Fundamental Electrochemical Properties of Liquid Metals in LiCl-KCl for Separation of Alkali/Alkaline-Earths (Cs, Sr, and Ba)
- Pennsylvania State Univ., University Park, PA (United States)
- Virginia Commonwealth Univ., Richmond, VA (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States)
In electrorefiner, uranium is recovered from used nuclear fuel using an electrorefining process in which a metallic used nuclear fuel anode is oxidized into molten LiCl-KCl-UCl3 electrolyte and pure U is preferentially reduced onto an inert cathode. While electrorefiner systems facilitate the recycling of substantial amounts of uranium from used nuclear fuel, they also contribute to the production of nuclear waste due to the build-up of fission products such as 90Sr and 137Cs in the molten salt electrolyte as they are electrochemically more active than U. The accumulation of alkali/alkaline-earth elements (Ba, Sr, Cs) in the electrolyte presents a problem as Sr and Cs isotopes have high heat densities and produce large amounts of highly ionizing radiation; these hazards combined with difficulty in removing the highly stable alkali/alkaline-earth elements from the electrolyte necessitates frequent replacement and disposal of the electrolyte, which then increases the overall volume of nuclear waste. This research project focuses on evaluating the viability of using liquid metal electrodes for electrochemical separation of alkali/alkaline-earths from molten salts utilizing the strong atomic interactions between candidate liquid metals and alkali/alkaline-earths. The strength of chemical interactions was quantified by determining the thermodynamic properties (e.g., activity) in liquid metals of Bi, Sb, and Pb. Thermodynamic properties, including activities, partial molar entropies, and partial molar enthalpies, were determined using electromotive force measurements for the Sr-Bi, Sr-Sb, Sr-Pb, Ba-Bi, and Ba-Sb binary systems in order to elucidate the strength of interactions between the alkaline-earth elements and each liquid metal, and to develop a comprehensive understanding of their behavior. Activities as low as aSr = 10-13 at xSr = 0.04 at T = 888 K were measured as well as liquid state solubility as high as 40 mol% at 988 K in Sr-liquid metal systems; activities as low as aBa = 10-15 at xBa = 0.05 at T = 888 K with liquid state solubility as high as 30 mol% at 988 K in Ba-liquid metal systems. Experimental data was used as input data towards computational efforts involving first-principles calculations as well as the CALPHAD (CALculation of PHAse Diagram) technique in the case of the Sr-Sb and Ba-Bi systems to develop improved phase diagrams and provide further basis for the use of computational models in elucidating strongly interacting binary systems. Attempts to remove Sr and Ba from molten salt electrolyte using an electrochemical cell with liquid metal cathodes were successful, with post-mortem elemental analysis of the electrodes confirming significant quantities of Sr (6.5 mol%) and Ba (12.8 mol%) deposited into Bi. Furthermore, deposition results correlated well with the deposition behavior predicted from the aforementioned electromotive force measurements, inviting the possibility of using liquid metal electrodes for selectively removing alkali/alkaline-earth elements from molten LiCl-KCl electrolyte to recycle the process salt in electrorefiner.
- Research Organization:
- Pennsylvania State Univ., University Park, PA (United States)
- Sponsoring Organization:
- USDOE Office of Nuclear Energy (NE)
- DOE Contract Number:
- NE0008425
- OSTI ID:
- 1490212
- Report Number(s):
- 15-8251; 15-8126
- Country of Publication:
- United States
- Language:
- English
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