Imperial College London
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ProfessorMaryRyan

Central Faculty, Office of the Provost

Vice-Provost (Research and Enterprise)
 
 
 
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Contact

 

+44 (0)20 7594 6755m.p.ryan

 
 
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Location

 

B338Royal School of MinesSouth Kensington Campus

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Summary

 

Publications

Citation

BibTex format

@article{Westhead:2023:10.1039/d2ta07686a,
author = {Westhead, O and Spry, M and Bagger, A and Shen, Z and Yadegari, H and Favero, S and Tort, R and Titirici, M and Ryan, MP and Jervis, R and Katayama, Y and Aguadero, A and Regoutz, A and Grimaud, A and Stephens, IEL},
doi = {10.1039/d2ta07686a},
journal = {Journal of Materials Chemistry A},
pages = {12746--12758},
title = {The role of ion solvation in lithium mediated nitrogen reduction},
url = {http://dx.doi.org/10.1039/d2ta07686a},
volume = {11},
year = {2023}
}
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RIS format (EndNote, RefMan)

TY  - JOUR
AB  - Since its verification in 2019, there have been numerous high-profile papers reporting improved efficiency of lithium-mediated electrochemical nitrogen reduction to make ammonia. However, the literature lacks any coherent investigation systematically linking bulk electrolyte properties to electrochemical performance and Solid Electrolyte Interphase (SEI) properties. In this study, we discover that the salt concentration has a remarkable effect on electrolyte stability: at concentrations of 0.6 M LiClO4 and above the electrode potential is stable for at least 12 hours at an applied current density of −2 mA cm−2 at ambient temperature and pressure. Conversely, at the lower concentrations explored in prior studies, the potential required to maintain a given N2 reduction current increased by 8 V within a period of 1 hour under the same conditions. The behaviour is linked more coordination of the salt anion and cation with increasing salt concentration in the electrolyte observed via Raman spectroscopy. Time of flight secondary ion mass spectrometry and X-ray photoelectron spectroscopy reveal a more inorganic, and therefore more stable, SEI layer is formed with increasing salt concentration. A drop in faradaic efficiency for nitrogen reduction is seen at concentrations higher than 0.6 M LiClO4, which is attributed to a combination of a decrease in nitrogen solubility and diffusivity as well as increased SEI conductivity as measured by electrochemical impedance spectroscopy.
AU  - Westhead,O
AU  - Spry,M
AU  - Bagger,A
AU  - Shen,Z
AU  - Yadegari,H
AU  - Favero,S
AU  - Tort,R
AU  - Titirici,M
AU  - Ryan,MP
AU  - Jervis,R
AU  - Katayama,Y
AU  - Aguadero,A
AU  - Regoutz,A
AU  - Grimaud,A
AU  - Stephens,IEL
DO  - 10.1039/d2ta07686a
EP  - 12758
PY  - 2023///
SN  - 2050-7488
SP  - 12746
TI  - The role of ion solvation in lithium mediated nitrogen reduction
T2  - Journal of Materials Chemistry A
UR  - http://dx.doi.org/10.1039/d2ta07686a
UR  - http://hdl.handle.net/10044/1/103267
VL  - 11
ER  -
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