Journal of the Electrochemical Society, Vol.145, No.8, 2684-2699, 1998
Phenomenological theory of electro-osmotic effect and water management in polymer electrolyte proton-conducting membranes
Partial dehydration of the proton-conducting membrane under working conditions is one of the major problems in low-temperature fuel cell technology. In this paper a model, which accounts for the electro-osmotically induced drag of water from anode to cathode and the counterflow in a hydraulic pressure gradient is proposed. A balance of these flows determines a gradient : of water content across the membrane, which causes a decline of the current-voltage performance. Phenomenological transport equations coupled with the capillary pressure isotherm are used, involving the conductivity, permeability. and electro-osmotic drag coefficients dependent on the local water content. The effects of membrane parameters on current-voltage performance are investigated. A.universal feature of the obtained current-voltage plots is the existence of a critical current at which the potential drop across the membrane increases dramatically due to the dehydration of membrane layers close to the anode. For a membrane with zero residual conductivity in its dry parts, the critical current is a limiting current. Well below the critical current the effect of dehydration is negligible and the current-voltage plot obeys Ohm's law. The shape of the capillary pressure isotherm determines the nonohmic corrections. A comparison of the results of this study to those of the pertinent diffusion-type models reveals qualitatively different features, the convection model is found to be closer to experimental observations.
Keywords:FUEL-CELLS;PERFLUOROSULFONIC MEMBRANES;MODEL;TEMPERATURE;TRANSPORT;DIFFUSION;KINETICS;NAFION