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通过LiPO修复策略实现降解的LiNiCoMnO阴极的界面修复

Interfacial Reviving of the Degraded LiNi Co Mn O Cathode by LiPO Repair Strategy.

作者信息

Feng Ze, Zhang Shan, Huang Xiaobing, Ren Yurong, Sun Dan, Tang Yougen, Yan Qunxuan, Wang Haiyan

机构信息

Hunan Provincial Key Laboratory of Chemical Power Sources, Hunan Provincial Key Laboratory of Efficient and Clean Utilization of Manganese Resources, College of Chemistry and Chemical Engineering, Central South University, Changsha, 410083, P. R. China.

Hunan Provincial Key Laboratory for Control Technology of Distributed Electric Propulsion Aircraft, Hunan Provincial Key Laboratory of Water Treatment Functional Materials, College of Chemistry and Materials Engineering, Hunan University of Arts and Science, Changde, 415000, P. R. China.

出版信息

Small. 2022 Apr;18(16):e2107346. doi: 10.1002/smll.202107346. Epub 2022 Mar 7.

Abstract

Nickel-rich cathode materials, owing to their high energy density and low cost, are considered to be one of the cathodes with the most potential in next-generation lithium-ion batteries. Unfortunately, this kind of cathode with highly active surface is easy to react with H O and CO when exposed to ambient air, resulting in the formation of lithium impurities and interfacial phase transition as well as deterioration of the electrochemical properties. In this work, the evolution mechanism of the structure and interface of LiNi Co Mn O during air-exposure is systematically investigated. Furthermore, a facile reviving strategy is proposed to restore the degraded LiNi Co Mn O by using LiPO as the repair agent. The lithium impurities on the surface of the degraded sample can transform into the repair/coating layer, and part of the rock salt phase on the subsurface can revive to layered phase after repair heat treatment. As a result, the optimized cathode delivers an initial discharge capacity of 198.3 mAh g at 0.1C and a capacity retention of 85.5% after 50 cycles. Although slightly lower than the bare sample (201 mAh g and 88%), they are obviously higher than the exposed samples (166.5 mAh g and 40.4%). The regenerated electrochemical properties should be attributed to the multifunctional repair layer that can efficiently reduce the surface lithium impurities, prevent the corrosion of electrolyte, and improve the interfacial Li diffusion kinetics. This work can effectively reduce the waste of the degraded Ni-rich ternary materials and realize the transformation of "waste" into wealth.

摘要

富镍正极材料因其高能量密度和低成本,被认为是下一代锂离子电池中最具潜力的正极材料之一。不幸的是,这种具有高活性表面的正极在暴露于环境空气中时容易与H₂O和CO₂反应,导致锂杂质的形成、界面相变以及电化学性能的恶化。在这项工作中,系统地研究了LiNiₓCo₁₋ₓ₋yMnₓO₂在空气暴露过程中的结构和界面演变机制。此外,提出了一种简便的修复策略,以Li₃PO₄作为修复剂来恢复降解后的LiNiₓCo₁₋ₓ₋yMnₓO₂。降解样品表面的锂杂质可以转化为修复/涂层,并且在修复热处理后,次表面的部分岩盐相可以恢复为层状相。结果,优化后的正极在0.1C下的初始放电容量为198.3 mAh/g,50次循环后的容量保持率为85.5%。虽然略低于未暴露的样品(201 mAh/g和88%),但明显高于暴露后的样品(166.5 mAh/g和40.4%)。再生的电化学性能应归因于多功能修复层,该修复层可以有效减少表面锂杂质,防止电解质腐蚀,并改善界面锂扩散动力学。这项工作可以有效减少降解的富镍三元材料的浪费,实现“废物”变财富。

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