Phase diagram of the system Na2MoO4–Li2MoO4, crystal structures of Na7Li(MoO4)4, Na3-Li1+(MoO4)2, and a metastable spinel-type form of Li2MoO4

Phase diagram of the system Na2MoO4–Li2MoO4, crystal structures of Na7Li(MoO4)4, Na3-Li1+(MoO4)2, and a metastable spinel-type form of Li2MoO4 Научная публикация

Журнал

Journal of Solid State Chemistry
ISSN: 0022-4596 , E-ISSN: 1095-726X

Вых. Данные

Год: 2025, Том: 342, Номер статьи : 125107, Страниц : 8 DOI: 10.1016/j.jssc.2024.125107

Ключевые слова

Sodium-lithium molybdates, Phase diagram, Crystal structure, Ionic conductivity, Bond-valence based calculations, Spinel

Авторы

Solodovnikov Sergey F. ¹ , Meshalkin Arkadiy B. ² , Grebenkin Sergey Yu. ³ , Yudin Vasiliy N. ¹ , Solodovnikova Zoya A. ¹ , Zolotova Evgeniya S. ¹ , Plyusnin Pavel E. ¹ , Sukhikh Aleksandr S. ¹

Организации

1	Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Acad. Lavrentyev Ave. 3, Novosibirsk, 630090, Russia
2	Kutateladze Institute of Thermophysics, Siberian Branch, Russian Academy of Sciences, Acad. Lavrentyev Ave. 1, Novosibirsk, 630090, Russia
3	Voevodsky Institute of Chemical Kinetics and Combustion, Siberian Branch, Russian Academy of Sciences, Institutskaya St. 3, Novosibirsk, 630090, Russia

The T-x phase diagram of the Na2MoO4–Li2MoO4 system was revised and two compounds, Na7Li(MоO4)4 (exists above 435 °C) and Na3-xLi1+x(MoO4)2 (0 ≤ x ≤ 0.2) were found, which melt incongruently at 544 and 515 °C, respectively. Orthorhombic Na7Li(MоO4)4 of a new structure type contains the [Li(MoO4)4]7– clusters of the central LiO4 tetrahedron sharing vertices with four MoO4 tetrahedra; the clusters are connected through NaO6 and NaO5 polyhedra in two types of layers, which alternate along the c axis. In monoclinic Na2.82Li1.18(MoO4)2, isostructural with Na3Li(MoO4)2, the trigonal bipyramids of NaO5 and (Na, Li)O5 share edges to form six-membered ribbons arranged along (101) in parquet-like layers resembling cuspidine-like layers with four-membered ribbons in Na7Li(MоO4)4. The layers in Na2.82Li1.18(MoO4)2 are connected by the MoO4 and LiO4 tetrahedra into a 3D framework. Under metastable crystallization conditions, the spinel-type Li2MoO4(sp) crystals were also obtained and structurally studied. Calculations of bond-valence-based energy barriers for potential diffusion of the lithium and sodium ions show probable 1D sodium-ion conductivity for Na7Li(MоO4)4. Possible 3D lithium-ion transport pathway in Li2MoO4(sp) passes through common triangular faces surrounding Li in octahedral 16d position and empty tetrahedral 8b site.

Solodovnikov S.F. , Meshalkin A.B. , Grebenkin S.Y. , Yudin V.N. , Solodovnikova Z.A. , Zolotova E.S. , Plyusnin P.E. , Sukhikh A.S.
Phase diagram of the system Na2MoO4–Li2MoO4, crystal structures of Na7Li(MoO4)4, Na3-Li1+(MoO4)2, and a metastable spinel-type form of Li2MoO4
Journal of Solid State Chemistry. 2025. V.342. 125107 :1-8. DOI: 10.1016/j.jssc.2024.125107 WOS Scopus OpenAlex

Поступила в редакцию:	4 сент. 2024 г.
Принята к публикации:	15 нояб. 2024 г.
Опубликована online:	20 нояб. 2024 г.
Опубликована в печати:	1 февр. 2025 г.

Web of science:	WOS:001367454600001
Scopus:	2-s2.0-85210045210
OpenAlex:	W4404555337

Пока нет цитирований