Lawrence Berkeley National Laboratory

Ion-conducting polymer, or ionomer, membranes play a key role as the ion-conducting electrolyte in electrochemical devices, including fuel cells and electrolyzers. The performance of ionomers, for example, its proton conductivity, is defined by its unique molecular structure and multiscale morphology. Perfluorinated sulfonic acid ionomers are the most used ionomers, and they are cast into membranes and thin films from alcohol-rich dispersions. In this work, we examine the connections between the dispersion solvent used for casting and resulting membrane properties. Understanding and controlling the hierarchical phase separated morphology of ionomer membranes and elucidating its relationship to transport properties is crucial for improving device performance. Synchrotron-based x-ray scattering is well-suited to probe the morphology in polymers that lack a high degree of long-range order, including ionomer membranes. However, it is still challenging for conventional high energy hard x-ray scattering to resolve all the morphological details in chemically heterogeneous ionomers. Here, we use emerging synchrotron tender resonant x-ray scattering (TReXS) near the sulfur K-edge to improve scattering contrast and enhance chemical specificity to the sulfonate groups in perfluorinated sulfonic acid ionomers. We find that TReXS reveals unique energy-dependent mesoscale morphological features not apparent in hard x-ray scattering, and these features depend on dispersion composition and ionomer chemistry. These structure-property relationships can be used to guide design of next-generation ionomers for energy applications. Furthermore, this work highlights synchrotron resonant x-ray scattering as an emerging tool for structural characterization of ionomers and electrochemically active polymers in general.