The dependence of the electrochemical properties of perfluorosulfonic acid membrane/water systems on repeat unit structure

Abstract

We developed a molecular thermodynamic framework to describe the dependence of the electrochemical properties of a perfluorosulfonic acid (PFSA) membrane/water system on the polymer structure. To better understand the behavior of the polymer membrane/water system, we developed a lattice model based on lattice cluster theory. We performed hypothetical calculations for a variety of repeat unit structures. We also investigated the correlation between the interaction energy and extending or reducing the chain length of the polymer repeat unit using COMPASS force fields. Our results indicate that the ionic conductivity of the nonpolar CF2CF2 group in the main chain varies with the length of the chain. In addition, the ionic conductivity of different CF2CF2 group chain lengths fluctuates according to hydration level. When OCF2CF3CF groups are substituted at 0 and 1, the predictions of the PFSA membrane agreed well with the experimental data from a Dow membrane. To obtain good ionic conductivity at a high vapor equilibrated hydration level, the nonpolar group in the polymer repeat unit and the substituted group chain connecting the nonpolar group length should both be short, and the substituted group chain connected with the sulfonic group should be long.