Electrochemical studies on the redox behavior of zirconium in the LiF-NaF eutectic melt

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. - Highlights: •The redox mechanism of zirconium in a fluoride salt system was investigated. •A multi-step redox process of Zr was found with various electrochemical methods. •Perspectives on zirconium electro-refining process were proposed.