Electrochemical measurement and analysis of YCl₃, ScCl₃, GdCl₃ and MgCl₂ in molten eutectic LiCl-KCl

Electrochemical measurements of YCl₃, ScCl₃, GdCl₃ and MgCl₂ were obtained in molten LiCl-KCl eutectic at 773 K using a three-electrode configuration. Tungsten rods were used as the working and counter electrodes. Two quasi- and one reference electrode(s) (glassy carbon, nickel wire, and Ni/NiO) were used to collect electrochemical measurements of the analyte salts. Cyclic voltammetry data were analyzed to calculate values of diffusion coefficient, exchange current density, and charge transfer resistance and were determined to be on the order of 10⁻⁵ cm² s⁻¹, 10⁻² A cm⁻², and 10⁰ Ω; respectively. In general, the values of diffusion coefficients were found to be consistent with those reported of high-temperature molten salts. Relatively large values of exchange current density corresponded with smaller values of charge transfer resistance. These values were found to be reasonable in comparison to results available in the literature. The measured cyclic voltammograms were normalized with respect to both lithium reduction and chloride ion oxidation potentials. Such a normalization technique is effective for comparing experimentally obtained cyclic voltammetry data to those that have been published. An analysis of experimentally obtained results indicates the relation of electrode reactions (e.g., differences of reduction potentials) are independent of the choice of reference electrode. Additionally, the choice of reference electrode did not affect the electrochemical window, exchange current density, or diffusion coefficient values.