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Study of bulk and grain-boundary conductivity of Ln2+xHf2−xO7−δ (Ln = Sm-Gd; x = 0, 0.096) pyrochlores

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Abstract

The electrical conductivity of new solid electrolytes Eu2.096Hf1.904O6.952 and Gd2Hf2O7 have been compared with those for different pyrochlores including titanates and zirconates Ln2+xМ2−xO7−δ (Ln = Sm-Lu; M = Ti, Zr; x = 0−0.81). Impedance spectroscopy data demonstrate that Eu2.096Hf1.904O6.952 and Gd2Hf2O7 synthesized from mechanically activated oxides have high ionic conductivity, comparable to that of their zirconate analogues. The bulk and grain-boundary components of conductivity in Sm2.096Hf1.904O6.952 (Тsynth = 1600ºС), Eu2.096Hf1.904O6.952 and Gd2Hf2O7 (Тsynth = 1670ºС) have been determined. The highest bulk conductivity is offered by the disordered pyrochlores prepared at 1600ºC and 1670ºC: ~1.5 × 10−4 S/cm for Sm2.096Hf1.904O6.952, 5 × 10−3 S/cm for Eu2.096Hf1.904O6.952 and 3 × 10−3 S/cm for Gd2Hf2O7 at 780ºС, respectively. The conductivity of the fluorite-like phases at the phase boundaries of the Ln2+xМ2−xO7−δ (Ln = Eu, Gd; M = Zr, Hf; x ~ 0.286) solid solutions, as well as that of the high-temperature fluorite-like phases Ln2+xМ2−xO7−δ (Ln = Eu, Gd; M = Zr, Hf; x = 0−0.286), is lower than the conductivity of the disordered pyrochlores Ln2+xМ2−xO7−δ (Ln = Eu, Gd; M = Zr, Hf; x = 0−0.096).

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Acknowledgements

This work was supported by the Presidium of the Russian Academy of Sciences (program “Synthesis of Inorganic Substances with Controlled Properties and Fabrication of Related Functional Materials,” grant no. 18P/2009), the Russian Foundation for Basic Research (grant no. 07-03-00716), the Department of Materials Sciences of the Russian Academy of Sciences (program of the Basic Investigations of New Metal, Ceramic, Glass- and Composite-Materials and the Deutsche Forschungsgemeinschaft (grant no. CZ 436RUS17/96/06).

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Authors and Affiliations

  1. Semenov Institute of Chemical Physics, Russian Academy of Sciences, ul. Kosygina 4, Moscow, 119991, Russia

    A. V. Shlyakhtina & L. G. Shcherbakova

  2. Faculty of Chemistry, Moscow State University, Leninskie gory 1, Moscow, 119991, Russia

    S. N. Savvin & A. V. Knotko

  3. Institute of Problems of Chemical Physics, Russian Academy of Sciences, Akad. N.N. Semenov avenue, Moscow, Russia

    A. V. Levchenko

  4. Hochschule Wismar Institute of Surface and Thin Film Technology, Philipp-Muller-Strasse, 23952, Wismar, Germany

    Petra Fedtke, Andreas Busch, Torsten Barfels & Marion Wienecke

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  1. A. V. Shlyakhtina
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  2. S. N. Savvin
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  3. A. V. Levchenko
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  4. A. V. Knotko
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Correspondence to A. V. Shlyakhtina.

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Shlyakhtina, A.V., Savvin, S.N., Levchenko, A.V. et al. Study of bulk and grain-boundary conductivity of Ln2+xHf2−xO7−δ (Ln = Sm-Gd; x = 0, 0.096) pyrochlores. J Electroceram 24, 300–307 (2010). https://doi.org/10.1007/s10832-009-9572-0

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