Electrochemical Properties of Uranyl Ion in Ionic Liquids as Media for Pyrochemical Reprocessing

We have proposed a new reprocessing process by using ionic liquids (ILs) instead of molten salts of alkali chlorides in pyrochemical process. In the proposed process, spent nuclear fuels are dissolved in ILs by using Cl2 as an oxidant, and UO2 2+ and PuO2 2+ ions in ILs are recovered as UO2 and PuO2 by electrochemical reduction. In order to examine applicability of ILs as media for reprocessing, we have studied electrochemical behavior of UO2 2+ in 1-butyl-3-methylimidazolium chloride (BMICl), 1-butyl-3-methylimidazolium tetrafluoroborate (BMIBF4), and 1-butyl-3-methylimidazolium nonafluorobutanesulfonate (BMINfO). Electrochemical properties of uranyl chloride dissolved into ILs were examined by cyclic voltammetry. In BMICl, an almost reversible redox couple was observed, and the formal potential and the diffusion coefficient were evaluated as _0:758V vs. Ag/AgCl and 4:8 × 10−8 cm2s−1, respectively. On the other hand, the electrochemical reactions of UO2 2+ in BMIBF4 and BMINfO were irreversible. In BMINfO, some reduction peaks and one sharp oxidation peak were observed in the range of −0:6∼–0:2V and around 0.85V vs. Ag/AgCl, respectively. The reduction and oxidation peaks were assigned to multi step reduction of UO2 2+ to U(IV) via U(V) and/or direct reduction of UO2 2+ to U(IV), and the oxidative dissolution of the resulting U(IV) compounds, respectively. The electrochemical reduction of UO2 2+ in BMINfO at −1:0V vs. Ag/AgCl produced the deposits on a carbon electrode as a cathode. Analyses of the deposits with the scanning electron microscope and the energy dispersive X-ray spectrometer indicated that the deposits are compounds containing uranium, oxygen, and chlorine. As a result, it is expected that the UO2 2+ in IL can be recovered electrolytically as uranium compounds such as UO2 and uranium oxychlorides.