Journal of Energy Chemistry 59 (2021) 83–99

Contents lists available at ScienceDirect

Journal of Energy Chemistry

journal homepage: www.elsevier.com/locate/jechem

Review

A review of lithium-ion battery safety concerns: The issues, strategies,

and testing standards
Yuqing Chen a,c,1, Yuqiong Kang b,1, Yun Zhao c,⇑, Li Wang c, Jilei Liu a,⇑, Yanxi Li d, Zheng Liang d,⇑,
Xiangming He c, Xing Li e, Naser Tavajohi f, Baohua Li b,⇑
a
College of Materials Science and Engineering, Hunan Province Key Laboratory for Advanced Carbon Materials and Applied Technology, Hunan University, Changsha, 410082, China
b
Engineering Laboratory for Next Generation Power and Energy Storage Batteries, Graduate School at Shenzhen, Tsinghua University, Shenzhen 518055, Guangdong, China
c
Institute of Nuclear & New Energy Technology, Tsinghua University, Beijing 100084, China
d
Department of Materials Science and Engineering, Stanford University, Stanford, CA 94305, USA
e
Technical Center, SAIC Motor, Shanghai 201804, China
f
Department of Chemistry, Umeå University, Umeå 90187, Sweden

a r t i c l e i n f o a b s t r a c t

Article history: Efficient and reliable energy storage systems are crucial for our modern society. Lithium-ion batteries
Received 7 August 2020 (LIBs) with excellent performance are widely used in portable electronics and electric vehicles (EVs),
Revised 9 October 2020 but frequent fires and explosions limit their further and more widespread applications. This review sum-
Accepted 18 October 2020
marizes aspects of LIB safety and discusses the related issues, strategies, and testing standards.
Available online 3 November 2020
Specifically, it begins with a brief introduction to LIB working principles and cell structures, and then pro-
vides an overview of the notorious thermal runaway, with an emphasis on the effects of mechanical, elec-
Keywords:
trical, and thermal abuse. The following sections examine strategies for improving cell safety, including
Lithium-ion batteries
Standards
approaches through cell chemistry, cooling, and balancing, afterwards describing current safety stan-
Safety dards and corresponding tests. The review concludes with insights into potential future developments
Thermal abuse and the prospects for safer LIBs.
Mechanical abuse Ó 2020 The Authors. Published by ELSEVIER B.V. and Science Press on behalf of Science Press and Dalian
Electrical abuse Institute of Chemical Physics, Chinese Academy of Sciences. This is an open access article under the CC BY-
NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction however, by their limited safety performance [7-11]. In recent

years, tons of LIBs have been recalled due to explosion and fire
Lithium-ion batteries (LIBs) have raised increasing interest due accidents [12-15], resulting in severe economic issues for related
to their high potential for providing efficient energy storage and market sectors and significantly damaging the reputation of LIBs
environmental sustainability [1]. LIBs are currently used not only [16-19]. Consequently, increasing attention is being paid to LIB
in portable electronics, such as computers and cell phones [2], safety issues and a large number of safety strategies are being
but also for electric or hybrid vehicles [3]. In fact, for all those developed.
applications, LIBs’ excellent performance and energy density have Battery safety is profoundly determined by the battery chem-
made them increasingly popular [4]. In addition, the battery mar- istry [20-22], its operating environment, and the abuse tolerance
ket for portable electronics is currently dominated by LIBs because [23,24]. The internal failure of a LIB is caused by electrochemical
of their inherent advantages over other battery systems, such as system instability [25,26]. Thus, understanding the electrochemi-
high specific capacity and voltage, no memory, excellent cycling cal reactions, material properties, and side reactions occurring in
performance, little self- discharge, and wide temperature range LIBs is fundamental in assessing battery safety. Voltage and tem-
of operation [5,6]. Further expansion of the LIB market and its perature are the two factors controlling the battery reactions.
large-scale implications in EVs are currently significantly hindered, Safety accidents are accompanied by continuous heat and gas gen-

⇑ Corresponding authors.
E-mail addresses: zhao.yun@sz.tsinghua.edu.cn, yzhao.zjut@hotmail.com (Y. Zhao), liujilei@hnu.edu.cn (J. Liu), lianzhen@stanford.edu (Z. Liang), libh@sz.tsinghua.edu.cn
(B. Li).
1
These authors contribute to this work equally.

https://doi.org/10.1016/j.jechem.2020.10.017
2095-4956/Ó 2020 The Authors. Published by ELSEVIER B.V. and Science Press on behalf of Science Press and Dalian Institute of Chemical Physics, Chinese Academy of
Sciences.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Y. Chen, Y. Kang, Y. Zhao et al. Journal of Energy Chemistry 59 (2021) 83–99

eration, which causes battery rupture and ignition of the com- transport from the anode side back to the cathode. The charge
bustible materials [27-29]. The external environment (which con- and discharge reactions are as follows:
trols the temperature, voltage, and electrochemical reactions) is
Charge þ
the leading cause of internal disturbances in batteries [30]. Thus, Cathode : LiCoO2
Lið1xÞ CoO2 þ xLi þ xe
Discharge
the environment in which the battery operates also plays a signif-
Charge
icant role in battery safety. Anode : 6C þ xLiþ þ xe
Lix C6
Safety standards and related tests have been developed to ana- Discharge

lyze battery performance and influential factors to meet the Charge

Reactions : LiCoO2 þ 6C
Lið1xÞ CoO2 þ Lix C6
required safety demands. For example, GB/T 31485–2015 standard Discharge
safety tests [31] were established in China, thereby helping the
Shuttling of Li+ during battery operations generates a significant
implementation of stringent standards for LIBs produced and used
amount of heat, which is released as a result of the Joule heat and
in China. These strict and vigorous battery safety tests ensure no
the chemical energy of the charge/discharge process [39]. This heat
future safety problems under normal working conditions. Stable
release is a normal part of battery operation, but if the generated
LIB operation under normal conditions significantly limits battery
heat has no efficient dissipation path in certain charge/discharge
damage in the event of an accident. As a result of all these mea-
states the battery would become excessively hot, which seriously
sures, current LIBs are much safer than previous generations,
compromise battery safety [40].
though additional developments are still needed to improve bat-
The four most commonly-used types of cell in LIBs are cylindri-
tery safety even further.
cal, prismatic, coin, and pouch cells (Fig. 1b-e) [41]. Cylindrical
Several high-quality reviews papers on battery safety have been
cells include both high- and low-capacity cells. Due to the high
recently published, covering topics such as cathode and anode
impedance of high-capacity cylindrical cells, low-capacity cells
materials, electrolyte, advanced safety batteries, and battery ther-
are used in most applications. Prismatic cells have large capacities,
mal runaway issues [32-35]. Compared with other safety reviews,
so fewer cells need to be connected to assemble a battery pack
the aim of this review is to provide a complementary, comprehen-
with the required capacity, with benefits for overall system stabil-
sive overview for a broad readership with special interest in root
ity [42]. Coin cells are small and typically used for laboratory mate-
causes of safety incidents, strategies to improve safety on different
rial testing. The pouch design does, however, offer flexibility in
levels, as well as a systematic introduction to various safety stan-
terms of matching the cell to a specific device shape. This advan-
dards and test specifications. This review summarizes various
tage has allowed pouch cells to achieve a majority market share.
aspects of LIB safety, with the main goal of describing the issues,
From the perspective of safety, a larger cell size typically makes
strategies, and testing standards for checking and improving such
it challenging to ensure its overall reliability. The safety risk
safety. It starts with a brief introduction to LIB structure and mate-
increases in the order of cylindrical cells < pouch
rials; we then summarize the processes leading to LIB thermal run-
cells < prismatic cells. The heat dissipation of prismatic cells is
away under mechanical, electrical, and thermal abuse conditions;
poor, which makes the cooling process and cell assembly more
afterwards we propose solutions for improving battery safety, in
challenging. The small size, lower energy stored of cylindrical cells
normal and abuse conditions, such as adjusting the cell chemistry,
as well as the gap between each single cell all together enable the
as well as improving cell cooling and cell balancing; lastly, we
cylindrical-based battery packs with better heat dissipation. The
review LIB safety standards and applicable tests worldwide. The
shell casing of cylindrical and prismatic cells is metallic and can
review then concludes with an overview of potential future devel-
withstand high pressure. In contrast, the aluminum-plastic com-
opments and strategies for improving LIB safety.
posite film in pouch cell’s shell casings deforms easily and with-
stands less pressure [43]. Once there is an internal safety issue, a
pouch cell battery will swell and bulging will occur at the weakest
2. LIB working principle
point on the battery surface, which may lead to a fire but not an
explosion. Currently, when selecting types of cell, automakers
LIBs typically consist of four major parts: cathode, anode, sepa-
mainly consider their own battery integration technology and the
rator, and electrolyte [36]. Cathodes and anodes are the charge car-
balance of overall battery performance. For example, cylindrical
riers contributing to LIB energy storage and release. The separator
cells are used in Tesla S3 models, prismatic cells in BYD Tang, Song,
physically divides the electrodes to prevent internal short-circuits
and Qin models, and pouch cells in SAIC Motor’s ROEWE R ER6
while allowing Li+ flow. The electrolyte carries ions, including Li+.
model.
The malfunction of these parts, together or individually, can nega-
In practical, hundreds to thousands cells are typically combined
tively affect LIB safety. When operating, the electrodes produce
(in parallel and in series) into one battery pack to obtain specific
heat, which might become uncontrollable during battery malfunc-
voltage and capacity (Fig. 1f) [44]. For example, the Tesla EV con-
tion [37]. If a separator is damaged, LIB processes transit from con-
tains about 7000 cylindrical cells with a total voltage and capacity
trolled to uncontrolled electrochemical reactions, with significant
of 400 V and 85 kWh, respectively [45]. Battery management in
heat generation [38]. In such cases, the electrolyte acts as a fuel
such a large battery pack is pretty challenging for battery safety.
supply for further heat generation, so appropriate safety regula-
tions, which can be established by researching the controllable
and uncontrollable factors in battery failures, are essential for 3. LIB safety issues
improving LIB safety performance.
The working mechanism of typical LIBs is shown in Fig. 1(a), Even under normal operating conditions, battery-generated
using a LiCoO2/graphite cell as an example [36]. During charging, heat cannot be entirely removed, especially on hot days or in a
Li+ de-intercalates from the cathode materials (LiCoO2, in this large battery pack [40]. Rising battery temperature would trigger
case), diffuses into the electrolyte and moves through the separator other undesirable parasitic reactions, causing thermal runaway,
nano-pores to intercalate into the anode material. Meanwhile, where battery heat generation cannot be controlled [46]. During
electrons move in the opposite direction through the external cir- mechanical (damage to shell casing, compression, punching, and
cuit to maintain electro-neutrality. During discharging, Li+ ions twisting of cells), electrical (overcharge/discharge and short cir-

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Fig. 1. (a) Schematic diagram of the fundamental structure of a LIB cell, which is the same for different cell types [36]. Copyright (2011) American Association for the
Advancement of Science [36]. Cell types: (b) cylindrical cell; (c) prismatic cell; (d) coin cell; (e) pouch cell. Copyright (2001) Macmillan Magazines Ltd [41]. (f) Schematic
diagram of the relationship between cell, module, and battery.

Fig. 2. An overview of battery safety issues. Battery accidents, disasters, defects, and poor control systems (a) lead to mechanical, thermal abuse and/or electrical abuse (b, c),
which can trigger side reactions in battery materials (d). Broken separators and oxygen released from cathodes are the main reasons for cell thermal runaway, which can
generate smoke, fires, and explosions with the help of oxygen from air (e). (f) Collision (mechanical abuse), charging (electrical abuse), self-ignition (thermal abuse) and
thermal shock (thermal abuse) caused electric vehicle fires. (1) The collision process causes the battery to squeeze, and the area with strong stress is damaged, resulting in the
internal short-circuit or the casing rupture, which can cause thermal runaway of batteries. (2) During the abused charging process, the heat generation is too late to diffuse,
resulting in heat accumulation inside the battery, leading to thermal runaway of batteries. (3) During the operation of the battery, if the heat generated is too late to diffuse, it
is easy to cause the battery thermal runaway. (4) When the battery receives a local thermal shock, it is easy to cause the battery to catch fire. The fire of an electric vehicle will
cause the burning of electric vehicles in the nearby area.

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cuit), and thermal abuse (thermal shock and local heating) situa- local forces, which in extreme cases can cause local damage to LIBs
tions, which could occur during accidents, thermal runaway will [59].
occur even quicker (Fig. 2a-c, and f) [47-49]. Understanding LIB Each cell includes a shell (made of aluminum plastic film or
performance in unsafe conditions is critical, therefore, for the pro- steel) and a jelly roll composed of cathode, anode as well as sepa-
duction of safer cells. rator. Under external forces, the weakest point of this cell is prone
to damage. Numerous battery ignition cases are caused by
3.1. Safety issues caused by undesirable chemical reactions mechanical abuse (mainly collisions) in electric vehicles every
year, but few details are publicly reported. Current research on
In the normal voltage and temperature range, only Li+ shuttle mechanical abuse focuses on theoretical simulation and experi-
occurs in the electrolyte during the insertion/extraction cycles at mental verification to provide reference data for battery manufac-
the cathode and anode. At high-temperature and high-voltage con- turers. Therefore, in this section, we mainly discuss the impact of
ditions, the electrochemical reactions become more complex, different kinds of mechanical abuse of batteries, largely based on
including decomposition of the solid electrolyte interface (SEI) theoretical simulations, to provide indications of their effects for
film, oxygen release at the cathode side, and additional elec- readers.
trolyte/electrode parasitic side reactions [50]. SEI film decomposi- The outer casing provides a cell’s first level of thermal and
tion and interfacial reactions initially accelerate the temperature mechanical protection. The shell casing needs to withstand
increase, thereby increasing risks of oxygen release from the active mechanical force and not break, and ensure that the internal struc-
cathode materials [51]. These reactions eventually lead to LIB ther- ture is not damaged under certain deformation conditions [60].
mal runaway, which causes battery rupture and explosion due to The mechanical behavior of the shell casing is an important aspect
the reaction of hot flammable gases from the battery with the of the overall LIB mechanical behavior, as it is the most vulnerable
ambient oxygen [52]. point during safety accidents, so it should be understood and taken
into account during LIB materials’ design and consideration [57].
Upon damage to it, air directly enters the battery system, reacting
3.2. Thermal runaway with the active components and electrolytes.
Even when the shell casing is only deformed, LIB internal com-
Thermal runaway is the most detrimental LIB safety issue. Fig. 2 ponents might still be severely damaged: metallic current collec-
shows the origins of thermal runaway in batteries, including side tors and separators with insufficient flexibility would break,
reactions of electrolyte, cathode, anode, and interfacial reactions causing direct contact between the electrodes [61]. When the heat
at the surface of electrodes and Li plating. These side reactions generated by the high-energy density LIB after a localized short cir-
are triggered by mechanical, thermal, and electrical abuse. Break- cuit is sufficient to trigger other internal short circuits in the area,
age of the separator and the oxygen evolution from the cathode thermal runaway occurs in overall battery [62].
side are the root causes to batteries’ thermal runaway (as shown The distribution of internal stresses in a cell varies depending
in the solid line of Fig. 2d). on the form of mechanical abuse [63]. Such stresses in certain areas
There are five types of causes for this phenomenon, which are of the battery could cause internal short circuits. Fracture predic-
illustrated in Fig. 2. The first type is uncontrollable internal heat tion and the possible internal short circuit inhibition are proved
generation, which causes oxygen release from the cathode mate- to be achieved by finite element simulations on cell’s cylindrical
rial, leading to numerous side reactions [37,53]. In the second type, casing as well as the cell housing. The experimental results agreed
separator defects (due to thermally-induced shrinkage or mechan- with the theoretical results: short circuit initiated at end of the
ical damage) create short circuits in the battery and rapid dis- cylinder, close to the connection section of battery electrode,
charge of the energy stored in it [54], accompanied by which was confirmed by an infrared image (Fig. 3a). Indentation
undesirable chemical chain reactions and release of massive damage caused the short circuit to appear close to the punch area
amounts of heat. The third type is electrical abuse [55]. Electrolyte (Fig. 3b), whereas bending mechanical damage caused the short
decomposition, especially in a high state of charge (SOC), occurs at circuit to form on the cylinder casing surface opposite the point
the cathode interface. This leads to heat accumulation and conse- of force (Fig. 3c).
quently release of oxygen from the cathode and damage to the sep- Cell damage by squeezing deformation can tear the separator,
arator. The fourth type consists of electrochemical side reactions causing the electrodes to come into direct contact. The resulting
caused by local thermal abuse. If the heat generated during normal damage and observations are quite different to those from short
LIB operations cannot be dissipated quickly enough, the separator circuiting caused by nail penetration. Pan et al. modeled the
in that specific place will shrink or rupture [41,56]. The fifth type changes in a LIB cell subjected to in-plane compression [64]. Dur-
occurs during mechanical battery damage, which causes short cir- ing the deformation under a 8.5% of nominal strain, no voids could
cuits and/or air to penetrate the battery [57]. The main causes of be observed at the bending site along shear band outer boundaries
battery safety accidents among these five categories are short- (Fig. 3d). At the final step of the compression, when the nominal
circuiting due to separator damage, electrical abuse, and mechan- strain reached 34%, the fraction of void volume at top region of
ical abuse [11,58]. the sample decreased compared with that near the bottom
(Fig. 3e).
3.3. Safety issues caused by mechanical abuse Shear strain could be introduced to the cell by a slight twisting,
which in turn increases the tension zone maximum strain and
Due to the high energy density of LIBs, local damage caused by stimulates polymer failure. Wang group demonstrated that under
external influences, for example in case of collisions, will release a a 12° twisting the maximum strain increased by over 77% in the
significant amount of heat, which can easily cause thermal run- tension zone (Fig. 3f and g) [65]. Under this condition, slip and stick
away. As a result their safety risk is high. As the number of EVs region were created due to partial slipping of the cell as well as
(containing LIBs) on the roads continues to increase, safety con- contact surface.
cerns over battery behavior during potential vehicle collisions are Under more extreme conditions, damage similar to that
becoming more prominent. A moving car’s battery experiences observed during nail penetration tests occurs: the separator

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Fig. 3. Comparison of short-circuit locations for different cells observed experimentally as well as their corresponding model predictions under various breakage cases
indicated: (a) ‘‘radial crushing”, (b) ‘‘indentation”, (c) ‘‘bending”. Copyright (2012) Elsevier [63]. Void space fraction distributions under nominal strains of (d) 8.5% and (e) 34%
of the constrained compression simulation. Copyright (2013) Elsevier [64]. Stress distribution in the separator layer by sumulations (f) before twisting and (g) after 12° angle
twisting. Copyright (2014) Elsevier [65]. (h) The temperature distribution of pouch cell during the nail penetration process [68].

becomes pierced and a small amount of air near the nail penetrates teries would become overcharged if they are charged any further
the cell, initiating vigorous exothermic oxidation reactions, with [70]. Overcharge first causes electrolyte decomposition at the cath-
excessive and heat that is difficult to dissipate, which increases ode interface [71]. This reaction slowly increases the battery tem-
the temperature of nearby areas (Fig. 3h) [66-68]. The ideal situa- perature. Subsequently, excessive Li+ deintercalation from the
tion is when the nail penetration generates only a small amount of cathode occurs. The cathode material becomes unstable and start
heat and self-passivation of the electrode material interface occurs to release oxygen, while excess Li+ deposits on the anode to form
quickly, thereby preventing a battery fire [67]. Wang et al. showed Li dendrite [72]. Heat and gas generation during the side reactions
that during LIB penetration with a small nail or during indentation, would lead to safety accidents, such as cell overheating and rup-
the metallic casing and the nail itself acted as heat sinks [68]. The ture [73]. Ouyang et al. summarized the overcharge process of a
same test performed with a LIB with higher capacity and voltage 40 Ah LIB containing LiyNi1/3Co1/3Mn1/3O2(NCM) + LiyMn2O4
resulted in more significant damage. LIB nail penetration tests of (LMO) composite cathode and graphite anode (Fig. 4a) [55]. In
LiCoO2 cell carried out by Doh et al. resulted in a fire and sudden stage I, the battery voltage increased steadily and exceeded its
voltage drop to 0 V, with the temperature increasing sharply to nominal cut-off voltage, marking the beginning of an overcharge
420 ℃ [69]. At the moment of penetration, a very high discharge process. In stage II, when the battery was overcharged by 1.2 V
current overflow from the battery occurred, generating high Joule above full SOC, side reactions began to occur inside the battery.
heat, which shrank the battery separator. Nature of the active cath- The battery temperature rose even more rapidly in stage III and
ode material, as well as cell’s specific capacity and state of charge the battery started to swell. In stage IV, the battery casing rup-
(SOC) profoundly influence the results of nail penetration test. tured, which damaged the separator and caused LIB thermal run-
Thus, the targeted design of the battery structure, or its enhance- away. Charging rate is often the most significant factor affecting
ments, and incorporation of built-in protective measures will dra- overcharge, as the overcharging current density determines the
matically improve LIB safety during use. rate of heat generation by the battery reactions: the higher the cur-
rent, the more heat is generated per unit time, thereby increasing
3.4. Safety issues induced by electrical abuse the risks of uncontrollable LIB behavior.
The principle of over-discharge is similar that of over-charge.
When a battery is in an overcharge or over-discharge state, or is Some cells reach the set state of discharge (SOD) in advance. Thus,
undergoing an external short circuit, it experiences electrical an over-discharge occurs if a cell is forced to continue to discharge
abuse, and a series of undesirable electrochemical reactions occurs [74]. Forced over-discharge continuously releases Li+ from the
in it. anode, which change the graphite structure and destroy the SEI.
There are many reasons for battery overcharging. One of the At very deep SOD, a copper current collector is oxidized, with the
main reasons is the inconsistency of battery cells. If the voltage released copper ions potentially being deposited on the cathode
of any battery cell cannot be effectively monitored by the manage- surface [75]. Too much copper deposition results in the short-
ment system, there will be risks of its overcharging. Since excess circuit of cell. The over-discharge profile of a 25 Ah commercial
energy is stored into the battery, overcharging is very dangerous. LIB pouch cell containing a NMC-based cathode and a graphite-
Typically, all batteries are first charged to a specific SOC, but some based anode can be described by three stages based on observed
batteries initially have higher SOC before charging. Thus, such bat- voltage variations (Fig. 4b) [76]. During stage I (up to 11% below

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Fig. 4. Schematic presentation of the (a) overcharge and (b) over-discharge process. Copyright (2017) Elsevier [55]. Copyright (2016) The Author(s) [76]. (c) Infrared radiation
image taken when cell rupture during a short circuit test. Copyright (2017) Elsevier [79].

SOD in the cited study), the voltage first drops rapidly due to Li+ 3.5. Safety issues caused by thermal abuse
deintercalation from the anode to intercalate into the cathode.
During stage II (up to 20% below SOD), Cu foil oxidization leads In thermal abuse situations, a battery experiences thermal
to a stable voltage. During the third stage, involving extensive shock, or its local temperature is too high [80]. Battery fires might
SOD, the voltage asymptotically decreases to 0 V due to short- occur during electric vehicle charging or if nearby vehicles are on
circuiting caused by Cu dendrite. Li et al. showed that SEI dissolu- fire. Combustibles in the air (such as very flammable pollen grains
tion is the main reason for degradation in over-discharge condi- or airborne seeds, flowers or leaves) in the vicinity of a malfunc-
tions at low voltages, as well as for dissatisfactory cycling tioning battery might ignite if they are very close to or in contact
performance [77]. with a hot battery, or a spark, setting everything around them on
An external short circuit occurs when a cathode and an anode of fire.
the same cell are in direct contact through a conductor. In such Localized high-temperature areas within a battery are typically
cases, instead of decoupled electron and ion transportation, both related to its design. Poor LIB design leads to high impedance at the
electron and ion transfer occur at the same place and Li+ migrates metal contacts or uneven heat dissipation, as manifested by the
quickly inside the cell, rapidly discharging the battery. During a non-uniform temperature distribution observed in a LIB under
safety accident, a LIB cathode and anode might indeed come into thermal shock [81], simulated by placing it in an oven at 155 °C
contact, releasing the heat relatively evenly and quickly [78]. It is for 1200 seconds [47]. Since the elevated surrounding temperature
found that the complicated short-circuit behavior could be divided caused exothermic reactions, the temperature distribution within
by three steps, as shown by Kriston et al. [79]. In the first step, a the battery was more associated with the heat generated from
rapid discharge under 274C was observed. In the second step, the these reactions than with the thermal energy distribution resulting
discharge rate was reduced to 50C – 60C, and mass transport from the elevated surrounding temperature. The highest tempera-
was the limiting factor. At the same time, cell temperature ramped ture was observed at the center. The non-uniformity of the temper-
up to 77 – 121 °C and the cell eventually ruptured, causing the ature distribution became more apparent with increased storage
electrolyte’s leakage (Fig. 4c). At the final stage, the cell current time. After 3600 seconds under these conditions, thermal runaway
continued to drop to the fading voltage. The ratio of external to occurred in the cell.
internal resistance after normalization had profoundly effect on In theory, battery cycling cannot cause safety accidents because
the discharge rate. the heat generated during normal anodic and cathodic reactions is
Overcharge is the most dangerous types of electrical abuse and insufficient to cause a sharp temperature increase. In reality, how-
one of the most frequently observed reasons for LIB safety acci- ever, the electrode heat release rate is often higher than its cooling
dents. The other two types of electrical abuse, over-discharge and rate. Heat dissipation of a LIB depends on its external surface area
external short circuiting, are relatively benign and do not cause and geometry. Heat dissipation by radiation helps to alleviate some
instant and fast-developing accidents. They can, however, still of the generated heat. As a result, some of the heat remains stored
impair a LIB’s state of health (SOH). inside the battery. At some point, if this heat continues to accumu-

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Table 1 neers believe that LiFePO4 will remain the mainstream active cath-
Temperature ranges and enthalpies of various exothermic reactions occurring in LIBs. ode material during the coming decades [99]. For a battery of the
Reactions Temperature range Enthalpy (J/ Ref. same capacity, if the oxygen release temperature of its active cath-
(℃) g) ode materials is below that of LiFePO4, rigorous safety testing is
SEI decomposition 100–130 186–257 85,86 recommended before using it in practical applications. LIBs con-
LiC6/electrolyte 110–290 1460–1714 87 taining Ni-rich Ni-Mn-Co-oxides need improved interface stability
LiC6/PVDF 220–400 1100–1500 88 and electrolyte and separator systems to pass current safety test
LixCoO2 decomposition 178–250 146 89
LixNi0.8Co0.2O2 175–340 115 90
standards [100]. In penetration tests, pouch cell assembled using
decomposition LFP-coated NMC333 material (LFP@NMC333) and graphite anode
LixCoO2/electrolyte 167–300 381–625 91 with 100% SOC reportedly passed, while violent fires occurred dur-
LixNi0.8Co0.2O2/electrolyte 180–230 600–1256 92 ing the penetration of uncoated NMC333 cells. Moreover, coating
Electrolyte decomposition 225–300 155–258 93
NMC333 can increase the time required for thermal runaway by
about 25%, which greatly improves the safety of the battery
[101]. In addition, various factors, such as element doping, elec-
late instead of being dissipated, exothermic side reactions start to trolyte film-forming additives, and high-voltage electrolyte addi-
occur, further concentrating thermal stress [82]. Table 1 shows the tives, can improve the interface stability of the cathode material
temperature ranges and enthalpy of the typical exothermic reac- [102,103].
tions occurring in LIBs [83–93]. Thermal stress and pressure A separator is a porous polymer film. Its role is to separate the
build-up (due to the release of volatile side-products of these par- cathode physically from the anode but allow the ions to pass
asitic reactions) cause the explosion. between them. Traditional separators are polyolefin-based porous
membranes, which are thermally unstable and structurally fragile
4. Strategies for LIB safety improvements [104]. They shrink at elevated temperatures, causing LIBs contain-
ing such separators to fail current safety standards (Table 2). Thus,
Battery safety is determined by the active material and elec- shrinkage resistance and prevention of the internal short-circuiting
trolyte chemistry, the speed of heat generation and dissipation, of the battery upon separator shrinkage, as well as the polyolefin
and the tolerance of external forces. On one hand, safety analysis separators’ overall mechanical stability, need to be addressed
should start with evaluating the electrode active materials, elec- [105-107]. Some modifications on commercial separators, includ-
trolytes, and separators, as these are the most controllable factors. ing coating with ceramic particles or other materials with high
On the other hand, strategies for alleviating the consequences of thermal stability can effectively increase the temperature at which
thermal and electrical abuse also need to be engineered into LIBs. thermal degradation starts to about 250 °C [108,109]. In addition,
Moreover, freshly-manufactured LIBs can be tested for safety new types of separator materials and structures have been devel-
before they are incorporated into devices. oped, which can greatly improve battery safety, and some separa-
Since undesirable and uncontrollable heat and gas generation tors can even work normally at high temperatures [92,110,111].
from various parasitic reactions are the leading causes of LIB safety Lithium plating in the anode is also a major problem affecting
accidents, efforts to improve battery safety need to focus on ways the safety of LIB, which is mainly caused by electrical and thermal
to prevent LIBs from generating excessive heat, keeping them abuse. Since the lithium insertion potential of the graphite anode
working at a suitable voltage range, and improving their cooling (0.1 vs Li+/Li) is very close to the deposition potential of metallic
rates. lithium. Metallic lithium and electrolyte are unstable, and exces-
sive metallic lithium deposition will cause the formation of den-
4.1. Internal strategies for LIB safety improvements drites to pierce the separator and cause battery short circuit. The
most ideal solution at present is to develop anode materials with
Internal strategies include safety enhancement of each LIB com- higher lithiation potential to reduce the risk of lithium deposition.
ponent: active materials, separator, and electrolyte. Adding appro- Among them, Li4Ti5O12 has a higher lithium insertion potential but
priate additives to any of these components might also improve LIB a lower specific capacity (175 mAh g1), which will reduce the
safety performance [91,92]. energy density of LIBs in practical applications [112]. Si and P have
Cathode material needs to be chemically and structurally stable a high lithiation potential and a very high specific capacity
to maintain a controllable chemical reaction during lithiation and [113,114]. They are theoretically very suitable as anode materials
delithiation [53,93]. The heat release for common battery materials for next-generation lithium-ion batteries, but both of them have
has been summarized [11], and its starting temperature for cath- a large lithiation volume expansion (~300%) and still have chal-
ode materials has been found to follow the order LiCoO2 lenge in practical applications. Through the nanometerization of
(LCO) < LiNixCoyAlzO2 (NCA) < LiNixCoyMnzO2 (NCM) < LiFePO4 materials, it has begun to be applied in practice [115].
(LFP) (Fig. 5a). A very popular active cathode material is LiFePO4, Batteries containing traditional liquid organic carbonate-based
which has an ordered olivine structure and strong P-O covalent electrolytes often combust or even explode when exposed to air
bonds forming a three-dimensional structure with excellent ther- (or other undesirable conditions) because of the extreme elec-
modynamic and kinetic stability [94]. LiFePO4 has low reactivity trolyte flammability [116]. Furthermore, the poor thermal stability
with typical organic electrolytes, so cathodes containing LiFePO4 of these electrolytes causes their decomposition and reactions with
can have excellent cyclability [95,96]. Recently developed Ni- and the electrode’s active materials [117]. If a flammability point or
Li-rich materials have better voltage and specific capacity than decomposition temperature can be increased, or fire-retarding
LiFePO4 [97], but intense interface reactions, low-temperature oxy- additives can be added to decrease liquid electrolyte flammability,
gen release, and high local heat generation hinder their more wide- the drawbacks of the carbonate-based electrolytes would be signif-
spread use. Between 2018 and 2020, NMC and LFP batteries icantly diminished. The combustion reaction is mainly composed
accounted for approximately ~ 60% and 11% of LIB-based EVs’ total of free radical reactions. Therefore introducing a radical scavenger
safety accidents, respectively [98]. Thus, many scientists and engi- to the electrolyte can greatly lower the battery flammability. The

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Fig. 5. (a) Diagram schematically illustrating energy release from a LIB. Copyright (2018) Elsevier [11]. (b) Results of nail penetration tests of NCM333/graphite and
LFP@NMC333/graphite pouch cells at high SOC (images above, and thermal runaway curves below). Copyright (2014) Elsevier [101]. (c) Lithiation potential curves for typical
anodes (Li4Ti5O12, graphite, red P, and Si). Copyright (2019) Cellpress [114]. (d) Schematic diagram of flame-retarding additives for LIB. Copyright (2018) Elsevier [118].

Table 2 mal LIB operation range is 15–35 °C [126]. Thus, an optimal cooling
Shutdown temperatures and melting points of various polyethylene (PE), polypropy- control system capable of maintaining this range is essential for
lene (PP), and trilayer hybrid PP/PE/PP membranes.
safe and prolonged battery service life and to reduce costs.
Membrane composition Shutdown temperature (℃) Melting point (℃) Depending on the method of heat transfer, typical battery ther-
PE 130–133 139 mal management systems include (1) traditional cooling systems
PP 156–163 162 (e.g., air-based systems with an electric fan), (2) liquid-based sys-
PP/PE/PP 134–135 165 tems containing water, glycols, etc., (3) phase-change material
(PCM)-based, and (4) heat pipe-based thermal management sys-
tems [127]. As outlined below, these systems all have advantages
currently reported electrolyte additives are mainly small mole- and disadvantages, as well as specific applications, but their pri-
cules including phosphorus and fluorine species and ionic liquids, mary purposes are to control battery temperatures and minimize
and the addition amount in the electrolyte is generally about 10% formation of localized hot spots.
[118]. Implementation of solid-state electrolytes (based on poly- Air cooling systems (i.e. systems that use air as a medium to
mers, glasses, or ceramic materials) [119-124], with their out- remove heat) are structurally simple and easy to maintain. They
standing structural and thermal stability, can eliminate some of are classified as either ‘natural’ or ‘forced’ cooling systems, depend-
these adverse effects [125]. ing on whether or not energy is specifically used to drive them.
Natural cooling simply relies on the temperature difference
4.2. External strategies for LIB safety improvements between a battery and ambient air to cool the battery. If convection
is insufficient to dissipate the internal heat of the battery at its
4.2.1. Cooling maximal charge and discharge rates, a fan or a blower can be used
High temperature operation and temperature inconsistency to increase (‘force’) the movement of air around it and improve
between battery cells will lead to accelerated battery aging, which thermal exchange [128].
trigger safety problems such as thermal runaway, which seriously In liquid cooling systems, a liquid is used as a refrigerant to
threatens vehicle safety. A well-engineered built-in cooling system remove heat generated by a battery. Compared with air, liquids
is an essential part of LIB safety since it allows control of the sys- have greater thermal conductivity, thinner boundary layers and
tem temperature. A cooling system might be needed when the heat greater heat capacities [129]. Depending on whether the liquid is
is generated too late during cycling to dissipate. Under non- in contact with the battery, the system provides either direct or
uniform temperature distribution conditions, a cooling system is indirect liquid cooling. Immersion cooling cools all sides of the bat-
also needed to adjust the overall temperature manually. An opti- tery, thereby helping to improve temperature consistency. For

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Fig. 6. (a) Top view of velocity and pressure distributions in an inlet manifold (left) with and (right) without ventilation of a LIB module. Copyright (2013) Elsevier [132]. (b)
Temperature distribution under different cooling channels. Copyright (2016) Elsevier [133]. (c) Thermal runaway spreading triggered by one runaway cell in air-cooled
module with (left) and without (right) PCM microencapsulation. Copyright (2009) Elsevier [138].

safety reasons, however, such as potential short circuits and elec- while bigger channels improve cooling efficiency they result in
trochemical corrosion, immersion cooling is not currently used in uneven temperature distributions, and optimization of spacing
EVs [130]. improves temperature uniformity over a module. Ideally, the chan-
The coolant selected relates profoundly the entire cooling pro- nel size should match the coolant’s Reynolds number [134]. Cool-
cess, the battery structure and cell arrangement, the position of ing of batteries with layout limitations is often uneven, so
the liquid and air inlets/outlets, coolant flow rate. In the Tesla liq- suitable gas or liquid flow paths must be designed. For example,
uid cooling system a water and ethylene glycol mixture (in a 1:1 in some designs, the vortices at the inlet manifold are suppressed
mass ratio) is used as a coolant, and the cooling pipes meander by the ventilation hole geometry, but this effect can be used to
through the 18,650 stack of cells to improve heat dissipation effi- obtain a more uniform flow velocity [135].
ciency [131]. Zhao et al. found that the performance of a fan- As the battery power density increases, raising the heat transfer
based air cooling system was best when the fan was positioned coefficient becomes increasingly crucial. This can be done by
on top of the module (Fig. 6a), and a forced air cooling cubic applying mini-channels and enabling the cold plates to dissipate
arrangement provided the optimal combination of cooling effect the heat effectively. Excellent cooling efficiency of such mini-
and cost [132]. To enhance the cooling effect even more, optimiza- channel cold-plate thermal management systems has been
tion of the inter-cell distance in a battery module is generally rec- achieved during battery discharge at 5C rate. In fact, the five-
ommended (Fig. 6b) [133]. Increasing the spacing between the channel design was sufficient [136]. Additional cooling (if needed)
cells and airflow rate can moderate temperature rises. However, can be provided via increasing the inlet flow rate.

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It involves selecting a PCM with a suitable melting temperature integrated circuits. In addition, thermal differences in a battery can
and using the heat it absorbs and releases during phase changes to cause different self-discharge rates in its cell components [148].
cool and warm a battery when the temperature respectively rises Battery balancing typically involves measurement and compar-
above and falls below that temperature. As it relies on the transfer ison of the voltages, capacities or SOCs of all cells after each charg-
of phase-change heat and there is no external energy input, this ing cycle and can be either passive or active [149]. Passive
involves a passive continuous circulation process. The thermal con- equalization technology is currently widely-used, but active equal-
ductivity is small, 0.1 ~ 0.3 W/(mK), and it is difficult to place a ization technology is becoming more and more popular and used
large amount of PCM in a limited space, so the heat exchange is in certain specific market segment.
limited, which can easily cause large temperature differences in Passive equalization involves use of energy-consuming compo-
the battery pack [137]. Thus, when used in battery thermal man- nents to convert excess power in a single cell into heat energy for
agement, PCM must be combined with other cooling methods. consumption, thereby decreasing the inconsistency between cells
As an effective and elegant approach for compact battery forced (Fig. 7a and b). The main type of passive balancing is switch resis-
air-cooling, PCM cooling allows for straightforward cooling designs. tance, in which equalizing resistance of the access circuit con-
In modeling that was reported, under a simulated air-cooling sys- sumes some of the battery energy through heat generation.
tem, battery thermal runaway could be triggered by even failure Passive equalization can release the electrical energy of the over-
of a single individual cell upon internal short-circuit, which led to charged high-capacity cells in the battery pack, but it cannot sup-
a local temperature increase up to 180 °C [138]. In sharp compar- plement the energy for the low-capacity cells. The circuit structure
ison, with the use of PCM-based cooling, thermal runaway did not used in passive equalization systems is relatively simple and the
occur and temperature of the module maintained within normal energy-consuming components can be continuously discharged.
operational limits. A PCM-graphite matrix with high thermal con- Moreover, they can also be discharged in an intermittent manner,
ductivity was enabled to absorb and spread heat rapidly (Fig. 6c), depending on the input signal [150]. During the battery charging
but PCM cooling does not conduct heat from cell to cell as quickly process, the equalization control circuit monitors the voltage,
as air cooling. To improve PCMs’ low thermal conductivity, and thus SOC and other state parameters of all cells in the battery pack
exploitation of its greater heat storage capacity, researchers have (Fig. 7d). By controlling the switch, the resistance is applied to dis-
proposed several possible solutions, including embedding metal- charge the high-power battery cell to consume energy, while the
based materials [139], impregnating porous media [140] and com- low-power cell switch is turned off, and no discharge energy is
bining them with fin structures to increase their thermal conductiv- consumed, and finally equilibrium is achieved (Fig. 7e). Since the
ity and mass [141]. Lin et al. used PCM to wrap batteries, with charging current of a single battery is automatically corrected
graphite sheets between the batteries to increase thermal conduc- according to its balance, as the charging progresses its voltage dif-
tivity, thereby enhancing the heat loss and significantly improving ference continuously declines, and a good balance is reached in
the uniformity of the battery pack temperature [142]. Zhang et al. later stages of the charging (Fig. 7f) [151].
used copper fiber as a skeleton and filled it with paraffin to form a Active equalization involves use of various kinds of circuit
coating material in tests showing that appropriate design can topologies and control strategies that non-dissipatively transfer
improve the heat transfer performance of the filling material and energy between different batteries and modules, thereby equaliz-
keep the maximum temperature difference of the battery pack used ing the system (Fig. 7a and c). Active equalization is superior to
in the tests to within 5 ℃ [143]. Ping et al. proposed the addition of passive equalization in terms of energy utilization and equalization
fins on the outer surface of the PCM to optimize the thermal man- efficiency. However, its application is currently limited by difficul-
agement structure and enhance the thermal conductivity of a bat- ties in developing small systems that are easy to integrate, cheap,
tery pack [144]. fast, and reliable. Current active equalization strategies include
A direct cooling and heat management system uses the phase- several approaches based on capacitance, inductance, and trans-
change heat of a refrigerant to reduce the battery temperature formers [152], which commonly adjust variables including actual
effectively and improve the consistency of the battery pack tem- voltage, battery capacity and SOC in the equalization process [153].
perature [145]. The coolant absorb additional and excessive heat Dong and Han proposed a new architecture in which equalizers
from the battery surface to cool battery by evaporation. Unsimilar (including switching devices, gate drivers, inductors and digital
to the traditional liquid cooling, which requires non-cost-effective signal processing controllers) are placed in parallel layers. All the
equipment, such as pumps, cold plates, and heat exchangers, evap- equalizers can storage energy from high SOC cells and charge to
oration is essentially an atmospheric process, so it requires mini- low SOC cells (Fig. 7g). As a result, it takes less than one hour to
mal energy and operating costs. have all the cells with 62%, 48%, 63%, and 42% SOCs have the same
SOCs at the end of the experiment (Fig. 7h) [154].
4.2.2. Cell balance
It is difficult to produce totally identical battery cells, due to
variations during the manufacturing and assembly processes, as 5. LIB safety standards and tests
well as surrounding environment. Thus, during battery operation,
even little differences between each single cell will intensify and LIB safety standards and test methods are intended to be devel-
accumulate if no measures are taken. In the absence of an appro- oped to ensure that LIBs and their components meet specified
priate balancing system, the voltage differences between the indi- safety criteria, especially if they are produced commercially. Stan-
vidual cells will amplify, severely compromising battery safety dardized settings and tests are essential for ensuring that batteries
[146]. To achieve a high-performance battery system, the cells available on the market are of sufficient quality for intended pur-
need to be continuously balanced for minimizing the variations poses. Thus, these tests are as crucial for the future development
between them [147]. of portable electronics and EVs as the LIBs themselves.
Both external and internal factors can lead to cell imbalance. To reduce the thermal runaway risk in commercially available
Internal factors include those related to variations in internal products, LIBs for vehicles should be certified in accordance with
impedance, and stability of electrode interface with electrolyte. relevant safety testing standards before mass production or sale.
External factors are for those related to multi-rank pack protection Safety test standards are designed to ensure that certified LIBs have

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Fig. 7. Charging battery is similar to adding water in water tank. (a) Adding water with the same flow rate to two cells with different water contents, so the water tank with
higher content will fill full firstly. Further adding water will spill over (overchare). (b) Further added water will be released to ground (passive equalization). (c) Further added
water will be released to the other cell (active equalization). (d) Topological structure of battery equalization. (e) Battery equalization using resistor equalizing circuit. (f) Cell
voltage without (left) and with (right) equalization circuit [151]. (g) Battery equalization architecture in which equalizers are placed in different nested layers. (h) Battery
equalization results [154].

sufficiently low risks of safety accidents in specified kinds of ther- eters [155-182], but with overlaps in their methodologies. For
mal runaway induction and expansion situations. example, for the hot box experiment, three of the standards require
Battery safety standards are constantly being updated and ‘hot box tests’ of batteries at 130 °C.
optimized, because current tests cannot fully guarantee their The test standards are formulated to reduce the probability of
safety in practical applications. This is still a very serious prob- thermal runaway accidents in actual use. Thus, they are intended
lem, as there are fires in electric vehicles almost every week to assess responses of batteries in real potential situations, with
around the world. Hence, various international safety organiza- continuous updates and upgrades in accordance with the ongoing
tions regulate battery safety, and governments of different coun- development of LIB technology, which reflects concerns about the
tries have formulated safety standards in accordance with causes and hazards of accidents that have occurred.
national requirements and conditions and have gradually Overcharge/over-discharge tests are intended to assess
improved the safety standards of lithium-ion batteries. Academics overcharge/over-discharge processes that occur in a cell when
and industrial groups have also carried out extensive research on the charge and discharge process is out of control. External short
battery safety. circuit tests assess the short circuiting that is caused by external
electrical connections of battery poles under abnormal conditions.
5.1. Safety standards Drop tests assess responses of batteries to rigid impact during
transportation and use. Heating tests assess the thermal runaway
Most countries and international organizations have developed caused by a battery being heated due to local overheating, and
LIB-safety oriented standards (Table 3), which include: the subsequent thermal runaway expansion. Crush tests assess
responses of battery cells being mechanically deformed by an
(1) Chinese standard GB/T 31,485 [155]; external force in a collision accident, resulting in separator rupture,
(2) Society of Automotive Engineers (SAE) standard 2464 [156]; cathode and anode connection, short circuiting, and eventually
(3) International Electrotechnical Commission (IEC) standard thermal runaway. Nail penetration tests assess effects of a battery
IEC62133 Edition 2.0 [157]; short circuiting if the separator is penetrated by impurities. Tem-
(4) United Nations (UN) standard UN38.3 [158]; perature shock tests assess batteries’ responses to extreme tem-
(5) Japanese Industrial Standard (JIS) C8714 [159]; peratures during operation.
(6) Underwriters Laboratories (UL) standard UL2580 Edition 2.0
[160]; 5.2. Safety tests
(7) International Standardization Organization (ISO) standard
ISO 16750–2 [161]. LIB safety assessment involves a myriad of tests that a battery
must pass to certify that it will not be hazardous under specified
The various safety test standards apply different methodologies, abuse conditions. Table 5 shows the main safety tests used to
so we provide in Table 4 a summary of some test requirements and examine key LIB properties. Analysis of the presence of various
comparisons of five test items in the standards. The table shows LIB defects and shortcomings can help to define specific LIB safety
that different standards have distinct and very specific test param- issues or hazards. Extensive testing uncovers these issues to assist
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Table 3
International safety test standards for LIBs intended for use in EVs.

Standard Standard Standard full name Published Standards series Application Technical characteristics
system code year Scope
Freedom SAND Electrical energy etorage system abuse test 2006 SAND 99–0497 [163] Battery cell, Requirements for electrical
CAR 2005– Manual for electric and hybrid electric module and performance, environmental
3123 [162] vehicle applications pack suitability and safety performance
SAE SAE J2464- Electric and hybird vehicle rechargeable Released in SAE J1715 [164] Battery pack Security requirements
2009 [156] Energy storage system safety and abuse 1999, SAE J1739 [165] and battery
testing revised in SAE J1950 [166] system
2009 SAE J2344 [167]
GB/T GB/T Safety requirements and test methods for 2015 GB/T 31484–2015 Battery cell Requirements for electrical
31485– traction battery of electric vehicles [168] and module performance, environmental
2015 [155] GB/T 31486–2015 suitability and safety performance
[169]
GB/T 31467.3–2015
[170]
UN UN38.3 United Nations manual on hazardous 2015 - Battery cell, Security requirements
[158] materials transport tests and standards, part module and
3, section 38.3 pack
ISO ISO Road vehicles - environmental conditions 2010 ISO 16750–1 [171] Battery cell, Reliability and safety test
16750–2 and testing for electrical and electronic ISO 16750–3 [172] module and specifications
[161] equipment - part 2: electrical loads ISO 16750–4 [173] pack
ISO 16750–5 [174]
IEC IEC Secondary Lithium Ion Cells for the 2010 IEC 62660–3-2016 Battery cell Reliability and safety test
62660–2- propulsion of electric road vehicles – part 2: [175] specifications
2010 [175] reliability and abuse testing IEC 60068–2-2 [176]
IEC 62133–2012 [177]
UL UL 2580– Battery safety standards for electric vehicles 2013 UL 1642–2009 [178] Battery cell, Requirements for electrical
2010 [125] UL 2054–2009 [179] module, pack performance, environmental
and system suitability and safety
GM GM- General motors battery test standard for 2016 - Battery cell Requirements for electrical
Modified electric vehicles and module performance and abuse tolerance
USABC
[180]
VW VW Volkswagen battery test standards for 2016 - Battery cell, Requirements for electrical
PV8450 electric vehicles module and performance and abuse test
[181] pack
SMTC SMTC Electrochemical performance test 2018 - Battery cell, Requirements for electrical
9 N20 Specification of electric vehicles for lithium- module and performance
011–2018 ion battery pack
[182]

efforts to ensure that future generations of batteries are safer and not combust or explode during or after the test it is considered
more reliable. Table 5 shows electrochemical, mechanical, and safe, its materials (electrolyte, active electrode materials, separa-
thermal tests included in current standards to ensure the safety tors etc.) are regarded as having adequate properties, and the
of LIBs before they enter the market. structural design is deemed satisfactory. The safety performance
In a safety test possible trigger modes are simplified so batter- under overcharge is closely related to the charge rate, so over-
ies’ thermal runaway characteristics are measurable in the labora- charging is performed at different rates to establish at which
tory. Laboratory environment test conditions must generally be extreme rate and voltage failure occurs. As various battery types
more stringent than ‘real-world’ conditions to ensure safety during are intended to have specific applications, batteries are typically
actual use. For example, batteries being tested have to be main- tested using tests corresponding to specific applications and condi-
tained at a 100% SOC. tions [157].
In addition to the actual cause of an accident, three principles
should be met in the process of formulating a safety standard:
5.2.2. Heating tests
Batteries swell and often explode at elevated temperatures,
(1) Test operability: the safety test should be feasible, with no
because their heat release rate is higher than their cooling rate,
unscientific or technically incorrect elements.
causing electrolyte decomposition and interfacial electrode–elec-
(2) Repeatability of the test: all aspects of the test should be as
trolyte reactions. Thus, as LIBs store large amounts of chemical
similar as possible, and consistent results should be obtained
energy, heating tests should be performed to examine their perfor-
in multiple tests of a given battery sample at the same test
mance in high-temperature conditions.
center, using the same experimental equipment, under the
Heating is used to analyze LIBs’ thermal stability and heat dis-
same conditions.
tribution to ensure they have sufficiently efficient heat manage-
(3) Test reproducibility: similar results should be obtained
ment and capability to forecast potential hazards. The results are
when the test is conducted in different centers, with similar
then used to assess how thermal abuse consequences can be alle-
equipment and the same test conditions.
viated. Specifically, data obtained from hot box experiments are
used to simulate their thermal characteristics, and distributions
5.2.1. Overcharge tests of internal and external temperatures, then assess possible
According to the IEC standard test, the cell is first discharged to improvements in their design, materials, cooling systems, etc.
3.0 V at 0.2C rate, and then is charged under 10 V and an arbitrarily Some electrochemical models also use thermal shock results to
set current I within the time is equal to 2:5  CI5 :. If the battery does simulate electrochemical reactions and heat transfer as functions
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Table 4
Comparison of selected items in six safety testing standards.

Test content Safety testing standard

GB/T31485 [155] IEC62133 [157] UL2580 [160] SAE J2464 [156] VW PV8450 [181] USABC-GM [180]
Heating Heating at 5 ℃/min 130 ℃, 10 mins 150 ± 2 ℃, 60 mins Max. stable 2 ℃/min to 130 ℃ 0.5 ℃/min, 50-150 ℃, hold
from 25 ℃ to 130℃, temperature or 200 ℃ hold for for 30 mins
hold for 30 mins 30 mins
Short-circuit Short circuit for 10 80±20 mX Short with R5 mX R5 mX for hard short 10 mins, Short circuit for 10 mins,
mins, R5 mX until explosion, fire or short; R5 mX for R1 mX, R = 5 R5 mX
no temp change soft short mX, R=10 mX
Overcharge 100% SOC Overcharge Overcharge to Overcharge to 200% Overcharge to Overcharge to 1.1 Overcharge the 100% SOC
to 1.5 Vmax or charge for 250% SOC at 1C SOC at 1C 200% SOC at 1C Vmax or 5 mins at cell at 1C for 1 hour or 1.5
1 hour at 1C 1C Vmax or venting
Over-discharge Over-discharge the Over-discharge the Over-discharge the 0% Over-discharge / Over-discharge the 100%
100% SOC cell at 1C for 0% SOC cell at 1C SOC cell at 1C for 90 the cell to 100% SOC cell at 1C until venting
1.5 hours for 90 mins mins SOC
Nail penetration1 Penetration rate 25 / 80 mm/s, u 3 mm, 100% 80 mm/s, u 3 mm, 0.1 mm/s, u 1 mm 80 mm/s, u 3 mm, 100%
mm/s, u 5~ 8mm, 100% depth 100% depth stainless steel, 2 depth
depth mm depth
1
u represents the nail diameter.

Table 5 Table 6
Current safety tests for LIBs before they enter the market. Standard test methods simulating LIB internal short-circuits.

Focal properties Main tests Test methods Standard number

Electrochemistry Overcharge and over-discharge, high- and low- Nail penetration GB 31485–2015 [31]UL 2580:2016 [156]
performance temperature discharge, external short circuit, and Heavy impact UN 38.3 [157]
forced discharge UL 2580:2016 [160]
Mechanical Drop, heavy impact, nail penetration, shake and Crush IEC62133:2012 [156]
properties squeeze, acceleration, and crush UL 2580:2016 [160]
Thermal Heating, thermal shock, and spark Forced internal short circuit JIS C8714:2007 [159]
performance
Surroundings Low pressure, high altitude, and soaking

spike tip angle of 45 ~ 60°, and surface that is clean, smooth, and
of the internal and external temperatures. According to the GB/T free of rust, oxidized layer and dirt) in a direction perpendicular
31,485 heating procedure, a battery should be placed in a hot to the polar plate at a speed of 25 ± 5 mm/s. The penetration posi-
box, heated to 130 ± 2 ℃ at 5 ℃/min and kept at this temperature tion should also be close to the geometric center of the penetrated
for 30 minutes. If the battery does not leak or combust during this surface, with the steel spike retained inside the battery. The test is
thermal shock test, it is considered safe. considered successful if the cell does not explode or combust.

5.2.3. Short circuit tests 5.2.3.4. Crush tests. During a crush test, a battery is mechanically
5.2.3.1. External short circuit tests. A designed external short-circuit compressed. According to GB/T 31485, the cells are first charged
test is aimed to evaluate the LIB safety performance. According to at 1C rate to 4.2 V, then the battery is placed between two planes
the GB31485-2015 procedure, the battery is kept at 25 ± 2 ℃ in a in a semi-cylinder with a 75 mm radius, and subjected to crushing
fully charged state for 30 minutes, then the cathode and anode ter- at 5 mm/s, with a load applied in the direction perpendicular to the
minals are connected with a wire, and the external resistance is battery’s polar plate. The crushing is ceased when the voltage
kept at 5 mX. During this test, the temperature and voltage are reaches 0 V, the deformation reaches 30%, or the crushing load
monitored simultaneously, throughout the entire test [31]. The test reaches 200 kN. The test has a positive outcome if no fire or explo-
is considered successful if the cell does not explode or combust. sion is observed.

5.2.3.2. Internal short circuit tests. High current passes through a 5.3. Hazard level
short-circuited site, generating a large quantity of heat, which
might casue thermal runaway. Thus, tests have been developed In evaluations of batteries’ safety condition based on results of
to assess battery performance under internal short-circuit condi- the above abuse tests, the EUCAR and SAE-J Hazard Levels and
tions, and the International Electrotechnical Commission (IEC), the associated criteria that are widely applied.
Institute of Electrical and Electronics Engineers (IEEE), Underwrit- Typically, hazard levels of Electrical Energy Storage System
ers Laboratories (UL), and other organizations have published (EESS) devices according to their responses to abuse conditions
reports on specific short-circuit simulation methods (see Table 6). are assigned by EUCAR and presented in Table 7 [162]. Manufac-
turers and integrators may find it helpful and useful to take these
5.2.3.3. Nail penetration tests. These tests are designed to simulate levels into consideration when evaluating a given EESS design’s
internal battery short circuits that may occur when a battery’s abuse response.
internal membrane is penetrated by impurities. According to GB/ The SAE recommends that results of each test should be
T 31485, a fully-charged battery should be penetrated with a high reported in terms of the Hazard Severity levels described in Table 8
temperature-resistant steel spike of u 5 ~ 8 mm (with a conical [156], and the use of such information in Battery safety and Hazard

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Table 7 prehensive analysis of their failure mechanisms in extreme condi-

EUCAR hazard level and descriptions. tions—such as over-(dis)charge, external short circuit, thermal, and
Hazard Description Classification criteria and effects mechanical abuse—has shown that LIB thermal runaway and the
level presence of flammable components are root causes of battery fires
0 No effect No effect, no loss of functionality and explosions. A series of effective strategies have been developed
1 Passive No defect, no leakage, no venting, fire, or flame, based on knowledge obtained regarding LIB structures and work-
protection no passive protection rupture, no explosion, no ing principles. LIB safety and performance stability can be signifi-
activated exothermic reaction or thermally activated
runaway. Cell reversibly damaged. Repair of
cantly improved by carefully choosing electrode materials,
protection device needed. separators, and electrolytes, and by optimizing battery design.
2 Defect/damage No leakage, no venting, fire, or flame, no External strategies, such as cooling and cell balancing, can also
rupture, no explosion, no exothermic reaction make significant contributions to LIB safety performance under
or thermal runaway. Cell irreversibly damaged.
normal conditions.
Repair needed.
3 Leakage No venting, fire, or flame, no rupture, no Various LIB safety standards and corresponding test programs
Dmass < 50% explosion. Weight loss < 50% of electrolyte have been developed, as reviewed in the preceding text. The main
weight (electrolyte = solvent + salt) goal of these programs is to provide references for battery safety
4 Venting No fire or flame, no rupture, no explosion. and standard ways to assess their performance under abnormal
Dmass > 50% Weight loss > 50% of electrolyte weight
conditions, thereby facilitating improvements in predictions of
(electrolyte = solvent + salt)
5 Fire or flame No rupture, no explosion (i.e., no flying parts) battery performance and alleviation of the detrimental processes
6 Rupture No explosion, but flying parts of the active mass of thermal runaway and various kinds of abuse that increase risks
7 Explosion Explosion (i.e., disintegration of the cell) of real-life accidents.
The following strategies are proposed for enhancing LIB safety,
both externally and internally (Fig. 8).
The most effective way to dissipate excessive heat is to pro-
Table 8 tect batteries from thermal and mechanical abuse by improving
Hazard severity levels and descriptions (adapted from EUCAR and SAND 2005–3123). their outer shells. This is becoming increasingly important as
Hazardseverity Description Classification criteria and effects the number of EVs on our roads is increasing, so there are corre-
level spondingly urgent needs to enhance LIB safety. There are also
0 No effect No effect, no loss of functionality. growing energy density requirements and demands for more
1 Passive No damage or hazard, reversible loss of powerful EV battery systems, which will generate even more
protection function. Replacement or re-setting of heat and pose even greater thermal management challenges.
activated protection device is sufficient to restore
The main strategies to meet these challenges focus on increasing
normal functionality.
2 Defect/damage No hazard but damage to RESS. the speed and uniformity of heat transfer in large, high-density
Irreversible loss of function. Replacement batteries. However, increasing the mechanical reinforcement of
or repair needed. LIBs to enhance their protection is also important, for example,
3 MinorLeakage/ Evidence of cell leakage or venting with
adjusting outer casing materials to increase their impact resis-
venting RESS weight loss < 50% of electrolyte
weight tance. Another solution would be to install batteries in parts of
4 MajorLeakage/ Evidence of cell leakage or venting with cars that are least affected during collisions and accidents. Ther-
Venting RESS weight loss > 50% of electrolyte mal shock can also severely compromise LIB safety, and an elec-
weight tric car fire can cause other nearby vehicles to catch fire, but LIB
5 Rupture Loss of mechanical integrity of the RESS
thermal shock tolerance can be enhanced by various external
container, resulting in release of
contents. The kinetic energy of released measures and design strategies to decrease accidents when ther-
materials is not sufficient to cause mal shock occurs.
physical damage external to the RESS. Heat generation and accumulation inside batteries are the main
6 Fire or Flame Ignition and sustained combustion of
causes of LIB safety accidents. Heat generation is often accompa-
flammable gas or liquid for more than
approximately one second. Sparks are
nied by gas formation, and both processes are controlled by the
not flames. battery voltage and temperature. Overcharge is one of the leading
7 Explosion Very fast release of energy sufficient to causes of heat generation. Thus, incorporating preventative mea-
cause pressure waves and/or projectiles sures to avoid spontaneous overcharging inside batteries would
that may cause considerable structural
complement the external overcharge protection measures. Ther-
and/or bodily damage, depending on the
size of the RESS. The kinetic energy of mal runaway is caused by a battery short-circuiting due to separa-
flying debris from the RESS may also be tor failure and the inability of the localized heat to dissipate
sufficient to cause damage. efficiently and quickly. The development of temperature-
sensitive materials to use inside batteries to prevent localized tem-
perature increases offers an excellent solution to the thermal run-
away problem. Another promising heat dissipation approach is to
risk migration approaches. Rechargeable Energy Storage System
provide internal pathways for rapid heat diffusion (for example,
(RESS) responses in abusive tests should be determined.
by incorporating materials with high thermal conductivity). Last,
but not least, careful selection of active electrode materials and
6. Summary electrolytes is also essential for reducing heat and gas production,
and to protect the electrode interfaces.
Broader application of LIBs is limited because safety concerns Successfully passing the nail penetration, crash, and other tests
regarding their performance have not been fully addressed. Com- does not guarantee a car battery’s safety in real-life performance

96
Y. Chen, Y. Kang, Y. Zhao et al. Journal of Energy Chemistry 59 (2021) 83–99

Fig. 8. (a) Strategies to improve lithium ion batteries’ safety. (b) Schematic diagram of advanced battery pack in the car of ROEWE R ER6.

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