High protonic resistance of hydrocarbon-based cathodes in PEM fuel cells under low humidity conditions: Origin, implication, and mitigation

Hydrocarbon-based electrodes for proton-exchange membrane fuel cells face challenges in closing the performance gap with electrodes based on perfluorosulfonic acid ionomers, particularly under low humidity conditions. Alongside increased oxygen transport resistance and higher kinetic-induced overpotentials, the protonic resistance of these fluorine-free electrodes is the primary hurdle to improved performance. This study systematically investigates the origin and impact of the cathode protonic resistance on fuel cell performance, utilizing sulfonated phenylated polyphenylenes as hydrocarbon ionomers. Electrochemical characterization at low relative humidity (≤50 %) reveal a high protonic resistance arising from both lower conductivity of the hydrocarbon thin film compared to the bulk membrane and increased cathode tortuosity at a gas transport-optimized ionomer to carbon (I/C) ratio of 0.2. The poor protonic resistance at low relative humidities leads to a non-homogeneous current distribution across the thickness of the cathode electrode, resulting in lower catalyst utilization. To address this issue, reducing the thickness of the cathode CL while maintaining a constant Pt loading (i.e., increasing the Pt on carbon ratio) significantly reduces protonic resistance. This improvement compensates for the kinetic disadvantages of highly loaded carbon particles and results in a considerable performance increase by 40 % at 0.75 V under low relative humidities. • First thin film (22 nm) measurements on sulfonated phenylated polyphenylenes. • Evidence on HC ionomer distribution in the CL: Tortuosity, possible pore intrusion. • Barely any catalyst contribution near the GDL to ORR due to protonic resistance. • Thin CLs as remediation: 40 % increase in current density at 0.75 V and 50 % RH.