The origin of overpotential in lithium-mediated nitrogen reduction
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Published version
Author(s)
Type
Journal Article
Abstract
The verification of the lithium-mediated nitrogen reduction system in 2019 has led to an explosion in the literature focussing on improving the metrics of faradaic efficiency, stability, and activity. However, while the literature acknowledges the vast intrinsic overpotential for nitrogen reduction due to the reliance on in situ lithium plating, it has thus far been difficult to accurately quantify this overpotential and effectively analyse further voltage losses. In this work, we present a simple method for determining the Reversible Hydrogen Electrode (RHE) potential in the lithium-mediated nitrogen reduction system. This method allows for an investigation of the Nernst equation and reveals sources of potential losses. These are namely the solvation of the lithium ion in the electrolyte and resistive losses due to the formation of the solid electrolyte interphase. The minimum observed overpotential was achieved in a 0.6 M LiClO4, 0.5 vol% ethanol in tetrahydrofuran electrolyte. This was −3.59 ± 0.07 V vs. RHE, with a measured faradaic efficiency of 6.5 ± 0.2%. Our method allows for easy comparison between the lithium-mediated system and other nitrogen reduction paradigms, including biological and homogeneous mechanisms.
Date Issued
2023
Date Acceptance
2022-11-29
Citation
Faraday Discussions, 2023, 243, pp.321-338
ISSN
1359-6640
Publisher
Royal Society of Chemistry
Start Page
321
End Page
338
Journal / Book Title
Faraday Discussions
Volume
243
Copyright Statement
This journal is © The Royal Society of Chemistry 2023 This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
License URL
Identifier
https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000974690600001&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=a2bf6146997ec60c407a63945d4e92bb
Subjects
AMMONIA-SYNTHESIS
Chemistry
Chemistry, Physical
COUPLING STRENGTH
EFFICIENCY
ELECTROCHEMICAL REDUCTION
ELECTRODE
N2
N-2 REDUCTION
OXIDATION POTENTIALS
Physical Sciences
Science & Technology
THERMODYNAMICS
Publication Status
Published
Date Publish Online
2022-11-29