Structure of the ion-rich phase in DVB cross-linked graft-copolymer proton-exchange membranes

We report on correlations between the proton conductivity, the water swelling and the dry-state morphology of ETFE-g-poly(sulfonated styrene-co-DVB) proton-exchange membranes (PEMs). We focus on the influence of the systematically varied monomer composition. Especially, the impact of the DVB cross-linker on the ion-rich phase aggregated in the dry PEM is studied by small-angle X-ray scattering. A modified hard-sphere fluid model describing the ion-rich phase is applied to interpret the observed scattering function. We find hereby that the size and number density of the ion-rich domains decrease with increasing cross-link level. Consequently, the distance between the ion-rich domains is proportional to the cross-link level. The total volume fraction of water in the hydrated membrane is proportional to the overall volume fraction of the ion-rich phase, and the number of water molecules per ion-rich aggregate is inversely proportional to the level of cross-linking. We show that there is a clear correlation between the structure of the ion-rich phase formed in the dry state and the proton conductivity of the hydrated membrane: beyond a threshold, indicating the onset of percolation of the aqueous network, the conductivity is proportional to the hydration level and inversely proportional to the mean distance between the ion-rich domains.