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Three-dimensional (3D) porous V2O5 octahedrons have been successfully fabricated via a solid-state conversion process of freshly prepared ammonium vanadium oxide (AVO) octahedrons. The formation of AVO octahedrons is a result of the selective adsorption of capping reagents and the favourable supersaturation of growth species. Subsequently, 3D porous V2O5 octahedrons were obtained by simple thermolysis of the AVO octahedrons via a calcination treatment. As cathode material for lithium batteries, the porous V2O5 octahedron cathode exhibits a capacity of 96 mA·g-1 at high rate up to 2 A·g-1 in the rang of 2.4–4 V and excellent cyclability with little capacity loss after 500 cycles, which can be ascribed to its high specific surface area and tunable pore architecture. Importantly, this facile solid-state thermal conversion strategy can be easily extended to controllably fabricate other porous metal oxide micro/nano materials with specific surface textures and morphologies.
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