In Situ Neutron Reflectometry Reveals the Interfacial Microenvironment Driving Electrochemical Ammonia Synthesis

Electrified interfaces are critical to the performance of energy systems and often demonstrate substantial complexity under operating conditions. A nanoscale understanding of the interfacial microenvironment, i.e., the solid-electrolyte interphase (SEI), in lithium-mediated nitrogen reduction (Li-N2R) is key for realizing efficient ammonia (NH3) production. Herein, we used time-resolved neutron reflectometry (NR) to observe SEI formation under Li-N2R conditions. We found that the LiBF4-based electrolyte provided a substantially more well-defined SEI layer than previous SEI NR interrogations that used LiClO4, highlighting the underlying chemistry that dictates electrolyte design and enabling new NR-based studies. Using in situ NR, we found that the LiBF4-derived SEI under Li-N2R conditions comprises a thick, diffuse outer layer and a thin, compact inner layer at low current cycling (<2 mA/cm2), revealing a structure which ex situ studies have not been able to probe. Increased current cycling and sustained current cycling led to the merging of the layers into a single-layer SEI. We used isotope contrast methods with d6-EtOH and d8-THF to drive time-resolved tracking of SEI growth at low current cycling, revealing that the proton donor modifies the inner layer, and the solvent modifies the outer layer. Li dendritic growth was observed in the absence of a proton donor. Neutron absorption also indicated the presence of boron in the SEI, underscoring the value of neutron-based interrogation. Our results inform Li-based systems and reaction microenvironments, and these methods can be applied broadly to interfacial energy technologies.