonal Journal Energy Research
Amatucci G, Tarascon JM. Journal of Power Sources 2016; 40:379–392.
1999; 81–82:54. 64. Karimi G, Dehghan AR. Thermal analysis of high-
48. Liu Y, Li X, Guo H, Wang Z, Hu Q, Peng W, Yang Y. power lithium-ion battery packs using flow network
Journal of Power Sources 2009; 189:721. approach. International Journal Energy Research
49. Kostecki R, Norin L, Song X, Mc Larnon F. Journal of 2014; 38:1793–1811.
the Electrochemical Society 2004; 151(4). 65. Malik M, Dincer I, Rosen M. Review on use of phase
50. Spotnitz R, Ferebee M, Callahan RW, Nguyen K, Yu change materials in battery thermal management for
WC, Geiger M, Dwiggens C, Fischer H, Hoffman D, electric and hybrid electric vehicles. Internal Journal
Proceedings of the 12th International Seminar on Energy Research 2016; 40:1011–1031.
DOI: 10.1002/er
66. Yamaki J, Liquid electrolytes, chapter 5, pp. 155–183, cells for improved performance: an overview. Journal
Advances in Lithium-Ion Batteries, W. van Schalkwijk of Electrochemical Society 2013; 160(11):
and B. Scrosati (Eds.), ISBN 978-0-306-47508-5, A2111–A2154.
Springer Science & Business Media New York, (2002). 71. Ramdon S, Bhushan B, Nagpure SC. In situ
67. Huang JY, Zhong L, Wang CM, Sullivan JP, Xu W, electrochemical studies of lithium-ion battery cathodes
Zhang LQ, Mao SX, Hudak NS, Liu XH, Subramanian using atomic force microscopy. Journal of Power
A, Fan H, Qi L, Kushima A, Li J. Science 2010; Sources 2014; 249:373–384.
330:1515. 72. Campana FP, Kotz R, Vetter J, Siegenthaler H. In-situ
68. Wang F, Yu H-C, Chen M-H, Wu L, Pereira N, atomic force microscopy study of dimensional changes
Thornton K, Van DVA, Zhu Y, Amatucci GG, Graetz during Li+ ion intercalation/de-intercalation in highly
J. Nature Communications 2012; 3:2185. oriented pyrolitic graphite. Electrochemistry
69. Nagpure S.C., Multi-scaled characterization of aged Communition 2005; 7:107–112.
Li-ion battery materials for improving performance, 73. Park J, Kalnaus S, Han S, Lee YK, Less GB, Dudney
Ph.D. Thesis, The Ohio State University, Department NJ, Daniel C, Sastry AM. In situ atomic force
of Mechanical and Aerospace Engineering, Columbus, microscope studies on lithium (de)intercalation-
Ohio (2012). induced morphology changes in LixCoO2 micro-
70. Nagpure SC, Bharat B, Babu SS. Multi-scale machined thin film electrodes. Journal of Power
characterization studies of aged Li-ion large format Source 2013; 222:417–425.
DOI: 10.1002/er

Er 3762

Uploaded by

Copyright:

Available Formats

Er 3762

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Er 3762

Uploaded by

Copyright:

Available Formats

INTERNATIONAL JOURNAL OF ENERGY RESEARCH

Int. J. Energy Res. (2017)

Degradation mechanisms in Li-ion batteries: a state-of-

Received 23 January 2017; Revised 2 April 2017; Accepted 2 April 2017

1. INTRODUCTION secondary battery technologies that are commercially

Copyright © 2017 John Wiley & Sons, Ltd.

comparison with the other battery chemistries, because

Until recently, very few studies have been conducted to

continuity loss, (ii) corrosion products attacking or 3.1. Anode degradation

interplay can lead to the degradation of mechanical 3.2. Cathode degradation

Table I. Li-ion anode aging-causes, effects, and impacts [25].

Cause Effect Results in Alleviated by Elevated by

This insertion/extraction of Li ions results in changing 3.2.3. Active material dissolution

Figure 9. Causes and effects of degradation in the cathode [39]

in surfaces. Eventually, over-discharging can contribute

4.1. Effect of cycling rate and cycle number

As vividly seen in the literature, aging is accelerated with

Figure 20 illustrates the effect of C-rate on the battery

4.4. Effect of moisture

Contaminants, in particular water or moisture, have also

Characterization technique Main requirement(s) Remarks

Optical techniques Top cover transparent to visible light

Raman microscope Structural and chemical composition

Solid-state Li-ion battery is used.

Scanning electron A lower vacuum in some SEM types

Neutron techniques Window transparent to It can quantify Li distribution and

Neutron depth proﬁling (NDP) It can measure Li concentration

Neutron imaging (NI)

Neutron diffraction Wound cathode, electrolyte, and anode stack

You might also like

Pfad - The Proxy pFad of © 2024 Garber Painting. All rights reserved.