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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 candidate to satisfy these demands, due to the lack of leakage, good
dimensional stability and outstanding chemical stability about its
Since its birth, lithium-ion batteries (LIBs), which own various ad- nature. As a solid-state electrolyte, poly(ethylene oxide) (PEO) has been
vantages such as high energy density and stable cycling performance, studied comprehensively as the skeleton material owing to several
have played a crucial role in the recent development of the electro- specific advantages including high safety, high energy density, good
chemical devices for energy storage, gradually [1–4]. Unfortunately, a electrochemical stability, and excellent compatibility with lithium salts
series of insecure events caused by the utilization of flammable and [9,10]. However, linear PEO could not be used directly for practical
volatile organic solvents in the system have aroused concern about the LIBs applications, because of its relatively low ionic conductivity that
security matters of the LIBs. To prevent the risks of leakage and related results from the declined segmental mobility of PEO in the crystalline
fire hidden peril about liquid electrolytes fundamentally, Masoud et al. domains especially at low temperature [11–13]. In order to elevate the
[5–8] exploited a kind of gel copolymer electrolyte by soaking com- amorphous state in polymer matrix for improving local relaxation and
mercial plasticizers in porous poly(vinylidene fluoride-co-hexa- segmental motion to allow ion (Li+) transport, fabricating cross-linked
fluoropropylene) (PVDF-co-HFP) polymer matrix, which demonstrated networks [14] or nanoparticle-containing composite polymer electro-
ideal electrochemical stability. Furthermore, the application of elec- lytes (CPEs) [15] have been demonstrated to be effective methods to
trolytes at the range of lithium metal batteries, which use metallic li- promote the physical-chemical performances of PEO based solid-state
thium as anode material to obtain higher theoretical specific capacity electrolytes utilized in LIBs.
but need more robust membranes to obstruct the growth of lithium The cross-linked polymer electrolytes, which are usually prepared
dendrite, an all-solid construction has been suggested as an ideal 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. Journal of Membrane Science 575 (2019) 200–208

of an initiator or radiation, show fully amorphous features due to the have also been proved to be effective fillers to prepare CPEs, which
difficulty of chain mobility to assume the appropriate position for showed gratifying mechanical and electrochemical performances.
crystallization. Thus, ionic conduction is more active in the cross-linked In this work, a series of cross-linked copolymers consisted of poly
system, and the mechanical strength of electrolytes is elevated owing to (ethylene glycol) methacrylate (PEGMA) and poly(ethylene glycol)
the tight network, additionally [16]. Yang et al. [17] prepared a tough diacrylate (PEGDA) were synthesized via one-step RAFT polymerization
and compact 3D cross-linked network gel polymer electrolyte via a in the presence of 2-cyanoprop-2-yl 1-dithionaphthalate (CPDN) as
novel initiator-free one-pot ring-opening polymerization reaction under chain-transfer agent, then the IBNs based on nanoscale silica coated
heating at 80 °C for a certain time. The 3D cross-linked membrane ex- polyether with sulfo-amino ionic connection, which were fabricated
hibited a perfect combination of mechanical strength, ionic con- successfully in our previous work [35], were blended with the copo-
ductivity, and suppression of Li dendrite growth. Guo et al. [18] fab- lymer facilely under different weight ratios to fabricate CPEs for facil-
ricated an inter-penetrating network of poly(ether-acrylate) (IPN-PEA) itating practical properties. The effects of the composition of the RAFT
and further realized via UV curing of ion-conductive PEO and branched system and IBNs content on the dimensional stability, thermal perfor-
acrylate. The IPN-PEA electrolyte integrated excellent mechanical mances, ionic conductivity, and electrochemical stability were sys-
strength, high ionic conductivity at ambient temperature, and good tematically investigated. By introducing the RAFT process in the pre-
compatibility with cathode materials. However, the traditional cross- paration of the copolymer, the electrolyte films were more flexible than
linked polymer is tough but brittle generally. Thus it's crucial to explore the materials prepared by conventional polymerization induced by ul-
a tradeoff issue between mechanical strength and flexibility. The re- traviolet light directly. In addition, higher ionic conductivity could be
versible addition-fragmentation chain transfer (RAFT) process has been obtained by the embedding of IBNs at a specific content in the com-
proved to be one of the most universal for the provision of polymers posites. Thus, the CPEs manufactured in this study acted as potential
with well-defined and flexible structure since its first reported by Thang candidates for application in LIBs.
et al. [19]. Lee et al. [20] prepared a series of organic/inorganic hybrid
branched and linear copolymer electrolytes, which were composed of 2. Experimental
poly(ethylene glycol) methyl ether methacrylate (PEGMA), methacry-
late functionalized polyhedral oligomeric silsesquioxane (MA-POSS) 2.1. Materials
and ethylene glycol dimethacrylate (EGDMA) via RAFT polymerization.
This kind of electrolytes could be utilized to assemble all-solid-state Poly(ethylene glycol) methacrylate (PEGMA, Mn = 475 g mol−1,
batteries for stable application at high temperature without causing containing 100 ppm MeHQ and 200 ppm BHT as inhibitor, Aladdin,
safety problems. hereafter M475) and poly(ethylene glycol) diacrylate (PEGDA, Mn =
CPEs are the impactful candidates used in the field of solid-state 400 g mol−1, containing 100 ppm MeHQ and 300 ppm BHT as in-
electrolytes, which are originated from the addition of α-alumina as the hibitor, Aladdin, hereafter D400) were passed through neutral Al2O3 to
inactive fillers in the polymer matrix introduced by Weston and Steele remove inhibitor prior to polymerization. LUDOX® SM colloidal silica
in 1982 [21]. Thereafter, SiO2 [22], TiO2 [23], MgO [24], LiAlO2 [25], (30 wt% suspension in H2O, Sigma-Aldrich) and 3-mercaptopropyl-
and other metal oxide were used as additives for preparing CPEs. It is trimethoxysilane (MPTMS, 95 wt%, Sigma-Aldrich) were used as re-
known to all, the blending of a filler can increase the amorphous phase ceived. The monoamines-terminated PEO derivative, JEFFAMINE®
due to the depression of the crystallization of polymer skeleton, which M2070, was gained form Huntsman Co., Ltd. Lithium perchlorate
will lead to an enhancement of ionic conductivity, as well as an im- (LiClO4, Aladdin) were dried at 150 °C in a vacuum oven for 24 h and
provement of the electrolyte/electrode interfacial property. Further- stored in the glove box before use. Other chemicals, including alcohol,
more, the functionalized particles have also been used to promote the 1-Bromonaphane, tetrahydrofuran (THF), carbon disulphide (CS2),
performances of CPEs. Archer et al. developed a novel family of na- magnesium, hydrochloric acid (HCl), chloroform, ethyl acetate, di-
noparticles with the characteristic of liquid-like behavior modified by methyl sulfoxide (DMSO), 2,2′-azobis(2-methylpropionitrile) (AIBN),
ionic segments [26–29]. Owning to the ionic connection between the petroleum ester, N,N-dimethylformamide (DMF), hexane, calcium hy-
core architecture and soft organic shell component, the nanoparticles dride (CaH2), hydrogen peroxide, acetonitrile, lithium iron phosphate
dispersed in the composite materials homogeneously, and the mobility (LFP), acetylene black (AB), polyvinylidene fluoride (PVDF), N-methyl-
was promoted, simultaneously [30]. Park [31] and Zheng [32] pre- 2-pyrrolidone (NMP) and 2-Hydroxy-2-methylpropiophenone (HOMPP)
pared a series of nanoparticle organic hybrid materials (NOHMs) with were purchased locally. AIBN was recrystallized from ethanol, dried at
liquid-like inorganic nanoscale fillers comprised, independently. The room temperature in vacuum, and stored in a refrigerator at − 15 °C.
spontaneous ordering of the tethered organic species on the surface of THF, CS2, DMSO, and DMF were dried over anhydrous CaH2 and then
nanoscale fillers was achieved due to the unique swelling behaviors of distilled prior to use. De-ionized (DI) water was used in all experiments.
NOHMs, which exhibited effective CO2 capture via the entropic effect.
Dong et al. [33] prepared solvent-free carbon nanotube fluids (CNT 2.2. Synthesis of chain-transfer agent
fluids) through an ion exchange method, and composite membranes for
full cells applications were manufactured by incorporating CNT fluids 2-cyanoprop-2-yl 1-dithionaphthalate (CPDN) was used as the
into a chitosan (CS) matrix. Benefit from the electrostatic interactions chain-transfer agent in this RAFT polymerization process, the schematic
between sulfonic acid groups in the CNT fluids and amino groups in the illustration of the synthesis route was shown in Scheme S1 (see
CS matrix, the proton conductivities of CS/CNT fluids composite Supporting information). A solution of 15 g (0.07 mol) 1-bromona-
membranes were improved. Zheng et al. [34] reported a nanofluid phane and 40 mL THF was added to a 150 mL bottle containing mag-
based on MnSn(OH)6 crystallite. Owing to the ionic connection between nesium (1.92 g, 0.08 mol) within 1 h and refluxed for 1 h under 50 °C.
the corona (-SO3- terminated organosilanes) and canopy (polyether Then the mixture was cooled to room temperature, CS2 5.6 g (0.07 mol)
amine), the material shows improved processability and fluidity at was added to the solution at room temperature and refluxed for 8 h. The
ambient temperature without any solvents, which have great potential mixture was poured into water, and the scarlet intermediate product
for application in plasticizers. Moreover, we synthesized ionic bond was obtained after filtering the unreacted magnesium. Acidified the
modified nanoparticles (IBNs) successfully, and PEO based CPEs were intermediate product by diluted HCl, the solution was extracted with
fabricated by blending IBNs in the system [35]. The physico-chemical chloroform for three times. After evaporated under vacuum, the re-
performances of CPEs shown that the ionic conductivity and electro- sident added with 40 mL ethyl acetate and reacted with 5 g DMSO in a
chemical stability were all elevated owing to IBNs loading. Besides that, 250 mL three-neck flask equipped with a condense pipe under nitrogen
other nanoparticles decorated by ionic liquid [36–38] or sulfonate [39] protection for 10 h at 30 °C. The mixture was added with 6.8 g

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(0.04 mol) AIBN and 60 mL ethyl acetate, then refluxed for another 15 h the changes in the pH value. The product was put into dialysis tubing
at 65 °C. After evaporation of the solvent, crude CPDN was obtained. and dialyzed for several days in DI water to remove any remaining free
Purified CPDN by chromatography on silica gel column with petroleum JEFFAMINE® M2070. Water was evaporated in a convection oven, and
ester-ethyl acetate = 9:1 as eluent. Finally, the obtained CPDN was a the product was dried extensively under vacuum and stored in the dried
dark red slurry, then kept it in the refrigerator at − 18 °C. 1H NMR form at room temperature.
[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) 2.5. Fabrication of solid-state polymer electrolytes
(Fig. S1).
The solid-state electrolytes based on PEGMA-PEGDA copolymer
network were prepared via solution casting procedure [3,42]. The RAFT
2.3. Preparation of copolymer network via RAFT polymerization
polymerization network and LiClO4 (EO/Li+ = 16) were dispersed in
THF, and stirred for 16 h at room temperature. After the polymer matrix
PEGMA-PEGDA copolymer network containing M475: D400: CPDN:
and the lithium salt were dissolved in THF, the mixture was a homo-
AIBN = 100: 15: 1: 0.5 (molar feeding ratio) was synthesized via RAFT
geneous composition, and then poured into a PTFE dish. The solvent
polymerization as follows. M475 (2.375 g, 5 mmol), D400 (0.3 g,
was slowly evaporated and further dried in vacuum drying oven for
0.75 mmol), CPDN (0.0136 g, 0.05 mmol) and AIBN (0.0041 g,
48 h to eliminate the trace content of THF, a flexible membrane was
0.025 mmol) were dissolved in 14 mL of distilled DMF, and the re-
thus obtained. The thickness of the film was kept at about 100 µm. The
sultant solution was added to a 50 mL Schlenk flask equipped with a
samples were denoted as RAFT1, RAFT2, RAFT3 and RAFT4 according
magnetic stirring bar and a condenser. The mixture was degassed by
to various compositions illustrated in Table 1. CPEs were fabricated by
three consecutive freeze-pump-thaw cycles to remove oxygen and the
blending IBNs in the RAFT1 system at different weight ratios as 5, 10,
reaction was performed in an oil bath thermostatted at 75 °C for 24 h
15 and 20 wt%, which were denoted as RAFT1-xIBN, where x was the
under a nitrogen atmosphere. After reacting at a predetermined time,
weight ratio of IBN in each composite. In addition, to study the me-
the flask was removed from the oil bath, it was exposed to air and
chanical and thermal performances systematically, another solid-state
diluted with a little DMF to quench the reaction. The unreacted
electrolyte, referred to M475-D400, was prepared by ultraviolet light
monomers were removed by precipitation in hexane three times. After
induced polymerization directly used HOMPP as photoinitiator with
being dried under vacuum at 40 °C for 48 h, a pink rubbery solid pro-
doping LiClO4 beforehand (EO/Li+ = 16), and the molar feeding ration
duct was obtained. Other PEGMA-PEGDA copolymer networks were
of M475 to D400 was fixed at 100: 25.
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
2.6. Characterization
(CH3-O) (Fig. S2).
1
H nuclear magnetic resonance (NMR) spectra were recorded on a
2.4. Preparation of ionic bond modified silica nanoparticles (IBNs) Bruker AVANCE III spectrometer (400 MHz) using CDCl3 (Cambridge
Isotope Laboratories) as the solvent at room temperature with tetra-
Briefly, the fabrication of IBNs was accomplished in two steps: first, methylsilane (TMS) as the reference. The structure of raw materials and
silica nanoparticles were functionalized by sulfonic acid groups [40]; products in this study was characterized via Fourier transformation
second, the sulfonated silica nanoparticles were reacted with JEFFA- infrared absorption spectra (FT-IR) using an FT interferometer (Equinox
MINE® M2070 to promote the acid-base neutralization between the 55, Bruker, Germany). The grafting densities of IBNs were estimated by
sulfonic acid groups coated on silica nanoparticles and the amino an STA449F3 Jupiter thermogravimetric analyzer (Netzsch, Germany)
groups terminated on JEFFAMINE® M2070 [41]. Specifically, MPTMS in the temperature range from ambient temperature to 800 °C at a
(10 mL) was dissolved in ethanol (40 mL) to form a transparent solu- heating rate of 10 °C min−1 under a nitrogen atmosphere. All the
tion. Then the solution was dripped into LUDOX® SM colloidal silica samples were dried at 60 °C under vacuum overnight before testing.
(20 mL) combined with DI water (120 mL) by intense mechanical stir- Differential scanning calorimetry (DSC) measurement was performed
ring (700 rpm). The reaction was carried out under reflux at 70 °C for on a Q2000 TA Instrument (USA) for a temperature range of − 90 to
24 h. After being separated by centrifugation and washed three times 150 °C under an argon atmosphere at constant heating rate of
with ethanol to remove the unreacted MPTMS, the thiol coated silica 10 °C min−1. To investigate the crystallization performances of the
nanoparticles, called SiO2-SH, were obtained by drying at 60 °C under solid-state electrolyte membranes, X-ray diffraction (XRD) scans were
vacuum for 24 h. The sulfonation of silica nanoparticles (hereafter ab- carried out by using an X-ray diffractometer (X′Pert PRO, PANalytical
breviated as SiO2-SO3H) was further performed by oxidizing the surface B.V., Netherlands) with CuKα radiation at room temperature. The XRD
thiol groups of silica into sulfonic acid groups with 30 wt% H2O2 so- patterns were recorded at the Bragg's angle (2θ) in the range of 5–80°
lution at 25 °C for 24 h. Then, SiO2-SO3H (10 g) was added in DI water, with a scan rate of 3 ° min−1. Tensile tests were performed on a SUNS
and the mixture was ultrasonicated for 30 min to disperse SiO2-SO3H in CMT4104 universal tensile testing machine at a loading rate of
the solution. JEFFAMINE® M2070 (10 g) was also dissolved in DI water 5 mm min−1. For each specimen, at least 5 tests were carried out. Ionic
(50 mL) separately, and SiO2-SO3H solution was added with continuous conductivity, electrochemical and stability window were carried out on
stirring. The linking reaction was allowed to proceed to completion an Autolab PGSTAT302N electrochemical test system (Eco Chemie,
over several days, and the termination of the reaction was evaluated by Netherlands). Ionic conductivity was determined by the two electrodes
AC impedance method over the frequency range from 1 MHz to 100 Hz
Table 1 using sinusoidal amplitude modulation of 10 mV at temperatures ran-
RAFT polymerizations of PEGMA and PEGDA. ging from 20 to 60 °C at 10 °C intervals. The electrochemical stability
Entry M475 D400 CPDN AIBN 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-
RAFT-I 100 15 1 0.5 thium foil and stainless steel (SS) electrode in a coin cell CR2032 as-
RAFT-II 100 20 1 0.5
sembled in an argon-filled glove box.
RAFT-III 100 25 1 0.5
RAFT-IV 100 30 1 0.5

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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


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
Fig. 4. DSC curves of M475, D400, RAFT3, and M475-D400 under both cooling
degree of crystallinity of the composition. It has been reported that the
and heating processes.
amorphous regions of polymer provide the ion transport channel, but
the crystalline domains hamper the ionic conductivity [53]. Therefore,
peak of the tetrahedral silica structures at 1105 cm−1 (Si-O stretching), RAFT1-10IBN(79), which owns more amorphous regions, could have a
as well as the Si-O-Si bending peak at 808 cm−1 are both observed. In promising high ionic conduction.
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.
3.5. Mechanical properties of the electrolyte membranes
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
The mechanical properties of the solid-state electrolytes are one of
stretching vibration peak disappears; however, three characterization the most crucial characterizations that dominate their processability
peaks at 1192 cm−1 (S=O stretching), 1053 cm−1 (S=O stretching),
and further influence the security of batteries, and the IBNs are ex-
and 741 cm−1 (S-O stretching) emerge, indicating the oxidation of the pected to reinforce membranes. The typical stress-strain curves of
thiol group into the sulfonic acid group. Compared to SiO2-SO3, the
RAFT1 and RAFT1-10IBN(79) are presented in Fig. 6, and the tensile
peak at 1468 cm−1 attributed to the NH3+ deformation vibration is properties of these polymer electrolyte membranes are shown in
observed from IBN(79), demonstrating the ionic modification of silica Table 3. A typical stress-strain curve of soft polymer material is ex-
nanoparticle. 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.


Fig. 7. Ionic conductivities of solid-state electrolytes based on RAFT poly-
and elongation at break of which are 3.4 MPa, 338 MPa and 697%, merization as functions of temperature. The solid lines and the dash lines re-
respectively. Depending on the IBNs loading, the incorporation of present the fitting results using Arrhenius equation for all the samples: elec-
RAFT1-10IBN(79) increases the yield stress and tensile modulus by trolytes with IBNs embedded (solid lines) and neat polymer electrolytes (dash
lines).
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 Table 4
from RAFT polymerization and the interfaces of IBNs [54,55]. 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

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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


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
Fig. 9. (a) Charge-discharge curves, (b) cycle performance of the Li|RAFT1- improved flexibility, which kept intact after bent. The stress-strain
10IBN(79)|LFP battery during galvanostatic cycling at 0.1 C-rate. The mea- testing also demonstrates that RAFT1-10IBN(79) increases the yield
surement was conducted at 60 °C. stress and tensile modulus by 23.5% and 56.5% compared with RAFT1,
respectively. The crystallization was depressed owing to the cross-
The electrochemical stability of RAFT3 and M745-D400 were ob- linked framework in the structure, thus promoted ionic conductivities
served by LSV, and the resulting LSV curves are shown in Fig. 8. The of the solid-state electrolytes, and the improvement became more
LSV result of RAFT3 shows that no decomposition in the electrolytes prominent when the system was consisted of a more M475 component,
takes place below 5.0 V vs. Li+/Li, revealing that the cross-linked indicating that the pendant polymer chains contributed more to the
electrolytes based on RAFT process have high anodic stability. 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

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

embedding IBN(79), the results indicated that CPEs could elevate the organic/inorganic hybrid branched-graft copolymers and their application to solid-
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