钠离子电池聚合物电解质研究进展

doi:10.19799/j.cnki.2095-4239.2020.0120

摘要/Abstract

摘要：

近年来钠离子电池的能量、功率密度与循环寿命均得到了长足发展，然而常规电解液/隔膜体系由于易燃、易挥发，导致钠离子电池存在严峻安全隐患。为了提高钠离子电池的安全性，近年来固态电解质得到了广泛的关注，尤其以聚合物为基底的固态、凝胶电解质得到了快速发展。本文首先梳理了聚合物电解质基础的发展脉络与研究常用的理论模型，接着综述了固态与凝胶两类聚合物电解质在钠离子电池中的应用研究进展，对涉及的不同材料改性技术、聚合物电解质制备工艺、新型材料设计进行了评价。综合分析表明，聚合物固态电解质采用低聚物、无机纳米颗粒掺杂、功能分子设计等方法，逐步实现了固态电池的适用温度由90 ℃向室温、低温的成功转变；凝胶电解质室温电导率较高，有机小分子与聚合物基底之间通过分子间力作用增强钠盐溶剂化作用，成功地与不同正、负极材料搭配，普遍实现了室温凝胶钠离子电池，同时回顾了水凝胶在构建水系钠离子电池中的优势与现阶段的研究不足。最后提出聚合物电解质在钠离子电池中应用的研究报道中需要注意的问题，并且展望了未来材料设计、表征技术的可能发展方向。

关键词: 钠离子电池, 固态电解质, 凝胶电解质, 复合材料, 储能

Abstract:

Recently, there has been rapid and profound progress with respect to the energy and power density of sodium-ion batteries. However, the conventional liquid organic electrolyte/separator system tends to evaporate and burst into flame, leading to wide concerns about its inherent low safety. To develop sodium ion batteries with high energy density and improved safety, solid electrolytes have gained attention, especially polymer-based electrolytes including solid and gel types. This article begins by reviewing the progress in fundamental mechanism and physical chemistry theoretical models for polymer electrolytes, followed by advancements in both solid and gel polymer electrolyte application in sodium ion batteries along with assessments of various material modification techniques, synthesis procedures, and novel material design. Based on the analysis, polymer electrolyte adopting oligomer, inorganic filler, and molecule design strategies are given for the successful conversion of a solid battery operation temperature from 90°C to room temperature or lower. A gel electrolyte relies on intermolecular forces and renders greater solvation effects for sodium salts, realizing quasi-solid batteries coupled with various electrodes generally at room temperature. In addition, a brief comment on hydrogel electrolytes concerning their great potential in aqueous sodium ion batteries is provided. Finally, an appeal is made concerning critical parameters, including volume and mass, in future reports, as well as a brief outlook concerning possible perspectives considering material design, and an in-situ polymer electrolyte technique in sodium ion batteries is proposed.

Key words: sodium ion battery, solid electrolyte, gel electrolyte, composite material, energy storage

中图分类号:

TM 912

高舒, 周敏, 韩静, 过聪, 谭媛, 蒋凯, 王康丽. 钠离子电池聚合物电解质研究进展[J]. 储能科学与技术, 2020, 9(5): 1300-1308.

Shu GAO, Min ZHOU, Jing HAN, Cong GUO, Yuan TAN, Kai JIANG, Kangli WANG. Progress on polymer electrolyte in sodium ion batteries[J]. Energy Storage Science and Technology, 2020, 9(5): 1300-1308.

图/表 2

表1

表2

参考文献 42

1	YANG J, ZHANG H, ZHOU Q, et al. Safety-enhanced polymer electrolytes for sodium batteries: Recent progress and perspectives[J]. ACS Applied Materials & Interfaces, 2019, 11(19): 17109-17127.
2	FENTON D. Complexes of alkali metal ions with poly(ethylene oxide)[J]. Polymer, 1973, 14: 589-595.
3	CHE H, CHEN S, XIE Y, et al. Electrolyte design strategies and research progress for room-temperature sodium-ion batteries[J]. Energy & Environmental Science, 2017, 10(5): 1075-1101.
4	WEST K, ZACHAU-CHRISTIANSEN B, JACOBSEN T, et al. Poly (ethylene oxide)-sodium perchlorate electrolytes in solid-state sodium cells[J]. British Polymer Journal, 1988, 20(3): 243-246.
5	OSMAN Z, ISA K B M, AHMAD A, et al. A comparative study of lithium and sodium salts in PAN-based ion conducting polymer electrolytes[J]. Ionics, 2010, 16(5): 431-435.
6	BOSCHIN A, JOHANSSON P. Characterization of NaX (X: TFSI, FSI)-PEO based solid polymer electrolytes for sodium batteries[J]. Electrochimica Acta, 2015, 175: 124-133.
7	VILLALUENGA I, BOGLE X, GREENBAUM S, et al. Cation only conduction in new polymer-SiO₂nanohybrids: Na⁺ electrolytes[J]. Journal of Materials Chemistry A, 2013, 1(29): 8348-8352.
8	KUMAR D, HASHMI S. Ionic liquid based sodium ion conducting gel polymer electrolytes[J]. Solid State Ionics, 2010, 181(8/9/10): 416-423.
9	EVANS J, VINCENT C A, BRUCE P G. Electrochemical measurement of transference numbers in polymer electrolytes[J]. Polymer, 1987, 28(13): 2324-2328.
10	KUMAR D, HASHMI S. Ion transport and ion-filler-polymer interaction in poly (methyl methacrylate)-based, sodium ion conducting, gel polymer electrolytes dispersed with silica nanoparticles[J]. Journal of Power Sources, 2010, 195(15): 5101-5108.
11	MA Y, DOEFF M M, VISCO S J, et al. Rechargeable Na/Na_xCoO₂ and Na₁₅Pb₄/Na_xCoO₂polymer electrolyte cells[J]. Journal of the Electrochemical Society, 1993, 140(10): 2726-2733.
12	QI X, MA Q, LIU L, et al. Sodium bis(fluorosulfonyl) imide/poly (ethylene oxide) polymer electrolytes for sodium-ion batteries[J]. ChemElectroChem, 2016, 3(11): 1741-1745.
13	BHARGAV P B, MOHAN V, SHARMA A, et al. Characterization of poly(vinyl alcohol)/sodium bromide polymer electrolytes for electrochemical cell applications[J]. Journal of Applied Polymer Science, 2008, 108(1): 510-517.
14	MINDEMARK J, MOGENSEN R, SMITH M J, et al. Polycarbonates as alternative electrolyte host materials for solid-state sodium batteries[J]. Electrochemistry Communications, 2017, 77: 58-61.
15	COL F, BELLA F, NAIR J R, et al. Cellulose-based novel hybrid polymer electrolytes for green and efficient Na-ion batteries[J]. Electrochimica Acta, 2015, 174: 185-190.
16	NI'MAH Y L, CHENG M Y, CHENG J H, et al. Solid-state polymer nanocomposite electrolyte of TiO₂/PEO/NaClO₄ for sodium ion batteries[J]. Journal of Power Sources, 2015, 278: 375-381.
17	ZHANG X, WANG X, LIU S, et al. A novel PMA/PEG-based composite polymer electrolyte for all-solid-state sodium ion batteries[J]. Nano Research, 2018, 11(12): 6244-6251.
18	CHANDRASEKARAN R, SELLADURAI S. Preparation and characterization of a new polymer electrolyte (PEO: NaClO₃) for battery application[J]. Journal of Solid State Electrochemistry, 2001, 5(5): 355-361.
19	NGELAND S C, YOUNESI R, MINDEMARK J, et al. Towards room temperature operation of all-solid-state Na-ion batteries through polyester-polycarbonate-based polymer electrolytes[J]. Energy Storage Materials, 2019, 19: 31-38.
20	DU G, TAO M, LI J, et al. Low-operating temperature, high-rate and durable solid-state sodium-ion battery based on polymer electrolyte and Prussian blue cathode[J]. Advanced Energy Materials, 2020, 10(5): 1903351-1903358.
21	CHEN S, FENG F, YIN Y, et al. Plastic crystal polymer electrolytes containing boron based anion acceptors for room temperature all-solid-state sodium-ion batteries[J]. Energy Storage Materials, 2019, 22: 57-65.
22	GAO H, GUO B, SONG J, et al. A composite gel-polymer/glass-fiber electrolyte for sodium-ion batteries[J]. Advanced Energy Materials, 2015, 5(9): 1402235-1402242.
23	ZHU Y, YANG Y, FU L, et al. A porous gel-type composite membrane reinforced by nonwoven: Promising polymer electrolyte with high performance for sodium ion batteries[J]. Electrochimica Acta, 2017, 224: 405-411.
24	LONCHAKOVA O, SEMENIKHIN O, ZAKHARKIN M, et al. Efficient gel-polymer electrolyte for sodium-ion batteries based on poly (acrylonitrile-co-methyl acrylate)[J]. Electrochimica Acta, 2020, 334: doi: 10.1016/j.electacta.2019.135512.
25	KIM J I, CHOI Y, CHUNG K Y, et al. A structurable gel-polymer electrolyte for sodium ion batteries[J]. Advanced Functional Materials, 2017, 27(34): 1701768-1701774.
26	LI H, DING Y, HA H, et al. An all-stretchable-component sodium-ion full battery[J]. Advanced Materials, 2017, 29(23): 1700898-1700904.
27	GUO J Z, YANG A B, GU Z Y, et al. Quasi-solid-state sodium-ion full battery with high-power/energy densities[J]. ACS Applied Materials & Interfaces, 2018, 10(21): 17903-17910.
28	KIM J I, CHUNG K Y, PARK J H. Design of a porous gel polymer electrolyte for sodium ion batteries[J]. Journal of Membrane Science, 2018, 566: 122-128.
29	BELLA F, COL F, NAIR J R, et al. Photopolymer electrolytes for sustainable, upscalable, safe, and ambient-temperature sodium-ion secondary batteries[J]. ChemSusChem, 2015, 8(21): 3668-3676.
30	COL F, BELLA F, NAIR J R, et al. Light-cured polymer electrolytes for safe, low-cost and sustainable sodium-ion batteries[J]. Journal of Power Sources, 2017, 365: 293-302.
31	GAO H, ZHOU W, PARK K, et al. A sodium‐ion battery with a low‐cost cross-linked gel-polymer electrolyte[J]. Advanced Energy Materials, 2016, 6(18): 1600467-1600474.
32	MANUEL J, ZHAO X, CHO K K, et al. Ultralong life organic sodium ion batteries using a polyimide/multiwalled carbon nanotubes nanocomposite and gel polymer electrolyte[J]. ACS Sustainable Chemistry & Engineering, 2018, 6(7): 8159-8166.
33	CAO C, LIU W, TAN L, et al. Sodium-ion batteries using ion exchange membranes as electrolytes and separators[J]. Chemical Communications, 2013, 49(100): 11740-11742.
34	HOU H, XU Q, PANG Y, et al. Efficient storing energy harvested by triboelectric nanogenerators using a safe and durable all-solid-state sodium-ion battery[J]. Advanced Science, 2017, 4(8): 1700072-1700076.
35	PAN Q, LI Z, ZHANG W, et al. Single ion conducting sodium ion batteries enabled by a sodium ion exchanged poly [bis (4-carbonyl benzene sulfonyl) imide-co-2, 5-diamino benzesulfonic acid] polymer electrolyte[J]. Solid State Ionics, 2017, 300: 60-66.
36	WANG P, ZHANG H, CHAI J, et al. A novel single-ion conducting gel polymer electrolyte based on polymeric sodium tartaric acid borate for elevated-temperature sodium metal batteries[J]. Solid State Ionics, 2019, 337: 140-146.
37	ZHANG J, WEN H, YUE L, et al. In situ formation of polysulfonamide supported poly (ethylene glycol) divinyl ether based polymer electrolyte toward monolithic sodium ion batteries[J]. Small, 2017, 13(2): 1601530-1601540.
38	YANG J, ZHANG M, CHEN Z, et al. Flame-retardant quasi-solid polymer electrolyte enabling sodium metal batteries with highly safe characteristic and superior cycling stability[J]. Nano Research, 2019, 12(9): 2230-2237.
39	SAROJA A P V K, ARUNKUMAR R, MOHARANA B C, et al. Design of porous calcium phosphate based gel polymer electrolyte for quasi-solid state sodium ion battery[J]. Journal of Electroanalytical Chemistry, 2020, 859: doi: 10.1016/j.jelechem.2020.113864.
40	ZHOU D, LIU R, ZHANG J, et al. In situ synthesis of hierarchical poly (ionic liquid)-based solid electrolytes for high-safety lithium-ion and sodium-ion batteries[J]. Nano Energy, 2017, 33: 45-54.
41	DE ANASTRO A F, LAGO N, BERLANGA C, et al. Poly(ionic liquid) iongel membranes for all solid-state rechargeable sodium battery[J]. Journal of Membrane Science, 2019, 582: 435-441.
42	ZHONG L, LU Y, LI H, et al. High-performance aqueous sodium-ion batteries with hydrogel electrolyte and alloxazine/CMK-3 anode[J]. ACS Sustainable Chemistry & Engineering, 2018, 6(6): 7761-7768.

电解质材料	测试温度/℃	电导率/S·cm^-1	测试体系	循环圈数	参考文献
PEO/NaTf	90	—	Na\|\|Na_0.9CO₂	300	[11]
P(EO)₂₀/NaFSI	80	4.1×10^-4	Na\|\|Na_0.67Ni_0.33MnO₂	50	[12]
P(EO)₂₀/NaFSI	80	4.1×10^-4	Na\|\|Na₃V₂(PO₄)₃	30	[12]
PVA/NaBr	30	1.362×10^-6	Na\|\|I₂	—	[13]
PTMC/NaTFSI	60	>10^-6	Na\|\|PB	8	[14]
PEO/Na-CMC/NaClO₄	60	>10^-5	Na\|\|NaFePO₄	20	[15]
PEO/TiO₂/NaClO₄	60	2.62×10^-5	Na\|\|Na_2/3Co_2/3Mn_1/3O₂	25	[16]
PMA/PEG/NaClO₄/α-Al₂O₃	70	1.46×10^-4	Na\|\|Na₃V₂(PO₄)₃	350	[17]
PEO/PEG/NaClO₄	30	3.4×10^-6	Na\|\|MnO₂	—	[18]
PCL/PTMC/NaFSI	22	3.9×10^-6	HC\|\|Na_2-_xFe(Fe(CN)₆)	120	[19]
PFSA/Na⁺	25	1.59×10^-4	Na\|\|PB	160	[20]
B-PCPE	20	3.6×10^-4	HC\|\| NaNi_1/3Fe_1/3Mn_1/3O₂	120	[21]

电解质材料	电导率/S·cm^-1	测试体系	循环圈数	参考文献
GF-PA-PVDF-HFP/PC/NaClO₄	5.4×10^-3	Na\|\|Na₂MnFe(CN)₆	100	[22]
NW/PVDF-HFP/NaClO₄/EC-DMC-EMC	8.2×10^-4	Na\|\|Na₄Mn₉O₈	—	[23]
P(AN-MA)/NaClO₄/PC	1.8×10^-3	Na\|\|Na₃V₂(PO₄)₃	700	[24]
GF/PVDF-HFP/NaClO₄/EC-PC	3.8×10^-3	Na\|\|HC	100	[25]
PVDF-HFP/NaClO₄/FEC-PC	—	HC\|\|VOPO₄	100	[26]
PVDF-HFP/NaClO₄/PC-FEC	4.2×10^-4	HC\|\|Na₃V₂(PO₄)₂O₂F	500	[27]
PVDF-HFP-GF/NaClO₄/EC-PC	4.1×10^-3	Na\|\|HC	100	[28]
BEMA-PEGMA/NaClO₄/PC	5.1×10^-4	Na\|\|TiO₂	60	[29]
PEO-NaClO₄-PC	>10^-4	Na\|\|TiO₂	1000	[30]
PMMA/PC/FEC/NaClO₄	6.2×10^-3	Sb\|\|Na₃V₂(PO₄)₃	100	[31]
PAN/NaClO₄/EC-PC-DME	3.01×10^-3	Na\|\|PI	3000	[32]
PFSA-Na/EC-PC	>10^-4	Na\|\|Na_0.44MnO₂	50	[33]
PFSA-Na/EC-PC	2.8×10^-4	Na\|\|Na_0.67Ni_0.23Mg_0.1Mn_0.67O₂	1000	[34]
PVDF-NaPA/EC-DMC	9.1×10^-5	Na\|\|Na₃V₂(PO₄)₃	65	[35]
PSTB-PVCA/PET/PC-DEC	1×10^-4	Na\|\|Na₃V₂(PO₄)₃	200	[36]
PSA/TEGDVE/NaClO₄/PC	1.2×10^-3	MoS₂\|\|Na₃V₂(PO₄)₃	1000	[37]
P(MVE-alt-MA)/NaClO₄/TEP-VC/BC	2.2×10^-4	Na\|\|Na₃V₂(PO₄)₃	1000	[38]
HAP/PVDF-HFP/PBMA/NaClO₄/EC-PC	1.086×10^-3	Na\|\|Na₃V₂(PO₄)₃	500	[39]
PDDATFSI/C1-4TFSI/EMITFSI	>10^-3	Na\|\|Na_0.9(Cu_0.22Fe_0.3Mn_0.48)O₂	100	[40]
PDADMAC-TFSI/C3mpyr-FSI/Al₂O₃/NaFSI	1.6×10^-3	Na\|\|NaFePO₄	60	[41]

[1]	姚祯, 张琦, 王锐, 刘庆华, 王保国, 缪平. 生物质衍生碳材料在全钒液流电池电极方面的应用[J]. 储能科学与技术, 2022, 11(7): 2083-2091.
[2]	时雨, 张忠, 杨晶莹, 钱薇, 李昊, 赵祥, 杨欣桐. 储能电池系统提供AGC调频的机会成本建模与市场策略[J]. 储能科学与技术, 2022, 11(7): 2366-2373.
[3]	曾伟, 熊俊杰, 李建林, 马速良, 武亦文. 基于权重自适应鲸鱼优化算法的多能系统储能电站最优配置[J]. 储能科学与技术, 2022, 11(7): 2241-2249.
[4]	韩健民, 薛飞宇, 梁双印, 乔天舒. 模糊控制优化下的混合储能系统辅助燃煤机组调频仿真[J]. 储能科学与技术, 2022, 11(7): 2188-2196.
[5]	鲁志颖, 江杉, 李全龙, 马可心, 傅腾, 郑志刚, 刘志成, 李淼, 梁永胜, 董知非. 全钒液流电池在充电结束搁置阶段的开路电压变化[J]. 储能科学与技术, 2022, 11(7): 2046-2050.
[6]	冯国会, 王天雨, 王刚. 封装方式对相变水箱蓄放热性能影响模拟分析[J]. 储能科学与技术, 2022, 11(7): 2161-2176.
[7]	董树锋, 刘灵冲, 唐坤杰, 赵海祺, 徐成司, 林立亨. 基于Simulink和低代码控制器的储能控制实验教学方法[J]. 储能科学与技术, 2022, 11(7): 2386-2397.
[8]	徐雄文, 聂阳, 涂健, 许峥, 谢健, 赵新兵. 普鲁士蓝正极软包钠离子电池的滥用性能[J]. 储能科学与技术, 2022, 11(7): 2030-2039.
[9]	郭雨涵, 郁丹, 杨鹏, 王子绩, 王金涛. 基于贪婪算法的分布式储能系统容量优化配置方法[J]. 储能科学与技术, 2022, 11(7): 2295-2304.
[10]	袁性忠, 胡斌, 郭凡, 严欢, 贾宏刚, 苏舟. 欧盟储能政策和市场规则及对我国的启示[J]. 储能科学与技术, 2022, 11(7): 2344-2353.
[11]	刘国静, 李冰洁, 胡晓燕, 岳芬, 徐际强. 澳大利亚储能相关政策与电力市场机制及对我国的启示[J]. 储能科学与技术, 2022, 11(7): 2332-2343.
[12]	杨孝杰, 王海云, 蒋中川, 宋章华. 应用于飞轮储能的BLDC电机功率双向流动策略设计[J]. 储能科学与技术, 2022, 11(7): 2233-2240.
[13]	李洪涛, 张帅, 李旭东, 纪运广, 孙明旭, 李欣. 单罐式储能换热系统在热风无纺布工艺中的应用[J]. 储能科学与技术, 2022, 11(7): 2250-2257.
[14]	吴田, 林闽城, 海浩, 孙海渔, 温兆银, 马福元. 面向一次调频的镍氢电池系统开发[J]. 储能科学与技术, 2022, 11(7): 2213-2221.
[15]	徐光福, 姜淼, 王万纯, 魏阳, 侯炜. 大型储能电池短路故障分析与保护策略[J]. 储能科学与技术, 2022, 11(7): 2222-2232.