Photo‐Assisted Li‐N2 Batteries with Enhanced Nitrogen Fixation and Energy Conversion

Abstract Li‐N 2 batteries have received widespread attention for their potential to integrate N 2 fixation, energy storage, and conversion. However, because of the low activity and poor stability of cathode catalysts, the electrochemical performance of Li‐N 2 batteries is suboptimal, and their electrochemical reversibility has rarely been proven. In this study, a novel bifunctional photo‐assisted Li‐N 2 battery system was established by employing a plasmonic Au nanoparticles (NPs)‐modified defective carbon nitride (Au‐N v ‐C 3 N 4 ) photocathode. The Au‐N v ‐C 3 N 4 exhibits strong light‐harvesting, N 2 adsorption, and N 2 activation abilities, and the photogenerated electrons and hot electrons are remarkably beneficial for accelerating the discharge and charge reaction kinetics. These advantages enable the photo‐assisted Li‐N 2 battery to achieve a low overpotential of 1.32 V, which is the lowest overpotential reported to date, as well as superior rate capability and prolonged cycle stability (≈500 h). Remarkably, a combination of theoretical and experimental results demonstrates the high reversibility of the photo‐assisted Li‐N 2 battery. The proposed novel strategy for developing efficient cathode catalysts and fabricating photo‐assisted battery systems breaks through the overpotential bottleneck of Li‐N 2 batteries, providing important insights into the mechanism underlying N 2 fixation and storage.