Ionomers are used as the solid-electrolyte in many electrochemical energy conversion technologies where they offer many functionalities such as ion conduction, electrical insulation, and water transport. These ionomers are found as nanometer-thick electrolyte thin films within the catalyst layers of fuel cells, electrolyzers, and hydrogen-based redox flow batteries where electrochemical reactions take place. The ionomer performance and durability are strongly related to their properties governed by a myriad of parameters such as chemical structure, water uptake, and morphology, all of which are stimulated differently by the external environment. Typically, the ionomer consists of the same ion-conducting polymer used as the electrode separator but exhibit disparate properties from the bulk membrane when nanometer thickness coatings are confined to a hard substrate (as in a catalyst layer), where the behavior is influenced by the ionomer affinity with the air and hard interfaces. Two motifs of ionomers exist, one as an acidic polymer (e.g. Nafion) and the alternative, and less studied, alkaline polymer (e.g. Sustainion).

This talk will focus on filling in the gaps between the disparate properties of alkaline ionomers in the thin film motif that have been extensively studied for acidic ionomers. Aspects such as different backbones (e.g. perfluorinated, aliphatic, aromatic) and side chains (e.g. length, functional group) are explored in X-ray scattering, hydration, and transport measurements. Small-angle X-ray scattering is used to probe the morphology of these different polymer thin-films. Quartz crystal microbalance and spectroscopic ellipsometry under different states of humidity are used to probe hydration and free volume. The resulting correlations provide insights on not only how different polymer respond to the confined environment but how chemistry can be tuned to boost performance in alkaline electrochemical energy devices.