Fe-substituted ceramic materials of the NASICON family, corresponding to the generally accepted formula Na3+yМ(III)yZr2–ySi2PO12, with a dopant concentration from 5 to 20 mol. % were studied. Doping changes the morphology and phase composition of ceramics. Electron paramagnetic resonance spectra indicate the presence of Fe3+ atoms both in the crystalline phase (with g ~ 2.0) and in disordered phases with a strong rhombic component of the crystal field on impurity ions (with g ~4.3 and ~4.2). A quantitative analysis of the distribution of paramagnetic centres in ceramics was performed. It was noted that the dopant is predominantly found in the crystalline phase of the sample. It was shown that Fe-substituted NASICON complexes correspond to the composition Na3М(III)yZr2–ySi2–yP1+yO12. The Fe3+ content in the crystalline phase of these complexes is 36% higher than in samples obtained in accordance with Na3+yМ(III)yZr2–ySi2PO12.
Dina N. Grishchenko – Candidate of Chemical Sciences, senior researcher, Institute of Chemistry, Far Eastern Branch of the Russian Academy of Sciences, Vladivostok, Russia
Denis A. Saritsky – junior research fellow, postgraduate student, Institute of Chemistry, Far Eastern Branch of the Russian Academy of Sciences, Vladivostok, Russia
Valery G. Kuryavyi – senior researcher, Candidate of Chemical Sciences, Institute of Chemistry, Far Eastern Branch of the Russian Academy of Sciences, Vladivostok, Russia
Albert M. Ziatdinov – head of the Laboratory, Doctor of Physical and Mathematical Sciences, chief researcher, Institute of Chemistry, Far Eastern Branch of the Russian Academy of Sciences, Vladivostok, Russia
Michael A. Medkov – head of the Laboratory, Doctor of Chemical Sciences, Professor, Institute of Chemistry, Far Eastern Branch of the Russian Academy of Sciences, Vladivostok, Russia
1. Ahmad H., Kubra K. T., Butt A., et al. Recent progress, challenges, and perspectives in the development of solid-state electrolytes for sodium batteries // Journal of Power Sources. 2023. V. 581. Ar. 233518.
2. Rao Y. B., Bharathi K. K., Patro L. N. Review on the synthesis and doping strategies in enhancing the Na ion conductivity of Na3Zr2Si2PO12 (NASICON) based solid electrolytes // Solid State Ionics. 2021. V. 366–367. P. 115671.
3. Fergus J.-W. Ion transport in sodium ion conducting solid electrolytes // Solid State Ionics. 2012. V. 227. P. 102 – 112.
4. Li C., Li R., Liu K., et al. NaSICON: A promising solid electrolyte for solid-state sodium batteries // Interdisciplinary Res. Mater. 2022. V. 1, No. 3. P. 396 – 416.
5. Kimura M., Tseng K.-T., Wolfenstine J., Sakamoto J. The use of hot-pressing to reduce grain boundary resistance in Nasicon of nominal composition Na3Zr2Si2PO12 // Solid State Ionics. 2024. V. 411. Р. 116561.
6. Jolley A. G., Cohn G., Hitz G. T., Wachsman E. D. Improving the ionic conductivity of NASICON through aliovalent cation substitution of Na3Zr2Si2PO12 // Ionics. 2015. V. 21, No. 11. P. 3031 – 3038.
7. Jolley A. G., Taylor D. D., Schreiber N. J., Wachsman E. D. Structural investigation of monoclinic-rhombohedral phase transition in Na3Zr2Si2PO12 and doped NASICON // J. Am. Ceram. Soc. 2015. V. 98, No. 9.P. 2902 – 2907.
8. Zhang Q., Liang F., Qu T., et al. Effect on ionic conductivity of Na3+xZr2-xMxSi2PO12 (M = Y, La) by doping rare-earth elements // IOP Conf. Ser. Mater. Sci. Eng. 2018. V. 423. Ar. 012122.
9. Zhang Z., Zhang Q., Shi J., et al. A self-forming composite electrolyte for solid-state sodium battery with ultralong cycle life // Adv. Energy Mater. 2016. V. 7. P. 1601196.
10. Fuentes R. O., Figueiredo F. M., Marques F. M. B., Franco J. I. Influence of microstructure on the electrical properties of NASICON materials // Solid State Ionics. 2001. V. 140, No. 1–2. P. 173 – 179.
11. Ma Q., Guin M., Naqash S., et al. Scandium-substituted Na3Zr2(SiO4)2(PO4) prepared by a solution-assisted solid-state reaction method as sodium-ion conductors // Chem. Mater. 2016. V. 28. P. 4821 – 4828.
12. Khakpour Z. Influence of M: Ce4+, Gd3+ and Yb3+ substituted Na3+xZr2-xMxSi2PO12 solid NASICON electrolytes on sintering, microstructure, and conductivity // Electrochim. Acta. 2016. V. 196. P. 337 – 347.
13. Ruan Y., Song S., Liu J., et al. Improved structural stability and ionic conductivity of Na3Zr2Si2PO12 solid electrolyte by rare earth metal substitutions // Ceramics International. 2017. V. 43, No. 10. P. 7810 – 7815.
14. Wen C., Luo Z., Liu X., et al. Enhanced electrochemical properties of NASICON-type Na3Zr2Si2PO12 solid electrolytes with Tb3+-ions-assisted sintering // Solid State Ionics. 2023. V. 393. P. 116185.
15. Chen D., Luo F., Zhou W., Zhu D. Influence of Nb5+, Ti4+, Y3+ and Zn2+ doped Na3Zr2Si2PO12 solid electrolyte on its conductivity // J. Alloys Compd. 2018. V. 757. P. 348.
16. Squattrito P. J., Rudolf P. R., Jorgensen J. D., et al. Sodium and oxygen disorder in a scandium-substituted Nasicon: A time-of-flight neutron powder diffraction study of Na2.5 Zr1.8 Sc0.2 Si1.3 P1.7 O12 // Solid State Ionics. 1988. V. 31. Р. 31 – 40
17. Subramanian M. A., Rudolf P. R., Clearfield A. The preparation, structure, and conductivity of scandium-substituted NASICONs // J. Solid State Chem. 1985. V. 60. Р. 172 – 181. ICSD 62176, ICSD 62177.
18. Grishchenko D. N., Medkov M. A. The effect of Na, Si, and P on the phase composition of zirconium and sodium silicophosphates (NASICON) // Theor. Found. Chem. Eng. 2024. V. 58, No. 2. P. 261 – 265.
19. Weil J., Bolton J. R. Electron paramagnetic resonance: elementary theory and practical applications. 2nd ed. New Jersey: Wiley Interscience, 2007. 688 p.
20. Bulka G. R., Vinokurov V. M., Galeev A. A., et al. Specific features of the substitution of Fe3+ impurity ions for Zr4+ in NaZr2(PO4)3 single crystals // Crystallogr. Rep. 2005. V. 50, No. 5. P. 827 – 835.
21. Kang E. T. Electron spin resonance study of Fe3+ in (40-x)BaOxFe2O360P2O5 glasses // J. Kor. Ceram. Soc. 2008. V. 45, No. 3. P. 179 – 184.
22. Rao M. V. S., Kumar A. S., Ram G. C., et al. Assessment of role of iron ions on the physical and spectroscopic properties of multi-component Na2O?PbO?Bi2O3?SiO2 glass ceramics // Phase Transitions. 2017. V. 91, No. 5. P. 1 – 16.
23. Castner T., Newell G. S., Holton W. C., Slichter C. P. Note on the paramagnetic resonance of iron in glass // J. Chem. Phys. 1960. V. 32. P. 668 – 673.
24. Клява Я. Г. ЭПР-спектроскопия неупорядоченных твердых тел. Рига: Зинатне, 1988. 320 с. ISBN 5-7966-0103-2
25. Zhuk N. A., Lutoev V. P., Makeev B. A., et al. EPR, Nexafs study and magnetic properties of Fe-doped ferroelectric ceramics // Rev. Adv. Mater. Sci. 2019. V. 57, No. 1. P. 35 – 41.
26. Amorelli A., Evans J. C., Rowlands C. C. An electron spin resonance study of rutile and anatase titanium dioxide polycrystalline powders treated with transition-metal ions // J. Chem. Soc. Faraday Trans. 1987. V. 83. P. 3541 – 3548.
27. Janes R., Knightley L. J., Harding C. J. Structural and spectroscopic studies of iron (III) doped titania powders prepared by sol-gel synthesis and hydrothermal processing // Dyes Pigm. 2004. V. 62. P. 199 – 212.
28. Elghniji K., Atyaoui A., Livraghi S., et al. Synthesis and characterization of Fe3+ doped TiO2 nanoparticles and films and their performance for photocurrent response under UV illumination // J. Alloys Compd. 2012. V. 541. 421 – 427.
The article can be purchased
electronic!
PDF format
700 руб
DOI: 10.14489/glc.2026.03.pp.018-029
Article type:
Research Article
Make a request
