Freeze-thaw integrity of modified Nafion membranes: Microstructure and MEA performance
Mensharapov R.M. Ivanova N.A. Spasov D.D. Sinyakov M.V. Bakirov A.V. Aliyev A.S. Grigoriev S.A. Fateev V.N.
November 2025Institution of Chemical Engineers
Process Safety and Environmental Protection
2025#203
Integrity of Nafion membranes in freeze-thaw cycles is an important factor which should be considered when developing proton exchange membrane fuel cells (PEMFC) for the wide range of operating temperatures. Freezing of the Nafion membrane swollen in water leads to desorption of free water/ice on the membrane surface, which causes delamination of catalyst layer, and changes in membrane microstructure. To increase Nafion stability, in situ sol-gel modification with silica nanoparticles was carried out. Morphological changes of pristine and modified membranes during freeze-thaw cycles were investigated by small angle X-ray scattering (SAXS), in addition water uptake and proton conductivity were determined. Stabilization of the structure of ionic domains due to the introduction of silica nanoparticles into the membrane was shown. The observed changes can be attributed to a decrease in the intensity of water sorption-desorption processes and stabilization of ionic domains by modifier nanoparticles. The MEAs fabricated using modified membranes demonstrated enhanced stability during freeze-thaw cycling.
Freeze-Thaw Cycling , Ionic clusters , Nafion membrane , Proton exchange membrane fuel cells , Small-angle X-ray scattering
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National Research Centre “Kurchatov Institute”, 1, Akademika Kurchatova Sq., Moscow, 123182, Russian Federation
“D.V. Sokolsky Institute of Fuel, Catalysis and Electrochemistry” JSC, 142 Kunayev str., Almaty, 050010, Kazakhstan
National Research University “Moscow Power Engineering Institute”, 14, Krasnokazarmennaya st., Moscow, 111250, Russian Federation
D. Mendeleev University of Chemical Technology of Russia, Miusskaya Sq., 9, Moscow, 125047, Russian Federation
Enikolopov Institute of Synthetic Polymer Materials RAS, 70 Profsoyuznaya str., Moscow, 117393, Russian Federation
M. Nagiyev Institute of Catalysis and Inorganic Chemistry, Ministry of Science and Education of the Republic of Azerbaijan, H. Cavid Ave. 113, AZ, Baku, 1143, Azerbaijan
A.N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences, 28–1 Vavilova st., Moscow, 119334, Russian Federation
HySA Infrastructure Center of Competence, Faculty of Engineering, North-West University, Potchefstroom, 2531, South Africa
National Research Centre “Kurchatov Institute”
“D.V. Sokolsky Institute of Fuel
National Research University “Moscow Power Engineering Institute”
D. Mendeleev University of Chemical Technology of Russia
Enikolopov Institute of Synthetic Polymer Materials RAS
M. Nagiyev Institute of Catalysis and Inorganic Chemistry
A.N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences
HySA Infrastructure Center of Competence
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