Highly efficient lithium extraction from magnesium-rich brines with ionic liquid-based collaborative extractants: Thermodynamics and molecular insights

Selective extraction of Li+ from high Mg2+/Li+ ratio brines with ionic liquid (IL) based collaborative extractants was investigated by experiments, thermodynamic analyses, and quantum chemical (QC) calculations. Effects of different IL cationic structures and organophosphorus ligands on extraction performances were studied. The results demonstrated that the system 1-(2-hydroxyethyl)-3-methylimidazolium bis(trifluoromethylsulfonyl) imide + trioctyl phosphate ([HOEMIM][Tf2N] + TOP) was considered as the best extractant, with the very high extraction efficiency of Li+ (83.16 %) and separation selectivity of Li+/Mg2+ (742.11), which is higher than values reported in literature. The thermodynamic model ePC-SAFT was first extended to quantitatively predict the phase equilibria of the so-called "organic-inorganic complex strong electrolyte system" presented in this work. The molecular-level extraction mechanism was explored by QC calculation, indicating that the strong multi-site intermolecular interactions between Li+ and [HOEMIM][Tf2N] + TOP break the Li+ hydration. This work provides guidance to rationally design novel IL-based extractants for efficient extraction of Li+