alternativeАльтернативная энергетика и экология (ISJAEE)Alternative Energy and Ecology (ISJAEE)1608-8298Международный издательский дом научной периодики "Спейс10.15518/isjaee.2017.31-36.048-062alternative-1244Research ArticleВОДОРОДНАЯ ЭКОНОМИКАHYDROGEN ECONOMYВЛИЯНИЕ ПРИРОДЫ ГАЛОГЕНА НА ПРОТОННЫЙ ТРАНСПОРТ В ПЕРОВСКИТОПОДОБНЫХ СОЕДИНЕНИЯХ Ba2CaNbO5,5 и Ba2In2O5INFLUENCE OF HALOGEN NATURE ON PROTON TRANSPORT IN PEROVSKITE-RELATED COMPOUNDS Ba2CaNbO5,5 AND Ba2In2O5ТарасоваН. А.TarasovaN. A.

канд. хим. наук, доцент 

ResearchID: E-4534-2017

Ph.D. in Chemistry, Associate Professor

ResearchID: E-4534-2017

Natalia.Tarasova@urfu.ruАнимицаИ. Е.AnimitsaI. E.

д-р хим. наук, профессор

D.Sc. in Chemistry, Professor

Natalia.Tarasova@urfu.ruУральский федеральный университет им. первого Президента России Б.Н. ЕльцинаРоссияUral Federal University named after the first President of Russia B.N. YeltsinRussian Federation201728012018031-364862Copyright © Международный издательский дом научной периодики "Спейс, 20182018Международный издательский дом научной периодики "СпейсМеждународный издательский дом научной периодики "Спейсhttps://www.isjaee.com/jour/about/submissions#copyrightNoticehttps://www.isjaee.com/jour/article/view/1244

Сложные оксиды с перовскитоподобной структурой, устойчивые в широком диапазоне температур и парциальных давлений кислорода, хорошо зарекомендовали себя в качестве электролитического материала твердооксидных топливных элементов. Оптимизация транспортных свойств этих оксидов достигается путем различного рода замещений. На сегодняшний день наиболее полно изучено катионное допирование. Перспективным методом является анионное допирование, которое открывает принципиально новые пути для модификации структуры и свойств соединений. Для понимания эффектов влияния аниона-допанта на транспортные свойства и выявление общих закономерностей протонного переноса в работе были исследованы фтор- и хлорзамещенные твердые растворы на основе перовскита Ba4Ca2Nb2O11 и браунмиллерита Ba2In2O5. Представлены результаты исследования термических и электрических свойств. Обсуждались вопросы влияния природы галогена-допанта на степень гидратации и парциальные (О2- , Н+ ) проводимости, а также на подвижность протонов. Методом твердофазного синтеза получены Fи Сl замещенные фазы на основе кислородно-дефицитных соединений − двойного оксида Ba4Ca2Nb2O11и браунмиллерита Ba2In2O5. Установлено, что галоген-допированные фазы Ba4Ca2Nb2O10,95Х0,1 и Ba2In2O4,95 Х0,1 (Х = F, Сl) способны к обратимому вне- дрению воды из газовой фазы и образованию протонных дефектов в виде ОНО* . Выполнен анализ кислородно-ионной проводимости и установлено, что введение донорного допанта как FО* , так и ClО* приводит к увеличению кислородной проводимости и в двойном перовските, и в браунмиллерите вследствие появления эффектов дополнительного электростатического отталкивания донорного допанта с вакансиями кислорода Vo**. Исследование протонного переноса показало симбатное изменение протонной и кислородно-ионной проводимостей в допированном Ba4Ca2Nb2O11, что позволяет говорить о влиянии динамики кислородной подрешетки на протонный транспорт: F и Сl допированные фазы с большей подвижностью кислорода характеризуются большими протонными проводимостями по сравнению с матричным составом. Для допированного браунмиллерита Ba2In2O5 введение F ионов приводило к увеличению, а присутствие Cl допанта – к уменьшению подвижности протонов, что обусловлено изменением ионности связи «металл − галоген» и сопряженным с этим ростом степени ковалентности соседних связей «металл − кислород». Описанный в работе метод анионного допирования демонстрирует новую стратегию увеличения кислородно-ионной и протонной проводимостей в перовскитах и перовскитоподобных соединениях.

 

The complex oxides with a perovskite-like structure stable in a wide range of partial pressures of oxygen and temperatures have successfully proven themselves as a promising material suitable for use as an electrolytic material of solid oxide fuel cells. Optimization of their transport properties is achieved by various kinds of substitutions. Today the cationic doping is the most studied method. A new promising method is anionic doping, which allows discovering fundamentally new ways to modify the structure and properties of compounds. In order to understand the consequences of the anion dopant influence on transport properties and to reveal general patterns of proton transfer, the paper studies the fluorine and chlorine-substituted solid solutions based on perovskite Ba4Ca2Nb2O11 and brownmillerite Ba2In2O5. The paper presents the results of investigation of thermal and electrical properties, and discusses the influence of the halogen dopant nature on the degree of hydration and partial (О 2- , Н + ) conductivity, as well as the mobility of protons. The Fand Clsubstituted phases based on oxygen-deficient compounds were synthesized by solid state method: the double oxide Ba4Ca2Nb2O11 and the brownmillerite Ba2In2O5. The halogen doped phases of Ba4Ca2Nb2O10.95Х0.1 and Ba2In2O4.95 Х0.1 (X = F, Cl) were found to be capable of reversible water uptake and the formation of proton defects ОНО* . The analysis of the oxygen ion conductivity has been performed. The introduction of the donor dopant, both FО* and ClО* , was found to lead to an increase in the oxygen conductivity in both the double perovskite and brownmillerite due to the appearance of the effects of additional electrostatic repulsion of the donor dopant with oxygen vacancies Vo**. The study of proton transfer showed a sympathetic change in the proton and oxygen ionic conductivities in doped Ba4Ca2Nb2O11 which allows one to speak of the influence of the dynamics of the oxygen sublattice on proton transport: F- and Cl-doped phases with greater oxygen mobility are characterized by large proton conductivities in comparison with the matrix composition. For doped brownmillerite Ba2In2O5, the introduction of F ions led to an increase in the proton mobility, and the presence of Cl-dopant led to a decrease due to a change in the ionicity of the metal halogen bonding and the associated increase in the degree of covalence of the neighboring metal oxygen bondings. The method of anionic doping described in the paper demonstrates a new strategy for increasing oxygen-ion and proton conductivities in perovskites and perovskite-like compounds.

 

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