On the electrochemical formation of Pu–Al alloys in molten LiCl–KCl

Properties of Pu–Al alloys were investigated in connection with development of pyrochemical methods for reprocessing of spent nuclear fuel. Electroseparation techniques in molten LiCl–KCl are being developed in ITU to group-selectively recover actinides from the mixture with fission products. In the process, actinides are electrochemically reduced on solid aluminium cathodes, forming solid actinide–aluminium alloys. This article is focused on electro-chemical characterisation of Pu–Al alloys in molten LiCl–KCl, on electrodeposition of Pu on solid Al electrodes and on determination of chemical composition and structure of the formed alloys. Cyclic voltammetry and chronopotentiometry were used to study Pu–Al alloys in the temperature range 400–550 °C. Pu is reduced to metal in one reduction step Pu3+/Pu0 on an inert W electrode. On a reactive Al electrode, the reduction of Pu3+ to Pu0 occurs at a more positive potential due to formation of Pu–Al alloys. The open circuit potential technique was used to identify the alloys formed. Stable deposits were obtained by potentiostatic electrolyses of LiCl–KCl–PuCl3 melts on Al plates. XRD and SEM–EDX analyses were used to characterise the alloys, which were composed mainly of PuAl4 with some PuAl3. In addition, the preparation of PuCl3 containing salt by carbochlorination of PuO2 is described.