锂离子电池高安全复合隔膜的挑战和未来展望

doi:10.19799/j.cnki.2095-4239.2023.0961

摘要/Abstract

摘要：

隔膜作为锂电池的重要结构组成部分，起阻隔正负极接触、吸收并固定电解液、传递离子等关键作用。锂电池用商用隔膜面临高温热收缩等问题，影响电池的持久安全性。本文首先简要介绍了锂离子电池隔膜在孔隙结构、电解液润湿性、结构/热/化学/电化学稳定性以及隔膜-电解液相互作用等方面的要求，并通过对近期相关文献的探讨，重点综述了耐高温聚合物隔膜的研究进展；重点分析了高耐热聚合物基隔膜、阻燃添加剂涂敷隔膜和聚合物基底复合等策略对于阻燃多功能复合隔膜的改善机制；对于复合隔膜的锂枝晶抑制策略，主要介绍了物理阻隔锂枝晶生长、均匀化锂沉积和调控锂离子迁移通量三种方法。综合分析表明，通过减薄聚烯烃隔膜同时引入高性能薄涂层、掺杂固态电解质、开发高耐热聚合物基底隔膜等策略，有望在实现高安全性的同时获得高离子电导率。

关键词: 锂离子电池, 高安全性, 复合隔膜

Abstract:

The separator is a crucial structural component of lithium-ion batteries, responsible for preventing direct contact between the positive and negative electrodes, absorbing and immobilizing electrolyte, and facilitating ion transfer. Commercial separators are currently challenged by issues such as thermal shrinkage at high temperatures, which compromises the long-term safety of the battery. This paper begins with an overview of the requirements for lithium-ion battery separators, including pore structure, electrolyte wettability, and stability-structural, thermal, chemical, and electrochemical-as well as separator-electrolyte interactions. It then reviews recent literature on high-temperature-resistant polymer separators, highlighting research advancements. The focus is on the analysis of strategies for high-heat-resistant polymer-based separators, flame-retardant additive-coated separators, and polymer-substrate composites. The paper discusses the mechanism behind the enhancements provided by flame-retardant multifunctional composite separators and explores strategies for inhibiting lithium dendrite formation through physical barriers, lithium deposition homogenization, and modulation of lithium-ion migration fluxes. Comprehensive analysis indicates that reducing the thickness of polyolefin separators, while integrating high-performance thin coatings, doping with solid electrolytes, and developing high-heat-resistant polymer-based separators, can achieve high ionic conductivity and ensure enhanced safety.

Key words: lithium-ion battery, high safety, composite separators

中图分类号:

TM 911

钟国彬, 姚鑫, 刘永超, 侯倩, 项宏发. 锂离子电池高安全复合隔膜的挑战和未来展望[J]. 储能科学与技术, 2024, 13(6): 1794-1806.

Guobin ZHONG, Xin YAO, Yongchao LIU, Qian HOU, Hongfa XIANG. Challenges and prospects of high-safety composite separators for lithium-ion batteries[J]. Energy Storage Science and Technology, 2024, 13(6): 1794-1806.

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序号	参数	要求
1	孔隙率	30%～70%
2	孔径大小	< 1 μm
3	厚度	在力学性能满足的情况尽可能小，< 40 μm
4	渗透率	< 8 (MacMullin =电解液离子电导率/隔膜浸润后离子电导率)
5	机械强度	偏移 < 2% (1000 psi, 1000 psi = 6.895 MPa)
6	穿刺强度	> 300 g/mil (1 mil = 25.4 μm)
7	热稳定性	< 5% (100 ℃，热处理1 h)
8	化学稳定性	不与电解液发生化学反应，耐强氧化、还原环境
9	透气率	200～800 s /100 mL
10	吸液率	一般要求越高越好
11	拉伸强度	一般要求纵向强度达到100 MPa以上，横向强度不能太大

Material	Melting points/℃	Dielectric constant	Material	Melting points/℃	Dielectric constant
PVDF	170	7.25	PTFE	327	2.02
PEEK	343	2.7～3.3	Cellulose	274	3.2
PI	400	3.5	PMMA	160	4.9
PBI	430	3.2	PET	260	3.16
PMIA	460	3.0	PAN	317	3.1
PEI	360	3.3	PPS	300	3.9～5.1

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