基于三维电化学热耦合析锂模型的锂离子电池参数设计

doi:10.19799/j.cnki.2095-4239.2022.0225

储能科学与技术 ›› 2022, Vol. 11 ›› Issue (8): 2600-2611.doi: 10.19799/j.cnki.2095-4239.2022.0225

基于三维电化学热耦合析锂模型的锂离子电池参数设计

马勇¹(), 李晓涵¹, 孙磊¹, 郭东亮¹, 杨景刚¹, 刘建军¹, 肖鹏¹, 钱广俊²()

^1.国网江苏省电力有限公司电力科学研究院，江苏南京 211103
^2.清华大学汽车安全与节能国家重点实验室，北京 100084

收稿日期:2022-04-25 修回日期:2022-05-14 出版日期:2022-08-05 发布日期:2022-08-03
通讯作者: 钱广俊 E-mail:ma.y@foxmail.com;qguangjun@163.com
作者简介:马勇（1986—），男，硕士，研究方向为电力系统输变电设备状态评估技术，E-mail：ma.y@foxmail.com；
基金资助:
国网江苏省电力有限公司“电动汽车动力电池状态检测与安全评估技术研究”项目(J2021042)

Parameter design of lithium-ion batteries based on a three-dimensional electrochemical thermal coupling lithium precipitation model

Yong MA¹(), Xiaohan LI¹, Lei SUN¹, Dongliang GUO¹, Jinggang YANG¹, Jianjun LIU¹, Peng XIAO¹, Guangjun QIAN²()

^1.State Grid Jiangsu Electric Power Co. , Ltd. Research Institute, Nanjing 211103, Jiangsu, China
^2.State Key Laboratory of Automotive Safety and Energy, Tsinghua University, Beijing 100084, China

Received:2022-04-25 Revised:2022-05-14 Online:2022-08-05 Published:2022-08-03
Contact: Guangjun QIAN E-mail:ma.y@foxmail.com;qguangjun@163.com

摘要/Abstract

摘要：

锂离子电池负极析锂可能会诱发热失控，进而导致安全事故。而通过优化电池设计参数能够有效减少析锂副反应的发生，因此本工作提出一种基于三维电化学热耦合析锂模型的锂离子电池参数设计优化方法。首先，将模型参数进行分类，分别采用实验、精确测量、文献查找和参数辨识等方法获取相应的参数。同时加入可逆锂重嵌入机制和产热模型，建立三维电化学热耦合析锂模型。模型建立完成后，对模型精度进行验证，验证结果表明模型可以较好地模拟电池在常温和低温下端电压的变化，并且能够定量描述在低温大倍率充电期间电池内部的析锂程度、温度分布等非均一现象。最后，通过分析电极尺寸和极耳位置，研究电池设计参数对非均一析锂的影响。仿真结果表明：电极长度增加会导致电极区域温度差异和电流密度的不一致性增大，综合影响下使电池析锂时间略有提前，但对电池总体析锂程度影响较小；电池极耳位置处于长度方向的轴线对侧时能够有效缓解负极析锂，相对析锂程度降低了16.7%。

关键词: 锂离子电池, 三维电化学热耦合, 重嵌入机制, 析锂模型

Abstract:

Lithium deposition on the negative electrode of lithium-ion batteries may induce thermal runaway that can lead to safety accidents. The occurrence of lithium precipitation side reactions can be reduced effectively by optimizing the battery design parameters. Therefore, this study proposes a parameter design optimization method for lithium-ion batteries based on a three-dimensional electrochemical, thermal coupled lithium precipitation model. First, the model parameters were classified, and the corresponding parameters were obtained using experiments, exact measurements, literature searches, and parameter identification, respectively. The reversible lithium re-embedding mechanism and heat production model were added to establish a three-dimensional electrochemical, thermal coupling lithium precipitation model. After constructing the model, the accuracy of the model was verified. The verification results showed that the model could simulate the changes in the terminal voltage of the battery at room temperature and low temperature and could quantitatively describe the nonhomogeneous phenomena, such as the degree of lithium precipitation and temperature distribution inside the battery during low temperature large rate charging. Finally, the effects of the battery design parameters on nonhomogeneous lithium precipitation were investigated by analyzing the electrode size and lug position. The simulation results showed that increasing the electrode length would increase the temperature difference in the electrode area and the inconsistency of the current density. The combined effect would advance the lithium precipitation time of the battery slightly, but the effect on the overall degree of lithium precipitation of the battery was relatively small. When the position of the battery tab was on the opposite side of the axis in the longitudinal direction, it could effectively alleviate lithium deposition on the negative electrode, and the relative lithium precipitation degree was reduced by 16.7%.

Key words: lithium-ion battery, three-dimensional electrochemical thermal coupling, re-embedding mechanism, lithium precipitation model

中图分类号:

TM 912

马勇, 李晓涵, 孙磊, 郭东亮, 杨景刚, 刘建军, 肖鹏, 钱广俊. 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.

Yong MA, Xiaohan LI, Lei SUN, Dongliang GUO, Jinggang YANG, Jianjun LIU, Peng XIAO, Guangjun QIAN. 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.

图/表 21

表1

电化学热耦合模型参数"

参数	参数意义	单位	负极	隔膜	正极
L	极片厚度	$μ m$	100^①	15^①	51^①
L_cc	集流体厚度	$μ m$	15.3^①	—	9^①
i_1C	1 C倍率下平均电流密度	A/m²	26.67^①
c_s,max	固相颗粒最大嵌锂浓度	mol/m³	25255^②	—	110995^②
x_0/100	负极初始时刻化学计量比	1	0.0073/0.9501^②
y_0/100	正极初始时刻化学计量比	1	0.9329/0.2904^②
A_total	活性物质总反应面积	m²	5.49^①
r_s	固相颗粒半径	$μ m$	12^③	—	10^③
κ_e	液相离子电导率	S/m	$κ e = 1 × 10 - 4 c - 10.5 + 0.074 T - 3.96 × 10 - 5 T 2 + 6.68 × 10 - 4 c - 1.78 × 10 - 5 T + 2.8 × 10 - 8 T 2 + 4.94 × 10 - 7 c 2 - 8.86 × 10 - 10 c 2 T 2$
σ_s	固相电导率	S/m	100^④	—	10^④
ε_e	液相体积分数	1	0.357^③	0.4^③	0.444^③
σ_s^eff	固相有效电导率	S/m	ε_s^1.5σ_s	—	ε_s^1.5σ_s
cl₀	电解质初始盐浓度	mol/m³	1000^③
E_a	活化能	J/mol	21350^⑤	—	20500^⑤
k_ref	参考温度下的反应速率常数	m/s	3e^-11④,⑤	—	4e^-11④,⑤
D_e	液相扩散系数	m²/s		$D e = 1 × 10 - 8.83 - 54 T - 5 × 10 - 3 c - 299 - 2.2 × 10 - 4 c$
D_s,ref	参考温度下的固相扩散系数	m²/s	3.9e^-14④,⑤	—	4.5e^-13④,⑤
T_ref	参考温度	K		298.15
α_a、α_c	传递系数	1	0.5	—	0.5
C_p	比热容	J/(kg·K)		1150^①
h	对流换热系数	W/(m²·K)		22^①
F	法拉第常数	C/mol		96485
R	理想气体常数	J/(mol·K)		8.314

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参考文献 19

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参数	单位	正极		隔膜	负极
参数	单位	NCM	集流体	隔膜	石墨	集流体
比热容C_p	J/(kg·K)	1100	900	1978	881	285
导热系数λ	W/(m·K)	1.58	238	0.344	1.04	400
密度ρ	kg/m³	2628	2700	1108	2270	8960
对流换热系h	W/(m²·K)	大面：1.1 极耳尾部：10

参数	物理意义	单位	负极
α_{a, pl}、α_c,_pl	析锂/锂溶解传递系数	1	0.3、0.7^[19]
k_pl/st	锂析出/溶解反应速率常数	m/s	6.5×10^-6
E_{a, pl/st}	析锂与锂溶解反应活化能	J/mol	50000
z₁、z₂、z₃	可逆锂/不可逆锂/SEI占比	1	0.57、0.375、0.05
σ_SEI	SEI膜电导率	S/m	5×10^-6[19]
δ_SEI	SEI膜t厚度	m	式(10)
ρ_SEI	SEI 膜密度	kg/m³	1690^[19]
ρ_Li	锂金属密度	kg/m³	534^[19]
M_SEI	SEI膜摩尔质量	kg/mol	0.162^[19]
M_Li	锂金属摩尔质量	kg/mol	6.94×10^-3[19]

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基于三维电化学热耦合析锂模型的锂离子电池参数设计

Parameter design of lithium-ion batteries based on a three-dimensional electrochemical thermal coupling lithium precipitation model

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