Correlation of Oscillation of Polymer Electrolyte Membrane Fuel Cells at Low Cathode Humidification with Nanoscale Membrane Properties

Kurzfassung

Oscillatory fluctuations of a single proton exchange membrane fuel cell appear upon operation with a dry cathode air supply and a fully humidified anode stream. Periodic transitions between a low and a high current operation point of the oscillating state were observed. The transition time of 20-25 s for the change from the low to the high operation is fast and does not depend on the operating parameters, while the downward transition depends strongly on the operating conditions. An insight into the transitions is obtained by current density distributions at distinct times indicating a propagating active area with defined boundaries. The observations are in agreement with assuming a liquid water reservoir at the anode with a downward transition period depending on the operation conditions. The high current operation possesses a high electro-osmotic drag and a high permeation rate (corresponding to liquid-vapor permeation) leading to a large water flux to the cathode. Subsequently, the liquid reservoir at the anode is consumed leading to an anode drying. The system establishes a new quasi-stable operation point associated with a low current, low electro-osmotic drag coefficient, and a low water permeation (corresponding to vapor-vapor permeation). When liquid water is formed at the anode interface after some time the fast transition to the high current operation occurs due also to a flooding effect leading to blockage of channels. Similar behavior is observed by conductive atomic force microscopy current images of the membrane showing a strong dependence of the ionic conductivity on the activation procedures with current flow and the need for liquid water. Oscillatory behavior has been found after the membrane is activated. The activation process could be followed by applying a voltage pulse. Specifically, activation with liquid water yields a high conductivity with currents larger by three orders of magnitude.