Hydration behavior of perfluorinated and hydrocarbon-type proton exchange membranes: Relationship between morphology and proton conduction

The relationships between morphology and proton conduction for Nafion membranes and hydrocarbon-type proton exchange membranes, namely, sulfonated poly(arylene ether ether ketone) (S-PEEK) and sulfonated poly(arylene ether sulfone) (S-PES), were investigated by small-angle X-ray scattering (SAXS) and atomic force microscopy (AFM). The direct simultaneous observation of surface morphology and active regions of proton conduction on membranes by combined high-resolution AFM phase imaging and an electrochemical technique at controlled humidity provided significant morphological information, particularly for the hydrocarbon-type membranes that exhibit few or no features on SAXS profiles. For the Nafion membranes, the active proton paths became denser and congregated with each other at over 60% RH, resulting in the formation of well-connected networks. For the hydrocarbon-type membranes, however, only the relatively small and dispersed proton paths were observed, which showed no significant change even as water content increased. We have demonstrated that the differences in microscopic morphology between the Nafion and hydrocarbon-type membranes are associated with the differences between their macroscopic proton conductivities.