一种用于磷酸铁锂电极的水性黏结剂制备与性能研究

doi:10.11949/0438-1157.20201085

化工学报 ›› 2021, Vol. 72 ›› Issue (2): 1169-1180.DOI: 10.11949/0438-1157.20201085

• 材料化学工程与纳米技术 • 上一篇下一篇

一种用于磷酸铁锂电极的水性黏结剂制备与性能研究

曹佳宁¹(),高翔^1,²(),罗英武¹,苏荣欣³

^1.化学工程联合国家重点实验室，浙江大学化学工程与生物工程学院，浙江杭州 310027
^2.浙江大学衢州研究院，浙江衢州 324000
^3.天津大学化工学院，化学工程联合国家重点实验室，天津 300072

收稿日期:2020-08-03 修回日期:2020-09-07 出版日期:2021-02-05 发布日期:2021-02-05
通讯作者: 高翔
作者简介:曹佳宁(1997—)，女，硕士研究生，21828161@zju.edu.cn
基金资助:
国家自然科学基金项目(21875213);化学工程联合国家重点实验室课题(SKL-ChE-19T01);浙江大学衢州研究院科技计划项目(IZQ2019-KJ-018)

Study on preparation and performance of aqueous binder for lithium iron phosphate electrodes in lithium-ion battery

CAO Jianing¹(),GAO Xiang^1,²(),LUO Yingwu¹,SU Rongxin³

^1.State Key Laboratory of Chemical Engineering, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China
^2.Institute of Zhejiang University-Quzhou, Quzhou 324000, Zhejiang, China
^3.State Key Laboratory of Chemical Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China

Received:2020-08-03 Revised:2020-09-07 Online:2021-02-05 Published:2021-02-05
Contact: GAO Xiang

摘要/Abstract

摘要：

磷酸铁锂作为锂离子电池正极材料应用广泛。目前在其电极制备中仍采用PVDF油系黏结剂体系，可用于该电极的水性黏结剂仍需进一步研究。通过反应型乳化剂共聚苯乙烯（St）与丙烯酸异辛酯（2-EHA）制备了不同结构的磷酸铁锂正极水系黏结剂PSEHA，探讨了黏结剂对电池性能的影响。PSEHA黏结剂不含不饱和双键，抗氧化性好，较低的溶胀率可以有效防止过度溶胀导致的结构破坏，而反应型乳化剂可以解决乳化剂残留问题。采用所得最优结构黏结剂制备的磷酸铁锂电极表现出优异的电化学稳定性，扣式电池1 C循环100圈后容量保留率仍有96%，而SBR仅有93.9%；软包全电池在1 C倍率下循环170圈后容量保留率仍有98.9%。该新型水性黏结剂对促进磷酸铁锂水性体系制备有重要意义。

关键词: 电化学, 电极黏结剂, 乳液, 聚合物, 丙烯酸酯黏结剂, 反应型乳化剂, 磷酸铁锂正极, 锂离子电池

Abstract:

LiFePO₄ is a widely used cathode material for lithium-ion batteries. Polyvinylidenefluoride (PVDF), as a traditional organic solvent soluble binder, is still used in the preparation of LiFePO₄cathode. The water-based binder which can be used in the preparation of LiFePO₄cathode still needs to be further studied. A novel water-based binder PSEHA with different structures for LiFePO₄ cathodes was prepared via copolymerizing polystyrene (St) and 2-ethylhexyl acrylate (2-EHA) with a reactive emulsifier to improve the performance of lithium-ion battery. The influence of binder structure on battery performance was studied. Without unsaturated double bonds, PSEHA binder has good oxidation resistance. Its low swelling ratio can effectively prevent structural damage caused by excessive swelling, and the use of reactive emulsifiers can solve the residue of emulsifier. The LiFePO₄cathode prepared with the optimal binder showed excellent electrochemical stability. After 100 cycles, the LiFePO₄cathode in coin cells maintained stable cycling performance with retention of 96% at the rate of 1 C, while the SBR was only 93.9%. The capacity retention rate of the soft-packed full battery after 170 cycles at 1 C rate is still 98.9%. This new type of water-based binder is of great significance to promote the preparation of LiFePO₄cathode in water-based systems.

Key words: electrochemistry, electrode binder, emulsions, polymers, acrylate binder, reactive emulsifier, LiFePO₄ cathode, lithium-ion battery

中图分类号:

TQ 028.8

曹佳宁, 高翔, 罗英武, 苏荣欣. 一种用于磷酸铁锂电极的水性黏结剂制备与性能研究[J]. 化工学报, 2021, 72(2): 1169-1180.

CAO Jianing, GAO Xiang, LUO Yingwu, SU Rongxin. Study on preparation and performance of aqueous binder for lithium iron phosphate electrodes in lithium-ion battery[J]. CIESC Journal, 2021, 72(2): 1169-1180.

图/表 15

图1 软包电池结构示意图

Fig.1 Schematic diagram of pouch lithium cell structure

图2 PSEHA黏结剂的合成路线

Fig.2 Synthesis reactions and the chemical structure of the PSEHA

表1 黏结剂胶乳合成的转化率

Table 1 Monomer conversion of binders with different monomer ratio

Polymer	Conversion/%
PSEHA-1∶11	99.57
PSEHA-3∶7	99.34
PEHA	99.45

表2 黏结剂粒径

Table 2 Size of PSEHA copolymers

Polymer	Particle size/nm	PDI
PSEHA-1∶11	64.03	0.027
PSEHA-3∶7	69.98	0.022
PEHA	58.8	0.067

图3 PSEHA-3∶7 的红外光谱

Fig.3 FTIR spectra of PSEHA-3∶7

表3 使用不同黏结剂的极片电解液溶胀率

Table 3 Electrolyte uptake of electrodes fabricated by different binders

Binder	Swelling ratio(25℃, 120 h)
PSEHA-1∶11	15.38
PSEHA-3∶7	14.81
PEHA	20.59
SBR	32.86
PVDF	42.31

图4 使用不同黏结剂的极片剥离测试

Fig.4 Peel test of electrodes fabricated by different binders

图5 循环前后不同黏结剂效果示意图

Fig.5 Schematic diagram of electrodes with different binders before and after cycles

图6 使用不同黏结剂制备极片的SEM图

Fig.6 SEM images of electrodes consists of different binders before and after cycles

图7 不同黏结剂磷酸铁锂正极的电化学性能图

Fig.7 Electrochemical performances of LiFePO4 cathodes with various binders

图8 磷酸铁锂正极EIS图谱（频率10-2~105 Hz）

Fig.8 EIS spectra of LFP/C electrodes prepared with PSEHA-1∶11 and SBR in frequency range between 10-2 and 105 Hz

表4 电池阻抗

Table 4 The resistances of the cells

State	Binder	R/Ω
before cycles	SBR	87.15
before cycles	PSEHA-1∶11	88.21
after cycles	SBR	188.4
after cycles	PSEHA-1∶11	123

图9 软包全电池的电化学性能图

Fig.9 Electrochemical performances of the pouch lithium cell with PSEHA-1∶11 binder

图10 PSEHA-1∶11黏结剂的电化学窗口（0.5 mV/s）

Fig.10 Electrochemical stability windows of PSRHA-1∶11 with a scanning rate of 0.5 mV/s

图11 使用PSEHA-1∶11及SBR黏结剂的电极浆料的稳定性

Fig.11 Stability of electrode slurries using PSEHA-1∶11 and SBR

参考文献 32

1	Chen H, Ling M, Hencz L, et al. Exploring chemical, mechanical, and electrical functionalities of binders for advanced energy-storage devices[J]. Chemical Reviews, 2018, 118(18): 8936-8982.
2	Tarascon J, Armand M. Issues and challenges facing rechargeable lithium batteries[J]. Nature, 2001, 414(6861): 359-367.
3	Goodenough J B, Park K. The Li-ion rechargeable battery: a perspective[J]. Journal of the American Chemical Society, 2013, 135(4): 1167-1176.
4	Xie J, Lu Y. A retrospective on lithium-ion batteries[J]. Nature Communications, 2020, 11(1): 2499.
5	Wu M, Xiao X, Vukmirovic N, et al. Toward an ideal polymer binder design for high-capacity battery anodes[J]. Journal of the American Chemical Society, 2013, 135(32): 12048-12056.
6	Shi Y, Zhou X, Yu G. Material and structural design of novel binder systems for high-energy, high-power lithium-ion batteries[J]. Accounts of Chemical Research, 2017, 50(11): 2642-2652.
7	Li J, Wu Z, Lu Y, et al. Water soluble binder, an electrochemical performance booster for electrode materials with high energy density[J]. Advanced Energy Materials, 2017, 7(24): 1701185.
8	Liu W, Yang M, Wu H, et al. Enhanced cycle life of Si anode for Li-ion batteries by using modified elastomeric binder[J]. Electrochemical and Solid-state Letters, 2005, 8(2): A100-A103.
9	Du Pasquier A, Disma F, Bowmer T, et al. Differential scanning calorimetry study of the reactivity of carbon anodes in plastic Li-ion batteries[J]. Journal of the Electrochemical Society, 1998, 145(2): 472-477.
10	Maleki H, Deng G, Kerzhner-Haller I, et al. Thermal stability studies of binder materials in anodes for lithium-ion batteries[J]. Journal of the Electrochemical Society, 2000, 147(12): 4470-4475.
11	Li C, Lin Y. Interactions between organic additives and active powders in water-based lithium iron phosphate electrode slurries[J]. Journal of Power Sources, 2012, 220: 413-421.
12	Cai Z P, Liang Y, Li W S, et al. Preparation and performances of LiFePO₄ cathode in aqueous solvent with polyacrylic acid as a binder[J]. Journal of Power Sources, 2009, 189(1): 547-551.
13	Chong J, Xun S, Zheng H, et al. A comparative study of polyacrylic acid and poly(vinylidene difluoride) binders for spherical natural graphite/LiFePO₄ electrodes and cells[J]. Journal of Power Sources, 2011, 196(18): 7707-7714.
14	Valvo M, Liivat A, Eriksson H, et al. Iron-based electrodes meet water-based preparation, fluorine-free electrolyte and binder: a chance for more sustainable lithium-ion batteries?[J]. ChemSusChem, 2017, 10(11): 2431-2448.
15	Jeong S S, Böckenfeld N, Balducci A, et al. Natural cellulose as binder for lithium battery electrodes[J]. Journal of Power Sources, 2012, 199: 331-335.
16	Huang S, Ren J, Liu R, et al. Enhanced electrochemical properties of LiFePO₄ cathode using waterborne lithiated ionomer binder in Li-ion batteries with low amount[J]. ACS Sustainable Chemistry & Engineering, 2018, 6(10): 12650-12657.
17	Gao S, Su Y, Bao L, et al. High-performance LiFePO₄/C electrode with polytetrafluoroethylene as an aqueous-based binder[J]. Journal of Power Sources, 2015, 298: 292-298.
18	Zhu C L, Tao C, Bao J J, et al. Waterborne polyurethane used as binders for lithium-ion battery with improved electrochemical properties[J]//Advanced Materials Research, 2015, 1090:199-204.
19	Nguyen V H, Wang W L, Jin E M, et al. Impacts of different polymer binders on electrochemical properties of LiFePO₄ cathode[J]. Applied Surface Science, 2013, 282: 444-449.
20	Prosini P P, Carewska M, Cento C, et al. Polyvinylacetate used as a binder for the fabrication of a LiFePO₄-based composite cathode for lithium-ion batteries[J]. Electrochimica Acta, 2014, 150: 129-135.
21	Qiu L, Shao Z, Wang D, et al. Carboxymethyl cellulose lithium (CMC-Li) as a novel binder and its electrochemical performance in lithium-ion batteries[J]. Cellulose, 2014, 21(4): 2789-2796.
22	Eliseeva S N, Levin O V, Tolstopyatova E G, et al. Effect of addition of a conducting polymer on the properties of the LiFePO₄-based cathode material for lithium-ion batteries[J]. Russian Journal of Applied Chemistry, 2015, 88(7): 1146-1149.
23	Tsao C, Wu E, Lee W, et al. Fluorinated copolymer functionalized with ethylene oxide as novel water-borne binder for a high-power lithium ion battery: synthesis, mechanism, and application[J]. ACS Applied Energy Materials, 2018, 1(8): 3999-4008.
24	Yamamoto H, Mori H. SBR binder (for negative electrode) and ACM binder (for positive electrode)[M]. Springer, 2009, 163-179.
25	Chou S, Pan Y, Wang J, et al. Small things make a big difference: binder effects on the performance of Li and Na batteries[J]. Physical Chemistry Chemical Physics, 2014, 16(38): 20347-20359.
26	Aoki S, Han Z, Yamagiwa K, et al. Acrylic acid-based copolymers as functional binder for silicon/graphite composite electrode in lithium-ion batteries[J]. Journal of the Electrochemical Society, 2015, 162(12): A2245-A2249.
27	Lee Y, Kim J, Noh J, et al. Wearable textile battery rechargeable by solar energy[J]. Nano letters, 2013, 13(11): 5753-5761.
28	Park G, Park Y, Park J, et al. Flexible and wrinkle-free electrode fabricated with polyurethane binder for lithium-ion batteries[J]. RSC Advances, 2017, 7(26): 16244-16252.
29	Han Z, Yabuuchi N, Shimomura K, et al. High-capacity Si-graphite composite electrodes with a self-formed porous structure by a partially neutralized polyacrylate for Li-ion batteries[J]. Energy & Environmental Science, 2012, 5(10): 9014-9020.
30	Zheng Z, Gao X, Luo Y, et al. Employing gradient copolymer to achieve gel polymer electrolytes with high ionic conductivity[J]. Macromolecules, 2016, 49(6): 2179-2188.
31	魏迪锋. 锂离子电池硅基负极制备及其负载量和电化学性能提升研究[D]. 杭州: 浙江大学, 2019.
	Wei D F. The preparation of silicon-based anode for lithium-ion battery and study on its loading and electrochemical performance improvement [D]. Hangzhou: Zhejiang University, 2019.
32	Xiao J, Li Q, Bi Y, et al. Understanding and applying coulombic efficiency in lithium metal batteries[J]. Nature Energy, 2020, 5187: 561-568.

[1]	程业品, 胡达清, 徐奕莎, 刘华彦, 卢晗锋, 崔国凯. 离子液体基低共熔溶剂在转化CO₂中的应用[J]. 化工学报, 2023, 74(9): 3640-3653.
[2]	康飞, 吕伟光, 巨锋, 孙峙. 废锂离子电池放电路径与评价研究[J]. 化工学报, 2023, 74(9): 3903-3911.
[3]	胡亚丽, 胡军勇, 马素霞, 孙禹坤, 谭学诣, 黄佳欣, 杨奉源. 逆电渗析热机新型工质开发及电化学特性研究[J]. 化工学报, 2023, 74(8): 3513-3521.
[4]	张琦钰, 高利军, 苏宇航, 马晓博, 王翊丞, 张亚婷, 胡超. 碳基催化材料在电化学还原二氧化碳中的研究进展[J]. 化工学报, 2023, 74(7): 2753-2772.
[5]	张蒙蒙, 颜冬, 沈永峰, 李文翠. 电解液类型对双离子电池阴阳离子储存行为的影响[J]. 化工学报, 2023, 74(7): 3116-3126.
[6]	汤晓玲, 王嘉瑞, 朱玄烨, 郑仁朝. 基于Pickering乳液的卤醇脱卤酶催化合成手性环氧氯丙烷[J]. 化工学报, 2023, 74(7): 2926-2934.
[7]	王志龙, 杨烨, 赵真真, 田涛, 赵桐, 崔亚辉. 搅拌时间和混合顺序对锂离子电池正极浆料分散特性的影响[J]. 化工学报, 2023, 74(7): 3127-3138.
[8]	葛加丽, 管图祥, 邱新民, 吴健, 沈丽明, 暴宁钟. 垂直多孔碳包覆的FeF₃正极的构筑及储锂性能研究[J]. 化工学报, 2023, 74(7): 3058-3067.
[9]	屈园浩, 邓文义, 谢晓丹, 苏亚欣. 活性炭/石墨辅助污泥电渗脱水研究[J]. 化工学报, 2023, 74(7): 3038-3050.
[10]	张澳, 罗英武. 低模量、高弹性、高剥离强度丙烯酸酯压敏胶[J]. 化工学报, 2023, 74(7): 3079-3092.
[11]	王杰, 丘晓琳, 赵烨, 刘鑫洋, 韩忠强, 许雍, 蒋文瀚. 聚电解质静电沉积改性PHBV抗氧化膜的制备与性能研究[J]. 化工学报, 2023, 74(7): 3068-3078.
[12]	刘杰, 吴立盛, 李锦锦, 罗正鸿, 周寅宁. 含乙烯基胺酯键聚醚类可逆交联聚合物的制备及性能研究[J]. 化工学报, 2023, 74(7): 3051-3057.
[13]	张谭, 刘光, 李晋平, 孙予罕. Ru基氮还原电催化剂性能调控策略[J]. 化工学报, 2023, 74(6): 2264-2280.
[14]	龙臻, 王谨航, 任俊杰, 何勇, 周雪冰, 梁德青. 离子液体协同PVCap抑制天然气水合物生成实验研究[J]. 化工学报, 2023, 74(6): 2639-2646.
[15]	李靖, 沈聪浩, 郭大亮, 李静, 沙力争, 童欣. 木质素基碳纤维复合材料在储能元件中的应用研究进展[J]. 化工学报, 2023, 74(6): 2322-2334.

一种用于磷酸铁锂电极的水性黏结剂制备与性能研究

Study on preparation and performance of aqueous binder for lithium iron phosphate electrodes in lithium-ion battery

RichHTML

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 15

参考文献 32

相关文章 15

编辑推荐

Metrics

本文评价