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-O-2 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 electro-chemistry leading to considerable improvement of efficiency of a range of renewable energy devices.