Thermal runaway characteristics and gas generation behavior of 100 Ah lithium iron phosphate pouch cell

doi:10.19799/j.cnki.2095-4239.2024.0764

Abstract

Abstract:

This study focuses on 100 Ah lithium iron phosphate pouch cells, triggering thermal runaway by side heating. By utilizing industry characterization tools such as Industrial Computer Tomography, Scanning Electron Microscopy, and Gas Chromatography, the thermal runaway characteristics and gas evolution patterns at 40%, 60%, 80%, and 100% SOC were systematically analyzed. The results show that the overheating trigger of battery thermal runaway can be subdivided into four stages: increased overheating temperature; by-product reaction gas expansion; separator shrinkage and cracking with smoke emission; and thermal runaway caused by severe temperature rise and gas production. Further calculation of heat generation energy revealed that at 100%, 80%, 60%, and 40% SOC, the peak heat generation rates reached 140.34, 115.44, 14.76, and 3.91 kW, respectively, and the energy released at 100% SOC is equivalent to 104.63 grams of TNT, with a destructive radius reaching 5.90 meters, representing nearly a 64.3% increase in hazard compared to that at 40% SOC. Characterization of battery materials post-thermal runaway indicated that the LFP cathode material transformed from a block shape to aggregated irregular spheres, and the graphite anode structure was transformed from layered to aggregated spherical particles due to accentuated internal side reactions. A comparison of gas evolution characteristics showed that with increased SOC, the amount of H₂produced by the battery increased, while the amount of CO₂ decreased. The explosion risk of the gases produced at various SOC levels is higher than that of Common hydrocarbon gases, with the explosion upper limit first decreasing and then increasing. The findings from this study provide a theoretical basis and practical guidance for the safety design of follow-up energy storage systems.

Key words: large capacity, thermal runaway, lithium iron phosphate pouch cell, debris characteristics, aerogenesis

CLC Number:

TK 02

Jinhao YE, Junhui HOU, Zhengguo ZHANG, Ziye LING, Xiaoming FANG, Silin HUANG, Zhiwen XIAO. Thermal runaway characteristics and gas generation behavior of 100 Ah lithium iron phosphate pouch cell[J]. Energy Storage Science and Technology, 2025, 14(2): 636-647.

Figures/Tables 14

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References 28

1	CHEN R J, LUO R, HUANG Y X, et al. Advanced high energy density secondary batteries with multi-electron reaction materials[J]. Advanced Science, 2016, 3(10): 1600051. DOI:10.1002/advs.201600051.
2	MA X T, AZHARI L, WANG Y. Li-ion battery recycling challenges[J]. Chem, 2021, 7(11): 2843-2847. DOI:10.1016/j.chempr. 2021.09.013.
3	BÖRGER A, MERTENS J, WENZL H. Thermal runaway and thermal runaway propagation in batteries: What do we talk about?[J]. Journal of Energy Storage, 2019, 24: 100649. DOI:10.1016/j.est.2019.01.012.
4	WANG H B, WANG Q Z, ZHAO Z Y, et al. Thermal runaway propagation behavior of the Cell-to-Pack battery system[J]. Journal of Energy Chemistry, 2023, 84: 162-172. DOI:10.1016/j.jechem.2023.05.015.
5	DENG J, CHEN B H, LU J Z, et al. Thermal runaway and combustion characteristics, risk and hazard evaluation of lithium-iron phosphate battery under different thermal runaway triggering modes[J]. Applied Energy, 2024, 368: 123451. DOI:10.1016/j.apenergy.2024.123451.
6	SONG L B, ZHENG Y H, XIAO Z L, et al. Review on thermal runaway of lithium-ion batteries for electric vehicles[J]. Journal of Electronic Materials, 2022, 51(1): 30-46. DOI:10.1007/s11664-021-09281-0.
7	ZHU X Q, SUN Z W, WANG Z P, et al. Thermal runaway in commercial lithium-ion cells under overheating condition and the safety assessment method: Effects of SoCs, cathode materials and packaging forms[J]. Journal of Energy Storage, 2023, 68: 107768. DOI:10.1016/j.est.2023.107768.
8	WANG Z P, YUAN J, ZHU X Q, et al. Overcharge-to-thermal-runaway behavior and safety assessment of commercial lithium-ion cells with different cathode materials: A comparison study[J]. Journal of Energy Chemistry, 2021, 55: 484-498. DOI:10.1016/j.jechem.2020.07.028.
9	WEI D, ZHANG M Q, ZHU L P, et al. Study on thermal runaway behavior of Li-ion batteries using different abuse methods[J]. Batteries, 2022, 8(11): 201. DOI:10.3390/batteries8110201.
10	WANG K, WU D J, CHANG C Y, et al. Charging rate effect on overcharge-induced thermal runaway characteristics and gas venting behaviors for commercial lithium iron phosphate batteries[J]. Journal of Cleaner Production, 2024, 434: 139992. DOI:10.1016/j.jclepro.2023.139992.
11	KANG R X, JIA C X, ZHAO J L, et al. Effects of capacity on the thermal runaway and gas venting behaviors of large-format lithium iron phosphate batteries induced by overcharge[J]. Journal of Energy Storage, 2024, 87: 111523. DOI:10.1016/j.est.2024.111523.
12	QIU M M, LIU J H, CONG B H, et al. Research progress in thermal runaway vent gas characteristics of Li-ion battery[J]. Batteries, 2023, 9(8): 411. DOI:10.3390/batteries9080411.
13	WANG S P, SONG L F, LI C H, et al. Experimental study of gas production and flame behavior induced by the thermal runaway of 280 Ah lithium iron phosphate battery[J]. Journal of Energy Storage, 2023, 74: 109368. DOI:10.1016/j.est.2023.109368.
14	JIA Z Z, WANG S P, QIN P, et al. Comparative investigation of the thermal runaway and gas venting behaviors of large-format LiFePO4 batteries caused by overcharging and overheating[J]. Journal of Energy Storage, 2023, 61: 106791.
15	WANG Q S, MAO B B, STOLIAROV S I, et al. A review of lithium ion battery failure mechanisms and fire prevention strategies[J]. Progress in Energy and Combustion Science, 2019, 73: 95-131. DOI:10.1016/j.pecs.2019.03.002.
16	QI C, LIU Z Y, LIN C J, et al. The gas production characteristics and catastrophic hazards evaluation of thermal runaway for LiNi_0.5Co_0.2Mn_0.3O₂ lithium-ion batteries under different SOCs[J]. Journal of Energy Storage, 2024, 88: 111678. DOI:10.1016/j.est.2024.111678.
17	XU C S, FAN Z W, ZHANG M Q, et al. A comparative study of the venting gas of lithium-ion batteries during thermal runaway triggered by various methods[J]. Cell Reports Physical Science, 2023, 4(12): 101705. DOI:10.1016/j.xcrp.2023.101705.
18	SHEN H J, WANG H W, LI M H, et al. Thermal runaway characteristics and gas composition analysis of lithium-ion batteries with different LFP and NCM cathode materials under inert atmosphere[J]. Electronics, 2023, 12(7): 1603. DOI:10.3390/electronics12071603.
19	FENG X N, LU L G, OUYANG M G, et al. A 3D thermal runaway propagation model for a large format lithium ion battery module[J]. Energy, 2016, 115: 194-208. DOI:10.1016/j.energy. 2016.08.094.
20	宋来丰, 梅文昕, 贾壮壮, 等. 绝热条件下280 Ah大型磷酸铁锂电池热失控特性分析[J]. 储能科学与技术, 2022, 11(8): 2411-2417. DOI: 10.19799/j.cnki.2095-4239.2022.0349.
	SONG L F, MEI W X, JIA Z Z, et al. Analysis of thermal runaway characteristics of 280 Ah large LiFePO₄ battery under adiabatic conditions[J]. Energy Storage Science and Technology, 2022, 11(8): 2411-2417. DOI: 10.19799/j.cnki.2095-4239.2022.0349.
21	GOLUBKOV A W, FUCHS D, WAGNER J, et al. Thermal-runaway experiments on consumer Li-ion batteries with metal-oxide and olivin-type cathodes[J]. RSC Advances, 2014, 4(7): 3633-3642. DOI:10.1039/C3RA45748F.
22	LIAO Z H, ZHANG S, ZHAO Y K, et al. Experimental evaluation of thermolysis-driven gas emissions from LiPF₆-carbonate electrolyte used in lithium-ion batteries[J]. Journal of Energy Chemistry, 2020, 49: 124-135. DOI:10.1016/j.jechem. 2020. 01.030.
23	KONG W H, LI H, HUANG X J, et al. Gas evolution behaviors for several cathode materials in lithium-ion batteries[J]. Journal of Power Sources, 2005, 142(1/2): 285-291. DOI:10.1016/j.jpowsour.2004.10.008.
24	ZOU K Y, HE K, LU S X. Venting composition and rate of large-format LiNi_0.8Co_0.1Mn_0.1O₂ pouch power battery during thermal runaway[J]. International Journal of Heat and Mass Transfer, 2022, 195: 123133. DOI:10.1016/j.ijheatmasstransfer. 2022. 123133.
25	WANG Q S, JIANG L H, YU Y, et al. Progress of enhancing the safety of lithium ion battery from the electrolyte aspect[J]. Nano Energy, 2019, 55: 93-114. DOI:10.1016/j.nanoen.2018.10.035.
26	DIAZ F, WANG Y, WEYHE R, et al. Gas generation measurement and evaluation during mechanical processing and thermal treatment of spent Li-ion batteries[J]. Waste Management, 2019, 84: 102-111. DOI:10.1016/j.wasman.2018.11.029.
27	XU L J, WANG S L, LI Y T, et al. Thermal runaway propagation behavior and gas production characteristics of NCM622 battery modules at different state of charge[J]. Process Safety and Environmental Protection, 2024, 185: 267-276. DOI:10.1016/j.psep.2024.03.011.
28	ZHANG Q S, NIU J H, ZHAO Z H, et al. Research on the effect of thermal runaway gas components and explosion limits of lithium-ion batteries under different charge states[J]. Journal of Energy Storage, 2022, 45: 103759. DOI:10.1016/j.est.2021.103759.

名称	参数
正极	LFP
负极	石墨
尺寸/mm	316.8×120.9×21.9
类型	软包
容量/Ah	100
标准电压/V	3.2
充放电平台/V	2.5～3.6
比热容/[kJ/(kg·K)]	980
热导率/[W/(m·K)]	X/Y/Z：20/20/0.6

SOC	T_onset/℃	T_max/℃	(dT/dt)_max/(℃/s)
40%	166.2	236.1	2.2
60%	162.9	291.3	8.3
80%	174.2	387.3	64.9
100%	162.8	422.8	78.9

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