Enhancing Hydration Stability and Proton Transport in Nafion/SiO₂ Membranes for Medium- to High-Temperature PEMFCs

Perfluorosulfonic acid (PFSA) membranes suffer from severe conductivity decay caused by dehydration at elevated temperatures, hindering their application in medium- to high-temperature proton exchange membrane fuel cells (MHT-PEMFCs). To address this, Nafion/SiO₂ composite membranes with systematically varied filler contents were fabricated via a sol-gel-assisted casting strategy to enhance hydration stability and proton transport. Spectroscopic and microscopic analyses reveal a homogeneous nanoscale dispersion of SiO₂ within the Nafion matrix, along with strong interfacial hydrogen bonding between SiO₂ and sulfonic acid groups. These interactions effectively suppress polymer crystallinity and stabilize hydrated ionic domains. Thermogravimetric analysis confirms markedly improved water retention in the composite membranes at intermediate temperatures. Proton conductivity measurements at 50% relative humidity (RH) identify the Nafion/SiO₂-3 membrane as exhibiting optimal transport behavior, delivering the highest conductivity of 61.9 mS·cm^-1 at 120 °C and significantly improved conductivity retention compared to Nafion 117. Furthermore, single-cell tests under MHT-PEMFC conditions (120 °C, 50% RH) demonstrate the practical efficacy of these membrane-level enhancements, with the Nafion/SiO₂-3 membrane exhibiting an open-circuit voltage and peak power density 11.2% and 8.9% higher, respectively, than those of pristine Nafion under identical MEA fabrication and operating conditions. This study elucidates a clear structure-property-transport relationship in SiO₂-reinforced PFSA membranes, demonstrating that controlled inorganic incorporation is a robust strategy for extending the operational temperature window of PFSA-based proton exchange membranes toward device-level applications.