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

Cover Page

Cite item

Full Text

Open Access Open Access
Restricted Access Access granted
Restricted Access Subscription Access

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.

Full Text

Restricted Access

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

References

  1. Goodenough J.B., Hong H.Y-P., Kafalas J.A. // Mater. Res. Bull. 1976. V. 11. № 2. P. 203. https://doi.org/10.1016/0025-5408(76)90077-5
  2. Hong H.Y-P. // Mater. Res. Bull. 1976. V. 11. № 2. P. 173. https://doi.org/10.1016/0025-5408(76)90073-8
  3. Li C., Li R., Liu K. et al. // Interdiscip. Mater. 2022. P. 1. https://doi.org/10.1002/idm2.12044
  4. Guin M., Tietz F. // J. Power Sources. 2015. V. 273. P. 1056. https://doi.org/10.1016/j.jpowsour.2014.09.137
  5. Lalere F., Leriche J.B., Courty M. et al. // J. Power Sources. 2014. V. 247. P. 975. https://doi.org/10.1016/j.jpowsour.2013.09.051
  6. Fergus J.-W. // Solid State Ionics. 2012. V. 227. P. 102. https://doi.org/10.1016/j.ssi.2012.09.019
  7. Narayanan S., Reid S., Butler S., Thangadurai V. // Solid State Ionics. 2019. V. 331. P. 22. https://doi.org/10.1016/j.ssi.2018.12.003
  8. Rao Y.B., Bharathi K.К., Patro L.N. // Solid State Ionics. 2021. V. 366–377. P. 115671. https://doi.org/10.1016/j.ssi.2021.115671
  9. Wang H., Zhao G., Wang S. et al. // Nanoscale. 2022. V. 14. № 3. P. 823. https://doi.org/10.1039/d1nr06959d
  10. Naqash S., Tietz F., Yazhenskikh E. et al. // Solid State Ionics. 2019. V. 336. P. 57. https://doi.org/10.1016/j.ssi.2019.03.017
  11. Грищенко Д.Н., Курявый В.Г., Подгорбунский А.Б., Медков М.А. // Журн. неорган. химии. 2023. Т. 68. № 1. С. 17. https://doi.org/10.31857/S0044457X22601043
  12. Fuentes R.O., Marques F.M.B., Franco J.I. // Bol. Soc. Esp. Cerám. Vidrio. 1999. V. 38. № 6. P. 631.
  13. Zhang S., Quan B., Zhiyong Z., Zhao B. // Materials Letters. 2004. V. 58. № 1. P. 226.
  14. Yang G., Zhai Y., Yao J. et al. // Chem. Commun. 2021. V. 57. P. 4023. https://doi.org/10.1039/d0cc07261c
  15. Brug G.J., van den Eeden A.L.G., Sluyters-Rehbach M., Sluyters J.H. // J. Electroanal. Chem. Interfacial Electrochem. 1984. V. 176. P. 275. https://doi.org/10.1016/S0022-0728(84)80324-1
  16. Bauerle J.E. // J. Phys. Chem. Solids. 1969. V. 30. P. 2657. https://doi.org/10.1016/0022-3697(69)90039-0
  17. Bauerle J.E., Hrizo J. // J. Phys. Chem. Solids. 1969. V. 30. P. 565. https://doi.org/10.1016/0022-3697(69)90011-0
  18. Kim S.K., Mao A., Sen S., Kim S. // Chem. Mater. 2014. V. 26. P. 5695. https://doi.org/10.1021/cm502542p
  19. Suzuki K., Noi K., Hayashi A., Tatsumisago M. // Scr. Mater. 2018. V. 145. P. 67. https://doi.org/10.1016/j.scriptamat.2017.10.010
  20. Ren K., Cao Y., Chen Y. et al. // Scripta Mater. 2020. V. 187. P. 384. https://doi.org/10.1016/j.scriptamat.2020.06.055
  21. Ngo Q.Q., Nguyen V.N., To V.N. et al. // Интеллектуальная электротехника. 2022. № 2. C. 16. https://doi.org/10.46960/2658-6754_2022_2_16

Supplementary files

Supplementary Files
Action
1. JATS XML
Download
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).

Download (225KB)
Indexing metadata
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).

Download (107KB)
Indexing metadata
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).

Download (124KB)
Indexing metadata
5. Fig. 4. The main diffraction maxima of the samples after firing at 1000 ° C: samples 8 (1), 9 (2), 10 (3), 11 (4).

Download (118KB)
Indexing metadata
6. Fig. 5. Micrographs of samples (composition 10) obtained at temperatures, ° C: 1000 (a), 1100 (b), 1200 (c).

Download (199KB)
Indexing metadata
7. Fig. 6. Diffractograms of samples (composition 10) obtained at temperatures, ° C: 1000 (1), 1100 (2), 1200 (3).

Download (178KB)
Indexing metadata
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).

Download (177KB)
Indexing metadata
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.

Download (93KB)
Indexing metadata

Copyright (c) 2024 Russian Academy of Sciences

This website uses cookies

You consent to our cookies if you continue to use our website.

About Cookies