Waste Lithium-ion Batteries Research Articles

Review on Life Cycle Assessment of Waste Lithium-ion Battery Recycling Process

Review on Life Cycle Assessment of Waste Lithium-ion Battery Recycling Process

Efficiency of Penicillium sp. and Aspergillus sp. for bioleaching lithium cobalt oxide from battery wastes in potato dextrose broth and sucrose medium

Lithium-ion batteries, a primary power source, generate electronic hazardous waste at the end of their lifespan, which is a richer source of highly concentrated metals such as cobalt and lithium than those in natural resources. The waste is a potential renewable resource for the extraction of metals. Bioleaching, a process utilizing microbial activity, was used in this study to investigate the cobalt and lithium leaching efficiency from battery wastes. Two fungal strains, Aspergillus sp. strain JMET 15 and Penicillium sp. strain JMET 24 were used with different organic carbon sources (sucrose medium and potato dextrose broth) at 1 % pulp density. The sucrose medium derived a higher acid quantity and leached higher concentration of cobalt and lithium than in potato dextrose broth. Leaching efficiency by JMET 24 was higher than JMET 15. Cobalt (32.57 % and 27.19 %) and lithium (65.07 % and 40.58 %) were bioleached by JMET 24 and JMET 15, respectively, after 30 d cultivation in the sucrose medium. Lower pulp density was conducted to achieved higher leaching efficiency by JMET24, cobalt (77.87 % and 74.5 %) and lithium (99.88 % and 78.4 %) were bioleached at 0.1 % and 0.5 % pulp density, respectively. Cobalt oxide (Co3O4) was the product of the one-step recovery (leaching and precipitation) process. Cobalt was transformed from lithium cobalt oxide to cobalt phosphate-oxalate by JMET 24 in the sucrose medium. Thus, the potential of bioleaching as an effective method for recovering valuable metals from lithium-ion battery waste is demonstrated, presenting a promising approach for both waste management and resource recovery.

Review on the recycling of anode graphite from waste lithium-ion batteries

Review on the recycling of anode graphite from waste lithium-ion batteries

Selective lithium recovery from waste lithium-ion batteries by H2SO4 roasting focused on process intensification and conversion mechanism

The purpose of this study is to prove the feasibility, efficiency and selectivity of lithium recovery from waste lithium-ion batteries (LIB) via sulfuric acid roasting-water leaching by thermodynamic analysis and experimental verification. The feasibility was proved by Gibbs free energy calculations and experiments. Then, the effects of H2SO4 concentration, roasting temperature and roasting time were assessed on the leaching rate of valuable metals. The results indicate that the leaching efficiency of lithium increases firstly and then decreases with the increase of H2SO4 concentration, roasting temperature and roasting time, more than 91 % lithium are leached under optimized experimental conditions: 50 wt% H2SO4, roasting temperature of 650°C, and roasting time of 2 h. Meanwhile, the selectivity of lithium is up to 88 % which means overwhelming majority lithium have been separated completely. In addition, the factors which cause sintering phenomenon such as high temperature and longtime roasting will change the microstructure of roasted product extremely, which is inconducive to the subsequent water leaching. The investigations of the phase conversion mechanism by thermodynamic simulation and instrumental characterization indicated that the leaching behaviors of valuable metals might be influenced by the different reaction pathways of the compounds while changing roasting conditions. The recovery process can be divided into two stages: the partial structure of LiNixCoyMnzO2 was destroyed to form metal sulfates at ambient temperature and the solid phase reaction between unreacted LiNixCoyMnzO2 which contained Li+ in the unstable layered structure with transition metal sulfates at high temperature. The fully reduced low-valence states are mainly (NiO)0.75(MnO)0.25 and CoO, and basically all Li within the crystalline LiNixCoyMnzO2 was de-intercalated and transformed to soluble Li2SO4. These results further confirm the advantages of H2SO4 roasting on selective Li recovery, and provide a better understanding of conversion mechanism by combining theory and experiments.

High-performance polyurea nanofiltration membrane for waste lithium-ion batteries recycling: Leveraging synergistic control of bulk and interfacial monomer diffusion

The development of high-performance nanofiltration (NF) membranes with extreme chemical stability is urgently needed for the recovery of spent lithium. In this study, a series of polyurea membranes with high lithium recovery efficiency and pH stability were fabricated by zone-regulated interfacial polymerization (IP). The reaction inhibitor Cu2+ in the bulk aqueous phase reduces IP intensity by reversibly binding to the amino groups of polyethyleneimine monomers through chelate bonds. Meanwhile, surfactant promote the uniform diffusion of macromolecular aqueous monomers at the phase interface. The milder polymerization reaction and the more stable phase interface endow the polyurea membrane (NF10k PEI-SDS-Cu2+) with higher water permeance (2.1 L m-2 h-1 bar-1), desirable MgCl2 rejection (94.7%), and excellent fabrication repeatability. Moreover, the membrane demonstrates stable separation selectivity for Co2+/Li+ and SO42-/Li+ under conditions of 0.05 mol L-1 H2SO4 and 2 mol L-1 LiOH, respectively. Our study provides a facile method for constructing NF membranes with extreme pH stability and confirms the feasibility of membrane-based lithium recovery.

Approach towards the Purification Process of FePO4 Recovered from Waste Lithium-Ion Batteries

The rapid development of new energy vehicles and Lithium-Ion Batteries (LIBs) has significantly mitigated urban air pollution. However, the disposal of spent LIBs presents a considerable threat to the environment. Recycling these waste LIBs not only addresses the environmental issues but also compensates for resource shortages and generates substantial economic benefits. Current recycling processes primarily focus on the extraction of valuable metals, often overlooking the treatment of residual waste post-extraction. This project targets the iron phosphate (FePO4) derived from waste lithium iron phosphate (LFP) battery materials, proposing a direct acid leaching purification process to obtain high-purity iron phosphate. This purified iron phosphate can then be used for the preparation of new LFP battery materials, aiming to establish a complete regeneration cycle that recovers lithium carbonate and iron phosphate from waste LFP materials for the production of LFP. The study investigates process parameters such as acid types and concentrations, leaching time, and the number of leaching cycles. The results demonstrate that, after purification, the levels of impurity metals decrease while the iron content increases correspondingly. Under optimized experimental conditions, the dilute sulfuric acid leaching rates of Al, Cu, Ca, and Ni reached 36.0%, 51.4%, 89.5%, and 90.9%, respectively. Furthermore, hydrothermal treatment in dilute phosphoric acid achieved leaching rates of 87.9%, 85.8%, 98.4%, and 99.1% for Al, Ca, Cu, and Ni, respectively. The microstructure characterization revealed significant changes in phase and grain morphology during the leaching process in dilute phosphoric acid, which are likely associated with the liberation of impurity atoms from the lattice. These findings indicate that acid leaching is highly effective in removing impurities from the iron phosphate recycled from waste LIBs.

Mildly expanded graphite with exceptional performance from waste lithium ion batteries by space-confined intercalation of deep eutectic solvent

Reclaiming the spent graphite (SG) in the anodes of end-of-life lithium-ion batteries (LIBs) is of tremendous significance for addressing resource shortage and eco-friendliness. The impurities embedded into the graphite interlayer after multiple charge–discharge cycles hinder the free migration of lithium ions, resulting in inferior lithium storage capacity. Herein, a space-confined intercalation of deep eutectic solvent (DES) strategy is proposed, to dissolve the impurities by utilizing its great ability to form hydrogen bonds (O–H…Cl-, O–H…O and O–H…F) with PVDF binder, SEI film and the residual electrolytes within the SG, simultaneously enlarging the interlayer distance to upgrade the anode graphite. After the further pyrolysis, the as-obtained mildly expanded graphite (MEG-800) exhibited well-defined graphite microcrystalline layer structure and high graphitization degree. The moderately enlarged graphite layers provided more space for the insertion and extraction of lithium ions, endowing MEG-800 with exceptional performance in LIBs, such as extremely high charge capacity of 477.4 mAh/g at a current density of 0.1 A/g and superior reversibility and desirable cycle stability. After 100 cycles at 0.1 A/g, its capacity still retained 470.9 mAh/g with a Coulombic efficiency as high as 99.76 %. The structure-dependent lithium-ion diffusion features of MEG-800 were also examined by electrochemical kinetics analysis. This study opened up a prospective avenue for the green and efficient recycling of spent anode graphite in retired LIBs, offering a solution to the problem of shortage of battery materials and promoting sustainable development.

Recycling Spent Ternary Cathodes to Oxygen Evolution Catalysts for Pure Water Anion-Exchange Membrane Electrolysis.

Recycling spent lithium-ion batteries (LIBs) to efficient water-splitting electrocatalysts is a promising and sustainable technology route for green hydrogen production by renewables. In this work, a fluorinated ternary metal oxide (F-TMO) derived from spent LIBs was successfully converted to a robust water oxidation catalyst for pure water electrolysis by utilizing an anion-exchange membrane. The optimized catalyst delivered a high current density of 3.0 A cm-2 at only 2.56 V and a durability of >300 h at 0.5 A cm-2, surpassing the noble-metal IrO2 catalyst. Such excellent performance benefits from an artificially endowed interface layer on the F-TMO, which renders the exposure of active metal (oxy)hydroxide sites with a stabilized configuration during pure water operation. Compared to other metal oxides (i.e., NiO, Co3O4, MnO2), F-TMO possesses a higher stability number of 2.4 × 106, indicating its strong potential for industrial applications. This work provides a feasible way of recycling waste LIBs to valuable electrocatalysts.

Waste plastics upcycled for high-efficiency H2O2 production and lithium recovery via Ni-Co/carbon nanotubes composites

The disposal and management of waste lithium-ion batteries (LIBs) and low-density polyethylene (LDPE) plastics pose significant environmental challenges. Here we show a synergistic pyrolysis approach that employs spent lithium transition metal oxides and waste LDPE plastics in one sealed reactor to achieve the separation of Li and transition metal. Additionally, we demonstrate the preparation of nanoscale NiCo alloy@carbon nanotubes (CNTs) through co-pyrolysis of LiNi0.6Co0.2Mn0.2O2 and LDPE. The NiCo alloy@CNTs exhibits excellent catalytic activity (Eonset = ~0.85 V) and the selectivity (~90%) for H2O2 production through the electrochemical reduction of oxygen. This can be attributed to the NiCo nanoalloy core and the presence of CNTs with abundant oxygen-containing functional groups (e.g., –COOH and C–O–C), as confirmed by density function theory calculations. Overall, this work presents a straightforward and green approach for valorizing and upcycling various waste LIBs and LDPE plastics.

Novel ternary deep eutectic solvents used for recycling lithium and cobalt from waste lithium-ion batteries

The escalating disposal of lithium-ion batteries (LIBs) poses significant environmental challenges but also offers substantial opportunities for resource recovery. In this work, we introduce a recycling strategy using a green, cost-effective ternary deep eutectic solvent (DES) composed of guanidine hydrochloride, ethylene glycol, and maleic acid. The DES can achieve >99.5 % leach efficiency of lithium (Li) and cobalt (Co) at 100 °C, 9h, and L/S=50. The kinetic study found that the chemical reaction rate at the interface was the key to controlling the leaching process. The study of leaching mechanisms found that the acidity and coordination ability of DES were the main driving forces of leaching. Co loaded in the DES phase can almost precipitate out by using oxalic acid, achieving the separation of Li and Co. After reusing three times, the maximum load of Li in the DES phase reached 4.1 mg/g. These outstanding performances, along with the avoidance of the use of hazardous chemicals and the reduction of high costs, confirmed that the DES possesses a promising prospect for sustainable, large-scale application in efficiently leaching valuable metals from LiCoO2.

A novel closed-loop biotechnology for recovery of cobalt from a lithium-ion battery active cathode material.

In recent years, the demand for lithium-ion batteries (LIBs) has been increasing rapidly. Conventional recycling strategies (based on pyro- and hydrometallurgy) are damaging for the environment and more sustainable methods need to be developed. Bioleaching is a promising environmentally friendly approach that uses microorganisms to solubilize metals. However, a bioleaching-based technology has not yet been applied to recover valuable metals from waste LIBs on an industrial scale. A series of experiments was performed to improve metal recovery rates from an active cathode material (LiCoO2; LCO). (i) Direct bioleaching of ≤0.5 % LCO with two prokaryotic acidophilic consortia achieved >80 % Co and 90 % Li extraction. Significantly lower metal recovery rates were obtained at 30 °C than at 45 °C. (ii) In contrast, during direct bioleaching of 3 % LCO with consortia adapted to elevated LCO levels, the 30 °C consortium performed significantly better than the 45 °C consortium, solubilizing 73 and 93 % of the Co and Li, respectively, during one-step bioleaching, and 83 and 99 % of the Co and Li, respectively, during a two-step process. (iii) The adapted 30°C consortium was used for indirect leaching in a low-waste closed-loop system (with 10 % LCO). The process involved generation of sulfuric acid in an acid-generating bioreactor (AGB), 2-3 week leaching of LCO with the biogenic acid (pH 0.9), selective precipitation of Co as hydroxide, and recirculation of the metal-free liquor back into the AGB. In total, 58.2 % Co and 100 % Li were solubilized in seven phases, and >99.9 % of the dissolved Co was recovered after each phase as a high-purity Co hydroxide. Additionally, Co nanoparticles were generated from the obtained Co-rich leachates, using Desulfovibrio alaskensis, and Co electrowinning was optimized as an alternative recovery technique, yielding high recovery rates (91.1 and 73.6% on carbon felt and roughened steel, respectively) from bioleachates that contained significantly lower Co concentrations than industrial hydrometallurgical liquors. The closed-loop system was highly dominated by the mixotrophic archaeon Ferroplasma and sulfur-oxidizing bacteria Acidithiobacillus caldus and Acidithiobacillus thiooxidans. The developed system achieved high metal recovery rates and provided high-purity solid products suitable for a battery supply chain, while minimizing waste production and the inhibitory effects of elevated concentrations of dissolved metals on the leaching prokaryotes. The system is suitable for scale-up applications and has the potential to be adapted to different battery chemistries.

Design of a continuous ion exchange process in battery metals recycling: From single column experiments towards a simulated moving bed configuration

In hydrometallurgical recovery of LIB metals, ion exchange (IX) has hitherto played only a minor role. Separation experiments were conducted in single laboratory-scale IX columns with the aim of laying the foundation for a continuously operated multicolumn IX process similar to a simulated moving bed (SMB) configuration. In this study, the initial process developed earlier was improved by reducing the number of process steps and external streams. The desorption step with oxalate solution was examined in single-column batch experiments to ensure complete desorption of iron in the proposed continuous multicolumn IX process. Additionally, the volume flowrates were adjusted to achieve acceptable switch times of 25 min in an SMB configuration. It was found that the bead size of the resin is a critical factor in IX recovery of battery metals. The raffinate purity for the case of processing 2.5 BV lithium-ion battery waste leachate (LIBWL) improved from 97.2 % to 99.8 % when the resin bead size was reduced from 0.55 ± 0.05 mm to 0.4 ± 0.04 mm and a narrower bead size distribution. The LIBWL feed concentration was varied to mimic the dilution of fresh feed in an SMB set-up. The percentage recovery of Co and Ni decreased from 93.7 % and 96.6 % to 80.8 % and 89.4 %, respectively, when the LIBWL was diluted. This was a result of the decrease in concentration of impurity metals in the feed. Less impurity metals were sorbed and consequently, more ion exchange sites were available for the sorption of the target metals, which enhanced the retention of Co and Ni. The results were used to develop an IX column operation strategy and to suggest an initial SMB design. The multicolumn configuration presented in this work offers great potential for continuous production of high-purity Li, Ni and Co-containing raffinate (> 99.5 %).

Environmental Impact Analysis of Waste Lithium-Ion Battery Cathode Recycling

Environmental Impact Analysis of Waste Lithium-Ion Battery Cathode Recycling

Membrane Based Recovery of Valuable Lithium Metals from Lithium Ion Battery Waste

Membrane Based Recovery of Valuable Lithium Metals from Lithium Ion Battery Waste

Summary of Pretreatment of Waste Lithium-Ion Batteries and Recycling of Valuable Metal Materials: A Review

The recycling of used lithium-ion batteries has become a growing concern. As a large number of rare metal elements are present in waste lithium-ion batteries, recycling them can significantly improve resource utilization and reduce the material cost of battery production. The process of recycling used lithium-ion batteries involves three main technology parts: pretreatment, material recovery, and cathode material recycling. Pretreatment includes discharge treatment, uniform crushing, and removing impurities. Material-recovery technology mainly involves traditional pyrometallurgical and hydrometallurgical technologies, as well as the developing biometallurgy technology. Analysis of existing data shows that pretreatment technology is crucial for the recycling of used lithium-ion batteries. Hydrometallurgical technology and pyro-hydrometallurgical technology are expected to be the most suitable industrialization technology paths in the future, with biometallurgical technology and direct recycling technology providing a low-pollution development direction. This article summarizes the different pretreatment techniques and valuable metal-recovery pathways. The advantages and disadvantages of each method were evaluated. The economic costs, environmental benefits, and degree of industrialization of each method were assessed. The possible development directions of various methods are summarized to provide reference for future research.

Development of Plasmonic Attapulgite/Co(Ti)Ox Nanocomposite Using Spent Batteries toward Photothermal Reduction of CO2

The rapid development of the battery industry has brought about a large amount of waste battery pollution. How to realize the high-value utilization of waste batteries is an urgent problem to be solved. Herein, cobalt and titanium compounds (LTCO) were firstly recovered from spent lithium-ion batteries (LIBs) using the carbon thermal reduction approach, and plasmonic attapulgite/Co(Ti)Ox (H-ATP/Co(Ti)Ox) nanocomposites were prepared by the microwave hydrothermal technique. H-ATP had a large specific surface area and enough active sites to capture CO2 molecules. The biochar not only reduced the spinel phase of waste LIBs into metal oxides including Co3O4 and TiO2 but also increased the separation and transmission of the carriers, thereby accelerating the adsorption and reduction of CO2. In addition, H-ATP/Co(Ti)Ox exhibited a localized surface plasmon resonance effect (LSPR) in the visible to near-infrared region and released high-energy hot electrons, enhancing the surface temperature of the catalyst and further improving the catalytic reduction of CO2 with a high CO yield of 14.7 μmol·g−1·h−1. The current work demonstrates the potential for CO2 reduction by taking advantage of natural mineral and spent batteries.

Mechanism and technological method of leaching metals from waste lithium-ion batteries by synergistic action of natural organic reductants and mechanochemical method

In this study, litchi peel powder (LPP) was selected as a natural organic reductant to study the mechanism of green leaching of valuable metals from spent lithium-ion batteries (LIBs) by ball milling. LPP and cathode material were co-ball-milled(CBM) with water and then leached, LPP-assisted ball milling reduces the agglomeration tendency of the particles and increases the dispersion. Premixing by CBM makes the LPP and the cathode material fully contracted and tightly fused, and the mechanical force provides the activation energy of the reaction to accelerate the leaching. The leaching rates of Li, Co, Mn and Ni were 99.21 wt%, 96.52 wt%, 98.21 wt% and 94.79 wt% when LPP was added at 0.15 g and only 0.2 mol/L H3Cit was used. Compared with direct leaching, the amount of organic acids was reduced by 86.67 %. The proanthocyanidins contained in the LPP are the key to act as a reducing agent, and proanthocyanidins are the products of the combination of anthocyanins and glycosides. The natural phenolic and ester components in LPP are hydrolyzed into phenolic acids (protocatechulic acid, salicylic acid) and flavonoids (catechins) under the action of H3Cit, which accelerates the dissolution of metal oxides. The mechanism of natural organic reductant in auxiliary ball milling and organic acid leaching was clarified, which provided a new idea for the selection of ball milling auxiliary materials and proposed a economic and environmental protection method to leach valuable metals from spent LIBs.

Carbon Footprint of Spent Ternary Lithium-Ion Battery Waste Recycling

Road transport is the primary source of greenhouse gas emissions in China's transportation field. As an important means to achieve the "double carbon" goal in the transportation field, the new energy automobile industry will face a large number of power battery scrapping in the future. In order to quantitatively assess the carbon emission reduction benefits generated by the spent ternary lithium-ion battery waste recycling industry, the carbon footprint accounting model of spent ternary lithium-ion battery waste recycling and utilization was constructed from the life cycle perspective. By optimizing the power structure and transportation structure, the carbon emission reduction potential of spent ternary lithium-ion battery waste recycling was predicted and evaluated. In addition, the uncertainty analysis was conducted using the propagation of uncertainty equation to ensure the reliability and effectiveness of the carbon footprint results. The results showed that the current carbon footprint of Chinese enterprises using wet technology to recover 1 kg waste lithium batteries was -2 760.90 g (directional recycling process) and -3 752.78 g (recycling process), and the uncertainty of the carbon footprint was 16 % (directional recycling process) and 15 % (recycling process), respectively. From the analysis of carbon emission contribution, the regenerated product stage was the primary source of carbon reduction in the wet recycling and utilization of waste ternary lithium batteries, whereas the battery acquisition, disassembly, and end treatment stages were the main sources of carbon increase. Compared to optimizing the transportation structure, optimizing the power structure could effectively achieve greater carbon emission reduction potential. Under the collaborative optimization scenario, compared to that before optimization, 14 %-19 % carbon emission reduction could be achieved. Compared with native products, the directional circulation process and recycling process could achieve 9 % and 11 % emission reduction potential, respectively.

Chemical-Free Recycling of Cathode Material and Aluminum Foil from Waste Lithium-Ion Batteries by Combining Plasma and Ultrasonic Technology.

With the rapid demand for lithium-ion batteries due to the widespread application of electric vehicles, a significant amount of battery electrode pieces requiring urgent treatment are generated during battery production and disposal. The strong bonding caused by the presence of binders makes it challenging to achieve thorough separation between the cathode active materials and Al foil, posing difficulties in efficient battery material recycling. To address this issue, a plasma-ultrasonically combined physical separation method is proposed in this study. This method utilizes plasma-generated excited-state radicals assisted by ultrasonic waves to separate active materials and current collectors. The results indicate that the binders are effectively decomposed under plasma treatment at 13.56 MHz, 100 W, and 10 min in an oxygen atmosphere, resulting in a separation efficiency of 96.8 wt % for the cathode materials. Characterization results demonstrate that the morphology, crystal structure, and chemical composition of the recycled cathode active materials remain unchanged, facilitating subsequent direct restoration and hydrometallurgical recycling. Simultaneously, the Al foil is also completely recycled for subsequent reuse. Compared with traditional methods of separating cathode active materials and aluminum foil, the method proposed in this study has significant economic and environmental potential. It can promote the recycling of battery materials and the development of sustainable transportation.

Rational design of waste anode graphite-derived carbon catalyst to activate peroxymonosulfate for atrazine degradation

As the rapidly growing number of waste lithium-ion batteries (LIBs), the recycling and reutilization of anode graphite is of increasing interest. Converting waste anode graphite into functional materials may be a sensible option. Herein, a series of carbonaceous catalysts (TG) were successfully prepared using spent anode graphite calcined at various temperatures and applied for activating peroxymonosulfate (PMS) to degrade atrazine (ATZ). The catalyst obtained at 800 °C (TG-800) showed the optimum performance for ATZ removal (99.2% in 6 min). Various experimental conditions were explored to achieve the optimum efficiency of the system. In the TG-800/PMS system, free radicals (e.g., SO4·−, HO·), singlet oxygen (1O2), together with a direct electron transfer pathway all participated in ATZ degradation, and the ketonic (CO) group was proved as the leading catalytic site for PMS activation. The potential degradation routes of ATZ have also been presented. According to the toxicity assessment experiments, the toxicity of the intermediate products decreased. The reusability and universal applicability of the TG-800 were also confirmed. This research not only provides an efficient PMS activator for pollutant degradation, but also offers a meaningful reference for the recovery of waste anode graphite to develop environmentally functional materials.