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.

After mechanical pre-treatment, the typical hydrometallurgical route of NdFeB magnet recycling starts with leaching in acidic solutions. However, due to the high concentration of iron ions in the leaching solution, the selective recovery of rare earths from the solution is challenging. In our work, the selective precipitation of rare earth oxalates as a potential separation method was proposed. The precipitation of neodymium oxalate was first tested on model solutions, which was then followed by experimental tests carried out on real solutions after the leaching of NdFeB magnets. The recovery of rare earths in the form of oxalates was investigated with the use of different amounts of oxalic acid in relation to its stoichiometric amount. The most efficient separation of rare earths was observed in the case where sulfuric acid was used for leaching. The use of oxalic acid in stoichiometric amounts resulted in the precipitation of about 93% of all rare earths present in the solution, whereas the concentration of Fe and other elements (Ni, Co, and B) practically did not change. An increase in oxalic acid of 20% and 40% more than the stoichiometric amount (100%) led to the increase in the precipitation efficiency of rare earths to 96.7% and 98.1%, respectively. However, the use of oxalic acid in a 1.4 ratio caused a 7% decrease in Fe concentration, which suggests Fe co-precipitation. In order to investigate a possibility of further increasing the separation of rare earths from iron, an additional method was tested, in which iron was first oxidized from Fe²⁺ to Fe³⁺ before the precipitation of rare earth oxalates.

A simplified approach for rare earth elements leaching from NdFeB (neodymium-iron-boron) magnets was investigated. The possibility of simplifying the magnet recycling process by excluding grinding, milling and oxidative roasting unit operations was studied. Attempts to skip the demagnetization step were also conducted by using whole, non-demagnetized magnets in the leaching process. The presented experiments were conducted to optimize the operating conditions with respect to the leaching agent and its concentration, leaching time, leaching temperature and the form of the feed material. The use of hydrochloric and sulfuric acids as the leaching agents allowed selective leaching of NdFeB magnets to be achieved while leaving nickel, which is covering the magnets, in a solid state. The application of higher leaching temperatures (40 and 60 °C for sulfuric acid and 40 °C for hydrochloric acid) allowed us to shorten the leaching times. When using broken demagnetized magnets as the feed material, the resulting rare earth ion concentrations in the obtained solutions were significantly higher compared to using whole, non-demagnetized magnets.

The global amount of waste electrical and electronic equipment (WEEE) is growing fast. Non-ferrous metals represent a large portion of this waste, and they can be potentially recovered via black copper smelting. Alumina and magnesia, originating from the e-waste or fluxes, can be present in the feed of a secondary copper smelter in varying concentrations. Our study focuses on the impact of MgO on the slag chemistry of high-alumina iron silicate slags. The distributions of tin and nickel as minor elements were also investigated and compared with literature data. The equilibrium study was performed at 1300 °C in reducing conditions. Three different slag mixtures with 0, 3, and 6 wt% MgO were used in the study. The MgO addition significantly reduced the solubility of alumina in the slag and changed the primary spinel phase composition. The combined effects of increasing MgO and decreasing Al₂O₃ concentration in the slag regarding the distribution of tin were noticeable, i.e., its deportment to metal phase increased, but for nickel the effect was negligible. Theoretical calculations were performed for estimating the isolated effect of MgO on the distributions and they confirmed the beneficial effect on the behavior of tin but showed no impact for nickel. Graphical Abstract

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.

Recycling of metals from different waste streams must be increased in the near future for securing the availability of metals that are critical for high-tech applications, such as batteries for e-mobility. Black copper smelting is a flexible recycling route for many different types of scrap, including Waste Electrical and Electronic Equipment (WEEE) and some end-of-life energy storage materials. Fundamental thermodynamic data about the behavior of battery metals and the effect of slag additives is required for providing data necessary for process development, control, and optimization. The goal of our study is to investigate the suitability of black copper smelting process for recycling of battery metals lithium, cobalt, manganese, and lanthanum. The experiments were performed alumina crucibles at 1300 °C, in oxygen partial pressure range of 10⁻¹¹–10⁻⁸ atm. The slags studied contained 0 to 6 wt% of MgO. Electron probe microanalysis (EPMA) and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) techniques were utilized for phase composition quantifications. The results reveal that most cobalt can be recovered into the copper alloy in extremely reducing process conditions, whereas lithium, manganese, and lanthanum deport predominantly in the slag at all investigated oxygen partial pressures.