Synthesis, Structure and Properties of NZP/NASICON Structured Materials

Authors: E. A. Asabina, V. I. Pet'kov, P. A. Mayorov, A. V. Markin, N. N. Smirnova, A. M. Kovalskii, A. A. Usenko

Abstract:

The purpose of this work was to synthesize and investigate phase formation, structure and thermophysical properties of the phosphates M_0.5+xM'_xZr_2–x(PO₄)₃ (M – Cd, Sr, Pb; M' – Mg, Co, Mn). The compounds were synthesized by sol-gel method. The results showed formation of limited solid solutions of NZP/NASICON type. The crystal structures of triple phosphates of the compositions MMg_0.5Zr_1.5(PO₄)₃ were refined by the Rietveld method using XRD data. Heat capacity (8–660 K) of the phosphates Pb_0.5+xMg_xZr_2-x(PO₄)₃ (x = 0, 0.5) was measured, and reversible polymorphic transitions were found at temperatures, close to the room temperature. The results of Rietveld structure refinement showed the polymorphism caused by disordering of lead cations in the cavities of NZP/NASICON structure. Thermal expansion (298−1073 K) of the phosphates MMg_0.5Zr_1.5(PO₄)₃ was studied by XRD method, and the compounds were found to belong to middle and low-expanding materials. Thermal diffusivity (298–573 K) of the ceramic samples of phosphates slightly decreased with temperature increasing. As was demonstrated, the studied phosphates are characterized by the better thermophysical characteristics than widespread fire-resistant materials, such as zirconia and etc.

Keywords: NASICON, NZP, phosphate, structure, synthesis, thermophysical properties.

Digital Object Identifier (DOI): doi.org/10.5281/zenodo.3607625

References:

[1] N. Anantharamulu, K. Koteswara Rao, G. Rambabu, B. Vijaya Kumar, Velchuri Radha and M. Vithal, “A wide-ranging review on Nasicon type materials”, J. Mater. Sci., vol. 46, no. 9, pp. 2821–2837, May 2011.
[2] M. Guin, F. Tietz and O. Guillon, “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, vol. 293, pp. 18–26, Oct. 2016.
[3] R. P. Forbes, D. H. Barrett, C. B. Rodella and D. G. Billing, “The thermoresponsive behaviour of Nasicon-like CuTi2(PO4)3”, Mater. Characterization, vol. 155, 109795, Sep. 2019.
[4] S. Chen, C. Wu, L. Shen, C. Zhu, Y. Huang, K. Xi, J. Maier and Y. Yu, “Challenges and perspectives for NASICON-type electrode materials for advanced sodium-ion batteries”, Adv. Mater., vol. 29, 1700431, 2017.
[5] L. Vijayan and G. Govindaraj, “NASICON materials: structure and electrical properties”, Polycrystalline Mater. – Theor. and Practical Aspects, pp. 77–106, Jan. 2012.
[6] P. Knauth, “Inorganic solid Li ion conductors: an overview”, Solid State Ionics, vol. 180, no. 14-16, pp. 911–916., 2009.
[7] D. K. Agrawal, C.-Y. Huang and H. A. McKinstry, “NZP: a new family of low-thermal expansion materials”, Int. J. Thermophys., vol. 12, no. 4, pp. 697–710, Jul. 1991.
[8] V. I. Pet'kov and A. I. Orlova, “Crystal-chemical approach to predicting the thermal expansion of compounds in the NZP family”, Inorg. Mater., vol. 39, no. 10, pp. 1013–1023, Oct. 2003.
[9] A. B. Ilin, N. V. Orekhova, M. M. Ermilova and A. B. Yaroslavtsev, “Catalytic activity of LiZr2(PO4)3 NASICON-type phosphates in ethanol conversion process in conventional and membrane reactors”, Catal. Today, vol. 268, pp. 29–36, Jun. 2016.
[10] Ch. S. Yoon, J. H. Kim, Ch. K. Kim and K. S. Hong, “Synthesis of low thermal expansion ceramics based on CaZr4(PO4)6–Li2O system”, Mater. Science and Eng., vol. B79, pp. 6–10, Jan. 2001.
[11] E. Breval, H. Mikinstry and D. K. Agrawal, “Synthesis and thermal expansion properties of the Ca(1+x)/2Sr(1+x)/2Zr4P6-2xSi2xO24 system”, J. Am. Ceram. Soc., vol. 81, no. 4, pp. 926–932, Apr. 1998.
[12] S. Y. Limaye, D. K. Agrawal and H. A. Mckinstry, “Synthesis and thermal expansion of MZr4P6O24 (M – Mg, Ca, Sr, Ba)”, J. Am. Ceram. Soc., vol. 70, no. 10, pp. C232–C236, 1987.
[13] S. Y. Limaye, D. K. Agrawal and R. Roy, “Synthesis, sintering and thermal expansion of Ca1-xSrxZr4P6O24 – an ultra-low thermal expansion ceramic system”, J. Mater. Sci., vol. 26, no. 1, pp. 93–98, Jan. 1991.
[14] V. I. Pet'kov, V. S. Kurazhkovskaya, A. I. Orlova and M. L. Spiridonova, “Synthesis and crystal chemical characteristics of the structure of M0.5Zr2(PO4)3 phosphates”, Crystallogr. Rep., vol. 47, no. 5, pp. 736–743, May 2002.
[15] E. Asabina, V. Pet'kov, P. Maiorov, D. Lavrenov, I. Shchelokov and A. Kovalsky, “Synthesis, structure and thermal expansion of the phosphates M0.5+xM'xZr2−x(PO4)3 (M, M'− metals in oxidation state +2)”, Pure Appl. Chem., vol. 89, no. 4, pp. 523-534, Apr. 2017.
[16] P. J. Elving and E. C. Olson, Analytical Chemistry, vol. 27, no. 11, pp. 1817-1820, 1955.
[17] R. Brochu, M. El-Yacoubi and M. Louer, “Crystal chemistry and thermal expansion of Cd0.5Zr2(PO4)3 and Cd0.25Sr0.25Zr2(PO4)3 ceramics”, Mater. Res. Bull., vol. 32, no. 1, pp. 15-23, Jan. 1997.
[18] P. A. Maiorov, E. A. Asabina, V. I. Pet'kov, E. Yu. Borovikova and A. M. Koval'skii, “Complex phosphates M0.5+xM′xZr2−x(PO4)3 (M = Cd, Sr, Pb; M′ = Ni, Cu; 0 ≤ x ≤ 2) with an-NZP Type Structure”, Rus. J. Inorg. Chem., vol. 64, no. 6, pp. 710–716, Jun. 2019.
[19] Y. I. Kim and F. Izumi, “Structure Refinements with a New Version of the Rietveld-Refinement Program RIETAN”, J. Ceram. Soc. Jpn., vol. 102, no. 1184, pp. 401–404, Apr. 1994.
[20] R. M. Varushchenko, A. I. Druzhinina and E. L. Sorkin, “Low-temperature heat capacity of 1-bromoperfluorooctane”, J. Chem. Thermodyn., vol. 29, no. 6, pp. 623-637, Jun. 1997.
[21] G. W. H. Hohne, W. F. Hemminger and H.-J. Flammersheim, “Differential Scanning Calorimetry, second ed.”, Springer-Verlag Berlin Heidelberg GmbH, New York, 2003.
[22] V. A. Drebushchak, “Calibration coefficient of a heat-flow DSC; Part II. Optimal calibration procedure”, J. Therm. Anal. Calorim., vol. 79, no. 1, pp. 213-218, Jan. 2005.
[23] A. Mouline, M. Alami, R. Brochu and R. Olazcuaga,” Structural and luminescent properties of a Nasicon-type phosphate CuI0.5MnII0.25Zr2(PO4)3”, J. Solid State Chem., vol. 152, no. 2, pp. 453–459, Jul. 2000.
[24] S. A. Larregola, J. A. Alonso, M. Alguero, R. Jiménez, E. Suard, F. Porcher and J. C. Pedregosa, “Effect of the Pb2+ lone electron pair in the structure and properties of the double perovskites Pb2Sc(Ti0.5Te0.5)O6 and Pb2Sc(Sc0.33Te0.66)O6: relaxor state due to intrinsic partial disorder”, Dalton Trans., vol. 39., no. 21, pp. 5159–5165, Jun. 2010.
[25] V. I. Pet'kov and E. A. Asabina, “Thermodynamic properties of compounds with kosnarite-type structure”, Ind. J. Chem., vol. 52A, no. 3, pp. 350–356, March 2013.
[26] V. Ya. Shevchenko and S. M. Barinov, “Engineering Ceramics”, Moscow, Nauka, 1993.