title: Ion transport with charge-protected and non-charge-protected cations in alcohol-based electrolytes using the compensated Arrhenius formalism. Part I: ionic conductivity and the static dielectric constant.
abstract: The temperature dependence of ionic conductivity and the static dielectric constant is examined for 0.30 m TbaTf- or LiTf-1-alcohol solutions. Above ambient temperature, the conductivity increases with temperature to a greater extent in electrolytes whose salt has a charge-protected cation. Below ambient temperature, the dielectric constant changes only slightly with temperature in electrolytes whose salt has a cation that is not charge-protected. The compensated Arrhenius formalism is used to describe the temperature-dependent conductivity in terms of the contributions from both the exponential prefactor σo and Boltzmann factor exp(-Ea/RT). This analysis explains why the conductivity decreases with increasing temperature above 65 °C for the LiTf-dodecanol electrolyte. At higher temperatures, the decrease in the exponential prefactor is greater than the increase in the Boltzmann factor.
authors.affiliation: Department of Chemistry and Biochemistry, University of Oklahoma , 101 Stephenson Parkway, Norman, Oklahoma 73019, United States.
authors.forename: Matt
authors.initials: M
authors.lastname: Petrowsky
authors.forename: Allison
authors.initials: A
authors.lastname: Fleshman
authors.forename: Roger
authors.initials: R
authors.lastname: Frech