Copper-Mediated Leaching of LiCoO₂ in H₃PO₄: Kinetics and Residue Transformation

The recycling of spent lithium-ion batteries (LIBs) requires efficient and sustainable methods for recovering critical metals. In this study, the leaching behavior of LiCoO₂ cathode material obtained from spent LIBs was investigated in phosphoric acid, using copper powder recovered from waste LIBs as a reducing agent. Leaching experiments were conducted under various conditions (temperature, solid-to-liquid ratio, agitation rate) and compared with systems without copper. In the absence of copper, lithium and cobalt, recoveries after 30 min were approximately 77% and 23%, respectively. The addition of copper significantly enhanced leaching, achieving >96% recovery for both metals at 80 °C, with most extraction occurring within the first 30 min. Kinetic analysis using the shrinking core model indicated a mixed-control mechanism involving both surface chemical reaction and product layer diffusion. The calculated activation energies were 20.2 kJ·mol⁻¹ for lithium and 16.1 kJ·mol⁻¹ for cobalt. Solid residues were characterized by X-ray diffraction (XRD) and scanning electron microscopy with energy-dispersive spectroscopy (SEM-EDS). XRD results revealed that the composition of the residues varied with leaching temperature: Co₃O₄ was consistently detected, whereas Cu₈(PO₃OH)₂₍PO₄)₄·7H₂O appeared only when leaching was performed above 50 °C. Thermodynamic calculations supported the reductive role of copper and provided insight into possible reaction pathways. These findings confirm the effectiveness of copper-mediated leaching in phosphoric acid and demonstrate that temperature strongly influences residue phase evolution, thereby offering valuable guidance for the design of sustainable LIB recycling processes.