Structure, conductivity and redox stability of solid solution Ce1− xCaxVO4 (0≤ x≤ 0.4125)

Christophe TG Petit, Rong Lan, Peter I Cowin, Arno Kraft, Shanwen Tao

    Research output: Contribution to journalArticle

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    Abstract

    A-site-substituted cerium orthovanadates, Ce1−x Ca x VO4, were synthesised by solid-state reactions. At room temperature, the solid solution limit in Ce1−x Ca x VO4 series is at x = 0.4125. The crystal structure was analysed by X-ray diffraction and it exhibits a tetragonal zircon structure of space group I41/amd with a = 7.4004 (1) and c = 6.4983 (6) Å for CeVO4. The UV–Visible absorption spectra indicated that the compounds have band gaps at room temperature in the range of 4.2–4.5 eV. Conductivity measurements were performed for the first time up to the calcium solid solution limit in both air and dry 5% H2/Ar with conductivity values at 600 °C ranging from 0.3 to 20 mS cm−1 in air to 3 to 30 mS cm−1 in reducing atmosphere. In general, the conductivity of Ca-doped CeVO4 is higher in air but lower in a reducing atmosphere comparing to pure CeVO4. The H2/air electrochemical cell measurement indicates that the conduction of sample Ce0.7Ca0.3VO4 is electronic dominant. Samples Ce0.9Ca0.1VO4 and Ce0.8Ca0.2VO4 are redox stable at a temperature below 600 °C although the conductivity is not high enough to be used as an electrode for solid oxide fuel cells.
    Original languageEnglish
    Pages (from-to)316-326
    Number of pages11
    JournalJournal of Materials Science
    Volume46
    Issue number2
    Early online date12 Aug 2010
    DOIs
    Publication statusPublished - Jan 2011

    Fingerprint

    Solid solutions
    Air
    Cerium
    Zircon
    Earth atmosphere
    Vanadates
    Electrochemical cells
    Solid oxide fuel cells (SOFC)
    Solid state reactions
    Temperature
    Absorption spectra
    Calcium
    Energy gap
    Crystal structure
    X ray diffraction
    Electrodes
    Oxidation-Reduction

    Keywords

    • Cerium
    • CeO2
    • Open Circuit Voltage
    • Lattice Contraction
    • Solid Solution Limit

    Cite this

    Structure, conductivity and redox stability of solid solution Ce1− xCaxVO4 (0≤ x≤ 0.4125). / Petit, Christophe TG ; Lan, Rong; Cowin, Peter I; Kraft, Arno; Tao, Shanwen .

    In: Journal of Materials Science, Vol. 46, No. 2, 01.2011, p. 316-326.

    Research output: Contribution to journalArticle

    Petit, Christophe TG ; Lan, Rong ; Cowin, Peter I ; Kraft, Arno ; Tao, Shanwen . / Structure, conductivity and redox stability of solid solution Ce1− xCaxVO4 (0≤ x≤ 0.4125). In: Journal of Materials Science. 2011 ; Vol. 46, No. 2. pp. 316-326.
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    abstract = "A-site-substituted cerium orthovanadates, Ce1−x Ca x VO4, were synthesised by solid-state reactions. At room temperature, the solid solution limit in Ce1−x Ca x VO4 series is at x = 0.4125. The crystal structure was analysed by X-ray diffraction and it exhibits a tetragonal zircon structure of space group I41/amd with a = 7.4004 (1) and c = 6.4983 (6) {\AA} for CeVO4. The UV–Visible absorption spectra indicated that the compounds have band gaps at room temperature in the range of 4.2–4.5 eV. Conductivity measurements were performed for the first time up to the calcium solid solution limit in both air and dry 5{\%} H2/Ar with conductivity values at 600 °C ranging from 0.3 to 20 mS cm−1 in air to 3 to 30 mS cm−1 in reducing atmosphere. In general, the conductivity of Ca-doped CeVO4 is higher in air but lower in a reducing atmosphere comparing to pure CeVO4. The H2/air electrochemical cell measurement indicates that the conduction of sample Ce0.7Ca0.3VO4 is electronic dominant. Samples Ce0.9Ca0.1VO4 and Ce0.8Ca0.2VO4 are redox stable at a temperature below 600 °C although the conductivity is not high enough to be used as an electrode for solid oxide fuel cells.",
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    AU - Kraft, Arno

    AU - Tao, Shanwen

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    N2 - A-site-substituted cerium orthovanadates, Ce1−x Ca x VO4, were synthesised by solid-state reactions. At room temperature, the solid solution limit in Ce1−x Ca x VO4 series is at x = 0.4125. The crystal structure was analysed by X-ray diffraction and it exhibits a tetragonal zircon structure of space group I41/amd with a = 7.4004 (1) and c = 6.4983 (6) Å for CeVO4. The UV–Visible absorption spectra indicated that the compounds have band gaps at room temperature in the range of 4.2–4.5 eV. Conductivity measurements were performed for the first time up to the calcium solid solution limit in both air and dry 5% H2/Ar with conductivity values at 600 °C ranging from 0.3 to 20 mS cm−1 in air to 3 to 30 mS cm−1 in reducing atmosphere. In general, the conductivity of Ca-doped CeVO4 is higher in air but lower in a reducing atmosphere comparing to pure CeVO4. The H2/air electrochemical cell measurement indicates that the conduction of sample Ce0.7Ca0.3VO4 is electronic dominant. Samples Ce0.9Ca0.1VO4 and Ce0.8Ca0.2VO4 are redox stable at a temperature below 600 °C although the conductivity is not high enough to be used as an electrode for solid oxide fuel cells.

    AB - A-site-substituted cerium orthovanadates, Ce1−x Ca x VO4, were synthesised by solid-state reactions. At room temperature, the solid solution limit in Ce1−x Ca x VO4 series is at x = 0.4125. The crystal structure was analysed by X-ray diffraction and it exhibits a tetragonal zircon structure of space group I41/amd with a = 7.4004 (1) and c = 6.4983 (6) Å for CeVO4. The UV–Visible absorption spectra indicated that the compounds have band gaps at room temperature in the range of 4.2–4.5 eV. Conductivity measurements were performed for the first time up to the calcium solid solution limit in both air and dry 5% H2/Ar with conductivity values at 600 °C ranging from 0.3 to 20 mS cm−1 in air to 3 to 30 mS cm−1 in reducing atmosphere. In general, the conductivity of Ca-doped CeVO4 is higher in air but lower in a reducing atmosphere comparing to pure CeVO4. The H2/air electrochemical cell measurement indicates that the conduction of sample Ce0.7Ca0.3VO4 is electronic dominant. Samples Ce0.9Ca0.1VO4 and Ce0.8Ca0.2VO4 are redox stable at a temperature below 600 °C although the conductivity is not high enough to be used as an electrode for solid oxide fuel cells.

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