Environmental friendly leaching reagent for cobalt and lithium recovery from spent lithium-ion batteries

We investigated an environmentally friendly leaching process for the recovery of cobalt and lithium from the cathode active materials of spent lithium-ion batteries. The easily degradable organic acid DL-malic acid (C₄H₅O₆) was used as a leaching reagent. The structural, morphology of the cathode materials before and after leaching were characterized by X-ray diffraction (XRD) and scanning electronic microscopy (SEM). The amount of Co and Li present in the leachate was determined by atomic absorption spectrophotometry (AAS). Conditions for achieving a recovery of more than 90 wt.% Co and nearly 100 wt.% Li were determined experimentally by varying the concentrations of leachant, time and temperature of the reaction as well as the initial solid-to-liquid ratio. We found that hydrogen peroxide in a DL-malic acid solution is an effective reducing agent because it enhances the leaching efficiency. Leaching with 1.5 M DL-malic acid, 2.0 vol.% hydrogen peroxide and a S:L of 20 g L^?1 in a batch extractor results in a highly efficient recovery of the metals within 40 min at 90 °C.     

酸浸—萃取—沉淀法回收废锂离子电池中的钴

采用酸浸—萃取—沉淀法回收废锂离子电池中的钴。实验结果表明:废锂离子电池在600℃下煅烧5 h可将正极材料上的有机黏结剂与正极活性物质分离;正极活性物质在Na OH溶液浓度为2.0 mol/L、n(Na OH)∶n(铝)=2.5、碱浸温度为20℃的条件下碱浸反应1 h后,铝浸出率达99.7%;已除铝的正极活性物质在硫酸浓度为2.5 mol/L、H_2O_2质量浓度为7.25 g/L、液固比为10、酸浸温度为85℃的条件下酸浸反应120 min,钴浸出率高达98.0%;酸浸液在p H为3.5、萃取剂P507与Cyanex272体积比为1∶1的条件下,经2级萃取,钴萃取率为95.5%;采用H_2SO_4溶液反萃后在硫化钠质量浓度为8 g/L、反萃液p H为4的条件下沉淀反应10 min,钴沉淀率达99.9%。     

Nickel and cobalt recycling from lithium-ion batteries by electrochemical processes

The presence of LiCoO(2) and LiCo(x)Ni((1-x))O(2) in the cathodic material of Li-ion and Li-polymer batteries has stimulated the recovery of Co and Ni by hydrometallurgical processes. In particular, the two metals were separated by SX method and then recovered by electrochemical (galvanostatic and potentiostatic) processes. The metallic Ni has been electrowon at 250 A/m(2), pH 3-3.2 and 50 degrees C, with 87% current efficiency and 2.96 kWh/kg specific energy consumption. Potentiostatic electrolysis produces a very poor Ni powder in about 1 h with current efficiency changing from 70% to 45% depending on Ni concentration in the electrolyte. Current efficiency of 96% and specific energy consumption of 2.8 kWh/kg were obtained for Co at 250 A/m(2), pH 4-4.2 and 50 degrees C, by using a solution containing manganese and (NH(4))(2)SO(4). The Co powder, produced in potentiostatic conditions (-0.9 V vs. SCE, pH 4, room temperature) appears particularly suitable for Co recycling as cobaltite in new batteries.     

A novel recycling process of LiFePO4 cathodes for spent lithium-ion batteries by deep eutectic solvents

Journal of Material Cycles and Waste Management - In this study, deep eutectic solvent synthesized by choline chloride (C5H14CINO) and oxalic acid dihydrate (C2H2O4·2H2O) was used to recycling...     

Novel approach for in situ recovery of cobalt oxalate from spent lithium-ion batteries using tartaric acid and hydrogen peroxide

Journal of Material Cycles and Waste Management - Recycling Co resource from spent lithium-ion batteries (LIBs) is significant for Co deficiency and environmental protection. A novel approach for...     

An overview on the processes and technologies for recycling cathodic active materials from spent lithium-ion batteries

This paper aims to make an overview on the current status and new tendency for recycling cathodic active materials from spent lithium-ion batteries. Firstly, it introduces several kinds of pretreatment technologies, followed by the summary of all kinds of single recycling processes mainly focusing on organic acid leaching and synergistic extraction. Then, several examples of typical combined processes and industrial recycling processes are presented in detail. Meanwhile, the advantages, disadvantages and prospect of each single process, combined process, as well as industrial recycling processes, are discussed. Finally, based on a novel acidic organic solvent, the authors briefly introduce an environmental friendly process to directly recycle and resynthesize cathodic active material LiNi_1/3Co_1/3Mn_1/3O₂ from spent lithium-ion batteries. The preliminary experimental results demonstrated the advantages of low reaction temperature, high separation efficiency and organic solvent cycling and preventing secondary pollution to the environment. This process may be used for large-scale recycling of spent lithium-ion batteries after further study.     

黄钠铁矾法氧化去除废锂电池硫酸浸出液中的铁

废锂电池中含有的Co、Ni和Cu等金属具有回收价值,Fe的存在降低了有价金属的回收效率。为去除废锂电池硫酸浸出液中的Fe,采用黄钠铁矾法分别以氯酸钠和过氧化氢作为氧化剂氧化除Fe,并优化了过氧化氢作为氧化剂的除Fe工艺参数。实验结果表明:过氧化氢作为氧化剂的除Fe效果好于氯酸钠;在n(H2O2)∶n(Fe)=0.5、初始溶液pH为1.8、终点pH为2.5、反应时间为2.0 h、搅拌速率为500 r/min的最佳工艺条件下,初始ρ(Fe)为0.212g/L的硫酸浸出液经除Fe处理后ρ(Fe)小于0.004 g/L,Fe去除率达98.0%,Co、Ni和Cu的损失率分别为1.04%、2.17%和1.41%。     

Characterization and recycling of lithium nickel manganese cobalt oxide type spent mobile phone batteries based on mineral processing technology

Journal of Material Cycles and Waste Management - The unprecedented increase in mobile phone spent lithium-ion batteries (LIBs) in recent times has become a major concern for the global community....     

氨基磺酸溶液浸出废锂离子电池负极活性材料中的锂

随着锂离子电池的广泛应用,产生了大量废锂离子电池,其负极活性材料中积累了高品位的锂。锂作为一种稀有金属,对其进行回收利用很有意义。选取了无毒、稳定性好的氨基磺酸作为浸出剂,浸取废锂离子电池负极活性材料中的锂,考察了预处理方式对负极活性材料成分和结构的影响以及浸出条件对锂浸出率的影响。结果表明:600℃下煅烧4 h,可完全去除附着在负极活性材料表面的有机物;在氨基磺酸浓度0.75 mol/L、固液比5 g/L、浸出温度40℃、浸出时间45 min的最佳浸出条件下,负极活性材料中锂浸出率达97.2%。     

Organic oxalate as leachant and precipitant for the recovery of valuable metals from spent lithium-ion batteries

Spent lithium-ion batteries containing lots of strategic resources such as cobalt and lithium are considered as an attractive secondary resource. In this work, an environmentally compatible process based on vacuum pyrolysis, oxalate leaching and precipitation is applied to recover cobalt and lithium from spent lithium-ion batteries. Oxalate is introduced as leaching reagent meanwhile as precipitant which leaches and precipitates cobalt from LiCoO(2) and CoO directly as CoC(2)O(4)·2H(2)O with 1.0 M oxalate solution at 80°C and solid/liquid ratio of 50 g L(-1) for 120 min. The reaction efficiency of more than 98% of LiCoO(2) can be achieved and cobalt and lithium can also be separated efficiently during the hydrometallurgical process. The combined process is simple and adequate for the recovery of valuable metals from spent lithium-ion batteries.     

Recovery of lithium and cobalt from waste lithium ion batteries of mobile phone

In view of the stringent environmental regulations, availability of limited natural resources and ever increasing need of alternative energy critical elements, an environmental eco-friendly leaching process is reported for the recovery of lithium and cobalt from the cathode active materials of spent lithium-ion batteries of mobile phones. The experiments were carried out to optimize the process parameters for the recovery of lithium and cobalt by varying the concentration of leachant, pulp density, reductant volume and temperature. Leaching with 2 M sulfuric acid with the addition of 5% H₂O₂ (v/v) at a pulp density of 100 g/L and 75 °C resulted in the recovery of 99.1% lithium and 70.0% cobalt in 60 min. H₂O₂ in sulfuric acid solution acts as an effective reducing agent, which enhance the percentage leaching of metals. Leaching kinetics of lithium in sulfuric acid fitted well to the chemical controlled reaction model i.e. 1 ? (1 ? X)^1/3 = k_ct. Leaching kinetics of cobalt fitted well to the model ‘ash diffusion control dense constant sizes spherical particles’ i.e. 1 ? 3(1 ? X)^2/3 + 2(1 ? X) = k_ct. Metals could subsequently be separated selectively from the leach liquor by solvent extraction process to produce their salts by crystallization process from the purified solution.     

Recovery of nickel, cobalt and some salts from spent Ni-MH batteries

This work provides a method to help recover nickel, cobalt metals and some of their salts having market value from spent nickel-metal hydride batteries (SNiB). The methodology used benefits the solubility of the battery electrode materials in sulfuric or hydrochloric acids. The results obtained showed that sulfuric acid was slightly less powerful in leaching SNiB compared to HCl acid. Despite that, sulfuric acid was extremely applied on economic basis. The highest level of solubility attained 93.5% using 3N sulfuric acid at 90 degrees C for 3h. The addition of hydrogen peroxide to the reacting acid solution improved the level of solubility and enhanced the process in a shorter time. The maximum recovery of nickel and cobalt metals was 99.9% and 99.4%, respectively. Results were explained in the light of a model assuming that solubility was a first order reaction. It involved a multi-step sequence, the first step of which was the rate determining step of the overall solubility. Nickel salts such as hydroxide, chloride, hexamminenickel chloride, hexamminenickel nitrate, oxalate and nickel oleate were prepared. With cobalt, basic carbonate, chloride, nitrate, citrate, oleate and acetate salts were prepared from cobalt hydroxide Cost estimates showed that the prices of the end products were nearly 30% lower compared to the prices of the same chemicals prepared from primary resources.     

Characterization and leaching of NiCd and NiMH spent batteries for the recovery of metals

Since NiMH and NiCd batteries are still used in the electronic devices market, a treatment and recycling plant has many advantages both from the environmental and the economic points of view. Unfortunately, there is no relationship between shape, size and chemical composition of spent batteries, consequently the characterization and the leaching method of the starting material becomes an important step of the overall treatment process in choosing the best conditions for the selective separation of the metals by hydrometallurgy. Leaching at 20 degrees C with H(2)SO(4) 2M for about 2h seems to be a good solution in terms of cost and efficiency for both battery types. The hydroxide compounds can be readily leached while Ni present as metallic form requires more aggressive conditions due to kinetic constraints. In this paper, the characterization of NiMH and NiCd spent batteries and the results of leaching tests in different conditions are reported.     

Cobalt extraction from spent lithium-ion battery cathode material using a sulfuric acid solution containing SO2

Journal of Material Cycles and Waste Management - To increase the degree of cobalt (Co) extraction, the process of the cathode material leaching was performed in a sulfuric acid (H2SO4) solution...     

A novel process for recycling and resynthesizing LiNi1/3Co1/3Mn1/3O2 from the cathode scraps intended for lithium-ion batteries

To solve the recycling challenge for aqueous binder based lithium-ion batteries (LIBs), a novel process for recycling and resynthesizing LiNi_1/3Co_1/3Mn_1/3O₂ from the cathode scraps generated during manufacturing process is proposed in this study. Trifluoroacetic acid (TFA) is employed to separate the cathode material from the aluminum foil. The effects of TFA concentration, liquid/solid (L/S) ratio, reaction temperature and time on the separation efficiencies of the cathode material and aluminum foil are investigated systematically. The cathode material can be separated completely under the optimal experimental condition of 15 vol.% TFA solution, L/S ratio of 8.0 mL g^?1, reacting at 40 °C for 180 min along with appropriate agitation. LiNi_1/3Co_1/3Mn_1/3O₂ is successfully resynthesized from the separated cathode material by solid state reaction method. Several kinds of characterizations are performed to verify the typical properties of the resynthesized LiNi_1/3Co_1/3Mn_1/3O₂ powder. Electrochemical tests show that the initial charge and discharge capacities of the resynthesized LiNi_1/3Co_1/3Mn_1/3O₂ are 201 mAh g^?1 and 155.4 mAh g^?1 (2.8–4.5 V, 0.1 C), respectively. The discharge capacity remains at 129 mAh g^?1 even after 30 cycles with a capacity retention ratio of 83.01%.     

Thermal treatment for recovery of manganese and zinc from zinc-carbon and alkaline spent batteries

The aim of this paper is the recovery of manganese and zinc from a mixture of zinc-carbon and alkaline spent batteries, containing 40.9% of Mn and 30.1% of Zn, after preliminary physical treatment followed by removal of mercury. Separation of the metals has been carried out on the basis of their different boiling points, being 357°C and 906°C the boiling point of mercury and zinc and 1564°C the melting point of Mn(2)O(3). Characterization by chemical analysis, TGA/DTA and X-ray powder diffraction of the mixture has been carried out after comminution sieving and shaking table treatment to remove the anodic collectors and most of chlorides contained in the mixture. The mixture has been roasted at various temperatures and resident times in a flow of air to set the best conditions to remove mercury that were 400°C and 10min. After that, the flow of air has been turned into a nitrogen one (inert atmosphere) and the temperatures raised, thus permitting the zinc oxide to be reduced to metallic zinc by the carbon present in the original mixture and recovered after volatilization as a high grade concentrate, while manganese was left in the residue. The recovery and the grade of the two metals, at 1000°C and 30min residence time, were 84% and 100% for zinc and 85% and 63% for manganese, respectively. The recovery of zinc increased to 99% with a grade of 97% at 1200°C and 30min residence time, while the recovery and grade of manganese were 86% and 87%, respectively, at that temperature. Moreover, the chlorinated compounds that could form by the combustion of the plastics contained in the spent batteries, are destroyed at the temperature required by the process.     

Pyrolysis and catalytic pyrolysis as a recycling method of waste CDs originating from polycarbonate and HIPS

Pyrolysis appears to be a promising recycling process since it could convert the disposed polymers to hydrocarbon based fuels or various useful chemicals. In the current study, two model polymers found in WEEEs, namely polycarbonate (PC) and high impact polystyrene (HIPS) and their counterparts found in waste commercial Compact Discs (CDs) were pyrolysed in a bench scale reactor. Both, thermal pyrolysis and pyrolysis in the presence of two catalytic materials (basic MgO and acidic ZSM-5 zeolite) was performed for all four types of polymers. Results have shown significant recovery of the monomers and valuable chemicals (phenols in the case of PC and aromatic hydrocarbons in the case of HIPS), while catalysts seem to decrease the selectivity towards the monomers and enhance the selectivity towards other desirable compounds.     

Recycling nickel from spent catalyst of Phu My fertilizer plant as a precursor for exhaust gas treatment catalysts preparation

In this study, a very promising way of treating and recycling spent nickel catalysts of fertilizer plants in Vietnam was proposed. Firstly, nickel was recovered from spent catalyst using HNO₃—leaching process. Results show that nickel recovery of over 90% with a purity of over 90% can be achieved with HNO₃ 2.1–2.5 M at 100?°C in 75 min. The residue after leaching is not considered as a hazardous waste according to the Vietnamese regulations. Then, the leachate solution was used as a precursor to prepare a model catalyst for exhaust gas (CO, HC, NO_x) treatment. In comparison with the catalyst prepared from the commercial nickel nitrate solution, the catalyst synthesized from recovered nickel exhibits similar properties and activities. The influence of Ni loading of Ni/alumina catalyst as well as the modification of active phase by some metals addition (Mn, Ba, Ce) was also investigated. It is feasible to modify active phase by transition metals such as Mn, Ba, and Ce for complete oxidation of CO and HC at 270?°C and a reduction of NO_x below 350?°C at high volumetric flow condition (GHSV?=?110.000 h^?1).     

Fabrication of green composite fibers from ground tea leaves and poly(lactic acid) as eco-friendly textiles with antibacterial property

Journal of Material Cycles and Waste Management - This work aims to prepare bio-based polymer composite fiber using poly(lactic acid) (PLA) and ground tea leaves (GTL) as a matrix and bio-based...     

Formulating a VET roadmap for the waste and recycling sector: A case study from Queensland, Australia

Vocational Education and Training (VET) is an essential tool for providing waste management and recycling workers with the necessary skills and knowledge needed to beneficially influence their own employment and career development; and to also ensure productivity and safe working conditions within the organisations in which they are employed. Current training opportunities within Queensland for the sector are limited and not widely communicated or marketed; with other States, particularly Victoria and New South Wales, realising higher numbers of VET enrollments for waste management courses. This paper presents current VET opportunities and trends for the Queensland waste management sector. Results from a facilitated workshop to identify workforce requirements and future training needs organised by the Waste Contractors and Recyclers Association of Queensland (WCRAQ) are also presented and discussion follows on the future training needs of the industry within Queensland.