JP3080606B2 - Device for deactivating non-aqueous electrolyte batteries - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus for deactivating a non-aqueous electrolyte battery, and more particularly to an apparatus for deactivating a non-aqueous electrolyte battery used in a step of regenerating valuable materials contained in the battery. .

[0002]

2. Description of the Related Art With the development of small portable devices, demand for batteries with high energy density tends to increase rapidly. For example, a lithium ion secondary battery known as a battery using a light-weight and high-capacity non-aqueous electrolyte has a positive electrode active material mainly composed of lithium cobalt oxide containing a valuable metal such as cobalt as an aluminum foil. To form a positive electrode, and a negative electrode active material mainly composed of carbon powder is applied to a copper foil to form a negative electrode.

[0003] These positive and negative electrodes are wound into a roll via a separator as an insulator made of an organic polymer film such as a porous polypropylene film to form an electrode element. After this electrode element is inserted into a battery can mainly composed of iron or the like, an electrolyte such as lithium 6-fluorophosphate is dissolved in an organic solvent such as diethyl carbonate and propylene carbonate not containing active hydrogen. The battery is formed by injecting the made electrolytic solution and finally closing the battery can.

[0004] Recovering valuable resources from a battery using such a non-aqueous electrolyte is not only important from the viewpoint of effective utilization of resources, but also because mere disposal leads to environmental pollution. Is growing.

As a specific conventional method for recovering such valuable resources, there is one disclosed in Japanese Patent Application Laid-Open No. 6-346160. This is because the sealed battery is baked (incinerated) at a high temperature, crushed, and then sieved to a predetermined particle size or less to separate valuable components regardless of the charge / discharge state of the battery to be treated. It was that.

[0006]

However, firing the battery in a sealed state may involve an unexpected danger. That is, the battery internal pressure only increases up to a certain battery temperature with the battery temperature rising,
If it exceeds this, the electrolyte inside the battery will evaporate and expand rapidly,
Inflammable gas is spouted or the battery can ruptures, which may cause rapid combustion in the firing furnace.

[0007] In particular, in the case of a battery in a charged state, these phenomena are observed as being more intense. It was necessary to construct a firing furnace capable of the above. For this reason, measures have been taken to reduce the amount of processing per unit time or to increase the size of the apparatus. However, this has been a factor of high processing costs.

After all, discharge treatment alone is not enough to prevent sudden gas ejection of the electrolyte, and it is effective to inactivate the battery. However, if the battery is simply opened in the atmosphere, the battery will fly off due to heat generation due to short-circuit current, etc., ignition of the electrolyte, or gas ejection, or in the worst case, it will react in a chain between adjacent batteries. Could be large. The damage was more severe and more unpredictable for large capacity batteries.

[0009] In addition, when gas is blown out along with the opening, a processing facility for detoxifying the gas may be required in some cases. As described above, there are many known techniques for recovering valuable resources from batteries. However, even if conventional methods are directly applied to used non-aqueous electrolyte batteries, safety and economical aspects of operation can be improved. For this reason, there are various problems, and there is a problem in application as it is.

[0010]

SUMMARY OF THE INVENTION Accordingly, the present invention has been made in view of the above-mentioned problems, and is a novel and useful non-aqueous electrolyte for the purpose of safely and quickly inactivating a used non-aqueous electrolyte battery. A battery deactivation device is provided.

[0011]

To achieve the above object, the present invention is configured as follows. In other words, soluble
A liquid tank and sodium chloride and sodium sulfate as solutions in the liquid tank.
Less selected from thorium and ammonium sulfate
An aqueous solution containing at least one of them as an electrolyte;
Ri formed by arranging in a state of being submerged destruction means, the destruction hands
Non-aqueous electrolyte battery is not divided and cut separately by step, and
Deactivate by opening to the extent that the contents are partially exposed
It is characterized by the following.

According to the present invention, the heat generated by the battery due to the opening is reduced.
If the battery temperature rises excessively and the organic electrolyte ignites or gas gushes out, the batteries in the adjacent area after the deactivation of the batteries are heated, and the electrolyte ignites or gas gushes out to spread the fire. Therefore, opening in the solution suppresses an excessive rise in temperature of the battery and adverse effects on adjacent batteries.

A solution used in a solution tank of the deactivating device;
Therefore, those which have large heat capacity and are nonflammable are preferable.
It is best to use an aqueous solution in consideration of cost.

In addition, when the electrolyte is added to the solution in advance, when the battery has a voltage, in addition to a short circuit between the positive and negative electrodes due to the opening, a discharge occurs in the solution and the battery is quickly deactivated. is Runode, the cell with the opening
The exotherm is caused by the presence of the electrolyte in the aqueous solution,
It becomes calm compared to the case of only. The electrolyte to be added is not particularly limited, but it is preferable to use an aqueous solution containing at least one selected from inorganic salts such as sodium chloride, sodium sulfate and ammonium sulfate. The amount of electrolyte to be added is sufficiently smaller than the amount of electrolyte required in a normal electrolytic reaction, and is sufficient.
Addition of 0.001 to 1.0 wt% is sufficient because the electrolyte in the electrolyte is added with the opening of the battery.

Regarding the destruction means for opening the battery, if the total area of the openings on the battery surface is too small, the organic electrolyte in the battery is unlikely to diffuse out of the system from the openings and the amount of heat stored in the battery is also reduced. It is not preferable because it becomes large.

On the other hand, in the case where the opening of the battery is made large enough to project the contents of the battery by cutting, the battery separator or the like protrudes outside the can of the battery, and if the blades of the crushing means are worn out, the cutting becomes difficult. There is a risk that valuables may be drawn out of the battery into the solution. In such a case, most of the valuables are diffused into the solution tank, which is not preferable because it causes troublesome re-collection from the solution and increases the amount of loss of the valuables.

From the above, when opening the battery,
Although the number of openings and the shape of the openings are not particularly limited, it is preferable to provide openings at a plurality of locations to expose the contents without releasing the contents from the viewpoints of deactivating the battery and collecting valuable resources. As destruction means for opening the battery, for example,
There are a cutting machine, a crushing machine, drilling with a drill, piercing of a nail-shaped object, and the like, but remote control is desirable from the viewpoint of safety. By opening the battery immersed in the solution, even if the battery generates heat, the heat is quickly radiated by the solution, and the maximum temperature of the battery is reduced, so that the deactivating operation can be performed more safely.

With this opening, even if a gas is blown out in a solution, the safety is higher than that of a gas blown out in the atmosphere. Therefore, the detoxification process is omitted or greatly simplified. Note that the opening contains electrolyte
The electrolyte separates and floats from the inside of the battery to the solution tank surface,
The electrolytic solution containing the electrolyte eluted into the solution tank may be subjected to waste liquid treatment by a conventional method.

Further, the destruction means is provided with a predetermined interval.
It consists of a pair of rotating shafts that are spaced apart and facing each other.
The rotating shaft is provided with a biting blade that bites into the battery.
In addition, an opening blade for cutting the battery is provided on the other rotating shaft.
You may do so.

Alternatively, the destruction means is separated by a predetermined distance.
It consists of a pair of rotating shafts arranged opposite to each other,
Is a biting blade that bites into the battery and an opening blade that cuts into the battery.
It is arranged alternately several times in order, and the other rotating shaft
The biting blade and the opening blade are alternately arranged several times in reverse order to
The embedding blade and the opening blade may be arranged to face each other. These bites
By selecting the arrangement of the insert blade and the opening blade,
Compared with the opening machine consisting of only
It can be performed reliably. The battery is divided separately
Because it is opened without being cut, gas ejection and explosion occur.
Even if the battery is bitten, the scattering of the battery can be suppressed.
This is also preferable.

By selecting the arrangement of the biting blades and the opening blades, the fixing and opening of the battery can be performed simultaneously and reliably as compared with the opening machine having only the opening blades. Furthermore, the battery is opened without being divided and cut separately, so that valuables are not released from the inside of the battery.Because the battery is bitten and fixed, it prevents scattering of the battery even if gas ejection or explosion occurs. Will contribute. Destructive hand in the present invention
The structure of the stage is a pre-process for handing over to the valuables recovery process,
And important in terms of ensuring safety when opening.
It is.

Further, a solution cooling means for cooling the solution is provided in the solution tank of the above apparatus. This is for suppressing the rise in the battery temperature after the opening as much as possible, and is preferable because an effect of reducing the rate of gas ejection accompanying the opening can be expected. The temperature of the solution to be cooled is preferably as low as possible, but in consideration of the effect of lowering the temperature of the solution tank and the necessary cooling means, etc.
° C. is desirable or less, temperature or does not freeze the solution at 0 ℃ below
It is more effective to cool with

For the same reason, a battery cooling means for further cooling the battery before processing may be provided. this
Indicates that the battery temperature rises even when the battery
Can be suppressed, and the gas
This is because the effect of lowering the outflow rate can be expected.
In addition, when viewed from a stand-alone battery, since the battery internal resistance increases due to a decrease in battery temperature, the current at the time of discharge can be suppressed and a rapid rise in battery temperature can be avoided. This is because the maximum temperature reached by the battery can be kept relatively low.

Further, by providing a carrying-out means for collecting the opened battery from the solution tank, the operation of inactivating the battery can be performed more safely. In addition, by providing a filtering means for filtering the solution and a collecting means for removing suspended matter, unnecessary substances such as battery contents and battery exterior generated along with the opening of the battery may be removed from the solution.

[0025]

Next, an embodiment of the present invention will be described in detail with reference to the drawings. FIG. 1 is a schematic diagram of a deactivator of a nonaqueous electrolyte battery of the present embodiment, and FIG. 2 is an explanatory diagram of a opening machine of the deactivator of the nonaqueous electrolyte battery of the present embodiment.

The non-aqueous electrolyte battery deactivator (hereinafter referred to as “the present device”) 1 of this embodiment mainly includes an opening machine 2, a supply unit 3, a battery cooling unit 4, a solution tank 5, and an unloading unit. , A filtration device 7, a solution cooling device 8, and a suspended solids recovery device 9.

The opening machine 2 as a breaking means has a plurality of opening blades 22 attached to a pair of rotating shafts 21 arranged opposite to each other, and is provided below a liquid surface of a solution 51 in a solution tank 5 described later. The opening blade 22 is installed so as to be submerged. In the upper part of the opening machine 2, an inlet 23 is provided and extends to the liquid level. On the lower side of the opening machine 2, an outlet 24 for discharging the battery 10 passed between the opening blades 22 is provided. Is provided.

Here, the configuration of the opening machine 2 itself is not significantly different from the configuration of the crusher having the rotary crushing blade, but the distance W between the rotating shafts 21 is changed according to the battery size (battery volume). By adjusting or replacing the opening blade 22, the battery 10 is not divided and cut separately, but the battery 1 is cut.
It is important to configure the structure so as to cause cleavage or opening to such an extent that the contents of the zero are partially exposed.

Above the inlet 23 of the opening machine 2, a transport conveyor 31 as a supply means 3 for the battery 10 to be processed,
The vibration feeder 32 and the hopper 33 are arranged, and further, the battery cooling device 4 is arranged on the preceding process side.

The transport conveyor 31 is a normal belt circulating transport mechanism, the outlet side 31a of which is disposed above the input port 23, and the inlet side 31b of which is a vibrating feeder 32 for sending out a battery to be processed at an appropriate supply speed. Is connected to the delivery port 32a.

Above the vibration feeder 32, a hopper 33 and a battery cooling device 4 as a battery cooling means are arranged. The battery 10 to be processed is cooled by the battery cooling device 4 in advance and then vibrated through the hopper 33. The power is supplied to the feeder 32.

The solution tank 5 for inactivating the opened battery 10 has a box shape with an open top, and contains therein a solution 5 comprising a 0.1 wt% aqueous solution of sodium chloride cooled to 0 ° C.
1 is filled, and the above-mentioned opening machine 2 is arranged in a submerged state.

The unloading means includes a collection conveyor 6 and a collection basket 6
1, the receiving conveyor 6 is disposed below the discharge port 24 of the underwater opening machine 2 on its receiving side 6a,
The discharge side 6b is disposed so as to protrude outward from the solution tank 5, and a collection basket 61 is disposed below the discharge side 6b.

The apparatus 1 further comprises a solution filtering device 7,
A solution cooling device 8 and a suspended matter recovery device 9 are provided. The filtering device 7 as a filtering means for the solution 51 is for filtering suspended substances and the like consisting of battery contents (for example, a battery active material) mixed into the solution 51 at the opening of the battery. A certain solution cooling device 8 is for cooling the solution to suppress an excessive rise in battery temperature after opening the battery, and both are connected in series to the same water passage.

The filtration device 7 absorbs the solution 51 from a water inlet 71 provided near the bottom surface of the solution tank 5 by an A water supply pump 72, passes water through a filter 73, and filters the solution.
After passing through the solution cooling device 8 for cooling, the solution is returned to the solution tank 5 from the water supply port 74, thereby filtering and cooling the solution.

The suspended matter collecting device 9 as a collecting means is for removing suspended matter such as a battery component and a battery covering material from the solution 51 when the suspended matter such as a battery component or a battery covering material is generated in the solution 51 at the opening of the battery. A mesh basket 9 for sucking floating substances together with the solution 51 from a suction port 91 arranged near the liquid surface of the solution tank 5 by a B water supply pump 92 and collecting the floating substances.
After passing the water through 3 to remove the suspended matter, the solution 51 is returned to the solution tank 5 from the return port 94 again.

[0037]

With the above arrangement, the present apparatus of the nonaqueous electrolyte battery according to the present embodiment operates as follows.

First, the battery 10 to be deactivated is cooled by the battery cooling device 4 and put into the hopper 33, and then sent out from the delivery port 32 a of the vibrating feeder 32 to the transport conveyor 31, where the battery 10 is opened. It is put into the inlet 23 and is opened in the solution 51 by the opening blade 22 of the opening machine 2.

The opened battery 10 is discharged from the discharge port 24 to the receiving portion 6a side of the collection conveyor 6, but it takes a certain time for the battery after opening to be deactivated. 10 is moved to the discharge side 6b at an appropriate speed while being inactivated on the recovery conveyor 6 in the solution 51, and is carried out to the recovery basket 61, and then subjected to a firing step for regenerating valuable resources. It will be.

The operation of the filtration device 7, the solution cooling device 8, and the suspended solids recovery device 9 purifies the solution 51, controls the temperature, and collects the suspended solids. [Example]
First, a 1 cubic meter aqueous solution of 0.1 wt% sodium chloride was used as the solution 51 in the solution tank 5, and was cooled to 0 ° C. by the solution cooling device 8.

Further, as a battery to be deactivated, a fully charged 18650 size single cell and ten battery packs each containing four such cells (hereinafter referred to as "battery etc.") were prepared.

Next, these batteries and the like are cooled by a battery cooling device 4 set at 0 ° C. for 2 hours and then put into a hopper 33 to operate the apparatus 1. The batteries and the like are conveyed from a vibration feeder 32. It was fed on the conveyor 31 and was charged into the battery inlet 20c of the opening machine 2, and was opened in the solution 51 by the opening blade 22 of the opening machine 2. At this time, gas was not ejected.

The opened battery or the like is discharged from the discharge port 24 to the receiving section 6a side of the collection conveyor 6, and the collection conveyor 6 is opened.
In the process of moving to the discharge side 6b by the rotation of the battery, the battery and the like were safely deactivated and carried out to the collection basket 61.

The suspended matter generated at the time of opening the battery or the like is collected in the mesh basket 93 by the suspended matter collection device 9, and the suspension or the like generated in the solution 51 is removed by the filtration device 7. The solution 51 is cooled by the solution cooling device 8.
Was kept at about 0 ° C. even after opening the battery or the like.

[0045]

[Possibility of Other Embodiments] In order to achieve the object of the present invention, the present embodiment can be modified as follows. Although the solution cooling device 8 of the present embodiment is connected in series with the filtration device 31, it is not limited to this.
It may be arranged as a pipe independent of the filtration device 7,
Further, the solution 51 may be cooled indirectly by cooling the solution tank 5.

Further, since the essential components of the present apparatus 1 are only the opening machine 2, the solution tank 5, and the solution 51, it is also possible to use a deactivating device for a non-aqueous electrolyte battery composed only of these. (Fig. 3).

In this case, the battery may be directly charged into the opening machine 2 and opened, and the battery 10 after the inactivation may be directly recovered from the solution tank 5, particularly when the target battery has a small throughput. Is preferable also from the viewpoint of miniaturization of the device.

When a large battery or a battery pack incorporating a plurality of batteries is inserted into the opening machine 2, for example,
The batteries may be reliably opened by being inserted into the opening machine 2 with these batteries aligned in a certain direction.

Further, one side of the opening blade 22 arranged opposite to the opening machine 2 is a biting blade for causing the battery to bite into the opening machine 2, and the other side is a predetermined outside of the battery can body. of
It is also possible to use an opening blade that cuts in for the purpose of cutting into an opening shape . In this case, assuming that the opening blade is A and the biting blade is B, only one A may be mounted on one rotating shaft and only B may be mounted on the other rotating shaft. May be combined as ABAB-... And the other rotation axis may be combined as BABA-. By making these arrays the same
Compared to an opener consisting only of blade-shaped opening blades,
The rubbing movement and the opening can be performed simultaneously and reliably.
Also, since the battery is opened without being divided and cut separately,
Even if gas explosion or explosion occurs, if you bite the battery,
This also suppresses battery scattering.

Alternatively, a pair of auxiliary biting blades may be arranged closer to the input port than the opening blades 22 of the opening machine 2 so that the battery can be reliably sent out between the opening blades 22 (see the figure). Omitted).

Although the present invention aims at inactivating a non-aqueous electrolyte battery, it is applicable to batteries using an aqueous electrolyte such as a nickel-cadmium battery, a nickel-metal hydride battery, and a lead battery. is there.

[0052]

As described above, the apparatus for deactivating a nonaqueous electrolyte battery according to the present invention has the following effects.

That is, since the battery immersed in the solution is opened to the extent that the contents are exposed without being divided and cut separately, loss of valuables inside the battery can be suppressed, and these treatments can be performed. Is carried out in a solution, so that even when the battery generates heat, the heat is quickly radiated to the solution, so that the maximum temperature of the battery can be lowered, and the deactivating operation can be performed more safely.

When an aqueous solution containing at least one selected from sodium chloride, sodium sulfate and ammonium sulfate as an electrolyte is used as the solution in the solution tank, if the battery has a voltage, it is accompanied by an opening. In addition to a short circuit between the positive and negative electrodes, a discharge occurs in the solution, so that the battery can be more quickly deactivated.

Further, even when gas is ejected from a battery in a solution, the safety is higher than gas ejection in the atmosphere, and gas components absorbed in the solution are: Detoxification processing can be omitted or greatly simplified.

Furthermore, since the battery which is safely opened and inactivated by the inactivation device according to the present invention does not involve a sudden gas ejection or the like in the firing step for recovering valuable resources, The industrial effects are remarkable, for example, it is possible to reduce the size of equipment such as a firing furnace and exhaust gas treatment.

[Brief description of the drawings]

FIG. 1 is a schematic view of an apparatus for deactivating a nonaqueous electrolyte battery according to an embodiment.

FIG. 2 is an explanatory diagram of an opening machine of the deactivator of the nonaqueous electrolyte battery according to the embodiment.

FIG. 3 is a schematic diagram of an apparatus for deactivating a non-aqueous electrolyte battery according to another embodiment.

[Explanation of symbols]

 1. Deactivator 2. Opening machine 21. Rotary shaft 22. Opening blade 23. Input port 24. Outlet 3. Supply means 31. Conveyor 31a. Outlet side 31b. Inlet side 32.・ ・ Vibration feeder 32a ・ ・ Sending port 33 ・ ・ Hopper 4 ・ Battery cooling device 5 ・ Solution tank 51 ・ ・ Solution 6 ・ Recovery conveyor 6a ・ ・ Receiver side 6b ・ ・ Discharge side 61 ・ ・ Recovery basket 7 ・ Filtering device 71 ・ ・ Suction port 72 ・ ・ A Water pump 73 ・ ・ Filter 74 ・ ・ Water port 8 ・ Solution cooler 9 ・ Floating matter recovery device 91 ・ ・ Suction port 92 ・ ・ B Water pump 93 ・ ・ Mesh basket 94 ・ ・Return port 10. Battery

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) H01M 10/54 H01M 6/52 B09B 3/00 JICST file (JOIS) WPI / L (QUESTEL)

Claims (7)

(57) [Claims] (1) a solution tank and sodium chloride as a solution in the solution tank.
From thorium, sodium sulfate and ammonium sulfate
Aqueous solution containing at least one selected as electrolyte
A liquid and a destruction means submerged in the aqueous solution.
And the nonaqueous electrolyte batteries are separated by the breaking means.
Open to the extent that it is exposed without splitting and releasing its contents
Non-aqueous electrolyte battery characterized by being deactivated
Pond deactivation device. 2. Destruction means are opposed to each other at predetermined intervals.
With a pair of rotating shafts, one of which is connected to the battery
In addition to disposing a biting blade for biting, the other rotating shaft
Has an opening blade for cutting the battery
The non-aqueous electrolyte battery deactivating device according to claim 1. 3. A destruction means is disposed oppositely at a predetermined interval.
With a pair of rotating shafts, one of which is connected to the battery
A plurality of biting blades to bite and opening blades to cut the battery in order
The other rotating shafts in reverse order.
Plunging blades and opening blades are alternately arranged several times to
And the opening blades are arranged to face each other.
3. The device for inactivating a non-aqueous electrolyte battery according to 2. 4. The non-aqueous electrolyte according to claim 1, 2 or 3.
In the battery deactivator, further cool the solution in the solution tank
-Aqueous electrolysis characterized by providing a solution cooling means for
Liquid battery deactivator. 5. The deactivating device for a non-aqueous electrolyte battery according to claim 1, further comprising a carry-out means for collecting the battery treated by the destruction means from the solution tank. A non-aqueous electrolyte battery deactivating device characterized by the above-mentioned. 6. A non-aqueous electrolyte battery deactivating device according to claim 1, further comprising a filtering means for filtering the solution in the solution tank. Deactivation device for non-aqueous electrolyte batteries. 7. The non-aqueous electrolyte battery deactivating device according to claim 1, further comprising a recovery unit for recovering suspended matter floating in the solution. A non-aqueous electrolyte battery deactivating device characterized by the above-mentioned.