Hydrogen pumping effect induced by fuel starvation in a single cell of a PEM fuel cell stack at galvanostatic operation

In a proton exchange membrane fuel cell stack, a single cell is potentially subjected to voltage reversal under fuel starvation conditions, which is extremely harmful to its durability. In this work, we develop a two-dimensional computational model to investigate the current and potential distributions in a single cell under these voltage reversal conditions. It is found that most of hydrogen under these conditions is oxidized in a narrow region close to the fuel-inlet, and the anode area before hydrogen depletion can be characterized into an activation limited region and a mass-transport limited region. Meanwhile, an unexpected hydrogen evolution phenomenon is discovered in the cathode catalyst layer (CCL) adjacent to the fuel inlet, owing to the imbalance between the localized ultrahigh hydrogen oxidation current density in the anode and the lower limiting current density of oxygen reduction reaction in the adjacent CCL. Furthermore, the evolved hydrogen gas is also found to be oxidized nearby due to the steep variation of electrolyte potential in the CCL, indicating the coexistence of hydrogen evolution, hydrogen oxidation and oxygen reduction within the micron-scale thickness of CCL, which significantly adds to the complexity of the coupled phenomena in the voltage-reversal single cell.

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► Fuel starvation leads to H2 evolution in part of the cathode of a PEMFC in stack.
► Localized ultrahigh current density near the inlet is the inducement of H2 evolution.
► The evolved H2 will be re-oxidized in the cathode electrode.
► HER, HOR and ORR coexist across the thickness of the cathode electrode.