Search Results (229)

Recovered graphite from spent lithium-ion batteries is an important secondary resource that can reduce reliance on primary graphite and lower the environmental footprint of battery production. In this work, graphite obtained as a carbon-rich residue after industrial hydrometallurgical leaching of NMC111 black mass (2 M H₂SO₄ + 3% H₂O₂) is subjected to three post-leaching washing treatments to assess how far simple, low-intensity steps can further clean the leach residue while preserving the carbon structure. The washing routes are water washing (GW), water washing with ultrasonication (GU) and mild sulfuric-acid washing with 0.1 M H₂SO₄ (GA). ICP-OES and SEM–EDX show that, relative to the leached black mass, all washing treatments reduce residual transition-metal contents by two to three orders of magnitude, and that the mild acid wash provides the lowest bulk metal levels, with several elements at or below detection limits. X-ray diffraction and Raman spectroscopy indicate graphite-dominated patterns and improved structural order, with the ID/IG ratio decreasing from 0.62 (GW) to 0.11 (GA) and the corresponding in-plane crystallite size increasing from 30.6 nm to 168 nm. Overall, the mild acid washing step is the most effective low-impact post-leaching purification route, yielding a thoroughly cleaned low-metal graphite fraction that preserves the graphite framework and constitutes a suitable intermediate for further upgrading or reuse in secondary applications. Full article

As lithium demand surges and primary resources face depletion, lithium-bearing wastewater from urban mines has become a crucial secondary resource. For highly alkaline (pH 9–12), low-lithium (Li⁺ 0.5–5 g/L), high-sodium (Na/Li mass ratio > 30) wastewater generated from the alkaline leaching-washing of spent lithium-ion batteries in urban mining, a single-component, synergist-free extraction process employing HBL121 in sulfonated kerosene was developed, and its extraction stoichiometry, reaction mechanism, and industrial feasibility were elucidated. Saponification significantly enhanced extraction under moderate alkalinity: the saponified system achieved over 99% extraction efficiency at pH 11.0, whereas the non-saponified system required pH > 13.5 for comparable performance, thereby lowering alkali consumption by 81%. Under optimal conditions (saponification degree 40%, 30% (v/v) HBL121 and 70% (v/v) sulfonated kerosene, organic-to-aqueous phase ratio O/A = 1:1, extraction time 5 min), single-stage extraction efficiency exceeded 99%. A McCabe-Thiele diagram was used to determine the theoretical stage number for lithium stripping, showing that essentially all lithium ions can be stripped via a three-stage countercurrent process. Using 3.0 mol/L H₂SO₄ at an aqueous-to-organic phase ratio of 1:4, the stripping efficiency exceeded 99% from the loaded organic. Slope analysis, FT-IR, and ESI-MS confirmed a coordination mechanism between HBL121 and metal ions, forming a stable anionic bisphosphonate complex [LiNa₂(C₂₈H₄₄O₇P₂)]⁻, whose neutral parent form is HLiNa₂(C₂₈H₄₄O₇P₂). Full article

Spent lithium-ion battery electrolytes contain fluorine-, sulfur-, and phosphorus-bearing toxins, necessitating deep detoxification and directional conversion into C₁–C₆ light hydrocarbons. To elucidate the specific catalytic roles and sequential activation of cathode metals (Li, Ni, Co, Mn), this work systematically deconvolutes their mono- and multi-metallic migration mechanisms over a CaO-ZSM-5* catalyst during vacuum catalytic pyrolysis (530 °C, 100 Pa). Results reveal that Li⁺ and Ni²⁺ dominate C–O bond cleavage in carbonates and CaO-ZSM-5*-assisted decarboxylation and oxygen fixation, significantly increasing the relative hydrocarbon content. Conversely, Co^2/3+ and Mn⁴⁺ release reactive oxygen species, causing deep oxidation of hydrocarbons into CO₂ and antagonizing the targeted conversion. In multi-metallic systems, forming composite metal oxides (M_xN_yO_z) increases the energy barrier for releasing active catalytic ions, hindering carbonate cleavage and leaving unreacted carbonate feedstocks. For detoxification, F and P are effectively immobilized as CaF₂ and Ca₂P₂O₇. The relative content of detected gas-phase nitriles is minimized to <2% due to the strong antagonistic effect of Ni²⁺ on Li⁺-promoted hexanedinitrile cleavage, while sulfur species derived from 1,3-propane sultone are converted to SO₂ and ultimately mineralized as calcium and metal-sulfur salts. Mechanistically, product distributions and crystallographic properties suggest a hypothesized sequential activation model—Li⁺ → Ni²⁺ → Mn⁴⁺—governing reactivity, whereas Co^2/3+ does not participate in the synergistic detoxification and selective upgrading process. This migration–reaction coupling framework provides critical insights for cathode-assisted in situ catalytic pyrolysis and closed-loop electrolyte recycling. Full article

In this paper we investigate the use of sucrose as a reducing agent for the carbothermal reduction in spent ternary cathode materials. During this process, lithium from the cathode material is converted into water-soluble Li₂CO₃, while the high-valent transition metals are reduced to insoluble metallic elements and oxides. The influence of various pyrolysis temperatures, sucrose dosages, and pyrolysis times on the reduction degree of high-valent metals. Furthermore, the influence of leaching conditions on lithium recovery efficiency is examined. Under the optimal conditions of a pyrolysis temperature of 650 °C, a sucrose dosage of 15 wt.%, a pyrolysis time of 30 min, a leaching solid–liquid ratio of 30 g/L, and a leaching time of 30 min, the lithium leaching rate reaches 97.9%. Characterization via XRD, XPS and SEM reveals that sucrose serves as an effective carbothermal reducing agent. It facilitates the reduction of high-valent transition metals to insoluble metallic elements and oxides while simultaneously enabling the recovery of lithium as Li₂CO₃. Consequently, this method achieves an efficient separation of lithium from other metallic elements. Compared to traditional recycling processes, it avoids the low lithium recovery rates often associated with subsequent separation steps. Full article

With the growing global demand for sustainable resources, recycling spent lithium-ion batteries has become a strategic priority. Conventional pyrometallurgical and hydrometallurgical methods suffer from high energy consumption, severe pollution, and structural destruction, making them unsuitable for regenerating high-nickel cathodes. In this work, spent polycrystalline high-nickel LiNi_0.9Mn_0.1O₂ cathodes were selected, and an upcycling strategy integrating acid etching, hydrothermal relithiation, short-time annealing, and simultaneous Li₄Ti₅O₁₂ (LTO) coating was developed. This process directly transformed degraded polycrystalline cathodes into single-crystal cathode materials with excellent structural stability and electrochemical performance. During regeneration, lithium compensation and lattice recrystallization effectively repaired lithium loss, reduced Li/Ni cation mixing, reactivated the degraded structure, and reconstructed a highly ordered layered single-crystal framework. The LTO coating further stabilized the cathode/electrolyte interface, suppressed side reactions, alleviated volume strain, and promoted Li⁺ transport kinetics. Electrochemical measurements showed that the regenerated single-crystal cathode exhibited superior structural integrity, strong resistance to crack propagation, low polarization, excellent rate capability, and long-term cycling stability. A capacity retention of 84.3% was achieved after 300 cycles at 1C, outperforming commercial polycrystalline cathodes. This strategy provides an efficient and promising route for the direct regeneration of spent high-nickel ternary cathodes. Full article

Using strategies employed in synthetic chemistry, we investigated the chemicals found in lithium iron phosphate (LFP) spent battery via an initial dichloromethane (DCM) extraction of the individual cathode and anode. The pre- and post-treated electrodes and DCM extracts were examined using a range of analytical techniques. A total of 26 compounds were identified, which included the following: (1) some of the benchmark materials, LFP, lithium hexafluorophosphate (LIPF₆), polyvinylidene fluoride (PVDF), graphite and carbon black; (2) NMR spectroscopy of DCM extract revealed five main chemicals, which were ethylene and propylene carbonate solvents, LiPF₆, lithium tetrafluoroborate (LiBF₄), and an unknown fluorochemical; (3) analysis of the water-treated DCM extract revealed 21 chemicals by GCMS, several fluorochemicals; (4) 12 chemicals were found in both cathode and anode and three only in the anode; (5) only 13 of the 21 chemicals could be properly named, whilst four had some notable functionality and three could not be identified; and (6) ICP analysis revealed high levels of Al, Cu, Fe, V, and Zn in both electrodes and spent electrolyte. The high number of chemicals present in the spent electrolyte and electrodes suggest battery manufacturers use many proprietary chemicals to enhance battery properties. This procedure allows insight and identification of chemicals present in waste LIBs which will require advanced chemical techniques to recover high yields and purity of recycled materials and the need to dispose of hazardous waste. Full article

The growing demand for portable power has triggered a sharp increase in end-of-life lithium–nickel–cobalt–manganese oxide (NCM) batteries. Efficient recovery of NCM cathode materials is crucial for resource security. This study investigates an ascorbic acid–tartaric acid leaching system for extracting cobalt and manganese from spent NCM batteries. Temperature influences the leaching efficiencies of cobalt and manganese. Leaching efficiencies increase from 50 to 80 °C, consistent with the Arrhenius law. However, beyond 80 °C, side reactions inhibit cobalt leaching. Leaching efficiency increases with time over the range of 40 to 120 min, and then stabilizes at equilibrium. Ascorbic acid concentration plays a critical role. Within 0–1.5 mol/L, ascorbic acid promotes dissolution through reduction and coordination. At higher concentrations, excess H⁺ ions hinder complex formation. Similarly, tartaric acid concentration has an optimum range of 0.2–0.5 mol/L, where both H⁺ and ligands are supplied effectively. Outside this range, ligand availability is reduced. The solid–liquid ratio also affects performance. The optimal range of 5–15 g/L promotes mass transfer. Outside this range, efficiency declines due to solid accumulation or reduced diffusion. The results show that under optimal conditions, leaching recovery reaches 94.8% for Co and 99.3% for Mn. The optimal leaching conditions were determined as follows: tartaric acid, 0.5 M; ascorbic acid, 1.5 M; liquid-to-solid ratio, 15 g/L; stirring speed, 300 rpm; temperature, 80 °C; and leaching time, 120 min. This system represents a promising laboratory-scale approach for recovering cobalt and manganese from spent NCM batteries, pending further validation in larger-scale studies. Full article

Recycling spent lithium-ion batteries (LIBs) is critical for resource sustainability and carbon neutrality. This work presents a green strategy in which NaA zeolite is used to preferentially recover lithium from leachate of spent NCM111 batteries, combined with temperature-regulated stepwise separation of transition metals. Benefiting from the distinct hydrated ionic radii and charge density between Li⁺ and divalent metal ions, NaA zeolite selectively adsorbs Ni²⁺, Co²⁺ and Mn²⁺, leaving Li⁺ in the raffinate. Under optimized conditions, two-stage adsorption achieves 95.6%, 96.7% and 99.7% removal of Ni²⁺, Co²⁺ and Mn²⁺, respectively, with 11% Li⁺ co-adsorption. Thermodynamic analysis reveals that the adsorption process is endothermic and thermodynamically spontaneous. The interaction strength between metal ions and NaA zeolite follows the order Ni²⁺ > Co²⁺ > Mn²⁺, and ion exchange is identified as the dominant mechanism. It is determined that 96.8% of Mn²⁺ can be recovered at 0 °C, followed by the desorption of 93.5% of Co²⁺ at 90 °C, and the sequential separation of Mn, Co and Ni is realized. Three consecutive adsorption–desorption cycles demonstrate the acceptable reusability of the Ni-loaded NaA adsorbent. High-purity Li₂CO₃ (purity 96.7%, yield 93.5%), MnO₂ (purity 99.3%, yield 98.4%) and Co₃O₄ (purity 98.8%, yield 97.6%) are obtained from the corresponding solutions. This approach provides a scalable closed-loop pathway for full-component recovery of valuable metals from spent LIBs. Full article

Leaching carbon residue (LCR) is a carbonaceous solid waste generated during the hydrometallurgical recycling of spent lithium-ion batteries. Although its high graphite content offers substantial potential for resource recovery, the residual heavy metals and fluorides present in LCR pose considerable environmental risks. Currently, LCR has not garnered sufficient attention within the industry, and the lack of recycling technologies suitable for large-scale disposal results in resource wastage and environmental pollution. To address these challenges, this study proposes an innovative strategy based on the concept of multi-field synergistic enhancement. The proposed approach involves recovering and regenerating graphite (RG) from LCR via low-temperature molten salt roasting assisted by high-pressure and mechanical activation. A combination of advanced characterization techniques was employed to compare the physicochemical properties of RG and commercial graphite (CG) and to systematically evaluate the technical feasibility of using regenerated graphite as an anode material for lithium-ion batteries. The results demonstrate that, under optimized molten salt roasting and aqueous leaching conditions, the carbon content of RG reaches 99.94 wt%, indicating the efficient removal of non-carbon impurities from the graphite matrix. Compared to CG, RG retains a typical layered structure; however, a lower carbon content (99.94 wt%) and poorer structural order (I_D/I_G = 0.30) are observed. In terms of electrochemical performance, RG delivers a discharge specific capacity of 394.64 mAh/g during the first cycle and exhibits excellent cycling stability, with a capacity retention of 86.50% after 100 cycles. This electrochemical performance is comparable to that of commercial graphite. The proposed multi-field-assisted low-temperature molten salt roasting technique enables the efficient recovery of high-value graphite resources from LCR, establishing a full-lifecycle recycling strategy tailored for lithium-ion battery applications. Full article

The extensive application of lithium-ion batteries (LIBs) in electronic devices, electric vehicles, and related applications has significantly enhanced the quality of spent LIBs. As a critical component of LIBs, cathode materials contain substantial amounts of valuable metals (e.g., lithium, cobalt, nickel, and manganese), and their efficient recovery offers significant environmental and economic advantages. Owing to its simple operating conditions, effective impurity removal, and high reaction efficiency, pyrometallurgical roasting has become an important approach for recycling spent LIB cathode materials. This review focuses on pyrometallurgical roasting technologies for prior lithium extraction from spent LIB cathodes. By examining the structural characteristics of different cathode materials and their property variations during recycling, the fundamental principles and characteristics of pyrometallurgical roasting are clarified. The applications of roasting-based prior lithium extraction in LIB recycling are systematically reviewed, covering conventional processes, emerging high-efficiency roasting routes, and other advanced strategies for prior lithium extraction. Finally, the development trends of pyrometallurgical roasting technologies for spent LIB cathode materials are discussed, with the objectives of supporting technological advancement in LIB recycling and facilitating the establishment of a more sustainable development framework for the battery industry. Full article

The growing production of lithium-ion batteries is leading to an increase in waste, which contains elements considered critical in industry, like cobalt, manganese and nickel. Urban mining offers an opportunity to recover these elements and reintroduce them into the value chain. This study aimed to detect and recover metals of interest present in discarded lithium-ion batteries and determine the influence of flotation operating parameters on the recovery of the detected elements through an experimental design. The batteries subjected to the flotation experiments were obtained from various types of common disused mobile devices. They were dismantled by separating the copper sheets from the anode and the aluminum sheets from the cathode, to be subjected to a comminution process and elemental composition analysis using X-ray fluorescence. Only the cathode components were subjected to flotation. The flotation process was carried out by controlling the level of agitation and aeration and the flotation time using an automated flotation cell. The experiments were configured in a 2³ experimental design. Average recoveries of approximately 67% for cobalt, 64% for manganese, and 63% for nickel were achieved at a pH of 12.5 and a pulp density of 3.33 g/L using MIBC as the sole reagent. Statistical analysis at a 95% confidence level identified agitation, aeration, and flotation time both individually and in combination as significant factors. Linear models were developed to predict metal recovery, showing good agreement with experimental data (errors < 10%; standard deviation < 3%). Full article

The strong adhesion between cathode materials and aluminium (Al) foil substrates presents a significant challenge in the recycling of spent lithium-ion batteries (LiBs). Conventionally, high temperatures and high concentrations of costly organic solvents such as N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAC), dimethylformamide (DMF), and dimethyl sulfoxide (DMSO) are used to enhance ultrasonication-based delamination. In this study, a novel, eco-efficient approach was demonstrated for delaminating cathode materials from Al foil using a low-concentration organic citric-acid-assisted low-power ultrasonic treatment coupled with a gentle, low-power-per-volume mechanical mixing system at room temperature. The separation mechanism was attributed to the structure disruption, possibly swelling, of the polyvinylidene fluoride (PVDF) binder using low-concentration citric acid and the cavitation effects induced by ultrasound. Key parameters influencing the delamination efficiency included the solvent type, temperature, ultrasonic power, and treatment duration. Under optimised conditions, citric acid was used as the sonication reagent, with a process temperature of 20 °C, 60 W ultrasonic power, and 80 min of ultrasonication; a delamination efficiency of approximately 92% was achieved. The recovered cathode materials exhibited low agglomeration, favouring subsequent leaching processes. This work proposes an environmentally friendly and effective method for cathode and Al foil recovery from spent LiBs, integrating manual dismantling, ultrasonic treatment, and material separation. Full article

Amid growing environmental pressure and increasing demand for resource sustainability, the efficient recovery of valuable metals from spent lithium-ion batteries (LIBs) has become a critical challenge in the field of resource recycling. Therefore, a novel approach is presented for selective lithium (Li) and manganese (Mn) separation from LiNi_xCo_yMn_1−x−yO₂ by combining carbothermic reduction roasting and selective leaching. Low-cost glucose (C₆H₁₂O₆) was selected as the reduction roasting reductant, which converts the cathode materials into water-soluble lithium carbonate (Li₂CO₃), water-insoluble cobalt (Co), nickel (Ni), and manganese oxide (MnO). Wet magnetic separation was employed to preferentially extract Li while simultaneously removing excess carbon from Ni, Co, and MnO. Under optimal roasting conditions at 600 °C for 90 min followed by wet magnetic separation with a liquid–solid ratio of 30 mL/g for 30 min, 95.42% of Li was preferentially extracted. Subsequently, at a formic acid (HCOOH) concentration of 1.6 mol/L, liquid–solid ratio of 6 mL/g, and leaching time of 30 min, 94.29% of Mn was selectively extracted from the wet magnetic separation products, whereas Ni and Co were leached at 6.13% and 7.22%, respectively. The acid-leaching residue can be recycled as a Ni-Co alloy. Full article

Traditional lithium-ion battery recycling relies mainly on pyrolysis or chemical leaching to separate current collectors from electrode materials, inevitably resulting in secondary pollution. In contrast, eddy current separation (ECS) applied to crushed lithium-ion battery residues can substantially reduce the introduction of contaminants while minimizing material losses. However, the heterogeneous composition and diverse surface characteristics of crushed battery products, together with the conductivity degradation of electrode materials after long-term use, make conventional empirical particle–trajectory correlations inadequate for accurate optimization of ECS operating parameters. In addition, the coupling between process parameters and the resultant forces acting on conductive particles, as well as the associated separation trajectories, remain insufficiently understood, which severely limits process controllability. A force–trajectory model was therefore developed for spent current collectors and conductivity-degraded LiFePO₄ to describe their particle dynamics in an alternating magnetic field. The results demonstrate that the trajectory of LiFePO₄ is very similar to that of non-conductive materials, thereby facilitating its effective separation from metallic components in battery scrap. Eddy current separation experiments further confirm the accuracy of the model predictions with respect to separation trajectories and the influence of key process parameters. On this basis, optimization of the operating parameters increased the separation efficiency of the cathode material to above 95.1%. The clarified ECS mechanism for current collectors and electrode materials provides new insights into the mechanical pre-sorting and mechanistic understanding of lithium-ion battery fragments, thereby contributing to reductions in contaminant introduction during battery material recycling. Full article

Biohydrometallurgical processing of spent lithium-ion batteries offers a low-impact route for critical metal recovery compared with conventional hydrometallurgy. In this work, the iron-oxidizing bacterium Acidithiobacillus ferrooxidans was evaluated for the bioleaching of cobalt (Co), nickel (Ni), lithium (Li) and copper (Cu) from pyrolyzed industrial black mass derived primarily from LiCoO₂-based batteries, containing both LiCoO₂ and LiNiO₂ layered oxide phases. Batch experiments were conducted in 9K medium at 30 °C, varying pulp density (1%–2%, w/v), inoculum volume (10–20 mL in 200 mL medium) and initial pH (with and without adjustment). At 1% pulp density and 10% v/v inoculum, metal recoveries after 6–7 days reached about 64%–70% Co, 57%–72% Ni, 52%–60% Li and 81%–100% Cu, with most dissolution occurring in the first 6 days. Higher inoculum loads without initial pH adjustment increased Li recovery up to 79%, but did not further improve Co and Cu, indicating a trade-off between microbial activity, metal toxicity and ferric iron availability. The temporal evolution of pH and metal dissolution is consistent with indirect redoxolysis by biogenic Fe³⁺ and sulfuric acid generated during ferrous iron and elemental sulfur oxidation. Overall, the results confirm the feasibility of A. ferrooxidans-assisted bioleaching as a green option for Co, Ni, Li and Cu recovery from spent LiCoO₂ batteries and provide operating windows for subsequent process optimization and scale-up. Full article