The hydrometallurgical extraction of metals from spent lithium-ion batteries (LIBs) was investigated. LIBs were first dismantled and a fraction rich in the active material was obtained by physical separation, containing 95% of the initial electrode, 2% of the initial steel and 22% of plastic materials. Several reducers were tested to improve metals dissolution in the leaching step using sulphuric acid. Sodium metabisulphite led to the best results and was studied in more detail. The best concentration of Na2S2O5 was 0.1 M. The metals dissolution increased with acid concentration, however, concentrations higher than 1.25 M are unnecessary. Best results were reached using a stirring speed of 400 min-1. The metals leaching efficiency from the active material (Li, Mn, Ni, Co) increased with the temperature and was above 80% for temperatures higher than 60 °C. The dissolution of metals also rose with the increase in the liquid/solid ratio (L/S), however, extractions above 85% can be reached at L/S as lower as 4.5 L/kg, which is favourable for further purification and recovery operations. About 90% of metals extraction can be achieved after only 0.5 h of leaching. Sodium metabisulphite can be an alternative reducer to increase the leaching of Li, Mn, Co, and Ni from spent LIBs.

The growing demand for lithium-ion batteries will result in an increasing flow of spent batteries, which must be recycled to prevent environmental and health problems, while helping to mitigate the raw materials dependence and risks of shortage and promoting a circular economy. Combining pyrometallurgical and hydrometallurgical recycling approaches has been the focus of recent studies, since it can bring many advantages. In this work, the effects of incineration on the leaching efficiency of metals from EV LIBs were evaluated. The thermal process was applied as a pre-treatment for the electrode material, aiming for carbothermic reduction of the valuable metals by the graphite contained in the waste. Leaching efficiencies above 70% were obtained for Li, Mn, Ni and Co after 60 min of leaching even when using 0.5 M sulfuric acid, which can be linked to the formation of more easily leachable compounds during the incineration process. When the incineration temperature was increased (600-700 °C), the intensity of graphite signals decreased and other oxides were identified, possibly due to the increase in oxidative conditions. Higher leaching efficiencies of Mn, Ni, Co, and Li were reached at lower temperatures of incineration (400-500 °C) and at higher leaching times, which could be related to the partial carbothermic reduction of the metals.

The lithium extraction from a lepidolite concentrate using roasting, followed by water leaching, was studied. Several alternative additives were initially tested. The use of sodium and calcium sulfates as additives was evaluated in more detail. The influence of some process variables, namely the roasting time, roasting temperature and the additive/concentrate mass ratio, was studied applying a design of experiments. The lithium extraction was modelled and the fitted and validated model was used to optimize the process response. The increase in the additive/concentrate mass ratio, roasting time and temperature seems to result in solid state reactions and transformations that lead to phase, morphological and particle size distribution modifications, which were assessed by XRPD, SEM, and particle size analyses. In this process, lithium sodium sulfate formation constitutes a crucial step enabling the Li water leaching. High lithium extractions were estimated for several combinations of factors. At 850°C, lithium extractions over 90% are obtained when the roasting time is above 1.90 hour and the additive/concentrate mass ratios are over 0.77. An increase in the temperature to 875°C also leads to lithium extractions over 90% for a roasting time of 1 hour and an additive/concentrate mass ratio of 0.60.

Manganese is a critical metal for the steelmaking industry, and it is expected that its world demand will be increasingly affected by the growing market of lithium-ion batteries. In addition to the increasing importance of manganese, its recycling is mainly determined by trends in the recycling of iron and steel. The recovery of manganese by solvent extraction has been widely investigated; however, the interaction of different variables affecting the process is generally not assessed. In this study, the solvent extraction of manganese from a solution based on lithium-ion batteries was modeled and optimized using factorial designs of experiments and the response surface methodology. Under optimized conditions (O:A of 1.25:1, pH 3.25, and 0.5 M bis(2-ethylhexyl) phosphoric acid (D2EHPA)), extractions above 70% Mn were reached in a single extraction stage with a coextraction of less than 5% Co, which was mostly removed in two scrubbing stages. A stripping product containing around 23 g/L Mn and around 0.3 g/L Co can be obtained under optimized conditions (O:A of 8:1, 1 M H₂SO₄ and around 13 min of contact time) in one stripping stage.

Selective leaching of Li from spent LIBs thermally pretreated by pyrolysis and incineration between 400 and 700 °C for 30, 60, and 90 min followed by water leaching at high temperature and high L/S ratio was examined. During the thermal pretreatment Li₂CO₃ and LiF were leached. Along with Li salts, AlF₃ was also found to be leached with an efficiency not higher than 3.5%. The time of thermal pretreatment did not have a significant effect on Li leaching efficiency. The leaching efficiency of Li was higher with a higher L/S ratio. At a higher leaching temperature (80 °C), the leaching of Li was higher due to an increase in the solubility of present Li salts. The highest Li leaching efficiency of nearly 60% was observed from the sample pyrolyzed at 700 °C for 60 min under the leaching condition L/S ratio of 20:1 mL g⁻¹ at 80 °C for 3 h. Furthermore, the use of an excess of 10% of carbon in a form of graphite during the thermal treatment did not improve the leaching efficiency of Li.