Journal of Membrane Science 575 (2019) 200–208

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Journal of Membrane Science

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

Poly(ethylene oxide)-based composite polymer electrolytes embedding with T

ionic bond modified nanoparticles for all-solid-state lithium-ion battery
⁎
Ji Hua,b, Wanhui Wangc, Binghua Zhoua, Yuezhan Fenga,d, Xiaolin Xiea, Zhigang Xuea,
a
Key Laboratory for Material Chemistry of Energy Conversion and Storage, Ministry of Education, School of Chemistry and Chemical Engineering, Huazhong University of
Science and Technology, Wuhan 430074, China
b
School of Materials Science and Engineering, Luoyang Institute of Science and Technology, Luoyang 471023, China
c
School of Environmental Engineering and Chemistry, Luoyang Institute of Science and Technology, Luoyang 471023, China
d
Key Laboratory of Materials Processing and Mold, Ministry of Education, National Engineering Research Center for Advanced Polymer Processing Technology, Zhengzhou
University, Zhengzhou 450002, China

A R T I C LE I N FO A B S T R A C T

Keywords: Flexible composite polymer electrolytes (CPEs) are fabricated by reversible addition-fragmentation chain
Composite polymer electrolytes transfer (RAFT) polymerization of poly(ethylene glycol) methacrylate (PEGMA) and poly(ethylene glycol) dia-
RAFT crylate (PEGDA), followed by physical doping with ionic bond modified nanoparticles (IBNs) based on nanoscale
Ionic conductivity silica. In reference to PEGMA-PEGDA cross-linked framework prepared by ultraviolet light irradiation directly,
Lithium-ion batteries
RAFT polymerization endows the electrolyte membranes with excellent flexibility, and further increase in yield
stress and tensile modulus achieved with IBNs adding in the system. CPEs obey Arrhenius law and its ionic
conductivity is found to be maximum of 6.77 × 10−5 S cm−1 at 30 °C, but that of the electrolytes consisted of the
same molar feeding ratio of PEGMA/PEGDA without IBNs blending is 3.76 × 10−5 S cm−1 at 30 °C, indicating
that the loading of IBNs improves the ionic conductivity, due to the elevated chain mobility. Besides, the
electrochemical stability of CPEs is promoted in comparison with the traditional linear poly(ethylene oxide)
(PEO) based electrolytes. Moreover, the electrolyte membrane exhibits good cycling performance with lithium
iron phosphate and retained 94.3% of capacity after 40 charge-discharge cycles, demonstrating the great po-
tential of this kind of CPEs prepared in this study as electrolyte materials for battery systems.

1. Introduction
Since its birth, lithium-ion batteries (LIBs), which own various ad-
vantages such as high energy density and stable cycling performance,
have played a crucial role in the recent development of the electro-
chemical devices for energy storage, gradually [1–4]. Unfortunately, a
series of insecure events caused by the utilization of flammable and
volatile organic solvents in the system have aroused concern about the
security matters of the LIBs. To prevent the risks of leakage and related
fire hidden peril about liquid electrolytes fundamentally, Masoud et al.
[5–8] exploited a kind of gel copolymer electrolyte by soaking com-
mercial plasticizers in porous poly(vinylidene fluoride-co-hexa-
fluoropropylene) (PVDF-co-HFP) polymer matrix, which demonstrated
ideal electrochemical stability. Furthermore, the application of elec-
trolytes at the range of lithium metal batteries, which use metallic li-
thium as anode material to obtain higher theoretical specific capacity
but need more robust membranes to obstruct the growth of lithium
dendrite, an all-solid construction has been suggested as an ideal
candidate to satisfy these demands, due to the lack of leakage, good
dimensional stability and outstanding chemical stability about its
nature. As a solid-state electrolyte, poly(ethylene oxide) (PEO) has been
studied comprehensively as the skeleton material owing to several
specific advantages including high safety, high energy density, good
electrochemical stability, and excellent compatibility with lithium salts
[9,10]. However, linear PEO could not be used directly for practical
LIBs applications, because of its relatively low ionic conductivity that
results from the declined segmental mobility of PEO in the crystalline
domains especially at low temperature [11–13]. In order to elevate the
amorphous state in polymer matrix for improving local relaxation and
segmental motion to allow ion (Li+) transport, fabricating cross-linked
networks [14] or nanoparticle-containing composite polymer electro-
lytes (CPEs) [15] have been demonstrated to be effective methods to
promote the physical-chemical performances of PEO based solid-state
electrolytes utilized in LIBs.
The cross-linked polymer electrolytes, which are usually prepared
by heat or ultraviolet light initiated radical polymerization with the aid

⁎
Corresponding author.
E-mail address: zgxue@mail.hust.edu.cn (Z. Xue).

https://doi.org/10.1016/j.memsci.2019.01.025
Received 22 November 2018; Received in revised form 8 January 2019; Accepted 14 January 2019
Available online 15 January 2019
0376-7388/ © 2019 Elsevier B.V. All rights reserved.
J. Hu et al.
of an initiator or radiation, show fully amorphous features due to the
difficulty of chain mobility to assume the appropriate position for
crystallization. Thus, ionic conduction is more active in the cross-linked
system, and the mechanical strength of electrolytes is elevated owing to
the tight network, additionally [16]. Yang et al. [17] prepared a tough
and compact 3D cross-linked network gel polymer electrolyte via a
novel initiator-free one-pot ring-opening polymerization reaction under
heating at 80 °C for a certain time. The 3D cross-linked membrane ex-
hibited a perfect combination of mechanical strength, ionic con-
ductivity, and suppression of Li dendrite growth. Guo et al. [18] fab-
ricated an inter-penetrating network of poly(ether-acrylate) (IPN-PEA)
and further realized via UV curing of ion-conductive PEO and branched
acrylate. The IPN-PEA electrolyte integrated excellent mechanical
strength, high ionic conductivity at ambient temperature, and good
compatibility with cathode materials. However, the traditional cross-
linked polymer is tough but brittle generally. Thus it's crucial to explore
a tradeoff issue between mechanical strength and flexibility. The re-
versible addition-fragmentation chain transfer (RAFT) process has been
proved to be one of the most universal for the provision of polymers
with well-defined and flexible structure since its first reported by Thang
et al. [19]. Lee et al. [20] prepared a series of organic/inorganic hybrid
branched and linear copolymer electrolytes, which were composed of
poly(ethylene glycol) methyl ether methacrylate (PEGMA), methacry-
late functionalized polyhedral oligomeric silsesquioxane (MA-POSS)
and ethylene glycol dimethacrylate (EGDMA) via RAFT polymerization.
This kind of electrolytes could be utilized to assemble all-solid-state
batteries for stable application at high temperature without causing
safety problems.
CPEs are the impactful candidates used in the field of solid-state
electrolytes, which are originated from the addition of α-alumina as the
inactive fillers in the polymer matrix introduced by Weston and Steele
in 1982 [21]. Thereafter, SiO2 [22], TiO2 [23], MgO [24], LiAlO2 [25],
and other metal oxide were used as additives for preparing CPEs. It is
known to all, the blending of a filler can increase the amorphous phase
due to the depression of the crystallization of polymer skeleton, which
will lead to an enhancement of ionic conductivity, as well as an im-
provement of the electrolyte/electrode interfacial property. Further-
more, the functionalized particles have also been used to promote the
performances of CPEs. Archer et al. developed a novel family of na-
noparticles with the characteristic of liquid-like behavior modified by
ionic segments [26–29]. Owning to the ionic connection between the
core architecture and soft organic shell component, the nanoparticles
dispersed in the composite materials homogeneously, and the mobility
was promoted, simultaneously [30]. Park [31] and Zheng [32] pre-
pared a series of nanoparticle organic hybrid materials (NOHMs) with
liquid-like inorganic nanoscale fillers comprised, independently. The
spontaneous ordering of the tethered organic species on the surface of
nanoscale fillers was achieved due to the unique swelling behaviors of
NOHMs, which exhibited effective CO2 capture via the entropic effect.
Dong et al. [33] prepared solvent-free carbon nanotube fluids (CNT
fluids) through an ion exchange method, and composite membranes for
full cells applications were manufactured by incorporating CNT fluids
into a chitosan (CS) matrix. Benefit from the electrostatic interactions
between sulfonic acid groups in the CNT fluids and amino groups in the
CS matrix, the proton conductivities of CS/CNT fluids composite
membranes were improved. Zheng et al. [34] reported a nanofluid
based on MnSn(OH)6 crystallite. Owing to the ionic connection between
the corona (-SO3- terminated organosilanes) and canopy (polyether
amine), the material shows improved processability and fluidity at
ambient temperature without any solvents, which have great potential
for application in plasticizers. Moreover, we synthesized ionic bond
modified nanoparticles (IBNs) successfully, and PEO based CPEs were
fabricated by blending IBNs in the system [35]. The physico-chemical
performances of CPEs shown that the ionic conductivity and electro-
chemical stability were all elevated owing to IBNs loading. Besides that,
other nanoparticles decorated by ionic liquid [36–38] or sulfonate [39]
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Journal of Membrane Science 575 (2019) 200–208
have also been proved to be effective fillers to prepare CPEs, which
showed gratifying mechanical and electrochemical performances.
In this work, a series of cross-linked copolymers consisted of poly
(ethylene glycol) methacrylate (PEGMA) and poly(ethylene glycol)
diacrylate (PEGDA) were synthesized via one-step RAFT polymerization
in the presence of 2-cyanoprop-2-yl 1-dithionaphthalate (CPDN) as
chain-transfer agent, then the IBNs based on nanoscale silica coated
polyether with sulfo-amino ionic connection, which were fabricated
successfully in our previous work [35], were blended with the copo-
lymer facilely under different weight ratios to fabricate CPEs for facil-
itating practical properties. The effects of the composition of the RAFT
system and IBNs content on the dimensional stability, thermal perfor-
mances, ionic conductivity, and electrochemical stability were sys-
tematically investigated. By introducing the RAFT process in the pre-
paration of the copolymer, the electrolyte films were more flexible than
the materials prepared by conventional polymerization induced by ul-
traviolet light directly. In addition, higher ionic conductivity could be
obtained by the embedding of IBNs at a specific content in the com-
posites. Thus, the CPEs manufactured in this study acted as potential
candidates for application in LIBs.
2. Experimental
2.1. Materials
Poly(ethylene glycol) methacrylate (PEGMA, Mn = 475 g mol−1,
containing 100 ppm MeHQ and 200 ppm BHT as inhibitor, Aladdin,
hereafter M475) and poly(ethylene glycol) diacrylate (PEGDA, Mn =
400 g mol−1, containing 100 ppm MeHQ and 300 ppm BHT as in-
hibitor, Aladdin, hereafter D400) were passed through neutral Al2O3 to
remove inhibitor prior to polymerization. LUDOX® SM colloidal silica
(30 wt% suspension in H2O, Sigma-Aldrich) and 3-mercaptopropyl-
trimethoxysilane (MPTMS, 95 wt%, Sigma-Aldrich) were used as re-
ceived. The monoamines-terminated PEO derivative, JEFFAMINE®
M2070, was gained form Huntsman Co., Ltd. Lithium perchlorate
(LiClO4, Aladdin) were dried at 150 °C in a vacuum oven for 24 h and
stored in the glove box before use. Other chemicals, including alcohol,
1-Bromonaphane, tetrahydrofuran (THF), carbon disulphide (CS2),
magnesium, hydrochloric acid (HCl), chloroform, ethyl acetate, di-
methyl sulfoxide (DMSO), 2,2′-azobis(2-methylpropionitrile) (AIBN),
petroleum ester, N,N-dimethylformamide (DMF), hexane, calcium hy-
dride (CaH2), hydrogen peroxide, acetonitrile, lithium iron phosphate
(LFP), acetylene black (AB), polyvinylidene fluoride (PVDF), N-methyl-
2-pyrrolidone (NMP) and 2-Hydroxy-2-methylpropiophenone (HOMPP)
were purchased locally. AIBN was recrystallized from ethanol, dried at
room temperature in vacuum, and stored in a refrigerator at − 15 °C.
THF, CS2, DMSO, and DMF were dried over anhydrous CaH2 and then
distilled prior to use. De-ionized (DI) water was used in all experiments.
2.2. Synthesis of chain-transfer agent
2-cyanoprop-2-yl 1-dithionaphthalate (CPDN) was used as the
chain-transfer agent in this RAFT polymerization process, the schematic
illustration of the synthesis route was shown in Scheme S1 (see
Supporting information). A solution of 15 g (0.07 mol) 1-bromona-
phane and 40 mL THF was added to a 150 mL bottle containing mag-
nesium (1.92 g, 0.08 mol) within 1 h and refluxed for 1 h under 50 °C.
Then the mixture was cooled to room temperature, CS2 5.6 g (0.07 mol)
was added to the solution at room temperature and refluxed for 8 h. The
mixture was poured into water, and the scarlet intermediate product
was obtained after filtering the unreacted magnesium. Acidified the
intermediate product by diluted HCl, the solution was extracted with
chloroform for three times. After evaporated under vacuum, the re-
sident added with 40 mL ethyl acetate and reacted with 5 g DMSO in a
250 mL three-neck flask equipped with a condense pipe under nitrogen
protection for 10 h at 30 °C. The mixture was added with 6.8 g
J. Hu et al.
(0.04 mol) AIBN and 60 mL ethyl acetate, then refluxed for another 15 h
at 65 °C. After evaporation of the solvent, crude CPDN was obtained.
Purified CPDN by chromatography on silica gel column with petroleum
ester-ethyl acetate = 9:1 as eluent. Finally, the obtained CPDN was a
dark red slurry, then kept it in the refrigerator at − 18 °C. 1H NMR
[400 MHz, CDCl3, δ (ppm), TMS ref] of CPDN: 2.01 (methyl, 6H); 7.46
(naphthalene backbone, 2H); 7.53 (naphthalene backbone, 2H); 7.88
(naphthalene backbone, 2H) and 8.14 (naphthalene backbone, 1H)
(Fig. S1).
2.3. Preparation of copolymer network via RAFT polymerization
PEGMA-PEGDA copolymer network containing M475: D400: CPDN:
AIBN = 100: 15: 1: 0.5 (molar feeding ratio) was synthesized via RAFT
polymerization as follows. M475 (2.375 g, 5 mmol), D400 (0.3 g,
0.75 mmol), CPDN (0.0136 g, 0.05 mmol) and AIBN (0.0041 g,
0.025 mmol) were dissolved in 14 mL of distilled DMF, and the re-
sultant solution was added to a 50 mL Schlenk flask equipped with a
magnetic stirring bar and a condenser. The mixture was degassed by
three consecutive freeze-pump-thaw cycles to remove oxygen and the
reaction was performed in an oil bath thermostatted at 75 °C for 24 h
under a nitrogen atmosphere. After reacting at a predetermined time,
the flask was removed from the oil bath, it was exposed to air and
diluted with a little DMF to quench the reaction. The unreacted
monomers were removed by precipitation in hexane three times. After
being dried under vacuum at 40 °C for 48 h, a pink rubbery solid pro-
duct was obtained. Other PEGMA-PEGDA copolymer networks were
also prepared using the same synthesis procedure with different
monomer feeding ratios as shown in Table 1. 1H NMR [400 MHz,
CDCl3, δ (ppm), TMS ref] of RAFT1: 3.48–4.21 (CH2-CH2-O) and 3.38
(CH3-O) (Fig. S2).
2.4. Preparation of ionic bond modified silica nanoparticles (IBNs)
Briefly, the fabrication of IBNs was accomplished in two steps: first,
silica nanoparticles were functionalized by sulfonic acid groups [40];
second, the sulfonated silica nanoparticles were reacted with JEFFA-
MINE® M2070 to promote the acid-base neutralization between the
sulfonic acid groups coated on silica nanoparticles and the amino
groups terminated on JEFFAMINE® M2070 [41]. Specifically, MPTMS
(10 mL) was dissolved in ethanol (40 mL) to form a transparent solu-
tion. Then the solution was dripped into LUDOX® SM colloidal silica
(20 mL) combined with DI water (120 mL) by intense mechanical stir-
ring (700 rpm). The reaction was carried out under reflux at 70 °C for
24 h. After being separated by centrifugation and washed three times
with ethanol to remove the unreacted MPTMS, the thiol coated silica
nanoparticles, called SiO2-SH, were obtained by drying at 60 °C under
vacuum for 24 h. The sulfonation of silica nanoparticles (hereafter ab-
breviated as SiO2-SO3H) was further performed by oxidizing the surface
thiol groups of silica into sulfonic acid groups with 30 wt% H2O2 so-
lution at 25 °C for 24 h. Then, SiO2-SO3H (10 g) was added in DI water,
and the mixture was ultrasonicated for 30 min to disperse SiO2-SO3H in
the solution. JEFFAMINE® M2070 (10 g) was also dissolved in DI water
(50 mL) separately, and SiO2-SO3H solution was added with continuous
stirring. The linking reaction was allowed to proceed to completion
over several days, and the termination of the reaction was evaluated by
Table 1
RAFT polymerizations of PEGMA and PEGDA.
Entry M475 D400 CPDN AIBN
RAFT-I 100 15 1 0.5
RAFT-II 100 20 1 0.5
RAFT-III 100 25 1 0.5
RAFT-IV 100 30 1 0.5
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Journal of Membrane Science 575 (2019) 200–208
the changes in the pH value. The product was put into dialysis tubing
and dialyzed for several days in DI water to remove any remaining free
JEFFAMINE® M2070. Water was evaporated in a convection oven, and
the product was dried extensively under vacuum and stored in the dried
form at room temperature.
2.5. Fabrication of solid-state polymer electrolytes
The solid-state electrolytes based on PEGMA-PEGDA copolymer
network were prepared via solution casting procedure [3,42]. The RAFT
polymerization network and LiClO4 (EO/Li+ = 16) were dispersed in
THF, and stirred for 16 h at room temperature. After the polymer matrix
and the lithium salt were dissolved in THF, the mixture was a homo-
geneous composition, and then poured into a PTFE dish. The solvent
was slowly evaporated and further dried in vacuum drying oven for
48 h to eliminate the trace content of THF, a flexible membrane was
thus obtained. The thickness of the film was kept at about 100 µm. The
samples were denoted as RAFT1, RAFT2, RAFT3 and RAFT4 according
to various compositions illustrated in Table 1. CPEs were fabricated by
blending IBNs in the RAFT1 system at different weight ratios as 5, 10,
15 and 20 wt%, which were denoted as RAFT1-xIBN, where x was the
weight ratio of IBN in each composite. In addition, to study the me-
chanical and thermal performances systematically, another solid-state
electrolyte, referred to M475-D400, was prepared by ultraviolet light
induced polymerization directly used HOMPP as photoinitiator with
doping LiClO4 beforehand (EO/Li+ = 16), and the molar feeding ration
of M475 to D400 was fixed at 100: 25.
2.6. Characterization
1
H nuclear magnetic resonance (NMR) spectra were recorded on a
Bruker AVANCE III spectrometer (400 MHz) using CDCl3 (Cambridge
Isotope Laboratories) as the solvent at room temperature with tetra-
methylsilane (TMS) as the reference. The structure of raw materials and
products in this study was characterized via Fourier transformation
infrared absorption spectra (FT-IR) using an FT interferometer (Equinox
55, Bruker, Germany). The grafting densities of IBNs were estimated by
an STA449F3 Jupiter thermogravimetric analyzer (Netzsch, Germany)
in the temperature range from ambient temperature to 800 °C at a
heating rate of 10 °C min−1 under a nitrogen atmosphere. All the
samples were dried at 60 °C under vacuum overnight before testing.
Differential scanning calorimetry (DSC) measurement was performed
on a Q2000 TA Instrument (USA) for a temperature range of − 90 to
150 °C under an argon atmosphere at constant heating rate of
10 °C min−1. To investigate the crystallization performances of the
solid-state electrolyte membranes, X-ray diffraction (XRD) scans were
carried out by using an X-ray diffractometer (X′Pert PRO, PANalytical
B.V., Netherlands) with CuKα radiation at room temperature. The XRD
patterns were recorded at the Bragg's angle (2θ) in the range of 5–80°
with a scan rate of 3 ° min−1. Tensile tests were performed on a SUNS
CMT4104 universal tensile testing machine at a loading rate of
5 mm min−1. For each specimen, at least 5 tests were carried out. Ionic
conductivity, electrochemical and stability window were carried out on
an Autolab PGSTAT302N electrochemical test system (Eco Chemie,
Netherlands). Ionic conductivity was determined by the two electrodes
AC impedance method over the frequency range from 1 MHz to 100 Hz
using sinusoidal amplitude modulation of 10 mV at temperatures ran-
ging from 20 to 60 °C at 10 °C intervals. The electrochemical stability
window of the CPEs was obtained by linear sweep voltammetry (LSV) at
a sweep rate of 10 mV s−1. The samples were sandwiched between li-
thium foil and stainless steel (SS) electrode in a coin cell CR2032 as-
sembled in an argon-filled glove box.
J. Hu et al. Journal of Membrane Science 575 (2019) 200–208

Scheme 1. Scheme illustration of the preparation of PEGMA-PEGDA cross-

linked polymer via RAFT polymerization.

3. Results and discussion

3.1. Synthesis of PEGMA-PEGDA cross-linked network

A series of PEGMA-PEGDA copolymer cross-linked network were

synthesized via RAFT polymerization. RAFT process has many ad- Fig. 1. Photographs of the solid-state electrolytes prepared in this study before
vantages over free radical polymerization because of the characteriza- and after bending of (a) RAFT1 and (b) M475-D400.
tion of preparing well-defined polymers with well-controlled molecular
weights and narrow polydispersities [43–45]. CPDN is one of the most
popular chain-transfer agents to mediate RAFT polymerization because
it has been used to prepare polymers with low PDI of methacrylate
monomers [46,47]. The isobutyl cyanide leaving group of CPDN in
RAFT process is the same as that of AIBN decomposed during the re-
action, indicating that CPDN has good compatibility with AIBN in the
practical polymerization.
The synthesis procedures of PEGMA-PEGDA copolymer networks
are illustrated in Scheme 1. The ethylene oxide (EO) segments of
PEGMA (red) is pendent in the system, while PEGDA acts as a cross-
linker agent due to the diacrylate groups in the structure, which gen-
erate bridges between liner chains through the EO components of
PEGDA (blue). By incorporating LiClO4 in the RAFT polymerization
compounds via solution casting procedure mentioned before, a trans-
parent solid-state electrolyte membrane was obtained. In comparison
with ultraviolet light initiated radical polymerization, RAFT procedure
follows the sequence of reversible addition-fragmentation-chain Fig. 2. TGA result for IBN(79).
transfer, and the reversible addition of chain growth free radicals en-
dows relaxation of the PEGMA-PEGDA network. Thus, RAFT1 exhibited
flexibility with good mechanical properties, but M475-D400 was
cracked after bent (Fig. 1), suggesting that the solid-state electrolytes
based on RAFT polymerization have satisfying mechanical perfor-
mances which can meet the requirements of the application in LIBs.

3.2. Fabrication of IBNs

IBNs were prepared via sulfonation of silica nanoparticles, and

subsequently, the neutralization reaction between SiO2-SO3H and
JEFFAMINE® M2070 was promoted. Thermogravimetric curves of the
IBNs are shown in Fig. 2. Obviously, 21% weight percentage of the IBNs
remained after TGA testing, indicating that a significant weight loss was
originated from the organic composition of the IBNs, and the IBNs were
denoted as IBN(79), where 79 was the weight percentage of the com-
ponent anchored on the surface of silica nanoparticles. The functiona-
lized nanoparticles clearly exhibited following two types of distinct
Fig. 3. FTIR spectra of pristine SiO2, SiO2-SH, SiO2-SO3H and IBN(79).
weight loss events: continuous rapid decomposition at approximately
200 °C due to the degradation of the anchored segment and the rela-
tively slow weight loss region at around 400–700 °C due to the inter- their excellent thermal stabilities.
molecular condensation of the silica nanoparticles [48]. The high de- The FT-IR spectra of the pristine silica, SiO2-SH, SiO2-SO3H and IBN
composition temperature of IBNs (approximately 223 °C) indicated (79) are shown in Fig. 3. For bare silica, the characteristic absorption

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J. Hu et al. Journal of Membrane Science 575 (2019) 200–208

interestingly, no exothermic peak appears in the cooling procedure of

RAFT3 and M475-D400, indicating that the cross-linked structure de-
pressed the crystallization effectively, which is advantageous to elevate
ionic conductivity of electrolytes. In addition, Tg is known to be a
crucial factor that influences the ionic conductivity of polymer elec-
trolytes, as ionic transference occurs only in the amorphous region
(above Tg) of the polymer matrix. Thus, the composite material with a
low value of Tg is more advantageous to ionic conduction [49]. The Tg
of RAFT3 is − 40.21 °C, which is around 5 °C lower than the values of
M475-D400. Noteworthy, the cross-linked copolymer samples, viz.
RAFT3 and M475-D400, have the same molar feeding ratio of M475 to
D400 (100: 25). Thus the significant distinction in the thermal features
of the two kinds of solid-state electrolytes results from the fabrication
procedure of each electrolyte membrane. The polymer matrix based on
RAFT polymerization owns a well-defined and relaxed chain connection
in the framework architecture, so the mobility of the polymer chains in
RAFT3 is more active than that in M475-D400.

3.4. Crystallization properties of the electrolyte membranes

Qualitative identification of the crystallization properties can be

Fig. 4. DSC curves of M475, D400, RAFT3, and M475-D400 under both cooling
and heating processes.
peak of the tetrahedral silica structures at 1105 cm−1 (Si-O stretching),
as well as the Si-O-Si bending peak at 808 cm−1 are both observed. In
the spectrum of SiO2-SH, the wave number at 2556 cm−1 presents a
small peak (S-H stretching), indicating the existence of the thiol group.
Moreover, the peak at 1342 cm−1 corresponding to the C–H bending
vibration can also be observed. In the spectrum of SiO2-SO3, the S-H
stretching vibration peak disappears; however, three characterization
peaks at 1192 cm−1 (S=O stretching), 1053 cm−1 (S=O stretching),
and 741 cm−1 (S-O stretching) emerge, indicating the oxidation of the
thiol group into the sulfonic acid group. Compared to SiO2-SO3, the
peak at 1468 cm−1 attributed to the NH3+ deformation vibration is
observed from IBN(79), demonstrating the ionic modification of silica
nanoparticle.
made by comparing the relative strength of X-ray diffraction peaks of
the sample pattern facilely [50–52]. The ambient temperature XRD
patterns observed for the various compositions of polymer electrolytes
are shown in Fig. 5. The addition of IBNs induce a significant amor-
phous domain in the polymer matrix based on RAFT polymerization at
first, as evident from the weaker and broader peak obtained at
2θ = 21.5°. However, the strength of the diffraction peak increases with
the enhancing of IBNs content, and even higher than that of RAFT1 on
account of the weight ratio of 20 wt%, suggesting an increase in the
degree of crystallinity of the composition. It has been reported that the
amorphous regions of polymer provide the ion transport channel, but
the crystalline domains hamper the ionic conductivity [53]. Therefore,
RAFT1-10IBN(79), which owns more amorphous regions, could have a
promising high ionic conduction.
3.5. Mechanical properties of the electrolyte membranes
The mechanical properties of the solid-state electrolytes are one of
the most crucial characterizations that dominate their processability
and further influence the security of batteries, and the IBNs are ex-
pected to reinforce membranes. The typical stress-strain curves of
RAFT1 and RAFT1-10IBN(79) are presented in Fig. 6, and the tensile
properties of these polymer electrolyte membranes are shown in
Table 3. A typical stress-strain curve of soft polymer material is ex-
hibited in the tensile process of RAFT1, the yield stress, tensile modulus

3.3. Thermal properties of the electrolyte membranes

The thermal behaviors, evaluated by DSC, of M475, D400, RAFT3,

and M475-D400 are shown in Fig. 4, and the crystallization tempera-
ture (Tc), glass transition temperature (Tg) as well as melting point (Tm)
are summarized in Table 2. The obvious exothermic peaks can be ob-
served in the DSC curves of M475 and D400 during the cooling process,
which are attributed to the crystalline transition of the materials. The Tc
of the two entries is − 14.40 and − 25.51 °C, respectively. Very

Table 2
Thermal behavior of M475, D400, RAFT3, and M475-D400.
Entry Tc/°C Tg/°C Tm/°C

M475 − 14.40 − 57.46 − 1.71

D400 − 25.51 − 42.43 − 16.36
RAFT3 –a − 40.21 –a
M475-D400 –a − 35.38 –a
Fig. 5. XRD patterns of RAFT1, RAFT1-5IBN(79), RAFT1-10IBN(79), RAFT1-
a
No signal observed in the DSC curves. 15IBN(79) and RAFT1-20IBN(79).

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J. Hu et al. Journal of Membrane Science 575 (2019) 200–208

Fig. 6. Stress-strain curves of solid-state electrolytes membranes.

and elongation at break of which are 3.4 MPa, 338 MPa and 697%,
respectively. Depending on the IBNs loading, the incorporation of
RAFT1-10IBN(79) increases the yield stress and tensile modulus by
23.5% and 56.5% compared with RAFT1, respectively. The doping of
IBNs leads to the increasing of the specific interracial area, which forms
the strong confinement between the unique chemical framework result
from RAFT polymerization and the interfaces of IBNs [54,55].
Fig. 7. Ionic conductivities of solid-state electrolytes based on RAFT poly-
merization as functions of temperature. The solid lines and the dash lines re-
present the fitting results using Arrhenius equation for all the samples: elec-
trolytes with IBNs embedded (solid lines) and neat polymer electrolytes (dash
lines).
Table 4
Corresponding values of σ, Ea and σ0 of PEGMA-PEGDA cross-linked solid-state
electrolytes based on RAFT polymerization.

3.6. Electrochemical properties of the electrolyte membranes Entry σ at 30 °C/10−5 S cm−1 Ea/eV σ0/103 S cm−1

RAFT1 3.76 0.584 179.24

Ionic conductivity is a crucial property for the application of solid- RAFT2 2.60 0.590 191.12
state electrolytes in energy storage devices [10]. Fig. 7 exhibits the RAFT3 2.01 0.592 210.15
temperature dependence of ionic conductivities for the electrolyte RAFT4 1.66 0.600 222.58
samples prepared in this study. As expected, the ionic conductivity RAFT1-5IBN(79) 4.69 0.561 93.97
RAFT1-10IBN(79) 6.77 0.532 46.59
increased with the increasing temperature for all the samples owing to RAFT1-15IBN(79) 5.23 0.559 64.17
the faster movement of ions and improved flexibility of polymer chains. RAFT1-20IBN(79) 3.35 0.589 181.26
As shown in Fig. 7 and Table 4, the ionic conductivities increase with
the rise of M475 content in the copolymer networks, and RAFT1 owns
the highest ionic conductivity of 3.76 × 10−5 S cm−1 at ambient electrolytes is liquid-like [58]. The Arrhenius equation can be re-
temperature, demonstrating that the pendant chain of M475 destroyed presented as σ = σ0exp(-Ea/kT), where σ is the ionic conductivity in
the crystal of the polymer skeleton effectively, and further promoted S cm−1, σ0 is the pre-exponential factor in S cm−1, Ea is the activation
polymer chain mobility. In addition, the ionic conductivity was im- energy in eV, k is the Boltzmann's constant, and T is the absolute
proved by blending IBN(79) in the system, indicating that the addition temperature in Kelvin. The activation energies (Ea) and σ0 are calcu-
of IBN(79) influenced the recrystallization kinetics of the PEO matrix, lated from this temperature range are listed in Table 4. For the elec-
thus ultimately improved the localized amorphous regions [56]. When trolytes prepared by neat RAFT polymerization matrix viz., RAFT1,
the weight ratio of IBN(79) was 10 wt%, the ionic conductivity RAFT2, RAFT3, and RAFT4, Ea and σ0 decrease with increase in M475
achieved highest (6.77 × 10−5 S cm−1 at 30 °C). However, as the contents due to enhancement of mobility of the polymer chains which
content of IBN(79) increased, the ionic conductivity of RAFT1-20IBN in turn elevates amorphous nature and charge carries in the system. On
(79) fell off to 3.35 × 10−5 S cm−1 at ambient temperature, which was the other hand, Ea and σ0 decrease further with IBNs embedded, reach a
even lower than that of RAFT1. This result indicates that ionic con- minimum at 10 wt% IBN(79) content, and thereafter increase. This may
ductivity is not only caused by the relaxation of polymer chains, but be owing to the interplay between opposing effects. Firstly, the amount
also from the lithium ion mobility. Higher content of additives is as- of charge carriers increases with increasing number of additives; sec-
sociated with high melt viscosity [57], which hampers the lithium ion ondly, the presence of fillers leads to the decrease of free volume, which
conduction. hinders the migration of charge carriers. Additionally, at relatively
Obviously, the plot of the ionic conductivity for each specimen higher IBN(79) concentrations a considerable amount of Li+ remains as
against the reciprocal absolute temperature is linear, suggesting that ion-pairs, that do not lead to the improvements of ionic conductivities
the conductivity of the electrolyte fabricated in this study obeys of the electrolytes [59]. These calculated results of Ea and σ0 come from
Arrhenius law. The Arrhenius relationship demonstrates that the charge the linear fitting based on Arrhenius law are consistent with the ionic
carriers are dissociated from the segmental motion of polymeric fra- conductivity measurements, and the best conducting electrolyte
mework, and the conductive tendency of Li+ ions in the solid-state RAFT1-10IBN(79) possesses the lowest Ea and σ0.

Table 3
Tensile properties of solid-state electrolytes membranes.
Entry Yield stress/MPa Tensile stress/MPa Tensile modulus/MPa Elongation at break/%

RAFT1 3.4 ± 0.15 4.8 ± 0.19 338 697.10

RAFT1-10IBN(79) 4.2 ± 0.27 4.2 ± 0.27 529 7.07

205
J. Hu et al. Journal of Membrane Science 575 (2019) 200–208

Furthermore, the electrochemical oxidation potential of M475-D400 is

4.91 V vs. Li+/Li, which is also higher than that of linear PEO of 4.4 V
vs. Li+/Li [12], suggesting that fabrication cross-linked network is
helpful for enhancing the electrochemical stability of solid-state elec-
trolytes.

3.7. Cyclic performance of battery

To confirm the usefulness of the composite polymer electrolytes

based on RAFT polymerization with IBN embedded, RAFT1-10IBN(79),
which has prominent ionic conductivity, was utilized as the separator to
assemble the all-solid-state LFP/Li battery. Fig. 9a demonstrated the
charge-discharge performance of Li|RAFT1-10IBN(79)|LFP cell cycled
at 60 °C with a certain current density as 0.1 C. The original discharge
capacity is observed to be approximate 140 mA h g−1 and 132 mA h g−1
of specific discharge capacity is still retained after 40 cycles. The slight
Fig. 8. LSV curves of RAFT3 and M475-D400.
capacity decay may attribute to the loss of cathode active materials and
the irreversible production arisen from the formation of new solid
electrolyte interphase (SEI). The charging curves show a distinct pla-
teau at 3.47 V, and the corresponding discharging cures illustrate a
voltage plateau at 3.39, low polarization of around 0.08 V (ΔV) between
charge and discharge plateaus suggests that the internal resistance of
cell is small. Due to the good reversibility of the redox processed during
the charge-discharge cycles on the solid-state battery system, the Cou-
lombic efficiency of the cell is higher than 93% (Fig. 9b), indicating that
RAFT1-10IBN(79) exhibits excellent stability during the charge-dis-
charge procedure.
In comparison with those polymer electrolytes based on RAFT
polymerization obtained from other previous literatures (Table 5), the
LIBs that employed the CPEs prepared in this work exhibited significant
comprehensive enhancement in properties, which mainly included
ionic conductivity, electrochemical oxidation potential and cycling
stability. Our study will be recommended as a promising solid elec-
trolyte for all-solid-state LIBs.

4. Conclusions

A series of PEGMA-PEGDA cross-linked electrolytes were prepared

Fig. 9. (a) Charge-discharge curves, (b) cycle performance of the Li|RAFT1-
10IBN(79)|LFP battery during galvanostatic cycling at 0.1 C-rate. The mea-
surement was conducted at 60 °C.
The electrochemical stability of RAFT3 and M745-D400 were ob-
served by LSV, and the resulting LSV curves are shown in Fig. 8. The
LSV result of RAFT3 shows that no decomposition in the electrolytes
takes place below 5.0 V vs. Li+/Li, revealing that the cross-linked
electrolytes based on RAFT process have high anodic stability.
based on RAFT polymerization with a different molar feeding ratio of
M475 to D400, and CPEs were further obtained by blending IBN(79) in
the RAFT architectures. Intuitively, compared to the polymer matrix
synthesized by traditional ultraviolet light initiated radical poly-
merization, the polymer skeleton prepared by RAFT process owned
improved flexibility, which kept intact after bent. The stress-strain
testing also demonstrates that RAFT1-10IBN(79) increases the yield
stress and tensile modulus by 23.5% and 56.5% compared with RAFT1,
respectively. The crystallization was depressed owing to the cross-
linked framework in the structure, thus promoted ionic conductivities
of the solid-state electrolytes, and the improvement became more
prominent when the system was consisted of a more M475 component,
indicating that the pendant polymer chains contributed more to the
ionic conduction. In addition, CPEs obey Arrhenius law, higher ionic
conductivities and lower activation energies were achieved by

Table 5
Comparison of electrochemical properties of solid-state electrolytes based on RAFT polymerization.
Polymer matrix Chain transfer agent σ at 30 °C/10−5 S cm−1 Electrochemical oxidation potential/V Cyclic stability Ref.

PEGMA-EGDA-POSS CPDN ~ 4.00 6.3 30 cycles charge-discharge with 65% capacity retention [20]
PVP-PEG-PVP macro-CTA ~ 3.00 N/A 30 cycles charge-discharge with 94.4% capacity [60]
retention
HBPS- (PVIMTFSI)17 HBPS-CTA 5.01 4.90 N/A [61]
P(PEGMA) CPDN 4.23 N/A N/A [62]
POSS-PEO3.5-PSFT3.3 RAFT-CTA-COOH 1.05 N/A N/A [63]
Our work CPDN 6.77 5.14 40 cycles charge-discharge with 94.3% capacity
retention

206
J. Hu et al.
embedding IBN(79), the results indicated that CPEs could elevate the
ionic transference more effectively. Owing to these outstanding fea-
tures, the all-solid-state battery assembled using RAFT1-10IBN(79) as
electrolyte membrane exhibited stable cycling performances. The en-
hanced ionic conductivity and good electrochemical stability illustrated
that CPEs fabricated in this study could be potentially applied to solid-
state LIBs.
Acknowledgments
We are grateful to the National Natural Science Foundation of China
(51473056, 51622303, and 51703080) and Natural Science Foundation
of Hubei Scientific Committee (2018CFA059) for support of this work.
The authors also acknowledge the Analytical and Testing Center of
HUST for use of measurement facilities.
Appendix A. Supplementary material
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.memsci.2019.01.025.
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