Molecular Dynamics Study on Proton Transport in Supported Nafion Ionomer Thin Films on Lennard-Jones Walls
Authors: Aochi Joji , Mabuchi Takuya , Tokumasu Takashi 
Published: February 2020

The catalyst layer, one of the components of membrane electrode assembly in polymer electrolyte fuel cells, was modeled by molecular dynamics methods, and proton transport in ionomer thin films was simulated to elucidate the effect of surface wetting interaction on the ionomer thin film morphology and proton transport property. Ionomer thin film properties are considered to be affected by the surface property of supported carbon due to their nano-scale thickness (4-10 nm thick). One of the surface properties is surface wetting interaction basically attributed to the physical or chemical property of surfaces.
In this study, modeled Nafion thin films with 4 nm and 10 nm thick were generated on the two ideal LJ smooth surfaces which have different strength of interactions to focus on the effect of the surface wetting interaction on the ionomer thin film morphology and proton transport. Protons exist as hydronium ions in ionomer thin films for chemical stability and are transported by the two transport mechanisms which are the vehicle mechanism (just move as hydronium ions) and the Grotthuss mechanism called proton hopping. It is common that proton transport model is restricted to only the vehicle mechanism when using classical molecular dynamics method, however, our proton transport model includes the Grotthuss mechanism by using aTS-EVB method (anharmonic two-state empirical valence bond method) in order to make proton transport model more reproducible.
From the analysis in the ionomer thin films with 4 nm thick, surface wetting interaction was found to affect the orientation of sulfonic group near the surface. The orientation is well-ordered on the higher hydrophobic surface, and the sulfonic groups point to the gas phase direction, while it is randomly distributed on the lower hydrophobic surface, which make differences in the water cluster connectivity and size in ionomer thin films between the two surfaces. Proton transport property was evaluated by the self-diffusion coefficient. The proton self-diffusion coefficient in ionomer thin films was indicated to be improved on higher hydrophobic surface probably because higher hydrophobic surface makes ideal water cluster structures for proton transport in ionomer thin films.
As compared to the ionomers with the different film thickness, the proton self-diffusion coefficient in ionomer thin films on higher hydrophobic surface was indicated to decrease in the increase of the film thickness, while that on lower hydrophobic surface was indicated to increase slightly. This result is expected to come from the confinement and interface effects which can be remarkable when the thickness decrease. The ionomer morphology on higher hydrophobic surface has advantages for proton transport probably thanks to the effects as observed in the ionomer with 4 nm thick, while that on lower hydrophobic surfaces has disadvantage. Since the effects can be weaker with the increase in the film thickness, the proton self-diffusion coefficient in ionomer thin films on higher hydrophobic surface was found to decrease with the increase in the film thickness, while that on lower hydrophobic surface was found to increase slightly.