Mechanochemically assisted persulfate activation for the facile recovery of metals from spent lithium ion batteries

A novel mechanochemically assisted persulfate activation method was proposed in this study to enhance the leaching of valuable metals from lithium-ion batteries by combining ball-milling, advanced oxidation processes and sucrose reduction. By optimizing leaching parameters including temperature, pH, milling time and solid-to-liquid ratio, high leaching efficiencies of 97.1%, 94.0%, 87.6% and 93.8% can be achieved for Li, Ni, Co and Mn respectively. In the mechanochemical process, the breakage of covalent bonds in cathode material is facilitated by free radicals generated from zero valent iron activated ammonia persulfate as well as mechanochemical activation. To further explore the role of free radicals, the mechanism of ammonia persulfate activation by zero valent iron was elucidated, and SO4•- was identified as the dominant reactive oxygen species in the mechanochemical process. Meanwhile, the synergistic effect of mechanochemically driven crystal dissolution and sulfate radical facilitated bond cleavage was revealed by ab initio molecular dynamics simulation. Moreover, the released metal was reduced by sucrose to a lower valent state of high solubility to promote transfer to the aqueous phase during the subsequent leaching process with dilute sulfuric acid. In this work, the insight on the mechanism of mechanochemical processes strengthened by free radicals may provide an inspiration for the recovery of valuable metals from LIBs.