Effect of Sulfonation Level on the Percolated Morphology and Proton Conductivity of Hydrated Fluorine-Free...

Using all-atom molecular dynamics simulations and a variety of experimental methods, we previously reported on a linear polyethylene with pendant phenyl sulfonated groups precisely on every fifth carbon along the backbone. With increasing relative humidity this fluorine-free polymer self-assembled to form nanoscale water channels and exhibited exceptional proton conductivity. Expanding upon those findings, here we explore partially sulfonated random copolymers, referred to as p5PhSH-Y. Using either acetyl sulfate or sulfuric acid, a wide range of sulfonation levels were prepared (Y = 34-98%) corresponding to ion-exchange capacities (IEC) of 2.0-4.4 mmol/g. Combining experimental techniques and all-atom molecular dynamics simulations, we study the effect of Y on water uptake, nanoscale morphology, and the proton/water transport properties of p5PhSH-Y. The proton conductivity of p5PhSH-Y increases with relative humidity and with Y and achieves values in excess of 0.1 S/cm. These high conductivities are attributed to high IEC and well-developed nanoscale percolated hydrophilic domains made possible by the flexible backbone. We quantitatively describe the nature of the water channels using the characteristic distance, channel width distribution, the area per sulfonate group at the hydrophilic/hydrophobic interface, and the fractal dimension. Notably, the channel widths and the areas per sulfonate group are nominally independent of the level of sulfonation, while depending significantly on the level of hydration. The fractal dimension of the water channels correlates strongly with the water diffusion coefficients calculated from the molecular dynamics (MD) simulations. These findings demonstrate that the p5PhSH-Y hydrocarbon copolymers can be modified to tune properties, particularly proton conductivity.