Enhancing Interfacial Dioxygen Bridging Dynamics of Waste‐Derived Cathode Catalysts for Augmented High‐Rate Performance in Li‐O2 Batteries

This study fabricates Fine Slag/Ti4O7@TiC hybrids with interfacial dioxygen bridge coupling to optimize oxygen redox dynamics in lithium‐oxygen batteries (LOBs). Lattice distortion from oxygen vacancies and inherent charge repulsion of Ti‐O‐C interfacial coupling reconstruct and refine the surface coordination environment. LOBs using this catalyst exhibit ultralong cycle stability (210 cycles at 3000 mA g−1) and ultra‐high rate performance (1000–10 000 mA g−1). ABSTRACT Lithium–oxygen batteries (LOBs) are widely regarded as promising candidates for next‐generation high‐specific‐energy storage systems. However, their development is hindered by the disorderly accumulation of insulating products and sluggish oxygen redox kinetics (including ORR and OER). The rational design of high‐efficiency cathode catalysts is therefore critical for improving the overall performance of LOBs. In this work, a novel concept of interfacial dioxygen bridge coupling to design bifunctional cathode electrocatalysts derived from mining solid waste is introduced. Specifically, lattice distortion induced by oxygen vacancies, together with the intrinsic charge repulsion of Ti–O–C bonds on the (1–20) plane, cooperatively drives surface reconstruction and refines the local coordination environment. This structural adjustment consequently enhances the adsorption properties for ORR/OER, thereby improving the overall electrochemical performance. The Fine Slag/Ti4O7@TiC hybrid exhibits modified chemical bonding and remarkable stability at high rates. LOBs fabricated with the Fine Slag/Ti4O7@TiC catalyst deliver a reduced voltage polarization of only 1.42 V, ultralong cycle stability of 210 cycles at 3000 mA g−1, and outstanding high‐rate performance (from 1000 to 10 000 mA g−1). DFT analysis and ex‐situ characterization further elucidate the pivotal role of interfacial dioxygen bridge coupling in governing the micro‐chemical composition and manipulating the formation pathway of Li2O2. This study fabricates Fine Slag/Ti 4 O 7 @TiC hybrids with interfacial dioxygen bridge coupling to optimize oxygen redox dynamics in lithium-oxygen batteries (LOBs). Lattice distortion from oxygen vacancies and inherent charge repulsion of Ti-O-C interfacial coupling reconstruct and refine the surface coordination environment. LOBs using this catalyst exhibit ultralong cycle stability (210 cycles at 3000 mA g −1 ) and ultra-high rate performance (1000–10 000 mA g −1 ). ABSTRACT Lithium–oxygen batteries (LOBs) are widely regarded as promising candidates for next-generation high-specific-energy storage systems. However, their development is hindered by the disorderly accumulation of insulating products and sluggish oxygen redox kinetics (including ORR and OER). The rational design of high-efficiency cathode catalysts is therefore critical for improving the overall performance of LOBs. In this work, a novel concept of interfacial dioxygen bridge coupling to design bifunctional cathode electrocatalysts derived from mining solid waste is introduced. Specifically, lattice distortion induced by oxygen vacancies, together with the intrinsic charge repulsion of Ti–O–C bonds on the (1–20) plane, cooperatively drives surface reconstruction and refines the local coordination environment. This structural adjustment consequently enhances the adsorption properties for ORR/OER, thereby improving the overall electrochemical performance. The Fine Slag/Ti 4 O 7 @TiC hybrid exhibits modified chemical bonding and remarkable stability at high rates. LOBs fabricated with the Fine Slag/Ti 4 O 7 @TiC catalyst deliver a reduced voltage polarization of only 1.42 V, ultralong cycle stability of 210 cycles at 3000 mA g −1, and outstanding high-rate performance (from 1000 to 10 000 mA g −1 ). DFT analysis and ex-situ characterization further elucidate the pivotal role of interfacial dioxygen bridge coupling in governing the micro-chemical composition and manipulating the formation pathway of Li 2 O 2. Advanced Science, EarlyView.