JP2020049460A - Waste lithium ion battery processing equipment and processing method - Google Patents

Abstract

To process a waste lithium ion battery safely and efficiently.SOLUTION: Waste lithium ion battery processing equipment 1 comprises: a heat-resistant container 2 for accommodating a waste lithium ion battery; a heat treatment furnace 3 for heating the heat-resistant container; a container transport device 4 for inputting/discharging the heat-resistant container to/from the heat treatment furnace; and a cooling device 31 which sprays cooling water to the waste lithium ion battery in the heat-resistant container discharged from the heat treatment furnace by the container transport device, thereby cooling the container. The equipment may comprise a pressure control device for controlling so that a negative pressure is generated in the cooling device, and further, may comprise an exhaust gas treatment device which feeds exhaust gas of the cooling device to an exhaust gas treatment system of a cement kiln.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a processing apparatus and a processing method for a waste lithium ion battery used as a power source of an electric vehicle, a hybrid vehicle, and the like.

  A lithium-ion battery is composed of a positive electrode material in which lithium, cobalt, nickel, or the like is applied to an aluminum foil, a negative electrode material in which graphite or the like is applied to a copper foil, an electrolytic solution, a separator, and the like. Lithium-ion batteries contain valuables such as lithium, cobalt, nickel, copper, and aluminum, and therefore, recovering these valuables from discarded lithium batteries is extremely beneficial for Japan, which has scarce resources. Therefore, in order to recover the valuable resources from the waste lithium ion battery, separation and recovery by roasting, crushing or pulverizing, sieving, sorting, and the like are performed.

However, the electrolyte solution of the lithium ion battery contains a fluorine compound (LiPF ₆ or the like) serving as an electrolyte. When LiPF ₆ reacts with water, it is hydrolyzed to generate toxic hydrogen fluoride. Therefore, when treating a waste lithium ion battery, Patent Document 1 discloses that in order to safely treat a volatile fluorine compound (LiPF ₆ or the like) or the like, the volatile component of the electrolyte solution containing the fluorine compound is heated under reduced pressure. There is described a method for treating a fluorine-containing electrolytic solution including a vaporization step of performing vaporization and a fluorine fixing step of reacting a fluorine component contained in the vaporized gas with calcium to fix it as calcium fluoride.

  On the other hand, Patent Literature 2 discloses that a battery pack in which a plurality of lithium-ion battery cells are arranged in a box-shaped housing is stored in a heat-resistant container provided with an exhaust port, Into a heat treatment furnace and heat the heat-resistant container from the outside at a temperature lower than the melting point of aluminum, thereby carbonizing the battery pack in the heat-resistant container to separate the carbonized mixture and volatilize the electrolyte in the battery. A method of recycling waste lithium ion batteries with extremely simple operations by converting the waste lithium ion batteries into heat treatment furnaces through an exhaust port of a heat-resistant container is disclosed.

JP 2013-229326 A JP 2016-22395 A

  However, after performing the heat treatment by the techniques described in Patent Documents 1 and 2, and then performing natural cooling in the atmosphere, the harmful gas containing hydrogen fluoride, hydrogen chloride, and the like is generated from the heated waste lithium ion battery. However, safety issues remain due to the possibility of the occurrence of a problem. In addition, natural cooling takes a long time, which hinders efficient processing.

  Therefore, the present invention has been made in view of the above-mentioned problems in the related art, and has as its object to safely and efficiently treat a waste lithium ion battery.

  In order to achieve the above object, the present invention provides a processing apparatus for a waste lithium-ion battery, comprising: a heat-resistant container for housing the waste lithium-ion battery; a heat treatment furnace for heating the heat-resistant container; And a cooling device for spraying cooling water onto the waste lithium ion battery in the heat-resistant container discharged from the heat treatment furnace by the container transferring device to cool the waste lithium ion battery. In the case where a battery pack in which a plurality of lithium ion battery cells are arranged in a heat-resistant container and a plurality of battery modules are housed in a box-shaped housing exists, cooling water is sprayed on the battery pack, and the battery module is The cooling water is sprayed on the battery module when it is present, and the cooling water is sprayed on the lithium ion battery when a lithium ion battery is present.

  According to the present invention, it is possible to cool the waste lithium ion battery after the heat treatment in a short time by spraying cooling water directly on the waste lithium ion battery in the heat-resistant container discharged from the heat treatment furnace with the cooling device, which is efficient. Waste lithium ion battery can be treated.

  In the waste lithium ion battery processing device, a pressure control device that controls the inside of the cooling device to have a negative pressure can be provided, whereby harmful gases including hydrogen fluoride, hydrogen chloride, and the like can be removed from the cooling device. It can be prevented from being released.

  In addition, an exhaust gas treatment device that supplies exhaust gas from the cooling device to an exhaust gas treatment system of a cement kiln can be provided, whereby harmful gases including hydrogen fluoride, hydrogen chloride, and the like are fixed to the cement raw material in the cement production process. Can be rendered harmless.

  Furthermore, the present invention is a method for treating a waste lithium ion battery, wherein the waste heat resistant container containing the waste lithium ion battery is heated, and the waste water is cooled by spraying cooling water on the waste lithium ion battery in the heated heat resistant container. It is characterized by the following. According to the present invention, the waste lithium ion battery in the heat-resistant container after heating can be directly sprayed with cooling water to cool the waste lithium ion battery after the heat treatment in a short time, and the waste lithium ion battery can be efficiently cooled. Can be processed.

  As described above, according to the present invention, waste lithium ion batteries can be treated safely and efficiently.

1 is an overall cross-sectional view showing one embodiment of a processing apparatus for a waste lithium ion battery according to the present invention. BRIEF DESCRIPTION OF THE DRAWINGS It is the whole longitudinal cross-sectional view which shows one Embodiment of the processing apparatus of the waste lithium ion battery which concerns on this invention. FIG. 3 is a schematic view showing a cooling device and the vicinity thereof, as viewed in the direction of arrow A in FIG. 2. It is a longitudinal cross-sectional view which shows the heat-resistant container used for the processing apparatus of the waste lithium ion battery which concerns on this invention. It is a cross-sectional view which shows the heat-resistant container just before throwing into a heat treatment furnace. It is a longitudinal section showing the heat-resistant container just before it is thrown into a heat treatment furnace. It is the schematic for demonstrating the injection | pouring operation | movement of a heat-resistant container to a heat treatment furnace. It is the schematic for demonstrating the injection | throwing-out operation | movement of the heat-resistant container to a heat treatment furnace. It is the schematic for demonstrating the injection | throwing-out operation | movement of the heat-resistant container to a heat treatment furnace. It is the schematic for demonstrating the injection | throwing-out operation | movement of the heat-resistant container to a cooling apparatus and a heat treatment furnace. It is a schematic diagram for explaining the discharge operation of the heat-resistant container from the cooling device.

  Next, an embodiment of the present invention will be described in detail with reference to the drawings.

  As shown in FIGS. 1 and 2, a waste lithium ion battery processing apparatus 1 according to the present invention includes a battery pack 50 in which a plurality of battery modules in which a plurality of lithium ion battery cells are arranged are housed in a box-shaped housing. To collect useful metals by subjecting the heat-resistant container 2 to heat treatment, a plurality of heat-resistant containers 2 mainly storing the battery pack 50, a heat treatment furnace 3, and a container conveyance for charging and discharging the heat-resistant container 2 to and from the heat treatment furnace 3. The apparatus includes a device 4 and a cooling device 31 for cooling the heat-resistant container 2 after the heat treatment.

  4 to 6, the heat-resistant container 2 includes a container body 2A and a lid 2B, and has a heat-resistant temperature of at least 650 ° C.

  The container body 2A includes an inner cylinder 2a opened upward and formed in a cylindrical shape, an outer cylinder 2b having a larger diameter than the inner cylinder 2a and arranged to surround the inner cylinder 2a, an inner cylinder 2a and an outer cylinder 2a. It comprises a plurality of wheels 2c arranged on the bottom surface of the cylinder 2b, two handles 2e fixed to the peripheral surface 2d of the outer cylinder 2b, and a hanger 2f protruding from the peripheral surface 2d of the outer cylinder 2b.

  On the other hand, the lid 2B includes a cylindrical main body 2n that opens downward, an exhaust pipe 2g that projects upward from the ceiling surface 2h and opens upward, and a handle 2m provided on the ceiling surface 2h of the main body 2n. It consists of.

  As shown in FIGS. 1 and 2, the heat treatment furnace 3 is a cylindrical vertical furnace, and is heated by four gas burners 8 (8A to 8D). A nozzle 11 (11A to 11D) is provided near the gas burner 8, and combustion and cooling air A sent through a fan (not shown) is supplied into the furnace. The hearth 17 of the heat treatment furnace 3 is rotated around a vertical axis by a hearth rotating device 19 provided with an electric motor (not shown), and is positioned at a predetermined position by a positioning sensor (not shown). A secondary combustion chamber, an exhaust chimney, and the like are provided downstream of the exhaust pipe 28.

  An opening 7a is formed in a part of the furnace wall 7 of the heat treatment furnace 3 and is vertically separated from the outside by a furnace door 7b that can be opened and closed. At a position opposed to the opening 7a, the container transfer device 4 for charging the heat-resistant container 2 into the heat treatment furnace 3 from the opening 7a and discharging the heat-resistant container 2 after making a round in the heat treatment furnace 3 from the heat treatment furnace 3 is provided. Provided.

  As shown in FIG. 1, FIG. 2 and FIG. 6, the container transporting device 4 extends in a direction (a left-right direction in FIG. 1) on a line connecting the opening 7a of the heat treatment furnace 3 and the center of the heat treatment furnace 3. The pusher portion 4a which comes into contact with the heat-resistant container 2 by the forward rotation of the heat-resistant container 2 and pushes the heat-resistant container 2 into the heat treatment furnace 3, and the claw 4c for locking the hanger 2f provided on the outer periphery of the container body 2A of the heat-resistant container 2 And a pull-out portion 4b for pulling the heat-resistant container 2 out of the heat treatment furnace 3 by the negative rotation of the motor 18. The pusher part 4a is arranged right above the pull-out part 4b.

  A furnace front chamber 23 is provided adjacent to the openable furnace door 7b (left side in FIG. 1), and a cooling device 31 is provided adjacent to the furnace front chamber 23 (right side in FIG. 3). . A slide base 21 which is movable by a transfer device 29 in a tangential direction (vertical direction in FIG. 1) of the heat treatment furnace 3 is installed. The slide base 21 is connected to a left space of a furnace front chamber 23 in FIG. It is configured to be movable between the furnace front chamber 23 and the cooling device 31 via the doors 24 and 25.

  The cooling device 31 is adjacent to the furnace front chamber 23 with a door 25 that can be opened and closed, and spray devices 31a and 31b for spraying cooling water are provided inside. The spray device 31 a sprays the cooling water onto the exhaust pipe 2 g of the ceiling surface 2 h of the heat-resistant container 2 in order to spray the cooling water directly onto the battery pack 50 in the heat-resistant container 2 discharged from the heat treatment furnace 3. On the other hand, the spray device 31b sprays cooling water on the side surface of the heat-resistant container 2. In addition, a drain port 31 c for collecting water after spraying is formed in the bottom surface of the cooling device 31.

  In addition, a pressure control device that controls the inside of the cooling device 31 to have a negative pressure is provided. The pressure control device suctions exhaust gas from the cooling device 31 with a pressure gauge that measures the pressure inside the cooling device 31. The apparatus includes a suction device, a controller for controlling the suction device such that the measured value of the pressure gauge becomes a negative pressure, and the like. Further, an exhaust gas treatment device (not shown) for supplying the exhaust gas of the cooling device 31 to the exhaust gas treatment system of the cement kiln is provided.

  Next, a method for treating a waste lithium ion battery using the waste lithium ion battery treatment apparatus 1 having the above configuration will be described. In the following description, a case where the processing apparatus 1 processes the battery pack 50 removed from a hybrid vehicle, an electric vehicle, or the like will be exemplified.

  The temperature inside the heat treatment furnace 3 is raised to 650 ° C., and the heat-resistant container 2N containing the battery pack 50 is placed on the right end of the slide base 21 using a crane or the like (not shown) as shown in FIG. Place. After the door 24 is opened, the slide base 21 is moved rightward through the transfer device 29, and the heat-resistant container 2 is moved to the front of the furnace door 7b. Then, the door 24 is closed and the furnace door 7b is opened. Then, the pusher portion 4a of the container transport device 4 is advanced to put the heat-resistant container 2N into the heat treatment furnace 3. Thereby, the heat-resistant container 2N is placed on the hearth 17 of the heat treatment furnace 3, at the position of 9 o'clock in FIG.

  After the pusher portion 4a of the container transfer device 4 is retracted, the furnace body door 7b is closed, and the hearth 17 is rotated 45 ° counterclockwise through the hearth rotating device 19. The rotation at 45 ° is not particularly limited. For example, by setting the hearth 17 to rotate 45 ° every 37.5 minutes, the hearth 17 is set to rotate once in 5 hours. ing.

  By repeating the above operation seven times, eight heat-resistant containers 2 are formed on the hearth 17 of the heat-treating furnace 3 in a state where the adjacent heat-resistant containers 2 are spaced at a predetermined interval, as shown in FIG. Placed on

  During the above operation, the heat-resistant container 2 is heated from the outside while making one round in the heat treatment furnace 3, so that the inside of the heat-resistant container 2 becomes a reducing atmosphere, and the resin pack of the battery pack 50 stored in the heat-resistant container 2 is made of resin. Plastics such as a housing are separated from materials containing useful metals such as lithium, cobalt, nickel, and manganese as a carbonized mixture by dry distillation. Since the heat-resistant container 2 is heated at a temperature (650 ° C.) lower than the melting point of aluminum (660 ° C.), the aluminum component used in the battery pack 50 does not melt. The electrolyte in the battery volatilizes and is discharged into the heat treatment furnace 3 from the exhaust pipe 2g of the heat-resistant container 2 together with a gas generated by thermal decomposition of a combustible substance such as plastic. The unburned gas in the heat treatment furnace 3 is guided to the secondary combustion chamber and burns at a temperature (800 ° C.) higher than the temperature of the heat treatment furnace 3 (650 ° C.).

  Before the heat-resistant container 2 makes one round in the heat treatment furnace 3, as shown in FIG. 8, the right half of the slide base 21 in which the new heat-resistant container 2N containing the battery pack 50 is placed at the left end is placed in the furnace front chamber. 23. At this time, the door 24 is closed.

  When the heat-resistant container 2 makes one round in the heat treatment furnace 3, the furnace body door 7b is opened and the pull-out portion 4b of the container transfer device 4 is advanced to the position of the heat-resistant container 2, and as shown in FIG. Is locked to a hanger 2f provided in the heat-resistant container 2. Then, the pull-out portion 4b is retracted, and as shown in FIG. 9, the heat-resistant container 2T is pulled out of the heat treatment furnace 3, placed on the slide base 21, and the furnace door 7b is closed.

  Next, after opening the doors 24 and 25, the slide base 21 is moved rightward, the new heat-resistant container 2N containing the battery pack 50 is moved to the front of the furnace door 7b, and the heat-treated heat-resistant container is heated. The 2T is moved to the cooling device 31, and the doors 24 and 25 are closed. This state is shown in FIG.

  From the state of FIG. 10, a new heat-resistant container 2 </ b> N is put into the heat treatment furnace 3 and heated as described above, and the heat-treated heat-resistant container 2 </ b> T is cooled by the cooling device 31. In the cooling device 31, cooling water is sprayed on the exhaust pipe 2g of the ceiling surface 2h of the heat-resistant container 2T by the spray device 31a, and the sprayed water directly hits the battery pack 50. In addition, cooling water may be sprayed on the side surface of the heat-resistant container 2 by the spraying device 31b in an auxiliary manner. In the conventional natural cooling, it took about 6 hours to cool the battery pack 50 heated to about 650 ° C. to about 150 ° C., but by directly spraying the battery pack 50 within 1 hour, that is, 1 / The cooling step is completed in 6 or less. However, if moisture is contained in the battery pack 50 after cooling, adverse effects are caused in the next step, so that the spraying time by the spraying devices 31a and 31b is controlled so that the temperature of the battery pack 50 does not drop too much. Further, even when the battery pack weight or the heating temperature changes, the cooling step can be shortened by adjusting the spray amount of water.

  Next, after opening the doors 24 and 25, the slide base 21 on which the cooled heat-resistant container 2C is placed is moved to the left, and transported to the next step by a crane or the like.

  After the heat treatment container 2C that has been subjected to the heat treatment after cooling, the internal battery pack 50 is crushed and classified to remove the carbonized mixture, and then a process of further separating useful metals such as lithium, cobalt, nickel, and manganese is performed. Further, the crushed product of the battery pack 50 is subjected to a magnetic separator to separate a magnetic substance such as an iron housing and screws, and a mic metal made of copper and aluminum. After being divided into a laminate of foil and aluminum foil, it can be further divided into copper foil and aluminum foil by a sorter.

  In addition, the harmful gas containing hydrogen fluoride, hydrogen chloride, and the like from the cooling device 31 is supplied to an exhaust gas treatment system of a cement kiln by an exhaust gas treatment device, and is fixed to a cement raw material in a cement manufacturing process to be harmless.

  The heat treatment furnace 3 does not need to rotate the hearth 17, and may be a batch type. Further, various furnaces using electricity or heavy oil can be used as a heat source, and exhaust gas from an existing manufacturing facility, for example, a cement firing device may be used as a heat source.

  Further, in the present embodiment, the battery pack 50 is subjected to the heat treatment without removing the battery cells individually, but the battery pack 50 is disassembled from the battery pack 50, or the battery cells are individually removed. Alternatively, the heat-resistant container 2 containing the container removed may be put into the heat treatment furnace 3 and subjected to heat treatment.

REFERENCE SIGNS LIST 1 Waste lithium ion battery treatment device 2 Heat-resistant container 3 Heat treatment furnace 4 Container transfer device 7 Furnace wall 8 (8A to 8D) Gas burner 11 (11A to 11D) Nozzle 17 Hearth floor 18 Motor 19 Hearth rotation device 21 Slide base 23 Furnace front chambers 24, 25 Door 29 Transfer device 31 Cooling device 50 Battery pack

Claims (4)

A heat-resistant container for storing the waste lithium-ion battery,
A heat treatment furnace for heating the heat-resistant container,
A container transfer device for charging and discharging the heat-resistant container into the heat treatment furnace,
A cooling device for spraying cooling water onto the waste lithium ion battery in the heat-resistant container discharged from the heat treatment furnace by the container transfer device to cool the waste lithium ion battery.   The processing apparatus for a waste lithium ion battery according to claim 1, further comprising a pressure control device that controls the inside of the cooling device to have a negative pressure.   The waste lithium ion battery treatment device according to claim 1 or 2, further comprising an exhaust gas treatment device that supplies exhaust gas from the cooling device to an exhaust gas treatment system of a cement kiln. Heat the heat-resistant container containing the waste lithium-ion battery,
A method for treating a waste lithium-ion battery, comprising spraying cooling water onto a waste lithium-ion battery in a heat-resistant container after heating to cool the battery.

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