Gas diffusion electrodes ͑GDEs͒ containing a graded distribution of Nafion were prepared and characterized, and their performance as fuel cell cathodes compared to GDEs possessing a uniform distribution of Nafion. Cyclic voltammetry, electrochemical impedance spectroscopy ͑EIS͒, and porosimetry are used to characterize the variations in electrochemical properties, ionic conductivity, and microstructures. The cathodic performance was improved over uniform electrodes at intermediate and high levels of polarization when the Nafion content in the GDE was higher toward the catalyst layer/membrane interface and lower toward the catalyst layer/carbon paper interface since this maximizes proton transport in the GDE in the region of greatest ion flux and maximizes porosity in the region of greatest gaseous flux, respectively. Fuel cell performance is much poorer when the gradient of Nafion content is reversed, i.e., highest at the catalyst layer/carbon paper interface since this distribution disfavors proton and gas transport in the regions where they need to be maximized.
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