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Energy Storage Science and Technology ›› 2021, Vol. 10 ›› Issue (6): 2069-2076.doi: 10.19799/j.cnki.2095-4239.2021.0160

• Energy Storage Materials and Devices • Previous Articles Next Articles

Preparation and properties of polyvinylidene fluoride/polyvinylidene fluoride sulfonate lithium/lithium salt composite solid electrolyte

Yue SU1(), Xuhua LIU1, Fanglei ZENG1,2, Yurong REN1,2, Bencai LIN1,2()

1.School of Materials Science and Engineering, Changzhou University2.Jiangsu Collaborative Innovation Center of Photovolatic Science and Engineering, Changzhou University, Changzhou 213164, Jiangsu, China

Received:2021-04-15 Revised:2021-05-31 Online:2021-11-05 Published:2021-11-03

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Abstract

Abstract:
Single-ion polymer electrolytes were recently developed and used in solid-state batteries. In single-ion polymer electrolytes, anions are attached to the main chain of polymers, and only lithium ions are allowed to pass through into the electrolyte. As a result, the single-ion polymer electrolytes had a high lithium-ion migration number, which will be beneficial in reducing the concentration polarization of lithium batteries. However, the low ion conductivity of single-ion polymer electrolytes limits their application in lithium batteries. In the present work, chlorosulfonic acid, polyvinylidene fluoride (PVDF), and lithium hydroxide were used to prepare sulfonated polyvinylidene fluoride (SPVDF) and polyvinylidene fluoride sulfonate lithium (SPVDFLi). The chemical structures of PVDF and SPVDF were confirmed by the 1H nuclear magnetic resonance spectra. A series of single-ion polymer electrolytes (SIPEx) were prepared by a solvent casting method from PVDF and SPVDFLi mixture solution. To improve the electrolyte's ion conductivity, PVDF/SPVDFLi/LiTFSI composite electrolytes (SPVDFLi/LiTFSI-y) were created by varying the amount of LiTFSI in the SIPE. The ion conductivity of SIPEs increased by increasing the content of SPVDFLi. The ion conductivity of PVDF/SPVDFLi/LiTFSI composite electrolytes further increased by increasing the content of LiTFSI, SPVDFLi/LiTFSI-40 showed the conductivity of 1.41×10-4 S/cm at 25 ℃, the steady voltage of up to 4.84 V, and the capacity retention rate of is 99.1% after 50 cycles at 0.2 C, because of its high conductivity, high lithium-ion migration number, and high efficiency in inhibiting the growth of lithium dendrites SPVDFLi, the excellent lithium-ion battery assembled with SPVDFLi/LiTFSI-40. These findings suggest that the PVDF/SPVDFLi/LiTFSI composite electrolytes will be used to create high-performance solid-state lithium-ion batteries.

Key words: polymer composite electrolytes, polyvinylidene fluoride sulfonate lithium, conductivity, lithium-ion migration number

CLC Number:

TM 912

Cite this article

Yue SU, Xuhua LIU, Fanglei ZENG, Yurong REN, Bencai LIN. Preparation and properties of polyvinylidene fluoride/polyvinylidene fluoride sulfonate lithium/lithium salt composite solid electrolyte[J]. Energy Storage Science and Technology, 2021, 10(6): 2069-2076.

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URL: https://esst.cip.com.cn/EN/10.19799/j.cnki.2095-4239.2021.0160

https://esst.cip.com.cn/EN/Y2021/V10/I6/2069

Figures/Tables 8

Fig. 1

Synthesis of SPVDFLi"
Fig. 1
Fig. 2

1H NMR spectra of PVDF and SPVDF"
Fig. 2
Fig. 3

(a) the conductivity of SPVDFLi-x varies with temperature, (b) the conductivity of SPVDFLi/LiTFSI-y and PVDF/LiTFSI varies with temperature"
Fig. 3
Table 1

Lithium ion migration number of various SPEs"

样品 I0/mA ISS/mA R0/Ω RSS/Ω tLi+
SPVDFLi-60 0.26 0.21 410 420 0.78
SPDVDFLi/LiTFSI-40 0.95 0.62 75 88 0.68
PVDF/LiTFSI 3.30 1.70 650 700 0.47
Table 1
Table 2

Tensile strength, Young's modulus and elongation at break of various SPEs"

样品拉伸强度/MPa 杨氏模量/MPa 断裂伸长率/%
SPVDFLi-60 2.3±0.3 13.7±0.6 23.0±0.2
SPVDFLi/LiTFSI-10 3.1±0.5 29.5±0.2 25.8±0.5
SPVDFLi/LiTFSI-20 4.0±0.2 14.8±0.9 33.7±0.4
SPVDFLi/LiTFSI-30 3.0±0.1 12.7±0.4 35.1±0.7
SPVDFLi/LiTFSI-40 4.2±0.2 16.5±0.3 56.5±0.1
PVDF/LiTFSI 8.0±0.4 55.2±0.2 35.8±0.2
Table 2
Fig. 4

Linear scanning voltammetry curves of various SPEs"
Fig. 4
Fig. 5

Galvanostatic cycling performance of symmetric Li/SPE/Li cells with PVDF/LiTFSI and SPVDFLi/LiTFSI-40 at room temperature (a), SEM images of the surface of the fresh Li anode (b), Li anode surface after 273 h with PVDF/LiTFSI (c) and Li anode surface after 334 h with SPVDFLi/LiTFSI-40"
Fig. 5
Fig. 6

Long-term cycling stability (a) and rate performance of the cell with SPVDFLi/LiTFSI-40"
Fig. 6
References 23

1 李杨, 丁飞, 桑林, 等. 全固态锂离子电池关键材料研究进展[J]. 储能科学与技术, 2016, 5(5): 615-626.

LI Y, DING F, SANG L, et al. A review of key materials for all-solid-state lithium ion batteries[J]. Energy Storage Science and Technology, 2016, 5(5): 615-626.

2 MILLER T F, WANG Z G, COATES G W, et al. Designing polymer electrolytes for safe and high capacity rechargeable lithium batteries[J]. Accounts of Chemical Research, 2017, 50(3): 590-593.

3 LYU F, WANG Z Y, SHI L Y, et al. Challenges and development of composite solid-state electrolytes for high-performance lithium ion batteries[J]. Journal of Power Sources, 2019, 441: doi: 10.1016/j.jpowsour.2019.227175.

4 CHEN J, WU J W, WANG X D, et al. Research progress and application prospect of solid-state electrolytes in commercial lithium-ion power batteries[J]. Energy Storage Materials, 2021, 35: 70-87.

5 RAMESH S, LU S C, MORRIS E. Towards magnesium ion conducting poly(vinylidenefluoride-hexafluoropropylene)-based solid polymer electrolytes with great prospects: Ionic conductivity and dielectric behaviours[J]. Journal of the Taiwan Institute of Chemical Engineers, 2012, 43(5): 806-812.

6 REN W H, DING C F, FU X W, et al. Advanced gel polymer electrolytes for safe and durable lithium metal batteries: Challenges, strategies, and perspectives[J]. Energy Storage Materials, 2021, 34: 515-535.

7 KNAUTH P. Inorganic solid Li ion conductors: An overview[J]. Solid State Ionics, 2009, 180(14/15/16): 911-916.

8 WANG Y, RICHARDS W D, ONG S P, et al. Design principles for solid-state lithium superionic conductors[J]. Nature Materials, 2015, 14(10): 1026-1031.

9 FENTON D E, PARKER J M, WRIGHT P V. Complexes of alkali metal ions with poly(ethylene oxide)[J]. Polymer, 1973, 14(11): doi: 10.1016/0032-3861(73)90146-8.

10 LOPEZ J, MACKANIC D G, CUI Y, et al. Designing polymers for advanced battery chemistries[J]. Nature Reviews Materials, 2019, 4(5): 312-330.

11 TANG S, GUO W, FU Y Z. Advances in composite polymer electrolytes for lithium batteries and beyond[J]. Advanced Energy Materials, 2021, 11(2): doi: 10.1002/aenm.202000802.

12 LIANG S W, CHEN Q, CHOI U H, et al. Plasticizing Li single-ion conductors with low-volatility siloxane copolymers and oligomers containing ethylene oxide and cyclic carbonates[J]. Journal of Materials Chemistry A, 2015, 3(42): 21269-21276.

13 LAGO N, GARCIA-CALVO O, LOPEZDELAMO J M, et al. All-solid-state lithium-ion batteries with grafted ceramic nanoparticles dispersed in solid polymer electrolytes[J]. ChemSusChem, 2015, 8(18): 3039-3043.

14 WANG H C, SHENG L, YASIN G, et al. Reviewing the current status and development of polymer electrolytes for solid-state lithium batteries[J]. Energy Storage Materials, 2020, 33: 188-215.

15 COSTA C M, LIZUNDIA E, LANCEROS-MÉNDEZ S. Polymers for advanced lithium-ion batteries: State of the art and future needs on polymers for the different battery components[J]. Progress in Energy and Combustion Science, 2020, 79: doi: 10.1016/j.pecs.2020.100846.

16 MENG N, ZHANG H N, LIANLI S Y, et al. Salt-with-Salt, a novel strategy to design the flexible solid electrolyte membrane for highly safe lithium metal batteries[J]. Journal of Membrane Science, 2020, 597: doi: 10.1016/j.memsci.2019.117768.

17 MARTINEZ-IBAÑEZ M, SANCHEZ-DIEZ E, QIAO L X, et al. Unprecedented improvement of single Li-ion conductive solid polymer electrolyte through salt additive[J]. Advanced Functional Materials, 2020, 30(16): doi: 10.1002/adfm.202000455.

18 周井. 含超级离域磺酰亚胺阴离子锂盐的合成及其性能表征[D]. 武汉: 华中科技大学, 2018.

ZHOU J. Synthesis and characterization of lithium salts containing super-delocalized sulfonimides anion[D]. Wuhan: Huazhong

University of Science and Technology, 2018.

19 XUE Z G, HE D, XIE X L. Poly(ethylene oxide)-based electrolytes for lithium-ion batteries[J]. Journal of Materials Chemistry A, 2015, 3(38): 19218-19253.

20 RICHARDS G N. Ion-exchange membranes by sulfonation of poly(vinylidene fluoride) films[J]. Journal of Applied Polymer Science, 1964, 8(5): 2269-2280.

21 FARROKHZAD H, KIKHAVANI T, MONNAIE F, et al. Novel composite cation exchange films based on sulfonated PVDF for electromembrane separations[J]. Journal of Membrane Science, 2015, 474: 167-174.

22 LU N, ZHANG X, NA R Q, et al. High performance electrospun Li+-functionalized sulfonated poly(ether ether ketone)/PVA based nanocomposite gel polymer electrolyte for solid-state electric double layer capacitors[J]. Journal of Colloid and Interface Science, 2019, 534: 672-682.

23 SHI X J, MA N Y, WU Y X, et al. Fabrication and electrochemical properties of LATP/PVDF composite electrolytes for rechargeable lithium-ion battery[J]. Solid State Ionics, 2018, 325: 112-119.

Related Articles 15

[1] LI Yitao, SHEN Kaier, PANG Quanquan. Advance in organics enhanced sulfide-based solid-state batteries [J]. Energy Storage Science and Technology, 2022, 11(6): 1902-1918.

[2] Chaochao WEI, Chuang YU, Zhongkai WU, Linfeng PENG, Shijie CHENG, Jia XIE. Research progress of Li3PS4 solid electrolyte [J]. Energy Storage Science and Technology, 2022, 11(5): 1368-1382.

[3] Liangtao XIONG, Jifen WANG, Huaqing XIE, Xuelai ZHANG. Effect of vacancy defects on thermal conductivity of single-layer graphene by molecular dynamics [J]. Energy Storage Science and Technology, 2022, 11(5): 1322-1330.

[4] Zhuo XU, Lili ZHENG, Bing CHEN, Tao ZHANG, Xiuling CHANG, Shouli WEI, Zuoqiang DAI. Overview of research on composite electrolytes for solid-state batteries [J]. Energy Storage Science and Technology, 2021, 10(6): 2117-2126.

[5] Bohui LU, Zhicheng SHI, Yongxue ZHANG, Hongyu ZHAO, Zixi WANG. Investigation of the charging and discharging performance of paraffin/nano-Fe3O4 composite phase change material in a shell and tube thermal energy storage unit [J]. Energy Storage Science and Technology, 2021, 10(5): 1709-1719.

[6] Yanfang ZHAI, Guanming YANG, Wangshu HOU, Jianyao YAO, Zhaoyin WEN, Shufeng SONG, Ning HU. Solvothermal synthesis of three-dimensional petaloid garnet electrolyte and its application in solid polymer electrolytes [J]. Energy Storage Science and Technology, 2021, 10(3): 905-913.

[7] Xie WU, Li ZHOU, Zhaoming XUE. Synthesis and performance of solid polymer electrolytes based on chelated boron lithium salts [J]. Energy Storage Science and Technology, 2021, 10(1): 96-103.

[8] Hang TU, Hang ZHANG, Lihui LIU, Jie LI, Xiaoqin SUN. Study on heat transfer of phase change materials imbedded in a concrete wall [J]. Energy Storage Science and Technology, 2021, 10(1): 287-294.

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[10] Manman JIA, Long ZHANG. Recent development on sulfide solid electrolytes for solid-state sodium batteries [J]. Energy Storage Science and Technology, 2020, 9(5): 1266-1283.

[11] Ge SUN, Zhixuan WEI, Xinyuan ZHANG, Nan CHEN, Gang CHEN, Fei DU. Recent progress of sodium-based inorganic solid electrolytes [J]. Energy Storage Science and Technology, 2020, 9(5): 1251-1265.

[12] Jie WU, Xiaobiao JIANG, Yang YANG, Yongmin WU, Lei ZHU, Weiping TANG. Progress of NASICON-structured Li1+xAlxTi2-x(PO4)3 (0 ≤x≤ 0.5) solid electrolyte [J]. Energy Storage Science and Technology, 2020, 9(5): 1472-1488.

[13] Jing YANG, Gaozhan LIU, Lin SHEN, Xiayin YAO. Research progress on NASICON-structured sodium solid electrolytes and their derived solid state sodium batteries [J]. Energy Storage Science and Technology, 2020, 9(5): 1284-1299.

[14] Linfeng PENG, Huanhuan JIA, Qing DING, Yuming ZHAO, Jia XIE, Shijie CHENG. Research progress of solid-state sodium batteries using inorganic sodium ion conductors [J]. Energy Storage Science and Technology, 2020, 9(5): 1370-1382.

[15] QU Chenying, HOU Zhaoxia, WANG Xiaohui, WANG Jian, WANG Kai, LI Siyao. Research progress of gel polymer electrolytes on solid supercapacitors [J]. Energy Storage Science and Technology, 2020, 9(3): 776-783.

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样品	I0/mA	ISS/mA	R0/Ω	RSS/Ω	tLi+
SPVDFLi-60	0.26	0.21	410	420	0.78
SPDVDFLi/LiTFSI-40	0.95	0.62	75	88	0.68
PVDF/LiTFSI	3.30	1.70	650	700	0.47

样品	拉伸强度/MPa	杨氏模量/MPa	断裂伸长率/%
SPVDFLi-60	2.3±0.3	13.7±0.6	23.0±0.2
SPVDFLi/LiTFSI-10	3.1±0.5	29.5±0.2	25.8±0.5
SPVDFLi/LiTFSI-20	4.0±0.2	14.8±0.9	33.7±0.4
SPVDFLi/LiTFSI-30	3.0±0.1	12.7±0.4	35.1±0.7
SPVDFLi/LiTFSI-40	4.2±0.2	16.5±0.3	56.5±0.1
PVDF/LiTFSI	8.0±0.4	55.2±0.2	35.8±0.2

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1	李杨, 丁飞, 桑林, 等. 全固态锂离子电池关键材料研究进展[J]. 储能科学与技术, 2016, 5(5): 615-626.
LI Y, DING F, SANG L, et al. A review of key materials for all-solid-state lithium ion batteries[J]. Energy Storage Science and Technology, 2016, 5(5): 615-626.
2	MILLER T F, WANG Z G, COATES G W, et al. Designing polymer electrolytes for safe and high capacity rechargeable lithium batteries[J]. Accounts of Chemical Research, 2017, 50(3): 590-593.
3	LYU F, WANG Z Y, SHI L Y, et al. Challenges and development of composite solid-state electrolytes for high-performance lithium ion batteries[J]. Journal of Power Sources, 2019, 441: doi: 10.1016/j.jpowsour.2019.227175.
4	CHEN J, WU J W, WANG X D, et al. Research progress and application prospect of solid-state electrolytes in commercial lithium-ion power batteries[J]. Energy Storage Materials, 2021, 35: 70-87.
5	RAMESH S, LU S C, MORRIS E. Towards magnesium ion conducting poly(vinylidenefluoride-hexafluoropropylene)-based solid polymer electrolytes with great prospects: Ionic conductivity and dielectric behaviours[J]. Journal of the Taiwan Institute of Chemical Engineers, 2012, 43(5): 806-812.
6	REN W H, DING C F, FU X W, et al. Advanced gel polymer electrolytes for safe and durable lithium metal batteries: Challenges, strategies, and perspectives[J]. Energy Storage Materials, 2021, 34: 515-535.
7	KNAUTH P. Inorganic solid Li ion conductors: An overview[J]. Solid State Ionics, 2009, 180(14/15/16): 911-916.
8	WANG Y, RICHARDS W D, ONG S P, et al. Design principles for solid-state lithium superionic conductors[J]. Nature Materials, 2015, 14(10): 1026-1031.
9	FENTON D E, PARKER J M, WRIGHT P V. Complexes of alkali metal ions with poly(ethylene oxide)[J]. Polymer, 1973, 14(11): doi: 10.1016/0032-3861(73)90146-8.
10	LOPEZ J, MACKANIC D G, CUI Y, et al. Designing polymers for advanced battery chemistries[J]. Nature Reviews Materials, 2019, 4(5): 312-330.
11	TANG S, GUO W, FU Y Z. Advances in composite polymer electrolytes for lithium batteries and beyond[J]. Advanced Energy Materials, 2021, 11(2): doi: 10.1002/aenm.202000802.
12	LIANG S W, CHEN Q, CHOI U H, et al. Plasticizing Li single-ion conductors with low-volatility siloxane copolymers and oligomers containing ethylene oxide and cyclic carbonates[J]. Journal of Materials Chemistry A, 2015, 3(42): 21269-21276.
13	LAGO N, GARCIA-CALVO O, LOPEZDELAMO J M, et al. All-solid-state lithium-ion batteries with grafted ceramic nanoparticles dispersed in solid polymer electrolytes[J]. ChemSusChem, 2015, 8(18): 3039-3043.
14	WANG H C, SHENG L, YASIN G, et al. Reviewing the current status and development of polymer electrolytes for solid-state lithium batteries[J]. Energy Storage Materials, 2020, 33: 188-215.
15	COSTA C M, LIZUNDIA E, LANCEROS-MÉNDEZ S. Polymers for advanced lithium-ion batteries: State of the art and future needs on polymers for the different battery components[J]. Progress in Energy and Combustion Science, 2020, 79: doi: 10.1016/j.pecs.2020.100846.
16	MENG N, ZHANG H N, LIANLI S Y, et al. Salt-with-Salt, a novel strategy to design the flexible solid electrolyte membrane for highly safe lithium metal batteries[J]. Journal of Membrane Science, 2020, 597: doi: 10.1016/j.memsci.2019.117768.
17	MARTINEZ-IBAÑEZ M, SANCHEZ-DIEZ E, QIAO L X, et al. Unprecedented improvement of single Li-ion conductive solid polymer electrolyte through salt additive[J]. Advanced Functional Materials, 2020, 30(16): doi: 10.1002/adfm.202000455.
18	周井. 含超级离域磺酰亚胺阴离子锂盐的合成及其性能表征[D]. 武汉: 华中科技大学, 2018.
ZHOU J. Synthesis and characterization of lithium salts containing super-delocalized sulfonimides anion[D]. Wuhan: Huazhong
University of Science and Technology, 2018.
19	XUE Z G, HE D, XIE X L. Poly(ethylene oxide)-based electrolytes for lithium-ion batteries[J]. Journal of Materials Chemistry A, 2015, 3(38): 19218-19253.
20	RICHARDS G N. Ion-exchange membranes by sulfonation of poly(vinylidene fluoride) films[J]. Journal of Applied Polymer Science, 1964, 8(5): 2269-2280.
21	FARROKHZAD H, KIKHAVANI T, MONNAIE F, et al. Novel composite cation exchange films based on sulfonated PVDF for electromembrane separations[J]. Journal of Membrane Science, 2015, 474: 167-174.
22	LU N, ZHANG X, NA R Q, et al. High performance electrospun Li+-functionalized sulfonated poly(ether ether ketone)/PVA based nanocomposite gel polymer electrolyte for solid-state electric double layer capacitors[J]. Journal of Colloid and Interface Science, 2019, 534: 672-682.
23	SHI X J, MA N Y, WU Y X, et al. Fabrication and electrochemical properties of LATP/PVDF composite electrolytes for rechargeable lithium-ion battery[J]. Solid State Ionics, 2018, 325: 112-119.

[1]	LI Yitao, SHEN Kaier, PANG Quanquan. Advance in organics enhanced sulfide-based solid-state batteries [J]. Energy Storage Science and Technology, 2022, 11(6): 1902-1918.
[2]	Chaochao WEI, Chuang YU, Zhongkai WU, Linfeng PENG, Shijie CHENG, Jia XIE. Research progress of Li3PS4 solid electrolyte [J]. Energy Storage Science and Technology, 2022, 11(5): 1368-1382.
[3]	Liangtao XIONG, Jifen WANG, Huaqing XIE, Xuelai ZHANG. Effect of vacancy defects on thermal conductivity of single-layer graphene by molecular dynamics [J]. Energy Storage Science and Technology, 2022, 11(5): 1322-1330.
[4]	Zhuo XU, Lili ZHENG, Bing CHEN, Tao ZHANG, Xiuling CHANG, Shouli WEI, Zuoqiang DAI. Overview of research on composite electrolytes for solid-state batteries [J]. Energy Storage Science and Technology, 2021, 10(6): 2117-2126.
[5]	Bohui LU, Zhicheng SHI, Yongxue ZHANG, Hongyu ZHAO, Zixi WANG. Investigation of the charging and discharging performance of paraffin/nano-Fe3O4 composite phase change material in a shell and tube thermal energy storage unit [J]. Energy Storage Science and Technology, 2021, 10(5): 1709-1719.
[6]	Yanfang ZHAI, Guanming YANG, Wangshu HOU, Jianyao YAO, Zhaoyin WEN, Shufeng SONG, Ning HU. Solvothermal synthesis of three-dimensional petaloid garnet electrolyte and its application in solid polymer electrolytes [J]. Energy Storage Science and Technology, 2021, 10(3): 905-913.
[7]	Xie WU, Li ZHOU, Zhaoming XUE. Synthesis and performance of solid polymer electrolytes based on chelated boron lithium salts [J]. Energy Storage Science and Technology, 2021, 10(1): 96-103.
[8]	Hang TU, Hang ZHANG, Lihui LIU, Jie LI, Xiaoqin SUN. Study on heat transfer of phase change materials imbedded in a concrete wall [J]. Energy Storage Science and Technology, 2021, 10(1): 287-294.
[9]	Youman ZHAO, Xiaobo YAN, Hongkun DUAN, Zewei CHEN. Exploring mechanism of carbon nanotubes as conductive agent for improving performance of a silicon/carbon anode in LIB [J]. Energy Storage Science and Technology, 2021, 10(1): 118-127.
[10]	Manman JIA, Long ZHANG. Recent development on sulfide solid electrolytes for solid-state sodium batteries [J]. Energy Storage Science and Technology, 2020, 9(5): 1266-1283.
[11]	Ge SUN, Zhixuan WEI, Xinyuan ZHANG, Nan CHEN, Gang CHEN, Fei DU. Recent progress of sodium-based inorganic solid electrolytes [J]. Energy Storage Science and Technology, 2020, 9(5): 1251-1265.
[12]	Jie WU, Xiaobiao JIANG, Yang YANG, Yongmin WU, Lei ZHU, Weiping TANG. Progress of NASICON-structured Li1+xAlxTi2-x(PO4)3 (0 ≤x≤ 0.5) solid electrolyte [J]. Energy Storage Science and Technology, 2020, 9(5): 1472-1488.
[13]	Jing YANG, Gaozhan LIU, Lin SHEN, Xiayin YAO. Research progress on NASICON-structured sodium solid electrolytes and their derived solid state sodium batteries [J]. Energy Storage Science and Technology, 2020, 9(5): 1284-1299.
[14]	Linfeng PENG, Huanhuan JIA, Qing DING, Yuming ZHAO, Jia XIE, Shijie CHENG. Research progress of solid-state sodium batteries using inorganic sodium ion conductors [J]. Energy Storage Science and Technology, 2020, 9(5): 1370-1382.
[15]	QU Chenying, HOU Zhaoxia, WANG Xiaohui, WANG Jian, WANG Kai, LI Siyao. Research progress of gel polymer electrolytes on solid supercapacitors [J]. Energy Storage Science and Technology, 2020, 9(3): 776-783.

Preparation and properties of polyvinylidene fluoride/polyvinylidene fluoride sulfonate lithium/lithium salt composite solid electrolyte

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