Search Results (137)

The increasing demand for lithium-ion batteries (LIBs) raises concerns about the security of critical raw material supply and the management of hazardous waste. Efficient recycling can alleviate these issues by transforming spent batteries into high-value secondary materials for the circular economy. Industrial recycling has traditionally focused on the recovery of nickel (Ni) and cobalt (Co), whereas lithium (Li) recovery has often been sidelined due to technical complexities and fluctuating economic incentives. To meet the European Union (EU) Batteries Regulation target of 80% lithium recovery by the end of 2031, technically effective and economically viable lithium recovery strategies are required. This study investigates the use of food-grade sucrose as an organic reductant for the targeted recovery of lithium from NMC622 and NCA battery materials. The process combines sucrose-assisted reductive roasting with selective water leaching. The effects of roasting temperature, holding time, sucrose dosage, and heating rate were systematically evaluated and optimised. Under the best conditions of 600 °C, 15 min, 15 wt% sucrose, and a heating rate of 20 °C/min, lithium leaching efficiencies of 93.2% and 87.6% were achieved for separated NMC622 cathode material and NMC622-derived black mass, respectively. The method was also applicable to NCA-based black mass, reaching 83.7% lithium recovery under the same conditions. Mechanistic analysis revealed that lithium release was strongly controlled by the extent of transition metal reduction. Cobalt was fully reduced to its metallic state under all tested conditions. However, maximum lithium recovery required nickel to be reduced to metallic Ni and manganese-containing phases to be converted to MnO. The sucrose-assisted roasting process was rapid and holding times longer than 15 min decreased lithium recovery. This decrease was caused by the formation of poorly soluble lithium-containing phases, such as LiF and Li₃PO₄. F composition analysis showed the black mass (1.06 wt%) and anode fractions (2.26 wt%) to contain significantly more F than the cathode fraction (0.46 wt%), hence leading to the 5% Li leaching efficiency difference between cathode and black mass fractions under most conditions tested. Overall, these results demonstrate that sucrose-assisted reductive roasting, followed by selective water leaching, provides a rapid and effective route for high-efficiency lithium recovery from NMC- and NCA-based battery materials. 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

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

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

In this work, iron–phosphorus-based composite biochar (FPBC) was prepared by modification with the leachate of spent LiFePO₄ batteries. The effects of solution pH, dosage, adsorption time, initial concentration, and temperature on the adsorption performance of FPBC were investigated by batch adsorption experiments with Pb(II) and Sb(III) as the target pollutants, and the adsorption mechanism was explored using SEM, BET, XPS, FTIR and XRD characterization. The results indicated that as the initial pH of the solution increased, the removal efficiency of FPBC for Pb(II) gradually increased, while the removal efficiency for Sb(III) remained largely unchanged. The removal of Pb(II) and Sb(III) by FPBC fitted the pseudo-second-order kinetic model and the three-step intraparticle diffusion model, indicating that their removal was primarily controlled by chemical adsorption. Isothermal adsorption studies revealed that FPBC adsorption of Pb(II) better fitted the Langmuir and D-R models, suggesting a monolayer-dominated adsorption process. In contrast, adsorption of Sb(III) fitted the Langmuir, Freundlich, and Temkin models, suggesting a combination of monolayer and multilayer adsorption characteristics. The maximum adsorption capacities of FPBC for Pb(II) and Sb(III) were 312.54 mg·g⁻¹ and 219.20 mg·g⁻¹ at 30 °C, which were approximately 12.85 and 3.37 times those of commercial corn stalk biochar (BC). Thermodynamic analysis confirmed that the removal of Pb(II) and Sb(III) by FPBC was a spontaneous and endothermic process. In addition, FPBC demonstrated strong selective adsorption of Pb(II) in the binary co-adsorption system of Pb(II) and Sb(III). Mechanism studies indicated that Pb(II) removal primarily occurred through co-precipitation, complexation, ion exchange, and electrostatic adsorption, while Sb(III) was mainly adsorbed by FPBC via redox reactions and complexation. Therefore, this work not only provides a low-cost, high-performance adsorbent for the remediation of water contaminated with Pb(II) and Sb(III), but also opens up new avenues for the resource recovery of the leachate of spent LiFePO₄ batteries. 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

The rapid expansion of lithium-ion battery (LIB) applications and the imminent surge in end-of-life batteries have intensified the demand for efficient, scalable recycling technologies. Physical separation of cathode and anode materials is a crucial pretreatment step that enables high-value metal recovery and direct material regeneration. This review critically examines recent advances in three major physical separation technologies—magnetic separation, gravity separation, and flotation—for processing spent LIB electrodes. Rather than offering a descriptive summary, the review systematically analyzes separation mechanisms, key controlling parameters, and pretreatment strategies across representative cathode chemistries, including LiFePO₄ (LFP), LiCoO₂ (LCO), and Ni–Co–Mn (NCM) systems. Particular emphasis is placed on emerging flotation-enhancement strategies, such as nanobubble-assisted and ultrasonic-enhanced flotation, and their underlying mechanistic roles in improving selectivity and recovery. Comparative evaluation indicates that magnetic separation has reached industrial maturity for LFP–graphite systems but remains chemistry-specific. Gravity separation is effective for coarse particles and centrifugal-assisted graphite recovery yet shows limited selectivity for fine particles. Flotation has become the dominant research focus for complex, fine-particle separations due to its tunable surface chemistry. Despite significant laboratory progress, challenges remain, including incomplete binder removal, limited understanding of electrode surface reconstruction during pretreatment, fine-particle entrainment, and the gap between bench-scale research and industrial implementation. Future research priorities include green reagent development, intelligent separation control, and integration with direct regeneration routes to advance closed-loop LIB recycling towards sustainable development. Full article

The electrochemical reuse of spent graphite from the negative electrodes of lithium-ion batteries is influenced by regeneration-induced changes in near-surface chemical and defect states. These states govern solid electrolyte interphase (SEI) re-formation, particularly when bulk contaminants are suppressed. Acidic malic-acid leaching and ethylenediaminetetraacetic acid chelation under alkaline conditions (pH 8.7) were compared under similar operating parameters to isolate the role of the leaching environment. This was followed by heat treatment at 1200 °C to decouple chemical cleaning from structural restoration. Both methods reduced the total impurities from 217.85 ppm to ~1.8 ppm, approaching that of commercial graphite. Despite the comparable bulk purity, depth-resolved X-ray photoelectron spectroscopy after formation cycling revealed distinct outermost surface states relevant to SEI re-formation: acidic processing yielded a more oxygenated carbon signature and higher LiOH fraction at the outermost surface (~16%), whereas alkaline chelation produced a more graphitic, carbonate-dominated surface with lower LiOH (~7%). Electrochemical and impedance measurements were consistent with these differences, suggesting that after the bulk impurities were minimized, resistance development was largely governed by the leaching-conditioned near-surface state, which biased the SEI composition. The comparison under matched conditions linked the regeneration environment to SEI-relevant surface speciation and provided a mechanistic basis for selecting regeneration routes to reuse spent graphite as a negative-electrode active material. Full article

The sustainable recycling of valuable metals from spent lithium-ion batteries (LIBs) is imperative for closing the resource loop. This study presents an integrated strategy for the stepwise recovery of metals from spent cathode sheets by in situ thermal reduction and selective leaching. The in situ thermal reduction converted the cathode material into a mixture of Li₂CO₃, LiAlO₂, Ni, Co, NiO, and CoO while simultaneously liberating the cathode materials from the Al current collector through binder removal. A combined process of water leaching, wet sieving, and filtration successfully achieved the separation and enrichment of Li-rich aqueous solution (near 60% Li), Al-rich coarse fraction (over 87% Al), and fine powder enriched with transition metals (over 90% of Ni, Co, and Mn). The pyrolysis gases released from binder decomposition were the key driver for forming Li₂CO₃, whereas the concurrent generation of LiF and LiAlO₂ limited direct water leaching efficiency. An alkaline leaching step was therefore introduced to co-extract Al and the associated Li from LiAlO₂, followed by an acid leaching step that recovered over 96% of the transition metals from the treated residue without external reductants. Complete mass balance analysis shows that the integrated process achieved overall recoveries of 91.86% for Li, 91.93% for Ni, 92.23% for Co, and 92.61% for Mn from all the combined leachate streams. Consequently, this work provides a reagent-saving, stepwise hydrometallurgical process for the comprehensive recycling of valuable metals from spent LIBs. Full article

This article focuses on the synthesis and characterization of an amorphous carbon derived from spent coffee grounds converted into a porous amorphous carbon (Cp₁) by carbonization up to 900 °C and subsequently combined with aluminum via mechanochemical treatment to obtain the composite Al@Cp₁. Powder X-Ray diffraction, Raman spectroscopy, and X-Ray photoelectron spectroscopy indicate turbostratic carbon domains (ID/IG ≈ 1.04) and an Al–O/Al–OH surface layer (Al₂O₃/Al(OH)₃) with a minor metallic Al contribution. Electrochemical performance in Li half-cells was evaluated by cyclic voltammetry, galvanostatic cycling, rate capability tests, and electrochemical impedance spectroscopy. At 0.02 A g⁻¹, Al@Cp₁ delivers 212.1 mAh g⁻¹, compared with 83.0 mAh g⁻¹ for Cp₁, with an initial coulombic efficiency of ~44%. Across increasing current densities, Al@Cp₁ retains higher reversible capacities than Cp₁ and shows stable cycling over extended tests (>160 cycles). Impedance analysis indicates a reduced interfacial/charge transfer resistance after electrode conditioning, consistent with interfacial stabilization by the Al-containing surface layer. These results demonstrate a simple, scalable route to upgrade coffee waste carbon into a higher-performance lithium-ion battery anode through mechanochemical interfacial engineering. Full article

With the increasing deployment of lithium iron phosphate (LiFePO₄) batteries in electric vehicles and energy storage systems, the recycling of these materials has become an urgent necessity. Specifically, the reclamation of lithium iron phosphate cathode materials presents a significant challenge in the recycling process. In this study, we proposed an efficient low-temperature hydrothermal direct regeneration method aimed at repairing lithium vacancies and Fe/Li inversion defects in spent lithium iron phosphate resulting from prolonged cycling. By using this method, spent lithium iron phosphate was successfully regenerated through a hydrothermal process conducted at 80 °C for 6 h, utilizing hydrazine hydrate (N₂H₄·H₂O) as a potent reducing agent and lithium hydroxide (LiOH·H₂O) as the lithium source. X-ray diffraction (XRD) analysis, coupled with Rietveld refinement, revealed a substantial reduction in the concentration of Fe/Li anti-site defects in the spent material, decreasing from 8.8% to 3.3% following regeneration. Consequently, the electrochemical performance was significantly restored. The initial specific discharge capacity increased from 118.0 mAh·g⁻¹ to 150.3 mAh·g⁻¹, and the capacity retention after 100 cycles (at 1 C) improved from 67.5% to 90.7%. The hydrothermal regeneration process introduced in this work effectively repairs the material structure and restores the active valence state of iron, thereby significantly enhancing lithium-ion diffusion and electron transport capabilities. This approach constitutes a technically viable solution for the efficient, environmentally friendly, and cost-effective recycling of spent lithium-ion batteries. Full article