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Ionic mobility and structure of fluorozirconates Rb2−x (NH4) x ZrF6 (x > 1.5) by NMR, x-ray structure analysis, and impedance spectroscopy

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Abstract

The ionic mobility in the temperature interval 180 to 480 K, structure, and electrophysical properties of rubidium-ammonium hexafluorozirconates Rb2−x (NH4) x ZrF6 (1.5 ≤ x ≤ 2.0) are studied by methods of the 19F, 1H NMR spectroscopy, x-ray structure analysis, differential thermal analysis, and impedance spectroscopy. Correlations between the composition of the cationic sublattice, the character of ionic motions, and the phase transition temperature (of the type order-disorder) are established in these compounds. The salient feature of the high-temperature modifications of these fluorozirconates with x ≥ 1.5 is the translation diffusion of ions inside the fluoride and ammonium sublattices and the 19F NMR spectra are characterized by monoaxial anisotropy of the magnetic shielding tensor of the fluorine nuclei. Fluorozirconates with x > 1.5 are shown to belong with the structural type (NH4)2ZrF6. The rubidium cations isomorphically replace the ammonium cations. The electrophysical characteristics of the compounds are examined in the temperature interval 300 to 480 K. It is established that the electroconductivity of these compounds increases with x.

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Authors and Affiliations

  1. Institute of Chemistry, Far East Division, Russian Academy of Sciences, pr. Stoletiya Vladivostoka 159, Vladivostok, 690022, Russia

    V. Ya. Kavun, A. V. Gerasimenko, A. B. Slobodyuk, N. A. Didenko & V. I. Sergienko

  2. Institute of Solid-State Chemistry and Mechanochemistry, Siberian Division, Russian Academy of Sciences, ul. Kutateladze 18, Novosibirsk, 630128, Russia

    N. F. Uvarov

Authors
  1. V. Ya. Kavun
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  2. A. V. Gerasimenko
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  3. A. B. Slobodyuk
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  4. N. A. Didenko
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  5. N. F. Uvarov
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  6. V. I. Sergienko
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Corresponding author

Correspondence to V. Ya. Kavun.

Additional information

Original Russian Text © V.Ya. Kavun, A.V. Gerasimenko, A.B. Slobodyuk, N.A. Didenko, N.F. Uvarov, V.I. Sergienko, 2007, published in Elektrokhimiya, 2007, Vol. 43, No. 5, pp. 563–570.

Based on the paper delivered at the 8th Meeting “Fundamental Problems of Solid-State Ionics”, Chernogolovka (Russia), 2006.

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Kavun, V.Y., Gerasimenko, A.V., Slobodyuk, A.B. et al. Ionic mobility and structure of fluorozirconates Rb2−x (NH4) x ZrF6 (x > 1.5) by NMR, x-ray structure analysis, and impedance spectroscopy. Russ J Electrochem 43, 537–544 (2007). https://doi.org/10.1134/S1023193507050060

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  • DOI: https://doi.org/10.1134/S1023193507050060

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