A study of the thermodynamic stability of lattice oxygen in Li-rich cathode Li1.25Ni0.5Mn0.25O2 during operation

IF 2.6 4区化学 Q3 ELECTROCHEMISTRY

Journal of Solid State Electrochemistry Pub Date : 2025-04-16 DOI:10.1007/s10008-025-06316-y

Huiyuan Chen, Chunhua Shu, Hao Deng, Kerong He, Wei Hu

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Abstract

Li-rich layered cathode materials are considered to be the most promising cathode materials for high energy density Li-ion batteries due to its high capacity. However, oxygen evolution leads to serious failure problems and hinders its wide application. To disclose the mechanism of oxygen evolution, the lattice distortion and thermodynamic stability of lattice oxygen in Li-rich layered cathode materials Li_1.25-xNi_0.5Mn_0.25O₂ are investigated by employing first-principles computational methods in this work. The results show that the change of lattice volume is mainly related to the expansion or collapse of the cell in the z-direction. In the ground state, oxygen vacancies (O-vacancies) easily occur when the Li content is below 0.7. The formation of O-vacancies in cathode materials is closely related to temperature and oxygen partial pressure. Increasing the temperature promotes the formation of O-vacancies. However, increasing the oxygen partial pressure is favorable to suppress the formation of O-vacancies. This study provides a theoretical basis for the design of Li-rich cathodes with high stability.

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富锂阴极Li1.25Ni0.5Mn0.25O2运行过程中晶格氧的热力学稳定性研究

富锂层状正极材料因其高容量被认为是高能量密度锂离子电池最有前途的正极材料。然而，析氧导致了严重的失效问题，阻碍了其广泛应用。为了揭示氧的析出机理，本文采用第一性原理计算方法研究了富锂层状正极材料Li1.25-xNi0.5Mn0.25O2中晶格氧的晶格畸变和热力学稳定性。结果表明，晶格体积的变化主要与晶格在z方向上的膨胀或坍缩有关。在基态中，当Li含量低于0.7时，容易出现氧空位（o -空位）。阴极材料中o空位的形成与温度和氧分压密切相关。温度的升高促进了o -空位的形成。而增加氧分压有利于抑制o -空位的形成。该研究为设计高稳定性的富锂阴极提供了理论依据。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Journal of Solid State Electrochemistry 工程技术-电化学

CiteScore

4.80

自引率

4.00%

发文量

227

审稿时长

4.1 months

期刊介绍： The Journal of Solid State Electrochemistry is devoted to all aspects of solid-state chemistry and solid-state physics in electrochemistry. The Journal of Solid State Electrochemistry publishes papers on all aspects of electrochemistry of solid compounds, including experimental and theoretical, basic and applied work. It equally publishes papers on the thermodynamics and kinetics of electrochemical reactions if at least one actively participating phase is solid. Also of interest are articles on the transport of ions and electrons in solids whenever these processes are relevant to electrochemical reactions and on the use of solid-state electrochemical reactions in the analysis of solids and their surfaces. The journal covers solid-state electrochemistry and focusses on the following fields: mechanisms of solid-state electrochemical reactions, semiconductor electrochemistry, electrochemical batteries, accumulators and fuel cells, electrochemical mineral leaching, galvanic metal plating, electrochemical potential memory devices, solid-state electrochemical sensors, ion and electron transport in solid materials and polymers, electrocatalysis, photoelectrochemistry, corrosion of solid materials, solid-state electroanalysis, electrochemical machining of materials, electrochromism and electrochromic devices, new electrochemical solid-state synthesis. The Journal of Solid State Electrochemistry makes the professional in research and industry aware of this swift progress and its importance for future developments and success in the above-mentioned fields.