Comparing selected morphological models of hydrated Nafion using large scale molecular dynamics simulations

Experimental elucidation of the nanoscale structure of hydrated Nafion, the most popular polymer electrolyte or proton exchange membrane (PEM) to date, and its influence on macroscopic proton conductance is particularly challenging. While it is generally agreed that hydrated Nafion is organized into distinct hydrophilic domains or clusters within a hydrophobic matrix, the geometry and length scale of these domains continues to be debated. For example, at least half a dozen different domain shapes, ranging from spheres to cylinders, have been proposed based on experimental SAXS and SANS studies. Since the characteristic length scale of these domains is believed to be ∼2 to 5 nm, very large molecular dynamics (MD) simulations are needed to accurately probe the structure and morphology of these domains, especially their connectivity and percolation phenomena at varying water content.;Using classical, all-atom MD with explicit hydronium ions, simulations have been performed to study the first-ever hydrated Nafion systems that are large enough (~2 million atoms in a ∼30 nm cell) to directly observe several hydrophilic domains at the molecular level. These systems consisted of six of the most significant and relevant morphological models of Nafion to-date: (1) the cluster-channel model of Gierke, (2) the parallel cylinder model of Schmidt-Rohr, (3) the local-order model of Dreyfus, (4) the lamellar model of Litt, (5) the rod network model of Kreuer, and (6) a 'random' model, commonly used in previous simulations, that does not directly assume any particular geometry, distribution, or morphology.;These simulations revealed fast intercluster bridge formation and network percolation in all of the models. Sulfonates were found inside these bridges and played a significant role in percolation. Sulfonates also strongly aggregated around and inside clusters. Cluster surfaces were analyzed to study the hydrophilic-hydrophobic interface. Interfacial area and cluster volume significantly increased during the simulations, suggesting the need for morphological model refinement and improvement. Radial distribution functions and structure factors were calculated. All nonrandom models exhibited the characteristic experimental scattering peak, underscoring the insensitivity of this measurement to hydrophilic domain structure and highlighting the need for future work to clearly distinguish morphological models of Nafion.