Recycling lithium (Li) from spent lithium-ion batteries (LIBs) due to the depletion of natural resources and potential toxicity is becoming a progressively favourable measure to realize green sustainability. Presently, the prevalent recycling technique relying on pyrometallurgy lacks the capability to extract lithium. Meanwhile, conventional hydrometallurgical processes frequently employ robust acidic solutions like sulfuric acid and precipitation agents such as sodium carbonate. Unfortunately, this approach tends to result in the extraction of lithium at the end of a lengthy process chain, leading to associated losses and creating challenges in managing complex waste. This study addresses a cost-effective and environmentally friendly early-stage lithium recovery from the thermally conditioned black mass. In this sense, a thermally conditioned black mass is subjected to the carbonization process in a water solution to transform the water-insoluble Li phase into soluble lithium bicarbonate (LiHCO₃) and carbonate (Li₂CO₃) facilitating its selective separation from other elements. Response surface methodology (RSM)—a statistical tool integrated with central composite design (CCD) is employed to optimize the parameters for Li recovery. Temperature, solid–liquid (S/L) ratio, leaching time and CO₂ flow rate are considered as variable factors in modelling the optimum recycling process. A quadratic regression model is developed for Li recovery and based on ANOVA analysis, (S/L) ratio, temperature and time are identified as statistically significant factors. Experimental results demonstrate a maximum leaching efficiency of lithium with optimized parameter set, achieving a recovery rate of 97.18% with a fit response of 93.54%.

The impact of rare earth oxide (REO) concentration on the deposition process and selective recovery of the metal being deposited from a molten fluoride salt system was investigated by applying deposition of Nd and Pr and varying the concentration of REO added to the electrolyte. A ternary phase diagram for the liquidus temperature of the NdF₃-PrF₃-LiF system was constructed to better predict the optimal electrolyte constitution. Cyclic voltammetry was used to record three redox signals, reflecting the processes involving Nd(III)/Nd and Pr(III)/Pr transformations. A two-step red/ox process for Nd(III) ions and a single-step red/ox process for Pr(III) ions were confirmed by square-wave voltammetry. The cyclic voltammetry results indicated the possibility of neodymium and praseodymium co-deposition. In order to sustain higher co-deposition rates on the cathode and to avoid increased production of PFC greenhouse gases on the anode, a low-overpotential deposition technique was used for Nd and Pr electrodeposition from the electrolyte with varying Nd₂O₃ and Pr₆O₁₁ concentrations. Co-deposited neodymium and praseodymium metals were characterized by electron probe microanalysis (EPMA) and X-ray diffraction (XRD) analysis. After electrodeposition, concentration profiles of neodymium and praseodymium were recorded, starting from the cathode surface towards the electrolyte bulk. The working temperature of 1050 °C of the molten fluoride salt basic electrolyte, in line with the constructed phase diagram, was validated by improved co-deposition and led to a more effective deposition process.

Al-Ti alloys were electrodeposited from equimolar chloroaluminate molten salts containing up to 0.1 M of titanium ions, which were added to the electrolyte by potentiostatic dissolution of metallic Ti. Titanium dissolution and titanium and aluminium deposition were investigated by linear sweep voltammetry and chronoamperometry at 200 and 300 °C. Working electrodes used were titanium and glassy carbon. The voltammograms on Ti obtained in the electrolyte without added Ti ions indicated titanium deposition and dissolution proceeding in three reversible steps: Ti⁴⁺ ⇄ Ti³⁺, Ti³⁺ ⇄ Ti²⁺ and Ti²⁺ ⇄ Ti. The voltammograms recorded with glassy carbon in the electrolyte containing added titanium ions did not always clearly register all of the three processes. However, peak currents, which were characteristics of Al, Ti and Al-Ti alloy deposition and dissolution, were evident in voltammograms on both working electrodes used. A constant potential electrodeposition regime was used to obtain deposits on the glassy carbon working electrode. The obtained deposits were characterized by SEM, energy-dispersive spectrometry and XRD. In the deposits on the glassy carbon electrode, the analysis identified an Al and AlTi₃ alloy formed at 200 °C and an Al₂Ti and Al₃Ti alloy obtained at 300 °C.

The Al-V alloys were synthetized by potentiostatic electrodeposition onto a glassy carbon electrode from equimolar AlCl₃ + NaCl bath containing vanadium ions at 200 °C. The alloy deposits were characterized by X-ray diffraction, scanning electron microscopy, and energy dispersive spectroscopy. The deposits were identified as Al₃V and AlV₃ alloys. It was found that intermetallic alloys were synthetized during aluminium underpotential deposition onto vanadium metal that was previously deposited on the glassy carbon electrode by diffusion-controlled overpotential deposition. Alloys were the result of solid-state interdiffusion between the initially deposited vanadium and the subsequently deposited aluminium. As a source to secure a constant concentration of vanadium in the electrolyte during deposition, vanadium anodic dissolution, and VCl₃ melt addition were studied. The effect of vanadium ion concentration in the electrolyte on the composition and the surface morphology of the obtained deposits was investigated. The results indicate that controlled vanadium and aluminium codeposition could be a further step to the successful development of an advanced technology for Al₃V and AlV₃ alloy synthesis.