Thermal runaway gas detection and early warning of lithium-ion batteries

doi:10.19799/j.cnki.2095-4239.2025.0016

Abstract

Abstract:

Thermal runaway of lithium-ion batteries (LIBs) is a significant safety concern because of the release of highly toxic and flammable gases. These hazardous emissions can increase the risk of asphyxiation and cause serious fire accidents. Therefore, using gas detection for early warning of thermal runaway is crucial for the safety design of battery cells and packs. In this study, a laser Raman spectroscopy analyzer was used to detect the composition and concentration of thermal runaway gases emitted by LIBs with different cathode materials at various states of charge (SOC). The results demonstrate that the gas signal of a lithium iron phosphate battery (LFP) is primarily concentrated between the opening of the battery valve and thermal runaway under different SOC conditions. In contrast, nickel cobalt manganese batteries (NCM) mainly showed gas signals after thermal runaway. These findings indicate that H₂, CO, CO₂, CH₄, and C₂H₄ are theoretically feasible as characteristic gases for providing early warning of thermal runaway in batteries. Based on the experimental results for the battery cells, the above characteristic gases were further used for thermal runaway gas detection and early warning verification in the battery packs. A composite gas sensor that can measure CO₂ and CO/H₂/HC concentrations in real-time was used to detect characteristic gas changes at different locations inside battery packs. The gas concentration information was collected and uploaded to the battery management system (BMS). Compared with traditional cell temperature and voltage monitoring, gas signals provide a practical and effective method for the early warning of thermal runaway in battery packs. The results demonstrate that: ① the gas signal is negatively correlated with the distance between the sensor and the thermal runaway trigger battery. ② The CO/H₂/HC signals are faster than CO₂. Remarkably, even at the farthest detection location, CO₂ gas can send an alarm signal at least 578 s before thermal runaway, demonstrating the effectiveness of gas-based early warning. ③ Compared with the temperature and voltage of traditional BMSs, gas signals offer a considerable competitive advantage for thermal runaway warnings. This study investigates gas generation during the thermal runaway process in LFP and NCM battery cells to verify the gas-based early warning system in their corresponding battery packs. The results demonstrate that gas-sensing technology can provide timely warning of thermal runaway in both LFP and NCM battery packs, providing a crucial reference for the development of LIB thermal-runaway early warning technology.

Key words: lithium-ion battery, thermal runaway, gas detection, gas early warning

CLC Number:

TM 911

Zijing ZHANG, Beibei YUAN, Hong LI, Ying GAO. Thermal runaway gas detection and early warning of lithium-ion batteries[J]. Energy Storage Science and Technology, 2025, 14(7): 2820-2832.

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项目	磷酸铁锂电池	三元锂电池
容量/Ah	52	50
标称电压/V	3.2	3.6
充放电电压范围/V	2.5～3.65	2.8～4.25
正极	LiFePO₄	Li(Ni _x Co _y Mn_1-_x_-_y )O₂
负极	导电碳黑	导电碳黑

电池类型	电池包尺寸	组成方式	标称能量/kWh	单体容量/Ah	单体充放电电压范围/V
LFP	25 cm×78 cm×115 cm	1P44S	42	300	2.7~3.6
NCM	14 cm×102 cm×124 cm	1P84S	17	55	2.8~4.3

电池基本信息		开阀/s	热失控/s	监测点最高温度/℃	气体最高温度/℃	最大气压/kPa	质量损失率/%
52 Ah LFP	50%SOC	558	1228	240.7	73.8	29.5	16.5
52 Ah LFP	100%SOC	403	700	259.2	76.7	39.4	18

50 Ah NCM	50%SOC	696	730	308.8	113.8	84	19.3
50 Ah NCM	100%SOC	432	439	408.9	176.9	239.2	32.9

电池	N₂/%	H₂/%	CO/%	CO₂/%	CH₄/%	C₂H₄/%
50% LFP	89.424	3.694	0.179	3.955	2.185	0.564
100% LFP	82.357	9.766	0.484	3.258	3.210	0.925
50% NCM	83.882	6.15	3.966	5.648	0.001	0.354
100% NCM	49.566	13.692	14.367	13.801	4.453	4.122