Mild and Selective Alkahest-Enabled Electrochemical Extraction of Critical Elements from Ores

Direct recovery of elemental antimony (Sb) and bismuth (Bi) from sulfide ores under mild conditions remains a fundamental challenge. Binary sulfides, such as stibnite (Sb 2 S 3 ) and bismuthinite (Bi 2 S 3 ), are abundant mineral sources of critical elements, yet their extremely low solubility precludes conventional electrowinning. Here, we report the first acid-free, room-temperature method for selective electrowinning of Sb and Bi, enabled by a thiol–amine “alkahest” solvent that dissolves otherwise intractable sulfides. This approach enables electrochemical reduction to dense, nanoscale-uniform Sb films from natural ore, maintaining high selectivity against associated sulfides and gangue. The Faradaic efficiency is 80% with an energy consumption of 2.6 kWh/kg for Sb. The same strategy enables Bi electrowinning from bismuthinite and bismite (Bi 2 O 3 ). These results establish a generalizable pathway for direct recovery of critical elements from sulfide and oxide ores and highlight alkahest solvents as a versatile platform for selective multielectron redox in complex solid–liquid systems.