JP2016117009A - Crushing method and crushing apparatus for battery - Google Patents

Abstract

Disclosed is a crushing method and a crushing apparatus for safely treating a battery and supplying the battery to a heat treatment furnace, in which organic matter does not easily remain inside the battery. An inlet and a shredder outlet are provided, a rotatable cutting blade is installed in the room, and a gas supply pipe for introducing a non-oxidizing gas is connected to the room. A battery crushing apparatus characterized in that the battery is crushed under, preferably a pretreatment machine for tearing the battery in a non-oxidizing atmosphere is connected to the inlet of the crushing chamber, The battery crushing method and crushing apparatus which supply the crushed battery crushed material from the crushing means to the heat treatment furnace immediately. [Selection] Figure 1

Description

  The present invention relates to a battery crushing method and a crushing apparatus for treating a lithium ion waste battery or the like. More specifically, it is suitable as a pretreatment crushing method or crushing apparatus for supplying waste batteries such as used lithium ion batteries to the heat treatment furnace, and it is difficult for organic substances to remain inside the battery, and the battery is safely treated to heat treat the furnace. The present invention relates to a crushing method and a crushing apparatus to be supplied.

  Since lithium ion batteries have a high energy density and can obtain a higher voltage than other batteries, in recent years, they have been put into practical use in fields such as electric vehicles and general homes.

  A typical lithium ion battery includes a positive electrode formed by applying an active material such as lithium manganate or lithium cobaltate on an aluminum foil as a current collector in a metal outer can such as stainless steel or aluminum, and the like. In a state in which a negative electrode formed by applying an active material such as graphite on a copper foil as an electric body and a separator made of a porous resin film such as polyethylene or polypropylene are wound in multiple layers between these electrodes in a dense state These are sealed in a can together with an electrolyte such as lithium hexafluorophosphate and an organic solvent of a carbonate compound.

  Lithium-ion batteries are disposed of as used batteries due to the end of their battery life or renewal of devices used. On the other hand, a used battery contains harmful substances and contains valuable metals and the like, and therefore, there is a demand for harmless batteries and recovery of valuable materials.

  As a method for recovering valuable metals from a used lithium ion battery, for example, a dry processing recovery technique as described in Patent Document 1 and Patent Document 2 has been proposed. In these techniques, a used lithium ion battery is directly put into a high-temperature furnace, and an outer can is destroyed by a rupture phenomenon of the battery itself due to a thermal reaction to take out an internal substance.

  In the above recovery technique, it is explained that it is preferable to set the furnace temperature to a high temperature of 800 ° C. or higher. However, in this temperature range, valuable aluminum foil melts and mixes with nearby active material, making it difficult to separate and recover. become. In addition, it has been described that reducing gas is generated by pyrolysis of organic matter in the outer can and the reduction of oxide progresses. However, the can-type battery has a dense winding structure, so it can be sufficiently used with reducing gas. Without contact with the pressure, the pressure inside the outer can rises and the reducing gas is released at once. Therefore, there is a problem that undecomposed resin and harmful substances remain.

  Further, Patent Document 3 discloses a battery crushing device having a crushing unit equipped with a crusher and cooling water jetting means. This crushing device is a device that prevents ignition during crushing by cooling the battery by jetting cooling water and washing the organic solvent, and facilitates maintenance by installing the crusher in the atmosphere. However, when water is sprayed, the organic solvent tends to remain inside the battery, and the organic solvent is mixed with a large amount of water, so that subsequent processing is troublesome.

Japanese Patent Laid-Open No. 10-330855 Japanese Patent No. 3079285 JP 2012-110850 A

  The present invention relates to a battery crushing method and a crushing apparatus, which solves the above-mentioned conventional problems, and organic matter hardly remains inside the battery, and the crushing method and crushing apparatus for safely processing the battery and supplying it to a heat treatment furnace I will provide a.

The present invention relates to a battery crushing method having the following configuration.
[1] A crushing means for crushing a battery in a non-oxidizing atmosphere and a heat treatment furnace for receiving the crushed material are connected to the crushing means, and the crushed battery that has been crushed in a non-oxidizing atmosphere is immediately heat-treated from the crushing means. A method for crushing a battery, characterized by being supplied to a furnace.
[2] Pre-treatment means for tearing the battery in a non-oxidizing atmosphere is provided in front of the crushing means, the battery is torn in the non-oxidizing atmosphere by the pre-treatment means, and the inside of the battery is exposed to remove the non-oxidizing gas. The battery crushing method according to the above [1], which is fed to the crushing means in a filled state.

Furthermore, this invention relates to the battery crushing apparatus which has the following structures.
[3] A crushing chamber is provided. The crushing chamber is provided with an inlet for supplying batteries and a discharge port for crushing pieces. A rotary cutting blade is provided in the chamber, and the chamber is non-oxidizing. A battery crushing apparatus, wherein a gas supply pipe for introducing gas is connected, and the battery is crushed in a non-oxidizing atmosphere.
[4] The battery crushing device according to [3], wherein nitrogen gas, water vapor, or carbon dioxide gas is introduced into the crushing chamber through a gas supply pipe.
[5] A pretreatment machine for tearing the battery in a non-oxidizing atmosphere is connected to the inlet of the crushing chamber, and a heat treatment furnace is connected to the outlet of the crushing chamber. 4] [6] A gas replacement chamber that fills the non-oxidizing gas is formed on the inlet side of the pre-processing machine, and is disposed between the gas replacement chamber and the outlet of the pre-processing machine. The battery crushing apparatus according to any one of [3] to [5] above, wherein means for tearing the battery in a non-oxidizing atmosphere is provided.

[Specific description]
The crushing method and crushing apparatus of the present invention are a method and apparatus for crushing a battery. The battery is, for example, a used lithium ion battery or another battery that is crushed. The battery to be crushed is preferably subjected to the pulverization treatment of the present invention by performing a discharge treatment to a residual voltage of 3 V or less. If the residual voltage is higher than 3V, heat may be generated at a high temperature or flammable gas may be generated during processing. The remaining voltage can be treated by connecting to a resistor such as an electronic load device, submerging in a conductive liquid, piercing the battery with a metal rod to cause an internal short circuit, or pressing the entire battery to deform it. Good.
The conceptual diagram of the crushing method and crushing apparatus of this invention is shown in FIG.

  In the crushing method of the present invention, a crushing means for crushing a battery in a non-oxidizing atmosphere and a heat treatment furnace for receiving the crushed material are communicated with the crushing means, and the crushing material of the battery crushed in a non-oxidizing atmosphere is crushed. A battery crushing method characterized in that the battery is immediately supplied from the means to a heat treatment furnace.

  As shown in FIG. 1, the crushing apparatus of the present invention includes a crushing chamber 10 as a crushing means for crushing the battery 20 in a non-oxidizing atmosphere as shown in FIG. The crushing chamber 10 is provided with an inlet 11 for supplying a battery at an upper portion thereof, and a discharge port 12 for crushing pieces at a lower portion thereof. A rotatable cutting blade 13 is installed in the room. Further, a gas supply pipe 14 for introducing a non-oxidizing gas into the chamber is connected to the crushing chamber 10.

  The battery 20 to be crushed is supplied from the inlet 11 to the crushing chamber 10. A non-oxidizing gas is introduced into the crushing chamber 10 through a gas supply pipe 14. The battery 20 is crushed under this non-oxidizing gas atmosphere. As the non-oxidizing gas, for example, nitrogen gas, water vapor, or carbon dioxide gas can be used. When water vapor is introduced into the crushing chamber 10, heating means (not shown) such as a heater may be provided in the crushing chamber 10 so as not to condense in the room.

  By crushing in a non-oxidizing atmosphere, ignition of the organic solvent sealed inside the battery can be prevented. Moreover, when water vapor | steam is used, an organic solvent can be volatilized with water vapor | steam and it can remove efficiently, while preventing the ignition of an organic solvent.

  When water vapor is used as the non-acid atmosphere gas, 120 to 200 ° C. is preferable and 130 to 160 ° C. is preferable in order to avoid condensation. Moreover, the organic solvent enclosed in the battery 20 can be extracted by heating to this temperature. If this temperature is too high, decomposition of the resin enclosed in the battery 20 starts, which may cause clogging of the crusher and the like. The decomposition of the resins is preferably performed in the next step (heat treatment furnace).

  For example, as shown in FIG. 2, the cutting blade 13 of the crushing chamber 10 is attached to a rotary shaft 15 and is formed to be rotatable. In the illustrated example, the cutting blades 13 are installed so that the opposing cutting blades 13 mesh with each other. Has been. The battery 20 is sandwiched between the cutting blades 13 and crushed.

  The structure of the cutting blade 13 is not limited to the illustrated biaxial structure. A uniaxial structure or a shear structure may be used. Further, in order to separate the outer can and the electrodes enclosed therein, the blade width of the cutting blade 13 and the cutting blade 13 is preferably a width that allows the electrodes to be easily separated, increasing the efficiency of the thermal decomposition treatment, In order to improve the efficiency of the sorting operation in the subsequent stage, the blade width of the cutting blade 13 is generally about 15 mm to 40 mm, preferably 20 mm to 30 mm.

  A heat treatment furnace 30 is continuously provided in the crushing chamber 10. The heat treatment furnace 30 may be installed below the discharge port 12 of the crushing chamber 10 to drop the crushed pieces into the heat treatment furnace 30 continuously or intermittently. Further, the internal pressure P2 of the crushing chamber 10 may be set larger than the furnace pressure P1 of the heat treatment furnace 30 (P1 <P2) so that the gas in the furnace does not flow into the crushing chamber 10.

  In the crushing method of the present invention, preferably, a pretreatment means for tearing the battery in a non-oxidizing atmosphere is provided in front of the crushing means, the battery is torn in a non-oxidizing atmosphere by the pretreatment means, and the inside of the battery is exposed. Then, it is fed to the crushing means in a state filled with non-oxidizing gas.

  In the crushing apparatus illustrated in the present invention, a pretreatment device 40 for tearing the battery in a non-oxidizing atmosphere is connected to the inlet 11 of the crushing chamber 10 in order to carry out the crushing method. A gas replacement chamber 41 filled with a non-oxidizing gas is formed on the inlet side of the pretreatment device 40, and means for tearing the battery in a non-oxidizing atmosphere between the gas replacement chamber 41 and the crushing chamber 10 42 is provided.

  Connected to the gas replacement chamber 41 are a supply pipe 43 for introducing a non-oxidizing gas such as nitrogen gas into the room and an exhaust pipe 44 for exhausting the room gas. Gates 45 and 46 are provided at the inlet and the outlet of the gas replacement chamber 41, respectively. After the battery 20 to be crushed is carried into the room from the entrance gate 45, a non-oxidizing gas such as nitrogen gas is introduced into the room through the supply pipe 43 with the entrance gate 45 and the exit gate 46 closed and the room sealed. On the other hand, the indoor air is discharged to the outside through the exhaust pipe 44, and the indoor battery is filled with the non-oxidizing gas. Next, the outlet gate 46 is opened, filled with non-oxidizing gas, and the battery 20 is sent to the tearing means 42 through the outlet gate 46.

  The tearing means 42 is provided in a chamber 47 that leads from the outlet gate 46 of the gas replacement chamber 41 to the inlet 11 of the crushing chamber 10, and a supply pipe for introducing a non-oxidizing gas such as nitrogen gas into the chamber 47. 48 is connected. Further, a gate 49 is provided between the crushing chamber 10 and the inlet 11. When the battery 20 is fed into the room 47, the gates 46 and 49 are closed to seal the room, and a non-oxidizing gas is supplied into the room. The battery 20 is torn in this non-oxidizing atmosphere.

The tearing means 42 has claw portions 50 and 51 that approach and move away from each other. The claw portions 50 and 51 move in a direction away from each other in a state where they are pierced by the battery 20 carried into the room 47, so that the battery 20 It is torn and the inside of the battery is exposed. Specifically, a jig having a claw having a sharp structure with a plurality of tips on one side and having a barb is inserted into the side surface (flat surface) of the battery 20 to a depth of about half the thickness of the battery 20, and then Move away from each other. At this time, the nail return portion hooks and tears the outer can portion of the battery 20 to expose the inside of the battery. Next, the gate 49 is opened, and the battery 20 whose interior is exposed is fed into the crushing chamber 10 in a non-oxidizing atmosphere and crushed by the cutting blade 13, and then the crushed pieces are put into the heat treatment furnace 30 together with the non-oxidizing gas.
Instead of the tearing means, cutting means, compression deformation means, and twist deformation means may be used.

  In the heat treatment furnace 30, the crushed pieces are heated to a high temperature (about 350 ° C. to about 500 ° C.) and thermally decomposed, and organic substances such as resin are gasified or carbonized without remaining. Further, since the metal material remains without being oxidized, it can be recovered as a valuable metal.

  According to the crushing method and crushing apparatus of the present invention, the battery is crushed in a non-oxidizing atmosphere, so that there is no ignition or ignition by combustible materials such as organic solvents and resins. Therefore, even if the organic solvent is sealed inside the battery like a lithium ion battery, the organic solvent does not ignite and can be processed safely. In addition, since it is crushed and sent to the heat treatment furnace, gasification of the resin component is promoted to the deep part of the electrode that is wound in multiple layers, and no undecomposed product is generated. Moreover, even if harmful fluorine compounds and phosphorus compounds are contained, they are efficiently thermally decomposed in a heat treatment furnace, so that they can be safely treated, and separation and recovery after thermal decomposition are easy.

  Further, according to the crushing method and crushing apparatus of the present invention, when water vapor of about 120 ° C. to about 200 ° C. is used as the non-oxidizing atmosphere gas, the organic solvent is easily extracted, and the organic solvent does not substantially remain in the battery.

  Furthermore, in the crushing method and crushing apparatus of the present invention, the pretreatment means (pretreatment machine) that tears the battery under a non-oxidizing atmosphere to expose the inside is provided in front of the crushing means (crushing chamber). Since the battery is crushed in a non-oxidizing atmosphere, ignition of the organic solvent can be reliably prevented.

  Since the crushing method and crushing apparatus of the present invention have the above-mentioned effects, it is suitable as a crushing method or crushing device for pretreatment for supplying a waste battery such as a used lithium ion battery to a thermal decomposition furnace.

The conceptual diagram of the crushing method and crushing apparatus of this invention. Explanatory drawing which shows an example of a cutting blade.

[Example 1]
The crushing method or crushing apparatus of the present invention shown in FIG. 1 is provided with a crushing chamber 10, which is provided with an inlet 11 for supplying a battery to the upper part thereof, and for discharging shredded pieces at the lower part thereof. An outlet 12 is provided, and a gas supply pipe 14 for introducing a non-oxidizing gas into the room is connected. In the crushing chamber 10, a rotatable cutting blade 13 is installed, and the cutting blade 13 is attached to a rotating shaft 15 as shown in FIG. 2 so that the opposing cutting blades 13 mesh with each other. is set up. A heat treatment furnace 30 is continuously provided below the discharge port 12 of the crushing chamber 10 so that the gas in the furnace does not flow into the crushing chamber 10 and the inside of the crushing chamber 10 is higher than the furnace pressure P1 of the heat treatment furnace 30. The pressure P2 is set large (P1 <P2).
Furthermore, a pretreatment machine 40 is connected to the crushing chamber 10. A gas replacement chamber 41 filled with a non-oxidizing gas is formed on the inlet side of the pretreatment machine 40. The gas replacement chamber 41 has a gas supply pipe 43 for introducing nitrogen gas into the chamber, and a gas in the chamber. A gas exhaust pipe 44 for exhaust is connected. Gates 45 and 46 are provided at the inlet and the outlet of the gas replacement chamber 41, respectively.
Between the gas replacement chamber 41 and the crushing chamber 10, means 42 for tearing the battery is provided. The tearing means 42 is provided in a chamber 47 that leads from the outlet gate 46 of the gas replacement chamber 41 to the inlet 11 of the crushing chamber 10, and the tearing means 42 has claw portions 50 and 51 that approach and separate from each other. . A gas supply pipe 48 for introducing nitrogen gas is connected to the tearing chamber 47, and a gate 49 is provided between the inlet 11 of the crushing chamber 10.
The battery 20 to be crushed is carried into the gas replacement chamber 41 of the pre-processing machine 40, filled with nitrogen gas, and then fed into the tearing chamber 47, and separated from each other with the claws 50 and 51 piercing the battery 20. Moving in the direction, the battery 20 is torn. The battery 20 with the exposed interior is fed into the crushing chamber 10 and crushed by the cutting blade 13 in a nitrogen gas atmosphere, and then the crushed pieces fall into the heat treatment furnace 30 together with the non-oxidizing gas and are thermally decomposed by the heat treatment furnace 30. .

[Example 2]
The used prismatic lithium ion battery discharged to a residual voltage of 3 V or less was put into the crushing chamber 10 of Example 1. The crushing chamber 10 was heated to 150 ° C., and superheated steam heated to about 160 ° C. was supplied into the chamber through the gas supply pipe 14 at a flow rate of 10 kg / hour. The cutting blade 13 was driven in this superheated steam atmosphere to crush the battery. The battery did not ignite during crushing. By this crushing, the battery was divided into 15-20 mm square electrode foil, a resin member, and a crushing piece of the battery outer can. The crushed pieces were continuously supplied to a heat treatment furnace 30 heated to 500 ° C., and after 20 minutes, the residue was taken out from the furnace. The resin member was completely pyrolyzed and did not remain. Moreover, the active material apply | coated on positive electrode foil and negative electrode foil was in the state which peeled only by applying a slight vibration.

[Comparative Example 1]
The used prismatic lithium ion battery discharged to a residual voltage of 3 V or less was put into a pyrolysis furnace at a furnace temperature of 500 ° C. controlled in a steam atmosphere without being crushed, and after 20 minutes, the battery was taken out from the furnace. The battery expanded only slightly, and the contents did not come out due to rupture or the like. When the battery outer can was disassembled, it was confirmed that the resin member wound between the positive electrode foil and the negative electrode foil inside the battery remained in a carbonized state. Moreover, the active material apply | coated on positive electrode foil and negative electrode foil was adhering firmly on foil, and it was in the state which was hard to isolate | separate and collect.

10-crushing chamber, 11-inlet, 12-discharge port, 13-cutting blade, 14-gas supply pipe, 15-rotating shaft, 20-battery, 30-heat treatment furnace, 40-pretreatment machine, 41-gas replacement chamber 42-tearing means, 43-gas supply pipe, 44-gas discharge pipe, 45, 46-gate, 47-tear chamber, 48-gas supply pipe, 49-gate, 50, 51-claw.

Claims (6)

A crushing means for crushing the battery in a non-oxidizing atmosphere and a heat treatment furnace for receiving the crushed material are connected to the crushing means, and the crushed battery material crushed in a non-oxidizing atmosphere is immediately supplied from the crushing means to the heat treatment furnace. A method for crushing a battery. A pretreatment means for tearing the battery in a non-oxidizing atmosphere is provided in front of the crushing means, the battery is torn in a non-oxidizing atmosphere by the pretreatment means, and the inside of the battery is exposed to be filled with a non-oxidizing gas. The battery crushing method according to claim 1, wherein the battery is fed into the crushing means. A crushing chamber is provided. The crushing chamber is provided with an inlet for supplying batteries and a discharge port for crushing pieces. A rotary cutting blade is installed in the chamber, and a non-oxidizing gas is introduced into the chamber. The battery crushing apparatus is characterized in that a gas supply pipe is connected and the battery is crushed in a non-oxidizing atmosphere. The battery crushing apparatus according to claim 3, wherein nitrogen gas, water vapor, or carbon dioxide gas is introduced into the crushing chamber through the gas supply pipe. The pretreatment machine for tearing the battery in a non-oxidizing atmosphere is connected to the inlet of the crushing chamber, and a heat treatment furnace is connected to the outlet of the crushing chamber. Battery crusher described in A gas replacement chamber filled with a non-oxidizing gas is formed on the inlet side of the pretreatment machine, and means for tearing the battery in a non-oxidizing atmosphere is provided between the gas replacement chamber and the outlet of the pretreatment machine. The battery crushing apparatus according to any one of claims 3 to 5.

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