富镍三元层状正极材料表面残碱去除工艺:研究进展、挑战及展望  

Removal process of residual alkali on surface of nickel-rich ternary layered cathode materials:Research progress,challenges and prospects

作　　者：袁绍辉 曾子豪 董煜 王天宇 崔鑫炜 杨越 孙伟[1] 叶飞 葛鹏 YUAN Shao-hui;ZENG Zi-hao;DONG Yu;WANG Tian-yu;CUI Xin-wei;YANG Yue;SUN Wei;YE Fei;GE Peng(School of Minerals Processing and Bioengineering,Central South University,Changsha 410083,China;Xinxiang Tianli Lithium Energy Co.,Ltd.,Xinxiang 453000,China;Institute of Advanced Technology,Zhengzhou University,Zhengzhou 450000,China)

机构地区：[1]中南大学资源加工与生物工程学院,长沙410083 [2]新乡天力锂能股份有限公司,新乡453000 [3]郑州大学先进技术研究院,郑州450000

出　　处：《中国有色金属学报》2023年第5期1554-1584,共31页The Chinese Journal of Nonferrous Metals

基　　金：国家自然科学基金资助项目(52004334);湖南省自然科学基金资助项目(2021JJ20073)。

摘　　要：富镍LiNi_(1-x-y)Co_(x)Mn_(y)O_(2)(NCM)/LiNi_(1-x-y)Co_(x)Al_(y)O_(2)(NCA)三元层状正极材料因其比容量高、成本低等优势,被认为是最具前景的锂电池正极材料之一。但由于其对空气中H_(2)O和CO_(2)的敏感效应,表面易生成残碱化合物LiOH/Li_(2)CO_(3)(RLCs),而RLCs的存在会急剧恶化富镍三元材料热稳定性能和电化学性能,致使其大规模商业化应用面临严峻挑战。本文首先综述了RLCs的组成和形成机理,并系统概括RLCs引起的微裂纹扩展、Li^(+)/Ni^(2+)混排、界面副反应和晶格相变等材料失效机制以及常用RLCs去除策略;重点阐述去离子水洗涤、无水乙醇洗涤、溶液洗涤及后续一体化处理等三种RLCs去除工艺的研究进展及对材料结构、形貌及电化学性能的影响机理。最后,归纳总结上述溶液洗涤去除RLCs策略的特点,并对富镍NCM/NCA三元层状正极材料表面残碱去除工艺的未来研究方向进行展望。The rich-nickel LiNi_(1-x-y)Co_xMn_yO_(2)(NCM)/LiNi_(1-x-y)Co_xAl_yO_(2)(NCA) ternary layered cathode materials are considered as one of the most promising lithium battery cathode materials due to its high specific capacity and low cost.However,the nickel-rich NCM/NCA ternary layered cathode materials are sensitive to H_(2)O and CO_(2) in the air,and is easy to generate residual alkali compound LiOH/Li_(2)CO_(3)(RLCs) on the surface.The existence of RLCs will dramatically deteriorate the thermal stability and electrochemical performance of nickel-rich ternary layered cathode materials,resulting in its large-scale commercial application faced severe challenges.This paper firstly reviewed the composition and formation mechanism of RLCs,and systematically summarized the failure mechanisms of materials caused by RLCs,such as microcrack propagation,Li~+/Ni~(2+) mixing,interfacial side reactions and lattice phase transformation.Meanwhile,the common RLCs removal strategies were also introduced.The research progress of deionized water washing,anhydrous ethanol washing,solution washing and subsequent integrated treatment in removing RLCs were deeply reviewed.In addition,the influencing mechanisms of washing process for the structure,morphology and electrochemical performance of high nickel ternary cathode materials were also highlighted.Finally,the characteristics of the solution washing strategy were summarized,and the future research and development of removal process for residual alkali compounds on the surface of rich-nickel NCM/NCA ternary layered cathode material were also prospected.

关 键 词：富镍NCM/NCA三元层状正极材料 残碱化合物LiOH/Li_(2)CO_(3) 去离子水洗涤 无水乙醇洗涤 溶液洗涤 后续一体化处理 

分 类 号：TM911.1[电气工程—电力电子与电力传动]