Revealing the illumination effect on the discharge products in high‐performance Li–O₂ batteries with heterostructured photocatalysts

Abstract Aprotic lithium–oxygen batteries (LOBs) have been recognized as novel energy storage devices for their outstanding specific energy density, while the large discharge/charge overpotential is a tough barrier to be overcome. Here, hetero‐structured MoS₂/ZnIn₂S₄ nanosheets have been prepared to capture visible light and the generated charge carriers are utilized for promoting both the oxygen reduction reaction and the oxygen evolution reaction. With the light illumination in the discharge process, the abundant photo‐inspired electrons serve as the reaction sites to promote the reduction of O₂ into LiO₂ which is finally deposited as Li₂O₂. On the contrary, the generated holes in the valence band can contribute to the low oxidization potential of Li₂O₂ during the charge process. It delivers a low charge potential of 3.29 V, with an excellent resulting energy efficiency of 96.7%, much superior to that of 69.2% in the dark condition. It is noted that the involvement of photoelectrons has influenced the growth of Li₂O₂ films on the MoS₂/ZnIn₂S₄ nanosheets through the surface‐adsorption pathway. The insights from the theoretical calculation confirm that the photoelectrons favor the absorption of LiO₂ and the formation of the Li₂O₂ film through the surface route. Therefore, this paper provides a deeper understanding of the mechanism of photo‐inspired charge carriers in LOBs and will enable further exploration of photo‐involved energy storage systems.