锂离子电池安全添加剂的研究进展

doi:10.16085/j.issn.1000-6613.2021-2586

摘要/Abstract

摘要：

锂离子电池具有高能量密度和良好的循环性能，是目前最为理想的动力电源储能体系。然而，由于大容量和高功率锂离子电池技术尚未成熟，存在安全隐患，导致其商业化应用受到了很大程度的限制。锂离子电池的安全问题主要有机械力破坏、异常充电、气体积聚和热失控等，本文分析了上述危险因素产生的原因以及抑制的方法。在这些增强电池安全性的方法中，使用安全添加剂是最为经济有效的手段，但要在电解液中找到一种对电池具有高安全性能且不牺牲其他性能的实用添加剂并不容易，未来同时具备多功能的添加剂将会是对电池性能提升最有希望的研究方向。本文分析了成膜添加剂、阻燃添加剂和防过充添加剂的作用机理，并对相关领域的发展方向进行了展望。

关键词: 锂离子电池, 安全, 添加剂, 热失控, 电解质, 再生能源

Abstract:

Lithium ion battery has high energy density and good cycle performance. It is the most ideal power supply and energy storage system at present. However, due to the immature technology of high-capacity and high-power lithium-ion battery and potential safety hazards, its commercial application has been limited to a great extent. The safety problems of lithium-ion battery mainly include mechanical damage, abnormal charging, gas accumulation and thermal runaway. This paper analyzed the causes of the above risk factors and the suppression methods. Among these methods to enhance battery safety, the use of safety additives was the most economical and effective means, but it was not easy to find a practical additive with high safety performance for the battery without sacrificing other performance in the electrolyte. In the future, multifunctional additives would be the most promising research direction for improving battery performance. This paper briefly analyzed the action mechanism of film-forming additives, flame retardant additives and anti overcharge additives, and prospectd the development direction of related fields.

Key words: lithium ion battery, safety, additive, thermal runaway, electrolytes, renewable energy

中图分类号:

TM912

胡华坤, 薛文东, 蒋朋, 李勇. 锂离子电池安全添加剂的研究进展[J]. 化工进展, 2022, 41(10): 5441-5455.

HU Huakun, XUE Wendong, JIANG Peng, LI Yong. Research progress of safety additives for lithium ion batteries[J]. Chemical Industry and Engineering Progress, 2022, 41(10): 5441-5455.

图/表 12

图1 锂离子电池工作原理[4]

图2 热失控机制过程[14]

图3 锂离子电池的四级热失控机理（Ⅰ阶段SEI膜分解，电池开始自热；Ⅱ阶段内部短路发生，隔膜严重收缩，但产生少量焦耳热；Ⅲ阶段随着温度升高，阳极和电解质发生反应导致产热增加，触发热失控；Ⅳ阶段阴极和阳极之间开始氧化还原反应，电池温度迅速升至T3[15]）

图4 演化过程分为4个阶段的示意图，即变形、内部短路、热失控和机械滥用负载下锂离子电池的爆炸/火灾行为[29]

图5 使用含EC电解质的电池首次充电时在不同SOC下产生的气体成分[39]

图6 VC和FEC的成膜机理

表1 成膜添加剂的种类及其特点

成膜添加剂	特点
VC、FEC	具有良好成膜性；提高库仑效率和充电容量保持率
腈类	较高的介电常数和较低的黏度；结合其他成膜添加剂等联合使用
锂盐类	热稳定性好，膜阻抗低

图7 (a)3种含磷阻燃剂的配方及DMMP可能的阻燃机理[74]；(b)含不同浓度TFMP和DMMP的电解液的自熄试验和电导率关系图[78]

图8 在放电倍率测试中，含有MCMB或NMC电极的LP57和不同含量TPP的锂电池的平均放电比容量与标准偏差[82]

表2 阻燃添加剂的种类及其特点

氮磷复合类阻燃剂

优异的阻燃性能和电化学性能；显著降低电池的自加热速率；增强电池的过充电耐受性

图9 (a)在基于含有氧化还原添加剂作为保护的电解质的过充电池中发生穿梭的示意图[4]；(b) DMMB (1)和DBBB (2)的X射线晶体结构[89]; (c)二甲苯阳极电聚合的机理[96]；(d) BP与3CA的反应机理[98]

表3 放过充类添加剂的种类及其特点

防过充添加剂	特点
茂金属族化合物	过充电后产生不同的放电行为增加了电池的放电容量
芳香族化合物	减轻分子间寄生反应，还可以减轻由于适度的电子供给效应而导致的自由基阳离子的电子缺乏
甲苯、二甲苯、联苯、环己基苯等	发生电聚合，在电极和隔膜之间形成一层聚合物膜避免电压升高

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