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Oxygen non-stoichiometry, high-temperature properties, and phase diagram of CaMnO3–δ

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Abstract

The oxygen content in CaMnO3–δ is studied by a coulometric titration technique depending on temperature and oxygen partial pressure variations in the ambient atmosphere. The δ–T phase diagram is derived from the obtained data where single-phase fields are outlined for orthorhombic, tetragonal, and cubic structures. The thermal expansion coefficient considerably larger in the cubic phase than in the tetragonal one is related with formation of large Mn3+ cations at depletion of oxygen from the crystalline lattice. Negative thermopower is explained by concomitant reactions of oxygen loss and charge disproportionation, \( {\hbox{2M}}{{\hbox{n}}^{{{4 + }}}}{\hbox{ = M}}{{\hbox{n}}^{{{3 + }}}}{\hbox{ + M}}{{\hbox{n}}^{{{5 + }}}}{ } \). The forbidden energy gap in CaMnO3–δ is evaluated to be about 0.5 eV.

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Acknowledgments

The authors are thankful to RF Samigullina and AA Markov for the help in TGA and conductivity measurements. Support of this work by the Russian Foundation for Basic Research under grant №10-03-00475a is gratefully acknowledged.

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Authors and Affiliations

  1. Institute of Solid State Chemistry, Ural Branch of Russian Academy of Sciences, 91 Pervomaiskaya Str., Ekaterinburg, Russian Federation

    Ekaterina I. Leonidova, Ilya A. Leonidov, Mikhail V. Patrakeev & Victor L. Kozhevnikov

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  1. Ekaterina I. Leonidova
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  2. Ilya A. Leonidov
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  3. Mikhail V. Patrakeev
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  4. Victor L. Kozhevnikov
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Correspondence to Ekaterina I. Leonidova.

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Leonidova, E.I., Leonidov, I.A., Patrakeev, M.V. et al. Oxygen non-stoichiometry, high-temperature properties, and phase diagram of CaMnO3–δ . J Solid State Electrochem 15, 1071–1075 (2011). https://doi.org/10.1007/s10008-010-1288-1

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  • DOI: https://doi.org/10.1007/s10008-010-1288-1

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