物理化学学报

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高能锂电池用层状正极材料研究进展与底层设计策略

王雨龙1,2,3, 刘世奇1,2,3, 王博亚4, 谷林4, 尉海军1,2,3   

  1. 1 北京工业大学新能源学院, 先进电池材料与器件研究所, 北京 100124;
    2 工大国创先进电池材料与器件研究院, 北京 100176;
    3 北京工业大学材料科学与工程学院, 材料循环低碳再生全国重点实验室, 北京 100124;
    4 清华大学材料学院, 北京国家电子显微镜中心与先进材料实验室, 北京 100084
  • 收稿日期:2026-06-11 修回日期:2026-08-05 录用日期:2026-09-03
  • 通讯作者: 尉海军Haijun Yu E-mail:hj-yu@bjut.edu.cn
  • 基金资助:
    本研究由国家重点研发计划(2022YFB2404400),国家自然科学基金(92572203和92263206),25高校科技创新服务能力建设-市属高校基本科研业务费(312000546325001)支持

Recent advances and fundamental design strategies of layered cathode materials for high-energy lithium batteries

Yulong Wang1,2,3, Shiqi Liu1,2,3, Boya Wang4, Lin Gu4, Haijun Yu1,2,3   

  1. 1 Institute of Advanced Battery Materials and Devices, College of New Energy, Beijing University of Technology, Beijing 100124, China;
    2 Institute of Gongda-Guochuang Advanced Battery Materials and Devices, Beijing 100176, China;
    3 College of Materials Science and Engineering, State Key Laboratory of Materials Low-Carbon Recycling, Beijing University of Technology, Beijing 100124, China;
    4 Beijing National Center for Electron Microscopy and Laboratory of Advanced Materials, School of Materials Science and Engineering, Tsinghua University, Beijing 100084, China
  • Received:2026-06-11 Revised:2026-08-05 Accepted:2026-09-03

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摘要： 随着便携式电子设备的轻量化升级与新能源汽车的产业化推进,高能量密度锂离子电池的市场需求呈现爆发式增长。在此背景下,高镍正极材料与富锂锰基层状正极材料(LLOs)因兼具高容量、高能量密度和低成本等优势而成为研究热点。本文首先解析了高镍与LLOs正极材料容量贡献的本质来源:前者以过渡金属阳离子氧化还原(MCR)反应为主要容量来源,后者则依赖于MCR反应与氧阴离子氧化还原(OAR)反应的协同贡献。其中,通过在高脱锂态下激活层状氧化物中的晶格氧以引发OAR反应,为正极材料提供"额外"容量,已成为突破传统正极材料能量密度瓶颈的关键途径。进而,本文从原子尺度的微观结构演变出发,系统总结并分析了高镍与LLOs正极材料在实际应用中存在的核心问题,并阐述了可行的改性方案。针对高比能正极材料中晶体结构衰变与OAR反应不可控等关键问题,通过体相内/外复合结构构筑及具有π键环的LiMn6六原子环调控等创新策略,可实现材料综合性能的显著提升,为新型高比能正极材料的设计开发提供了理论指导与技术参考。

关键词: 锂离子电池, 高能量密度, 富锂锰基层状正极材料, LiMn6六原子环, π键环, 改性策略

Abstract: The lightweight development of portable electronic devices and the industrialization of new-energy vehicles are driving explosive growth in the demand for high-energy-density lithium-ion batteries (LIBs). Against this backdrop, Ni-rich layered oxide and Lithium-rich layered oxides (LLOs) cathode materials have attracted intensive interest because of their high capacity, high energy density, and low cost. This review first clarifies the fundamental origins of capacity in Ni-rich layered oxide cathode and LLO cathodes. The former derive their capacity primarily from transition-metal cation redox (MCR), whereas the latter exploit the coupled contributions of MCR and oxygen anionic redox (OAR). Activating lattice oxygen in layered oxides at high states of delithiation to trigger OAR and provide additional capacity has become a key route to overcome the energy-density ceiling of conventional cathodes. We then examine the core challenges facing Ni-rich layered oxide cathode and LLO cathodes from the perspective of atomic-scale microstructural evolution. In particular, to address crystal-structure degradation and poorly controlled OAR in high-specific-energy cathodes, emerging approaches based on composite-structure construction inside/outside grains and regulation of LiMn6 hexatomic-ring with π-bond ring are discussed. These strategies enable substantial improvements in overall electrochemical performance and provide mechanistic guidance for the design and development of next-generation high-specific-energy cathode materials.

Key words: Lithium-ion battery, High-energy density, Lithium-rich Mn-based layered cathode material, LiMn6 hexatomic-ring, π-bond ring, Modification strategy