Degradation effects in polymer electrolyte membrane fuel cell stacks by sub-zero operation—An in situ and ex situ analysis

The effect of low temperatures down to −40 °C on the performance and component properties of a polymer electrolyte membrane (PEM) fuel cell stack was investigated. By analyzing the temperature-dependent high-frequency resistance, the mechanism of ice formation within the stack was investigated during freeze/thaw (F/T) cycling while the stack was not operating and during a cold start-up. A step-like change in conductivity at 0 °C indicates that the membranes are dehydrated at sub-zero temperatures due to a change in capillary pressure at the interface membrane/catalyst. Furthermore, it was found that the stack shows little degradation when it is dried out before cooling down. Freezing in a wet state and additional cold start-ups resulted in performance degradation which was mainly attributed to changes in wetting properties. Ex situ environmental scanning electron microscope (ESEM) investigations showed distinct damage and increasing porosity of the electrode in the wet frozen stack, which was most likely the reason for the change in wetting properties. Inductively coupled plasma (ICP) mass spectroscopy showed distinct concentrations of platinum in the exhaust gas of the dry cycled stack, but no additional platinum was found when the stack was cycled in a wet state. Additional ex situ F/T investigations of gas diffusion layers (GDLs) and membrane electrode assemblies (MEAs) within an ESEM confirmed the results, found by in situ investigations of the fuel cell stacks. Serious detachment of electrode material was found without the compressive force applied to an assembly.