A Combined Theory‐Experiment Analysis of the Surface Species in Lithium‐Mediated NH3 Electrosynthesis

Jay A. Schwalbe, Michael J. Statt, Cullen Chosy, Aayush R. Singh, Brian A. Rohr, Adam C. Nielander, Suzanne Zamany Andersen, Joshua M. McEnaney, Jon G. Baker, Thomas F. Jaramillo, Jens K. Norskov, Matteo Cargnello*

*Corresponding author for this work

Research output: Contribution to journalJournal articleResearchpeer-review

Abstract

Electrochemical processes for ammonia synthesis could potentially replace the high temperature and pressure conditions of the Haber‐Bosch process, with voltage offering a pathway to distributed fertilizer production that leverages the rapidly decreasing cost of renewable electricity. However, nitrogen is an unreactive molecule and the hydrogen evolution reaction presents a major selectivity challenge. An electrode of electrodeposited lithium in tetrahydrofuran solvent overcomes both problems by providing a surface that easily reacts with nitrogen and by limiting the access of protons with a nonaqueous electrolyte. Under these conditions, we measure relatively high faradaic efficiencies (ca. 10 %) and rates (0.1 mA cm−2) toward NH3. We observe the development of a solid electrolyte interface layer as well as the accumulation of lithium and lithium‐containing species. Detailed DFT studies suggest lithium nitride and hydride to be catalytically active phases given their thermodynamic and kinetic stability relative to metallic lithium under reaction conditions and the fast diffusion of nitrogen in lithium.
Original languageEnglish
JournalChemElectroChem
Volume7
Number of pages9
ISSN2196-0216
DOIs
Publication statusPublished - 2020

Cite this

Schwalbe, J. A., Statt, M. J., Chosy, C., Singh, A. R., Rohr, B. A., Nielander, A. C., ... Cargnello, M. (2020). A Combined Theory‐Experiment Analysis of the Surface Species in Lithium‐Mediated NH3 Electrosynthesis. ChemElectroChem, 7. https://doi.org/10.1002/celc.201902124
Schwalbe, Jay A. ; Statt, Michael J. ; Chosy, Cullen ; Singh, Aayush R. ; Rohr, Brian A. ; Nielander, Adam C. ; Andersen, Suzanne Zamany ; McEnaney, Joshua M. ; Baker, Jon G. ; Jaramillo, Thomas F. ; Norskov, Jens K. ; Cargnello, Matteo. / A Combined Theory‐Experiment Analysis of the Surface Species in Lithium‐Mediated NH3 Electrosynthesis. In: ChemElectroChem. 2020 ; Vol. 7.
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title = "A Combined Theory‐Experiment Analysis of the Surface Species in Lithium‐Mediated NH3 Electrosynthesis",
abstract = "Electrochemical processes for ammonia synthesis could potentially replace the high temperature and pressure conditions of the Haber‐Bosch process, with voltage offering a pathway to distributed fertilizer production that leverages the rapidly decreasing cost of renewable electricity. However, nitrogen is an unreactive molecule and the hydrogen evolution reaction presents a major selectivity challenge. An electrode of electrodeposited lithium in tetrahydrofuran solvent overcomes both problems by providing a surface that easily reacts with nitrogen and by limiting the access of protons with a nonaqueous electrolyte. Under these conditions, we measure relatively high faradaic efficiencies (ca. 10 {\%}) and rates (0.1 mA cm−2) toward NH3. We observe the development of a solid electrolyte interface layer as well as the accumulation of lithium and lithium‐containing species. Detailed DFT studies suggest lithium nitride and hydride to be catalytically active phases given their thermodynamic and kinetic stability relative to metallic lithium under reaction conditions and the fast diffusion of nitrogen in lithium.",
author = "Schwalbe, {Jay A.} and Statt, {Michael J.} and Cullen Chosy and Singh, {Aayush R.} and Rohr, {Brian A.} and Nielander, {Adam C.} and Andersen, {Suzanne Zamany} and McEnaney, {Joshua M.} and Baker, {Jon G.} and Jaramillo, {Thomas F.} and Norskov, {Jens K.} and Matteo Cargnello",
year = "2020",
doi = "10.1002/celc.201902124",
language = "English",
volume = "7",
journal = "ChemElectroChem",
issn = "2196-0216",
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Schwalbe, JA, Statt, MJ, Chosy, C, Singh, AR, Rohr, BA, Nielander, AC, Andersen, SZ, McEnaney, JM, Baker, JG, Jaramillo, TF, Norskov, JK & Cargnello, M 2020, 'A Combined Theory‐Experiment Analysis of the Surface Species in Lithium‐Mediated NH3 Electrosynthesis', ChemElectroChem, vol. 7. https://doi.org/10.1002/celc.201902124

A Combined Theory‐Experiment Analysis of the Surface Species in Lithium‐Mediated NH3 Electrosynthesis. / Schwalbe, Jay A.; Statt, Michael J.; Chosy, Cullen; Singh, Aayush R.; Rohr, Brian A.; Nielander, Adam C.; Andersen, Suzanne Zamany; McEnaney, Joshua M.; Baker, Jon G.; Jaramillo, Thomas F.; Norskov, Jens K.; Cargnello, Matteo.

In: ChemElectroChem, Vol. 7, 2020.

Research output: Contribution to journalJournal articleResearchpeer-review

TY - JOUR

T1 - A Combined Theory‐Experiment Analysis of the Surface Species in Lithium‐Mediated NH3 Electrosynthesis

AU - Schwalbe, Jay A.

AU - Statt, Michael J.

AU - Chosy, Cullen

AU - Singh, Aayush R.

AU - Rohr, Brian A.

AU - Nielander, Adam C.

AU - Andersen, Suzanne Zamany

AU - McEnaney, Joshua M.

AU - Baker, Jon G.

AU - Jaramillo, Thomas F.

AU - Norskov, Jens K.

AU - Cargnello, Matteo

PY - 2020

Y1 - 2020

N2 - Electrochemical processes for ammonia synthesis could potentially replace the high temperature and pressure conditions of the Haber‐Bosch process, with voltage offering a pathway to distributed fertilizer production that leverages the rapidly decreasing cost of renewable electricity. However, nitrogen is an unreactive molecule and the hydrogen evolution reaction presents a major selectivity challenge. An electrode of electrodeposited lithium in tetrahydrofuran solvent overcomes both problems by providing a surface that easily reacts with nitrogen and by limiting the access of protons with a nonaqueous electrolyte. Under these conditions, we measure relatively high faradaic efficiencies (ca. 10 %) and rates (0.1 mA cm−2) toward NH3. We observe the development of a solid electrolyte interface layer as well as the accumulation of lithium and lithium‐containing species. Detailed DFT studies suggest lithium nitride and hydride to be catalytically active phases given their thermodynamic and kinetic stability relative to metallic lithium under reaction conditions and the fast diffusion of nitrogen in lithium.

AB - Electrochemical processes for ammonia synthesis could potentially replace the high temperature and pressure conditions of the Haber‐Bosch process, with voltage offering a pathway to distributed fertilizer production that leverages the rapidly decreasing cost of renewable electricity. However, nitrogen is an unreactive molecule and the hydrogen evolution reaction presents a major selectivity challenge. An electrode of electrodeposited lithium in tetrahydrofuran solvent overcomes both problems by providing a surface that easily reacts with nitrogen and by limiting the access of protons with a nonaqueous electrolyte. Under these conditions, we measure relatively high faradaic efficiencies (ca. 10 %) and rates (0.1 mA cm−2) toward NH3. We observe the development of a solid electrolyte interface layer as well as the accumulation of lithium and lithium‐containing species. Detailed DFT studies suggest lithium nitride and hydride to be catalytically active phases given their thermodynamic and kinetic stability relative to metallic lithium under reaction conditions and the fast diffusion of nitrogen in lithium.

U2 - 10.1002/celc.201902124

DO - 10.1002/celc.201902124

M3 - Journal article

VL - 7

JO - ChemElectroChem

JF - ChemElectroChem

SN - 2196-0216

ER -