A New Electrode Paradigm Enabled by Co‐Axial Electrospinning

ABSTRACT A conventional electrode in a polymer electrolyte membrane fuel cell (PEMFC) often imposes competing requirements on the ionomer, which must enable efficient proton conduction while allowing sufficient oxygen transport. To address these material‐level requirements, a co‐axial electrospun electrode comprising of a pristine ionomer core and a multifunctional platinum‐carbon‐ionomer shell is introduced. By decoupling proton and oxygen transport pathways, this architecture enables independent tailoring of core and shell chemistries and their interfaces. The core–shell structure of the electrospun fibers is confirmed by microscopy, while electrochemical and transport properties are quantified using electrochemical impedance spectroscopy and limiting‐current diagnostics. The co‐axial fibers in their current version meet or exceed the performance of conventional ultrasonically sprayed electrode at relative humidities above 75%, enabled by improvements in non‐Fickian diffusion processes. This work establishes co‐axial electrospun electrodes as a versatile platform for advanced PEMFC electrodes and a wide range of electrochemical applications, including CO 2 electrolysis, water electrolysis, and critical mineral separations.