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This work considers the relationship between the morphology of porous carbon materials used for supercapacitors and the electrochemical impedance spectroscopy (EIS) response. EIS is a powerful tool that can be used to study the porous 3-dimensional electrode behavior in different electrochemical systems. Porous carbons prepared by treatment of cellulose with different compositions of potassium hydroxide (KOH) were used as model systems to investigate the form vs. electrochemical function relationship. A simple equivalent circuit that represents the electrochemical impedance behavior over a wide range of frequencies was designed. The associated impedances with the bulk electrolyte, Faradaic electrode processes and different pore size ranges were investigated using a truncated version of the standard transmission line model. The analysis considers the requirements of porous materials as electrodes in supercapacitor applications, reasons for their non-ideal performance and the concept of ‘best capacitance’ behavior in different frequency ranges. Graphical Abstract: The electrolyte ions penetrate the macropores, into the mesopores and finally reach the micropores. The capacitance measured by impedance spectroscopy is a function of frequency and porous structure.

The need to understand the effects of degradation in polymer electrolyte fuel cells (PEFCs) has led to the development of in-situ and operando imaging studies of failure mechanisms occurring in their constituent materials, but studies using X-ray computed tomography (X-ray CT) for imaging have focussed primarily on a single region of the PEFC flow channel. Whilst studies have shown local variation in degradation rates using electrochemical techniques, this work employs identical-location X-ray CT imaging to elucidate the local degradation of a membrane electrode assembly (MEA) at various locations along-the-channel of a serpentine flow field. Using a carbon corrosion specific accelerated stress test (AST), in-depth analyses of the catalyst layers (CLs) and crack network allow for quantification of the material’s degradation at the inlet, middle and outlet regions of the flow channel on the cathode side. Imaging of the regions was done after 0, 2000 and 5000 cycles and results show significant regional variation in the extent of degradation of the cathode CL. The order of degradation was found to be outlet > middle > inlet, with the outlet CL found to be thinner than the middle and inlet regions, with a greater extent of cracking. Furthermore, additional land and channel degradation effects were probed, with the land regions found to be less degraded than channel regions. This work further highlights the need to understand and develop ASTs that can promote a more uniform degradation rate across an MEA.