Nafion Composite Membranes Impregnated with Polydopamine and Poly(Sulfonated Dopamine) for High-Performance Proton Exchange Membranes

[Image: see text] We prepared Nafion composite membranes by impregnating Nafion-212 with polydopamine, poly(sulfonated dopamine), and poly(dopamine-co-sulfonated dopamine) using the swelling–filling method to generate nanopores in the Nafion framework that were filled with these polymers. Compared to the pristine Nafion-212 membrane, these composite membranes showed improved thermal and mechanical stabilities due to the strong interactions between the catecholamine of the polydopamine derivatives and the Nafion matrix. For the composite membrane filled with poly(sulfonated dopamine) (N-PSDA), further interactions were induced between the Nafion and the sulfonic acid side chain, resulting in enhanced water uptake and ion conductivity. In addition, filling the nanopores in the Nafion matrix with polymer fillers containing aromatic hydrocarbon-based dopamine units led to an increase in the degree of crystallinity and resulted in a significant decrease in the hydrogen permeability of the composite membranes compared to Nafion-212. Hydrogen crossovers 26.8% lower than Nafion-212 at 95% relative humidity (RH) (fuel cell operating conditions) and 27.3% lower at 100% RH (water electrolysis operating conditions) were obtained. When applied to proton exchange membrane-based fuel cells, N-PSDA exhibited a peak power density of 966 mW cm(–2), whereas N-PSDA showed a current density of 4785 mA cm(–2), which is 12.4% higher than Nafion-212 at 2.0 V and 80 °C.