Aprotic Alkali Metal–O₂ Batteries: Role of Cathode Surface-Mediated Processes and Heterogeneous Electrocatalysis

Alkali metal–O2 batteries (i.e., Li/Na–O2) with high specific energies are promising alternatives to state-of-the-art metal-ion batteries. However, they are plagued by challenges arising from the underlying redox chemistry, resulting in reduced efficiencies. These challenges for Li/Na–O2 batteries stem from the nature of the interface between solid discharge product(s) and either (i) the aprotic electrolyte or (ii) the solid cathode. In the former, the reactive nature of the solid/liquid interface leads to chemical disproportionation of the discharge product(s) and the electrolyte, while in the latter, the presence/lack of atomistic interactions at the solid–solid interface leads to large overpotential losses (>1 V) during charging. Approaches to overcome these challenges would involve decoupling these factors. For instance, the use of inert aprotic electrolytes would facilitate catalytically driven, surface-mediated discharge product(s) growth, providing avenues to use cathode surface modifications as levers to enhance voltaic efficiency and discharge product stability, resulting in improved performance.