Operando Investigations of the Solid Electrolyte Interphase in the Lithium Mediated Nitrogen Reduction Reaction

12 March 2024, Version 1


The lithium-mediated nitrogen reduction reaction (Li-NRR) represents a promising approach for electrochemical nitrogen activation, in which the solid electrolyte interphase (SEI) layer formed on the electrochemically plated lithium plays a key role. Herein, we used time-resolved, operando, grazing incidence wide-angle X-ray scattering (GI WAXS) to identify SEI species and reaction intermediates in the Li-NRR, comparing LiBF4 and LiClO4 as electrolyte salts. We demonstrated how the SEI composition influences the Li-NRR performance by regulating proton transport to the plated Li. When LiBF4 is used as electrolyte salt, the formation of LiF and Lithium ethoxide (LiEtO) is observed. Reaction intermediates such as LiH and LiNxHy species were found and provide insight into reaction pathways towards undesired and desired products, respectively. Observed restructuring of the Cu (111) single crystal substrate also indicates interaction with plated Li that could possibly influence the Li-NRR performance. Together, these experiments give molecular insight on how to design Li-NRR systems and their SEI layers for optimal performance.


Electrochemical Ammonia Synthesis
Lithium mediated ammonia synthesis
Nitrogen Reduction Reaction
Solid Electrolyte Interphase
Li plating
In operando
grazing incidence
Wide Angle X-ray scattering

Supplementary materials

Electronic Supporting Information
Additional Figures and additional experimental data


Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.