Mussel-Inspired Polydopamine-Treated Reinforced Composite Membranes with Self-Supported CeO_x Radical Scavengers for Highly Stable PEM Fuel Cells

The physical and chemical degradations of a state-of-the-art proton exchange membrane (PEM) composed of a perfluorinated sulfonic acid (PFSA) ionomer and polytetrafluoroethylene (PTFE) reinforcement are induced through the repeated expansion/shrinkage of the ionomer and free radical attacks. Such degradations essentially originate from the loose structure of the materials and the low interactive binding force among the PEM constituents. In this study, the need for simplified design principles of adhesives led to the use of mussel-inspired polydopamine (PD) as an interfacial modifier for the fabrication of highly durable PEM. Indeed, a self-polymerized dopamine layer acts as an interfacial glue, and enables efficient impregnation of a hydrophilic PFSA ionomer into porous hydrophobic PTFE with high packing density, resulting in strong adhesion between the PTFE and the PFSA polymers in the membrane. In addition, the redox property of the PD end groups spontaneously reduces the partial Ce salts in the ionomer solution and anchors them to the PD@PTFE substrate as defective cerium oxide (CeO_x) nanoparticles, reducing the dissolution and subsequent migration under cell operations. Finally, a CePD@PTFE membrane shows outstanding durability in fuel cells under an accelerated humidity cycling test with a reduction in the degree of physical and chemical failures.