Vanadium(III) Acetylacetonate as an Efficient Soluble Catalyst for Lithium–Oxygen Batteries

High donor number (DN) solvents in Li—O₂ batteries that dissolve superoxide intermediates in lithium peroxide (Li₂O₂) formation facilitate high capacities at high rates and avoid early cell death. However, their beneficial characteristics also result in an instability towards highly reactive superoxide intermediates. Furthermore, Li—O₂ batteries would deliver a superior energy density, but the multiphase electrochemical reactions are difficult to achieve when operating with only solid catalysts. Herein we demonstrate that vanadium(III) acetylacetonate (V(acac)₃) is an efficient soluble catalyst that can address these problems. During discharge, V(acac)₃ integrates with the superoxide intermediate, accelerating O₂ reduction kinetics and reducing side reactions. During charge, V(acac)₃ acts as a redox mediator that permits efficient oxidation of Li₂O₂. The cells with V(acac)₃ exhibit low overpotential, high rate performance, and considerable cycle stability.