Unravel-engineer-design: a three-pronged approach to advance ionomer performance at interfaces in proton exchange membrane fuel cells.

Proton exchange membrane fuel cells (PEMFCs), which use hydrogen as fuel, present an eco-friendly alternative to internal combustion engines (ICEs) for powering low-to-heavy-duty vehicles and various devices. Despite their promise, PEMFCs must meet strict cost, performance, and durability standards to reach their full potential. A key challenge lies in optimizing the electrode, where a thin ionomer layer is responsible for proton conduction and binding catalyst particles to the electrode. Enhancing ion transport within these sub-μm thick films is critical to improving the oxygen reduction reaction (ORR) at the cathodes of PEMFCs. For the past 15 years, our research has targeted this limitation through a comprehensive "Unravel - Engineer - Design" approach. We first unraveled the behavior of ionomers, gaining deeper insights into both the average and distributed proton conduction properties within sub-μm thick films and at interfaces that mimic catalyst binder layers. Next, we engineered ionomer-substrate interfaces to gain control over interfacial makeup and boost proton conductivity, essential for PEMFC efficiency. Finally, we designed novel nature-derived or nature-inspired, fluorine-free ionomers to tackle the ion transport limitations seen in state-of-the-art ionomers under thin-film confinement. Some of these ionomers even pave the way to address cost and sustainability challenges in PEMFC materials. This feature article highlights our contributions and their importance in advancing PEMFCs and other sustainable energy conversion and storage technologies.