锂离子电池热失控产气特性及其可燃极限

doi:10.19799/j.cnki.2095-4239.2021.0618

摘要/Abstract

摘要：

锂离子电池热失控安全相关问题一直是困扰电动汽车发展的痛点。本文以SOC为50%、100%的某款三元18650锂离子电池为研究对象，通过试验及仿真研究了热失控过程的释放气体可燃极限、火焰传播特性。首先在加速量热仪内进行加热热失控触发实验，记录该过程中电池温度、压力变化，收集热失控过程中产生的混合气体并使用气相色谱仪分析混合气体的具体组分，研究SOC状态对电池热失控产气综合特征的影响。进而，通过仿真模拟了热释放气体在不同初始温度及压力条件下的层流火焰传播速度及可燃极限。结果表明，当热释放气体的初始温度较高时，可燃下限接近10%，具有很高的着火危险性；可燃下限随初始温度的增加线性降低，可燃上限随初始温度的增加线性升高；初始压力改变时，对可燃下限影响不大，可燃上限随压力升高而增大。

关键词: 锂离子电池, 热失控, 电池产气, 可燃极限

Abstract:

The safety problem of thermal runaway of lithium ion battery has always been a pain point for the development of electric vehicles. In this paper, the thermal runaway release gas and its flammability limit and flame propagation characteristics of ternary 18650 lithium-ion battery at SOC of 50% and 100% were studied by experiment and simulation. Firstly, the heating triggered thermal runaway experiment is carried out in the accelerated calorimeter. The vented gas was collected and its components proportion was then detected using the gas chromatograph to study the effect of SOC on the comprehensive characteristics of thermal runaway gas production. The laminar flame speed and flammability limit of heat release gas at different initial temperatures and pressures were simulated. The results show that when the initial temperature of heat release gas is high, the lower flammability limit is close to 10%, which has a high ignition risk; The lower flammability limit decreases linearly with the increase of initial temperature, and the upper flammability limit increases linearly with the increase of initial temperature; When the initial pressure changes, it has little effect on the lower flammability limit, and the upper flammability limit increases with the increase of pressure.

Key words: lithium ion battery, thermal runaway, battery venting gas, flammability limits

中图分类号:

TK 02

马彪, 林春景, 刘磊, 马小乐, 马天翼, 刘仕强. 锂离子电池热失控产气特性及其可燃极限[J]. 储能科学与技术, 2022, 11(5): 1592-1600.

Biao MA, Chunjing LIN, Lei LIU, Xiaole MA, Tianyi MA, Shiqiang LIU. Venting characteristics and flammability limit of thermal runaway gas of lithium ion battery[J]. Energy Storage Science and Technology, 2022, 11(5): 1592-1600.

图/表 13

图1

图2

图3

图4

图5

表1

图6

表2

图7

图8

图9

图10

图11

参考文献 22

1	FENG X N, OUYANG M G, LIU X, et al. Thermal runaway mechanism of lithium ion battery for electric vehicles: A review[J]. Energy Storage Materials, 2018, 10: 246-267.
2	温宏炎, 匡中付, 丁铭奕, 等. 锂离子动力电池市场分析及技术进展[J]. 电池工业, 2020, 24(6): 326-329, 334.
	WEN H Y, KUANG Z F, DING M Y, et al. Lithium-ion power battery market analysis and technological progress[J]. Chinese Battery Industry, 2020, 24(6): 326-329, 334.
3	KARP. Flammability limits of lithium-ion battery thermal runaway vent gas in air and the inerting effects of halon 1301[D]. Rutgers, The State University of New Jersey, 2016: 64.
4	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.
5	王贺武, 张亚军, 李成, 等. 锂离子动力电池中等荷电状态下热失控产物喷发过程[J]. 储能科学与技术, 2019, 8(6): 1076-1081.
	WANG H W, ZHANG Y J, LI C, et al. Venting process of lithium-ion power battery during thermal runaway under medium state of charge[J]. Energy Storage Science and Technology, 2019, 8(6): 1076-1081.
6	崔潇丹, 丛晓民, 赵林双. 锂离子电池热失控气体及燃爆危险性研究进展[J]. 电池, 2021, 51(4): 407-411.
	CUI X D, CONG X M, ZHAO L S. Research progress in thermal runaway gases and explosion hazards of Li-ion battery[J]. Battery Bimonthly, 2021, 51(4): 407-411.
7	郭超超, 张青松. 锂离子电池热解气体爆炸极限测定及其危险性分析[J]. 中国安全生产科学技术, 2016, 12(9): 46-49.
	GUO C C, ZHANG Q S. Determination on explosion limit of pyrolysis gas released by lithium-ion battery and its risk analysis[J]. Journal of Safety Science and Technology, 2016, 12(9): 46-49.
8	LI W F, WANG H W, ZHANG Y J, et al. Flammability characteristics of the battery vent gas: A case of NCA and LFP lithium-ion batteries during external heating abuse[J]. Journal of Energy Storage, 2019, 24: 100775.
9	SOMANDEPALLI V, MARR K, HORN Q. Quantification of combustion hazards of thermal runaway failures in lithium-ion batteries[J]. SAE International Journal of Alternative Powertrains, 2014, 3(1): 98-104.
10	郭志慧, 崔潇丹, 赵林双, 等. 高镍三元锂离子电池火灾及气体爆炸危险性实验[J]. 储能科学与技术, 2022, 11(1): 193-200.
	GUO Z H, CUI X D, ZHAO L S, et al. Fire and gas explosion hazards of high-nickel lithium-ion battery[J]. Energy Storage Science and Technology, 2022, 11(1): 193-200.
11	BAIRD A R, ARCHIBALD E J, MARR K C, et al. Explosion hazards from lithium-ion battery vent gas[J]. Journal of Power Sources, 2020, 446: 227257.
12	MA B, LIU J, YU R G. Study on the flammability limits of lithium-ion battery vent gas under different initial conditions[J]. ACS Omega, 2020, 5(43): 28096-28107.
13	KEE R J, GRCAR J F, SMOOKE M D, et al. PREMIX: a Fortran program for modeling steady laminar one-dimensional premixed flames[R]. Sandia National Laboratories Report, 1985, SAND84-8249.
14	LAW C K, EGOLFOPOULOS F N. A kinetic criterion of flammability limits: The C-H-O-inert system[J]. Symposium (International) on Combustion, 1991, 23(1): 413-421.
15	LAW C K, EGOLFOPOULOS F N. A unified chain-thermal theory of fundamental flammability limits[J]. Symposium (International) on Combustion, 1992, 24(1): 137-144.
16	JU Y G, MASUYA G, RONNEY P D. Effects of radiative emission and absorption on the propagation and extinction of premixed gas flames[J]. Symposium (International) on Combustion, 1998, 27(2): 2619-2626.
17	RUAN J M, KOBAYASHI H, NIIOKA T, et al. Combined effects of nongray radiation and pressure on premixed CH₄/O₂/CO₂ flames[J]. Combustion and Flame, 2001, 124(1/2): 225-230.
18	周镇. 合成气层流预混火焰燃烧特性实验与数值研究[D]. 北京: 中国科学院研究生院(工程热物理研究所), 2013.
	ZHOU Z. Experimental and numerical investigation on laminar combustion characteristics of premixed svn-gas flame[D]. Beijing: Institute of Physics, Chinese Academy of Sciences, 2013.
19	MEHL M, PITZ W J, WESTBROOK C K, et al. Kinetic modeling of gasoline surrogate components and mixtures under engine conditions[J]. Proceedings of the Combustion Institute, 2011, 33(1): 193-200.
20	NISHIOKA M, LAW C K, TAKENO T. A flame-controlling continuation method for generating S-curve responses with detailed chemistry[J]. Combustion and Flame, 1996, 104(3): 328-342.
21	陈莹. 工业火灾与爆炸事故预防[M]. 北京:化学工业出版社, 2010.CHEN Y. Prevention of industrial fire and explosion accidents[M]. Beijing: Chemical Industry Press, 2010.
22	WIERZBA I, WANG Q. The flammability limits of H₂-CO-CH₄ mixtures in air at elevated temperatures[J]. International Journal of Hydrogen Energy, 2006, 31(4): 485-489.

特征参数	1#	2#
SOC	100%	50%
密封罐中气氛	氮气	氮气
热失控电池最高温度T_max/℃	586.840	615.181
加热开始至热失控时间∆t_max/min	100.493	102.762
瞬时最大气压p/bar	5.516	3.841
瞬时最大产气量/L	6.372	3.794
稳态产气量/L	4.280	2.370
瞬时最大产气速率dV/dt /(L/min)	52.946	8.306
测试前电池质量/g	47.10	46.52
测试后电池质量/g	28.99	32.20
电池质量损失率/%	38.45	30.78

组分	SOC=100%	SOC=50%
H₂	17.611	8.189
CO	26.723	11.231
CO₂	45.241	70.287
CH₄	5.748	4.091
C₂H₄	1.91	2.538
C₃H₆	0.069	0.161

[1]	李海涛, 孔令丽, 张欣, 余传军, 王纪威, 徐琳. N/P设计对高镍NCM/Gr电芯性能的影响[J]. 储能科学与技术, 2022, 11(7): 2040-2045.
[2]	陈龙, 夏权, 任羿, 曹高萍, 邱景义, 张浩. 多物理场耦合下锂离子电池组可靠性研究现状与展望[J]. 储能科学与技术, 2022, 11(7): 2316-2323.
[3]	易顺民, 谢林柏, 彭力. 基于VF-DW-DFN的锂离子电池剩余寿命预测[J]. 储能科学与技术, 2022, 11(7): 2305-2315.
[4]	祝庆伟, 俞小莉, 吴启超, 徐一丹, 陈芬放, 黄瑞. 高能量密度锂离子电池老化半经验模型[J]. 储能科学与技术, 2022, 11(7): 2324-2331.
[5]	王宇作, 王瑨, 卢颖莉, 阮殿波. 孔结构对软碳负极储锂性能的影响[J]. 储能科学与技术, 2022, 11(7): 2023-2029.
[6]	孔为, 金劲涛, 陆西坡, 孙洋. 对称蛇形流道锂离子电池冷却性能[J]. 储能科学与技术, 2022, 11(7): 2258-2265.
[7]	霍思达, 薛文东, 李新丽, 李勇. 基于CiteSpace知识图谱的锂电池复合电解质可视化分析[J]. 储能科学与技术, 2022, 11(7): 2103-2113.
[8]	邓健想, 赵金良, 黄成德. 高能量锂离子电池硅基负极黏结剂研究进展[J]. 储能科学与技术, 2022, 11(7): 2092-2102.
[9]	刘显茜, 孙安梁, 田川. 基于仿生翅脉流道冷板的锂离子电池组液冷散热[J]. 储能科学与技术, 2022, 11(7): 2266-2273.
[10]	于春辉, 何姿颖, 张晨曦, 林贤清, 肖哲熙, 魏飞. 硅基负极与电解液化学反应的分析与抑制策略[J]. 储能科学与技术, 2022, 11(6): 1749-1759.
[11]	丁奕, 杨艳, 陈锴, 曾涛, 黄云辉. 锂离子电池智能消防及其研究方法[J]. 储能科学与技术, 2022, 11(6): 1822-1833.
[12]	张言, 王海, 刘朝孟, 张德柳, 王佳东, 李建中, 高宣雯, 骆文彬. 锂离子电池富镍三元正极材料NCM的研究进展[J]. 储能科学与技术, 2022, 11(6): 1693-1705.
[13]	欧宇, 侯文会, 刘凯. 锂离子电池中的智能安全电解液研究进展[J]. 储能科学与技术, 2022, 11(6): 1772-1787.
[14]	韩俊伟, 肖菁, 陶莹, 孔德斌, 吕伟, 杨全红. 致密储能：基于石墨烯的方法学和应用实例[J]. 储能科学与技术, 2022, 11(6): 1865-1873.
[15]	辛耀达, 李娜, 杨乐, 宋维力, 孙磊, 陈浩森, 方岱宁. 锂离子电池植入传感技术[J]. 储能科学与技术, 2022, 11(6): 1834-1846.