Search Results (108)

The traditional recycling process of spent lithium-ion battery(LIB) with high Mn content faces the defects of high cost of neutralization and precipitation, poor economics of Mn extraction, and serious Li loss. Therefore, this paper introduces a comprehensive hydrometallurgical method for extracting valuable metals from high-Mn spent LIB. Particularly, directional precipitation of Mn was achieved by utilizing its redox properties, and shot-process extraction and enrichment of Li was realized by using the extractant HBL121. In a sulfuric acid system, control of the oxidant dosage to 0.8% resulted in high leaching efficiencies for Li, Ni, Co, and Mn, with values of 96.58%, 96.13%, 95.22%, and 94.24%, respectively, under optimal conditions which were C(H₂SO₄) of 3.5 mol/L, V(H₂O₂) of 0.8% (v/v), L/S of 10:1, temperature of 60 °C, and time of 60 min. Subsequently, the addition of KMnO₄ dosage (K_p/K_t) in a ratio of 1:1 resulted in the precipitation of 98.47% of Mn as MnO₂, with Ni and Li precipitation efficiencies of 0.2% and 0.1%, respectively. Cascade extraction of Ni and Co was reached by using Cyanex272 extractant from the solution after Mn precipitation. At an organic-to-aqueous phase ratio (O/A) of 1:5, the Co extraction efficiency reached 98.68%, whereas the loss efficiency of Ni was 5.53%, and Li was less than 0.1%. Adjusting the O/A to 1:1 increased the Ni extraction efficiency to 89.99% and Li loss to 8.95%. Finally, the HBL121 extractant was utilized to extract Li from the Li-rich solution, achieving 95.08% extraction efficiency. The Li was stripped with 2 mol/L H₂SO₄ from the load organic phase, realizing a Li concentration of 11.44 g/L. Thus, this process facilitates the comprehensive and efficient recovery of valuable metals such as Li, Ni, Co, and Mn from spent high-Mn LIB. Full article

With the advancement of global carbon reduction efforts and the rapid development of battery industries, the scale of spent lithium-ion batteries (LIBs) has increased dramatically. Extracting lithium from spent LIBs to synthesize Li₄SiO₄ sorbents not only addresses the challenge of battery recycling but also reduces the production cost of CO₂ sorbents, making it a research hotspot. However, the CO₂ adsorption behavior of these sorbents under the effect of impurities may differ from the traditional Li₄SiO₄, and there is a lack of systematic research on the adsorption kinetics. To address this issue, two Li₄SiO₄ sorbents are prepared from spent ternary LIBs, and their adsorption kinetics are comprehensively investigated using classical kinetic models. Results show that the reaction order of LSO and Na-LSO is 0.41 and 1.63, respectively, with activation energies of 72.93 kJ/mol and 99.23 kJ/mol in the initial kinetic-controlled stage, and 323.15 kJ/mol and 176.79 kJ/mol in the following diffusion-controlled stage. In the cyclic processes, loss-in-capacity is observed on LSO due to the simultaneous decrease in rate constants in both the kinetic and diffusion-controlled stages, while Na-LSO could almost maintain its capacity by having a much bigger rate constant during the kinetic-controlled stage. This study reveals the adsorption kinetics of Li₄SiO₄ prepared from spent LIBs and could provide theoretical support for the targeted design of efficient and low-cost CO₂ sorbents. Full article

The literature clearly indicates that both academia and industry are strongly committed to developing comprehensive processes for spent Li-ion battery (LIB) recycling. In this regard, the current study presents an original contribution by providing a quantitative assessment of a large-scale recycling plant designed for the treatment of completely spent LIBs. In addition to a concept of the basic process, this assessment also considers a case study of a thermal integration and CO₂ capture subsystem. Process flow modeling software was used to evaluate the contribution of all process steps and equipment to overall energy consumption and to mass balance the data required for the technical assessment of the large-scale recycling plant. To underline the advantages and identify the optimal novel process concept, several key performance indicators were determined, such as recovery efficiency, specific energy/material consumption, and specific CO₂ emissions. In addition, the economic potential of the recycling plants was evaluated for the defined case studies based on capital and O&M costs. The results indicate that, even with CO₂ capture applied, the thermally integrated process with the combustion of hydrogen produced in the recycling plant remains the most promising large-scale configuration for spent LIB recycling. Full article

The conventional spent lithium-ion batteries (LIBs) recycling method suffers from complex processes and excessive chemical consumption. Hence, this study proposes an electrochemical strategy for achieving reductant-free leaching of high-valence transition metals and efficient separation of valuable components from spent cathode sheets (CSs). An innovatively designed sandwich-structured electrochemical reactor achieved efficient reductive dissolution of cathode materials (CMs) while maintaining the structural integrity of aluminum (Al) foils in a dilute sulfuric acid system. Optimized current enabled leaching efficiencies exceeding 93% for lithium (Li), cobalt (Co), manganese (Mn), and nickel (Ni), with 88% metallic Al foil recovery via cathodic protection. Multi-scale characterization systematically elucidated metal valence evolution and interfacial reaction mechanisms, validating the technology’s tripartite innovation: simultaneous high metal extraction efficiency, high value-added Al foil recovery, and organic removal through single-step electrochemical treatment. The process synergized the dissolution of CM particles and hydrogen bubble-induced physical liberation to achieve clean separation of polyvinylidene difluoride (PVDF) and carbon black (CB) layers from Al foil substrates. This method eliminates crushing pretreatment, high-temperature reduction, and any other reductant consumption, establishing an environmentally friendly and efficient method of comprehensive recycling of battery materials. Full article

Pyrometallurgical recycling of lithium-ion batteries presents distinct advantages including streamlined processing, simplified pretreatment requirements, and high throughput capacity. However, its industrial implementation faces challenges associated with high energy demands and lithium loss into slag phases. This investigation develops an integrated reduction smelting–chloridizing volatilization process for the comprehensive recovery of strategic metals (Li, Mn, Cu, Co, Ni) from spent ternary lithium-ion batteries; calcium chloride was selected as the chlorinating agent for this purpose. Thermodynamic analysis was performed to understand the phase evolution during reduction smelting and to design an appropriate slag composition. Preliminary experiments compared carbon and aluminum powder as reducing agents to identify optimal operational parameters: a smelting temperature of 1450 °C, 2.5 times theoretical CaCl₂ dosage, and duration of 120 min. The process achieved effective element partitioning with lithium and manganese volatilizing as chloride species, while transition metals (Cu, Ni, Co) were concentrated into an alloy phase. Process validation in an induction furnace with N₂-O₂ top blowing demonstrated enhanced recovery efficiency through optimized oxygen supplementation (four times the theoretical oxygen requirement). The recovery rates of Li, Mn, Cu, Co, and Ni reached 94.1%, 93.5%, 97.6%, 94.4%, and 96.4%, respectively. This synergistic approach establishes an energy-efficient pathway for simultaneous multi-metal recovery, demonstrating industrial viability for large-scale lithium-ion battery recycling through minimized processing steps and maximized resource utilization. Full article

In the wake of global energy transition and the “dual-carbon” goal, the rapid growth of electric vehicles has posed challenges for large-scale lithium-ion battery decommissioning. Retired batteries exhibit dual attributes of strategic resources (cobalt/lithium concentrations several times higher than natural ores) and environmental risks (heavy metal pollution, electrolyte toxicity). This paper systematically reviews pyrometallurgical and hydrometallurgical recovery technologies, identifying bottlenecks: high energy/lithium loss in pyrometallurgy, and corrosion/cost/solvent regeneration issues in hydrometallurgy. To address these, an integrated recycling process is proposed: low-temperature physical separation (liquid nitrogen embrittlement grinding + froth flotation) for cathode–anode separation, mild roasting to convert lithium into water-soluble compounds for efficient metal oxide separation, stepwise alkaline precipitation for high-purity lithium salts, and co-precipitation synthesis of spherical hydroxide precursors followed by segmented sintering to regenerate LiNi_1/3Co_1/3Mn_1/3O₂ cathodes with morphology/electrochemical performance comparable to virgin materials. This low-temperature, precision-controlled methodology effectively addresses the energy-intensive, pollutive, and inefficient limitations inherent in conventional recycling processes. By offering an engineered solution for sustainable large-scale recycling and high-value regeneration of spent ternary lithium ion batteries (LIBs), this approach proves pivotal in advancing circular economy development within the renewable energy sector. Full article

Next-generation recycling technologies must be urgently innovated to tackle huge volumes of spent batteries, photovoltaic panels or printed circuit boards (WPCBs). Current e-waste recycling industrial technology is dominated by traditional recycling technologies. Herein, ionic liquids (ILs), deep eutectic solvents (DESs) and promising oxidizing additives that can overcome some traditional recycling methods of metal ions from e-waste, used in our works from last year, are presented. The unique chemical environments of ILs and DESs, with the application of low-temperature extraction procedures, are important environmental aspects known as “Green Methods”. A closed-loop system for recycling zinc and manganese from the “black mass” (BM) of waste, Zn-MnO₂ batteries, is presented. The leaching process achieves a high efficiency and distribution ratio using the composition of two solvents (Cyanex 272 + diethyl phosphite (DPh)) for Zn(II) extraction. High extraction efficiency with 100% zinc and manganese recovery is also achieved using DESs (cholinum chloride/lactic acid, 1:2, DES 1, and cholinum chloride/malonic acid, 1:1, DES 2). New, greener recycling approaches to metal extraction from the BM of spent Li-ion batteries are presented with ILs ([N_8,8,8,1][Cl], (Aliquat 336), [P_6,6,6,14][Cl], [P_6,6,6,14][SCN] and [Benzet][TCM]) eight DESs, Cyanex 272 and D2EHPA. A high extraction efficiency of Li(I) (41–92 wt%) and Ni(II) (37–52 wt%) using (Cyanex 272 + DPh) is obtained. The recovery of Ni(II) and Cd(II) from the BM of spent Ni-Cd batteries is also demonstrated. The extraction efficiency of DES 1 and DES 2, contrary to ILs ([P_6,6,6,14][Cl] and [P_6,6,6,14][SCN]), is at the level of 30 wt% for Ni(II) and 100 wt% for Cd(II). In this mini-review, the option to use ILs, DESs and Cyanex 272 for the recovery of valuable metals from end-of-life WPCBs is presented. Next-generation recycling technologies, in contrast to the extraction of metals from acidic leachate preceded by thermal pre-treatment or from solid material only after thermal pre-treatment, have been developed with ILs and DESs using the ABS method, as well as Cyanex 272 (only after the thermal pre-treatment of WPCBs), with a process efficiency of 60–100 wt%. In this process, four new ILs are used: didecyldimethylammonium propionate, [N_10,10,1,1][C₂H₅COO], didecylmethylammonium hydrogen sulphate, [N_10,10,1,H][HSO₄], didecyldimethylammonium dihydrogen phosphate, [N_10,10,1,1][H₂PO₄], and tetrabutylphosphonium dihydrogen phosphate, [P_4,4,4,4][H₂PO₄]. The extraction of Cu(II), Ag(I) and other metals such as Al(III), Fe(II) and Zn(II) from solid WPCBs is demonstrated. Various additives are used during the extraction processes. The Analyst 800 atomic absorption spectrometer (FAAS) is used for the determination of metal content in the solid BM. The ICP-OES method is used for metal analysis. The obtained results describe the possible application of ILs and DESs as environmental media for upcycling spent electronic wastes. Full article

The rapid growth of lithium iron phosphate (LiFePO₄, LFP)-based lithium-ion batteries in energy storage raises urgent challenges for resource recovery and environmental protection. In this study, we propose a novel method for rapid and selective lithium extraction and the resynthesis of cathodes from spent LFP batteries, aiming to achieve an economically feasible and efficient recycling process. In this process, a selective leaching H₂SO₄-H₂O₂ system is employed to rapidly and selectively extract lithium, achieving a leaching efficiency of 98.72% within just 10 min. Through an exploration of the precipitation conditions of the lithium-containing solution, high-purity Li₂CO₃ is successfully obtained. The recovered FePO₄ and Li₂CO₃ are then used to resynthesize LFP cathode materials through a carbon-thermal reduction method. A preliminary economic analysis reveals that the disposal cost of spent LFP batteries is approximately USD 2.63 per kilogram, while the value of regenerated LFP reaches USD 4.46, highlighting the economic advantages of this process. Furthermore, with an acid-to-lithium molar ratio of only 0.57—just slightly above the stoichiometric 0.5—the process requires minimal acid usage, offering clear environmental benefits. Overall, this work presents a green, efficient, and economically viable strategy for recycling spent LFP batteries, showcasing strong potential for industrial application and contributing significantly to the development of a circular lithium battery economy. Full article

The increasing demand for lithium-ion batteries (LIBs) and their limited lifespan emphasize the urgent need for sustainable recycling strategies. This study investigates the application of tetrabutylphosphonium-based ionic liquids (ILs) as alternative leaching agents for recovering critical metals, Li(I), Co(II), Ni(II), and Mn(II), from spent NMC cathode materials. Initial screening experiments evaluated the leaching efficiencies of nine tetrabutylphosphonium-based ILs for Co(II), Ni(II), Mn(II), and Li(I), revealing distinct metal dissolution behaviors. Three ILs containing HSO₄⁻, EDTA²⁻, and DTPA³⁻ anions exhibited the highest leaching performance and were selected for further optimization. Key leaching parameters, including IL and acid concentrations, temperature, time, and solid-to-liquid ratio, were systematically adjusted, achieving leaching efficiencies exceeding 90%. Among the tested systems, [TBP][HSO₄] enabled near-complete metal dissolution (~100%) even at room temperature. Furthermore, an aqueous biphasic system (ABS) was investigated utilizing [TBP][HSO₄] in combination with ammonium sulfate, enabling the complete extraction of all metals into the salt-rich phase while leaving the IL phase metal-free and potentially suitable for reuse, indicating the feasibility of integrating leaching and extraction into a continuous, interconnected process. This approach represents a promising step forward in LIB recycling, highlighting the potential for sustainable and efficient integration of leaching and extraction within established hydrometallurgical frameworks. Full article

The rising demand for lithium-ion batteries (LIBs), driven by the growing consumption of electronic devices and the expansion of electric vehicles, is leading to a concerning depletion of primary metal resources and a significant accumulation of electronic waste. This urgent challenge highlights the need for sustainable recovery methods to extract valuable metals from spent LIBs, aligning with circular economy principles. In this study, the preparation of spent batteries for the bioleaching process was achieved with minimal manipulation. This included a preliminary discharge to ensure safety in subsequent processes and a brief crushing to facilitate the access of leaching agents to valuable metals. Unlike most studies that grind batteries to obtain powders between 70 and 200 microns, our approach works with particles sized around 5 mm. Additionally, our preparation process avoids any thermal or chemical treatments. This straightforward pre-treatment process marks a significant advancement by reducing the complexity and cost of processing. A systematic study was conducted on various fractions of the large particle sizes, using Fe (III) produced through bio-oxidation by A. ferrooxidans and biogenically obtained H2SO4 from A. thiooxidans. The highest metal extraction rates were achieved using the unsorted fraction, directly obtained from the black mass after the grinding process, without additional particle separation. When treated with bio-oxidized Fe (III), this fraction achieved a 95% recovery of Cu, Ni, and Al within 20 min, and over 90% recovery of Co, Mn, and Li within approximately 30 min. These recovery rates are attributed to the combined reducing power of Al and Cu already present in the black mass and the Fe (II) generated during the oxidation reactions of metallic Cu and Al. These elements actively facilitate the reduction of transition metal oxides into their more soluble, lower-valence states, enhancing the overall metal solubilization process. The extraction was carried out at room temperature in an acidic medium with a pH no lower than 1.5. These results demonstrate significant potential for efficient metal recovery from spent batteries with minimal pre-treatment, minimizing environmental impact. Additionally, the simplified residue preparation process can be easily integrated into existing waste management facilities without the need for additional equipment. Full article

Recycling the positive electrode materials of spent Li-ion batteries is critical for environmental sustainability and resource security. To facilitate the attainment of the goal, this study presents a novel approach for recovering valuable metals from positive electrode materials of spent lithium-ion batteries (LIBs) in an H-shaped cell containing aqueous NaCl electrolyte. The process employs hydrochloric acid that could be derived from the chlorine cycle as the leaching agent. The electrolytic device is engineered to generate a high pH gradient, thereby enhancing the leaching of metal elements and eliminating the requirement for external acid or base addition. This green recycling approach adheres to the principles of a circular economy and provides an environmentally friendly solution for sustainable battery material recycling. Full article

LiFePO₄ (LFP) batteries are among the earliest commercialized and most discarded lithium-ion batteries. Although existing recovery technologies focus on the conversion of LiFePO₄ to Li₂CO₃, challenges associated with achieving near-full recovery and high-value products remain. This study proposes a strategy for the conversion of spent LiFePO₄ to LiF by mechanical chlorination coupled with a fluorination reaction. The optimum conditions were determined to be a ball-to-powder ratio (BPR) = 15, NH₄Cl:LFP = 3, H₂O₂ = 2.0 mL, rotation speed = 600 rpm, and grinding time = 12 h. Results showed that 97.14% Li was converted into LiCl by H₂O₂–NH₄Cl mechanical chlorination. When chlorinated intermediates were immersed in water, FePO₄ could be harvested, and 96.79% Li could be recovered as LiF with a purity of 99.50% after adding NH₄F. When Cl-functionalized renewable resin was used to exchange 99.89% F⁻, 0.63 g NH₄Cl per litre of LiF conversion residual liquid was derived. The favourable results were attributed to the ¹O₂ generated by H₂O₂, which had a strong electron affinity to break Li–O bonds and provided superior conditions for the combination of Li and Cl. During fluorination, the formation of LiF reduced the ion concentration, and the entropy decreased, contributing to the spontaneous reaction. Therefore, the proposed method paves the way for near-full recovery and high-value products of spent LiFePO₄. Full article

This study explores the use of a deep eutectic solvent (DES) composed of choline chloride and pyrogallol (1:1 molar ratio) for the recovery of lithium, cobalt, and nickel from spent lithium-ion battery cathodes based on LiNi_0.33Co_0.33Mn_0.33O₂ (NMC111). The DES exhibits moderate viscosity, intrinsic redox activity, and strong complexation ability, enabling efficient metal dissolution under mild conditions. The effects of both temperature (50–80 °C) and time (up to 12 h) on leaching efficiency were systematically investigated. Optimal leaching parameters—80 °C, 8 h, and a liquid-to-solid ratio of 50—yielded extraction efficiencies of 92% for Li, 85% for Co, and 88% for Ni. Kinetic modeling indicated pseudo-first-order behavior with activation energies of 26.6, 22.1, and 25.2 kJ/mol for Li, Co, and Ni, respectively. Mechanistic analysis confirmed the dual role of pyrogallol as both reducing agent (facilitating Co³⁺ to Co²⁺ conversion) and chelating ligand. Full article

This study investigates advanced strategies for r regenerating and recycling lithium iron phosphate (LiFePO₄, LFP) materials from spent lithium-ion batteries. Recovery techniques are categorized into direct regeneration, which restores positive electrode materials with high electrochemical performance, and recycling, which produces intermediate compounds such as lithium carbonate and iron phosphate. Additionally, resynthesis methods are explored to convert recovered precursors into high-quality LFP materials, ensuring their reuse in battery production. Innovative approaches, including carbothermic reduction, doping, and hydrothermal resynthesis, are highlighted for their ability to enhance material properties, improve energy efficiency, and maintain the olivine structure of LFP. Key advancements include the use of eco-friendly reagents, automation, and optimization strategies to reduce environmental impacts and costs. Regenerated and resynthesized positive electrodes demonstrated performance metrics comparable to or exceeding commercial LFP, showcasing their potential for widespread application. This work underscores the importance of closed-loop recycling systems and identifies pathways for scaling, improving economic feasibility, and minimizing the ecological footprint of the lithium-ion battery lifecycle. Full article

Deep eutectic solvents are widely employed in the recycling and reuse of spent lithium-ion battery cathode materials because of their non-toxicity, low cost, and recyclability. Although DESs have a high recovery rate for metals and are more environmentally friendly, they typically require a longer time or higher temperatures. High temperature and pressure considerably improve leaching efficiency in traditional aqueous systems; this study investigates whether the same is true in DES systems. The physicochemical properties of a DES composed of choline chloride (ChCl) and malonic acid (MA) (1:1) were measured before and after high-temperature and high-pressure treatments, along with their effects on the leaching efficiency of cathode materials for spent lithium-ion batteries (LIBs). The results show that after treatment, the 632.03 cm⁻¹ twisted vibration peak of C-O was red-shifted to 603 cm⁻¹ and the alkyl chain of the DES was lengthened, whereas the 1150.52 cm⁻¹ C-O peak was blue-shifted to 1219 cm⁻¹ and the hydrogen-bonding effect was weakened. At long reaction times, crystals appeared inside the DES. Over time, the crystals increased in size and became less dense, and the color of the material changed from clear to blue to green. After pressurization treatment, the conductivity of the DES increased considerably over its value at atmospheric pressure. The leaching efficiency of Li, Co, Ni, and Mn were 53.20, 47.24, 26.27, and 48.57%, respectively, at 3 h of leaching at atmospheric pressure. The leaching efficiency increased to 78.20, 79.74, 69.76, and 81.80%, respectively, after being pressurized at 3.3 MPa. On this basis, the reaction time was extended to 6 h, and the leaching efficiency of Li, Co, Ni, and Mn were 96.41, 97.62, 98.13, and 97.34%, respectively, trending towards complete leaching. The leaching efficiency of spent LIB cathode materials in DESs was considerably improved under pressurized conditions, providing an efficient method for recovering spent LIB cathode materials using DESs. Full article