Electrochemical characterisation of CaCl2 deficient LiCl–KCl–CaCl2 eutectic melt and electro-deoxidation of solid UO2

Abstract

The CaCl2 deficient ternary eutectic melt LiCl–KCl–CaCl2 (50.5: 44.2: 5.3 mol %) was electrochemically characterised by cyclic voltammetry and polarization techniques in the context of its probable use as the electrolyte in the electrochemical reduction of solid UO2 to uranium metal. Tungsten (cathodic polarization) and graphite (anodic polarization) working electrodes were used in these studies carried out in the temperature range 623 K–923 K. The cathodic limit of the melt was observed to be set by the deposition of Ca2+ ions followed by Li+ ions on the tungsten electrode and the anodic limit by oxidation of chloride ions on the graphite electrode (chlorine evolution). The difference between the onset potential of deposition of Ca2+ and Li+ was found to be 0.241 V at a scan rate of 20 mV/s at 623 K and the difference decreased with increase in temperature and vanished at 923 K. Polarization measurements with stainless steel (SS) cathode and graphite anode at 673 K showed the possibility of low–energy reactions occurring on the UO2 electrode in the melt. UO2 pellets were cathodically polarized at 3.9 V for 25 h to test the feasibility of electro-reduction to uranium in the melt. The surface of the pellets was found reduced to U metal.