Ion-Exchange Strategy Enabling Direct Reformation of Unreliable Perfluorinated Cationic Polymer for Robust Proton Exchange Membrane towards Hydrogen Fuel Cells

Perfluorosulfonated anionic ionomers are known for their robust ion conductivity and chemical and mechanical stability. However, the structure and transport property degradation of perfluorinated cationic polymers (PfCPs) are not well understood. Herein, we propose an ion-exchange strategy to identify the structural degradation, ion transport mechanisms, and architectural reformation of PfCPs. Particularly, we demonstrate that the utility of a –SO 2 –N + strategy employing the Menshutkin reaction cannot yield reliable PfCPs and anion-exchange membranes, but can yield an unreliable zwitterionic intermediate (cations–anions molar ratio is approximately 7.6%). Moreover, the degradation products were efficiently reformed as proton exchange membranes (PEMs), and the as-reformed PEMs achieved an ion-exchange capacity (IEC) value (0.89 mmol g −1 ), meanwhile retaining more than 94.7% of their initial capacity. Furthermore, the fuel cell assembled with reformed PEMs displayed a power density of 0.91 Wcm −2 at 2.32 A cm −2 , which was 90.1% of that of the robust perfluorosulfonic acid PEMs. Our combined findings shed some fresh light on the state of understanding of the structure–property relationship in PfCPs.