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Highly Permeable Perfluorinated Sulfonic Acid Ionomers for Improved Electrochemical Devices: Insights into Structure-Property Relationships

submitted on 03.09.2019 and posted on 06.09.2019 by Adlai Katzenberg, Anamika Chowdhury, Minfeng Fang, Adam Z. Weber, Yoshiyuki Okamoto, Ahmet Kusoglu, Miguel Modestino

Rapid improvements in polymer-electrolyte fuel-cell (PEFC) performance have been driven by the development of commercially available ion-conducting polymers (ionomers) that are employed as membranes and catalyst binders in membrane-electrode assemblies. Commercially available ionomers are based on a perfluorinated chemistry comprised of a polytetrafluoroethylene (PTFE) matrix that imparts low gas permeability and high mechanical strength but introduces significant mass-transport losses in the electrodes. These transport losses currently limit PEFC performance, especially for low Pt loadings. In this study, we present a novel ionomer incorporating a glassy amorphous matrix based on a perfluoro(2-methylene-4-methyl-1,3-dioxolane) (PFMMD) backbone. The novel backbone chemistry induces structural changes in the ionomer, restricting ionomer domain swelling under hydration while disrupting matrix crystallinity. These structural changes slightly reduce proton conductivity while significantly improving gas permeability. The performance implications of this tradeoff are assessed, which reveal the potential for substantial performance improvement by incorporation of highly permeable ionomers as the functional catalyst binder. These results underscore the significance of tailoring material chemistry to specific device requirements, where ionomer chemistry should be rationally designed to match the local transport requirements of the device architecture.




Email Address of Submitting Author


New York University


United States of America

ORCID For Submitting Author


Declaration of Conflict of Interest

The authors declare no conflict of interest.