Ordered Dynamic Networks Proton Exchange Membrane for Humidity‐Resilient High‐Performance Fuel Cells

Abstract Maintaining proton conductivity of sulfonated proton exchange membranes (PEMs) under low humidity remains a critical challenge for fuel cell applications. This study presents an innovative interfacial engineering strategy through the integration of perfluorosulfonic acid nanofibers (PFSANF) with hydroxyl‐functionalized Tröger's base polymer containing tertiary amine groups (HTB), constructing an ordered dynamic network membrane. The system achieves multi‐level performance optimization via synergistic 3D hydrogen‐bond networks and acid‐base interactions: 1) Nanofiber create high‐speed proton transport networks; 2) Hydroxyl and tertiary amine groups cooperatively enhance water retention while creating additional proton‐hopping sites. The resulting ordered dynamic architecture demonstrates remarkable humidity‐adaptive proton conduction, achieving a proton conductivity of 123 mS cm⁻¹ – 1.9 times higher than commercial Nafion NC at 90 °C and 30% relative humidity (RH). The optimized membrane demonstrates outstanding peak power density of 1.2 W cm⁻² in H₂/O₂ fuel cells. This innovative interfacial engineering approach establishes a new paradigm for developing humidity‐resilient proton exchange membranes through synergistic molecular design and ordered nanostructure.