Correlation between structure and conductivity of stretched Nafion

TL;DR

This study uses coarse-grained simulations to explore how uniaxial stretching of Nafion membranes influences their internal structure and proton conductivity, revealing enhanced conductivity along the stretch direction and altered water distribution.

Contribution

It provides new insights into the relationship between mechanical stretching, morphological changes, and proton conductivity in Nafion membranes through simulation.

Findings

Conductivity is enhanced along the stretching direction.

Perfluorinated side chains orient perpendicular to stretch.

Water forms a network with narrow bridges at low water content.

Abstract

We have used coarse-grained simulation methods to investigate the effect of stretching-induced structure orientation on the proton conductivity of Nafion-like polyelectrolyte membranes. Recent experimental data on the morphology of ionomers describe Nafion as an aggregation of polymeric backbone chains forming elongated objects embedded in a continuous ionic medium. Uniaxial stretching of a recast Nafion film causes a preferential orientation of these objects in the direction of stretching. Our simulations of humid Nafion show that this has a strong effect on the proton conductivity, which is enhanced along the stretching direction, while the conductivity perpendicular to the stretched polymer backbone is reduced. Stretching also causes the perfluorinated side chains to orient perpendicular to the stretching axis. This in turn affects the distribution of water at low water contents. The water forms a continuous network with narrow bridges between small water clusters absorbed in head-group multiplets.