Hydrocarbon ionomers bear the potential to significantly lower the material cost and increase the efficiency of proton‐exchange membrane water electrolyzers (PEMWE). However, no fully hydrocarbon membrane electrode assembly (MEA) with a performance comparable to Nafion‐MEAs has been reported. PEMWE‐MEAs are presented comprising sPPS as membrane and electrode binder reaching 3.5 A cm−2 at 1.8 V and thus clearly outperforming state‐of‐the‐art Nafion‐MEAs (N115 as membrane, 1.5 A cm−2 at 1.8 V) due to a significantly lower high frequency resistance (57 ± 4 mΩ cm² vs 161 ± 7 mΩ cm²). Additionally, pure sPPS‐membranes show a three times lower gas crossover (<0.3 mA cm−2) than Nafion N115‐membranes (>1.1 mA cm−2) in a fully humidified surrogate test. Furthermore, more than 80 h of continuous operation is shown for sPPS‐MEAs in a preliminary durability test (constant current hold at 1 A cm−2 at 80 °C). These results rely on the unique transport properties of sulfonated poly(phenylene sulfone) (sPPS) that combines high proton conductivity with low gas crossover.

Polymer electrolyte membrane (PEM) water electrolysis is a key technology for sustainable hydrogen based energy supply. Gas permeation through the PEM leads to hydrogen in oxygen at the anode side posing a safety hazard and therefore restricting the operation window of PEM water electrolysis, especially when operating under pressure. In this work the hydrogen in oxygen content at the anode is significantly reduced when a recombination interlayer is integrated into the membrane electrode assemblies (MEAs) compared to reference MEAs without interlayer. The recombination interlayer with a platinum loading of 0.02 mg cm −2 is sprayed between two membranes that are coated with anode and cathode catalysts on the outside. The permeating H 2 and O 2 forms water at the recombination interlayer, leading to higher gas purity and resolving safety issues. In case of the MEAs with interlayer also a constant current hold at 1 A cm −2 for 245 h revealed only a slight increase of the hydrogen in oxygen content (below 140•10 −6 vol.% h −1) whereas for the reference MEAs without interlayer a stronger increase was observed (above 1250•10 −6 vol.% h −1). Furthermore, the long-term experiments showed no increased degradation rates compared to the reference MEAs.

The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/aenm.202103559.

High‐power, durable composite fuel cell membranes are fabricated here by direct membrane deposition (DMD). Poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVDF‐HFP) nanofibers, decorated with CeO2 nanoparticles are directly electrospun onto gas diffusion electrodes. The nanofiber mesh is impregnated by inkjet‐printed Nafion ionomer dispersion. This results in 12 µm thin multicomponent composite membranes. The nanofibers provide membrane reinforcement, whereas the attached CeO2 nanoparticles promote improved chemical membrane durability due to their radical scavenging properties. In a 100 h accelerated stress test under hot and dry conditions, the reinforced DMD fuel cell shows a more than three times lower voltage decay rate (0.39 mV h−1) compared to a comparably thin Gore membrane (1.36 mV h−1). The maximum power density of the DMD fuel cell drops by 9%, compared to 54% measured for the reference. Impedance spectroscopy reveals that ionic and mass transport resistance of the DMD fuel cell are unaffected by the accelerated stress test. This is in contrast to the reference, where a 90% increase of the mass transport resistance is measured. Energy dispersive X‐ray spectroscopy reveals that no significant migration of cerium into the catalyst layers occurs during degradation. This proves that the PVDF‐HFP backbone provides strong anchoring of CeO2 in the membrane.