Oxygen Vacancy‐Mediated Growth of Amorphous Discharge Products toward an Ultrawide Band Light‐Assisted Li–O₂ Batteries

Abstract Photoassisted electrochemical reaction is regarded as an effective approach to reduce the overpotential of lithium–oxygen (Li–O₂) batteries. However, the achievement of both broadband absorption and long term battery cycling stability are still a formidable challenge. Herein, an oxygen vacancy‐mediated fast kinetics for a photoassisted Li–O₂ system is developed with a silver/bismuth molybdate (Ag/Bi₂MoO₆) hybrid cathode. The cathode can offer both double advantages for light absorption covering UV to visible region and excellent electrochemical activity for O₂. Upon discharging, the photoexcited electrons from Ag nanoplate based on the localized surface plasmon resonance (LSPR) are injected into the oxygen vacancy in Bi₂MoO₆. The fast oxygen reaction kinetics generate the amorphous Li₂O₂, and the discharge plateau is improved to 3.05 V. Upon charging, the photoexcited holes are capable to decompose amorphous Li₂O₂ promptly, yielding a very low charge plateau of 3.25 V. A first cycle round‐trip efficiency is 93.8% and retention of 70% over 500 h, which is the longest cycle life ever reported in photoassisted Li–O₂ batteries. This work offers a general and reliable strategy for boosting the electrochemical kinetics by tailoring the crystalline of Li₂O₂ with wide‐band light.