Microbial Bioleaching of Critical Metals from Spent Lithium-Ion Batteries: A Biohydrometallurgical Approach

Biohydrometallurgical processing of spent lithium-ion batteries offers a low-impact route for critical metal recovery compared with conventional hydrometallurgy. In this work, the iron-oxidizing bacterium Acidithiobacillus ferrooxidans was evaluated for the bioleaching of cobalt (Co), nickel (Ni), lithium (Li) and copper (Cu) from pyrolyzed industrial black mass derived primarily from LiCoO2-based batteries, containing both LiCoO2 and LiNiO2 layered oxide phases. Batch experiments were conducted in 9K medium at 30 °C, varying pulp density (1%–2%, w/v), inoculum volume (10–20 mL in 200 mL medium) and initial pH (with and without adjustment). At 1% pulp density and 10% v/v inoculum, metal recoveries after 6–7 days reached about 64%–70% Co, 57%–72% Ni, 52%–60% Li and 81%–100% Cu, with most dissolution occurring in the first 6 days. Higher inoculum loads without initial pH adjustment increased Li recovery up to 79%, but did not further improve Co and Cu, indicating a trade-off between microbial activity, metal toxicity and ferric iron availability. The temporal evolution of pH and metal dissolution is consistent with indirect redoxolysis by biogenic Fe3+ and sulfuric acid generated during ferrous iron and elemental sulfur oxidation. Overall, the results confirm the feasibility of A. ferrooxidans-assisted bioleaching as a green option for Co, Ni, Li and Cu recovery from spent LiCoO2 batteries and provide operating windows for subsequent process optimization and scale-up.