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鋰離子電池富鋰正極材料的包覆改性研究進展

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

  • 摘要: 隨著新能源汽車及儲能行業的快速發展,傳統正極材料難以滿足人們對電池高能量、高密度鋰電池的要求。富含Li和Mn的層狀氧化物xLi2MnO3·(1–x)LiMO2 (M=Ni,Mn,Co),其高比容量可超過250 mA·h·g–1,有希望成為下一代鋰離子電池最理想的正極材料。但是,富鋰材料仍存在首次循環不可逆容量高、循環性能差和倍率容量低等問題,為解決這些問題,本文闡述了富鋰正極材料的結構和電化學反應之間的構效關系,討論了金屬氧化物、金屬氟化物、碳、導電聚合物和鋰離子導體等涂層材料對富鋰正極材料電化學性能的影響規律及作用機理,同時還對以上涂層在富鋰正極材料中應用的優缺點進行了總結。最后,對鋰離子電池富鋰正極材料的包覆改性的未來發展發現作出展望。

     

    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.

     

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