Institut de Chimie et Matériaux Paris-Est, GESMAT, UMR 7182 CNRS et Université Paris-Est Créteil, 2 rue Henri Dunant, 94320 Thiais, France.
Inorg Chem. 2012 Mar 5;51(5):3194-201. doi: 10.1021/ic202651b. Epub 2012 Feb 23.
We report here the Raman spectrum and lattice dynamics study of a well-crystallized β-V(2)O(5) material prepared via a high-temperature/high-pressure (HT/HP) route, using α-V(2)O(5) as the precursor. Periodic quantum-chemical density functional theory calculations show good agreement with the experimental results and allow one to assign the observed spectral features to specific vibrational modes in the β-V(2)O(5) polymorph. Key structure-spectrum relationships are extracted from comparative analysis of the vibrational states of the β-V(2)O(5) and α-V(2)O(5) structures, and spectral patterns specific to the basic units of the two V(2)O(5) phases are proposed for the first time. Such results open the way for the use of Raman spectroscopy for the structural characterization of vanadium oxide-based host lattices of interest in the field of lithium batteries and help us to greatly understand the atomistic mechanism involved in the α-to-β phase transition of vanadium pentoxide.
我们在此报告了通过高温高压 (HT/HP) 路线用 α-V2O5 作为前体制备的结晶良好的β-V2O5 材料的拉曼光谱和晶格动力学研究。周期性量子化学密度泛函理论计算与实验结果吻合良好，使我们能够将观察到的光谱特征分配给β-V2O5 多晶型物中的特定振动模式。通过对β-V2O5 和 α-V2O5 结构的振动状态的比较分析，得出了关键的结构-光谱关系，并首次提出了两种 V2O5 相基本单元特有的光谱模式。这些结果为拉曼光谱在锂电池领域中感兴趣的氧化钒基主体晶格的结构表征开辟了道路，并帮助我们更好地理解五氧化二钒的α-到-β 相变中的原子机制。
