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.     

Characterization of spent AA household alkaline batteries

The aim of this work is identification of the structural components of actual domestic spent alkaline AA batteries, as well as quantification of some of their characteristics. Weight, humidity, ash content, zinc and zinc oxide on anode, manganese on cathode and other metals, potassium hydroxide on the internal components and heating values for papers, anode and cathode were determined in several batteries. As expected, cathode, anode and the steel can container are the main contributors to the 23.5 g average weight of the batteries. Cathode is also the major contributor to the positive heating value of the batteries as well as to the heavy metals content. Mercury was detected in very low levels in these mercury-free batteries. Zinc and zinc oxide amounts in the anodes are highly variable. Results obtained were compared to information on alkaline batteries in the literature from 1993 to 1995; and a positive evolution in their manufacture is readily apparent. Data from the producer of batteries shows some small discrepancies relative to the results of this experimental work.     

Laboratory study on the leaching potential of spent alkaline batteries using a MSW landfill leachate

Two leaching tests were carried out, one with whole batteries and another with cross-cut batteries. In both cases, NEN 7343 (a Nederland’s Standard) procedure was followed using a municipal solid waste (MSW) landfill leachate as extraction solution. Seven fractions were collected corresponding to cumulative liquid/solid (L/S) ratio from 0.1 to 10.0. Those fractions were separately characterized in terms of pH, conductivity, redox potential, density, sulphate, chloride, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb, Tl and Zn. Results showed that the influence of the alkaline batteries in the landfill leachate composition varies with their physical integrity and with the L/S ratio, and several variations were observed throughout the tests. The leachate pH and redox potential increased as result of the contact with batteries, particularly pH in the test with the cross-cut batteries. The leachate density and conductivity did not change significantly with the whole batteries, in contrast with the test with cross-cut batteries.     

Recycling of spent nickel-cadmium batteries based on bioleaching process

Only 1-2 percent of discarded dry batteries are recovered in China. It is necessary to find an economic and environmentally friendly process to recycle dry batteries in this developing country. Bioleaching is one of the few techniques applicable for the recovery of the toxic metals from hazardous spent batteries. Its principle is the microbial production of sulphuric acid and simultaneous leaching of metals. In this study, a system consisting of a bioreactor, settling tank and leaching reactor was developed to leach metals from nickel-cadmium batteries. Indigenous thiobacilli, proliferated by using nutritive elements in sewage sludge and elemental sulphur as substrates, was employed in the bioreactor to produce sulphuric acid. The overflow from the bioreactor was conducted into the settling tank. The supernatant in the settling tank was conducted into the leaching reactor, which contained the anode and cathodic electrodes obtained from nickel-cadmium batteries. The results showed that this system was valid to leach metals from nickel-cadmium batteries, and that the sludge drained from the bottom of the settling tank could satisfy the requirements of environmental protection agencies regarding agricultural use.     

Current situation of used household batteries in Iran and appropriate management policies

Used household batteries are considered as hazardous wastes in many countries due to the potential environmental and human health risks associated with the heavy metals present in batteries. This article presents the current situation of waste household batteries and policies in Iran. Iran with more than 70 million people is a developing country where latest technologies like cell phones and laptops are in widespread use and battery consumption increases accordingly. The household battery demand in Iran has rapidly grown since 2001 and it is expected to increase more quickly in next years, due to increasing technological development. Based on the available data, more than 9800 metric tons of household batteries were imported into Iran in recent decade, with the market value of about US$ 42.6 million. At present, there is no program available in Iran regarding to collection, separation, recycling or safe disposal of used batteries. Therefore, almost all of the spent household are discarded into municipal solid waste (MSW) and sent to sanitary landfills. Appropriate policies to meet safe disposal of household batteries in Iran is also discussed in this investigation.     

WEEE and portable batteries in residual household waste: Quantification and characterisation of misplaced waste

A total of 26.1 Mg of residual waste from 3129 households in 12 Danish municipalities was analysed and revealed that 89.6 kg of Waste Electrical and Electronic Equipment (WEEE), 11 kg of batteries, 2.2 kg of toners and 16 kg of cables had been wrongfully discarded. This corresponds to a Danish household discarding 29 g of WEEE (7 items per year), 4 g of batteries (9 batteries per year), 1 g of toners and 7 g of unidentifiable cables on average per week, constituting 0.34% (w/w), 0.04% (w/w), 0.01% (w/w) and 0.09% (w/w), respectively, of residual waste. The study also found that misplaced WEEE and batteries in the residual waste constituted 16% and 39%, respectively, of what is being collected properly through the dedicated special waste collection schemes. This shows that a large amount of batteries are being discarded with the residual waste, whereas WEEE seems to be collected relatively successfully through the dedicated special waste collection schemes. Characterisation of the misplaced batteries showed that 20% (w/w) of the discarded batteries were discarded as part of WEEE (built-in). Primarily alkaline batteries, carbon zinc batteries and alkaline button cell batteries were found to be discarded with the residual household waste. Characterisation of WEEE showed that primarily small WEEE (WEEE directive categories 2, 5a, 6, 7 and 9) and light sources (WEEE directive category 5b) were misplaced. Electric tooth brushes, watches, clocks, headphones, flashlights, bicycle lights, and cables were items most frequently found. It is recommended that these findings are taken into account when designing new or improving existing special waste collection schemes. Improving the collection of WEEE is also recommended as one way to also improve the collection of batteries due to the large fraction of batteries found as built-in. The findings in this study were comparable to other western European studies, suggesting that the recommendations made in this study could apply to other western European countries as well.     

Evaluation of heavy metal leaching from spent household batteries disposed in municipal solid waste

Batch leaching tests and simulated landfill lysimeter tests were performed to evaluate the contents of heavy metals leached from spent batteries in the municipal solid waste. The toxicity characteristic leaching procedure was utilized to perform the batch leaching tests of 36 spent batteries. Four lysimeters were prepared with battery contents ranging from 0% to 100% by weight for column tests, and the experiments were performed at ambient temperature. The age of all the batteries used in the study ranged from freshly disposed up to approximately 3 years old. The results from the batch tests showed that the type of battery influenced the heavy metal concentrations in the leached solutions. The lysimeter experiment results illustrated that at lower pH levels more metals are leached than at higher pH levels. The increasing amount of batteries disposed in landfills can contribute to the leaching of more metals, especially Mn and Zn, into the environment. These results indicate that the direct disposal of spent household batteries into a MSW landfill can increase the heavy metal contents in the landfill leachate.     

Removal of batteries from solid waste using trommel separation

This paper describes the design and testing of a trommel for separation of batteries from solid waste. A trommel is a cylindrical separation device that rotates and performs size separation. It has also been used in areas such as municipal solid waste (MSW) processing, classifying construction and demolition debris, screening mass-burn incinerator ash and compost processing. A trommel has been designed based on size separation to separate household batteries from solid waste, which can then be used as feedstock for alternative applications of solid waste combustion, particularly where the metal content of the product is also a critical parameter, such as the Co-Co process for integrated cement and power production. This trommel has been tested with batches of university office and restaurant wastes against various factors. The recovery efficiency of batteries increases with decreasing inclination angle of the trommel and decreasing rotational speed. A physical characterization of the university solid waste has been performed with a 20-kg sample of the tested waste. It was found that there is a trend of decreasing recovery of batteries with increasing paper composition, and a trend of increasing recovery of batteries with increasing organic materials composition.     

Laboratory study on the leaching potential of spent alkaline batteries

Four different leaching tests were carried out with spent alkaline batteries as an attempt to quantify the environmental potential burdens associated with landfilling. The tests were performed in columns filled up with batteries either entire or cross-cut, using either deionized water or nitric acid solution as leachant. In a first set of tests, the NEN 7343 standard procedure was followed, with leachant circulating in open circuit from bottom to top through columns. These tests were extended to another leaching step where leachant percolated the columns in a closed loop process.Leachate solutions were periodically sampled and pH, conductivity, density, redox potential, sulphates, chlorides and heavy metals (As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb, Tl and Zn) were determined in the samples.The results showed that the total amount of substances leached in tests with cross-cut batteries was higher than with entire ones; zinc and sulphates were the substances found the most in the leachate solutions. In general, the amount of substances dissolved in open circuit is higher than in closed loop due to the effect of solution saturation and the absence of fresh solution addition.Results were compared with metal contents in the batteries and with legal limits for acceptance in landfill (Decision 2003/33/CE and Decree-Law 152/2002). None of the metals were meaningfully dissolved comparatively to its content in the batteries, except Hg. Despite the differences in the experiment procedure used and the one stated in the legislation (mixing, contact time and granulometry), the comparison of results obtained with cross-cut batteries using deionized water with legal limits showed that batteries studied could be considered hazardous waste.     

Laboratory study on the behaviour of spent AA household alkaline batteries in incineration

The quantitative evaluation of emissions from incineration is essential when Life Cycle Assessment (LCA) studies consider this process as an end-of-life solution for some wastes. Thus, the objective of this work is to quantify the main gaseous emissions produced when spent AA alkaline batteries are incinerated. With this aim, batteries were kept for 1h at 1273K in a refractory steel tube hold in a horizontal electric furnace with temperature control. At one end of the refractory steel tube, a constant air flow input assures the presence of oxygen in the atmosphere and guides the gaseous emissions to a filter system followed by a set of two bubbler flasks having an aqueous solution of 10% (v/v) nitric acid. After each set of experiments, sulphur, chlorides and metals (As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb, Tl and Zn) were analyzed in both the solutions obtained from the steel tube washing and from the bubblers. Sulphur, chlorides and metals were quantified, respectively, using barium sulfate gravimetry, the Volhard method and atomic absorption spectrometry (AAS). The emissions of zinc, the most emitted metal, represent about 6.5% of the zinc content in the batteries. Emissions of manganese (whose oxide is the main component of the cathode) and iron (from the cathode collector) are negligible when compared with their amount in AA alkaline batteries. Mercury is the metal with higher volatility in the composition of the batteries and was collected even in the second bubbler flask. The amount of chlorides collected corresponds to about 36% of the chlorine in the battery sleeve that is made from PVC. A considerable part of the HCl formed in PVC plastic sleeve incineration is neutralized with KOH, zinc and manganese oxides and, thus, it is not totally released in the gas. Some of the emissions are predictable through a thermodynamic data analysis at temperatures in the range of 1200-1300K taking into account the composition of the batteries. This analysis was done for most of potential reactions between components in the batteries as well as between them and the surrounding atmosphere and it reasonably agrees the experimental results. The results obtained show the role of alkaline batteries at the acid gases cleaning process, through the neutralization reactions of some of their components. Therefore, LCA of spent AA alkaline batteries at the municipal solid waste (MSW) incineration process must consider this contribution.     

Survey of mercury,cadmium and lead content of household batteries

The objective of this work was to provide updated information on the development of the potential impact of heavy metal containing batteries on municipal waste and battery recycling processes following transposition of the new EU Batteries Directive 2006/66/EC. A representative sample of 146 different types of commercially available dry and button cells as well as lithium-ion accumulators for mobile phones were analysed for their mercury (Hg)-, cadmium (Cd)- and lead (Pb)-contents. The methods used for preparing the cells and analysing the heavy metals Hg, Cd, and Pb were either developed during a former study or newly developed. Several batteries contained higher mass fractions of mercury or cadmium than the EU limits. Only half of the batteries with mercury and/or lead fractions above the marking thresholds were labelled. Alkaline–manganese mono-cells and Li-ion accumulators, on average, contained the lowest heavy metal concentrations, while zinc–carbon batteries, on average, contained the highest levels.     

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%.     

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.     

The BATINTREC process for reclaiming used batteries

The Integrated Battery Recycling (BATINTREC) process is an innovative technology for the recycling of used batteries and electronic waste, which combines vacuum metallurgical reprocessing and a ferrite synthesis process. Vacuum metallurgical reprocessing can be used to reclaim the mercury (Hg) in the dry batteries and the cadmium (Cd) in the Ni-Cd batteries. The ferrite synthesis process reclaims the other heavy metals by synthesizing ferrite in a liquid phase. Mixtures of manganese oxide and carbon black are also produced in the ferrite synthesis process. The effluent from the process is recycled, thus significantly minimizing its discharge. The heavy metal contents of the effluent could meet the Integrated Wastewater Discharge Standard of China if the ratio of the crushed battery scrap and powder to FeSO4.7H2O is set at 1:6. This process could not only stabilize the heavy metals, but also recover useful resource from the waste.     

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.     

Depollution benchmarks for capacitors,batteries and printed wiring boards from waste electrical and electronic equipment (WEEE)

The article compiles and analyses sample data for toxic components removed from waste electronic and electrical equipment (WEEE) from more than 30 recycling companies in Switzerland over the past ten years. According to European and Swiss legislation, toxic components like batteries, capacitors and printed wiring boards have to be removed from WEEE. The control bodies of the Swiss take back schemes have been monitoring the activities of WEEE recyclers in Switzerland for about 15 years. All recyclers have to provide annual mass balance data for every year of operation. From this data, percentage shares of removed batteries and capacitors are calculated in relation to the amount of each respective WEEE category treated. A rationale is developed, why such an indicator should not be calculated for printed wiring boards. The distributions of these de-pollution indicators are analysed and their suitability for defining lower threshold values and benchmarks for the depollution of WEEE is discussed. Recommendations for benchmarks and threshold values for the removal of capacitors and batteries are given.     

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.     

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).     

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.