Synthesis and structure of complex phosphates Na3,5MIІ 0,5Fe1,5(PO4)3 (MII — Mg, Ni), obtained under condition of the crystallization of multicomponent self-fluxes

Authors

  • N.Yu. Strutynska Taras Shevchenko National University of Kyiv
  • A.V. Spivak Taras Shevchenko National University of Kyiv
  • V.N. Baumer SSI “Institute for Single Crystals” of the NAS of Ukraine, Kharkiv
  • M.S. Slobodyanik Taras Shevchenko National University of Kyiv

DOI:

https://doi.org/10.15407/dopovidi2021.02.100

Keywords:

crystallization of self-fluxes, single crystal, powder X-ray diffraction, FTIR spectroscopy

Abstract

The regularities of the formation of complex phosphates in the system Na2O—P2O5—Fe2O3—MIIO (MII — Co, Mg, Ni at the crystallization of multicomponent self-fluxes at the values of molar ratios: Na/P = 1,3, Fe/P = 0,3, Fe/MII = 2, over the temperature interval of 1000-650 °С have been investigated. The single crystals of complex phosphates of Na3,5MIІ0,5Fe1,5(PO4)3 (MII — Mg, Co, Ni) 5 mm in size have been grown. In the FTIR spectra of synthesized complex phosphates Na3,5MIІ0,5Fe1,5(PO4)3 (MII — Mg, Co, Ni), the characteristic modes in the regions of 900-1200 сm–1 (symmetric and asymmetric stretching vibrations (v4, v1, and v3) of a phosphate tetrahedron) and 400-600 сm–1 (corresponding deformation vibration) have been confirmed the presence of an orthophosphate–type anion in their composition. The calculated cell parameters for obtained phosphates (trigonal system, space group R-3c) are in the range of values (а, b) = 8,68 ÷ 8,80 Å and c = 21,47 ÷ 21,58 Å and depend on the nature of MII. The basic building block of the structure of complex phosphates Na3,5MIІ0,5Fe1,5(PO4)3 (MII — Mg, Co, Ni) is the [(MІІ/Fe)2 (PO4)3] unit, which consists of two (MІІ/Fe)O6 polyhedra interlinked by three bridging PO4-tetrahedra. The Na+ cations are distributed over two partially occupied sites in the cavities of the framework. The presence of vacancies in the cationic sublattice of complex phosphates with NASICONrelated structure will further affect the ion-conducting properties of solid electrolytes based on them.

Downloads

Download data is not yet available.

References

Guin, M., Tietz, F. & Guillon, O. (2016). New promising NASICON material as solid electrolyte for sodium-ion batteries: Correlation between composition, crystal structure and ionic conductivity of Na3+xSc2SixP3−xO12. Solid State Ionics, 293, pp. 18-26. https://doi.org/10.1016/j.ssi.2016.06.005

Feng, J.K., Lu, L. & Lai, M.O. (2010). Lithium storage capability of lithium ion conductor Li1.5Al0.5Ge1.5(PO4)3. J. Alloys Compd., 501, No. 2, pp. 255-258. https://doi.org/10.1016/j.jallcom.2010.04.084

Hou, M., Liang, F., Chen, K., Dai, Y. & Xue, D. (2020). Challenges and perspectives of NASICON-type solid electrolytes for all-solid-state lithium batteries. Nanotechnology, 31, No. 13. https://doi.org/10.1088/1361-6528/ab5be7

Park, J.Y., Shim, Y., Kim, Y., Choi, Y., Lee, H.J., Park, J., Wang, J.E., Lee, Y., Chang, J. H., Yim, K., Ahn, C.W., Lee, C.-W., Kim, D. K. & Yuk, J.M. (2020). Iron-doped NASICON type sodium ion battery cathode for enhanced sodium storage performance and its full cell applications. J. Mater. Chem., A, 8, pp. 20436-20445. https://doi.org/10.1039/D0TA07766F

El-Shinawi, H., Regoutz, A., Payne, D.J., Cussen, E.J. & Corr, S.A. (2018). NASICON LiM2(PO4)3 electrolyte (M = Zr) and electrode (M = Ti) materials for all solid-state Li-ion batteries with high total conductivity and low interfacial resistance. J. Mater. Chem. A, 6, pp. 5296-5303. https://doi.org/10.1039/C7TA08715B

Wu, M., Ni W., Hu, J. & Ma, J. (2019). NASICON-structured NaTi2(PO4)3 for sustainable energy storage. Nano-Micro Lett., 11, No. 44. https://doi.org/10.1007/s40820-019-0273-1

Hatert, F. (2009). Na4Fe2+Fe3+(PO4)3, a new synthetic NASICON-type phosphate. Acta Crystallogr., Sect. E., 65, i30. https://doi.org/10.1107/S1600536809009210

Essehli, R., El Bali, B., Benmokhtar, S., Bouziane, K., Manoun, B., Abdalslam, M.A. & Ehrenberg, H. (2011). Crystal structures and magnetic properties of iron (III)-based phosphates: Na4NiFe(PO4)3 and Na2Ni2Fe(PO4)3. J. Alloys Compd., 509, pp. 1163-1171. https://doi.org/10.1016/j.jallcom.2010.08.159

Strutynska, N.Yu., Zatovsky, I.V. Yatskin, M.M., Slobodyanik, N.S. & Ogorodnyk, I.V. (2012). Crystallization from Na2O—P2O5—Fe2O3—MIIO (MII — Mg, Ni) melts and the structure of Na4MgFe(PO4)3. Inorg. Mater., 48, No. 4, pp. 402-406. https://doi.org/10.1134/S0020168512040176

Yatskin, M.M., Strutynska, N.Yu., Zatovsky, I.V. & Slobodyanik, N.S. (2012). Phase formation in the flux systems Na2O—P2O5—Fe2O3—MeIIO (MeII — Mn, Co, Cu, Zn). Dopov. Nac. akad. nauk Ukr., No. 4, pp. 145-148 (in Ukrainian).

Zatovsky, I.V., Strutynska, N.Yu., Ogorodnyk, I.V., Baumer, V. N., Slobodyanik, N.S., Yatskin, M.M., & Odynets, I.V. (2016). Peculiarity of formation of the NASICON-related phosphates in the space group R32:

Downloads

Published

30.04.2021

How to Cite

Strutynska, N., Spivak, A., Baumer, V., & Slobodyanik, M. (2021). Synthesis and structure of complex phosphates Na3,5MIІ 0,5Fe1,5(PO4)3 (MII — Mg, Ni), obtained under condition of the crystallization of multicomponent self-fluxes. Reports of the National Academy of Sciences of Ukraine, (2), 100–107. https://doi.org/10.15407/dopovidi2021.02.100

Issue

No. 2 (2021): Reports of the National Academy of Sciences of Ukraine

Section

Chemistry

License

Copyright (c) 2021 Reports of the National Academy of Sciences of Ukraine

Creative Commons License

This work is licensed under a Creative Commons Attribution-NonCommercial 4.0 International License.

Most read articles by the same author(s)

<< < 1 2 3 > >>