锂离子电池过放电状态的阻抗特性研究*

doi:10.11985/2022.04.007

摘要/Abstract

摘要：

目前锂电池被广泛应用于电化学储能系统，但由于电池单体间的差异，单体电池常常存在过放电现象，给电池模组及储能系统的应用带来安全隐患，因此对过放电状态的锂电池进行检测与分析对于其安全应用具有重要意义。本文设计了正常循环和不同程度过放电的电池循环试验，利用弛豫时间分布法、阻抗差异分析法和容量增量法对过放电状态的锂离子电池全寿命周期内的阻抗特性进行分析。结果表明，过放电会加速电池老化，可提高充放电过程温升；相较于正常循环，过放电循环使电池欧姆内阻与电荷转移电阻增大，SEI膜内阻减小，电荷传递电阻无明显变化，锂离子固相扩散电阻随着过放电程度增加，先减小后增大。本文结果为锂电池过放电内部特性研究和过放电检测提供理论依据。

关键词: 锂离子电池, 过放电, 电化学阻抗谱, 容量增量分析

Abstract:

At present, lithium-ion batteries are widely used in electrochemical energy storage systems. However, due to the differences between batteries, single batteries often have over discharge phenomenon, which brings safety risks to the application of battery modules and energy storage systems. Therefore, the detection and analysis of lithium-ion batteries in over discharge state are of great significance for their safety applications. Cycle tests of normal cycle and different degrees of over discharge are designed. The relaxation time distribution method, impedance difference analysis method and capacity increment method are used to analyze the impedance characteristics of lithium-ion batteries in the whole life cycle of over discharge state. The results show that over-discharge can accelerate battery aging and increase the temperature rise during charging and discharging. Compared with the normal cycle, the ohm internal resistance and charge transfer resistance increase in the over discharge cycle, the internal resistance of SEI film decreases, and the charge transfer resistance has no significant change. The solid-phase diffusion resistance of lithium-ion decreases first and then increases with the increase of over discharge degree. The results provide a theoretical basis for the study of the internal characteristics of lithium-ion battery over discharge and the detection of over discharge.

Key words: Lithium-ion battery, over discharge, electrochemical impedance spectroscopy, incremental capacity method

中图分类号:

TM911

刘王泽宇, 李青, 庾甜甜, 熊锦晨, 张洪源, 董明, 任明. 锂离子电池过放电状态的阻抗特性研究^*[J]. 电气工程学报, 2022, 17(4): 51-60.

LIU Wangzeyu, LI Qing, YU Tiantian, XIONG Jinchen, ZHANG Hongyuan, DONG Ming, REN Ming. Study on Impedance Characteristics of Lithium-ion Battery in Over Discharge State[J]. Journal of Electrical Engineering, 2022, 17(4): 51-60.

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参考文献 17

[1]	TIAN J Q, WANG Y J, LIU C, et al. Consistency evaluation and cluster analysis for lithium-ion battery pack in electric vehicles[J]. Energy, 2020, 194:11694.
[2]	郑岳久. 车用锂离子动力电池组的一致性研究[D]. 北京: 清华大学, 2014.
	ZHANG Yuejiu. Research on the consistency of lithium-ion power battery pack for vehicle[D]. Beijing: Tsinghua University, 2014.
[3]	张东羽. 基于结构与性能的动力电池过充/过放检测[D]. 广州: 华南理工大学, 2018.
	ZHANG Dongyu. Power battery overcharge/ overdischarge detection based on structure and performance[D]. Guangzhou: South China University of Technology, 2018.
[4]	叶佳娜. 锂电子电池过充电和过放电条件下热失控(失效)特性及机制研究[D]. 合肥: 中国科学技术大学, 2017.
	YE Jiana. Study on thermal runaway (failure) characteristics and mechanism of lithium electron battery under overcharge and overdischarge conditions[D]. Hefei: University of Science and Technology of China, 2017.
[5]	MA T, WU S, WANG F, et al. Degradation mechanism study and safety hazard analysis of overdischarge on commercialized lithium-ion batteries[J]. ACS Applied Materials & Interfaces, 2020, 12(50):56086-56094.
[6]	庄全超, 杨梓, 张蕾, 等. 锂离子电池的电化学阻抗谱分析研究进展[J]. 化学进展, 2020, 32(6):761-791. doi: 10.7536/PC191116
	ZHUANG Quanchao, YANG Zi, ZHANG Lei, et al. Research progress on diagnosis of electrochemical impedance spectroscopy in lithium-ion batteries[J]. Progress in Chemistry, 2020, 32(6):761-791. doi: 10.7536/PC191116
[7]	董明, 范文杰, 刘王泽宇, 等. 基于特征频率阻抗的锂离子电池健康状态评估[J/OL]. 中国电机工程学报:1-11[2022-09-12].DOI:10.13334/j.0258-8013.pcsee.212036. doi: 10.13334/j.0258-8013.pcsee.212036
	DONG Ming, FAN Wenjie, LIU Wangzeyu, et al. Health evaluation of lithium-ion battery based on characteristic frequency impedance[J/OL]. Proceedings of the CSEE:1-11[2022-09-12]. DOI:10.13334/0258-8013.J.pcsee.212036. doi: 10.13334/0258-8013.J.pcsee.212036
[8]	LIU Y, LIU Q, LI Z, et al. Failure study of commercial LiFePO₄ cells in over-discharge conditions using electrochemical impedance spectroscopy[J]. Journal of The Electrochemical Society, 2014, 161(4):A620-A632. doi: 10.1149/2.090404jes
[9]	ZHENG Y, QIAN K, LUO D, et al. Influence of over-discharge on the lifetime and performance of LiFePO₄/graphite batteries[J]. RSC Advances, 2016, 6:30474-30483. doi: 10.1039/C6RA01677D
[10]	KAYPMAZ T C, TUNCAY R N. An advanced cell model for diagnosing faults in operation of Li-ion polymer batteries[C]// 2011 IEEE Vehicle Power and Propulsion Conference, September 6-9,2011,Chicago,IL,USA. IEEE, 2011:1-5.
[11]	范文杰, 徐广昊, 于泊宁, 等. 基于电化学阻抗谱的锂离子电池内部温度在线估计方法研究[J]. 中国电机工程学报, 2021, 41(9):3283-3293.
	FAN Wenjie, XU Guanghao, YU Boning, et al. On-line estimation method for internal temperature of lithium-ion battery based on electrochemical impedance spectroscopy[J]. Proceedings of the CSEE, 2021, 41(9):3283-3293.
[12]	丁伟. 锂离子动力电池热效应分析及散热优化[D]. 哈尔滨: 哈尔滨工业大学, 2020.
	DING Wei. Thermal effect analysis and heat dissipation optimization of lithium-ion power battery[D]. Harbin: Harbin Institute of Technology, 2020.
[13]	阮一钊. 基于动态阻抗谱的锂离子电池健康状态评估方法研究[D]. 北京: 北京化工大学, 2020.
	RUAN Yizhao. Research on health status assessment method of lithium-ion battery based on dynamic impedance spectroscopy[D]. Beijing: Beijing University of Chemical Technology, 2020.
[14]	刘洪利, 陈涛, 李风姣, 等. SEI膜对锂金属负极电化学性能影响的研究进展[J]. 电源技术, 2021, 45(12):1646-1649.
	LIU Hongli, CHEN Tao, LI Fengjiao, et al. Effect of SEI film on electrochemical performance of lithium anode[J]. Chinese Journal of Power Sources, 2021, 45(12):1646-1649.
[15]	GUO R, LU L, OUYANG M, et al. Mechanism of the entire overdischarge process and overdischarge-induced internal short circuit in lithium-ion batteries[J]. Scientific Reports, 2016, 6(22):30248-30257. doi: 10.1038/srep30248
[16]	ZHANG C, JIANG J, ZHANG L, et al. A generalized SOC-OCV model for lithium-ion batteries and the SOC estimation for LNMCO battery[J]. Energies, 2016, 9(11):900. doi: 10.3390/en9110900
[17]	薛楠, 孙丙香, 白恺, 等. 基于容量增量分析的复合材料锂电池分区间循环衰退机理[J]. 电工技术学报, 2017, 32(13):145-152.
	XUE Nan, SUN Bingxiang, BAI Kai, et al. Mechanism of interzone cycle decay of composite lithium battery based on capacity increment analysis[J]. Transactions of China Electrotechnical Society, 2017, 32(13):145-152.

参数类型	参数指标	参数类型	参数指标
额定电压/V	3.60	充电电压/V	4.20±0.03
标准容量/(mA·h)	3 100	放电截止电压/V	2.50
最大放电电流/A	10(0~40 ℃)	标准充电电流/A	3.1

电池组别	初始值	循环 1次	循环 2次	循环 3次	容量差
2.00 V过放电	2 501	2 489	2 477	2 464	12~13
1.50 V过放电	2 521	2 507	2 492	2 476	14~16
1.00 V过放电	2 517	2 498	2 479	2 458	19~21
2.5 V正常老化	2 497	2 488	2 480	2 470	8~10