过充循环对锂离子电池容量衰减及安全性影响

doi:10.19799/j.cnki.2095-4239.2022.0405

储能科学与技术 ›› 2022, Vol. 11 ›› Issue (12): 3978-3986.doi: 10.19799/j.cnki.2095-4239.2022.0405

过充循环对锂离子电池容量衰减及安全性影响

许卓¹^,²^,³(), 李希超¹^,²^,³, 贾隆舟¹^,²^,³, 陈兵¹^,²^,³, 戴作强¹^,²^,³(), 郑莉莉¹^,²^,³

^1.青岛大学机电工程学院
^2.青岛大学动力集成及储能系统工程技术中心
^3.电动汽车智能化动力集成技术国家地方联合工程技术中心（青岛），山东青岛　266071

收稿日期:2022-07-18 修回日期:2022-08-23 出版日期:2022-12-05 发布日期:2022-12-29
通讯作者: 戴作强 E-mail:xuzhuoxz@163.com;daizuoqiangqdu@163.com
作者简介:许卓（1998—），女，硕士研究生，主要研究方向为新能源电动汽车，E-mail：xuzhuoxz@163.com；
基金资助:
电动汽车储电系统电（储能电池）-电（动力电池/超级电容）耦合成组技术研究(40518060027)

Effect of overcharge cycle on capacity attenuation and safety of lithium-ion batteries

Zhuo XU¹^,²^,³(), Xichao LI¹^,²^,³, Longzhou JIA¹^,²^,³, Bing CHEN¹^,²^,³, Zuoqiang DAI¹^,²^,³(), Lili ZHENG¹^,²^,³

^1.College of Mechanical and Electrical Engineering
^2.Engineering Technology Center of Power Integration and Energy Storage System, Qingdao University
^3.National and Local Joint Engineering Technology Center for Intelligent Power Integration Technology for Electric Vehicles (Qingdao), Qingdao 266071, Shandong, China

Received:2022-07-18 Revised:2022-08-23 Online:2022-12-05 Published:2022-12-29
Contact: Zuoqiang DAI E-mail:xuzhuoxz@163.com;daizuoqiangqdu@163.com

摘要/Abstract

摘要：

随着能源问题的出现，锂离子电池已成为人们关注的热点。本工作以18650型NCM811锂离子电池为研究对象，将电池过充至3个不同的截止电压(4.3 V、4.4 V、4.5 V)并循环一定的次数(180次)直到电池容量大幅度衰减，基于测试分析4.5 V过充循环电池的交流阻抗谱和容量增量曲线来定性和定量地研究电池容量衰减机理。研究发现活性锂离子的损失和活性材料的损失是电池容量衰减的主要原因，电池电导率的损失对电池容量衰减影响不大。通过绝热加速量热仪(adiabatic rate calorimeter，ARC)研究新电池，4.3 V、4.4 V和4.5 V过充循环电池在100% SOC下的热失控特征参数(自产热起始温度T₁、热失控触发温度T₂、热失控最高温度T₃)。发现在热失控发生过程中，电池达到相同的温度时，4个电池的温升速率大小分别是新电池<4.3 V过充循环电池<4.4 V过充循环电池<4.5 V过充循环电池。电池在经过过充循环之后热稳定性变差。过充循环后，电池的自产热起始温度降低、热失控触发温度降低。

关键词: 锂离子电池, 过充循环, 电化学阻抗谱, 热失控

Abstract:

Lithium-ion batteries have become a hot spot with the emergence of energy problems. This study takes the 18650 NCM811 lithium-ion battery as the research object. It overcharges the battery to three different cut-off voltages (4.3 V, 4.4 V, and 4.5 V) and cycles it several times (180 times) until the battery capacity decays significantly. The test and analysis of the 4.5 V overcharged circulating battery's AC impedance spectrum and capacity increment curve reveal the mechanism of battery capacity decay, which is studied both qualitatively and quantitatively. It was discovered that the main cause of battery capacity attenuation is the loss of active lithium ions and active materials, whereas the loss of battery conductivity has little effect. The thermal runaway characteristic parameters (self-heating starting temperature T₁, thermal runaway triggering temperature T₂, maximum thermal runaway temperature T₃) of new batteries, 4.3 V, 4.4 V, and 4.5 V, overcharged circulating batteries at 100% SOC, which was investigated by adiabatic rate calorimeter. It was found that in the thermal runaway process when the battery reached the same temperature, the temperature rise rates of the four batteries were new battery<4.3 V overcharge cycle battery<4.4 V overcharge cycle battery<4.5 V overcharge cycle battery, respectively. The thermal stability of the battery becomes worse after the overcharge cycle. After the overcharge cycle, the starting temperature of the self-generated heat of the battery decreases. In addition, the trigger temperature of the thermal runaway decreases.

Key words: lithium ion battery, overcharge cycling, electrochemical impedance spectroscopy, thermal runaway

中图分类号:

TM 912

许卓, 李希超, 贾隆舟, 陈兵, 戴作强, 郑莉莉. 过充循环对锂离子电池容量衰减及安全性影响[J]. 储能科学与技术, 2022, 11(12): 3978-3986.

Zhuo XU, Xichao LI, Longzhou JIA, Bing CHEN, Zuoqiang DAI, Lili ZHENG. Effect of overcharge cycle on capacity attenuation and safety of lithium-ion batteries[J]. Energy Storage Science and Technology, 2022, 11(12): 3978-3986.

图/表 12

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组件	相关衰退模式	潜在老化机理
R_b	电导率损失(CL)	集流体腐蚀、黏结剂分解
R_SEI&R_ct	活性锂离子损失(LLI)	电解液分解、电解液氧化、锂电镀、锂颗粒的形成、溶剂共嵌
R_W	活性材料损失(LAM)	电极分解、电解液氧化、插入梯度活跃应变粒子、锂颗粒的形成、晶体结构无序化、过渡金属溶解

参数	参数性质
正极	Li(Ni_0.8Co_0.1Mn_0.1)O₂
负极	石墨
隔膜	PP/PE
电解液	LiPF₆/DMC∶EC∶EMC=1∶1∶1
工作电压	2.75～4.2 V
额定容量	2.9 Ah
最大放电倍率	2 C

工步序号	工步名称	参数设置
1	放电	0.5 C恒流放电至电压≤2.75 V
2	静置	静置30 min
3	恒流充电	0.5 C恒流充电至4.3 V、4.4 V、4.5 V
4	恒压充电	恒压充电至电流≤0.05 C
5	静置	静置30 min
6	循环	工步1～5循环

参数	参数设置
试验开始温度	60 ℃
初次标定时间	120 min
温升台阶	5 ℃
自产热判断依据	0.03 ℃/min
试验截至温度	300 ℃

参数	新电池	4.3 V过充循环电池	4.4 V过充循环电池	4.5 V过充循环电池
T₁/℃	78.62	75.44	76.06	73.76
T₂/℃	241.42	229.91	237.54	222.72
T₃/℃	512.26	517.23	656.79	656.30
T₄/℃	195.93	178.71	180.89	183.59
T₅/℃	208.97	199.78	201.09	199.36
T_d/℃	137.77	132.86	128.39	127.88
试验前质量/g	44.13	44.08	44.21	44.02
试验后质量/g	12.69	14.57	19.85	17.54
减重比/%	71.24	66.75	55.10	60.15

过充循环对锂离子电池容量衰减及安全性影响

Effect of overcharge cycle on capacity attenuation and safety of lithium-ion batteries

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