Transport properties of sulfonated poly (styrene‐isobutylene‐styrene) membranes with counter‐ion substitution

In this study, the transport properties of poly(styrene‐isobutylene‐styrene) (SIBS) were determined as a function of sulfonation level (0–94.9%) and counter‐ion substitution (Ba⁺², Ca⁺², Mg⁺², Mn⁺², Cu⁺², K⁺¹) for fuel cell applications. Increasing the sulfonation level improved the ion exchange capacity (IEC) of the membranes up a maximum (1.71 mequiv/g), suggesting a complex three‐dimensional network at high sulfonation levels. Results show that proton conductivity increases with IEC and is very sensitive to hydration levels. Methanol permeability, although also sensitive to IEC, shows a different behavior than proton conductivity, suggesting fundamental differences in their transport mechanism. The incorporation of counter‐ion substitution decreases both methanol and proton transport. Methanol permeability seems to be related to the size of the counter‐ion studied, while proton conductivity is more sensitive to water content, which is also reduced upon the incorporation of counter‐ions. To complement the studies, selectivity (i.e., proton conductivity/methanol permeability) of the studied membranes was determined and compared to Nafion® 117. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013