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通过综合策略稳定 P2-NaMnFeO 正极中的晶格氧,实现高性能钠离子电池

Stabilizing Lattice Oxygen in a P2-NaMnFeO Cathode via an Integrated Strategy for High-Performance Na-Ion Batteries.

机构信息

Center of Materials Science and Optoelectronics Engineering, College of Materials Science and Optoelectronic Technology, University of Chinese Academy of Sciences, Beijing 100049, P. R. China.

State Key Laboratory for Mesoscopic Physics, School of Physics, Peking University, Beijing 100871, P. R. China.

出版信息

Inorg Chem. 2023 Jun 19;62(24):9314-9323. doi: 10.1021/acs.inorgchem.2c04118. Epub 2023 Jun 7.

Abstract

P2-type NaMnFeO (MF) has attracted great interest as a promising cathode material for sodium-ion batteries (SIBs) due to its high specific capacity and low cost. However, its poor cyclic stability and rate performance hinder its practical applications, which is largely related to lattice oxygen instability. Here, we propose to coat the cathode of SIBs with LiZrO, which realizes the "three-in-one" modification of LiZrO coating and Li, Zr co-doping. The synergy of LiZrO coating and Li/Zr doping improves both the cycle stability and rate performance, and the underlying modification mechanism is revealed by a series of characterization methods. The doping of Zr increases the interlayer spacing of MF, reduces the diffusion barrier of Na, and reduces the ratio of Mn/Mn, thus inhibiting the Jahn-Teller effect. The LiZrO coating layer inhibits the side reaction between the cathode and the electrolyte. The synergy of LiZrO coating and Li, Zr co-doping enhances the stability of lattice oxygen and the reversibility of anionic redox, which improves the cycle stability and rate performance. This study provides some insights into stabilizing the lattice oxygen in layered oxide cathodes for high-performance SIBs.

摘要

P2 型 NaMnFeO(MF)因其高比容量和低成本而作为钠离子电池(SIB)的一种很有前途的正极材料而受到极大关注。然而,其较差的循环稳定性和倍率性能阻碍了其实际应用,这在很大程度上与晶格氧的不稳定性有关。在此,我们提出用 LiZrO 来包覆 SIB 的正极,实现了 LiZrO 涂层和 Li、Zr 共掺杂的“三合一”改性。LiZrO 涂层和 Li/Zr 掺杂的协同作用提高了循环稳定性和倍率性能,并通过一系列的表征方法揭示了其潜在的改性机制。Zr 的掺杂增加了 MF 的层间距,降低了 Na 的扩散势垒,降低了 Mn/Mn 的比值,从而抑制了 Jahn-Teller 效应。LiZrO 涂层抑制了正极与电解质之间的副反应。LiZrO 涂层和 Li、Zr 共掺杂的协同作用增强了晶格氧的稳定性和阴离子氧化还原的可逆性,从而提高了循环稳定性和倍率性能。本研究为稳定高性能 SIB 层状氧化物正极中的晶格氧提供了一些思路。

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