Pathways to sustainable lithium-mediated ammonia electrosynthesis: tuning reaction environment and advancing reactor...

Electrochemical lithium-mediated nitrogen reduction (Li-NRR) represents a highly promising, renewable-powered alternative to the energy-intensive Haber-Bosch process for green ammonia synthesis. By electrochemically reducing lithium ions to metallic lithium, which subsequently dissociates the inert N₂ molecule, modern Li-NRR systems have achieved unprecedented faradaic efficiencies and remarkable long-term stability. This review critically assesses the recent milestones and fundamental chemistry underpinning Li-NRR. We detail how rational electrolyte engineering-encompassing lithium salts, organic solvents, and proton carriers-can be tailored to actively control the composition of the solid-electrolyte interphase and suppress parasitic side reactions. We further provide insights into the physical operational parameters governing interfacial mass transport, highlighting the kinetic mismatch between rapid lithium deposition and sluggish reactant diffusion. Finally, we discuss the evolution of reactor design, from high-pressure batch cells to gas diffusion electrode flow cells. Concluding with a forward-looking perspective, this review outlines the critical challenges of Li-NRR that must be addressed to realize a sustainable, decentralized ammonia economy.