锂离子电池微过充循环老化特性与失效机理研究

doi:10.19799/j.cnki.2095-4239.2024.0256

储能科学与技术 ›› 2024, Vol. 13 ›› Issue (10): 3343-3356.doi: 10.19799/j.cnki.2095-4239.2024.0256

锂离子电池微过充循环老化特性与失效机理研究

闵越明¹^,²(), 张闯¹^,², 刘文杰¹^,², 刘素贞¹^,², 徐志成¹^,²()

^1.河北工业大学省部共建电工装备可靠性与智能化国家重点实验室，天津 300401
^2.河北工业大学河北省电磁场与电器可靠性重点实验室，天津 300401

收稿日期:2024-03-22 修回日期:2024-04-18 出版日期:2024-10-28 发布日期:2024-10-30
通讯作者: 徐志成 E-mail:202121401001@stu.hebut.edu.cn;xzc@hebut.edu.cn
作者简介:闵越明（1999—），男，硕士研究生，研究方向为锂离子电池老化机理与检测，E-mail：202121401001@stu.hebut.edu.cn
徐志成，硕士生导师，研究方向为锂离子电池多物理场耦合建模、储能系统状态估计及安全管理技术，E-mail：xzc@hebut.edu.cn。
基金资助:
国家自然科学基金(52307238);河北省中央引导地方科技发展专项(216Z4406G);电力系统国家重点实验室课题(SKLD21KZ04)

Study on aging characteristics and failure mechanism of lithium-ion battery under slight-overcharge cycling

Yueming MIN¹^,²(), Chuang ZHANG¹^,², Wenjie LIU¹^,², Suzhen LIU¹^,², Zhicheng XU¹^,²()

^1.State Key Laboratory of Reliability and Intelligence of Electrical Equipment, Hebei University of Technology, Tianjin 300401, China
^2.Key Laboratory of Electromagnetic Field and Electrical Apparatus Reliability of Hebei Province, Hebei University of Technology, Tianjin 300401, China

Received:2024-03-22 Revised:2024-04-18 Online:2024-10-28 Published:2024-10-30
Contact: Zhicheng XU E-mail:202121401001@stu.hebut.edu.cn;xzc@hebut.edu.cn

摘要/Abstract

摘要：

锂离子电池在实际工作中会因为电池组的不一致性或充电系统故障而出现微过充现象，长期循环会引发安全隐患。为探究微过充循环对锂离子电池老化特性及其失效机理的影响，将电池分别过充至不同截止电压，应用电化学阻抗谱、弛豫时间分布和容量增量分析等技术对其进行老化分析，并结合拆解后电极的扫描电子显微镜(SEM)、能量色散X射线谱(EDS)和X射线光电子能谱(XPS)表征加以验证。实验结果表明，与正常循环相比，微过充循环会显著加速电池老化，导致电池比容量衰减速度加快；随着循环次数的增加，电池内部的可用锂离子和活性材料不断消耗，电池各类阻抗明显增加，其中4.5 V微过充循环电池的电荷转移电阻较初始状态增加了196.15%；微过充循环还会加剧电池极化现象，降低材料的循环稳定性；微过充循环后，电池的活性材料逐渐从集流体上脱落，正极材料的活性颗粒破裂，负极材料表面固体电解质界面(SEI)膜增厚，F、P元素含量显著增加。

关键词: 锂离子电池, 微过充循环, 电化学阻抗谱, 老化特性, 失效机理

Abstract:

In real-world applications, lithium-ion batteries can occasionally undergo slight overcharging due to inconsistency within the battery pack or malfunctions in the charging system. Prolonged exposure to such overcharge conditions can pose significant safety hazards. To investigate the effects of slight-overcharge cycling on the aging characteristics and failure mechanisms of lithium-ion batteries, experiments were conducted with batteries subjected to different cut-off voltages during overcharging. The aging analysis was analyzed using electrochemical impedance spectroscopy (EIS), distribution of relaxation time (DRT), and incremental capacity analysis (ICA). These techniques were further corroborated by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) on disassembled electrodes. The experimental results show that slight-overcharge cycling significantly accelerates battery aging compared to normal cycling, leading to a more rapid decline in specific capacity. Additionally, as the number of cycles increases, the depletion of lithium ions and active materials within the battery is expedited, leading to a noticeable increase in various types of battery impedance. Notably, the charge transfer resistance of batteries cycled at 4.5 V slight-overcharge increased by 196.15% from their initial state. This overcharging condition also exacerbates battery polarization and deteriorates the cycling stability of the materials. Post-cycling analysis revealed that slight-overcharge cycling causes active materials to detach from the current collectors, with significant fracturing observed in in the cathode's active particles and thickening of the solid electrolyte interface (SEI) film on the anode. Additionally, there was a notable increase in the contents of F and P elements.

Key words: lithium-ion battery, slight-overcharge cycling, electrochemical impedance spectroscopy, aging characteristics, failure mechanism

中图分类号:

TM 912

闵越明, 张闯, 刘文杰, 刘素贞, 徐志成. 锂离子电池微过充循环老化特性与失效机理研究[J]. 储能科学与技术, 2024, 13(10): 3343-3356.

Yueming MIN, Chuang ZHANG, Wenjie LIU, Suzhen LIU, Zhicheng XU. Study on aging characteristics and failure mechanism of lithium-ion battery under slight-overcharge cycling[J]. Energy Storage Science and Technology, 2024, 13(10): 3343-3356.

图/表 17

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电池编号	充电容量 /mAh	放电容量 /mAh	充放电效率/%	内阻/mΩ
1	2494.4	2480.7	99.45	37.93
2	2492.4	2479.7	99.49	37.81
3	2491.0	2479.5	99.54	38.24
4	2485.4	2472.7	99.49	38.52

老化模式	主要相关阻抗	内部老化机理
电导率损失	欧姆阻抗	集流体破损、黏结剂损坏

活性锂离子损失	SEI膜阻抗、电荷转移阻抗	SEI膜分解、电解质反应、锂枝晶生长

活性材料损失	扩散阻抗	负极析锂并与电解液反应、电极和活性材料分解、晶体结构紊乱、过渡金属锂被溶解

元素	原子百分比/%				质量分数/%
元素	原始	4.3 V	4.4 V	4.5 V	原始	4.3 V	4.4 V	4.5 V
C	45.3	43.8	43.7	44.3	25.20	23.93	22.84	25.32
O	27.7	28.5	27.5	24.4	20.51	20.76	20.57	18.57
F	9.6	9.6	11.4	15.5	8.40	8.34	9.96	13.99
P	0.5	0.4	0.5	1	0.67	0.50	0.83	1.41
Ni	8.3	8.7	8.2	7.2	22.49	23.26	23.03	20.21
Co	3.3	3.4	3.3	2.9	9.04	9.07	8.85	8.25
Mn	5.4	5.7	5.5	4.7	13.69	14.15	13.91	12.26

元素	原子百分比/%				质量分数/%
元素	原始	4.3 V	4.4 V	4.5 V	原始	4.3 V	4.4 V	4.5 V
C	87.8	38.3	35.7	40.6	83.65	29.95	28.06	31.93
O	10.0	44.6	48.9	40.7	12.75	46.47	51.04	42.64
F	1.9	14.1	13.2	16.1	2.80	17.47	16.39	20.02
P	0.3	2.8	2.2	2.6	0.81	5.66	4.50	5.20
S	0.0	0.0	0.0	0.1	0.00	0.00	0.00	0.21
Ni	0.0	0.1	0.0	0.0	0.00	0.46	0.00	0.00

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锂离子电池微过充循环老化特性与失效机理研究

Study on aging characteristics and failure mechanism of lithium-ion battery under slight-overcharge cycling

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