物理化学学报 >> 2025, Vol. 41 >> Issue (3): 100021.doi: 10.3866/PKU.WHXB202311005

所属专题: 能源化学

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高性能双金属氧化物负极的理性设计及储锂特性

林学宇1, 王瑞琦2,*(), 董武杰3, 黄富强1,3,4,*()   

  1. 1 北京大学化学与分子工程学院, 北京分子科学国家研究中心, 稀土材料化学与应用国家重点实验室, 北京 100871
    2 中国科学院大学化学工程学院, 北京 101408
    3 中国科学院上海硅酸盐研究所, 高性能陶瓷和超微结构国家重点实验室, 上海 200050
    4 上海交通大学材料科学与工程学院, 金属基复合材料国家重点实验室, 上海 200240
  • 收稿日期:2023-11-03 修回日期:2023-12-08 录用日期:2023-12-11 发布日期:2024-01-02
  • 通讯作者: Email: wangruiqi@ucas.ac.cn (王瑞琦)huangfq@pku.edu.cn (黄富强)
  • 基金资助:
    国家自然科学基金(22005006)

Rational Design of Bimetallic Oxide Anodes for Superior Li+ Storage

Xueyu Lin1, Ruiqi Wang2,*(), Wujie Dong3, Fuqiang Huang1,3,4,*()   

  1. 1 College of Chemistry and Molecular Engineering, Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Rare Earth Materials Chemistry and Applications, Peking University, Beijing 100871, China
    2 School of Chemical Engineering, University of Chinese Academy of Sciences, Beijing 101408, China
    3 State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
    4 State Key Lab of Metal Matrix Composites, School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
  • Received:2023-11-03 Revised:2023-12-08 Accepted:2023-12-11 Published:2024-01-02
  • Contact: Email: wangruiqi@ucas.ac.cn (Ruiqi Wang)huangfq@pku.edu.cn (Fuqiang Huang)
  • Supported by:
    the National Natural Science Foundation of China(22005006)

摘要:

高能量密度、高功率密度的“双高”锂离子电池(LIBs)的实现依赖于创新突破高容量、高倍率及长循环寿命电极材料。插入型负极,以d0过渡金属氧化物为代表,含有强金属-氧键,表现出高循环稳定性和高倍率性能。然而,由于金属离子变价较少,其比容量相对较低。转化-合金型负极,以p区金属氧化物为代表,具备高理论比容量,但嵌锂过程中的相团聚和体积膨胀易导致容量快速衰减和倍率性能不佳。通过引入插入型或转化型功能基元构建双金属氧化物负极,可以优化电极中的电子/离子传导,从而改善循环性能和倍率性能,有望实现负极材料高容量、高倍率及长循环的统一。本文通过对各类金属氧化物中的化学键及电子结构特征进行分析,并提出一种新的图示表达方式,将负极锂离子插脱嵌的电化学反应储能过程表达为态密度(DOS)图示。文章阐述了双金属氧化物负极的多步储锂机制,并结合近期相关研究进展,为发展高容量、高倍率及高稳定的双金属化合物负极提供理论参考和实践依据。

关键词: 锂离子电池, 负极材料, 双金属化合物, 储锂机制

Abstract:

The rapid advancement of scientific technology leads to a growing need for energy storage equipment in modern society. Lithium-ion batteries (LIBs) are extensively utilized in portable electronics, handy electric tools, medical electronics, and other industries due to their exceptional features such as high energy density, high power density, long lifespan, low self-discharge rate, wide operating temperature range and environmentally-friendly nature. However, the recent rapid development of mobile electronics and electric vehicles requires energy storage devices with even higher energy and power densities. To achieve this goal, it is essential to develop advanced electrode materials featuring high capacity, high rate capability, and long cycle life. The design of high-performance anode materials is an important aspect of constructing the ideal LIB devices. Besides the commercialized graphite, many metal oxides can also act as anode in the LIBs. In detail, the oxides that served as LIB anodes can be classified into intercalation-type, conversion-type and conversion-alloying-type anodes based on their Li+ storage mechanisms. Due to their robust metal-oxygen bonds, intercalation-type anodes, such as d0 metal oxides, exhibit stable cycling performance and high-rate capability. However, the limited valence change of intercalation-type metal ions often results in low theoretical capacities. In comparison, conversion-alloying type anodes, exemplified by p-block metal oxides, offer high theoretical capacities and low Li+ extraction potential, making them suitable for high-energy-density LIBs. Nevertheless, the Li+ intercalation process induces severe phase agglomeration and volume expansion, leading to rapid capacity decay and poor rate capability. Therefore, these drawbacks severely limit the wild utilization s of metal oxide anodes in commercialized LIBs. Recently, substantial efforts have been made to design novel bimetallic oxide anodes. Among these anodes, the incorporation of intercalation-type or conversion-type motifs into conversion-alloying-type metal oxides enables the creation of bimetallic oxide anodes with optimized electronic and ionic conductivities. This approach has the potential to combine the advantages of high capacity, high-rate capability, and long cycle life in a single system. To uncover the underlying Li+ storage mechanisms, this review analyzes the bond situations and electronic structures of various metal oxides. Additionally, it introduces a new graphic representation of the Li+-ion charge/discharge process using density-of-states (DOS) graphs. The multi-step lithium storage mechanisms in bimetallic oxide anodes are also discussed. Drawing on recent progress in the field, this review provides fundamental academic insights and practical perspectives for the development of high-capacity, high-rate, and robust bimetallic compound anodes.

Key words: Lithium-ion battery, Anode materials, Bimetallic compound, Li+ storage mechanism