JPWO2000019557A1 - Battery disassembly method - Google Patents

Abstract

(57) [Abstract] The present invention provides a safe and efficient method for dismantling and processing used lithium-ion batteries. More specifically, the present invention is characterized by comprising a case breaking and sorting process in which the plastic cases protecting the sealed battery cells are stably and reliably separated outside the system, and valuable materials such as lithium cobalt oxide, a lithium-transition metal composite oxide, aluminum, and copper are separated and recovered. The process involves cooling the batteries to -50°C or below and repeatedly vibrating or applying clamping pressure to the batteries using multiple objects that are more rigid and have a higher specific gravity than the plastic, thereby separating the batteries into sealed battery cells and plastic cases; a heating and separation process in which the sealed battery cells sorted in the case breaking and sorting process are heated to a temperature of at least 200°C or higher in a non-oxidizing atmosphere to separate mainly organic materials; and one or more sorting processes in which noise substances are sequentially removed from the crushed material crushed in the cell crushing process to separate the target useful materials.

Description

Detailed Description of the Invention

Technical Field This invention relates to a sealed battery (sealed battery cell) protected by a plastic case.
This invention relates to a method for dismantling and treating batteries, particularly non-aqueous solvent batteries, and more particularly to a method for dismantling and treating batteries.
The present invention relates to a method for treating a battery in which the electrolyte contains a salt consisting of a cation and a Lewis acid ion.
In particular, used lithium-ion batteries containing lithium hexafluorophosphate as the electrolyte
This article describes a safe and efficient method for disposing of non-aqueous batteries. Here, non-aqueous solvent batteries use a non-aqueous solvent as the electrolyte and a light battery such as lithium as the negative electrode.
This refers to non-aqueous electrolyte secondary batteries that use metals. Non-aqueous solvents refer to all solvents other than water, including pure solvents other than water.
This includes not only solvents but also mixtures of several solvents. Background Technology In light of the recent trend toward global warming, the expansion of new thermal power plants has been curtailed, and the availability of electricity is becoming increasingly
There is a call for efficient use, and one way to achieve this is to temporarily store surplus electricity at night and release it during the day.
It is also possible to encourage the leveling of power usage, and secondary batteries for power storage that can accommodate this are being developed.
The emergence of large-scale second-generation solar power plants as a power source for automobiles is expected from the standpoint of preventing air pollution.
It is hoped that rechargeable batteries will soon be put into practical use. Small rechargeable batteries are also being used as backup power sources for computers, word processors, etc., and for small
As the power supply for household appliances, especially portable electrical appliances, becomes more widespread and performance improves, demand is increasing year by year.
In response to this expanding demand for batteries,
There is also a strong demand for the effective use of chemical substances and the establishment of measures to prevent environmental pollution caused by batteries.
These secondary batteries require high performance in proportion to the performance of the equipment they are used in.
The positive electrode active material is mainly an intercalation compound containing lithium ions.
Lithium-ion batteries that use graphite as the negative electrode active material have been put into practical use.
The lithium-ion battery contains valuable reusable materials such as lithium and transition metals.
However, they react easily with negative electrode active materials such as reactive alkali metals and water.
Electrolytes containing harmful substances are also used. Therefore, when dismantling used non-aqueous solvent batteries such as lithium-ion batteries,
Safely deactivates active materials such as electrolytes and other reactive substances while providing valuable, reusable materials.
It is necessary to efficiently recover materials and dismantle them safely. However, lithium-ion batteries contain metals that react with water to generate hydrogen.
The compound contains lithium and an organic solvent, and the mixture of these flammable compounds
It is difficult to recover valuable materials such as lithium cobalt oxide from lithium batteries that contain
For example, Japanese Patent Application Laid-Open Nos. 6-346160 and 7-245126 disclose the use of used
To recover valuable materials including cobalt (lithium cobalt oxide) from lithium secondary batteries,
To do this, used lithium secondary batteries are roasted and then crushed, and the crushed material is sieved.
A technology has been disclosed for recovering valuable materials from the underside of the sieve using magnetic sorting, etc. In addition, Japanese Patent Laid-Open Publication No. 7-207349 discloses a technology for recovering valuable materials from the underside of the sieve using magnetic sorting, etc.
The sieve obtained by first burning at 0 to 1000°C, then crushing the material, and then sieving the crushed material.
The bottom is subjected to secondary combustion, then treated with acid, and then an oxidizing gas is blown into the treated liquid.
The pH of the treated liquid is adjusted to 4 to 5.5, and the liquid is filtered. Then, an alkali is added to the filtrate.
A technology has been disclosed for recovering valuable materials from the sediment. However, the sealed battery cells of lithium-ion batteries are protected by a plastic case.
The battery is sealed and contains the negative electrode active material, separator, and positive electrode active material.
The battery, electrolyte, current collector, etc. are protected in a sealed battery cell case made of stainless steel or iron.
Therefore, unlike any of the above technologies, it is not possible to recycle used lithium secondary batteries for 35 minutes.
When primary combustion occurs at 0 to 1000°C, the heat of combustion causes the cobalt in the sealed battery cell to
The lithium oxide decomposes to generate oxygen, and at the same time, the volatile (flammable) solvent in the electrolyte
The evaporation pressure causes the cell case to rupture, and the evaporated flammable organic solvent
The agent and oxygen may ignite or explode due to a sudden increase in internal pressure.
Also, Japanese Patent Laid-Open No. 6-251805 describes a method for removing a liquid by using a water jet or other means.
After opening the lithium battery case by cutting or drilling,
The lithium, hydrogen by-product, and electrolyte are recovered.
By using it in this way, it can be recycled safely and efficiently without causing ignition that could lead to a fire.
In particular, the technology to prevent ignition of hydrogen from cutting the battery case is disclosed.
The process is carried out under an inert gas atmosphere to prevent this, but because a water jet is used,
The temperature is room temperature, and the presence of water at room temperature can cause
The reactive lithium contained in the fuel reacts violently with moisture in the air to produce flammable hydrogen gas.
This generates gases, causing problems as described below. Furthermore, JP-A-6-338352 discloses that in step 1, a negative electrode containing lithium is exposed.
In addition to the step 2 of separating the electrolyte from the battery,
In order to prevent the generation of a large amount of hydrogen due to contact with lithium ion, the first condition is
The negative electrode surface containing the polymer is treated with a treatment solution such as alcohol or water, and then subjected to the second condition.
The inside of the negative electrode containing lithium was treated with the treatment solution as described above in step 3.
And in the prior art, the process of exposing the lithium-containing negative electrode involves drying.
Hammer crushers, diamond cutters, cutter mixers, etc. in dry air
However, as mentioned above, the technology of crushing the sealed battery cells into a single unit is
The plastic case and the metal sealed battery cell case are simultaneously sealed.
The cutting is performed integrally, so that the fragments of the cell case do not contain any plastic case residue.
Not only is it difficult to separate and remove the undischarged lithium ion battery,
When the pond is crushed, the positive and negative electrodes come into contact and a short-circuit current flows.
The temperature inside the battery rises due to the generated Joule heat, and the positive electrode is
The lithium cobalt oxide that forms the electrolyte decomposes to generate oxygen, and at the same time, the volatile
The (flammable) solvent evaporates, and the evaporated flammable organic solvent and oxygen are used for cutting.
The resulting sparks may ignite the container, or the sudden rise in internal pressure may cause an explosion.
In addition, in the above-mentioned prior art, contact of lithium with water or alcohol can cause
In order to prevent the generation of large amounts of hydrogen, a two-stage treatment was carried out under the first and second conditions.
However, in order to carry out the two-stage treatment, the amount of hydrogen generated is monitored while supplying it.
The composition and supply amount of the processing solution must be controlled, and this control is complicated.
Not only that, but the fundamental drawback of hydrogen generation cannot be resolved. Next, taking into account the problems of the prior art described above, we will discuss the Li-ion battery, which is a representative dismantled battery of the present invention.
This article explains the structure of lithium-ion batteries and their basic issues. These lithium-ion batteries consist of multiple sealed battery cells (battery
The cell manufacturing substrate and the wiring for electrical connection are covered with plastic.
The sealed battery cell has a plastic case, with the plastic case accounting for 20% by weight. Furthermore, the sealed battery cell includes a positive electrode, a positive electrode current collector coated with the positive electrode, a negative electrode, and a negative electrode
A coated negative electrode current collector, a separator interposed between the two current collectors, and a cell housing
The positive electrode current collector is made of a thin plate-like material such as aluminum foil, and the negative electrode current collector is made of
Thin plate-like materials such as copper foil are used. The positive electrode active material is made of lithium ions such as lithium cobalt oxide and a specific metal.
The present invention is composed of a lithium-containing composite metal oxide, a mixture thereof, or a surface solution thereof.
The positive electrode is made of the above-mentioned positive electrode active material and an electron conduction supplement such as acetylene black.
Auxiliary material (conductive agent), polypyridinium chloride, and solvent n-methylpyrrolidone
The cathode current collector, such as aluminum foil, is coated with a coating agent prepared from lithium. The anode active material is a substance that can absorb and release lithium, such as lithium metal or
Lithium-containing compounds are widely used in these devices, but these lithium-containing compounds contain lithium.
Lithium-containing compounds other than lithium alloys include, for example, carbon with a turbostratic structure.
Materials such as graphite can be used as anodes, even if they do not contain lithium at the time of manufacture.
When the negative electrode is charged, it becomes lithium-containing through chemical and electrical processes. The negative electrode is then charged with the above negative electrode active material and a binder consisting of polypyridinium chloride.
and a solvent, n-methylpyrrolidone, is used to prepare a coating agent for negative electrode current collectors such as copper foil.
The electrolyte is applied to the body. Next, the electrolyte is, for example, ethylene carbonate, diethylene carbonate,
ester, dimethyl carbonate, diethyl ether, etc., alone or in combination
The solvent may be, for example, lithium hexafluorophosphate LiPF₆Fluorine compounds such as
An organic electrolyte solution containing two or more types of electrolytes is used. The separator is made of a porous resin film such as a porous polypropylene film.
The sealed battery cell is made of the sheet-shaped electrode current collector formed as described above and the sheet
The spiral structure formed by interposing a separator between the negative electrode current collector and the organic electrolytic capacitor is
The liquid is mixed with a cell housing made of nickel-plated copper or stainless steel.
The cell housing is generally sealed in a housing with internal pressure.
A safety valve is installed to prevent explosion due to overheating. In contrast to the above lithium primary batteries, non-aqueous electrolyte batteries using metallic lithium as the negative electrode are also available.
In this case, the negative electrode is depleted by repeated charging and discharging.
Metallic lithium and other substances grow into dendrites, causing short circuits with the positive electrode and shortening the battery life.
To solve this problem, carbon materials have recently been used as negative electrode active materials.
In this case, a non-aqueous electrolyte secondary battery using a lithium complex as a positive electrode active material has been proposed.
By using alloy oxides, it is possible to create a safe, long-life, high-energy-density secondary battery.
Therefore, the lithium-ion battery is unstable in its battery activity due to the atmosphere, water, or temperature.
Because they contain reactive substances and electrolytes, the following problems arise when processing them: (1) In addition to sealed battery cells, waste batteries may contain single or multiple sealed battery cells.
The plastic case that holds the battery accounts for 20% of the weight, and cobalt is recovered.
It is economical to separate it from the system as quickly as possible. (2) For example, an undischarged lithium-ion battery using lithium cobalt oxide as the positive electrode material.
When crushed at room temperature, the positive and negative electrodes come into contact with each other, causing a short-circuit current to flow.
This causes the temperature inside the battery to rise due to the Joule heat generated. (3) This temperature rise further causes the lithium cobalt oxide that makes up the positive electrode to decompose.
At the same time that oxygen is generated, the volatile (flammable) solvent in the electrolyte evaporates. The evaporated flammable organic solvent and oxygen are ignited by the sparks generated during cutting.
This may cause a fire or an explosion due to a sudden increase in internal pressure. This type of fire may also occur in discharged batteries. (4) Furthermore, the reactive lithium contained in undischarged lithium-ion batteries
reacts violently with moisture in the air to produce flammable hydrogen gas.
This can also occur in ponds, potentially generating flammable hydrogen gas. (5) Also, fluorine compounds such as lithium hexafluorophosphate, which are used as electrolytes, react with moisture in the air.
There is a risk of reaction to generate toxic gases such as phosphorus pentafluoride and hydrogen fluoride.
Examples of the electrolyte for the lithium ion battery include ethylene carbonate,
Diethylene carbonate, dimethyl carbonate, diethyl ether, etc.
or a mixed solvent of two or more kinds thereof, for example, lithium hexafluorophosphate LiPF₆Fluorine etc.
An organic electrolyte in which one or more compounds are dissolved is used.
Fluorine compounds such as lithium hexafluorophosphate react with moisture in the air to form pentafluorine.
There is a risk of generating toxic gases such as phosphorus chloride and hydrogen fluoride.
As a substance, arsenic hexafluoride phosphate generates toxic gases such as arsenic fluoride and hydrogen fluoride.
This reaction also occurs in other non-aqueous discharge batteries, and pentafluoride
There is a risk of generating toxic gases such as phosphorus pentafluoride, arsenic pentafluoride, and hydrogen fluoride. (6) In addition, lithium-ion batteries use an electrolyte as an intermediary to charge lithium cobalt oxide.
The aluminum is a positive electrode piece coated with a coating agent on aluminum foil, and the graphite is a copper foil current collector.
The negative electrode piece is coated with a coating agent, and polypropylene and polyethylene are used as separators.
The container components, such as steel and aluminum, are used as the cell housing.
However, when the battery is processed, these components are reusable.
In particular, the positive electrode pieces contain valuable materials such as coating agents.
Separation and recovery of lithium cobalt oxide from coated aluminum and anode pieces
In this case, it is more difficult to separate and recover copper than when graphite is applied. (7) Secondary batteries (hereinafter referred to as positive) used in laptop computers and mobile phones, etc.
A battery pack is one in which the plastic case is enclosed, and a battery in which the plastic case is enclosed is
In the case of a battery cell, a sealed battery cell is enclosed
The plastic case accounts for 20% of the weight, and the cobalt is recovered.
As mentioned above, it is economical to separate the product from the system as quickly as possible.
However, as will be shown in the following Prior Art section, hammer crushers and diamond cutters
Furthermore, the plastic case is opened using a cutter mixer or similar tool to expose the sealed battery cell.
When I tried to do this, the plastic case residue stuck to the crushed cell case.
This not only makes it difficult to separate and remove the sealed battery cells, but also makes it difficult to crush the sealed battery cells in a later process.
When the cathode and anode are connected, the residue causes contact between the cathode and anode, causing a short-circuit current to flow.
There is a possibility of explosion due to a sudden rise in internal pressure within the cell. On the other hand, the battery pack can be incinerated to burn the outer plastic case.
Even if you do, the heat of combustion will decompose the lithium cobalt oxide inside the sealed battery cell.
At the same time, the volatile (flammable) solvent in the electrolyte evaporates, generating oxygen.
Flammable organic materials and oxygen may ignite, or an explosion may occur due to a sudden increase in internal pressure.
Therefore, even if the battery is crushed or burned at room temperature, the plastic case and
It was difficult to safely and efficiently crush sealed battery cells using conventional technology. Therefore, in the prior art of WO94/25167, a battery pack was sealed in a plastic container.
In order to separate and rupture the battery case and battery cells, the battery pack is placed in a liquid nitrogen bath or the like.
After lowering the temperature to approximately -100°C, the object is dropped from a height of 5 to 20 meters.
More specifically, the impact energy is 700 to 1000 times the energy of the impact energy.
The rotor has a scoop blade with a rotational force of about 900 rpm.
The plastic case was then dropped by applying an acceleration force to the battery and crashing it into the wall of the drop tower.
However, a large impact energy of 100 J/kg to 600 J/kg can be generated in a single impact.
It is also difficult to apply the force stably by collision alone, and as a result, this conventional technology is not practical.
It can be said that this is poorly effective. Furthermore, Japanese Patent Application Laid-Open No. 10-241748 is a technology similar to the above-mentioned prior art and the present invention.
However, this prior art does not allow the sealed battery cell and the plastic to be separated by freezing and breaking.
It is not sorted into a plastic case, but is a safe container after removing the plastic case.
This involves freezing and crushing the sealed battery cells themselves, which have full valves, but the target is different. Disclosure of the Invention The objective of this invention is to provide a safe and efficient method for dismantling used lithium-ion batteries.
More specifically, the plastic case that protects the sealed battery cell is
The primary objective is to stably and reliably separate the source from the system as quickly as possible.
The second purpose is to investigate the cause of short circuit between positive and negative electrodes when opening a lithium-ion battery.
The third purpose is to prevent short circuits in order to prevent accidents caused by excessive short circuit currents. The third purpose is to prevent the decomposition of lithium cobalt oxide, a component of the positive electrode, due to temperature rise.
This prevents oxygen generation due to the oxidation of the electrolyte and prevents evaporation of the volatile solvent in the electrolyte.
The fourth purpose is to dissolve reactive lithium remaining in the lithium battery in water in the atmosphere.
The fifth purpose is to prevent the generation of flammable hydrogen gas by reacting with fluorine compounds such as lithium hexafluorophosphate in the electrolyte and the atmosphere.
The sixth objective is to extract electrolytes, solvents containing electrolytes, and solids from the crushed and pulverized mixture.
The seventh objective is to carry out the dismantling process while completely separating the solvent system and the solids processing system.
In particular, in the treatment of solids, toxic electrolyte fluorine compounds and flammable solvents are used.
Remove any intervening materials and dismantle the material without any consideration for them.
The eighth objective is to improve the recovery efficiency of lithium cobalt oxide and the purity of the recovered material.
The ninth object is to provide a method for treating a battery containing a salt consisting of a cation and a Lewis acid ion, particularly a lithium battery.
The present invention provides a safe and efficient method for dismantling and processing lithium-ion batteries.
prevents the generation of toxic gases from fluorine compounds such as lithium hexafluorophosphate in the electrolyte.
The object of the present invention is to provide a method for safely disposing of lithium-ion batteries while taking into account the above-mentioned factors. Other objects of the present invention will become clear from the description of the invention and the examples below.
However, both are lithium-transition metal composite oxides, lithium cobalt oxide and aluminum
Safe and efficient separation and recovery of valuable materials such as aluminum and copper, especially from lithium-ion batteries
The objective of this invention is to provide an efficient disposal method. Next, the configuration of this invention will be explained. The present invention relates to a sealed battery body (hereinafter referred to as a battery cell) made of plastic.
A method for treating a battery pack (hereinafter referred to as "battery") protected by a case, wherein the battery is cooled to -50°C or below and is made of a material that is more rigid than the plastic.
Repeated vibration or clamping pressure is applied to the battery using multiple objects with high specific gravity.
The batteries are then sorted into sealed battery cells and plastic cases.
and a step of separating the sealed battery cells selected in the case-breaking sorting step from the sealed battery cells in a non-oxidizing atmosphere.
The battery cell is heated to a temperature of at least 200°C to separate mainly organic materials.
It is characterized by including a thermal separation process. That is, as explained in the prior art, a large amount of 100 J/kg to 600 J/kg is
It is difficult to apply collision energy stably in only one collision.
The battery is repeatedly subjected to vibration or clamping pressure to remove the battery from the sealed battery cell.
The plastic cases are crushed and sorted. More specifically, the case crushing and sorting process involves cooling the plastic cases to -50°C or below.
Vibration was applied to a mixture of multiple objects with higher rigidity and specific gravity than plastic and the battery.
The vibration is preferably low frequency vibration, for example, by using a ball vibration device.
In this case, the size of the vibration-imparting ball is 0.2 times the volume of the separated battery cells.
1 times or less. The case breaking and sorting step involves cooling the plastic under conditions of -50°C or less.
The plastic is sandwiched between multiple objects with higher rigidity and specific gravity than plastic, and vibration is applied.
The pack case and the battery cell are preferably crushed and separated.
The object is rotated when cooled to -50°C or below and has a circular, elliptical, or
It is a square shaft (including hollow shafts), and the vibration applied to the rotation space is low frequency vibration.
It is preferable that the battery be sealed and protected by a plastic case. The present invention is also directed to a method of treating a battery in which the sealed battery cell is protected by a plastic case.
This is not necessarily limited to lithium-ion batteries or non-aqueous solvent batteries.
Do not do this. The separation of the plastic case and sealed battery cell is also important because the sealed battery cell case is magnetic.
In the case of aluminum, magnetic separation may be performed.
The materials can be selected by using differences in specific gravity or sieving, and the selection method is optional. Next, the second aspect of the invention will be explained. As mentioned above, aluminum foil is used as the positive electrode current collector for lithium-ion batteries.
A thin plate-like member such as copper foil is used as the negative electrode current collector.
When a battery cell containing these is burned in air, the positive electrode aluminum in the cell
The aluminum and anode copper are oxidized to aluminum oxide and copper oxide.
Aluminum and copper oxide are fragile, so they are used as a positive electrode current collector, with fine particles attached to aluminum foil, etc.
When the lithium cobalt oxide particles are peeled off, the aluminum oxide particles are also peeled off.
These are mixed with the recovered lithium cobalt oxide to produce the cobalt oxide product.
The purity of lithium decreases. On the other hand, in JP 10-241748 A, the sealed battery cell is treated with an electrolyte solvent.
However, this prior art technology involves crushing sealed battery cells while maintaining the temperature below their melting point, which can lead to the following problems:
Such problems arise. Sealed battery cells contain polyethylene and polypropylene, which form separators, etc. The bulk density of these materials is approximately 0.2, and they must be efficiently separated in post-processing.
To process the batteries efficiently, they must be large-scaled. Furthermore, it is difficult to completely separate the metal components from the resin components, such as polyethylene and polypropylene, using only freeze-shredding. Therefore, the second feature of this invention is that the sealed battery cells are equipped with safety valves.
The sealed battery cells that have undergone the case rupture screening process of the first aspect are then subjected to a non-oxidizing treatment.
The battery cell is heated to a temperature of at least 200°C in an atmosphere, and the
The process is characterized by including a heating and separation process to separate the materials. The temperature is set to 500°C or higher to completely separate and remove the organic resin components.
It is preferable to do so, and in order to further suppress the generation of dioxins and other substances in the exhaust gas,
It is preferable to heat the material at a temperature of approximately 800°C or higher. Furthermore, non-oxidizing atmospheres include vacuum atmospheres and inert gas atmospheres. According to the present invention, as shown in Figures 1 and 7, for example, a vacuum or inert gas atmosphere is used.
When the sealed battery cell is heated to 200°C or higher in a gas atmosphere, polypropylene and
Separator components such as polyethylene, electrolyte lithium hexafluorophosphate, etc.
Ethylene carbonate, diethylene carbonate, dimethyl carbonate as catalysts
nate, diethyl ether, etc., in other words, the thermal decomposition of organic solvents and organic resins
When substances are released and dispersed from the safety valve of the battery cell, the gases that are dispersed are flammable.
Highly flammable organic solvents are also included, but the atmosphere is vacuum or inert gas atmosphere.
Since the container is in an oxygen-containing atmosphere, there is a risk of explosion due to ignition by oxygen or a sudden increase in internal pressure.
Furthermore, the reactive lithium contained in undischarged lithium-ion batteries is
Also, aluminum foil coated with lithium cobalt oxide as a positive electrode piece and graphite
The copper foil as the negative electrode piece to which the oxidizing agent is applied is also not oxidized, and as a result, the battery cell
The aluminum and copper foil inside will not oxidize, in other words, will not become brittle.
Therefore, when peeling off fine particles of lithium cobalt oxide that have adhered to aluminum foil, etc.
These do not become minute, but remain in the form of foil or metal molecules (when melted by heat).
Even in the case of lithium cobalt oxide, the recovery of lithium cobalt oxide is easy, and it can be used as a product.
The purity of the lithium cobalt oxide is improved. That is, when the non-oxidizing atmosphere is a vacuum atmosphere,
The organic materials such as the organic solvent and the thermal decomposition product of the organic resin separated by heating are cooled and recovered.
According to the present invention, the non-oxidizing atmosphere is preferably nitrogen, helium, argon, or neodymium.
In the case where the gas material is heated and separated under an inert gas atmosphere such as argon,
Heating other liquid or solid materials in an inert gas or other non-oxidizing gas atmosphere
The roasting is carried out after the battery is removed. Furthermore, the invention in claim 5 and following claims specifically describes the battery disassembly processing method in order.
and a case-breaking sorting process to separate the batteries into sealed battery cells and plastic cases.
and Separating mainly organic materials from the sealed battery cells sorted in the case cracking sorting process.
As mentioned above, the process further includes the step of crushing the cells in the cell crushing step.
One or more selection methods are used to sequentially remove noise substances from the crushed material and select the target useful substance.
The invention described in claim 6 is characterized by including a separate process. And in the invention described in claim 6, ultrasonic vibration or ball
Separating the positive (negative) electrode active material from the metal foil by vibration peeling means such as vibration.
Similarly, in the invention described in claim 7, the peeling agent is used, or
The peeling agent is combined with a vibration peeling means to remove the positive (negative) electrode active material from the metal foil.
It is specified that the strong acid or strong alkaline solution is separated. Furthermore, in the invention described in claim 8,
This method dissolves the metal foil and separates the positive (negative) electrode active material. This method separates metal foil, such as aluminum foil or copper foil, from valuable cobalt oxide.
Lithium and spherical graphite are separated, but the lithium cobalt oxide and spherical graphite fine particles
Since it is a powder, it is difficult to handle it during subsequent roasting etc.
Therefore, in the present invention, the powder material containing the metal foil and the positive (negative) electrode active material is sieved.
The invention is characterized in that after separation by granulation, the powder material is granulated. According to this invention, the lithium cobalt oxide and spherical graphite powder are
This results in a more briquette-like texture, which makes subsequent roasting easier. Note that roasting is not necessarily a necessary condition, and as described in claim 15,
The metal foil and the powder material containing the positive (negative) electrode active material are separated by sieving, and then the
The recovered material is separated by settling in water to remove carbon and other substances, and the resulting lithium cobaltate is
In this case, the effluent discharged from the submerged sedimentation process is subjected to floatation separation to remove carbon and other substances.
Advantageously, the method further comprises a step of removing the recovered material from the water in the submerged sedimentation step.
If there is an aqueous solution of ions such as fluoride ions and phosphate ions dissolved in water,
As described above, after the floatation separation process to remove carbon, etc., the ion aqueous solution
It is preferable to include a process of fixing the material by adding a fixing agent such as slaked lime. Now, let's consider a metal foil such as aluminum foil or copper foil, and a valuable material such as lithium cobalt oxide and spherical black metal foil.
The solid matter treatment system for lead and resin etc. and the solvent system must be carried out in separate treatment systems.
In particular, in solids processing, toxic electrolyte fluorine compounds and flammable
The dismantling process is carried out without any consideration for the presence of volatile solvents.
Therefore, in the present invention, the selection process for selecting the target useful substance involves washing with water.
The harmful substance lithium hexafluorophosphate is dissolved in an aqueous solution and then separated.
The lithium hexafluorophosphate solution, which contains the lithium hexafluorophosphate and is further dissolved in an aqueous solution, is described below.
In other words, the present invention is a method of treating and fixing lithium hexafluorophosphate separated by a predetermined sorting process.
After decomposing into fluoride ions and phosphate ions in the presence of a hot aqueous acid solution,
The method is characterized by adding a fixing agent such as slaked lime to the aqueous solution of ammonium nitrate to fix the particles. Furthermore, the above-mentioned prior art methods disclosed in JP-A-6-346160 and JP-A-7-245126
is to recover valuable materials such as lithium cobalt oxide from used lithium secondary batteries.
The used lithium secondary batteries are roasted and then crushed, and the crushed material is sieved.
The lithium cobalt oxide is recovered from the underside of the sieve.
Because the particle size is so small, it adheres to the impurities on the sieve and is not sufficiently removed by the under sieve alone.
Therefore, in the present invention, the resin components and the like are removed by heating, and then washed with water.
A positive (negative) electrode active material such as lithium cobalt oxide having a small particle size is dispersed in water,
The method is characterized by including a step of recovering the dispersed material. Furthermore, the present invention is characterized in that the fixation of the ion-containing gas, etc. is carried out not by the wet treatment described above, but by
Alternatively, the heat separation step may be carried out by dry treatment using a bag filter or the like.
Harmful substances such as lithium hexafluorophosphate are converted into fluoride ions and phosphate ions by heating.
After decomposing into ion-containing gas such as ions, the ion-containing gas is mixed with a fixing agent such as powdered slaked lime.
The step of dry contacting and immobilizing the target useful substance is included in the selection step of selecting the target useful substance.
This invention is characterized by the fact that it is a dry process using a bag filter, etc., making it easy to handle.
This leads to simplification and miniaturization of the device. Furthermore, the present invention uses the metal foil and positive (negative)
After separating the powdery material containing the active material by sieving, iron is removed by magnetic separation, etc.
According to this invention, by adding the magnetic separation process, the particles mixed in the recovered material can be separated.
High-purity lithium cobalt oxide can be obtained by removing iron. In some cases, the iron content in the recovered lithium cobalt oxide may be suitable for the intended use.
In this case, the magnetic separation process can be omitted. Now, the "heating means + exhaust gas treatment" or predetermined separation process such as water washing in the above invention
After separation into water by the method, the lithium hexafluorophosphate aqueous solution is stable as an aqueous solution.
Specifically, it exists stably in water without ionization.
In the state of slaked lime Ca(OH)₂Addition of CaF₂and Ca₃(P.O.₄
)₂) cannot be produced, in other words, it cannot be immobilized. Therefore, an acid is added to the lithium hexafluorophosphate aqueous solution to keep the aqueous solution in the acid side.
By doing so, it has been investigated to promote (hydrolysis) as shown in the following formula 1).
However, even if an acid is added at room temperature or the concentration of the acid is increased, the (hydrolysis) decomposition does not occur.
It was found that increasing the acid concentration does not promote the corrosion of equipment and safety.
There is also the issue of gender. LiPF₆+5H₂O→LiOH+HF+PO(OH)₃...1) As a result of various experiments, the applicant has found that the acid is heated, specifically, at 65°C to 10°C.
By using an aqueous acid solution heated to 0°C (a temperature below boiling),
It was found that decomposition is rapidly promoted. The acid used in the present invention is the acid generated by hydrolysis {in the case of formula 1), HF
(hydrofluoric acid)}, for example,
As shown in the Chemical Handbook, Basic Edition, Revised 4th Edition, page II-323 (edited by the Chemical Society of Japan),
Looking at a table showing the relationship between the concentration of an acid solution and its ionic strength,
The stronger one is HClO₄, HCl, HSO₄When the HF concentration is low,
If HNO₃are also included in this range. And these have high ionic strength with respect to HF even in dilute acid solutions with low concentrations.
Therefore, the hydrolysis of the above formula 1) is efficiently promoted. Note that the aqueous solution after the hydrolysis contains slaked lime Ca(OH)₂Add the following 2)
3) such as stable (CaF₂and Ca₃(P.O.₄)₂) can be generated.
Yes, it is possible. Ca(OH)₂+HF → +CaF₂+2H₂O…2) 3Ca(OH)₂+2PO(OH)₃→ Ca₃(P.O.₄)₂+6H₂O ... 3) Therefore, the acid added to promote the hydrolysis is dilute hydrochloric acid as well as dilute sulfuric acid.
It is preferable to use a dilute strong acid solution such as dilute hydrochloric acid or dilute nitric acid, and the dilute hydrochloric acid is used at a temperature of about 65°C or higher.
It is preferable to heat it to around 90 to 100°C before use. The inventions described in claims 23 to 26 use lithium hexafluorophosphate as the electrolyte.
The main focus is on the treatment of lithium-ion batteries containing
In addition, there are also batteries in which the electrolyte contains a salt consisting of cations and Lewis acid ions.
The scope of application is as follows. That is, the cation that forms the salt of the electrolyte is lithium ion (Li⁺)apart from,
Examples include sodium ions, potassium ions, and tetraalkylammonium ions.
The Lewis acid ion that forms the salt of the electrolyte is BF^4-, P.F.^6-, AsF^6
−, ClO^6-These cations and Lewis acid ions form
The salts are heated under reduced pressure to be sufficiently dehydrated and deoxidized.
It is used as an electrolyte. Therefore, the present invention specifies a salt separation method by washing with water, and the method for treating the battery
In the method, the crushed battery material containing the salt is washed with water to separate the salt into an aqueous solution.
Then, a heated aqueous acid solution is added to the aqueous solution containing the salt to form the Lewis acid ion.
The decomposition of ions is promoted, and a fixing agent such as slaked lime is added to the ion solution to solidify it.
More specifically, the electrolyte contains lithium hexafluorophosphate.
In the method for treating a lithium ion battery,
The crushed battery material is subjected to the aforementioned "heating means + exhaust gas treatment" or a predetermined sorting process such as washing with water.
The heated acid solution was added to the lithium hexafluorophosphate-containing aqueous solution separated in water.
After adding fluoride ions and phosphate ions, the ion solution is added with slaked stone.
The method is characterized by including a step of adding a fixing agent such as ash to fix the material. BEST MODE FOR CARRYING OUT THE INVENTION The following describes in detail an exemplary embodiment of the present invention with reference to the drawings. However, this embodiment
The order, types, relative combinations, etc. of the components described in the examples are not particularly limited.
Unless otherwise specified, the scope of the present invention is not limited to the above.
This is merely an illustrative example. Figure 1 shows the disassembly process for a lithium ion battery according to the first embodiment of the present invention.
In the flow chart, a granulation process is added before the roasting process, and ball vibration is used.
The metal foil is peeled off. First, the waste battery packs targeted in this example consist of multiple batteries, each equipped with a safety valve.
Lithium-ion packs with sealed battery cells housed in a plastic case
A secondary battery (hereinafter referred to as battery or secondary battery) in which the plastic case accounts for the weight
In total, lithium-ion secondary batteries account for 20% of the total.
Since it is widely used in personal computers and mobile phones and is well known, it is not shown in the illustration. The positive electrode side is made of a positive electrode active material such as lithium cobalt oxide, which is applied to aluminum foil with a coating agent.
Next, the negative electrode side is coated with graphite negative electrode active material on copper foil with a coating agent.
Next, the electrolyte may be, for example, ethylene carbonate or diethylene carbonate.
ester, dimethyl carbonate, diethyl ether, etc., alone or in combination
The solvent may contain, for example, lithium hexafluorophosphate (LiPF₆Fluorine compounds such as
An organic electrolyte solution containing two or more types of inorganic oxides is used.
The sealed battery cell is made of the above-mentioned sheet-shaped positive electrode current collector and sheet-shaped negative electrode current collector.
The spiral body formed with a separator interposed therebetween was then mixed with the organic electrolyte solution and nickel.
The case is enclosed in a case cell made of a Kel-plated steel plate,
It is also well known that the cell is provided with a safety valve for discharging gas. The disassembly process for a lithium-ion secondary battery with such a configuration is shown in Figure 1.
First, the waste battery 1 is frozen to below -50°C in the freeze-opening process (S1).
Then, the plastic case 2 is broken open by the vibration or clamping pressure of the rod or ball.
By doing this, the sealed battery cells 1a housed in the waste battery 1 are sealed in plastic.
The battery pack shown in Figure 1 is then frozen and opened, and the plastic case and sealed battery are removed. The structure will be explained with reference to Figures 8 and 9. Figure 8 shows the battery pack shown in Figure 1 after being frozen and opened, and the plastic case and sealed battery are removed.
Overall overview of the case sorting device that separates waste into pond cells. Cases are sorted using rod vibration processing.
Figure 9 is a diagram corresponding to Figure 8, in which case sorting is performed by ball vibration processing.
In Figure 8, 30 is a battery refrigeration device, which refrigerates the waste batteries 1 through an inlet 32.
After immersing in nitrogen 31 and cooling to below -50°C,
The material is fed into the continuous processing rod vibrator 40A through the discharge port 41. As shown in view A, the rod vibrator 40A is made of a stainless steel shaft with a diameter of 25 mm.
Eight rods 49A each consisting of the above-mentioned components are arranged in a plurality of rows vertically inside the vibrating tub 45.
In the state where the mixture 49A is mixed, the vibration generator 44 is driven to vibrate the mixture supported by the spring 44a.
The waste batteries 1 are vibrated in the vibration tub 45, and then the broken cells are removed.
The scraps are dropped into the dust receiver 46a through the porous portion 46, and then discharged through the belt conveyor
Alternatively, the mixture is introduced into a magnetic separator 50 via a vibrating sieve 47. The reason for setting the temperature at about -50°C is
The melting point of diethyl carbonate, the organic solvent enclosed in the battery cell, is -4
This is to keep the temperature below 3°C. The rod is made of multiple rods that are more rigid and have a higher specific gravity than the plastic case.
As long as the rod is made of stainless steel, it is not limited to stainless steel.
The rod shaft is a shaft body (including a hollow shaft) having a circular, elliptical or rectangular cross section,
The clamping rod shaft rotates in a state cooled to -50°C or less by vibration.
The vibration was set to a total amplitude of 48 mm, an amplitude of 20 Hz, and a vibration time of 1 to 3 minutes. The magnetic separator 50 placed the broken and separated plastic cases 2 in a non-magnetic material receiver 51.
After being inserted, the magnetic material consisting of the sealed battery cells 1a is conveyed by using the belt conveyor 52.
It is then passed on to the next process. Figure 9 shows a continuous processing ball vibration device that separates the waste by ball vibration instead of rod vibration.
The ball vibration device 40B is shown in FIG.
The batteries 1 and balls 49 are mixed in the inlet 42 and then the mixture is transferred to the vibration generator 44.
The waste batteries 1 are broken down by driving the vibration tub 45 supported by the spring 44a.
First, the debris generated by the tearing is dropped into the dust receiver 46a through the porous portion 46.
After that, the waste is led from the discharge port to the magnetic separator 50 via a belt conveyor or a vibrating sieve 47.
The reason for setting the temperature at about -50°C is that the organic solvent, diethylene glycol, sealed in the battery cell
This is to keep the temperature below -43°C, which is the melting point of carbonate. The ball 49 can be made of stainless steel, as long as it has higher rigidity and specific gravity than plastic.
It is preferable to use a stainless steel or zirconia ball. The ball 49 has a diameter of 35 mm.
In the case of millimeter diameter, it is better to mix 10 or more per battery, and the vibration is the total amplitude.
The rod vibration was set to 48 mm, the amplitude was 20 Hz, and the vibration time was set to 1 to 3 minutes.
In both of the above devices, the frequency of the vibration is approximately 20 Hz or more.
In this embodiment, the plastic that has been fractured and separated in the magnetic separator 50 is
After the case 2 is placed in the non-magnetic material receiver 51, the ball 49 and the sealed battery cell 1a
The magnetic material is guided to a size sorting device 55 using a belt conveyor 52.
The separating device 55 is attached to a guide rail plate 53 formed to a predetermined width by a vibration generating device 44.
Vibration is applied to separate the sealed battery cell 1a from the ball 49. Therefore, in both of the above devices, the stored sealed battery cell 1a is separated from the ball 49.
Remove the battery from the stick case 2 and check that the sealed battery cell case is made of magnetic iron.
Utilizing this, the sealed battery cells 1a are separated into plates in a magnetic separation process (S2) using a magnetic separator 50.
The rod vibrating device 40A is removed from the stick case 2.
This is preferable because it eliminates the need for processes such as battery cell recovery. In addition, both devices allow the sealed battery cells 1a to be sealed in the plastic case without being ruptured.
The same applies in that only the plastic case 2 can be ruptured and separated from the system in its initial state. Next, the sealed battery cell 1a that has been separated and exposed from the plastic case 2 is inactivated.
Heat treatment is performed in a gas atmosphere (S3), and a safety valve provided in the sealed cell is opened.
The organic solvents and organic resins that have been gasified in the cell are released, resulting in the generation of volatile substances and toxic gases.
After removing the causative substances, the cells are crushed using the usual process. Heat treatment (S3) involves crushing the sealed battery cells in an inert gas (nitrogen gas) atmosphere for 5 minutes.
00°C or higher (for example, heating for 10 minutes), preferably 850°C (for dioxin removal)
In the case of a rotary kiln, the material is steamed (pyrolyzed) at a temperature of 1000 or higher.
The organic solvent and organic resin gasified in the cell by baking are placed in the sealed battery cell.
The gas is released through a safety valve, which removes volatile substances and substances that cause toxic gases.
After that, the evaporated gas after the steaming is discharged from the cooling means and the filter through the exhaust pipe.
The organic resin separated by the solid-gas separation means (S31) is introduced into the solid-gas separation means (S31).
Solidified substances such as fat (including liquids) are either recovered as they are or processed in a roasting process (
S8), and exhaust gases such as volatile substances and toxic gases are treated through a roasting process (S8).
The wastewater is then led to the exhaust gas treatment step (S9) or directly to the exhaust gas treatment step (S9).
In addition, the remaining sealed battery cells after being steamed in a rotary kiln do not emit volatile substances or toxic gases.
Therefore, according to this embodiment, the sealed battery cells can be crushed at room temperature (S4) in an inert gas atmosphere for, for example, 5 minutes.
When heated to 00°C or higher, separator components such as polypropylene and polyethylene
, a solvent such as lithium hexafluorophosphate, and ethylene carbonate as an electrolyte.
Materials such as diethylene carbonate, dimethyl carbonate, and diethyl ether,
In other words, organic solvents, organic resins, etc. are released and dispersed from the safety valve of the battery cell.
The gases that are released during this process include highly flammable organic solvents, etc.
The atmosphere is an inert gas, so there is no risk of fire due to oxygen or sudden internal pressure.
Furthermore, there is no risk of explosion due to heating.
The reaction of reactive lithium, which is present in the battery, is also inhibited. Also, aluminum foil and graphite as positive electrode pieces coated with lithium cobalt oxide are
The copper foil on which the oxide is applied as the negative electrode piece does not oxidize, and remains in its thin foil state.
Or when the heating temperature is high (melting point of aluminum: 660°C, melting point of copper: 1
At temperatures of 080°C, these metal foils melt but are not oxidized.
Cobalt fine particles adhering to aluminum foil, etc., are removed during the mechanical treatment (S6) and sieving process (S7).
When the lithium nitrate is peeled off, it does not break down into fine particles and can be easily peeled off from foil or metal.
Because it can maintain a molten solid state (even when melted by heat), lithium cobalt oxide
The lithium is easily recovered, improving the purity of the resulting lithium cobalt oxide.
According to this step (S3), the processing space is heated while maintaining an inert gas atmosphere.
As a result, the reaction between reactive lithium and oxygen and the ignition prevention of gas generated from battery components
This process prevents the generation of toxic gases due to reactions between the electrolyte and the atmosphere.
Step (S3) can be applied to both undischarged and discharged batteries. Figure 10 is a schematic diagram showing the sealed battery cell crushing device in the crushing step (S4). In Figure 10, crushing device 60A is placed in a nitrogen gas atmosphere and crushes the sealed battery cells.
The lure 1a is fed into the cutter mill 65 from the outlet 63 by using the rotary blade 62.
The magnetic components such as the cell casings are then separated from the batteries by a belt conveyor 66 and transported to a magnetic separator 70.
The sealed battery cells 1a are separated into non-magnetic components.
Alternatively, the aluminum may be crushed using a roll or hammer mill. If the temperature during the heat separation process (S3) is below the melting point of aluminum (660°C),
In this case, the aluminum foil of the positive electrode housed in the battery cell 1a and
The shape of the negative electrode copper foil remains intact, and each is approximately 5 cm x 50 cm x 0
Since the size of the battery is 0.02 cm, it can be crushed into pieces of several centimeters square or larger. Next, in the magnetic separation process (S5) using the magnetic separator 70, the iron parts of the sealed battery cell casing are crushed.
The sealed battery cell cases (magnetic portion) separated in the magnetic separation process (S5) are then washed with water.
After washing with water in step (S11), only iron 3 is separated and recovered. The reason for this washing is that the electrolyte, phosphorus hexafluoride, which adheres to the iron part during crushing
The solvents ethylene carbonate and dimethyl carbonate
Taking advantage of its water-soluble nature, the material is dissolved in an aqueous solution in a water washing step (S11).
The polypyridene chloride that was peeled off from the aluminum foil of the positive electrode and attached to the iron part was
The lithium cobalt oxide particles coated on the surface are very small, measuring just 5 μm in diameter, and are insoluble in water.
In addition, since its specific gravity is about 5, by dispersing it in water in the water washing step (S11),
It can be separated from iron 3. Also, acetylene black peeled off from the aluminum foil of the positive electrode
The graphite (spherical graphite) on the negative electrode side is also dissolved in water in the water washing step (S11).
The magnetic separation residue separated in the magnetic separation step (S5) can then be dispersed in a ball vibration device (
S6) is used to perform ball vibration for 15 minutes, followed by a 0.3 mm
The crushing step (S4) is then carried out by sieving (S7). To reiterate, the crushing step (S4) is a heating separation step in an inert gas atmosphere.
(S3) After that, the aluminum foil of the positive electrode was removed from the lithium cobaltate 7 and the negative electrode
Graphite (spherical graphite) is peeled off from the copper foil. At this time, the solvent, ethylene
Carbonate, dimethyl carbonate, polypyridinium chloride and electrolyte
Some of the lithium hexafluorophosphate is released in the previous heating and separation step (S3).
Furthermore, polypropylene or polyethylene as a separator is used in the previous step.
The decomposition occurs in the thermal separation step (S3).
The resulting gas is treated in the roasting operation (S8) together with gases generated in other operations.
Or it is directly subjected to exhaust gas treatment (S9). More specifically, in the thermal separation step (S3), the
By heating at a temperature of 00 to 1500°C, preferably at a temperature of about 500 to 1300°C,
The polymer that binds the acetylene black and lithium cobalt oxide that make up the electrode
Viridene chloride is thermally decomposed. This thermal decomposition produces acetylene black and
The adhesive strength between the lithium nitrate and the aluminum foil is reduced, and the subsequent crushing step (S4) and
After the magnetic separation process and the eddy current treatment process (S5'), the mixture is passed through a ball mill (S6) in this state.
By using the crushing vibration treatment, acetylene black and cobalt oxide
Lithium 7 can be separated from the aluminum foil. Similarly, by heating with inert gas in the thermal separation step (S3),
The thermal decomposition of polypyridene chloride causes the copper foil and the graphite coated on it to separate.
The adhesion force between the particles and the threads is reduced, and in this state, the subsequent crushing step (S4) and magnetic separation step are carried out.
The ball vibration treatment (S6) is carried out through the eddy current treatment process (S5) and the eddy current treatment process (S5').
By performing this process, the graphite can be separated from the copper foil. The ball vibration device (S6) is similar to the one shown in Figure 9 and performs the heating separation process (S3).
After being heated and crushed in the crushing step (S4), the material is subjected to magnetic separation treatment or eddy current treatment (
In the state where the magnetic separation residue and the balls are mixed, the vibration generator 44 is driven.
The aluminum foil or copper foil is peeled off by vibrating it in a vibrating tub 45 supported by a spring 44a.
The applicant has introduced the magnetic separation residue into a rotating cylinder together with the balls,
The ball mill vibrates while rotating to separate the material from the aluminum or copper foil.
A dynamic test was conducted, and the ball vibration device (S
6) produced better results. In other words, with ball mill vibration, the magnetic separation process and the eddy current treatment process (S5, S6) described below were
5') The magnetic separation residue was heated at 300°C for 6 minutes, then heated at 400°C for 5 minutes,
A ball mill was used with 5 mm diameter zirconia balls for 30 minutes (cylindrical rotation).
Then, the result was sieved through a 0.3 mm sieve.
53% of the total weight was recovered, and the purity of the composition as lithium cobalt oxide was 9.
The composition of the aluminum foil recovered by sieving was 63% cobalt.
The aluminum content was 9%, which means that lithium cobalt oxide was not sufficiently peeled off from the aluminum foil.
On the other hand, the ball vibration device is divided into two processes: the magnetic separation process and the eddy current treatment process described below.
The magnetic separation residue from steps (S5, S5') was heated at 300°C for 10 minutes and subjected to zirconia grinding with a 5 mm diameter.
Balling was performed for 20 minutes with a zirconia ball and for 10 minutes with a 19 mm φ zirconia ball.
The result was sieved through a 0.3 mm sieve.
The weight recovered below 100 m was 43% of the total weight, and its composition was lithium cobalt oxide.
The purity of the aluminum foil recovered by sieving was 95%.
As a result, lithium cobalt oxide was sufficiently extracted from the aluminum foil.
It can be seen that the particles are separated into small pieces. Following the ball vibration process (S6), the particles are separated into small pieces by the sieving process (S7).
Lithium cobalt oxide 7 of particle size, acetylene black, and graphite were placed on a copper foil.
and separated from the aluminum foil. That is, the aluminum foil and copper foil crushed in the crushing step (S4) are crushed into pieces several centimeters square or larger.
and the particle sizes of acetylene black, graphite, and lithium cobalt oxide are
Since the particle size is less than 0.1 mm, sieve it through a sieve of about 0.3 to 3 mm.
Aluminum foil and copper foil are placed on a sieve, and lithium cobalt oxide and acetylene black are added.
The aluminum foil and graphite can be separated on the sieve. In addition to the aluminum foil and copper foil, there is a possibility that the substances described below may be attached to the sieve.
Therefore, washing with water (S12) is performed. That is, the copper foil and aluminum foil separated on the sieve are washed with water (S12),
The electrolytes attached to the surface were lithium hexafluorophosphate and polypyridene chloride.
The solvents ethylene carbonate and dimethyl carbonate were dissolved in an aqueous solution.
The lithium cobalt oxide 7 and the coating 7 adhered to the copper foil and aluminum foil were dissolved.
The acetylene black used in this product has minute particle diameters and is insoluble in water.
The copper foil and aluminum foil 4 are separated and collected by washing with water (S12).
Lithium cobalt oxide + carbon 6 is separated below the sieve. The lithium cobalt oxide, acetylene black, and
Carbon such as graphite and polypyridinium chloride adhered to them.
Lithium hexafluorophosphate and the solvents ethylene carbonate and dimethicone
Granulation is carried out as necessary together with chill carbonate (S13), followed by a freeze-crushing step (S4A
), the magnetic separation step (S5), and the heat treatment step (S3).
Roasting with fuel 8 together with ethylene carbonate and dimethyl carbonate
(S8), and the carbon content is burned by the roasting (S8) to obtain lithium cobalt oxide.
Sieving (S7) separates the under-sieve lithium cobalt oxide, acetylene black, and cellulose.
The carbon black and graphite are the same as those of the polycarbonate that remain even after the heating separation step (S3).
Granulation (S13) with pyridine chloride and lithium hexafluorophosphate
This prevents powder from scattering and enables efficient combustion during roasting (S8). Furthermore, by using water for washing (S11, S12) and granulation (S13), magnetic separation is possible.
Lithium cobalt oxide 7 and cell case (iron part) 1a recovered by subsequent water washing
Lithium hexafluorophosphate, polypyridinium chloride, ethylene carbonate attached to the
Since carbonate and dimethyl carbonate are also granulated together,
This allows for incineration in the roasting process (S8) following granulation (S13). In the roasting process (S8), lithium cobalt oxide 7, acetylene black, and granules are roasted.
Graphite, lithium hexafluorophosphate electrolyte, and coated polypyridinium
and ethylenediamine chloride, which is the solvent that was not volatilized in the heat separation step (S3).
Ethylene carbonate and dimethyl carbonate, and freeze-shredding step (S4A
), the subsequent magnetic separation step (S5) and the etching generated in the thermal separation step (S3)
ethylene carbonate, dimethyl carbonate, and polypyridene chloride
The roasting process (S8) is then carried out to recover lithium cobalt oxide 7. The reason for carrying out the roasting process (S8) is that lithium cobalt oxide 7
It does not burn or transform, and lithium hexafluorophosphate contains most of its phosphorus and
By utilizing the fact that the fluorine portion moves to the gas side, cobalt oxide is produced by roasting (S8).
Lithium 7 can be recovered.
Ethylene carbonate generated in the separation step (S5) and the thermal separation step (S3)
, dimethyl carbonate, and polypyridinium chloride and a thermolysis process
(S3) Polypyridene chloride, hexahydrate remaining after the operation and not yet completely decomposed and burned
Lithium fluorophosphate, ethylene carbonate, and dimethyl carbonate were roasted.
The exhaust gas generated by the roasting (S8) can be treated by combustion.₂Solution 5 is sprayed
After exhaust gas treatment (S9) consisting of an absorption tower irradiated with water, further wastewater treatment/solid-liquid separation is performed.
The lithium hexafluorophosphate is separated into solid waste 10 (CaF₂
and Ca₃(P.O.₄)₂) and is separated from the wastewater 11 and recovered. That is, the wastewater generated from lithium hexafluorophosphate by the exhaust gas treatment (S9)
Fluoride and phosphate compounds are Ca(OH)₂Reacts with solution 5 and becomes poorly soluble in water
Ca₃F₂and Ca₃(P.O.₄)₂By utilizing the property that Ca(OH)₂
The solid waste 10 is separated into solid waste 10 by the wastewater treatment/solid-liquid separation treatment tank (S10) to which the solution 5 is added.
(CaF₂and Ca₃(PO4)₂) and collect it from the wastewater 11.
During the heating and separation process (S3) and roasting (S8), lithium hexafluorophosphate
The reaction product, lithium fluoride, is washed with water (S11) and (S12).
Therefore, the aqueous solution washed with water (S11) and (S12) can also be used for wastewater treatment/solid-liquid separation treatment.
The fluorine ions separated in the water are introduced into the tank (S10) and converted to Ca(OH)₂Solution 5 and
Reacts with CaF, which is poorly soluble in water₂By utilizing the property of generating Ca(OH)₂Solution 5
By adding wastewater treatment, solid waste 10 (CaF₂and Ca₃(P.O.₄)₂
) can be separated from the wastewater 11 and recovered. Also, gas is separated from the wastewater by the heating separation step (S3) and the like, and the water is washed with water (S11), (
S12) and the exhaust gas generated by the roasting (S8) is treated with Ca(OH)₂solution 5
After exhaust gas treatment (S9) consisting of an absorption tower injecting hexafluorophosphoric acid
Since the lithium aqueous solution is stable as an aqueous solution, it is necessary to dispose of it in the wastewater treatment/solid-liquid separation treatment tank (S10
90g of dilute hydrochloric acid was added to the reaction mixture to maintain the aqueous solution on the acidic side.
) promotes the (hydrolysis) decomposition of the formula. LiPF₆+5H₂O→LiOH+HF+PO(OH)₃...1) Next, slaked lime Ca(OH)₂to form a stable (C
aF₂and Ca₃(P.O.₄)₂) is produced. Ca(OH)₂+HF → +CaF₂+2H₂O…2) 3Ca(OH)₂+2PO(OH)₃→ Ca₃(P.O.₄)₂+6H₂O ... 3) In order to accelerate the (hydrolysis) process, a wastewater treatment/solid-liquid separation treatment tank (S10
The acid to be added to the tank is diluted hydrochloric acid, as well as diluted sulfuric acid, diluted nitric acid, or other diluted strong acid solution.
The dilute hydrochloric acid 9 is preferably heated to a temperature of about 65°C or higher, and more preferably to about 90 to 100°C.
It is best to use it after heating. To explain more specifically, as is clear from Figure 15,
In order to do this, a strong acid solution (20% HCl solution, room temperature) with a high acid concentration was added at room temperature.
It was found that the hydrolysis was only achieved at about 28%, and was not significantly promoted.
. Increasing the acid concentration can cause corrosion of equipment and safety issues, so the acid concentration
A dilute hydrochloric acid solution (1% HCl solution) with a significantly reduced concentration of 1% was heated to 65°C.
It was found that the hydrolysis rate was 40% or more. Furthermore, when a dilute hydrochloric acid solution (1% HCl solution) heated to 95°C was used, the
It was found that the hydrolysis was 100%. Next, a diluted hydrochloric acid solution heated to 95°C was used, with the concentration increased to 2%, and the hydrolysis was 100%.
It was found that the reaction time for decomposition of water was shortened. That is, as a result of the above experiment, when the 1-2% concentration dilute hydrochloric acid was heated, specifically to 65°C,
By using an aqueous acid solution heated to 100°C (a temperature below boiling),
It was found that hydrolysis was rapidly promoted. Next, a similar experiment was carried out using dilute sulfuric acid, and as is clear from Figure 16,
(30% H₂SO₄In aqueous solution at room temperature, only 17% hydrolysis was achieved.
It was found that the effect was not very pronounced and was not promoted much.₂SO₄When the aqueous solution was heated to 65°C,
Decomposition was achieved by 50% or more. Furthermore,₂SO₄Aqueous solutions with concentrations of 5%, 10%, 20%, and 30%
When each of these was heated to 95°C, the (hydrolysis) rate reached 100%.
It was found that this was achieved. Next, the 95°C heating H₂SO₄If the concentration of the aqueous solution is 10% or more,
The reaction time for the hydrolysis was short for both the 0.05% and 30% samples, and there was not much difference.
From these experimental results, it was found that the acid used in the present invention is an acid produced by hydrolysis {1)
In the formula, if the ionic strength is higher than HF (hydrofluoric acid), HCl, H₂S
O₄Either of these may be used, but even if the HCl concentration is lower, 100% (water added)
It was also found that decomposition was achieved. Then, slaked lime Ca(OH) was added to the hydrolyzed aqueous solution.₂Add the above 2),
3) such as stable (CaF₂and Ca₃(P.O.₄)₂) can be generated.
Therefore, this embodiment can achieve the following effects: (1) In the freeze-opening step (S1), the waste batteries 1 are opened and the sealed battery cells stored therein are
Remove the battery 1a from the plastic case 2 and check that the battery case is made of magnetic iron.
Taking advantage of this, the sealed battery cells 1a are separated in a magnetic separation step (S2) using a magnetic separator.
By removing it from the plastic case 2, the plastic case 2 can be restored to its original state.
It was possible to separate it outside the system. (2) In the heating separation process (S3) and the crushing process (S4) under an inert gas atmosphere,
Crushing was possible without generating toxic gases such as phosphorus pentafluoride and hydrogen fluoride, or causing explosions.
(3) Magnetic separation (S5) is performed using a magnetic separator to separate the iron from the other parts.
(4) The water washing step (S11) removes the hexahydrate, an electrolyte that adhered to the iron part during crushing.
Lithium fluorophosphate and the solvents ethylene carbonate and dimethyl
The carbonate was dissolved in water and peeled off from the aluminum foil of the positive electrode and attached to the iron part.
Lithium cobalt oxide 7 was dispersed in water and separated from iron 3. (5) A heating separation process (S3) and a crushing process (S4) under an inert gas atmosphere.
By combining the magnetic separation process and the eddy current treatment process (S5'), the aluminum foil and the aluminum
The lithium cobalt oxide 7 containing acetylene black coated on the Lumi foil
The negative electrode copper foil and graphite were also separated. The solvents used were ethylene carbonate, dimethyl carbonate, and polyvinyl alcohol.
denchloride and lithium hexafluorophosphate, polypropylene as separator
(6) By sieving (S7), lithium cobalt oxide 7, acetylene black, and polyethylene were removed from the system.
The aluminum foil and graphite were separated from the aluminum and copper foil. (7) After sieving (S7), the residue was washed with water (S12), which allowed for the heating and separation process.
(S3) Operation and ball vibration (S6) Polyvinyl chloride attached to the aluminum foil and copper foil 4
ethylene chloride and the solvents ethylene carbonate and dimethyl carbonate
Carbonate, acetylene black, graphite, and lithium cobalt oxide 7 are separated.
, aluminum foil, and copper foil 4 were effectively separated and recovered.
Carbon 6 is separated. (8) Lithium cobalt oxide 7 and acetylene bromide separated under the sieve in the sieving step (S7)
Carbon 6 such as rack and graphite is removed by the heating separation step (S3).
The resulting mixture is granulated together with polypyridinium chloride and lithium hexafluorophosphate (S13
) prevents powder from scattering and ensures efficient combustion in roasting (S8).
Furthermore, by washing with water (S12, S11) and granulating with water (S13), the magnetic
The lithium cobalt oxide 7 and hexafluoride attached to the iron part were recovered by washing with water after the separation.
Lithium phosphate, polyvinyl chloride, ethylene carbonate and dimethicone
The chill carbonate can be efficiently treated by subsequent incineration in the roasting step (S8).
(9) The roasting step (S8) converts lithium cobalt oxide 7 into lithium hexafluorophosphate.
It was possible to separate and recover the material from carbon such as rubber and graphite. (10) Freezing and crushing process (S4A), followed by magnetic separation process (S5) and eddy current treatment
The ethylene carbon generated in the thermal separation step (S14)
acrylate, dimethyl carbonate, and polypyridinium chloride and heat separation
Polypyridinium that has not yet been completely vaporized or decomposed and burned in the step (S3) operation
ammonium chloride, lithium hexafluorophosphate, ethylene carbonate and dimethyl
The carbonate was roasted (S8) and then burned. (11) By washing with water (S12, S11), lithium cobalt oxide 7 was converted into hexafluoride.
It can be separated from lithium fluoride, which is a reaction product from lithium phosphate.
(12) Ca(OH)₂Wastewater treatment/solid-liquid separation treatment tank (S10) to which solution 5 is added
) wastewater treatment, fluorine ions generated from lithium fluoride are
0 (CaF₂) and could be separated from the wastewater 11 and recovered.
By using an acid aqueous solution heated to 100°C, the (hydrolysis) decomposition is rapidly carried out.
The aqueous solution after hydrolysis is accelerated, and the aqueous solution after hydrolysis is slaked lime Ca(OH)₂Stable by adding
(CaF₂and Ca₃(P.O.₄)₂) can be produced. (13) Ca(OH)₂Wastewater treatment/solid-liquid separation treatment tank (S10) to which solution 5 is added
) by the wastewater treatment, and by the exhaust gas treatment step (S9), lithium hexafluorophosphate
Fluoride compounds and phosphate compounds generated from the solid waste 10 (CaF₂Oh
and Ca₃(P.O.₄)₂) and recovered from the wastewater 11. In addition, instead of the ball vibration device (S6), an ultrasonic vibration peeling process (S16) was performed.
Similar effects can be obtained by using a lithium ion battery. Figure 2 shows the disassembly process for a lithium ion battery according to a second embodiment of the present invention.
In this flow chart, instead of the ball vibration peeling in FIG. 1, ultrasonic vibration is used in (S16).
The metal foil is peeled off. Figure 3 shows the disassembly process for a lithium ion battery according to a third embodiment of the present invention.
In the flow diagram, the metal foil is peeled off by combining ultrasonic vibration peeling with a peeling agent.
In this example, the magnetic separation residue from the magnetic separation step (S5) is treated with a release agent (
The aluminum foil was then peeled off with ultrasonic vibration (S16) in a chemical (S13) to remove the cobalt oxide.
After separating the lithium foil, the release agent 13 is removed by gravity, centrifugal force or other separation means (S
21) The separator is specifically a filter or a centrifugal separator.
In this case, the solvents ethylene carbonate, dimethyl carbonate, and hexafluoropropane are
Since lithium fluoride phosphate is separated into the solution, the stripping agent separation step (S21)
The separated stripping agent solution 13 was repeatedly used in the ultrasonic vibration stripping step (S16).
Then, it is sent to the wastewater treatment/solid-liquid separation step (S10) via the water washing step (S12).
. The lithium cobalt oxide foil from which the release agent 13 has been separated is then subjected to ball vibration or ball
The particles are crushed in the milling process (S22). Specifically, the process is described as follows:
"Synthol YS (product name)" (N,N-dipolyoxyethylene) manufactured by Nisshin Chemical Laboratory Co., Ltd.
Ethylene-N-alkylamine, phosphoric acid) in a 1% aqueous solution of the stripping agent.
The magnetic separation residue from the magnetic separation step (S5) was immersed in the mixture, and ultrasonic vibration was applied for 8 minutes (S16).
As a result of this, the lithium cobalt oxide foil was completely separated from the aluminum foil without any damage.
At that time, the ethylene carbohydrate, which was the solvent remaining in the heating step (S3), was removed.
Carbonate, dimethyl carbonate and lithium hexafluorophosphate are soluble in aqueous solution.
Then, the release agent 13 is separated by a filter, gravity, centrifugal force, or other separation means (S2
1), followed by ball vibration or ball milling (S22) to separate the cobalt oxide.
The lithium foil is crushed to form fine particles of lithium cobalt oxide.
The lithium cobalt oxide and the carbon dioxide are separated by sieving using a 100 mm sieve (S7).
According to this embodiment, there is no need to heat the magnetic separation residue from the magnetic separation step (S5).
This makes it safer and less expensive. Furthermore, according to this embodiment, the release agent 13 separates the edge of the positive electrode from the aluminum foil.
Lithium phosphate was successfully peeled off. In this case, the solvents ethylene carbonate, dimethyl carbonate, and hexafluoropropane were
Lithium fluoride phosphate was separated into the solution. Also, ethylene carbonate and dimethyl ether separated in the stripping agent separation step (S21) were
The immersion solution containing dicarbonate and lithium hexafluorophosphate was washed with water (S12
) process, and the detoxification process was completed. Figure 4 shows the disassembly process for a lithium-ion battery according to the fourth embodiment of the present invention.
In the flow diagram, a strong acid, HCl aqueous solution 14A, is used to peel (dissolve) the metal foil.
This embodiment, like the third embodiment, uses ultrasonic vibration peeling (S16) and a peeling agent 13.
After separating the aluminum foil into lithium cobalt oxide foil,
Instead of crushing in the mill vibration step (S22), the aluminum is directly crushed using dilute hydrochloric acid 14A.
The lithium cobalt oxide is obtained by dissolving the lithium foil. In this case, as is clear from the table in Figure 13, 14A of dilute HCl hydrochloric acid is dissolved at room temperature.
In this case, the aluminum foil will not dissolve unless the HCl aqueous solution 14A has a concentration of 5% or more.
Such an aqueous HCl solution 14A of 5% or more is not recommended from a safety standpoint, and
The amount of lithium cobalt oxide dissolved in the HCl aqueous solution 14A also increases, which is undesirable. On the other hand, as is clear from the table in Figure 14, heating the HCl dilute hydrochloric acid 14A to 95°C
Then, even with HCl hydrochloric acid 14A with a concentration of 1% or less and a pH of 0.87, the aluminum foil was dissolved.
This pH of 0.87 is preferable from a safety standpoint.
The amount of lithium cobalt oxide dissolved in the HCl aqueous solution 14A is also reduced, which is preferable. In other words, this example has the property of dissolving aluminum foil and copper foil in dilute hydrochloric acid aqueous solution 14A.
Using this, lithium cobalt oxide 7 was extracted from the aluminum foil of the positive electrode and graphite was extracted from the copper foil of the negative electrode.
The fights can be peeled off (S24).
To achieve this, a mixer stirrer is used to perform forced stirring. At this time, the solvents ethylene carbonate, dimethyl carbonate, and hexafluoropropane are mixed.
Lithium fluoride phosphate can also be separated into the dilute hydrochloric acid aqueous solution 14A. Subsequently, the hydrochloric acid aqueous solution is separated using a solid-liquid separator (S25), and the peeling process (S24) is carried out.
) and reuse them in the solid-liquid separator.
The magnetic separation residue after separating the HCl solution 14A using a filter (S25) is 0.3 m
The aluminum and copper dissolved in dilute hydrochloric acid solution 14A were sieved using a 1/2 mm sieve.
The property of forming precipitates of aluminum hydroxide 17 and copper hydroxide in the ranges 4 to 6 and 8.
Utilizing this, sodium hydroxide solution 16A is added to the aluminum precipitation tank (S26).
After that, aluminum and copper are separated in an aluminum separator (S27).
According to this embodiment, a hydrochloric acid solution is added to remove cobalt from the aluminum foil of the positive electrode.
The lithium oxide was removed from the negative electrode and the graphite was peeled off from the copper foil. Figure 5 shows the disassembly process for a lithium-ion battery according to the fifth embodiment of the present invention.
In the flow diagram, a strong alkaline NaOH solution 14B is used to peel off the metal foil.
In this example, Na is used instead of the diluted hydrochloric acid used in the fourth example.
OH solution 14B was used. In other words, in this example, aluminum is dissolved in sodium hydroxide solution 14B.
Using this property, lithium cobalt oxide is peeled off from the aluminum foil of the positive electrode (S28).
In this case, the solvents ethylene carbonate and dimethyl carbonate
The carbonate and lithium hexafluorophosphate can be separated into solution.
In this case, the aluminum foil was completely removed by keeping it in NaOH solution 14B for 30 minutes.
It was confirmed that aluminum dissolved in sodium hydroxide solution 14B had a pH of 2 to 4.
16B of hydrochloric acid is used to produce aluminum hydroxide precipitates.
After adding it to the precipitation tank (S26), aluminum is separated in the aluminum separator (S27).
The magnetic separation residue separated by the NaOH solution separation means (S30) can be separated as needed.
After physical peeling and granulation by ball vibration (S7), etc.,
The copper foil 15 is separated on the sieve by sieving.
Lithium cobalt oxide + carbon 6 is separated below. Meanwhile, the sodium hydroxide aqueous solution 1 separated by the NaOH solution separation means (S30)
4B is reused in the peeling step (S28).
As mentioned above, filters, centrifugal separators, and sedimentation separators are used as the separation equipment.
According to this example, sodium hydroxide solution 14B is added to the positive electrode.
Lithium cobalt oxide 7 can be peeled off from the aluminum foil. In this case, the solvents ethylene carbonate, dimethyl carbonate, and hexafluoropropane
Lithium fluoride phosphate was separated into the solution. As explained above, in all examples, used lithium ion batteries
can be safely disposed of. Figure 6 shows the disassembly process for a lithium ion battery according to a sixth embodiment of the present invention.
In the flow chart, exhaust gas treatment is carried out by dry treatment using a bag filter, etc.
That is, the sealed battery cell is heated in an inert gas atmosphere and the exhaust gas from the combustion and the roasting (
In the above example, the exhaust gas generated by S8) was Ca(OH)₂solution 5
The treatment is carried out in an exhaust gas treatment step (S9) consisting of an absorption tower into which
In such wet processing, not only does the equipment become larger, but the wastewater treatment is also difficult.
Therefore, in this embodiment, the exhaust gas treatment (S9) is performed using a bag filter or the like.
This is done using a dry process. This prevents the fluoride compounds and phosphate compounds generated from lithium hexafluorophosphate.
Harmful gases such as slaked lime Ca(OH) entrained in the bag filter₂50
It reacts with Ca, which is poorly soluble in water.₃F₂and Ca₃(P.O.₄)₂Taking advantage of the nature of
Solid waste 10 (CaF₂and Ca₃(P.O.₄)₂) can be obtained
In addition, after dry exhaust gas treatment (S9), lithium hexafluorophosphate is stable.
For this purpose, the wastewater is introduced into a wastewater treatment/solid-liquid separation treatment tank (S10), and diluted hydrochloric acid 9 is added to the treatment tank.
In addition, by maintaining the aqueous solution on the acidic side, the (hydrolysis) of the above formula 1) can be
This promotes the fluorination generated from lithium hexafluorophosphate.
The compound and the phosphate compound were added to the solid waste 10 (CaF₂and Ca₃(P.O.₄)₂
) can be separated and recovered from the wastewater 11 as described above.
. Figure 7 shows the disassembly process for a lithium ion battery according to a seventh embodiment of the present invention.
In this flow chart, unlike the previous embodiment, the heat treatment in (S3) is performed in an inert gas atmosphere.
The process is carried out in a vacuum atmosphere (S3') instead of a vacuum atmosphere, and the exhaust gas treatment (S9) is
It can be done either by dry processing using a gasket filter or by wet processing.
That is, the heat treatment (S3) is performed in a vacuum atmosphere (S3') rather than in an inert gas atmosphere.
The reason for this is that when heat treatment is performed in an inert gas atmosphere, the internal pressure of the battery cell
However, if the pressure rises above the surrounding external pressure, the safety valve will operate and the material will melt due to heat treatment.
Alternatively, sublimated organic resin or harmful gases are released to the outside of the battery cell. Therefore, in a configuration using such a safety valve, the pressure difference between the safety valves is reliant on, and therefore, the external
When heated in an inert gas atmosphere at normal pressure, the inside of the battery cell melts or sublimes.
The organic resin and harmful gases that have been absorbed cannot be completely released outside the battery cell.
This drawback can be overcome by creating a negative pressure in an active gas atmosphere.) In this embodiment, the external pressure of the battery cell is evacuated as shown in (S3'),
The opening pressure of the safety valve is lowered, in other words, the safety valve is made to operate easily, and the heating process is
The organic resin and harmful gases that melt or sublimate during the process are completely released outside the battery cell.
In this case, since it is a vacuum, it is not necessary to fill it with an inert gas, but
Alternatively, an inert gas may be filled in the chamber to create a high negative pressure state, almost like a vacuum. The vacuum heating step (S3') can lower the evaporation temperature of organic resins, etc.
This makes it possible to prevent danger and effectively utilize thermal energy. The exhaust gas obtained by the vacuum heating process (S3') is then cooled in the cooling process (S3
2) The organic resin or the like is separated into gas-liquid or solid-gas, and the separated liquid or solid
Drain components such as organic resins (S34) are removed, and the remaining exhaust gas is passed through the exhaust gas treatment process (
The exhaust gas is then guided to the exhaust gas treatment process (S33) where a predetermined exhaust gas treatment is carried out.
This may be the same as the exhaust gas treatment process in S9), or may be provided separately. Figure 11 shows the disassembly process for lithium ion batteries according to the eighth embodiment of the present invention.
In the flow chart shown in FIG. 1, unlike the previous examples, the battery cells are crushed by freeze crushing.
FIG. 12 shows the freeze-crushing device for sealed battery cells, which is the third step in FIG.
This is a schematic diagram of the battery cell 1a that has been separated and exposed from the plastic case 2.
In the freeze-crushing step (S4A), freeze-crushing is performed. In Figure 12, the freeze-crushing device 60B is placed in a nitrogen gas atmosphere, and the battery
The cell 1a was immersed in liquid nitrogen 61B and cooled to below -50°C.
62, and the material is fed into a cutter mill 65 through a discharge port 63 and kept at -50°C or below.
The crushed pieces are then guided by a belt conveyor 66 to a magnetic separator 70, where magnetic particles such as cell cases are separated.
The reason for setting the temperature below approximately -50°C is that the ambient temperature is
As in the previous example, this is to keep the temperature below -43°C, which is the melting point of ethylenediamine.
The battery cell 1a in a solidified state was then cut into pieces in an atmosphere of -50°C or less using the cutter mill.
In addition to the above, the aluminum foil of the positive electrode and the aluminum foil of the negative electrode contained in the battery may be frozen and crushed using a roll or hammer mill.
Since the dimensions of each copper foil are approximately 5 cm x 50 cm x 0.02 cm,
The particles can be crushed to a size of several centimeters square or larger. According to this step (S4A), the processing atmosphere temperature can be set to a value below the melting point of the electrolyte solvent (e.g.,
For example, around -50°C, hereinafter referred to as "freezing low temperature") and the processing space is kept
The reaction is maintained under an inert gas or high-dryness air.
Prevents the generation of flammable hydrogen gas due to reaction with moisture in the ambient air, and prevents fuel from entering the battery components.
Prevents oxygen generation, ignition of generated gas, and reaction between electrolyte and moisture in the ambient air
This makes it possible to prevent the generation of toxic gases, etc. The magnetic separation residue separated in the magnetic separation step (S5) denoted by reference numeral 70 is then subjected to a heating step (S1
4) is heated at about 300°C for 10 minutes, and then heated using an ultrasonic vibrator (S16).
The mixture is subjected to ultrasonic vibration for 15 minutes, and then sieved (
S7) is performed. That is, in the heating step (S14), lithium cobalt oxide 7 and
Graphite (spherical graphite) is peeled off from the copper foil of the negative electrode.
Ethylene carbonate, dimethyl carbonate, polyvinyl chloride and
and lithium hexafluorophosphate will evaporate or decompose.
The polypropylene or polyethylene decomposes and burns.
The gas generated in the roasting operation (S14) is used together with the gas generated in other operations.
S8) or is directly subjected to exhaust gas treatment (S9). More specifically, the magnetic separation residue is heated to approximately 300 to 500°C in an inert gas atmosphere.
By heating the cathode, the acetylene black and lithium cobalt oxide that make up the cathode are
The polypyridinium chloride that binds the lithium is thermally decomposed.
The adhesive strength between acetylene black, lithium cobalt oxide and aluminum foil is reduced, and
In this state, the ball is vibrated (S6) or the ultrasonic vibrator (S16) is used.
By performing vibration treatment, acetylene black and lithium cobalt oxide 7
can be separated from the aluminum foil. Similarly, the polypyridinium chloride on the negative electrode side is thermally decomposed, separating it from the copper foil.
The adhesion strength of the graphite ball to the surface of the ball is reduced, and in this state, ball vibration and superheat
By applying ultrasonic vibration, the graphite can be separated from the copper foil. At this time, the solvents ethylene carbonate, dimethyl carbonate, and polyvinyl alcohol
The ethylene chloride and lithium hexafluorophosphate are evaporated or decomposed, and the separator
The polypropylene or polyethylene used as the raw material is removed from the system by decomposition and combustion.
The particles are then removed and sent to the exhaust gas treatment (S9). Following the ball vibration treatment (S6), the particles are separated by sieving (S7).
Lithium cobalt oxide 7 of particle size, acetylene black, and graphite were placed on a copper foil.
The process of separating the frozen material from the aluminum foil is the same as in the previous embodiment. Accordingly, this embodiment combines the freeze-crushing process (S3A) and the heating process (S14).
When combined, toxic gases such as phosphorus pentafluoride and hydrogen fluoride may be generated, and explosions may occur.
18 shows the disassembly process for a lithium ion battery according to the ninth embodiment of the present invention.
In the flow diagram shown, lithium cobalt oxide and carbon are mixed by sedimentation in water rather than by granulation and roasting.
This is an example corresponding to Figure 1. In addition, in this invention, high-purity cobalt oxide is obtained by avoiding the contamination of iron in the recovered lithium cobalt oxide.
The aim is to recover lithium. The difference from the flow diagram in Figure 1 is that in this example, after screening in (S7),
A magnetic separation process (S29) is included to remove iron 24 from the recovered lithium cobalt oxide.
In addition, the "lithium cobalt oxide and the iron content 3 removed in the magnetic separation step (S29)"
The recovered material such as carbon is not sent to the roasting process (S8) but is sent to the underwater sedimentation separation process (
S40) by dispersing in water 20, water-soluble fluoride compound and phosphate compound
is dissolved in water and the water-insoluble lithium cobalt oxide 7 is extracted.
The specific gravity of lithium cobalt oxide is about 6, which is much larger than that of carbon (about 2).
There is a large difference in specific gravity, so specific gravity separation is easy. Then, the remaining "carbon + water-soluble fluoride compounds and phosphate compounds" 21
The water is introduced into a suspended solids separator (S41) to separate the carbon 22. Then, the water-soluble fluoride compounds and phosphoric acid discharged from the suspended solids separator (S41) are separated.
The compound-containing water 23 is returned to the water washing step (S11). According to this embodiment, by adding the magnetic separation step (S29), the recovered material
High-purity lithium cobalt oxide can be obtained by removing the iron 3 mixed in. In addition, even if the iron content in the recovered lithium cobalt oxide 7 matches the intended use,
In this case, the magnetic separation step (S29) can be omitted. Furthermore, according to the above example, not only carbon 22 but also fluoride compounds and phosphate compounds are extracted.
23 is an ionic compound and dissolves in water, making it easy to remove. Figures 19 and 20 show lithium ion batteries according to the 10th and 11th embodiments of the present invention.
Flow diagram showing the pond dismantling process, in which lithium cobalt oxide and carbon are granulated and roasted.
It is extracted by sedimentation in water, and corresponds to Figures 2 and 3.
This is an example. According to this example, the ultrasonic vibration in (S16) is performed in water or an aqueous solution.
Therefore, the "water-soluble fluoride compound and phosphate compound" 23 is subjected to an ultrasonic vibration process.
In the submerged sedimentation step (S40), the recovered material contains "cobalt".
The only thing that needs to be done is to separate the lithium fluoride and carbon.
The mixture and the phosphoric acid compound 23 are not dissolved in the suspension separator (S41).
This allows separation of carbon 22, simplifying the separation steps (S40) and (S41).
. The effluent discharged from the floating matter separator (S41) can be discharged as is.
Alternatively, the process may be returned to the water washing step (S11) to form a closed circuit. Figure 21 shows the disassembly process for a lithium ion battery according to a twelfth embodiment of the present invention.
4, which shows the magnetic separation step (S29), the underwater sedimentation step (S30), and the like.
The separation step (S40) and the suspended solids separation step (S41) are provided in the same manner as in the previous embodiment.
According to this example, the "water-soluble fluoride compound and phosphate compound" is a HCl solution component.
In the separation step (S25), the recovered material is removed, and in the submerged sedimentation step (S40), the recovered material is
All that is required is to separate the lithium cobalt oxide from the carbon.
The fluoride compounds and phosphate compounds are not dissolved in the suspended matter separator (S41).
The separation of carbon 22 is possible, and the separation steps (S40) and (S41) are simplified.
Also, the effluent discharged from the floating matter separator (S41) may be discharged as it is.
In addition, the water may be returned to the water washing step (S11) to form a closed circuit.
Figure 22 shows the disassembly process for a lithium ion battery according to the 13th embodiment of the present invention.
5, which is a flow chart showing the magnetic separation step (S29), the underwater sedimentation step (S30), and the like.
This is the same as the previous embodiment, which includes a separation step (S40) and a floating matter separation step (S41).
. The effluent discharged from the floating matter separator (S41) may be discharged as is.
In addition, the point that the water may be returned to the water washing step (S11) to form a closed circuit is also mentioned in the above embodiment.
In this embodiment, the aluminum dissolving and stripping step (S28) is followed by the Na
A filter is provided in the OH solution separation step (S30) to separate the copper 15.
5, the aluminum is directly fed to the aluminum precipitation tank (S26) without passing through the water washing step (S12).
Figure 23 shows the disassembly process for a lithium ion battery according to the 14th embodiment of the present invention.
In the flow chart showing the embodiment corresponding to FIG. 6, the upstream side of the magnetic separation step (S29)
Since there is no water treatment process, as in Figure 18, "water-soluble fluoride compounds and phosphate
The "fluoride compounds and phosphate compounds" are contained in the recovered material. Then, after being discharged from the floating matter separator (S41),
Unlike FIG. 18, the water-containing wastewater is not subjected to a water washing process but to a wastewater treatment solid-liquid separation process (S10).
and solidified as calcium fluoride or calcium phosphate.
Figure 24 shows the disassembly process for a lithium ion battery according to the 15th embodiment of the present invention.
In the embodiment corresponding to FIG. 7, the heating treatment in (S3) is carried out using an inert gas.
The same as in FIG. 18 except that the test was performed in a vacuum atmosphere (S3') instead of a normal atmosphere.
Figures 25 to 27 show battery cell housings with aluminum surfaces instead of magnetic materials.
Other than using a cell housing made of non-magnetic material such as aluminum treated with Mite
In the example, the difference in specific gravity between plastic and aluminum is small, so the plastic can be separated by sieving.
The cell housing is separated. That is, Figure 25 shows the disassembly process for a lithium ion battery according to the 16th embodiment of the present invention.
This is a flowchart showing the processing process for a battery cell housing made of aluminum.
Therefore, the magnetic separation step (S2) after the battery freezing and breaking step (S1) in FIG.
The battery cell and plastic are separated by changing the separation process (S2'). Figure 27 shows the first step of Figures 25 and 26, in which the battery is frozen and opened.
This is an overview of the case sorting equipment that separates the plastic cases and sealed battery cells.
After case selection is performed by rod vibration treatment, a screening process (S2') is added.
In Figure 27, 30 is a battery refrigeration device, which refrigerates the waste batteries 1 through an inlet 32.
After immersing the sample in nitrogen 31 and cooling it to below -50°C, the sample is cooled by rotating blades 33.
The battery 1 and rod 49A are then fed into the continuous treatment rod vibrating device 40A through the discharge port 41. The rod vibrating device 40A vibrates the battery 1 and rod 49A in a mixed state.
The grey fabric 44 is driven and vibrated in a vibrating tub 45 supported by a spring 44a.
The plastic case of the pond 1 is broken open, and the debris generated by the breaking is first removed from the porous part.
After dropping into the dust receiver 46a from 46, the dust is discharged from the discharge port via the belt conveyor 52.
Or it is led to a vibrating sieve 55. Then, a size classification device 55 consisting of a vibrating sieve
In this case, a vibration generator 44 vibrates a guide rail plate 53 formed to a predetermined width.
This separates the sealed battery cell 1a from the plastic case 2. In this device, the housing is made of a non-magnetic material with a small difference in specific gravity.
The sealed battery cell 1a, which is a plastic material, is removed from the plastic case 2.
Taking advantage of the fact that the housing is made of aluminum,
The sealed battery cell 1a is removed from the plastic case 2. Figure 26 shows the disassembly process for a lithium-ion battery according to the 17th embodiment of the present invention.
This is a flow chart showing the battery cell housing made of aluminum.
Therefore, the magnetic separation process (S2) after the battery freezing and cracking process (S1) is changed to a screening process (S2').
Furthermore, the aluminum material was effectively removed by eddy current treatment (S5').
4 and the improved embodiment of FIG. 25, in which the sealed battery cell housing is
Since it is a lumi material, the magnetic separator 70 is used as in the previous embodiment in which a steel material is used.
By using an eddy current processing step (S5') using an eddy current machine without using the step (S5),
The aluminum part of the sealed battery cell housing is separated from the eddy current residue.
As shown in the figure, the eddy current treatment step (S5') was not used, and the ball vibration treatment (S
The aluminum case may be directly removed along with the copper by screening (S7) in step 6. Effects of the Invention As described above, according to the inventions described in claims 1 to 5, the plus
The battery case is safely and securely opened, and the sealed battery cell and plastic case are separated.
This allows for easy sorting and protects the sealed battery cells 1a.
It is possible to separate the case from the system as quickly as possible and to make it inactive or
By heating and crushing the material while maintaining a vacuum, the volatile solvent in the electrolyte may ignite.
It can prevent the generation of harmful substances and also reduce the plastic case
The opening of the hole can be carried out safely and reliably. Furthermore, according to the invention described in claim 4, the presence or absence of magnetism, differences in specific gravity, and sieving can be performed.
By using this method, the sealed battery cells 1a and plastic cases can be securely separated.
According to the invention described in claim 6, ultrasonic vibration, ball vibration, etc.
The positive (negative) electrode active material can be smoothly separated from the metal foil by the vibration peeling means. Also, in the invention described in claim 7, the peeling agent can be used to
By combining the agent with a vibration peeling means, the positive (negative) electrode active material can be smoothly separated from the metal foil.
Furthermore, in the invention described in claim 8, a strong acid or strong alkaline solution is used.
The metal foil can be dissolved using a solvent to smoothly separate the positive (negative) electrode active material. According to the invention described in claim 9,
The powdery material is separated by sieving, and then granulated to form the so-called
This results in a briquette-like charcoal that can be easily roasted afterwards. According to the invention described in claim 10, lithium hexafluorophosphate, a harmful substance, is not present.
By dissolving and separating the solid matter 7 in the aqueous solution, the solid matter processing system and the solvent system are respectively
This can be done in a separate treatment system, and the use of toxic electrolytes, especially in solids treatment, is avoided.
Eliminate the presence of fluorine compounds and flammable solvents, and do not take any precautions against them.
Dismantling can be carried out from the solution, and phosphorus hexafluoride dissolved in an aqueous solution can be used.
The lithium oxide is decomposed into fluoride ions and phosphate ions, and then the ion aqueous solution is
By adding a fixing agent such as slaked lime to the wastewater, it can be safely treated. Furthermore, according to the invention described in claim 11, the exhaust gas treatment can be carried out by a dry treatment method.
This process allows for simplification of the equipment and simplification of wastewater treatment. According to the inventions described in claims 12 and 13, cobalt particles with minute particle diameters are used.
Even lithium oxide can be recovered safely, reliably and efficiently. According to the inventions described in claims 14 to 17, iron and carbon mixed in the recovered material can be removed.
It is possible to effectively remove ions to obtain high-purity lithium cobalt oxide.
According to the invention of claim 17, the fluoride dissolved in the wastewater of the recovered material
The ions and phosphate ions can be fixed by adding a fixative such as slaked lime to the aqueous solution.
According to the inventions of claims 18 to 21, the processing of the waste material is more secure.
The invention described above can be effectively implemented. According to the invention described in claim 22, the inventions described in claims 18 to 21 can be effectively implemented.
The battery is repeatedly subjected to vibration or clamping pressure to form a sealed battery cell.
This includes a case breaking and sorting process to sort the products into plastic cases.
The sealed battery cells selected in the case rupture selection process are kept below the melting point of the electrolyte solvent.
Even if the battery cell crushing process is combined with the conventional battery cell crushing process in which the battery cell is crushed while being held in place, the same effect as the invention described above can be obtained.
It has similar effects. In particular, by combining the above invention with the inventions described in claims 23 to 26,
The lithium hexafluorophosphate separated in the aqueous solution is decomposed into fluoride by (hydrolysis).
After decomposing the ion into cation ions and phosphate ions, a fixative such as calcium hydroxide is added to the ion solution.
It can be safely disposed of by adding and fixing it.

[Brief explanation of the drawings]

FIG. 1 is a flow chart showing the disassembly process for lithium-ion batteries according to a first embodiment of the present invention, in which a granulation process is added before the roasting process. FIG. 2 is a flow chart showing the disassembly process for lithium-ion batteries according to a second embodiment of the present invention, in which the metal foil is peeled using ultrasonic vibration instead of the ball vibration peeling method shown in FIG. 1. FIG. 3 is a flow chart showing the disassembly process for lithium-ion batteries according to a third embodiment of the present invention, in which the metal foil is peeled using ultrasonic vibration peeling in combination with a peeling agent. FIG. 4 is a flow chart showing the disassembly process for lithium-ion batteries according to a fourth embodiment of the present invention, in which the metal foil is peeled (dissolved) using an aqueous HCl solution. FIG. 5 is a flow chart showing the disassembly process for lithium-ion batteries according to a fifth embodiment of the present invention, in which the metal foil is peeled (dissolved) using an aqueous NaOH solution, which is a strong alkali. FIG. 6 is a flow chart showing the disassembly process for lithium-ion batteries according to a sixth embodiment of the present invention, in which exhaust gas treatment is performed by dry processing using a bag filter or the like. Figure 7 is a flow chart showing the dismantling process for lithium-ion batteries according to a seventh embodiment of the present invention. Unlike the previous embodiments, the heating process (S3) is performed in a vacuum atmosphere rather than an inert gas atmosphere, and exhaust gas treatment is performed by dry processing using a bag filter or the like. Figure 8 is a schematic diagram of a case sorting device that freezes and breaks open batteries to separate plastic cases and sealed battery cells, the first step in Figure 1. Case sorting is performed using a rod vibration process. Figure 9 is a diagram corresponding to Figure 8, where the case sorting is performed using a ball vibration process. Figure 10 is a schematic diagram showing a sealed battery cell crushing device after the heating process, the third step in Figure 1. Figure 11 is a flow chart showing the dismantling process for lithium-ion batteries according to an eighth embodiment of the present invention. Unlike the previous embodiments, battery cells are crushed by freeze crushing. Figure 12 is a schematic diagram showing a freeze crushing device for sealed battery cells, the third step in Figure 11. Figure 13 shows the relationship between HCl concentration and aluminum foil solubility when the HCl solution is at room temperature. Figure 14 shows the relationship between HCl concentration and aluminum foil solubility when the HCl solution is heated to 95°C. Figure 15 is a table showing the acid decomposition behavior of lithium hexafluorophosphate separated in an aqueous solution by hydrochloric acid. Figure 16 is a table showing the acid decomposition behavior of lithium hexafluorophosphate separated in an aqueous solution by sulfuric acid. Figure 17 is a table showing the relationship between the concentration of an acid aqueous solution and ionic strength (source: Chemistry Handbook, Basic Edition, Revised Fourth Edition, p. II-323, edited by the Chemical Society of Japan). Figure 18 is a flow chart showing the disassembly process for a lithium-ion battery according to a ninth embodiment of the present invention, in which lithium cobalt oxide and carbon are extracted by aqueous sedimentation rather than granulation and roasting, and corresponds to Figure 1. Fig. 19 is a flow chart showing the disassembly process of a lithium-ion battery according to a tenth embodiment of the present invention, in which lithium cobalt oxide and carbon are extracted by aqueous sedimentation separation rather than granulation roasting, and is an embodiment corresponding to Fig. 2. Fig. 20 is a flow chart showing the disassembly process of a lithium-ion battery according to an eleventh embodiment of the present invention, in which lithium cobalt oxide and carbon are extracted by aqueous sedimentation separation rather than granulation roasting, and is an embodiment corresponding to Fig. 3. Fig. 21 is a flow chart showing the disassembly process of a lithium-ion battery according to a twelfth embodiment of the present invention, in which lithium cobalt oxide and carbon are extracted by aqueous sedimentation separation rather than granulation roasting, and is an embodiment corresponding to Fig. 4. Fig. 22 is a flow chart showing the disassembly process of a lithium-ion battery according to a thirteenth embodiment of the present invention, in which lithium cobalt oxide and carbon are extracted by aqueous sedimentation separation rather than granulation roasting, and is an embodiment corresponding to Fig. 5. Fig. 23 is a flow chart showing the disassembly process for lithium-ion batteries according to a fourteenth embodiment of the present invention, in which lithium cobalt oxide and carbon are extracted by aqueous sedimentation separation rather than granulation and roasting, and is an embodiment corresponding to Fig. 6. Fig. 24 is a flow chart showing the disassembly process for lithium-ion batteries according to a fifteenth embodiment of the present invention, in which lithium cobalt oxide and carbon are extracted by aqueous sedimentation separation rather than granulation and roasting, and is an embodiment corresponding to Fig. 7. Fig. 25 is a flow chart showing the disassembly process for lithium-ion batteries according to a sixteenth embodiment of the present invention, in which aluminum material is used for the battery cell housing rather than magnetic material, and therefore the magnetic separation process (S2) after battery freeze-opening (S1) is changed to a sieving process (S2'), and is an embodiment corresponding to Fig. 24. FIG. 26 is a flow chart showing the disassembly process for lithium ion batteries according to a seventeenth embodiment of the present invention. In this case, aluminum material is used for the battery cell housing. Therefore, the magnetic separation process (S2) after the battery freeze-opening (S1) is changed to a screening process (S2'), and further, an eddy current process (S5') is carried out to effectively remove the aluminum material.
This is an embodiment corresponding to Fig. 4 and an improved embodiment of Fig. 25. Fig. 27 is an overall schematic diagram of a case sorting device that freezes and opens batteries to separate them into plastic cases and sealed battery cells, which is the first step in Figs. 25 and 26, and after case sorting is performed using rod vibration processing, a screening step (S2') is added.

───────────────────────────────────────────────────── Continued from the front page (72) Inventor: Takeo Kamimura 2-1 Shinhama, Arai-cho, Takasago City, Hyogo Prefecture, Japan No. 1 Takaryo Engineering Co., Ltd. (72) Inventor: Kenji Sasaki 1-1 Wadazaki-cho, Hyogo-ku, Kobe City, Hyogo Prefecture, Japan No. 1 Mitsubishi Heavy Industries, Ltd. Kobe Shipbuilding Co., Ltd. (72) Inventor: Masakazu Yabuki 2-1 Shinhama, Arai-cho, Takasago City, Hyogo Prefecture, Japan No. 1 Takaryo Engineering Co., Ltd. (72) Inventor: Kiyonori Nishida 2-1 Shinhama, Arai-cho, Takasago City, Hyogo Prefecture, Japan No. 1 Takaryo Engineering Co., Ltd. (Note) This publication is based on the publication published internationally by the International Bureau of International Patent Office (WIPO). Please note that the effect of the international publication of the Japanese-language patent application (Japanese-language utility model registration application) related to this publication arises pursuant to Article 184-10, Paragraph 1 of the Patent Act (Article 48-13, Paragraph 2 of the Utility Model Act), and is unrelated to this publication.

Claims (26)

[Claims] [Claim 1] A method for dismantling and processing a battery pack (hereinafter referred to as "battery") in which one or more sealed battery bodies (hereinafter referred to as "sealed battery cells") are protected by a plastic case, comprising: a case breaking and sorting process in which, while the battery is cooled to -50°C or below, multiple objects having a higher rigidity and specific gravity than the plastic are used to repeatedly vibrate or apply clamping pressure to the battery, thereby separating the battery into sealed battery cells and plastic cases; and a heating and separation process in which the sealed battery cells sorted in the case breaking and sorting process are heated to a temperature of at least 200°C or higher in a non-oxidizing atmosphere, thereby separating mainly organic materials. [Claim 2] The battery disassembly processing method according to claim 1, wherein the non-oxidizing atmosphere is a vacuum atmosphere, and the organic material separated by heating is cooled and recovered. [Claim 3] A method for dismantling and processing a battery according to claim 1, wherein the non-oxidizing atmosphere is an inert gas atmosphere such as nitrogen, helium, argon, neon, etc., and wherein liquid or solid organic materials other than the gaseous material separated by heating are heated and roasted in an inert gas or other non-oxidizing gas atmosphere. [Claim 4] A battery disassembly processing method as described in claim 1, characterized in that the sorting means for separating the sealed battery cells and plastic cases is a sorting device that utilizes the presence or absence of magnetism, differences in specific gravity, or sieving. [Claim 5] A method for dismantling batteries, in which one or more sealed battery cells are protected by a plastic case and the sealed battery cells each have a current collector made of metal foil coated with an electrode layer containing reusable positive (negative) electrode active material, comprising: a case breaking and sorting process in which, while the battery is cooled to -50°C or below, multiple objects having a higher rigidity and specific gravity than the plastic are used to repeatedly vibrate or clamp the battery to separate the sealed battery cells from the plastic case; a heating and separation process in which the sealed battery cells sorted in the case breaking and sorting process are heated to a temperature of at least 200°C or higher in a non-oxidizing atmosphere to separate mainly organic materials; and one or more sorting processes in which noise substances are sequentially removed from the crushed material crushed in the cell crushing process to separate the target useful materials. [Claim 6] The step of separating the target useful substance according to claim 5, wherein the positive (
6. The method for disassembling a battery according to claim 5, further comprising a step of separating the negative electrode active material. 7. The step of selecting the target useful substance according to claim 5,
5. The method according to claim 4, further comprising a step of separating the positive (negative) electrode active material from the metal foil by using a peeling agent or by combining the peeling agent with a vibration peeling means.
A method for dismantling and processing a battery as described in paragraph 1. [Claim 8] A battery disassembly processing method as described in claim 5, characterized in that the sorting process for sorting the target useful substances as described in claim 5 includes a process for dissolving the metal foil using a strong acid or strong alkaline solution to separate the positive (negative) electrode active material. 9. The step of selecting the target useful substance according to claim 5,
6. The battery disassembly method according to claim 5, further comprising a step of granulating the powder material after separating the metal foil and the powder material containing the positive (negative) electrode active material by sieving. 10. The method for dismantling and treating batteries according to claim 5, wherein the batteries are lithium ion batteries, wherein the step of decomposing harmful substances such as lithium hexafluorophosphate into ion-containing gases such as fluoride ions and phosphate ions by heating in the thermal separation step, and then treating the gases with an aqueous solution, and then adding a fixing agent such as slaked lime to the aqueous ion solution to fix the gases, is included in the step of selecting the target useful substances. [Claim 11] A battery disassembly processing method according to claim 5, wherein the battery is a lithium ion battery, characterized in that the sorting process for selecting the target useful substances includes a step of decomposing harmful substances such as lithium hexafluorophosphate into ion-containing gases such as fluoride ions and phosphate ions by heating in the thermal separation process, and then fixing the ion-containing gases by dry contact with a fixing agent such as powdered slaked lime. [Claim 12] A method for dismantling and processing a battery according to claim 5, wherein the battery is a lithium ion battery, characterized in that the sorting step for selecting the target useful substance includes a step of washing with water the material from which resin components and the like have been removed by a heating operation, dispersing positive (negative) electrode active material such as lithium cobalt oxide having a very small particle diameter in water, and recovering the dispersed material. [Claim 13] A battery disassembly processing method according to claim 5 for recovering lithium cobalt oxide from a lithium ion battery having an electrode current collector made of a metal foil coated with an electrode agent containing lithium cobalt oxide as a positive (negative) electrode active material, characterized in that the sorting step for selecting the target useful substance comprises the steps of separating the metal foil and a powdery material containing the electrode active material by sieving, then granulating the powdery material, and roasting the granules to recover lithium cobalt oxide. [Claim 14] A battery disassembly processing method as described in claim 5, characterized in that the sorting process for selecting the target useful substances as described in claim 5 includes a process for separating the powdery substances containing the metal foil and positive (negative) electrode active material by sieving, and then removing iron by magnetic separation or the like. [Claim 15] A battery disassembly processing method according to claim 5 for recovering lithium cobalt oxide from a lithium ion battery having an electrode current collector made of metal foil coated with an electrode agent containing lithium cobalt oxide as a positive (negative) electrode active material, characterized in that the sorting step for selecting the target useful substance comprises a step of separating the metal foil and powdery material containing the positive (negative) electrode active material by sieving, and then sedimenting and separating the recovered material by sieving in water to recover lithium cobalt oxide from which carbon and the like have been removed. 16. The method for dismantling and treating batteries according to claim 15, further comprising a step of removing carbon and the like by flotation separation of the discharged water discharged in the underwater sedimentation separation step according to claim 15. [Claim 17] A method for dismantling and processing batteries as described in claim 15, characterized in that the aqueous ion solution of fluoride ions, phosphate ions, etc. dissolved in water from the recovered material in the underwater sedimentation separation step as described in claim 15 is subjected to a flotation separation step for removing carbon, etc., and then a step of adding a fixing agent such as hydrated lime to the ion aqueous solution to fix it. 18. The case breaking and sorting step according to claim 1 or 5,
6. A method for dismantling a battery according to claim 1 or 5, characterized in that vibration is applied to a mixture of the battery and a plurality of objects having higher rigidity and specific gravity than the plastic under cooling at -50°C or below, and the vibration is low-frequency vibration. 19. The battery disassembly processing method according to claim 18, wherein the volume of the vibration-applying object is 0.2 to 1 times or less the volume of the separated battery cells. 20. The case breaking and sorting step according to claim 1 or 5,
A battery disassembly method according to claim 1 or 5, characterized in that the plastic case and battery cells are crushed and separated by applying pressure and vibration between a plurality of objects having greater rigidity and specific gravity than the plastic under cooling at -50°C or below. [Claim 21] A battery dismantling method as described in claim 20, characterized in that the object to be clamped is a shaft (including hollow shafts) with a circular, elliptical, or rectangular cross section that is rotating while cooled to -50°C or below, and the vibration applied to the rotating space is a low-frequency vibration. [Claim 22] A method for dismantling batteries in which one or more sealed battery cells are protected by a plastic case, and the sealed battery cells each have a current collector made of metal foil coated with an electrode layer containing reusable positive (negative) electrode active material, comprising: a case breaking and sorting process in which, while the battery is cooled to -50°C or below, multiple objects having a higher rigidity and specific gravity than the plastic are used to repeatedly vibrate or clamp the battery to separate the sealed battery cells from the plastic case; a battery cell crushing process in which the sealed battery cells sorted in the case breaking and sorting process are crushed while maintaining the sealed battery cells below the melting point of the electrolyte solvent; and one or more sorting processes in which noise substances are sequentially removed from the crushed material crushed in the cell crushing process to select the desired useful materials. [Claim 23] A method for dismantling batteries, wherein one or more sealed battery cells are protected by a plastic case, and the sealed battery cells each contain a battery cell containing an electrolyte containing a salt of cations and Lewis acid ions, together with electrode current collectors made of metal foil coated with an electrode layer containing reusable positive (negative) electrode active material, the method comprising: a case breaking and sorting step for separating the batteries into sealed battery cells and plastic cases; a battery cell crushing step for crushing the sealed battery cells crushed in the case breaking and sorting step; and one or more sorting steps for sequentially removing noise substances from the crushed battery cells crushed in the cell crushing step and selecting target useful substances, wherein the one or more sorting steps include the steps of washing the crushed battery cells containing the salt with water to separate the salt into an aqueous solution, adding a heated aqueous acid solution to the aqueous solution containing the salt to promote decomposition of the Lewis acid ions, and adding a fixative such as slaked lime to the aqueous ion solution to fix it. [Claim 24] The battery disassembly processing method according to claim 23, characterized in that the one or more sorting steps include: a step of heating the crushed battery material containing the salt by means of thermal decomposition, baking or the like to cause the salt to be contained in the exhaust gas; an exhaust gas treatment step of bringing the exhaust gas into contact with an aqueous solution of a fixing agent such as slaked lime to trap the salt in the fixing agent aqueous solution; and a step of adding a heated aqueous acid solution to the aqueous solution of salt trapped in the exhaust gas treatment step to promote decomposition of the Lewis acid ions, and adding a fixing agent such as slaked lime to the aqueous ion solution to fix them. [Claim 25] A method for dismantling and processing a battery according to claim 23, wherein the battery cells are lithium ion batteries containing lithium hexafluorophosphate as an electrolyte, the method comprising the steps of adding a heated acidic aqueous solution to an aqueous solution containing lithium hexafluorophosphate separated by a predetermined sorting step to decompose the ions into fluoride ions and phosphate ions, and then adding a fixing agent such as slaked lime to the aqueous ionic solution to fix the ions. 26. A method for treating a battery, wherein the heated acidic aqueous solution according to claim 23, ₂₄ or ₂₅ is an acidic aqueous solution of HCl, _H2SO4 , _HNO3 or HClO4, and the heating temperature is 65°C to 100°C.