锂离子电池用三维网状水系黏结剂的研究进展

doi:10.11868/j.issn.1001-4381.2019.001112

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摘要

硅材料由于具有很高的理论比容量（4200 mAh·g^-1）而成为下一代锂离子电池的关键负极材料之一，但是其在嵌/脱锂过程中会产生巨大的体积变化，使电极的循环性能变差。黏结剂作为电极的主要成分之一承担着连接电极组分、维持电极结构稳定的重要作用，使用合适的黏结剂对于改善硅基负极的循环稳定性至关重要。带有极性官能团的水系黏结剂由于可以有效改善硅基负极的电化学性能而成为现在的研究热点。本文综述硅基负极水系黏结剂的研究进展，首先对单一线性结构黏结剂的性质进行归纳总结。在此基础上，对具有三维网状结构的复合黏结剂的研究进展进行重点介绍，详细讨论不同类型三维网状黏结剂的结构和性能特点，以及应用于硅基负极时对电极性能的改善效果。最后，提出硅基负极水系黏结剂所应具备的特性，旨在为硅基负极水系黏结剂的开发和选择提供思路。

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	张健华
	张伟
	余章龙
	史碧梦
	杨娟玉

关键词 ：锂离子电池, 硅基负极, 水系黏结剂, 三维网状黏结剂

Abstract：

Silicon has been a pivotal material for the next generation lithium-ion batteries, owing to its superior theoretical capacity (4200 mAh·g^-1). However, the huge volume change of silicon during the process of lithiation/delithiation will lead to the instability of silicon-based anode. As a main composition of electrode, the binder plays a critical role in connecting the electrode components together and maintaining the stability of electrode, the use of an appropriate binder is essential to improve the cycling stability of silicon-based anode. Water-soluble binders which have abundant functional groups have received extensive attention due to their excellent performance in improving the electrochemical performance of silicon-based anodes. In this paper, the research progress of water-soluble binders used in silicon-based anode was reviewed. First, the properties of one-dimensional linear binders were summarized. On this basis, the research progress of composite binders with three-dimensional (3D) network structure was mainly introduced. The structure and properties of different 3D network binders were systematically analyzed. Finally, the preferred structure and properties of the water-soluble binders for silicon-based anode were proposed, and a train of thought for water-soluble binders' choice and design was provided.

Key words： lithium-ion battery silicon-based anode water-soluble binder 3D network binder

收稿日期: 2019-12-02 出版日期: 2021-06-22

中图分类号:

TM911

基金资助:国家重点研发计划项目(2016YFB0100400);国家自然科学基金项目(51604032);北京市优秀人才培养资助项目(2017000097607G094)

通讯作者: 杨娟玉 E-mail: juanyuyang@163.com

作者简介: 杨娟玉(1975-), 女, 教授, 博士, 主要从事锂离子电池负极材料制备技术及其在锂离子电池中的应用研究, 联系地址: 北京市西城区新街口外大街2号北京有色金属研究总院(100088), E-mail: juanyuyang@163.com

引用本文:

张健华, 张伟, 余章龙, 史碧梦, 杨娟玉. 锂离子电池用三维网状水系黏结剂的研究进展[J]. 材料工程, 2021, 49(6): 44-54.
Jian-hua ZHANG, Wei ZHANG, Zhang-long YU, Bi-meng SHI, Juan-yu YANG. Research progress in 3D network structured water-soluble binders for lithium-ion batteries. Journal of Materials Engineering, 2021, 49(6): 44-54.

链接本文:

http://jme.biam.ac.cn/CN/10.11868/j.issn.1001-4381.2019.001112 或 http://jme.biam.ac.cn/CN/Y2021/V49/I6/44

Fig.1 CMC黏结剂^[20]
(a)CMC与硅颗粒之间的氢键作用示意图；(b)CMC黏结剂在硅电极充放电过程中的作用机理示意图

Fig.2 溶解在水中的PAH，PAH_0.2Na_0.8和PAANa的聚合物链构象示意图^[27]

Table 1 不同线性黏结剂的官能团类型和性能表现

Fig.3 PAA-PVA黏结剂的结构以及与硅颗粒相互作用示意图^[39]

Fig.4 PVDF和Alg-C-CS黏结剂的作用机理示意图^[48]

Fig.5 β-CDp和6AD动态交联黏结剂的作用机理及金刚烷客体分子的化学结构示意图^[52]

Fig.6 PR-PAA黏结剂^[58]
(a)分子结构示意图；(b)PR-PAA黏结剂消除SiMP反复体积变化过程中的应力示意图；(c)PR-PAA-SiMP电极的放电容量保持率和库仑效率

Table 2 不同黏结剂的结构特点以及性能对比

Fig.7 高性能三维网状黏结剂在硅基负极中的作用机理

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