RESUMEN

Effective recovery of Li, Co, Ni and Mn from cathode materials of spent lithium-ion batteries (LIBs) has become a global concern. In this study, electrolysis of copper sulfate to produce sulfuric acid and electrons were utilized to recover Li, Co, Ni and Mn from spent LIBs. The obtained results showed that 93 % of Ni, 91 % of Co, 89 % of Mn and 94 % of Li were leached and 99 % of Cu was deposited during leaching process by adopting the 0.225 mol/L of copper sulfate with a solid/liquid ratio of 15 g/L at a current density of 50 mA/m2 and 80 °C for 4.5 h. Then, a current efficiency of 72 % for the cathode and 30 % for the anode was achieved at a current density of 40 mA/m2, 70 °C and pH 2.5 during electrodeposition process. The Ni-Co deposition followed the principle of anomalous codeposition and the complete deposition time of Co, Ni and Mn were 3 h, 9 h and 10 h, respectively. Eventually, the Ni, Co, Mn, Li and Cu can be recovered as Ni-Co alloy, MnO2 and Li2CO3 and Cu metals with the corresponding recovery rates of 99.40 %, 91.00 %, 90.68 %, 85.59 % and 89.55 %, respectively. This study proposes a promising strategy for recycling cathode materials from spent LIBs without addition of chemical reductants and acids.

Asunto(s)

Suministros de Energía Eléctrica , Litio , Reciclaje , Reciclaje/métodos , Litio/química , Electrodos , Técnicas Electroquímicas/métodos , Residuos Electrónicos , Metales/química , Ácidos Sulfúricos/química

RESUMEN

Residual electricity in spent lithium-ion batteries (LIBs) may cause safety issues during their dismantling and shredding in pretreatment processes. However, the migration and transformation of pollutants generated from spent LIBs during discharging were rarely reported, which is critical for prevention of pollution risk and facilitation of discharging efficiency. Herein, this work is focused on the evolution fate of battery chemistry during discharging processing. Here, migration of metal ions inside battery, galvanic corrosion on surface of battery and chemical evolution outside battery were investigated to attain the comprehensive understanding of discharging process. Firstly, efficient and complete discharging can be achieved using 5 wt% CuSO4 as discharging medium, which mainly drive the migration of Li, instead of transition metals, from anode to cathode, resulting in enrichment of Li in cathode material. Besides, different degrees of galvanic corrosion phenomena on surface of spent LIBs can be discovered in different electrolyte solutions, involving with the corrosion of Al or Fe shells and resulting in the leakage of organic electrolytes inside battery into electrolyte solution. The detailed characterization results of the composition of solute indicate that hydroxide precipitates liberated from corroded shell and organic pollutants are their main existence states.

RESUMEN

Efficient and sustainable recycling of metal resources from spent lithium-ion batteries (LIBs) is critical for the metal resources security and environment protection. However, the intact exfoliation of cathode materials (CMs) from current collectors (Al foils) and selective extraction of Li towards the in-situ and sustainable recycling of cathodes from spent LIBs are still pending issues. A self-activated and ultrasonic-induced endogenous advanced oxidation process (EAOP) was proposed in this study for selective removal of PVDF and in-situ extraction of Li from CMs of waste LiFePO4 (LFP) to address the above issues. Over 99 wt% CMs can be detached from Al foils after EAOP treatment under the optimized operation conditions. High purity of Al foil can be directly recycled as metallic forms and nearly 100 % of Li can be in-situ extracted from the detached CMs and then recovered as Li2CO3 (>99.9 % in purity). With induction and reinforcement of ultrasonic, S2O82- was self-activated by LFP to generate an increased amount of SO4•- radicals that will attack the PVDF binders to ensure their degradation. The degradation pathway of PVDF and density functional theory (DFT) calculation can also support the analytical and experimental results. Then, the complete and in-situ ionization of Li can be achieved by the further oxidization of SO4•- radicals from LFP powders. This work provides a novel strategy towards efficient and in-situ recycling of valuable metals from spent LIBs with minimized environmental footprint.