Single-Source Alkoxide Precursor Approach to Titanium Molybdate, TiMoO(5), and Its Structure, Electrochemical Properties, and Potential as an Anode Material for Alkali Metal Ion Batteries

单源醇盐前驱体法制备钼酸钛TiMoO(5)及其结构、电化学性能和作为碱金属离子电池负极材料的潜力

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Abstract

Transition-metal oxide nanostructured materials are potentially attractive alternatives as anodes for Li ion batteries and as photocatalysts. Combining the structural and thermal stability of titanium oxides with the relatively high oxidation potential and charge capacity of molybdenum(VI) oxides was the motivation for a search for approaches to mixed oxides of these two metals. Challenges in traditional synthetic methods for such materials made development of a soft chemistry single-source precursor pathway our priority. A series of bimetallic Ti-Mo alkoxides were produced by reactions of homometallic species in a 1:1 ratio. Thermal solution reduction with subsequent reoxidation by dry air offered in minor yields Ti(2)Mo(2)O(4)(OMe)(6)(O(i)Pr)(6) (1) by the interaction of Ti(O(i)Pr)(4) with MoO(OMe)(4) and Ti(6)Mo(6)O(22)(O(i)Pr)(16)(iPrOH)(2) (2) by the reaction of Ti(O(i)Pr)(4) with MoO(O(i)Pr)(4). An attempt to improve the yield of 2 by microhydrolysis, using the addition of stoichiometric amounts of water, resulted in the formation with high yield of a different complex, Mo(7)Ti(7+x)O(31+x)(O(i)Pr)(8+2x) (3). Controlled thermal decomposition of 1-3 in air resulted in their transformation into the phase TiMoO(5) (4) with an orthorhombic structure in space group Pnma, as determined by a Rietveld refinement. The electrochemical characteristics of 4 and its chemical transformation on Li insertion were investigated, showing its potential as a promising anode material for Li ion batteries for the first time. A lower charge capacity and lower stability were observed for its application as an anode for a Na ion battery.

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