JP3137286B2 - Method and apparatus for collecting sealed battery member - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for recovering a member constituting a sealed battery, and more particularly to a method and an apparatus for recovering a member constituting a sealed battery by safely opening the same. .

[0002]

2. Description of the Related Art Recently, since the amount of CO ₂ gas contained in the atmosphere is increasing, it has been pointed out that the greenhouse effect may cause global warming. Thermal power plants convert thermal energy obtained by burning fossil fuels and the like into electric energy. However, since a large amount of CO ₂ gas is emitted by combustion, it is becoming difficult to construct a new thermal power plant.
Therefore, as an effective use of electric power generated by generators such as thermal power plants, surplus electric power at night is stored in secondary batteries installed in ordinary households and used during the daytime when power consumption is high. In other words, a so-called load leveling in which the load is leveled has been proposed.

[0003] In addition, for electric vehicles, which are characterized in that they do not emit air pollutants related to air pollution including CO _x , NO _x , CH, etc., development of secondary batteries with high energy density is expected. Furthermore, for the power supply of portable devices such as book-type personal computers, word processors, video cameras, and mobile phones, there is an urgent need to develop small, lightweight, and high-performance secondary batteries.

As storage batteries (secondary batteries) used for the above-mentioned applications, sealed (sealed) lead storage batteries, nickel-
In addition to cadmium storage batteries, new high energy density nickel-hydrogen (storage alloy) storage batteries, lithium secondary batteries, and lithium ion secondary batteries (storage batteries) have been developed. These batteries employ a sealed battery housing to achieve long life or to ensure safety, and most have a safety valve to further ensure safety. . This safety valve is
When the pressure inside the battery housing exceeds a certain cause or more, the battery housing is opened so that the atmosphere outside the battery housing communicates with the inside of the battery housing.

[0005] A nickel-hydrogen storage alloy storage battery utilizes an electrochemical oxidation-reduction reaction of hydrogen ions, and uses a hydrogen storage alloy as a negative electrode material (active material layer). Hydrogen that has been reduced from hydrogen ions in the electrolyte is stored, and the stored hydrogen is oxidized and discharged as hydrogen ions into the electrolyte during discharge. Nickel hydroxide (nickel nickel hydroxide, Ni (OH) ₂ ) is used as the positive electrode material (active material layer), and is oxidized during charging, reduced during discharging, and returns to the original nickel hydroxide. In order to efficiently store hydrogen in the hydrogen storage alloy of the negative electrode during charging and to increase the capacity of the battery, a type that is usually sealed in a battery housing (container) is employed.

[0006] A lithium battery is a battery utilizing an electrochemical oxidation-reduction reaction of lithium ions. Lithium reacts with moisture in the air to cause a reduction in the capacity of the battery. A non-aqueous organic solvent or inorganic solvent that has been sufficiently removed is used, and a sealed battery housing is employed. The battery is assembled in an atmosphere from which moisture is sufficiently removed. Lithium metal is used for a negative electrode material (active material) layer in currently marketed lithium primary batteries and lithium metal secondary batteries being studied. Also, commercially available so-called “lithium ion batteries” use a carbon material such as graphite, which can intercalate lithium ions between layers during charging, as a negative electrode material (active material) layer. The transition metal compound which can intercalate is used.
(Here, a lithium primary battery, a lithium metal secondary battery, and a lithium ion battery are collectively referred to as a lithium battery.)

Various types of sealed batteries, such as the above-mentioned storage batteries, which are already used in many portable devices, will be developed for use in electric vehicles, road conditioners, and electric power storage in addition to the development of new portable devices. However, it is expected that consumption will continue to increase, and it is considered that collection of the sealed battery and reuse of battery internal members will be essential.

However, in order to recover the components from the sealed battery, the sealed battery housing must first be opened, and the positive electrode and the negative electrode contact each other at the time of opening.
It causes a short circuit, the remaining electric capacity is rapidly consumed in a short time, heat is generated, and there is a case where the components of the battery are deteriorated, and the recovery rate of reusable members is reduced. There was a problem. Therefore, in the above sealed battery, it is desired to develop a method for recovering the battery member, including an opening method in which even if the positive electrode and the negative electrode contact each other at the time of opening, the damage such as deterioration of the battery constituent members is minimized.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned conventional problems, and is more secure in recovering the components of a sealed battery and is less likely to cause damage such as deterioration. An object of the present invention is to provide a method and a device (system) for collecting a sealed battery member.

[0010]

SUMMARY OF THE INVENTION A first aspect of the present invention is a method of recovering the components of a sealed battery, wherein at least the step of reducing the ionic conductivity between the positive electrode and the negative electrode and the step of reducing the ionic conductivity are described. After the step of opening the battery housing, and after the step of opening the battery housing, a step of taking out a battery constituent member from the battery housing ;
After removing the battery component, the battery configuration
And recovering the sealed battery member.

A second aspect of the present invention is a device for recovering the components of a sealed battery, a means for reducing at least the ionic conductivity between the positive electrode and the negative electrode, a means for opening the battery housing, and a method for removing the battery components from the battery housing. And a means for separating and collecting the battery components.

In the method and apparatus for recovering the components of a sealed battery according to the present invention, prior to opening the sealed battery, a step of reducing the ionic conductivity between the positive electrode and the negative electrode, or a part for performing the step is performed. It is the most characteristic in that it has

When the battery housing is opened using the method and apparatus for recovering a sealed battery member according to the present invention, for example, the electrolyte solution in the sealed battery housing or the solvent in the electrolyte solution is taken out of the battery housing to remove the negative electrode and the positive electrode. By lowering the ionic conductivity between the negative electrode and the positive electrode in the event that the negative electrode and the positive electrode are short-circuited when opening the housing or taking out the member from the housing in the subsequent process, it is possible to suppress rapid energy release and ignition due to the short-circuit, As a result, the members constituting the battery can be collected more safely without deterioration or loss, and the member collection of the sealed battery which is safe and has a high collection rate can be realized.

The present invention is effective as a method for recovering members constituting a sealed battery regardless of whether the sealed battery is a primary battery or a secondary battery.

[0015] As a sealed battery to which the recovery method and apparatus of the present invention can be particularly preferably employed, for example, a lithium battery utilizing a redox reaction of lithium ions (a so-called negative electrode using a carbon material intercalating lithium for a negative electrode). Including lithium ion secondary batteries), storage batteries that use hydrogen-absorbing alloys as negative electrodes by utilizing the oxidation-reduction reaction of hydrogen ions,
Nickel-cadmium storage batteries and lead storage batteries are exemplified.

As for lithium batteries, a lithium primary battery using lithium metal for a negative electrode, which is already used in many cameras and wristwatches, and a lithium secondary battery which is expected to increase in consumption are combined. It is naturally expected that the disposal of lithium-containing lithium batteries will become a major problem in the future like other sealed batteries, and the components such as the negative electrode, positive electrode, electrolyte, separator, and housing will be separated and collected for regeneration. It is requested to do.

In order to separate and recover various components from a used lithium battery, a battery housing (container) which is hermetically sealed so as to suppress intrusion of moisture from the outside which causes deterioration of battery characteristics. Must be opened.

As for the lithium battery, mechanical cutting is considered as the simplest method of opening the battery housing (container). In particular, a lithium battery has a very high energy per unit volume and unit weight, and is flammable. Since the organic solvent and the like are contained in the battery, it is not completely impossible to cause the sparking or the short-circuit between the negative electrode and the positive electrode of the battery housing.

When the battery components contained in the battery housing after opening are taken out, the lithium battery is likely to be short-circuited because the negative electrode and the positive electrode are close to each other. , Causing rapid heat generation.

Therefore, in the lithium battery, there is a need for a battery recovery method and a recovery device which are safer and do not cause damage when recovering the battery constituent materials, and the recovery method and the device of the present invention are particularly preferably applied. You.

In the method for recovering a sealed battery member according to the present invention, the step of lowering the ionic conductivity between the positive electrode and the negative electrode of the battery, particularly in the case of a battery using an electrolytic solution, includes at least the electrolytic solution in the battery housing or It is preferable to remove the solvent in the electrolyte from the battery housing.

When a safety valve is provided in the sealed battery, the operation of taking out the electrolytic solution or its solvent out of the housing is performed, for example, by reducing the pressure of the atmosphere outside the battery housing through the safety valve. It is preferable from the viewpoint of workability and the like that the safety valve is actuated and generated through a differential pressure generated inside and outside the battery housing by increasing the pressure inside the housing. The electrolyte or the solvent in the electrolyte taken out of the housing of the sealed battery can be recovered and regenerated.

In the method for recovering a sealed battery member according to the present invention, it is also preferable that the step of reducing the ionic conductivity between the positive electrode and the negative electrode of the sealed battery is performed at least by a method of cooling the sealed battery.

When employing this method, particularly when a solvent is used in the electrolyte of the sealed battery, it is preferable to cool the electrolyte to a temperature below the freezing point of the solvent of the electrolyte of the sealed battery. When a polymer solid electrolyte immobilized using a polymer is used in a sealed battery, it is preferable to cool the polymer solid electrolyte to a temperature lower than the glass transition point of the polymer of the polymer.

As a specific example of the cooling method of the above sealed battery, there is a method of cooling using one or more kinds of noncombustible compressed gas selected from nitrogen gas, argon gas, helium gas, carbon dioxide and fluorocarbon. No.

Further, as a method of cooling the above sealed battery,
It is also preferable to adopt a method of cooling the sealed battery by immersing it in a cryogen or liquefied gas. As the cryogen, for example, dry ice-methanol or dry ice-ethanol is used. As the liquefied gas, for example, liquid nitrogen is used. Alternatively, the sealed battery may be immersed in water, frozen with water, and cooled. in this case,
It is preferable to open the sealed battery while it is sealed in ice.

In the method for recovering a sealed battery member according to the present invention, after the ionic conductivity between the positive electrode and the negative electrode is reduced in the above step, in the step of opening the battery, the atmosphere for performing the opening is a non-flammable atmosphere. It is preferred that By using a non-flammable atmosphere, oxidation of battery components,
Combustion can be suppressed, and damage to the member to be collected can be suppressed as much as possible. As a result, safe and high-recovery sealed battery member recovery is realized.

Examples of the non-flammable atmosphere for performing the above-mentioned opening include nitrogen gas, argon gas, helium gas,
An atmosphere composed of one or more gases selected from carbon dioxide, water vapor and fluorocarbon is employed. In the case where the above-mentioned cooling means is employed for reducing the ion conductivity between the positive electrode and the negative electrode inside the battery, it is preferable that the gas type constituting the above-mentioned opening atmosphere and the gas type used for the cooling means are the same.

As the opening method, for example, high pressure water,
A cutting method selected from energy beam and mechanical cutting, and a method in which high-pressure water mixed with an abrasive is sprayed from a jet nozzle onto a battery housing to cut the battery housing.

In the present invention, it is possible to open the sealed battery more safely by discharging the battery before opening (preferably, before the ion conductivity between the positive electrode and the negative electrode decreases). By this discharge, the composition of the constituent materials of the positive electrode active material layer and the negative electrode active material layer becomes uniform regardless of the remaining capacity before the discharge, and uniform collection of the positive electrode member and the negative electrode member becomes possible. In addition, the discharge allows the energy remaining in the sealed battery to be recovered.

In addition, before the ionic conductivity between the positive electrode and the negative electrode of the sealed battery is reduced, the members constituting the battery can be efficiently collected by preliminarily selecting the battery according to the shape or type of the sealed battery. Will be possible.

The apparatus for recovering a sealed battery member according to the present invention comprises means (parts) for sequentially performing the steps of the above-described recovery method. A preferable example of the means for reducing the ionic conductivity between the positive electrode and the negative electrode of the battery is preferably a means for extracting at least the electrolytic solution in the battery housing or the solvent in the electrolytic solution to the outside of the battery housing.

In the case where a safety valve is provided in the sealed battery, the means for reducing the pressure of the atmosphere outside the battery housing or increasing the pressure inside the battery housing through the safety valve, for example, Generates differential pressure inside and outside the housing. Accordingly, it is preferable to have at least a function of operating the safety valve and a means for extracting the electrolyte solution or the solvent in the electrolyte solution from the battery housing to the outside of the battery housing.

It is preferable that the means for taking out the electrolytic solution or the solvent in the electrolytic solution outside the sealed battery housing comprises a container to which at least an exhaust means is connected.

Further, the container provided with the exhaust means has a member which comes into close contact with or is joined to the outer wall surface of the battery housing including the battery lid around the safety valve of the sealed battery, and the electrolyte or the electrolyte to be removed from the battery. It is preferable that a port (passage) for transferring the solvent in the electrolytic solution to the container is provided.

A port through which air, nitrogen or a nonflammable gas can be introduced may be provided in the above-mentioned container via a valve.
In the recovery device (system), for example, a sealed space formed by part or all of the outer wall of the housing including the lid of the sealed battery (including a portion for removing the electrolyte or the solvent in the electrolyte) and the container In a state where the safety valve portion of the battery is included in the space, the pressure in the space is reduced from the pressure in the sealed battery to remove the electrolyte solution in the battery housing or the solvent in the electrolyte solution. It can be collected in the container via a safety valve.

In the above-mentioned recovery device (system), after the pressure in the container provided with the exhaust means is reduced from the atmospheric pressure by the exhaust means, the container is drained of the electrolyte in the battery housing or the solvent in the electrolyte. It is preferable to connect to a region including a location (for example, a safety valve portion) to form a space including the outer wall of the sealed battery housing and the container.

Further, in the above-mentioned collection device (system),
After forming a space sealed by the container and the outer wall of a sealed battery housing, which connects the container provided with the exhaust means and the region containing the electrolyte or the solvent of the electrolyte in the battery housing (for example, a safety valve portion). The pressure in the space can be reduced from the pressure inside the sealed battery by an exhaust unit connected to the container.

In the sealed battery member recovery apparatus (system) of the present invention, another preferable example of the means for reducing the ionic conductivity between the positive electrode and the negative electrode of the sealed battery is at least means for cooling the sealed battery. It is.

A nitrogen gas,
Cooling is preferably performed using one or more noncombustible compressed gas selected from argon gas, helium gas, carbon dioxide and fluorocarbon. In addition, a cooling agent or a liquefied gas, or a member that immerses the battery in water, freezes it, and seals it in ice can be used as the cooling means of the sealed battery.

On the other hand, in the device (system) for recovering a member of a sealed battery according to the present invention, as means for opening the battery housing, high-pressure water cutting means, energy beam cutting means, and mechanical cutting means can be preferably used. .

[0042] The means for performing such opening may be, for example, a nitrogen gas, an argon gas, a helium gas, a non-flammable atmosphere.
It is set in one or more types of gas selected from carbon dioxide, water vapor and fluorocarbon.

[0043]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below.
This will be described with reference to FIGS. FIG. 1 is a process diagram showing an example of a main part of a method for collecting a sealed battery member according to the present invention. An example of the flow of collecting the sealed battery member of the present invention will be described with reference to FIG.

In order to efficiently carry out a method for recovering battery components, used sealed batteries are first classified according to shape or type (a2). Next, the ionic conductivity between the positive electrode and the negative electrode in the battery housing is reduced (a3). As a specific method for lowering the ionic conductivity, as described above, in one case, the electrolyte present between the positive electrode and the negative electrode or the solvent in the electrolyte is passed through a safety valve attached to the battery housing or the like. A method of extracting the battery from the battery housing (when an electrolytic solution is used between the positive electrode and the negative electrode) is used. Another method is to lower the ionic conductivity of the electrolyte or the electrolyte by cooling the battery. Next, the battery housing is opened (a4), the battery components in the battery housing are taken out (a5), washed (a6), and the individual members are separated and collected (a7).

FIG. 2 shows that the sealed battery is a lithium battery in particular. After cooling, the ion conductivity between the positive electrode and the negative electrode in the battery housing is reduced, the battery housing is opened, and the members constituting the battery are formed. FIG. 5 shows an example of a more specific recovery flow for recovering the garbage. FIG. 2 is described below.

In order to carry out the decomposition and recovery efficiently, first, the used batteries are separated by shape or type (b)
2). Next, the battery is cooled to lower the ionic conductivity of the electrolyte and increase the internal resistance (b3). Next, the battery housing cooled in a non-flammable atmosphere is opened (b).
4). Next, for example, when the sealed battery is a lithium battery, the reactant is caused to react with active lithium in the battery housing to reduce reactivity (b5). Thereafter, the battery components in the battery housing are taken out (b6). If the electrolyte is in a liquid state, the battery is washed with an organic solvent (b7), and the battery components are separated and collected (b8).

In some cases, although not shown in the examples of FIGS. 1 and 2, it is safer to discharge the battery and discharge the remaining energy of the battery after sorting by battery shape. The housing can be opened and disassembled and collected.
As a specific method for discharging the remaining energy of the battery, a resistor is connected between the positive electrode and the negative electrode to discharge. Alternatively, a method of connecting a capacitor between the positive electrode terminal and the negative electrode terminal to charge the capacitor may be used. It is preferable to discharge until the capacity of the used battery sharply decreases.

Next, as a method for reducing the ionic conductivity between the positive electrode and the negative electrode in the above-described battery, an electrolytic solution is extracted from the battery. Examples of the steps will be specifically described with reference to the drawings.

FIG. 3 shows the recovery device (recovery device for a sealed battery member) of the present invention, in which the electrolyte is removed before opening the sealed battery (battery housing), and the ionic conductivity between the positive electrode and the negative electrode is measured. FIG. 2 is a schematic cross-sectional configuration diagram illustrating an example of a device (part) for lowering. FIG. 4 shows another example of a device (part) for extracting an electrolytic solution and reducing the ionic conductivity between the positive electrode and the negative electrode before opening the sealed battery (battery housing) in the recovery device (system) of the present invention. FIG. 2 is a schematic cross-sectional configuration diagram of the device showing the above.

The apparatus shown in FIGS. 3 and 4 extracts and recovers the electrolytic solution or the solvent in the electrolytic solution through a safety valve or the like without opening the sealed battery, and collects the positive electrode and the negative electrode in the sealed battery. 1 is an example of a system for lowering the ionic conductivity between them. In the apparatus shown in FIG. 3, the safety valve of the sealed battery is closely contacted with the outer wall of the battery housing, and the pressure around the safety valve is locally reduced to generate a differential pressure between the inside and outside of the housing. , For extracting the electrolytic solution or the solvent in the electrolytic solution. In the apparatus shown in FIG. 4, after the sealed battery is housed in the sealable container, the pressure in the container is reduced, the internal pressure in the housing of the sealed battery is increased, and a differential pressure is generated inside and outside the housing to operate the safety valve. Things.

The system (device) and operation shown in FIG. 3 will be described in detail. In FIG. 3, 100 is a sealed battery, 101 is a battery housing, 102 is a safety valve attached to the sealed battery, 1
03 is an electrolyte extraction tube for extracting the electrolyte or the solvent in the electrolyte, 104 is an electrolyte storage tank for storing the electrolyte or the solvent in the electrolyte extracted from the sealed battery, and 105 is a vacuum pump Such as an exhaust means, 106 is an O-ring used for close contact, 107 is an exhaust pipe, 10
Reference numeral 8 denotes a valve for extracting an electrolytic solution, which is an open / close valve for extracting an electrolytic solution or a solvent in the electrolytic solution; 109, an exhaust valve including an open / close valve for connecting to an exhaust system;
Reference numeral 110 denotes a drain valve for discharging the extracted electrolyte or a solvent in the electrolyte from the tank, and 113 denotes a leak valve for introducing air or non-combustible gas into the reduced pressure system.

The electrolyte extraction tube 103 has an O-ring 10 at one end including the periphery of the safety valve of the sealed battery (battery lid) at one end.
Opening provided with a valve 6 and an electrolyte wiping valve 1
A second opening at the other end through the opening 08 and an opening through which a non-combustible gas provided with a leak valve 113 is branched. The first opening side of the electrolyte extraction tube 103 is tightly joined or joined to the outer wall of the housing including the vicinity of the safety valve 102 (battery lid) of the sealed battery 100 via an O-ring 106. The electrolyte extraction tube 103 is inserted into the electrolyte storage tank 104 at the second opening side, and connects the sealed battery 100 with the inside of the tank 104.

In the above system, a part of the housing outer wall including the safety valve 102 of the sealed battery 100 and the extraction tube 10
And an exhaust pipe 107 having an exhaust valve 109 in the electrolyte storage tank 104.
The inside of the system is reduced in pressure by the exhaust means 105 connected through the above, so that the above space becomes lower than the pressure inside the sealed battery 100. Here, the sealed battery 100 is a safety valve 1
02 is disposed facing downward. Thus, the safety valve 102 of the sealed battery 100 is operated (opened), and the electrolyte inside the battery is discharged through the extraction pipe 103 into the tank 1.
Extracted into 04 and collected. Thus, the sealed battery 1
No electrolyte solution is present between the positive electrode and the negative electrode in 00, and the ionic conductivity is reduced. In the above operation, it is preferable to operate the leak valve 113 as necessary to introduce air, nitrogen, or a noncombustible gas into the system.

The electrolyte solution extracted into the electrolyte solution storage tank 104 can be discharged to the outside via the waste liquid valve 110 by operating the waste liquid valve 110 at a fixed amount, collected and regenerated.

The system (apparatus) shown in FIG. 4 and its operation will be described in detail. In the system shown in the figure, a battery container 111 is provided at one end of the electrolyte extraction tube 103 in communication therewith,
The sealed battery 100 is housed inside. The container 111
On the opening side, a battery storage container lid 112 is provided via an O-ring 106, and the inside of the storage container is sealed. Further, a leak valve 113 is provided on one wall surface of the housing 111.
Is provided. The electrolyte extraction tube 103 has an electrolyte extraction valve 108 and is inserted into the electrolyte storage tank 104 at the other end. The structure and arrangement of other members are the same as in the system shown in FIG.

In the above system, the battery container 111
A space including the battery container lid 112, the entire outer wall of the housing including the safety valve 102, the extraction pipe 103, and the tank 104 is formed, and is connected to the electrolyte storage tank 104 via the exhaust pipe 107 having the exhaust valve 109. The inside of the system (from the electrolyte extraction tube 103 to the electrolyte storage tank 104) is depressurized by the evacuation means 105, and the space is sealed
00 so that it is lower than the internal pressure. Thus,
The safety valve 102 of the sealed battery 100 operates (opens),
The electrolytic solution inside the battery is extracted and collected in the tank 104 via the extraction tube 103. Thus, the ionic conductivity is reduced between the positive electrode and the negative electrode in the sealed battery 100 due to the absence of the electrolytic solution.

In the sealed battery from which the electrolyte has been extracted in the system shown in FIG. 3 or FIG. 4, the electric housing is opened by various methods while the ionic conductivity between the positive electrode and the negative electrode is reduced. Then, the contents are collected.

Next, in the method for reducing the ionic conductivity between the positive electrode and the negative electrode in the sealed battery and recovering the battery member, a step of cooling the battery to increase the electric resistance inside the battery, and further comprising the steps of: An example of the step of opening the housing will be described with reference to FIG.

FIG. 5 is a schematic structural view showing an example of a portion for cooling the sealed battery and opening the battery housing in the sealed battery member collecting device of the present invention. In the device of FIG. 5, a method of cooling using a compressed gas is adopted as a cooling device for a sealed battery, and the same non-combustible gas used for cooling is used as the atmosphere when the battery housing is opened. showed that. Further, there is also provided a means for collecting, purifying, compressing and reusing the gas used for cooling the battery. High pressure water or an energy beam is used to open the battery housing.

The device and operation shown in FIG. 5 will be described in detail. In FIG. 5, reference numeral 200 denotes a sealed battery, 201 denotes a cooling device (low-temperature gas discharge device), 202 denotes a low-temperature gas, 203
Is a non-flammable atmosphere, 204 is a device for opening the battery housing,
205 is a high-pressure water or energy beam, 206 is a partition wall between the cooling and cutting lines and the outside air, 207 is a fixed base for the sealed battery, 208 is a transfer device for the sealed battery, 209 is a gas supply pipe for compressed gas, and 210 is a compressor , 211 is a device for removing impurities such as moisture, 212 is a nonflammable gas recovery device,
Reference numeral 213 denotes a gas sending pipe for recovering nonflammable gas, 214 denotes a high pressure water or energy beam generator, and 215 denotes a high pressure water transport pipe or an energy beam transmission pipe.

In the apparatus shown in the figure, a sealed battery 200 used on a fixing table 207 provided in a transfer device 208 provided in a chamber partitioned by a partition 206 is used.
Are transported sequentially to a cooling process area having the cooling device 201 and an opening process area having the opening device 204. In the space defined by the partition wall 206, both the region of the cooling device 201 and the region of the opening device 204 are similarly filled with a nonflammable gas (nonflammable atmosphere 203).

In the cooling device 201, a low-temperature gas 202 obtained by cooling the non-combustible gas is supplied to the sealed battery 200, and the internal electrolyte is cooled to reduce its ionic conductivity. Here, as the low-temperature gas 202, preferably, the non-combustible gas in the partition wall 206 is circulated and used. That is, the non-combustible gas is supplied to the non-combustible gas recovery device 212 through the gas recovery gas supply pipe 213 connected to the chamber partitioned by the partition.
Is removed by the impurity removing device 211, and further compressed by the compressor 210.
It is supplied to the cooling device 201. Then, the low-temperature gas (compressed gas) 202 is supplied to the sealed battery 200.

In the cooling step of the above sealed battery,
For example, the battery can be cooled using a cryogen or a liquefied gas. Alternatively, the battery can be cooled by immersing the sealed battery in water, freezing it as it is, and sealing it in ice.

Subsequently, in the unsealing device 204, for example, high-pressure water or an energy beam 205 is applied to the sealed battery 200 cooled in the above-described process to open the battery housing. The high-pressure water or energy beam is formed by the high-pressure water or energy beam generator 214, and is opened through the transport pipe or the transmission pipe 215.
04.

A more detailed setting in the cooling step when the above-described apparatus is used will be described. To [the cooling temperature] sealed battery lowers the ionic conductivity of the electrolyte in the case of a lithium battery, specifically when the solvent in the electrolytic solution of the lithium battery is used, the electrolyte solvent In the case where a polymer solid electrolyte which is cooled to a temperature below the freezing point and is immobilized using a polymer as an electrolyte is used, it is preferable to cool the polymer solid electrolyte to a temperature below the glass transition point of the polymer. More specific cooling temperature ranges include:
0 ° C. or lower is preferable, and -20 ° C. or lower is more preferable. The cooling temperature is preferably in the above range even for nickel-hydrogen batteries, nickel-cadmium batteries, lead batteries, and the like in which water is used as the solvent for the electrolyte of the sealed battery.

[Cooling Means] As a more specific means for lowering the ionic conductivity of the electrolyte of the sealed battery, cooling using a non-combustible compressed gas (device 201 shown in FIG. 5)
And a cooling method such as cooling with a liquefied gas or a cryogen.

As an example of the cooling device utilizing the expansion of the compressed gas, a cooling gas supply port 705 and a pressure regulating valve 70 shown in FIG.
A tube-type cooling device including a hot air outlet 708 with a cooling gas outlet 6, a cooling gas outlet 702, and a vortex generator 703 is exemplified. The cooling gas 701 is discharged from the cooling gas outlet 702 by flowing the supply compressed gas 704 to the high pressure gas supply port 705 of the cooling device. When a gas at a temperature of 16 ° C. is supplied to the high-pressure gas supply port at a pressure of 3 to 7 kg / cm 2, cold air of about −10 to −50 ° C. is obtained. As the gas type of the compressed gas used for this cooling device,
In the present invention, it is preferable to use one or more gases selected from the group consisting of nitrogen gas, argon gas, helium gas, carbon dioxide, and fluorocarbon, which are nonflammable gases.

Thus, particularly when the battery is cooled and the subsequent opening process is performed in a continuous atmosphere, even if the negative electrode and the positive electrode are short-circuited when the battery housing is opened by a method such as cutting, a spark is generated. Can be suppressed. In addition, even in sealed batteries that use a battery housing that can be disassembled and opened without performing operations such as cutting, the negative electrode and the positive electrode short-circuit when the electrodes are taken out and fire
The collection work can be performed safely because it can be avoided.

As a method of using a liquefied gas, a battery to be opened is directly immersed in a liquefied gas such as liquid nitrogen or liquid helium to cool it, or a low-temperature gas of a liquefied gas is blown into a battery housing for cooling. You can take the way.

When a cryogen is used, specific examples of the cryogen include dry ice-methanol or dry ice-methanol.
Examples include ethanol and ice. Alternatively, the sealed battery can be immersed in water, frozen together with water, sealed in ice, and cooled.

Subsequently, for example, in the opening step of the sealed battery in which the ionic conductivity of the electrolyte is reduced by the apparatus shown in FIG. 4 or the opening step by the apparatus shown in FIG. 5, which is employed in the method of the present invention. A more detailed setting will be described.

[Opening Atmosphere] (In the apparatus shown in FIG.
3) In the method of the present invention, the atmosphere in which the battery housing is opened is a nonflammable gas such as nitrogen gas, argon gas,
It is preferable to use at least one gas selected from helium gas, carbon dioxide, water vapor, and fluorocarbon. Thus, even if the negative electrode and the positive electrode are short-circuited by the time of opening the battery housing, it is possible to suppress the generation of sparks and the damage due to oxidation of the battery components. In the case where a means for blowing a low-temperature gas by the cooling means to cool is employed, by using a gas of the same type as the low-temperature gas in the opening atmosphere, the operation is easy including the recovery and reuse of the gas. This has the advantage that the operating cost is reduced.

Examples of the fluorocarbon include tetrafluoromethane, hexafluoroethane, perfluoropropane, trifluoromethane, monobromotrifluoromethane, dichlorodifluoromethane, chlorotrifluoromethane and the like.

[Opening means] (20 in the apparatus shown in FIG. 5)
4) In the method of the present invention, examples of opening means for opening the sealed battery housing include high-pressure water, an energy beam, and mechanical cutting.

Cutting with high-pressure water is 1,000 kg / c
m ² or more, more preferably one cutting blown to the battery housing in a jet-like a 3,000 kg / cm ² or more ultra-high pressure water from the nozzle. Depending on the material of the battery housing, it is also possible to mix the abrasive with ultra-high pressure water and spray it to cut. Examples of the energy beam of the opening means include a laser beam and an electron beam. Examples of the mechanical cutting means of the opening means include a device for cutting a disk-shaped blade by rotating at a high speed, a shear, and the like. When the battery is sealed in ice and cooled as described above, it is preferable to open the battery in a sealed state.

As described above, for a sealed battery in which the ionic conductivity of the electrolyte has been reduced and the housing has been opened, the inside of the housing is washed if necessary, and then the battery components are removed. It is moved to a separation and separation process, and finally, the members constituting the battery are collected.

[Reduction of Reactivity of Active Lithium and Recovery of Lithium Element] When the sealed battery is a lithium battery, the reactivity of active lithium contained in the lithium battery is reduced after opening the battery housing. By
Thereafter, it is possible to safely collect the components constituting the battery. As a means for reducing the reactivity of highly reactive active lithium, a method of reacting a reactant can be used. Also, from the reaction product of the reactant and lithium,
Recovery of lithium element is also facilitated. Specific examples of the above-mentioned reactants include one or more kinds of reactants selected from water, alcohol, acid, and carbon dioxide.

[Recovery of Electrolyte] When the internal pressure of the sealed battery is increased to extract the electrolyte out of the battery housing, and then the battery housing is opened, the recovery of the electrolyte can be easily performed. On the other hand, when the sealed battery is cooled and the battery housing is opened, the electrolytic solution is recovered in the following procedure.

When the electrolyte of the sealed battery is an aqueous solution, the battery can be washed after opening the battery housing, the washing solution can be collected and filtered, and the water can be evaporated to recover the electrolyte.

When the sealed battery to be opened and the constituent members to be recovered is a lithium battery and an electrolytic solution in which an electrolyte is dissolved in an organic solvent is used, a step of washing with an organic solvent after opening the battery housing. And recovering the electrolyte through a fractional distillation operation. When an organic solvent that does not form an azeotrope with water is used as the organic solvent used in this washing step, cutting with high-pressure water can be adopted as the means for cutting the battery housing, and active lithium can be used. Inexpensive water can be employed as a reactant for reducing the reactivity of the compound.

[Organic solvent for cleaning that does not form an azeotrope with water] When the present invention is applied to a lithium battery, an organic solvent that does not form an azeotrope with water should be used as an organic solvent for cleaning after opening. Thus, even when inexpensive water is used as the active lithium reactant in the lithium battery, the water and the organic solvent for washing can be easily separated by fractional distillation.

Examples of organic solvents for washing which do not form an azeotrope with water include methanol, acetone, 1,2-propanediol, dimethylsulfoxide, butyrolactone,
Examples include ethylene carbonate and propylene carbonate.

FIG. 7 is a conceptual diagram showing a cross section of the basic structure of a sealed battery in which constituent members are recovered by the recovery method of the present invention. A negative electrode 301, a positive electrode 302, a separator and an electrolyte 303 are formed in a battery housing 304. It is composed and stored in. When a solid electrolyte is used as the electrolyte, a separator may not be provided in some cases. A negative electrode terminal 305 is connected to the negative electrode 301, and a positive electrode terminal 306 is connected to the positive electrode 302.

The specific shape of the sealed battery (especially a secondary battery) accommodating the constituent members in the present invention includes, for example, a flat shape, a cylindrical shape, a rectangular parallelepiped shape, and a sheet shape. In addition, examples of the structure of the battery include a single-layer type, a multilayer type, and a spiral type. Among them, the spiral cylindrical battery has a feature that the electrode area can be increased by winding the separator between the negative electrode and the positive electrode with the separator interposed therebetween, and a large current can flow during charging and discharging. Also,
A rectangular parallelepiped or sheet type battery has a feature that a storage space of a device configured to store a plurality of batteries can be effectively used.

Hereinafter, the shape and structure of the battery will be described in more detail with reference to FIGS. 8, 9 and 10.
FIG. 8 is a cross-sectional view of a single-layer flat (coin-shaped) battery,
FIG. 9 is a sectional view of a spiral cylindrical battery, and FIG. 10 is a sectional view of a rectangular parallelepiped battery. These lithium batteries have basically the same configuration as that of FIG. 7 and include a negative electrode, a positive electrode, an electrolyte / separator, a battery housing, and an output terminal.

In FIGS. 8, 9 and 10, 401 and 5
02 and 601 are negative electrodes, 403, 508 and 603 are positive electrodes,
405, 505, and 605 are negative electrode terminals (negative electrode caps);
406, 506 and 606 are positive terminals (positive cans), 407
, 507 and 607 are separator / electrolyte, 410 and 51
0 is a gasket, 500 and 600 are negative electrode current collectors, 504
Is a positive electrode current collector, 511 is an insulating plate, 512 is a negative electrode lead,
513 is a positive electrode lead, 514 and 614 are safety valves, and 60
9 is a battery housing (container).

In the flat type (coin type) sealed battery shown in FIG. 8, a positive electrode 403 including a positive electrode active material layer and a negative electrode 401 including a negative electrode material layer are laminated via a separator 407 holding at least an electrolytic solution. This laminate is accommodated in a positive electrode can 406 as a positive electrode terminal from the positive electrode side, and the negative electrode side is covered with a negative electrode cap 405 as a negative electrode terminal. Then, a gasket 410 is arranged in another portion in the positive electrode can.

In the spiral cylindrical sealed battery shown in FIG. 9, the positive electrode (material) formed on the positive electrode current collector 504
A positive electrode 508 having a layer 503 and a negative electrode 502 having a negative electrode (material) layer 501 formed on a negative electrode current collector 500
Are opposed to each other via a separator 507 holding at least an electrolytic solution, and form a multi-layered laminated body having a cylindrical structure. The laminate having the cylindrical structure is accommodated in a positive electrode can 506 as a positive electrode terminal. Further, a negative electrode cap 505 as a negative electrode terminal is provided on the opening side of the positive electrode can 506, and a gasket 510 is arranged at another portion in the positive electrode can. The stacked body of electrodes having a cylindrical structure is separated from the negative electrode cap side via an insulating plate 511. For the negative electrode 502, a negative electrode lead 512
Is connected to the negative electrode cap 505. The positive electrode 508 is connected to the positive electrode can 50 via a positive electrode lead 513.
6 is connected. On the side of the negative electrode cap, a safety valve 514 for adjusting the internal pressure inside the battery and for extracting the electrolytic solution to the outside as described above is provided.

In the example of the rectangular battery shown in FIG.
A plurality of unit cells each consisting of / a separator 607 containing an electrolytic solution / a positive electrode 603 are stacked via a separator and connected in parallel, and these are connected in a battery case 609 (battery case).
The negative electrode 601 housed in the
The positive electrode 603 is connected to the positive electrode terminal 606, and the sealed battery is provided with a safety valve 614 as described later.

The following describes the mode of the members in the above-described example of the sealed battery. (Gasket) As a material of the gasket (410, 510), for example, a fluorine resin, a polyamide resin, a polysulfone resin, and various rubbers can be used. As a method for sealing the battery, in the structure shown in FIGS. 8 and 9, preferably, a method in which a gasket is used to “sew” the negative electrode caps (405, 505) is used. , Welding, soldering and the like are used.

As the material of the insulating plate (511) in FIG. 9, various organic resin materials and ceramics are used.

(Battery Housing / Positive Electrode Can, Negative Cap) As the battery housing for accommodating each member in the sealed battery recovered in the present invention, for example, as shown in FIGS. Also serves as an electrode terminal, a positive electrode can and a negative electrode cap. In the example shown in FIG. 8, the positive electrode can 406 and the negative electrode cap 405 are provided. In the example shown in FIG.
6 and the negative electrode cap 505 serve as battery housings which also serve as input / output terminals. As a material of the battery housing also serving as the input / output terminal, stainless steel is preferably used. In particular, a titanium clad stainless steel plate, a copper clad stainless steel plate, a nickel plated steel plate and the like are frequently used.

In particular, in the example shown in FIGS.
The above stainless steel is preferable because 6, 506 also serves as the battery housing. On the other hand, when the positive electrode can or the negative electrode can do not double as the battery housing as in the example shown in FIG. 10, the material of the battery housing may be a metal such as zinc other than stainless steel, a plastic such as polypropylene, or a metal or metal. A composite material of glass fiber and plastic is exemplified.

(Safety Valve) In the sealed battery to be recovered in the present invention, a safety valve (514 in the example shown in FIG. 9 and 614 in the example shown in FIG. 10) is provided as a safety measure when the internal pressure of the battery increases. Is preferably provided. As the safety valve, for example, rubber, spring, metal ball, bursting foil, or the like can be used. Such a safety valve can be applied to a member for extracting the electrolyte in the battery as described above.

Next, the members constituting the sealed battery used in the present invention will be described. [Negative electrode] As the electrolyte of the sealed battery used in the present invention is an aqueous solution, examples thereof include a lead storage battery, a nickel-cadmium storage battery, a nickel-hydrogen (hydride) storage battery,
Nickel-zinc storage batteries. The negative electrodes of these batteries are composed of negative electrode materials (active materials) of lead, cadmium, a hydrogen storage alloy, and zinc, and a current collector.

When the sealed battery according to the present invention is a lithium battery, the negative electrode may be one that retains lithium before discharging, such as lithium metal, a carbon material intercalated with lithium, or a transition metal oxide. And a main component such as a transition metal sulfide or a lithium alloy, and at least a current collector.

[Current Collector of Negative Electrode] The current collector of the negative electrode in the sealed battery used in the present invention has a function of efficiently supplying a current consumed in an electrode reaction at the time of charging / discharging or collecting current generated. Is responsible for. Therefore, as a material for forming the current collector of the negative electrode, a material that has high conductivity and is nonflammable in battery reaction is desirable.

Preferred materials include nickel, titanium, copper, aluminum, stainless steel, platinum,
Examples include palladium, gold, zinc, various alloys, and two or more composite metals of the above materials. As the shape of the current collector,
For example, formed shapes such as plate, foil, mesh, sponge, fiber, punching metal, expanded metal and the like are employed.

[Positive Electrode] The positive electrode in the sealed battery used in the present invention comprises a current collector, a positive electrode material (active material), a conductive auxiliary material, a binder and the like. This positive electrode is manufactured by molding a mixture of a positive electrode active material, a conductive auxiliary material, a binder, and the like on the surface of a current collector.

Examples of the conductive auxiliary material used for the positive electrode include graphite, carbon black such as Ketjen black and acetylene black, and fine metal powder such as nickel.

As the binder used for the positive electrode, for example,
When the electrolytic solution is a non-aqueous solvent system, a polyolefin such as polyethylene or polypropylene, or a fluororesin such as polyvinylidene fluoride or tetrafluoroethylene polymer may be used. When the electrolytic solution is an aqueous solution, celluloses, polyvinyl alcohol, polyvinyl chloride, and the like are used in addition to the binder material used in the nonaqueous solvent system.

The positive electrode active materials of a lead storage battery, a nickel-cadmium battery, a nickel-hydrogen (hydride) battery, and a nickel-zinc storage battery, which are typical examples of sealed batteries using an aqueous electrolytic solution, are lead oxide, oxy-oxide, and the like. Nickel (III) hydroxide or nickel hydroxide is used.

When the sealed battery is a lithium battery, a transition metal oxide, a transition metal sulfide, a lithium-transition metal oxide, or a lithium-transition metal sulfide is generally used as a positive electrode material (active material). As the transition metal element of the transition metal oxide or the transition metal sulfide, for example, d
Sc, which is an element having a shell or f-shell,
Y, lanthanoid, actinoid, Ti, Zr, Hf,
V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re,
Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, P
t, Cu, Ag, and Au. In particular, Ti, V, Cr, Mn, Fe, Co, N
i and Cu are preferably used.

[Positive Electrode Current Collector] The positive electrode current collector used in the sealed battery according to the present invention has a function of efficiently supplying a current consumed in an electrode reaction during charging and discharging or collecting a generated current. I am carrying it. Therefore, as a material for forming the current collector of the positive electrode, a material having high conductivity and being nonflammable in battery reaction is desirable.

Preferred materials include nickel, titanium, copper, aluminum, stainless steel, platinum,
Examples include palladium, gold, zinc, various alloys, and two or more composite metals of the above materials. However, those which are easily eluted into the electrolyte solution by themselves need to be coated with another stable metal which does not elute. As the shape of the current collector, for example, a plate shape, a foil shape, a mesh shape, a sponge shape,
Shapes such as fibrous, punched metal, and expanded metal have been adopted.

In the present invention, the term "active material" refers to a material that participates in the repetition of the electrochemically reversible reaction of charging and discharging in a battery. Furthermore, the above-mentioned substances, which themselves participate in the above-mentioned reaction and other substances which participate in the above-mentioned reaction, are also included. [Separator] The separator in the sealed battery according to the present invention has a role of preventing a short circuit between the negative electrode and the positive electrode. In some cases, it has a role of holding an electrolytic solution.

The separator must have pores through which ions relating to the charge / discharge reaction of the battery can move, and must be insoluble and stable in the electrolytic solution. Therefore, as the separator, for example, a nonwoven fabric or a material having a micropore structure such as glass, polyolefin such as polypropylene or polyethylene, fluororesin, or polyamide is preferably used. Further, a metal oxide film having fine pores or a resin film in which a metal oxide is compounded can be used.

[Electrolyte] The electrolyte can be used in the sealed battery according to the present invention in the following three ways. (1) A method used as it is. (2) A method of using as a solution dissolved in a solvent. (3) A method in which a gelling agent such as a polymer is added to a solution to be used as an immobilized one.

In general, an electrolytic solution obtained by dissolving an electrolyte in a solvent is retained on a porous separator for use. The conductivity of the electrolyte is preferably 1 × as a value at 25 ° C.
10 ^-3 S / cm or more, more preferably 5 × 10 ^-3 S / c
m or more.

In a lead storage battery, a sulfuric acid aqueous solution is used as an electrolyte. In a nickel-cadmium storage battery, a nickel-hydrogen (hydride) storage battery, and a nickel-zinc storage battery, an alkaline aqueous solution is used for an electrolyte, and generally, a potassium hydroxide aqueous solution to which lithium hydroxide is added is used.

In a lithium battery, the following electrolyte and its electrolyte are used.
Is preferably used. As the electrolyte, for example,
H_Two SO_Four , HCl, HNO_Three Such as acid, lithium ion
(Li⁺ ) And Lewis acid ion (BF_Four ^- , PF₆ ^- ,
AsF₆ ^- , ClO _Four ^- , CF_Three SO_Three ^- , BPh_Four ^- 
(Ph: phenyl group)), and mixtures thereof.
Salts may be mentioned. Also, sodium ion, potassium
Ions and tetraalkylammonium ions
Salts consisting of on and Lewis acid ions can also be used. Above salt
Heat under reduced pressure to perform sufficient dehydration and deoxygenation.
It is desirable to keep.

Examples of the solvent for the electrolyte include acetonitrile, benzonitrile, propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, dimethylformamide, tetrahydrofuran, nitrobenzene, dichloroethane, diethoxyethane, 1,2-dimethoxyethane, and chlorobenzene. , Γ-butyrolactone, dioxolan, sulfolane,
Nitromethane, dimethyl sulfide, dimethyl sulphoxide, methyl formate, 3-methyl-2-oxazolidinone, 2-methyltetrahydrofuran, 3-propylsidnone, sulfur dioxide, phosphonyl chloride, thionyl chloride,
Sulfuryl chloride or a mixture thereof can be used.

For use in a lithium battery, the above solvent is dehydrated with, for example, activated alumina, molecular sieve, phosphorus pentoxide, calcium chloride, or the like, or is distilled in a nonflammable gas in the presence of an alkali metal depending on the solvent. Then, impurities are removed and dehydration is performed.

In order to prevent the electrolyte solution from leaking, it is preferable to form a gel. As the gelling agent, it is desirable to use a polymer that absorbs the solvent of the electrolytic solution and swells.
As such a polymer, polyethylene oxide, polyvinyl alcohol, polyacrylamide and the like are used.

[0115]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail based on embodiments. Note that the present invention is not limited to these examples.

Example 1 In this example, the rectangular nickel-hydride storage battery shown in FIG. 10 was used based on the flow sheet shown in FIG. After decreasing the ion conductivity between the positive electrode and the negative electrode, the battery housing was opened, and after cleaning, the members constituting the battery were taken out and separated and collected.

The used nickel-hydride storage battery used here has a positive electrode in which porous nickel is filled with nickel hydroxide and nickel fine particles, and a negative electrode in which porous nickel is filled with a hydrogen storage alloy powder and a binder. The components were collected using a sealed battery in which the filled electrolyte was an aqueous solution of potassium hydroxide with lithium hydroxide and the battery housing was made of polypropylene.

Hereinafter, with reference to FIG. 1 and FIG. 3, a description will be given of the ion conductivity reduction, opening, and collection in the battery in order.

A capacitor was connected to the output terminal of the used square nickel-hydride battery to discharge the remaining amount of electricity. The discharged battery was set as shown in FIG. 3 with the safety valve portion of the battery down.

The vacuum pump serving as the exhaust means 105 is started, the exhaust valve 109 is opened, and the electrolyte storage tank 10 is opened.
After the inside of the battery 4 has been decompressed, the exhaust valve 109 is closed, and then the electrolyte extraction valve 108 is opened, the safety valve of the battery is operated, and the electrolyte is pushed out at the increased pressure in the battery housing. Then, the electrolytic solution in the battery was drained. Thereafter, the leak valve 113 was opened, nitrogen gas was introduced, the inside of the storage tank 104 was returned to atmospheric pressure, and the battery from which the electrolyte was removed was removed. As a matter of course, the ionic conductivity between the positive electrode and the negative electrode in the battery from which the electrolyte was removed decreased, and the internal resistance of the battery increased. The electrolyte was collected in the storage tank 104. The obtained electrolyte can be reused by filtration and purification.

The battery from which the electrolytic solution was removed by the above operation was set in a high-pressure water cutting device, and mixed with abrasive powder.
High-pressure water of 500 kg / cm ² was sprayed to cut and open the battery housing. After opening the battery housing, the positive electrode, the negative electrode, and the separator were taken out, washed with water, dried, and then separated and collected.

Since the electrolytic solution was previously extracted in the operation described above, even if the positive electrode and the negative electrode contacted particularly when the electrode was taken out, energy could not be released and the recovery operation could be performed safely. Incidentally, when the impedance between the positive electrode terminal and the negative electrode terminal of the battery before the removal of the electrolyte was measured by an impedance meter, it was 2 mΩ, whereas the battery after the removal of the electrolyte was 5 MΩ or more. An increase in impedance was observed. It was found that the internal resistance of the battery was increased by the operation of extracting the electrolytic solution.

In the first embodiment, the operation of recovering the battery components of the nickel-hydride storage battery was described. However, the present invention is not limited to this. For example, a nickel-cadmium storage battery, a lithium storage battery including a lead storage battery, and a lithium ion battery. Any sealed battery with a safety valve having a liquid electrolyte can be applied.

A sealed battery without a safety valve was used, a hole was made in the battery housing, and the electrolyte solution outlet with an O-ring shown in FIG. 3 having a tubular shape was inserted into the above hole to extract the electrolyte solution. Then, the subsequent steps were performed, and the battery internal members were collected in the same manner as described above. Similarly, even when the positive electrode and the negative electrode were in contact with each other when the electrodes were taken out, no energy was released, and the recovery operation was performed safely.

Embodiment 2 In this embodiment, the cylindrical lithium battery shown in FIG. 9 was opened using the cooling / opening device shown in FIG. 5 based on the flow sheet shown in FIG. The members constituting the battery were taken out and separated and collected.

The used lithium battery used here had a negative electrode formed by pressing a lithium metal foil on nickel expanded metal, and a positive electrode comprising manganese dioxide positive electrode active material and acetylene black as a conductive auxiliary material. N-methyl-2- was mixed with polyvinylidene fluoride as a binder.
The paste prepared by adding pyrrolidone is applied to a nickel mesh and dried to form a separator. The separator is a polyethylene microporous separator, and the electrolyte is a mixed solvent of ethylene carbonate (EC) and dimethyl carbonate (DMC) in an equal amount. Lithium tetrafluoroborate salt was added at 1M (mol
/ L) A lithium primary battery that had been dissolved and was sealed with a negative electrode cap caulked. Note that stainless steel was used as the battery housing.

In the following, with reference to FIGS. 2 and 5, a description will be given of the flow chart of FIG. Liquid nitrogen was used as a cooling means.

In order to discharge and recover the remaining amount of electricity of the used cylindrical lithium primary battery, a capacitor was connected to the output terminal of the battery, the battery was discharged, and the remaining amount of electricity was stored in the capacitor.

The discharged battery was immersed in liquid nitrogen (cooling device 201 in FIG. 5), cooled to a temperature below the freezing point of the organic solvents ethylene carbonate and dimethyl carbonate used in the electrolytic solution, and the ionic conductivity inside the battery was reduced. Lowered.
When the impedance between the positive electrode terminal and the negative electrode terminal of the battery before and after cooling was measured using an impedance meter in the same manner as in Example 1, the internal resistance of the battery increased to 60 mΩ before cooling and 50 kΩ or more after cooling. Was found to be increasing. The electrolyte used for the battery was cooled under the same conditions as above, and the ionic conductivity of the electrolyte before and after cooling was measured.
It was less than 10.

The battery cooled by the above operation is taken out under an atmosphere of argon gas, put on a fixed base (207), and transferred to a high-pressure water cutting device (opening device 204 in FIG. 5) (transfer device 208). 3500kg / from nozzle
Ultra high pressure water containing an abrasive of cm ² was blown to cut.

The cut cylindrical lithium primary battery was washed with methanol to convert active lithium to lithium alcoholate, and then a mixed solvent of an electrolytic solution and methanol was recovered. The negative electrode, the separator, and the positive electrode were taken out and collected from the cylindrical can serving as the battery housing.

Embodiment 3 In this embodiment, the coin-shaped lithium battery shown in FIG. 8 is opened using the cooling / opening device shown in FIG. 5 based on the flow sheet shown in FIG. The members constituting each battery were taken out and separated and collected.

The used lithium battery used here has a negative electrode formed by pressing a lithium metal foil on nickel expanded metal, and a positive electrode comprising a lithium-nickel oxide positive electrode active material and a conductive auxiliary material. A paste formed by mixing acetylene black and polyvinylidene fluoride as a binder, adding N-methyl-2-pyrrolidone, applying the paste to a nickel mesh, and drying the paste. The electrolyte is formed of diethyl carbonate and propylene carbonate. Lithium tetrafluoroborate salt is added to an equal volume mixed solvent at 1 M (mo
1 / l) A lithium secondary battery which was a solid polymer electrolyte obtained by adding polyethylene oxide to a solution and solidifying it, and which was caulked and sealed. Note that stainless steel was used as the battery housing.

Hereinafter, with reference to FIG. 2 and FIG. 5, the cooling, unsealing, and recovery of the battery in the flowchart of FIG. 2 will be sequentially described. As a cooling means, a cooling device 201 (US VO) utilizing compressed gas as shown in FIG.
RTEX (VORTEX TUBE) was used.
Carbon dioxide gas was used as the compressed gas.

The used coin-type lithium secondary battery was charged at 5 kg /
supplying carbon dioxide gas cm ^2, by blowing cold air -40 ℃ carbon dioxide is cooled to below the glass transition point of the polyethylene oxide using a solid polymer electrolyte,
The ionic conductivity inside the battery was reduced. The impedance between the positive electrode terminal and the negative electrode terminal before and after cooling of the battery was measured in the same manner as in Example 1.
After cooling, it was 5 MΩ or more, and it was recognized that the internal resistance of the battery had increased. According to this result and the measurement result of the ionic conductivity of the electrolytic solution in Example 2, it is recognized that the ionic conductivity of the electrolytic solution is reduced by the above-described cooling operation.

The battery cooled by the above operation is taken out in a carbon dioxide atmosphere and put on a fixed base (207), and the YAG laser cutting device (opening device 204 shown in FIG. 5).
(Conveying device 208), and cut by irradiation with a laser beam. The negative electrode, the polymer electrolyte and the positive electrode were taken out from the cut coin-shaped lithium secondary battery can and collected.

Embodiment 4 In this embodiment, the cylindrical lithium secondary battery shown in FIG. 9 was opened using the cooling / opening device shown in FIG. 5 based on the flow sheet shown in FIG. After the washing, the members constituting each battery were taken out and separated and collected.

The used lithium battery used here was coated with a paste prepared by mixing natural graphite and polyvinylidene fluoride as a binder in a copper foil and adding N-methyl-2-pyrrolidone to the negative electrode. Dry-formed, positive electrode prepared by mixing acetylene black as a conductive auxiliary material and polyvinylidene fluoride as a binder with a positive electrode active material of lithium cobalt oxide and adding N-methyl-2-pyrrolidone The resulting paste is applied to an aluminum foil and dried to form a separator, the separator is a microporous separator made of polyethylene, and the electrolyte is lithium tetrafluoroborate in a mixed solvent of equal amounts of ethylene carbonate (EC) and dimethyl carbonate (DMC). A lithium secondary battery in which a salt was dissolved at 1 M (mol / l) was used.
Note that stainless steel was used as the battery housing.

In the following, with reference to FIGS. 2 and 5, a description will be given of the flow chart of FIG. As a cooling means, as shown in FIG. 5, a cooling device 201 using compressed gas (VORTEX, manufactured by VORtex, USA)
TUBE) was used. Argon gas was used as the compressed gas.

In order to discharge and recover the remaining amount of electricity of the used cylindrical lithium secondary battery, a capacitor was connected to the output terminal of the battery, the battery was discharged, and the remaining capacity was stored in the capacitor.

To the cylindrical lithium secondary battery discharged by the above operation, 7 kg / cm ² of argon gas was supplied to a supply port of a cooling device (201 shown in FIG. 5), and cold air of -30 ° C. was supplied. By spraying, the mixture was cooled to a temperature below the freezing point of ethylene carbonate and dimethyl carbonate used in the electrolytic solution to lower the ionic conductivity inside the battery. As in the case of Example 1, the impedance between the positive and negative terminals of the battery before and after cooling was measured.
It was 0 mΩ and 5 kΩ after cooling, and it was recognized that the ionic conductivity was reduced to 1/10 or less, and the internal resistance of the battery was increased. Considering this result and the measurement result of the ionic conductivity of the electrolytic solution in Example 2,
It can be seen that the ionic conductivity of the electrolytic solution is also reduced in the cooling operation.

The battery cooled by the above operation is taken out under an atmosphere of argon gas, put on a fixed base (207), and conveyed to an ultrahigh-pressure water cutting device (opening device 204) (conveying device 208). From which ultra-high pressure water of 3500 kg / cm ² mixed with abrasive powder was sprayed.

The cylindrical lithium secondary battery cut by the above operation was washed with water to change the active lithium to lithium hydroxide, and then further washed with methanol to recover a mixed solution of the electrolyte solution, methanol and water. . The negative electrode, the separator, and the positive electrode were taken out from the cylindrical can as the battery housing and collected. The mixed solution of the electrolyte, methanol and water was subjected to fractional distillation to collect the electrolyte, the organic solvent and the methanol, respectively.

Example 5 In this example, the same lithium secondary battery as that used in Example 4 was used. The lithium battery housing was opened based on the flow sheet shown in FIG. Was taken out and collected separately.

In the following, with reference to FIG. 2, a description will be given of the flow chart of FIG. Cooling is
The test was performed with the battery sealed in ice.

In order to discharge and recover the remaining amount of electricity of the used cylindrical lithium secondary battery, a capacitor was connected to the output terminal of the battery, the battery was discharged, and the remaining capacity was stored in the capacitor.

The cylindrical lithium secondary battery discharged by the above operation was filled with water, immersed in a container, and rapidly frozen to enclose the battery in ice to reduce the ionic conductivity inside the battery. When the impedance between the positive electrode terminal and the negative electrode terminal of the battery before and after cooling was measured as in Example 1, the internal resistance of the battery increased to 80 mΩ before cooling and to 3 kΩ or more after cooling. Was. Considering this result and the measurement result of the ionic conductivity of the electrolytic solution in Example 2 above, it is recognized that the ionic conductivity of the electrolytic solution is reduced by the cooling operation.

The battery sealed in ice by the above operation is taken out under a nitrogen gas atmosphere, placed on a fixed base, transported to a disk cutter for cutting by rotating a disk-shaped blade at a high speed, and putting together the ice. Cut.

After the cut cylindrical lithium secondary battery was thawed, it was further washed with acetone to recover a mixed solution of an electrolytic solution, acetone and water. The negative electrode, the separator, and the positive electrode were taken out from the cylindrical can as the battery housing and collected. The electrolyte, the organic solvent, and acetone were recovered by fractionating the mixed solution of the electrolyte, acetone, and water.

Example 6 In this example, the rectangular lithium secondary battery shown in FIG. 10 was opened based on the flow sheet of FIG. 2, the lithium battery housing was opened, and after cleaning, the members constituting each battery were taken out and separated. Collected. Although not shown in FIG. 10, this prismatic battery has a housing made of an aluminum alloy, and a lid with an input / output terminal and a safety valve attached with screws via an O-ring. It was used.

The used lithium battery used here was coated with a paste prepared by mixing natural graphite and polyvinylidene fluoride as a binder on a copper foil and adding N-methyl-2-pyrrolidone to the negative electrode. What was formed by drying, the positive electrode was prepared by mixing acetylene black as a conductive auxiliary material and polyvinylidene fluoride as a binder with a positive electrode active material of lithium cobalt oxide, and adding N-methyl-2-pyrrolidone. What was formed by applying the paste to aluminum foil and drying, the separator is a polyethylene microporous separator,
The electrolytic solution is a solution obtained by dissolving lithium tetrafluoroborate (1 M, mol / l) in a mixed solvent of equal amounts of ethylene carbonate (EC) and dimethyl carbonate (DMC), in order to reduce the distance between the positive electrode and the negative electrode. A lithium secondary battery in which a leaf spring for applying pressure was inserted was used.

In the following, with reference to FIG. 2, a description will be given of the flow chart of FIG. Dry ice-methanol was used as a cooling means.

In order to discharge and recover the remaining amount of electricity of the used prismatic lithium secondary battery, a capacitor was connected to the output terminal of the battery, the battery was discharged, and the remaining amount of electricity was stored in the capacitor.

The prismatic lithium secondary battery discharged by the above operation was immersed in a cryogen dry ice-methanol prepared by adding dry ice to methanol, and cooled to a temperature below the freezing point of ethylene carbonate and dimethyl carbonate used in the electrolyte. Cooling reduced the ionic conductivity inside the cell. When the impedance of the battery before and after cooling was measured in the same manner as in Example 1, 70 m before cooling.
Ω and 1 MΩ after cooling, indicating that the internal resistance of the battery was increased.

The battery cooled by the above operation was loosened under an argon gas atmosphere to remove the lid with the input / output terminal and the safety valve, and the battery housing was opened. Considering this result and the measurement result of the ionic conductivity of the electrolytic solution in Example 2 above, it is recognized that the ionic conductivity of the electrolytic solution is reduced by the cooling operation.

The negative electrode, the separator, the positive electrode, and the leaf spring are taken out of the prismatic lithium secondary battery opened by the above operation, washed with methanol, and the mixed solution of the negative electrode, the separator, the positive electrode, the leaf spring, and the electrolytic solution and methanol is removed. Was recovered. The mixed solution of the electrolytic solution and methanol was subjected to fractional distillation to recover an electrolyte, an organic solvent, and methanol, respectively.

In the above Examples 2 to 6, the recovery operation was similarly performed for each of the ten batteries. However, in each case, no smoke or ignition occurred, no damage was caused by burning of the members, and the lithium battery was not damaged. Was able to be recovered.

In Examples 2 to 6, a lithium battery was used as a sealed battery. However, the results of these Examples are not limited thereto, and a nickel-hydrogen (hydride) storage battery, a nickel-cadmium storage battery, It is recognized that the present invention can be applied to other sealed batteries such as storage batteries.

[0159]

As described above, according to the present invention,
In the collection of the member constituting the sealed battery, the member can be collected more safely while suppressing damage to the member. Also,
Device (system) for recovering components of sealed battery of the present invention
By using, the collection can be performed relatively easily and at low cost.

[Brief description of the drawings]

FIG. 1 is a process chart showing an example of a main method of collecting members constituting a sealed battery of the present invention.

FIG. 2 is a process diagram showing another example of a main method of collecting members constituting the sealed battery of the present invention.

FIG. 3 is a schematic cross-sectional configuration diagram showing an example of a device for extracting an electrolyte and lowering ionic conductivity between a positive electrode and a negative electrode before opening a sealed battery which is a part of the recovery device of the present invention. .

FIG. 4 is a schematic cross-sectional view of another example of a device for extracting an electrolytic solution and reducing the ionic conductivity between a positive electrode and a negative electrode before opening a sealed battery which is a part of the recovery device of the present invention. It is a block diagram.

FIG. 5 is a conceptual diagram showing a device portion having a cooling means and an opening means, which is a main part of a device for collecting members constituting a sealed battery of the present invention.

FIG. 6 is a cross-sectional view illustrating an example of a cooling device used in the battery member recovery device of the present invention.

FIG. 7 is a schematic sectional view showing an example of a sealed battery recovered in the present invention.

FIG. 8 is a cross-sectional view illustrating an example of a coin-type battery.

FIG. 9 is a sectional view showing an example of a spiral cylindrical battery.

FIG. 10 is a cross-sectional view illustrating an example of a prismatic battery.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 100 Sealed battery 101 Battery housing 102 Safety valve 103 Electrolyte extraction tube 104 Electrolyte storage tank 105 Exhaust means 106 O-ring 107 Exhaust pipe 108 Electrolyte extraction valve 109 Exhaust valve 110 Drain valve 111 Battery storage container 112 Battery storage container lid 113 Leak valve 201 Cooling device (low-temperature gas discharge device) 202 Low-temperature gas 203 Non-flammable atmosphere 204 Battery device opening device 205 High-pressure water or energy beam 206 Partition wall with outside air of cooling and cutting line 207 Sealing type battery fixed base 208 Sealing Type battery transfer device 209 Gas supply pipe for compressed gas 210 Compressor 211 Device for removing impurities such as moisture 212 Noncombustible gas recovery device 213 Gas supply tube for noncombustible gas recovery 214 High pressure water or energy beam generator Placement 215 High-pressure water transport pipe or energy beam transmission pipe 301, 401, 502, 601 Negative electrode 302, 403, 508, 603 Positive electrode 303, 407, 507, 607 Separator / electrolyte 304, 609 Battery housing (container) 305, 405, 505, 605 Negative terminal 306, 406, 506, 606 Positive terminal 500, 600 Negative current collector 410, 510 Gasket 501 Negative layer 503 Positive layer 504 Positive current collector 511 Insulating plate 512 Negative lead 513 Positive lead 514, 614 Safety valve 701 Cooling gas 702 Cooling gas outlet 703 Vortex generator 704 Supply compressed gas 705 Supply port 706 Regulator valve 707 Hot air 708 Hot air outlet 709 Vortex

────────────────────────────────────────────────── ─── Continued on the front page (56) References US Patent 5352270 (US, A) WO 94/25167 (WO, A1) German Patent Application 4444225 (DE, A1) (58) Fields investigated (Int .Cl. ⁷ , DB name) H01M 10/54 JICST file (JOIS) WPI (DIALOG)

Claims (66)

(57) [Claims] In a method for recovering a component of a sealed battery, at least a step of reducing ionic conductivity between a positive electrode and a negative electrode, and a step of opening a battery housing after the step of reducing ionic conductivity, After the step of opening the battery housing , the step of taking out the battery component from the battery housing, and the step of taking out the battery component
And separating and collecting the removed battery components . 2. The method according to claim 1, wherein the sealed battery has an electrolyte between a positive electrode and a negative electrode, and the step of reducing the ionic conductivity between the positive electrode and the negative electrode comprises: 2. The method for collecting a sealed battery member according to claim 1, wherein the battery is taken out of the battery housing. 3. The sealed battery has a safety valve, a differential pressure is generated between the outside of the battery housing and the inside of the battery housing through the safety valve to operate the safety valve, and an electrolyte in the sealed battery housing is provided. 3. The method according to claim 2, wherein the solvent in the electrolyte is taken out of the battery housing. 4. The method for recovering a sealed battery member according to claim 3, wherein the electrolyte or the solvent in the electrolyte is taken out of the battery housing from the safety valve portion with the portion where the safety valve of the sealed battery is provided downward. . 5. The method for recovering a sealed battery member according to claim 2, wherein the electrolyte taken out of the housing of the sealed battery or a solvent in the electrolyte is recovered. 6. A method for recovering a component of a sealed battery having an electrolytic solution between a positive electrode and a negative electrode, wherein the sealed battery is cooled to a temperature equal to or lower than a freezing point of a solvent of the electrolytic solution so that at least a portion between the positive electrode and the negative electrode is cooled. Lowering the ionic conductivity, and after the step of reducing the ionic conductivity, opening the battery housing, and after opening the battery housing, removing the battery component from the battery housing The method for collecting a sealed battery member according to claim 1. 7. A method for recovering a component of a sealed battery using a polymer solid electrolyte immobilized by using a polymer, wherein the sealed battery is a glass transition point of a polymer of the polymer solid electrolyte. A step of lowering the ionic conductivity between at least the positive electrode and the negative electrode by cooling to the following temperature, and a step of opening the battery housing after the step of reducing the ionic conductivity, and a step of opening the battery housing. 2. The method for collecting a sealed battery member according to claim 1, further comprising a step of removing the battery component member from the battery housing. 8. The cooling step of the sealed battery, wherein the battery is cooled by using at least one non-combustible compressed gas selected from nitrogen gas, argon gas, helium gas, carbon dioxide and fluorocarbon. 8. The method for collecting a sealed battery member according to claim 7. 9. The method for recovering a sealed battery member according to claim 6, wherein in the cooling step of the sealed battery, the sealed battery is cooled by being immersed in a cryogen or a liquefied gas. 10. The method according to claim 9, wherein the cryogen is dry ice-methanol or dry ice-ethanol. 11. The method according to claim 9, wherein the liquefied gas is liquid nitrogen. 12. The sealed battery according to claim 6, wherein the sealed battery is immersed in water, frozen with water, sealed in ice, and then the sealed battery is opened. For collecting battery cells. 13. The method according to claim 1, wherein the atmosphere in which the opening step is performed is a nonflammable atmosphere. 14. The non-flammable atmosphere in which the opening step is performed is an atmosphere composed of at least one gas selected from nitrogen gas, argon gas, helium gas, carbon dioxide, water vapor and fluorocarbon. A method for collecting sealed battery members. 15. The gas type constituting the atmosphere for performing the opening step and the gas type performing the cooling step are the same.
A method for collecting a sealed battery member according to the above. 16. The method according to claim 1, wherein in the opening step, a cutting method selected from high-pressure water, energy beam, and mechanical cutting is adopted. 17. The method for recovering a sealed battery member according to claim 16, wherein in the opening step, high-pressure water mixed with an abrasive is sprayed from a jet nozzle onto the battery housing to cut the battery. 18. The method according to claim 16, wherein the energy beam used in the opening step is a laser beam. 19. The method according to claim 1, wherein the sealed battery is a lithium battery utilizing a redox reaction of lithium ions. 20. The method for recovering a sealed battery member according to claim 1, wherein the sealed battery is a storage battery using a hydrogen storage alloy as a negative electrode by utilizing a redox reaction of hydrogen ions. 21. The method according to claim 1, wherein the sealed battery is a nickel-cadmium storage battery. 22. The method according to claim 1, wherein the sealed battery is a lead storage battery. 23. The sealed battery member according to claim 19, further comprising a step of reducing a reactivity of active lithium by reacting a reactant with lithium contained in the sealed lithium battery after the opening step. Collection method. 24. The method according to claim 23, wherein one or more substances selected from water, alcohol, acid and carbon dioxide are used as the reactant with lithium. 25. The method according to claim 19, further comprising a step of washing with an organic solvent after opening the sealed battery. 26. The method of claim 25, wherein the organic solvent used in the step of washing the organic solvent is an organic solvent that does not form an azeotrope with water. 27. The method according to claim 2, further comprising a step of separating and recovering members constituting the sealed battery after the washing with the organic solvent.
6. The method for recovering a sealed battery member according to 5. 28. The method for recovering a sealed battery member according to claim 1, wherein, after selecting the shape or type of the sealed battery, the process proceeds to a step of reducing the ionic conductivity between the positive electrode and the negative electrode of the sealed battery. 29. The sealed battery member according to claim 1, further comprising, before the step of reducing the ion conductivity between the positive electrode and the negative electrode of the sealed battery, discharging the remaining amount of electricity of the sealed battery. Collection method. 30. The method for recovering a sealed battery member according to claim 29, wherein in the step of discharging the remaining amount of electricity of the sealed battery, energy simultaneously discharged is recovered. 31. A device for recovering a component of a sealed battery, comprising: means for reducing the ionic conductivity between at least the positive electrode and the negative electrode; means for opening the battery housing; means for removing the battery component from the battery housing; Battery configuration
And a means for separating and recovering the member. 32. The sealed battery has an electrolytic solution between the positive electrode and the negative electrode, and the means for reducing the ionic conductivity between the positive electrode and the negative electrode comprises an electrolytic solution in the sealed battery housing or a solvent in the electrolytic solution. 32. The device for collecting a sealed battery member according to claim 31, wherein the device is a means for taking out the battery outside the battery housing. 33. The sealed battery has a safety valve, a differential pressure is generated between the outside of the battery housing and the inside of the battery housing through the safety valve, and the safety valve is operated to operate the electrolyte in the sealed battery housing. 33. The sealed battery member recovery device according to claim 32, further comprising at least means for removing a solvent in the electrolyte solution from the battery housing. 34. A means for taking out an electrolytic solution or a solvent in the electrolytic solution outside the sealed battery housing,
4. The exhaust means comprises a connected container.
4. The recovery device for a sealed battery member according to 3. 35. The container, wherein the container has a member that adheres or joins to an outer wall surface of a battery housing including a safety valve of the sealed battery, and a port for transferring an electrolyte to be extracted from the battery or a solvent in the electrolyte to the container. Claim 3 provided
5. The recovery device for a sealed battery member according to 4. 36. The sealed battery member recovery device according to claim 34, wherein a passage through which air, nitrogen, or a nonflammable gas can be introduced is provided in the container via a valve. 37. A sealed space comprising a part or all of the outer wall of the housing including the lid of the sealed battery and the container is formed, and the safety valve portion of the battery is included in the space. 34. Recovery of the sealed battery member according to claim 33, wherein the pressure of the space is reduced from the pressure inside the sealed battery to recover the electrolyte solution in the battery housing or the solvent in the electrolyte solution into the container via a safety valve. apparatus. 38. The apparatus for recovering a sealed battery member according to claim 37, wherein a space formed by the outer wall of the sealed battery housing and the container is formed after the pressure in the container is reduced below the atmospheric pressure by the exhaust means. 39. In the collecting device, after forming a space sealed by the outer wall of the sealed battery housing and the container, the pressure of the space is reduced by the exhaust means connected to the container to the inside of the sealed battery. 4. The pressure is lower than the pressure of
8. A recovery device for a sealed battery member according to claim 7. 40. A device for recovering a component of a sealed battery having an electrolytic solution between a positive electrode and a negative electrode, wherein the sealed battery is cooled to a temperature equal to or lower than the freezing point of a solvent of the electrolytic solution so that at least a portion between the positive electrode and the negative electrode. And means for lowering the ionic conductivity of the battery, means for opening the battery housing, and means for removing the battery components from the battery housing.
2. The collection device for a sealed battery member according to claim 1. 41. An apparatus for recovering a component of a sealed battery using a polymer solid electrolyte immobilized by using a polymer, wherein the sealed battery is a glass transition point of a polymer of the polymer solid electrolyte. 32. Means for reducing at least the ionic conductivity between the positive electrode and the negative electrode by cooling to the following temperature, means for opening the battery housing, and means for removing the battery component from the battery housing.
An apparatus for collecting a sealed battery member according to the above. 42. The cooling means for the sealed battery is means for cooling using one or more kinds of noncombustible compressed gas selected from nitrogen gas, argon gas, helium gas, carbon dioxide and fluorocarbon. Item 40. The sealed battery member recovery device according to Item 40 or 41. 43. The apparatus for recovering a sealed battery member according to claim 40, wherein a cooling agent or a liquefied gas is used as a cooling means for the sealed battery. 44. Dry ice-methanol or dry ice-ethanol is used as the cryogen.
An apparatus for collecting a sealed battery member according to the above. 45. The apparatus according to claim 43, wherein the liquefied gas is liquid nitrogen. 46. The means for cooling the sealed battery is a means for immersing the battery in water, freezing the whole water, and sealing in ice, and the means for opening the sealed battery in ice. 42. The device for recovering a sealed battery member according to claim 40 or 41, which is means for opening the sealed battery. 47. The apparatus for recovering a sealed battery member according to claim 31, wherein the means for performing the opening includes means for maintaining the atmosphere in a nonflammable atmosphere. 48. The sealed mold according to claim 47, wherein at least one kind of gas selected from nitrogen gas, argon gas, helium gas, carbon dioxide, water vapor and fluorocarbon is used as the non-flammable atmosphere of the means for performing the opening. Battery member recovery device. 49. The sealed battery member recovery device according to claim 42, wherein the gas species constituting the atmosphere of the opening means and the gas species used for the battery cooling means are the same. 50. The apparatus for recovering a sealed battery member according to claim 31, wherein said opening means is a cutting means selected from high-pressure water cutting means, energy beam cutting means and mechanical cutting means. 51. The opening means has a jet nozzle, and is a means for blowing high-pressure water mixed with an abrasive from the jet nozzle to cut the battery housing.
0. A recovery device for a sealed battery member according to 0. 52. The energy beam of the opening means,
The device for collecting a sealed battery member according to claim 50, wherein the device is a laser beam. 53. The device for recovering a sealed battery member according to claim 31, wherein the sealed battery is a lithium battery utilizing a redox reaction of lithium ions. 54. The apparatus for recovering a sealed battery member according to claim 31, wherein the sealed battery is a storage battery using a hydrogen storage alloy for a negative electrode by utilizing a redox reaction of hydrogen ions. 55. The recovery device for a sealed battery member according to claim 31, wherein the sealed battery is a nickel-cadmium storage battery. 56. The apparatus for recovering a sealed battery member according to claim 31, wherein the sealed battery is a lead storage battery. 57. A means for reducing the reactivity of active lithium by reacting a reactant with active lithium contained in the sealed lithium battery after the opening.
4. The recovery device for a sealed battery member according to 3. 58. The apparatus for recovering a sealed battery member according to claim 57, wherein at least one kind of substance selected from water, alcohol, acid and carbon dioxide is used as the reactant. 59. The collection device for a sealed battery member according to claim 31, further comprising means for washing the inside of the battery with an organic solvent after opening the sealed battery. 60. The recovery device for a sealed battery member according to claim 59, wherein the organic solvent used for washing the organic solvent is an organic solvent that does not form an azeotrope with water. 61. The apparatus for recovering a sealed battery member according to claim 59, further comprising means for recovering a component of the sealed battery after the washing with the organic solvent. 62. The apparatus for recovering a sealed battery member according to claim 31, further comprising means for selecting the shape or type of the sealed battery before reducing the ion conductivity between the positive electrode and the negative electrode of the sealed battery. . 63. The collection of a sealed battery member according to claim 31, further comprising means for discharging the remaining amount of electricity of the sealed battery before reducing the ion conductivity between the positive electrode and the negative electrode of the sealed battery. apparatus. 64. The apparatus for recovering a sealed battery member according to claim 63, wherein the means for discharging the remaining amount of electricity of the sealed battery is provided with means for recovering energy discharged at the same time. 65. The apparatus for recovering a sealed battery member according to claim 47, further comprising means for recovering the non-flammable gas in the open atmosphere of the sealed battery, removing impurities, regenerating and reusing the impurities. 66. The apparatus for recovering a sealed battery member according to claim 42, further comprising means for recovering a gas used for cooling the sealed battery, removing impurities, regenerating and recycling the gas.