Self‐Enhancement of Perfluorinated Sulfonic Acid Proton Exchange Membrane with Its Own Nanofibers

Abstract High‐performance proton exchange membrane (PEM) is crucial for the proton exchange membrane fuel cell (PEMFC). Herein, a novel “self‐enhanced” PEM is fabricated for the first time, which is composed of perfluorinated sulfonic acid (PFSA) resin and its own nanofibers as reinforcement. With this strategy, the interfacial compatibility issue of conventional fiber‐reinforced membranes is fully addressed and up to 80 wt% loading of PFSA nanofibers can be incorporated. Furthermore, on account of chain orientation within the PFSA nanofiber, single fiber exhibits super‐high conductivity of 1.45 S cm⁻¹, leading to state‐of‐the‐art proton conductivity (1.1 S cm⁻¹) of the as‐prepared “self‐enhanced” PEM so far, which is an order of magnitude increase compared with the bulk PFSA membrane (0.29 S cm⁻¹). It surpasses any commercial PEM including the popular GORE‐SELECT and Nafion HP membranes and is the only PEM with conductivity at 10⁰ S cm⁻¹ level. In addition, the mechanical strength and swelling ratio of membranes are both substantially improved simultaneously. Based on the high‐performance “self‐enhanced” PEM, high peak power densities of up to 3.6 W cm⁻² and 1.7 W cm⁻² are achieved in H₂‐O₂ and H₂‐Air fuel cells, respectively. This strategy can be applied in any polymeric electrolyte membrane.