najoNanosystems: Physics, Chemistry, MathematicsНаносистемы: физика, химия, математика2220-80542305-7971Университет ИТМО10.17586/2220-8054-2025-16-6-850-864najo-1624Research ArticleCHEMISTRY AND MATERIALS SCIENCEХИМИЯ И НАУКА О МАТЕРИАЛАХSynthesis, structure and properties of composite proton-conducting membranes based on a Nafion-type perfluorinated copolymer with Zr1−xYxO2−0.5x nanoparticlesСинтез, структура и свойства композитных протонпроводящих мембран на основе перфторированного сополимера типа Нафион с наночастицами Zr1-xYxO2-0.5xhttps://orcid.org/0000-0003-1052-4919БугровА. Н.BugrovA. N.

Alexander Nikolaevich Bugrov- Branch of Petersburg Nuclear Physics Institute named by B.P. Konstantinov; Department of Physical Chemistry

St. Petersburg, 199004

bugrov.an@mail.ruГубановаГ. Н.GubanovaG. N.

Galina Nikolaevna Gubanova – Branch of Petersburg Nuclear Physics Institute named by B.P. Konstantinov

St. Petersburg, 199004

gubanovagn@yandex.ruhttps://orcid.org/0000-0003-1637-8537ПримаченкоО. Н.PrimachenkoO. N.

Oleg Nikolaevich Primachenko – Branch of Petersburg Nuclear Physics Institute named by B.P. Konstantinov

St. Petersburg, 199004

alex-prima@mail.ruhttps://orcid.org/0000-0002-1939-2660ГофманИ. В.GofmanI. V.

Iosif Vladimirovich Gofman – Branch of Petersburg Nuclear Physics Institute named by B.P. Konstantinov

St. Petersburg, 199004

gofman@imc.macro.ruhttps://orcid.org/0000-0002-4823-0695ИванковаЕ. М.Ivan’kovaE. M.

Elena Mikhailovna Ivan’kova – Branch of Petersburg Nuclear Physics Institute named by B.P. Konstantinov

St. Petersburg, 199004

ivelen@mail.ruhttps://orcid.org/0000-0001-8470-8994ПоповаЕ. Н.PopovaE. N.

Elena Nikolaevna Popova – Branch of Petersburg Nuclear Physics Institute named by B.P. Konstantinov

St. Petersburg, 199004

men682003@mail.ruhttps://orcid.org/0000-0002-1571-209XКириленкоД. А.KirilenkoD. A.

Demid Aleksandrovich Kirilenko

St. Petersburg, 194021

demid.kirilenko@mail.ioffe.ruhttps://orcid.org/0000-0002-9930-4666ЛаврентьевВ. К.LavrentyevV. K.

Victor Konstantinovich Lavrentyev – Branch of Petersburg Nuclear Physics Institute named by B.P. Konstantinov

St. Petersburg, 199004

lavrentev1949@mail.ruhttps://orcid.org/0000-0002-4644-0445ВласоваЕ. Н.VlasovaE. N.

Elena Nikolaevna Vlasova – Branch of Petersburg Nuclear Physics Institute named by B.P. Konstantinov

St. Petersburg, 199004

evl021960@gmail.comhttps://orcid.org/0000-0001-5468-3909КононоваС. В.KononovaS. V.

Svetlana Viktorovna Kononova – Branch of Petersburg Nuclear Physics Institute named by B.P. Konstantinov

St. Petersburg, 199004

svetlanavkononova@gmail.comNRC “Kurchatov Institute” – PNPI – IMC; Saint Petersburg Electrotechnical University (ETU “LETI”)Russian FederationNRC “Kurchatov Institute” – PNPI – IMCRussian FederationIoffe InstituteRussian Federation202506012026166850864Copyright © Bugrov A.N., Gubanova G.N., Primachenko O.N., Gofman I.V., Ivan’kova E.M., Popova E.N., Kirilenko D.A., Lavrentyev V.K., Vlasova E.N., Kononova S.V., 20262026Бугров А.Н., Губанова Г.Н., Примаченко О.Н., Гофман И.В., Иванкова Е.М., Попова Е.Н., Кириленко Д.А., Лаврентьев В.К., Власова Е.Н., Кононова С.В.Bugrov A.N., Gubanova G.N., Primachenko O.N., Gofman I.V., Ivan’kova E.M., Popova E.N., Kirilenko D.A., Lavrentyev V.K., Vlasova E.N., Kononova S.V.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://nanojournal.ifmo.ru/jour/article/view/1624

Zr1−xYxO2−0.5x nanoparticles were introduced into the sulfonic acid form of the Nafion-type perfluorinated copolymer prior to membrane formation to improve its water retention, thermal stability, and proton conductivity. Since the conditions under which nanoparticles are formed can significantly influence their size, phase composition, morphology, and surface chemistry, various approaches to filler synthesis were considered in this study. It was found that among the wet-chemical methods used to produce zirconia-based nanoparticles, solvothermal synthesis offers the most promise in terms of increasing the surface proton conductivity of composite membranes. This method ensures small size, large specific surface area, and high hydrophilicity of the nanoparticles. Consequently, their incorporation into a Nafion-type perfluorinated copolymer increases the membrane’s moisture retention and improves to its proton-conducting properties. In the case of Zr1−xYxO2−0.5x nanoparticles formed under solution combustion conditions, their more hydrophobic surface did not contribute to an increase in the moisture content of the perfluorinated copolymer, but did allow its maximum operating temperature to be increased by 20 °C.

Наночастицы Zr1-xYxO2-0.5x были введены в сульфокислотную форму перфторированного сополимера Нафион типа перед формированием мембраны для улучшения ее водоудерживающей способности, термической стабильности и протонной проводимости. Поскольку условия формирования наночастиц могут существенно влиять на их размер, фазовый состав, морфологию и химию поверхности, в работе были рассмотрены разные подходы по синтезу наполнителя. Было установлено, что среди мокрохимических методов, которые применялись для получения наночастиц на основе диоксида циркония, наиболее перспективным с точки зрения повышения поверхностной протонной проводимости композитных мембран является сольвотермальный синтез. Данный метод обеспечивает малый размер, большую удельную площадь поверхности и высокую степень гидрофильности наночастиц, вследствие чего их введение в перфторированный сополимер Нафион типа повышает влагоудержание мембраны и способствует улучшению ее протонпроводящих свойств. В случае наночастиц Zr1-xYxO2-0.5x сформированных в условиях растворного горения, их более гидрофобная поверхность не способствовала повышению содержания влаги в перфторированном сополимере, но позволила повысить его максимально возможную рабочую температуру на 20°С.

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