Recovery and Purification of Lithium Hydroxide from Spent Cathode Crucibles via Sulfation and Conversion Processes

This study presents an integrated process for the recovery and purification of lithium hydroxide (LiOH) from lithium sulfate (Li₂SO₄) solution obtained by sulfuric acid leaching of spent crucibles used for producing the cathodes of LIBs. The recovered leachate contains considerable concentrations of metallic impurities, including Na, K, Mg, Ca, Al, and Ni, which hinder the direct production of high-purity LiOH. To overcome this limitation, a pretreatment step combining cation- and anion-exchange resins was introduced to control impurity levels and condition the solution prior to conversion. Under the optimized ion-exchange condition of 10 g cation-exchange resin and 50 g anion-exchange resin, the solution pH was adjusted to 6-7, resulting in effective impurity removal through combined ion-exchange and solution-conditioning effects. More than 90% of Al was removed, while Mg, Ca, Na, K, and Ni were removed by approximately 70-75%. After purification, LiOH was produced through a double-displacement conversion reaction using Ba(OH)₂. The results showed that the reaction temperature and the [OH]:[Li] molar ratio were the key parameters governing the sulfate-removal-based apparent conversion efficiency and filtrate-based LiOH purity. Excess OH^- promoted the formation of dissolved and complexed species, thereby lowering the purity of the LiOH-containing filtrate. In contrast, the optimum condition was identified at 70 °C and an [OH]:[Li] molar ratio of 1:1, under which SO₄^2- was effectively removed as solid BaSO₄. Under these conditions, the sulfate-removal-based apparent conversion efficiency reached 91.91%, and the filtrate-based LiOH purity was 98.84%. X-ray diffraction analysis confirmed the coexistence of LiOH·H₂O and LiOH phases in the final recovered product, whereas the precipitate was identified as single-phase BaSO₄, indicating effective sulfate removal. Overall, this study demonstrates the feasibility of producing high-purity LiOH from sulfation-derived Li₂SO₄ leachate through a sequential process consisting of impurity removal, conversion, and drying. The findings provide fundamental process data for the design of lithium recovery and purification routes using spent cathode crucibles as secondary lithium resources.