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%。     

Chemical and process mineralogical characterizations of spent lithium-ion batteries: An approach by multi-analytical techniques

Mineral processing operation is a critical step in any recycling process to realize liberation, separation and concentration of the target parts. Developing effective recycling methods to recover all the valuable parts from spent lithium-ion batteries is in great necessity. The aim of this study is to carefully undertake chemical and process mineralogical characterizations of spent lithium-ion batteries by coupling several analytical techniques to provide basic information for the researches on effective mechanical crushing and separation methods in recycling process. The results show that the grade of Co, Cu and Al is fairly high in spent lithium ion batteries and up to 17.62 wt.%, 7.17 wt.% and 21.60 wt.%. Spent lithium-ion batteries have good selective crushing property, the crushed products could be divided into three parts, they are Al-enriched fraction (+2 mm), Cu and Al-enriched fraction (?2 + 0.25 mm) and Co and graphite-enriched fraction (?0.25 mm). The mineral phase and chemical state analysis reveal the electrode materials recovered from ?0.25 mm size fraction keep the original crystal forms and chemical states in lithium-ion batteries, but the surface of the powders has been coated by a certain kind of hydrocarbon. Based on these results a flowsheet to recycle spent LiBs is proposed.     

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.     

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.     

Reclaiming the spent alkaline zinc manganese dioxide batteries collected from the manufacturers to prepare valuable electrolytic zinc and LiNi0.5Mn1.5O4 materials

A process for reclaiming the materials in spent alkaline zinc manganese dioxide (Zn–Mn) batteries collected from the manufacturers to prepare valuable electrolytic zinc and LiNi_0.5Mn_1.5O₄ materials is presented. After dismantling battery cans, the iron cans, covers, electric rods, organic separator, label, sealing materials, and electrolyte are separated through the washing, magnetic separation, filtrating, and sieving operations. Then, the powder residues react with H₂SO₄ (2 mol L^?1) solution to dissolve zinc under a liquid/solid ratio of 3:1 at room temperature, and subsequently, the electrolytic Zn with purity of ?99.8% is recovered in an electrolytic cell with a cathode efficiency of ?85% under the conditions of 37–40 °C and 300 A m^?2. The most of MnO₂ and a small quantity of electrolytic MnO₂ are recovered from the filtration residue and the electrodeposit on the anode of electrolytic cell, respectively. The recovered manganese oxides are used to synthesize LiNi_0.5Mn_1.5O₄ material of lithium-ion battery. The as-synthesized LiNi_0.5Mn_1.5O₄ discharges 118.3 mAh g^?1 capacity and 4.7 V voltage plateau, which is comparable to the sample synthesized using commercial electrolytic MnO₂. This process can recover the substances in the spent Zn–Mn batteries and innocuously treat the wastewaters, indicating that it is environmentally acceptable and applicable.     

Physical separation,mechanical enrichment and recycling-oriented characterization of spent NiMH batteries

Nickel–metal hydride (NiMH) batteries contain high amount of industrial metals, especially iron, nickel, cobalt and rare earth elements. Although the battery waste is a considerable secondary source for metal and chemical industries, a recycling process requires a suitable pretreatment method before proceeding with recovery step to reclaim all valuable elements. In this study, AA- and AAA-type spent NiMH batteries were ground and then sieved for size measurement and classification. Chemical composition of the ground battery black mass and sorted six different size fractions were determined by an analytical technique. Crystal structures of the samples were analyzed by X-ray diffraction. Results show that after mechanical treatment, almost 87 wt% of the spent NiMH batteries are suitable for further recycling steps. Size classification by sieving enriched the iron content of the samples in the coarse fraction which is bigger than 0.25 mm. On the other hand, the amounts of nickel and rare earth elements increased by decreasing sample size, and concentrated in the finer fractions. Anode and cathode active materials that are hydrogen storage alloy and nickel hydroxide were mainly collected in finer size fraction of the battery black mass.     

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.     

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%.     

Tannic acid as a novel and green leaching reagent for cobalt and lithium recycling from spent lithium-ion batteries

Tannic acid–acetic acid is proposed as novel and green chemicals for cobalt and lithium recycling from spent lithium-ion batteries through a leaching process. The synergism of both acids was documented through batch and continuous studies. Tannic acid promotes cobalt dissolution by reducing insoluble Co³⁺ into soluble Co²⁺, while acetic acid is critical to improve the dissolution and stabilize the metals in the pregnant leach solution. Based on batch studies, the optimum conditions for metal recovery at room temperature are acetic acid 1 M, tannic acid 20 g/L, pulp density 20 g/L, and stirring speed 250 rpm (94% cobalt and 99% lithium recovery). The kinetic study shows that increasing temperature to 80 °C improves cobalt and lithium recovery from 65 to 90% (cobalt) and from 80 to 99% (lithium) within 4 h at sub-optimum condition (tannic acid 10 g/L). Kinetic modeling suggests the leaching process was endothermic, and high activation energy indicates a surface chemical process. For other metals, the pattern of manganese and nickel recovery trend follows the cobalt recovery trend. Copper recovery was negatively affected by tannic acid. Iron recovery was limited due to the weak acidic condition of pregnant leach solution, which is beneficial to improve leaching selectivity.

     

Study concerning the recovery of zinc and manganese from spent batteries by hydrometallurgical processes

Used batteries contain numerous metals in high concentrations and if not disposed of with proper care, they can negatively affect our environment. These metals represent 83% of all spent batteries and therefore it is important to recover metals such as Zn and Mn, and reuse them for the production of new batteries. The recovery of Zn and Mn from used batteries, in particular from Zn–C and alkaline ones has been researched using hydrometallurgical methods. After comminution and classification of elemental components, the electrode paste resulting from these processes was treated by chemical leaching. Prior to the leaching process the electrode paste has been subjected to two washing steps, in order to remove the potassium, which is an inconvenient element in this type of processes. To simultaneously extract Zn and Mn from this paste, the leaching method in alkaline medium (NaOH solution) and acid medium (sulphuric acid solution) was used. Also, to determine the efficiency of extraction of Zn and Mn from used batteries, the following variables were studied: reagents concentration, S/L ratio, temperature, time. The best results for extraction yield of Zn and Mn were obtained under acid leaching conditions (2 M H₂SO₄, 1 h, 80 °C).     

Removal of inorganic colour pigments from acrylonitrile butadiene styrene by dissolution-based recycling

Reinserting thermoplastic industrial scrap materials back into the production process must be feasible and cost-effective. Unfortunately, many thermoplastic materials contain colour pigments that cause undesired colour effects and, therefore, have to be removed before recycling. The purpose of this study was to reduce the inorganic colour pigments titanium dioxide, chromium(III) oxide and iron(III) oxide from acrylonitrile butadiene styrene. Based on experiences with dissolution-based polymer recycling, the two methods for removing these colour pigments studied in this project were filtration and centrifugation. Multiple laboratory-scale experiments were performed with two solvent formulations, acetone and CreaSolv^? SB. Using the filtration method, both solvent formulations achieved reduction rates of 80% for titanium and iron and 90% for chromium. While similar reduction rates were obtained with high-speed laboratory-type centrifuges for acetone solutions, the results for CreaSolv^? SB solutions were considerably lower under the same experimental conditions. Increasing the temperature or centrifugation speed, however, will also increase the reduction rates. Thereby, CreaSolv^? SB solutions become suitable for industrial-scale processes. This is important because industrial processes based on CreaSolv^? SB solutions are significantly safer than acetone-based processes.     

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).     

Chemical and physical characterization of electrode materials of spent sealed Ni-Cd batteries

The present work aimed at the chemical and physical characterization of spent sealed MONO-type Ni-Cd batteries, contributing to a better definition of the recycling process of these spent products. The electrode material containing essentially nickel, cadmium and some cobalt corresponds to approximately 49% of the weight of the batteries. The remaining components are the steel parts from the external case and the supporting grids (40%) containing Fe and Ni, the electrolyte (9%) and the plastic components (2%). Elemental quantitative analysis showed that the electrodes are highly concentrated in metals. The phase identification achieved by X-ray powder diffraction combined with chemical analysis and leaching tests allowed the authors to proceed with the composition of the electrode materials as following: cathode: 28.7% metallic Ni, 53.3% Ni(OH)2, 6.8% Cd(OH)2 and 2.8% Co(OH)2; anode: 39.4% metallic Ni and 57.0% Cd(OH)2. The morphology of the electrodes was studied by microscopic techniques and two phases were observed in the electrodes: (1) a bright metallic phase constituted of small nickel grains that acts as conductor, and (2) the main hydroxide phase of the active electrodes into which the nickel grains are dispersed. The disaggregation of the electrode particles from the supporting plates was easily obtained during the dismantling procedures, indicating that a substantial percentage of the electrodes can be efficiently separated by wet sieving after shredding the spent batteries.     

Transmission electron microscopy (TEM) investigations of Mn-oxide rich cathodic material from spent disposable alkaline batteries

Transmission electron microscopy (TEM) techniques were used to investigate the spent cathodic material of a single common brand of disposable alkaline batteries. Mn-oxide particles are anhedral and irregular in shape and compose an estimated 99-95% of the <10mum size fraction of sample material. Diameters of particles vary widely and typically are between 50nm and 3mum; however, most particles are approximately 200-400nm in diameter. Chemical composition varies for Mn-oxide particles with concentrations being SiO(2) (0.00-1.52wt%), TiO(2) (0.49-4.58wt%), MnO (65.85-92.06wt%), ZnO (1.00-7.53wt%), K(2)O (4.97-20.48wt%) and SO(3) (0.43-2.21wt%). Discrete prismatic zinc crystals occur and vary from a maximum of approximately 0.8mum longx0.15mum wide, to 100nm longx20nm wide. Titanium metal was also observed in samples and composes approximately 0.25-1.0% of the <10mum size fraction of sample material. Results of this study suggest that battery components may be recycled in some special applications. Examples are low energy-low material requirement products such as paint pigments and Zn nanoparticles. This investigation provides detailed constraints on the nature of spent cathodic materials to improve existing recycling methods and develop new technologies.     

Enhancement of the recycling of waste Ni-Cd and Ni-MH batteries by mechanical treatment

A serious environmental problem was presented by waste batteries resulting from lack of relevant regulations and effective recycling technologies in China. The present work considered the enhancement of waste Ni-Cd and Ni-MH batteries recycling by mechanical treatment. In the process of characterization, two types of waste batteries (Ni-Cd and Ni-MH batteries) were selected and their components were characterized in relation to their elemental chemical compositions. In the process of mechanical separation and recycling, waste Ni-Cd and Ni-MH batteries were processed by a recycling technology without a negative impact on the environment. The technology contained mechanical crushing, size classification, gravity separation, and magnetic separation. The results obtained demonstrated that: (1) Mechanical crushing was an effective process to strip the metallic parts from separators and pastes. High liberation efficiency of the metallic parts from separators and pastes was attained in the crushing process until the fractions reached particle sizes smaller than 2 mm. (2) The classified materials mainly consisted of the fractions with the size of particles between 0.5 and 2 mm after size classification. (3) The metallic concentrates of the samples were improved from around 75% to 90% by gravity separation. More than 90% of the metallic materials were separated into heavy fractions when the particle sizes were larger than 0.5 mm. (4) The size of particles between 0.5 and 2 mm and the rotational speed of the separator between 30 and 60 rpm were suitable for magnetic separation during industrial application, with the recycling efficiency exceeding 95%.     

Eco-friendly recovery process of lithium from reduction roasting residue powder based on hydrothermal extraction

Journal of Material Cycles and Waste Management - To cater to the increasing demand for secondary lithium-ion batteries, the recovery of valuable metal species in spent batteries is increasingly...     

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.     

Waste battery treatment options: Comparing their environmental performance

Waste consumer batteries are recycled using different routes based on hydrometallurgical and pyrometallurgical processes. Two hydrometallurgical and two pyrometallurgical treatment scenarios are compared starting from an average composition of Belgian waste batteries. The environmental performance is compared using life cycle analysis (LCA). The recycling rate is studied through mass balance calculation.Each treatment scenario results in a specific recycling rate. The environmental impact and benefits also vary between the treatment options. There is no such thing as a typical hydrometallurgical or pyrometallurgical treatment. When applying a hydrometallurgical treatment scenario, the focus lies on zinc and iron recycling. When allowing manganese recycling, the energy demand of the hydrometallurgical process increases considerably. Both pyrometallurgical options recycle zinc, iron and manganese. According to the LCA, none of the treatment scenarios performs generally better or worse than the others. Each option has specific advantages and disadvantages. The Batteries Directive 2006/66/EC sets out a recycling rate of 50% for consumer waste batteries. Based on metal recycling alone, the mass balances show that the target is difficult to obtain.     

Pyrolysis of municipal plastic wastes: Influence of raw material composition

The objective of this work is the study of pyrolysis as a feedstock recycling process, for valorizing the rejected streams that come from industrial plants, where packing and packaging wastes are classified and separated for their subsequent mechanical recycling. Four real samples collected from an industrial plant at four different times of the year, have been pyrolysed under nitrogen in a 3.5 dm³ autoclave at 500 °C for 30 min. Pyrolysis liquids are a complex mixture of organic compounds containing valuable chemicals as styrene, ethyl-benzene, toluene, etc. Pyrolysis solids are composed of the inorganic material contained in the raw materials, as well as of some char formed in the pyrolysis process, and pyrolysis gases are mainly composed of hydrocarbons together with some CO and CO₂, and have very high gross calorific values (GCV).It has been proved by the authors that the composition of the raw material (paper, film, and metals contents) plays a significant role in the characteristics of pyrolysis products. High paper content yields water in the pyrolysis liquids, and CO and CO₂ in the gases, high PE film content gives rise to high viscosity liquids, and high metals content yields more aromatics in the liquid products, which may be attributed to the metals catalytic effect.     

失效动力锂离子电池再利用和有用金属回收技术研究

动力锂离子电池以其贮电能力大、充放电速度快等优点被广泛应用在电动汽车上,近年来失效电动汽车动力锂离子电池报废量不断增加,但未得到有效处理回收,造成了巨大的资源浪费和环境污染.失效电池还有80％左右的容量可以使用,可以在场地车或者储能电站进行再利用,以达到材料和电池的最大利用率;同时电池中含有多种有用金属（如Co,Al,Ni,Li等）且相对含量较高,极具回收价值.针对失效动力锂离子电池的再利用和有用金属的各种回收方法进行了评述.