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

Mei, Wenwen; Han, Aijie; Hickey, Robert J.; Colby, Ralph H.

doi:10.1063/5.0074100

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

Journal Article · 26 December 2021 · Journal of Chemical Physics

DOI: https://doi.org/10.1063/5.0074100 · OSTI ID:1982368

^[1]; Han, Aijie ^[1];

^[2];

^[2]

Pennsylvania State Univ., University Park, PA (United States)
Pennsylvania State Univ., University Park, PA (United States). Materials Research Institute

Materials with high dielectric constant, ε_s, are desirable in a wide range of applications including energy storage and actuators. Recently, zwitterionic liquids have been reported to have the largest ε_s of any liquid and, thus, have the potential to replace inorganic fillers to modulate the material ε_s. Although the large ε_s for zwitterionic liquids is attributed to their large molecular dipole, the role of chemical substituents attached to the zwitterion cation on ε_s 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 ε_s (50 < ε_s < 300 at room temperature). Dielectric relaxation spectroscopy reveals that molecular reorientation is the main contributor to the high ε_s. 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 ε_s 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.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); National Science Foundation (NSF)

Grant/Contract Number:: SC0012704

OSTI ID:: 1982368

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 24 Vol. 155; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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