Synthesis, Ionic Mobility and Conductivity of Composites of Tin and Lead Difluorides Based on 19F NMR and Impedance Spectroscopy Data

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Abstract

Ionic mobility and conductivity of eutectic composites and compounds of the close composition obtained in PbF2–SnF2 system by different pathways were studied by means of 19F NMR and impedance methods. The stages of transformation of the 19F NMR spectra of the obtained samples, their connection with the types of ionic movements and possible factors influencing the value of ionic conductivity were considered. It has been established that the composition of most composites includes a fluorite phase, characterizing by high values of ionic mobility and conductivity. In a region close to the eutectic, a single-phase sample with a fluorite structure was obtained for the first time. The value of the specific conductivity of the resulting phase (5 × 10–3 S/cm at 390 K) allows us to consider the latter as the basis for obtaining functional materials.

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About the authors

A. B. Slobodyuk

Institute of Chemistry of the Far East Branch of the Russian Academy of Sciences

Author for correspondence.
Email: ampy@ich.dvo.ru
Russian Federation, Vladivostok

I. A. Telin

Institute of Chemistry of the Far East Branch of the Russian Academy of Sciences

Email: ampy@ich.dvo.ru
Russian Federation, Vladivostok

M. M. Polyantsev

Institute of Chemistry of the Far East Branch of the Russian Academy of Sciences

Email: ampy@ich.dvo.ru
Russian Federation, Vladivostok

N. F. Uvarov

Institute of Solid State Chemistry and Mechanochemistry of the Siberian Branch of the Russian Academy of Sciences

Email: ampy@ich.dvo.ru
Russian Federation, Novosibirsk

V. Ya. Kavun

Institute of Chemistry of the Far East Branch of the Russian Academy of Sciences

Email: kavun@ich.dvo.ru
Russian Federation, Vladivostok

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Supplementary files

Supplementary Files
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2. Fig. 1. X-ray diffraction patterns of the studied samples. 1-3: samples E1 - E3, 4, 5 - samples MC1 and MC2, 6 - α-PbSnF4

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3. Fig. 2. 19F NMR spectra of model samples of β-PbF2 (a) and SnF2 (b) at different temperatures. Decomposition of one of the spectra into components described by Blombergen-Rowland and Gauss functions (b, dashed line)

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4. Fig. 3. Transformation of 19F NMR spectra of PbSnF4 samples (a) and fluorite phases MC1 and MC2 (b, c) at temperature variations

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5. Fig. 4. 19F NMR spectra of E1-E3 eutectics (a-c) at different temperatures

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6. Fig. 5. Temperature dependences of the second moment of the 19F NMR spectra of the studied samples

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7. Fig. 6. Impedance hodographs of samples E1, E2, MC1 and MC2 obtained at 323 K, graphs (a) - (d), respectively. Dots - experimental data, lines - curves obtained for the theoretical dependences obtained for the equivalent circuit presented in the graph (a)

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8. Fig. 7. Temperature dependences of specific conductivity of the studied samples

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