vuzbiochemiИзвестия вузов. Прикладная химия и биотехнологияProceedings of Universities. Applied Chemistry and Biotechnology2227-29252500-1558ИРНИТУ10.21285/2227-2925-2022-12-4-514-520vuzbiochemi-894Research ArticleХИМИЧЕСКИЕ НАУКИCHEMICAL SCIENCESПолучение, термические и диэлектрические характеристики Rb5Li1/3Zr5/3(MoO4)6Synthesis, thermal and dielectric characteristics of Rb5Li1/3Zr5/3(MoO4)6https://orcid.org/0000-0003-2071-1152ДоржиеваС. Г.DorzhievaS. G.

Cэсэгма Гэлэгжамсуевна Доржиева - кандидат химических наук, старший научный сотрудник.

670047, Улан-Удэ, ул. Сахьяновой, 6

bsesegma@mail.ruhttps://orcid.org/0000-0002-1231-0116БазароваЖ. Г.BazarovaJ. G.

Жибзема Гармаевна Базарова - доктор химических наук, профессор, главный научный сотрудник.

670047, Улан-Удэ, ул. Сахьяновой, 6

Baikal Institute of Nature Management, SB RAS

jbaz@binm.ruБайкальский институт природопользования, СО РАНРоссияBaikal Institute of Nature Management, SB RASRussian Federation202201012023124514520Copyright © Доржиева С.Г., Базарова Ж.Г., 20232023Доржиева С.Г., Базарова Ж.Г.Dorzhieva S.G., Bazarova J.G.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://vuzbiochemi.elpub.ru/jour/article/view/894

Цель работы состояла в направленном синтезе новой фазы Rb5Li1/3Zr5/3(MoO4)6 и определении ее кристаллографических, термических и электрофизических свойств. Методом твердофазной реакции проведен направленный синтез фазы Rb5Li1/3Zr5/3(MoO4)6 в диапазоне температур 350–470 °С. Установлено, что синтезированное соединение Rb5Li1/3Zr5/3(MoO4)6 кристаллизуется в тригональной сингонии (пр. гр. R3с, Z = 6) и согласно данным дифференциальной сканирующей калориметрии претерпевает размытый фазовый переход первого рода. Структура тройного молибдата Rb5Li1/3Zr5/3(MoO4)6 состоит из MoO4-тетраэдров и октаэдрически координированных MO6-полиэдров. Для данной структуры характерно статистическое распределение атомов лития и циркония в позиции M (M1 = 0,790 Zr + 0,210 Li, M2 = 0,877 Zr + 0,123 Li). Атомы Rb располагаются в крупных пустотах тетраэдро-октаэдрического каркаса. Исследованы электрофизические свойства тройного молибдата Rb5Li1/3Zr5/3(MoO4)6, обладающего каркасной структурой, благоприятной для ионного транспорта. Выявлена корреляция диэлектрических и термических характеристик в высокотемпературной области вблизи фазового перехода. Температурные и частотные зависимости электропроводности измерены в интервале температур 473–873 К в режимах нагрева и охлаждения в частотном диапазоне 1–10 кГц. Соединение обладает высокой термоактивированной проводимостью, достигающей при температуре 480 °С значения 1,48·10–2 См К/см с энергией активации в диапазоне 0,6–0,8 эВ. Спектры импеданса керамического образца Rb5Li1/3Zr5/3(MoO4)6 при различных температурах образуют хорошо сформированные полуокружности в низкочастотной области и неразрешенные дуги в высокочастотном регионе, изменяющиеся с повышением температуры. Эволюция мнимой части (Z″) как функции действительной части (Z') комплексного импеданса подобна поведению комплексного импеданса для соединений с ионной проводимостью.

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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The authors declare that there are no conflicts of interest present.