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.

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.

Lithium-ion batteries contain many of critically important metals and their effective recycling is key to the EU?s sustainable development. In the past, only metals such as Co, Ni, and Cu were recycled by pyrometallurgy, while Li and Al were concentrated in the slags and not further processed. The novel approach of pyrometallurgical treatment of the black mass offers the possibility of further hydrometallurgical utilization of the slags. This paper examines the refining of the solution obtained by leaching the slag in sulfuric acid. The most valuable element in the leach solution is Li, but it also contains Al, Si, Co, Mn, Ni and Cu, which must be removed before high-purity Li recovery is possible. Purification is achieved by adjusting the pH by adding NaOH. The results confirm that Al and Mn can be removed by 100%, Si by 93.56%, Cu by 86.36% and Cu by 61.75%. The results also confirmed that solution refining by the adding NaOH causes lithium losses ranging from 10% at pH 7 to 28% at pH 12. Therefore, it is suggested that further solution refining methods should be combined before precipitating pure Li2CO3 with minimal losses.

Currently, recycling of spent lithium-ion batteries is carried out using mechanical, pyrometallurgical and hydrometallurgical methods and their combination. The aim of this article is to study a part of the pyro-hydrometallurgical processing of spent lithium-ion batteries which includes lithium slag hydrometallurgical treatment and refining of the obtained leachate. Leaching was realized via dry digestion, which is an effective method capable of transferring over 99% of the present metals, such as Li, Al, Co, Cu, and others, to the leachate. In this work, the influence of three types of precipitation agents (NaOH, NH₄OH, Na₃PO₄) on the precipitation efficiency of Al and Li losses was investigated. It was found that the precipitation of aluminum with NaOH can result in the co-precipitation of lithium, causing total lithium losses up to 40%. As a suitable precipitating agent for complete Al removal from Li leachate with a minimal loss of lithium (less than 2%), crystalline Na₃PO₄ was determined under the following conditions: pH = 3, 400 rpm, 10 min, room temperature. Analysis confirmed that, in addition to aluminum, the precipitate also contains the REEs La (3.4%), Ce (2.5%), Y (1.3%), Nd (1%), and Pr (0.3%). The selective recovery of these elements will be the subject of further study.

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.

In this work, a method for leaching black mass from spent Li batteries using oxalic acid was developed and experimentally verified with the objective of selectively separating lithium and cobalt. Oxalic acid proved to be an efficient and selective leaching agent. Under 1 M C₂H₂O₄, 120 min, L:S = 20, 80 °C and 300 rpm, a lithium yield of 90% was achieved, while cobalt dissolution remained low at 1.57%. Subsequently, cobalt spontaneously precipitated from the leachate within several hours, and the solid phase was fully separated after 24 h. The leachate contained minor amounts of accompanying metals, with dissolution yields of 0.5% Mn, 8% Fe and 1.4% Cu. These impurities were removed from the leachate by controlled pH adjustment using NaOH at ambient temperature and 450 rpm, with complete precipitation at pH 12. This procedure generated a purified lithium-rich leachate, which was converted into lithium oxalate by crystallisation at 105 °C. Subsequent calcination of the resulting solid at 450 °C for 30 min produced Li₂CO₃ with a purity of 91%. Based on the experimental findings, a conceptual technological process for selective lithium leaching using oxalic acid was proposed, demonstrating the potential of this method for sustainable lithium recovery.