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There is a small current overshoot before stabilization. It was also observed experimentally is some cases but the stabilization time is longer (some minutes). It can be explained by the fact that the catalyst is covered by some kind of poisoning species that are not easily and quickly oxidized (Pt3-COH and Pt-COOH in this case). When the cell is started, the coverage of these species will increase and reduce available catalyst for methanol adsorption. Consequently, less protons can be formed and the cell current decrease. When the cell is started, the anode overpotential increases while the cathode overpotential decreases when the cell voltage increases to keep a constant current density (Figures 49, 51, 53). A negative overshoot can be seen for cathodic over potential. It is related to the current density overshoot. When it occurs, more protons are formed at anode than at the steady state. Consequently, the cathodic over potential has to be decreased to improve oxygen reduction. The coverage of the catalytic surface decreases with the cell voltage (Figures 48, 50, 52). A higher cell voltage, of course means a higher anode potential. It helps oxidation of the methanol decomposition products. Consequently their poisoning effect is lowered. However, the coverage of Pt3-COH (which is higher than Pt-COOH) never exceeds 0.435. It is another proof that methanol decomposition is the rate limiting step. This is a surprising result as the poisoning species coverage (Pt-COH and Pt-COOH) close to one is expected for reaction 1 to be the rate limiting step. d. Modeling of the polarization curve In dynamic mode, the evolution of the different parameters with time matched what was expected theoretically. The fitted rate constants seem to give acceptable results. The code was forced to give a polarization curve close to the experimental one in specific conditions (117 Nafion membrane, 80oC, Fanode = 1ccm, CCH3OH = 1M and PC = 0atm rel.), however by fitting rate constants. In order to be trusted and used to predict the cell behavior it has to match the experiments when working conditions are changed. The - 78 -PDF Image | Direct Methanol Fuel Cell (DMFC) Performance
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