储能科学与技术 ›› 2019, Vol. 8 ›› Issue (6): 1003-1016.doi: 10.12028/j.issn.2095-4239.2019.0111

• 锂电池失效分析与测试技术专刊 • 上一篇    下一篇

锂离子电池三元层状氧化物正极材料失效模式分析

陈晓轩1, 李晟1, 胡泳钢1, 郑时尧1, 柴云轩1, 李东江2, 左文华1, 张忠如1, 杨勇1   

  1. 1 厦门大学固体表面物理化学国家重点实验室, 化学与化工学院化学系, 福建 厦门 361005;
    2 德国尤里希研究所(IEK-9), 德国 尤里希 D-52425
  • 收稿日期:2019-05-02 修回日期:2019-06-10 出版日期:2019-11-01 发布日期:2019-11-01
  • 通讯作者: 张忠如,高级工程师,研究方向为锂离子电池失效机理分析与电化学模拟,E-mail:zrzhang@xmu.edu.cn;杨勇,教授,研究方向为高能电池材料与电化学过程,E-mail:yyang@xmu.edu.cn。
  • 作者简介:陈晓轩(1995-),女,硕士研究生,研究方向为锂离子电池失效机理分析与电化学模拟,E-mail:cxx0205@126.com
  • 基金资助:
    国家重点研发计划资助(2018YFB0104400,2018YFB0905400)。

Failure mechanism of Li1+x(NCM)1-xO2 layered oxide cathode material during capacity degradation

CHEN Xiaoxuan1, LI Sheng1, HU Yonggang1, ZHENG Shiyao1, CHAI Yunxuan1, LI Dongjiang2, ZUO Wenhua1, ZHANG Zhongru1, YANG Yong1   

  1. 1 Collaborative Innovation Center of Chemistry for Energy Materials, State Key Lab of Physical Chemistry of Solid Surface, Department of Chemical and Biological Engineering and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, China;
    2 Forschungszentrum Jülich, Fundamental Electrochemistry(IEK-9), D-52425 Jülich, Germany
  • Received:2019-05-02 Revised:2019-06-10 Online:2019-11-01 Published:2019-11-01

摘要: 镍钴锰三元层状氧化物(NCM)正极材料由于其优越的综合性能在动力/储能电池系统(ESS)领域得到广泛应用。虽然Ni含量的增加可提高三元材料的比容量及电池的能量密度,但相关电池体系的容量保持率和安全性将会变差。如何有效解决该矛盾是此类NCM电池所面临的关键问题。本文从NCM电池体系循环过程中常见的体相结构破坏和正极-电解液界面组成改变两方面失效现象出发,结合近年来国内外对NCM失效模式研究中所提出的新理论、方法、应用,从机械破坏、结构演变、电化学极化、化学副反应、正负极协同效应等多个角度对NCM材料的衰退机理提出见解,对指导电池用户合理制定充放电协议、缓解电动汽车(EV)里程焦虑乃至材料设计本身均有重要的指导及借鉴意义。

关键词: 锂离子电池, 三元正极材料, 失效现象, 老化机理, 表界面行为, 体相结构

Abstract: Ternary layered oxide (NCM) cathode materials are widely used in today's energy storage systems (ESS) due to their advantages of high energy/power density, high specific capacity and high oxidation-reduction potential (ORP). Cathode material specific capacity increases with the improvement of Ni content while its stability, safety and capacity retention rate are decreasing. So how to deal with this contradiction effectively is the key to develop ternary material system. This paper starts from the failure phenomenon on account of bulk phase structure destruction and cathodeelectrolyte interface composition change during the cycle of NCM battery system. Combined with the new theory, new method and new application in the research of NCM failure mode at home and abroad in recent years, the possible decline mechanism and life decay reasons of mechanical damage, structural evolution, electrochemical polarization, chemical side reaction process and synergistic effect of cathode and anode electrodes are giving. The results guide users to rationally formulate charging and discharging protocols and alleviate electric vehicles (EV) range anxiety and the design of the material.

Key words: lithium ion batteries, NCM cathode material, failure behavior, ageing mechanism, surface and interface, bulk structure

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