Since the current volumes of collected end-of-life lithium ion batteries (LIBs) are low, one option to increase the feasibility of their recycling is to feed them to existing metals production processes. This work presents a novel approach to integrate froth flotation as a mechanical treatment to optimize the recovery of valuable metals from LIB scrap and minimize their loss in the nickel slag cleaning process. Additionally, the conventional reducing agent in slag cleaning, namely coke, is replaced with graphite contained in the LIB waste flotation products. Using proper conditioning procedures, froth flotation was able to recover up to 81.3% Co in active materials from a Cu-Al rich feed stream. A selected froth product was used as feed for nickel slag cleaning process, and the recovery of metals from a slag (80%)–froth fraction (20%) mixture was investigated in an inert atmosphere at 1350 °C and 1400 °C at varying reduction times. The experimental conditions in combination with the graphite allowed for a very rapid reduction. After 5 min reduction time, the valuable metals Co, Ni, and Cu were found to be distributed to the iron rich metal alloy, while the remaining fraction of Mn and Al present in the froth fraction was deported in the slag.
One possible way of recovering metals from spent lithium-ion batteries is to integrate the recycling with already existing metallurgical processes. This study continues our effort on integrating froth flotation and nickel-slag cleaning process for metal recovery from spent batteries (SBs), using anodic graphite as the main reductant. The SBs used in this study was a froth fraction from flotation of industrially prepared black mass. The effect of different ratios of Ni-slag to SBs on the time-dependent phase formation and metal behavior was investigated. The possible influence of graphite and sulfur contents in the system on the metal alloy/matte formation was described. The trace element (Co, Cu, Ni, and Mn) concentrations in the slag were analyzed using the laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) technique. The distribution coefficients of cobalt and nickel between the metallic or sulfidic phase (metal alloy/matte) and the coexisting slag increased with the increasing amount of SBs in the starting mixture. However, with the increasing concentrations of graphite in the starting mixture (from 0.99 wt.% to 3.97 wt.%), the Fe concentration in both metal alloy and matte also increased (from 29 wt.% to 68 wt.% and from 7 wt.% to 49 wt.%, respectively), which may be challenging if further hydrometallurgical treatment is expected. Therefore, the composition of metal alloy/matte must be adjusted depending on the further steps for metal recovery.
In the search for more sustainable alternatives to the chemical reagents currently used in froth flotation, the present work offers further insights into the behavior of functionalized cellulose nanocrystals as mineral hydrophobization agents. The study corroborates that hexylamine cellulose nanocrystals (HACs) are an efficient collector for the flotation of quartz and also identifies some particular characteristics as a result of their colloidal nature, as opposed to the water-soluble reagents conventionally used. To investigate the individual and collective effects of the frother and HACs on the attachment of particles and air bubbles, an automated contact timer apparatus was used. This induction timer measures particle-bubble attachment probabilities ( P att ) without the influence of macroscopic factors present in typical flotation experiments. This allowed the study of the combined influence of nanocellulose and frother concentration on P att for the first time. While HACs readily adsorb on quartz modifying its wettability, the presence of a frother leads to a drastic reduction in P att up to 70%. The improved recovery of quartz in flotation cells might thus be attributed to froth stabilization by HACs, perhaps acting as a Pickering foam stabilizer. Among the main findings, a tendency of HACs to form mineral agglomerates was identified and further explained using the extended DLVO theory in combination with measured adsorption rates in a quartz crystal microbalance. Therefore, this study distinguishes for the first time the antagonistic effect of frothers on P att and their synergies with HACs on the stabilization of orthokinetic froths through the hydrophobization mechanism unlike those of typical water-soluble collectors.
In this study, industrial lithium-ion battery (LIB) waste was treated by a froth flotation process, which allowed selective separation of electrode particles from metallic-rich fractions containing Cu and Al. In the flotation experiments, recovery rates of ~80 and 98.8% for the cathode active elements (Co, Ni, Mn) and graphite were achieved, respectively. The recovered metals from the flotation fraction were subsequently used in high-temperature Cu-slag reduction. In this manner, the possibility of using metallothermic reduction for Cu-slag reduction using Al-wires from LIB waste as the main reductant was studied. The behavior of valuable (Cu, Ni, Co, Li) and hazardous metals (Zn, As, Sb, Pb), as a function of time as well as the influence of Cu-slag-to-spent battery (SB) ratio, were investigated. The results showcase a suitable process to recover copper from spent batteries and industrial Cu-slag. Cu-concentration decreased to approximately 0.3 wt.% after 60 min reduction time in all samples where Cu/Al-rich LIB waste fraction was added. It was also showed that aluminothermic reduction is effective for removing hazardous metals from the slag. The proposed process is also capable of recovering Cu, Co, and Ni from both Cu-slag and LIB waste, resulting in a secondary Cu slag that can be used in various applications.
The recycling of active materials from Li-ion batteries (LIBs) via froth flotation has gained interest recently. To date, recycled graphite has not been pure enough for direct reuse in LIB manufacturing. The present work studied the effect of particle sizes on the grade of recycled graphite. Furthermore, selective flocculation is proposed as a novel approach to control particle sizes and thus improve graphite grade by preventing the entrainment of cathode components. Zeta potential and particle size measurements were performed to find an optimal pH for electrically selective flocculation and to study the interaction of flocculants, respectively. Batch flotation experiments were performed to investigate the effect of particle size on the purity of the recovered graphite. Results suggested that, in the absence of ultrafine fine particles, battery-grade graphite of 99.4% purity could be recovered. In the presence of ultrafine particles, a grade of 98.2% was observed. Flocculating the ultrafine feed increased the grade to 98.4%, although a drop in recovery was observed. By applying a dispersant in addition to a flocculant, the recovery could be increased while maintaining a 98.4% grade. Branched flocculants provided improved selectivity over linear flocculants. The results suggest that particle size needs to be controlled for battery-grade graphite to be recovered.
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