基于电化学阻抗谱的锂离子电池析锂检测方法

doi:10.3969/j.issn.1674-8484.2021.04.016

摘要/Abstract

摘要：

根据无析锂和析锂锂离子电池在不同温度下电化学阻抗谱变化趋势,应用等效电路模型分别拟合电化学阻抗谱中的Ohm阻抗和固体-电解液界面阻抗,提出了EIS-Ohm法和EIS-SEI法,利用扫描电镜和化学方法对析锂检测方法进行了验证。随着温度升高,析锂电池的电化学阻抗谱中的Ohm阻抗先增大后减小,固体-电解液界面阻抗变化较小;扫描电镜观察和化学方法确定了电池电极表面析出锂金属形貌和化学变化特性。结合电池工作温度 (-10~60 ℃) 和检测时间 (> 21 min),讨论了2种析锂检测方法的可行性。结果表明：基于电化学阻抗谱开发的2种检测方法能够清晰地判断电池发生析锂现象,这一快速、非解体检测方法对电池寿命和安全管理具有重要意义。

关键词: 锂离子电池, 电化学阻抗谱, 析锂检测, Ohm阻抗, 界面阻抗

Abstract:

The EIS-Ohm method and the EIS-SEI method were proposed based on the variation tendency of electrochemical impedance spectroscopy (EIS) in different temperatures for the lithium ion batteries with and without lithium plating, and the equivalent circuit model was applied to fit the Ohmic impedance and the solid-electrolyte interface impedance in the EIS respectively. With temperature increase, the EIS of the lithium plating batteries showed an increase and then a decrease in Ohmic impedance, while the impedance at the solid-electrolyte interface showed a smaller change. Scanning electron microscopy (SEM) and chemical methods were used to determine the morphology and chemical transformation of the plating lithium metal from the electrode surface. The feasibility of two lithium identification methods was discussed by combining the operating temperature (-10~60 °C) and detection time (> 21 min) of the battery. The results show that the two detection methods developed based on electrochemical impedance spectroscopy can clearly identify the lithium plating, and the rapid, non-dissembling identification methods have important applications for battery life and safety management.

Key words: lithium ion battery, electrochemical impedance spectra, lithium plating identification, Ohmic impedance, interface impedance

中图分类号:

TM911.3

董鹏, 张剑波, 王震坡. 基于电化学阻抗谱的锂离子电池析锂检测方法[J]. 汽车安全与节能学报, 2021, 12(4): 570-579.

DONG Peng, ZHANG Jianbo, WANG Zhenpo. Lithium plating identification based on electrochemical impedance spectra of lithium ion batteries[J]. Journal of Automotive Safety and Energy, 2021, 12(4): 570-579.

图/表 9

图 1 软包电池阻抗谱测试实验THT-ARC和Autolab电化学工作站装置组装示意图

图2 2个析锂电池的容量保持率随等效循环次数变化

图3 ARC测试过程中无析锂电池和析锂电池的升温及阻抗谱随温度变化曲线

图4 不同温度下无析锂电池与析锂电池的相角与阻抗模随频率变化结果

图5 EIS结果基于ECM拟合出的欧姆阻抗和SEI阻抗

图6 试验前及不同温度及条件（4.25 V, 0.5 C / 0.7 C, 5.88 kN）下试验后对石墨负极的SEM测试结果

图7 析锂石墨负极片在空气中随着时间推移的颜色变化

图8 低温（-20 ℃）条件下软包析锂电池不同温度下的EIS结果

图9 低温（0 ℃）条件下软包析锂电池80% SOH下不同温度的EIS结果

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