  Morphology of polymer electrolytes membranes (PEM), e.g., Nafion, inside PEM
fuel cell catalyst layers has significant impact on the electrochemical
activity and transport phenomena that determine cell performance. In those
regions, Nafion can be found as an ultra-thin film, coating the catalyst and
the catalyst support surfaces. The impact of the hydrophilic/hydrophobic
character of these surfaces on the structural formation of the films has not
been sufficiently explored yet. Here, we report about Molecular Dynamics
simulation investigation of the substrate effects on the ionomer ultra-thin
film morphology at different hydration levels. We use a mean-field-like model
we introduced in previous publications for the interaction of the hydrated
Nafion ionomer with a substrate, characterized by a tunable degree of
hydrophilicity. We show that the affinity of the substrate with water plays a
crucial role in the molecular rearrangement of the ionomer film, resulting in
completely different morphologies. Detailed structural description in different
regions of the film shows evidences of strongly heterogeneous behavior. A
qualitative discussion of the implications of our observations on the PEMFC
catalyst layer performance is finally proposed.
