Sustainable and Selective Recycling of Lithium Metal from Spent Cathodes: Direct Pathway to Anode Regeneration

Abstract The rapid expansion of lithium‐ion batteries (LIBs) is driving the depletion of critical resources and the accumulation of spent batteries, underscoring the urgent need for sustainable recycling strategies. In this study, an innovative recovery strategy that extracts lithium ions from spent battery cathodes, producing high‐purity lithium metal films, is presented. This process eliminates the need for harsh chemicals, such as acids or alkalis, and eliminates wastewater and gas emissions. Electrochemical measurements and characterization demonstrate the successful deintercalation of lithium from multiple spent cathodes, demonstrating the versatility of this approach. Additionally, the synergistic effects of Li‐ion solvation environments and interfacial engineering on enhancing lithium deposition selectivity, achieving a lithium purity of 99.23 wt.%, are emphasized. Moreover, the nucleation and growth mechanisms of lithium metal in the electrodeposition process are investigated, revealing randomly oriented crystallites without preferred orientation along the (110) crystallographic plane. The electrodeposited glassy lithium metal forms a semi‐spherical shape morphology with discontinuous growth, suggesting a sudden influx or accumulation of lithium atoms before the growth direction shifted. Finally, A techno‐economic analysis reveals significant cost advantages of this strategy compared to present recycling methods, while substantially reducing the environmental footprint of spent LIBs processing.