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采用阴离子/阳离子共掺杂和碳酸锂包覆的双重策略来提升富锂层状氧化物的电化学性能

Dual Strategies with Anion/Cation Co-Doping and Lithium Carbonate Coating to Enhance the Electrochemical Performance of Lithium-Rich Layered Oxides.

作者信息

Chen Huai, Ma Jun, Liu Fei, Yao Mengqin

机构信息

Department of Chemical Engineering, School of Chemistry and Chemical Engineering, Guizhou University, Guiyang, Guizhou 550025, China.

Guizhou Key Laboratory for Green Chemical and Clean Energy Technology, Guiyang, Guizhou 550025, China.

出版信息

Chemistry. 2023 Dec 19;29(71):e202302569. doi: 10.1002/chem.202302569. Epub 2023 Nov 5.

Abstract

Lithium-rich layered oxides (LLOs, Li Mn Ni Co O ) are widely used as cathode materials for lithium-ion batteries due to its high specific capacity, high operating voltage and low cost. However, the LLOs are faced with rapid decay of charge/discharge capacity and voltage, as well as interface side reactions, which limit its electrochemical performance. Herein, the dual strategies of sulfite/sodium ion co-doping and lithium carbonate coating were used to improve it. It founds that modified LLOs achieve 88.74 % initial coulomb efficiency, 295.3 mAh g first turn discharge capacity, in addition to 216.9 mAh g at 1 C, and 87.23 % capacity retention after 100 cycles. Mechanism research indicated that the excellent electrochemical performance benefits from the doping of both Na and SO , and it could significantly reduce the migration energy barrier of Li and promote Li migration. Meanwhile, anion and cation are co-doped greatly reduces the band gap of LLOs and increase its electrical conductivity, and its binding effect on Li is weakened, making it easier for Li to shuttle through the material. In addition, the lithium carbonate coating significantly inhibits the occurrence of interfacial side reactions of LLOs. This work provides a theoretical basis and practical guidance for the further development of LLOs with higher electrochemical performance.

摘要

富锂层状氧化物(LLOs,LiMnNiCoO)因其高比容量、高工作电压和低成本而被广泛用作锂离子电池的正极材料。然而,LLOs面临着充放电容量和电压的快速衰减以及界面副反应,这限制了其电化学性能。在此,采用亚硫酸盐/钠离子共掺杂和碳酸锂包覆的双重策略对其进行改进。结果发现,改性后的LLOs初始库仑效率达到88.74%,首次放电容量为295.3 mAh g,在1 C下的放电容量为216.9 mAh g,100次循环后容量保持率为87.23%。机理研究表明,优异的电化学性能得益于Na和SO的掺杂,它可以显著降低Li的迁移能垒,促进Li的迁移。同时,阴离子和阳离子的共掺杂大大降低了LLOs的带隙,提高了其电导率,并且其对Li的束缚作用减弱,使得Li更容易在材料中穿梭。此外,碳酸锂包覆显著抑制了LLOs界面副反应的发生。这项工作为进一步开发具有更高电化学性能的LLOs提供了理论依据和实践指导。

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