Enhancing proton exchange membrane water electrolysis by building electron/proton pathways

Proton exchange membrane water electrolysis (PEMWE) plays a critical role in practical hydrogen production. Except for the electrode activities, the widespread deployment of PEMWE is severely obstructed by the poor electron-proton permeability across the catalyst layer (CL) and the inefficient transport structure. In this work, the PEDOT:F (Poly(3,4-ethylenedioxythiophene):perfluorosulfonic acid) ionomers with mixed proton-electron conductor (MPEC) were fabricated, which allows for a homogeneous anodic CL structure and the construction of a highly efficient triple-phase interface. The PEDOT:F exhibits strong perfluorosulfonic acid (PFSA) side chain extensibility, enabling the formation of large hydrophilic ion clusters that form proton-electron transport channels within the CL networks, thus contributing to the surface reactant water adsorption. The PEMWE device employing membrane electrode assembly (MEA) prepared by PEDOT:F-2 demonstrates a competitive voltage of 1.713 ​V under a water-splitting current of 2 ​A ​cm⁻² (1.746 ​V at 2A cm⁻² for MEA prepared by Nafion D520), along with exceptional long-term stability. Meanwhile, the MEA prepared by PEDOT:F-2 also exhibits lower ohmic resistance, which is reduced by 23.4 ​% and 17.6 ​% at 0.1 ​A ​cm⁻² and 1.5 ​A ​cm⁻², respectively, as compared to the MEA prepared by D520. The augmentation can be ascribed to the superior proton and electron conductivity inherent in PEDOT:F, coupled with its remarkable structural stability. This characteristic enables expeditious mass transfer during electrolytic reactions, thereby enhancing the performance of PEMWE devices.