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Based on hydrothermally treated phosphosilicate (SiO2–P2O5) glass and sulfonated poly(ether ether ketone) (SPEEK) polymer, perfluorosulfonate‐free SiO2–P2O5/SPEEK composite membranes are prepared. The morphology, thermal and mechanical properties, pore structure, proton conductivity, water uptake, as well as the fuel cell performances of the SiO2–P2O5/SPEEK composite membranes are investigated. The SiO2–P2O5/SPEEK composite membranes with proton conductive SiO2–P2O5 glass powders of more than 50 wt.% were determined to be flexible due to the incorporation of the SPEEK polymer component, and it showed proton conductivities of above 10–2 S cm–1. A single H2/O2 fuel cell was assembled based on the SiO2–P2O5/SPEEK composite membrane, and was found to release a peak power density of 355.6 mW cm–2 at 68 °C.

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