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

doi:10.19799/j.cnki.2095-4239.2022.0405

Abstract

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

CLC Number:

TM 912

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.

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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