J - Energy Storage 2023 v73 108873

Journal of Energy Storage 73 (2023) 108873
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Journal of Energy Storage

journal homepage: www.elsevier.com/locate/est
Review article
Composite separators for internal thermal management in rechargeable

lithium batteries: A review
Amrit Kumar Thakur a, i, *, Anuj Kumar b, Hyeona Park c, Hyerim Kim c,
Mohammad Shamsuddin Ahmed d, Ahmed Mortuza Saleque e, Muthuraman Ponrajan Vikram f,
R. Saidur g, Yanbao Ma a, Jang-Yeon Hwang c, h, **
a
Department of Mechanical Engineering, University of California, CA 95343, Merced, USA
b
Department of Mechanical Engineering, Indian Institute of Technology Bombay, Maharashtra 40076, Powai, India
c
Department of Energy Engineering, Hanyang University, 04763 Seoul, Republic of Korea
d
Institute for Energy Studies, University of North Dakota, ND 58202, Grand Forks, USA
e
Department of Electrical and Computer Engineering, University of California, CA 95616, Davis, USA
f
Department of Mechanical Engineering, Saveetha School of Engineering, SIMATS, Chennai 602105, Tamil Nadu, India
g
Research Centre for Nanomaterials and Energy Technology (RCNMET), School of Engineering and Technology, Sunway University, Jalan University, 47500 Bandar
Sunway, Selangor, Malaysia
h
Department of Battery Engineering, Hanyang University, 04763 Seoul, Republic of Korea
i
Department of Mechanical Engineering, KPR Institute of Engineering and Technology, Arasur, Coimbatore, Tamil Nadu 641407, India
A R T I C L E I N F O A B S T R A C T
Keywords: Separators are thin microporous membranes that allow lithium-ion (Li+) transport across interfaces and through
Lithium ion batteries electrolyte, have a vital role in maintaining stable performance and safety of lithium batteries. However, con
Separator ventional separators for rechargeable lithium batteries suffer from temperature-induced shrinkage, poor
Safety
wettability, and low tensile stability, resulting in poor battery performance, short battery life, and safety hazards.
Thermal management
To address these issues, it is crucial to address these challenges in engineering separators to meet the re
Coating
quirements of next-generation energy storage systems. Herein, we first discuss fundamental properties and re
quirements of separators for rechargeable lithium batteries. From the scientific societies, therefore, various
physical and chemical modifications have been made to conventional separators, resulting in functional com
posite separators. This review summarizes and discusses how composite separators manage internal thermal
safety in rechargeable lithium batteries, along with other benefits, including Li+ conductivity, structural integ
rity, wettability, better rate capability, and suppression of crossover.
1. Introduction Computers, mobile, e-packaging, disposable medical testers [4,5],

and electric vehicles (EVs) and hybrid EVs (HEVs), rely heavily on the
The constant advancement of science and technology, as well as the performance and development of energy storage devices, particularly
constant rise in living standards in modern society, have fueled an ever- batteries with specific performance profiles [6]. Among different energy
increasing demand for energy. Because oil, coal, and other conventional storage devices, lithium-based batteries are preferred because of their
fossil fuels are nonrenewable, the advancement and spread of wind combined advantages of long service life, light weight, low memory
energy, hydrogen energy, and other clean energy resources are critical effect, low self-discharge, low pollution, high energy density, and large
as they aid in the revolution of innovative storage devices [1–3]. Energy numbers of charging/discharging cycles compared to nickel metal hy
storage devices are becoming increasingly important in highly mobile dride and lead acid batteries [7–9]. It is noteworthy that among different
and interconnected societies, and novel methods for addressing major batteries, lithium-ion batteries (LIBs) account for 75 % of the global
energy concerns are required to attain a more sustainable world. market [10]. LIBs have made noteworthy strides in electronic devices
* Correspondence to: A.K. Thakur, Department of Mechanical Engineering, University of California, CA 95343, Merced, USA.
** Correspondence to: J.-Y. Hwang, Department of Energy Engineering, Hanyang University, 04763 Seoul, Republic of Korea.
E-mail addresses: [email protected] (A.K. Thakur), [email protected] (J.-Y. Hwang).
https://doi.org/10.1016/j.est.2023.108873
Received 5 July 2023; Received in revised form 24 August 2023; Accepted 29 August 2023
Available online 8 September 2023
2352-152X/© 2023 Elsevier Ltd. All rights reserved.
A.K. Thakur et al. Journal of Energy Storage 73 (2023) 108873
Fig. 1. Schematic of commercial LIBs comprising of graphite anode and LiCoO2 cathode along with charging/discharging modes.
and alternative-energy vehicles in recent years; however, a few chal electrolytes. There is a concerted effort to substitute these separators
lenges remain. For the next generation of LIBs, safety and high energy with solid electrolytes, which currently have significant drawbacks,
density are the most important considerations. The main components of including low ionic conductivity and electrode interfaces, which are the
LIBs are the anode, cathode, and separator, as shown in Fig. 1 [11]. primary barriers to obtaining solid-state batteries with excellent cycling
Separators are indispensable components of LIBs, although they are not performance at room temperature [22]. Solid-state Li batteries are ex
directly involved in electrochemical reactions. The anode and cathode pected to become viable in the next few years owing to the latest de
are physically separated, and a medium function is achieved that favors velopments in liquid electrolytes and separator membranes in terms of
Li-ion (Li+) transport [12–14]. The microstructural properties of the safety, ionic conductivity, shelf life, mechanical stability, and energy
separator and its chemical composition significantly influence the density, along with an enriched understanding of the electrochemical
safety, capacity, internal resistance, and long-term cycling performance interfaces between electrodes and solid electrolytes [23–25].
of batteries. High ionic conductivity, low internal resistance, high With a major focus on separators, this state-of-the-art critical review
porosity, superior mechanical strength, and satisfactory thermal stabil summarizes the latest advancements in various separator types for LIBs,
ity are desirable characteristics of battery separators. [15–20]. In terms with a measurable study with respect to ionic conductivity and capacity,
of safety and electrochemical performance, separator thickness is an among other significant features. The detailed requirements of the
important factor for Li-based batteries [21]. Separator thickness in ac separators, along with the role of separator thickness on battery energy
ademic research is presently limited to 20–25 μm to match the thickness density, are presented. Finally, the chief development methods and
of traditional polyolefin separators such as polyethylene (PE) and prospective trends in Li batteries are discussed.
polypropylene (PP). However, as the demand for Li-based high-energy-
density batteries has increased, a growing number of coated membranes 2. Effect of separators on energy density
have been developed, and the trend toward thinner and lighter sepa
rators has become evident. With the rapid expansion of electronic equipment, power tools, and
With recent developments in materials engineering, thin separators intelligent manufacturing, energy storage devices with high energy
have gained significant attention in research and industry for improving densities are in high demand. Over the years, procedures have been
battery performance. Thin separators decrease internal resistance and utilized to achieve long-term strategic goals of 300Wh kg− 1 and 700 Wh
increase ion conductivity, leading to superior battery performance. L− 1 [26]. Generally, the active material systems of the anode and
However, a smaller thickness reduces both the puncture and mechanical cathode determine the energy density of Li-based batteries. Neverthe
strength, which causes higher risk of battery short circuiting. The less, optimizing the inactive materials is critical for achieving high en
separator should have the least thickness to ensure satisfactory me ergy density, leading to a larger theoretical and actual energy density
chanical strength for effective resistance to dendrite growth pressure, gap in real-time applications. Reducing separator thickness reduces the
while also providing excellent electrochemical performance, with high proportion of inactive materials in the batteries and improves the per
ionic conductivity. In general, battery separators are composed of formance of the battery to some extent. Volumetric and gravimetric
porous membranes with several polymer matrices soaked in different energy densities are two types of energy density. Because the separator
electrolytic solutions (Li-salts mixed in organic solvents). Safety, short is only 1 % of the mass of a typical pouch cell, separator thickness has a
circuits, and flammability are only a few dangers posed by these liquid minor influence on gravimetric energy density. In contrast, the effect of
2
Table 1 performance and reliability of Li-based batteries. Various testing ap

Required separator thickness for various battery systems for attaining energy proaches, including thermal stability, wettability, mechanical proper
densities. ties, and porosity, have been extensively used to comprehensively
Volumetric energy density (Wh Type of battery Thickness of separator measure and assess the properties of separators. These features are
L− 1) (μm) critical to ensure the safety and consistency of Li-based batteries. Table 2
500 LiNi0.6Co0.2 Mn0.2O2 ≤57.7 lists the specifications of the ideal separators used in Li batteries, which
LiNi0.8Co0.1Mn0.1O2 ≤88.7 are discussed in detail in this section.
LiMn2O4 ≤6.2
LiNixCoyAlzO2
3.1. Ionic conductivity
≤86.4
LiCoO2 ≤125.1
LiNi0.5M1.5O4 ≤58.6
Li-rich materials ≤120.9 The ion transport in faster mode inside Li-based batteries is prom
700 LiNi0.6Co0.2Mn0.2O2 ≤10 ising because of their high ionic conductivities. Generally, the high ionic
LiNi0.8Co0.1Mn0.1O2 ≤30.5
conductivity of separators is mainly dependent on the presence of pores
LiCoO2 ≤55
LiNi0.5M1.5O4 ≤12.5 with proper pore sizes. A liquid electrolyte with good wettability is
LiNixCoyAlzO2 ≤28.7 critical for the ionic conductivity of the separator. It is also important to
Li-rich materials ≤52.4 note that the ionic conductivity of a separator filled with an electrolyte
900 LiCoO2 ≤16.0 must be higher than the standard of 10− 3 S/cm for most applications
LiCoO2
[12]. The ionic conductivities of the separators are calculated using the
≤14.3
following equation:
Table 2 D
λ= (1)
General requirement of LIB separators and their relevance [29–31]. A.Rb
Parameters Requirements Relevance
where, λ is the ionic conductivity; A and D are the separator area and
Ionic conductivity 10− 3
S/cm Effects energy and power of thickness, Rb is the bulk resistance.
battery
Wettability High enough, so that it can It mainly regulates the
absorb the liquid electrolyte quantity reserved in 3.2. Wettability
electrolyte separator
Porosity Should be >40 % Affects the separator’s swelling Separator wettability is a crucial property that regulates ion trans
Pore size Should be >1 μm process port in Li-based batteries. With good wettability, a sufficient volume of
Thickness Should be >25 μm Determines the separators
mechanical strength, prevents
liquid electrolyte can be absorbed by separators, and it can be retained
short-circuit of battery, and throughout the entire charge/discharge cycle, which leads to a lower
influences rate capability. internal resistance for separators and batteries, thus contributing to
Mechanical Offset at 1000 psi < 2 % Provide robust and long-lasting long-term electrochemical performance. Furthermore, the speed at
strength [14] operation
which the separators are wetted should be high to expedite liquid
Permeability MacMullin number should Lower permeability illustrates
be >11 [29] better performance and electrolyte filling and cell assembly. The porosity, pore size, tortuosity,
reliability of cell and membrane properties determine the wettability of the separators.
Thermal stability Should be >5 % after heat Provides long term thermal Eqs. (2) and (3) are generally used to analyze the uptake and retention of
treatment at 90 ◦ C for an shrinkage analyses and give electrolytes:
hour [31,32] information regarding high
temperature stability Wwet − Wdry
Chemical and Stable for a long time, 0–5 Stability of separators in Uptake (%) of Electrolyte = × 100 (2)
Wdry
electro-chemical V oxidative and reducing
stability atmosphere
Wwet − Wdry
Retention (%) of Electrolyte = × 100 (3)
Wwet
separator thickness on volumetric energy density is more critical. The
required separator thickness for various systems to attain the target where, Wdry and Wwet represent the weight of dry and wet membrane,
volumetric energy densities of 500, 700 and 900 Wh L− 1 is presented in respectively.
Table 1 [27].
Generally, for all battery cell systems, the volumetric energy density 3.3. Porosity
increases significantly as the separator thickness decreases [28].
Decreasing the separator thickness can result in a noteworthy rise in Porosity is the most basic requirement for Li-based battery separators
volumetric energy density; however, it can also pose security risks. for transporting Li ions. To maintain high ionic conductivity, an
Currently, the thinnest commercially available separator is 5 μm thick. adequate volume of liquid electrolyte must be trapped within the
However, the improvement in novel polymers (which exhibit superior interconnected channels and micropores in the separator. Separators
mechanical strength) and the development of thin-functional coatings must have a porosity exceeding 40 % generally. High porosity leads to
under 1 μm imply that 5 μm is not the thickness limit of the separator. high electrolyte uptake and low internal resistance; both are advanta
geous for battery performance. However, they also lead to poor me
3. Requirements for separators chanical strength, which may decrease battery safety. In contrast,
separators with low porosity are more likely to shut down in extreme
In general, any Li-based battery has three major components: anode, conditions, but they are deleterious to electrolyte retention. The weight
cathode, and separator. Separators are crucial components of batteries, before and after absolute electrolyte absorption is the most commonly
although they are not directly involved in electrochemical reactions. used parameter for calculating porosity:
The morphology, composition, structure, and physical and chemical W − W0
Porosity (%) = (4)
properties of separators are factors in guaranteeing outstanding elec ρL .V0
trochemical performance and long-term viability of batteries. Different
parameters, which are closely interconnected, are used to determine the where W and W0 are the separators weight before and after being
3
immersed in electrolyte, respectively, ρL is electrolyte density and V0 explosion. Normally, thermal shrinkage must be <5 % after heat treat
denotes membrane initial volume. ment for 1 h at 90 ◦ C. To determine the thermal stability of separators,
the thermal breakdown temperature, that is, the temperature at which
3.4. Pore-size the separator begins to rupture during heating, has also been used.
Separators must have pore diameters smaller than 1 μm and a 3.10. Chemical and electro-chemical stability
comparatively even pore-size distribution so that the current distribu
tion inside Li-based batteries is uniform. A sub-micrometer pore size The separator is assumed to be inactive inside the battery cell. The
reduces the battery short-circuit risk by preventing dendrite growth and ability of a separator to withstand dissolution or degradation in an
electrode material penetration. However, the pore size should be suffi oxidizing or reducing atmosphere during the charging and discharging
ciently large to permit fast transportation of Li+ by the separator with cycles mainly relies on its electrochemical stability. In addition, the
the help of a liquid electrolyte. Generally, scanning electron microscopy electrochemical and chemical stabilities of the separators safeguard cell
is used to characterize pore size and distribution of pore-size. stability along with smooth operation without producing impurities,
which can have negative effects.
3.5. Thickness
3.11. Dimensional stability
The separator thickness of Li-based batteries is a significant factor
that influences safety and electrochemical performance. For practical Uneven/nonuniform separators are normally observed in practical
application, ideal separators must have a thickness <25 μm. A applications, and the disordered/misalignment between separators and
comparatively uniform thickness also aids in the mild distribution of the electrodes can endanger the safety of the cell and its application.
current that occurs during battery operation. Reducing the thickness Shrinking or crisping of the separators should not occur so that the
lowers the volume occupied by the separator, which leads to a signifi electrodes can fit perfectly, which is essential for the stability of the cell.
cant increase in the energy density of batteries [28]. Meanwhile, the
internal resistance reduction in batteries with thin separators results in 3.12. Other critical requirements
higher ionic conductivity. However, reducing the thickness degrades the
mechanical properties, possibly posing a safety risk during assembly and Besides basic requirements, the battery separator must be able to cut-
operation. off the current loop before it exceeds the thermal runaway temperature
under abnormal operating conditions. In addition, the separator should
3.6. Mechanical strength have the ability to extinguish fire during thermal runaway conditions.
These separators should have flame-retardant properties to improve
During assembly and operation of the battery, physical pressure battery safety [23–25]. Furthermore, the separator must have high self-
exists, and if the mechanical strength is insufficient, it can lead to a high healing properties such that any crack or damage to the separator during
risk of short-circuiting [29]. The tensile strength in the transverse and operation can be repaired by itself, which can significantly improve
longitudinal directions is widely used to evaluate the strength of sepa battery safety [26,27]. Unfortunately, to-date, a single separator does
rators. For long-lasting cyclic stability, the mechanical strength of the not exhibit any of these properties. Table 2 summarizes the general re
separator is inversely correlated with its ionic conductivity; thus, a quirements of separators for effective battery construction [29–31].
suitable balance must be achieved. The mechanical strength of a sepa The fundamental threat to battery safety is internal heat generation
rator varies significantly when wetted by a liquid electrolyte [12]. Me owing to electrochemical reactions and ohmic internal resistance. This
chanical strength differs based on the materials and processes involved heat generation increases the operating temperature of the cells. To
during manufacturing. Generally, separators can tolerate higher pres maximize the efficiency of batteries their operating temperature should
sures during assembly if the offset (at 1000 psi) is <2 % [14]. be maintained in the range of 15–40 ◦ C, with a minimum temperature
gradient (<5 ◦ C) inside the battery pack [32]. Overheating the battery
3.7. Permeability also has a detrimental effect on its electrochemistry, which may result in
an extra exothermic reaction and a rapid temperature rise. This rapid
The MacMullin number is frequently used to characterize separator temperature rise causes thermal runaway in the battery, increasing the
permeability. This is defined as the ratio of the separator resistance filled risk of battery expansion or explosion. In addition, the capacity of the
with liquid electrolyte to resistance of liquid electrolyte alone. A high battery is decreased when exposed to high temperatures. Amin et al.
porosity of the separators can be obtained at a lower MacMullin number, [33] reported that the capacity of a battery was reduced by 70 % at 55 ◦ C
which demonstrates better cell reliability and performance [14]. The compared to 40 % at 37 ◦ C after 100 cycles. Similarly, Shim et al. [34]
ideal MacMullin number is approximately one [29], whereas in practical found that the capacity of a battery fades by 65 % when it is exposed to
applications, a value <8, is acceptable for Li battery separators [12]. 60 ◦ C compared to 4 % at 25 ◦ C. In addition to high thermal stability, a
robust mechanical strength is required for the separator to bolster stress
3.8. Puncture strength and sustain the penetration of active material particles and dendrites
during operation. Furthermore, separators should be designed with
To avoid short circuits throughout assembly and operation, the reversible or irreversible thermal shutdown capabilities under over
puncture strengths of separators is examined. Generally, separators with heating or short-circuit conditions. To date, no separator meets all these
greater thicknesses are more resilient to puncture [30]. Li-based batte requirements. Therefore, it is critical to strike a balance between sepa
ries are more protected and dependable when they have high puncture rator safety, dependability, and performance.
resistance [13].
4. Internal battery thermal management via separator
3.9. Thermal stability modification
Thermal stability is a very important factor in terms of the safety and Among the entire components, the separator is a major limiting
dependability of Li-based batteries, and both academia and industry factor for heat transfer in batteries. Despite the several advantages of
have paid considerable attention to maximizing it [31,32]. Under high- LIBs over conventional commercial batteries, electrochemical reactions
temperature operation, the separator may shrink, leading to an during charge and discharge lead to high heat generation. High
4
Fig. 2. Schematic diagram of typical thermal runaway process.
temperatures reduce the cycle life and are a common cause of thermal surfaces with ceramic nanoparticles (NPs) [34], thermally stable poly
runaway, especially in high-energy and high-power-density batteries mers [39], polymer blends [40], and copolymers [41] improves the
[35]. Common causes of thermal runaway in batteries are overcharging, electrochemical reaction rate and thermal conductivity. Other methods,
overheating, and internal short circuits. All these factors lead to smoke, including employing carbon, oxide, or graphene particles [42–44], as
fire, gas emissions, and decomposition of the electrolyte, separator, and flame retardants for fabricating laminated separators [45], can also
electrode material. The step-by-step process involved in a thermal satisfy the demand for separator stability.
runaway is illustrated in Fig. 2. In recent years, advanced internal battery thermal management
To ensure thermal stability of the battery, an efficient battery ther using separator coatings has gained popularity. Laminating or coating
mal management solution (BTMS) is required to decrease temperature the separator with functional material is a most effective way to improve
inhomogeneity and heat released by the LIB cells. The BTMS are broadly thermal stability, along with wettability and other physical properties
classified into internal and external types. In an internal BTMS, internal [16,46]. In the present study, based on the composition of the coating on
modification of the cell components (anode, cathode, electrolyte, and/or the separator surface, internal BTMS is classified into three types: (i)
separator) is performed to reduce the internal thermal resistance, BTMS via inorganic coating material or laminating the separator with
thereby improving thermal performance. An external BTMS uses a different inorganic materials, including ceramic, polymers, and co
different fluid medium, including air or liquid, and a phase-change polymers; and (ii) BTMS via organic coating material carbon, graphene;
material externally, without changing the battery components, to in and (iii) BTMS via inorganic/organic hybrid coating.
crease heat transfer. The main disadvantages of this system are its
installation complexity, high cost, poor dependability, and high energy 4.1. BTMS via inorganic/organic coating
consumption. The very low thermal conductivity of Li+ cell separators
(~0.2 W/mK) is one of the major barriers to heat transfer; thus, To increase the thermal stability and rate of electrochemical reac
improving the thermal conductivity of the separator by coating it with a tion, researchers have prepared composites by mixing inorganic parti
highly thermal conductive material could avoid thermal-related failure cles with an organic polymer and then coating them on a separator.
of the battery [36]. Inorganic coating modification of the separator is also known as ceramic
In addition to developing an external BTMS, it is important to un coating modification. Commonly used inorganic materials to improve
derstand and manage the heat transfer inside the cells. The separators the performance of battery separators include SiO2, TiO2, ZrO2, Al2O3,
used in commercial LIBs are mostly microporous polyolefin membranes NaY and zeolite [47–51]. These particles can improve mechanical,
made of PE and PP because of their low cost, excellent mechanical electrical, and thermal properties by reducing the crystallinity of the
strength, and acceptable electrochemical performance [37]. However, polymer and enhancing the transportation of Li+. The main advantages
the main drawback of these separators is their low thermal conductivity, of these NPs are their enhanced wettability [52–54], good flame-
which may cause safety issues at elevated temperatures. In addition, the retardant properties, and excellent thermal stability. Furthermore, the
low melting temperature of PE materials is in the range 135–165 ◦ C inorganic coating can prevent oxidation of the polymer matrix [55].
[38]. The breaking or decomposition of separators at elevated temper However, the major concern with inorganic coatings on battery sepa
atures leads to major safety issues, including short circuits, thermal rators is the reduction in ion conductivity and poor charge–discharge
runaway, and even explosions. Furthermore, low porosity, low con capacity [36]. Dispersion, mixing, coating, and in situ procedures are
ductivity, and poor wetting characteristics of these separators limit their used to manufacture inorganic composites [56]. The coating process
application for high-performance LIBs. Therefore, it is crucial to develop comprises dip coating, chemical vapor deposition, and roll-to-roll (R2R)
advanced separators with high thermal stability, conductivity, and coating [31].
electrolyte wettability to improve the safety and performance of LIBs. Shi et al. [38] experimentally investigated an inorganic-organic
Thus, in addition to the thermal stability of the electrolyte and electrode, based composite separator to enhance the thermal stability and elec
the safety issues of the separators are directly related to the safety of trochemical performance of 5 V LIBs. The authors coated inorganic
LIBs. The present study focuses on improving the internal battery ther particles of the lithium ionic conducting glass ceramic Li1.5Al0.5
mal management through an advanced composite separator. In recent Ge1.5(PO4)3 (LAGP) onto an organic PP separator. A conventional
years, many researchers have demonstrated that coating separator melting-quenching method was employed to obtain the LAGP particles.
5

Fig. 3. (a) The thermal shrinkage after being treated at different temperatures for 1 h. (i) the water contact angles; (ii) a photograph of the wetting behavior with
liquid electrolyte of the LAGP-PP and PP separators; (iii) (b) schematic of lithium ionic transport in the coating layer of LAGP-PP and AL-PP separators. (Reproduced
with permission from Ref. [38], © Elsevier B.V., 2014) (c) Steps for coating ceramic slurry on a separator membrane. (i) ceramic slurry preparation; and (ii) roll-to-
roll compatible coating with a scale bar of 12 μm; (d) the thermal conductivity and thermal shrinkage of the separators with different coatings after a heat treatment
of 130◦ C in vacuum for 30 min. (Reproduced with permission from Ref. [36], © Elsevier B.V., 2021).
The performance of the LAGP-PP separator was compared to the tradi separator exhibited only 0.6 % shrinkage while the uncoated separator
tional Al2O3 coated PP separator. The thermal stability of the separator exhibited 6 % shrinkage under the same conditions (Fig. 5). Further,
was determined by observing the thermal shrinkage, and it was found they observed that for all coated separators, thermal conductivity was
that the LAGP-coated PP separator exhibited better thermal stability increased by a factor of 3.2 times for 100 % Al2O3 coated separator
than the PP separator (Fig. 3a) [38]. The wettability of the separator was (Fig. 3d). In addition, the electrolyte wettability, electrochemical
evaluated by measuring the water contact angle and placing a drop of impedance, and self-discharge rate of the coated separator were better
liquid electrolyte on the surface of the separator. The introduction of the than those of the uncoated separator.
LAGP-PP separator improved wettability, ion conductivity, and inter Enhancing the thermal conductivity of the separator leads to higher
facial stability, which led to an enhanced C-rate and LIBs capability. In heat dissipation, increased temperature homogeneity, and reduced
addition, the LAGP-PP separator exhibited higher ion conductivity than thermal stress. Yang et al. [57] performed numerical simulations using
the traditional Al2O3-PP separator (Fig. 3b). Polymer separators are COMSOL software and observed a temperature rise in 18,650 cell under
among the least widely used conducting materials for LIBs. To augment different thermal conductivities. The authors found that under 3C rate
the performance of LIBs, it is necessary to develop separators with a temperature rise decreases from 8 ◦ C to 6 ◦ C when thermal conductivity
higher electrolyte uptake and improved conductivity. Parikh et al. [36] increases from 0.185 to 1 W/m-K, respectively. The temperature uni
investigated a thin layer of binary ceramic coating on a separator formity inside the cell was also improved with higher thermal conduc
membrane to exploit the benefits of each ceramic. Ceramic slurries were tivity (Fig. 4a).
prepared by mixing Al2O3 and TiO2 particles at different weight frac To improve thermal transport inside the battery, Al2O3 NPs were
tions (100/0, 50/50, 75/25, 25/75, and 0/100) with Poly vinylidene coated on a commercial PE/PP separator (Fig. 4b). The authors reported
fluoride-co-hexafluoropropylene (PVDF-HFP) binder. The slurries were five times enhancement in thermal conductivity in a modified separator
then tapped onto the separator as shown in Fig. 3c. After 30 min compared to a commercial separator with similar ionic conductivity,
exposure to 130◦ C the slurry with 100 % Al2O3 coated on the PP thus reducing excessive Joule heating, as shown in their conceptual
6
Fig. 4. (a) Temperature distribution in the cross-section of an 18,650 cell. Inset: conceptual schematic of adding Al2O3 NPs to improve thermal conductivity and
dependence of keff on k of electrolyte Elsevier Ltd. (b) a LIB generally consists of a typical separator and polymer coated Al2O3 NPs. (Reproduced with permission
from Ref. [57], © Elsevier Ltd., 2016) (c) the TG curves of PVDF/SiO2 membrane and PP membrane; (d) cycle performance of cell-batteries with PVDF/SiO2 separator
and PP separator at different current rate of 0.1C and 0.5C. Inset: The SEM images of PVDF/SiO2 membrane. (Reproduced with permission from Ref. [59], © Elsevier
B.V., 2020) (e) Schematic illustration for the structure of Al2O3/PAALi composite separator (Reproduced with permission from Ref. [61], © Wiley-VCH GmbH, 2020)
(f) procedure used to fabricate the vermiculite-PVDF modified separators. (Reproduced with permission from Ref. [62], © Elsevier B.V., 2021).
scheme (Fig. 4a inset). Lithium metal batteries have gained much Choi et al. [58] coated pristine PE separators with rod-like inorganic
attention in recent years due to high energy density (3860 mAh g− 1), but ZnO NPs. They concluded that the electrochemical performance of the
the formation of Li-dendrites leads to major reliability issues. These ZnO-laminated separator was better than that of the PP separator owing
dendrites can pierce the pristine separator, causing internal short cir to the suppression of dendrite formation. However, thicker coatings
cuits and serious thermal runaway problems. To address this problem, exhibited reduced pore properties and permeability.
7
Fig. 5. (a) Schematic of covalent bond grafting strategy for advanced a SiO2/PP separator. (b) Attraction effect of PP-g-mSiO2 separator toward the LiPF6 electrolyte.
(c) Long-term cycling performance of the cells with PP, PP-SiO2 and PP-g-mSiO2 separators at 5C for 1000 cycles. (Reproduced with permission from Ref. [64], ©
Elsevier B.V., 2020) (d) Tensile strength of ME and MLL separators. (Reproduced with permission from Ref. [65], © Elsevier Ltd. and Techna Group S.r.l., 2020) inset:
photograph of PP, PP/SiO2, and mesoporous PP/SiO2 separators at 170 ◦ C (b). (Reproduced with permission from Ref. [64], © Elsevier B.V., 2020); photographs of
thermal stability for PE, ME and MLL separators at 160◦ C for 30 min (d). (Reproduced with permission from Ref. [65] © Elsevier Ltd. and Techna Group S.r.l., 2020).
Ma et al. [59] prepared and tested PVDF/SiO2 nanofiber composite to degrade at temperatures exceeding 80 ◦ C. However, the BC-Al2O3-
membrane separators to improve the thermal stability and electro based separator remained dimensionally stable even at temperatures
chemical performance of LIBs. Electrospinning was used to fabricate a exceeding 200◦ C. In addition, the BC-Al2O3 separator exhibited a lower
PVDF/SiO2 separator. The prepared separator exhibited a higher interfacial resistance, which is beneficial for ion transport.
porosity and electrolyte uptake than commercial PP separators. In Laminating separators with ceramic particles improve their electrical
addition, interfacial resistance was reduced and the thermal stability of properties, mechanical strength, and thermal stability. However,
the PVDF/SiO2 separator was higher than that of the pristine separator. ceramic particles are usually coated on the surface of a polyolefin
To evaluate thermal stability, a thermogravimetric analysis (TGA) of the separator with the help of PVDF binder, which is neither healthy nor
developed composite was performed, as shown in Fig. 4c. They environmentally friendly for volatilizing organic binders. To address
demonstrated that onset temperature of degradation of the developed these issues, Xu et al. [61] selected lithium polyacrylate as a novel
composite separator (PVDF/SiO2) was 389.05 ◦ C (Fig. 4c), much higher binder and prepared Al2O3-based ceramic composites using a water-
than the 218.87 ◦ C of commercial PP separator, ensuring superior based slurry. Polyacrylic acid (PAA) is a polymer that has a high adhe
thermal stability and better thermal performance of the LIBs (Fig. 4d). sive strength. This forms a channel for transmitting Li+ after lithiation,
Xu et al. [60] employed an Al2O3 coating on a bacterial cellulose which is beneficial for battery safety and performance. The authors re
(BC) nanofibrous membrane as a LIBs separator. A simple in situ thermal ported that the developed composite separator could withstand a tem
decomposition method was employed to coat Al2O3 onto the BC nano perature of 136 ◦ C for 30 min without any shrinkage. Furthermore, they
fibrous separator, and the performance of the composite separator was concluded that the developed separator had a stronger bonding ability,
compared with that of the pristine PP separator. Multiple performance excellent ionic conductivity, and wettability, which would lead to a high
parameters of the developed composite separator, including porosity, cycling ability and higher discharge capacity. The mechanism of better
wettability, thermal shrinkage, tensile strength, and ionic conductivity, performance was explained in the illustration (Fig. 4e). Al2O3/PAALi
were evaluated and compared with those of a commercial PP-PE-PP composite separator improved the Li+ transference number of 0.41 by
separator. The authors reported that the novel composite separator facilitating negatively charged carboxyl groups which resulting in the
exhibited higher porosity, superior thermal stability, larger electrolyte higher discharge capacity retention (88 %) after 180 cycles. Carter et al.
uptake, smaller interfacial resistance, and improved electrochemical [62] modified a pristine separator with a flame-retardant vermiculite
stability compared to the PP-PE-PP separator. The authors observed that material to delay the melting and thermal runaway of the battery and to
the obtained BC-Al2O3 separator was quickly wetted by liquid electro provide a smooth passage for Li-ion transportation. PVDF was selected
lyte droplets, ensuring better retention of the electrolyte and exhibited as the binder with a vermiculite-to-binder ratio of 1:9. The thickness of
low internal resistance, thus improving the battery’s thermal perfor the composite separator was optimized based on the vermiculite and
mance. This was confirmed by observing the thermal shrinkage versus binder ratio and was found to be 7 μm. The LiFePO4/Li battery con
temperature curve after 30 min. The pristine PP-PE-PP separator began taining a vermiculite-modified separator exhibited better
8
Fig. 6. (a) Comparison of ionic conductivity and tLi+ between PP and MOFs@PP separators. (b) Schematic of the working principle of PP and MOFs@PP separator
suppressing Li-dendrites. (Reproduced with permission from Ref. [67], © Wiley-VCH GmbH, 2021) (c) SEM image of PE-PVDF separator. (d) Nyquist plots of the
liquid electrolyte-soaking separators. Inset: SEM image of a bare PE separator. (e) Rate performance of the cells with bare PE and PE-PVDF separators. (Reproduced
with permission from Ref. [68], CC BY 4.0).
electrochemical performance and thermal stability. The vermiculite- composite separator showed excellent mechanical strength, with a ten
modified separator enhanced the safety of the battery by lowering en sile strength of 14.5 MPa (Fig. 5d), which was nearly two times higher
ergy release (Fig. 4f). than that of the PE separator, owing to the mechanical interlocking ef
Besides, ceramic-coated separators provide thermal stability and fect of the ZrO2 particles and PVA nanofibers. The authors observed that
increase electrolyte uptake; however, these separators may become the novel composite separator exhibited excellent thermal stability with
delaminate over time and tend to fall off from the separator surface. This 0 % shrinkage at 160◦ C for 30 min of heating (Fig. 5d inset).
leads to deterioration of the properties of the separator, including From the above discussion, it can be seen that inorganic particle-
blockage of the pores of the separator. In addition, the coating tech coated composite separators and inorganic particle-filled composite
nology applied increases the thickness, resulting in an increased ionic separators can address the problems associated with pure commercial
transmission distance, and occupies more space in the battery, making PE/PP separators. NPs can improve thermal stability, mechanical
the battery less compact and lower in energy density [63]. To address strength, and compatibility with liquid electrolytes. This leads to delays
this issue, Qi et al. [64] employed a covalent-grafting interface engi in the thermal runaway of the battery and enhances safety and perfor
neering technique to prepare a highly stable and efficient PE/SiO2 mance. However, there are some issues associated with inorganic par
separator by anchoring mesoporous SiO2 onto a PP separator via cova ticles, including particles falling off over time at higher temperatures.
lent bonding. Mesoporous SiO2(mSiO2) separators were prepared by a However, the performance of inorganic-coated composite separators can
ring-opening reaction between the new amine functional group on the be improved by adopting efficient coating technologies, including
separator and the epoxy group of SiO2 (Fig. 5a). Covalent bonding blending, electrospinning, and electrospraying.
provided high interfacial stability, and the SiO2 particles did not detach
from the PP separator, even after 1000 charge/discharge cycles. The 4.2. BTMS via separators organic coating
developed composite separator can withstand temperatures exceeding
170 ◦ C without any thermal shrinkage, while PP and mesoporous SiO2/ High temperatures can accelerate battery aging, reduce battery
PP separators could withstand only 120◦ C without shrinkage. In addi performance, and increase the risk of thermal runaway. One approach to
tion, the covalently grafted mSiO2 layer greatly facilitated the migration improve thermal management is the use of separators with an organic
of Li+ owing to the formation of H–F bonds between H atoms in PP-g- coating, which can enhance heat dissipation and thermal stability of the
mSiO2 and F in the PF6-anions (Fig. 5b). As a result, excellent cycling battery. Organic coatings can also act as barriers to prevent the migra
stability, with a capacity of 93 % even after 1000 charge/discharge tion of active materials and formation of dendrites, which can cause
cycles at 5C rate, was observed (Fig. 5c). short circuits and safety hazards. Overall, the use of organic coated
Xiao et al. [65] designed and fabricated a multilayer composite separators can improve the safety and performance of LIBs, particularly
separator (MLL) by electrospinning polyvinyl alcohol (PVA) nanofibers in high-temperature environments.
and electrospraying ZrO2 NPs onto a pristine separator (ME). The au Many organic materials have a melting temperature exceeding
thors reported that the construction of such a layer-by-layer structure 200◦ C. Some polymers, including polyacrylonitrile (PAN), polyether
not only enhanced electrolyte uptake/retention and thermal resistance imide, polytetra fluoroethylene, and polyimide (PI) have a melting
but also improved the mechanical strength of the separator. The novel temperature exceeding 300◦ C. These polymers can also improve the
9
Fig. 7. (a) Schematic diagrams of LSB with the pristine Celgard and LBL-f separator. (b) The cycling performance of cells with the pristine Celgard and functional
separators during the disruption period. (c) Long-term cycle performance of the pristine Celgard and functional separators at 1C and 30 ◦ C. (d) The specific capacity
utilizations in the function of rate. (Reproduced with permission from Ref. [69], © Elsevier B.V., 2020) (e) Liquid electrolyte uptake and (f) LSV curves of the LSBs
assembled with EVAs/PP and Celgard PP separators. (g) Thermal imaging of EVAs/PP and Celgard PP separators heated at 130◦ C. (Reproduced with permission from
Ref. [70], © Elsevier B.V., 2021).
wettability of the separator to the electrolyte owing to their high po capacity decreased from 1000 mAh g− 1 to 234 mAh g− 1 after 1000
larity. Furthermore, metal-organic framework (MOF) polymers exhibit cycles.
large porous structures and large specific surface areas, which can The uniform porous structure of the MOF coating facilitated ho
promote the conduction of Li+, thereby improving battery performance. mogenous Li deposition; hence, [67] devised a functional separator to
Bai et al. [66] developed a microporous MOF and graphene oxide regulate ion transport by coating a PP separator with an MOFs. Fig. 6a
(MOF@GO) separator for lithium‑sulfur batteries (LSBs). They built an shows that functionalization of the MOFs coating increased both the
MOF@GO separator with Cu3(BTC)2 (HKUST-1) because of the exis transference number and Li+ conductivity of the PP separator. The ionic
tence of high-order micropores within its three-dimensional channel conductivity of the PP and MOFs@PP separators were 0.19 and 0.26 mS
structure, which is ideal for blocking polysulfide anions (S2−
x ). In their
cm− 1, respectively. The increased wettability and ultrahigh surface area
illustration, the MOF pore size close to 9 Å, which was smaller than S2−
x
resulted in an improved ion transport. Furthermore, lithium metal bat
(Li2Sx, 4 < x ≤ 8), leading to improved battery cycle stability. The size teries Bs equipped with the MOFs@PP separator outperformed the PP
impact caused by the homogenous porous framework of the separator is separator in terms of cyclic stability. After 50 cycles at 2C, the capacity
essential for its stable performance. For example, the battery with the retention ratio was 98.08 % of the initial value. The superior perfor
MOF@GO separator displayed a fairly stable cycling performance from mance of the MOFs@PP separator originates from the suppression of Li
870 mAh g− 1 to 855 mAh g− 1 at 100th and 1500th cycle, respectively, dendrites. The intrinsic nanopores in MOFs make it difficult for anions to
with a fading rate as low as 0.019 % per cycle. In contrast, the GO pass through because of their large sizes. In contrast, the negatively
separator-fabricated battery exhibited dramatic capacity decay. The charged MOFs particles restricted the free transport of anions by strong
10
Fig. 8. (a) Separator fabrication and post-treatment process. (b) Porosity and electrolyte uptake of the separator. (c) Cycling stability of the batteries with different
separators at 0.5C. (Reproduced with permission from Ref. [71], © Elsevier B.V., 2021) (d) Schematic representation of Mn-BTC MOF coated separator. (f) C-rate
performance of LSBs at Celgard 2320 and Mn-BTC MOF-coated membranes. (Reproduced with permission from Ref. [72], © Elsevier Ltd., 2018).
electrostatic interaction, which enhanced the tLi+ and prolonged the present in the PVDF particles, which gives the separator a larger specific
“Sand’s time” of Li-dendrites nucleation (Fig. 6b). area that, in turn, absorbs a larger amount of electrolyte. As a result, LIBs
An improvement in the stability and electrolyte wettability of LIBs using the PE-PVDF separator exhibited better ionic conductivity
was obtained by [68] surface coating a PE separator with PVDF. This PE- (Fig. 6d) and discharge capacities at high current densities (2, 3, and 5C)
PVDF enhanced ionic conductivity and porosity from 1.53 mS cm− 1 to (Fig. 6e).
0.55 mS cm− 1 and from 61.4 % to 0.55 mS cm− 1, 51.2 %, respectively, Shi et al. [69] developed a separator with an orderly structure and
compared to a PE separator. A retention capacity of 70 % at 0.5C was multifunctional properties through electrostatic LBL self-assembly of
observed at 200 cycles demonstrating a better electrochemical perfor positively charged poly diallyl dimethyl ammonium chloride (PDDA)
mance of PE-PVDF owing to the electron removal functional group wrapped covalent triazine framework (CTF) (CTF@PDDA) and nega
present in its molecular structure. The sub-microspheres (Fig. 6c) are tively charged poly 3, 4-ethylenedioxythiophene-poly styrene sulfonate
11
(caption on next page)

12
Fig. 9. (a) Schematic representation of the synthesis of the DMTA-COF, galvanostatic charge− discharge profiles of cells containing ceramic separators that coated
with DMTA-COF, super-P, and pristine ceramic separator at 0.5C, (c) discharge capacity for the corresponding ceramic separator at different rates. (Reproduced with
permission from Ref. [74], CC BY 4.0) (d) structure, metal nodes, and the Li2S6 adsorption sites in the Ce-MOF-1 and Ce-MOF-2; (e) CV curves of symmetrical cells
using different coating materials with and without Li2S6 at a scan rate of 50 mV s− 1; (f) cyclic performance of cells with different separator at 1C for 800 cycles.
(Reproduced with permission from Ref. [76], © American Chemical Society, 2019) inset: scheme of MOFs/CNT composites with a conversion reaction of S2− x as the
separator coating materials for Li− S battery.
(PEDOT: PSS) as shown in Fig. 7a. The high current rate and long-term Li2S6 and Li2S4. Discharge capacity of 1430 mAh g− 1 with a sulfur uti
battery performance of the separators were tested at 1C for 1000 cycles. lization of 85.5 % was transported with Mn-BTC MOF-coated mem
The cell comprising the pristine Celgard exhibited an initial specific branes in the LSBs. A high Coulombic efficiency of 94 % at 0.1C in the
capacity of 970 mAh g− 1 (sulfur utilization: 57.9 %) after 3 cycles of LSBs was exhibited by Mn-BTC MOF coated membrane compared to the
activation at 0.1C (Fig. 7b). Under the same conditions, the cells con uncoated membrane.
taining the functional separators exhibited much higher initial specific The “shuttle effect” produces soluble Li2Sx (4 ≤ x ≤ 8) during
capacities of 1205 mAh g− 1 (sulfur utilization: 71.9 %) and 1202 mAh discharge and this lowers the Coulombic efficiency and reduces the
g− 1 (sulfur utilization: 71.8 %) for the LBL20-f separator and BC-f battery capacity [73,74]. The utilization of various porous materials to
separator, respectively. The 26th discharge initial voltage of the LBL20- f immobilize the S2−x was an effective strategy. Wang et al. [74] prepared
separator (2.25 V) was higher than that of the pristine Celgard (2.17 V) covalent organic frameworks (COFs) host material for trapping sulfur in
and BC-f separator (2.21 V) after 72 h of interruption, followed by the LSBs which had a pore size of 0.56 nm. The 2D DMTA-COF was con
25th charge (Fig. 7c). These results indicate that the cell with the LBL20-f nected by imine-linkage, which prepared through the Schiff-based re
separator had the best reversibility for external interference. action in between DMTA and ETTA monomers (Fig. 9a). The successful
Wei et al. [70] investigated the thermal response and thermal sta preparation was confirmed by the Fourier-transform infrared technique
bility of PP separators coated with ethylene-vinyl acetate copolymer by detecting a new stretching vibration band of corresponding C– –N
microspheres (EVA/PP). This mainly acts as a shutdown separator, as it bond at 1616.75 cm− 1. The DMTA-COF coated ceramic separator was
responds rapidly to overheating, forming an insulating medium on the implemented in the LSB which shows an improved cycling and rate
top layer of the LSBs owing to its rapid thermal reaction. EVA contains performances. The high capacity was observed along with the smallest
polar groups (esters) that augment the affinity of the separator for the overpotential between charge/discharge (Fig. 9b) compared to the
electrolyte. Ion migration was significantly influenced by the increase in pristine ceramic and Super-P coated ceramic separators. Additionally,
electrolyte absorption, which was 143.4 % greater in EVA/PP separators an improved rate performance was demonstrated in Fig. 9c, in which
than in PP separators (96.3 %; Fig. 7e). This difference can be attributed cells assembled by the DMTA-COF-coated ceramic separator gave the
to the higher porosity of EVA/PP. Furthermore, because of the decreased best performance at every current rate. Even the battery delivered a
current flow at voltages below 4.6 V, no reaction occurred in the sepa remarkable capacity of 455 mAh g− 1 when the current density was
rator components (Fig. 7f). Thermal shutdown separators made of EVAs increased to 5C. Hong et.al [75] used a dual functional cage-like MOF (i.
and PP are appropriate for LSBs’ operating voltage range of 1.7 to 2.8 V e., Cu-MOF), Cu-TDPAT with a combination of Lewis basic sites of ni
versus Li/Li+ and are not engaged in the battery’s charge/discharge trogen atoms of the ligand H6TDPAT with Lewis acidic sites from Cu (II)
processes [70]. In addition, it exhibited an approximately 15 ◦ C lower open metal sites (OMSs), which was employed as the sulfur host in a LSB
temperature when heated at 130◦ C at the EVAs/PP separator, which was for Li+ and S2− 2−
x . The optimum Sx sorption sites were located in cages
attributed to the improved specific heat capacity of the separator due to near the N-rich ligands and Cu-TDPAT. For the S2− x (2 ≤ x ≤ 8), in all
the EVA microspheres. As a result, the EVA/PP separator provided cages the terminal sulfur atom of the chain binds to the Cu2+. Li+
strong thermal regulation (Fig. 7g). interacted with the N-functional group, and Li+ preferentially interacted
By electrospinning three distinct polymer materials with various with secondary amines, probably owing to the formation of better co
characteristics, Leng et al. [71] developed a novel composite separator ordination bonds. The calculated adsorption energy between S2− x and
for LIBs via dual hybridization of materials and processes. Fig. 8a clearly
Cu-TDPAT suggested the strongest interaction between Li2S4 and Cu-
shows the enhancement in the crosslink bonding after each treatment.
TDPAT. The specific capacities of different cathode materials with
The high thermal stability of PAN supports the separator structure
respect to particle size were investigated and test results demonstrated
within its framework. PVP was used as the pore-forming agent, and
that the porous S@Cu-TDPAT composite cathode material of 100 nm
PVDF-HFP was used as a binder to increase the tensile strength of the
exhibited good cycling performance.
separator after heat treatment (HT). Hydrolysis (HD) increased the
In another study, Hong et al. [76] experimented with cerium (Ce)-
porosity by 74.5 % (Fig. 8b), electrolyte absorption and ionic conduc
based MOFs combined with carbon nanotubes (CNTs) to form Ce-MOF/
tivity. Finally, the separator showed excellent thermal dimensional
CNT composites as separator coating materials for Li–S battery systems.
stability at 200◦ C with the combined process of (HT-HD) which high
According to the density functional theory calculation, the distance
lights its potential for high-temperature safety of LIBs. After heat
between terminal S of Li2S6 and the Ce(IV) was ~3.291 Å in Ce-MOF-1
treatment, a uniform current density was produced, as the HD-HT
which was higher than the distance between terminal S of Li2S6 and Ce
separator showed no adhesion and no Li dendrites on the anode sur
(IV) (2.304 Å) for Ce-MOF-2 due to the unsaturated coordination sites of
face. Fig. 8c shows the improved discharge capacities and better elec
hexanuclear clusters. In addition, Li+ can interact with the coordinating
trochemical performance of the HD-HT separator at a current density of
hydroxyl oxygen, which leads to a higher binding energy (2.48 eV) than
0.2C at 50 cycles.
that of Ce-MOF-1 (1.23 eV). This suggests the S2− x can be effectively
Suriyakumar et al. [72] used a PP separator and a coated synthesized
immobilized by Ce-MOF-2 (Fig. 9d). Furthermore, the CV curves show
Mn-BTC MOF using a simple phase inversion method for membranes in
that the current response of the Ce-MOF-2/CNT symmetrical battery
an LSB. Fig. 8d shows a schematic diagram of the Mn-BTC MOF, where
with Li2S6 was much higher than those of the Ce-MOF-1/CNT and CNT.
S2− exists as an anion in the organic electrolytes. Li+ over S2− with
x x This indicates that Ce-MOF-2/CNT immobilizes Li2S6 and facilitates the
COO− functional groups on the Mn-BTC MOF was selected because of
redox reaction of S2− x (Fig. 9e). They observed outstanding electro
physical and chemical barrier effects. Fig. 8e depicts the specific ca
chemical performance under high sulfur loading and improved capacity
pacities of the LSBs with uncoated and Mn-BTC MOF-coated membranes
retention in Li–S batteries.
at different C-rates. The discharge plateaus at 2.3 V shows the conver
The specific capacity of 1021.8 mAh g− 1 at 1C was attained first in
sion of S8 molecules into a series of intermediate S2−x species, including the Li− S cell with the Ce-MOF-2/CNT coated separator with a lower
13
Fig. 10. (a) An illustration of the fabrication of PCN@CNT; transmission electron microscopy image of PCN@CNT and schematic of LSB employing the PCN@CNT
modified separator; (b) rate capability of cells at various current densities; (c) schematic illustration of the function of PCN@CNT for suppressing the polysulfide
shuttle. (Reproduced with permission from Ref. [77], © American Chemical Society, 2019) (d) The in situ infrared thermography of PPY/Li-MMT@PP, AB@PP, and
PP separators. (Reproduced with permission from Ref. [78], © Elsevier B.V., 2021) (e) Fabrication of preparing the ZrO2@PI membrane via in situ reinforcing
technique. (Reproduced with permission from Ref. [82], © Elsevier B.V., 2020) (f) Schematic of the fabrication strategy for the in situ SiO2@(PI/SiO2) hybrid
separator; and stress− strain curves of the pristine PI and in situ SiO2@(PI/SiO2) hybrid separator. (Reproduced with permission from Ref. [85], © Elsevier
Inc., 2020).
sulfur loading of 2.5 mg cm− 2. After 800 cycles the specific capacity was Thus, excellent performance was achieved, and this was attributed to the
gradually reduced to 838.8 mAh g− 1, a lower decay rate (0.022 %) and efficient adsorption of Ce-MOF-2 to Li2S6 species and its catalytic con
Coulombic efficiency (100 %) (Fig. 9f). The cell using a Ce-MOF-2/CNT version of S2− 2−
x that clearly showed the suppressed shuttle effect of Sx in
separator coating showed good performance, when the sulfur loading Li− S batteries.
was increased to 6 mg cm− 2 with an initial specific capacity of 993.5 Hu et al. [77] used a functional separator coating composed of a
mAh g− 1 at 0.1C and after 200 cycles it remained at 886.4 mAh g− 1. pristine zirconium-MOF (Co-PCN-222) with catalytic cobalt-porphyrin
14
linker link-decorated carbon nanotubes (PCN@CNT) (Fig. 10a). Trans incorporated the hybrid separator displayed enhanced safety perfor
mission electron microscopy suggests that an interconnected network mance, as demonstrated by the reduced thermal runaway and negligible
structure not only facilitates electron transfer but also avoids the ag gas evolution during charge-discharge cycling. Babiker et al. [83] uti
gregation of PCN particles, which is expected to be effective for lized a scalable biaxial stretching process to fabricate hybrid UHMWPE/
anchoring and reusing S2− x . LSBs coupled with a PCN@CNT-coated
SiO2 nanocomposites and developed a lithium battery separator. The
separator exhibited a higher specific capacity of 1157 mAh g− 1 at resulting separator exhibited exceptional electrochemical performance,
0.1C (Fig. 10b) and good rate capability with a reversible capacity of featuring a high ionic conductivity of 2.11 mS cm− 1 and a low electro
696 mAh g− 1 at 2C. There was excellent cyclic performance with a much lyte uptake of 38.2 %, thereby achieving an excellent electrochemical
lower capacity attenuation rate of 0.067 % after 500 cycles at 1C. The stability window of 5.0 V. The hybrid separator also displayed notable
S2−
x redox kinetics were significantly boosted by the strong adsorption
thermal stability, retaining its structural integrity even after exposure to
and catalytic activity of the uniformly dispersed cobalt and nitrogen high temperatures of 300◦ C. These findings suggest that the scalable
sites in the porphyrin linkers (Fig. 10c). biaxial stretching process has significant potential for the production of
Yang et al. [78] used an effective heat-release layer to enhance the high-performance lithium battery separators. Dong et al. [84] employed
high-temperature stability of LSBs by incorporating a conductive an in-situ reinforcing approach to develop ZrO2-armored hybrid PI
polypyrrole-modified Li-montmorillonite (PPY/Li-MMT) on the PP separators for advanced and safe LIBs (Fig. 10e). The resulting hybrid
separator. No thermal shrinkage at temperatures to 150◦ C was apparent. separators displayed impressive electrochemical properties, including a
The in situ infrared thermography images of PPY/Li-MMT@PP, AB@PP, high ionic conductivity of 2.29 mS cm− 1, excellent thermal stability to
and PP are shown in Fig. 10d, where the PPY/Li-MMT@PP separator 300◦ C, and an outstanding electrochemical stability window of 5.5 V.
showed excellent thermal stability compared to the PP and AB@PP The separators also exhibited superior mechanical strength, with
separators. Their results show that the high electrolyte uptake of 348.6 standing tensile strains to 310 %, while maintaining their structural
% with the use of PPY/Li-MMT modified PP separator. In addition, a integrity. Additionally, the in situ reinforcement approach improved the
high ionic conductivity of 3.63 mS cm− 1 was achieved, with stable safety performance of the separator by preventing thermal runaway and
performance over 600 cycles. Thus, the PPY/Li-MMT@PP used in this minimizing gas evolution during cycling. Fu et al. [85] developed a
work is likely to improve thermal safety and capacity retention. composite separator with a high strength and thermal stability for use in
A co-modified polymethyl methacrylate-Li7La3Zr2O12/PP/acetylene LIBs. The separator was composed of a coaxial electrospun composite
black (PMMA-LLZO/PP/AB) separator was fabricated and used by Xie consisting of PAN/hollow carbon nanofibers (HCNFs)@PVDF/UiO-66.
et al. [79] to improve LSB safety. The cell with the co-modified separator The composite separator demonstrated excellent mechanical strength
exhibited high specific capacities of 1456 mAh g− 1 at 0.1C and 969 mAh and thermal stability, as well as superior electrochemical performance,
g− 1 at 1.0C. After 500 cycles, the capacity was 413 mAh g− 1, corre including a high Li + conductivity (1.44 mS cm− 1) and a stable capacity
sponding to a retention of 42.6 % and a low decay rate of 0.11 %/cycle. of 128.2 mAh g− 1 after 50 cycles. These findings suggest that the PAN/
The increase in sulfur loading in the cathode of 2.5–3.0 mg cm− 2 HCNF @PVDF/UiO-66 composite separator is an effective candidate for
exhibited a higher capacity and a lower decay. Thus, the PMMA-LLZO high-performance LIBs. Jia et al. [86] presented an ecofriendly ceramic
side possesses a good affinity with the liquid electrolyte and can effec hybrid separator for LIBs using a simple paper-making process. The
tively inhibit S2− separator was composed of wood pulp fibers and xonotlite nanowires,
x diffusion due to the physical and chemical adsorption
of the layer on S2− which offer high ionic conductivity and mechanical properties. The
x and can be effectively used in LSBs. Thus, the use of
ceramic hybrid separator displayed an excellent ionic conductivity (1.2
various multifunctional separators [80,81] designed and fabricated by
mS cm− 1) and a stable capacity of 95.5 mAh g− 1 after 50 cycles.
the researchers demonstrated the possibility of commercializing LSBs
Furthermore, the separator’s mechanical strength was outstanding, and
because of their higher electrochemical performance, higher safety,
it retained its structural integrity even after being subjected to tensile
lower shuttle effect, and slower degradation during cycling in high-
strains to 180%. Kong et al. [87] developed a robust and fire-resistant
power applications.
hybrid separator for use in advanced safe batteries. The separator was
created using an in situ armoring approach that involved coating a
4.3. BTMS via separators with an inorganic/organic (hybrid) coating commercial PE separator with a thin layer of SiO2 NPs and then modi
fying it with a layer of polydopamine (Fig. 10f). The resulting hybrid
This method uses separators with inorganic and organic coatings. separator exhibited high wettability, excellent thermal stability (to
Inorganic coatings on the separator can enhance thermal stability and 300 ◦ C) and mechanical stability. The separator also demonstrated su
flame retardancy, whereas organic coatings can improve thermal sta perior electrochemical performance, including a high ionic conductivity
bility, electrochemical performance, and reduce the growth of Li den (1.64 mS cm− 1) and an outstanding electrochemical stability window of
drites. Hybrid coatings are typically composed of an organic polymer 5.5 V. Moon et al. [88] reported the development of an ultrathin
matrix and inorganic NPs or oxides that provide enhanced mechanical inorganic-organic hybrid layer on commercial polymer separators for
strength, thermal stability, and ion conductivity. Hybrid coatings, which advanced LIBs. The hybrid layer was comprised of a ZrO2 NPs-anchored
combine the benefits of inorganic and organic coatings, can therefore PAA layer, which improved wettability, thermal stability, and electro
provide improved thermal stability and electrochemical performance. chemical performance of the separator. The resulting hybrid separator
Various coatings have been used to optimize the thickness, composition, exhibited enhanced ionic conductivity and maintained a stable capacity
and uniformity to achieve the desired performance, as now discussed. of 120 mAh g− 1 after 100 cycles. These findings suggest that the ultra
Ahn et al. [82] developed a hybrid separator by coating a commer thin inorganic-organic hybrid layer has potential as an effective strategy
cial separator with a layer of nanostructured alumina via a straightfor for improving the performance of commercial polymer separators in
ward sol-gel method. The performance of the hybrid separator was LIBs. Zhi et al. [89] developed UV-curable organic-inorganic hybrid
evaluated by constructing LIBs with LiFePO4 cathodes and Li4Ti5O12 coatings on microporous PE separators to enhance their mechanical and
anodes. The electrochemical properties of the batteries were studied electrochemical performance for use in LIBs. Hybrid coatings were
using cyclic voltammetry, electrochemical impedance spectroscopy, and prepared by incorporating a SiO2 precursor into a UV-curable resin and
galvanostatic charge-discharge cycling. The batteries exhibited an initial applying it to the separator surface. The resulting coated separator
discharge capacity of 143 mAh g− 1 and maintained a steady capacity of exhibited significantly improved tensile strength and electrochemical
138 mAh g− 1 after 100 cycles. The hybrid separator also exhibited a stability, with a capacity retention rate of 97 % after 100 cycles. Na et al.
lower interfacial resistance and improved Li+ diffusion, as confirmed by [90] tested the performance of LIBs with and without a UV-curable
electrochemical impedance spectroscopy. Additionally, batteries that polysilsesquioxane binder in the separator. Batteries with the
15
Table 3
Summary of nanomaterials and characterization used in composite separator of secondary batteries.
Material Matrix Preparation method Porosity Electrolytes Thermal stability Ionic conductivity Ref.
[%] uptake [%] [mS cm− 1]
Al2O3 PP Blade coating 0.6 % in 130 ◦ C for – [36]

30 min
Al2O3 & PFR solution PE Drying 45.3 73 0 % in 130 ◦ C for 0.62 [37]
30 min
SiOxCyHz PE Roll-to-roll plasma coating – 103.1 4 % in 120 ◦ C for 0.361 [40]
60 min
Polydopamine PE Filtration 40.4 0 % in 160 ◦ C for 0.617 [41]
60 min
Graphene Oxide (GO) PP Tape casting – – – – [43]
ANFs/PPS composite – Filtration 65.9 240.7 ~0 % in 200 ◦ C 1.43 [46]
Al2O3 PP ALD ~2 % in 100◦ C for [47]
30 min
TiO2 PP ALD – – – 8.52 [48]
TSL-8233@SiO2 PP Coating – 281 17.5 % in 150◦ C 1.90 [50]
for 30 min
P(VDF–TrFE) and NaY Zeolite – Solvent casting ~36 ~230 – 0.00233 [51]
– Al2O3 Platelets and sintering 70 200 – 3.45 [52]
3
SiO2/PVDF-HFP PET Dip coating 61.2 1.08 g cm− 0 % in 150 ◦ C for 0.91 [53]
30 min
Al2O3 PP/PE/PP Coating – – – 0.044 [55]
Al2O3 – Drop casting – – – – [57]
ZnO PE Blade coating 114 50 % in 140 ◦ C for 0.418 [58]
30 min
PVDF/SiO2 composite – Electrospinning 131.33 1514.79 – [59]
Al2O3 Bacterial Soaking matrix in Al2O3 solution 74.7 625 0 % at 180 ◦ C for 4.91 [60]
cellulose 30 min
PAA/ZrO2 multilayer PE Coating – 325 ~80 % in 140◦ C 0.51 [63]
mSiO2 PP Immersion 60 379 0 % at 120◦ C for 0.87 [64]
30 min
ZrO2 nanoparticles PVA nanofiber Electrospinning and 73 350 0 % at 160◦ C 2.19 [65]
electrospray
MOF GO Filtration – – – – [67]
PVDF PE Dip coating 61.4 208 48 % at 140◦ C for 1.53 [68]
30 min
– PAN, PVDF- Electrospinning and heat 70.7 584.2 0 % at 200 ◦ C for 1.78 [71]
HFP, PVP treatment, Hydrolysis 60 min
Ce-MOFs-1,2/CNT Celgard 2400 Blade coating – – – – [74]
PCN@CNT PP Blade coating – – 0.44 [75]
Pyrrole and Lithium-ion PP Coating – 384.6 ~0 % at 150◦ C 3.63 [76]
montmorillonite
PMMA and LLZO&AB-PVDF PP Coating – – – 1.10 [77]
Graphene and nano-Al2O3 PP Coating – – – – [78]
Al2O3 PE Blade coating 45 – 3 % at 140 ◦ C for 0.51 [80]
60 min
SiO2 nanofiber UHMWPE E-beam irradiation ~60 ~470 1 % at 200 ◦ C for 1.6 [81]
60 min
ZrO2 Polyimide Electrospinning and heat 83.7 345.1 ~0 % at 300 ◦ C 3.73 [82]
treatment
PAN/HCNFs@PVDF/UiO-66 – Electrospinning and hot pressing 77.61 570.97 0 % at 200◦ C for 1.59 [83]
composite 60 min
Wood pulp fibers and – Hydrothermal method 67 198 0 % at 600 ◦ C for 1.148 [84]
xonotlite nanowires 30 min
SiO2@(PI/SiO2) PAA/TEOS In-situ 73 296 0 % at 300 ◦ C 1.67 [85]
Al2O3 and PDA PE ALD coating and dip coating – 450 26.3 % at 140 ◦ C ~0.62 [86]
for 30 min
SiO2 PE UV curable coating – – – – [87]
polysilsesquioxane binder exhibited improved cycling stability and wettability and compatibility of the separator with the electrolyte.
reduced dendrite formation compared to batteries without a binder. Further research is required to optimize the formulation and commercial
Specifically, the batteries with the binder showed a higher capacity application of these coatings.
retention rate after 100 cycles, with a retention rate of 88 %, compared
with 68 % for batteries without the binder. From this discussion of the 4.4. BTMS via gel polymer electrolyte/separators
results of various researchers, it is formulated that organic/inorganic
hybrid coatings have the ability to suppress the growth of Li-dendrites, Gel polymer electrolytes (GPEs) are prepared by gelling liquid
which can cause short circuits and compromise battery safety. The polymer matrices and/or combination of GPEs and separator as an in
hybrid coatings also provided improved electrochemical stability and tegrated membrane1, which have advantages over liquid electrolytes
cycling performance, resulting in a longer battery life and higher energy [18]. GPEs can effectively prevent electrolyte leakage and reduce the
density. Furthermore, the use of hybrid coatings can address the issue of firing hazard which is essential for battery safety. Compared with liquid
compatibility between electrolyte and separator, which can lead to electrolytes, GPEs can effectively prevent electrolyte leakage and reduce
degradation of the separator and reduced battery performance. The the firing hazard, which leads to the high safety of batteries. Particu
incorporation of inorganic materials into an organic matrix can improve larly, significant efforts have been made to enhance thermal properties
16
at high temperatures. Additionally, GPEs can provide better ionic con electrochemistry, mechanical engineering, polymer science, and mate
ductivity, a wide range of electrochemical potential window, excellent rials science. Nanomaterials play an important role in developing
interface contact, buffer electrode volume variations and good thermal advanced composite separators with enhanced thermophysical proper
stability [91–94]. Consequently, GPEs can be a promising alternative ties (Table 3). Non-traditional materials should be explored, focusing on
among various electrolytes for various advantages such as better flexi heat-conductive polymers and inorganic components. Therefore, artifi
bility, cycling stability and enhanced safety. cial intelligence and machine learning can be introduced. In addition,
Usually, GPEs are obtained by incorporation of a liquid electrolyte materials with enhanced thermophysical properties can be used in other
into the polymer matrix. Thus, the performance of GPEs mostly depends battery parts, including anodes and cathodes. Effective and innovative
on the properties of polymer and polyethylene oxide (PEO), PVDF, composite materials with conductive, heat-absorptive, and hydrophilic
PVDF-HFP, PAN, PMMA etc. are commonly used as for LIBs. In addition, properties must be explored instead of physical functionalization of the
many GPEs have their own properties. For example, Chen et al. [95] separators. The prospective application of composite separators to the
have prepared a supramolecular cross-linked polymer network that has other next-generation battery systems is huge. Sodium- and potassium-
the advantages of good flexibility, high mechanical strength, and ionic ion battery systems also require composite separators to minimize
conductivity (7.5 × 10− 4 S/ cm at room temperature). Importantly, it thermal issues. Considering the similar battery electrochemistry, similar
has the ability to be self-repaired without external stimulation. This approach could be enough to get the primary success. Sulfur batteries
novel GPE has prepared by adding supramolecular copolymer, PEG- are also vulnerable without an efficient composite separator which
UPy, to the cross-linking matrix of PEO and PVDF-HFP. The as pre could successfully eliminate the ‘shuttle effect’ [97,98]. However,
pared GPE has a good self-healing capability at 25 ◦ C. Experimentally it intensive research should be continued to pursuit the commercial
eliminates puncturing caused by lithium dendrite growth during standard. In conclusion, to commercialize safe next-generation energy-
charging and discharging which successfully boosts the safety of LIB. storage systems, more attention should be paid to the internal thermal
Jeong et al. [96] have prepared an in situ cross-linked GPEs of using poly management of rechargeable lithium batteries using low-cost materials
(vinylidene fluoride-cohexafluoropropylene) as a polymer matrix with and simple preparation processes.
GO which found to have highly porous structure leading to the high
liquid electrolyte penetration and high ionic conductivity. Importantly,
Declaration of competing interest
the as-synthesized cross-linked GPE was successful in suppressing the
lithium dendrite growth which resulting in improved cycle performance
The authors declare that they have no known competing financial
compared to the conventional Celgard-liquid electrolyte system. Addi
interests or personal relationships that could have appeared to influence
tionally, the as prepared cross-linked GPEs showed thermal stability up
the work reported in this paper.
to 270 ◦ C which suggesting the possible application for high-
temperature battery systems.
Data availability
The current technology of GPEs is more advanced and it already
shows huge potential to implement in the LIBs particularly for thermal
Data will be made available on request.
management inside the battery system. However, GPEs are facing
several technical challenges in commercial applications. For example, to
Acknowledgement
incorporate the additional advantages into GPEs, many additives are
being used. The use of ionic liquids as plasticizers flame-retarding agents
Amrit Kumar Thakur and Y. Ma would like to acknowledge financial
are beneficial to battery safety and flexibility but unfavorable to battery
support from NSF (Award # 1856112). This research was also supported
cost. Therefore, further improvement in the GPEs is anticipated along
by the research fund of Hanyang University (HY-202300000001172).
with the synergetic development of electrode materials and electrolytes
to commercialization.
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Contents lists available at ScienceDirect

Journal of Energy Storage

Composite separators for internal thermal management in rechargeable

1. Introduction Computers, mobile, e-packaging, disposable medical testers [4,5],

Table 1 performance and reliability of Li-based batteries. Various testing ap

Fig. 2. Schematic diagram of typical thermal runaway process.

(caption on next page)

Al2O3 PP Blade coating 0.6 % in 130 ◦ C for – [36]

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J - Energy Storage 2023 v73 108873

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J - Energy Storage 2023 v73 108873

Uploaded by

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Copyright

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Journal of Energy Storage 73 (2023) 108873

Contents lists available at ScienceDirect

Journal of Energy Storage

Composite separators for internal thermal management in rechargeable

1. Introduction Computers, mobile, e-packaging, disposable medical testers [4,5],

Table 1 performance and reliability of Li-based batteries. Various testing ap­

Fig. 2. Schematic diagram of typical thermal runaway process.

(caption on next page)

Al2O3 PP Blade coating 0.6 % in 130 ◦ C for – [36]

You might also like

Table 1 performance and reliability of Li-based batteries. Various testing ap