锂离子电池富锂正极材料的包覆改性研究进展

Research progress on coating modification of lithium-rich cathode materials for lithium-ion batteries

  • 摘要: 随着新能源汽车及储能行业的快速发展,传统正极材料难以满足人们对电池高能量、高密度锂电池的要求。富含Li和Mn的层状氧化物xLi2MnO3·(1–x)LiMO2 (M=Ni,Mn,Co),其高比容量可超过250 mA·h·g–1,有希望成为下一代锂离子电池最理想的正极材料。但是,富锂材料仍存在首次循环不可逆容量高、循环性能差和倍率容量低等问题,为解决这些问题,本文阐述了富锂正极材料的结构和电化学反应之间的构效关系,讨论了金属氧化物、金属氟化物、碳、导电聚合物和锂离子导体等涂层材料对富锂正极材料电化学性能的影响规律及作用机理,同时还对以上涂层在富锂正极材料中应用的优缺点进行了总结。最后,对锂离子电池富锂正极材料的包覆改性的未来发展发现作出展望。

     

    Abstract: With the rapid development of new energy vehicles and the energy storage industry, traditional cathode materials often do not meet people’s expectations of high energy output and high density for lithium-ion batteries. The layered oxide xLi2MnO3·(1−x)LiMO2 (M=Ni, Mn, Co), rich in Li and Mn, is expected to be an ideal anodic material for the next generation of lithium-ion batteries owing to its high specific capacity exceeding 250 mA·h·g−1. However, the Li-rich materials still suffer from high irreversible capacity loss at the first cycle, poor cycle performance, and inferior rate capacity. The voltage decay mechanism of lithium-rich manganese-based cathode materials involves factors such as surface phase transition, anion redox, transition metal migration, and oxygen release. As a commonly used modification method, the coating can effectively solve these problems. At present, the coating modification mechanism of cathode materials mainly includes the following three types. (1) Surface coatings can reduce the direct contact between lithium-rich materials and electrolytes. They stabilize the interface, prevent excessive metal dissolution, and effectively prevent the surface structure of the active material from collapsing. (2) Surface coatings can reduce oxygen activity, improve irreversible oxygen loss, inhibit solid electrolyte interphase (SEI) film growth, and improve material thermal stability. (3) Surface coatings can improve the conductivity of the positive electrode active material, which builds a conductive network on the surface to provide a fast transmission channel for electrons and lithium ions. Surface modification can optimize the surface and structure of the lithium-rich layered material, and the modified material shows a higher discharge capacity and good cycle stability, with superior rate performance and thermal stability. This paper expounded upon the lithium-rich cathode material structure and electrochemical reaction between the structure–activity relationship and discussed the influence of metal oxides, metal fluoride, carbon, conductive polymer, and lithium-ion conductors on the coating material, the electrochemical performance of lithium-ion battery cathode materials, and the mechanism of action. We also summarized the advantages and disadvantages of the abovementioned coating in the application of lithium-ion battery cathode materials. Finally, future developments in the coating modification of lithium-rich cathode materials for lithium-ion batteries were discussed.

     

/

返回文章
返回