锂离子电池热失控气体产物检测及分析技术研究进展

doi:10.19799/j.cnki.2095-4239.2024.0537

摘要/Abstract

摘要：

锂离子电池热失控会释放出大量气体，引起了许多研究者的关注。对热失控气体产物进行检测和分析是锂离子电池热失控研究中的重要组成部分。首先介绍了热失控不同阶段发生的反应并梳理出主要气体产物的来源。然后重点综述了当前锂离子电池热失控气体产物的主要检测和分析技术，包括气体传感器、傅里叶变换红外光谱(FTIR)、气相色谱(GC)、气相色谱-质谱联用(GC-MS)、拉曼光谱、离子色谱(IC)、复合气体分析仪及上述技术的组合联用，归纳了各种技术的实际运用效果，分析了每种技术存在的不足，提出了解决问题的方法建议，并总结出每种技术的优缺点及发展和应用情况。接着针对锂离子电池热失控气体产物检测结果的研究现状，从产气机理、气体成分和产气量、燃爆危险性、毒害、监测预警五个方面进行了阐述分析，可为锂离子电池的安全使用和发展提供帮助。最后基于对检测技术优点及气体产物研究内容的分析，推荐气体传感器和GC-MS+气体传感器为相对最适合气体分析的技术，可为检测技术的选择提供借鉴。文章结尾展望了气体产物检测和分析技术未来优化发展方向和前景，为相关技术的研发工作提供参考。

关键词: 锂离子电池, 热失控, 气体产物, 检测分析技术, 优缺点

Abstract:

The thermal runaway of lithium-ion batteries releases a significant amount of gas, drawing considerable attention from researchers. Detecting and analyzing these gas products is a crucial aspect of studying thermal runaway in lithium-ion batteries. This review first introduces the reactions occurring at various stages of thermal runaway and identifies the sources of the main gas products. It then focuses on the current primary detection and analysis technologies for thermal runaway gas products from lithium-ion batteries, including gas sensors, Fourier transform infrared spectroscopy (FTIR), gas chromatography (GC), gas chromatography-mass spectrometry (GC-MS), Raman spectroscopy, ion chromatography (IC), composite gas analyzers, and combinations of these technologies. The review summarizes the practical applications of each technology, evaluates their limitations, suggests problem-solving methods, and discusses the advantages, disadvantages, development, and application of these technologies. Furthermore, the current research status on the detection results of thermal runaway gas products is elaborated and analyzed from five aspects: gas generation mechanism, gas composition and production, combustion and explosion hazards, toxicity, and monitoring and warning, providing valuable insights for the safe use and development of lithium-ion batteries. Finally, based on an analysis of the advantages of detection technologies and research on gas products, gas sensors, and GC-MS combined with gas sensors are recommended as the most suitable gas analysis technologies, offering guidance for selecting appropriate detection methods. The future optimization, development directions, and prospects of gas product detection and analysis technologies are discussed, providing a reference for the advancement of related technologies.

Key words: lithium-ion battery, thermal runaway, gas products, detection and analysis technology, advantages and disadvantages

中图分类号:

TM 911

卫寿平, 孙杰, 李吉刚, 周添, 陈静, 党胜男, 唐娜, 张帆. 锂离子电池热失控气体产物检测及分析技术研究进展[J]. 储能科学与技术, 2024, 13(11): 4155-4176.

Shouping WEI, Jie SUN, Jigang LI, Tian ZHOU, Jing CHEN, Shengnan DANG, Na TANG, Fan ZHANG. Research progress on detection and analysis of thermal runaway gas products from lithium-ion batteries[J]. Energy Storage Science and Technology, 2024, 13(11): 4155-4176.

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表1

不同锂离子电池热失控气体产物检测分析技术的优缺点"

技术	优点	缺点
气体传感器	响应速度快、灵敏度高，适合气体的实时在线监测和分析；选择性好、检测范围宽，适合特定高浓度气体产物的准确测量；成本低、操作简便，可灵活配备不同数量、不同类型传感器	易受环境因素影响，容易被外部因素干扰，稳定性和可靠性相对不高，不能用于低浓度气体的精确测量，多气体检测时需要配备多个传感器
FTIR	分辨率高、波数精度高、灵敏度高、扫描速度快、光谱范围宽，适合多种气体的实时在线分析	无法鉴别化学结构相似的物质，无红外特征基团吸收的物质不能检测，谱图比较复杂，对分析人员要求高，谱图易受环境因素影响出现波动和干扰，需要额外添加样品预处理设备，复杂样品的重叠峰多且不易分辨
GC	分离能力强、灵敏度高、选择性好、性能稳定、适用性广，适合复杂气体样品的检测分析	物质定性方面能力有限，定性需要标准物，不适用未知成分的检测，对复杂混合物的检测时间较长，不能实时分析
GC-MS	综合了GC和MS的优点，对复杂混合气体的分离和定性能力强，检测的物质种类最多且能同时进行检测，检测结果准确可靠；灵敏度高、检测限低，低含量锂电热失控气体产物也能准确检测；技术发展成熟，应用最广泛	不适合分子量小于40的气体产物的检测，分析周期相对较长，无法反映热失控瞬时状态的气体信息变化，在采样过程中会破坏和消耗气体样本，仪器价格贵
拉曼光谱	除单原子气体外的所有气体都能检测，检测方式非接触、无损伤，不干扰电池内部反应，可对气体进行瞬态原位测量	拉曼信号比较弱，检测限相对较高，技术还不够成熟，仪器价格昂贵
IC	具有一般液相色谱的所有优点，可同时准确测定多种离子	不能直接检测气体，应用范围小
复合气体分析仪	不但具备单个气体传感器的优点，还能进行多个气体的快速自动化实时检测	具有和气体传感器类似的缺点，比气体传感器的造价高，缺乏灵活性，需要防止气体信号之间的交叉干扰
技术组合	综合每种技术的优点，弥补不足，适合用于锂离子电池热失控气体产物的全面检测分析	与单一技术相比，操作流程上会相对繁琐，且经济成本会增加

表1

图18

表2

文献中关于锂离子电池热失控气体产物研究的总结"

研究内容	技术	选用技术及其检测的气体	文献
产气机理分析	GC	CO、CO₂、H₂、O₂、C _x H _y	[11]
	GC	CO、CO₂、H₂、CH₄、C₂H₄、C₂H₆	[43]
	FTIR	CO₂、POF₃、EC	[33]
	GC+FTIR	CO、CO₂、H₂、CH₄、C₂H₄、C₂H₆	[26]
	GC-MS	CO、CO₂、O₂、有机气体	[27]
		CO₂、C₃H₆O₂等多种有机物、电解液	[31]
		CO₂、POF₃、CH₃F、CH₃OLi、CH₃OCH₃、DMC等	[70]
	GC-MS+气体传感器	CO、CO₂、CH₄、C₂H₆、C₂H₄等共25种气体(大多为有机物)以及HF	[60]

气体成分和产气量	GC	CO、CO₂、H₂、N₂、CH₄、C₂H₆、C₃H₈、C₂H₄、C₃H₆	[57]
	GC	CO、CO₂、H₂、O₂、N₂、CH₄、C₂H₂、C₂H₄、C₂H₆、C₃H₆、C₃H₈、水蒸气	[58]
	GC+复合气体分析仪	CO、CO₂、H₂、总碳氢化合物、HF	[68]
	拉曼光谱+气体传感器	H₂、CO、CO₂、O₂	[22]
	GC-MS	CO、CO₂以及CH₄、C₂H₆、C₂H₄等有机物共25种	[60]
		CO、CO₂以及PF₃、C₂H₄、C₂H₆等有机物共25种	[20]
		CO、CO₂以及C₂H₄、C₂H₆、C₃H₆等有机物共31种	[45]
	GC-MS+FTIR	CO、CO₂、HF、POF₃、可燃气、电解液	[72]
	GC-MS+气体传感器	CO₂、H₂、多种有机物	[20]

燃爆危险性	GC	N₂、CO、CO₂、H₂、O₂、C₁～C₄烃类	[25]
	GC	CO、CO₂、H₂、总烃	[24]
	FTIR	CO、CO₂	[54]
	FTIR	电解液、CH₄、H₂、N₂、CO₂	[56]
	拉曼光谱	CO₂、CO、H₂、CH₄、C₂H₄、C₃H₆	[23]
	拉曼光谱	CO、CO₂、H₂、CH₄	[52]
	复合气体分析仪	CO、CO₂、O₂	[64]
	GC-MS	CO₂、不饱和烃和电解液等共20多种物质	[73]
		CO、CO₂、H₂以及CH₄等大量有机物	[74]
		CO、CO₂、CH₄、C₂H₄	[7]
	GC-MS+气体传感器	CO、CO₂以及多种有机物	[28]

毒害	气体传感器	CO、CO₂、O₂、SO₂、HF、HCN、CH₄	[52]
	FTIR	CO、NO、SO₂、HCl、HF	[54]
	FTIR	HF、POF₃、PF₅	[44]
	气体传感器+FTIR	CO、CO₂、HF、POF₃	[75]
	气体分析仪	CO、CO₂、H₂、O₂	[76]
	IC	含氟物质、含氯物质	[63]
	GC-MS+气体传感器+IC	CO、CO₂、PO _x 、HF和100多种有机气体	[69]

监测预警	气体传感器	CO₂	[40]
		CO、CO₂、H₂	[51]
		CO、CO₂、H₂、CH₄、C₂H₄、C₂H₆	[48]
		CO、CO₂、H₂、HCl、HF	[77]
		CO、H₂	[4]
		CO、H₂、VOC	[21]
		CO、H₂、VOCs等	[3]

表2

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