Carbonyl Coordinating Polymers For High Voltage Solid State Lithium Batteries Solid Polymer Electrolytes

MRS Energy & Sustainability: A Review Journal
page 1 of 25
© Materials Research Society, 2020
doi:10.1557/mre.2020.3
Review
Carbonyl-coordinating polymers Hongli Xu and Jingbing Xie, Department of Materials Science and
Engineering, School of Innovation and Entrepreneurship, Academy for
Advanced Interdisciplinary Studies, Southern University of Science and
for high-voltage solid-state Technology, Shenzhen 518055, China
lithium batteries: Solid polymer Zhongbo Liu, Shenzhen Capchem Technology Co., Ltd., Shenzhen 518118,
China
electrolytes Jun Wang and Yonghong Deng, Department of Materials Science

and Engineering, School of Innovation and Entrepreneurship, Academy for
Advanced Interdisciplinary Studies, Southern University of Science and
Technology, Shenzhen 518055, China
Address all correspondence to Jun Wang at wangj9@sustech.edu.cn and
Yonghong Deng at dengyh@sustech.edu.cn
(Received 22 January 2020; accepted 3 March 2020)
ABSTRACT
Solid polymer electrolytes are a crucial class of compounds in the next-generation solid-state lithium batteries featured by high safety
and extraordinary energy density. This review highlights the importance of carbonyl-coordinating polymer-based solid polymer electro-
lytes in next-generation safe and high–energy density lithium metal batteries, unraveling their synthesis, sustainability, and electro-
chemical performance.
With the massive consumption of fossil fuel in vehicles nowadays, the resulted air pollution and greenhouse gases issue have now
aroused the global interest on the replacement of the internal combustion engines with engine systems using renewable energy. Thus,
the commercial electric vehicle market is growing fast. As the requirement for longer driving distances and higher safety in commercial
electric vehicles becomes more demanding, great endeavors have been devoted to developing the next-generation solid-state lithium
metal batteries using high-voltage cathode materials, e.g., high nickel (Ni) ternary active materials, LiCoO2, and spinel LiNi0.5Mn1.5O4.
However, the most extensively investigated solid polymer electrolytes (SPEs) are based on polyether-based polymers, especially the
archetypal poly(ethylene oxide), which are still suffering from low ionic conductivity (10−7 to 10−6 S/cm at room temperature), limited
lithium ion transference number (<0.2), and narrow electrochemical stability window (<3.9 V), restricting this type of SPEs from realizing
their full potential for the next-generation lithium-based energy storage technologies. As a promising class of alternative polymer hosts for
SPEs, carbonyl-coordinating polymers have been extensively researched, exhibiting unique and promising electrochemical properties.
Herein, the synthesis, sustainability, and electrochemical performance of carbonyl-coordinating SPEs for high-voltage solid-state lithium
batteries will be reviewed.
Keywords: solid polymer electrolyte; carbonyl-coordinating polymers; polycarbonate; polyester
DISCUSSION POINTS • W
hat makes the carbonyl-coordinating polymers outperform their
polyether-based analogues in terms of electrochemical properties?
• C
arbonyl-coordinating polymer-based SPEs exhibit unique
electrochemical properties compared with their polyether-based • T
he bio-based synthesis approach and biodegradable
analogues, making them promising for the next-generation characteristics endow the carbonyl-coordinating polymers with
solid-state high–energy density lithium batteries. increasing attention from both industry and academia.
Downloaded from https://www.cambridge.org/core. IP address: 5.62.149.65, on 26 Dec 2020 at 16:03:03, subject to the Cambridge Core terms of use, available at https://www.cambridge.org/core/terms.
https://doi.org/10.1557/mre.2020.3
Introduction industry have been dedicated to the polyether-related polymers,
especially PEO, owing to its comparatively low Tg (≈ −60 °C) and
Why solid polymer electrolytes excellent solvation of various types of lithium salts.16 PEO is
The world overall energy consumption has increased tre- an excellent complexing agent for Li+, even though the dielec-
mendously over the past several decades.1 Take the USA as an tric constant is rather low (≈5).17–19 Besides, polyethers are
example, it consumed 101.3 quadrillion Btu (British thermal generally recognized as one of the most (electro)chemically
unit, equals approximately 1.1 × 1018 Joule) of energy in 2018, of stable polymer hosts against lithium metal anode, and the solid
which 80% was based on fossil fuels (petroleum, natural gas, electrolyte interface (SEI) layer formed on the anode side is
and coal) and 28% was used in the transportation systems.2 originated from the lithium salt decomposition and water
Such massive utilization of fossil fuel gives rise to the world traces.20,21 However, polyether-based SPEs are hardly to real-
severe challenges of air pollution and greenhouse gases issues ize the full potentials of solid-state batteries due to several
(mainly carbon dioxide and methane).3 To tackle these issues shortcomings, of which primarily are low ambient-tempera-
and to replace the heavy dependence on fossil fuel, renewable ture ionic conductivity (<10−6 S/cm), low lithium ion trans-
energy techniques, i.e., the classical lithium ion batteries, have ference number (<0.2), and narrow electrochemical window
been advanced dramatically and are considered as one of the (<3.8 V), as reviewed in many publications.7,22–28
most successful energy conservation systems in human his- As a promising class of alternative SPE hosts, carbonyl-
tory.4 However, the conventional lithium ion batteries based on coordinating polymers, primarily aliphatic polycarbonates and
liquid electrolyte systems are virtually impossible to satisfy the polyesters, endow the SPEs with superior electrochemical
stringent and booming demand for higher energy density and properties owing to their fast chain segmental motions, high
safety from 3 C electronics, auto industry, and grid energy con- dielectric constant, and unique lithium ion complexation and
servation systems. Developing lithium ion batteries with lower transport mechanism.29 Their aromatic analogues generally
cost, higher energy density, longer calendar life, and more satis- show very poor ionic conductivity because of the low local seg-
fying safety level is still in desperate need. mental motion of the rigid polymer chain and high degree of
Many leading economies, i.e., China, Germany, Japan, and crystallinity. The electrochemical properties, i.e., ionic con-
the USA, have set up their own ambitious milestones toward the ductivity, lithium ion transference number, and electrochemi-
next-generation high safety and high–energy density lithium cal stability, are critically important when one benchmarking
battery.5 The state-of-art lithium ion battery industry is built on an SPE. The unique properties of carbonyl-coordinating poly-
the liquid electrolyte systems with highly volatile and flamma- mers will be discussed in the following sections. To the best of
ble solvents, which also suffer from inadequate electrochemical our knowledge, polyketones (PKs) and polyanhydrides were
and thermal stabilities and low ion selectivity.6,7 To solve these rarely reported as SPE hosts, despite they are also in the family
problems, the replacement of liquid electrolytes with solid-state of carbonyl-coordinating polymers. This is most likely due to
electrolytes, and the employment of high–energy density anode their chemical instability, high crystallinity, poor solubility,
and cathode has been regarded as the best choice.4,8–10 As one of and the resulted extremely low ionic conductivity.
the most promising solid-state electrolytes, solid polymer elec- In the following sections, the three main indexes in measur-
trolytes (SPEs) show proximity with respect to device integra- ing electrochemical performance, i.e., ionic conductivity, lith-
tion, processing cost, and mechanical properties over inorganic ium ion transference number, and electrochemical stability
solid electrolytes.11 The first successful landmark of com- window (ESW), are compared between polyether-based SPEs
mercial EV applications of SPE was made by the launch of and carbonyl-based SPEs.
pure electric vehicles (Bluecar) provided by Bolloré in 2011 Ionic conductivity
in Paris.12,13 The battery using polyethylene oxide (PEO)-
based SPE and LiFePO4 cathode (working plateau at 3.5 V) The ionic conductivity represents the capability of an SPE
coupled with lithium metal anode delivers a competitive energy that shuttles ions. With respect to PEO-based SPE, the conduc-
density of 180–200 Wh/kg over liquid electrolyte-based auto- tion of Li+ is realized by solvating and coordinating lithium ions
motive batteries. As an encouraging industrial demonstration with the ether oxygen on PEO segments and transporting in
terms of dynamically breaking/forming lithium–oxygen (Li–O)
of the realistic application of solid-state batteries, SPEs are
bonds by intrachain or interchain hooping in the PEO seg-
exhibiting more than just potentials toward the next-generation
ments. Owing to such dynamical displacement of the ligands for
lithium batteries.
the solvation of lithium ions, the continuous polymer chain seg-
mental motion (local chain motion) results in a long-range
Why carbonyl-coordinating polymers motion of lithium ions.27,30,31 The dynamical rearrangement of
The dawn of the investigation on SPEs was from the work of this complexation in ionic transport can be well simulated by
P.V. Wright, who studied the ionic conductivity of PEO doped the dynamic bond percolation model.32,33 Typically, the ionic
with sodium and potassium salts,14 and was boosted by the conductivity of a polyether-based SPE at room temperature is in
seminal work of M. Armand, who used this type of material in the order of 10−7 to 10−6 S/cm, which is consequentially lower
electrochemical systems, especially in lithium batteries.15 than the generally recognized sufficient value of 10−4 S/cm
Since then, tremendous efforts from both academia and toward usable solid-state batteries for realistic applications.34,35
2 n MRS Energy & Sustainability // V O L U M E 7 // e 2 // www.mrs.org/energy-sustainability-journal

Compared with other ligand candidates such as carbonates and
esters, PEO solvates and coordinates lithium ions with a much
higher complexation strength.36 A good example is that in the
electrolyte system consisting of ≈90 mol% of propylene car-
bonate (PC) and ≈10 mol% of tetraethylene glycol dimethyl
ether (TEGDME), most lithium ions chelate to ether units of
TEGDME.17 However, such good complexation not only facili-
tates high salt dissolution but also highly restricts the breaking
of Li+/ether oxygen complexation by local segmental motions.
Thus, the complexation renders the polymer chain a very stable
coordination structure and the ions therefore inferiorly mobile,
despite a low Tg (≈ −60 °C). Besides, the ion–dipole interactions
between Li+/ether oxygen have significant impacts on the
microscopic morphology of SPEs, and in most cases, they act as
intermolecular cross-linker in SPEs to increase Tg.37,38 Hence,
the favorable complexation of Li+/ether oxygen that makes
PEO dissolve lithium salt well indeed also serves to restrict its
segmental motion. Furthermore, PEO is a highly crystalline Figure 1. Comparison of the ionic conductivity as a function of the salt
polymer, with a high degree of crystallization of approximately concentration for (a) polyether-based (PEO) SPE and (b) carbonyl-coordinating
80% at room temperature.39 Substantial evidences suggested polymer–based (polyethylene carbonate, PEC) SPE. Reproduced with
that the dominant lithium ions transportation takes place in the permission.46 Copyright 2014, Royal Society of Chemistry.
amorphous region,7 due to the higher polymer chain dynamics
on the amorphous nature. Although some reports presented
the superior ionic conductivity of Li+ in the crystal lattice of
PEO,40 prevailingly PEO crystallization is generally considered Lithium ion transference number
to be detrimental to lithium ions transportation due to the sac- Lithium ion transference number ( tLi+ ) is another fundamen-
rificed polymer chain dynamics.41 tal electrochemical parameter.49 A high t Li+ implies that the
As a promising analogue, carbonyl-coordinating polymer– conductivity primarily depends on the lithium ion transport
based SPEs generally exhibit relatively high ionic conductivity rather than on the anionic mobility. As only the mobility of lith-
at ambient temperature.42 In carbonyl-coordinating polymer– ium ions is the effective migration, which takes part in the elec-
based SPEs, the lithium ions are coordinated by the carbonyl trochemical redox reaction in electrodes, a high t Li+ (ideally, a
group oxygen (primarily) and the alkoxy oxygen adjacent to the unity of t Li+) is desired in lithium batteries to avoid local deple-
carbonyl group ether oxygen atoms (partly) on polymer seg- tion and high internal resistance caused by gradient polariza-
ments in a similar fashion to the polyether-based SPEs.28,43–45 tion from anion migrations. Besides, it was found that an SPE
With the processes of dynamically breaking/forming lithium– with high t Li+ is effective in the utilization of active electrode
oxygen bonds, the lithium ions transport is realized by the materials and the suppression of lithium dendrite growth.50–52
intrachain or interchain hooping in the carbonyl-coordinating Unfortunately, a low value of ≈0.2 was typically reported on the
polymer segments. Owing to the continuous displacement of PEO/LiTFSI systems,53 implying the high anion dynamics. The
the ligands for the solvation of Li+ by the segmental rear- reason is that the anion mobility is less restricted by the polymer
rangement of glass transitions, the long-range conduction of segmental motions, while the lithium cations are dominantly
lithium ions is thus occurred. Compared with polyether- complexed with ether oxygen as mentioned above.54,55
based SPEs, carbonyl-coordinating polymer–based SPEs To date, all the carbonyl-coordinating polymer–based SPEs
show significantly faster lithium ion transport, attributed to exhibited significantly higher t Li+ than the PEO/LiTFSI sys-
their fast “decoupling” during ion transport and segmental tems. As discussed above, the lithium ion shuttle in PEO-based
dynamics.46 Generally, the ionic conductivity of carbonyl- SPE system is realized by the dynamically breaking/forming
coordinating polymer–based SPEs closely correlates to Tg lithium–oxygen (Li–O) bonds of intrachain or interchain hoop-
and reaches a maximum value at high lithium salt loadings ing and assisted by the polymer chain local segmental motions.
(polymer-in-salt systems), where the Tg is significantly Due to the high donor numbers of ethers, the dynamic coordi-
depressed owing to the plasticizing effect.46–48 This may ena- nation cage formed by the polymer chains in polyether-based
ble the carbonyl-coordinating SPEs baring with high lithium SPE systems is quite stable and hard to break.56 The lower donor
salt loadings to achieve high ionic conductivity at ambient tem- numbers of carbonyl-coordinating polymers translate into an
perature and realize the practical applications. A comparison of enhanced dissociation ability and favorable dynamic dislocation
the ionic conductivity as a function of the salt concentration of lithium ions. The typical DC polarization and AC impedance
for polyether-based (PEO) SPE and carbonyl-coordinating results of both the PEO-based SPE and the PEC-based SPE at
polymer–based (polyethylene carbonate, PEC) SPE is pre- 60 °C are presented in Fig. 2, showing the much higher t Li+ of
sented in Fig. 1. the PEC/LiFSI SPE system.
MRS Energy & Sustainability // V O L U M E 7 // e 2 // www.mrs.org/energy-sustainability-journal n 3

generally unable to sustain an operating voltage higher than
3.9 V.60,61 This highly restricts the further improvement
toward the high–energy density systems, with the employment
of high-voltage cathodes, e.g., LiNi1−x−yCoxMnyO2, LiCoO2,
LiNi0.5Mn1.5O4, and Li-rich Mn-based oxides.62 Up to date,
LiFePO4 seems to be the only successful cathode candidate for
the utilization of PEO electrolyte.
Numerous publications on carbonyl-coordinating SPEs claimed
the significant enhancement of high-voltage compatibility, with a
typical onset of oxidation in the range of 4.5–5 V versus Li/Li+.63–65
However, there are still limited reports on underlying the mecha-
nism of high-voltage compatibility of SPEs, even for the most
investigated PEO-based SPEs.37 Ramprasad et al. presented the
theoretical estimation of ESW for polyethers [PEO and polypropyl-
Figure 2. Comparison of the DC polarization (left) and AC impedance ene oxide (PPO)] and carbonyl-coordinating SPEs [polycaprolac-
(right) experiment results of the (a) PEO-based SPE and (b) PEC-based SPE tone (PCL), polyketone (PK), polymethyl methacrylate (PMMA),
at 60 °C. Reproduced with permission.46 Copyright 2014, Royal Society of and polyethyl acrylate (PEA)] using first-principles density func-
Chemistry. tional theory computations,57 as shown in Fig. 3. The carbonyl-
coordinating SPEs showed improved high-voltage compatibility
because the valence band minimum (VBM) is lower than the elec-
trochemical potential of cathode (μC). In a similar fashion but
Electrochemical stability window involved the impacts of SEI and cathode electrolyte interface
A sufficiently wide ESW is another prerequisite for SPEs (CEI), Zhou et al. implied that the higher LUMO values of carbon-
toward high-voltage lithium batteries, as it determines the cycle yl-coordinating SPEs [PMMA, polypropylene carbonate (PPC) and
life of lithium batteries.4,8,9,24,36,58,59 It should be noted that the polyvinyl carbonate (PVCA)] compared to their polyether-based
morphological and chemical aspects of the polymer matrix and SPE (PEO) analogues were responsible for their better high-
its complex interactions with lithium salts have obvious impacts voltage compatibility.37
on the ESW of SPEs, which should be considered when evaluat- Benefitted from the unique structural characteristics of the
ing an SPE host.57 In general, a lithium battery often operates carbonyl groups, the carbonyl-coordinating polymer–based
to 4.3 V versus Li/Li+ and sometimes approaching 5 V in the SPEs present more appealing properties and surpass PEO-
case of using high-voltage cathode materials, which is a tough based analogues with respect to ionic conductivity, lithium ion
challenge for SPEs. Even though the polyether-based SPEs are transference number, and ESW, as summarized in Table 1. The
(electro)chemically stable with lithium metal anode, they are differences are rooted in the different donor numbers of the
Figure 3. Energy diagram of the electrolyte interface with anode and cathode. ESW of the SPE is determined by its reduction and oxidation potentials,
controlled by the conduction band maximum (CBM) and the VBM, respectively. μA and μC are the electrochemical potentials of the anode and the cathode,
respectively. Adapted with permission. 57 Copyright 2019, John Wiley and Sons.

Table 1. A brief comparison of electrochemical properties between carbonyl-coordinating polymer–based SPEs and polyether-based SPEs.
Carbonyl-coordinating polymer–based SPEs Polyether-based SPEs

σ High (10−4 S/cm at room temperature in the case of Low at room temperature (10−7 to 10−6 S/cm), high at
polymer-in-salt systems) elevated temperature (10−4 S/cm)
t Li+ High (generally >0.5) Low (generally <0.2)
ESW Broad (typically >4.5 V) Narrow (generally <3.9 V)
σ: ionic conductivity; t Li+ : lithium ion transference number; ESW: electrochemical stability window.
functionalities, the disparate dielectric constants, the diverse largest families of natural biomacromolecules and are capable
polymer segmental motion abilities and the distinct Li+/oxygen to undergo environmentally friendly biodegradation with
coupling energy.29 appropriate structures.66 A vast number of review articles on
These advantages bring carbonyl-coordinating polymer– the synthesis, characterization, properties, application, and
based SPEs even closer toward the implementation in commer- degradation of aliphatic polyesters and polycarbonates have
cial devices. As summarized in Fig. 4, carbonyl-coordinating been reported in the literature.67–85 Herein, a brief summary of
polymer–based SPEs exhibit several potential advantages: the synthesis strategies and sustainability of aliphatic polyes-
(i) high ionic conductivity, (ii) excellent lithium ion transfer- ters and polycarbonates, which can potentially be involved in
ence number, (iii) superior electrochemical stability, (iv) versa- the application of SPEs, will be discussed in the context below.
tile chemistry approach, and (v) environmental benignity.
Synthesis approach toward polycarbonates
Synthesis and sustainability Traditionally, there are primarily three synthesis methods
Carbonyl-coordinating polymers (primarily aliphatic poly- toward polycarbonates, i.e., polycondensation, ring-opening
carbonate and polyester) have long been recognized as biode- polymerization (ROP), and CO2–epoxide coupling reaction, as
gradable and sustainable polymers. This is because the summarized in Scheme 1. Recently, Tamura et al. presented a
ester- and the carbonate-linked polymers are among one of the synthesis approach for versatile polycarbonates from various
diols and CO2 directly, which was promising in terms of the sim-
ple and environmentally friendly chemistry.86 Aliphatic poly-
carbonates were initially prepared via polycondensation
involved aliphatic phosgene or derivatives, which was not a fine
chemistry, and the obtained polymers generally were with low
molecular weight and high polydispersity.87 By using the melt
polycondensation and post transesterification techniques,
high–molecular weight aliphatic polycarbonates were obtained
via the polycondensation from dialkyl carbonates and aliphatic
diols.88–90 In addition, the polycondensation technique enables
one to prepare various structured polycarbonates straightfor-
ward from different diol-functionalized aliphatic oligomers.
As an alternative, ROP of cyclic carbonates is a more effec-
tive strategy to synthesize polycarbonates with high molecular
weight and narrow polydispersity without the formation and
removal of any by-products as in polycondensation. The most
commonly used monomers for ROP were the five- and
six-membered rings of cyclic carbonates, e.g., trimethylene
carbonate (TMC), a well-known biodegradable material.91 The
thermodynamic analysis of ROP showed that the high angular
strain (Bayer’s strain) of the small (three- or four-membered)
size rings had a favorable enthalpy effect, while the medium
(six-membered) and larger size rings were primarily driven by
Figure 4. Structural characteristics of carbonyl-coordinating polymer– entropy.92–94 Various types of catalysts such as transition metal
based SPEs (polycarbonates and polyesters) and their unique advantages. catalysts, alkyl halides, basic and acidic organocatalysts, as well
as enzyme catalysts were reported to be effective in catalyzing

coordination complexes has been revealed in depth in several
excellent reviews.98,101,102
Synthesis strategies toward polyesters

Despite the very similar chemical structure to polycar-
bonates, the synthesis strategies for polyesters are slightly
different. Aliphatic polyesters were primarily prepared via
polycondensation and ROP, as shown in Scheme 2.66,103
The most traditional way of synthesizing polyesters involves
the step-growth mechanism (polycondensation) from dicarbox-
ylic acid (or dicarboxylic acid derivatives, such as diacid chlo-
ride) and diols, or from an oxyacid or its ester derivatives. The
study of polycondensation of aliphatic polyesters was pioneered
by Carothers et al. 87 to extract the fundamental knowledge
related to the step-growth polymerization and the relationship
between molecular weight and extent of reaction, the stoichio-
metric imbalance of functionalities. However, polycondensa-
tion suffer from some major drawbacks, e.g., high reaction
temperature, long reaction time, and removal of reaction
by-products. Polyesters with sufficiently high molecular weight
could only be achieved in the case of very high conversion and
precise stoichiometry.103 Oligomers with molecular weight of
several thousand (g/mol) were easily obtained, which could be
further improved by chain extension treatment.104–106
Scheme 1. Synthesis strategies for aliphatic polycarbonates. (a) Polyconden- To tackle these challenges, the ROP approach was developed
sation, (b) ROP, (c) CO2–epoxide coupling reaction, and (d) CO2–diol coupling to achieve a high molecular weight at mild reaction conditions.
reaction. The monomers used in the ROP involve cyclic esters, e.g., lac-
tones, cyclic diesters (lactides and glycolides), and cyclic ketene
acetals. In sharp contrast to polycondensation, ROP can be car-
the ROP of cyclic carbonates.95 Depending on the selection of ried out with complete monomer conversion and virtually free
catalyst, the ROP could be conducted in different mechanisms from side reactions, providing very good control over molecular
including cationic, anionic, coordination–insertion, monomer structures, e.g., molecular weight, polydispersity, and end-
activation, monomer and initiator dual activation, and enzymatic group functionalization. In most cases, both the synthesis
activation, in solution or in bulk.95 Notably, enzyme-catalyzed
ROP was also powerful for synthesizing polycarbonates, with
respect to the unique advantages of enzymes over conventional
catalysts due to their milder reaction conditions, higher toler-
ance for functional groups, and higher selectivity. However, the
catalyzing efficiency and the control on molecular weight and
polydispersity were rather restricted.77,84
As one of the most promising and sustainable strategies of
green chemistry, synthesizing polycarbonates from carbon
dioxide (CO2) has aroused extensive research interest to tackle
the greenhouse gas pollution issue and to alleviate the shortage
in conventional petroleum fuel supplies.96–99 Ever since the
first report of copolymerizing CO2 with epoxide by Inoue et al.
in 1969,100 this copolymerization strategy has now turned into
one of the most innovative techniques involved in the utiliza-
tion of CO2 in industry. The main challenge of this synthesis
strategy is searching for a highly efficient and selective catalyst
while suppressing the side reactions, e.g., polyether formation
from epoxide, backbiting reactions leading to cyclic car-
bonates.95 A bunch of organometal catalysts have been devel-
oped, e.g., zinc-containing catalysts, aluminum complex, and Scheme 2. Synthesis strategies toward aliphatic polyesters. (a) Polycon-
transition metal complex.99 The mechanism of the alternating densation, including AA + BB type and AB type, and (b) ROP.
copolymerization of CO2 with epoxide catalyzed by metal

approaches for aliphatic polyesters were carried out in the pres-
ence of catalysts, e.g., protonic acid (HCl, RCO2H, etc.), Lewis
acids (AlCl3, BF3, etc.), and organometallic compounds (stan-
nous octoate, etc.),107 even though some lactones polymerized
spontaneously on heating. In principle, most catalysts utilized
in the ROP of cyclic carbonates are also effective for the ROP of
cyclic esters owing to the chemical structural similarity. The
mechanism of ROP is highly dependent on the selection of cata-
lysts and monomers, including cationic, anionic, free radical,
active hydrogen, zwitterionic, and coordination.107 Like the
enzyme-catalyzed synthesis of polycarbonates, enzymatic syn-
thesis of polyesters via both the polycondensation and the ROP
techniques has been studied extensively. However, enzymatic
polymerization generally yielded product with low molecular
weight (<10,000 g/mol) and broad molecular weight distribu-
tion,66,77,79,84 which is in need for further improvement.
Sustainability
In the past several decades, environmental concerns have
spurred tremendous research interest in renewable resources
and green chemistry. As a promising class of sustainable alter-
natives to commodity plastics,66,85 the synthesis, characteriza- Figure 5. The cycle life of PLA. Adapted with permission.80 Copyright 2007,
tion, properties, and application of bio-based and biodegradable Royal Society of Chemistry.
polycarbonates and polyesters have been studied extensiv
ely.67,79,85,103,108–112 The sustainable and eco-friendly synthesis
approaches for polycarbonates and polyesters have been sum- highlights the commercial and environmental potential for
marized above, among which enzyme-catalyzed polymeriza- plastics sourced from plants, with renewable life cycles and
tions are promising with respect to their unique advantages of which are carbon neutral. The mentioned green aspects of
low requirement of reaction conditions, high tolerance for func- enzyme catalysis are expected to contribute to solving the envi-
tional groups, and high selectivity. However, enzyme-catalyzed ronmental problems.
polymerizations also show drawbacks, which must be improved The synthesis, properties, application, and recycling of poly-
by further study. Notably, polycarbonates can be synthesized esters and polycarbonates have been explored extensively over
effectively in large scale by copolymerization of CO2 with epox- the years. As a promising class of high-voltage SPEs, aliphatic
ides. As one of the most abundant and renewable carbon polyester and polycarbonate-based SPEs for lithium batteries
resources, the industrial scale utilization of CO2 and the selec- have also been studied. In this review, we will summarize the
tive transformation of CO2 into degradable polycarbonates recent key advances in polycarbonate- and polyester-based
are regarded as the most successful green and sustainable SPEs. The primary focus will be on the electrochemical prop-
chemistries.95 erty, lithium ion transport mechanism, and battery perfor-
The carbonate and ester functionalities are naturally mance (if available). Based on our understanding and to the best
formed, thus can go easy naturally breaking under certain con- of our knowledge, we tentatively suggest some challenges and
ditions and appreciate backbone structures. As an example, Li perspective for aliphatic polycarbonate- and polyester-based
et al. reported the enzyme-catalyzed biodegradation of poly(tri- SPEs in the last part of this review. We hope this review may give
methylene carbonate) (PTMC) in the presence of lipases from some helpful hints on understanding the correlation between
Candida antarctica.113 It was found that the PTMC degraded structure and electrochemical performance and advancing the
rapidly by Candida antarctica lipase, with 98% mass loss after carbonyl-coordinating polymer-based SPEs.
9 days, which was promising in terms of green recycling of
battery materials. To date, the well-studied example of bio- Polycarbonate-based SPEs
degradable material is the bio-based polylactide (PLA), which is
currently manufactured on a large scale by the ROP of lactide, a Side chain polycarbonate-based SPEs
cyclic ester from the fermentation product based on corn or To date, conventional liquid electrolytes are still the domi-
wheat, as shown in Fig. 5.80 PLA has been utilized in a variety of nant player in the field of lithium batteries, of which the major-
applications, e.g., sutures, stents, dental implants, vascular ity are based on the carbonate solvent families, such as ethylene
grafts, bone screws, and pins, because of its biocompatibility. carbonate (EC), vinylene carbonate (VC), PC, and dimethyl
Under certain conditions, such as enzyme, PLA is capable of carbonate (DMC).36 From a chemical perspective, the poly-
undergoing enzyme-catalyzed biodegradation into lactic acid carbonates are essentially the linearly polymerized carbonates
and further into CO2 and H2O. This great success of PLA with high molecular weights either in the main chain or in the

side chain, thus can solvate, coordinate, and conduct lithium (>75 mol%) were mechanically brittle, failing to perform the
ions in a similar fashion. The strategy of polymerizing car- electrochemical measurements.
bonates endows polycarbonate-based SPEs with unique proper- By copolymerizing poly(VC) with a series of poly(methoxy
ties in terms of lithium ion conductivity, lithium ion transference oligo(ethyleneoxy)ethyl vinyl ether) with different chain
number, ESW, and mechanical properties, etc. The molecular lengths, the poly(1a-g-alt-VC) alternating copolymer–based
structures of polymer hosts and electrochemical properties of SPEs showed a significant increase in ionic conduction, as
some typical polycarbonate-based SPEs are summarized in shown in Entry 5 of Table 2.121 The highest ionic conductivity
Table 2. reached 1.2 × 10−4 S/cm at 30 °C due to the incorporation of
The earlier work of applying polycarbonates for SPEs was large amount of flexible oligoether side chains. As a compro-
provided by Holt et al.114 using poly(vinylene carbonate) (PVIC) mise, the electrochemical stability and lithium ion transfer-
as the polymer host (Entry 1 in Table 2). By integrating with ence number were consequentially sacrificed, indicating
crown ether (12-crown-4) and LiCF3SO3, such polycarbonate- that the ion conduction is mainly coupled with the ether seg-
based SPE showed considerably high ionic conductivity of mental motions indeed. Wang et al. recently reported the
2.5 × 10−4 S/cm at ambient temperature. Shriver and Wei block copolymer of poly(vinylene carbonate-acrylonitrile)
also reported the SPEs based on PVIC or poly(1,3-dioxolan- [P(VC-AN)], aiming to achieve high-voltage cathode mate-
2-one-4,5-diyloxalate) (PVICOX) with LiCF3SO3,115 delivering rial (LiNi0.5Mn1.5O4) compatibility by taking complementary
ionic conductivities of 1 × 10−6 S/cm (PVIC) and 1 × 10−4 S/cm advantages of EC and nitrile functionality, as shown in Entry 6
(PVICOX) at 60 °C, respectively. The enhanced ionic con- of Table 2.122 However, the SPE most likely shows low ionic
ductivity of PVICOX/LiCF3SO3 SPE system was attributed to conductivity (not presented in the paper) due to the highly
the larger free volume of PVICOX over the PVIC analogue. rigid polymer chain and possible crystallinity. Gel polymer
Besides, the crystalline behavior did not appear to suppress electrolyte was prepared to perform all the electrochemical
the ion conduction in such highly rigid chain SPE, which was experiments and battery cycling tests. To avoid using such a
in contrast with polyether-based SPEs.27 The ion transport highly rigid backbone structure, preparing flexible block
was decoupled from the polymer chain segmental motion in copolymers with pendant carbonate moieties seems to be a
these SPEs. By replacing the backbone of poly(vinylethylene reasonable choice. To this end, Wegner et al. synthesized
carbonate) with highly flexible polysilanes, the polycar- block copolymers of polyacrylate and polymethacrylate with
bosilanes, i.e., polySBMC and polySBDC, delivered impres- flexible carbonate functionalities at the side chain, as shown
sively high ionic conductivities of 6.1 × 10−5 and 1.5 × 10−4 S/ in Entry 7 of Table 2.123 The ionic conductivity was still insuf-
cm at 30 °C, respectively, and at high LiTFSI loading (Entry 2 ficient for the electrochemical application at room tempera-
in Table 2).116 As the result, the mechanical properties were ture. Preparing gel electrolyte using PC was able to reach an
severely compromised by such high lithium salt concentration. order of 10−4 in ionic conductivity.
Recently, Chai et al. reported the in situ polymerized poly
(vinylene carbonate)/lithium difluoro(oxalate)borate (PVC/ Main chain polycarbonate-based SPEs
LiDFOB)-integrated SPE for high-voltage lithium metal bat- Typically, aromatic polycarbonates exhibit high Tg and
tery, as shown in Fig. 6 and Entry 3 of Table 2.117 A high ionic poor segmental motions due to the rigid backbone of the pol-
conductivity of 9.8 × 10−5 S/cm, high t Li+ of 0.57 and wide elec- ymer chain, which are detrimental for lithium ion transpor-
trochemical window of 4.5 V were obtained at 50 °C, ensuring tation. The exploration of applying aromatic polycarbonates
the outstanding electrochemical performance of LiCoO2/Li as SPE hosts has been reported in the early stage. Spiegel
cell. The in situ technique intrinsically endowed the cell with et al. reported the solvation behavior of lithium salts using
superior interfacial stability and structural integrity, thus the poly(dimethyl siloxane)/poly(bisphenol-A carbonate) block
high-voltage LiCoO2/Li cell delivered satisfactory rate capa- copolymers with LiCF3SO3 (Entry 1 in Table 3).125 Even
bility (0.5 C, 73 mAh/g) and long-term cycling stability (84% though the ionic conductivity could be improved signifi-
after 150 cycles at 0.1 C). However, the abnormally high ionic cantly from 7 × 10−9 S/cm to 8.1 × 10−7 S/cm (both at room
conductivity is more likely because of plasticizing effect from temperature) by the induction of soft poly(dimethyl silox-
the unreacted VC monomers rather than the contribution ane) block, such ionic conductivity was still far below the
from the polymer host. essential value (10−4 S/cm). Attempts to improve the ionic
Compared with their homopolymer-based analogues, SPEs conductivity of aromatic polycarbonate-based SPEs using
from block copolymer are capable of exhibiting combined oligo(ethylene oxide) side chains were effective (Entry 2 in
properties from each block,118 thus to achieve balanced prop- Table 3); however, the electrochemical stability and lithium
erties with respect to ionic conductivity, electrochemical sta- ion transference number were compromised.126 This is easy
bility, and mechanical strength.119 Itoh et al. reported the to be understood that the ion conduction is dominated by the
integrated SPE from block copolymers of poly(AcIM/VC) and ether segmental motions.121 All these results further confirm
LiTFSI, exhibiting a significantly higher ionic conductivity the failure of using aromatic polycarbonates as SPE host.
value (7 × 10−4 S/cm at 80 °C) compared with poly(AcIM) Nevertheless, aromatic polycarbonates are potentially useful
homopolymer–based SPE (8.5 × 10−5 S/cm), as shown in Entry in strengthening the mechanical properties of SPEs via pre-
4 of Table 2.120 The block copolymers with high VC content paring block copolymer strategy.

Table 2. Molecular structure and electrochemical characteristics of side chain polycarbonate-based SPEs.
Entry Polymer host Lithium salt σ (S/cm) ESW t Li+ References

1 LiCF3SO3 PVIC: 2.5 × 10−4 (25 °C)114 N/A N/A 114 and 115
PVIC: 1.0 × 10−6 (60 °C),

PVICOX: 1.0 × 10−4
(60 °C)115
2 LiCF3SO3 polySBMC: 6.1 × 10−5 N/A N/A 116

(30 °C)
LiTFSI polySBDC: 1.5 × 10−4

(30 °C)
3 LiDFOB 9.8 × 10−5 (50 °C) 4.5 V (50 °C) 0.57 117
4 LiTFSI Poly(AcIM): 8.5 × 10−5 N/A N/A 120

(80 °C), 1.7 × 10−6 (30 °C)
Poly(AcIM/VC): 7.0 × 10−4

(80 °C), 6.7 × 10−5 (30 °C)
5 LiTFSI 1.2 × 10−4 (30 °C) 4.1–4.6 V (80 °C) 0.1–0.3 (80 °C) 121
6 LiPF6 2.6 × 10−4 (25 °C) 5.2 V 0.52 122
7 LiTFSI PDOA: 3.7 × 10−6 (40 °C) N/A N/A 123
σ: ionic conductivity; ESW: electrochemical stability window; LiCF3SO3: lithium trifluoromethanesulfonate; LiDFOB: lithium difluoro(oxalate) borate; LiTFSI:
lithium bis(trifluoromethanesulfonyl)imide; LiPF6: lithium hexafluorophosphate.

Figure 6. (a) In situ polymerization of PVC-based SPE and (b) self-standing SPE film. (c–f) Battery cycling performance of LiCoO2/Li cells with PVC/
LiDFOB-integrated electrolyte. Reproduced with permission under CC BY-NC-ND 4.0,117 Copyright 2016, the Authors.
As a contrast, aliphatic polycarbonates undergo polymer via the green chemistry of the copolymerization of carbon diox-
chain segmental motions much easier due to the higher molec- ide with epoxides,85 rather than the ring-opening reaction from
ular flexibility of aliphatic backbones. The simplest aliphatic EC owing to its thermodynamic stability of the five-membered
polycarbonate used as SPE host was the principal ring-opening ring structure of EC.127 Besides, the ROP on EC is generally
products from cyclic carbonates (EC) with the characteristic associated with the emission of carbon dioxide, resulting in
backbone structure of –O–(C=O)–O–, as shown in Entry 3 of polymer backbones with ether junctions alongside with car-
Table 3. Practically, this polymer was more often synthesized bonate linkages.128 Novakov and colleagues investigated the

Table 3. Molecular structures and electrochemical characteristics of main chain polyester-based SPEs.

1 LiCF3SO3 4.4 × 10−6 (25 °C) N/A N/A 125
2 LiTFSI 1 × 10−6 to 4.3–5.0 V 0.35–0.67 126

1 × 10−4 (80 °C) (80 °C)
3 LiClO4 9.6 × 10−4 (80 °C) N/A N/A 129
LiFSI 4.1 × 10−4 (60 °C) N/A >0.5 46, 47, 135,
and 136
LiTFSI LiTFSI: 10−4 (80 °C) >4.3 V LiTFSI: 0.63 130–134
LIClO4 LIClO4: 10−5 (80 °C) LIClO4: 0.26
LiBF4 LiBF4: 10−5 (80 °C) LiBF4: 0.22
LiPF6 LiPF6: 10−5 (80 °C) LiPF6: 0.4
4 LiTFSI 10−5 (25 °C) N/A N/A 124, 137,

142, and
143
5 LiCF3SO3, 3 × 10−4 (95 °C) 4.5 V N/A 64 and 144

LiClO4,
LiBF4
LiSbF6 6 × 10−5 (85 °C) 5.0 V N/A 145
LiPF6 4.8 × 10−6 (98 °C) 4.5 V N/A 65
1.8 × 10−8 (25 °C)
LiTFSI 10−7 (60 °C) 5.0 V N/A 63
LiTFSI N/A N/A 0.8 (60 °C) 148
Continued

Table 3. Continued
6 LiTFSI 1 × 10−4 (25 °C) 4.0 V (60 °C) N/A 149
7 LiTFSI 1.1 × 10−5 (25 °C) 4V 0.39 150
2.0 × 10−4 (80 °C)
8 LiTFSI 1.7 × 10−4 (25 °C) 4.5 V 0.47 151
9 LiTFSI 1 × 10−3 (80 °C) 4.9 V 0.4 152
4 × 10−4 (60 °C)
4 × 10−5 (25 °C)
10 LiCF3SO3 10−4 (60 °C) N/A N/A 138
11 LiCF3SO3 10−4 (60 °C) N/A N/A 153
12 LiTFSI 1 × 10−4 (60 °C) N/A N/A 154

6 × 10−6 (20 °C)
13 LiClO4 8.4 × 10−3 (25 °C) N/A 0.42 155
1.4 × 10−2 (50 °C)
Continued

Table 3. Continued
14 LiClO4 1 × 10−4 (30 °C) 4.7 V (60 °C) N/A 156
5 V (25 °C)
15 N/A 1.61 × 10−4 (80 °C) 4.3 V 0.86 (25 °C) 157
16 N/A 1.2 × 10−4 (70 °C) N/A 0.89 158
17 Blend of PPC, polybutadiene and PEG LiPF6 1.3 × 10−3 (25 °C) 4.5 V N/A 159
3.5 × 10−3 (80 °C)
18 PVDF/PPC blend LiPF6 4.1 × 10−3 (30 °C) 5.2 V N/A 160
19 LiODFB 1.1 × 10−3 (25 °C) 5V 0.68 161
20 LiClO4 1.5 × 10−3 (25 °C) N/A N/A 165
Continued

Table 3. Continued
21 LiTFSI 5.2 × 10−4 (20 °C) 4.6 V 0.75 166
σ: ionic conductivity; ESW: electrochemical stability window; LiCF3SO3: lithium trifluoromethanesulfonate; LiTFSI: lithium bis(trifluoromethanesulfonyl)imide;
LiClO4: lithium perchlorate; LiFSI: lithium bis(fluorosulfonyl)amide; LiBF4: lithium tetrafluoroborate; LiPF6: lithium hexafluorophosphate; LiSbF6: lithium
hexafluoroantimonate; LiDFOB: lithium difluoro(oxalate) borate.
Li+-carbonyl group coordination behavior in PEC/LiClO4 SPE

systems using Fourier Transform Infrared (FTIR).129 Tominaga
et al. extensively studied the lithium ion conduction behavior of
PEC-based SPE using various types of lithium salts.46,47,124,130–140
Some lithium salts, e.g., LiBF4, LiFSI, and LiTFSI, have signif-
icant plasticizing effects on PEC-based SPE systems at high con-
centrations due to the declined intermolecular interactions by
highly saturated ion pairs and aggregated ions and suppressed
intramolecular interactions between carbonyl and CH2 arising
from ion–dipole interaction.133 Distinctly, the PEC/LiCF3SO3
and PEC/LiClO4 SPE systems behaved more similarly to their
polyether-based analogues, with respect to the dependencies of
ionic conductivity and Tg on lithium salt loadings.130 Besides, Figure 7. (a) Tg and storage elastic modulus as a function of LiTFSI molar
the PEC-based SPEs showed uniquely high t Li+ value (>0.5) ratio versus monomer unit of PEC. Reprinted with permission.48 Copyright
despite high salt concentration,134 clearly outperforming the 2014, Elsevier B.V. (b) Ionic conductivity of PEC/LiTFSI SPE systems as a
polyether-based SPEs, which exhibited a drastically decreased function of temperature and various lithium salt loadings. Reprinted with
t Li+ at elevated salt concentrations.141 Especially, the ionic con- permission.124 Copyright 2016, Japan Science and Technology.
ductivity of PEC/LiFSI-integrated SPE was estimated to be
higher than 10−4 S/cm at room temperature, with a t Li+ value of
0.63.134 Even better electrochemical properties in terms of typical order of 10−8 S/cm at 80 °C, and the flexible side groups
ionic conductivity (4 × 7 × 10−4 S/cm) and t Li+ (0.88) at 20 °C (such as ethyl and n-propyl) suppressed Tg (<13 °C) and brought
were reported by Okumura et al. based on the PEC/LiTFSI-in- much higher ionic conductivity in an order of 10−5 S/cm at room
tegrated SPE systems.48 These unique properties made PEC a temperature.124 This is clearly because the bulky side substitutes
promising SPE host, which was well summarized in a focused impede segmental motions, whereas the inclusion of flexible side
review by Tominaga.124 Even though high ionic conductivity groups increases the free volume and lowers Tg. Aside from the
and t Li+ are achievable at high lithium salt concentrations, the coordination and conduction effects of lithium ions by carbonyl
plasticization is accompanied by a notable suppression of Tg and groups, the embodiment of ether-based side groups has consider-
deterioration of mechanical properties, as depicted in Fig. 7. able enhancement on lithium ion transport. Hitherto, the ether-
While the PEC-based SPEs surpassed their PEO-based ana- based substituents, e.g., ethyl, i-propyl, n-butyl, t-butyl, phenyl,
logues regarding the electrochemical properties, the versatile and oxyethylene groups, have been investigated by Tominaga
chemistry of the synthesis of PEC enabled one to explore various et al.137 However, the electrochemical stability and t Li+ were
functional PEC-derivatives toward higher ionic conductivity.124 found to be deteriorated with the involvement of ether-based
Several different side groups functionalized PECs were prepared side groups due to the lower stability of ethers toward electro-
by Tominaga et al. via the green chemistry approach starting chemical oxidation and stronger chelation of lithium ion with
from CO2 and a set of epoxides as electrolyte materials, as sum- ether oxygen compared with carbonyl groups.
marized in Entry 4 of Table 3.124,137,142,143 The side functionali- By increasing the number of flexible methylene unit of PEC,
ties used were methyl, ethyl, n-propyl, methylene phenyl, etc. the developed PTMC emerged as a promising SPE host candi-
Depending on the selection of the substituents, the Tg’s of poly- date due to its low Tg (≈ −15 °C) and amorphous nature (Entry 5
mers were tunable within the temperature range 3–45 °C. The in Table 3). Smith et al. investigated the influence of various
bulky groups (such as methylene phenyl) substituted PEC SPEs lithium salts, e.g., LiCF3SO3, LiClO4, LiBF4, LiSbF6, and
showed high Tg (≈45 °C) and low ionic conductivities with a LiPF6, on the ionic conduction of PTMC-based SPEs.64,65,144,145

The lithium salt–dependent ionic conductivity (<10−4 S/cm at initial discharge capacity of 141.4 mAh/g and a good capacity
80 °C) and electrochemical stability (>4.5 V) are summarized in retention with high Coulombic efficiency.
Entry 5 of Table 3. The PTMC-based SPE systems were also To further improve the ionic conductivity, polycarbonate–
comprehensively studied using LiTFSI as the lithium salt by polyether block copolymer was investigated toward the
Brandell et al.63,146–148 The flexible PTMC/LiTFSI-integrated one-component polymer hosts for high-performance SPEs,
SPE delivered high electrochemical stability (>5 V) and high t Li+ as summarized in Entries 10–16 of Table 3.138,153–157 Höcker
(0.8 at 60 °C), with a moderate ionic conductivity (10−7 S/cm at et al. first reported the preparation of SPE based on poly
60 °C). Interestingly, even though the PTMC had a much lower (2,2-dimethyltrimethylene carbonate)-b-poly(ethylene oxide)-b-
Tg (−15 °C)63 than PEC (13 °C),124 the ionic conductivity did poly(2,2-dimethyltrimethylene carbonate) (PDTC-b-PEO-
not outperform PEC. This is because of the lack of lithium salt PDTC) triblock copolymer and LiCF3SO3, showing a moderate
plasticizing effect in the PTMC-based systems at high lithium ionic conductivity value at the order of 10−4 S/cm at 60 °C.153
salt loadings, which plays a decisive role in the high ionic con- Tominaga et al. also reported the high ionic conductivity (4.8 ×
ductivity of PEC/LiFSI or PEC/LiTFSI systems as mentioned 10−4 S/cm at 60 °C) and high t Li+ (0.66) obtained from the ran-
above. The PTMC/LiTFSI systems behaved more like PEO/ dom block copolymer of poly(ethylene carbonate/ethylene
LiTFSI analogues, showing increased Tg with increasing LiTFSI oxide)-based SPE.138 By cross-linking, the ionic conductivity of
concentration, and a maximum value of ionic conductivity at a the poly(ethylene carbonate/ethylene oxide) was severely low-
moderate LiTFSI loading could be obtained.63 By further ered to an order of magnitude of 10−6 S/cm at 20 °C due to the
increasing the number of methylene units, Mecerreyes et al. hindered polymer chain segmental motions.154 FTIR experiment
reported the synthesis and properties of a series of polycar- proved that the Li+ had no preference in chelating with carbonyl
bonates containing 4–12 methylene units by polycondensation groups or ether units, which was in sharp contrast with the PEC
of aliphatic diols and DMCs, showing low Tg of approximately systems containing oligoether side moieties.137 However, the
−40 °C.149 High ionic conductivity (1 × 10−4 S/cm at room electrochemical stability of the polycarbonates is most likely
temperature) and high electrochemical stability (>4 V) were compromised from the induction of ether units. Single-ion con-
achieved for poly(dodecamethylene carbonate) at high LiTFSI ducting polymer electrolyte was prepared based on block copoly-
concentration (80 wt%), as shown in Entry 6 of Table 3. By using mer of poly(carbonate-ether) by Deng et al., 157 with a high ionic
the same polycondensation approach using diethylene glycol or conductivity of 1.6 × 10−4 S/cm at 80 °C and very high t Li+ (0.86).
triethylene glycol with DMCs, He et al. reported the synthesis of This work highlighted a facile, efficient, and eco-friendly way of
poly(carbonate-ether)s (PEDC and PTEC) incorporating with preparing single ion–conducting polymer electrolyte with high
ether units, as shown in Entry 7 of Table 3.150 Compared with ionic conductivity. A similar single ion–conducting polymer elec-
PEC, the polycarbonates with ether units showed significantly trolytes from poly(ethylene oxide carbonate) was reported by
superior electrochemical properties, i.e., an optimized ionic con- David et al., 158 delivering a high ionic conductivity value of 1.2 ×
ductivity of 1.1 × 10−5 S/cm at 25 °C, a decent t Li+ of 0.39, and a 10−4 S/cm at 70 °C and a high t Li+ (0.89).
broad electrochemical window of approximately 4.5 V. The Apart from the polymer backbone design, several ways
LiFePO4//SPE//Li cell with PTEC-based SPE was stably cycled have been explored in enhancing the ionic conductivity of
at low C rates and at room temperature. The high-voltage cath- polycarbonate-based SPEs. Soaking with liquid electrolytes
ode material of LiFe0.2Mn0.8PO4 (4.35 V) was also used, exhibit- together with preparing gel polymer electrolytes seems to be
ing decent rate capability and good cycling performance at the most effective way in improving ionic conductivity, reaching
ambient temperature using PTEC-based SPE. The rate capability an order of magnitude of 10−4 to 10−2 S/cm at 25 °C. Different
and cycling performance of the LiFePO4//PTEC-LiTFSI//Li and polycarbonates (Entries 17–19 of Table 3) have been used as the
LiFe0.2Mn0.8PO4//PTEC-LiTFSI//Li cells at 25 °C are displayed polymer hosts, including polybutadiene/PPC interpenetrat-
in Fig. 8. Through the in situ polymerization strategy, Liu et al. ing network,159 poly(vinylidene fluoride)/PPC,160 cellulose-
provided an interpenetrating network IPN-PDEC SPE using supported poly(propylene carbonate),161 cross-linked poly
acrylate functionalized poly(diethylene glycol carbonate), shown (propylene carbonate maleate).155 However, such gel polymer
in Entry 8 of Table 3.151 The as-prepared IPN-PDEC-LiTFSI electrolytes sacrificed the inherently high security and reliability
exhibited a decent ionic conductivity of 1.6 × 10−4 S/cm at 25 °C of SPEs. Ionic liquid has long been regarded as an efficient addi-
and a high electrochemical oxidation voltage of 4.5 V. The tive in plasticizing SPEs.162–164 Tominaga et al. reported the
LiFe0.2Mn0.8PO4//IPN-PDEC–LiDFOB//Li cells were capable PEC-based composite SPE with ionic liquid (N-n-butyl-N-
of being cycled up to 4.35 V and showed a capacity retention of methylpyrrolidinium bis(trifluoromethanesulfonyl)imide, labe-
96% (140 mAh/g) at 0.1 C after 100 cycles. Kim et al. also led as Pyr14TFSI) and LiTFSI, showing a low ionic conductivity
reported the electrochemical performance of a cross-linked in the order of 10−7 S/cm at ambient temperature,131,132 which
poly(carbonate-ether)-based SPE room temperature for solid- was the reason for its poor electrochemical performance in
state batteries using an in situ cross-linking strategy (Entry 9 of solid-state batteries. Much better electrochemical perfor-
Table 3).152 The LiNi0.6Co0.2Mn0.2O2//PEEC-based SPE//Li mance of the ionic liquid–containing SPE was reported by Lu
cells delivered an ionic conductivity value of 4 × 10−5 S/cm at et al., using PPC as the matrix, LiClO4 as the lithium salt, and
25 °C and a broad electrochemical window (4.9 V), capable of 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM+BF4−)
being reversibly cycled at ambient temperature, delivering an as the additive, as shown in Entry 20 of Table 3.165

Figure 8. (a) The charge/discharge curves and (b) rate capability of LiFePO4//PTEC-LiTFSI//Li cells with varied C-rates at 25 °C. (c) The charge/
discharge curves and (d) cycling performance of LiFe0.2Mn0.8PO4//PTEC-LiTFSI//Li cells at 25 °C. Reproduced with permission.150 Copyright 2017,
Elsevier B.V.
Dispersing inorganic fillers, e.g., TiO2,46 SiO2,132 To date, most side chain polyester-based SPEs are in the realm
LLZTO,166,167 and POSS,156 in polycarbonate-based SPEs has of gel polymer electrolytes and are beyond the scope of this
been regarded as an effective way to improve their electrochem- review.30,169 Florjańczyk et al. performed a systematic work
ical performance, especially the ionic conductivity (Entries 14 on the SPEs with polymer matrices of poly(acrylonitrile-
and 21 of Table 3). Traditionally, such enhancement is attrib- co-butyl acrylate), poly(methyl methacrylate), and poly(butyl
uted to the reduction of the crystallinity and lower Tg; however, acrylate).170–172 A considerably high ionic conductivity in the
the real case is more complex. A Lewis acid–base model of the order of 10−4 S/cm at 30 °C was obtained for poly(butyl acrylate)
interactions between inorganic fillers and polymer hosts was containing 58 wt% LiI, due to its very low Tg (−55 °C) and the
recently proposed, which provided an explanation of the plasticizing effect of the concentrated lithium salt. Recently, a
strengthening effect of ionic conductivity from a unique per- grafted copolymer composed of polyrotaxane backbone and
spective.37 As an example, the fabrication of PEOEC/POSS PCL grafted side chains was utilized as SPE host,168 as shown in
hybrid semi-IPN SPEs is shown in Fig. 9. Fig. 10. The polyrotaxanes were prepared via self-assembly of
cyclodextrin (CD) host molecules threading onto polyethyl-
Polyester-based SPEs enoxide (PEO) chains, and the CD severed as the initiator for
the ROP of CL to afford pendant PCL side chains with a few
Side chain polyester-based SPEs repeating units. Extraordinary ionic conductivity (10−3 S/cm at
The SPEs based on side chain–type polyesters with pendant 60 °C and 10−4 S/cm at 25 °C), high t Li+ (0.6 at 60 °C), and
ester moieties attached to the backbone have also been devel- superior electrochemical oxidative voltage (up to 4.7 V) were
oped, of which the majority are acrylates and methyl acrylates. obtained for this SPE.

Figure 9. Fabrication of PEOEC/POSS hybrid semi-IPN SPEs. Reproduced with permission.156 Copyright 2014, Elsevier B.V.
nature, which resulted in low ionic conductivity (10−6 S/cm at

room temperature, for both LiSCN and LiClO4) at low lithium
salt loadings of 10–15 wt% (Entry 1 in Table 4). Similar systems
of PPL/LiClO4 exhibited a moderate ionic conductivity of 3.5 ×
10−5 S/cm at 70 °C.179 Surprisingly, quenching of the electro-
lyte system increased the ionic conductivity by 1–3 orders of
magnitude, achieving 3.7 × 10−4 S/cm, as shown in Entry 2 of
Table 4. This is most likely due to the decrease in crystallinity by
quenching, because mostly the lithium ion coordination and
conduction occur in amorphous regions. The restricted lithium
ion conductions were also reported in other semicrystalline
polyester-based SPE systems with limited ionic conductivities
Figure 10. (a) Grafted polyrotaxane structure with cyclodextrin in blue, PEO (Entries 3 and 4 in Table 4), e.g., PEA/LiClO4 (1.06 × 10−5 S/cm
backbone in green, and PCL side chains in orange. (b) General synthesis at 30 °C),178 PBA/LiClO4 (9 × 10−7 S/cm at 30 °C),178 PHA/
scheme for the synthesis of GPR with (1) functionalization of PEO ends, LiClO4 (5 × 10−6 S/cm at 30 °C),178 PE-2,4/LiClO4 (10−5 S/cm
(2) complexation with CD, and (3) end capping and simultaneous grafting. at 90 °C),180,181 PE-2,4/LiBF4 (3.4 × 10−6 S/cm at 65 °C),182
(c) ROP of ε-caprolactone initiated by CD. Reprinted with permission.168 PE-2,4/LiSCN (4.9 × 10−7 S/cm at 87 °C),181 and PE-2,10/
Copyright 2019, Elsevier B.V. LiSCN (2.2 × 10−8 S/cm at 53 °C).181 It is clear that the ionic
conductivity of an SPE is highly dependent on carbonyl groups
distributions, Tg, polymer chain rigidity, crystallinity, electron
donation strength of carbonyl group, lithium salt, etc. Shriver
Main chain polyesters et al. also reported a moderate ionic conductivity (1.6 × 10−6 S/cm
Esters were used as electrolyte solvents mainly due to their at 25 °C) of a noncrystalline polyester-based SPE system of
high electrochemical stability against anodic decomposition at PEM/LiCF3SO3,183 as shown in Entry 5 of Table 4. All the inves-
cathode surfaces.36 Sharing the similar skeleton of esters but in tigations were performed at low lithium salt concentrations
the polymeric form, main chain–type polyesters used in SPEs (≈10 wt%). As discussed above, high-concentration imide-type
are generally obtained via the ROP of cyclic esters or polycon- lithium salts, e.g., LiFSI and LiTFSI, have significant plasticiz-
densation of a diacid derivative and a diol, as discussed above. ing effect and potentially lower Tg, achieving higher ionic con-
Similar to polycarbonates, FTIR confirmed that the coordina- ductivity for polycarbonate-based SPE systems.124 Considering
tion and Li+ transport behavior in polyester-based SPEs primar- the similarity in the skeletons of these two polymers, it is rea-
ily occurred between Li+ and carbonyl groups, rather than sonable to assume that such plasticizing mechanism is also valid
alcohol residue ester oxygen.173 for polyesters with imide-type lithium salt systems.
Some typical polyester-based SPEs explored by pioneers are Better electrochemical performance was reported for two
summarized in Table 4. To date, the well-studied main chain– series of systematically studied ether side chain–modified
type polyester-based SPE system is based on sustainable PCL, polyester-based SPE systems, as summarized in Table 4. By dop-
with various lithium salts like LiSCN 174,175 and LiClO4.176–178 ing with LiTFSI (Entry 6 in Table 4), the ionic conductivity fell
The ion transport was rather limited due to its semicrystalline in the range of 1.4 × 10−4 to 3.0 × 10−4 S/cm at 90 °C, except

Table 4. Molecular structures and electrochemical characteristics of side chain polyester-based SPEs.
1 LiSCN 1.0 × 10−6 (25 °C) ≈5 V (25 °C) N/A 174–178
LiClO4 1.2 × 10−6 (25 °C)
2 LiClO4 3.7 × 10−4 (70 °C) N/A 0.82 179
3 LiClO4 PEA: 1.06 × 10−5 (30 °C) N/A N/A 178
PBA: 1.3 × 10−6 (30 °C)
PHA: 9.5 × 10−7 (30 °C)
4 LiClO4 PE-2,4: 10−5 (90 °C) N/A N/A 180–182
LiBF4 PE-2,4: 3.4 × 10−5 (65 °C)
LiSCN PE-2,4: 4.9×10−7 (87 °C),

PE-2,10: 2.2×10−8 (53 °C)
5 LiCF3SO3 1.6 × 10−6 (25 °C) N/A N/A 183
6 LiTFSI 1a: 1.5 × 10−4 (90 °C); N/A N/A 184 and 185
2a: 1.4 × 10−4 (90 °C)
3a: 3.0 × 10−4 (90 °C);

1b: 3.8 × 10−4 (90 °C)
2b: 2.5 × 10−4 (90 °C);

3b: 2.1 × 10−4 (90 °C)
σ: ionic conductivity; ESW: electrochemical stability window; LiSCN: lithium thiocyanate; LiClO4: lithium perchlorate; LiBF4: lithium tetrafluoroborate;
LiCF3SO3: lithium trifluoromethanesulfonate; LiTFSI: lithium bis(trifluoromethanesulfonyl)imide.

that of 1b polymer was approximately one order of magnitude consistency with the structure–dynamics model provided by MD
lower (10−5 S/cm) owing to its higher Tg and slower segmental simulations. However, by increasing the TMC content to 60%,
motion.184,185 Most of the SPEs showed low mechanical proper- the highest ionic conductivity achievable was significantly
ties at room temperature, which was due to their low molecular depressed, with a value of 7.9 × 10−7 S/cm at 25 °C, despite the
weight (<10,000 g/mol). By using the long-timescale molecular totally amorphous nature.187 The reduced lithium ion mobility
dynamics (MD) simulations, the lithium ion solvation and diffu- further confirmed the FTIR results of the preferential coordina-
sion mechanisms in the above-mentioned polymers (as well as tion of Li+ with ester carbonyls.148
PEO) were analyzed, showing that the intrachain hopping of Li+
took place in PEO only. The Li+ transport in the polyesters pri- Summary and perspective
marily depended on the interchain hopping behavior, which
As one of the most successful energy storage systems in his-
was intrinsically slow.
tory, liquid electrolyte–based lithium ion batteries have been
used massively, despite their inherent limitations of high vola-
SPEs from polyester/polycarbonate copolymers tilities and flammability. To realize the application of lithium
As a sustainable material, biodegradable PCL has been stud- ion batteries with high energy density, low cost, and excellent
ied thoroughly as SPE host for high–energy density solid-state safety, using solid-state lithium batteries with SPEs seems to be
lithium batteries. However, the PCL-based SPEs show restricted promising and probably an inevitable choice. Taking the inher-
lithium ion diffusion (with an ionic conductivity in an order of ent advantages of SPEs, solid-state lithium batteries can allevi-
10−6 S/cm at room temperature) due to the semicrystalline ate the low energy density and safety concerns and endow the
nature. In polymer science, preparing block copolymers with two energy storage system with improved flexibility and process-
distinct repeating units has been regarded as an effective strategy ability. Given the lower donor number and weaker complexa-
to reduce the chain regular arrangement and thus to suppress tion strength of Li+ with carbonyl groups in polycarbonates and
crystallinity.186 To this end, the PCL backbone with randomly polyesters than with ether units in polyethers, the carbonyl-
distributed carbonate repeating units (TMC) was prepared by coordinating polymers deliver superior electrochemical proper-
Mindemark et al. via bulk ROP at a TMC/CL ratio of 2:8.58,148 ties with respect to ionic conductivity and t Li+. A unique property
The as-prepared PTMC/PCL block copolymer-based SPE deliv- regarding the ionic conductivity in carbonyl-coordinating poly-
ered a high ionic conductivity of 4.1 × 10−5 S/cm at 25 °C and a mers is that the maximum value is generally obtained at high
high t Li+ (>0.6). The corresponding cell could be operated at tem- lithium salt concentrations due to the plasticizing effect, while
peratures down to as low as 23 °C, dramatically surpassing their the high lithium salt loading in polyethers ordinarily causes
polyether-based SPE analogues. The rate capability of the cells inter-/intrachain cross-linking and polymer chain stiffening.
using the PTMC/PCL block copolymer–based SPE is presented Besides, considering the electrochemical oxidation mechanism
in Fig. 11. The enhanced ionic conductivity was attributed to the of SPEs with high-voltage cathode materials, the carbonyl-
higher lithium ion mobilities by the random copolymerization coordinating polymers exhibit broader ESW compared with
with carbonate units in polyesters. FTIR experiments indicated their polyether-based analogues.
that the Li+ preferentially coordinated with ester carbonyl Carbonyl-coordinating polymer–based SPEs have emerged as
group rather than with carbonate carbonyl moiety, which was in a promising class of material for electrochemical applications, in
Figure 11. (a) Rate performance and coulombic efficiencies for a Li/SPE/LiFePO4 cell at room temperature and (b) initial charge/discharge voltage curves
cycled at different temperatures and C-rates (right). Reprinted with permission.58 Copyright 2015, Elsevier B.V.

the sense that this type of material exhibits several major advan- of the polymer crystallinity without sacrificing the
tages over the polyether-based analogues, including higher mechanical strength.
ionic conductivity, higher t Li+ and wider electrochemical win- (3) Appropriate evaluation of cathodic stability with high-
dow. However, such superior electrochemical properties are voltage cathode materials. Despite most of the carbonyl-
generally obtained at high lithium salt concentrations or in coordinating polymers show satisfying results from
polymer-in-salt systems, arousing a series of challenges. For linear sweep and cyclic voltammetry measurements,
example, how can we solve the contradiction between ionic con- very few work investigated the long-term cycling and
ductivity and mechanical strength? Is there any difference in electro(chemical) decomposition of such SPEs in con-
terms of the lithium ion conduction mechanism between tact with high-voltage cathode materials (such as
salt-in-polymer and polymer-in-salt systems? What is the spe- LiMn0.5Fe0.5PO4, lithium nickel cobalt manganese oxide
cial role of polymer dynamics at such high salt concentrations? (NCM), or lithium nickel cobalt aluminium oxide (NCA)),
What is the influence of high lithium salt concentrations on not to mention the building up of the practical energy stor-
the ESW? How can we further improve the ESW of carbonyl- age devices. A technique that can simulate the realistic
coordinating SPEs to higher than 4.5 V or even 5 V? What is the high-voltage lithium battery internal environment should
electrochemical decomposition mechanism of the carbonyl- be developed to evaluate the realistic cathodic stability of
coordinating SPEs at high lithium salt concentrations and the SPEs. It is noteworthy that most of the high-voltage
high voltage (>4.5 V)? How can we improve the interfacial sta- cathode materials, e.g., NCM and NCA, are strong base,
bility of SPE/cathode or SPE/anode at such high lithium salt which may cause base-catalyzed degradation on the car-
concentrations and very high voltage? All these questions bonyl-coordinating polymers. Tailoring the SPE/cathode
remain mystery, and much more efforts are still needed to fur- interface or coating the cathode active materials with high
ther study and refine the carbonyl-coordinating polymer– chemical stability layers should be helpful.
based SPEs for high-voltage electrochemical applications. (4) Amelioration of the lithium metal compatibility. In
In this review, we summarized and highlighted the synthesis, theory, a healthy battery requires both the good
sustainability, and ionic conduction of carbonyl-coordinating anodic and the cathodic stabilities with SPE. Due to
polymers and the SPEs thereof. To the best of our knowledge the extremely high reactivity, the chemical and elec-
and our understanding on SPEs, we tentatively suggest the fol- trochemical stability and compatibility of carbonyl-
lowing challenges and perspective: coordinating polymer–based SPEs with lithium metal
anode should be accessed comprehensively. Prepar-
(1) Further improvement of ionic conductivity. The trans- ing a dual-layered SPE constructed with both anodic
port of lithium ions highly depends on the lithium ion electrolyte (such as polyethers) and cathodic electrolyte
dynamic complexation with the polymer chains and the with high cathodic stability (such as polycarbonates)
segmental motions. Given this mechanism, the ionic should be promising.
conductivity of carbonyl-coordinating polymer–based (5) Adopting advanced characterization technologies. The
SPEs is possible to be enhanced. Strategies on improv- interfacial properties of the SPE with electrodes are
ing the ionic conductivity of polyether-based SPEs have critical for the healthy long-term cycling of a lithium
been explored extensively, including the fabrication of battery. Using advanced in situ techniques, such as in
organic/inorganic hybrid solid electrolyte, advanced situ FTIR, Raman, XRD, and cryo-TEM, to study the
polymer architecture modification, and incorporation interfacial layer formation, development and composi-
of novel lithium salts, which are seldom reported for car- tions, and lithium dendrite growth during long-term
bonyl-coordinating SPEs. cycling is meaningful.
(2) Balance between mechanical strength and ionic con- (6) Recycling of lithium battery materials. With the current
duction. As the Li+ transport is highly relied on the pol- massive application of lithium batteries in electrical
ymer chain segmental motions, while the mechanical vehicles, millions of tons of lithium battery will be
strength is in the retro-correlation with the segmental retired in the coming several years, and the recycling of
movements. To tackle this predicament, preparing lithium battery material is increasingly urgent. The
block copolymers containing both the hard block and recycling of lithium battery is seriously challenging due
the soft ion conductive block seems to a reasonable to the versatile battery components and rich chemistry.
strategy. The self-assembled nanostructures composed While most attentions on battery material recycling are
of the hard block and soft block enable the SPE thereof focused on valuable anodic and cathodic materials, the
with both satisfied mechanical strength and unacted liquid electrolytes in current lithium ion batteries con-
high ionic conductivity. As a bonus, the lithium den- tain hazardous organic materials and need to be treated
drite growth problem is solved by this approach. Taking very carefully. Developing the alternative solid electro-
the advantage of the interaction between polymer and lytes for lithium batteries from bio-based and biodegrad-
other additives in SPE, e.g., plastic crystal and inor- able polymers emerges as an important and attractive
ganic particles, the ionic conductivity is improved by strategy in terms of environmental benignity, lower
enhancing the lithium salt dissociation and suppression cost, and higher operability.

Acknowledgments 22. Di Noto V., Lavina S., Giffin G.A., Negro E., and Scrosati B.: Polymer
electrolytes: Present, past and future. Electrochim. Acta 57, 4 (2011).
The authors gratefully acknowledge the financial support 23. Meyer W.H.: Polymer electrolytes for lithium-ion batteries. Adv. Mater. 10,
from National Key R&D Program of China (2018YFB0104300), 439 (1998).
24. Agrawal R.C. and Pandey G.P.: Solid polymer electrolytes: Materials
Shenzhen Key Laboratory of Solid State Batteries
designing and all-solid-state battery applications: An overview. J. Phys. D:
(ZDSYS201802081843465), and Guangdong Provincial Key Appl. Phys. 41, 223001 (2008).
Laboratory of Energy Materials for Electric Power 25. Fergus J.W.: Ceramic and polymeric solid electrolytes for lithium-ion
(2018B030322001). batteries. J. Power Sources 195, 4554 (2010).
26. Hallinan D.T. and Balsara N.P.: Polymer electrolytes. Annu. Rev. Mater.
Res. 43, 503 (2013).
REFERENCES:
27. Xue Z., He D., and Xie X.: Poly(ethylene oxide)-based electrolytes for
1. Mohanty D., Li J., Nagpure S.C., Wood D.L., and Daniel C.: Understanding lithium-ion batteries. J. Mater. Chem. A 3, 19218 (2015).
the structure and structural degradation mechanisms in high-voltage, 28. Mindemark J., Lacey M.J., Bowden T., and Brandell D.: Beyond PEO—
lithium-manganese–rich lithium-ion battery cathode oxides: A review of Alternative host materials for Li+-conducting solid polymer electrolytes.
materials diagnostics. MRS Energy Sustainability 2, E15 (2015). Prog. Polym. Sci. 81, 114 (2018).
2. US Energy Information Administration (2018). Available at: http://www. 29. Zhang J., Yang J., Dong T., Zhang M., Chai J., Dong S., Wu T., Zhou X., and
eia.gov/ (accessed February 2020). Cui G.: Aliphatic polycarbonate-based solid-state polymer electrolytes for
3. Lewis N.S.: Powering the planet. MRS Bull. 32, 808 (2007). advanced lithium batteries: Advances and perspective. Small 14, 1800821
4. Goodenough J.B. and Kim Y.: Challenges for rechargeable Li batteries. (2018).
Chem. Mater. 22, 587 (2010). 30. Manuel Stephan A.: Review on gel polymer electrolytes for lithium
5. Bresser D., Hosoi K., Howell D., Li H., Zeisel H., Amine K., and Passerini S.: batteries. Eur. Polym. J. 42, 21 (2006).
Perspectives of automotive battery R&D in China, Germany, Japan, and the 31. Xu K.: Nonaqueous liquid electrolytes for lithium-based rechargeable
USA. J. Power Sources 382, 176 (2018). batteries. Chem. Rev. 104, 4303 (2004).
6. Tarascon J.M. and Armand M.: Issues and challenges facing rechargeable 32. Druger S.D., Nitzan A., and Ratner M.A.: Dynamic bond percolation
lithium batteries. Nature 414, 359 (2001). theory: A microscopic model for diffusion in dynamically disordered
7. Quartarone E. and Mustarelli P.: Electrolytes for solid-state lithium systems. I. Definition and one-dimensional case. J. Chem. Phys. 79, 3133
rechargeable batteries: Recent advances and perspectives. Chem. Soc. Rev. (1983).
40, 2525 (2011). 33. Webb M.A., Savoie B.M., Wang Z.-G., and Miller T.F. III: Chemically
8. Goodenough J.B. and Park K.-S.: The Li-ion rechargeable battery: specific dynamic bond percolation model for ion transport in polymer
A perspective. J. Am. Chem. Soc. 135, 1167 (2013). electrolytes. Macromolecules 48, 7346 (2015).
9. Goodenough J.B. and Singh P.: Review—Solid electrolytes in rechargeable 34. Song J.Y., Wang Y.Y., and Wan C.C.: Review of gel-type polymer
electrochemical cells. J. Electrochem. Soc. 162, A2387 (2015). electrolytes for lithium-ion batteries. J. Power Sources 77, 183 (1999).
10. Goodenough J.B.: How we made the Li-ion rechargeable battery. Nat. 35. Wang C., Wang T., Wang L., Hu Z., Cui Z., Li J., Dong S., Zhou X., and
Electron. 1, 204 (2018). Cui G.: Differentiated lithium salt design for multilayered PEO
11. Manthiram A., Yu X., and Wang S.: Lithium battery chemistries enabled by electrolyte enables a high-voltage solid-state lithium metal battery. Adv.
solid-state electrolytes. Nat. Rev. Mater. 2, 16103 (2017). Sci. 6, 1901036 (2019).
12. Osada I., de Vries H., Scrosati B., and Passerini S.: Ionic-liquid-based polymer 36. Xu K.: Electrolytes and interphases in Li-ion batteries and beyond. Chem.
electrolytes for battery applications. Angew. Chem., Int. Ed. 55, 500 (2016). Rev. 114, 11503 (2014).
13. Sarabi S., Kefsi L., Merdassi A., and Robyns B.: Supervision of plug-in 37. Zhou Q., Ma J., Dong S., Li X., and Cui G.: Intermolecular chemistry in
electric vehicles connected to the electric distribution grids. Int. J. Electr. solid polymer electrolytes for high-energy-density lithium batteries. Adv.
Energy 1, 256 (2013). Mater. 31, e1902029 (2019).
14. Wright P.V.: Electrical conductivity in ionic complexes of poly(ethylene 38. Zaheer M., Xu H., Wang B., Li L., and Deng Y.: An in situ polymerized
oxide). Br. Polym. J. 7, 319 (1975). comb-like PLA/PEG-based solid polymer electrolyte for lithium metal
15. Armand M.: Polymer solid electrolytes—An overview. Solid State Ionics batteries. J. Electrochem. Soc. 167, 070504 (2020).
9–10, 745 (1983). 39. Takahashi Y. and Tadokoro H.: Structural studies of polyethers,
16. Wang C., Zhang H., Li J., Chai J., Dong S., and Cui G.: The interfacial (–(CH 2)m–O–)n. X. Crystal structure of poly(ethylene oxide).
evolution between polycarbonate-based polymer electrolyte and Li-metal Macromolecules 6, 672 (1973).
anode. J. Power Sources 397, 157 (2018). 40. Gadjourova Z., Andreev Y.G., Tunstall D.P., and Bruce P.G.: Ionic
17. Fish D. and Smid J.: Solvation of lithium ions in mixtures of tetraethylene conductivity in crystalline polymer electrolytes. Nature 412, 520
glycol dimethyl ether and propylene carbonate. Electrochim. Acta 37, 2043 (2001).
(1992). 41. Cheng S., Smith D.M., and Li C.Y.: How does nanoscale crystalline structure
18. Zhang C., Ueno K., Yamazaki A., Yoshida K., Moon H., Mandai T., affect ion transport in solid polymer electrolytes? Macromolecules 47, 3978
Umebayashi Y., Dokko K., and Watanabe M.: Chelate effects in glyme/ (2014).
lithium bis(trifluoromethanesulfonyl)amide solvate ionic liquids. I. 42. Zhou Q., Zhang J., and Cui G.: Rigid–flexible coupling polymer
Stability of solvate cations and correlation with electrolyte properties. electrolytes toward high-energy lithium batteries. Macromol. Mater.
J. Phys. Chem. B 118, 5144 (2014). Eng. 303, 1800337 (2018).
19. Wu J., Rao Z., Cheng Z., Yuan L., Li Z., and Huang Y.: Ultrathin, flexible 43. Matsubara K., Kaneuchi R., and Maekita N.: 13C NMR estimation of
polymer electrolyte for cost-effective fabrication of all-solid-state lithium preferential solvation of lithium ions in non-aqueous mixed solvents. J. Chem.
metal batteries. Adv. Energy Mater. 9, 1902767 (2019). Soc., Faraday Trans. 94, 3601 (1998).
20. Xu C., Sun B., Gustafsson T., Edström K., Brandell D., and Hahlin M.: 44. Ong M.T., Verners O., Draeger E.W., van Duin A.C.T., Lordi V., and
Interface layer formation in solid polymer electrolyte lithium batteries: An Pask J.E.: Lithium ion solvation and diffusion in bulk organic
XPS study. J. Mater. Chem. A 2, 7256 (2014). electrolytes from first-principles and classical reactive molecular
21. Wei Z., Chen S., Wang J., Wang Z., Zhang Z., Yao X., Deng Y., and Xu X.: dynamics. J. Phys. Chem. B 119, 1535 (2015).
Superior lithium ion conduction of polymer electrolyte with comb-like 45. Bogle X., Vazquez R., Greenbaum S., Cresce A.v.W., and Xu K.:
structure via solvent-free copolymerization for bipolar all-solid-state Understanding Li+–solvent interaction in nonaqueous carbonate
lithium battery. J. Mater. Chem. A 6, 13438 (2018). electrolytes with 17O NMR. J. Phys. Chem. Lett. 4, 1664 (2013).

46. Tominaga Y. and Yamazaki K.: Fast Li-ion conduction in poly(ethylene 70. Dai Y. and Zhang X.: Recent development of functional aliphatic
carbonate)-based electrolytes and composites filled with TiO2 polycarbonates for the construction of amphiphilic polymers. Polym.
nanoparticles. Chem. Commun. 50, 4448 (2014). Chem. 8, 7429 (2017).
47. Kimura K., Motomatsu J., and Tominaga Y.: Correlation between solvation 71. Hussain T., Tausif M., and Ashraf M.: A review of progress in the dyeing of
structure and ion-conductive behavior of concentrated poly(ethylene eco-friendly aliphatic polyester-based polylactic acid fabrics. J. Clean. Prod.
carbonate)-based electrolytes. J. Phys. Chem. C 120, 12385 (2016). 108, 476 (2015).
48. Okumura T. and Nishimura S.: Lithium ion conductive properties of 72. Yu Y., Wu D., Liu C., Zhao Z., Yang Y., and Li Q.: Lipase/esterase-catalyzed
aliphatic polycarbonate. Solid State Ionics 267, 68 (2014). synthesis of aliphatic polyesters via polycondensation: A review. Process
49. Doyle M., Fuller T.F., and Newman J.: The importance of the lithium ion Biochem. 47, 1027 (2012).
transference number in lithium/polymer cells. Electrochim. Acta 39, 2073 73. Malmstroem E., Johansson M., and Hult A.: Hyperbranched aliphatic
(1994). polyesters. Macromolecules 28, 1698 (1995).
50. Thomas K.E., Sloop S.E., Kerr J.B., and Newman J.: Comparison of 74. Undin J., Plikk P., Finne-Wistrand A., and Albertsson A.-C.: Synthesis of
lithium-polymer cell performance with unity and nonunity transference amorphous aliphatic polyester-ether homo- and copolymers by radical
numbers. J. Power Sources 89, 132 (2000). polymerization of ketene acetals. J. Polym. Sci., Part A: Polym. Chem. 48,
51. Doyle M. and Newman J.: The use of mathematical modeling in the design 4965 (2010).
of lithium/polymer battery systems. Electrochim. Acta 40, 2191 (1995). 75. Mehta R., Kumar V., Bhunia H., and Upadhyay S.N.: Synthesis of
52. Brissot C., Rosso M., Chazalviel J.N., and Lascaud S.: Dendritic growth poly(lactic acid): A review. J. Macromol. Sci. Part C: Polym. Rev. 45, 325
mechanisms in lithium/polymer cells. J. Power Sources 81–82, 925 (1999). (2005).
53. Gorecki W., Jeannin M., Belorizky E., Roux C., and Armand M.: Physical 76. Jiang Z.: Lipase-catalyzed synthesis of aliphatic polyesters via
properties of solid polymer electrolyte PEO(LiTFSI) complexes. J. Phys.: copolymerization of lactone, dialkyl diester, and diol. Biomacromolecules
Condens. Matter 7, 6823 (1995). 9, 3246 (2008).
54. Borodin O. and Smith G.D.: Mechanism of ion transport in amorphous 77. Varma I.K., Albertsson A.-C., Rajkhowa R., and Srivastava R.K.: Enzyme
poly(ethylene oxide)/LiTFSI from molecular dynamics simulations. catalyzed synthesis of polyesters. Prog. Polym. Sci. 30, 949 (2005).
Macromolecules 39, 1620 (2006). 78. Zhang J., Shi H., Wu D., Xing Z., Zhang A., Yang Y., and Li Q.: Recent
55. Mao G., Saboungi M.-L., Price D.L., Armand M.B., and Howells W.S.: developments in lipase-catalyzed synthesis of polymeric materials. Process
Structure of liquid PEO-LiTFSI electrolyte. Phys. Rev. Lett. 84, 5536 Biochem. 49, 797 (2014).
(2000). 79. Douka A., Vouyiouka S., Papaspyridi L.-M., and Papaspyrides C.D.: A review
56. Kim C.S. and Oh S.M.: Importance of donor number in determining on enzymatic polymerization to produce polycondensation polymers: The
solvating ability of polymers and transport properties in gel-type polymer case of aliphatic polyesters, polyamides and polyesteramides. Prog. Polym.
electrolytes. Electrochim. Acta 45, 2101 (2000). Sci. 79, 1 (2018).
57. Chen L., Venkatram S., Kim C., Batra R., Chandrasekaran A., and 80. Williams C.K.: Synthesis of functionalized biodegradable polyesters. Chem.
Ramprasad R.: Electrochemical stability window of polymeric electrolytes. Soc. Rev. 36, 1573 (2007).
Chem. Mater. 31, 4598 (2019). 81. Liu Z.-L., Zhou Y., and Zhuo R.-X.: Synthesis and properties of functional
58. Mindemark J., Sun B., Törmä E., and Brandell D.: High-performance solid aliphatic polycarbonates. J. Polym. Sci., Part A: Polym. Chem. 41, 4001
polymer electrolytes for lithium batteries operational at ambient (2003).
temperature. J. Power Sources 298, 166 (2015). 82. Wang X.-L., Zhuo R.-X., Liu L.-J., He F., and Liu G.: Synthesis and
59. Manuel Stephan A. and Nahm K.S.: Review on composite polymer characterization of novel aliphatic polycarbonates. J. Polym. Sci., Part A:
electrolytes for lithium batteries. Polymer 47, 5952 (2006). Polym. Chem. 40, 70 (2002).
60. Sun C., Liu J., Gong Y., Wilkinson D.P., and Zhang J.: Recent advances in 83. Tempelaar S., Mespouille L., Coulembier O., Dubois P., and Dove A.P.:
all-solid-state rechargeable lithium batteries. Nano Energy 33, 363 (2017). Synthesis and post-polymerisation modifications of aliphatic
61. Cheng X.B., Hou T.Z., Zhang R., Peng H.J., Zhao C.Z., Huang J.Q., and poly(carbonate)s prepared by ring-opening polymerisation. Chem. Soc.
Zhang Q.: Dendrite-free lithium deposition induced by uniformly Rev. 42, 1312 (2013).
distributed lithium ions for efficient lithium metal batteries. Adv. Mater. 84. Gross R., Kalra B., and Kumar A.: Polyester and polycarbonate synthesis
28, 2888 (2016). by in vitro enzyme catalysis. Appl. Microbiol. Biotechnol. 55, 655
62. Yang Q., Li W., Dong C., Ma Y., Yin Y., Wu Q., Xu Z., Ma W., Fan C., and (2001).
Sun K.: PIM-1 as an artificial solid electrolyte interphase for stable lithium 85. Taherimehr M. and Pescarmona P.P.: Green polycarbonates prepared by the
metal anode in high-performance batteries. J. Energy Chem. 42, 83 (2020). copolymerization of CO2 with epoxides. J. Appl. Polym. Sci. 131, 41141
63. Sun B., Mindemark J., Edstrom K., and Brandell D.: Polycarbonate-based (2014).
solid polymer electrolytes for Li-ion batteries. Solid State Ionics 262, 738 86. Tamura M., Ito K., Honda M., Nakagawa Y., Sugimoto H., and Tomishige
(2014). K.: Direct copolymerization of CO2 and diols. Sci. Rep. 6, 24038 (2016).
64. Silva M.M., Barros S.C., Smith M.J., and MacCallum J.R.: Characterization 87. Carothers W.H., Dorough G.L., and Natta F.J.v.: Studies of polymerization
of solid polymer electrolytes based on poly(trimethylenecarbonate) and and ring formation. X. The reversible polymerization of six-membered
lithium tetrafluoroborate. Electrochim. Acta 49, 1887 (2004). cyclic esters. J. Am. Chem. Soc. 54, 761 (1932).
65. Barbosa P.C., Rodrigues L.C., Silva M.M., and Smith M.J.: 88. Bendler J.T.: Handbook of Polycarbonate Science and Technology, 1st ed.
Characterization of pTMCnLiPF6 solid polymer electrolytes. Solid State (CRC Press, New York, 1999).
Ionics 193, 39 (2011). 89. Zhu W., Huang X., Li C., Xiao Y., Zhang D., and Guan G.: High-molecular-
66. Kobayashi S.: Enzymatic ring-opening polymerization and weight aliphatic polycarbonates by melt polycondensation of dimethyl
polycondensation for the green synthesis of polyesters. Polym. Adv. carbonate and aliphatic diols: Synthesis and characterization. Polym. Int.
Technol. 26, 677 (2015). 60, 1060 (2011).
67. Artham T. and Doble M.: Biodegradation of aliphatic and aromatic 90. Park J.H., Jeon J.Y., Lee J.J., Jang Y., Varghese J.K., and Lee B.Y.:
polycarbonates. Macromol. Biosci. 8, 14 (2008). Preparation of high-molecular-weight aliphatic polycarbonates by
68. Cameron D.J.A. and Shaver M.P.: Aliphatic polyester polymer stars: condensation polymerization of diols and dimethyl carbonate.
Synthesis, properties and applications in biomedicine and nanotechnology. Macromolecules 46, 3301 (2013).
Chem. Soc. Rev. 40, 1761 (2011). 91. Mespouille L., Coulembier O., Kawalec M., Dove A.P., and Dubois P.:
69. Brannigan R.P. and Dove A.P.: Synthesis, properties and biomedical Implementation of metal-free ring-opening polymerization in the
applications of hydrolytically degradable materials based on aliphatic preparation of aliphatic polycarbonate materials. Prog. Polym. Sci. 39,
polyesters and polycarbonates. Biomater. Sci. 5, 9 (2017). 1144 (2014).

92. Möller M., Hedrick J.L., Degée P., and Dubois P.: Ring opening 114. Kaplan M.L., Rietman E.A., Cava R.J., Holt L.K., and Chandross E.A.:
polymerization. In Encyclopedia of Materials: Science and Technology, Crown ether enhancement of ionic conductivity in a polymer-salt system.
Buschow K.H.J., Cahn R.W., Flemings M.C., Ilschner B., Kramer E.J., Solid State Ionics 25, 37 (1987).
Mahajan S. and Veyssière P., eds. (Elsevier, Oxford, 2001); p. 8202. 115. Wei X. and Shriver D.F.: Highly conductive polymer electrolytes containing
93. Jérôme C. and Lecomte P.: Recent advances in the synthesis of aliphatic rigid polymers. Chem. Mater. 10, 2307 (1998).
polyesters by ring-opening polymerization. Adv. Drug Delivery Rev. 60, 116. Matsumoto K., Kakehashi M., Ouchi H., Yuasa M., and Endo T.: Synthesis
1056 (2008). and properties of polycarbosilanes having 5-membered cyclic carbonate
94. Paul S., Zhu Y., Romain C., Brooks R., Saini P.K., and Williams C.K.: groups as solid polymer electrolytes. Macromolecules 49, 9441 (2016).
Ring-opening copolymerization (ROCOP): Synthesis and properties of 117. Chai J., Liu Z., Ma J., Wang J., Liu X., Liu H., Zhang J., Cui G., and Chen
polyesters and polycarbonates. Chem. Commun. 51, 6459 (2015). L.: In situ generation of poly(vinylene carbonate) based solid electrolyte
95. Xu J., Feng E., and Song J.: Renaissance of aliphatic polycarbonates: New with interfacial stability for LiCoO2 lithium batteries. Adv. Sci. 4, 1600377
techniques and biomedical applications. J. Appl. Polym. Sci. 131, 39822 (2017).
(2014). 118. Xu H., Bijleveld J., Hedge M., and Dingemans T.: Synthesis and
96. D’Alessandro D.M., Smit B., and Long J.R.: Carbon dioxide capture: characterization of aromatic-PDMS segmented block copolymers and their
Prospects for new materials. Angew. Chem., Int. Ed. 49, 6058 (2010). shape-memory performance. Polym. Chem. 10, 5052 (2019).
97. Fukuoka S., Kawamura M., Komiya K., Tojo M., Hachiya H., Hasegawa K., 119. Soo P.P., Huang B., Jang Y.I., Chiang Y.M., Sadoway D.R., and Mayes A.M.:
Aminaka M., Okamoto H., Fukawa I., and Konno S.: A novel non-phosgene Rubbery block copolymer electrolytes for solid-state rechargeable lithium
polycarbonate production process using by-product CO2 as starting batteries. J. Electrochem. Soc. 146, 32 (1999).
material. Green Chem. 5, 497 (2003). 120. Mitsuda H., Uno T., Kubo M., and Itoh T.: Solid polymer electrolytes based
98. Darensbourg D.J., Mackiewicz R.M., Phelps A.L., and Billodeaux D.R.: on poly(1,3-diacetyl-4-imidazolin-2-one). Polym. Bull. 57, 313 (2006).
Copolymerization of CO2 and epoxides catalyzed by metal salen complexes. 121. Itoh T., Fujita K., Inoue K., Iwama H., Kondoh K., Uno T., and Kubo M.:
Acc. Chem. Res. 37, 836 (2004). Solid polymer electrolytes based on alternating copolymers of vinyl ethers
99. Sugimoto H. and Inoue S.: Copolymerization of carbon dioxide and with methoxy oligo(ethyleneoxy)ethyl groups and vinylene carbonate.
epoxide. J. Polym. Sci., Part A: Polym. Chem. 42, 5561 (2004). Electrochim. Acta 112, 221 (2013).
100. Inoue S., Koinuma H., and Tsuruta T.: Copolymerization of carbon dioxide 122. Wang P., Chai J., Zhang Z., Zhang H., Ma Y., Xu G., Du H., Liu T., Li G.,
and epoxide. J. Polym. Sci., Part B: Polym. Lett. 7, 287 (1969). and Cui G.: An intricately designed poly(vinylene carbonate-acrylonitrile)
101. Lu X.-B., Ren W.-M., and Wu G.-P.: CO2 copolymers from epoxides: copolymer electrolyte enables 5 V lithium batteries. J. Mater. Chem. A 7,
Catalyst activity, product selectivity, and stereochemistry control. Acc. 5295 (2019).
Chem. Res. 45, 1721 (2012). 123. Britz J., Meyer W.H., and Wegner G.: Blends of poly(meth)acrylates with
102. Coates G.W. and Moore D.R.: Discrete metal-based catalysts for the 2-oxo-(1,3)dioxolane side chains and lithium salts as lithium ion
copolymerization of CO2 and epoxides: Discovery, reactivity, optimization, conductors. Macromolecules 40, 7558 (2007).
and mechanism. Angew. Chem., Int. Ed. 43, 6618 (2004). 124. Tominaga Y.: Ion-conductive polymer electrolytes based on poly(ethylene
103. Albertsson A.-C. and Varma I.K.: Aliphatic Polyesters: Synthesis, Properties carbonate) and its derivatives. Polym. J. 49, 291 (2017).
and Applications, Degradable Aliphatic Polyesters (Springer Berlin 125. Spiegel E.F., Adamic K.J., Williams B.D., and Sammells A.F.: Solvation of
Heidelberg, Berlin, Heidelberg, 2002); p. 1. lithium salts within single-phase dimethyl siloxane bisphenol—A carbonate
104. Park E.-S., Cho H.-C., Kim M.-N., and Yoon J.-S.: Chain extension and block copolymer. Polymer 41, 3365 (2000).
mechanical properties of unsaturated aliphatic copolyesters based on 126. Matsumoto M., Uno T., Kubo M., and Itoh T.: Polymer electrolytes based
poly(L-lactic acid). J. Appl. Polym. Sci. 90, 1802 (2003). on polycarbonates and their electrochemical and thermal properties. Ionics
105. Eyvazzadeh Kalajahi A., Rezaei M., Abbasi F., and Mir Mohamad Sadeghi G.: 19, 615 (2013).
The effect of chain extender type on the physical, mechanical, and shape 127. Abdul-Karim R., Hameed A., and Malik M.I.: Ring-opening polymerization
memory properties of poly(ε-caprolactone)-based polyurethane-ureas. of ethylene carbonate: Comprehensive structural elucidation by 1D &
Polym. Plast. Technol. Eng. 56, 1977 (2017). 2D-NMR techniques, and selectivity analysis. RSC Adv. 7, 11786 (2017).
106. Zhao J.-B., Wu X.-F., and Yang W.-T.: Synthesis of aliphatic polyesters by a 128. Lee J.-C. and Litt M.H.: Ring-opening polymerization of ethylene
chain-extending reaction with octamethylcyclotetrasilazane and carbonate and depolymerization of poly(ethylene oxide-co-ethylene
hexaphenylcyclotrisilazane as chain extenders. J. Appl. Polym. Sci. 92, carbonate). Macromolecules 33, 1618 (2000).
3333 (2004). 129. Dukhanin G.P., Dumler S.A., Sablin A.N., and Novakov I.A.: Solid
107. Löfgren A., Albertsson A.-C., Dubois P., and Jérôme R.: Recent advances in polymeric electrolyte based on poly(ethylene carbonate)-lithium
ring-opening polymerization of lactones and related compounds. J. perchlorate system. Russ. J. Appl. Chem. 82, 243 (2009).
Macromol. Sci. Part C: Polym. Rev. 35, 379 (1995). 130. Tominaga Y., Nanthana V., and Tohyama D.: Ionic conduction in
108. Webb A.R., Yang J., and Ameer G.A.: Biodegradable polyester elastomers poly(ethylene carbonate)-based rubbery electrolytes including lithium
in tissue engineering. Expert Opin. Biol. Ther. 4, 801 (2004). salts. Polym. J. 44, 1155 (2012).
109. Tokiwa Y. and Calabia B.P.: Review degradation of microbial polyesters. 131. Kimura K., Hassoun J., Panero S., Scrosati B., and Tominaga Y.:
Biotechnol. Lett. 26, 1181 (2004). Electrochemical properties of a poly(ethylene carbonate)-LiTFSI
110. Silvers A.L., Chang C.-C., Parrish B., and Emrick T.: Strategies in Aliphatic electrolyte containing a pyrrolidinium-based ionic liquid. Ionics 21, 895
Polyester Synthesis for Biomaterial and Drug Delivery Applications, (2015).
Degradable Polymers and Materials: Principles and Practice, 2nd ed. 132. Kimura K., Matsumoto H., Hassoun J., Panero S., Scrosati B., and
(American Chemical Society, Washington D.C., 2012); p. 237. Tominaga Y.: A quaternary poly(ethylene carbonate)-lithium
111. Hakkarainen M.: Aliphatic Polyesters: Abiotic and Biotic Degradation and bis(trifluoromethanesulfonyl)imide-ionic liquid-silica fiber composite
Degradation Products (Degradable Aliphatic Polyesters, Springer, Berlin, polymer electrolyte for lithium batteries. Electrochim. Acta 175, 134
Heidelberg, 2002); p. 113. (2015).
112. Hilf J. and Frey H.: Propargyl-functional aliphatic polycarbonate obtained 133. Motomatsu J., Kodama H., Furukawa T., and Tominaga Y.: Dielectric
from carbon dioxide and glycidyl propargyl ether. Macromol. Rapid relaxation behavior of a poly(ethylene carbonate)-lithium bis-
Commun. 34, 1395 (2013). (trifluoromethanesulfonyl) imide electrolyte. Macromol. Chem. Phys.
113. Liu F., Yang J., Fan Z., Li S., Kasperczyk J., and Dobrzynski P.: Enzyme- 216, 1660 (2015).
catalyzed degradation of biodegradable polymers derived from 134. Tominaga Y., Yamazaki K., and Nanthana V.: Effect of anions on lithium
trimethylene carbonate and glycolide by lipases from Candida Antarctica ion conduction in poly(ethylene carbonate)-based polymer electrolytes. J.
and Hog pancreas. J. Biomater. Sci. Polym. Ed. 23, 1355 (2012). Electrochem. Soc. 162, A3133 (2015).

135. Kimura K., Motomatsu J., and Tominaga Y.: Highly concentrated in the preparation of crosslinked polymer electrolytes. J. Polym. Sci., Part
polycarbonate-based solid polymer electrolytes having extraordinary A: Polym. Chem. 44, 2195 (2006).
electrochemical stability. J. Polym. Sci., Part B: Polym. Phys. 54, 2442 155. Yu X., Xiao M., Wang S., Han D., and Meng Y.: Fabrication and properties
(2016). of crosslinked poly(propylene carbonate maleate) gel polymer electrolyte
136. Kimura K., Yajima M., and Tominaga Y.: A highly-concentrated for lithium-ion battery. J. Appl. Polym. Sci. 118, 2078 (2010).
poly(ethylene carbonate)-based electrolyte for all-solid-state Li battery 156. Kwon S.-J., Kim D.-G., Shim J., Lee J.H., Baik J.-H., and Lee J.-C.:
working at room temperature. Electrochem. Commun. 66, 46 (2016). Preparation of organic/inorganic hybrid semi-interpenetrating network
137. Morioka T., Ota K., and Tominaga Y.: Effect of oxyethylene side chains on polymer electrolytes based on poly(ethylene oxide-co-ethylene carbonate)
ion-conductive properties of polycarbonate-based electrolytes. Polymer 84, for all-solid-state lithium batteries at elevated temperatures. Polymer 55,
21 (2016). 2799 (2014).
138. Morioka T., Nakano K., and Tominaga Y.: Ion-conductive properties of a 157. Deng K., Wang S., Ren S., Han D., Xiao M., and Meng Y.: A novel
polymer electrolyte based on ethylene carbonate/ethylene oxide random single-ion-conducting polymer electrolyte derived from CO2-based
copolymer. Macromol. Rapid Commun. 38, 1600652 (2017). multifunctional polycarbonate. ACS Appl. Mater. Interfaces 8, 33642
139. Motomatsu J., Kodama H., Furukawa T., and Tominaga Y.: Dielectric (2016).
relaxation and ionic transport in poly(ethylene carbonate)-based 158. Meabe L., Goujon N., Li C., Armand M., Forsyth M., and Mecerreyes D.:
electrolytes. Polym. Adv. Technol. 28, 362 (2017). Single-ion conducting poly(ethylene oxide carbonate) as solid polymer
140. Kimura K. and Tominaga Y.: Understanding electrochemical stability and electrolyte for lithium batteries. Batteries Supercaps 3, 68 (2020).
lithium ion-dominant transport in concentrated poly(ethylene carbonate) 159. Huang X., Huang J., Wu J., Yu X., Gao Q., Luo Y., and Hu H.: Fabrication
electrolyte. ChemElectroChem 5, 4008 (2018). and properties of polybutadiene rubber-interpenetrating cross-linking
141. Munshi M.Z.A., Owens B.B., and Nguyen S.: Measurement of Li+ ion poly(propylene carbonate) network as gel polymer electrolytes for
transport numbers in poly(ethylene oxide)–LiX complexes. Polym. J. 20, lithium-ion battery. RSC Adv. 5, 52978 (2015).
597 (1988). 160. Huang X., Zeng S., Liu J., He T., Sun L., Xu D., Yu X., Luo Y., Zhou W., and
142. Tominaga Y., Shimomura T., and Nakamura M.: Alternating copolymers of Wu J.: High-performance electrospun poly(vinylidene fluoride)/
carbon dioxide with glycidyl ethers for novel ion-conductive polymer poly(propylene carbonate) gel polymer electrolyte for lithium-ion batteries.
electrolytes. Polymer 51, 4295 (2010). J. Phys. Chem. C 119, 27882 (2015).
143. Nakamura M. and Tominaga Y.: Utilization of carbon dioxide for polymer 161. Zhao J., Zhang J., Hu P., Ma J., Wang X., Yue L., Xu G., Qin B., Liu Z.,
electrolytes [II]: Synthesis of alternating copolymers with glycidyl ethers as Zhou X., and Cui G.: A sustainable and rigid-flexible coupling cellulose-
novel ion-conductive polymers. Electrochim. Acta 57, 36 (2011). supported poly(propylene carbonate) polymer electrolyte towards 5 V
144. Smith M.J., Silva M.M., Cerqueira S., and MacCallum J.R.: Preparation high voltage lithium batteries. Electrochim. Acta 188, 23 (2016).
and characterization of a lithium ion conducting electrolyte based on 162. Shin J.-H., Henderson W.A., and Passerini S.: Ionic liquids to the rescue?
poly(trimethylene carbonate). Solid State Ionics 140, 345 (2001). Overcoming the ionic conductivity limitations of polymer electrolytes.
145. Manuela Silva M., Barbosa P., Evans A., and Smith M.J.: Novel solid Electrochem. Commun. 5, 1016 (2003).
polymer electrolytes based on poly(trimethylene carbonate) and lithium 163. Shin J.-H., Henderson W.A., and Passerini S.: PEO-based polymer
hexafluoroantimonate. Solid State Sci. 8, 1318 (2006). electrolytes with ionic liquids and their use in lithium metal-polymer
146. Sun B., Mindemark J., Edström K., and Brandell D.: Realization of high electrolyte batteries. J. Electrochem. Soc. 152, A978 (2005).
performance polycarbonate-based Li polymer batteries. Electrochem. 164. Wu H., Xu Y., Ren X., Liu B., Engelhard M.H., Ding M.S., El-Khoury P.Z.,
Commun. 52, 71 (2015). Zhang L., Li Q., Xu K., Wang C., Zhang J.-G., and Xu W.: Polymer-in-
147. Sun B., Xu C., Mindemark J., Gustafsson T., Edström K., and Brandell D.: “Quasi-ionic liquid” electrolytes for high-voltage lithium metal batteries.
At the polymer electrolyte interfaces: The role of the polymer host in Adv. Energy Mater. 9, 1902108 (2019).
interphase layer formation in Li-batteries. J. Mater. Chem. A 3, 13994 165. Zhou D., Zhou R., Chen C., Yee W.-A., Kong J., Ding G., and Lu X.:
(2015). Non-volatile polymer electrolyte based on poly(propylene carbonate), ionic
148. Sun B., Mindemark J., Morozov E.V., Costa L.T., Bergman M., Johansson liquid, and lithium perchlorate for electrochromic devices. J. Phys. Chem.
P., Fang Y., Furó I., and Brandell D.: Ion transport in polycarbonate based B 117, 7783 (2013).
solid polymer electrolytes: Experimental and computational investigations. 166. Zhang J., Zang X., Wen H., Dong T., Chai J., Li Y., Chen B., Zhao J.,
Phys. Chem. Chem. Phys. 18, 9504 (2016). Dong S., Ma J., Yue L., Liu Z., Guo X., Cui G., and Chen L.: High-voltage
149. Meabe L., Lago N., Rubatat L., Li C., Müller A.J., Sardon H., Armand M., and free-standing poly(propylene carbonate)/Li6.75La3Zr1.75Ta0.25O12
and Mecerreyes D.: Polycondensation as a versatile synthetic route to composite solid electrolyte for wide temperature range and flexible solid
aliphatic polycarbonates for solid polymer electrolytes. Electrochim. Acta lithium ion battery. J. Mater. Chem. A 5, 4940 (2017).
237, 259 (2017). 167. He Z., Chen L., Zhang B., Liu Y., and Fan L.: Flexible poly(ethylene
150. He W., Cui Z., Liu X., Cui Y., Chai J., Zhou X., Liu Z., and Cui G.: carbonate)/garnet composite solid electrolyte reinforced by
Carbonate-linked poly(ethylene oxide) polymer electrolytes towards high poly(vinylidene fluoride-hexafluoropropylene) for lithium metal batteries.
performance solid state lithium batteries. Electrochim. Acta 225, 151 J. Power Sources 392, 232 (2018).
(2017). 168. Imholt L., Dörr T.S., Zhang P., Ibing L., Cekic-Laskovic I., Winter M., and
151. Liu X., Ding G., Zhou X., Li S., He W., Chai J., Pang C., Liu Z., and Cui G.: Brunklaus G.: Grafted polyrotaxanes as highly conductive electrolytes for
An interpenetrating network poly(diethylene glycol carbonate)-based lithium metal batteries. J. Power Sources 409, 148 (2019).
polymer electrolyte for solid state lithium batteries. J. Mater. Chem. A 5, 169. Zhu M., Wu J., Wang Y., Song M., Long L., Siyal S.H., Yang X., and Sui G.:
11124 (2017). Recent advances in gel polymer electrolyte for high-performance lithium
152. Jung Y.-C., Park M.-S., Kim D.-H., Ue M., Eftekhari A., and Kim D.-W.: batteries. J. Energy Chem. 37, 126 (2019).
Room-temperature performance of poly(ethylene ether carbonate)-based 170. Florjańczyk Z., Zygadło-Monikowska E., Wieczorek W., Ryszawy A.,
solid polymer electrolytes for all-solid-state lithium batteries. Sci. Rep. 7, Tomaszewska A., Fredman K., Golodnitsky D., Peled E., and Scrosati B.:
17482 (2017). Polymer-in-salt electrolytes based on acrylonitrile/butyl acrylate
153. Melchiors M., Keul H., and Höcker H.: Preparation and properties of copolymers and lithium salts. J. Phys. Chem. B 108, 14907 (2004).
solid electrolytes on the basis of alkali metal salts and poly(2,2- 171. Łasińska A.K., Marzantowicz M., Dygas J.R., Krok F., Florjańczyk Z.,
dimethyltrimethylene carbonate)-block-poly(ethylene oxide)-block- Tomaszewska A., Zygadło-Monikowska E., Żukowska Z., and Lafont U.:
poly(2,2-dimethyltrimethylene carbonate). Polymer 37, 1519 (1996). Study of ageing effects in polymer-in-salt electrolytes based on
154. Elmér A.M. and Jannasch P.: Synthesis and characterization of poly(acrylonitrile-co-butyl acrylate) and lithium salts. Electrochim. Acta
poly(ethylene oxide-co-ethylene carbonate) macromonomers and their use 169, 61 (2015).

172. Florjańczyk Z., Zygadło-Monikowska E., Affek A., Tomaszewska A., 180. Watanabe M., Rikukawa M., Sanui K., Ogata N., Kato H., Kobayashi T.,
Łasińska A., Marzantowicz M., Dygas J.R., and Krok F.: Polymer and Ohtaki Z.: Ionic conductivity of polymer complexes formed by
electrolytes based on acrylonitrile–butyl acrylate copolymers and lithium poly(ethylene succinate) and lithium perchlorate. Macromolecules 17, 2902
bis(trifluoromethanesulfone)imide. Solid State Ionics 176, 2123 (2005). (1984).
173. Wu I.D. and Chang F.-C.: Determination of the interaction within 181. Watanabe M., Rikukawa M., Sanui K., and Ogata N.: Effects of polymer
polyester-based solid polymer electrolyte using FTIR spectroscopy. structure and incorporated salt species on ionic conductivity of polymer
Polymer 48, 989 (2007). complexes formed by aliphatic polyester and alkali metal thiocyanate.
174. Ravi M., Song S.-H., Gu K.-M., Tang J.-N., and Zhang Z.-Y.: Effect of Macromolecules 19, 188 (1986).
lithium thiocyanate addition on the structural and electrical properties 182. Dupon R., Papke B.L., Ratner M.A., and Shriver D.F.: Ion transport in the
of biodegradable poly(ε-caprolactone) polymer films. Ionics 21, 2171 polymer electrolytes formed between poly(ethylene succinate) and lithium
(2015). tetrafluoroborate. J. Electrochem. Soc. 131, 586 (1984).
175. Ravi M., Song S., Gu K., Tang J., and Zhang Z.: Electrical properties of 183. Lee Y.-C., Ratner M.A., and Shriver D.F.: Ionic conductivity in the
biodegradable poly(ɛ-caprolactone): Lithium thiocyanate complexed poly(ethylene malonate)/lithium triflate system. Solid State Ionics 138,
polymer electrolyte films. Mater. Sci. Eng., B 195, 74 (2015). 273 (2001).
176. Polo Fonseca C. and Neves S.: Electrochemical properties of a 184. Pesko D.M., Jung Y., Hasan A.L., Webb M.A., Coates G.W., Miller T.F., and
biodegradable polymer electrolyte applied to a rechargeable lithium Balsara N.P.: Effect of monomer structure on ionic conductivity in a
battery. J. Power Sources 159, 712 (2006). systematic set of polyester electrolytes. Solid State Ionics 289, 118 (2016).
177. Fonseca C.P., Rosa D.S., Gaboardi F., and Neves S.: Development of a 185. Webb M.A., Jung Y., Pesko D.M., Savoie B.M., Yamamoto U., Coates G.W.,
biodegradable polymer electrolyte for rechargeable batteries. J. Power Balsara N.P., Wang Z.-G., and Miller T.F.: Systematic computational and
Sources 155, 381 (2006). experimental investigation of lithium-ion transport mechanisms in
178. Lin C.-K. and Wu I.D.: Investigating the effect of interaction behavior on polyester-based polymer electrolytes. ACS Cent. Sci. 1, 198 (2015).
the ionic conductivity of polyester/LiClO4 blend systems. Polymer 52, 186. Van Horn R.M., Steffen M.R., and O’Connor D.: Recent progress in block
4106 (2011). copolymer crystallization. Polym. Cryst. 1, e10039 (2018).
179. Watanabe M., Togo M., Sanui K., Ogata N., Kobayashi T., and Ohtaki Z.: 187. Mindemark J., Törmä E., Sun B., and Brandell D.: Copolymers of
Ionic conductivity of polymer complexes formed by poly(β-propiolactone) trimethylene carbonate and ε-caprolactone as electrolytes for lithium-ion
and lithium perchlorate. Macromolecules 17, 2908 (1984). batteries. Polymer 63, 91 (2015).


Carbonyl Coordinating Polymers For High Voltage Solid State Lithium Batteries Solid Polymer Electrolytes

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Carbonyl Coordinating Polymers For High Voltage Solid State Lithium Batteries Solid Polymer Electrolytes

Uploaded by

Copyright:

Available Formats

MRS Energy & Sustainability: A Review Journal

electrolytes Jun Wang and Yonghong Deng, Department of Materials Science

Keywords: solid polymer electrolyte; carbonyl-coordinating polymers; polycarbonate; polyester

2 n MRS Energy & Sustainability // V O L U M E 7 // e 2 // www.mrs.org/energy-sustainability-journal

MRS Energy & Sustainability // V O L U M E 7 // e 2 // www.mrs.org/energy-sustainability-journal n 3

4 n MRS Energy & Sustainability // V O L U M E 7 // e 2 // www.mrs.org/energy-sustainability-journal

Carbonyl-coordinating polymer–based SPEs Polyether-based SPEs

t Li+ High (generally >0.5) Low (generally <0.2)

ESW Broad (typically >4.5 V) Narrow (generally <3.9 V)

MRS Energy & Sustainability // V O L U M E 7 // e 2 // www.mrs.org/energy-sustainability-journal n 5

Synthesis strategies toward polyesters

6 n MRS Energy & Sustainability // V O L U M E 7 // e 2 // www.mrs.org/energy-sustainability-journal

MRS Energy & Sustainability // V O L U M E 7 // e 2 // www.mrs.org/energy-sustainability-journal n 7

8 n MRS Energy & Sustainability // V O L U M E 7 // e 2 // www.mrs.org/energy-sustainability-journal

Entry Polymer host Lithium salt σ (S/cm) ESW t Li+ References

PVIC: 1.0 × 10−6 (60 °C),

2 LiCF3SO3 polySBMC: 6.1 × 10−5 N/A N/A 116

LiTFSI polySBDC: 1.5 × 10−4

4 LiTFSI Poly(AcIM): 8.5 × 10−5 N/A N/A 120

Poly(AcIM/VC): 7.0 × 10−4

6 LiPF6 2.6 × 10−4 (25 °C) 5.2 V 0.52 122

7 LiTFSI PDOA: 3.7 × 10−6 (40 °C) N/A N/A 123

MRS Energy & Sustainability // V O L U M E 7 // e 2 // www.mrs.org/energy-sustainability-journal n 9

10 n MRS Energy & Sustainability // V O L U M E 7 // e 2 // www.mrs.org/energy-sustainability-journal

Entry Polymer host Lithium salt σ (S/cm) ESW t Li+ References

2 LiTFSI 1 × 10−6 to 4.3–5.0 V 0.35–0.67 126

3 LiClO4 9.6 × 10−4 (80 °C) N/A N/A 129

LiTFSI LiTFSI: 10−4 (80 °C) >4.3 V LiTFSI: 0.63 130–134

LIClO4 LIClO4: 10−5 (80 °C) LIClO4: 0.26

LiBF4 LiBF4: 10−5 (80 °C) LiBF4: 0.22

LiPF6 LiPF6: 10−5 (80 °C) LiPF6: 0.4

4 LiTFSI 10−5 (25 °C) N/A N/A 124, 137,

5 LiCF3SO3, 3 × 10−4 (95 °C) 4.5 V N/A 64 and 144

LiSbF6 6 × 10−5 (85 °C) 5.0 V N/A 145

LiPF6 4.8 × 10−6 (98 °C) 4.5 V N/A 65

1.8 × 10−8 (25 °C)

LiTFSI 10−7 (60 °C) 5.0 V N/A 63

LiTFSI N/A N/A 0.8 (60 °C) 148

MRS Energy & Sustainability // V O L U M E 7 // e 2 // www.mrs.org/energy-sustainability-journal n 11

Entry Polymer host Lithium salt σ (S/cm) ESW t Li+ References

6 LiTFSI 1 × 10−4 (25 °C) 4.0 V (60 °C) N/A 149

7 LiTFSI 1.1 × 10−5 (25 °C) 4V 0.39 150

2.0 × 10−4 (80 °C)

8 LiTFSI 1.7 × 10−4 (25 °C) 4.5 V 0.47 151

9 LiTFSI 1 × 10−3 (80 °C) 4.9 V 0.4 152

4 × 10−4 (60 °C)

4 × 10−5 (25 °C)

10 LiCF3SO3 10−4 (60 °C) N/A N/A 138

11 LiCF3SO3 10−4 (60 °C) N/A N/A 153

12 LiTFSI 1 × 10−4 (60 °C) N/A N/A 154

13 LiClO4 8.4 × 10−3 (25 °C) N/A 0.42 155

1.4 × 10−2 (50 °C)

12 n MRS Energy & Sustainability // V O L U M E 7 // e 2 // www.mrs.org/energy-sustainability-journal

Entry Polymer host Lithium salt σ (S/cm) ESW t Li+ References

14 LiClO4 1 × 10−4 (30 °C) 4.7 V (60 °C) N/A 156

16 N/A 1.2 × 10−4 (70 °C) N/A 0.89 158

3.5 × 10−3 (80 °C)

19 LiODFB 1.1 × 10−3 (25 °C) 5V 0.68 161

20 LiClO4 1.5 × 10−3 (25 °C) N/A N/A 165

MRS Energy & Sustainability // V O L U M E 7 // e 2 // www.mrs.org/energy-sustainability-journal n 13

Entry Polymer host Lithium salt σ (S/cm) ESW t Li+ References

21 LiTFSI 5.2 × 10−4 (20 °C) 4.6 V 0.75 166

Li+-carbonyl group coordination behavior in PEC/LiClO4 SPE