The high chemical activity of metallic Li hinders its efficient electrochemical extraction at low temperatures, necessitating the use of energy- and cost-intensive methods such as vacuum thermal reduction or electrodeposition from ionic-liquid and molten-salt electrolytes. Herein, we report the direct room-temperature electrowinning of metallic Li from a simple low-cost electrolyte, namely a solution of LiCl in dimethylacetamide (DMAc), determine the optimal concentration of LiCl, and examine the redox processes in the optimized system. Potentiostatic deposition on high-purity Al is shown to induce solid-state cathode alloying and thus produce a uniform, flat, and dense coating of a LiAl master alloy comprising spherical clusters formed by LiAl alloy nanosheets. Finally, the direct smelting of electrodeposited films is proposed as a method of rapidly realizing the “thin film” to “bulk” transformation of electrodeposited materials to stabilize metallic Li and form bulk Li-based alloys. Thus, this study provides a basis for the continuous, low-cost, sustainable, and fast electrochemical production of bulk active metals or their alloys.
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