Poly(fluorenyl-co-aryl piperidinium)-based AEMWEs reach outstanding current density values of 7.68 A cm−2 at 2.0 V with a cell durability of 1000 h.

We report semi-interpenetrating polymer network (semi-IPN) membranes prepared easily from a cross-linked network using poly­(acrylic acid) (PAA) and poly­(vinyl alcohol) (PVA) with interpenetrated Nafion for both proton-exchange membrane fuel cell (PEMFC) and proton-exchange membrane water electrolyzer (PEMWE) applications. Thermal esterification between PAA and PVA induced three-dimensional cross-linking to improve mechanical toughness and reduce hydrogen crossover, while the hydrophilic nature of the PAA–PVA-based cross-linked matrix still enhanced the water uptake (WU) and hence conductivity of the Nafion penetrant. The semi-IPN membrane (NPP-95) composed of Nafion, PAA, and PVA with a ratio of 95:2.5:2.5 showed a hexagonal cylindrical morphology and improved thermal, mechanical, and dimensional stability compared to a recast Nafion membrane (re-Nafion). The membrane was also highly effective at managing water due to its low WU and high conductivity. Furthermore, its hydrogen permeability was 49.6% lower than that of re-Nafion under the actual fuel cell operating conditions (at 100% RH and 80 °C). NPP-95 exhibited significantly improved conductivity and PEMFC performance compared to re-Nafion with a current density of 1561 mA/cm2 at a potential of 0.6 V and a peak power density of 1179 mW/cm2. Furthermore, in the PEMWE performances, NPP-95 displayed about a 1.5-fold higher current density of 4310 mA/cm2 at 2.0 V and much lower ohmic resistance than re-Nafion between 60 and 80 °C.

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.

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