First-Principles Design of Graphene-Based Active Catalysts for Oxygen Reduction and Evolution Reactions in the Aprotic Li-O₂ Battery

Using first-principles density functional theory (DFT) calculations, we demonstrate that catalytic activities toward oxygen reduction and evolution reactions (ORR and OER) in a Li-O₂ battery can be substantially improved with graphene-based materials. We accomplish the goal by calculating free energy diagrams for the redox reactions of oxygen to identify a rate-determining step controlling the overpotentials. We unveil that the catalytic performance is well described by the adsorption energies of the intermediates LiO₂ and Li₂O₂ and propose that graphene-based materials can be substantially optimized through either by N doping or encapsulating Cu(111) single crystals. Furthermore, our systematic approach with DFT calculations applied to design of optimum catalysts enables screening of promising candidates for the oxygen electrochemistry leading to considerable improvement of efficiency of a range of renewable energy devices.