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Investigation of Cs(H2PO4)1 − x (HSO4) x (x = 0.15–0.3) superprotonic phase stability

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Abstract

A detailed investigation of the highly conductive Cs(H2PO4)1−x (HSO4) x (x = 0.15–0.3) proton electrolyte, its structural properties, and ageing behavior was carried out using X-ray diffraction, DSC, and impedance and NMR spectroscopy. The high conductivity of electrolytes (∼2 × 10−2 S/cm) remains stable during long-term ageing at 180–200°C due to stabilization of the high temperature phase to lower temperatures. The room temperature 1H MAS NMR spectrum of (CsH2PO4)1−x (CsHSO4) x demonstrates the predominantly highly mobile protons present in these materials with the residual low-mobile protons, which agrees with the XRD data. According to XRD and 1H NMR data, the cubic phase of Cs(H2PO4)1 − x (HSO4) x (x = 0.15–0.3) that stabilizes at room temperature gradually transforms to a low-temperature monoclinic one. The kinetics of the phase transformation for mixed salt depends markedly on the relative air humidity. A possible stabilization mechanism of the Cs(H2PO4)1 − x (HSO4) x superionic phase with high proton mobility at low temperatures is discussed.

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Authors and Affiliations

  1. Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia

    V. G. Ponomareva, I. N. Bagryantseva & G. V. Lavrova

  2. Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia

    N. K. Moroz

  3. Novosibirsk State University, Russia, Novosibirsk

    V. G. Ponomareva

Authors
  1. V. G. Ponomareva
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  2. I. N. Bagryantseva
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  3. G. V. Lavrova
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  4. N. K. Moroz
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Correspondence to V. G. Ponomareva.

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Original Russian Text © V.G. Ponomareva, I.N. Bagryantseva, G.V. Lavrova, N.K. Moroz, 2014, published in Neorganicheskie Materialy, 2014, Vol. 50, No. 7, pp. 770–777.

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Ponomareva, V.G., Bagryantseva, I.N., Lavrova, G.V. et al. Investigation of Cs(H2PO4)1 − x (HSO4) x (x = 0.15–0.3) superprotonic phase stability. Inorg Mater 50, 716–722 (2014). https://doi.org/10.1134/S0020168514070127

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  • DOI: https://doi.org/10.1134/S0020168514070127

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