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Ionic Mobility, Phase Transitions, and Superionic Conduction in Solid Solutions (100 − x)PbF2-xZrF4 and Crystals K2ZrF6, (NH4)2ZrF6, KSnZrF7, and M(NH4)6Zr4F23 (M = Li, Na)

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Abstract

Methods of (19F, 1H) NMR and impedance spectroscopy are used to investigate the internal mobility and ionic conduction in solid solutions arising in the system PbF2-ZrF4 and polycrystals KSnZrF7, Li(Na)(NH4)6Zr4F23, and M2ZrF6 (M = K, NH4). Factors responsible for the form of ionic motions and their energetics at 170–550 K are considered. It is established that the phase transitions in these compounds are connected with the crystal transition to a superionic state and that the high ionic (superionic) conductivity of beta phases is due to the diffusion of fluoride ions, ammonium cations, and possibly alkali metal cations. The obtained data testify to a substantial role of chainlike aggregation of anionic groupings and a variableness of structural mechanisms of formation of such chains in fluorozirconates for the development of translational diffusion in these compounds.

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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. B. Slobodyuk, V. K. Goncharuk, A. Yu. Kotenkov, I. A. Tkachenko, A. V. Gerasimenko & 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. N. F. Uvarov
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  3. A. B. Slobodyuk
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  4. V. K. Goncharuk
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  5. A. Yu. Kotenkov
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  6. I. A. Tkachenko
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  7. A. V. Gerasimenko
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  8. V. I. Sergienko
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Correspondence to V. Ya. Kavun.

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__________

Translated from Elektrokhimiya, Vol. 41, No. 5, 2005, pp. 573–582.

Original Russian Text Copyright © 2005 by Kavun, Uvarov, Slobodyuk, Goncharuk, Kotenkov, Tkachenko, Gerasimenko, Sergienko.

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Kavun, V.Y., Uvarov, N.F., Slobodyuk, A.B. et al. Ionic Mobility, Phase Transitions, and Superionic Conduction in Solid Solutions (100 − x)PbF2-xZrF4 and Crystals K2ZrF6, (NH4)2ZrF6, KSnZrF7, and M(NH4)6Zr4F23 (M = Li, Na). Russ J Electrochem 41, 501–509 (2005). https://doi.org/10.1007/s11175-005-0096-x

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  • DOI: https://doi.org/10.1007/s11175-005-0096-x

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