Effect of superstoichiometric amounts of sodium and phosphorus on the phase composition and ionic conductivity of zirconium and sodium silicophosphates (NASICON)

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Abstract

Using the method of pyrolysis of solutions in a melt, the phase formation of sodium and zirconium silicophosphates Na1+xZr2SixP3–xO12 was studied depending on the concentrations of sodium and phosphorus in the precursors. The influence of the content of these components, as well as firing conditions on the change in the ionic conductivity of NASICON was studied. Methods of X-ray phase analysis, scanning electron microscopy, full-profile Rietveld analysis, and electrochemical impedance spectroscopy were used. The specific values of grain conductivity (σb) and grain boundaries (σgb) of the samples were calculated. It was found that the reason for the change in ionic conductivity is a change in the composition of NASICON with increasing concentrations of sodium and phosphorus in the precursor. The main condition for high conductivity of the material is the formation of a crystalline phase corresponding to the composition Na3Zr2Si2РO12, as well as a minimum amount of impurities and glass phase. The conductivity of the NASICON sample (x = 2) under certain processing conditions is ~ 1 · 10-3 S/cm.

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About the authors

D. N. Grishchenko

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

Author for correspondence.
Email: grishchenko@ich.dvo.ru
Russian Federation, Vladivostok, 690022

A. B. Podgorbunsky

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

Email: grishchenko@ich.dvo.ru
Russian Federation, Vladivostok, 690022

M. A. Medkov

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

Email: grishchenko@ich.dvo.ru
Russian Federation, Vladivostok, 690022

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Supplementary files

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2. Fig. 1. Diffractograms of samples with stoichiometric ratio of components annealed at temperature , °C: 600 (1); 700 (2); 800 (3); 900 (4); 1000 (5); 1100 (6).

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3. Рис. 2. Штрихрентгенограммы: PDF 01-084-1317 (х = 2.12) (а); PDF 01-084-1200 (х = 2) (б); PDF 01-084-1182 (х ~ 1.9) (в), PDF 01-078-0489 (х ~ 1.84) (г).

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4. Fig. 3. The main diffraction maxima of samples obtained at firing temperatures, ° C: 1200 (sample 4) (1), 1200 (sample 10) (2), 1000 (sample 8) (3).

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5. Fig. 4. The main diffraction maxima of the samples after firing at 1000 ° C: samples 8 (1), 9 (2), 10 (3), 11 (4).

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6. Fig. 5. Micrographs of samples (composition 10) obtained at temperatures, ° C: 1000 (a), 1100 (b), 1200 (c).

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7. Fig. 6. Diffractograms of samples (composition 10) obtained at temperatures, ° C: 1000 (1), 1100 (2), 1200 (3).

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8. Fig. 7. Micrography of sample 1 obtained at a temperature of 1200 °C (a) and its energy dispersion spectra in the scanning regions: 1 (b), 2 (c).

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9. Figure 8. Impedance spectrum of sample 4 (a), high-frequency region of the spectrum with an equivalent circuit (b): 1 — experimental spectrum, 2 — curve modeling the spectrum in the extended frequency range.

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