Electrochemical separation of uranium in the molten system LiF–NaF–KF–UF4

Abstract This article is focused on the electrochemical investigation (cyclic voltammetry and related studies) of possible reduction of U 4+ ions to metal uranium in the molten system LiF–NaF–KF(eut.)–UF 4 that can provide basis for the electrochemical extraction of uranium from molten salts. Two-step reduction mechanism for U 4+ ions involving one electron exchange in soluble/soluble U 4+ /U 3+ system and three electrons exchange in the second step were found on the nickel working electrode. Both steps were found to be reversible and diffusion controlled. Based on cyclic voltammetry, the diffusion coefficients of uranium ions at 530 °C were found to be D (U 4+ ) = 1.64 × 10 −5  cm 2  s −1 and D (U 3+ ) 1.76 × 10 −5  cm 2  s −1 . Usage of the nickel spiral electrode for electrorefining of uranium showed fairly good feasibility of its extraction. However some oxidant present during the process of electrorefining caused that the solid deposits contained different uranium species such as UF 3 , UO 2 and K 3 UO 2 F 5 .