The Interplay between Salt Association and the Dielectric Properties of Low Permittivity Electrolytes: The Case of LiPF 6 and LiAsF 6 in Dimethyl Carbonate

Publication Type

Journal Article

Date Published

02/2018

Abstract

In this article, we present evidence that the dielectric constant of an electrolyte solution can be effectively used to infer the association regime of the salt species from computational methods. As case studies, we consider the low dielectric constant solvent dimethyl carbonate with LiAsF6 and LiPF6 salts at low concentrations. Using both quantum “ab initio” methods as well classical molecular dynamics simulations, we elucidate the salt’s contribution to the dielectric constant as well as the dipolar relaxation times, which act as quantitative signatures. By comparing to previously published measurements, we provide strong evidence for the presence of contact-ion pairs at these low concentrations. Interestingly, these ion pairs increase the dielectric constant of the solution, allowing for significantly improved ionic conductivity as a function of salt concentrations. We also discuss the role of multimeric equilibrium species as contributors to the functional properties of designer electrolytes, such as dielectric properties of the solution and ionic conductivity.

Journal

The Journal of Physical Chemistry C

Volume

122

Year of Publication

2018

Issue

4

Pagination

1990 - 1994

ISSN

1932-7447

Short Title

J. Phys. Chem. C

Refereed Designation

Refereed