Humidity-Dependent Hydration and Proton Conductivity of PFSA Ionomer Thin Films at Fuel-Cell-Relevant Temperatures: Effect of Ionomer Equivalent Weight and Side-Chain Characteristics.

Studies on the hydration properties, proton conductivity, and water content of perfluorinated ionomer thin films at temperatures relevant to fuel cell operation temperatures (around 80 °C) and the effect of ionomer chemistry are scarce. In this work, we report the water content and proton conductivity properties of thin-film ionomers (30 nm) at 80 °C over a wide range of relative humidity (0-90%) for seven different ionomers differing in the side-chain structure, including the number of protogenic groups, with the equivalent weight ranging from 620 to 1100 g/mol of sulfonic acid. The results show that the acid content or equivalent weight of the ionomer is the strongest determinant of both the swelling and the proton conductivity of ionomer films at a given relative humidity. The molar water content (λ) of ionomer films normalized to the molar protogenic group is observed to be equivalent-weight-dependent, implying that the affinity for water is acid-content-dependent. At high relative humidity conditions (>70%) pertinent to fuel cell operations, the proton conductivity of low-equivalent-weight ionomers was higher than that of higher-equivalent-weight ionomers. However, upon correlating the proton conductivity with molar water content (λ), the differences reduce dramatically, highlighting that water content is the controlling factor for proton conduction. Significantly higher values of both water content and proton conductivity are observed at 80 °C compared to those at 30 °C, implying that room temperature data are not reliable for estimating ionomer properties in the fuel cell catalyst layer.