Extending Ring‐Chain Coupling Empirical Law to Lithium‐Mediated Electrochemical Ammonia Synthesis.

With its efficient nitrogen fixation kinetics, electrochemical lithium‐mediated nitrogen reduction reaction (LMNRR) holds promise for replacing Haber–Bosch process and realizing sustainable and green ammonia production. However, the general interface problem in lithium electrochemistry seriously impedes the further enhancement of LMNRR performance. Inspired by the development history of lithium battery electrolytes, here, we extend the ring‐chain solvents coupling law to LMNRR system to rationally optimize the interface during the reaction process, achieving nearly a two‐fold Faradaic efficiency up to 54.78±1.60 %. Systematic theoretical simulations and experimental analysis jointly decipher that the anion‐rich Li+ solvation structure derived from ring tetrahydrofuran coupling with chain ether successfully suppresses the excessive passivation of electrolyte decomposition at the reaction interface, thus promoting the mass transfer of active species and enhancing the nitrogen fixation kinetics. This work offers a progressive insight into the electrolyte design of LMNRR system. [ABSTRACT FROM AUTHOR]