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Measuring fundamental properties in operating solid oxide electrochemical cells by using in situ X-ray photoelectron spectroscopy

Nature Materials volume 9, pages 944–949 (2010)Cite this article

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Abstract

Photoelectron spectroscopic measurements have the potential to provide detailed mechanistic insight by resolving chemical states, electrochemically active regions and local potentials or potential losses in operating solid oxide electrochemical cells (SOCs), such as fuel cells. However, high-vacuum requirements have limited X-ray photoelectron spectroscopy (XPS) analysis of electrochemical cells to ex situ investigations. Using a combination of ambient-pressure XPS and CeO2−x/YSZ/Pt single-chamber cells, we carry out in situ spectroscopy to probe oxidation states of all exposed surfaces in operational SOCs at 750 °C in 1 mbar reactant gases H2 and H2O. Kinetic energy shifts of core-level photoelectron spectra provide a direct measure of the local surface potentials and a basis for calculating local overpotentials across exposed interfaces. The mixed ionic/electronic conducting CeO2−x electrodes undergo Ce3+/Ce4+ oxidation–reduction changes with applied bias. The simultaneous measurements of local surface Ce oxidation states and electric potentials reveal the active ceria regions during H2 electro-oxidation and H2O electrolysis. The active regions extend ∼150 μm from the current collectors and are not limited by the three-phase-boundary interfaces associated with other SOC materials. The persistence of the Ce3+/Ce4+ shifts in the ∼150 μm active region suggests that the surface reaction kinetics and lateral electron transport on the thin ceria electrodes are co-limiting processes.

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Figure 1: Electrochemical activity spreads over ∼150 μm of the ceria anode.
Figure 2: In situ XPS directly measures local potentials on the surface of the 50-nm-thick ceria cell.
Figure 3: The cerium oxidation state changes in a 100–150 μm region near the Au current collector.
Figure 4: Ce 4d spectra obtained with a two-dimensional area detector (ALS beamline 9.3.2) reveal the 150 μm active region of the ceria electrode near the edge of the Au current collector.

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Acknowledgements

This work was financially supported by the ONR through Contract number N000140510711. We thank the University of Maryland Nanocenter and the University of Maryland Energy Research Center (UMERC) for support. The Advanced Light Source is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under Contract No. DE-AC02-05CH11231. Work at Sandia National Laboratories is supported by the Laboratory Directed Research and Development programme under contract DE-AC04-94AL85000 of the United States Department of Energy.

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  1. Mark A. Linne

    Present address: Present address: Chalmers University of Technology, 41296 Gothenburg, Sweden,

Authors and Affiliations

  1. Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742, USA

    Chunjuan Zhang & Bryan W. Eichhorn

  2. Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA

    Michael E. Grass, Zhi Liu & Zahid Hussain

  3. Sandia National Laboratories, Livermore, California 94551, USA

    Anthony H. McDaniel, Farid El Gabaly, Kevin F. McCarty, Roger L. Farrow & Mark A. Linne

  4. Department of Mechanical Engineering, University of Maryland, College Park, Maryland 20742, USA

    Steven C. DeCaluwe & Gregory S. Jackson

  5. Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA

    Hendrik Bluhm

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Contributions

All co-authors contributed to the conception and design of experiments. The ALS team collected and analysed the XPS data. The Sandia team collected the electrochemical data. The Maryland team fabricated and characterized cells and collated data analysis. Z.H. and M.A.L. initiated and partially financially supported the collaboration.

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Correspondence to Gregory S. Jackson, Hendrik Bluhm or Bryan W. Eichhorn.

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The authors declare no competing financial interests.

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Zhang, C., Grass, M., McDaniel, A. et al. Measuring fundamental properties in operating solid oxide electrochemical cells by using in situ X-ray photoelectron spectroscopy. Nature Mater 9, 944–949 (2010). https://doi.org/10.1038/nmat2851

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