Relay orbital hybridization on MnMoO₄ catalysts for durable lithium–oxygen batteries

MnMoO₄ holds great promise as a cathode material for lithium–oxygen batteries (LOBs), but its poor conductivity and weak interaction with oxygenated intermediates substantially impede its electrocatalytic properties. Herein, electron-deficient P atoms were incorporated with MnMoO₄ hollow nanospheres (P-doped MnMoO₄) to realize internal orbital interactions between Mo 4d and P 3p, activating external orbital hybridization between catalysts and LiO₂ during cycling. This relay orbital hybridization not only promoted charge transfer but also optimized the adsorption and desorption abilities of catalysts toward LiO₂, thereby reducing the reaction energy barriers. Consequently, LOBs with P-doped MnMoO₄ cathode catalysts sustained steady operation for 380 cycles under 1000 mA g⁻¹, which is even better than some of their noble metal counterparts and points to their commercial promise for use in future large-scale applications. This work provides general guidance for constructing relay orbital hybridization through P doping on catalysts for LOBs and other electrocatalytic systems. © 2025 The Authors.