Dynamic Interfacial Microstructure for Lithium‐Mediated Ammonia Synthesis: Advances and Mechanistic Insights

Ammonia acts as a pivotal platform chemical in industry and an ideal hydrogen carrier in renewable energy sector. Lithium‐mediated nitrogen reduction (Li‐NRR) is a highly promising electricity‐driven ammonia synthesis route intrinsically compatible with intermittent renewable energy. Distinguished from electrocatalytic processes, Li‐NRR process integrates both electrochemical and thermochemical reaction steps, where the collective effects of their kinetics and mass transports on the overall Li‐NRR performance are ambiguous. Moreover, the complex interfacial structure dynamics and the interplay between each individual reaction step remain less understood. These knowledge gaps severely hinder further improvements in reaction performance and long‐term stability. In this review, the Li‐NRR process is decoupled first to identify the bottlenecks of individual reaction steps and overall performance. Recent advances are then summarized in terms of four core aspects of Li‐NRR from a perspective of surface dynamics and reaction kinetics. The underpinning mechanisms are discussed to derive design principles to further optimize Li‐NRR performance. This review outlines directions for advancing Li‐NRR toward industrial application and also offers insights applicable to other gas‐involved electrochemical synthesis systems in organic electrolytes.