Morphology and Dynamics in Hydroxide-Conducting Polysulfones

In alkaline zinc-manganese dioxide batteries, there is a need for selective polymeric separators that have good hydroxide ion conductivity but that prevent the transport of zincate (Zn(OH)(4))(2-). Here we investigate the nanoscale structure and hydroxide transport in two cationic polysulfones that are promising for these separators. We present the synthesis and characterization for a tetraethylammonium-functionalized polysulfone (TEA-PSU) and compare it to our previous work on an N-butylimidazolium-functionalized polysulfone (NBI-PSU). We perform atomistic molecular dynamics (MD) simulations of both polymers at experimentally relevant water contents. The MD simulations show that both polymers develop well phase separated nanoscale water domains that percolate through the polymer. Calculation of the total scattering intensity from the MD simulations reveal weak or nonexistent ionomer peaks at low wave vectors. The lack of an ionomer peak is due to a loss of contrast in the scattering. The small water domains in both polymers, with median diameters on the order of 0.5-0.7 nm, lead to hydroxide and water diffusion constants that are 1-2 orders of magnitude smaller than their values in bulk water. This confinement lowers the conductivity but also may explain the strong exclusion of zincate from the PSU membranes seen experimentally.

Automated summary

This study compares two cationic polysulfones for their potential application in alkaline zinc-manganese dioxide batteries. Atomistic molecular dynamics simulations reveal well phase separated nanoscale water domains in both polymers, leading to a reduction in hydroxide and water diffusion constants compared to bulk water, explaining the strong exclusion of zincate from the polysulfone membranes observed experimentally.