一种水性负极黏结剂的合成及性能

doi:10.16085/j.issn.1000-6613.2021-1355

摘要/Abstract

摘要：

黏结剂对电极的性能有着重要的影响。本文设计并制备了一种新型水性聚(乙烯-乙烯醇)-磺酸锂（EVOH-SO₃Li，简称ES-Li）电极黏结剂，并对其键接结构及组成进行分析；对其溶解性、电解液稳定性、热稳定性进行测试；对所制电极柔性、微观形貌及电化学性能进行研究。经与聚(乙烯-乙烯醇)（EVOH）及商业的聚偏氟乙烯（PVDF）黏结剂进行对比。结果表明：ES-Li水性黏结剂具有不溶解于电解液，热稳定性良好等优点；ES-Li黏结剂制备负极柔性及微观形貌优良，采用ES-Li作为负极黏结剂的电池在电化学稳定窗口、界面阻抗、首次循环效率、循环及倍率等方面均表现优异，ES-Li负极的首次库仑效率为89.93%，在1C下循环100次的容量保持率为96.93%，且在2C、5C倍率下的循环性能均优于EVOH及PVDF制备的负极，具有应用潜力及商业化前景。

关键词: 锂离子电池, 水性黏结剂, 负极, 合成, 电化学, 溶解性

Abstract:

The binder has an important influence on the performance of the electrode. This paper designed and prepared a new type of water-based poly(ethylene-vinyl alcohol)-lithium sulfonate (EVOH-SO₃Li, ES-Li) electrode binder. Its bonding structure and composition, solubility, electrolyte stability and thermal stability were analyzed. The flexibility, microscopic morphology and electrochemical performance of the prepared electrode were studied. It was compared with poly(ethylene vinyl alcohol) (EVOH) and commercial polyvinylidene fluoride (PVDF) binders. The results showed that ES-Li water-based binder had the advantages of insoluble in electrolyte and good thermal stability. The negative electrode prepared by ES-Li binder had excellent flexibility and microscopic morphology. The battery using ES-Li as the negative electrode binder had excellent performance in electrochemical stability window, interface impedance, first cycle efficiency, cycle and rate, etc. The first coulombic efficiency of the anode with ES-Li was 89.93%, the capacity retention rate after 100 cycles of 1C was 96.93%, and the cycle performance at 2C and 5C rates was better than that of the anode prepared by EVOH and PVDF, which had application potential and commercialization prospects.

Key words: lithium ion battery, water-based binder, negative electrode, synthesis, electrochemistry, solubility

中图分类号:

TQ317

马续, 邹明贵, 崔巍巍, 付安然, 廖小龙, 巩桂芬. 一种水性负极黏结剂的合成及性能[J]. 化工进展, 2022, 41(6): 3138-3145.

MA Xu, ZOU Minggui, CUI Weiwei, FU Anran, LIAO Xiaolong, GONG Guifen. Synthesis and performance of a kind of water soluble negative electrode binder[J]. Chemical Industry and Engineering Progress, 2022, 41(6): 3138-3145.

图/表 12

图1 EVOH及ES-Li的红外曲线

图2 EVOH磺化反应机制

表1 EVOH及ES-Li的溶解性表

条件	EVOH	ES-Li-10	ES-Li-20	ES-Li-30	ES-Li-40	ES-Li-50	ES-Li-60
12h	-	+	+	+++	+++	+++	+++
24h	-	+	++	+++	+++	+++	+++
4℃	-	+	+	++	++	++	++
60℃	-	++	+++	+++	+++	+++	+++

表2 EVOH及ES-Li在电解液溶解实验中的质量变化 (mg)

条件	EVOH	ES-Li-10	ES-Li-20	ES-Li-30	ES-Li-40	ES-Li-50	ES-Li-60
初始	40.285	85.554	134.000	92.011	78.744	77.810	67.579
第1天	40.285	86.412	134.385	92.879	79.645	78.465	68.459
第30天	40.286	86.546	134.402	93.001	79.747	78.805	68.556
第30天溶胀率/%	0	0.12	0.30	1.08	1.27	1.37	1.45

图3 初始、第1天及第30天的样品状态

图4 EVOH与ES-Li溶胀率变化

图5 PVDF及ES-Li的DSC曲线

图6 电极折叠、卷曲图

图7 采用ES-Li-30为黏结剂的负极循环前后的微观形貌图

图8 电化学稳定窗口

图9 交流界面阻抗图

图10 电池的首效、循环及倍率

参考文献 24

1	王亚丽, 刘丙学, 田国峰, 等. 高性能锂离子电池正极黏合剂研究进展[J]. 高分子学报, 2020, 51(4): 326-337.
	WANG Yali, LIU Bingxue, TIAN Guofeng, et al. Research progress of cathode binder for high performance lithium-ion battery[J]. Acta Polymerica Sinica, 2020, 51(4): 326-337.
2	王策. 锂离子电池正极材料合成及改性[J]. 化工进展, 2021, 40(9): 4998-5011.
	WANG Ce. Synthesis and modification of cathode materials for lithium ion batteries[J]. Chemical Industry and Engineering Progress, 2021, 40(9): 4998-5011.
3	巩桂芬, 邹明贵, 崔巍巍, 等. 锂离子电池隔膜材料EVOLi-OMMT的制备及其性能[J]. 复合材料学报, 2022, 39(3): 1169-1176.
	GONG Guifen, ZOU Minggui, CUI Weiwei, et al. Preparation and performance of EVOLi-OMMT separator material for lithium ion batteries[J].Acta Materiae Compositae Sinica, 2022, 39(3): 1169-1176.
4	CAO P F, NAGUIB M, DU Z J, et al. Effect of binder architecture on the performance of silicon/graphite composite anodes for lithium ion batteries[J]. ACS Applied Materials & Interfaces, 2018, 10(4): 3470-3478.
5	HE X, LIU Z M, GAO G P, et al. Revealing the working mechanism of a multi-functional block copolymer binder for lithium-sulfur batteries[J]. Journal of Energy Chemistry, 2021, 59: 1-8.
6	RAJEEV K K, NAM J, KIM E, et al. A self-healable polymer binder for Si anodes based on reversible Diels-Alder chemistry[J]. Electrochimica Acta, 2020, 364: 137311.
7	LIU H, CHEN T Q, XU Z X, et al. High-safety and long-life silicon-based lithium-ion batteries via a multifunctional binder[J]. ACS Applied Materials & Interfaces, 2020, 12(49): 54842-54850.
8	黄书. 水性离子聚合物黏结剂制备及其对电极性能的影响[D]. 哈尔滨: 哈尔滨工业大学, 2019.
	HUANG Shu. Preparation of waterborne ionomer binders and their effects on electrochemical performances of electrodes[D]. Harbin: Harbin Institute of Technology, 2019.
9	彭黎波, 叶诚曦, 童庆松, 等. 改性PVDF或替代PVDF黏结剂在锂电池中的应用研究进展[J]. 材料导报, 2021, 35(5): 5174-5180.
	PENG Libo, YE Chengxi, TONG Qingsong, et al. Research progress of replacing traditional PVDF binder with functional binder for lithium batteries[J]. Materials Review, 2021, 35(5): 5174-5180.
10	HUANG W B, WANG W, WANG Y, et al. Overcoming the fundamental challenge of PVDF binder use with silicon anodes with a super-molecular nano-layer[J]. Journal of Materials Chemistry A, 2021, 9(3): 1541-1551.
11	YU L M, LUO Z, GONG C R, et al. Water-based binder with easy reuse characteristics for silicon/graphite anodes in lithium-ion batteries[J]. Polymer Journal, 2021, 53(8): 923-935.
12	YANG Z H, WU Z J, JIANG D W, et al. Ultra-sensitive flexible sandwich structural strain sensors based on a silver nanowire supported PDMS/PVDF electrospun membrane substrate[J]. Journal of Materials Chemistry C, 2021, 9(8): 2752-2762.
13	邵丹, 骆相宜, 梁俊超, 等. 水性黏结剂羧甲基纤维素钠对锂离子电池钛酸锂负极性能的影响[J]. 化工新型材料, 2020, 48(5): 155-158.
	SHAO Dan, LUO Xiangyi, LIANG Junchao, et al. Influence of CMC water-soluble binder on electrochemical performance of Li₄Ti₅O₁₂ cathode-based Li-ion battery[J]. New Chemical Materials, 2020, 48(5): 155-158.
14	GORDON R, ORIAS R, WILLENBACHER N. Effect of carboxymethyl cellulose on the flow behavior of lithium-ion battery anode slurries and the electrical as well as mechanical properties of corresponding dry layers[J]. Journal of Materials Science, 2020, 55(33): 15867-15881.
15	ZHANG Z A, ZENG T, LAI Y Q, et al. A comparative study of different binders and their effects on electrochemical properties of LiMn₂O₄ cathode in lithium ion batteries[J]. Journal of Power Sources, 2014, 247: 1-8.
16	CHEN F, LI H, CHEN T J, et al. Constructing crosslinked lithium polyacrylate/polyvinyl alcohol complex binder for high performance sulfur cathode in lithium-sulfur batteries[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2021, 611: 125870.
17	谢功山, 王志成, 袁爱宁, 等. 锂离子电池用水性聚氨酯黏结剂的制备与性能[J]. 精细化工, 2019, 36(9): 1956-1961.
	XIE Gongshan, WANG Zhicheng, YUAN Aining, et al. Preparation and properties of waterborne polyurethane binders for lithium-ion battery[J]. Fine Chemicals, 2019, 36(9): 1956-1961.
18	邹树良, 马先果, 葛武杰, 等. 锂二次电池水性黏合剂研究进展[J]. 电源技术, 2019, 43(12): 2017-2021.
	ZOU Shuliang, MA Xianguo, GE Wujie, et al. Research progress of water-based binder for lithium secondary battery[J]. Chinese Journal of Power Sources, 2019, 43(12): 2017-2021.
19	宫璐, 谢媛媛, 刘成士. 聚丙烯酸黏结剂在锂离子电池中的应用[J]. 电池, 2014, 44(5): 307-309.
	GONG Lu, XIE Yuanyuan, LIU Chengshi. Application of polyacrylic acid as binder in Li-ion battery[J]. Battery Bimonthly, 2014, 44(5): 307-309.
20	LIAO J B, LIU Z, WANG J L, et al. Cost-effective water-soluble poly(vinyl alcohol) as a functional binder for high-sulfur-loading cathodes in lithium-sulfur batteries[J]. ACS Omega, 2020, 5(14): 8272-8282.
21	HE C X, GENDENSUREN B, KIM H, et al. Electrochemical performance of polysaccharides modified by the introduction of SO₃H as binder for high-powered Li₄Ti₅O₁₂ anodes in lithium-ion batteries[J]. Journal of Electroanalytical Chemistry, 2020, 876: 114532.
22	ZOU K Y, DENG W T, CAI P, et al. Prelithiation/presodiation techniques for advanced electrochemical energy storage systems: concepts, applications, and perspectives[J]. Advanced Functional Materials, 2021, 31(5): 2005581.
23	中华人民共和国国家质量监督检验检疫总局, 中国国家标准化管理委员会. 锂离子电池正极/负极水性黏结剂: T/ZZB 1302—2019 [S]. 北京: 中国标准出版社, 2020.
	General Administration of Quality Supervision, Inspection and Quarantine of the People’s Republic of China, Standardization Administration of the People’s Republic of China. Lithium-ion battery positive/negative water-based binder: T/ZZB 1302—2019 [S]. Beijing: Standards Press of China, 2020.
24	VANNINI M, MARCHESE P, CELLI A, et al. Synergistic effect of dipentaerythritol and montmorillonite in EVOH-based nanocomposites[J]. Journal of Applied Polymer Science, 2015, 132(28): 42265.

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