Electronic structure evolution upon lithiation: A Li K-edge study of silicon oxide anode through X-ray Raman spectroscopy

IF 5.4 Q2 CHEMISTRY, PHYSICAL
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Abstract

The comprehensive understanding of the local structural changes surrounding lithium in lithium silicate (LixSiOy) and silicide (LixSi) within Li/SiOx batteries during the reversible structural transformations has been hindered by the limitations of current methodologies. In this work, the evolution of electronic structure at various lithiation stages has been addressed well by examining the Li K-edge spectra through X-ray Raman spectroscopy (XRS). The features observed in the Li K-edge XRS spectra provide insights into the development and alteration of LixSiOy, which emerges in the initial phases and may be accompanied by a reduction in the ionicity of Li–O bonding during lithiation. These features also agree well with the accompanying FDMNES code simulation. The correlation between electrochemical mechanisms and spectral characteristics is further explored by applying pseudo-Voigt peaks and cumulative pseudo-Voigt functions for fitting purposes. The absence of a significant edge shift indicates a similarity in the electronic structure of LixSi throughout lithiation, and no evidence of Li2O formation has also been observed. The Li K-edge XRS spectra exhibit strong agreement with the electrochemical behavior, establishing it as a valuable tool for investigating the evolution of electronic structure in Li/SiOx batteries.

锂化过程中的电子结构演变:通过 X 射线拉曼光谱研究氧化硅阳极的锂 K 边
在锂/氧化硅电池中,硅酸锂(LixSiOy)和硅化锂(LixSi)在可逆结构转变过程中围绕锂的局部结构变化的全面理解一直受到现有方法的限制。在这项研究中,通过 X 射线拉曼光谱(XRS)检查锂 K 边光谱,很好地解决了不同锂化阶段的电子结构演变问题。在锂 K 边 XRS 光谱中观察到的特征有助于深入了解 LixSiOy 的发展和变化,这种变化出现在初始阶段,并可能伴随着锂化过程中 Li-O 键离子性的降低。这些特征与随附的 FDMNES 代码模拟也非常吻合。通过应用伪伏依格特峰和累积伪伏依格特函数进行拟合,进一步探讨了电化学机制与光谱特征之间的相关性。没有明显的边缘偏移表明 LixSi 在整个锂化过程中的电子结构相似,也没有观察到 Li2O 形成的证据。锂 K 边 XRS 光谱与电化学行为非常吻合,是研究锂/氧化硅电池电子结构演变的重要工具。
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
CiteScore
9.10
自引率
0.00%
发文量
18
审稿时长
64 days
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