Self-Catalyzed Rechargeable Lithium-Air Battery by in situ Metal Ion Doping of Discharge Products: A Combined Theoretical and Experimental Study

Lithium-air battery has emerged as a viable electrochemical energy technology;yet a substantial overpotential is typically observed,due to the insulating nature of the discharge product Li_(2)O_(2) that hinders the reaction kinetics and device performance.Furthermore,finite solid–solid/-liquid interfaces are formed between Li_(2)O_(2) and catalysts and limit the activity of the electrocatalysts in battery reactions,leading to inadequate electrolytic efficiency.Herein,in-situ doping of Li_(2)O_(2) by select metal ions is found to significantly enhance the lithium-air battery performance,and Co^(2+)stands out as the most effective dopant among the series.This is ascribed to the unique catalytic activity of the resulting Co-O_(x) sites towards oxygen electrocatalysis,rendering the lithium-air battery self-catalytically active.Theoretical studies based on density functional theory calculations show that structural compression occurs upon Co^(2+)doping,which lowers the energy barrier of Li_(2)O_(2) decomposition.Results from this study highlight the significance of in situ electrochemical doping of the discharge product in enhancing the performance of lithium-air battery.