Experimental and Computational Study of the Structure and Electrochemical Properties of LixM2(PO4)3 Compounds with the Monoclinic and Rhombohedral Structure
Experimental and Computational Study of the Structure and Electrochemical Properties of LixM2(PO4)3 Compounds with the Monoclinic and Rhombohedral Structure
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DOI：
10.1021/cm020348o
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发表时间：
2002-10
影响因子：
8.6
通讯作者：
D. Morgan;G. Ceder;M. Saidi;J. Barker;Jeffrey Swoyer;A. H. Huang;G. Adamson
中科院分区：
文献类型：
--
作者：
D. Morgan;G. Ceder;M. Saidi;J. Barker;Jeffrey Swoyer;A. H. Huang;G. Adamson
本文对单斜斜和菱形LixM2(PO4)3的结构和电化学性能（重点是M = V）进行了计算和实验相结合的研究。确定了稀Li占位和稳定Li有序相的首选位置。电压曲线的特征可以理解为来自于位点能量学、锂有序和氧化还原偶对。发现这些特征在很大程度上与合金无关，并提出了一个简单的加性模型来分析单斜结构中任何阳离子取代的电压曲线。该模型对理解一些取代化合物的实验结果非常有用。大多数重要阳离子的电压都是由第一性原理计算出来的，并且可以与简单的模型相结合来预测新的合金单斜体系的电压曲线。
This paper presents a combined computational and experimental study of the structural and electrochemical properties of monoclinic and rhombohedral LixM2(PO4)3 (with a focus on M = V). The preferred sites for dilute Li occupation and stable Li ordered phases are identified. Features of the voltage curve are understood as emerging from site energetics, Li ordering, and redox couples. These features are found to be largely independent of alloying and a simple additive model is proposed to analyze the voltage curve for any cation substitution in the monoclinic structure. The model is shown to be very useful for understanding experimental results for a number of substituted compounds. Voltages for most important cations are calculated from first principles and can be combined with the simple model to predict voltage curves for new alloyed monoclinic systems.