储能科学与技术 ›› 2021, Vol. 10 ›› Issue (2): 448-453.doi: 10.19799/j.cnki.2095-4239.2020.0394

• 储能材料与器件 • 上一篇    下一篇

锂离子电池析锂及析锂回嵌行为的三电极分析

朱振东(), 吴欢欢(), 张峥, 彭文, 李丽娟   

  1. 合肥国轩高科动力能源有限公司,安徽 合肥 230000
  • 收稿日期:2020-11-16 修回日期:2020-12-22 出版日期:2021-03-05 发布日期:2021-03-05
  • 作者简介:朱振东(1984—),男,博士,工程师,研究方向为锂离子电池工作机理、相关表征方法的开发及锂离子电芯的设计,E-mail:zhuzhendong@gotion.com.cn|吴欢欢,工程师,研究方向为锂离子电池工作机理及相关表征方法的开发,E-mail:wuhuanhuan@gotion.com.cn
  • 基金资助:
    国家重点研发计划项目(2016YFB0100304)

Analysis of lithium plating-stripping process in lithium-ion batteries by three-electrode measurements

Zhendong ZHU(), Huanhuan WU(), Zheng ZHANG, Wen PENG, Lijuan LI   

  1. Hefei Gotion High-Tech Power Energy Co. Ltd. , Hefei 230000, Anhui, China
  • Received:2020-11-16 Revised:2020-12-22 Online:2021-03-05 Published:2021-03-05

摘要:

利用三电极电池研究了锂离子电池在不同条件下的析锂行为,并通过X射线衍射(XRD)及原子吸收(AAS)进行了相应的材料表征。结果表明,当锂离子电池在充电过程发生析锂时,其负极对参比的电势曲线在接近0 V左右会出现析锂电势平台,在接下来的放电过程中同样在0 V附近出现析锂回嵌的电势平台。因此充放电过程中在0 V新出现的平台可以作为锂枝晶形成和回嵌的判断依据,具体反应可表示为:Li+ + e-? Li。由于电极电势平台代表着相应的相变反应,故通过该电势平台对应的时间与相应的充电或者放电电流可定量分析析锂过程中可逆锂及不可逆锂的占比。此外,结合低温析锂后负极对参比电势曲线的变化及相应的相变表征结果发现,负极表面形成的锂枝晶在常温搁置期间能够重新嵌入到石墨内部。主要原因是锂枝晶与石墨形成了浓差电池,在搁置期间发生了局部放电,导致部分锂嵌入石墨。本工作提供了一种锂离子电池析锂的定量分析方法,为析锂行为的发生及预测提供实验的依据,对分析锂离子反应及失效过程有一定指导意义。

关键词: 锂离子电池, 析锂反应, 三电极电池, 负极电势平台

Abstract:

Lithium deposition reactions of lithium-ion batteries under different conditions are studied using three-electrode batteries. The corresponding material characterization is performed using X-ray diffraction (XRD) and atomic absorption spectrophotometry (AAS). Considering the changes in the electrode potential of low negative to positive ratio (N/P) batteries and low-temperature charging batteries during charging and discharging processes, the results show that once the lithium deposition reaction occurs, an additional potential plateau appears around 0 V during the charging process, and another additional potential plateau appears around 0 V during the next discharging process. The pair of additional potential plateaus that appeared around 0 V during the charging and discharging processes can be used as the criteria for the formation and stripping of lithium dendrite, expressed as Li+ + e- ? Li. In addition, because the potential plateaus are referred to as the phase transitions in the electrodes, the proportion of reversible and irreversible lithium can be quantitatively analyzed using the corresponding charging or discharging time of the potential plateaus and the corresponding current. Furthermore, it is demonstrated that part of the deposited lithium on the anode surface can reinsert into the graphite layer during the next relaxation process at room temperature. The main reason is that concentration cells are formed between the deposited lithium and the graphite bulk, and partial discharge occurs during shelving, causing some of the deposited lithium to reinsert into the graphite layer. This work provides a quantitative analysis method for the lithium deposition reaction. It can be used as an experimental basis to predict the occurrence of lithium dendrites, which has a certain significance for the failure processes.

Key words: lithium-ion batteries, lithium deposition reaction, three-electrode batteries, the anode potential plateaus

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