The Effect of Applied Potential on the Li-mediated Nitrogen Reduction Reaction Performance

The Li-mediated nitrogen reduction reaction (Li-NRR) has been proposed as one of the most promising ambient production routes for green ammonia. However, the effect of the applied potential (E_we) on the reaction performance and the properties of the solid electrolyte interphase (SEI) remain poorly understood. Herein, we combine potential controlled experiments using a reliable Li_xFePO₄ based reference electrode with post-mortem SEI characterization techniques, wherein we observe both an increase in the LiF concentration in the SEI, originating from LiTFSI decomposition, and the Faradaic efficiency (FE_NH3) with an increasing E_we. The transition from a predominantly organic SEI at low E_we (−3.2 V_SHE) to a LiF-enriched layer at higher E_we indicates the existence of kinetic barriers for the SEI formation reactions. Moreover, thicker and denser SEI structures observed at a higher E_we enhance the Li-NRR by improving the mass transport regulation between reactant species. However, these thicker and denser SEI morphologies lead to current instabilities due to dynamic SEI thickening and breakdown.