Physical State and Mass Transport of Metals in Liquid Cadmium Cathodes: A Review

Liquid metal cathodes, particularly liquid cadmium (Cd), are widely used in molten salt electrorefining and pyrochemical reprocessing of spent nuclear fuel due to their high electrical conductivity, strong affinity for actinides, and favorable alloying characteristics. During electrorefining, reduced metal species enter the liquid Cd phase and may exist as dissolved atoms, liquid alloys, or intermetallic compounds, all of which significantly influence deposition behavior, separation selectivity, and cathode performance. Although numerous experimental and theoretical studies have investigated metal solubility, alloy formation, and diffusion in liquid Cd systems, the current understanding remains fragmented. Thermodynamic phase behavior and mass transport kinetics are often discussed separately, and reported diffusion data show considerable discrepancies owing to variations in experimental techniques and interpretations. In addition, the relationship between phase stability, diffusion mechanisms, and electrochemical conditions in practical electrorefining environments has not yet been systematically clarified. This review aims to present an integrated thermodynamic–kinetic perspective on the behavior of metals in liquid Cd cathodes. Recent progress in dissolution behavior, alloy phase formation, and diffusion-controlled transport processes is critically summarized. The differences in solubility and precipitation behavior of actinides, rare-earth elements, and selected transition metals are analyzed in relation to binary phase diagrams and thermodynamic stability. Furthermore, experimental methods for determining diffusion coefficients, including capillary techniques and electrochemical approaches, are comparatively evaluated. By correlating thermodynamic phase stability with diffusion-driven mass transport, this work provides a coherent framework for understanding metal behavior in liquid Cd cathodes and offers insights for optimizing molten salt electrorefining and advanced nuclear fuel cycle technologies.