Composite Membranes for High Temperature PEM Fuel Cells and Electrolysers: A Critical Review

Polymer electrolyte membrane (PEM) fuel cells and electrolysers offer efficient use and production of hydrogen for emission-free transport and sustainable energy systems. Perfluorosulfonic acid (PFSA) membranes like Nafion^® and Aquivion^® are the state-of-the-art PEMs, but there is a need to increase the operating temperature to improve mass transport, avoid catalyst poisoning and electrode flooding, increase efficiency, and reduce the cost and complexity of the system. However, PSFAs-based membranes exhibit lower mechanical and chemical stability, as well as proton conductivity at lower relative humidities and temperatures above 80 °C. One approach to sustain performance is to introduce inorganic fillers and improve water retention due to their hydrophilicity. Alternatively, polymers where protons are not conducted as hydrated H₃O⁺ ions through liquid-like water channels as in the PSFAs, but as free protons (H⁺) via Brønsted acid sites on the polymer backbone, can be developed. Polybenzimidazole (PBI) and sulfonated polyetheretherketone (SPEEK) are such materials, but need considerable acid doping. Different composites are being investigated to solve some of the accompanying problems and reach sufficient conductivities. Herein, we critically discuss a few representative investigations of composite PEMs and evaluate their significance. Moreover, we present advances in introducing electronic conductivity in the polymer binder in the catalyst layers.