Recycling of Valuable Metals from the Priority Lithium Extraction Residue Obtained through Hydrogen Reduction of Spent Lithium Batteries

The selective separation of lithium from spent ternary positive materials is achieved through hydrogen reduction followed by water leaching. Almost 98% of the Li is transformed into soluble LiOH⋅H2O, while the Ni, Co and Mn species are all transformed into insoluble metals or their oxides, so the recovery of Ni, Co and Mn at this stage is challenging. The traditional acid leaching process has drawbacks such as high oxidant consumption, the low recovery of valuable metals and high production costs. Thus, sulfation roasting followed by water leaching was studied in this project. The leaching levels of Ni, Co, Mn and Al reached 87.13%, 99.87%, 96.21% and 94.95%, respectively, with 1.4 times the theoretical amount of sulfuric acid used at 180 °C for 120 min. To avoid the adverse effects of Mn and Al on the quality of the Ni and Co sulfate products, Mn2+ was first separated and precipitated via the KMnO4 oxidation–precipitation method, and >98% of the Mn was removed and precipitated within 30 min with a Kp/Kt (ratio of actual usage to theoretical usage of KMnO4) of 1.0 at pH = 2.0 and 25 °C. After removal of the Mn, the solvent extraction method was adopted by using P204 as an extractant to separate Al. More than 98% of the Al was extracted in 30 min with 20% (v/v) P204 + 10% (v/v) TBP with an A/O ratio of 1:1 at 30 °C. This optimized process for extracting lithium residues improved the hydrogen reduction process of waste lithium batteries and will enable industrialization of the developed processes.