Phosphorus Vacancies and Heterojunction Interface as Effective Lithium‐Peroxide Promoter for Long‐Cycle Life Lithium–Oxygen Batteries

Abstract An electrocatalyst with excellent performance is widely perceived as core materials to solve the practical application of lithium–oxygen batteries (LOBs). Vacancy/interfacial engineering can affect reaction intermediate adsorption and catalytic activity by manipulating the local electronic structure, which is key to improving the performance of LOBs. Here, MoO₂‐supported Mo₃P@Mo nanocomposites with phosphorus vacancy and interfacial contact are facile synthesized and used as the electrocatalyst to control the morphology of lithium peroxide (Li₂O₂) and to boost the electrochemical performance of LOBs. The nanocomposites exhibit excellent electrochemical performance with lower overpotential and super long cycling stability, can stably cycle for 500 cycles at 500 mA g⁻¹ with a round‐trip efficiency close to 100%, and can work for 1370 h with failure at the lower cut‐off of 2 V. The influence of the interface and phosphorus vacancy, and the catalytic mechanism are explained by the result about first‐principles calculations and experimental studies.