Energy Storage Materials 66 (2024) 103174

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Energy Storage Materials

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Fire-safe polymer electrolyte strategies for lithium batteries

Minghong Wu a, b, Shiheng Han a, Shumei Liu b, Jianqing Zhao b, *, Weiqi Xie a, *
a
School of Minerals Processing and Bioengineering, Central South University, Changsha 410083, China
b
School of Materials Science and Engineering, Key Laboratory of Guangdong High Property & Functional Polymer Materials, Key Laboratory of Polymer Processing
Engineering (Ministry of Education), South China University of Technology, Guangzhou 510640, China

A R T I C L E I N F O A B S T R A C T

Keywords: Over the past decade, the widespread deployment of lithium-ion batteries has led to an increasing number of fire
Polymer electrolytes and explosion incidents, posing significant risks to human life and property. These safety concerns are partic­
Fire-safe ularly pronounced in high energy density lithium metal batteries, which inhibit their large-scale commerciali­
Lithium batteries
zation. Consequently, addressing battery safety has become a critical research priority. The employment of
highly flammable liquid electrolytes (LEs) is a primary contributor to these safety incidents. As such, the
development of safer electrolytes for lithium batteries is of paramount importance. Polymer electrolytes (PEs)
have emerged as a promising alternative to conventional LEs for next-generation lithium batteries, offering a
multitude of advantages, such as exceptional processability and increased flexibility. Despite these benefits, PEs
continue to face significant fire safety challenges due to the inherent flammability of polymers and organic
solvents. In this review, we provide a comprehensive overview of the advancements in fire-safe polymer elec­
trolytes, elucidating various flame-retardant design strategies and their impact on electrochemical properties. It
is anticipated that this review will serve as a valuable reference and offer guidance for the design and devel­
opment of highly safe polymer electrolyte systems, ultimately fostering further progress in battery safety
research.

1. Introduction leakage, and limited electrochemical stability windows (ESW) [10].

Consequently, the development of fire-resistant and high-performance
The rapid development of lithium-ion batteries (LIBs) since their electrolytes holds paramount significance in advancing the safety and
commercialization in the 1990s has revolutionized the energy industry efficiency of lithium batteries.
[1], powering a wide array of electronic devices and electric vehicles [2, Compared to LEs, polymer electrolytes (PEs) reduce the possibility of
3]. However, over the past decade, a succession of safety incidents has electrolyte leakage due to their low mobility characteristics [11]. In
given rise to substantial concerns about the safety of LIBs and their addition, the polymer hosts in PEs not only provide flexibility, stretch­
potential risks to human life and property [4]. Furthermore, even the ability and processability, but also help to inhibit lithium dendrite
most advanced LIBs employing graphite anodes have struggled to meet growth and reduce the risk of short circuits [12]. Nevertheless, PEs face
the growing demand for higher energy density, prompting the explo­ challenges related to their low ionic conductivity (IC) and high elec­
ration of alternative anode materials [5]. Lithium metal stands out as a trode/electrolyte interface resistance, which hinder their application in
promising candidate due to its ultra-high theoretical specific capacity advanced lithium batteries [13]. As a result, current reviews of polymer
and ultra-negative electrochemical potential [6]. Nevertheless, the electrolytes predominantly emphasize their electrochemical properties
broader adoption of lithium metal batteries (LMBs) remains impeded by [3,14,15].
their heightened safety concerns [7,8]. Beyond their underwhelming electrochemical attributes, various
Commonly utilized liquid electrolytes (LEs), such as ethylene car­ polymers utilized in PEs, such as poly(ethylene oxide) (PEO) and poly
bonate (EC) and dimethyl carbonate (DMC), are highly volatile and (methyl methacrylate) (PMMA), remain flammable, falling short of the
flammable, making them susceptible to ignition and the release of criteria for fire-resistant electrolytes [16]. Numerous safety incidents
substantial heat during thermal runaway [9]. Moreover, liquid electro­ have alerted that fire safety is a prerequisite for the development of
lytes are plagued by several shortcomings, including toxicity, electrolyte high-performance electrolytes. Consequently, the last two decades saw

* Corresponding authors.
E-mail addresses: [email protected] (J. Zhao), [email protected] (W. Xie).

https://doi.org/10.1016/j.ensm.2024.103174
Received 6 July 2023; Received in revised form 3 December 2023; Accepted 2 January 2024
Available online 3 January 2024
2405-8297/© 2024 Elsevier B.V. All rights reserved.
M. Wu et al. Energy Storage Materials 66 (2024) 103174

an explosion in the number of publications on fire resistant polymer maximum temperature reached during thermal runaway (T3) [18].
electrolytes (Fig. 1). As flame retardancy serves as a passive defense The initial stage of battery malfunction is triggered by various fac­
measure for batteries in the event of thermal runaway, it stands out as a tors, such as mechanical abuse, thermal abuse, and electrical abuse.
crucial final line of protection for battery safety. These inappropriate operating conditions lead to internal exothermic
Herein, the progress of fire-safe polymer electrolytes applied in reactions, which gradually raise the temperature of the battery to T1.
lithium batteries is summarized in terms of fire-safe strategies. This During this mild heat accumulation phase [19], the solid electrolyte
paper describes the flame-retarded principles of different design stra­ interface (SEI) starts to decompose, typically between 80 ◦ C ~ 120 ◦ C,
tegies, followed by their effects on electrochemical properties in poly­ resulting in the production of flammable gases and oxygen [20]. The
mer electrolytes. This review also involves safety testing of pouch decomposition of the SEI further induces an exothermic reaction be­
batteries under abuse conditions, which is important in the practical tween the intercalated lithium in the anode and the organic solvents in
application of batteries, but are often-overlooked in previous reviews of the electrolyte, releasing flammable hydrocarbon gases (ethane,
polymer electrolytes. We also discuss the existing limitations and future methane, etc.) and further increasing the temperature [21].
prospects of fire-safe polymer electrolytes, aiming to provide a valuable As the temperature continue to rise, the separators lose their struc­
reference for the advancement of fire-safe, high-performance electro­ tural integrity and begin to melt, leading to an increased risk of internal
lytes for cutting-edge energy storage devices and systems. short circuits (ISC). Reports suggest that during an ISC, up to 70% of the
battery’s energy can be rapidly released within a minute, causing a
2. Lithium battery safety issues significant temperature surge [22]. This indicates that the battery tem­
perature reaches T2 and the battery is in the trigger critical state for TR.
2.1. Thermal runaway of lithium batteries The cathode also undergoes exothermic degradation to produce oxygen,
further increasing temperature and pressure, thereby accelerating the
When the battery temperature surpasses the safe operating limit, it reaction.
goes through a heat-temperature-reaction (HTR) cycle, a self- The final outcome of the HTR cycle is thermal runaway, wherein the
accelerating process where heat causes an exothermic chemical reac­ temperature rises rapidly and eventually reaches T3, surpassing the
tion, leading to more heating and subsequent reactions [17]. In the case ignition point of the organic components in the batteries. The combus­
of LIBs, thermal runaway can be divided into different stages based on tion process is fueled by the organic solvents and gases produced
three key temperatures: the temperature at which abnormal heating through electrolyte decomposition. Therefore, all three elements of the
starts (T1), the temperature that triggers thermal runaway (T2), and the fire triangle (heat, oxygen, and fuel) are present, creating a suitable

Fig. 1. The development timeline of fire-safe polymer electrolytes with various design strategies. Copyright 2005, Elsevier; Copyright 2011, American Chemical
Society; Copyright 2013, The Royal Society of Chemistry; Copyright 2015, Wiley-VCH; Copyright 2016, Elsevier; Copyright 2017, American Chemical Society;
Copyright 2018, American Chemical Society; Copyright 2019, Springer Nature; Copyright 2020, American Chemical Society; Copyright 2021, Elsevier; Copyright
2022, Wiley-VCH; Copyright 2023, Cell Press.

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M. Wu et al. Energy Storage Materials 66 (2024) 103174

environment for ignition. A fire is initiated through an external ignition For instance, cylindrical or prismatic batteries, which are enclosed in a
source, such as electric sparks or arcs [20]. rigid container, are prone to rupture or explode during thermal
After the ignition of organic solvents and combustible gases, the runaway, whereas pouch batteries are more likely to catch fire or swell.
combustion process produces highly reactive radicals, such as H•, which When batteries are assembled into packs through series or parallel
readily reacts with oxygen to form O• and HO•. These reactive species configurations, a single battery experiencing thermal runaway can cause
can further engage with the hydrogen gas produced by the reductive adjacent batteries to also fail catastrophically [23]. The process of
decomposition of electrolytes, generating more H• and additional heat lithium battery safety accidents is shown in Fig. 2.
[4]. This self-sustaining chain reaction supports the combustion process. Compared to LIBs employing graphite anodes, LMBs with lithium
The result of thermal runaway can differ depending on the battery type. metal anodes introduce a higher degree of safety concerns. LMBs often

Fig. 2. The process of battery safety issues and the corresponding flame-retardant strategies. Copyright 2019, Elsevier.

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M. Wu et al. Energy Storage Materials 66 (2024) 103174

encounter severe lithium dendrite growth, which stems from the uneven 3. Polymer electrolyte safety assessment
deposition of lithium during the cycling process [24]. This poses a sig­
nificant safety risk as lithium dendrites can eventually puncture the 3.1. Flame retardant tests
battery separators, leading to internal short circuits [25]. Another issue
is the formation of high-surface-area dead lithium (i.e., metallic lithium Flame retardant testing for polymer electrolytes stands as a funda­
wrapped by SEI) on the surface of lithium metal anode during cycling. mental and indispensable examination to assess their safety. Flame
Once the SEI is destroyed, the metallic lithium will react directly with retadancy serves as the ultimate protective barrier after a fire outbreak
the electrolyte, leading to the heat accumulation and temperature in­ in batteries, making it the last line of defense for battery safety. If the
crease during the initial stages of thermal runaway [26]. Furthermore, polymer electrolyte can successfully impede the progression of flames, it
the abuse of LMBs may further cause deformation and rupture of the significantly mitigates the potential for more severe consequences, such
battery casing, which will allow highly-reactive lithium metal to contact as explosions or other hazardous outcomes. Typically, the testing
with air and moisture, releasing hydrogen gas and a large amount of methods for flame-retardant polymer electrolytes encompass the
heat, leading to thermal runaway of the battery and causing more following:
damage [27]. Given the complexity and severity of the safety issues of
LMBs, designing safe polymer electrolytes for LMBs becomes more 3.1.1. Ignition tests and self-extinguishing time (SET)
important and challenging. The flammability of an electrolyte can be initially evaluated by a
facile ignition test. The electrolyte is placed in a container and the
2.2. Safety risks of polymer electrolytes sample is ignited in air. If the electrolyte burns, it is considered to be
flammable; otherwise, it is non-flammable. SET is the time it takes for a
In comparison to conventional LEs, solid polymer electrolytes (SPEs) sample to extinguish after the fire is removed, typically normalized to
present several advantages, such as enhanced mechanical strength and the sample mass and given in s⋅g− 1, thus the SET test for a certain mass of
unique toughness, which contribute to the increased physical tolerance electrolyte enables a quantitative determination of its flammability.
and reduced electrolyte leakage during abuse conditions. These robust Most SET measurements are based on the standard specification UL
mechanical properties also inhibit the growth of lithium dendrites and 94HB. In a typical measurement, the electrolyte is exposed to a flame,
reduce the risk of ISC. LEs pose significant challenges due to their and the time is recorded until the flame is completely extinguished.
limited thermal stability and the potential release of flammable gases Depending on the value of SET, flammability can be divided into three
upon decomposition. In contrast, SPEs are theoretically free of liquid categories: (1) “flammable” when SET > 20 s⋅g− 1; (2) “flame retardant”
solvents and are more thermally stable, which greatly reduces the when 6 s⋅g− 1 < SET < 20 s⋅g− 1, and (3) “nonflammable” when SET < 6
release of flammable gases at high temperatures [28]. s⋅g− 1 [34].
However, the backbone of the polymer consists mostly of carbon and
hydrogen, which are intrinsically flammable [29]. A classic example of a 3.1.2. Limiting oxygen index (LOI)
polymer electrolyte matrix, polyethylene oxide (PEO), exhibits a notably LOI is defined as the minimum value of O2 to support the combustion
low limiting oxygen index (LOI) of 16%, accompanied by severe melt of a material. Specifically, according to ISO 4589, the sample is placed
dripping during combustion, which is indicative of its high flammability vertically in a combustion tube and charged with an oxygen/nitrogen
[30]. The combustion of polymers typically unfolds in several stages. mixture [O2/N2]. The oxygen concentration will continue to increase
When subjected to sufficient heat, polymers undergo thermal decom­ until it is sufficient to sustain the combustion of the materials. The
position, causing polymer chains to break down, yielding volatile frag­ critical oxygen concentration, expressed as a percentage, is the LOI
ments and forming a flammable gaseous mixture, effectively acting as value. The relative flammability of a material can be determined from
fuel. Typically, thermal decomposition is a complex interaction of heat the value of LOI, which is “highly flammable” for LOI < 22%; “flame
and oxygen, as the polymer reacts with the atmospheric oxygen, retardant” for 22% < LOI < 27%, and “nonflammable” for LOI > 27%
yielding low molecular weight products, along with the release of [26].
reactive H• and HO•. This gas mixture is ignited when the temperature
rises to the auto-ignition temperature and the heat released by the 3.1.3. Cone calorimetry tests (CCT)
combustion process induces the polymer to decompose more flammable The principle of the CCT experiment is to measure the reduction of
material to maintain combustion [31]. oxygen concentration in the sample combustion gas at a given heat flux.
While SPEs exhibit commendable mechanical properties, they come The gas produced by the sample combustion passes through the heating
with drawbacks such as high electrode/electrolyte interfacial resistance cone and is captured by the system. The gas flux and oxygen concen­
and unsatisfied IC [32]. To overcome these limitations, the introduction tration are measured to calculate the heat release rate (HRR, kW⋅m− 2)
of liquid plasticizers or solvent components into the polymer-salt system and its peak (PHRR). In addition, the integration of the HRR versus time
has emerged as an effective solution. Gel polymer electrolytes (GPEs), curve provides the total heat release (THR, kJ⋅m− 2). CCT also provides
which represent an intermediate state between LEs and SPEs, offer a other combustion data such as the effective heat of combustion (EHC),
well-balanced combination of mechanical strength and the high IC time of flameout (TOF), carbon monoxide yield (COY), carbon dioxide
typically associated with LEs [13]. Nevertheless, the inclusion of organic yield (CO2Y), mass loss during combustion, and total smoke release
solvents or plasticizers in GPEs frequently comes with flammable traits, (TSR). The data acquired through these testing methods allow for a
which might pose a risk to the overall safety of the electrolyte system quantitative assessment of the fire risk associated with combustible
[33]. For example, the most widely used plasticizers, carbonates, are materials. In this paper, it may take the form of micro-scale combustion
highly flammable. Furthermore, these organic solvents not only calorimeter (MCC) [31].
compromise the structural integrity of GPE but also impair their thermal
stability, consequently diminishing their ability to hinder lithium den­ 3.2. Thermal and mechanical performance tests
drites and exacerbating membrane deformation under high tempera­
tures, thereby worsening safety concerns. A holistic evaluation of battery safety also necessitates a thorough
examination of the mechanical and thermal properties of polymer
electrolytes. The mechanical strength of PEs is of great importance
because it plays a vital role in curtailing the formation and growth of
lithium dendrites [10]. Assessing the mechanical properties of PEs, such
as modulus and tensile strength, is essential to understand their ability to

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resist mechanical stresses and ensure the integrity of the battery over when the battery voltage reaches 120% or when the SOC reaches 130%
time. By enhancing the mechanical properties of polymer electrolytes, [39].
engineers can design safer batteries with improved resistance to ISC. The
common method for assessing the mechanical properties of polymer 4. Strategies for fire-safe polymer electrolytes
membranes involves conducting tensile tests according to ASTM D638
standards [35]. The preceding analysis underscores the pressing need for enhancing
The thermal stability of polymer electrolytes is equally significant for the fire safety of polymer electrolytes. Over more than two decades, a
battery safety. Polymer electrolytes can undergo morphological multitude of design strategies have emerged to enhance the flame
changes, such as shrinkage or swelling, when exposed to high temper­ retardancy of polymer electrolytes. These methods can be categorized as
atures. Evaluating the thermal stability of polymer electrolytes is inte­ follows. One common approach involves the direct incorporation of
gral to ensuring that the battery can operate safely across a range of flame retardants into the polymer electrolytes. Alternatively, re­
operating conditions without compromising its structural morphology. searchers have explored the modification of polymer molecular struc­
Polymer electrolytes can be placed at high temperatures for a period of tures through molecular design or copolymerization, introducing flame-
time and observed for changes in their morphology to indicate their heat retardant units into the polymer’s composition. Another method centers
resistance. US Advanced Battery Consortium’s (USABC) goal for thermal on the substitution of flammable organic solvents with non-flammable
shrinkage of battery separators is <5% at 200 ◦ C [36]. Thermogravi­ alternatives, thereby diminishing the inherent fire risk. Lastly, an
metric analysis (TG) is also used to assess the thermal stability of poly­ increasingly utilized strategy involves the adoption of non-flammable
mer electrolytes, which involves monitoring the changes in the weight of polymer matrices, such as polyvinylidene fluoride (PVDF) and poly­
polymer electrolytes during the programmed heating. Additionally, the imide (PI), which inherently reduce the risk of combustion. (Fig. 2)
couple of TG with Fourier transform infrared spectroscopy (TG-FTIR) is These strategies primarily employ mechanisms for flame retardancy
commonly applied to analyze the gas composition emitted during the that fall into two categories: gas-phase flame retardancy and condensed-
polymer pyrolysis process, which helps to further determine the flame phase flame retardancy. Gas-phase flame retardancy involves mecha­
retardancy mechanism [27]. nisms such as fuel dilution and free radical annihilation, which aim to
inhibit the propagation of flames in the gaseous state. By diluting the
3.3. Battery abuse tests fuel-rich environment with inert gases, such as nitrogen or carbon di­
oxide, the concentration of flammable gases in the atmosphere is
Evaluating battery safety encompasses a broad spectrum of consid­ reduced. Gas-phase radical-chain reactions are chemical processes that
erations that extend beyond traditional flame-retardant tests. It is disrupt the chain reactions responsible for flame propagation. Flame
essential to recognize that most battery safety incidents do not originate retardants can interfere with these radical-chain reactions by acting as
from direct fire ignition; instead, they typically arise from abuse con­ radical scavengers. They react with and neutralize the radicals, dis­
ditions. Battery abuse tests are an integral part of ensuring safety in rupting the chain reaction and slowing down or preventing the spread of
battery systems, as they help to assess the potential hazards associated the flame.
with battery use. As pouch batteries have gained prominence due to Another mechanism, condensed-phase flame retardancy includes
their flexibility and adaptability in various applications, analyzing their processes like endothermic decomposition and the catalytic formation of
behavior under abuse conditions provides valuable insights into the char, which serve to impede the combustion of materials in their solid or
safety and reliability of battery technologies. The test methods outlined condensed form. Flame retardants that promote endothermic decom­
below provide a basic framework for assessing battery safety, but it is position absorb heat during a fire, thereby reducing the energy available
important to note that additional testing may be required depending on for sustaining the combustion process. These materials may release
the specific application and intended use of the battery. cooling agents, such as water or other volatile compounds, when
exposed to high temperatures, which also helps to lower the temperature
3.3.1. Thermal abuse tests and slow down the combustion process. The formation of catalytic char
Various methods are available to evaluate thermal abuse, including is a process in which a charred, non-flammable layer is created on the
high-temperature endurance test, thermal shock cycle test, and damp surface of the polymers. This char layer acts as a physical barrier,
heat cycle test. Accelerating rate calorimetry (ARC) is a prevalent testing insulating the underlying material from the heat source and preventing
method in battery safety assessments, in which the battery is heated in the access of oxygen. These combined flame retardancy mechanisms
an adiabatic state until thermal runaway is triggered. ARC records sig­ play a crucial role in enhancing the fire safety of polymer electrolytes by
nals such as temperature and voltage, which are further used to analyze addressing the different stages of the combustion process.
the thermal runaway mechanism [37]. When designing strategies, while flame retardancy functions as the
ultimate safeguard for battery safety, it is also essential to consider
3.3.2. Mechanical abuse tests thermal and mechanical performance, reducing the risk of ISC and
Mechanical abuse testing aims to simulate scenarios in which bat­ thermal runaway. Furthermore, an advanced strategy not only enhances
teries may endure physical damage, potentially leading to issues such as the battery safety but also improves the electrochemical performance,
internal short circuits and electrolyte leakage. Types of mechanical thereby contributing to the overall battery performance.
abuse usually encompass impact, crushing, bending, and penetration.
For instance, in the penetration test, as per the standards of SAE J2464- 4.1. Passive inorganic fillers
2021, a 3 mm diameter steel needle penetrates a single battery at a speed
of 8 cm/s until the battery is completely pierced [38]. The development of composite polymer electrolytes (CPE) by
incorporating inorganic fillers into polymer electrolyte has been proven
3.3.3. Electrical abuse tests to be an effective way to simultaneously improve their electrochemical
Electrical abuse testing involves subjecting batteries to conditions of properties as well as the mechanical strength and thermal stability. The
overcharging, over-discharging, and external short circuits. Among inorganic fillers in the current studies are mainly divided into two cat­
these, overcharging represents one of the most hazardous forms of egories: passive fillers and active fillers, depending on whether they
electrical abuse and is a frequent contributor to safety incidents have ionic conductivity. Passive nanofillers, while initially non-
involving lithium-ion batteries. According to the IEC 62660-3-2022 conductive, impact ion transport by inhibiting polymer crystallization
standard, an overcharging test involves initially charging the battery and lowering their Tg, and thereby enhancing IC. According to the Lewis
to 100% state of charge (SOC). The overcharging process is terminated acid-base theory, the specific surface of some passive nanofillers actively

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M. Wu et al. Energy Storage Materials 66 (2024) 103174

interacts with ion pairs and promotes their further dissociation, reduce the dripping during combustion. Additionally, certain minerals,
contributing to lithium transfer number (LTN) [40]. Passive inorganic such as metal hydroxides, can absorb heat and decompose, generating
nanofillers provide additional ion migration sites on the surface and are water at high temperatures, which directly interfere with the polymer
able to modify the behavior of the polymer chains at their interfaces and combustion process.
create Li+ transport paths independent of chain segment motion.
Additionally, most inorganic fillers are stable at high voltages, and 4.1.1. Zero-dimensional (0D) fillers
well-designed CPEs can expand the ESW by preventing direct contact of 0D fillers generally refer to inorganic nanoparticles, which are the
thermodynamically unstable components [41]. most extensively researched and applied nano-fillers in CPEs [40]. This
Inorganic fillers also contribute to the flame retardancy of electro­ is primarily because 0D particles are easily accessible and, when uni­
lytes. They have been extensively employed in a variety of polymer formly dispersed, can decrease the crystallization of polymers, thereby
applications due to their cost-effectiveness, low toxicity, minimal cor­ accelerating Li+ transport. Mechanical mixing methods have been
rosive properties, and reduced smoke emission, constituting approxi­ widely adopted as the preferred approach for creating CPEs due to their
mately half of the global flame-retardant usage [42]. These fillers play a convenience and cost-effectiveness [43]. In flame-retardant PEs,
pivotal role in enhancing the mechanical properties, thermal stability, metallic nanoparticles and silicon compounds are commonly employed.
and fire resistance of polymer electrolytes, primarily by serving as a
rigid framework and potential cross-linking agents within the polymer 4.1.1.1. Metal compounds. Metal compounds such as metal hydroxides
matrices. Inorganic fillers indirectly affect the combustibility of poly­ are commonly used as cost-effective fillers in battery applications [44],
mers by the following mechanisms. (1) their intrinsic non-combustibility offering improved mechanical properties and electrochemical perfor­
reduces the content of the combustible part of the polymer system; (2) mance, and contributing to thermal stability and flame retardancy [45].
they change the thermal conductivity of the materials and their ther­ When heated, they decompose to produce metal oxides and nonflam­
mophysical properties (3) they alter the viscosity of the material and mable gas, diluting the flammable gases [46]. Taking magnesium

Fig. 3. (a) Stress-strain curves of polymer films with different Mg (OH)2 contents. Copyright 2017, Elsevier. (b) Combustion testing of full pouch batteries with
CPVH–NE. Copyright 2022, Elsevier. (c) Li+ conduction pathways in PEG and PEG-TEP-TiO2. Copyright 2021, Elsevier. (d) Ionic conductivities of PEG-TEP and PEG-
TEP-TiO2. Copyright 2021, Elsevier. (e) Synthesis route of PEA@ZHS. Copyright 2022, Elsevier. (f) HRR curves of PEO and PX with various PEA@ZHS loadings.
Copyright 2022, Elsevier.

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M. Wu et al. Energy Storage Materials 66 (2024) 103174

hydroxide as an example, its decomposition process is usually endo­ compounds in polymer electrolytes due to their cheap price and easy
thermic[31], and the absorption of heat inhibits the degradation of the availability. Nevertheless, these compounds tend to exhibit limited
polymer. Lee et al. have demonstrated that the introduction of 40 wt% flame-retardant efficiency [42], necessitating substantial quantities for
Mg(OH)2 into poly (vinylidene fluoride-co-hexafluoropropylene) satisfactory fire resistance, which, in turn, often leads to aggregation and
(PVDF-HFP) based composite polymer electrolyte (CPE) could compromises electrochemical performance. While chemical modifica­
improve their flame retardancy and also enhance the IC to 0.54 mS⋅cm− 1 tion offers a balanced approach, it introduces extra procedural steps and
[47]. However, this strategy suffered from the relatively large filler costs. A promising strategy lies in the combination of metal compounds
content and the deterioration of mechanical properties (Fig. 3a). with other flame retardants, especially non-flammable solvents, as this
Metal carbonates represent another category of metal compounds holds the potential to simultaneously enhance flame resistance and
utilized in flame-retardant polymer electrolytes. Wang et al. prepared electrochemical properties. Thus, innovative approaches for future
60 wt% nano-CaCO3/PVDF-HFP (CPVH), which was activated with research could encompass the development of tailored metal com­
LiPF6 in flame retardant solvents (trimethylphosphate (TMP) and fluo­ pounds with enhanced flame-retardant properties or exploration of
rinated ethylene carbonate (FEC)), to prepare CPVH nonflammable synergistic effect in hybrid flame-retardant strategies.
electrolyte (CPVH–NE). The CPE showed an improved IC of 0.18
mS⋅cm− 1 at 25 ◦ C, and a LTN of 0.63 with a high ESW of 5.1 V. [45]. 4.1.1.2. Silicon. Besides metal oxides, other oxide ceramics, such as
CPVH–NE based LiFePO4 (LFP)//Li batteries maintained an open cir­ SiO2, have garnered significant attention in polymer electrolyte research
cuit voltage of approximately 3.5 V for 90 min at 150 ◦ C, which effec­ due to their easy availability and abundant reserves [41]. SiO2 has also
tively prevented ISC at high temperatures. Additionally, pouch cells did been reported to inhibit the potential of lithium dendrite growth by
not ignite even when exposed to flame for 20 s (Fig. 3b), further proving modulating Li+ deposition through polar functional groups (Si–O,
the fire safety. H–O) [54,55]. Long et al. demonstrated that the addition of SiO2 to
Oxide ceramics constitute another extensively investigated category PVDF-HFP/PMMA-based GPE enhanced the electrolyte-electrode inter­
of passive fillers in CPEs. Notably, metal oxides stand out as one of the face stability and brought about flame retardancy with high heat resis­
earliest fillers employed in electrolyte materials [48]. Beyond their role tance [56]. This GPE remained difficult to ignite after 3 s of exposure to
in enhancing the transport of Li+, metal oxides also impart flame, and did not shrink significantly after 5 h of heat treatment at 80
flame-retardant properties by catalyzing the formation of a protective ◦
C. The cross-linking of PVDF-HFP and PMMA increased the amorphous
char layer at high temperatures and anchoring in the char layer, which region and facilitated the chain segment movement, resulting in an IC of
improves the integrity of the char layer and the barrier effect to inhibit 0.49 mS⋅cm− 1 at RT and a LTN of 0.62. The assembled Li-O2 cells
heat transfer and pyrolysis product emissions [49]. Yang’s group initi­ delivered high discharge capacity and good cycling stability, with no
ated the polymerization of 1,3-dioxolane (DOL) with acid-treated Al2O3 electrolyte leakage after extrusion and could continue to power LEDs
and prepared GPE [50]. The -OH on the surface of acid-treated nano-­ under bending conditions. SiO2 has also found application in poly­
Al2O3 attracted the TFSI− anion to promote the dissolution of LiTFSI and urethane (PU) matrix to fabricate flexible, flame-resistant and
thus increased the IC and LTN to 3.37 mS⋅cm− 1 at room temperature dendrite-impermeable GPE [57].
(RT) and 0.74, respectively. In addition, the LOI of the prepared GPE was Polyhedral oligomeric silsesquioxane (POSS) is another silicon-based
improved to 22.2% due to the fire-retarding effect of Al2O3. filler with a highly ordered cage-like structure consisting of Si–O–Si
TiO2 is regarded as a promising option for enhancing IC due to its bonds. It has been reported that the introduction of POSS not only in­
high Lewis-acidic character when compared to counterparts like Al2O3, hibits the crystallization of the polymer backbone, but also facilitates Li+
SiO2, and ZrO2 [51]. A related study was the preparation of noncom­ conduction and enhances heat resistance, flame retardancy and elec­
bustible GPE by incorporating the commercial flame retardant triethyl trochemical stability due to its internal inorganic silica oxides [58]. The
phosphate (TEP) and nano-TiO2 into polyethylene glycol diacrylate eight side arms of POSS offer versatile chemical modification possibil­
(PEGDA) matrix [52]. This GPE showed excellent fire resistance with ities and serve as potential cross-linking sites within polymers. Li et al.
only a small amount of white smoke appeared after the flame removal. synthesized a cross-linked POSS-PEG network structure and highlighted
Interestingly, fast Li+ transfer channels were constructed in the PEGDA that different cross-linking densities can be achieved by controlling the
matrix by the synergistic effect of TEP and nano-TiO2 (Fig. 3c). This dual amount of POSS and the molecular weight of PEG, thus balancing the
accelerated conduction mechanism improved electrochemical perfor­ mechanical and electrochemical properties of GPE [59].
mance (Fig. 3d) and efficiently inhibited lithium dendrite growth, Wunder’s study revealed two flame retardant mechanisms for POSS
leading to a stable cell cycling performance. in polymer electrolytes (a) they have low volatility due to their high
Inorganic particles often grapple with compatibility issues within molar mass, which also reduced the volatility of the polymer compo­
polymer matrices, tending to aggregate. To address this challenge, nents, and (b) their capacity to generate oxidation-stabilized, imper­
various strategies have emerged, with functional group modification meable inorganic surface char that are fire resistant and passivate
standing as a prevalent solution. This approach not only enhances surfaces [60]. Zhang et al. demonstrated that GPE with hybrid cross­
dispersion but also allows for tailored interfacial properties through the linking system consisting of POSS and poly(ionic liquid) not only had a
application of a diverse array of grafting functional groups. Ma and co- high IC of 2.5 mS⋅cm− 1 but also displayed remarkable thermal stability
workers prepared a flame retardant unit (PEA@ZHS, Fig. 3e) by modi­ up to 360 ◦ C and self-extinguishing during direct ignition tests [61].
fying a novel non-toxic flame retardant zinc hydroxystannate (ZHS) with When applied in a LFP//graphite battery, it yielded a large capacity and
a lithium conductive polyether amine (PEA) and applied it to polyamide could power cellular phones under harsh conditions such as folding,
6 (PA6) reinforced PEO matrix to prepare PX-PEA@ZHS flame retardant cutting, and exposure to sunlight.
SPE [53]. The PEA@ZHS inorganic nanoparticles exhibited excellent
dispersion in the PEO matrix, granting the SPE high mechanical prop­ 4.1.2. One-dimensional (1D) filler
erties and flame retardancy. MCC tests revealed a significant reduction Compared to isolated nanoparticles, 1D nanofillers possessing a high
in heat release rate (HRR) (Fig. 3f), and combustion tests confirmed aspect ratio, such as nanowires or nanotubes, can construct a fast and
self-extinguishing properties. This SPE demonstrated an improved IC of continuous Li+ conduction channel across much longer distance and
0.43 mS⋅cm− 1 at 55 ◦ C, attributed to the reduced crystallinity and produce effective transfer network in the electrolyte to improve IC
enhanced polymer-filler interface. The assembled LFP//Li cells also (Fig. 4a) [62–64]. 1D nanofillers also offer distinct advantages in terms
achieved high capacity and cycle stability at a high temperature of 110 of flame retardancy. Their high aspect ratio plays a crucial role in
◦
C. creating a tortuous route for flammable gases, serving as a physical
Extensive research has focused on the incorporation of metal

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M. Wu et al. Energy Storage Materials 66 (2024) 103174

Fig. 4. (a) Schematic illustration for Li+ transport in the CPEs with nanoparticle and nanowire. Copyright 2016, American Chemical Society. (b) The preparation of
HAP–PEO hybrid solid polymer electrolyte. Copyright 2020, American Chemical Society. (c) LSV curves of the HAP–PEO electrolyte at 60 ◦ C and 160 ◦ C. Copyright
2020, American Chemical Society. (d) The SEM image of HNT/PEI nanofiber membrane. Copyright 2018, Elsevier. (e) Flammability tests of Celgard 2500, PEI and
HNT/PEI nanofiber membranes.

barrier to disrupt the direct diffusion path of gases and restrict the fuel Other 1D fillers such as nanotubes have also been applied in flame
supply [53]. retardant polymer electrolytes. Yang et al. introduced halloysite nano­
In the work by Xu et al., self-supported hydroxyapatite (HAP) tubes (HNTs) into a polyetherimide (PEI) matrix to create highly ther­
nanowire membranes were integrated into a PEO matrix. (Fig. 4b) The mally stable porous membranes (HNT/PEI, Fig. 4d) with excellent
robust structure and thermal stability of the HAP membrane ensured saturated liquid uptake and conservation rate [66]. The HNT/PEI
that, upon ignition of the HAP-PEO hybrid solid electrolyte, only the nanofiber membranes exhibited flame retarding capability due to the
polymer burned, leaving the HAP membrane skeleton intact, thus existence of inherent flame retarded PEI and clay-type nanofillers.
mitigating the risk of ISC [65]. The HAP nanowire, rich in oxygen (Fig. 4e) The hollow lumen of HNT provided additional Li+ transport
groups, significantly increased the amorphous region of the PEO, pro­ channels, and its abundant hydroxyl groups promoted the dissociation
moting anion immobilization and lithium salt dissociation, resulting in of lithium salts. The resulting GPE demonstrated an IC of 5.30 mS⋅cm− 1
an IC of 0.01 mS⋅cm− 1 and a LTN of 0.69. Even at extreme temperatures with a LTN of more than 0.5.
up to 160 ◦ C, the electrolyte maintained an ESW of 4.9 V, (Fig. 4c) 1D fillers effectively avoid the isolated distribution of nanoparticle
enabling stable operation of the LFP//Li cell at high temperatures. fillers in the polymer matrix, frequently improving IC by establishing

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M. Wu et al. Energy Storage Materials 66 (2024) 103174

continuous ion transport channels. Nevertheless, the inherent tendency semi-penetrating polymer network not only increased IC to 1.6 mS⋅cm− 1
of nanowire fillers to aggregate, forming filler-filler random contacts, at 25 ◦ C (Fig. 5a) but also imparted self-extinguishing ability (Fig. 5b)
poses a persistent challenge due to their lack of inherent binding affinity. [73]. Another 2:1 layered clay, Vermiculite (VMT), possesses a higher
One viable solution involves the formation of 3D continuous nanoscale cation exchange capacity and negative charge on the silicate layers [74].
networks with interconnected remote ion transport. This approach Exfoliated Vermiculite sheets (VS, Fig. 5c) have been introduced to
serves to regulate filler aggregation, and provide more robust and or­ PEO-based SPEs to enhance the thermal stability (>200 ◦ C) and me­
dered conductive pathways, which will be further discussed in subse­ chanical properties while reducing the flammability [75]. The highly
quent sections. reactive interface between VS and PEO promotes Li+ transport (Fig. 5d),
resulting in an IC of 0.03 mS⋅cm− 1 at 25 ◦ C and a LTN of 0.25. Natural
4.1.3. Two-dimensional (2D) filler ore materials like lepidolite have also shown lithium conductivity, Wang
2D fillers can create a substantial interface with polymers due to and co-workers revealed that DMF plasticizer and lepidolite could form
their high surface area. Their influence on ion conduction extends a synergistic effect in PVDF matrix, increasing the IC to 0.13 mS⋅cm− 1
beyond reducing polymer crystallinity; they can also disrupt Lewis acid- [76] This CPE also possessed excellent nonflammability and thermal
base interactions between ions and polymers [67]. Moreover, exfoliated stability (>100 ◦ C) with enhanced mechanical properties to suppress the
high aspect ratio layers provide a significant interfacial contact area lithium dendrites growth.
with polymers, enhancing lithium salt solubility and shortening ion Metal-containing nanosheets, such as Molybdenum disulfide (MoS2),
diffusion pathways [68,69]. Regarding flame retardancy, nanosheets can facilitate lithium salt dissociation [77,78] and catalyze char for­
within the polymer matrix form a protective layer during combustion mation [79,80], contributing to both electrochemical properties and
[31]. The extensive interface area and short distance between nano­ flame retardancy. Xie and co-workers constructed an ionic conducting
sheets contribute to forming a thermally conductive network during network through 2D MoS2 and 1D surfactant oxidized cellulose nano­
combustion. This network transfers heat from the combustion side to a crystal (OCNC) (Fig. 5e) in a CPE [81], leading to a high IC of 0.8
cooler area, extending ignition time [70]. Additionally, the filler mS⋅cm− 1 at 30 ◦ C. MCC showed a 48% decrease in HRR and a 37%
network increases material viscosity, preventing flame dripping and reduction in THR of CPE compared to that of pure polymer electrolyte
reducing the risk of flame spread. (Fig. 5f and g), demonstrating its flame retardancy. Other 2D nano­
Clays are a group of commonly used layered fillers, which usually materials, like MXene, are also being explored for applications in
have stable physical and chemical properties with high heat resistance. fire-safe polymer electrolytes [82]. As the first reported MXene [83],
Montmorillonite (MMT), a typical 2:1 layered clay, reinforces mechan­ Ti3C2Tx was incorporated into PVDF-HFP to impart high heat resistance
ical properties and imparts flame retardancy to various polymers [71]. and flame retardancy. The flame retardancy mechanism involves the
The weak bonding within MMT layers allows free ion transports be­ conversion of Ti3C2Tx MXene into TiO2/C protective layers after expo­
tween them [72]. Park et al. demonstrated that MMT in a sure to fire (Ti3C2 + 3O2 → 3TiO2 + 2C) [84].

Fig. 5. (a) Room temperature ionic conductivity of the U-CPCEs with various MMT contents. Copyright 2020, Wiley-VCH. (b) Ignition test of the U-CPCE. Copyright
2020, Wiley-VCH. (c) Cross-sectional SEM images of the VS film. Copyright 2018, Wiley-VCH. (d) The mechanism of Li+ migration in VS-enhanced SPE. Copyright
2018, Wiley-VCH. (e) Schematics of MoS2/OCNC nano-hybrid. Copyright 2018, Elsevier. (f) HRR, and (g) THR curves of PE and nh-CPE. Copyright 2018, Elsevier.

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M. Wu et al. Energy Storage Materials 66 (2024) 103174

4.1.4. Three-dimensional (3D) filler a 3D continuous SiO2 network in the crosslinked-PEO electrolyte.
The adoption of 3D networks emerges as an effective strategy for (Fig. 6a) The interconnected mesoporous SiO2 network imparted low
achieving high-performance CPEs. These networks not only provide flammability and improved mechanical strength to the CPE, demon­
multi-dimensional pathways for ion transport but also prevent the un­ strating robust structural stability even under repeated exposure to
desirable agglomeration and precipitation of fillers within the polymer intense flames. A threefold increase in IC was observed after doping the
matrix, thereby contributing to the enhancement of IC [85]. 3D net­ SiO2 aerogel, reaching about 0.6 mS⋅cm− 1 at 30 ◦ C [87].
works also contribute to the fire safety of CPEs by increasing the melt The integration of 3D networks into CPEs yields a substantial
viscosity of polymer nanocomposites and restricting the thermal enhancement in mechanical strength, effectively impeding the forma­
movement of polymer chains. When exposed to fires, they can also serve tion and proliferation of dendrites, also contributing to safety. An
as barriers against the evolution of flammable volatiles and the entry of example is the work of Nanda et al., who reported the development of a
oxygen into the condensed phase [86]. For example, Cui et al. embedded crosslinked EPO CPE incorporating woven glass fibers (GF) (Fig. 6b).

Fig. 6. (a) Schematic showing the synthetic procedures of the SiO2-aerogel-reinforced CPE. Copyright 2018, Wiley-VCH. (b) The preparation of the GF-reinforced
CPE based on the thermal-triggered curing process of PEGDGE and Jeffamine. Copyright 2021, Elsevier. (c) Flammability test of the GF composite membrane.
Copyright 2021, Elsevier. (d) Images of the bendable pouch-type cell powering an LED light at once-folded (left) and tripled-folded (right) conditions at 25 ◦ C.
Copyright 2021, Elsevier.

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M. Wu et al. Energy Storage Materials 66 (2024) 103174

This incorporation resulted in a remarkable increase in the elastic 4.2. Active ceramic fillers
storage modulus, reaching up to 2.5 GPa [88]. This enhanced mechan­
ical strength enabled the CPE to withstand a substantial plasticizer Compared to passive inorganic fillers, active ceramics have intrin­
loading of 33%, leading to an impressive IC of 0.12 mS⋅cm− 1 at RT. sically high IC [90], Li+ typically has three migration paths in such
Furthermore, the introduction of GF endowed the CPE with flame composite electrolytes: the polymer bulk phase, the ceramic bulk phase,
retardant properties, ensuring the maintenance of its morphological and the interfacial region between polymer and ceramic [89]. Previous
integrity even after exposure to fire for over 43 s. (Fig. 6c) The pouch cell research also revealed that the primary ion transport pathway can shift
folded once or even 3 times was still capable of powering an LED light. from the polymer phase to the ceramic phase as the proportion of the
(Fig. 6d) ceramic increases [91]. Tu et al. constructed a spongy
Despite the advantages of 3D frameworks in providing a continuous PVDF-HFP/Li6.4La3Zr1.4Ta0.6O12 (LLZTO) porous framework by a phase
pathway for the transport of Li+, the composite may exhibit numerous inversion method, with a large number of internal interfaces forming a
voids and these poorly connected interfaces can potentially impede ion continuous fast Li+ transport network in the electrolyte (Fig. 7a) [92].
transport [89]. Additionally, the construction of 3D frameworks always The resulting GPE showed an IC of 0.55 mS⋅cm− 1 at 25 ◦ C and a LTN of
involves tedious design and synthesis, and some intricate 3D frame­ 0.58, with high thermal stability (400 ◦ C) and non-flammability.
works are susceptible to collapse, rendering them unsuitable for indus­ The geometry of perovskite fillers plays a crucial role in influencing
trial applications. Consequently, the imperative lies in the development the conduction of Li+. Cui et al. demonstrated that incorporating
of robust and cost-effective 3D frameworks for fire-safe polymer Li0.33La0.557TiO3 (LLTO) nanoparticles led to a tenfold improvement in
electrolytes. the conductivity of the composite electrolyte, whereas the addition of
LLTO nanowires resulted in an impressive three-orders-of-magnitude
enhancement, as the high-aspect-ratio ceramic nanowires provided
long-distance Li+ transport channels [64]. Liu et al. proposed a

Fig. 7. (a) The Li+ rapid conducting pathways of PVdF-HFP/LLZTO porous CPE. Copyright 2021, American Chemical Society. (b) SEM image of in-situ PLE.
Copyright 2022, The Royal Society of Chemistry. (c) Ignition Tests of In-situ PLE. Copyright 2022, The Royal Society of Chemistry. (d) SHE Janus interface for high-
performance LAGP-based lithium metal batteries. Copyright 2020, American Chemical Society. (e) Self-healing properties of ASHE and CHSE. Copyright 2020,
American Chemical Society. (f) Ionic conductivity of LAGP and the ASHE|LAGP|CSHE composite as a function of temperature. Copyright 2020, American Chemical
Society. (g) LiCoO2/PMLSE/Li pouch cell test in liquid nitrogen. Copyright 2020, Wiley-VCH.

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M. Wu et al. Energy Storage Materials 66 (2024) 103174

topological chemistry-driven polymerization strategy to obtain poly(1, as high as 56 [96].

3-dioxolane) (PDOL) in a self-supporting LLTO skeleton by cationic Another strategy to address the LAGP instability with the metallic Li
polymerization of 1,3-dioxolane (DOL) [93]. This method produced a and the poor interfacial compatibility with the cathode is to construct
biphasic ion-conducting composite electrolyte with chemically stable polymer electrolytes on both sides of the LAGP, which serves as an
interfaces (Fig. 7b), achieving an IC of 0.66 mS⋅cm− 1 at RT and a LTN of interface that can maintain an integrated electrode/electrolyte contact
0.6, along with a wide ESW of 5.5 V. Compared with flammable PDOL, during cycling, thus eliminating Li/LAGP interfacial side reactions.
the incorporation of flame-retardant LLTO nanofibers endowed these Wang et al. constructed self-healing polymer electrolytes (SHE) as Janus
electrolytes with self-extinguishing properties (Fig. 7c). interfaces, which included IL-based anolyte SHE (ASHE) and adiponi­
NASICON-type ceramic particles, such as Li1.5Al0.5Ge1.5(PO4)3 trile (AN)-based catholyte SHE (CSHE), for LAGP-based Li metal batte­
(LAGP) and Li1.4Al0.4Ti1.6(PO4)4 (LATP), exhibit high IC, wide ESW, and ries (Fig. 7d) [95]. Both ASHE and CSHE recovered spontaneously
robust air stability. However, like LLTO, they suffer from chemical within 1 h after deep cutting at RT (Fig. 7e). They can also withstand
instability with lithium anodes [94]. Ge4+ in LAGP can be irreversibly temperatures up to 150 ◦ C and are difficult to ignite by flames due to the
reduced to Ge2+ and Ge when in contact with lithium metal, resulting in presence of flame-retardant IL and AN. The ASHE/LAGP/CSHE com­
the accumulation of side reaction products that obstruct Li+ transport posite showed a high IC of 2.75 mS⋅cm− 1 at 25 ◦ C (Fig. 7f) and inte­
[95]. Combining LAGP particles with polymer electrolytes has proven grated interfacial contact with the electrode, thus the assembled
effective in mitigating these challenges. LAGP was chosen as a medium Li//LiMn2O4(LMO) cells provide high reversible capacity and stable
for ionic conduction in a PVDF-HFP based SPE with a highly-safe ionic cycling performance.
liquid plasticizer (EMITFSI). This CPE possessed an improved IC of 0.96 Wang et al. proposed a bilayer heterostructure aimed at mitigating
mS⋅cm− 1 at RT and increased the compatibility of lithium anode, thus the inherent gap and unstable connection reactions at the interface be­
inhibiting the growth of lithium dendrites. It is non-flammable even tween the solid electrolyte and the electrode [97]. They prepared a
after exposed in an acetylene flame (1300 ◦ C) for a long time with a LOI tough ion-conductive matrix with garnet nanowires and PVDF-HFP to

Fig. 8. (a) Li+ transport pathways between MOF, PEO and LiTFSI. Copyright 2021, Elsevier. (b) Cycling performance of LFP/CSPE/Li battery at 0.5 C. Copyright
2021, Elsevier. (c) HRR curves of SPE with different HKUST-1 contents. Copyright 2021, Elsevier. (d) LOI test of PL3Z/PA. Copyright 2022, Elsevier. (e) Inhibition of
lithium dendrite growth in PE-ZIF-8@MXene. Copyright 2022, Elsevier. (f) Schematic diagram of the distribution of amorphous EACe2 ICPs network and crystalline
discrete MOF particles in PEO matrix. Copyright 2021, Elsevier.

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M. Wu et al. Energy Storage Materials 66 (2024) 103174

provide the flexibility and high voltage stability for the cathode. This generated by PL10HM (i.e., SPE with 10 wt% HKUST-1) was reduced by
matrix was complemented by a soft-humid composite gel, composed of 42% compared to that of PEO/LiTFSI, proving that the introduction of
MOF and PEO/PVDF-HFP, which enhanced the interface for contacting HKUST-1 improved the fire safety of the electrolyte. The introduction of
the lithium anode and stabilizing electrochemical reactions. In addition, HKUST-1 also resulted in an IC of 0.35 mS cm− 1, a LTN of 0.38 with an
solid-state batteries with this bilayer heterostructure solid electrolyte ESW of 4.71 V at 50 ◦ C. The LFP/PL10HM/Li battery exhibited a good
could be safely use in extreme conditions. (Fig. 7g) cycling and rate performance with a high specific capacity of 160
mAh⋅g− 1 at 0.1 C.
4.3. Metal-organic frameworks Compared to the direct addition of MOF, utilizing the porous struc­
ture of MOF to encapsulate non-flammable liquids can lead to the
Metal-organic frameworks (MOFs)are a class of crystalline materials derivation of multifunctional fillers with both flame retardancy and
composed of metal ions or clusters coordinated by organic ligands to ionic conductivity. For example, ZIF-8 with a large specific surface area
form a repeating network structure. Compared with conventional inor­ is employed to absorb the ionic liquid LiTFSI/EMIM-TFSI (Li-ILs) to
ganic fillers, as organic-inorganic hybrids, MOFs possess improved facilitate Li+ transport. This Li-ILs@ZIF-8 was subsequently added to a
compatibility with polymers. In addition to less aggregation, other 3D flame retardant skeleton 3DPA, consisting of PVDF-HFP and
unique advantages of MOFs include tunable particle size, tailored aluminium diethylphosphinate (ADP) flame retardant, and finally PEO
porosity, and ease of chemical functionalization. was introduced to obtain PEO/LiTFSI- 3DPA-30 wt%Li-ILs@ZIF-8
Beyond reducing polymer crystallinity like traditional inorganic (PL3Z/PA) SPE. The electrochemical performance of this SPE showed
fillers, the highly porous crystalline structure of MOF provides well- an enhanced IC of 0.91 mS⋅cm− 1, a LTN of 0.40, and an ESW of 4.8 V
defined Li+ transport pathways [98]. The introduction of MOF can at 55 ◦ C. PL3Z/PA also showed self-extinguishing in air with a LOI of
lead to a decrease in the glass transition temperature (Tg) and crystal­ 20.5% (Fig. 8d) due to the synergistic effect of 3DPA and Li-ILs@ZIF-8
linity of the polymer, thereby improving the IC. MOFs also contribute to [106].
the improvement of LTN, mainly through the following two effects. While MOFs exhibit improved compatibility with polymer matrices
Fig. 8a shows that the open metal site (OMS) of the activated MOF also compared to traditional inorganic nanofillers, they still encounter
facilitates the trapping of anions and promotes the dissociation of challenges associated with partial agglomeration, particularly at higher
lithium salts, releasing more free Li+ [99]. Lu et al. proposed the method concentrations, leading to phase separation, which deteriorates the well-
of deactivated-MOF polymer composites, which were prepared using defined ion-conducting channels and causes a decrease in ionic con­
untreated MOF particles, to verify the OMS effect [100]. Another ductivity and energy density [107]. Additionally, most MOFs exist as
function is the confinement effect of the MOF nanopores on the separate crystals, which make them difficult to establish continuous
large-sized TFSI− anions, allowing Li+ to migrate along the MOF in­ pathways for Li+ transport within polymer electrolytes [108]. To sur­
terfaces or surfaces. mount these challenges, a practical solution involves the development of
As determined by Zhang and colleagues, the notable porosity of hybrid nanosheets in which MOFs are horizontally extended on
MOFs, along with the Lewis acidity of its central metal, showed the two-dimensional (2D) frameworks. This approach enhances the disper­
capacity to absorb minute impurities and trace water molecules within sion and facilitates the creation of contiguous Li+ transport pathways.
the electrolyte, ultimately contributing to an extended ESW [101]. For instance, a 2D ZIF-8@MXene nanosheet was synthesized by growing
MOFs further improve the uniformity of cation deposition during ZIF-8 directly on MXene layers and incorporated into a composite matrix
cycling and fosters enhanced interface stability. Li et al. demonstrated consisting of PEO and PVDF-HFP to form a CPE (PE-ZIF-8@MXene)
that the direct introduction of 10 wt% Ce-based MOF into PEO-based [109]. Impressively, this CPE exhibited non-flammability after a 10 s of
SPE increased the IC to 0.03 mS⋅cm− 1 at 60 ◦ C with a high LTN of exposure to fire, coupled with improved electrochemical properties,
0.75 and an ESW of 4.5 V [102]. This excellent electrochemical stability including an IC of 4.4 mS⋅cm− 1 and a LTN of 0.76. Moreover, the
and the ability to hinder dendrite growth enabled the Li/CSPE/LFP cells incorporation of PE-ZIF-8@MXene effectively mitigated the formation
to exhibit excellent cycling performance with an almost 100% EC of lithium dendrites, as illustrated in Fig. 8e, and
(Fig. 8b). Nonetheless, an excessive addition of MOF can give rise to LFP/PE-ZIF-8@MXene/Li cells demonstrated robust cycling stability,
agglomeration issues, diminishing the interfacial interaction between retaining 89.6% of their capacity after 500 cycles.
MOFs and the polymer, consequently causing a reduction in conduc­ In contrast to conventional highly crystalline MOFs with separate
tivity. Another problem is that MOF-based all-solid-state electrolytes are crystalline grains, infinite coordination polymers (ICPs) are created
commonly operated at high temperatures, typically exceeding 60 ◦ C, through the self-assembly of metal cation salts and functionalized ligand
owing to their relatively low IC and high interfacial resistance. In precursors [110], typically resulting in semi-crystalline and amorphous
addition to its positive impact on electrochemical properties, Ce-MOF structures. These structures are highly interconnected and
also exerts a notable influence on the thermal and mechanical charac­ self-assembled networks that serve as three-dimensional (3D) scaffolds
teristics of the electrolyte, while enhancing flame retardancy, as evi­ within polymer matrices, offering a multitude of Li+ transport channels
denced by the minor morphological changes in the Ce-MOF SPE even at various scales and enhancing their mechanical properties (Fig. 8f). Li
after an 80-second exposure to fire. and coworkers engineered an ICP, named EACe2, synthesized by the
Currently, extensive research has unveiled the notable flame- self-assembly of cerium ions (Ce3+) and ellagic acid (EA), and integrated
retardant and smoke-suppressing attributes of MOFs when integrated it into a PEO matrix to produce SPE (CSPE-EACe2) [111]. These elec­
into polymer matrices. These effects are principally underpinned by the trolytes demonstrated an IC of 0.28 mS⋅cm− 1 and a LTN of 0.47 at 60 ◦ C,
catalytic effect of the metal clusters within MOFs, which promotes the with improved toughness. CSPE-EACe2 exhibited only slight morpho­
formation of char during combustion [49,103]. Simultaneously, the logical shrinkage after exposure to fire for 17 s, demonstrating its
thermal decomposition of MOFs generates metal oxides that act as high-temperature resistance and fire-proof properties. The
physical barriers, encapsulating burning materials and inhibiting further LFP/CSPE-EACe2/Li battery displayed an initial discharge capacity of
combustion. These metal oxides also play a pivotal role in efficiently 161.3 mAh⋅g− 1 at 0.5 C, along with promising cycling and rate
adsorbing hazardous gases and smoke, thereby mitigating the overall performance.
fire hazard. This multifaceted mechanism positions MOFs as promising MOF/polymer electrolytes, although promising, are still in their in­
flame-retardant fillers, finding particularly relevant applications in fancy and face limitations in various aspects. As coordinated porous
enhancing the safety of lithium batteries [104]. Wang et al. incorporated materials, MOFs encounter challenges in maintaining long-term stability
HKUST-1, a highly thermal stable MOF, into PEO/LiTFSI to improve its within the intricate electrochemical environment of batteries, poten­
flame retardancy [105]. MCC tests (Fig. 8c) showed that the heat tially limiting the battery performance of rate and cycle stability [112].

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M. Wu et al. Energy Storage Materials 66 (2024) 103174

Additionally, the lack of effective methods for achieving uniformly transport.

dispersed MOF-based film preparation hinders scalable production
[113]. The cumbersome fabrication process and the high cost of MOFs
4.4. Halogen
further compound this issue. This challenge is particularly pronounced
in the case of delicate MOF structures such as MOF sheets or even MOF
Halogen compounds, a widely utilized class of highly efficient flame
skeletons as their synthesis often involves precise molecular tuning,
retardants, operate through a gas-phase free radical scavenging mech­
albeit they offer long-range ordered channels that facilitate Li+
anism [114]. Their thermal decomposition yields halogen radicals that

Fig. 9. (a) Flame retardant mechanism of the Br-based flame retardant (DBDPE). Copyright 2022, American Chemical Society. (b) HRR curves of PEO/LiTFSI and Br-
FRPE SPE. Copyright 2022, American Chemical Society. (c) Transformation mechanism of CEI with LiBr on the anode surface. Copyright 2022, American Chemical
Society. (d) Chemical structures of DBDPE and polyimide. Copyright 2020, American Chemical Society. (e) SET of PEO/LiTFSI with various DBDPE loadings.
Copyright 2020, American Chemical Society. (f) Flame abuse test of pouch batteries with different electrolytes. Copyright 2020, American Chemical Society.

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M. Wu et al. Energy Storage Materials 66 (2024) 103174

capture the highly reactive H• and OH• radicals released during poly­ To enhance the flame retardancy of fluorinated polymer electrolytes,
mer combustion, thereby weakening or terminating the combustion a promising approach involves the direct use of fluoropolymers as a
chain branching reaction (Fig. 9a) [115]. Furthermore, the gaseous matrix, thereby increasing the fluorine content. Yan and colleagues
products dilute oxygen concentration between the heat source and synthesized poly(fluoroethylene carbonate) (PFEC) through ring-
polymers, curtailing heat and mass transfer and, consequently, retarding opening polymerization, and combined it with a lithium salt (LiDFOB)
polymer combustion [116]. In terms of flame retardant efficiency (I > to create a non-flammable, high-voltage tolerant polymer electrolyte
Br > Cl > F), iodine exhibits the highest efficacy, but its limited thermal (HVTPE) [122]. HVTPE exhibited exceptional resistance to oxidation
stability restricts its application in polymers, making bromine-based and electrochemical stability, attributed to the potent
compounds the preferred choice among halogen flame retardants. electron-withdrawing effect of the fluorine atom, which prevented the
electrolyte from decomposing or depleting near the cathode. Addition­
4.4.1. Bromine ally, pouch batteries with HVTPE demonstrated remarkable safety,
Decabromodiphenyl ethane (DBDPE), developed in the 1990s, stands maintaining stable voltage levels without any incidence of flame or
out as an environmentally friendly Br-based flame retardant, possessing explosion when subjected to mechanical abuse such as folding, punch­
a high bromine content, excellent thermal stability, and recyclability ing, and cutting.
without generating environmental pollutants during thermal decom­ Highly porous polytetrafluoroethylene (PTFE) membranes have been
position [117]. Hence, DBDPE was directly integrated into the PEO employed as adsorption carriers for gel electrolytes [123]. The excep­
matrix to enhance its flame-retardant properties and voltage resistance tional thermal and mechanical stability of PTFE not only served as a
[118]. When compared to the PEO/LiTFSI solid electrolyte, the intro­ reliable support structure but also enhanced the toughness, heat resis­
duction of the Br flame retardant polymer electrolyte (Br-FRPE) resulted tance, and more importantly, imparted flame-retardant properties to the
in a significant reduction of 69.9% in PHRR and 54.5% in THR, as GPE. Nevertheless, fluorinated compounds, especially high-performance
illustrated in Fig. 9b. This material exhibited a SET of less than 10 s and a fluoropolymers, can be expensive to produce, particularly when utilized
high LOI of 34.2%, further confirming its flame retardancy. In Fig. 9c, as a matrix or backbone. This cost factor may limit their widespread
the decomposition of Br-FRPE into LiBr at high potential led to the adoption in battery manufacturing, especially for low-cost consumer
formation of an organic-rich cathode/electrolyte interphase (CEI), electronics.
enabling rapid Li+ transfer across the interface and achieving an IC of In addition to fluoropolymers polymers, fluorinated small molecules
0.17 mS⋅cm− 1 at 60 ◦ C with a high-voltage resistance of 4.5 V. also contribute to battery safety. The plasticizers in most GPE are highly
To further enhance the flame retardancy of the PEO/LiFSI system, flammable carbonates, thus the flammability of GPE can be reduced by
one strategy is combining the merits of DBDPE with intrinsic flame introducing nonflammable fluorinated solvents as plasticizers. The
retardant or nonflammable polymers such as polyimide (PI). Cui et al. enhancement of flame retardancy in a PVDF-based GPE was achieved by
introduced DBDPE and a porous PI film into the PEO/LiFSI matrix to introducing Fluoroethylene carbonate (FEC) and methyl 2,2,2-trifluor­
prepare SPE (Fig. 9d) [119]. This work demonstrated that a relatively oethyl carbonate (FEMC) as nonflammable plasticizers, preventing
high addition (15 wt%) was required to reduce SET to 0 by adding combustion when exposed to a flame for 3 s [124]. Additionally, the
DBDPE alone (Fig. 9e). Interestingly, the introduction of PI alone into inclusion of fluorine facilitated the formation of LiF-rich SEIs, effectively
the PEO/LiFSI system failed to confer flame retardant properties, despite mitigating dendrite growth on Li metal anodes. This modified GPE
the inherent nonflammable nature of PI. However, the combination of showed a high IC of 4.41 mS⋅cm− 1 at 30 ◦ C because the
DBDPE and PI enabled PI/DBDPE/PEO/LiTFSI SPE to self-extinguish high-dielectric-constant FEC facilitated the solvation of Li+ and disso­
within 2 s. This study also tested the safety performance of pouch bat­ ciation of lithium salts.
teries under thermal abuse (Fig. 9f). The pouch cells with LE or PEO/­ Apart from potential cost concerns, environmental impacts should
LiTFSI failed to light the LED bulb after 18 s and 24 s of ignition, also be taken into account when developing fluorinated solvents or
respectively. In contrast, the LED bulb continued to shine after the fluorinated lithium salts for safer polymer electrolytes. For instance,
PI/DBDPE/PEO/LiTFSI pouch cell was exposed to fire for 24 s. LiFP6, a commonly-used salt in commercial secondary batteries, exhibits
While bromine demonstrates significant fire retardancy, there has thermal instability and susceptibility to trace amounts of moisture,
been limited research into bromine-based polymer electrolytes due to making it extremely challenging to recycle. This not only raises the
their environmental and health concerns. The combustion of bromine- recycling costs for the remaining battery components but also results in
based compounds can produce carcinogenic dioxins and brominated the production of toxic and hazardous degradation products, including
furans, which are persistent organic pollutants and have adverse envi­ HF and PF5 [125].
ronmental impacts [120]. Some Br-based flame retardants can be toxic
and pose health risks. Consequently, certain brominated flame re­ 4.5. Phosphorus
tardants have encountered regulatory restrictions in various regions.
Researchers and industries are working to develop alternative flame In the quest for environmentally friendly alternatives to halogen
retardants that provide the same level of fire safety while addressing flame retardants, various halogen-free flame-retardant systems have
these drawbacks and minimizing their impact on the environment and been developed, with phosphorus compounds emerging as a popular
human health. choice. Phosphorus-based flame retardants exert their effects in both the
gas and condensed phases [126]. Phosphorus interrupts free radical
4.4.2. Fluorine chain reactions by generating radicals like PO•, HPO2•, and HPO•,
Fluorinated compounds, while inherently non-combustible, face effectively trapping H• and OH• radicals in the gas phase (Fig. 10a).
challenges in conferring effective flame-retardant properties to other Volatile phosphorus compounds are one of the most effective combus­
polymers. Unlike bromine, fluorinated compounds have limited release tion inhibitors, since phosphorus-based radicals are, on average, 5 and
of F• radicals due to their strong C-F bonds, and their highly reactive HF 10 times more effective than bromine radicals and chlorine radicals,
or F• radicals rapidly react in condensed phase, resulting in flame respectively [127]. They can also promote char formation or attach
retardancy less efficient than that of bromine or chlorine. In a study by sticky phosphoric acid to the surface of the char in the condensed phase.
Kim et al., a nonflammable fluorosulfonylimide group was incorporated This phosphoric acid readily condenses into a pyrophosphate structure,
into a poly (ethylene glycol) dimethacrylate (PEGDMA) matrix to releasing water that dilutes the flammable gas phase. Both phosphoric
facilitate Li+ transport, yielding an IC of 0.35 mS⋅cm− 1 and a LTN of 0.47 acid and pyrophosphoric acid play catalytic roles in the formation of
at 30 ◦ C [121]. Nevertheless, during ignition tests, the incorporation of char layers, which act as a physical barrier to reduce the transfer of heat
fluorine had a limited effect, merely slowing down the combustion rate. and oxygen, and prevent the dripping of burning polymers.

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M. Wu et al. Energy Storage Materials 66 (2024) 103174

Fig. 10. (a) Flame retardant mechanism of the phosphorus-based flame retardants. Copyright 2021, Elsevier. (b) Chemical structures of TMP, TEP and FEC (c)
Ignition tests of rigid-flexible coupling quasi-solid electrolyte. Copyright 2022, Elsevier. (d) Cycling performances for 4.5 V NCM811/Li batteries with different
electrolytes. Copyright 2022, Elsevier. (e) Cutting and burning test of the pouch NCM523 /Li cells. Copyright 2019, Wiley-VCH.

While the preparation of phosphorus-containing polymer electro­ high boiling point (197 ◦ C), and is therefore frequently employed as a
lytes is an efficient approach to impart flame retardancy, previous flame retardant and plasticizer in lithium-ion batteries [128–130].
studies have consistently shown that phosphorus tends to undergo sig­ Ciucci et al. introduced TMP solvent and LLZTO ceramic filler into the
nificant reductive decomposition on graphite anodes, leading to poor PVDF/LiCLO4 system to prepare nonflammable and thermal stable CPE
cycling performance as well as capacity decay. Thus, the reduction in with a high IC of 0.47 mS⋅cm− 1 at RT [131]. In contrast to CPE
flammability with the addition of these phosphorus-containing flame employing flammable DMF solvent, the incorporation of TMP rendered
retardants comes at the expense of electrochemical performance. the CPE non-combustible. TMP has also found application in other
Therefore, there is a need to trade off electrochemical performance for polymer matrices, such as PMMA[132], poly(butyl acrylate) (PBA)
flame retardancy in phosphorus-containing electrolytes [133], and poly(hexanone diol) (PCL)[134].
Another phosphorus-containing solvent, triethyl phosphate (TEP,
4.5.1. Phosphorus-containing solvents Fig. 10b), is derived by substituting the methyl group in the TMP
Organic solvents commonly used in electrolytes, are typically highly structure with an ethyl group, also widely employed in flame retardant
volatile and flammable, posing a risk of ignition at high temperatures. electrolytes. Guo and coworkers prepared a quasi-solid electrolyte by
An alternative approach is to replace traditional flammable organic introducing TEP solvent into poly(vinyl acetate) (PVAC) and triethylene
solvents with phosphorus-containing solvents or plasticizers. Trimethyl glycol diacrylate (TEGDA) copolymers [135]. The rigidity of TEGDA
phosphate (TMP, Fig. 10b) exhibits excellent thermal stability with a provided the electrolyte with basic physical support and superior

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 M. Wu et al. Energy Storage Materials 66 (2024) 103174

mechanical properties, while the flexibility of PVAC contributed to the 4.75 V. The non-flammability was attributed to the combination of the
high IC (1.02 mS⋅cm− 1 at RT) and good interfacial compatibility. The flame retardant TEP/FEC solvent, PVDF-HFP matrix and nonflammable
oxidative stability was also enhanced with no noticeable oxidative LLZO-Ga. The corresponding pouch battery exhibited high safety and
current observed until 5.2 V. When applied in a high-voltage LiNi0.8 can light up the diode even after thermal and mechanical abuse
Co0.1Mn0.1O2 (NCM811)/Li cell, this quasi-solid electrolyte demon­ (Fig. 10e).
strated an exceptionally high specific capacity exceeding 224.7 mAh⋅g-1
at 0.1 C, along with enhanced cycling stability compared with batteries 4.5.2. Organophosphorus additives
employing TEP liquid electrolytes (Fig. 10d). The introduction of TEP Organophosphates, encompassing organophosphate esters (OPEs),
also confers self-extinguishing properties to the electrolyte after removal phosphonates, and phosphinates, represent widely employed flame re­
of the fire (Fig. 10c), and accordingly the assembled battery passes the tardants. The direct addition of these compounds into the polymer
thermal and mechanical abuse tests. matrix is considered one of the simplest methods to reduce the flam­
Compared with unstable phosphorus-containing solvents, organic mability of polymer electrolytes. Hu et al. prepared flame retardant SPE
fluorine solvents such as FEC (Fig. 10b) can construct robust LiF-rich by incorporating Aluminum diethyl hypophosphite (ADP) and PEO/
SEIs on lithium metal and are well compatible with high-voltage an­ LiFSI [138]. The introduction of ADP had the dual effect of hindering the
odes [136]. However, FEC suffers from its prohibitive price, thus crystallization of PEO, leading to an improved IC of 0.04 mS⋅cm− 1 at 30
combining fluorinated and phosphorus-containing solvents is a strategy ◦
C (Fig. 11a), and generating an aluminum- and phosphorus-enriched
to realize both cost savings and performance improvements. Wen and SEI layer during cycling. Additionally, ADP served as a flame retar­
coworkers employed a mixture of flame retarded solvents (TEP and FEC, dant to increase the LOI from 16 (PEO) to 22 (PEO/15%ADP) with a SET
7:3, v/v)) and an ion-conductive filler Li6.4Ga0.2La3Zr2O12 (LLZO-Ga) to of 80 s after ignition, reducing the heat release rate of PEO and inhib­
prepare fireproof PVDF-HFP-based GPE [137]. Under optimization, the iting the combustion of PEO.
IC reached 1.84 mS⋅cm− 1 at 20 ◦ C with a LTN of 0.56 and an ESW of The chemical bonding of phosphorus flame-retardant components to

Fig. 11. (a) Ionic conductivity of SPEs with various ADP contents at different temperatures. Copyright 2021, American Chemical Society. (b) Temperature-time
curves and (c) Maximum temperature of LFP/LE/graphite and LFP/GPE-3/graphite pouch cells during overheating test. Copyright 2018, Wiley-VCH. (d) Thermal
abuse of LFP/GPE-3/graphite pouch cell. Copyright 2018, Wiley-VCH. (e) Schematic illustration of the flame-retardant mechanism of BP nanosheet-modified GPEs
Copyright 2023, American Chemical Society. (f) Graphite/GPE-0.5P/LFP pouch cell used in an LED lamp under harsh conditions. Copyright 2023, American
Chemical Society.

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M. Wu et al. Energy Storage Materials 66 (2024) 103174

the polymer chain reduces the side reaction between phosphorus and the 4.6. Nitrogen
electrode, resulting in a balance of flame-retardant and electrochemical
properties. Copolymerization of phosphorus-containing monomers with 4.6.1. Schiff bases
ether-based monomers provides a viable route for this strategy. For Nitrogen-containing flame retardants offer distinct advantages of
example, A phosphorus-containing nonflammable GPE was designed by low toxicity, low smoke emission and environmentally friendly prop­
in-situ co-polymerization of triethylene glycol dimethacrylate erties. The mechanism of nitrogen-based flame retardant, taking mel­
(TEGDMA) and tris(acryloyloxyethyl) phosphate (TAEP) [139]. GPE amine as an example, it sublimates at 350 ◦ C to absorb a lot of heat,
with 7.5 wt% flame retardant TAEP (GPE-3) exhibited an IC of 0.51 mS acting as a heat sink. In addition, the decomposition at high tempera­
cm− 1 (RT) and could not be ignited after being heated by fire for >10 s. tures produces a large number of non-combustible gases (e.g., ammonia)
MCC tests showed that the oxygen consumption of GPE-3 in combustion during combustion, diluting oxygen and combustible gases, and leading
is significantly lower than that of LE, further indicating its high fireproof to the formation of thermally stable products [31].
safety. LFP/GPE-3/graphite pouch cells not only exhibited excellent In addition to the nitrogen flame retardant effects described above,
long cycle stability and high capacity, but also passed mechanical abuse Schiff bases with the imine bond (-C– –N-) further prompt the formation
and thermal abuse tests. In ARC tests GPE-3 also showed lower tem­ of an adaptive network based on imines in the polymer matrix. If a
peratures and higher safety compared to LE. (Fig. 11b and c). No fires or sufficient amount of N is introduced to this network, it will impart fire
electrolyte leaks occurred in GPE-3 based battery during all tests resistance to the material [147]. Aromatic Schiff bases are
(Fig. 11d). Other co-polymers like phosphorus-block copolymers have self-crosslinked at high temperatures and can form nitrogen-containing
also been explored for applications in fire-safe polymer electrolytes hexatomic rings during combustion [148]. (Fig. 12a) This stable
[140]. cross-linked network plays a key role in the formation of thermally
In contrast to the previous studies centered on linear polymer protective coatings on surfaces and also in increasing the melt viscosity
structures, the utilization of branched topologies can enhance the of polymers.
mobility of polymer chain segments and increase IC. The incorporation The limited IC of polymer electrolytes necessitates the reduction of
of phosphorus-containing side groups into the polymer electrolyte ma­ electrolyte film thickness in battery manufacturing, yet this thinness
trix via graft copolymerization is anticipated to enhance both flame makes them susceptible to irreversible mechanical damage from
retardancy and electrochemical performance. He and co-workers graf­ external stresses and prolonged cycling. Polymers with low mechanical
ted lithium phenyl phosphate (LPPO) onto PVDF to form a poly(PVDF- strength can easily lead to electrolyte rupture and breakdown during
LPPO) SPE with a branched structure [141]. The LPPO branched to­ processes like encapsulation, complex deformation, and cycling. The
pology significantly reduced the Tg and crystallinity of the polymer and preparation of polymer electrolytes with self-healing ability provides
increased the IC to 0.48 mS⋅cm− 1 at 25 ◦ C. As a single ionic conductor, new insights into reducing battery accidents and extending their lifetime
LPPO also enhanced the LTN from 0.23 to 0.47. Solid-state 4.5 V [149]. In addition to their flame-retardant properties, Schiff bases can
NCM811/PVDF-LPPO/Li cells exhibited good cycling and rate perfor­ act as reversible dynamic bonds, exhibiting self-healing and recycling
mance. Compared with the continuous combustion of PVDF SPE, no properties without catalysts, including three equilibrium processes:
burning was observed in PVDF-LPPO after fire removal, indicating that imine condensation/hydrolysis, imine exchange, and imine recombi­
the grafting of noncombustible LPPO greatly retarded the combustion of nation, which further enhances battery safety.
PVDF with DMF. Current strategies for the introduction of Schiff bases into polymer
electrolytes focus on the polymerization of amino monomers with
4.5.3. Inorganic phosphorus additives carbonyl monomers. Meng et al. constructed highly reversible imine
A well-known inorganic phosphorus flame retardant is red phos­ bonds of polymer electrolyte through the Schiff base reaction between
phorus, but in the research of polymer electrolytes, another isomer of poly (ethylene glycol) diamine (NH2-PEG-NH2) and benzene-1,3,5-
phosphorus, black phosphorus (BP), is becoming increasingly popular. tricarbaldehyde (BTA), which resulted in flame retardancy and self-
BP offers significant advantages in flame retardancy, serving as both a healing properties (Fig. 12b) [150]. This electrolyte also showed a
physical barrier and a catalyst for char formation in the condensed high IC of 4.79 mS⋅cm− 1 at 30 ◦ C with a LTN of 0.38 and also inhibited
phase. Additionally, BP exhibits a radical-trapping effect in the gas dendrite growth, allowing the LFP//Li cell to exhibit good cycling per­
phase by generating PO• radicals (Fig. 11e) [142]. Beyond its formance and rate capability.
flame-retardant properties, BP provides an extremely low diffusion Fang and co-workers reported a recyclable and self-healing SPE
barrier (0.08 eV) along the zigzag direction, resulting in a highly based on a dynamic network of soybean protein isolate (SPI, Fig. 12c)
anisotropic diffusion of Li, which is 100 times faster than that of MoS2 with imine bonds[151]. SPI is a natural polymer consisting of 18
[143]. Previous literature has revealed that a small amount of BP in different amino acids covalently linked by peptide bonds. Positively
polymer electrolytes could effectively trap anions and facilitate the charged amino acids trapped anions and promoted Li+ migration,
dissociation of Li+ from lithium salts [144]. resulting in an IC of more than 0.33 mS⋅cm− 1 at 30 ◦ C. This electrolyte
Xie and colleagues demonstrated that a PMMA-based GPE with 0.5 also exhibited non-flammability in ignition test and its morphology
wt% BP (GPE-0.5P) could achieve self-extinguishing behavior and in­ remained essentially unchanged at 150 ◦ C for half an hour. Nonetheless,
crease LOI from 20.6% to 23.3% [145]. MCC tests further showed that Schiff base structures suffer from low flame-retarded efficiency, often
the incorporation of BP significantly reduced PHRR and THR. This GPE necessitating substantial quantities of this structure to achieve adequate
also had high toughness and heat resistance. BP promoted Li+ transport flame resistance, but an excessive presence of Schiff bases may
in GPE, resulting in a higher IC of 1.08 mS⋅cm− 1 at 30 ◦ C and a LTN of compromise the thermal stability.
0.43, with a wide ESW of 5.2V. The graphite/GPE-0.5P/LFP pouch
battery successfully powered LEDs even when subjected to various 4.6.2. Phosphorus-nitrogen synergy
mechanical abuses such as folding and cutting (Fig. 11f). BP can also be Nitrogen-based flame retardants, when used alone, generally exhibit
utilized in conjunction with other nanofillers; for instance, Fu et al. limited effectiveness, falling between the performance of halogen
combined BP with Bi2S3 nanorods to enhance both the flame-retardancy compounds and metal hydroxides [152]. A prevalent approach involves
and electrochemical properties, resulting in batteries with reliable fire their combination with phosphorus-based flame retardants to create a
safety, longer cycling stability, and dendrite-free lithium [146]. How­ synergistic effect, enhancing overall flame retardant efficacy. P–N
ever, BP suffers from environmental instability (sensitive to oxygen and bonds are more reactive than P–O bonds during phosphorylation, so the
water) and therefore, BP passivation is important before its application. formation of phosphorus-nitrogen intermediates can accelerate the
in-situ production of phosphoric acid and promote more intensive char

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M. Wu et al. Energy Storage Materials 66 (2024) 103174

Fig. 12. (a) Conjectural cross-linking structure of Schiff base groups. Copyright 2018, Elsevier (b) Chemical structure of NH2-PEG-NH2 and BTA. Copyright 2022,
Elsevier (c) SPI dynamic network with imine bond. Copyright 2022, Wiley-VCH. (d) Lithium-ion migration in AEP. Copyright 2021, The Royal Society of Chemistry.
(e) Ignition tests of AEP with/without PFPN. Copyright 2021, The Royal Society of Chemistry. (f) Synthesis route of HCP. Copyright 2020, American Chemical
Society. (g) Surface temperature changes of NCM811/Graphite pouch cells with LEs, PEGGPE, or PEGGPE@HT upon ignition. Copyright 2022, Elsevier.

formation [31]. Cyclophosphonitrile (CP) derivatives are after 500 cycles. Apart from direct addition, the P–Cl bond on the CP
organic-inorganic materials containing alternating phosphorus and ni­ can be further reacted and chemically bonded to the polymer matrix. For
trogen atoms in a ring structure. The phosphates with their derivatives example, hexa(4-ethylacrylamidophenoxy) cyclotriphosphazene (HCP,
produced by the thermal decomposition of phosphonitrile-based poly­ Fig. 12f) was employed as a cross-linking agent and copolymerized with
mers form a non-volatile protective film on the surface of the polymer, acrylate monomers to impart flame retardancy, and improve thermal
isolating it from the air. In addition, the release of non-flammable gases stability (up to 300 ◦ C) as well as mechanical strength of the polymer
such as CO2, NH3 and N2 cuts off the oxygen supply to achieve syner­ electrolyte [158].
gistic flame retardancy [153]. Free radicals appear to be the culprit in causing both fires and
Compared with organophosphorous flame retardants, cyclo­ degrading performances of lithium batteries, and extending the radical
phosphonitrile (CP) also shows better stability with the anode and annihilation mechanism to electrolytes can fundamentally prevent the
cathode [154]. Ethoxy (pentafluoro) cyclotriphosphazene (PFPN) is a generation and diffusion of radicals from electrolytes since they act as
CP derivative that has found application in lithium batteries [155]. hosts for radical generation in thermal runaway and high voltage in­
Previous research revealed that electrolytes using a low content (5%) of terfaces. Zhang et al. constructed a multi-scale radical annihilation
PFPN can be completely non-flammable [156]. Wei et al. incorporated system in electrolytes to simultaneously improve the high voltage sta­
PFPN and FEC solvents into a single ion-conducting polymer electrolyte bility and fire safety of electrolytes [159]. They designed a hexa­
(AEP) on electrospun PVDF membranes [157]. The allylboronic acid chlorocyclotriphosphazene cross-linked tannic acid (HT) microsphere,
pinacol ester (AAPE) component of AEP could trap anions (Fig. 12d), which could not only annihilate the radicals produced by the decom­
resulting in a LTN as high as 0.79 and an IC of 2.52 mS⋅cm− 1 at 25 ◦ C. In position of PEGGPE at the high-voltage interface, but also eliminate the
addition, AEP was nonflammable through the synergistic effect of PFPN radical chain reaction in thermal runaway at high temperature. The GPE
and FEC solvents (Fig. 12e). AEP could construct robust LiF-rich SEIs on (PEGGPE@HT) prepared by in situ polymerization of HT and PEGDA
lithium metal anodes and effectively restrain lithium dendrites growth, showed excellent flame retardancy, being non-flammable upon initial
resulting in a long-term cycling stability with a 93.2% capacity retention ignition and self-extinguishing at second ignition, with a SET of 6 s⋅g− 1.

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M. Wu et al. Energy Storage Materials 66 (2024) 103174

The incorporation of HT accelerated the Li+ migration, resulting in an IC Tetracoordinate boron centers function as fixed anions in polymer
of 0.99 mS⋅cm− 1 (30 ◦ C) with a LTN of 0.54. NCM811//graphite pouch electrolytes, and consequently, the LTN of tetracoordinate borate-based
batteries have successfully passed thermal and mechanical abuse tests. PEs is close to unity [162]. While neutral tricoordinate boron centers can
The ignition tests on pouch batteries (Fig. 12 g) showed that the surface serve as anion acceptors. These boron atoms possessing unoccupied p
temperature of PEGGPE@HT pouch batteries is 211.8 ◦ C and 130.0 ◦ C orbitals serve as Lewis acid sites, enabling them to establish coordina­
lower than that of LE and PEGGPE, respectively. tion bonds with lithium salt anions and promoting the dissociation of
cation-anion pairs.
In addition to improved electrochemical performance, Boron com­
4.7. Boron pounds offer an environmentally friendly alternative to highly polluting
halogen flame retardants, with low toxicity and versatility. They can
Boron has been extensively studied for use in lithium battery com­ operate in both the condensed and gas phases. In general, boron tends to
ponents, including electrodes, electrolytes, separators, additives, and promote char formation in the condensed phase, which helps inhibit
binders [160]. The structural uniqueness of boron compounds allows for dripping and acts as a barrier against heat and oxygen. In the gas phase,
enhanced lithium-ion transport, better thermal stability, and a more most inorganic boron compounds undergo decomposition and release
stable interface [161]. Boron atoms can be hybridized in two ways: sp3 water after absorbing heat, functioning as a heat sink and diluting the
and sp2 hybridization, forming an anionic tetracoordinate boron center fuel [163]. A previous work has proved that PEO-based electrolytes with
and a neutral tricoordinate boron center, respectively. The introduction 3 wt% hydrogenated borophene (HB) nanosheets (3 wt% HB-PEO)
of boron moieties is an effective strategy to improve LTN.

Fig. 13. (a) Structure of HB nanosheets. Copyright 2022, Elsevier. (b) TEM images of Mg2B2O5 nanowires. Copyright 2018, American Chemical Society. (c) Li+
migration in PEO-based SSEs with Mg2B2O5. Copyright 2018, American Chemical Society. (d) Rate performance of LFP/Li LIBs using SSEs with and without Mg2B2O5
at 50 ◦ C. Copyright 2018, American Chemical Society. (e) Cationic polymerization of DOL initiated by TB. Copyright 2021, The Royal Society of Chemistry. (f) Li-S
pouch batteries lighting LEDs after mechanical abuse. Copyright 2021, The Royal Society of Chemistry. (g) Schematic of a single-ion conducting borate network
polymer. Copyright 2020, Wiley-VCH (h) Structure of the anionic borate network polymer. Copyright 2020, Wiley-VCH.

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M. Wu et al. Energy Storage Materials 66 (2024) 103174

(Fig. 13a) exhibited superior thermal stability and significantly sup­ transport and increasing storage capacity at high temperature. In the
pressed the dripping during combustion [164]. Additionally, 3 wt% presence of the IL, Li+ transportation primarily occurred through a
HB-PEO also showed a higher IC of 3.1 mS⋅cm− 1 at 25 ◦ C, which is diffusion mechanism via the anion exchange of Li+ with cations. Thus,
attributed to the enhanced ion-pair dissociation in the solid-state this SPE showed an IC of 5.24 mS⋅cm− 1 at RT and was highly stabilized
electrolyte. at voltages up to 5 V.
Metal borates are a class of ceramic materials with excellent me­ Ionic liquids have emerged as promising options for enhancing the
chanical properties and chemical stability. Within this group, Mg2B2O5 self-healing characteristics of materials. Their abundance of anions and
nanowires (Fig. 13b) have garnered significant attention for their high cations offers a significant impetus for self-repair using electrostatic
toughness and wear resistance, cost-effective production, and effective interactions. Additionally, ILs exhibit remarkable stability over pro­
flame retardancy [165]. Tao and coworkers employed Mg2B2O5 nano­ longed periods compared to traditional liquid electrolytes, enabling the
wires as a multifunctional additive to PEO-based SPE, which improved sustained preservation of their functional properties. 1-ethyl-3-methyli­
the electrochemical performance with an IC of 0.37 mS⋅cm− 1 at 50 ◦ C midazolium bis(trifluoromethylsulfonyl)imide (EMI-TFSI), one of the
[166]. Besides reducing the polymer’s crystallinity, Mg2B2O5 also pro­ most widely studied ionic liquids, has been employed by Yang’s group
motes the dissociation of lithium salts. Additionally, Fig. 13c showed for flame retardant and self-healing polymer electrolytes (SHSPE) [174].
that Li+ can migrate in the two-phase interface between the electrolyte This SPE could tolerate high temperature at 200 ◦ C and exposure to
and Mg2B2O5 due to the presence of abundant Lewis acid sites. The flame for 10 s without morphological changes. The remarkable
assembled Li/SPE/LFP cells also provided enhanced rate performance self-healing capability (recovery time < 1 h, 25 ◦ C) of SHSPE was
and higher cyclic capacity (Fig. 13d). Mg2B2O5 also contributed to attributed to the unique interaction between EMI and fluorine atoms.
improved flame retardancy by facilitating the formation and stabiliza­ (Fig. 14a) SHSPE-based pouch batteries could be bent and folded,
tion of a char layer. proving its potential for application in flexible wearable electronic de­
Specific organic boron compounds can also serve as initiators for vices (Fig. 14b).
polymerization, facilitating the preparation of in-situ polymer electro­ While ILs offer versatility as additives to fire-safe polymer electro­
lytes with low interfacial resistance. Huang et al. prepared a flame lytes, their widespread adoption in large-scale applications is primarily
retardant electrolyte by in situ cationic polymerization of DOL initiated hindered by cost considerations. Nonetheless, it has been reported that a
by tris(pentafluorophenyl)borane (TB) (Fig. 13e) [167]. In addition to tenfold increase in production could lead to a significant price reduction
initiating the polymerization, TB also acted as an efficient flame retar­ of 50–70% [175]. Many high-performing ILs currently in use are fluo­
dant due to the combination of boron and fluorine, and also contributed rinated compounds. Efforts have been directed toward exploring ILs
to the formation of a highly stable LiF-rich SEI, thus suppressing Li with more cost-effective anions as potential substitutes for fluorinated
dendrites growth. LTN was significantly increased from 0.19 to 0.58 by ones. However, this investigation into fluorine-free ILs should be
the interaction between TB and TFSI− anion. Additionally, Li-S pouch coupled with a thorough assessment of their electrochemical stability, as
batteries with PDEs could light up LEDs under various mechanical fluorine has demonstrated its role in facilitating the formation of LiF SEIs
abuses (Fig. 13f). [176].
In contrast to the incorporation of SP2-hybridized boron as a filler in
polymer electrolytes, the utilization of SP3-hybridized boron has pri­ 4.8.2. Polymeric ionic liquids
marily revolved around developing ion-selective SPE. These materials High additions of ionic liquids in electrolytes can potentially
feature anionic groups anchored to the polymer backbone, allowing only compromise mechanical strength, a concern mitigated through the
Li+ cations to move freely through the substance, thus these single-ion oligomerization or polymerization of ionic liquids [177]. Hsu et al.
conductors can theoretically display LTN close to unity. (Fig. 13 g) synthesized an oligomeric ionic liquid (OIL, Fig. 14c) and blended it
Long and co-workers designed a fluorine-containing single-ion con­ with PVDF-HFP [178]. The resulting GPE was nonflammable (LOI = 29)
ducting borate network polymer (Fig. 13h), and employed it to create a and thermal stable. It also exhibited a high IC of 2.0 mS⋅cm− 1 at 30 ◦ C,
quasi-solid electrolyte with a high IC of 0.15 mS⋅cm− 1 and a LTN up to with low interfacial resistance and long-term durability.
0.95 at 26 ◦ C [168]. Owing to the fluorine substitution on the polymer Poly(ionic liquids) (PILs) not only inherit the distinctive attributes of ILs,
phenyl groups and the boron in the polymer structure, this electrolyte such as non-flammability and robust electrochemical stability but also
did not ignite in a flame. Another boron-based single lithium-ion con­ endow them with the mechanical flexibility and processability inherent to
ducting polymer electrolyte prepared by Cheng’s group also possessed polymers [179]. PILs have found extensive application in polymer elec­
excellent intrinsic nonflammability and a high LTN of 0.85 [169]. trolytes [180], unlike conventional PEO-based SPEs, the unique aspect of
PIL-based SPE lies in the fact that no supplementary salts are required in the
4.8. Ionic liquids and analogues SPE preparation since the pendant counter-ion is free to move and
responsible for the ionic conductivity [177]. Enhancements in conductivity
4.8.1. Ionic liquids are achievable by combining PIL with liquid components. Liu et al. reported
Ionic liquids (ILs) are salts composed of cations and anions and have a PIL (poly(1,2-diethoxyethylimidazolium) bis(trifluoromethanesulfonyl)
a unique set of properties such as low vapor pressure, non-flammability, imide (PDEIm)/PVDF-HFP composite film (Fig. 14e) with a high LE uptake
non-volatility, excellent electrochemical properties, and high thermal of 187.2%, resulting in a high IC of 1.78 mS⋅cm− 1 at 25 ◦ C (Fig. 14f) for the
stability [170,171]. Various ILs have been successfully introduced into resulting GPE [181]. The ionic dipole interactions between PIL and P
polymer matrix for flame retardant polymer electrolytes with better (VDF-HFP) endowed the PIL/P(VDF-HFP) composite film with signifi­
electrochemical properties [172], among which, quaternary cantly enhanced mechanical properties and thermal stability. Moreover,
nitrogen-based cation-derived ionic liquids are stable at the potential of this GPE exhibited rapid self-extinguishing (Fig. 14d), owing to the inherent
lithium metal, especially 1‑butyl‑1-methylpyrrolidinium bis(tri­ non-flammable characteristics of PIL and P(VDF-HFP).
fluoromethanesulfonyl)imide (PYR14TFSI) attracts widespread attention Preparing copolymers containing ionic liquids provides additional
for its wide ESW, high IC and low viscosity. PYR14TFSI was incorporated insights into the electrochemical properties and safety of polymer
into a cellulose triacetate (CTA)/PEGMA matrix to prepare a SPE with electrolytes. For instance, a self-healing SPE (PEO@BPIL, Fig. 14 g) was
improved flame retardancy and higher thermal stability [173]. Vertical prepared by yang research group via the integration of imidazole-based
flammability testing showed that the PCIL membrane was PIL@ PEGMA block co-polymer (BPIL) with PEO matrix [182]. The
self-extinguishing, indicating that the addition of IL improved the safety addition of PILs not only effectively reduced the crystallinity of PEO, but
of the polymer system. The synergistic effect of the polymer and ionic also induced an exceptional orderly and disordered microphase sepa­
liquid led to increased mobility of charge carriers, facilitating ion ration structure in PEO@BPIL, which facilitated Li+ transport. The IC

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M. Wu et al. Energy Storage Materials 66 (2024) 103174

Fig. 14. (a) SHSPE film that healed for 2 h before and after stretching. Copyright 2021, The Royal Society of Chemistry. (b) Photos of SHSPE-based pouch batteries
being folded and bent. Copyright 2021, The Royal Society of Chemistry. (c) Synthesis of OIL. Copyright 2016, Elsevier. (d) Ignition test of PDEIm-40%/PVDF-HFP
GPE. Copyright 2020, Elsevier. (e) Preparation of the porous PDEIm/PVDF-HFP composite membrane. Copyright 2020, Elsevier. (f) Ionic conductivities of the
Celgard 2325 separator with LE and the PDEIm-40%/P(VDF-HFP) GPE. Copyright 2020, Elsevier. (g) Synthesis procedure of BPIL. Copyright 2022, American
Chemical Society. (h) Open circuit voltage of laminated polymer cells at different bending angles. Copyright 2022, American Chemical Society.

and LTN of this SPE reached 0.22 mS⋅cm− 1 at 60 ◦ C and 0.63, respec­ 4.8.3. Ionic liquid analogues
tively, with an ESW of 5V. Notably, PEO@BPIL exhibited excellent Deep eutectic solvents (DESs) are eutectic mixtures consisting of
self-healing ability (recovery time <30 min at 60 ◦ C) and non-flamma­ hydrogen bond donors (HBD) and hydrogen bond acceptors (HBA), akin
bility after exposure to fire for 20 s. The laminate polymer cells assem­ to ILs in terms of low vapor pressure and non-flammability [184]. They
bled with PEO@BPIL could withstand multi-angle bending and maintain also show unique advantages such as synthetic simplicity and lower cost
a stable open-circuit voltage (Fig. 14h). compared to ILs. A polymer eutectogels (P-ETG) was prepared by
The development of crosslinked PIL networks serves a dual purpose encapsulating liquid DES electrolytes in a solid amide-based polymer
by enhancing the substrate’s strength and facilitating increased liquid backbone [185], yielding an IC of 0.76 mS⋅cm− 1 at 25 ◦ C with notable
component absorption, thereby achieving improvements in both me­ flame retardancy marked by a SET of 14 s⋅g− 1. Gerasopoulos et al.
chanical properties and ionic conductivity. Zhang et al. reported a developed an eutectic GPE (EGPE) by mixing acrylic copolymers with a
double-network-supported ionogel electrolyte (DN-Ionogel) consisting DES composed of LiTFSI and N-Methylacetamide (NMA) [186]. EGPE
of crosslinked PIL and PVDF-HFP that can capture 300 wt% EMIm-TFSI demonstrated a reduced SET compared to that of liquid DES and LE,
without loss of its mechanical properties, thus achieving a high IC of 1.8 showcasing the pivotal role of both the DES and polymer in suppressing
mS⋅cm− 1 at RT [183]. This DN-Ionogel exhibited low interfacial resis­ the flame.
tance with the electrode and effectively suppressed the growth of Organic plastic salts (OPSs) are solid counterparts to ionic liquids
lithium dendrites. Its double crosslinked network structure ensured (ILs) and offer impressive attributes such as exceptional thermal prop­
minimal alteration in morphology and dimensions during heat treat­ erties, nonflammability, electrochemical stability, and shape variability
ment. Benefiting from non-flammable EMIm-TFSI and PIL components, [187]. They embody an ordered conductive crystalline phase that allows
the DN-Ionogel also showed high flame retardancy. Moreover, for the rapid movement of appropriate ions even in the solid state.
DN-Ionogel-based pouch batteries demonstrated a high capacity and Hirano and co-workers prepared “polymer-in-plastic salts” electrolytes
long service life, remaining operational even under bending and cutting (PIPSEs) using a synthetic OPS N-ethyl-N-methylpiperidine bis(fuor­
abuse conditions. osulfonyl)imide (PP12FSI), combined with PVDF-HFP and LiFSI [188].
The intrinsic nonflammability of PP12FSI endowed PIPSEs to exhibit

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M. Wu et al. Energy Storage Materials 66 (2024) 103174

enhanced thermal resistance and mechanical strength, with flame the polymer, which in turn increases the IC. Wang et al. introduced
retardancy even after 10 s exposure to flame. PP12FSI also promoted an amide side groups into a PEG-based polyester by Passerini three-
ion-conducting SEI layer composed of Li3N and LiF, which prevented component polymerization [189], a large number of amide side
electrolyte depletion and effectively inhibited lithium dendrites. The groups not only improved the IC to 0.06 mS⋅cm− 1 (25 ◦ C), but also
dendrite-free symmetric Li battery utilizing PIPSE exhibited an endowed self-extinguishing capability to the polymer electrolyte and
ultra-long cycle life of more than 1000 h at 2.0 mA⋅cm− 2. increased the LOI from 21% to 25%.
Apart from constructing flame-retardant side groups, another
method involves introducing flame-retardant molecules into the poly­
4.9. Intrinsic flame-retarded polymer hosts
mer via cross-linking reactions. Wei et al. constructed a polyamide-
based quasi-solid electrolyte (PAM-QSE) by in situ gelation using N,
4.9.1. Polyamide
N’-methylenebisacrylamide (MBA) as a cross-linking agent [190].
The application of intrinsically flame-retardant or nonflammable
PAM-QSE effectively reduced burn time and inhibits flame spread, ul­
polymers as a host for polymer electrolytes can fundamentally solve the
timately achieving self-extinguishing after ignition. The mechanism is
problem of flammability. A current strategy involves the incorporation
that the amide polymer network generates N-containing free radicals
of flame-retardant side groups into polymers, which not only lowers the
and non-flammable ammonia/water gas. PAM-QSE exhibited a high IC
flammability of the polymer, but also reduces the crystallinity and Tg of

Fig. 15. (a) Li+ pathways in the PA/PEO/LiTFSI electrolyte. Copyright 2021, American Chemical Society. (b) Schematic demonstration of the roll-to-roll fabrication
process with the PA/PEO/LiTFSI electrolyte. Copyright 2021, American Chemical Society. (c) Chemical structures of OPTTA and BEPA. Copyright 2021, Elsevier. (d)
IFR-SPE ignition test. Copyright 2021, Elsevier. (e) Schematic diagram of PI film with vertical nanochannels. Copyright 2019, Springer Nature. (f) Folding tests of the
Li/PI/PEO/LiTFSI/LFP pouch battery. Copyright 2019, Springer Nature. (g) The SEM image of the LiTFSI/PEI/PVP/PVDF film. Copyright 2021, American Chemical
Society. (h) Interactions between PBI, PEO and LiTFSI. Copyright 2020, Wiley-VCH.

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M. Wu et al. Energy Storage Materials 66 (2024) 103174

of 1.39 mS⋅cm− 1 at 25 ◦ C due to the high electrolyte uptake (97 wt%) of PEO can inhibit the crystallization of PEO by forming hydrogen bonds
the crosslinked network. Other electrochemical properties such as LTN and the N atoms may promote the Li salts dissociation (Fig. 15h),
(0.63) and ESW (5.64 V) were also excellent. This GPE spontaneously resulting in improved electrochemical properties and flame retardancy
built composite SEI structures (N–(C)3 and Li3N) on the lithium metal [199]. He and co-workers developed a flame-retardant polymer elec­
surface to guide the homogeneous Li+ distribution and inhibit lithium trolyte (PBI/PVDF/LiTFSI SPE) by modifying PVDF with nonflammable
dendrites growth, along with a robust CEI to isolate cathode and elec­ polybenzimidazole (PBI) [200]. The PBI/PVDF-based SPE possessed
trolyte, enabling the NCM//Li battery to achieve 80% capacity retention excellent self-extinguishing properties through the PBI-catalyzed dehy­
after 700 cycles. drogenation and fluorination, which converted part of PVDF into a
The above approaches have focused on the preparation of flame- fire-resistant PTFE segment. PBI owned a large adsorption energy with
retardant polymer electrolyte hosts by chemical synthesis and poly­ LiTFSI and shared an overlapping electron density with lithium anodes,
merization, but the incorporation of flame-retardant components into which accelerates Li+ conduction at RT and homogenizes the interfacial
the polymer chains often involves additional steps in the synthesis electric field.
process, which may increase the complexity of manufacturing and
potentially add to the cost of production. Utilizing porous polymer films 5. Summary and outlook
as hosts for traditional polymer electrolytes is an effective approach to
enhance the multiple properties of PEs, given their inherent high The search for flame-retardant polymer electrolytes represents a
porosity and flexibility. Porous polyamide (PA) films were infiltrated crucial area in the evolution of battery safety. The urgency of this work
with PEO/LiTFSI to prepare SPEs with sufficient toughness and me­ has been underscored by global concerns regarding the safety of lithium-
chanical strength, effectively mitigating the growth of lithium dendrites ion batteries, given the frequent occurrences of fires and explosions. The
[191]. The crystallinity of PEO was effectively reduced due to the mi­ widespread use of traditional organic liquid electrolytes, while efficient
cropores in PA, leading to an IC of 0.21 mS⋅cm− 1 at 30 ◦ C. (Fig. 15a) in energy transfer, has been a persistent challenge to battery safety due
PA/PEO/LiTFSI only shrank without combustion when contacted with to their sensitivity to thermal runaway. Simultaneously, the potential of
fire, and pouch batteries also showed high safety during the mechanical polymer electrolytes, with their inherent flexibility and lower flamma­
abuse test. Furthermore, batteries assembled with PA/PEO/LiTFSI bility, is highly desirable, although largely confined to laboratory-scale
solid-state electrolytes exhibit easy scalability to be fabricated by a manufacturing. This dilemma highlights the pressing need to develop
roll-to-roll process. (Fig. 15b) more effective and economically viable fire-safe strategies that can drive
the industrialization of fire-resistant polymer electrolytes, thereby
4.9.2. Polyimide mitigating risks associated with lithium battery technology.
In comparison to PA, polyimides (PI) generally offer better thermal
stability and mechanical properties [192], PI is known for its inherent
non-flammability and the ability to form a substantial residual char 5.1. Challenges in fire-safe polymer electrolytes
when exposed to high temperature, making porous PI films an attractive
choice for serving as host materials in polymer electrolytes [193]. Liang As researchers explore various strategies to enhance the fire resis­
et al. prepared an inherently flame-retardant SPE (IFR-SPE) by one-step tance of battery components, striking a balance between effectiveness
in situ cross-linking of two novel synthetic P-containing monomers and practicality becomes crucial. Some additives, such as inorganic
(OPTTA and BEPA, Fig. 15c) using porous PI films as support carriers fillers, hold the potential for enhancing fire resistance but always require
[194]. This SPE was nonflammable due to the synergistic effect of large additions. Additionally, materials like metal-organic frameworks
phosphorus and PI (Fig. 15d). IFR-SPE could form a LiF/Li3PO4-rich SEI (MOFs) and ionic liquids (IL) may be expensive and unsuitable for large-
layer to effectively suppress lithium dendrites, improving the cycling scale production. Moreover, complex structural designs may pose chal­
stability of the LFP//Li cell. lenges in terms of synthesis and scalability. A practical approach in­
In contrast to the aforementioned porous films, the polyimide (PI) volves integrating diverse fire-resistant materials or methodologies
film designed by Cui’s research team, using a track etching technique, within polymer electrolytes. An example lies in the synergistic effects of
featured vertically aligned channels (Fig. 15e), resulting in an IC of 0.23 phosphorus-nitrogen compounds, resulting in a comprehensive defense
mS⋅cm− 1 at 30 ◦ C after permeation with PEO/LiSFI [195]. The mechanism.
non-flammability and high mechanical strength of this PI film improved The electrochemical performance of most polymer electrolytes still
the flame retardancy and dendrites inhibition. Thus, the LFP/SPE/Li cell falls short of the stringent standards required for practical deployment.
showed good rate performance and cycling stability and the pouch Unfortunately, the pursuit of enhanced fire resistance through the
battery also passed the abuse test (nail penetration, cutting and folding, introduction of flame retardants often negatively impacts the electro­
Fig. 15f). Combination of PI film with flame retardant solvents or plas­ chemical performance of these electrolytes. A novel exploration for this
ticizers further improved flame retardancy. For example, PI and TMP trade-off involves the development of multifunctional additives that go
were introduced into PVDF to fabricate non-flammable, robust and beyond the singular goal of flame retardancy. These multifaceted ad­
flexible composite PI-reinforced PVDF-based polymer-polymer electro­ ditives such as ILs have the potential to provide a range of benefits,
lytes (PPEs) [196]. including enhanced electrochemical performance and improved thermal
Blending with flame retardant polymers is another straightforward stability.
strategy to improve the flame retardancy of conventional polymer The prevailing focus on flame retardant testing for polymer elec­
electrolytes. Cui et al. incorporated poly (vinylpyrrolidone) (PVP) and trolytes, divorced from their integration into assembled batteries,
PEI into PVDF and took advantage of the difference in interfacial ten­ cannot directly reflect the real performance of battery safety. Current
sion, the bottom layer wrinkled during solidification when the temper­ flame-retardant tests, typically involving direct ignition, are essential
ature increased, creating micropores to form Li+ channels (Fig. 15 g), but may not capture the full spectrum of potential safety concerns.
resulting in an IC of 0.51 mS⋅cm− 1 at RT and a LTN of 0.51 [197]. This Battery safety concerns often stem from abuse conditions, such as
SPE also showed self-extinguishing ability with high thermal stability extreme mechanical stress, thermal conditions, or electrical anomalies -
and tensile strength. situations where flame-retardant polymer electrolytes are truly put to
the test. By focusing on the evaluation of assembled pouch batteries
4.9.3. Polybenzimidazole under these abuse conditions, researchers can simulate more accurately
Polybenzimidazole (PBI), is another flame-retardant and highly heat- the complex challenges that batteries may encounter during their
resistant aromatic polymer [198]. The introduction of aromatic PBI into operational lifespan.

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M. Wu et al. Energy Storage Materials 66 (2024) 103174

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