Enzyme‐Inspired Room‐Temperature Lithium–Oxygen Chemistry via Reversible Cleavage and Formation of Dioxygen Bonds

Abstract Li‐O 2 batteries are promising energy storage systems due to their ultra‐high theoretical capacity. However, most Li‐O 2 batteries are based on the reduction/oxidation of Li 2 O 2 and involve highly reactive superoxide and peroxide species that would cause serious degradation of cathodes, especially carbon‐based materials. It is important to explore lithium‐oxygen reactions and find new Li‐O 2 chemistry which can restrict or even avoid the negative influence of superoxide/peroxide species. Here, inspired by enzyme‐catalyzed oxygen reduction/oxidation reactions, we introduce a copper(I) complex 3 N‐Cu I (3 N=1,4,7‐trimethyl‐1,4,7‐triazacyclononane) to Li‐O 2 batteries and successfully modulate the reaction pathway to a moderate one on reversible cleavage/formation of O−O bonds. This work demonstrates that the reaction pathways of Li‐O 2 batteries could be modulated by introducing an appropriate soluble catalyst, which is another powerful choice to construct better Li‐O 2 batteries.