Volume 126, Issue 36 pp. 9671-9675

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Defect Chemistry of Singly and Doubly Doped Ceria: Correlation between Ion Transport and Energetics^†

Dr. Salih Buyukkilic,

Dr. Salih Buyukkilic

Department of Chemical Engineering and Materials Science, University of California, Davis, CA 95616 (USA)

Peter A. Rock Thermochemistry Laboratory and NEAT ORU University of California, Davis, CA 95616 (USA)

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Prof. Sangtae Kim,

Corresponding Author

Prof. Sangtae Kim

[email protected]

Department of Chemical Engineering and Materials Science, University of California, Davis, CA 95616 (USA)

Department of Chemical Engineering and Materials Science, University of California, Davis, CA 95616 (USA)Search for more papers by this author

Prof. Alexandra Navrotsky,

Corresponding Author

Prof. Alexandra Navrotsky

[email protected]

Department of Chemical Engineering and Materials Science, University of California, Davis, CA 95616 (USA)

Peter A. Rock Thermochemistry Laboratory and NEAT ORU University of California, Davis, CA 95616 (USA)

Department of Chemical Engineering and Materials Science, University of California, Davis, CA 95616 (USA)Search for more papers by this author

Dr. Salih Buyukkilic,

Dr. Salih Buyukkilic

Department of Chemical Engineering and Materials Science, University of California, Davis, CA 95616 (USA)

Peter A. Rock Thermochemistry Laboratory and NEAT ORU University of California, Davis, CA 95616 (USA)

Search for more papers by this author

Prof. Sangtae Kim,

Corresponding Author

Prof. Sangtae Kim

[email protected]

Department of Chemical Engineering and Materials Science, University of California, Davis, CA 95616 (USA)

Department of Chemical Engineering and Materials Science, University of California, Davis, CA 95616 (USA)Search for more papers by this author

Prof. Alexandra Navrotsky,

Corresponding Author

Prof. Alexandra Navrotsky

[email protected]

Department of Chemical Engineering and Materials Science, University of California, Davis, CA 95616 (USA)

Peter A. Rock Thermochemistry Laboratory and NEAT ORU University of California, Davis, CA 95616 (USA)

Department of Chemical Engineering and Materials Science, University of California, Davis, CA 95616 (USA)Search for more papers by this author

First published: 09 July 2014

https://doi.org/10.1002/ange.201404618

Citations: 5

^†

We thank Tien Tran Roehling for the SPS experiments and Seong Kim for technical support with the impedance measurements. This work was supported by the U.S. Department of Energy, Office of Basic Energy Sciences (03ER46053).

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Abstract

Earlier studies have shown a strong correlation between the enthalpy of formation, ΔH_f,ox, and the ionic conductivity, σ_i, near room temperature in doped ceria systems, which are promising solid electrolytes for intermediate-temperature solid oxide fuel cells (IT-SOFCs). The present work demonstrates that this correlation holds at the operating temperature of IT-SOFCs, 600–700 °C. Solid solutions of Ce_1−xNd_xO_2−0.5x, Ce_1−xSm_xO_2−0.5x, and Ce_1−xSm_0.5xNd_0.5xO_2−0.5x are studied. The ΔH_f,ox at 702 °C is determined by considering the excess heat content between 25 and 702 °C combined with the value of ΔH_f,ox at 25 °C. Both σ_i and ΔH_f,ox show maxima at x=0.15 and 0.20 for the singly and doubly doped ceria, respectively, suggesting that the number of mobile oxygen vacancies in these solid solutions reaches a maximum near those compositions. An increase in temperature results in a shift of the maximum in both ΔH_f,ox and σ_i towards higher concentrations. This shift results from a gradual increase in dissociation of the defect associates.

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Defect Chemistry of Singly and Doubly Doped Ceria: Correlation between Ion Transport and Energetics^†