Oxidation state of vanadium in amorphous MnV2O6 formed during discharge-charge cycle and the improvement of its synthesis condition

Crystalline powders of anhydrous MnV2O6 were successfully synthesized at a temperature below 200 degrees C under autogenous hydrothermal condition. MnV2O6 powders, which were synthesized using high concentration solutions, more than 0.1 mol/L, gave a relatively high reversible capacity of 600 mA h/g and interesting cyclic performance, reversible capacity increasing to more than an initial charge capacity after the 3rd or 4th cycle of charge-discharge. The change in oxidation state of V ion on the course of the 1st discharge-charge process was investigated by different techniques, such as XAFS and XPS. During discharging, V5+ was found to change gradually to V4+, but it returned back completely to V5+ on charging process. The thinner particles of MnV2O6 crystals with rod-like morphology were synthesized at 135 degrees C, and much better anodic performance was achieved, much smaller irreversible capacity as about 300 mA h/g, stable reversible capacity as 600 mA h/g, and 100% Coulombic efficiency. (c) 2006 Published by Elsevier B.V.