The feasibility and advantages of room-temperature deep eutectic solvents (DESs) as alternative media for lithium isotope separation via electromigration are explored, addressing critical needs in nuclear energy applications. A systematic screening of hydrogen bond donors and acceptors was conducted to elucidate the compositional effects on separation performance. Combined spectroscopic characterizations, quantum chemical calculations, and molecular dynamics simulations revealed that the hydroxyl-chloride hydrogen-bonding interactions play a pivotal role in modulating the solvation structure of Li⁺, thereby governing the isotope discrimination efficiency. The effects of key process parameters-including temperature, voltage, lithium salt concentration, time, convection, and cascade operation-were systematically investigated, and their influence patterns on separation performance were clarified, further confirming the potential for scale-up and practical engineering deployment. DESs, featuring green chemistry attributes, low cost, and facile preparation, effectively circumvent the drawbacks of conventional high-temperature molten salts or expensive ionic liquids. This study provides a new, environmentally benign, and efficient electrochemical route for lithium isotope enrichment, and offers fundamental insights into solvent design for advanced separation technologies in molten salt and ionic liquid chemistry, with promising implications for nuclear fuel cycles and isotope processing.

Deep eutectic solvents,Lithium isotope separation,Electromigration