Multiscale Structure–Transport–Performance Relationships in Porous Catalyst Layers for Electrochemical Hydrogen Compression

The electrochemical performance of hydrogen compressors (EHCs) depends critically on the hierarchical microstructure of their catalyst layers (CLs), where platinum, carbon, and ionomer phases govern coupled charge and mass transport across nanometric (Nano) and mesoporous (Meso) scales, the latter characterized by agglomerate and pore phases. This work presents an experimental–computational framework to establish quantitative microstructure–transport–performance relationships in EHC CLs. CLs were fabricated by electrospray deposition on Nafion® 117 membranes and characterized by scanning electron microscopy, from which 33 representative Meso MCs were extracted and used to assemble an EHC cell for experimental polarization curves. Statistically equivalent Nano MCs resolved phase connectivity within the agglomerate phase and determined the effective catalyst area from neighboring phase configurations. Effective transport coefficients for electronic conductivity, protonic conductivity, and H2 diffusivity were computed via the finite volume method and multiscale-coupled into an analytical polarization model. Electronic and protonic conductivities are controlled by conductive-phase connectivity at the Nano scale, while H2 diffusivity is governed by the pore fraction and spatial distribution at the Meso scale, with variations exceeding three orders of magnitude. Multiscale transport coupling factors obtained via inverse calibration reduced model–experiment discrepancies to 0.05 V, validating the framework for EHC electrode design.