The separation of resistances during their measurement is important because it helps to identify contributors in polymer electrolyte membrane (PEM) fuel cell performance. The major methodologies for separating the resistances are electrochemical impedance spectroscopy (EIS) and polarization curves. In addition, an equivalent circuit was selected for EIS analysis. Although the equivalent circuit of PEM fuel cells has been extensively studied, less attention has been paid to the separation of resistances, including protonic resistance in the cathode catalyst layer (CCL). In this study, polarization curve and EIS analyses were conducted to separate resistances considering the charge transfer resistance, mass transport resistance, high frequency resistance, and protonic resistance in the CCL. A general solution was mathematically derived using the recursion formula. Consequently, resistances were separated and analyzed with respect to variations in relative humidity in the entire current density region. In the case of ohmic resistance, high frequency resistance was almost constant in the main operating load range (0.038–0.050 Ω cm2), while protonic resistance in the CCL exhibited sensitivity (0.025–0.082 Ω cm2) owing to oxygen diffusion and water content.
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