动力电池老化诱发热失控机理仿真

doi:10.19799/j.cnki.2095-4239.2022.0396

摘要/Abstract

摘要：

近年来，新能源汽车热失控燃烧起火的事故屡见报道，既危及消费者的生命财产安全，又影响了大众对电动汽车的信任与接受度，给新能源汽车市场的推广普及造成严重阻碍。为了从根本上为热失控防治提供有效指导，本文首先依托电池的传热传质，建立了电化学-老化-热失控-热耦合模型。接着，利用有限元软件以三元锂软包电池为对象建立了仿真模型并进行了初步验证。最后，针对以循环次数为表征的电池老化致内短路热失控问题，本文在深入其机理研究的同时，建立仿真模型探究了不同老化程度对电池温升的影响，并设计了“到达副反应阈值温度的快慢”这一无量纲风险指数β，得出了热失控发生的临界风险指数，有助于日常使用过程中热失控的预测与防治。

关键词: 动力电池, 热失控, 老化, 风险指数

Abstract:

Recently, the thermal runaway combustion of new energy vehicles has been reported frequently, which not only endangers the safety of consumers' lives and property but also affects the public's trust and acceptance of electric vehicles, causing severe obstacles to the promotion and popularization of the new energy vehicle market. This study first established an electrochemical-aging-thermal runaway-thermal coupling model based on the heat and mass transfer of the battery to fundamentally provide effective guidance for the prevention and control of thermal runaway. Then, the finite element software was used to establish a simulation model for the ternary lithium soft-packed battery and conduct a preliminary verification. Finally, aiming at the thermal runaway problem of internal short circuits caused by battery aging characterized by cycle times, this paper establishes a simulation model to explore the influence of different aging degrees on the temperature rise of the battery and designs the dimensionless risk index β of "the speed of reaching the threshold temperature of the side reaction" and obtains the critical risk index of thermal runaway, which is helpful for the prediction and prevention of thermal runaway in daily use.

Key words: lithium-ion battery, thermal runaway, aging, risk index

中图分类号:

TM 911

陈桂泉, 沙盈吟, 赵威风, 邓业林. 动力电池老化诱发热失控机理仿真[J]. 储能科学与技术, 2022, 11(12): 3987-3998.

Guiquan CHEN, Yingyin SHA, Weifeng ZHAO, Yelin DENG. Simulation study on the mechanism and process of thermal runaway induced by aging of lithium-ion batteries[J]. Energy Storage Science and Technology, 2022, 11(12): 3987-3998.

图/表 19

图1

图2

图3

表1

电池基本参数"

参数	数值
额定容量	20 Ah
尺寸	130 mm $×$ 40 mm $×$ 2.4 mm
充电限制电压	4.2 V
放电截止电压	2.8 V

表1

表2

表3

表4

副反应计算参数初始值"

参数	初始值	来源
$c S E I$	0.150	文献[23]
$c n e g$	0.750	文献[23]
$z 0$	0.033	文献[23]
$α$	0.040	文献[23]
$c e l e$	1	文献[23]

表4

表5

表6

表7

COMSOL内置函数"

方程	函数
固相导电	$∂ ∂ x σ i e f f ∂ ∂ x ϕ s = j t o t$
固相传质	$∂ c s ∂ t = D s, i r 2 ∂ ∂ r r 2 ∂ c s ∂ r$
液相导电	$∂ ∂ x κ e f f ∂ ∂ x ϕ e = - ∂ ∂ x κ D e f f ∂ ∂ x l n c e - j t o t$
液相传质	$∂ ∂ t ε e, i c e = ∂ ∂ x D e, i e f f ∂ c e ∂ x + 1 - t + j t o t F$
电极-电解液界面反应	$j i n t = a s, i i 0, i e x p α a, i n t F R T η a c t, i n t - e x p α c, i n t F R T η a c t, i n t$

表7

图4

图5

图6

图7

图8

表8

表9

表10

图9

参考文献 26

1	杨茜. 2022年我国汽车市场趋势分析[J]. 汽车纵横, 2022(2): 54-56.
	YANG X. Analysis of my country's auto market trends in 2022[J]. Auto Review, 2022(2): 54-56.
2	FRANZÒ S, FRATTINI F, LATILLA V M, et al. The diffusion of electric vehicles in Italy as a means to tackle main environmental issues[C]//2017 Twelfth International Conference on Ecological Vehicles and Renewable Energies (EVER). Monte Carlo, Monaco. IEEE, : 1-7.
3	WEN J W, YU Y, CHEN C H. A review on lithium-ion batteries safety issues: Existing problems and possible solutions[J]. Materials Express, 2012, 2(3): 197-212.
4	RAMADASS P, FANG W F, ZHANG Z M. Study of internal short in a Li-ion cell I. Test method development using infra-red imaging technique[J]. Journal of Power Sources, 2014, 248: 769-776.
5	ZHAO W, LUO G, WANG C Y. Modeling nail penetration process in large-format Li-ion cells[J]. Journal of the Electrochemical Society, 2014, 162(1): A207-A217.
6	MALEKI H, HOWARD J N. Internal short circuit in Li-ion cells[J]. Journal of Power Sources, 2009, 191(2): 568-574.
7	SPOTNITZ R, FRANKLIN J. Abuse behavior of high-power, lithium-ion cells[J]. Journal of Power Sources, 2003, 113(1): 81-100.
8	ZAVALIS T G, BEHM M, LINDBERGH G. Investigation of short-circuit scenarios in a lithium-ion battery cell[J]. Journal of the Electrochemical Society, 2012, 159(6): A848-A859.
9	COMAN P T, DARCY E C, VEJE C T, et al. Modelling Li-ion cell thermal runaway triggered by an internal short circuit device using an efficiency factor and Arrhenius formulations[J]. Journal of the Electrochemical Society, 2017, 164(4): A587-A593.
10	WANG S R, LU L L, LIU X J. A simulation on safety of LiFePO₄/C cell using electrochemical-thermal coupling model[J]. Journal of Power Sources, 2013, 244: 101-108.
11	陈芬放. 高能量密度NCA正极锂离子电池老化过程产热特性研究[D]. 杭州: 浙江大学, 2021.
	CHEN F F. Study on the heat generation characteristics of high-specific-energy lithium ion batteries with NCA cathode during aging[D]. Hangzhou: Zhejiang University, 2021.
12	JIN X. Aging-Aware optimal charging strategy for lithium-ion batteries: Considering aging status and electro-thermal-aging dynamics[J]. Electrochimica Acta, 2022, 407: doi:10.1016/j.electacta.2021.139651.
13	XIONG R, PAN Y, SHEN W X, et al. Lithium-ion battery aging mechanisms and diagnosis method for automotive applications: Recent advances and perspectives[J]. Renewable and Sustainable Energy Reviews, 2020, 131: doi:10.1016/j.rser.2020.110048.
14	REN D S, HSU H, LI R H, et al. A comparative investigation of aging effects on thermal runaway behavior of lithium-ion batteries[J]. eTransportation, 2019, 2: doi: 10.1016/j.etran.2019.100034.
15	YUAN W, LIANG D, CHU Y Y, et al. Aging effect delays overcharge-induced thermal runaway of lithium-ion batteries[J]. Journal of Loss Prevention in the Process Industries, 2022, 79: doi: 10.1016/j.jlp.2022.104830.
16	ABADA S, PETIT M, LECOCQ A, et al. Combined experimental and modeling approaches of the thermal runaway of fresh and aged lithium-ion batteries[J]. Journal of Power Sources, 2018, 399: 264-273.
17	YANG M J, YE Y J, YANG A J, et al. Comparative study on aging and thermal runaway of commercial LiFePO₄/graphite battery undergoing slight overcharge cycling[J]. Journal of Energy Storage, 2022, 50: doi: 10.1016/j.est.2022.104691.
18	LIU J L, WANG Z R, BAI J L, et al. Heat generation and thermal runaway mechanisms induced by overcharging of aged lithium-ion battery[J]. Applied Thermal Engineering, 2022, 212: doi: 10.1016/j.applthermaleng.2022.118565.
19	黄文才. 基于COMSOL的锂离子电池热失控模拟分析和研究[D]. 成都: 西南交通大学, 2019.
	HUANG W C. Simulation and research on thermal runaway of lithium ion battery based on COMSOL[D]. Chengdu: Southwest Jiaotong University, 2019.
20	SAITO Y. Thermal behaviors of lithium-ion batteries during high-rate pulse cycling[J]. Journal of Power Sources, 2005, 146(1/2): 770-774.
21	庞辉. 基于电化学模型的锂离子电池多尺度建模及其简化方法[J]. 物理学报, 2017, 66(23): 312-322.
	PANG H. Multi-scale modeling and its simplification method of Li-ion battery based on electrochemical model[J]. Acta Physica Sinica, 2017, 66(23): 312-322.
22	DOYLE M, FULLER T F, NEWMAN J. Modeling of galvanostatic charge and discharge of the lithium/polymer/insertion cell[J]. Journal of the Electrochemical Society, 1993, 140(6): 1526-1533.
23	陶欢. 锂离子动力电池热失控实验与模拟研究[D]. 武汉: 华中科技大学, 2017.
	TAO H. Experimental and simulation study on thermal runaway of lithium-ion battery[D]. Wuhan: Huazhong University of Science and Technology, 2017.
24	张明轩, 冯旭宁, 欧阳明高, 等. 三元锂离子动力电池针刺热失控实验与建模[J]. 汽车工程, 2015, 37(7): 743-750, 756.
	ZHANG M X, FENG X N, OUYANG M G, et al. Experiments and modeling of nail penetration thermal runaway in a NCM Li-ion power battery[J]. Automotive Engineering, 2015, 37(7): 743-750, 756.
25	马勇, 李晓涵, 孙磊, 等. 基于三维电化学热耦合析锂模型的锂离子电池参数设计[J]. 储能科学与技术, 2022, 11(8): 2600-2611.
	MA Y, LI X H, SUN L, et al. Parameter design of lithium-ion batteries based on a three-dimensional electrochemical thermal coupling lithium precipitation model[J]. Energy Storage Science and Technology, 2022, 11(8): 2600-2611.
26	王远. 锂离子电池用聚乙烯隔膜改性及其性能研究[D]. 南昌: 南昌大学, 2020.
	WANG Y. Study on the properties of the modified polyethylene membrane for lithium-ion battery[D]. Nanchang: Nanchang University, 2020.

参数	铝	正极	隔膜	负极	铜	来源
布鲁格曼曲折指数	—	2.98	2.15	2.5	—	文献[19]
电解质初始浓度/(mol/m³)	—	—	1200	—	—	文献[19]
最大负极容量/(mol/m³)	—	49000	—	31507	—	文献[19]
初始Li⁺浓度/(mol/m³)	—	4900	—	29932	—	COMSOL内置材料
电解质相体积分数	—	0.40	0.6	0.3	—	文献[19]
电极相体积分数	—	0.53	—	0.7	—	文献[19]
厚度/μm	8	85	20	11	8	文献[19]
粒子半径/μm	—	2.50	—	2.5	—	文献[19]
电导率/(S/m)	3.77×10⁷	—	100	—	6.4×10⁷	文献[19]
扩散系数/(m²/s)	—	5×10^-13	—	1.45×10^-13	—	文献[19]
密度/(kg/m³)	2700	2328.5	492.16	1347.33	8960	文献[19]
比热容c_p /[J/(kg·K)]	900	1269.21	1978.16	1437.4	385	文献[19]
导热系数/[W/(m·K)]	238	1.58	0.344	1.04	400	文献[19]

参数	SEI膜	负极-电解液	正极-电解液	电解液	来源
频率因子A/(1/s)	1.7×10¹⁵	2.5×10¹³	6.7×10¹³	5.14×10²⁵	文献[24]
活化能E_a/(J/mol)	1.4×10⁵	1.4×10⁵	1.4×10⁵	2.7×10⁵	文献[24]
放热量H/(J/kg)	2.57×10⁵	1.7×10⁶	3.15×10⁵	1.6×10⁵	文献[24]
材料密度W/(kg/m³)	6.1×10²	6.1×10²	9.25×10²	5×10²	文献[24]

反应类别	反应起始温度/℃	来源
SEI膜分解	80	文献[24]
负极-电解液反应	120	文献[24]
正极-电解液反应	200	文献[24]
电解液分解	250	文献[24]

参数	数值	来源
膜电导率/(S/m)	5×10^-6	文献[11]
摩尔质量/(kg/mol)	0.07388	文献[11]
密度/(kg/m³)	2110	文献[11]
参考膜厚/m	1×10^-9	文献[11]

循环次数	β
1000	1.12
1250	1.34
1500	1.57
1750	1.79
2000	1.92