Insight into Fluoride Additives to Enhance Ammonia Production from Lithium‐Mediated Electrochemical Nitrogen Reduction Reaction

• Published in: Small (Weinheim an der Bergstrasse, Germany) Germany), 2024-10, Vol.20 (40), p.e2404525-n/a
• Main Authors: Shin, Dongwoo, Jeon, Yeongbae, Nguyen, Vy Thuy, Kang, Shinmyeong, Hong, Yewon, Lim, Chaeeun, Yong, Kijung, Shin, Hyeyoung, Hwang, Yun Jeong
• Format: Article
• Language: English
• Subjects: Additives; Ammonia; ammonia synthesis; Bulk density; Chemical reactions; Chemical reduction; Density functional theory; electrochemical nitrogen reductions; Electrolytes; Lithium; Lithium fluoride; lithium‐mediated nitrogen reduction; Molecular orbitals; Production increases; Protonation; solid electrolyte interphases; Solid electrolytes
• ISSN: 1613-6810; 1613-6829; 1613-6829
• DOI: 10.1002/smll.202404525

Demands for green ammonia production increase due to its application as a proton carrier, and recent achievements in electrochemical Li‐mediated nitrogen reduction reactions (Li‐NRRs) show promising reliability. Here, it is demonstrated that F‐containing additives in the electrolyte improve ammonia production by modulating the solid electrolyte interphase (SEI). It is suggested that the anionic additives with low lowest unoccupied molecular orbital levels enhance efficiency by contributing to the formation of a conductive SEI incorporated with LiF. Specifically, as little as 0.3 wt.% of BF4− additive to the electrolyte, the Faradaic efficiency (FE) for ammonia production is enhanced by over 15% compared to an additive‐free electrolyte, achieving a high yield of 161 ± 3 nmol s−1 cm−2. The BF4− additive exhibits advantages, with decreased overpotential and improved FE, compared to its use as the bulk electrolyte. The observation of the Li3N upper layer implies that active Li‐NRR catalytic cycles are occurring on the outermost SEI, and density functional theory simulations propose that an SEI incorporated with LiF facilitates energy profiles for the protonation by adjusting the binding energies of the intermediates compared to bare copper. This study unlocks the potential of additives and offers insights into the SEIs for efficient Li‐NRRs. Incorporating F‐containing additives with low lowest unoccupied molecular orbital (LUMO) energies provides a conductive solid electrolyte interphase (SEI), which significantly enhances ammonia production from Li‐mediated nitrogen reduction reactions (Li‐NRRs). The Li3N in the outermost layer coupled with the development of a LiF‐enriched layer from additives assists the enhanced ammonia production from Li‐NRRs.