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Title: Selective high-temperature CO2 electrolysis enabled by oxidized carbon intermediates

Abstract

High-temperature CO2 electrolysers offer exceptionally efficient storage of renewable electricity in the form of CO and other chemical fuels, but conventional electrodes catalyse destructive carbon deposition. Ceria catalysts are known carbon inhibitors for fuel cell (oxidation) reactions; however, for more severe electrolysis (reduction) conditions, catalyst design strategies remain unclear. In this study, we establish the inhibition mechanism on ceria and show selective CO2 to CO conversion well beyond the thermodynamic carbon deposition threshold. Operando X-ray photoelectron spectroscopy during CO2 electrolysis—using thin-film model electrodes consisting of samarium-doped ceria, nickel and/or yttria-stabilized zirconia—together with density functional theory modelling, reveal the crucial role of oxidized carbon intermediates in preventing carbon build-up. Using these insights, we demonstrate stable electrochemical CO2 reduction with a scaled-up 16 cm2 ceria-based solid-oxide cell under conditions that rapidly destroy a nickel-based cell, leading to substantially improved device lifetime.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [2]; ORCiD logo [2];  [2]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [5]; ORCiD logo [6]; ORCiD logo [4]; ORCiD logo [2]; ORCiD logo [1]
  1. Technical Univ. of Denmark, Roskilde (Denmark); Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  2. Stanford Univ., Stanford, CA (United States)
  3. Technical Univ. of Denmark, Roskilde (Denmark)
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  6. Trinity College, Dublin (Ireland)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1577318
Grant/Contract Number:  
AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Nature Energy
Additional Journal Information:
Journal Volume: 4; Journal Issue: 10; Journal ID: ISSN 2058-7546
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Skafte, Theis L., Guan, Zixuan, Machala, Michael L., Gopal, Chirranjeevi B., Monti, Matteo, Martinez, Lev, Stamate, Eugen, Sanna, Simone, Garrido Torres, Jose A., Crumlin, Ethan J., García-Melchor, Max, Bajdich, Michal, Chueh, William C., and Graves, Christopher. Selective high-temperature CO2 electrolysis enabled by oxidized carbon intermediates. United States: N. p., 2019. Web. https://doi.org/10.1038/s41560-019-0457-4.
Skafte, Theis L., Guan, Zixuan, Machala, Michael L., Gopal, Chirranjeevi B., Monti, Matteo, Martinez, Lev, Stamate, Eugen, Sanna, Simone, Garrido Torres, Jose A., Crumlin, Ethan J., García-Melchor, Max, Bajdich, Michal, Chueh, William C., & Graves, Christopher. Selective high-temperature CO2 electrolysis enabled by oxidized carbon intermediates. United States. https://doi.org/10.1038/s41560-019-0457-4
Skafte, Theis L., Guan, Zixuan, Machala, Michael L., Gopal, Chirranjeevi B., Monti, Matteo, Martinez, Lev, Stamate, Eugen, Sanna, Simone, Garrido Torres, Jose A., Crumlin, Ethan J., García-Melchor, Max, Bajdich, Michal, Chueh, William C., and Graves, Christopher. Mon . "Selective high-temperature CO2 electrolysis enabled by oxidized carbon intermediates". United States. https://doi.org/10.1038/s41560-019-0457-4. https://www.osti.gov/servlets/purl/1577318.
@article{osti_1577318,
title = {Selective high-temperature CO2 electrolysis enabled by oxidized carbon intermediates},
author = {Skafte, Theis L. and Guan, Zixuan and Machala, Michael L. and Gopal, Chirranjeevi B. and Monti, Matteo and Martinez, Lev and Stamate, Eugen and Sanna, Simone and Garrido Torres, Jose A. and Crumlin, Ethan J. and García-Melchor, Max and Bajdich, Michal and Chueh, William C. and Graves, Christopher},
abstractNote = {High-temperature CO2 electrolysers offer exceptionally efficient storage of renewable electricity in the form of CO and other chemical fuels, but conventional electrodes catalyse destructive carbon deposition. Ceria catalysts are known carbon inhibitors for fuel cell (oxidation) reactions; however, for more severe electrolysis (reduction) conditions, catalyst design strategies remain unclear. In this study, we establish the inhibition mechanism on ceria and show selective CO2 to CO conversion well beyond the thermodynamic carbon deposition threshold. Operando X-ray photoelectron spectroscopy during CO2 electrolysis—using thin-film model electrodes consisting of samarium-doped ceria, nickel and/or yttria-stabilized zirconia—together with density functional theory modelling, reveal the crucial role of oxidized carbon intermediates in preventing carbon build-up. Using these insights, we demonstrate stable electrochemical CO2 reduction with a scaled-up 16 cm2 ceria-based solid-oxide cell under conditions that rapidly destroy a nickel-based cell, leading to substantially improved device lifetime.},
doi = {10.1038/s41560-019-0457-4},
journal = {Nature Energy},
number = 10,
volume = 4,
place = {United States},
year = {2019},
month = {9}
}

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