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Structural degradation of Nafion® and SiO2/Nafion® PEMs under thermal cycling: Ionic domain fragmentation and proton conductivity loss

Ruslan Mensharapov, Artem Bakirov, Darya Grineva, Matvey Sinyakov, Vladimir Fateev, Dmitry Spasov

Abstract


The thermal stability of proton exchange membranes is one of the crucial aspects that should be considered during the optimization, design, and formulation of proton exchange membrane fuel cells (PEMFCs) adapted to varying and high temperatures. In this work, the effect of thermal cycling in the temperature range of 25–150 ℃ on the structural and transport properties of pristine and SiO2-modified (5 wt.%) Nafion® solution-cast membranes was investigated. Thermogravimetric analysis and impedance spectroscopy revealed that the incorporation of pre-formed nanoparticles leads to a decrease in thermal stability and does not prevent the degradation of proton conductivity, which declines by 85% after 120 heating-cooling cycles. Fourier-transform infrared spectroscopy during thermal cycling identified chemical degradation of the polymer chains for both membrane samples. Quantitative analysis of small-angle X-ray scattering data established that the degradation of transport properties is caused by an irreversible restructuring of the membranes. A decrease in the size of ionic domains and in the mean distance between neighboring domains was observed, indicating fragmentation of ionic clusters during thermal cycling and a reduction in their connectivity while the overall water uptake capacity of the samples was preserved. The obtained results demonstrate that membrane modification by the incorporation of pre-formed SiO2 nanoparticles does not ensure stabilization of the ionomer nanostructure, pointing to the need to adopt alternative modification approaches.

Keywords


PEM; thermal cycling; Nafion; SAXS; degradation; PEMFC

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References


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DOI: https://doi.org/10.15826/chimtech.10047

Copyright (c) 2026 Ruslan Mensharapov, Artem Bakirov, Darya Grineva, Matvey Sinyakov, Vladimir Fateev, Dmitry Spasov

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