Lithium‐Mediated Nitrogen Reduction for Ammonia Synthesis: Reviewing the Gap between Continuous Electrolytic Cells and Stepwise Processes through Galvanic Li─N 2 Cells

Abstract Electrochemical N 2 reduction reaction (E‐NRR) has recently gained increasing interest within the scientific community, due to the ongoing energy crisis and pursuit of process sustainability. In this scenario, emerging lithium‐mediated (Li‐m) strategies are obtaining promising Faradaic efficiency (FE) and NH 3 production rate values. In this work, the Li‐m scenarios are classified and explained toward a more sustainable process. Continuous processes, with a lithium salt and a proton donor in an electrolytic cell, are analyzed and compared with stepwise pathways. Different parameters are summarized in relation to the system stability, for which the importance of a tailored solid electrolyte interphase (SEI) layer emerged. Among stepwise processes, the thermochemical direct nitridation of lithium is discussed together with the recently developed Galvanic Li─N 2 cell strategy.