In the present paper, a detailed study of the redox behavior of zirconium in the eutectic LiF-NaF system was carried out on an inert molybdenum electrode at 750 °C. Several transient electrochemical methods were used such as cyclic voltammetry, square wave voltammetry, chronopotentiometry, and open circuit voltammetry. The reduction of Zr (IV) was found to follow a two-step mechanism of Zr (IV)/Zr (II) and Zr (II)/Zr at the potentials of about −1.10 and −1.50 V versus Pt, respectively. The theoretical evaluations of the number of transferred electrons according to both cyclic voltammetry and square wave voltammetry further confirmed the Zr reduction mechanism. The estimations of Zr (IV) diffusion coefficient in the LiF-NaF eutectic melt at 750 °C through cyclic voltammetry and chronopotentiometry are in fair agreement, as to be approximately 1.13E-5 and 2.42E-5 cm²/s, respectively.

In this paper, a detailed study of the electrochemical behavior of zirconium in the molten LiF-KF-ZrF₄ system on an inert molybdenum electrode was carried out at 600 °C. Several electrochemical techniques were employed such as cyclic voltammetry, chronoamperometry and square wave voltammetry. The reduction of zirconium was found to be a multi-step process that at the potentials of 1.15, 1.50 and 1.62 V versus Pt, the corresponding cathodic reactions of Zr⁴⁺/Zr²⁺, Zr²⁺/Zr⁺ and Zr⁺/Zr occurred. The result was further confirmed by the theoretical calculation of the number of transferred electrons according to the cyclic voltammetry and square wave voltammetry analysis. Moreover, based on the cyclic voltammograms, the diffusion coefficient of Zr⁴⁺ ions in the eutectic LiF-KF containing 1 wt% ZrF₄ at 600 °C was estimated to be about 8.31 × 10^-6 cm² s^-1. The present electrochemical study on zirconium in the molten fluoride system will be a theoretical reference for future zirconium electrorefining from Zr alloy or scraps.