Electrodeposition and electrochemical behaviour of molybdenum ions in ZnCl2-NaCl-KCl molten salt

In this paper, a method for extracting and refining metallic molybdenum using low-temperature ZnCl2-NaCl-KCl molten salt was proposed. The electrochemical behaviour of molybdenum ions in ZnCl2-NaCl-KCl molten salt was investigated in detail, and pure metallic molybdenum was collected on the cathode. The reduction and diffusion processes of Mo(V) ions in ZnCl2-NaCl-KCl molten salt were determined through a series of electrochemical methods. The diffusion coefficients and nucleation modes of Mo(V) ions were also studied, and electrolysis was conducted for a prolonged period at a constant current density. The results indicated that the electrode reduction of Mo(V) ions in ZnCl2-NaCl-KCl molten salt proceeds through a three-step reaction: Mo(V) → Mo(IV) → Mo(III) → Mo at 250°C. The Mo(V) → Mo(IV) reaction was reversible and diffusion-controlled, with a Mo(V) diffusion coefficient of 6.02 × 10-6 cm2 s-1. Additionally, the nucleation mode of Mo(V) ions was instantaneous nucleation. The products electro-deposited were confirmed of metallic molybdenum with a particle size of less than 1 μm.