Solvation Effects on the Dielectric Constant of 1 M LiPF6 in Ethylene Carbonate: Ethyl Methyl Carbonate 3:7

Abstract

We report the dielectric constant of 1 M LiPF₆ in EC:EMC 3:7 w/w (ethylene carbonate/ethyl methyl carbonate) in addition to neat EC:EMC 3:7 w/w. Using three Debye relaxations, the static permittivity value, or dielectric constant, is extrapolated to 18.5, which is compared to 18.7 for the neat solvent mixture. The EC solvent is found to strongly coordinate with the Li⁺ cations of the salt, which results in a loss of dielectric contribution to the electrolyte. However, the small amplitude and large uncertainty in relaxation frequency for EMC cloud definitive identification of the Li⁺ solvation shell. Importantly, the loss of the free EC permittivity contribution due to Li⁺ solvation is almost completely balanced by the positive contribution of the associated LiPF₆ salt, demonstrating that a significant quantity of dipolar ion pairs exists in 1 M LiPF₆ in EC:EMC 3:7.

Keywords

batteries / dielectric relaxation spectroscopy / electrolytes

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