Effect of chemical substituents attached to the zwitterion cation on dielectric constant.

Abstract

Materials with high dielectric constant, εs, are desirable in a wide range of applications including energy storage and actuators. Recently, zwitterionic liquids have been reported to have the largest εs of any liquid and, thus, have the potential to replace inorganic fillers to modulate the material εs. Although the large εs for zwitterionic liquids is attributed to their large molecular dipole, the role of chemical substituents attached to the zwitterion cation on εs is not fully understood, which is necessary to enhance the performance of soft energy materials. Here, we report the impact of zwitterionic liquid cation chemical substituents on εs (50 < εs < 300 at room temperature). Dielectric relaxation spectroscopy reveals that molecular reorientation is the main contributor to the high εs. The low Kirkwood factor g calculated for zwitterionic liquids (e.g., 0.1-0.2) suggests the tendency for the antiparallel zwitterion dipole alignment expected from the strong electrostatic intermolecular interactions. With octyl cation substituents, the g is decreased due to the formation of hydrophobic-rich domains that restrict molecular reorientation under applied electric fields. In contrast, when zwitterion cations are functionalized with ethylene oxide (EO) segments, g increases due to the EO segments interacting with the cations, allowing more zwitterion rotation in response to the applied field. The reported results suggest that high εs zwitterionic liquids require a large molecular dipole, compositionally homogeneous liquids (e.g., no aggregation), a maximized zwitterion number density, and a high g, which is achievable by incorporating polar chemical substituents onto the zwitterion cations.