A Computer Simulation Study of the Mesoscopic Structure of the Polyelectrolyte Membrane Nafion

Abstract

We studied the mesoscopic structure of the perfluorinated sulfonic acid membrane Nafion containing water using a dissipative particle dynamics (DPD) simulation. A Nafion polymer is modeled by connecting coarse-grained particles, which correspond to the hydrophobic backbone of polytetrafluoroethylene and perfluorinated side chains terminated by hydrophilic end particles of sulfonic acid groups. Water is also modeled by the same size particle as adopted in the Nafion model, corresponding to a group of four H2O molecules. The Flory–Huggins χ-parameters between DPD particles are estimated from the mixing energy calculation using an atomistic simulation. In the DPD simulation, water particles and hydrophilic particles of Nafion side chains spontaneously form aggregates and are embedded in the hydrophobic phase of the Nafion backbone. This structure is a bicontinuous phase of Nafion and water regions and has a continuous path in the cavity of water in any direction. Although this sponge-like structure is essentially identical to the cluster-network model proposed from the experimental studies, the shape of the water clusters is not spherical but irregular, and the water regions are indistinguishable structures of water clusters and their channels. The cluster size and its dependence on the water content are in good agreement with experimental reports; therefore, the simulated mesoscopic structure is confirmed to be a highly possible one.