Mesoscale modeling of hydrated morphologies of 3M perfluorosulfonic acid-based fuel cell electrolytes.

Dissipative particle dynamics (DPD) simulations have been carried out to study the hydrated morphology of 3M perfluorosulfonic acid (PFSA) fuel cell membranes as a function of the equivalent weight (EW), molecular weight (MW), and hydration level. The 3M PFSA ionomers were modeled using typical EWs of 578, 640, and 790 g/mol, and molecular weights were varied from about 45,000 to 90,000 g/mol in order to be close to the experimental range. The morphology changes corresponding to the EW, MW, and hydration level were comparatively investigated by inspecting the water distributions, followed by quantitative analysis by radial distribution functions and Bragg spacing according to the periodicity of water domains. Compared to the morphologies of short-side-chain PFSA membrane (Wu, D.; Paddison, S. J.; Elliott, J. A. Macromolecules 2009, 42, 3358-3367), the longer side chain in 3M PFSA membrane provides more flexibility for the sulfonate-terminated side chains and generally results in the stronger aggregation of water clusters. This results in lower water uptake for higher EW, corresponding to a lower ion-exchange capacity (IEC), which is attributed experimentally to a higher crystallinity of the fluorocarbon phase, although our simulations were not able to observe the crystallites directly.