Enhancing Ammonia Production by Ag Incorporation in Li-Mediated Nitrogen Reduction Reactions

Conventional ammonia production relies on the Haber–Bosch process, which is an energy-intensive process and emits significant amounts of CO 2 . Recent advances in electrochemical Li-mediated nitrogen reduction reactions (Li-NRRs) provide sustainable pathways. While efforts have been made to develop electrolytes and devices, research on cathode materials for Li-NRRs is still limited. This study demonstrates that the introduction of Ag into the copper cathode system significantly contributes to the ammonia production activity of Li-NRRs, and improved performance is obtained especially for various Li salts containing fluorine in electrolytes. Small amounts of Ag salts enhance the selectivity toward ammonia, forming LiF and Ag–Li alloys in the solid electrolyte interphase. We demonstrate that lithiophilic Ag effectively mediates Li cycling, decreasing the overpotentials required for Li plating during Li-NRRs. Our insights provide perspectives on the development of electrode materials and the potential to utilize unexplored metals as electrodes for Li-NRRs.