| 235 | 0 | 57 |
| 下载次数 | 被引频次 | 阅读次数 |
在镍钴锰三元（NCM）正极锂离子电池中，过渡金属离子溶出会导致电池容量衰减。本文应用RelaxIS软件对三电极电池的交流阻抗谱进行弛豫时间分布（DRT）分析，结合d V/d Q曲线，分别研究Ni、Co、Mn过渡金属离子对电池循环的影响，分析过渡金属离子溶出造成容量衰减的原因。过渡金属离子溶出后，在负极表面沉积，导致负极阻抗整体增加，从而影响锂离子在负极的脱嵌，造成负极表面锂的均匀分布变差，负极副反应加速，消耗活性锂。Mn离子影响最大，Ni离子影响最小。
Abstract：In nickel cobalt manganese oxide(NCM) cathode lithium-ion batteries, transition metal dissolution will cause cell aging. In this work, relaxation time distribution(DRT) analysis of AC impedance spectrum of three-electrode cells were performed by RelaxIS software and d V/d Q curves were combined to study the influence of Ni, Co and Mn transition metal ions on the battery cycle, and the causes of capacity degradation caused by the dissolution of transition metal ions were analyzed. After the dissolution of transition metal ions, they deposit on the surface of the anode, causing an overall increase in anode impedance, which affects the extraction and insertion of lithium ions, decreasas the uniform distribution of lithium on the anode surface, leads to the acceleration of anode side reactions and the consumption of active lithium. The order of influence is Mn>Co>Ni, with Mn ion having the greatest influence and Ni ion having the smallest influence.
[1] SOLCHENBACH S,HONG G,FREIBERG A,et al.Electrolyte and SEI decomposition reactions of transition metal ions investigated by on-line electrochemical mass spectrometry[J].Journal of the Electrochemical Society,2018, 165(14):A3304-A3312.
[2] XU H Y,LI Z P,LIU T C,et al. Impacts of dissolved Ni2+on the solid electrolyte interphase on a graphite anode[J].Angewandte Chemie,2022,61(30):e202202894.
[3] XIE Q M,CHEN J W,XING L D,et al.Revealing the critical effect of solid electrolyte interphase on the deposition and detriment of Co（Ⅱ） ions to graphite anode[J].Journal of Energy Chemistry,2022,69:389-396.
[4] KOMABA S,KUMAGAI N,KATAOKA Y. Influence of manganese(II),cobalt(II),and nickel(II)additives in electrolyte on performance of graphite anode for lithium-ion batteries[J].Electrochimica Acta,2002,47(8):1229-1239.
[5] KEIL P,JOSSEN A.Calendar aging of NCA lithiumion batteries investigated by differential voltage analysis and coulomb tracking[J].Journal of the Electrochemical Society,2016,164(1):A6066-A6074.
[6] BLOOM I,JANSEN A N,ABRAHAM D P,et al.Differential voltage analyses of high-power,lithium-ion cells 1.Technique and application[J].Journal of Power Sources,2005,139(1/2):295-303.
[7] LEWERENZ M,MARONGIU A,WARNECKE A,et al.Differential voltage analysis as a tool for analyzing inhomogeneous aging:A case study for Li Fe PO4|Graphite cylindrical cells[J].Journal of Power Sources,2017,368:57-67.
[8] LEWERENZ M,WARNECKE A,SAUER D U.Postmortem analysis on LiFePO4|Graphite cells describing the evolution&composition of covering layer on anode and their impact on cell performance[J]. Journal of Power Sources,2017,369:122-132.
[9] PLANK C,RüTHER T,JAHN L,et al.A review on the distribution of relaxation times analysis:A powerful tool for process identification of electrochemical systems[J].Journal of Power Sources,2024,594:233845.
基本信息:
DOI：10.19996/j.cnki.ChinBatlnd.2025.05.002
中图分类号:TM912
引用信息:
[1]夏玉佳,陈丹丹,宋林霏,等.过渡金属溶出对电池循环的影响[J].电池工业,2025,29(05):351-356+366.DOI:10.19996/j.cnki.ChinBatlnd.2025.05.002.
基金信息: