alternativeАльтернативная энергетика и экология (ISJAEE)Alternative Energy and Ecology (ISJAEE)1608-8298Международный издательский дом научной периодики "Спейс10.15518/isjaee.2018.01-03.070-093alternative-1266Research ArticleВОДОРОДНАЯ ЭКОНОМИКАHYDROGEN ECONOMYСТРУКТУРА, ТРАНСПОРТНЫЕ СВОЙСТВА И ЭЛЕКТРОХИМИЧЕСКОЕ ПОВЕДЕНИЕ СЛОИСТЫХ НИКЕЛАТОВ ЛАНТАНОИДОВ, ДОПИРОВАННЫХ КАЛЬЦИЕМSTRUCTURE, TRANSPORT PROPERTIES AND ELECTROCHEMICAL BEHAVIOR OF THE LAYERED LANTHANIDE NICKELATES DOPED WITH CALCIUMhttps://orcid.org/0000-0001-8176-9417ПикаловаЕ. Ю.PikalovaE. Yu.

канд. хим. наук, ст. науч. сотрудник лаборатории ТОТЭ, ИВТЭ УрО РАН, вед. науч. сотрудник, доцент кафедры экономики природопользования УрФУ; постоянный член Американского керамического общества и Европейского электрохимического общества

Researcher ID: L-6877-2017 

Scopus: 16242376500

Ph.D. in Chemistry, Senior Researcher, Laboratory of SOFCs, IHTE UB RAS, Leading Researcher, Associated Professor of the Department of Environmental Economics, Ural Federal University; Permanent member of American Ceramic Society, European Electrochemical Society

Researcher ID: L-6877-2017

Scopus: 16242376500

e.pikalova@list.ruhttps://orcid.org/0000-0002-9160-9764КольчугинА. А.KolchuginA. A.

инженер лаборатории ТОТЭ ИВТЭ УрО РАН, мл. науч. сотрудник УрФУ

Researcher ID: E-8650-2017

РИНЦ: 919161

Scopus: 56105439200

Engineer at Laboratory of SOFCs, IHTE UB RAS, Junior Researcher of Ural Federal University

Researcher ID: E-8650-2017

РИНЦ: 919161

Scopus: 56105439200

e.pikalova@list.ruhttps://orcid.org/0000-0003-2404-0325СадыковВ. А.SadykovV. A.

д-р хим. наук, главный научный сотрудник, зав. лабораторией Института катализа СО РАН (Новосибирск); зав. лаб., профессор Новосибирского государственного университета; член Американского химического общества и Общества по изучению свойств материалов

Researcher ID: F-9131-2012

D.Sc. in Chemistry, Chief Research Scientist, Head of the Laboratory at the Boreskov Institute of Catalysis SB RAS; Professor and Head of Laboratory of Novosibirsk State University; a Member of American Chemical Society and Materials Research Society

Researcher ID: F-9131-2012

sadykov@catalysis.ruСадовскаяЕ. М.SadovskayaE. M.

канд. тех. наук, проф., ст. науч. сотрудник, Институт катализа СО РАН, Новосибирский государственный университет

Researcher ID: A-8318-2014

РИНЦ: 47816

Scopus: 6601984831

D.Sc. in Engineering, Senior Researcher, Boreskov Institute of Catalysis SB RAS, Novosibirsk State University

Researcher ID: A-8318-2014

РИНЦ: 47816

Scopus: 6601984831

sadykov@catalysis.ruФилоноваЕ. А.FilonovaE. A.

канд. хим. наук, доцент кафедры физической и неорганической химии Института естественных наук и математики, ФГАОУ ВО «Уральский федеральный университет им. первого Президента России Б.Н. Ельцина»

Scopus: 6602857032

Ph.D. in Chemistry, Associated Prof. at Chair of the Physical and Inorganic Chemistry, Institute of Natural Sciences and Mathematics, Federal State Autonomous Educational Institution of Higher Education “Ural Federal University named after the first President of Russia B.N. Yeltsin”

Scopus: 6602857032

e.pikalova@list.ruЕремеевН. Ф.YeremeevN. F.

канд. хим. наук, научный сотрудник Института катализа СО РАН

Researcher ID: D-7148-2012

РИНЦ: 642122

Scopus: 55645818400

Ph.D. in Chemistry, Researcher, Boreskov Institute of Catalysis SB RAS

Researcher ID: D-7148-2012

РИНЦ: 642122

Scopus: 55645818400

sadykov@catalysis.ruБогдановичН. М.BogdanovichN. M.

науч. сотрудник Лаборатории ТОТЭ ИВТЭ УрО РАН

РИНЦ: 152914

Scopus: 7006746016

Researcher at Laboratory of SOFCs, IHTE UB RAS

РИНЦ: 152914

Scopus: 7006746016

e.pikalova@list.ruИнститут высокотемпературной электрохимии УрО РАН; Уральский федеральный университет имени первого Президента России Б. Н. ЕльцинаРоссияInstitute of High Temperature Electrochemistry UB RAS; Ural Federal University named after the first President of Russia B.N. YeltsinRussian FederationИнститут катализа им. Г.К. Борескова СО РАН; Новосибирский государственный университетРоссияBoreskov Institute of Catalysis SB RAS; Novosibirsk State UniversityRussian FederationУральский федеральный университет имени первого Президента России Б. Н. ЕльцинаРоссияUral Federal University named after the first President of Russia B.N. YeltsinRussian FederationИнститут катализа им. Г.К. Борескова СО РАНРоссияBoreskov Institute of Catalysis SB RASRussian FederationИнститут высокотемпературной электрохимии УрО РАНРоссияInstitute of High Temperature Electrochemistry UB RASRussian Federation20181203201801-37093Copyright © 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/1266

Прогресс в области водородной энергетики и перспективные направления ее современного развития тесно связаны с разработкой топливных элементов, в том числе, твердооксидных топливных элементов и твердо- фазных мембран для получения водорода, кислорода и синтез-газа. Необходимым условием производства конкурентоспособных устройств в данной области является использование электродных материалов, сочетающих высокую электрохимическую активность, стабильность характеристик во времени и низкую стоимость. Оксиды Ln2NiO4 со слоистой структурой Раддлесдена – Поппера с высокой смешанной ионно- электронной проводимостью и умеренными коэффициентами теплового расширения являются перспективными материалами для кислородпроводящих мембран и катодов среднетемпературных твердооксидных топливных элементов. В настоящей работе проведены исследования структуры, электропроводности, подвижности кислорода и электрохимических свойств Ln2-xCaxNiO4+δ (Ln = La, Pr, Nd; x = 0; 0,3) с целью выявления факторов, оказывающих наиболее значительное влияние на электрохимическую активность и стабильность электродов. Установлено, что допирование кальцием приводит к стабилизации структуры и увеличению электропроводности материалов. Однако электрохимическая активность электродов с введением кальция снижается в разной степени, зависящей от природы лантаноида. Прямой связи такого снижения ни с электрическими свойствами, ни с содержанием междоузельного кислорода не было обнаружено. Выявлена корреляция поляризационного сопротивления электродов с реакционной способностью (константой обмена) и подвижностью (коэффициентом самодиффузии) кислорода в электродном материале. С помощью метода C18O2 SSITKA показано, что общая подвижность кислорода в допированных материалах падает при уменьшении содержания высокоподвижного междоузельного кислорода и нарушении кооперативного механизма переноса кислорода. В случае La1,7Ca0,3NiO4+δ это приводит к появлению канала медленной диффузии и существенному уменьшению суммарного коэффициента диффузии, что может быть причиной значительного увеличения поляризационного сопротивления электродов. В материалах с празеодимом и неодимом такое явление не наблюдалось. Разработанные в данном исследовании электроды на основе Pr1,7Ca0,3NiO4+δ и Nd1,7Ca0,3NiO4+δ имеют приемлемый уровень электрохимической активности наряду с высокой электропроводностью и повышенной стабильностью по сравнению с недопированными составами и могут быть рекомендованы в качестве катодов среднетемпературных топливных элементов.

 

 

 

 

Progress in hydrogen energy and promising directions for its modern development are closely related to the development of fuel cells, including solid oxide fuel cells, and solid state membranes for hydrogen, oxygen and synthesis gas production. A necessary condition for fabrication the economically competitive devices in this area is the use of cheap electrode materials combining high electrochemical activity and long-term stability. Ln2NiO4+δ oxides with the Ruddlesden–Popper layered structure with a high mixed ion-electron conductivity and moderate values of the coefficients of thermal expansion are promising materials for the development of oxygen-conducting membranes and cathodes of intermediate-temperature solid oxide fuel cells. The paper studies the structure, electrical conductivity, oxygen mobility and electrochemical properties of Ln2-xCaxNiO4+δ (Ln = La, Pr, Nd; x = 0; 0.3) in order to determine the factors that have the most significant effect on the electrochemical activity of electrodes and their stability. We have found that doping with calcium leads to stabilization of the structure and an increase in the electrical conductivity of materials. However, addition of calcium decreases the electrochemical activity of the electrodes in varying degrees depending on the nature of the lanthanide. There is no direct interrelation of such a decrease of activity with either the electrical properties or the interstitial oxygen content. We have revealed correlation of the polarization resistance of electrodes between characteristics of oxygen transfer in the electrode material (self-diffusion coefficient, surface exchange constant). Using the C18O2 SSITKA method, the total oxygen mobility in the doped materials is shown to fall due to a decrease in the content of highly mobile interstitial oxygen and hampering of the cooperative oxygen transport mechanism. In the case of La1.7Ca0.3NiO4+δ , this leads to the appearance of a slow diffusion channel and a substantial decrease in the total diffusion coefficient value which leads to a sharp increase in the polarization resistance of the electrodes. This phenomenon is not observed in materials with praseodymium and neodymium. The electrodes based on Pr1. La1.7Ca0.3NiO4+δ and Nd1.7 La1.7Ca0.3NiO4+δ, developed in this work, have an acceptable level of the electrochemical activity along with a high electrical conductivity and increased stability in comparison with undoped compositions and can be recommended for use as cathodes for intermediate temperature fuel cells.

 

водородная энергетикатвердооксидные топливные элементы (ТОТЭ)керамические мембраныкатодLn2NiO4+δфазы Раддлесдена – Поппераимпедансная спектроскопияизотопный обменhydrogen energysolid oxide fuel cellsceramic membranescathodeLn2NiO4+δRuddlesden–Popper phasesimpedance spectroscopyisotopic exchangeСинтез материалов, исследование структуры и электрических свойств и электрохимических характеристик электродов проведены в рамках бюджетной тематики № АААА-А16-116051110161-6 ИВТЭ УрО РАН. Работы по изучению подвижности и реакционной способности кислорода осуществлялись при финансовой поддержке РНФ (Проект № 16-13-00112).The materials’ synthesis, structure, electrical properties and electrodes electrochemical characteristics studies were carried out within the framework of budget project No АААА- А16-116051110161-6 for IHTE UB RAS. 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The authors declare that there are no conflicts of interest present.