The kinetics of cathodic oxygen reduction reaction (ORR) in a proton exchange membrane fuel cell (PEMFC) is significantly modulated by the resistances for transport of reactants to the catalytic sites offered by different components of the fuel cell. This modulation governs the polarization curve of the PEMFC. Consequently, the various operating, geometric and material parameters of the fuel cell dictate the polarization curve. The effects of these parameters on the polarization curve over the entire range of current density, from zero to limiting current, can be predicted using detailed numerical simulations, which are however expensive. Analytical models, although simple can capture the essential details of physico-chemical processes occurring inside a PEMFC and are significantly inexpensive. In this article, we derive an analytical equation of the polarization curve which is valid over the entire range of current density. Specifically, the representative situation of a humidified low temperature PEMFC is considered wherein oxygen transport resistance in the cathode catalyst layer (CCL) is encountered at lower current density than proton transport resistance in the CCL. A novel experimental methodology is illustrated to confirm that this is indeed the case. Next, we elucidate a procedure to determine in-situ oxygen diffusion coefficients in the various domains of an operational PEMFC. Finally, it is shown that the analytical polarization curve predicted using these parameters is in excellent agreement with the experimental and numerically simulated polarization curves over the entire range of current density. The significance of this work is that the analytical model relates the performance of a PEMFC to all operating and geometric parameters as well as the average transport and kinetic properties of the materials used in its different components, without the need for computationally expensive numerical simulations. The model can therefore provide useful insights for enhancing the performance of PEMFC in different regimes of current density as well as for diagnostic purposes. (C) 2019 Elsevier Ltd. All rights reserved.

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