Abstract
Using material-sensitive and conductive atomic force microscopy (AFM) on cross sections of perfluorinated and sulfonated membranes at low humidity, crystalline polymer lamellae were imaged and their thickness determined to approximately 6nm. In the capacitive current, water-rich and water-poor areas with different phase structures were investigated. The formation of a local electrochemical double layer within the water-rich ionically conductive areas at the contact of the AFM tip with the electrolyte enabled their visibility. The large water-filled ionically conductive areas include numerous ionic domains. Under equilibrium conditions, these areas are spherical (appearing circular in the images) and with distinct size distribution. Forcing a current through the membranes (current-induced activation) led to merging of the water-filled ionically conductive areas in the voltage direction and resulted in an anisotropic ionically conducting network with flat channels. The distribution of the current in the membrane and catalytic layers of a pristine membrane electrode assembly (MEA) was analyzed. From the adhesion force mappings, an inhomogeneous distribution of ionomer in the catalytic layer was detected. Cross currents between Pt/C particles through large ionomer particles within the catalytic layer were detected and the ionomer content across an electrode was evaluated.
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