Due to the increasing demand for battery raw materials such as cobalt, nickel, manganese, and lithium, the extraction of these metals not only from primary, but also from secondary sources like spent lithium-ion batteries (LIBs) is becoming increasingly important. One possible approach for an optimized recovery of valuable metals from spent LIBs is a combined pyro- and hydrometallurgical process. According to the pyrometallurgical process route, in this paper, a suitable slag design for the generation of slag enriched by lithium and mixed cobalt, nickel, and copper alloy as intermediate products in a laboratory electric arc furnace was investigated. Smelting experiments were carried out using pyrolyzed pelletized black mass, copper(II) oxide, and different quartz additions as a flux to investigate the influence on lithium-slagging. With the proposed smelting operation, lithium could be enriched with a maximum yield of 82.4% in the slag, whereas the yield for cobalt, nickel, and copper in the metal alloy was 81.6%, 93.3%, and 90.7% respectively. The slag obtained from the melting process is investigated by chemical and mineralogical characterization techniques. Hydrometallurgical treatment to recover lithium is carried out with the slag and presented in part 2.

The objective of this study is to describe primary lithium production and to summarize the methods for combined mechanical and hydrometallurgical recycling of lithium-ion batteries (LIBs). This study also aims to draw attention to the problem of lithium losses, which occur in individual recycling steps. The first step of hydrometallurgical treatment is leaching, which is an effective method capable of transferring over 99% of the present metals to the leach solutions. Extraction of metals after leaching can be conducted using various methods, with precipitation being the most commonly used. The precipitation of other metals can result in the co-precipitation of lithium, causing total lithium losses up to 30%. To prevent such losses, solvent extraction methods are used to selectively remove elements, such as Co, Ni, Al, and Mn. Solvent extraction (SX) is highly effective, reducing the losses to 3% per extraction stage and reducing overall lithium losses to 15%. After the refining, lithium is precipitated as lithium carbonate. High lithium carbonate solubility (1.5 g/L) and high liquid to solid leaching ratios require costly and avoidable operations to be implemented in order to enhance lithium concentration. Therefore, it is suggested that more studies should focus on multistage leaching with lower L/S ratios.

Due to the increasing demand for battery raw materials, such as cobalt, nickel, manganese, and lithium, the extraction of these metals, not only from primary, but also from secondary sources, is becoming increasingly important. Spent lithium-ion batteries (LIBs) represent a potential source of raw materials. One possible approach for an optimized recovery of valuable metals from spent LIBs is a combined pyro- and hydrometallurgical process. The generation of mixed cobalt, nickel, and copper alloy and lithium slag as intermediate products in an electric arc furnace is investigated in part 1. Hydrometallurgical recovery of lithium from the Li slag is investigated in part 2 of this article. Kinetic study has shown that the leaching of slag in H₂SO₄ takes place according to the 3-dimensional diffusion model and the activation energy is 22–24 kJ/mol. Leaching of the silicon from slag is causing formation of gels, which complicates filtration and further recovery of lithium from solutions. The thermodynamic study presented in the work describes the reasons for the formation of gels and the possibilities of their prevention by SiO₂ precipitation. Based on these findings, the Li slag was treated by the dry digestion (DD) method followed by dissolution in water. The silicon leaching efficiency was significantly reduced from 50% in the direct leaching experiment to 5% in the DD experiment followed by dissolution, while the high leaching efficiency of lithium was maintained. The study takes into account the preparation of solutions for the future trouble-free acquisition of marketable products from solutions.

This paper provides an overview of the current state of the field in spent portable lithium battery recycling at both the research and industrial scales. The possibilities of spent portable lithium battery processing involving pre-treatment (manual dismantling, discharging, thermal and mechanical-physical pre-treatment), pyrometallurgical processes (smelting, roasting), hydrometallurgical processes (leaching followed by recovery of metals from the leachates) and a combination of the above are described. The main metal-bearing component of interest is the active mass or cathode active material that is released and concentrated by mechanical-physical pre-treatment procedures. The metals of interest contained in the active mass include cobalt, lithium, manganese and nickel. In addition to these metals, aluminum, iron and other non-metallic materials, especially carbon, can also be obtained from the spent portable lithium batteries. The work describes a detailed analysis of the current state of research on spent lithium battery recycling. The paper presents the conditions, procedures, advantages and disadvantages of the techniques being developed. Moreover, a summary of existing industrial plants that are focused on spent lithium battery recycling is included in this paper.

Copper anode furnace dust is waste by-product of secondary copper production containing zinc, lead, copper, tin, iron and many other elements. Hydrometallurgical Copper Anode Furnace dust recycling method was studied theoretically by thermodynamic calculations and the proposed method was verified experimentally on a laboratory scale. The optimum condition for leaching of zinc from dust was identified to be an ambient leaching temperature, a liquid/solid ratio of 10 and H₂SO₄ concentration of 1 mol/L. A maximum of 98.85% of zinc was leached under the optimum experimental conditions. In the leaching step, 99.7% of lead in the form of insoluble PbSO₄ was separated from the other leached metals. Solution refining was done by combination of pH adjustment and zinc powder cementation. Tin was precipitated from solution by pH adjustment to 3. Iron was precipitated out of solution after pH adjustment to 4 with efficiency 98.54%. Copper was selectively cemented out of solution (99.96%) by zinc powder. Zinc was precipitated out of solution by addition of Na₂CO₃ with efficiency of 97.31%. ZnO as final product was obtained by calcination of zinc carbonates.

The paper describes cementation as a suitable method applied in the refining of EAFD leachates in order to obtain required purity of ZnO for specific industrial application. For study of cementation conditions, the leachate from alkaline leaching with (NH₄)₂CO₃ was used. The leachates contained a high amount of zinc (8000–12,000 µg/mL) and a low content of impurities such as iron, lead, copper, chromium and manganese in the range of 1–21 µg/mL. Cementation conditions were predicted by thermodynamic study, theoretically confirming the viability of the proposed experiments at the considered pH = 8–9. Cementation experiments were carried out using powdered zinc and aluminium (5 g/L) as cementation agents in the first phase separately. To increase the cementation efficiency, their combination was used (2.5:2.5 g/L or 5:5 g/L) at temperatures of 20, 40, 60 and 80 °C for 30 min. The optimum cementation conditions were established as: Zn:Al = 5:5 g/L, 60 °C. Under the given conditions, 100% of Fe, Cu, Pb and Mn were removed from the leachate. The ZnO with the maximum purity of 96.67% was obtained by crystallization of cemented leachate at 105 °C, followed by calcination at 900 °C for 4 h. ZnO with such a purity is suitable for use in the electrical or rubber industries.