Synthesis, thermal and dielectric characteristics of Rb&lt;sub&gt;5&lt;/sub&gt;Li&lt;sub&gt;1/3&lt;/sub&gt;Zr&lt;sub&gt;5/3&lt;/sub&gt;(MoO&lt;sub&gt;4&lt;/sub&gt;)&lt;sub&gt;6&lt;/sub&gt;

S G Dorzhieva,J G Bazarova

doi:10.21285/2227-2925-2022-12-4-514-520

Abstract

This work addressed the directed synthesis of a new phase Rb5Li1/3Zr5/3(MoO4)6, along with the determination of its crystallographic, thermal and electrophysical properties. The directed synthesis of the Rb5Li1/3Zr5/3(MoO4)6 phase was carried out using the solid-state reaction in the temperature range of 350–470 °C. According to differential scanning calorimetry, the synthesised compound Rb5Li1/3Zr5/3(MoO4)6, crystallised in trigonal form (space group R3c, Z = 6), undergoes a diffused first-order phase transition. The structure of triple molybdate Rb5Li1/3Zr5/3(MoO4)6 comprises MoO4 tetrahedra and octahedrally coordinated MO6-polyhedra. This structure is characterised by a statistical distribution of lithium and zirconium atoms in the M position (M1 = 0.790 Zr + 0.210 Li, M2 = 0.877 Zr + 0.123 Li). Rb atoms are located in the large voids of the tetrahedronoctahedral framework. The electrophysical properties of triple molybdate Rb5Li1/3Zr5/3(MoO4)6 having a scaffold structure favourable for ion transport, were studied. The correlation between dielectric and thermal characteristics in the high-temperature region near the phase transition was revealed. The temperature and frequency dependences of electrical conductivity were measured at 473–873 K in heating and cooling modes in the frequency range of 1–10 kHz. The compound exhibited a high thermally activated conductivity, reaching 1.48·10-2 Cm K/cm with activation energy in the range of 0.6–0.8 eV at a temperature of 480 °C. Well-shaped semicircles in the low-frequency region and unresolved arcs in the high-frequency region changing with increasing temperature were observed in the impedance spectra of ceramic Rb5Li1/3Zr5/3(MoO4)6 sample at various temperatures. The evolution of the imaginary part (Z'') as a function of the real part (Z') of the complex impedance resembled that of the complex impedance for compounds having ionic conductivity.

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