Optoelectronic, magnetic, EFG and NMR properties of olivine-type LiMPO4 (M = Fe, Mn, Co, Mg) cathodes for application in lithium-ion battery by DFT

IF 4.6 2区物理与天体物理 Q2 MATERIALS SCIENCE, MULTIDISCIPLINARY

Results in Physics Pub Date : 2025-09-08 DOI:10.1016/j.rinp.2025.108425

H. Vahidi , H.A. Rahnamaye Aliabad , Evren Görkem Özdemir

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引用次数: 0

Abstract

In this study, we present a comprehensive first-principles investigation into the structural, electronic, optical, magnetic, and hyperfine properties of olivine-type LiMPO₄ compounds (M =Co, Fe, Mg, Mn), using the full-potential linearized augmented plane wave (FP-LAPW) method within density functional theory (DFT). All compounds crystallize in the orthorhombic Pnma space group, with structural parameters exhibiting systematic variation according to the ionic radius of the M−site cation. Electronic band structure analysis reveals insulating behavior in LiFePO₄ and LiMgPO₄ with wide band gap, while LiCoPO₄ and LiMnPO₄ are identified as wide-bandgap semiconductors, owing to transition metal 3d–O 2p hybridization. Optical studies demonstrate pronounced anisotropy in dielectric response and absorption spectra, with LiMgPO₄ exhibiting the highest absorption threshold. Spin-polarized calculations unveil high-spin magnetic configurations in transition-metal-based compounds, with total cell magnetic moments. Furthermore, hyperfine interaction analysis, including electric field gradients and magnetic shielding tensors, and highlights significant anisotropy effects, particularly for Fe2⁺ and Mn2⁺ centers. The quadrupole coupling constants (C_Q) and asymmetry parameters (η) provide insights into local symmetry breaking and electron density distribution around metal centers. This integrated computational approach underscores the tunability of LiMPO₄ compounds for next-generation lithium-ion battery cathodes and multifunctional materials with optoelectronic and magnetic properties.

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用DFT研究了锂离子电池用橄榄石型LiMPO4 （M = Fe, Mn, Co, Mg）阴极的光电、磁、EFG和NMR性能

在本研究中，我们利用密度泛函理论（DFT）中的全势线性化增广平面波（FP-LAPW）方法，对橄榄石型LiMPO4化合物（M =Co, Fe, Mg, Mn）的结构、电子、光学、磁性和超精细性质进行了全面的第一性原理研究。所有化合物均在正交Pnma空间群中结晶，结构参数根据M -位阳离子的离子半径有系统的变化。电子能带结构分析表明，LiFePO4和LiMnPO4具有宽带隙的绝缘性能，而LiCoPO4和LiMnPO4由于过渡金属3d-O - 2p杂化而被确定为宽带隙半导体。光学研究表明，介质响应和吸收光谱具有明显的各向异性，其中LiMgPO4具有最高的吸收阈值。自旋极化计算揭示了过渡金属基化合物中具有总磁矩的高自旋磁构型。此外，超精细相互作用分析，包括电场梯度和磁屏蔽张量，并强调了显著的各向异性效应，特别是对Fe2+和Mn2+中心。四极耦合常数（CQ）和不对称参数（η）为研究金属中心周围的局部对称性破缺和电子密度分布提供了新的视角。这种综合计算方法强调了LiMPO4化合物在下一代锂离子电池阴极和具有光电和磁性能的多功能材料中的可调性。

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

Results in Physics MATERIALS SCIENCE, MULTIDISCIPLINARYPHYSIC-PHYSICS, MULTIDISCIPLINARY

CiteScore

8.70

自引率

9.40%

发文量

754

审稿时长

50 days

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