JP2001096236A - Device for classifying battery pack - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a device for classifying battery packs capable of classifying the battery packs with the simple device. SOLUTION: In classifying the battery packs 1, not the kinds of the battery packs 1 are discriminated by a magnetism measuring means 5 alone but the kinds of the battery packs are discriminated with the information having decreased measurement errors by the postures of the battery packs, such as the weight, area or volume information by a weight measuring means 7, an area measuring means utilizing a photographic device 11, etc., or a volume measuring means, by which the surer discrimination of the battery packs 1 is made possible.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for selecting a battery pack, and more particularly to a method for selecting a battery pack suitable for selecting a plurality of specified batteries.

[0002]

2. Description of the Related Art Various devices such as OA devices, audio devices, and wireless devices have been miniaturized with the development of semiconductor technology. Accordingly, battery packs of various types and shapes have been manufactured and sold for use in respective devices. Accordingly, various types of batteries such as lead-acid batteries, nickel-cadmium batteries, nickel-metal hydride batteries, lithium-ion batteries, and alkaline batteries have been developed.

[0003] In recent years, collection and recycling of these batteries have been required.

[0004] However, lead-acid batteries require the work of separating lead together with the recovery of sulfuric acid, and nickel-cadmium batteries use a vacuum furnace to recover metal cadmium by utilizing the difference in vapor pressure between cadmium and nickel. Since the recovery method differs depending on the type of the battery, such as the need for heat treatment, it is necessary to select various types of batteries.

On the other hand, although the collection of batteries has been progressing in recent years, it has not been sufficient to separate batteries by type, and various batteries are stored together and discharged after a certain amount is stored. It was seen as it was.

[0006] As described above, these batteries are classified based on the judgment criteria based on the difference in the shape and pattern of the battery for each product device, so that in the past it has been necessary to rely on manual labor.

On the other hand, recently, a method of sorting without relying on humans has also been proposed.

For example, in addition to a method of exciting a battery pack and detecting this signal, a method of applying a voltage to a battery to make a determination (Japanese Patent Application Laid-Open No. 6-215803) and a method of making a determination based on discharge characteristics (Japanese Patent Application Laid-Open No. 8-255636) ), A method of judging from internal resistance (JP-A-8-318223), a method of reading and judging a display (JP-A-8-287965), and the like.

However, in the method of exciting the battery pack, in order to determine a battery pack having a variety of shapes and structures having different excitation characteristics depending on the electrode direction of the battery inside the pack, the measurement result depends on the difference in the posture to be measured. Differently, there was a problem that it was not possible to sort by type accurately. Furthermore, even if the battery pack is arranged at a predetermined position with its orientation aligned, a problem arises in that a complicated device is required.

[0010]

As described above, the conventional method of separating battery packs has a problem that it cannot be accurately separated by excitation and requires a complicated apparatus.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a battery pack sorting apparatus capable of sorting with a simple apparatus.

[0012]

SUMMARY OF THE INVENTION The present invention provides a transporting means for transporting a battery pack, a first measuring means for measuring magnetism of the transported battery pack, and a weight and area of the transported battery pack. And a second measuring means for measuring one physical property value selected from the following, and a separating means for separating the battery pack according to the magnetism and physical property values obtained by the first and second measuring means. A battery pack sorting device, comprising:

That is, although the method of determining the type of the battery pack based on the measurement results of the magnetism is an effective method, the measurement results are different due to a difference in the attitude (direction) of the battery pack. In the present invention, the difference in the measurement results due to the difference in the posture of the battery pack is unlikely to occur, and the battery pack is discriminated by using the result of the weight measurement, the area measurement, or the volume measurement as a judgment material to more reliably separate the battery packs. be able to.

[0014]

Embodiments of the present invention will be described below with reference to the drawings.

FIG. 1 is a flowchart showing the flow of the present embodiment.

As shown in FIG. 1, in this embodiment, a personal computer equipped with a battery pack was disassembled, the disassembled parts were separated, and a battery pack was selected from the disassembled parts. Magnetization information, weight information, and area information are obtained from the battery pack by magnetization measurement means, weight measurement means, and area measurement means, and the information of these pieces of information is arithmetically processed. The type of the battery pack was determined by comparing it with the information value of the battery pack, and the result of this determination was transmitted to the classification means to separate the battery pack. Further, each material was recovered from the separated battery pack through a battery processing step.

FIG. 2 shows a separating means comprising the magnetization measuring means, the weight measuring means, the area measuring means and the separating means in FIG.

The battery pack 1 removed from the personal computer is conveyed to the magnetization measuring means 5 by the belt conveyor 3 to measure the magnetization, and the weight measuring means 7 continues.
Transported to The battery pack 1 weighed by the weight measuring means 7 is further conveyed to the area measuring means 11 by the belt conveyor 9 and the area is measured. The type of the battery pack is determined from the information obtained by the magnetization measuring means 5, the weight measuring means 7 and the area measuring means 9, and the battery pack 1 is placed in the containers 13a, 13b according to the result.
Alternatively, it was separated to 13c by the separation means 15.

This will be described more specifically.

This time, three types of laptop computers equipped with a battery pack were prepared, and the batteries,
It has been disassembled into components such as boards, keyboards, and liquid crystal displays.

The removed battery pack contained three types of nickel cadmium secondary battery, nickel hydride secondary battery, and lithium ion secondary battery.

These were applied to the battery pack sorting apparatus shown in FIG. First, the belt conveyor 3
Poured in. The posture of the battery pack 1 was set to the most mechanically stable posture so that the axis of the longitudinal direction of the battery pack 1 and the conveying direction of the belt conveyor 3 were substantially the same. However, the posture is not particularly limited as long as the posture is the same, and there is no particular problem with the posture as long as the posture is not limited by the information on the weight and the area.

A superconducting magnet 5-1 was used as the magnetization measuring means 5, and a magnetization measuring device 5-2 was installed at the subsequent stage. this time,
Hooke's law was used for the magnetization measuring means 5. That is, the magnet 5-1 was fixed to the spring, suspended from the spring 5-3, and the force attracted to the magnetized battery pack 1 was measured. This is not limited to force, and the distribution of magnetization may be measured with a coil or with a Hall element.

This time, the magnetization of the lithium ion secondary battery was determined as a ratio with respect to the nickel hydrogen secondary battery (magnetization ratio = (tensile force due to the magnetization of the lithium ion secondary battery)).
/ (Tensile force due to magnetization of nickel-metal hydride secondary battery)).

Further, these magnetisms may be independently derived from a simulation to determine the material, the ferromagnetic portion may be determined from the main physical quantity, or only the ferromagnetic portion may be estimated or obtained. Then, the information of the ferromagnetic portion and the magnetization of the vacuum may be subtracted from the obtained signal to determine from the information of the other portions.

Next, the battery pack 1 is connected to the weight measuring means 7.
And weighed.

The weight measuring means in FIG. 2 uses a balance, such as a balance, which uses a balance. However, it may be a scale that uses the Hooke's law, or data that can be converted into weight, such as frictional force.

Further, the battery pack 1 was conveyed by the belt conveyor 9 and the area was measured by the area measuring means 11.

The area measuring means 11 projected the area from the upper part of the battery pack 1 by an image photographing device arranged on the upper part of the belt conveyor 9 and calculated the area by image processing. Also, the battery pack 1 to be photographed
It is desirable to have 100 million pieces as a stable posture. Further, in this embodiment, the image is taken from the upper surface of the battery pack placed in a stable posture, but it is also possible to take an image from the side and measure the area.

Further, the image photographing apparatus may be a volume measuring means according to the present invention. That is, it is also possible to measure the volume of the battery pack 1 by performing arithmetic processing based on the area of the battery pack 1 measured by the image capturing device. Alternatively, a volume measuring means using a method of immersing the battery pack 1 in a liquid and obtaining from the increased amount of the liquid may be employed.

The measured physical quantity is determined by referring to the data group stored in the data holding device in advance and determining its position in the space. Although a norm space is generally introduced for this determination, the present invention is not particularly limited to this, and may be a determination method in which it is sufficient to be within a certain range.

Table 1 shows the ratios, weights, and areas of the three types of magnetization force of the nickel cadmium secondary battery, nickel hydride secondary battery, and lithium ion secondary battery obtained by the above-described measuring means. .

[Table 1] From these results, three-dimensional data has been obtained, and the result is mapped as shown in FIG.

The measured physical quantity is determined by referring to the data group stored in the data holding device in advance and determining its position in the space. Although a norm space is generally introduced for this determination, the present invention is not particularly limited to this, and may be a determination method in which it is sufficient to be within a certain range.

The battery packs thus discriminated are separated by a crane as the separating means 15 at the subsequent stage, and the containers 13a, 13a are provided for each of the nickel cadmium secondary battery, the nickel hydrogen secondary battery, and the lithium ion secondary battery.
b and 13c, and decided to carry out recycling suitable for each battery pack.

As the separating means 15, magnetism may be used. That is, the separation may be performed naturally by utilizing the magnetic force. In this case, the arithmetic processing may be omitted in some cases.

In the present embodiment, it is not necessary to use all physical quantities of magnetism, weight, area, and volume, but discrimination can be made by increasing the combination of magnetism, weight, area, and volume, and magnetism, weight, area, and volume. Accuracy can be increased.

Further, the separated battery packs were recycled as follows.

First, the separated nickel cadmium secondary battery is first roasted to remove organic substances and moisture, and then heated under reduced pressure until cadmium is vaporized. The vaporized cadmium is aggregated by a condenser and recovered as cadmium metal. Since oxidized nickel remains in the residue, this is used as a raw material such as stainless steel.

The nickel-hydrogen secondary battery is roasted to remove organic substances and moisture, and then melted in an electric furnace to form a magnetic material as an ingot.

Next, a method of recycling a lithium ion secondary battery will be described.

FIG. 4 is a flow chart of the recycling of the lithium ion secondary battery. The recycling of the lithium ion secondary battery was performed in such a flow.

First, it was immersed in about 1.0 mol / L hydrochloric acid aqueous solution and discharged. Of course, the acid in this case is not limited to hydrochloric acid, and the concentration is not limited to 1.0 mol / L. However, as compared with aqueous solutions of the same concentration of sulfuric acid, nitric acid, and sodium hydroxide, hydrochloric acid has an excellent effect of opening a part of the battery and extracting an internal electrolytic solution. However, the sulfuric acid has the shortest discharge time for batteries or battery packs having the same residual voltage, so that the safety of the device and the safety improvement by opening the battery, the length of discharge time and the throughput of the device, processing space, etc. It is preferable to select an acid in consideration of the above.

Next, it was confirmed that the voltage was 1.0 V / cell or less per cell, and crushed by a 3.7 kW uniaxial crusher (screen φ10 mm), the crushed pieces were about 5 to 10 m.
It was about m square. This crushing step is not limited to a simple uniaxial type. As described above, a manual operation or a robot may be used as long as the inside of the battery or the battery pack is exposed in an independent manner.

In the crushing process, it is more safe to completely short-circuit the battery with a twin-screw crusher and then crush with a single-screw crusher, but this time, the residual voltage is measured before crushing, Since the properties were confirmed, biaxial crushing was omitted.

The electrolyte volatilized during the crushing, which was adsorbed with activated carbon. Of course, this is not limited to activated carbon adsorption, but may be a combustion type.

The crushed pieces after the crushing were first subjected to magnetic separation to remove a magnetic substance mainly composed of a soft iron casing outside the battery. In some cases, the terminals of the battery pack are plated with gold, and the terminals enter the magnetic material. It is also possible to collect gold from this.

Next, the residue after removing the magnetic substance was sieved through a 1 mm sieve, and separated under and above the sieve. The portion under the sieve was directly sent to the subsequent acid dissolving step. On the sieve, inertia specific gravity sorting was performed. The processing conditions are such that aluminum is discharged to the lightweight side,
The conditions were such that separation was performed at a specific gravity of 2.69 g / cm ³ . This is because the aluminum casing of the lithium ion secondary battery having the aluminum casing cannot be removed in the magnetic separation step, but can be separated and recovered in the specific gravity separation step. Thus, a heavy object (aluminum foil coated with LiCoO ₂ as an active material, a PC resin, a circuit board, etc.) and a light object (copper coated with carbon as an active material, a separator,
(Aluminum housing).

The inertia specific gravity selection is based on balance between buoyancy due to wind force, frictional force due to vibration, and gravity due to swing. Therefore, depending on the shape, the sorting effect may be poor for small objects. 5-10 in our study
The order of mm square is the most excellent sorting efficiency, and if it is larger than this, the overlap on the deck is increased, so that it is difficult to uniformly give buoyancy. In addition, when it is smaller than this, the influence of the specific gravity difference is almost ignored, and the sorting efficiency is reduced.

[0049] This weighted product was treated with H ₂ SO ₄ (concentration 2.0mo).
1 / L) and hydrogen peroxide H ₂ O ₂ (0.6%) in an acid treatment solution (heated to 70 ° C.) for 2 hours to dissolve the positive electrode active material and the like. Although the sulfuric acid concentration is not limited to this concentration, it is preferable that the sulfuric acid be added in a theoretical equivalent amount or more with respect to Co. However, if added too much, the amount of waste liquid increases and the cost of the chemical solution also increases, so that an appropriate amount exists.

Hydrogen peroxide has the effect of accelerating the dissolution reaction of LiCoO ₂ , and it is preferable to add it in a theoretical equivalent amount to Co. Of course, the treatment time may be extended without the addition. The immersion time is not particularly limited to 2 hours, but is preferably determined in consideration of the amount of cobalt dissolved and the amount of copper dissolved. Other acids may be used for sulfuric acid. In this case, if electrolysis is used in the step of removing impurities, a gas such as Cl _{2 for} hydrochloric acid and NO _{2 for} nitric acid are generated. Need to use another method.

H ₂ O ₂ in this case acts as a reducing agent for the oxide. The solution contains Li ⁺ , Co ²⁺ ,
SO ₄ ²⁻ , and other impurities such as Cu ²⁺ , Fe ²⁺ , and A
l ^{3 +} etc. are dissolved.

The acid-treated solution is subjected to solid-liquid separation to remove those that do not dissolve such as resin (not shown), and then introduced into electrolytic dialysis. Cu deposited on the Cu electrode on the negative electrode side has high purity and can be reused. On the other hand, a part of the anion (SO ₄ ⁻ ) was separated into the positive electrode side electrode chamber by the anion separation membrane and sent to the subsequent concentration step. The condition is current control (8 A / dm ² )
Electrolysis was performed until Cu became 1 ppm (weight ratio) or less with respect to Co.

As mentioned above, the removal of copper is not limited to electrolysis. This time, electrolysis was performed to reduce the concentration of copper to a very small amount, but it is of course possible to remove it by pH adjustment described later. In addition, dialysis was performed at the same time,
This also has the purpose of reducing the amount of waste liquid by reducing the amount of alkali added at the time of pH adjustment in the subsequent stage while performing acid recovery with the amount of electric power performed in electrolysis. Of course, dialysis need not be performed.

Next, LiOH is added to the processing solution after Cu is removed.
The aqueous solution was spray added to raise the pH to 6.0. Co,
Most of metal ions such as Al and Fe other than Ni and alkali metals were precipitated as hydroxides, and these were removed by solid-liquid separation. This pH treatment is not limited to LiOH, and other alkalis such as NaOH can be used. However, if an alkali metal other than lithium is contained in the final recovered cobalt, the charge / discharge characteristics when this cobalt is used in a battery However, it is preferable to use LiOH. When using another alkali, it is necessary to carefully wash the recovered cobalt. Further spraying LiOH aqueous solution to the treatment liquid after lithium separation, raising the pH to 10 or more,
Co (OH) ₂ was precipitated and collected by solid-liquid separation. In this case, it is preferable to take the above-mentioned consideration into consideration for the added alkali.

The solution after the separation contains Li ⁺ as a cation.
Only included. Using a fluorine-based cation separation membrane, Li ⁺ was separated from the solution by electrolytic dialysis. The condition is a current control of 5 A / dm ² . Although the two-chamber type electrodialysis was used this time, the three-chamber type electrodialysis may be performed to collect sulfuric acid at the same time.

Next, a concentration operation was performed using an electrodialysis apparatus. Concentration of about 2 to 4 times is possible by electrodialysis. In electrodialysis, the final concentration of the recovered liquid is LiOHaq (20 g /
L) and H ₂ SO ₄ aq (2.0 mol / L). FIG. 5 shows the state of concentration of LiOHaq. Electrodialysis preferably uses Li ₂ SO ₄ aq for the electrode solution. Li is the smallest metal ion, but the surface charge density as an ion is the highest, so water molecules surround lithium ions in an aqueous solution, and the apparent radius of the ions is much larger than that of sodium or potassium. It has become. For this reason, if a cation exchange membrane having a relatively high molecular weight cutoff, for example, a molecular weight cutoff of 300, is used, the treatment can be performed easily and the concentration of the concentrate can be increased. An example of this concentration is shown in FIG. In order to compare this effect, FIG. 6 shows an example of concentration using a membrane having a molecular weight cut off of 100. As is clear from FIGS. 5 and 6, the concentration of Li is preferably such that the molecular weight cutoff has a certain size.

A part of the concentrated lithium was used again in the same step as an alkaline reagent. The remaining Li can be used as a battery raw material. Since the solubility of Li ₂ CO ₃ is smaller than that of other alkali elements, the method of recovering Li is generally to add sodium carbonate Na ₂ CO ₃ to make a solid. However, in this method, a waste liquid of NaOHaq is finally generated, so that CO ₂ gas is blown into the liquid to remove Li _2.
It is preferable to use a solid as CO ₃ because no waste liquid is generated. Also, dry ice may be added. As a form other than lithium carbonate, water is evaporated off to remove hydroxide LiO
It may be recovered in the form of H and its hydrate.

On the other hand, the recovered solution of sulfuric acid may be used again in the discharging step and the acid dissolving step of the battery treatment step, or can be used as another raw material. Water from which Li and SO ₄ have been removed can also be reused as industrial water in the process.

The substrate separated earlier is the harmful substance Pb.
This removal is carried out. Although this method is not particularly limited, for example, after removing organic matter and moisture in a dry distillation furnace, Pb is vaporized and recovered under reduced pressure heating, a vacuum heating method, and after dissolving in an acid solution, the pH is adjusted. Any of a wet method of adjusting and collecting the precipitate, a roasting method, and a copper mat, which is put into a copper blast furnace and collected in slag, and a mechanical separation method of scraping with a brush or the like may be used. Currently, under the Pb regulation, the above processing requires a processing cost,
Local governments or companies that are active in environmental conservation are trying each method, but if regulations are tightened in the future, the wet method and the vacuum heating method are expected to become mainstream.

This time, after removing the organic substances and moisture by dry distillation at 600 ° C. for 3 hours, the mixture was once cooled and then put into a heating furnace capable of reducing pressure again. When treated at 900 ° C. in an atmosphere of 0.01 Torr for 3 hours, 99% or more of Pb was recovered from the substrate. Copper, glass cloth, and carbon were recovered from the residue in the vacuum heating furnace. Copper was sold, and glass cloth and carbon were glass-solidified.

After the liquid crystal panel was crushed, it was placed in a supercritical apparatus, and water was used as a solvent to extract and decompose the liquid crystal in a subcritical state. The decomposition rate was 99% or more. Recovered materials are aromatic organic matter and glass. Aromatic organic matter was used as the heat source of the gasification combustion furnace. Glass was used as a base material for glass melting and solidification.

[0062]

According to the present invention, a battery pack can be easily identified, and processing and recycling suitable for reuse as battery raw materials can be performed.

[Brief description of the drawings]

FIG. 1 is a flowchart showing a battery recycling process performed in an embodiment of the present invention.

FIG. 2 is a battery pack sorting apparatus according to the present invention.

FIG. 3 is mapping data of a battery pack determination result.

FIG. 4 is a flowchart showing processing steps of a battery pack of a lithium ion secondary battery.

FIG. 5 is a diagram showing a time transition when Li is concentrated using a membrane having a molecular weight cutoff of 300.

FIG. 6 is a diagram showing a time transition when Li is concentrated using a membrane having a molecular weight cut off of 100.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Battery pack 3, 9 ... Belt conveyor 5 ... Magnetic measuring means 7 ... Weight measuring means 11 ... Photographing device (area measuring means or volume measuring means) 13 ... Container

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masaru Hayashi 1 Toshiba R & D Center, Komukai-shi, Kawasaki-shi, Kanagawa Pref. 1F Toshiba Town F-term in Toshiba R & D Center (reference) 3F079 AD06 CA26 CA27 CA29 CA36 CB04 CB12 CB24 5H031 AA09 RR04

Claims (1)

[Claims] 1. A transport means for transporting a battery pack, and a first means for measuring magnetism of the transported battery pack.
Measuring means, a second measuring means for measuring one physical property value selected from the weight, area and volume of the conveyed battery pack; and magnetism and physical properties obtained by the first and second measuring means. Separating means for separating the battery pack according to a value.