A model for zwitterionic polymers and their capacitance applications.

Abstract

Zwitterions have been shown experimentally to enhance the dielectric constant of ionic media, owing to their large molecular dipole. Many studies since explored the enhancement of ionic conductivity with zwitterion additives as well as bulk behavior of zwitterions. Here, we examine the capacitance behavior of zwitterions between charged parallel plates using a mean-field theory. Employing only chain connectivity of a cation and anion with neutral monomers in between with mean-field electrostatics, we show that our model captures the high-dielectric behavior of zwitterions. We also predict an optimum in the capacitance of zwitterionic media as a function of chain length. To address the issue of zwitterion screening near charged surfaces, we demonstrate that zwitterions simultaneously partially screen charged walls and act as a pure dielectric that propagates the electric field far from the surface. Moreover, we show that salt solutions with zwitterionic additives outperform the energy density of both salt-only and zwitterion-only capacitors. We find that salt-only capacitors perform better at low applied potential, whereas salt capacitors with zwitterionic additives perform better at high applied potential.