绝热条件下280 Ah大型磷酸铁锂电池热失控特性分析

doi:10.19799/j.cnki.2095-4239.2022.0349

摘要/Abstract

摘要：

随着新能源产业的快速发展，锂离子电池在储能领域得到广泛应用。为了更好地防控储能电站火灾爆炸事故，需要对储能用磷酸铁锂电池的热失控特性进行更加深入的研究。本工作使用280 Ah磷酸铁锂电池进行绝热条件下电池热失控实验，得到自产热温度T₁为70.26 ℃、热失控触发温度T₂为200.65 ℃、热失控最高温度为340.72 ℃，热失控过程中出现两个温升速率峰值分别为3.59 ℃/s和1.28 ℃/s。同时定量分析了电池自产热阶段的动力学参数，电池热失控过程中释放的总热量为1511 kJ。最后分析了电池在绝热环境中破裂损坏的原因，是由于内部压力过大，反应较为剧烈所导致的。本工作研究内容弥补了280 Ah大型磷酸铁锂电池绝热条件下电池热失控特性研究的空白，对储能电站火灾爆炸事故具有理论指导意义。

关键词: 磷酸铁锂电池, 热失控, 绝热环境, 温度特征参数, 动力学参数

Abstract:

With the rapid development of the new energy industry, lithium-ion batteries are extensively used in the energy storage field. To better prevent and control fire and explosion accidents in energy storage stations, the thermal runaway characteristic of lithium iron phosphate batteries for energy storage requires to be examined more thoroughly. In this study, under adiabatic conditions 280 Ah lithium iron phosphate battery thermal runaway experiment was performed, and the self-generated thermal temperature T₁ was 70.26 ℃, the thermal runaway trigger temperature T₂ was 200.65 ℃, and the maximum thermal runaway temperature was 340.72 ℃. Two temperature rise rate peaks of 3.59 ℃/s and 1.28 ℃/s occurred during the thermal runaway process. Meanwhile, the kinetic parameters of the battery were also quantified in the self-generated thermal phase, and the total heat released during the thermal runaway of the battery was 1511 kJ. Finally, the study analyzed the causes of battery rupture and damage in the adiabatic environment that was due to the high internal pressure and violent reaction. The research content of this study compensated the gap in the study of thermal runaway characteristics of 280 Ah large lithium iron phosphate battery under adiabatic conditions and has theoretical guidance importance for fire and explosion accidents in energy storage stations.

Key words: lithium iron phosphate battery, thermal runaway, adiabatic environment, temperature characteristic parameters, kinetic parameters

中图分类号:

TM 911

宋来丰, 梅文昕, 贾壮壮, 王青松. 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.

Laifeng SONG, Wenxin MEI, Zhuangzhuang JIA, Qingsong WANG. 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.

图/表 11

图1

表1

图2

图3

表2

图4

表3

图5

图6

表4

280 Ah磷酸铁锂电池自产热阶段的动力学参数表"

阶段	SOC	质量/kg	E_a/eV	A/min^-1	$Δ T a d$ /℃
阶段二	100%	5435	0.254	38.038	46.79

表4

图7

参考文献 19

1	WANG F, HARINDINTWALI J D, YUAN Z Z, et al. Technologies and perspectives for achieving carbon neutrality[J]. The Innovation, 2021, 2(4): doi: 10.1016/j.xinn.2021.100180.
2	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.
3	WANG H B, XU H, ZHAO Z Y, et al. An experimental analysis on thermal runaway and its propagation in Cell-to-Pack lithium-ion batteries[J]. Applied Thermal Engineering, 2022, 211: doi: 10.1016/j.applthermaleng.2022.118418.
4	李建林, 王剑波, 葛乐, 等. 电化学储能电站群在特高压交直流混联受端电网应用技术研究综述[J]. 高电压技术, 2020, 46(1): 51-61.
	LI J L, WANG J B, GE L, et al. Review on application technology of electrochemical energy storage power station group in ultra high voltage AC/DC hybrid receiver power grid[J]. High Voltage Engineering, 2020, 46(1): 51-61.
5	YUAN L M, DUBANIEWICZ T, ZLOCHOWER I, et al. Experimental study on thermal runaway and vented gases of lithium-ion cells[J]. Process Safety and Environmental Protection, 2020, 144: 186-192.
6	PEREA A, PAOLELLA A, DUBÉ J, et al. State of charge influence on thermal reactions and abuse tests in commercial lithium-ion cells[J]. Journal of Power Sources, 2018, 399: 392-397.
7	LEI B X, ZIEBERT C, ZHAO W J, et al. Experimental analysis of thermal runaway in 18650 cylindrical Li-ion cells using an accelerating rate calorimeter[J]. Batteries. 2017, 3(4): doi: 10.3390/batteries3020014.
8	LIU P J, LI Y Q, MAO B B, et al. Experimental study on thermal runaway and fire behaviors of large format lithium iron phosphate battery[J]. Applied Thermal Engineering, 2021, 192: doi: 10.1016/j.applthermaleng.2021.116949.
9	LIU P J, LIU C Q, YANG K, et al. Thermal runaway and fire behaviors of lithium iron phosphate battery induced by over heating[J]. Journal of Energy Storage, 2020, 31: doi: 10.1016/j.est.2020.101714.
10	黄峥, 秦鹏, 石晗, 等. 过热条件下86 Ah磷酸铁锂电池热失控行为研究[J]. 高电压技术, 2022, 48(3): 1185-1191.
	HUANG Z, QIN P, SHI H, et al. Study on thermal runaway behavior of 86 Ah lithium iron phosphate battery under overheat condition[J]. High Voltage Engineering, 2022, 48(3): 1185-1191.
11	QIN P, JIA Z Z, WU J Y, et al. The thermal runaway analysis on LiFePO₄ electrical energy storage packs with different venting areas and void volumes[J]. Applied Energy, 2022, 313: doi: 10.1016/j.apenergy.2022.118767.
12	LI H, DUAN Q L, ZHAO C P, et al. Experimental investigation on the thermal runaway and its propagation in the large format battery module with Li(Ni_1/3Co_1/3Mn_1/3)O₂ as cathode[J]. Journal of Hazardous Materials, 2019, 375: 241-254.
13	王莉, 冯旭宁, 薛钢, 等. 锂离子电池安全性评估的ARC测试方法和数据分析[J]. 储能科学与技术, 2018, 7(6): 1261-1270.
	WANG L, FENG X N, XUE G, et al. ARC experimental and data analysis for safety evaluation of Li-ion batteries[J]. Energy Storage Science and Technology, 2018, 7(6): 1261-1270.
14	FENG X N, ZHENG S Q, REN D S, et al. Investigating the thermal runaway mechanisms of lithium-ion batteries based on thermal analysis database[J]. Applied Energy, 2019, 246: 53-64.
15	HUANG Z H, LI X, WANG Q S, et al. Experimental investigation on thermal runaway propagation of large format lithium ion battery modules with two cathodes[J]. International Journal of Heat and Mass Transfer, 2021, 172: doi: 10.1016/j.ijheatmasstransfer.2021.121077.
16	JIA Z Z, QIN P, LI Z, et al. Analysis of gas release during the process of thermal runaway of lithium-ion batteries with three different cathode materials[J]. Journal of Energy Storage, 2022, 50: doi: 10.1016/j.est.2022.104302.
17	QIN P, SUN J H, WANG Q S. A new method to explore thermal and venting behavior of lithium-ion battery thermal runaway[J]. Journal of Power Sources, 2021, 486: doi: 10.1016/j.jpowsour.2020.229357.
18	BUGRYNIEC P J, DAVIDSON J N, CUMMING D J, et al. Pursuing safer batteries: Thermal abuse of LiFePO₄ cells[J]. Journal of Power Sources, 2019, 414: 557-568.
19	XIANG H F, WANG H, CHEN C H, et al. Thermal stability of LiPF₆-based electrolyte and effect of contact with various delithiated cathodes of Li-ion batteries[J]. Journal of Power Sources, 2009, 191(2): 575-581.

参数	单位	数值
几何尺寸	mm	173.7(宽)×72(厚)×207.5(高)
容量	Ah	280
质量	g	5435
标称电压	V	3.2
充放电电压	V	2.5～3.65
荷电状态	—	100%
比热容	J/(kg·℃)	1029.49
密度	kg/m³	2118
导热系数	W/(m·℃)	X/Y/Z：21.63/21.63/2.11

参数	数值及单位
开始温度	50 ℃
结束温度	300 ℃
温度步长	5 ℃
温度检测阈值	0.02 ℃/min

参考文献	电池型号	容量	实验方式	T₁	T₂	T₃
Yuan等^[5]	26650	3.8 Ah	ARC	200 ℃	—	399 ℃
Perea等^[6]	26650	3 Ah	ARC	100.2 ℃	—	455 ℃
Lei等^[7]	18650	1.1 Ah	ARC	90 ℃	—	259 ℃
Jia等^[16]	26700	4 Ah	ARC	129.85 ℃	196.85 ℃	360.85 ℃
Liu等^[8]	方形	243 Ah	面加热	—	188.4 ℃	492.1 ℃
Liu等^[9]	方形	22 Ah	面加热	—	184.4 ℃	398.3 ℃
本研究	方形	280 Ah	ARC	70.62 ℃	200.65 ℃	340.72 ℃

[1]	尹涛, 贾隆舟, 常修亮, 戴作强, 郑莉莉. 软包磷酸铁锂电池高电压浮充后热安全研究[J]. 储能科学与技术, 2022, 11(8): 2546-2555.
[2]	王洋, 卢旭, 张宇新, 刘龙. 动力电池热失控排气策略[J]. 储能科学与技术, 2022, 11(8): 2480-2487.
[3]	张青松, 赵洋, 刘添添. 荷电状态和电池排列对锂离子电池热失控传播的影响[J]. 储能科学与技术, 2022, 11(8): 2519-2525.
[4]	喻航, 张英, 徐超航, 余思瀚. 锂电储能系统热失控防控技术研究进展[J]. 储能科学与技术, 2022, 11(8): 2653-2663.
[5]	许磊, 刘晓鹏, 王勇俞. 全尺寸预制舱式储能柜热失控早期征兆分析[J]. 储能科学与技术, 2022, 11(8): 2463-2470.
[6]	石爽, 吕娜伟, 马敬轩, 尹康涌, 孙磊, 张宁, 金阳. 不同类型气体探测对磷酸铁锂电池储能舱过充安全预警有效性对比[J]. 储能科学与技术, 2022, 11(8): 2452-2462.
[7]	蔡兴初, 朱一鸣, 姜可尚, 席旭峰, 张艺超, 林惟实. 全氟己酮气体灭火系统在磷酸铁锂电池储能预制舱的应用[J]. 储能科学与技术, 2022, 11(8): 2497-2504.
[8]	卓萍, 朱艳丽, 齐创, 王聪杰, 高飞. 锂离子电池组过充燃烧爆炸特性[J]. 储能科学与技术, 2022, 11(8): 2471-2479.
[9]	陆剑心, 张英, 马出原, 邓康, 雷春英. 水凝胶对磷酸铁锂电池灭火实验性能[J]. 储能科学与技术, 2022, 11(8): 2637-2644.
[10]	张越, 孔得朋, 平平. 液冷板抑制锂离子电池组热失控蔓延性能及优化设计[J]. 储能科学与技术, 2022, 11(8): 2432-2441.
[11]	徐成善, 鲁博瑞, 张梦启, 王淮斌, 金昌勇, 欧阳明高, 冯旭宁. 储能锂离子电池预制舱热失控烟气流动研究[J]. 储能科学与技术, 2022, 11(8): 2418-2431.
[12]	张肖洒, 王宏源, 李振彪, 夏志美. 废旧磷酸铁锂电池电极材料的硫酸化焙烧-水浸新工艺[J]. 储能科学与技术, 2022, 11(7): 2066-2074.
[13]	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.
[14]	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.
[15]	李磊, 李钊, 姬丹, 牛慧昌. 过充电触发的LFP和NCM锂离子电池的热失控行为：差异与原因[J]. 储能科学与技术, 2022, 11(5): 1419-1427.