Molybdenum Substituted Vanadyl Phosphate ε-VOPO4 with Enhanced Two-Electron Transfer Reversibility and Kinetics for Lithium-Ion Batteries
2016
We have investigated the possibility of molybdenum substitution into e-VOPO4 structure and its effects on the electrochemical performance of this material as a cathode in Li-ion battery. We have found that up to 5% of Mo can substitute V upon hydrothermal synthesis at 180 °C with further annealing at 550 °C. The substitution is confirmed by the increase of the unit cell volume with Mo content. A combination of X-ray absorption and photoelectron spectroscopy, magnetic studies, and density functional theory calculations indicates an Mo6+ oxidation state which is charge compensated by reduction of the same amount of V to 4+. Mo-substituted samples show much smaller particle size as compared to unsubstituted e-VOPO4 and significantly improved electrochemical behavior. e-V0.95Mo0.05OPO4 shows the initial reversible capacity ∼250 mAh/g (∼1.6 Li) and ∼80% retention for up to 20 cycles at C/25. Sloping voltage profile, faster kinetics, and lower voltage hysteresis of Mo substituted VOPO4 are demonstrated by the g...
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