基于气体分析的锂离子电池热失控早期预警研究进展

doi:10.19595/j.cnki.1000-6753.tces.220832

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摘要

锂离子电池由于能量密度高、循环寿命长、自放电率低和环境友好等优势得到了广泛应用,但其安全方面仍存在隐患,在遭遇滥用时可能会引发电池失效甚至发生火灾爆炸事故,阻碍了其在电动汽车和储能电站方面的大规模应用。针对锂离子电池的安全预警方面的研究引发了相关人员的极大关注,其中,基于电池气体分析的热失控早期预警机制相比于传统的电、热信号在可靠性、准确性、反应速度等方面有所提高。该文总结了锂离子电池在热失控过程中的气体来源,全面对比分析了触发方式、阴极材料、电池型号、荷电状态（SOC）及健康状态（SOH）对热失控产气组分、含量以及产气总量的影响规律,回顾了锂离子电池热失控过程中温度-压力演化特性的研究现状,总结了目前基于气体成分和内部压力的早期预警方案,并对现有研究的不足和潜在研究方向进行了讨论。

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	杨梦洁
	杨爱军
	叶奕君
	杨晖
	张智棋
	何桂荣
	江智元
	王小华
	袁欢
	荣命哲

关键词 ：锂离子电池, 热失控, 排气行为, 温度-压力演化特性, 早期预警

Abstract：

Li-ion batteries are widely used in electric vehicles, portable electronic devices, and distributed energy storage systems due to their high energy density, long cycle life, low self-discharge rate, and eco-friendly. However, there are still potential safety hazards. It may lead to failure or even fire and explosion accidents when cells are subjected to stress and abuse from mechanical, electrical, and thermal perspectives, posing a significant threat to the overall safety of a variety of battery systems. Therefore, studies on the thermal runaway and safety warning of Li-ion batteries have aroused great concern. On the premise of passing the battery manufacturer's safety tests, a lot of methods for monitoring and detecting thermal runaway events have been developed to enhance the safety and robustness of Li-ion batteries in various application scenarios. Among these, the gas-based thermal runaway early warning mechanism has improved in reliability, accuracy, and response speed compared with the traditional electrical and thermal signals.
Firstly, this paper summarizes the chemical reactions and their onset temperatures during the thermal runaway of Li-ion batteries, as well as the gases released. The decomposition of the solid electrolyte interphase membrane, the reactions between the active materials, and the decomposition of the electrolyte, especially the intercalated lithium with solvents, can release large amounts of combustible gases including H₂, CO, CO₂, and hydrocarbons. Flammable gases and solvent vapors are a potential fire hazard when mixed with oxygen. However, Li-ion batteries in various states may exhibit different characteristics of thermal runaway gas production. Thus, the effects and laws of the triggering method, cathode material, cell type, state of charge, and state of health on the components, content, and total amount of gas produced during thermal runaway were comprehensively compared and analyzed. Then the current status of research on the temperature-pressure evolution characteristics during thermal runaway of Li-ion batteries is reviewed from experimental and simulation perspectives, respectively, and the conclusions and limitations of existing studies are summarized. Experimental studies of Li-ion battery eruptions are generally conducted based on sealed chambers, and the output parameters are usually cell temperature, the pressure inside the pressure tank, and gas production components. But these studies are difficult to determine the gas temperature. Therefore, some researchers have simulated gas generation, pressure buildup, gas emission, and combustion processes based on gas production kinetic models. Finally, the current early warning schemes based on gas composition and internal pressure are summarized, and the shortcomings of existing research and potential research directions are discussed to further enhance the safety and robustness of Li-ion battery systems. Early warning methods based on gases (such as H₂, CO, electrolyte vapor, etc.) can provide effective early warning for thermal runaway of Li-ion batteries. However, the early warning techniques of a single sensor may not meet the detection requirements of practical engineering applications. The fusion mechanism based on the co-monitoring of multiple parameters may be more effective and comprehensive for the identification of Li-ion battery faults.
Monitoring the thermal runaway processes with gas sensors has proven to be a more effective method than with voltage or with temperature sensors. In addition, the development of new portable gas sensors, such as the MEMS micro-optical gas sensors, the photoacoustic spectrometers, and the infrared spectrometers, may be beneficial in generating accurate early warning signals for applications involving Li-ion batteries with a potential thermal runaway problem.

Key words： Li-ion batteries thermal runaway vent behavior temperature-pressure evolution characteristics early warning

收稿日期: 2022-05-15

PACS:

TM911.9

基金资助:

国家自然科学基金（U2166214, 52106111, 52207170）、中央高校基本科研业务费专项资金和王宽诚教育基金资助项目

通讯作者: 杨爱军男,1986年生,教授,博士生导师,研究方向为电力设备状态诊断。E-mail：yangaijun@mail.xjtu.edu.cn

作者简介: 杨梦洁女,1997年生,博士研究生,研究方向为锂离子电池热失控早期预警。E-mail：mjyang19@stu.xjtu.edu.cn

引用本文:

杨梦洁, 杨爱军, 叶奕君, 杨晖, 张智棋, 何桂荣, 江智元, 王小华, 袁欢, 荣命哲. 基于气体分析的锂离子电池热失控早期预警研究进展[J]. 电工技术学报, 2023, 38(17): 4507-4538. Yang Mengjie, Yang Aijun, Ye Yijun, Yang Hui, Zhang Zhiqi, He Guirong, Jiang Zhiyuan, Wang Xiaohua, Yuan Huan, Rong Mingzhe. Research Progress on Early Warning of Thermal Runaway of Li-Ion Batteries Based on Gas Analysis. Transactions of China Electrotechnical Society, 2023, 38(17): 4507-4538.

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https://dgjsxb.ces-transaction.com/CN/10.19595/j.cnki.1000-6753.tces.220832 https://dgjsxb.ces-transaction.com/CN/Y2023/V38/I17/4507