Physical degradation of membrane electrode assemblies undergoing freeze/thaw cycling: Diffusion media effects

Abstract

In this work, the effects of properties of diffusion media (DM) (stiffness, thickness and micro-porous layer (MPL)) on the physical damage of membrane electrode assembly (MEA) subjected to freeze/thaw cycling were studied. Pressure uniformity of the diffusion media onto the catalyst layer (CL) was determined to be a key parameter to mitigate freeze-induced physical damage. Stiffer diffusion media, enabling more uniform compression under the channels and lands, can mitigate surface cracks, but flexible cloth diffusion media experienced severe catalyst layer surface damage. The thickness of the diffusion media and existence of a micro-porous layer were not observed to be major factors to mitigate freeze-damage when the catalyst layer is in contact with liquid. Interfacial delamination between diffusion media and catalyst layers, but not between the catalyst layer and membrane, was observed. This permanent deformation of the stiff diffusion media in the channel locations as well as fractures of carbon fibers increased electrical resistance, and may increase water flooding, resulting in reduced longevity and operational losses. Although use of a freeze-tolerable MEA design (negligible virgin cracked catalyst layers with thinner reinforced membrane) [S. Kim, M.M. Mench, J. Power Sources, in press] with stiff diffusion media can reduce the freeze-damage in the worst case scenario test condition of direct liquid contact, extensive irreversible damage (diffusion media/catalyst layer interfacial delamination) was not completely prevented. In addition to proper material selection, liquid water contact with the catalyst layer should be removed prior to shutdown to a frozen state to permit long-term cycling damage and facilitate frozen start.