Deep Removal of Fluoride Ions from Spent Ternary Lithium-Ion Batteries Leachate Using Porous La@Zr Adsorbent

Hydrometallurgy is currently the mainstream industrial process for recovering valuable components (nickel, cobalt, manganese, lithium, etc.) from spent ternary lithium-ion battery cathode materials. During the crushing of lithium batteries, cathode materials, anode materials (graphite), and electrolytes become mixed. Consequently, fluoride ions inevitably enter the leaching solution during the hydrometallurgical recycling process, with concentrations as high as 100–300 mg/L. These fluoride ions not only adversely affect the quality of the recovered precursor products but also pose environmental risks. To address this issue, this study employs a synthesized lanthanum–zirconium (La@Zr) composite material, with a specific surface area of 67.41 m2/g and a pore size of 2–50 nm, which can reduce the fluoride ion concentration in the leaching solution to below 5 mg/L, significantly lower than the 20 mg/L or higher that is typically achieved with traditional calcium salt defluorination processes, without introducing new impurities. Under optimal adsorption conditions, the lanthanum–zirconium adsorbent exhibits a fluoride ion adsorption capacity of 193.4 mg/g in the leaching solution, surpassing that of many existing metal-based adsorbents. At the same time as the valuable metals, Li, Ni, and Co, are basically not adsorbed, the selective adsorption of fluoride ions can be achieved. Adsorption isotherm studies indicate that the adsorption process follows the Langmuir model, suggesting monolayer adsorption. The secondary adsorption process is primarily governed by chemical adsorption, and elevated temperatures facilitate the removal of fluoride ions. Kinetic studies demonstrate that the adsorption process is well described by the pseudo-second-order model. After desorption and regeneration with NaOH solution, the adsorbent still has a favorable fluoride removal performance, and the adsorption rate of fluoride ions can still reach 95% after four cycles of use. With its high capacity, rapid kinetics, and excellent selectivity, the adsorbent is highly promising for large-scale implementation.