Spent Lithium Ion Batteries Research Articles

Scalable Direct Recycling of Cathode Black Mass from Spent Lithium-Ion Batteries

End of life (EoL) lithium-ion batteries (LIBs) are piling up at an intimidating rate which is alarming for the environmental health and balance. The rise of renewable technologies such as electric vehicles (EV) needs to be balanced with LIB recycling to reduce the carbon footprint, ensure sustainable development, and create a circular supply chain. LiNixCoyMnzO2 (NCM) cathode materials being a dominant chemistry in high energy LIBs makes a huge portion of this waste accumulation. Direct recycling is one of the most promising ways to turn this waste to wealth but has been limited to lab-scale due to lack of robustness, namely the tedious pretreatment required which involve toxic organic solvents. Herein, we have demonstrated a process which integrates the pretreatment and relithiation of the cathode black. Cathode material from EoL EV batteries is treated in 100g per batch operation and the regenerated cathode active material demonstrates 100% electrochemical performance recovery, with 91% yield rate, and showed promise to further scale up. No use of toxic organic solvents makes our process unique with minimal environmental impact. This process has the advantages of integration, scalability, and universality, which clears the barricade for the direct recycling to move from lab to industry scale with considerable profitability.

Removal of fluoride from the mixed Ni-Co-Mn sulfate leach solution of spent lithium ion batteries using polyaluminum sulfate

The mechanism and application of defluorination in a simulated leaching solution of spent lithium-ion batteries (LIBs) using poly‑aluminum sulfate (PAS) were studied. The experimental results indicated that reaction parameters such as the molar ratio of Al to F, pH of the solution, reaction temperature, initial concentration of fluorine, and concentration of lithium and nickel, significantly affected the reaction efficiency. Under the optimum reaction conditions, the percentage of defluorination was 95.5 (wt%). During the defluorination reaction, Al3+, Al(OH)3 reacted with F−, HF to generate AlF3 and AlF(OH)2. The crystallinity of AlF3, AlF(OH)2, and Al(OH)3 and the chemical stability of the precipitates improved with the increase in temperature and pH. The Li+ concentration in the solution increased the defluorination efficiency by forming LiAlF4. At the same time, high concentrations of NiSO4 inhibited the defluorination effect and were lost in association with the solids, NiSO4·6H2O and Ni(OH)2. According to the study of reaction kinetics, the rate equation of the aluminum‑fluorine reaction was -d[F]/dt = 0.0384exp(−8.59/RT) [F0]1.11[Al]0.31. The activation energy of the precipitation reaction was 8.59 kJ/mol, and the reaction rate was relatively high. In the actual defluorination process of the acid-leaching solution of waste battery powder with Ni-Mn-Co chemistry, the F− concentration reduced from 1205 mg/L to 48 mg/L and the loss of valuable metals was <6%, and the Ni, Co, and Mn in the precipitates were predominantly sulfates and hydroxides.

A Comparative Study of Malonic and l-Glutamic Acids for Metal Leaching from Spent Lithium-Ion Batteries: Kinetic and Optimization Analysis

In this research, two different hydrometallurgical processes were introduced for recycling the cathodes of lithium-ion batteries (LIBs) from spent LIBs. The cathode materials were leached by malonic acid (MOA), as a leaching agent, and ascorbic acid (AA), as a reducing agent, in the first process, and by l-Glutamic acid (l-Glu), as a leaching agent, and AA, as a reducing agent, in the second process. The results of the tests showed that, with a similar solid-to-liquid (S/L) ratio of 10 g/L and a recovery time of 2 h for both processes, when using MOA of 0.25 M and AA of 0.03 M at 88 °C, 100% lithium (Li), 80% cobalt (Co), 99% nickel (Ni), and 98% manganese (Mn) were extracted, and when using l-Glu of 0.39 M and AA of 0.04 M at 90 °C, 100% Li, 79% Co, 91% Ni, and 92% Mn were extracted. The kinetics of the leaching process for the two systems were well justified by the Avrami equation, which was diffusion-controlled in the MOA + AA system, with the apparent activation energy of 3.23, 14.72, 7.77, and 7.36 kJ/mol for Mn, Ni, Co, and Li, respectively. The l-Glu + AA involved chemical-diffusion kinetic control, with the apparent activation energy for Mn, Ni, Co, and Li of 9.95, 29.42, 20.15, and 16.08 kJ/mol, respectively. Various characterization techniques were used to explain the observed synergistic effect in the l-Glu + AA system, which resulted in reduced acid consumption and enhanced recovery compared to the case of MOA + AA. This occurred because l-Glu is not able to reduce and recover metals without a reductant, while MOA has reductant properties.

Application of vacuum membrane distillation process for lithium recovery in spent lithium ion batteries (LIBs) recycling process

The feasibility of using vacuum membrane distillation (VMD) for lithium recovery by concentrating the discharged leachate from spent lithium ion batteries (LIBs) recycling process was evaluated. The performance of VMD was compared with that of direct contact membrane distillation (DCMD) in terms of water flux, concentration rate, membrane wetting, and economic feasibility. VMD achieved a higher volume concentration factor (VCF) of 45 compared to the VCF of 25 achieved by DCMD in the LiCl feed solution. In the Li2SO4 feed solution, VMD and DCMD were concentrated to VCF15 and VCF 17, respectively, before wetting occurred. The stability of the MD process was verified using feed solutions containing nickel and manganese, which are cathode materials that can cause scaling even at low concentrations. Low concentrations of nickel and manganese did not significantly affect the maximum VCF or wetting; however, high concentrations of nickel and manganese affected the stability of the MD process. VMD exhibited a higher flux and 32 % lower thermal energy consumption than DCMD. Furthermore, the expected cost of Li2CO3 production with VMD for leachate concentration was $8.31–10.65/kg. The VMD concentration process is a feasible option for recovering lithium from the discharged leachate from spent LIBs recycling process.

Recycling of Lithium Iron Phosphate Cathode Materials from Spent Lithium-Ion Batteries: A Mini-Review

Recycling of Lithium Iron Phosphate Cathode Materials from Spent Lithium-Ion Batteries: A Mini-Review

Hydrometallurgical treatment of spent lithium ion batteries using environmentally friendly leachant and extractant

Hydrometallurgical treatment of spent lithium ion batteries using environmentally friendly leachant and extractant

Development of Pd@MWCNT-Co3O4 Electrode Sensors Using Cobalt Recovered from Spent Lithium Ion Batteries

The rampant use of various types of energy storage devices for different applications poses a great threat to the environment as most of the materials after their usage are not recycled properly. Battery materials that are exposed to the environment without proper recycling or recovery protocol are of more concern. In the present work, the chemical components recovered from spent lithium batteries were processed through suitable methods and were utilized for the fabrication of electrode materials for sensor application. The present work demonstrates a highly sensitive and cost-effective method for fabricating disposable non-enzymatic glucose sensors based on Pd functionalized MWCNT-Co3O4 electrode using cobalt recovered from a spent Li-ion battery. The incorporation of palladium onto the multi-walled carbon nanotube (MWCNT) and further deposition of this composite onto the Co3O4 substrate greatly enhanced the glucose sensing characteristics. The sensing behavior of the Co3O4 electrode and Pd@MWCNT-Co3O4 electrode towards glucose electro-oxidation were compared using Cyclic Voltammetry (CV) and Chrono- amperometric (CA) techniques. A very low detection limit of 0.6 μM was obtained by the Pd@MWCNT-Co3O4 electrode towards glucose sensing. The sensor fabrication process was economical and possessed excellent stability, selectivity and good reproducibility.

Recycling Hazardous and Valuable Electrolyte in Spent Lithium-Ion Batteries: Urgency, Progress, Challenge, and Viable Approach.

Recycling spent lithium-ion batteries (LIBs) is becoming a hot global issue due to the huge amount of scrap, hazardous, and valuable materials associated with end-of-life LIBs. The electrolyte, accounting for 10-15 wt % of spent LIBs, is the most hazardous substance involved in recycling spent LIBs. Meanwhile, the valuable components, especially Li-based salts, make recycling economically beneficial. However, studies of electrolyte recycling still account for only a small fraction of the number of spent LIB recycling papers. On the other hand, many more studies about electrolyte recycling have been published in Chinese but are not well-known worldwide due to the limitations of language. To build a bridge between Chinese and Western academic achievements on electrolyte treatments, this Review first illustrates the urgency and importance of electrolyte recycling and analyzes the reason for its neglect. Then, we introduce the principles and processes of the electrolyte collection methods including mechanical processing, distillation and freezing, solvent extraction, and supercritical carbon dioxide. We also discuss electrolyte separation and regeneration with an emphasis on methods for recovering lithium salts. We discuss the advantages, disadvantages, and challenges of recycling processes. Moreover, we propose five viable approaches for industrialized applications to efficiently recycle electrolytes that combine different processing steps, ranging from mechanical processing with heat distillation to mechanochemistry and in situ catalysis, and to discharging and supercritical carbon dioxide extraction. We conclude with a discussion of future directions for electrolyte recycling. This Review will contribute to electrolyte recycling more efficiently, environmentally friendly, and economically.

A novel green deep eutectic solvent for one-step selective separation of valuable metals from spent lithium batteries: Bifunctional effect and mechanism

This study used a novel green bifunctional deep eutectic solvent (DES) containing ethylene glycol (EG) and tartaric acid (TA) for the efficient and selective recovery of cathode active materials (LiCoO2 and Li3.2Ni2.4Co1.0Mn1.4O8.3) used in lithium-ion batteries through one-step in-situ separation of Li and Co/Ni/Mn. The effects of leaching parameters on the recovery of Li and Co (ηLi and ηCo) from LiCoO2 are discussed, and the optimal reaction conditions are verified, for the first time, using a response surface method. The results demonstrate that under optimal conditions (120 °C, 12 h, EG to TA mole ratio (MEG:TA) of 5:1, and solid to liquid ratio (RS/L) of 20 g/L), the ηLi from LiCoO2 reached 98.34%, and Co was formed as a purple precipitate of cobalt tartrate (CoC4H4O6), which was transformed into a black powder of Co3O4 after calcination. Notably, the ηLi for DES 5 EG:1 TA was maintained at 80% after five cycles, indicating good cyclic stability. When the as-prepared DES was used to leach the spent active material Li3.2Ni2.4Co1.0Mn1.4O8.3, the in-situ selective separation of Li (ηLi = 98.86%) from other valuable elements such as Ni, Mn, and Co, was achieved, indicating the good selective leaching capacity and practical application potential of the DES.

Preferential Recovery of Lithium Based on Mineral Phase Reconstruction from Spent Lithium-Ion Batteries

Preferential Recovery of Lithium Based on Mineral Phase Reconstruction from Spent Lithium-Ion Batteries

Recovery of valuable metals from spent lithium-ion batteries using microbial agents for bioleaching: a review.

Spent lithium-ion batteries (LIBs) are increasingly generated due to their widespread use for various energy-related applications. Spent LIBs contain several valuable metals including cobalt (Co) and lithium (Li) whose supply cannot be sustained in the long-term in view of their increased demand. To avoid environmental pollution and recover valuable metals, recycling of spent LIBs is widely explored using different methods. Bioleaching (biohydrometallurgy), an environmentally benign process, is receiving increased attention in recent years since it utilizes suitable microorganisms for selective leaching of Co and Li from spent LIBs and is cost-effective. A comprehensive and critical analysis of recent studies on the performance of various microbial agents for the extraction of Co and Li from the solid matrix of spent LIBs would help for development of novel and practical strategies for effective extraction of precious metals from spent LIBs. Specifically, this review focuses on the current advancements in the application of microbial agents namely bacteria (e.g., Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans) and fungi (e.g., Aspergillus niger) for the recovery of Co and Li from spent LIBs. Both bacterial and fungal leaching are effective for metal dissolution from spent LIBs. Among the two valuable metals, the dissolution rate of Li is higher than Co. The key metabolites which drive the bacterial leaching include sulfuric acid, while citric acid, gluconic acid and oxalic acid are the dominant metabolites in fungal leaching. The bioleaching performance depends on both biotic (microbial agents) and abiotic factors (pH, pulp density, dissolved oxygen level and temperature). The major biochemical mechanisms which contribute to metal dissolution include acidolysis, redoxolysis and complexolysis. In most cases, the shrinking core model is suitable to describe the bioleaching kinetics. Biological-based methods (e.g., bioprecipitation) can be applied for metal recovery from the bioleaching solution. There are several potential operational challenges and knowledge gaps which should be addressed in future studies to scale-up the bioleaching process. Overall, this review is of importance from the perspective of development of highly efficient and sustainable bioleaching processes for optimum resource recovery of Co and Li from spent LIBs, and conservation of natural resources to achieve circular economy.

Sustainable and facile process for Li2CO3 and Mn2O3 recovery from spent LiMn2O4 batteries via selective sulfation with waste copperas

Spent lithium-ion batteries (LIBs) are essential secondary resource, containing valuable metal elements including lithium, cobalt, nickel, manganese. Recovering valuable metals from spent LIBs is significant for achieving environmental protection and alleviating resource shortages. Herein, a sustainable and facile process for Li2CO3 and Mn2O3 recovery from spent LiMn2O4 batteries (LMO) was proposed via sulfation roasting with waste copperas. The leaching efficiencies of Li and Mn reached approximately 100 % and 82 % under the optimal conditions, and the final recovered products were Li2CO3 and Mn2O3 with high purities. The sulfation reaction between LMO and copperas was the transition from solid-solid to gas-solid reaction. During the sulfation reaction, LMO spinel structure was decomposed into MnO2 and Mn2O3 crystal structures, and the anti-fluorite structure Li2O embedded in the spinel structure was released. The Li2O was easily to be sulfated, while MnO2 was partly reduced by Fe2+ to more stable spinel structure Mn2O3. Furthermore, FeSO4 decomposed into SO2 gas, which greatly improved the sulfation reaction through permeating into the unreacted core of LMO. As a result, the spinel structure of Mn2O3 was broken, and Mn was escaped to combine with SO42- to form MnSO4. This research provided an alternative technological route for green recovery of spent LMO batteries, demonstrating high potential for broad application.

A Novel and Sustainable Approach to Enhance the Li-Ion Storage Capability of Recycled Graphite Anode from Spent Lithium-Ion Batteries.

The ubiquitous manufacturing of lithium-ion batteries (LIBs) due to high consumer demand produces inevitable e-waste that imposes severe environmental and resource sustainability challenges. In this work, the charge storage capability and Li-ion kinetics of the recovered water-leached graphite (WG) anode from spent LIBs are enhanced by using an optimized amount of recycled graphene nanoflakes (GNFs) as an additive. The WG@GNF anode exhibits an initial discharge capacity of 400 mAh g-1 at 0.5C with 88.5% capacity retention over 300 cycles. Besides, it delivers an average discharge capacity of 320 mAh g-1 at 500 mA g-1 over 1000 cycles, which is 1.5-2 times higher than that of WG. The sharp increase in electrochemical performance is due to the synergistic effects of Li-ion intercalation into the graphite layers and Li-ion adsorption into the surface functionalities of GNF. Density functional theory calculations reveal the role of functionalization behind the superior voltage profile of WG@GNF. Besides, the unique morphology of spherical graphite particles trapping into graphene nanoflakes provides mechanical stability over long-term cycling. This work explains an efficient strategy to upgrade the electrochemical compatibility of recovered graphite anode from spent LIBs toward next-generation high-energy-density LIBs.

Recycling Spent Lithium-Ion Batteries Using Waste Benzene-Containing Plastics: Synergetic Thermal Reduction and Benzene Decomposition.

Spent lithium-ion batteries (LIBs) and benzene-containing polymers (BCPs) are two major pollutants that cause serious environmental burdens. Herein, spent LIBs and BCPs are copyrolyzed in a sealed reactor to generate Li2CO3, metals, and/or metal oxides without emitting toxic benzene-based gases. The use of a closed reactor allows the sufficient reduction reaction between the BCP-derived polycyclic aromatic hydrocarbon (PAH) gases and lithium transition metal oxides, achieving the Li recovery efficiencies of 98.3, 99.9, and 97.5% for LiCoO2, LiMn2O4, and LiNi0.6Co0.2Mn0.2O2, respectively. More importantly, the thermal decomposition of PAHs (e.g., phenol and benzene) is further catalyzed by the in situ generated Co, Ni, and MnO2 particles, which forms metal/carbon composites and thus prevent the emissions of toxic gases. Overall, the copyrolysis in a closed system paves a green way to synergistically recycle spent LIBs and handle waste BCPs.

Sodium sulfite roasting for preferential lithium extraction from cathode material of spent lithium-ion batteries

Spent lithium-ion batteries can be recycled to effectively re-utilize them. This can be conducive to secondary resource utilization as well as environmental protection. Here, it is suggested to roast the spent cathode materials with sodium sulfite to extract lithium more effectively. Under the ideal circumstances of a roasting temperature of 750 °C, the molar ratio of Na2SO3 to spent cathode material of 3.0, and a roasting period of 2 h, the leaching efficiency of Li reaches 94.06%. During the sodium sulfite roasting process, the spent LiNi0.6Co0.2Mn0.2O2 materials were transformed into LiNa(SO4), LiMnO2, NiO, LiMn2O4, Co9S8, and Ni, Co, and Mn. The LiNi0.6Co0.2Mn0.2O2 materials that were produced using the recovered Li2CO3 exhibit good electrochemical performance. The closed-loop process based on Sodium sulfite roasting is expected to be applied in the recycling industry of spent lithium-ion batteries.

Extraction of valuable metals from spent cathode materials by reductive roasting in methane atmosphere

Against the backdrop of the increasing amounts of lithium-ion batteries, it is reducing environmental pollution and relieving the stress on resource requirements through the sustainable recycling of spent lithium batteries. Here we targeted the reduction of the material phase by methane roasting and then achieved a step separation of Li, Ni, Co, and Mn by differentiation in water solubility and magnetic strength. The principal reduction factors were also optimized. The results show that the spent cathode powder converts mainly to water-soluble Li2CO3, that the leaching selectivity of lithium is 100%, and that other metals can be separated by wet magnetic separation under optimal conditions. A reasonable explanation of the phase conversion during the reduction process is provided, and a preliminary process evaluation is presented at the end. Notably, this work has the strengths of step recovery of elements, rapid processing, and zero chemical use, which has great potential for the industrial recycling field and provides a new idea for the development of green and efficient valuable metal recovery technologies for spent LIBs.

High performance lithium ion battery cathode based reduced holey graphene oxides from spent lithium ion batteries

The search of alternatives to the commercial electrodes is a key to the development of advanced lithium ion batteries (LIBs). Compared to extensive efforts and progress made on their anode applications for LIBs, the graphene and its derivatives as cathodes have attracted less concerns. Herein, a series of reduced holey graphene oxides (rhG-x) with different “worm-like” and holey structures were synthesized based on the modified Hummer's treatment and thermal reduction of graphite anode from spent LIBs. Benefiting form the rhG-x annealed at x = 400 °C with optimized oxygen-containing groups and electronic conductivity, as well as the “worm-like” and holey structures, the rhG-400 as cathode for LIBs delivers a high reversible capacity (e.g., 109.6 mAh g−1 at 0.05 A g−1) and excellent rate capability (e.g., 75.0, 68.2, 50.3 and 37.0 mAh g−1 at 2, 5, 10 and 20 A g−1, respectively) and maintains an ultra-long cycling life over 2000 cycles with high reversible capacity of 137.4 mAh g−1.

Closed-Loop Graphite Recycling from Spent Lithium-Ion Batteries through Bioleaching

Research into the recycling of electrode materials has gained attention due to the exponential increase in spent and discarded lithium-ion batteries (LIBs). While cathode electrode recovery has perennially been a research priority due to its economic benefits, anode electrode (graphite) recycling has yet to be accomplished. Currently, the focus has shifted to recycling the anodes from spent LIBs to deal with the scarcity of graphite resources and protect the environment because the anode is a crucial part of a LIB. The primary goal of this research is to recycle and regenerate anode graphite from the bioleaching residue. Unlike other hydrometallurgical LIB recycling, the bioleaching residue contains a considerable amount of iron salts with unleached cathode metal. Graphite was recycled using mild acid cleaning to remove vast amounts of iron salts and unleached cathode materials, followed by calcination treatments. Inductively coupled plasma optical emission spectroscopy (ICP-OES) analysis revealed that the regenerated graphite had a purity of 99.78%. The morphology and structure of the regenerated graphite were confirmed to be identical to the commercial material using scanning electron microscopy (SEM), X-ray diffraction (XRD), and Raman spectroscopy. The regenerated graphite samples show excellent electrochemical performance, with a charging/discharging capacity higher than 400 mAh/g and a retention rate of 100% after 200 cycles, surpassing commercial graphite (366 mAh/g).

Upcycling end of lithium cobalt oxide batteries to electrocatalyst for oxygen reduction reaction in direct methanol fuel cell via sustainable approach

Recycling spent lithium-ion batteries (SLIBs) has become essential to preserve the environment and reclaim vital resources for sustainable development. The typical SLIBs recycling concentrated on separating valuable components had limitations, including high energy consumption and complicated separation processes. This work suggests a safe hydrometallurgical process to recover usable metallic cobalt from depleted LiCoO2 batteries by utilizing citric acid as leachant and hydrogen peroxide as an oxidizing agent, with ethanol as a selective precipitating agent. The anode graphite was also recovered and converted to graphene oxide (GO). The above components were directly resynthesized to cobalt-integrated nitrogen-doped graphene (Co@NG).The Co@NG showed a decent activity towards oxygen reduction reaction (ORR) with a half-wave potential of 0.880 V vs. RHE, almost similar to Pt/C (0.888 V vs. RHE) and with an onset potential of 0.92 V vs. RHE. The metal-nitrogen-carbon (Co-N-C) having the highest nitrogen content has decreased the barrier for ORR since the reaction was enhanced for Co@NG-800, as confirmed by density functional theory (DFT) simulations. The Co@NG cathode catalyst coupled with commercial Pt-Ru/C as anode catalyst exhibits excellent performance for direct methanol fuel cell (DMFC) with a peak power density of 34.7 mW cm−2 at a discharge current density of 120 mA cm−2 and decent stability, indicating the promising utilization of spent battery materials in DMFC applications. Besides, lithium was recovered from supernatant as lithium carbonate by coprecipitation process. This work avoids sophisticated elemental separation by utilizing SLIBs for other renewable energy applications, lowering the environmental concerns associated with recycling.

Material and Waste Flow Analysis for Environmental and Economic Impact Assessment of Inorganic Acid Leaching Routes for Spent Lithium Batteries’ Cathode Scraps

With the development trend and technological progress of lithium batteries, the battery market is booming. This means that the demand for lithium batteries has increased significantly, resulting in a large number of discarded lithium batteries. The consumption of plenty of lithium batteries may lead to the scarcity and expending of relevant raw material metal resources, as well as serious heavy metal environmental pollution. Therefore, it is of great significance to recycle valuable metal resources from discarded lithium batteries. The proper recycling of these valuable metals can reduce the shortage of mineral resources and environmental hazards caused by a large number of scrapped vehicle batteries. Recently, different systematic approaches have been developed for spent lithium battery recovery. However, most of these approaches do not account for the hidden costs incurred from various processing steps. This work is determined by the concept of material flow cost accounting (MFCA). Hence, in this research, a MFCA-based approach is developed for the leaching process of spent lithium batteries recovery, taking into consideration the hidden costs embedded in process streams. In this study, hydrochloric acid had the worst leaching efficiency due to its high solid-to-liquid ratio and the lowest acid concentration, so it was excluded in the first stage selection. It takes TWD 16.03 and TWD 24.10 to leach 10 g of lithium battery powder with sulfuric acid and nitric acid, respectively. The final sulfuric acid was the acid solution with the highest leaching efficiency and relatively low cost among inorganic acids.