Diffusion Coefficients of the Rare Earth Elements in Fused LiCl-KCl Eutectic – A Literature Review

"Interest in the efficient production and recycling of rare earth elements has increased in recent years along with the prices of these elements. The molten LiCl-KCl eutectic is one ionic solvent which can be utilized for these purposes. The LiCl-KCl eutectic has also been selected as the electrolyte for focused research for advanced pyrochemical recycling processes for used nuclear fuel in several nations. Rare earth elements are fission products with notable neutron absorption characteristics, and thorough understanding of the properties and behavior of these elements is critical to their successful partition from the electrochemically-similar actinide elements. The number of research papers investigating individual rare earth elements has greatly expanded in the approximately 35 years since the last review. These research papers are presented in a variety of languages and technical formats, making data difficult to compare, and are sometimes contradictory. A review and summary of diffusion properties of rare earths in LiCl-KCl eutectic was performed, and the data translated to a common format for evaluation. INTRODUCTIONThe rare earth elements have experienced growing importance in recent decades due to their application in high technology, including optical lenses, lasers, high-temperature superconductors, improved alloys, high energy-density batteries, and powerful magnets for compact electronic devices. Their historic production methods and uses are detailed in several texts (Hampel 1971; Bautista &Jackson 1992; Gupta & Krishnamurthy 2005). A s the p rice o f these e lements has r isen in r ecent years, so has interest in their efficient production and possible recycling options. Rare earth oxides are concentrated through hydrometallurgical techniques, but the high thermochemical stability of their oxides precludes production of rare earth metals in aqueous systems. However, the wide electrochemical window and better control of pO2- in fused salt systems allows the production of these reactive metals from their halides or oxides. The high ionic conductivity and diffusivity of the molten ionic electrolyte allow high currents with limited resistive losses (Fray 1980). Electrolytic methods in fused salts are commonly adopted for the production of bulk rare earths in a variety of molten salt systems. Fluorides are sometimes proposed for oxide electrowinning processes due to ability to dissolve the rare earth oxide, reduced hygroscopic behavior, and the wider electrochemical separation between O2 and halide gas evolution (Mohan Das, Damodaran et al. 1988; Gibilaro, Pivato et al. 2011). However, in most electrolytic production processes, such as that for mischmetal, the rare earth oxides are converted to chloride prior to electrolysis in a chloride bath (Gschneidner Jr. & Eyring 1978; Sharma 1987). Of the chlorides, the LiCl-KCl eutectic is one specific medium in which metal production and production-related investigations have been conducted (Gschneidner J r. & Eyring 1978; Driscoll & Fray 1993). L iCl-KCl eutectic has the advantages o f h igh conductivity, but relatively low viscosity and operating temperature. The low operating temperature allows simpler design, with reduced energy consumption, salt volatility and cell corrosion."