Conductive polymers are exceptionally promising for modular electrochemical applications including chemical sensors, bioelectronics, redox-flow batteries, and photoelectrochemical systems due to considerable synthetic tunability and ease of processing. Despite well-established structural heterogeneity in these systems, conventional macroscopic electroanalytical methods-specifically cyclic voltammetry-are typically used as the primary tool for structure-property elucidation. This work presents an alternative correlative multimicroscopy strategy. Data from laboratory and synchrotron-based microspectroscopies, including conducting-atomic force microscopy and synchrotron nanoscale infrared spectroscopy, are combined with potentiodynamic movies of electrochemical fluxes from scanning electrochemical cell microscopy (SECCM) to reveal the relationship between electrode structure and activity. A model conductive polymer electrode system of tailored heterogeneity is investigated, consisting of phase-segregated domains of poly(3-hexylthiophene) (P3HT) surrounded by contiguous regions of insulating poly(methyl methacrylate) (PMMA), representing an ultramicroelectrode array. Isolated domains of P3HT are shown to retain bulk-like chemical and electronic structure when blended with PMMA and possess approximately equivalent electron-transfer rate constants compared to pure P3HT electrodes. The nanoscale electrochemical data are used to model and predict multiscale electrochemical behavior, revealing that macroscopic cyclic voltammograms should be much more kinetically facile than observed experimentally. This indicates that parasitic resistances rather than redox kinetics play a dominant role in macroscopic measurements in these conductive polymer systems. SECCM further demonstrates that the ambient degradation of the P3HT electroactivity within P3HT/PMMA blends is spatially heterogeneous. This work serves as a roadmap for benchmarking the quality of conductive polymer films as electrodes, emphasizing the importance of nanoscale electrochemical measurements in understanding macroscopic properties.
Keywords: electrochemistry; electron-transfer kinetics; parasitic resistances; poly(3-hexylthiophene); polymer degradation; scanning electrochemical cell microscopy.