Review

Cite This: ACS Appl. Energy Mater. 2019, 2, 3937−3971 www.acsaem.org

Strategic Structural Design of a Gel Polymer Electrolyte toward a

High Efficiency Lithium-Ion Battery
Febri Baskoro,†,‡,§ Hui Qi Wong,† and Hung-Ju Yen*,†
†
Institute of Chemistry, Academia Sinica, 128 Academia Road, Section 2, Nankang, Taipei 11529, Taiwan
‡
Sustainable Chemical Science and Technology, Taiwan International Graduate Program, Academia Sinica, 128 Academia Road,
Section 2, Nankang, Taipei 11529, Taiwan
§
Department of Applied Chemistry, National Chiao Tung University, Hsinchu 300, Taiwan
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ABSTRACT: Electrolytes have played critical roles in electrochemical energy storage. In

Li-ion battery, liquid electrolytes have shown their excellent performances over decades,
Downloaded via NOTTINGHAM TRENT UNIV on July 17, 2019 at 04:53:10 (UTC).

such as high ionic conductivity (∼10−3 S cm−1) and good contacts with electrodes.
However, the use of liquid electrolytes often brought risks associated with leakage and
combustion of organic electrolytes. Hence, polymer electrolytes become potential
candidates to replace liquid electrolyte systems. Although solid polymer electrolytes
(SPEs) offer better safety and good mechanical properties to take over liquid electrolytes,
most of them only deliver low ionic conductivities (∼10−8 S cm−1) and poor contact with
electrodes, resulting in poor cycle performance and low electrical capacity of the batteries.
In addition, gel polymer electrolytes (GPEs) have received increasing research attention
due to their relevant characteristics, which extend from liquid electrolytes and solid polymer
electrolytes. In this review, state-of-the-art samples of gel polymer electrolytes are
elucidated with respect to their structural design and electrochemical properties to
determine their application potential in Li-ion batteries (LIBs). First, we present the general requirements of GPEs for LIBs
applications, followed by important electrochemical properties of GPEs for LIBs including ionic conductivity, transference
number, and ionic transport mechanisms. Furthermore, recent progress of common polymers, namely, polyether, polyvinyl,
polynitrile, polycarbonate, and polyacrylate, as polymer host of GPEs has been carefully explained. Finally, the alternative
polymers were also discussed to provide new approaches for further developments of GPEs to fulfill the demanded properties
for practical applications.
KEYWORDS: Li-ion battery, electrolytes, gel polymer electrolytes, ionic conductivity, ionic transport mechanism

1. INTRODUCTION including their lightweight, high energy density, high open-

1.1. Overview of Lithium-Ion Battery Development. circuit potential, minimal memory effects, fast charging, low
Because of the continuous increase of environmental problems self-discharge rate, and environmental friendliness.2−6 As
related to greenhouse gases in the atmosphere and the shown in Figure 1, a conventional LIB consists of a positive
exhaustion of nonrenewable fossil fuels, the use of alternative electrode (cathode), negative electrode (anode), nonaqueous
renewable energy sources, such as wind, solar, and geothermal, electrolyte system, and separator to prevent physical contact
etc., has become an important research focus. However, between two electrodes. In principal, when the battery is being
availability issues limit the production of energy from certain charged, the Li ion moves from the cathode to the anode
renewable energy sources, such as wind and solar energy. through the electrolyte and carries the current, and during
Therefore, an efficient energy storage system is absolutely discharge, the Li ion will move back from the anode to the
needed to provide a continuous energy supply. Among energy cathode. Generally, Li-intercalated materials, such as LiCoO2
storage technologies, electrochemical energy storage based on (a lithium metal oxide with layered structure), have been used
batteries shows promising features that include high round-trip as the cathode material (lithium source) and graphite has been
efficiency, flexible power, a long cycle life, low maintenance, used as the anode to hold the Li ion in its layers. Both
and energy characteristics to meet different grid functions.1 Li- materials for the electrodes can reversibly insert and remove
ion batteries (LIBs) are a type of electrochemical energy the Li ion from its respective structure.3
storage based on the use of Li intercalating compounds, and For the past 2 decades, improvements have been made to
they have attracted considerable research attention over the fulfill the demands of energy storage systems for portable
past 2 decades. LIBs were commercialized in the 1990s by devices and electric vehicles. Inside the LIB, the chosen
Sony Corp., and these batteries have recently dominated the
entire market of portable electronic devices, such as notebooks, Received: February 12, 2019
personal telephones, and cameras. Moreover, the use of LIBs Accepted: May 2, 2019
was projected for electric vehicles due to the desirable features, Published: May 2, 2019

© 2019 American Chemical Society 3937 DOI: 10.1021/acsaem.9b00295

ACS Appl. Energy Mater. 2019, 2, 3937−3971
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lyte compatibility issue that has also arisen from the use of high
voltage materials (mainly cathode) to increase the energy
density of LIBs will lead to the decomposition of electrolytes
because of the poor electrochemical stability at high
voltage.12,13 Since the electrode−electrolytes compatibility
mainly lies on the electrochemical window of the electrolytes,7
therefore, the compatibility between electrolytes and the high
voltage cathode materials became a major direction and cannot
be ignored in the electrolyte development.4 A list of accidents
related to LIBs has shown that most of the accidents were
caused by overheating during operation, which leads to
fire.8,14,15 For instance, in January 2016, a Tesla Model S
caught fire while fast-charging at a supercharger station in
Gjerstad, Norway due to a short circuit.15 Therefore, the
replacement of liquid electrolyte in LIBs is in high demand for
the safety issues.
Solid electrolytes, including inorganic solid electrolytes
(such as ceramic materials) and polymer electrolytes, have
attracted attention as a replacement for liquid electrolytes.
Figure 1. Schematic of a conventional Li-ion battery. Moreover, among these types of solid electrolytes, polymer
electrolytes have drawn considerable attention as a replace-
electrodes (mainly cathode) are the main factors for battery ment for liquid electrolytes due to their intrinsic properties,
performance, i.e., energy density and cyclability. Meanwhile the such as freestanding, shape versatility, security, flexibility,
electrolytes do determine the current (power) density, time lightweight, and reliability.2,11,13 In general, there are two types
stability, and battery safety since they directly interact with all of polymer electrolytes: solvent-free solid polymer electrolytes
battery components including anode, cathode, and the (SPEs) and gel polymer electrolytes (GPEs). However, the
separator.1 As shown in Figure 2, the development of cathode boundary between SPEs and GPEs can become blurred due to
materials has been focused on high voltage materials, such as the presence of “plasticizers” in the SPEs, which allow them to
Li-rich cathode materials (Li1−xMn2−yMyO4), which are behave similarly to GPEs; moreover, polymers or oligomers
capable of reaching over 4 V of operating voltage. In addition, may present molecular weights near the threshold (average Mw
research on anode materials has focused on higher capacity 5,000−10,000) of polymers.12
materials, including carbon materials and 3D metal oxides, 1.2. Solid Polymer Electrolytes. Generally, SPEs are
capable of reaching higher capacities (∼1000 Ah/kg). In constructed by the dissolution of lithium salts in a polymeric
addition, a safety issue is associated with the use of flammable matrix to provide ionic conductivity. In SPEs, lithium salts are
organic solvents, and the leakage of electrolytes has hindered dissolved via complexation between the Li ion and the strong
the commercialization of LIBs based on a liquid electro- electron donor of the polymer backbone, in which the electron
lyte.1,2,7−10 Organic solvents can generate highly flammable donor panel in the polymer is involved in solvation with the
gases, such as CO, CH4, C2H4, C2H6, C3H6, and C3H8, etc., cation component in the dopant salt and then facilitates ion
when LIBs are overheated due to overcharging, abuse, internal separation, which leads to an ionic hopping mechanism that
short circuits, manufacturing defects, physical damage, or other generates ionic conductivity.2,16,17 The development of SPEs
failure mechanisms.8,11 Furthermore, the electrodes−electro- began with the discovery of ionic conductivity of ions (alkali

Figure 2. Development of electrode materials for a Li-based battery. Reprint with permission from ref 4. Copyright 2001 Springer Nature
Publications.

3938 DOI: 10.1021/acsaem.9b00295

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Scheme 1. Schematic Common Polymer Backbone for SPEs

metal) inside poly(ethylene oxide) (PEO) in 1973 by addition, the ionic conductivities of SPEs studied to date are
Wright.13 Since that time, the number of research works in still in a range of 10−8 to 10−5 S cm−1, which significantly
the field of SPEs has grown tremendously, thus reflecting the hinders the commercialization of SPEs in LIBs.10
progress of development and understanding of the molecular The second obstacle to the application of SPEs in LIBs is
architecture, which is necessary to achieve fast ion transport in based on their interfacial contact between electrodes and the
polymers. There are several advantages of SPEs over liquid electrolytes. It is well-known that liquid electrolytes have
electrolytes in LIBs, such as nonvolatility, flexibility, mechan- higher ionic conductivity and excellent wetting ability to the
ical properties, improved safety, and ease of device fabrication, electrodes, thereby extending the electrode−electrolyte inter-
etc.17−19 As shown in Scheme 1, many existing polymer face into the porosity of the electrode.10,23 The nature of the
backbones have been used as SPEs for LIB applications.20 solid polymer prevents the SPEs from having a good interface
Among these polymers, PEO is the most promising candidate with the electrodes as a liquid electrolyte. Therefore, the
as a solid solvent for lithium salts because of its flexible interface of SPEs with the electrodes is limited only in the area
ethylene oxide segments and ether oxygen atoms, which have a of actual contact on the surface of electrodes. This
strong donor character and thus readily solvate Li+ cations.2 phenomenon increases the interfacial impedance of the system
Moreover, an alternative polymer polysiloxane (PSi) has and directly influences the battery performance.23 Another
recently been investigated, and each of its backbones provides significant issue of SPEs for LIB applications is based on the
two cross-linkable sites or functional site chains that are electrochemical stability window of the polymer host. For
favorable for a comb polyelectrolytes complex.21,22 oligoether-based SPEs, in particular, the oxidized cathode often
In SPEs, the most tremendous challenges are always related presents an insurmountable barrier because the breakdown
to low ionic conductivity, interfacial contact between the potential for ether linkages may be below 4.0 V.12
electrode and the electrolyte, and the poor electrochemical 1.3. Gel Polymer Electrolytes. Compared with SPEs,
stability window.12 The low ionic conductivity in SPEs is GPEs have greater potential for practical applications in LIBs
considered a trade-off for mechanical properties. Initially, these by combining high ionic conductivity and good mechanical
polymer−salt complex systems may exhibit mechanical proper- properties, which are based on liquid electrolytes and SPEs,
ties that are similar in most ways to those of true solids due to respectively.18,23 Feuillade and Perche proposed the concept of
chain entanglement of the polymer host, whereas, in a GPEs in 1975, in which a polymer is plasticized with an aprotic
microscopic environment, a lithium ion remains liquid-like solution containing an alkali metal salt in which the organic
and the ion conductivity is “coupled” to the local segmental solution of the alkali metal salt remains trapped within the
motion of the polymer at the amorphous region. 23 matrix of the polymer.2,11,24 Until 1994, Bellcore (currently
Consequently, the glass transition temperature (Tg) of the Telcordia) reported for the first time the utilization of GPEs
polymer host is the key to determining the mechanical based on coke/GPE/LiMn2O4 in LIBs, in which the GPEs
properties and processability of polymer material for consisted of a poly(vinylidene fluoride)-co-hexafluoropropy-
SPEs.2,13,18 Several attempts have been made to lower the Tg lene (PVDF-HFP) copolymer matrix and were gelled by a
to improve the ionic conductivity via copolymerization, cross- solution of LiPF6 in ethylene carbonate (EC)/dimethyl
linking, blending, and plasticizer application, etc. However, carbonate (DMC).24 Generally, GPEs are obtained by
lowering the Tg of the host polymer will result in reduced incorporating a certain amount of liquid plasticizer and/or
mechanical properties, which represents a conflict with the solvent into the polymer−salt system.2 According to the
fundamental expectation for SPEs in LIB applications.23 In preparation method, the GPEs are classified into two different
3939 DOI: 10.1021/acsaem.9b00295
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categories: physical and chemical gels.17 The physical gels 10−2 S cm−1.10,20,26 Therefore, to facilitate Li+ conduction
mean that the liquid electrolytes are confined inside a polymer through the polymer electrolyte, a GPE should have an ionic
matrix without any bond formation between the polymer and conductivity of at least one order so that the conductivity of
the solvent. In addition, the chemical gels consist of a cross- the liquid electrolyte is greater than 10−4 S cm−1.2,7,17,24,26
linker that leads to the formation of chemical bonding between 2.1.2. High Cationic Transference Number (T+). The
the functional group of the polymer and the cross-linker agent. cationic transference number is the cation mobility measure-
Due to the combined system of polymer−plasticizer/solvent ment relative to the anion in single salts of GPEs. The low ion
and Li salts, the electrochemical properties of GPEs generally diffusivity and mobility of the anion in the GPEs greatly affect
are determined by the liquid/plasticizer component while the the LIB performance by increasing the concentration polar-
safety, morphology, and mechanical properties are defined by ization phenomenon of the electrolyte during charge/
the polymeric matrix.16 A debate remains as to the exact nature discharge, thereby lowering the Li+-ion transference number
of the polymer−plasticizer/solvent−salts interaction on the and reducing the discharge capacity.11,20,24,27 Therefore, the
performance of GPEs, especially for Li+ transport properties.19 GPEs need to have a Li+ transference number close to unity
The host polymer in GPEs is maintained in semi-solid (T+ ≈ 1) in the electrolyte system.2,7,17,19,20,24,26
macroviscosity due to the presence of the plasticizer/solvent; 2.1.3. Electrochemical Stability. The electrochemical
thus, the microscale of Li+ is similar to that of the liquid stability of GPEs determines the operational potential of
environment inside a GPE. Hence, many researchers consider LIBs during charging/discharging. GPE materials have to be
that Li+ motion transport is completely independent from the inert to both electrodes (cathode/anode), which means that
polymeric segmental relaxation,12 although many have pointed the oxidation potential must be higher than the embedding
out that the polymer phase may contribute to ionic transport potential of Li+ in the cathode and the reduction potential
within GPEs.19,25 must be lower than that of the lithium metal in the anode.2
Various polymer matrices, including PEO, polyacrylonitrile Since the LIB generally operates in various potential windows
(PAN), poly(vinylidene fluoride) (PVDF), poly(methyl between 0 and 4 V vs Li/Li+ (and occasionally reaches high
methacrylate) (PMMA), poly(vinyl alcohol) (PVA), and voltages of ∼5 V), the electrochemical stability of the GPE
poly(vinyl chloride) (PVC), etc., have been investigated for materials is fully required within this potential window for a
GPEs in LIBs.2,17,19,24 Although GPEs present greater benefits truly thermodynamically stable system.2,7,11,19,20,24,26
over SPEs in terms of ionic conductivity, they present 2.1.4. Good Chemical and Thermal Stability. Since a GPE
additional problems related to the nature of the liquid and is sandwiched between the cathode and the anode, it should be
solid electrolytes, such as dual-ion conductivity, low ionic chemically stable and not undergo undesired chemical
conductivity at room temperature, and poor thermal reactions when in direct contact with the electrodes. Although
stability.1,10 Several attempts have been made to overcome GPEs could provide ionic conductivity close to that of the
these problems and obtain appropriate properties for LIB liquid electrolyte, due to the solvent embedded inside of GPEs,
applications, such as inorganic filler addition, functional they can occasionally undergo an irreversible capacity loss
polymer introduction, copolymerization, combinations with associated with the formation of a passivation layer at the
different polymer matrix types, cross-linking, and single ion surface of the electrode.7,24 The passivation reactions are
polymer conduction.2,10 In this review, we first state and usually initiated by the presence of organic solvents in the
discuss the fundamental aspects of GPEs, such as their general polymer electrolytes along with unstable anions of the Li salt,
requirements and significant properties, including ionic which result in their decomposition at electrode surfa-
conductivity, transference number, and ionic transport ces.20,28,29 Furthermore, the reaction products of the anion
mechanism. In the following sections, we systematically discuss could initiate the degradation reactions of the polymer
the recent progress of GPEs for LIBs based on the structural chains.24 Fortunately, this issue can be prevented by using an
design of their polymer matrix for improved electrochemical electrolyte additive20,30 and stable Li salts, such as lithium
performance, such as compatibility with electrodes, ionic bis(trifluoromethanesulfonyl)imide (LiTFSI).24
conductivity, and ionic transport mechanism. Finally, the Generally, a certain amount of heat can be generated and
remaining polymer alternatives and the future direction of released in the LIB when a short circuit, overcharge, or
GPEs in LIB applications are also presented. improper operation happens. Generated heat can initiate the
degradation of solvent embedded inside the GPEs or cause a
2. CRITICAL PROPERTIES AND ION TRANSPORT melting process of the polymers under conditions of poor
MECHANISM OF GPES thermal stability. GPEs represent a hybrid electrolyte system of
2.1. General Requirements of GPEs. In LIBs, GPEs are polymer metrics and organic liquids as plasticizer; therefore,
placed between the cathode and the anode (lithium metal, the polymer metrics play an important role in maintaining the
graphite, and so on) and function as both an electrolyte and thermal stability of the GPEs. Therefore, a thermally stable
separator. Therefore, GPEs play critical roles in the perform- polymer is needed for the GPE system.2,11,19,24,26 Instead of
ance of LIB. Due to their importance in the LIB system, GPEs using a single polymer chain, a composite polymer could
should possess several properties. significantly enhance the thermal stability of GPEs. 31
2.1.1. Good Ionic Conductivity. A GPE should facilitate the Furthermore, a mixture of organic liquids, such as propylene
ionic (Li+) transport and inhibit the self-discharge of the carbonates (PCs) and ethylene carbonates (ECs), could
cathode or anode material; therefore, a GPE must exhibit good increase the thermal stability as well as extend their potential
ionic conductivity and electronic insulation.2 The ionic window toward the lithium electrode.32
conductivity of GPEs is usually measured based on the 2.1.5. Good Mechanical Properties. GPEs play dual
electrochemical behavior and the internal resistance at various important roles in LIBs as a conductive medium of the two
charge/discharge rates. Generally, the ionic conductivities of electrodes and a separator. Therefore, polymers with good
liquid electrolytes containing Li salts are in the range of 10−3 to mechanical properties are necessary for applying GPEs into
3940 DOI: 10.1021/acsaem.9b00295
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LIBs.2,11,17,26 However, the polymer electrolyte based on increasing either the charge carrier concentration (n) or the
plasticized linear polymer chains often reveals poor mechanical ionic species mobility in the system.33
properties.19 This phenomenon is a trade-off between ionic Moreover, n generally relies on both the dissociation energy
conductivity and mechanical properties due to the organic (U) and the dielectric constant (ε′) of the host material as
liquids inside of GPEs. To increase the mechanical properties, given below:35,36

ji U zyz
n = no expjjj−
the polymer chains with cross-linkable components could be
z
j ε′kBT zz
incorporated into GPEs.19,26 Furthermore, introducing a three-
k {
phase system consisting of a polymer network and a solution of
(2)
inorganic salts could represent another approach to increasing
the mechanical properties of GPEs.19 To that end, the where kB is the Boltzmann constant and T is the absolute
incorporation of inorganic fillers into GPEs is an effective temperature. In addition, the dielectric constant (ε′) is related
method of enhancing their mechanical strength as well as their to the ratio of the material capacitance (C) to the empty cell
transport and electrochemical properties.2 capacitance (Co) (ε′ = C/Co) and the capacitance is also
2.1.6. Porosity and Electrolyte Uptake. The porosity and related to the amount of stored charge (C = Q/V), where Q is
electrolyte uptake become important parameters in GPEs, the total charge and V is applied voltage, which results in a
especially for LIB applications, and both parameters directly direct connection between the dielectric permittivity and the
influence the other. The porosity is defined as the ratio of the charge carrier, and an increase of dielectric constant could be
void volume to the apparent geometric volume in a polymer interpreted as a fractional increment in the charge concen-
membrane,11 which directly influences the electrolyte uptake tration in the electrolyte.33 According to eq 1, the ionic
ability of organic liquid electrolytes as well as the mechanical conductivity strongly depends on the charge carrier concen-
properties of a GPE.6 With greater membrane porosity, more tration and the ionic mobility. In addition, eq 2 shows that the
electrolytes can be absorbed into the GPE, although the charge carrier concentration could be enhanced by increasing
mechanical properties will be reduced. In addition, electrolyte the dielectric constant of the medium (polymer matrix and/or
uptake is a measurement of the weight ratio of a dry polymer organic liquid in the GPE system). In conclusion, based on eqs
membrane that is completely swollen by absorbing the 1 and 2, the ionic conductivity increases as the dielectric
electrolyte to the weight of the dry polymer membrane.11 As constant of the medium increases. The above explanation
we increase the electrolyte uptake of GPEs, the ionic further supports the phenomenon that GPEs possess higher
conductivity can be significantly enhanced. Therefore, the ion conductivity than SPEs. Since the organic liquids
balance between porosity and electrolyte uptake should be embedded in GPEs are carbonate-based organic solvents
carefully considered while designing GPEs for LIBs. with higher dielectric constant,12 the charge carrier concen-
Therefore, the main criteria must be considered in the tration and ionic conductivity of GPEs can therefore be
design and preparation of GPEs for LIB applications. Since the enhanced.
main function of GPEs is to shuttle ions from/to both The ionic conductivity of GPEs is measured by using an AC
electrodes, the ionic conductivity and transference number are impedance instrument. In this measurement, the GPE
the most fundamentally important properties when bench- membranes are sandwiched between two stainless steel
marking a GPE material. The following section provides a electrodes and measured in a blocking-type cell.11 The ionic
further explanation and discussion of the ionic conductivity conductivity of GPEs can be calculated as follows:
and transference number.
2.2. Ionic Conductivity. High ionic conductivity is one of σ = l /(R bA) (3)
the most crucial requirements of polymer electrolytes,
including both SPEs and GPEs, and it represents the ability where σ is the ionic conductivity (S cm−1), Rb is the bulk
of ionic (Li+) conduction inside a polymeric matrix. In GPEs, resistance (Ω), l is the thickness of GPE membrane (cm), and
the ionic conductivity is strongly related to the degree of A is the effective contact area of the GPEs with the two
crystallinity, porosity, and uptake ability of the polymer electrodes (cm2).11,20,37−42
matrix.11 Furthermore, the organic liquid inside the polymer 2.3. Transference Number (T+). The Li+ transference
matrix also represents the major contribution to higher ionic number is defined as the number of moles of Li transferred by
conductivity for GPEs than SPEs. In addition, the concen- migration inside of the GPEs per Faraday charge.20 In GPEs,
tration of ionic species in organic liquids and polymers is the cation (Li+) and its associated anion are considered mobile
generally related to the dielectric constant of the medium, in the GPEs. However, because only Li+ is involved in the
which governs the shielding of charges from each other and electrochemical redox process and not its anion, the migration
thereby influences the ion pairing.20 In other words, a higher of its anion will therefore trigger a concentration gradient at
dielectric constant of the medium and/or a lower lattice energy the interface between electrodes and electrolytes as the current
of the additive salt corresponds to a higher charge of the carrier passes through the cell.20,43,44 A severe concentration gradient
concentration.33,34 Therefore, the ionic conductivity, σ, is will cause significant concentration polarization in the system
directly proportional to the concentration of charge carrier and ultimately result in a high internal resistance and reduced
species and their mobility as follows:20,33 discharge capacity.11,17,20 In general, if the transference number
of Li+ in the system is equal to 1 (T+ = 1), then concentration
σ= ∑ niqiui (1) polarization would not form.45 Therefore, it is important for
GPEs to have a transference number close to 1 (T+ ≈
where ni is the concentration of the charge carrier species− 1).2,7,17,19,20,24,26
dissolved ions or charged mobile clusters; qi is the ionic charge; Initially, in a simple binary electrolyte system containing
and ui is the mobility of each charge carrier. Equation 1 dissociated salt M+X−, the cation transference number can be
indicates that the ionic conductivity (σ) can be enhanced by given as follows:17,43,44
3941 DOI: 10.1021/acsaem.9b00295
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I M+ represents the common method of determining the Li+

T+ =
I M+ + I X − (4) transference number.11,20 In this method, a polymer electrolyte
was placed between a symmetric Li||Li cell as shown in Figure
where T+ is the cation transference number and IM+ and IX− 4. Subsequently, a small constant potential (∼10 mV) was
represent the currents carried by the cation and the anion, applied to the two electrodes, and the initial current value will
respectively. Equation 4 is based on the assumption that the Li decrease until a steady-state value is achieved.20,46 If there is no
salts will completely dissociate as cation and anion, which are redox reaction with the associated anion, the anion current will
Li+ and its associate anion, respectively. However, in most vanish in the steady-state condition and the total current will
cases, the Li salts do not fully dissociate in the electrolyte be directly related to the cation.43 In this condition, the
system; therefore, a series of equilibria are likely to occur in cationic transference number can be easily obtained by
which associated species are formed:43 dividing the steady-state cationic current to the initial current
just after turning on the polarizing voltage. Moreover, the
M+ + X− F MX passivation layer at the surface of the electrodes caused by
anion transport usually generates an additional contact
M+ + MX F M 2X +
resistance. Therefore, an additional drop in voltage will
X− + MX F MX 2− occur, and it needs to be subtracted from the applied potential
difference. The contact resistance caused by the passivating
In addition, when a DC current is applied to the electrolyte layer at the surface of the electrodes may vary with time.
system, the charge will be transported by the positively and Therefore, the contact resistance has to be measured
negatively charged species. Since these species may be mobile immediately before and after the potentiostatic polarization.43
in the electrolyte system, a concentration gradient will be Based on this consideration, Evans et al. proposed that the
developed within the electrolyte due to the blocked anions transference number for the cation can be given as follows:43
toward the electrodes, and the charge will only be transported
by the mobile positively charged species through the Iss(ΔV − IoR o)
electrolyte. Furthermore, the uncharged species will be T+ =
Io(ΔV − IssR ss) (5)
transported by the concentration gradient and thus contribute
to the charge transport (see Figure 3).44 where Iss is the steady-state current, Io is the initial current, ΔV
According to this phenomenon, Evans, Vincent, and Bruce is the applied potential, Rss is the steady-state resistance, and Ro
established a method for determining the Li+ transference is the initial resistance.
number based on potentiostatic polarization,43,44,46 which now 2.4. Ionic Transport Mechanism. The ionic transport
mechanism in a polymer electrolyte is a very complicated
phenomenon that depends on various factors, such as cation
size, dielectric constant of polymer host, ion pairing,
amorphous phase character, and the mobility of charge carriers
(both anion and cation). However, the concept of the Li-ion
transport mechanism is still unclear, and additional inves-
tigations are required to propose a reliable mechanism of ion
migration inside the polymer electrolyte. Basically, polymer
electrolytes are formed by dissolving the low lattice energy of
Li salts in the polar polymer matrix, in which the cation (Li+) is
responsible for ionic conductivity.33 Consequently, the
effective number of mobile ions is strongly related to the
degree of dissociation of the salts inside of the polymeric
matrix. Consistent with the theoretical ionic transport in high
molar mass polymer electrolytes, the ion (cation) can
dissociate between neighboring coordinating sites, whether it
is situated on the host molecules or nearby molecules.33,47
Therefore, the cation (Li+) could be assumed to form an
unstable bond with polar groups in the polymer host and could
be transported via segmental motion inside the polymer
matrix2,17,33 as shown in Figure 5. Nevertheless, another new
concept of ion transport (Li+) has been recently proposed by
Bruce et al.,48 who suggested that the crystalline phase of
P(EO)6-LiX (X = PF6, AsF6, and SbF6) pairs within PEO
chains is folded with cylindrical tunnels. In this mechanism, the
Li+ ion is located and coordinated inside of the channel, while
the associated anion is located outside of the channel, which
means that the Li+ ion could be transported from one side to
another through the channel without the help of segmental
Figure 3. Transport of the ionic species through the electrolyte and motion of the host polymer (Figure 6).48
the concentration profile at equilibrium and under non-steady-state In general, a polymer host inside a polymer electrolyte is
and steady-state conditions. Reproduced with permission from ref 44. both amorphous and crystalline, and ionic transport principally
Copyright 2014 The Electrochemical Society. occurs in amorphous regions above their glass transition
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Figure 4. Schematic symmetric Li||Li test cell.

Figure 5. Schematic of segmental motion that assists the diffusion of Li inside the PEO matrix. Reprinted with permission from ref 13. Copyright
1998 John Wiley and Sons.

2.4.1. Arrhenius Behavior for Ion Transport. The famous

Arrhenius model can explain the relationship between ionic
conductivity and temperature. In the polymer electrolyte, the
ion transport behavior based on Arrhenius behavior generally
related to the ion hopping mechanism is decoupled from long-
chain motion of the polymer host at amorphous and crystalline
states with the temperature below its Tg.49 The Arrhenius
behavior of ionic conductivity in polymer electrolytes can

ÅÄÅ ÑÉ
usually be expressed as follows:2,11,33,49

Å −E ÑÑ
σ = σo expÅÅÅÅ a ÑÑÑÑ
ÅÅÇ kBT ÑÑÖ (6)

where σo is the pre-exponential factor which is related to the

charge carrier, Ea is the activation energy, and kB is the
Figure 6. Crystalline structure of P(EO)6−LiAsF6 polymer electro-
lyte. Left: View of the structure along the chain axis showing rows of
Boltzmann constant. Furthermore, the energy activation can be
lithium ions perpendicular to the page. Right: View of the structure easily calculated from the best linear fit of the log σ vs 1/T
showing the relative positions of the chains and their conformations (K −1 ). 2,11,49 When the data of the temperature and
(hydrogens are not shown). Blue spheres represent lithium; white conductivity are consistent with the Arrhenius relationship (a
spheres represent arsenic; pink spheres represent fluorine; light green linear plot of log σ vs 1/T), then the cationic transport can be
represents carbon in chain 1; dark green represents oxygen in chain 1; associated with the hopping mechanism, in which the ion
light red represents carbon in chain 2; and dark red represents oxygen jumps to the closest empty vacant sites to form a new
in chain 2. Thin lines indicate coordination around the Li+ cations. coordination inside of the polymer matrix, thus promoting
Reprinted with permission from ref 48. Copyright 2001 Springer
ionic conductivity inside of the polymer electrolyte.33,50 Taking
Nature Publications.
one of the recently studied GPEs as an example, Gong et al.51
prepared a new type of GPE based on an environmentally
temperature.2,17,33 In other words, the ion transport in the friendly material (natural lignin) with typical Arrhenius
polymer electrolytes is strongly temperature dependent. behavior observed as a linear curve (Figure 7). The results
According to the temperature-dependent conductivity, the indicate that the ionic transport mechanism is based on a
ion transport mechanism can be explained by the Vogel− hopping mechanism decoupled from the motion of the host
Tammann−Fulcher (VTF) and Arrhenius behavior.2,11,33,49 material.51
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transport in the polymer electrolyte, the phase transition of the

polymer host should be taken into account.
2.4.2. Vogel−Tammann−Fulcher Behavior for Ion Trans-
port. The VTF theory was proposed in the 20th century to
elucidate the diffusion process in glassy disordered materi-
als2,17,52 and to explain the effect of unusual Arrhenius
behavior on ionic transport behavior related to the phase
transition. The VTF definition of ionic conductivity was
developed for pure polymeric systems and is usually in
agreement with the free volume theory, in which the polymer
dynamic is related to the temperature and amount of free space
available for macromolecule motion.20 In addition, based on
this theory the ionic transport mechanism in the polymer
electrolyte was caused by ion hopping motion coupled with
long-range segmental motion of the polymer host and/or
Figure 7. Arrhenius plots of the ionic conductivity of GPEs based on
natural lignin. Reprinted with permission from ref 51. Copyright 2016
solvent molecules.49 The segmental motion of the polymer
Elsevier. host inside the polymer electrolyte could promote ionic
movement by formatting and destructing the coordination of
the solvated ion, thereby creating free volume and allowing the
ion to diffuse inside of the polymeric matrix.17 Furthermore,
In most cases, the polar polymer used to prepare polymer the VTF behavior is usually expressed as fol-

ÅÄÅ É
electrolytes is a semicrystalline polymer that contains both lows:2,11,17,20,33,53,54

Å ÑÑÑ
σ = AT −1/2 expÅÅÅÅ− ÑÑ
amorphous and crystalline phases. For instance, the most

Ñ
ÅÅÇ (T − To) ÑÑÑÖ
popular polar polyether PEO has a melting temperature (Tm) B
of approximately 68 °C, while Tg is −67 °C, which means that
PEO is a mixture of its amorphous and crystalline phases at (7)
room temperature. The presence of the crystalline phase (high
where σ is the ionic conductivity, A is the pre-exponential
crystallinity) could prohibit segmental motion of the PEO, and
factor which is associated with the number of charge carriers, B
this phase will be reduced when the temperature is close to Tm,
is the pseudoactivation energy for the conductivity, and To is a
in which segmental motion would be expected.33 As shown in
reference temperature related to Tg (or an “equilibrium glass
Figure 8, the ionic conductivity increases significantly when the
transition temperature”, with To ≈ Tg − (50 K)). The
temperature is close to Tm, which indicates that there are many
pseudoactivation energy could be calculated from the best
significant contributions of the phase transition to the ionic
fitting of the linear plot σ vs 1/T.11 Moreover, if the plot σ vs
conductivity and ionic transport mechanism inside the polymer
1/T in the polymer electrolyte is a typical nonlinear plot, then
electrolyte. Therefore, to elucidate the true mechanism of ion
the conductivity mechanism based on the ionic hopping
motion is coupled with the segmental motion of polymeric
chains and/or solvent molecules.2,33,49 The movement of the
polymeric matrix is generally sufficient for promoting ionic
conductivity at the Tg, and the mobility of the polymeric matrix
will become very restricted to provide new favorable
coordination environments for ion to move inside the polymer
electrolyte at To.20 As shown in Figure 8, the ionic conductivity
typically increases when the temperature is above the Tg and is
2 orders of magnitude higher than that below the Tg, which
indicates that the ion mobility is limited by the presence of the
crystalline region within the polymer host.55 At high
temperatures, the energy would be large enough to overcome
the barriers created between sites, thereby enhancing the free
volume in the system so that the polymer chain will gain
internal modes faster with segmental motion initiated by bond
rotation.33 Therefore, the ions will be easily transported
according to the hopping mechanism. In addition, this theory
also points out that the presence of a plasticizer or residual
solvent could enhance the free volume and promote free space
for the ion and polymer host to move, thereby increasing the
ion conductivity.56,57 This finding is consistent with GPEs
having higher ionic conductivities due to more free space for
ions and polymers to perform segmental motion, which is
provided by the organic solvent inside the polymeric matrix.
Figure 8. Temperature dependence of dc conductivity of (a) pure Furthermore, it can also explain why a higher concentration of
PEO, (b) PEO + NaClO3 (90:10), (c) PEO + NaClO3 (80:20), and salts results in decreased ionic conductivity even with an
(d) PEO + NaClO3 (70:30). Reprinted with permission from ref 33. increase in the charge carrier concentration inside the polymer
Copyright 2018 Elsevier. electrolyte, which is attributed to the induced physical cross-
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Scheme 2. Structures of the (a) Tris(cyanoethoxymethyl) Group (MCA) Poly(ethylene glycol) Dimetharylate (PGM400),a
(b) 2,3-Dimethyl-1-hexyl Imidazolium Bis(trifluoromethanesulfonyl) Imide (DMHxImTFSI),b (c) Phytic Acid (PA),c and (d)
GPEs Prepared by Initiator-Free Photopolymerization of Poly(ethylene glycol) Dimethacrylate (Acrylate Monomer) and
Pentaerythritol Tetrakis(3-mercaptopropionate) (Thiol Monomer);d (e) Synthesis Strategy of GPEs Based on PEO Star
Polymers via Atom Transfer Radical Polymerization (ATRP)e

a
Reproduced with permission from ref 59. Copyright 2016 Elsevier. bReproduced with permission from ref 60. Copyright 2012 Elsevier.
c
Reproduced with permission from ref 66. Copyright 2016 Elsevier. dReproduced with permission from ref 67. Copyright 2012 Elsevier.
e
Reproduced with permission from ref 68. Copyright 2015 Elsevier.

Scheme 3. Synthetic Routes of (a) Side-Chain Grafting Polyether with Single Ion Conductor,a (b) Thermal Cross-Linking of
Entrapped Polyether in Poly(ethylene glycol) Methyl Ether Acrylate (PEGMEA) and Poly(ethylene glycol) Diacrylate
(PEGDA),b (c) Polysiloxane-Grafted Polyether-Based GPE,c and (d) Polysiloxane/Polyether-Based Hybrid GPEs after
Activating with Salt Solutionds

a
Reproduced with permission from ref 69. Copyright 2016 Elsevier. bReproduced with permission from ref 70. Copyright 2011 Elsevier.
c
Reproduced with permission from ref 71. Copyright 2017 Elsevier. dReproduced with permission from ref 72. Copyright 2016 Elsevier.

3945 DOI: 10.1021/acsaem.9b00295

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Scheme 4. Synthetic Routes of (a) Lithiated Poly(arylene ether) and Lithiated Polyamide-Based Polymer Electrolytes,
Lithiated Poly[bis(4-hydroxybenzene) ether-alt-bis(4-fluorine benzene sulfonyl)imide ether] (LiPHFE), Lithiated Poly[bis(4-
aminobenzene) ether-alt-bis(4-carboxylbenzenesulfonyl)imide amide] (LiPACA);a (b) Bis(4-hydroxylbenzenesulfonyl)imide
and Poly(arylene ether) Copolymers, Bis(4-hydroxylbenzenesulfonyl)imide (HBSI), Lithiated
Poly[bis(benzenesulfonyl)imide ether] (LiPBIE), and Lithiated Poly[bis(4-fluorine benzenesulfonyl)imide-alt-2,2-bis(4
hydroxyphenyl)propane] (LiPAFEb); and (c) 1,4-Bis(4-hydroxyphenyl)-2,5-bis(methoxypoly(ethylene oxide))benzence

a
Reproduced with permission from ref 73. Copyright 2017 Elsevier. bReproduced with permission from ref 74. Copyright 2017 Elsevier.
c
Reproduced with permission from ref 75. Copyright 2014 Elsevier.

linking between polymer chains in the system and enhanced Nakano et al.59 prepared a polyether GPE based on 2a through
activation energy of the main-chain bond rotation caused by photoinitiated radical polymerization using 2-benzoyl-2-prop-
the high charge carrier, thus reducing the polymer mobility and anol as an initiator. Furthermore, lithium bis-
increasing the Tg.20 (trifluoromethylsulfonyl)amide (LiTFSA) was used as a Li
salt, while propylene carbonate (PC) was used as the
3. TYPICAL POLYMERS FOR GPES plasticizer. The resultant GPE shows an ionic conductivity of
3.1. Polyether. Polyether is one of the most common 3.8 × 10−4 S cm−1 at nearly room temperature (293 K) and 40
polymers in the application of polymer electrolytes for LIBs. mol % LiTFSA relative to the molar amount of PC. Another
Among polyethers, PEO represents the earliest polymer study from Sekhon et al.60 used an ionic liquid 2b, PEO, and
electrolyte system since it was discovered in 1973 by Wright.13 PC to prepare GPEs. The resulting GPE exhibited ionic
Typically, the Li ion exhibits coordination bonding with conductivity on the order of 10−3 S cm−1 at room temperature
oxygen atoms on the PEO backbone, and ionic transfer could as shown in Figure 9h. In this GPE, the lower viscosity, higher
be performed by segmental motion as shown in Figure 5. dielectric constant, and the plasticizing nature of the ionic
Although the polymer electrolytes based on PEO present a low liquid 2b likely resulted in increased ionic conductivity of the
ionic conductivity of approximately 10−8 to 10−4 S cm−1,26,58 resulting GPE, while the role of PEO as a stiffener resulted in a
the main reasons for using PEO as a polymer electrolyte are small increase in ionic conductivity.60 Another ionic liquid, 1-
related to its lower Tg (∼60 °C) and good complexing ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide
characteristics for Li ions.20 The structural designs of (EMIMTFSI), has also been added in the mixed system of
polyethers for GPEs are presented through Schemes 2−5. polymers and Li salts to enhance LIB performance. Balo et al.61
Generally, traditional GPEs are obtained by dissolving Li salts reported that, by the addition of ionic liquid EMIMTFSI into
in gel polymers, which represents a typical strategy to GPE together with lithium bis(trifluoromethylsulfonyl)imide
incorporate new types of Li salts and ionic liquid into GPEs. (LiTFSI), the electrochemical properties of the resulting GPE
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Scheme 5. Synthetic Routes of (a) PEO-Based Copolymers I (PPy(x)PEO(y)coPSF) and II (PPy(x)PEO(y)coDF) by

Copolymerization with Different Arylfluorides and (b) PEO-Based Terpolymers I (PPy(x)PEOPh(y)TM(z)terPSF) and II
(PPy(x)PEOPh(y)BPy(z)terPSF) by Modification of Dihydroxyl-Based Terpolymersa

a
Reproduced with permission from ref 75. Copyright 2014 Elsevier.

were enhanced and showed an increased ionic conductivity up performance of GPEs, the salt concentration gradients
to ∼2.08 × 10−4 S cm−1 at 30 °C, a high lithium transference generated on this system lead to a poor performance, including
number (TLi+ = 0.39), and a high electrochemical stability high internal impedances, voltage losses, and undesirable
window (∼4.6 V). Another study also showed that reactions in the electrolyte state, such as phase transitions or
incorporating both the ionic liquid and Li salts could increase salt precipitation.10
the ionic conductivity, thermal stability, and potential Another approach to improving the electrochemical
window.62 Furthermore, ion−polymer interactions may occur performance of GPEs is reducing the internal impedance and
in response to the complexation of cation in Li salts and ionic voltage loss by forming heterogeneous GPEs. In general,
liquid with oxygen atoms.62 Although the simple mixing of Li heterogeneous GPEs consist of more than one phase, which
salts and/or ionic liquid already shows the reasonable can be a hybrid system of polymer-embedded liquid electro-
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Figure 9. Surface morphology images of MPEs with various mass fractions of star polymers 2e (a, 0 wt %; b, 10 wt %; c, 20 wt %; d, 30 wt %; e, 40
wt %). (f) Cross-section image of MPEs with 30 wt % star polymer 2e. Reprinted with permission from ref 68. Copyright 2015 Elsevier. (g)
Discharge capacity of the LiFePO4 cathode at 1 C under room temperature for 1000 cycles assembled using a dense transparent single ion
conductor 3a blended PVDF-HFP. Reprinted with permission from ref 69. Copyright 2016 Elsevier. (h) Variation of conductivity with temperature
for ion gel (2b + 2 wt % PEO). Reprinted with permission from ref 60. Copyright 2012 Elsevier. (i) Rate capability of full cell under room
temperature assembled with 4a LiPHFE GPEs. Reprinted with permission from ref 73. Copyright 2017 Elsevier.

lytes or a three-phase system consisting of a liquid solvent, a that by mixing PVDF/PEO with the weight ratio of 1:5, the
gel swollen by solvents, and a polymer matrix. The preparation maximum ionic conductivity of 4.8 × 10−3 S cm−1 could be
of heterogeneous GPEs mostly leads to two consequences: the achieved with electrochemical stability up to 4.8 V vs Li/Li+ at
formation of a porous polymer membrane and its activation by room temperature. Moreover, GPEs based on blending of
liquid electrolyte uptake.2 Li et al.63 prepared a nanofibrous three polymers, PVDF-HFP (copolymerization of vinylidene
GPE based on PEO and PVDF by electrospinning and fluoride (VDF) and hexafluoropropylene (HFP)), PEO, and
activated by dipping in 1 M lithium hexafluorophosphate PMMA, have been fabricated and activated by the absorption
(LiPF6) in EC/PC/DMC (1:1:1, v/v/v). The results showed of 1 M LiPF6 in EC/DMC (1:1, v/v).64 The resulting GPE
3948 DOI: 10.1021/acsaem.9b00295
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exhibited ionic conductivity ∼8.1 × 10−4 S cm−1 and a high Furthermore, side-chain grafting and copolymerization have
electrochemical window up to 5.0 V vs Li/Li+ at room also received considerable attention for their ability to enhance
temperature. The blending of PEO-PMMA-PVDF-HFP is the performance of GPEs (Scheme 3). Pan et al.69 prepared
responsible for the formation of the amorphous structure in the single ion conductor GPE poly(ethylene-alt-maleic
the polymer matrix and porous morphology with a higher pore anhydride) (3a) via grafting of 50% 4-amino-4′-trifluoromethyl
ratio and dimension, which can accommodate much more bis(benzenesulfonyl)imide as side chains. Compound 3a was
liquid electrolyte with a more stable liquid holding capability further blended with PVDF-HFP to form a dense and
than the pristine PVDF-HFP polymer membrane and thus transparent single ion conductor GPE with an ionic
could provide more Li+-ion transport.64 conductivity up to 1.04 × 10−4 S cm−1 at room temperature,
Furthermore, additional fillers in the composite membrane a Li+ transference number of 0.92, and a stable LiFePO4
have been reported to influence the performance of polyether- discharge capacity of 100 mAh g−1 at 1 C under room
based GPEs. Liao et al.65 reported that by doping 10 wt % temperature after 1000 cycles (Figure 9g).69 The side-chain-
nano-Al 2O 3 (inorganic filler) in PEO-PVDF-HFP, the grafted comb-like single ion conducting polymer electrolyte
mechanical strength increased from 9.3 to 14.3 MPa, the was found to be largely responsible for the excellent
porosity of the membrane increased from 42% to 49%, the electrochemical performance. The single ion conducting
electrolyte uptake increased from 176% to 273%, and the ionic polymer represents an approach to avoiding concentration
conductivity of the corresponding GPE was improved by up to polarization, which leads to poor performance of GPEs by
3.8 × 10−3 S cm−1. The increased ionic conductivity could be holding an anion to become a steady phase so that the anion
associated with the ability of certain inorganic fillers to operate free movement could be limited or totally eliminated.10
as Lewis acids to compete with Li+ ions and prevent their Different strategies were applied in 3b−3d in which the
reaction with the polymer, thereby avoiding ion coupling, polyether, especially PEO, is used as side-chain “arms” to
promoting the dissociation of the salt, and increasing the promote coordination with Li+, while the backbone polymer is
number of free carriers.10 In addition, the study suggested that used to maintain the mechanical properties of the resulting
enhanced mechanical properties can be ascribed to the GPEs. Li et al.70 fabricated 3b through thermal cross-linking
function of nano-Al2O3 as a temporary mechanical connection with different weight percents of polyether. After activation by
point, which helps to form the net structure and connects 1 M LiPF6 in EC/DMC/ethyl methyl carbonate (EMC) with a
firmly with the PEO and PVDF-HFP polymer in the blending 1:1:1 by weight ratio, the corresponding GPE exhibits an ionic
system.65 Other organic fillers, such as 2c, can act as a cross- conductivity of 1.1 × 10−3 S cm−1. Boaretto et al.71,72 studied
linker to plasticize porous GPE membranes and changing them the polysiloxane/polyether-based GPE 3c and GPE 3d, and
into soft but tough and flexible materials based on PEO- they showed the maximum ionic conductivity of 8 × 10−5 S
PMMA-LiClO4 composite GPEs, which result in a good cm−1 at 30 °C, a stable electrochemical window reaching 4.5−
electrochemical window (>5 V) and a low interfacial 5 V at room temperature, and good thermomechanical
resistance.66 behavior up to 100 °C. This study found that extending the
Recently, a novel structural design of heterogeneous GPEs length of the mobile polyether chains could increase the ionic
based on polyether has been applied to improve the conductivity, although the degree of networking is therefore
electrochemical performance via the cooperation with other increased. In addition, the decreased polyether ratio in the
monomers. Ryou et al.67 fabricated a GPE 2d by initiator-free polymer network leads to the enhancement of Tg, which can
photopolymerization of a poly(ethylene glycol) dimethacrylate reduce the ionic conductivity.72 An improvement has been
(acrylate monomer) and pentaerythritol tetrakis(3-mercapto- made by synthesizing 3c through a sol−gel synthesis and
propionate) (thiol monomer) blend. The resulting GPE subsequent radical polymerization by incorporating the
exhibits an ionic conductivity of 1.1 × 10−3 S cm−1 at 25 °C inorganic filler TiO2. The resulting GPE exhibited a storage
with 50 wt % thiol content and a stable electrochemical shear modulus of 50 kPa at 100 °C and an ionic conductivity
window up to 4.4 V vs Li/Li+ after activation by dipping in 1 of 1.5 × 10−4 S cm−1 at room temperature.71 The enhanced
M LiPF6 in EC/diethyl carbonate (DEC)/(PC) by 30:65:5 ionic conductivity could be attributed to the plasticizing effect
weight ratio. Another GPE based on a PEO star-shaped of TiO2, which decreases the Tg and allows for free space for
polymer 2e blended with PVDF to form a microporous polyether arm mobility to coordinate the Li+. The results also
polymer electrolyte (MPE) was reported by Deng et al.,68 and showed that the poor particle distribution could play a critical
the GPE exhibited an ionic conductivity of 3.3 × 10−3 S cm−1 role in hindering the charge migration process.71
at room temperature and its electrochemical stability window Another strategical structural design for alternating the
was above 5.0 V vs Li/Li+ after activation by dipping into 1 M copolymerization of aromatic polyether as the polymer
LiClO4 in EC/PC (1:1, v/v). A series of PEO star-shaped backbone is presented in Schemes 4 and 5. This strategy is
polymers have been synthesized by atom transfer radical proposed to enhance the mechanical properties while
polymerization (ATRP) using PEO-Br as the macroinitiator maintaining the ability of polyether to form complexation
and divinylbenzene (DVB) as the core template to place PEO with Li+ and thus promotes the charge transfer. Chen et al.73
arms. The SEM images in Figure 9a−f show that the synthesized a single ion conductor GPE based on 4a by using
morphology of the resulting GPE has a microporous structure, lithiated poly(arylene ether) and lithiated polyamide. The
where the distribution of pores on the surface becomes denser resulting GPE shows that the poly(arylene ether)-based single
with a higher content of star polymer due to the interaction of ion conductor LiPHFE has a higher ionic conductivity than
hydrophilic segments of star-shaped PEO. In this case, star- that of polyamide-based LiPACA.73 This phenomenon is
shaped PEO could help the formation of pores and thereby mainly due to the morphological and electrochemical differ-
promote electrolyte uptake, which results in a higher ionic ences between the two copolymers. LiPACA with a large pore
conductivity of up to 3.3 × 10−3 S cm−1 at room size effectively reduces the contact area between GPE film and
temperature.68 the electrode, while LiPHFE generates a uniform film due to a
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higher content of flexible poly(arylene ether). Furthermore, polymer matrix.26,58 The first investigation of GPEs based on
the ether segments in poly(arylene ether) may effectively PVDF was reported by Watanabe et al. in 1981, in which a
facilitate ion conduction via a strong electrostatic interaction homogeneous hybrid film of PVDF can be obtained with a Li
with Li ions in the polymer matrix of LiPHFE.73 A good rate salt, EC, and/or PC in the proper proportions.76 To date, the
capability of LiFePO4 full cell batteries is shown in Figure 9i, simple preparation of GPEs by dissolving Li salts into gel
suggesting the excellent performance of single ion conductor polymer is still used due to its simplicity and suitability for roll-
LiPHFE. In addition, bis(4-hydroxybenzene sulfonyl)imide to-roll mass fabrication. Fasciani et al.77 also prepared PVDF-
and bisphenol A were chosen by Chen et al. to copolymerize based GPEs by simply dissolving PVDF in EC:DMC (1:1, v/v)
with bis(4-fluorine benzenesulfonyl)imide separately and form under ambient air conditions to obtain a 20:80 mixed solution.
poly(arylene ether)-based copolymers as shown in 4b.74 The corresponding GPE exhibited good ionic conductivity of
Furthermore, a microporous single ion conducting GPE was 0.5 × 10−3 S cm−1 at 30 °C and 1.2 × 10−3 S cm−1 at 60 °C. In
formed by taking advantage of the phase separation between addition, a low molecular weight organogellator, 1,3:2,4-di-O-
rigid aromatic ionomers 4b and aliphatic polymer PVDF-HFP. methylbenzylidene-D-sorbitol (MDBS), has been added to
The distinct electrochemical performance of the resulting GPE prepare 6a to avoid liquid leakage and enhance liquid uptake
was again determined by the morphological differences into GPEs.78 The resulting GPE showed that the addition of
between the two GPEs, LiPBIE and LiPAFE. The results organogellator could dramatically decrease the liquid leakage
showed that an interconnected micropore was formed in the and increase the ionic conductivity up to 1.12 × 10−3 S cm−1 at
polymer matrix when LiPBIE was mixed with aliphatic PVDF- 20 °C, with a stable electrochemical window of 4.7 V vs Li/
HFP, and it is beneficial to solvent uptake via capillary Li+.78 Furthermore, an inorganic filler, such as Al2O3,79 and
condensation, which facilitates ion solvation and reduces the carbon material graphene,40 are reported to effectively improve
threshold temperature of segment motion of the poly(arylene the ionic conductivity by avoiding ion coupling, thereby
ether) chains with a higher ionic conductivity at room promoting the dissociation of the salt and increasing the
temperature by up to 5.2 × 10−4 S cm−1 compared to LiPAFE number of free carriers. Interesting results have been obtained
(9.1 × 10−5 S cm−1).74 by incorporating inorganic filler Al2O3/BN-nanoparticles and
In addition, Voge et al.75 studied series of poly(arylene macroparticles, in which the ionic conductivity declined
ether) copolymers 4c and 5a with different PEO length and because of the pristine PVDF GPEs after activation by 1 M
content and terpolymers 5b that contain a pyridine group LiPF6 with ionic liquid solvents mixture of 1-ethyl-3-
through systemic copolymerization reactions. The pyridine methylimidazolium triluoromethanesufonate (EMI-TF)/EC/
group and PEO side chain on 4c are expected to promote ionic PC with ratio 2:1:1 (v/v/v).79 The decreased ionic
conductivity while the aromatic backbone is used to maintain conductivity could be attributed to the reduced volume
the mechanical properties. Compound 4c copolymers with fraction of the electrolyte mixture in the PVDF matrix
various PEO lengths were synthesized using the aromatic resulting from the loading of micro-/nanoparticles, which
polycondensation reaction of aromatic di- and polyfluorides leads to higher internal resistance.79 In contrast, the ionic
with diols bearing PEO side chains (Mw, 350,750) or by conductivity of PVDF-based GPEs could be enhanced from
modifying the dihydroxy-functionalized precursor with poly- 1.85 × 10−3 S cm−1 (pristine PVDF) to 3.61 × 10−3 S cm−1
(ethylene oxide) methyl ether tosylate (PEO Mw, 350,750 and with a stable electrochemical stability window up to 4.7 V for
2,000). The results also showed that the Tg can be tuned by LiCoO2/Li cells by incorporating 0.002 wt % graphene.40 The
varying the PEO content, while the thermal stability can be addition of graphene to the GPE not only increases the ionic
affected by the PEO length, with a shorter PEO side chain conductivity by reducing the PVDF crystallinity and enhancing
corresponding to higher thermal stability. After doping in 1 M the porosity so that the electrolyte uptake could be increased
LiPF6 in EC/DMC with a 1:1 volume ratio, the 5b terpolymer up to nearly three times higher but also markedly enhances the
I with a higher PEO side chain (Mw, 750) exhibited ionic rate capability and the cycling performance due to its high
conductivity as high as 5.5 × 10−4 S cm−1 at room temperature, conductivity.40
and it further increased to 2.4 × 10−3 S cm−1 at 80 °C. The The formation of composite membranes is the second most
improved lithium-ion mobility could be attributed to the popular strategy in the development of polyvinyl-based GPEs,
longer PEO side chains (Mw, 750) and higher PEO content especially for PVDF-based GPEs. As shown in Table 1, several
absorption as well as higher charge carrier concentration of polymers have been mixed with PVDF to enhance the
PEO. However, the 5b terpolymer II faced an instability issue electrochemical properties, and they include poly-
in liquid electrolyte because of the interaction of the polar (dimethylsiloxane) (PDMS),80 polyethylene (PE),81 PEO,82
pyridine side group and liquid electrolyte, which caused an polystyrene (PSt),83 and cellulose.81,84 Furthermore, Prasanth
extreme swelling phenomenon.75 et al.85 prepared a hybrid inorganic−organic GPE by mixing
3.2. Polyvinyl. Similar strategies, such as mixing with ionic PVDF with nanoclay in different ratios. After activation by
liquid, composite formation, side-chain grafting, and copoly- immersing the hybrid GPE into 1 M LiPF6 in EC/DEC (1:1,
merization, have also been applied in polyvinyl, which is the w/w), the ionic conductivity enhanced to 3.08 × 10−3 S cm−1
second most popular GPE for LIBs. A summary of recent at room temperature with 2 wt % nanoclay. The enhanced
GPEs based on polyvinyl is presented in Table 1. Among the ionic conductivity is due to the decreased crystallinity of
polyvinyl GPEs, PVDF is the most common for LIBs due to its composite membrane and higher porosity so that the liquid
favorable properties. PVDF-based GPEs are expected to be electrolytes are well-swollen inside the polymer matrix with
highly anodically stable due to the strongly electron-with- higher electrolyte uptake.85 Another interesting design of GPEs
drawing functional group (F−C−F). Furthermore, due to the based on a PVDF/hydroxyethyl cellulose (HEC)/PVDF
higher dielectric constant as a polymer (ε = 8.4), PVDF can sandwiched structure has been investigated by Zhang et al.84
produce greater ionization of Li salts, thereby providing a high The GPEs exhibited ionic conductivity up to 0.88 × 10−3 S
concentration of charge carriers by dissolution Li+ inside of the cm−1 and Li+ T+ of 0.57 at room temperature after activation
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 Table 1. Summary of GPEs Based on Polyvinyl Polymersa
Li+
ionic conductivity transference porosity electrolyte
strategy polymer liquid electrolyte preparation (S cm−1) no. (%) uptake (wt %) ref.
polyvinyl composite PVDF 1 M LiPF6 in EC/DMC (1:1, v/v) direct blending 0.5 × 10−3 at 0.24 80 77
25 °C
PVDF + MDBS 1 M LiClO4 in PC/EC (1:1, v/v) phase inversion 1.12 × 10−3 at 78 190 78
20 °C
PVDF + Al2O3 + BN ceramic 1 M LiPF6 in EMI-TF/EC/PC (2:1:1, v/v) direct blending 4.1 × 10−3 79
nano-/microparticle
PVDF + graphene 1 M LiPF6 in EC/DMC/EMC (1:1:1, v/v/v) non-solvent-induced 3.61 × 10−3 0.59 88 470 40
phase separation
ACS Applied Energy Materials

PVDF + PDMS 1 M LiPF6 in EC/DMC/EMC (1:1:1, v/v) direct blending 1.17 × 10− at 55 250 80
25 °C
PVDF + LiPAAOB 1 M LiPF6 in EC/DMC/EMC (1:1:1, v/v) electrospinning 0.35 × 10−3 at 0.58 91.8 86
25 °C
PVDF + nanoclay 1 M LiPF6 in EC/DEC (1:1, w/w) phase inversion 3.08 × 10−3 at 75 263 85
30 °C
nonwoven + PVDF 1 M LiPF6 in EC/DMC/EMC (1:1:1, v/v/v) casting 0.3 × 10−3 at 0.43 83.2 102
25 °C
PVDF + CAB 1 M LiPF6 in EC/EMC (2:3, w/w) blending 2.48 × 10−3 40 152 81
PVDF + PLS 1 M LiPF6 in EC/PC/DMC (1:1:1, v/v/v) thermal phase separation 4.49 × 10−3 0.489 44.36 175.72 87
PVDF + PEO 1 M LiTFSI in EC/DEC (1:1, v/v) electrospinning 4.9 × 10−3 at 85 750 82
25 °C
PVDF + HEC + PVDF 1 M LiPF6 in EC/DMC/EMC (1:1:1, v/v/v) electrospinning 0.88 × 10−3 at 0.57 135.4 84
25 °C

3951
PVDF/P(VC-Vac) 1 M LiPF6 in EC/DMC/EMC (1:1:1, v/v/v) phase inversion 3.57 × 10−3 79.58 285 103
PVDF + graft (SPS/PEO) 1 M in LiClO4 in EC/PC (1:1, v/v) phase inversion 3.05 × 10−3 at 82.3 326 83
25 °C
polyvinyl side-chain LiPVAOB PC physical cross-link 6.11 × 10−6 at 28.1 27
grafting 25 °C
polyvinyl PVDF-HFP + mesoporous SiO2 ether-functionalized pyrrolidinium-imide ionic casting 0.25 × 10−3 at 0.27 88
copolymer liquid (PYRA12O1TFSI) 25 °C
PVDF-HFP MPPyrr-TFSA direct blending 1.91 × 10−3 at 89
20 °C
PVDF-HFP + phenolic epoxy resin-based 1 M LiPF6 in EC/DEC (1:1, v/v) direct blending 2.0 × 10−3 at 13 90
oligomeric ionic liquid 20 °C
PVDF-HFP + 6 wt % nano-SiO2 1 M LiTFSI/PMImTFSI electrospinning 1.1 × 10−3 at 0.064 91
20 °C
PVDF-HFP/Pyr13TFSI-LiTFSI 0.5 M LiTFSI in Pyr13TFSI intense shear-driven 0.51 × 10−3 at ∼70 92
aggregation 25 °C
PVDF-HFP + LiTFSI + EMIMFSI 20 wt % LiTFSI, 40 wt % EMIMFSI direct blending 3.81 × 10−4 at 0.39 93
25 °C
PVDF-HFP + SiO2PPTFSI 1 M LiPF6 and 1 M LiDFOB in DMC/EC/FEC electrospinning 0.64 × 10−3 at 0.6 83 552 94
(6:2:2, w/w/w) 25 °C
PVDF-HFP + SiO2(Li+) 1.15 M LiPF6 in EC/DEC (3:7, v/v) radical copolymerization ∼10−3 0.48 ∼180 96
PVDF-HFP + SiO2(Li+) 1.15 M LiPF6 in EC/DEC (3:7, v/v) radical copolymerization 1.4 × 10−3 at 0.35 ∼180 97
25 °C
PVDF-HFP + nano-Al2O3 1 M LiPF6 in EC/DMC (1:1, v/v) electrospinning 4.1 × 10−3 at ∼600 95
20 °C
Review

ACS Appl. Energy Mater. 2019, 2, 3937−3971

DOI: 10.1021/acsaem.9b00295
ACS Applied Energy Materials Review

by 1 M LiPF6 solution in EC/DMC/EMC (1:1:1, w/w/w).

LiDFOB, lithium difluoro(oxalato)borate; FEC, fluoroethylene carbonate; LiPAAOB, lithium poly(acrylic acid) oxalate borate; LiPSIPA, lithium poly(bis(phenylsulfonyl imide isophthalate amide
diphenylsulfoneamide)); LiPVAOB, lithium poly(vinyl alcohol) oxalate borate; MA-PVDF, maleic anhydride-grafted-poly(vinylidene fluoride); MDBS, 1,3:2,4-di-O-methylbenzylidene-D-sorbitol;
MPPyrr-TFSA, 1-methyl-1-propylpyrrolidinium bis(trifluoromethylsulfonyl) azanide; PDMS, poly(dimethylsiloxane); PLS, polyurethane lithium salt; PMImTFSI, 1-propyl-3-methylimidazolium
bis(trifluoromethysulfonyl)imide; (P(MVE-MA)), poly(methyl vinyl ether-alt-maleic anhydride); P(VC-VAc), poly(vinyl chloride-co-vinyl acetate); Pyr13TFSI, N-propyl-N-methylpyrrolidinium
Abbreviations: CAB, cellulose acetate butyrate; EMIMFSI, 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide; fa-SIPE, fully aromatic single-ion conducting polymer; HEC, hydroxyethyl cellulose;
100

101

104

105
ref.
98

99
The higher Li+ transference is associated with the special
structural design of sandwiched GPE (Scheme 6b). Moreover,
uptake (wt %)
the polarity of the PVDF matrix contributes to the improve-
electrolyte

ment of the Li+-ion transference number since H atoms within

86.2
131

192

424

342
the PVDF main chain will interact with F atoms in the PF6̅
anions to form strong H−F hydrogen bonds and hinder the
movement of the anions. Moreover, there is also a strong H−F
hydrogen-bonding interaction between F atoms in PF6̅ anions
porosity

bis(trifluoromethanesulfonyl)imide; SiO2PPTFSI, silica nanoparticle-tethered 1-methyl-1-propylpiperidinium bis(trifluoromethanesulfonyl)imide; SPS, sulfonated polystyrene

(%)

and H atoms in the -OH groups of the hydroxyethyl cellulose

50

78
(HEC) host, which also hinders the movement of PF6̅ anions
from passing through and avoids concentration polarization,
transference

thereby promoting a higher ionic conductivity and Li+

no.
0.82

0.88
Li+

transference number.84
An interesting performance has been shown by mixing
PVDF with 6c, which offers an ionic conductivity of 0.35 ×
ionic conductivity

10−3 S cm−1, Li+ T+ of 0.58, and flame-retardant property after

0.37 × 10−3 at

3.84 × 10−3 at

0.93 × 10−3 at

1.03 × 10−3 at

1.31 × 10−3 at
(S cm−1)

1.6 × 10−3 at

activation by 1 M LiPF6 solution in EC/DMC/EMC (1:1:1,

w/w/w) at room temperature (Figure 10a−d). The good Li+
25 °C

25 °C

25 °C

25 °C

25 °C

25 °C

transference is related to the property of LiPAAOB, which is

capable of solvating Li+ and keeping the contrary anion in
steady phase. The concentration polarization could therefore
be minimized, which results in the increased mobility of Li+
in situ polymerization

and higher transference number.86 A similar strategy of

self-adhered coating
preparation

preparing hybrid microporous GPEs based on PVDF and 6d

electrospinning
direct blending

was performed by Xing et al.87 The resulting GPE exhibited

self-assembly

breath-figure

ionic conductivity of 4.49 × 10−3 S cm−1 at room temperature.

A side-chain modification was also performed by Zhu et al.27
for preparing the polyvinyl-based single ion conducting
polymer 6e. Although the ionic conductivity of 6e was slightly
low (∼6.11 × 10−6 S cm−1), it shows an electrochemical
1 M LiPF6 in EC/DMC/EMC (1:1:1, v/v/v)

1 M LiPF6 in EC/DMC/EMC (5:3:2, v/v/v)

window that is stable up to 7 V vs Li/Li+ and presents great

potential for higher voltage LIBs. Furthermore, the study
1 M LiPF6 in EC/DMC (1:1, v/v)

1 M LiPF6 in EC/DMC (1:1, v/v)

1 M LiPF6 in EC/DMC (1:1, v/v)

shows that the resulting GPEs present Arrhenius behavior,

indicating that the Li+-ion motion is dependent on the
liquid electrolyte

flexibility of the polymer side chain.27

Although the PVDF-based GPEs showed interesting results
by mixing with plasticizer and organic/inorganic fillers, the
EC/PC (1:1, v/v)

incorporation of more plasticizer could reduce the mechanical

properties while improving the electrochemical performance.
The copolymer of PVDF and hexafluoropropylene (PVDF-
HFP) could overcome the negative issues, the amorphous
domains in pristine PVDF are capable of trapping large
amounts of liquid electrolytes, and the crystalline regions can
provide sufficient mechanical integrity for the processing of
freestanding films, thereby eliminating the required cross-
linking step.26 A similar strategy has also been applied for
copolymer PVDF-HFP, such as incorporating with an ionic
liquid88−94 and making a composite polymer by blending with
inorganic filler 95−97 or mixing with another polymer
polymer

PVDF-HFP/P(MVE-MA)
MA-PVDF/PVDF-HFP +
PVDF-HFP + LiPSIPA

matrix.64,98−101 Kuo et al.90 also fabricated hybrid GPEs by

10 wt % nano-Al2O3
PVDF-HFP + fa-SIPE

PVDF-HFP/PMMA

blending PVDF-HFP with oligomeric organic liquid to form 6f,

which exhibited ionic conductivity of 2.0 × 10−3 S cm−1 at 30
°C and 6.6 × 10−3 S cm−1 at 80 °C and presented high thermal
PVDF-HFP

stability up to 150 °C. Although the electrolyte uptake was

reduced to ∼50% relative to the pristine PVDF-HFP, the
Table 1. continued

oligomerization in ionic liquid is responsible for enhancing the

mechanical properties of the resulting GPEs and offering high
conductivity with flame-retardant capabilities, which is
strategy

attributed to nonflammable pyrrolidinium- and imidazolium-

based ionic liquids.90 Freestanding GPE that consists of PVDF-
HFP and inorganic/ceramic filler nanosized Al2O3 ceramic
particles was fabricated by Kim et al. via the electrospinning
a

3952 DOI: 10.1021/acsaem.9b00295

ACS Appl. Energy Mater. 2019, 2, 3937−3971
ACS Applied Energy Materials Review

Scheme 6. (a) Schematic of Gelled Microporous Polymer Electrolyte (GMPE) Structure (PVDF + Organogellator);a (b)
Schematic Illustration of Some Interactions in the GPEs [(Left) Interactions between PVDF and LiPF6; (Right) Interaction
between the Lithium Salt (LiPF6) and the -OH Groups in the HEC Host];b (c) Synthetic Route of Lithium Polyacrylic Acid
Oxalate Borate (LiPAAOB);c (d) Synthetic Route for Polyurethane Lithium Salt (PLS) via Condensation Polymerization and
Neutralization with LiOH;d (e) Synthetic Route of Lithium Poly(vinyl alcohol) Oxalate Borate (LiPVAOB);e (f) Synthesis
and Preparation of the GPE PVDF-HFP/Oligomeric Ionic Liquid Membrane;f (g) Formation of a Fast Ion Channel of GPEs
Based on PVDF-HFP and Poly(methyl vinyl ether-alt-maleic anhydride) (P(MVE-MA);g (h) Synthetic Procedure of Fully
Aromatic Lithium Poly[bis(phenylsulfonyl imide isophthalate amide diphenylsulfonamide)] (LiPSIPA) and the Aliphatic
Lithium Poly[bis(phenylsulfonyl imide isophthalate amide octylamide amide)] (LiPSIOAh)

a
Reprinted with permission from ref 78. Copyright 2014 Elsevier. bReprinted with permission from ref 84. Copyright 2017 Elsevier. cReproduced
with permission from ref 86. Copyright 2013 Royal Society of Chemistry. dReproduced with permission from ref 87. Copyright 2014 Elsevier.
e
Reproduced with permission from ref 27. Copyright 2013 Elsevier. fReproduced with permission from ref 90. Copyright 2016 Elsevier. gReprinted
with permission from ref 101. Copyright 2018 Elsevier. hReproduced with permission from ref 98. Copyright 2016 Elsevier.

3953 DOI: 10.1021/acsaem.9b00295

ACS Appl. Energy Mater. 2019, 2, 3937−3971
ACS Applied Energy Materials Review

Figure 10. (a) Combustion test of (a, c) Celgard 2730 and (b, d) the PVDF−LiPAAOB composite membrane. Reprinted with permission from ref
86. Copyright 2013 Royal Society of Chemistry. (e) Capacity profile of Li/GPE/LiNi0.5Mn1.5O4 coin cell under a rate of 1 C in the voltage range of
3.0 and 4.9 V at ambient temperature; M1, M2, M3, and M4 represent the P(MVEMA) content in the total weights of GPEs of 0%, 25%, 50%, and
75%, respectively. Reprinted with permission from ref 101. Copyright 2018 Elsevier. (f, g) Surface and cross-section SEM images of prepared GPEs
PVDF-HFP/LiPSIPA; (h, i) Surface and cross-section SEM images of prepared GPEs PVDF-HFP/LiPSIOA. Reprinted with permission from ref
98. Copyright 2016 Elsevier.

process.95 After activation with 1 M LiPF6 in EC/DMC, the the Raman spectrum of the corresponding GPE shows that the
resulting GPEs showed good ionic conductivity of 4.1 × 10−3 S incorporation of nanosized Al2O3 could effectively enhance the
cm−1 at 25 °C and 7.8 × 10−3 S cm−1 at 80 °C. This solvation of Li+ ions and promote Li+-ions transfer.95 To
phenomenon is due to the effect of nanosized Al2O3, which enhance the electrochemical properties, Li et al.101 used the
increases electrolyte uptake to 20% higher than that of the electrospinning method to fabricate a novel GPE composite
pristine PVDF-HFP prepared by electrospinning. Furthermore, polymer 6g, which consists of PVDF-HFP and poly(methyl
3954 DOI: 10.1021/acsaem.9b00295
ACS Appl. Energy Mater. 2019, 2, 3937−3971
 Table 2. Summary of GPEs Based on PANa
ionic conductivity Li+ transference porosity electrolyte uptake
strategy polymer liquid electrolyte preparation (S cm−1) no. (%) (wt %) ref
−3
PAN + Li salts/ionic acrylonitrile 0.5 M LiTFSI in Py1, 4-TFSI free-radical polymerization 1.7 × 10 at 25 °C 109
liquid
PAN composite PAN + PMMA 1 M LiTFSI in PYR14TFSI + PEGDME electrospinning 3.6 × 10−3 86 480 110
polymer
PAN + TiO2−SiO2 1 M LiPF6 in sulfolane casting 9.8 × 10−4 at 25 °C - - - 111
PAN+PMMA (core−shell 1 M LiPF6 in EC/DEC (1:1, v/v) coaxial-electrospinning 5.1 × 10−3 0.48 89 1048 112
structure)
PAN + TEGDA-BA 1 M LiPF6 in EC/DMC/EMC in situ thermal polymerization 5.9 × 10−3 at 25 °C 0.481 113
(1:1:1, v/v/v)
ACS Applied Energy Materials

−3
PAN + PEO (core−shell structure) 1 M LiPF6 in EC/DMC (1:1, v/v) coaxial-electrospinning 5.36 × 10 0.74 77.3 870 114
PAN + PEO + SWy 1 M LiCF3SO3 in EC/PC (1:1, v/v) direct blending 2.8 × 10−3 at 25 °C 0.68 300 115
PAN + OMMT 1 M LiPF6 in EC/DMC/EMC non-solvent-induced phase 2.23 × 10−3 at 25 °C 95 375.5 116
(1:1:1, v/v/v) separation
PAN copolymer P(ANVAc)/nonwoven fabric PE 1 M LiPF6 in EC/DEC/DMC coating 3.8 × 10−3 0.52 380 117
(1:1:1, v/v/v)
P(MMA-AN-EA) 1 M LiPF6 in EC/DMC (1:1, v/v) emulsion polymerization 3.82 × 10−3 155 118
P(MMA-AN-BA) 1 M LiPF6 in EC/DMC/DEC emulsion polymerization 1.7 × 10−3 at 25 °C 234.2 120
(3:5:2, w/w/w)
P(MMA-BA-AN-St)/PE 1 M LiPF6 in EMC/EC/DEC emulsion polymerization 2.7 × 10−3 at 25 °C 67 465 121
(5:3:2, w/w/w)
P(BMA-AN-St)/PE + 1 M LiPF6 in EC/DMC (1:1, v/v) emulsion polymerization 1.9 × 10−3 75 257 122
10 wt % nano-SiO2

3955
P(AN-MA) 1 M LiPF6 in EC/DMC/EMC phase inversion 3.03 × 10−3 at 25 °C 0.57 74.3 355.5 123
(1:1:1, v/v/v)
P(AN-POSS) 1 M LiPF6 in EC/DMC (3:7, v/v) phase inversion 6.06 × 10−3 0.59 83.1 471.7 124
a
Abbreviations: OMMT, organic montmorillonite; P(AN-MA), poly(acrylonitrile-maleic anhydride); P(AN-POSS), poly(acrylonitrile-polyhedral oligomeric silses-quioxane); P(AN-VAc),
poly(acrylonitrile-vinyl acetate); PE, polyethylene; PEGDME, poly(ethylene glycol)dimethyl ether; P(MMA-AN-BA), poly(methyl methacrylate-acrylonitrile-butyl acrylate); P(MMA-AN-EA),
poly(methyl methacrylate-acrylonitrile-ethyl acrylate); P(MMA-BA-AN-St)/PE, poly(methyl methacrylate-butyl acrylate-acrylonitrile-styrene)/polyethylene; PYR14TFSI, N-methy-N-butylpyrrolidinium
bis(trifluoromethanesulfonyl)imide; SWy, organic sodium smectite clay; TEGDA-BA, triethylene glycol diacetate-2-propenoic acid butyl ester.
Review

ACS Appl. Energy Mater. 2019, 2, 3937−3971

DOI: 10.1021/acsaem.9b00295
ACS Applied Energy Materials Review

Figure 11. (a) Capacity profile of multiwall carbon nanotube (MWCNT)−LiFePO4 (LFP) cell that used GPEs based on free radical
polymerization of acrylonitrile and LiTFSI-[Py1,4-TFSI] ionic liquid. Reprinted with permission from ref 109. Copyright 2011 Royal Society of
Chemistry. (b) Schematic Li+ transport through PAN/PEO nanofiber GPEs. Reprinted with permission from ref 114. Copyright 2015 Elsevier. (c)
Cycle performance and columbic efficiency of coin cells at a rate of 1 C for GPEs based on PAN/OMMT. Reprinted with permission from ref 116.
Copyright 2018 Elsevier. (d) Cycle capability of P(AN-POSS)0% and P(AN-POSS)8% at various C-rates. Reprinted with permission from ref 124.
Copyright 2018 Elsevier.

vinyl ether-alt-maleic anhydride) (P(MVE-MA)) and uses ity of approximately 3.7 × 10−4 S cm−1 over that from PVDF-
polyethylene (PE) as support. The ionic conductivity of the HFP mixed LiPSIOA (∼7.9 × 10−5 S cm−1) at room
resulting GPEs shows that mixing 75 wt % P(MVE-MA) could temperature after soaking in EC/PC (1:1, v/v). The higher
increase the ionic conductivity up to 1.6 × 10−3 S cm−1 at 25 electrochemical properties of PVDF-HFP mixed LiPSIPA are
°C and provide for superior cycle stability with a negligible related to their porous morphology with interconnected
capacity loss after 100 cycles after activation in 1 M LiPF6 channels, which can uptake more solvent and improve ion
EMC/EC/DEC (5:3:2, w/w/w) (Figure 10e). The electro- transfer inside the GPEs.98 This study demonstrated that the
chemical performance of GPEs is significantly enhanced by porous structure of GPEs plays a critical role in LIB
introducing the P(MVE-MA) copolymer into the PVDF-HFP performance and suggests a facile approach to preparing
system. The presence of P(MVE-MA) enhances the invasion porous GPE membranes for developing better LIBs with
of the liquid solvent, thereby creating fast ion channels that can outstanding performance.
increase the uptake ability of liquid electrolytes, which 3.3. Polynitrile. Among polymers, the application of
accelerates the process of intercalation/deintercalation.101 polynitriles in LIBs has attracted interest, especially as a
Freestanding GPEs were also prepared by blending with single polymer electrolyte. Polyacrylonitrile (PAN) is one of the most
ionic conducting polymer 6h. The results show that the investigated polynitriles for GPEs. Thus, far, many scientists
morphology of the GPE was significantly different between the have suggested that PAN could offer a homogeneous and
PVDF-HFP mixed LiPSIPA and PVDF-HFP mixed LiPSIOA hybrid electrolyte film in which the salt and the plasticizer are
(Figure 10f−i). The PVDF-HFP mixed LiPSIPA showed a molecularly dispersed.58 Early studies reported by Watanabe et
porous structure with interconnected channels, while PVDF- al.106,107 showed the direct mixing of PAN with plasticizer (EC
HFP mixed LiPSIOA becomes a dense film. When mixing with and PC) and formation of a complex with LiClO4 to prepare
PVDF-HFP, the nature aromatic backbone of the LiPSIPA and PAN-based GPEs. The investigations found that PAN is
aliphatic backbone of PVDF-HFP led to poor chemical inactive toward the Li+ transport mechanism and only acts as a
compatibility, which induced phase separation during the matrix for structural stability.26,58 In addition, by using Raman
blending process and a porous structure of the resulting and infrared (IR) spectroscopy, another study demonstrated
membrane. The same aliphatic backbone of LiPSIOA and that there is a strong interaction between Li+ and CN groups
PVDF-HFP presented good chemical compatibility; therefore, on the PAN.108 Nevertheless, the Li+ transport mechanism on
a dense freestanding film could be achieved.98 The electro- PAN-based GPEs is still under debate and requires additional
chemical performance indicates that GPEs prepared from investigation to provide a complete understanding.26 Fur-
PVDF-HFP mixed LiPSIPA exhibited higher ionic conductiv- thermore, three strategies have been used to develop PAN-
3956 DOI: 10.1021/acsaem.9b00295
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ACS Applied Energy Materials Review

Scheme 7. (a) In Situ Copolymerization of Triethylene Glycol Diacetate (TEGDA-BA);a (b) Synthetic Route of Poly(methyl
methacrylate-acrylonitrile-ethyl acrylate) (P(MMA-AN-EA)) Terpolymer Prepared by Emulsion Polymerization;b (c)
Synthesis Route of Quaternary Polymer Poly(methyl methacrylate-butyl acrylate-acrylonitrile-styrene) (P(MMA-BA-AN-St))
by Emulsion Polymerization;c (d) Synthetic Route Poly(acrylonitrile-maleic anhydride) (P(AN-MA));d (e) Synthesis
Reaction of Poly(acrylonitrile-polyhedral oligomeric silsesquioxane) (P(AN-POSS))e

a
Reproduced with permission from ref 113. Copyright 2015 Elsevier. bReproduced with permission from ref 118. Copyright 2014 Elsevier.
c
Reproduced with permission from ref 121. Copyright 2016 Elsevier. dReproduced with permission from ref 123. Copyright 2018 Elsevier.
e
Reproduced with permission from ref 124. Copyright 2018 Elsevier.

based GPEs: incorporation of Li salts/ionic liquid, 109 of electrolytes and increases the loading amount of liquid
formation of composite polymer,110−116 and copolymeriza- electrolyte (1 M LiPF6 in EC/DMC/EMC (1:1:1, v/v/v)) and
tion.117−124 The summary of PAN-based GPEs is presented in thus is beneficial for fast Li+ mobility.113 Furthermore, Zhang
Table 2. Patel et al.109 prepared a novel soft GPE via free et al.114 used the coaxial-electrospinning method to prepare a
radical polymerization of an acrylonitrile monomer under GPE composite based on PAN and PEO. Taking advantage of
room temperature with an ionic liquid electrolyte, N,N-methyl PAN, a GPE fabricated from nanofibers with a core−shell
butyl pyrrolidinium-bis(trifluoromethanesulphonyl)imide-lith- structure was prepared (PAN, core; PEO, shell) and activated
ium bis(trifluoromethanesulphonyl)imide (LiTFSI-[Py1,4- by immersing in 1 M LiPF6 in EC/DMC (1:1, v/v). This study
TFSI]). The corresponding GPE was found to exhibit higher revealed that ionic transport occurs through the amorphous
ionic conductivity up to 1.8 × 10−3 S cm−1 at 25 °C and good region of PEO and PAN (Figure 11b). In the PAN phase, the
cyclability for LiFePO4 battery performance (Figure 11a). The lithium ions are present around the CO groups in EC and
study found that the Li+ transport is associated with the CN groups in PAN, and the segmental motion of EC and
presence of ionic liquid, while the crystallinity region generated PAN can affect the movement of lithium ions. In the PEO
from the acrylonitrile polymer matrix does not contribute to phase, lithium-ion transport can occur mainly through an
the ionic conductivity.109 association−disassociation between the ions and the PEO.114
The formation of a PAN-based polymer composite is the The electrochemical performance of the resulting GPE
most common strategy to prepare GPEs for LIBs. This strategy exhibited an ionic conductivity of 4.9 × 10−3 S cm−1 and
could be achieved by blending with another polymer was slightly enhanced to 5.3 × 10−3 S cm−1 after it was radiated
matrix110,112−114 and/or inorganic filler.111,115,116 Another with an electron beam to form cross-linking reactions, which
interesting strategy demonstrated by Wang et al.113 is the not only destroyed the regularity of the molecular chains but
mixing of PAN-based GPEs with three-dimensional network also reduced the degree of crystallinity of polymers in the
structures 7a through in situ thermal polymerization (Scheme nanofiber membranes, thereby accelerating the Li+ transfer
7). Triethylene glycol diacetate-2-propenoic acid butyl ester primarily in the amorphous region.114
(TEGBA-BA) is known to enhance the ionic conductivity of In addition, a GPE composite has recently been constructed
GPEs due to the good dispersion of liquid electrolytes in from PAN/organic montmorillonite (MMT) through a non-
TEGBA-BA polymer networks, which is primarily responsible solvent-induced phase separation method by He et al.116 MMT
for the migration of Li+ inside of GPEs.125 The resulting GPEs is a well-known inorganic filler based on a layered silicate with
with 5 wt % PAN exhibits ionic conductivity up to 5.9 × 10−3 S a central alumina octahedral sheet sandwiched between two
cm−1 at 25 °C and a high Li+ transference number up to 0.481. silica tetrahedral sheets, which can improve the thermal
This performance is associated with the synergistic effects of stability.126 After activation by 1 M LiPF6 in EC/DMC/EMC
cross-linked short-chain monomers (TEGBA-BA) and a linear (1:1:1, v/v/v), the resulting GPE showed high ionic
long-chain polymer (PAN), which enhances the compatibility conductivity of 2.5 × 10−3 S cm−1, a stable potential window
3957 DOI: 10.1021/acsaem.9b00295
ACS Appl. Energy Mater. 2019, 2, 3937−3971
ACS Applied Energy Materials Review

up to 4.62 V, and thermal stability up to 150 °C. This study formation of a super network structure and the low consistency
revealed that the incorporation of organic MMT has a direct of the electronic charge between SiO2 and Al2O3 contributed
effect on the membrane morphology via the formation of a in the effective connection points119 By using a similar strategy,
highly porous structure with high liquid uptake up to 375.5%, a novel quaternary polymer 7c was successfully synthesized via
which is responsible for its electrochemical performance.116 emulsion polymerization, in which PMMA and acrylonitrile
Moreover, the cycling performance of LIB based on a LiCoO2 were introduced to provide a good affinity to liquid electrolyte,
cathode shows a high capacity of 141 mAh g−1 after 100 cycles and butyl acrylate (BA) supplied adhesive characteristics while
and high capacity retention of 95.9% at 1 C (Figure 11c), polystyrene offered mechanical strength.121 However, the
indicating the cyclic compatibility and low interfacial electrochemical performance of the resulting GPE showed a
resistant.116 slight improvement compared with the terpolymer by
The structural design of copolymerizing PAN with other presenting an ionic conductivity as high as 2.7 × 10−3 S
monomer and/or other functional groups has been intensively cm−1 and electrochemical stability up to 5.3 V vs Li/Li+ at
investigated by many scientists. Taking advantage of poly(vinyl room temperature. This phenomenon could be associated with
acetate) to solvate Li+ and the good mechanical strength of the higher internal resistance of the quaternary polymer than
PAN, a copolymer poly(acrylonitrile-vinyl acetate) (P(AN- that of the terpolymer. For long-term operations, the
VAc)) has been successfully synthesized by Li et al.117 The quaternary polymer 7c exhibited higher internal resistance,
resulting copolymer was coated on PE nonwoven fabric and which started at 300 Ω cm2 on the first day and increased to
activated by 1 M LiPF6 in DMC/DEC/EC (1:1:1, v/v/v). The 514 Ω cm2 after 15 days of testing,121 while the internal
corresponding GPE revealed an ionic conductivity up to 3.8 × resistance of terpolymer 7b increases from 62 Ω cm2 initially to
10−3 S cm−1 at room temperature, Li+ transference number as 69 Ω cm2 after 15 days.118 These results show that the addition
high as 0.52, and stable electrochemical windows from 5.0 to of polystyrene would increase the internal resistance and lead
5.6 V vs Li/Li+. The resultant morphology of the P(AN-VAc)/ to lower ionic conductivity.
PE nonwoven material was highly porous (higher pore volume Recently, a random copolymer 7d consisting of PAN and
density) and beneficial for more liquid electrolyte uptake with maleic anhydride (MA) was successfully fabricated with good
fast Li+ transfer,117 demonstrating that the morphology of the electrochemical properties after activation by 1 M LiPF6 in
GPE membrane plays an important role in the electrochemical EC/DMC/EMC (1:1:1, w/w/w), such as ionic conductivity
performance. A novel GPE based on terpolymer 7b was up to 3.03 × 10−3 S cm−1, Li+ transference number of 0.57, and
successfully fabricated through emulsion polymerization by a high electrochemical stability window up to 5.4 V vs Li/Li+ at
Sun et al.118 The purpose of forming a terpolymer based on room temperature.123 The good electrochemical performance
polynitrile and polyacrylate is to combine the good mechanical
is attributed to the additional MA, which contains a five-
properties and Li+ solvation contributed by polynitrile and
membered ring with strong negatively charged groups thus
polyacrylate, respectively, which are expected to exhibit good
could disrupt the interaction between CN and PAN. In
performance for LIBs.118 The addition of ethyl acrylate is used
addition, the steric effects of MA might weaken the
as a soft monomer with good cohesiveness for the synthesized
electrostatic interaction between the polar groups CN and
macromolecule.127 Furthermore, a pore-forming agent, poly-
(ethylene glycol) 400 (PEG-400), was added during the phase lithium metal electrodes to some extent, thereby resulting in
inversion and further activated by 1 M LiPF6 in EC/DMC good compatibility with the lithium electrode. Moreover, the
(1:1, v/v). GPEs based on terpolymer P(MMA-AN-AE) show strong negatively charged groups of MA may also hinder the
an ionic conductivity up to 3.82 × 10−3 S cm−1 at room movement of negatively charged carriers, resulting in a high
temperature and are electrochemically stable up to 5.2 V vs Li/ effective current for Li+ mobility.123 The GPEs based on
Li+, and these properties are suitable for high voltage cathode copolymer 7e demonstrated an outstanding electrochemical
materials. The investigation shows that the ionic conductivity performance, such as a high ionic conductivity of 6.06 × 10−3 S
is proportional to the electrolyte uptake, which is strongly cm−1 at ambient temperature after activation by 1 M LiPF6 in
dependent on the pore structure and coupled with special EC/DMC (3:7, v/v), Li+ transference number of 0.59, and
polymer−solvent interactions due to the existence of the electrochemical stability up to 5.7 V vs Li/Li+.124 Moreover,
strong polar groups CN and CO in the terpolymer the better cycle capability of copolymer 7e has been performed
matrix.118 by incorporating 8% POSS content in the GPE within the Li/
Furthermore, inorganic fillers, such as nano-SiO2 and nano- GPE/LiFePO4 half-cell at different current rates (Figure 11d).
Al2O3, have been added to improve the electrochemical The excellent electrochemical property is due to the
performance of GPEs.119 Although they only provide a slight incorporation of polyhedral oligomeric silsesquioxane
improvement of ionic conductivity, the combination of 5 wt % (POSS), which is an intramolecular-level organic (alkyl or
nano-SiO2 and 5 wt % nano-Al2O3 inside of terpolymer vinyl groups)−inorganic (Si−O−Si bonds) hybrid nano-
P(MMA-AN-AE)-based GPEs enhanced the electrochemical particle that possesses a type of three-dimensional cage
stability up to 5.6 V vs Li/Li+. The improvement of the structure with a general formula of (RSiO1.5)n.124,128 By
electrochemical stability was due to the synergic effect of nano- incorporating POSS on the PAN backbone polymer, the
SiO2 and nano-Al2O3 fillers.119 The Si−O bonds or Al−O organic double bonds of CC in POSS disrupt the
bonds as the connection points contribute to building a polymerization sequence of AN monomers and form a
stronger polymer network structure by the formation of Si− network-like copolymer structure, which contributes to
O−C or Al−O−C covalent bonds, and the interaction weakening the interaction of polar groups CN between
between the polymer and liquid electrolyte is therefore adjacent polymer segments, enhancing the compatibility with
strengthened. The addition of both nano-SiO2 and nano- Li metal, expanding the amorphous region of the GPEs,
Al2O3 fillers makes the interaction between the polymer and improving the electrolyte uptake, and accelerating Li +
liquid electrolyte become even stronger, which is due to the mobility.124
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Scheme 8. (a) Synthesis of the Monomer Cyclic Carbonate Methacrylate (CCMA); (b) Polymerization of Oligo(ethylene
glycol) Methyl Ether Methacrylate (OEGMA) and CCMA by UV-Induced Free Radical Polymerizationa

a
Reproduced with permission from ref 132. Copyright 2014 Elsevier.

Figure 12. (a) Cycling performance of LiNi0.5Mn1.5O4/Li batteries in liquid electrolyte (LE) and PPC-cellulose (GPE). Reprinted with permission
from ref 134. Copyright 2016 Elsevier. (b) Cycling performance of Li/GPE/LiFePO4 cells assembled with Celgard PE, pure PVDF (VGE-100),
and PVDF−PPC20% (CGE-20) at 0.1 C. Reprinted with permission from ref 133. Copyright 2015 American Chemical Society.

3.4. Polycarbonate. Because of the success of carbonate- butyl-3-methylimidazolium tetrafluoroborate (BMIM+BF4−).

based liquid electrolytes, polycarbonate has been selected as an The advantages of PPC, which has a structure similar to that
alternative in polymer electrolytes to overcome the safety of carbonate-based organic solvent and a low Tg, were
issues related to carbonate-based liquid electrolytes. Poly- exploited, and a combination with a small amount of ionic
carbonates are expected to have properties similar to those of liquid could turn PPC to a rubbery state, thereby facilitating
carbonate-based electrolytes and minimal/eliminated natural the motion of Li+ within the polymer matrix.131 The results
flammability, which is a typical problem from carbonate-based show that the ionic conductivity of GPE based on PPC/
liquid electrolytes. The carbonate groups used in polymer LiClO4/BMIM+BF4− with a weight ratio of 1/0.2/3 is 1.5 ×
construction are capable of providing a polar environment that 10−3 S cm−1 at ambient temperature. Furthermore, the study
is suitable for the dissociation of salts and the solvation of also revealed that the ionic transport inside of GPE follows the
ions.129 Polycarbonates can coordinate with Li+ via the Arrhenius equation, which means that Li+ is transported
carbonyl group oxygen, which is similar to the Li+-coordinating
through an ion hopping mechanism and decoupled from the
ether oxygens of PEO and other polyether electrolyte hosts.20
long-chain motion of the polymer host at both amorphous and
Moreover, coordination by the alkoxy oxygens (sometimes
crystalline states below the Tg. Another strategy demonstrated
referred to as “ether oxygens”) adjacent to the carbonyl group
has also been implicated in carbonate solvents.130 Because of by Tillmann et al.132 is to copolymerize 8a and oligo(ethylene
the properties that are similar to that of PEO, more research glycol) methyl ether methacrylate (OEGMA) to form 8b by
efforts have focused on the application of polycarbonates as using UV-induced free radical polymerization (Scheme 8). The
polymer electrolytes, especially for SPEs, and this class of electrochemical performance of the resulting GPE shows an
alternative host materials has recently attracted the most ionic conductivity of 2.3 × 10−3 S cm−1 at 25 °C after
intense research attention and progress.20 Nevertheless, the activation by 1 M LiPF6 in EC:DMC (1:1, w/w) with
application of polycarbonates for GPEs has recently drawn electrolyte uptake of nearly 550%. The results are consistent
attention among the scientists since the lower ionic with the expectation that both monomers have interactions
conductivity hinders the use of SPEs in real LIB applications. with the cyclic carbonate moiety in liquid electrolyte within the
Zhou et al.131 fabricated GPEs by mixing a poly(propylene polymer matrix. The strong interactions could improve the
carbonate) (PPC) host with LiClO4 and an ionic liquid 1- gelation behavior of the GPEs compared to other ethylene
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Scheme 9. (a) Synthesis Route of the PMA/PEG-Based Gel Polymer Loading LiClO4/DMSO Electrolyte;a (b) Synthesis
Route of the GPEs Based on Poly(ethylene glycol) Methyl Ether Methacrylate (PEGM)−Poly(ethylene glycol) Dimethacrylate
(PEGDM) and Structure of Methylpropylpyrrolidinium Bis(trifluoromethanesulfonyl)imide (MPPY·TFSI) Ionic Liquid;b (c)
Synthesis Route of Copolymer Poly(butyl methacrylate-styrene) (P(BMA-St)) Prepared by Emulsion Polymerization;c (d)
Polymerization of Oligo(ethylene glycol) Methyl Ether Methacrylate (OEGMA) and Benzyl Methacrylate (BnMA) by UV
Light;d (e) Synthesis Route of Poly(methyl methacrylate-co-butyl acrylate) (P(MMA-co-BA));e (f) Synthesis Route of Methyl
Methacrylate-Maleic Anhydride Copolymer (P(MMA-MAh)) Grafted PEGMEf

a
Reproduced with permission from ref 137. Copyright 2013 John Wiley and Sons. bReproduced with permission from ref 136. Copyright 2013
Elsevier. cReproduced with permission from ref 138. Copyright 2010 Elsevier. dReproduced with permission from ref 139. Copyright 2013 Elsevier.
e
Reproduced with permission from ref 140. Copyright 2016 Springer Nature. fReproduced with permission from ref 135. Copyright 2010 Elsevier.

glycol-based polymer systems and can therefore enhance the cellulose may be due to the strong polarity groups CO in the
electrolyte uptake and Li+ mobility.132 polymer matrix, which effectively retain the liquid electrolyte
Recently, PPCs have attracted research attention for and form more ionic transport channels with high dissociation
application as a polymer electrolyte in LIBs. As GPEs for of salt and Li+ mobility.134 Huang et al.133 prepared the GPE
LIBs, the polar group (ester group) on the PPC backbone is based on an electrospinning membrane made of PPC and
beneficial for ionic conduction by trapping and storing liquid PVDF. The corresponding GPE exhibited an ionic con-
electrolytes.133 Furthermore, because of the low Tg of PPC, the ductivity of 2.11 × 10−3 S cm−1 at 30 °C and stable
local relaxation and segmental motion of PPC chain is electrochemical window up to 5.2 V vs Li/Li+. As shown in
favorable for transporting Li+ inside of GPEs. However, the Figure 12b, the cyclic performance of Li/GPE/LiFePO4 half-
low mechanical properties significantly hindered the practical cell shows higher capacity compared to that from pure PVDF
application of PPCs for LIBs.133,134 Zhao et al.134 therefore with a commercial Celgard PE separator. This study revealed
cast PPC on a cellulose membrane to improve the mechanical that the formation of Li+···(δ−) F−C (δ+) and PF6−···(δ+) C
property. After activation by 1 M lithium oxalyldifluoroborate O (δ−) complexes in the polymer framework can separate the
(LiODFB)-PC (1:1, v/v), the resulting GPE exhibited an ionic Li + and PF 6 − anions, which effectively prevents the
conductivity as high as 1.14 × 10−3 S cm−1, Li transference simultaneous reconnection between Li+ and PF6− anions and
number up to 0.68, and stable electrochemical window up to creates more free Li+, thereby improving the transport ability
5.0 V vs Li/Li+ at 30 °C. Furthermore, the battery performance of lithium ions.133
shows a much better capacity retention of up to 91.3% for 3.5. Polyacrylate. Among polyacrylates, PMMA is the
LiNi0.5Mn1.5O4/Li batteries compared with the common liquid most common polymer applied as a GPE for LIBs. In early
electrolyte, which has a capacity of only 78% (Figure 12a). The studies, PMMAs were used as plasticizer or gelatinization agent
stable electrochemical performance of GPE based on PPC- in polymer electrolyte to increase the mechanical proper-
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Figure 13. (a) Effect of the LiClO4 concentration on the ionic conductivity of the liquid and GPEs based on PMA/PEG. Reprinted with
permission from ref 137. Copyright 2013 John Wiley and Sons. (b) Ionic conductivity of the GPEs based on PEGM−PEGDM with different
amounts of MPPY·TFSI. Reprinted with permission from ref 136. Copyright 2013 Elsevier.

ties.26,58 Recently, PMMA has been widely used as a primary temperature with a stable electrochemical window up to 5.2 V
backbone polymer for GPEs via simple blending or vs Li/Li+. The improvement can be ascribed to the porous
copolymerization.135−137 Similar to polyether and polycarbon- morphology generated from fumed silica, which also reveals
ates, PMMA was expected to be beneficial for Li+ transport and that high affinity with liquid electrolytes thus can tightly trap
have the ability to solvate the Li+ or the liquid electrolyte the liquid electrolyte inside the membrane and results in good
inside of the polymer matrix by the CO polar group in oxidative stability of GPEs.138
PMMA. Studies have revealed that a consistent fraction of By exploiting polyacrylates, the copolymers 9d139 and 9e140
lithium is lost upon cycling and therefore a large excess of were fabricated, and they were expected to solvate the Li+ and
lithium would be required to ensure an acceptable battery exhibit strong affinity toward liquid electrolytes. After
life.58 Huang et al.137 prepared a hybrid GPE 9a consisting of activation by immersing the resulting GPEs into 1 M LiPF6
poly(methyl acrylate)/poly(ethylene glycol) (PMA/PEG) and in EC/DMC (1:1, v/v), GPEs 9d and 9e exhibited almost
formed a quasi-solid-state electrolyte with ionic conductivity of similar ionic conductivities at 25 °C of 1.8 × 10−3 and 1.2 ×
0.57 × 10−3 S cm−1 after activation by LiClO4 in DMSO 10−3 S cm−1, respectively. Another structural design of the
(Scheme 9). Furthermore, this study also confirmed that the polyacrylate 9f-based GPE was reported by Wang et al.135
ionic conductivity increases as the concentration of LiClO4 through the formation of three comb-like methyl methacrylate
inside of GPEs increases (Figure 13a). This finding was copolymer matrices. In addition, the copolymer methyl
consistent with the theory that ionic conductivity could be methacrylate-maleic anhydride (P(MMA-MAh)) was first
enhanced by increasing the charge carriers.33 prepared as the main backbone for grafting poly(ethylene
In addition, copolymerization is the most popular strategy of glycol) monomethyl ether (PEGME) with different molecular
structural design for polyacrylate-based GPEs. GPE 9b was weights to form three comb-like 9f GPEs.135 Although the
prepared by the copolymerization of poly(ethylene glycol) three comb-like 9f GPEs exhibited relatively lower ionic
methyl ether methacrylate (PEGM) and poly(ethylene glycol) conductivity at approximately 1.22 × 10−3 S cm−1 at 60 °C
dimethacrylate (PEGDM).136 After introducing 60 wt % after incorporating 1 M LiClO4 in PC, the study revealed that
content of ionic liquid methylpropylpyrrolidinium bis- the ionic conductivity increased significantly by increasing the
(trifluoromethanesulfonyl)imide (MPPY·TFSI) as a plasticizer side-chain length of the copolymers. As the side-chain length of
and mobile charge carrier, the resulting GPE copolymer the copolymer increased, the number of pendant ethylene
exhibited ionic conductivity of 1.0 × 10−3 S cm−1 at 25 °C. As oxide segments will also increase in the copolymer network,
presented in Figure 13b, the ionic conductivity can be further which results in a decreased Tg and an increased fractional free
enhanced by increasing the amount of ionic liquid. This study volume with enhanced Li+ transport.135 This study also
again confirmed that the enhancement of ionic conductivity is confirmed that ionic transport inside of the three comb-like
consistent with an increased charge.33 In addition, by GPE 9f follows the VTF behavior, in which segmental motion
increasing the ionic liquid content over 60 wt %, the GPEs of polymer host inside the GPE promotes the ionic movement
will lose their mechanical properties and result in a gel-like by the formation and destruction of solvated ion coordina-
electrolyte.136 Liao et al.138 successfully fabricated GPE 9c by tion.17
copolymerization of PMMA and PSt, and it presented a good
combination of a higher affinity toward the liquid electrolytes
and good mechanical properties.138 The resultant P(BMA-St)-
4. ALTERNATIVE POLYMER TYPES FOR GPES
based GPE exhibited ionic conductivity of 1.1 × 10−3 S cm−1 at 4.1. Polyaromatic Polymer. The application of poly-
room temperature and a stable electrochemical window up to aromatic polymers for GPE construction has attracted
4.7 V vs Li/Li+ after activation by immersing into 1 M LiPF6 in considerable research attention. Polyaromatic polymers have
EC/DMC/EMC (1:1:1, v/v/v). The ionic conductivity and been used to improve the mechanical and thermal proper-
electrochemical stability of P(BMA-St) could be further ties.141 In addition, the nature rigid structure of the
enhanced by incorporating with fumed silica, which resulted polyaromatic polymers enhances ionic conductivity by
in an ionic conductivity up to 2.2 × 10−3 S cm−1 at room increasing liquid electrolyte uptake through the formation of
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Scheme 10. (a) Synthesis Route of PSF−PEO Segmented Polysulfone Copolymers;a (b) General Synthesis of Single Ion
Conducting Polymer GPEs Based on PEEbK

a
Reproduced with permission from ref 142. Copyright 2013 Elsevier. bReproduced with permission from ref 143. Copyright 2016 Royal Society of
Chemistry.

Figure 14. (a) Temperature dependence of the ionic conductivities of GPEs based on segmented copolymers based on PSF−PEOs with different
PEO contents. Reprinted with permission from ref 142. Copyright 2013 Elsevier. (b) Ionic conductivity of GPE 10b as a function of temperature
and in the dry form with 5 wt % DMC, PC/EC, or acetonitrile as plasticizers. Reprinted with permission from ref 143. Copyright 2016 Royal
Society of Chemistry.

a more porous structure of GPEs.98 Recently, a polyaromatic backbone of GPEs but also single ion conducting polymers.
polymer with anion anchored on the backbone was applied to The poly(arylene ether)-containing pyridine group was
prepare a single ion conducting polymer, and the charges were synthesized and used as a main backbone for the GPEs 4c,
therefore partially delocalized by an aryl group; thus, Li+ poorly 5a, and 5b.75 To promote the ionic conductivity of the GPEs,
paired with the constituent anion and facilitated transport.98 various molecular weights of PEO were grafted on the polymer
Furthermore, ion polarization could also be minimized by backbone of 4c, 5a, and 5b. However, the resulting GPEs
keeping anions in an immobile state via the application of exhibited a relatively low ionic conductivity of 5.5 × 10−4 S
single ion conductor polymers.10 Several polyaromatic cm−1 at room temperature, although it increased to ∼2.4 ×
polymers have been introduced as GPEs by direct blending, 10−3 S cm−1 by increasing the temperature to 80 °C.
composite polymer formation, or copolymerization. Aromatic Furthermore, the investigation found that the mechanical
polysulfone (PSF) has been used as a segment of copolymer properties of GPEs are still maintained even if the Tg or
10a by condensation polymerization (Scheme 10).142 The thermal stability are changed by tuning the PEO content or
resulting copolymer was then used as a GPE by introducing Li length.75
salts in succinonitrile (SN) as the plasticizer. As shown in In addition, various single ion conducting polymers have
Figure 14a, the ionic conductivity of GPEs based on copolymer been prepared based on aromatic poly(arylene ether) and
10a depends on the PEO content, indicating that PSF was only applied as GPEs for LIBs. Poly(arylene ether) has been used as
used as a framework to improve the mechanical and thermal single ion conducting polymers 4a, 4b, and 6h to improve the
properties of aliphatic PEO.142 Recently, aromatic poly(arylene electrochemical performance and mechanical properties.73,74,98
ether) has been used to prepare not only the polymer In a single ion conducting polymer, the anion is kept in an
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Figure 15. (a) Temperature dependence of ionic conductivities of GPE-based PVA−PAA doped by 70 mol % ionic liquid PYRTFSI. Reprinted
with permission from ref 144. Copyright 2015 John Wiley and Sons. (b) Cycle performance of GPEs based on HNTs/PEI with different charge
rate. Reprinted with permission from ref 150. Copyright 2018 Elsevier.

Scheme 11. (a) Synthesis Procedure of Polymerization and Imidization Reactions Polyimide;a (b) One-Step Method Synthesis
Procedure for the Copolyimide 0CN−2CNb; (c) Structure of Polyetherimide (PEI)c

a
Reproduced with permission from ref 147. Copyright 2014 Elsevier. bReproduced with permission from ref 149. Copyright 2016 Elsevier.
c
Reproduced with permission from ref 150. Copyright 2018 Elsevier.

immobile state (as polymer backbone) and the benzene ring polymer 10b is the absence of fluorine in its repeat unit, which
(aryl group) on poly(arylene ether) could be partially is highly advisible from an environmental compatibility point
delocalized Li+ with poor pairing, which is beneficial for Li+ of view.143 As shown in Figure 14b, the highest ionic
transport inside GPEs. Because of the phase separation of the conductivity of GPE based on the single ion conducting
incompatible rigid structure of poly(arylene ether) with other polymer 10b was nearly 10−4 S cm−1 at 20 °C and increased as
aliphatic polymers, the single ion conducting polymer based on the temperature increased to ∼10−3 S cm−1 at 65 °C after
poly(arylene ether) could also enhance the ionic conductivity
activation using 5 wt % acetonitrile as plasticizer. This study
by forming a more porous structure, which results in increased
electrolyte uptake.98 Another fully aromatic polymer, poly- indicates that the plasticizing effect of the solvent has a
(ether ether ketone) (PEEK), has been used to prepare a new considerable impact on the ionic conductivity of the resulting
class of single ion conducting polymer 10b for GPEs.143 The GPEs. In summary, polyaromatic polymers could represent a
single ion conducting polymer 10b was achieved by grafting potential alternative polymer for the preparation of high
with sulfonamide and bis(sulfonyl)-imide groups. The most performance GPEs for LIBs due to their good mechanical
interesting feature of GPEs based on the single ion conducting properties. In addition, the aryl groups can further promote the
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interaction with Li+ and minimize ionic polarization via coordination through electrostatic interactions; thus, it results
enhanced electrochemical and mechanical properties. in higher electrolyte retention and uptake.148 Maceiras et al.149
4.2. Hydrogen-Bonding Polymer. Recently, a polymer reported the copolymerization of two aromatic diamines, 1,3-
capable of forming hydrogen-bonding networks has achieved bis-2-cyano-3-(3-aminophenoxy)phenoxybenzene (diamine
popularity based on its ion conduction. The polar networks are 2CN) and 1,3-bis(3-aminophenoxy)benzene (diamine 0CN)
expected to dissolve large amounts of salt and tend to show with 4,4′-oxidiphtalic anhydride (ODPA) to synthesize a new
interesting ion transport behavior, such as Arrhenius-type amorphous PI 11b for elucidating the effect of the cyano group
conduction, and appreciable conductivity below T g. 20 (-CN) on the electrochemical performance of GPEs.149 The
Furthermore, the hydrogen-bonding polymers are intended resulting PI 11b was further prepared as a fiber using
to have interactions similar to that of liquid electrolytes and electrospinning process by dissolving in N,N-dimethylforma-
can tightly hold the liquid electrolyte inside the GPEs and mide and DMAc (1:1, v/v). After being activated by
avoid the leakage. Several hydrogen-bonding polymers have immersion into 1 M LiPF6 in EC/DMC (1:1, v/v), the
been investigated for the application of GPEs in LIBs, such as resulting GPE exhibited an ionic conductivity of 0.7 × 10−3 S
poly(vinyl alcohol) (PVA) and polyimide (PI). A polymer cm−1 at room temperature and a higher degree of porosity up
blend of 25 mol % poly(acrylic acid) (PAA) and 75 mol % to ∼80%. The study revealed that the ionic conductivity values
PVA is used to prepare GPEs by loading 70 wt % electrolyte, are influenced by the presence of -CN dipolar groups in PI
which contains an ionic liquid, 1-butyl-1-methylpyrrolidinium 11b; however, the specific mechanism was not explained
bis(trifluoromethanesulfonyl)imide (PYRTFSI), with 0.2 M clearly in this study.149
LiTFSI.144 This study focuses on blending PVA and PAA, Poly(ether imide) (PEI) 11c is expected to also have good
which are self-associated, and the OH groups are involved in affinity between the skeleton materials and the polar liquid
hydrogen-bonding interactions between the polymer chains. electrolyte due to the existence of ether bonds and amide
The results revealed that the hydrogen bonding is helpful for bonds as well as the similar structure and polarity with PI.150
improving the miscibility of polymer blends and directly affects Recently, a GPE composite based on 11c and halloysite
the thermal, mechanical, and optical properties.144 In addition, nanotubes (HNTs) as fabricated by electrospinning technol-
the PVA-PAA GPE composites exhibited ionic conductivity of ogy. After being activated by immersing into 1 M LiPF6 in
2.0 × 10−4 S cm−1 at 25 °C and increased to 1.4 × 10−3 S cm−1 EC/DMC (1:1, v/v), the corresponding GPE exhibited ionic
as the temperature was increased to 90 °C, which is typical of conductivity of 5.30 × 10−3 S cm−1, a lithium transference
Arrhenius temperature dependence behavior (Figure 15a). number beyond 0.5, and a stable electrochemical window up to
Moreover, a further electrochemical study revealed that the 5.4 V vs Li/Li+ with only 1 wt % HNTs. As shown in Figure
PVA-PAA GPE composites had a Li+ transference number of 15b, the GPEs based on 1 wt % HNTs in PEI exhibited better
0.4 and stable electrochemical window up to 5.0 V vs Li/ electrochemical performance with a higher capacity in Li/
Li+.145 In addition, by taking advantage of the OH groups on GPEs/LiCoO2 cells with different charge rates as opposed to
the PVA backbone, PVA was used and modified to prepare the the conventional Celgard separator and pure PEI film. The
single ion conducting polymer 6e.27 The modification of PVA investigation revealed that the excellent electrochemical
as a single ion conducting polymer is performed by physical performance was due to synergic advantages of PEI and
cross-linking with boric acid through hydrogen-bonding and HNT filler. The abundant carboxy groups of PEI molecules
ionic interactions in the hydrated state. Although the PVA- formed a hydrogen-bonding interaction with the liquid
based single ion conducting polymer possesses a relatively low electrolyte and possessed a high electrolyte uptake, which
ionic conductivity of 6.11 × 10−6 S cm−1, which is far from the assisted in the transmission of Li+ ions in the electrolytes. In
practical requirement, it exhibits a stable electrochemical addition, the abundant hydroxyl groups on the external surface
window up to 7 V vs Li/Li+, which is potentially compatible and the lumen of HNT were beneficial to decreasing the
with higher voltage LIBs.27 complex between the Li+ ions, thus promoting the lithium salt
In addition, recent investigations have reported the use of dissociation.150 In summary, hydrogen-bonding polymers gave
PIs to prepare GPEs for LIB applications. PIs are highly polar a new opportunity to further enhance the electrochemical
material and thus are expected to have strong coordination performance of GPEs by increasing liquid electrolyte uptake
within polymer chains with polar solvents, such as EC and and tightly holding it inside of the GPEs via hydrogen bonding.
EMC, due to the electron donor and acceptor groups, which 4.3. Biodegradable Polymer. The increasing focus on
largely enhance the retention ability of electrolytes.146 clean energy storage has led to more environmentally friendly
Moreover, PIs have been reported to have excellent thermal production of LIBs. However, well-known polymers for GPEs.
stability over 500 °C and are able to effectively avoid the short including PEO, PAN, PVDF, and PMMA, are all derived from
circuits caused by shrinkage at high temperature.147,148 Wang the petroleum industry and nonbiodegradable, which will
et al.147 used pyromellitic dianhydride (PMDA) and 4,4′- generate new environmental waste as the LIBs are
oxidianiline (ODA) to synthesize PI 11a (Scheme 11), which discarded.151 Therefore, many scientists are investigating
was then dissolved in N,N′-dimethylacetamide (DMAc) and biodegradable polymers as an alternative polymer for GPEs.
used to prepared an electrospun fiber. After activation by Cellulose has therefore drawn considerable attention due to its
immersing PI-based fiber into 1 M LiPF6 in EC/EMC/DMC outstanding properties, such as biocompatibility, biodegrad-
(1:1:1, v/v/v), the resulting GPE exhibited ionic conductivity ability, chemical stability, and good mechanical strength and
of 2.0 × 10−3 S cm−1 at 25 °C and a stable electrochemical thermal stability.152 A GPE based on cellulose as a polymer
window up to 5.0 V vs Li/Li+. Furthermore, a GPE based on host using a simple coating of PVDF on both surfaces of
PI 11a exhibited higher electrolyte uptake of ∼559% and high methyl cellulose (MC) to form a sandwich structure was
retention ability of 0.62. Further investigation found that the reported by Xiao et al.31 The GPE based on PVDF/MC/
high ionic conductivity could be associated with the good PVDF structure shows an ionic conductivity of 1.5 × 10−3 S
affinity of PI 11a, which holds liquid electrolyte via cm−1 at 25 °C, a lithium transference number of 0.47, and a
3964 DOI: 10.1021/acsaem.9b00295
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Figure 16. (a) Cycle behavior of LiFePO4 tested by using MC and PVDF/MC/PVDF at 0.1 C. Reprinted with permission from ref 31. Copyright
2014 Elsevier. (b) Cycle performance of GPEs based on porous CMC with different charge rates using Li/GPEs/LiFePO4 cell. Reprinted with
permission from ref 152. Copyright 2015 Elsevier. (c) Cycle performance of Li/LiFePO4 cell using GPEs based on nonwoven/TPU at the rate of 2
C at 80 °C. Reprinted with permission from ref 155. Copyright 2016 Elsevier.

stable electrochemical window up to 4.8 V vs Li/Li+ after electrochemical performance of GPE based on bacterial
activation by immersion into 1 M LiPF6 in EC/DEM/EMC cellulose (BC).154 The BC-based GPE was prepared through
(1:1:1, w/w/w). A stable cycling behavior of LiFePO4 using an ecofriendly fast freeze-drying method that does not involve
GPE sandwiched with PVDF/MC/PVDF is presented in any toxic or costly solvents as shown in 12c. After activation by
Figure 16a and indicates good compatibility with the cathode immersion in liquid electrolyte with 1 M LiPF6 in EC/DMC
electrode. This study shows that the synergic effect of PVDF (1:1, v/v), the BC-based GPE exhibited an ionic conductivity
polarity and hydroxyl groups on the surface of MC could of 4.04 × 10−3 S cm−1, a lithium transference number of 0.514
hinder PF6̅ anion mobility and promote the movement of Li+ at 25 °C, and a reversible capacity of 75.2 mAh g−1, and it was
ions.31 Furthermore, carboxymethyl cellulose (CMC) has maintained under a high rate of 9 C, which indicates that the
already been used to prepare porous GPE 12a by Zhu et al. BC-based GPE is suitable for fast-charging LIBs.154
(Scheme 12).152 Although the porous CMC-based GPE Another biodegradable polymer, polyurethane, has also been
resulted in relatively lower ionic conductivity of approximately studied for GPE applications. Liu et al.155 used polymer 12d to
4.8 × 10−4 S cm−1 at 25 °C and low electrolyte uptake for only fabricate novel GPE composites based on cellulose-coated
75.9 wt %, it showed a high lithium transference number up to polyurethane by the solution-casting method. Although the
0.49 and better cycle performance for CMC-2 (GPE with 2 mL resulting GPE showed relatively low ionic conductivity of
of N,N-dimethylformamide (DMF), porosity agent) compared approximately 2.3 × 10−4 S cm−1 at 25 °C, it exhibited stable
with commercial Celgard 2730 (Figure 16b). Another type of discharge capacity of the Li/LiFePO4 cell of approximately
cellulose polymer, HEC, has also been explored to identify its 128.2 mAh g−1 after 200 cycles and 91% of the capacity
performance as a GPE for LiBs.153 Interestingly, the HEC- retention at a charge/discharge rate of 2 C at 80 °C (Figure
based GPE formed a dense membrane without evidence of 16c). The study suspected that the reaction between the O−H
pores, although it also showed electrolyte uptake of up to 78.3 group of the cellulose and polar groups of thermoplastic
wt %, ionic conductivity of 1.8 × 10−4 S cm−1 at 25 °C, and a polyurethane (TPU) formed a stable structure and the
lithium transference number of 0.48 after activation by 1 M cellulose provided more channels of ions, thereby facilitating
LiPF6 in EC/DMC/EMC (1:1:1, w/w/w), which is close to ion transportation and enhancing the electrochemical perform-
the performance of the CMC-based porous GPEs. Further- ance.155 Biodegradable poly-ε-caprolactone (PCL) has also
more, the study revealed that the hydrogen-bonding attracted attention among the scientists as a polymer
interaction of carbonate-based liquid electrolytes with the electrolyte. A polymer electrolyte for zinc batteries was
polymer matrix is beneficial for retaining the liquid electrolyte implemented by Sownthari and Suthanthiraraj via solution
inside GPE and promoting fast Li+ mobility as shown in casting of PCL and zinc triflate [Zn(CF3SO3)2].156 This study
12b.153 The interaction between the solvent and cellulose shows an ionic conductivity of 8.8 × 10−6 S cm−1 and
polymer host on the 12b has also been applied to explain the electrochemical window stable up to 3.7 V at 25 °C. Although
3965 DOI: 10.1021/acsaem.9b00295
ACS Appl. Energy Mater. 2019, 2, 3937−3971
ACS Applied Energy Materials Review

Scheme 12. (a) Illustration Procedure for the Preparation Process of the Porous CMC Membrane by Using DMF as a
Nonsolvent;a (b) Illustration of the Interactions between Carbonate-Based Organic Electrolytes and Hydroxyl Groups in
HEC;b (c) Preparation Process of BC-GPE;c (d) Molecular Structure of Thermoplastic Polyurethane (TPU) with Ether
Bondd

a
Reprinted with permission from ref 152. Copyright 2015 Elsevier. bReproduced with permission from ref 153. Copyright 2015 Elsevier.
c
Reprinted with permission from ref 154. Copyright 2018 American Chemical Society. dReproduced with permission from ref 155. Copyright 2016
Elsevier.

the study shows a very low electrochemical performance for on composite formation and co-/terpolymer leads to improved
zinc batteries, it opens new opportunities for the further ionic conductivity associated with the morphology and
development of PCL-based GPEs for LIB applications and electrolyte uptake, a bulky terpolymer can lead to instability
provides insights for the development of environmentally issues and result in low ionic conductivity. On the basis of
friendly LIBs. structural design, the incorporation of ionic liquid and single
ion conductor polymer represents a promising strategy to
5. CONCLUSIONS AND PERSPECTIVES enhance the ionic conductivity and Li+ transport properties of
Li batteries. The ionic liquid provides the resulting GPEs with
Because of their characteristics as liquid and solid electrolytes,
GPEs have received increasing research attention because of greater electrochemical and thermal stability compared with
their high ionic conductivity (above 10−4 S cm−1), wide conventional liquid electrolytes. In addition, the single ion
electrochemical window, favorable mechanical properties, conducting polymer represents another method of Li+-ion
thermal stability, and compatibility with electrodes during transport and provides an immobile negative charge carrier in
cycling. The general requirements and crucial properties of which the concentration of polarization could be minimized
GPEs for LIB applications have been discussed in detail. during the cycling process, thereby enhancing Li+ transport.
Furthermore, the transport mechanism of Li+ ions have also Alternative polymer types, such as polyaromatic, hydrogen-
been explained in detail. With the great potential of applying bonding, and biodegradable polymers, have also been carefully
GPEs for LIBs, recent progress on GPEs based on different reviewed for GPE applications in LIBs to further increase the
polymer types has been carefully reviewed. In general, electrochemical performance and environmentally friendliness.
polyether, polyvinyl, polynitrile, polycarbonate, and polyacry- The rigid structure of polyaromatic polymers offers good
late are the most common polymer types for GPEs. However, mechanical properties and is expected to partially solvate the
each of these substances has pros and cons. Many studies Li+ through aryl groups; hence, the concentration polarization
focused on structural design of GPEs have been performed to can also be inhibited. Furthermore, higher electrolyte uptake
improve the electrochemical performance and fulfill the could be achieved by forming GPEs with more porous
requirements. Although the strategic design of GPEs based structures due to the incompatibility issue observed with
3966 DOI: 10.1021/acsaem.9b00295
ACS Appl. Energy Mater. 2019, 2, 3937−3971
ACS Applied Energy Materials Review

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for lithium-ion batteries. J. Mater. Chem. A 2015, 3 (38), 19218−
AUTHOR INFORMATION 19253.
(19) Marcinek, M.; Syzdek, J.; Marczewski, M.; Piszcz, M.;
Corresponding Author Niedzicki, L.; Kalita, M.; Plewa-Marczewska, A.; Bitner, A.;
*E-mail: [email protected]. Wieczorek, P.; Trzeciak, T.; Kasprzyk, M.; Łężak, P.; Zukowska, Z.;
ORCID Zalewska, A.; Wieczorek, W. Electrolytes for Li-ion transport −
Febri Baskoro: 0000-0001-8408-6726 Review. Solid State Ionics 2015, 276, 107−126.
Hung-Ju Yen: 0000-0002-6316-9124 (20) Mindemark, J.; Lacey, M. J.; Bowden, T.; Brandell, D. Beyond
PEOAlternative host materials for Li+-conducting solid polymer
Notes electrolytes. Prog. Polym. Sci. 2018, 81, 114−143.
The authors declare no competing financial interest.

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(21) Karatas, Y.; Banhatti, R. D.; Kaskhedikar, N.; Burjanadze, M.;
Funke, K.; Wiemhöfer, H.-D. Synthesis and Modeling of Polysiloxane-
ACKNOWLEDGMENTS Based Salt-in-Polymer Electrolytes with Various Additives. J. Phys.
H.-J.Y. acknowledges the financial support by Innovative Chem. B 2009, 113 (47), 15473−15484.
Materials and Analysis Technology Exploration (i-MATE; (22) Zhang, Z.; Sherlock, D.; West, R.; West, R.; Amine, K.; Lyons,
Grants AS-iMATE-107-92 and AS-iMATE-108-22), the L. J. Cross-Linked Network Polymer Electrolytes Based on a
Ministry of Science and Technology in Taiwan (Grant Polysiloxane Backbone with Oligo(oxyethylene) Side Chains: Syn-
MOST 107-2113-M-001-007-MY2), and the Sinica-ITRI thesis and Conductivity. Macromolecules 2003, 36 (24), 9176−9180.
corporation project (Grant AS-ITRI-106-03). (23) Xu, K. Nonaqueous Liquid Electrolytes for Lithium-Based

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Rechargeable Batteries. Chem. Rev. 2004, 104 (10), 4303−4418.
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