This paper presents the fabrication of yolk–shell V2O5 powders with a low melting temperature of 690 °C by using a simplified two-step process. The spherical V2O3–C composite obtained by spray pyrolysis transforms into yolk–shell V2O5 powder by a simple combustion process at 400 °C. The yolk–shell V2O5 powders are composed of nanoplate crystals several tens of nanometers in size, and have a BET surface area of 15 m2 g−1. The powders exhibit initial discharge and charge capacities of 271 and 264 mA h g−1 at a current density of 1000 mA g−1, respectively, and a corresponding Coulombic efficiency of 97.4%. After 100 cycles, the discharge capacity of the yolk–shell V2O5 powders is 201 mA h g−1. In contrast, spherical V2O5 powders with a dense structure exhibit low initial discharge and charge capacities of 160 and 145 mA h g−1, respectively. The structural stability of the yolk–shell during Li-ion insertion and extraction improves the electrochemical properties of the V2O5 powders, even at high current densities.
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