高比能锂离子电池高镍正极材料的表面包覆改性研究进展

doi:10.11949/0438-1157.20240740

摘要/Abstract

摘要：

层状镍钴锰酸锂（LiNi_1－_x_－_y Co _x Mn _y O₂，0<x+y<1）因具有能量密度高和成本低等优点，是备受关注的动力锂离子电池正极材料之一。然而，该材料在充放电循环过程中因锂离子脱出和晶格氧逸散引起的不可逆相变、过渡金属离子溶出等因素导致容量衰减、结构损坏和安全隐患，严重制约了其在电动汽车上的应用。表面包覆改性技术通过增加正极材料与电解质之间的界面稳定性、抑制微裂纹产生以及提高电池的热稳定性，能够有效提升正极材料的循环稳定性和安全性能。本文在分析高镍三元正极材料界面降解机制的基础上，系统介绍本课题组在提升高镍正极材料电化学性能方面开展的一系列创新性包覆策略，旨在为高性能锂离子电池正极材料的开发应用提供新的思路。

关键词: 锂离子电池, 能量密度, 高镍正极材料, 界面降解, 包覆改性

Abstract:

Layered lithium nickel cobalt manganese oxide (LiNi_1-_x_-_y Co _x Mn _y O₂, 0<x+y<1) is one of the most popular cathode materials for power lithium-ion batteries due to its high energy density and low cost. However, issues such as irreversible phase transitions and transition metal ion dissolution during lithium cycling, caused by lithium ion extraction and lattice oxygen loss, lead to capacity degradation, structural deterioration, and safety concerns. These issues severely limit its application in electric vehicles. Surface coating modification techniques aim to enhance the cycling stability and safety performance of the cathode materials by improving interface stability between the cathode material and electrolyte, suppressing micro-crack formation, and enhancing the thermal stability of the batteries. This article systematically introduces a series of innovative coating strategies developed by our research group to improve the electrochemical performance of high-nickel ternary cathode materials, based on the analysis of interface degradation mechanisms of high-nickel ternary cathode materials. The goal is to provide new insights for the development and application of high-performance lithium-ion battery cathode materials.

Key words: lithium-ion battery, energy density, nickel-rich cathode materials, interface degradation, coating modification

中图分类号:

TM 911

胡成志, 王国贤, 唐伟建, 李阿飞, 陈章贤, 杨则恒, 张卫新. 高比能锂离子电池高镍正极材料的表面包覆改性研究进展[J]. 化工学报, 2024, 75(11): 4020-4036.

Chengzhi HU, Guoxian WANG, Weijian TANG, Afei LI, Zhangxian CHEN, Zeheng YANG, Weixin ZHANG. Research progress on surface coating modification of nickel-rich cathode materials for high energy density lithium-ion battery[J]. CIESC Journal, 2024, 75(11): 4020-4036.

图/表 10

图1 锂离子电池工作原理与电极材料发展示意图[27]

Fig.1 The working principle of lithium-ion batteries and the development of electrode materials[27]

图2 高镍三元正极材料的晶胞和电子结构[28-30]

Fig.2 The crystal cell and electronic structures of nickel-rich cathode materials[28-30]

图3 正极材料失效机理及包覆改性的作用机制示意图

Fig.3 Schematic mechanism of cathode material degradation and its coating modification

图4 面向高镍正极材料的挑战，实施包覆改性策略示意图

Fig.4 Scheme of coating modification strategies for nickel-rich cathode materials facing the challenges

图5 基于近平衡态沉积策略在NCM811正极材料表面均匀包覆Li2TiO3[68]

Fig.5 Uniform coating of Li2TiO3 on the surface of NCM811 cathode material based on near-equilibrium deposition strategy[68]

图6 AlCl3蚀刻诱导的包覆改性策略稳定NCM811正极材料[69]

Fig.6 Stabilization of NCM811 cathode material via AlCl3 etching-induced coating modification strategy[69]

图7 基于共价界面工程均匀包覆NCM811正极材料[70]

Fig.7 Uniform coating of NCM811 cathode materials via covalent interface engineering[70]

图8 基于乳酸辅助策略在NCM811正极材料表面构建非晶稳定包覆层[76]

Fig.8 Constructing amorphous stabilizing coating on NCM811 cathode material surface via lactic acid assisted strategy[76]

图9 基于电化学转化策略形成稳定LiNi0.5Mn1.5O4包覆层[60]

Fig.9 Formation of stable LiNi0.5Mn1.5O4 coating based on electrochemical conversion strategy[60]

图10 表面富集策略诱导均匀LiTaO3包覆层[77]

Fig.10 Inducing uniform LiTaO3 coating based on surface enrichment strategy[77]

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