New molybdates in the Rb2MoO4–MI2MoO4–Zr(MoO4)2 (MI – Na, K) systems as promising ion-conducting materials

S.G. Dorzhieva, B.G. Bazarov, J.G. Bazarova show affiliations and emails
Received 14 September 2018; Accepted 14 November 2018;
This paper is written in Russian
Citation: S.G. Dorzhieva, B.G. Bazarov, J.G. Bazarova. New molybdates in the Rb2MoO4–MI2MoO4–Zr(MoO4)2 (MI – Na, K) systems as promising ion-conducting materials. Lett. Mater., 2019, 9(1) 17-21
BibTex   https://doi.org/10.22226/2410-3535-2019-1-17-21

Abstract

New molybdates Rb5MI1/3Zr5/3(MoO4)6 (MI – Na, K) are synthesized. Their crystallographic parameters are determined.Phase equilibria in the Rb2MoO4-Na2MoO4-Zr(MoO4)2 system were studied for the first time, quasi-binary cuts in the concentration triangle were determined, and triangulation was performed. The formation of a new phase of molybdate Rb5Na1 / 3Zr5 / 3(MoO4)6 was established in the system. New triple molybdates Rb5MI1 / 3Zr5 / 3(MoO4)6 (MI — Na,K) were synthesized by the solid-phase reaction in the temperature interval 400 – 510°C. The physicochemical characteristics of the prepared materials were carried out by Х-ray diffraction, differential scanning calorimetry, IR-spectroscopy, and scanning electron microscopy. It was established that synthesized molybdates crystallized in the trigonal space group R-3С, Z = 6. The crystal structure consists of MoO4-tetrahedra and octahedrally coordinated MO6-polyhedra. Rubidium cations are located in the cavities of the framework. Cation (sodium, potassium) and zirconium atoms are statistically distributed in M positions. The curves of differential-scanning calorimetry are characterized by endothermic effects corresponding to phase transitions and melting of the samples. The phase transitions found in the high-temperature region as a result of multiple measurements in the heating and cooling modes without melting the samples belong to the first-order phase transitions due to the temperature hysteresis. The IR spectra contain intense absorption bands associated with stretching vibrations of Mo-O bonds in MoO4-tetrahedra. In the final annealing product, the particle size is 80 – 400 nm, as measured at electron micrographs. The identified compounds of the composition Rb5MI1 / 3Zr5 / 3(MoO4)6 (MI — Na, K) have a framework structure with channels appropriate for ion transport, which is a prerequisite for ion-conducting properties and use of the compounds as promising solid electrolytes.

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