vestichИзвестия Национальной академии наук Беларуси. Серия химических наукProceedings of the National Academy of Sciences of Belarus, Chemical Series1561-83312524-2342The Republican Unitary Enterprise Publishing House "Belaruskaya Navuka"10.29235/1561-8331-2023-59-2-95-104vestich-808Research ArticleФИЗИЧЕСКАЯ ХИМИЯPHYSICAL CHEMISTRYМобильный кислород в слоистых никелатах перовскитного типаMobile oxygen in layered nickelates of perovskite-typeУсенкоА. Е.UsenkaA. E.

Усенко Александра Евгеньевна – канд. хим. наук, доцент

ул. Ленинградская, 14, 220030, Минск

Usenka Alexandra E. – Ph. D (Chemistry), AssociateProfessor

14, Leningradskaya Str., 220030, Minsk

alexandrausenka@mail.ruХарламоваИ. М.KharlamovaI. M.

Харламова Инга Михайловна – аспирант, науч. сотрудник

ул. П. Бровки, 15, 220072, Минск

Kharlamova Inga M. – Ph. D. student, Researcher

15, P. Brovka Str., 220072, Minsk

МахначЛ. В.MakhnachL. V.

Махнач Леонид Викторович – канд. хим. наук, ст.науч. сотрудник

ул. Ленинградская, 14, 220030, Минск

Makhnach Leonid V. – Ph. D (Chemistry), Senior Researcher

14, Leningradskaya Str., 220030, Minsk

ПаньковВ. В.PankovV. V.

Паньков Владимир Васильевич – д-р. хим. наук, профессор

ул. Ленинградская, 14, 220030, Минск

Pankov Vladimir V. – D. Sc. (Chemistry), Professor

14, Leningradskaya Str., 220030, Minsk

КоробкоЕ. В.KorobkoE. V.

Коробко Евгения Викторовна – д-р техн. наук, профессор, зав. лаб.

ул. П. Бровки, 15, 220072, Минск

Korobko Evguenia V. – D. Sc. (Engineering), Professor,Head of the Laboratory

15, P. Brovka Str., 220072, Minsk

Белорусский государственный университетBelarusian State UniversityИнститут тепло- и массообмена имени А. В. Лыкова Национальной академии наук БеларусиA. V. Luikov Heat and Mass Transfer Institute of the National Academy of Sciences of BelarusИнститут тепло- и массообмена имени А. В. Лыкова Национальной академии наук БеларусиBelarus20230306202359295104Copyright © Усенко А.Е., Харламова И.М., Махнач Л.В., Паньков В.В., Коробко Е.В., 20232023Усенко А.Е., Харламова И.М., Махнач Л.В., Паньков В.В., Коробко Е.В.Usenka A.E., Kharlamova I.M., Makhnach L.V., Pankov V.V., Korobko E.V.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://vestichem.belnauka.by/jour/article/view/808

Проведено исследование влияния различных видов мобильного кислорода на структуру и электропроводящие свойства никелатов перовскитного типа. Методом твердофазного синтеза получены никелаты La2NiO4+δ, La0,6Sr1,4NiO4–δ, Sr3Al0,75Ni1,25O7–δ. Фазовый состав определяли методом РФА. Кислородосодержание образцов уточняли йодометрическим методом. Процессы сорбции–десорбции кислорода изучали методом твердотельной кислородной кулонометрии. Электропроводящие свойства исследовали на постоянном токе четырехзондовым методом. При помощи кулонометрического метода найдено три вида междоузельного мобильного кислорода и один узловой в слоистых никелатах перовскитного типа со структурами P/RS и 2P/RS. Эти четыре вида мобильного кислорода различаются энергией связи с кристаллической решеткой и кристаллографическими позициями. Протекающие процессы десорбции–сорбции различных видов мобильного кислорода оказывают разное влияние на термическое расширение параметров кристаллической ячейки. Наибольшие отклонения вызывает узловой мобильный кислород, находящийся в вершинах кислородных октаэдров. Данный кислород существенно меняет вид кривых температурной зависимости удельного сопротивления. Междоузельный мобильный кислород таких аномалий не вызывает. 

The influence of the different types of oxygen on the structure and electrical conductivity of the perovskite-type nickelates were investigated. The nickelates La2NiO4+δ, La0,6Sr1,4NiO4–δ, Sr3Al0,75Ni1,25O7–δ were synthesised using the solidstate reaction route. Phase composition was determined by X-ray powder diffraction analysis. The iodometric titration technique was used to specify the oxygen content of the powders. Oxygen desorption and absorption, including oxygen index variation, were investigated by oxygen solid electrolyte coulometry (OSEC). Electroconductive properties of samples were studied by a standard DC four-point method. Utilizing OSEC technique, three mobile and one regular type of oxygen were observed in the perovskite layered nickelates with P/RS and 2P/RS structure. These four types of mobile oxygen differ in the binding energy to the crystal lattice and crystallographic positions. The desorption-sorption processes of various types of mobile oxygen have different effects on the thermal expansion of crystal lattice parameters. The regular oxygen, occupying the apex of octahedron, affects the lattice parameters most prominently. This type of oxygen changes the character of the temperature dependence of specific resistivity sufficiently. Interstitial oxygen does not yield such anomalies. 

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