Vanadium Doping Enhanced Electrochemical Performance of Molybdenum Oxide in Lithium‐Ion Batteries

Abstract Molybdenum trioxide (MoO 3 ) suffers from poor conductivity, a low rate capability, and unsatisfactory cycling stability in lithium‐ion batteries. The aliovalent ion doping may present an effective way to improve the electrochemical performances of MoO 3 . Here, it is shown, by first‐principle calculations, that doping MoO 3 with V by 12.5% can modulate significantly electronic structure and provide a small diffusion barrier for enhancing the electrochemical performance of MoO 3 . The ultralong Mo 0.88 V 0.12 O 2.94 nanostructures, which retain the h‐MoO 3 structure and present an exceptionally high conductivity and fast ionic diffusion due to the substitution of V, facilitating lithiation/delithiation behavior, and induce a fine nanosized structure with a reduced volume change are prepared. As a result, the stress and strain are alleviated during the Li‐ion intercalation/deintercalation processes, improving the cycling stability and rate capability. Such a large improvement in the electrochemical properties can be ascribed to the stabilizing effect of V, the small migration energy barrier, and short diffusion path, which arise from the introduction of V into MoO 3 . The unique engineering strategy and facile synthesis route open up a new avenue in modifying and developing other species of electrode materials.