Cation disorder dominates the defect chemistry of high-voltage LiMn1.5Ni0.5O4 (LMNO) spinel cathodes

Jiayi Cen, Bonan Zhu, Seán R. Kavanagh, Alexander G. Squires, David O. Scanlon*

*此作品的通讯作者

科研成果: 期刊稿件文章同行评审

18 引用 (Scopus)

摘要

High-voltage spinel LiMn1.5Ni0.5O4 (LMNO) can exist in a Mn/Ni ordered P4332 or disordered Fd3̄m arrangement with a majority of literature studies reporting improved electrochemical performance for the disordered phase. Through modifying synthesis conditions, the Mn/Ni ordering can be tuned, however oxygen and Mn3+ stoichiometries are also affected, making it difficult to decouple these responses and optimise performance. Here, we investigate all intrinsic defects in P4332 LMNO under various growth conditions, using density functional theory (DFT) calculations. We find that the majority of defects are deep and associated with small polarons (Mn3+, Mn2+ and Ni3+) formation. The tendency for cation disorder can be explained by the low formation energy of the antisite defects and their stoichiometric complexes. The intrinsic Fermi level of LMNO varies from moderately n-type under oxygen-poor conditions to weakly p-type under oxygen-rich conditions. Our work explains experimental observations (e.g. the Mn/Ni disorder) and provides guidelines for defect-controlled synthesis.

源语言英语
页(从-至)13353-13370
页数18
期刊Journal of Materials Chemistry A
11
25
DOI
出版状态已出版 - 12 4月 2023
已对外发布

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