JP6716389B2 - Method of collecting valuables from waste lithium-ion battery and method of creating database - Google Patents

Description

The present invention relates to a method for recovering valuable materials from a waste lithium-ion battery and a method for creating a database used in the recovery method.

A lithium-ion battery used as a power source for an electric vehicle such as a hybrid vehicle or an electric vehicle is a battery in which a plurality of lithium-ion battery cells are arranged in a battery module, and the battery modules are housed in a box-shaped housing made of resin or metal. It is mounted on the vehicle as a pack. In this battery pack, a plurality of battery modules are electrically connected by a wire harness or the like, and the battery pack is further equipped with a battery control system, a circuit for breaking a high-power circuit, a switch, and the like.

A lithium-ion battery is composed of a positive electrode material obtained by applying lithium, cobalt, nickel, etc. to an aluminum foil, a negative electrode material obtained by applying graphite, etc., to a copper foil, an electrolytic solution, a separator, etc., and thus lithium, cobalt, nickel, copper. Including valuable materials such as aluminum and aluminum. Therefore, it is extremely beneficial for Japan, which lacks resources, to recover these valuable materials from the discarded lithium batteries.

In order to recover the valuable materials from the waste lithium-ion battery, separation and recovery by roasting, crushing or crushing, sieving, selection, etc. are performed. The roasting treatment aims to thermally decompose and remove the organic solvent such as propylene carbonate and ethylene carbonate contained in the electrolytic solution, the supporting salt of lithium hexafluorophosphate, and the separator such as polyethylene and polypropylene. A method for roasting a lithium-ion secondary battery or a method for recovering a valuable material is described in Patent Documents 1 to 3 and the like.

JP, 2014-227565, A JP, 2005-170480, A JP, 2005-219948, A

In order to recycle a waste lithium-ion battery, it is important not only to melt the aluminum electrode, but also not to make the foil-like aluminum electrode brittle and to collect the foil as it is. However, the cells of the lithium-ion battery are roughly classified into a cylindrical type, a square type, and a laminated type, and according to the study of the present inventors, even if roasted at the same temperature for all types, valuable materials are suitable. It cannot always be collected. Specifically, the cylindrical type and the square type are housed in a robust case, and the internal electrodes do not become brittle when roasted at a high temperature to some extent, but the laminated type is a metal-coated resin case, Electrodes tend to become brittle at relatively low temperatures. None of the above Patent Documents 1 to 3 considers changing the roasting conditions such as temperature for each type of lithium ion battery, and there is room for improvement.

The object of the present invention has been made in view of the above conventional problems, and can be efficiently recovered without embrittlement of valuable materials such as electrodes, regardless of specifications such as the type of the waste lithium-ion battery. It is intended to provide a method for collecting a valuable material from a waste lithium-ion battery and a method for creating a database which can be suitably used in the method.

A method of recovering valuable materials from a waste lithium-ion battery of the present invention (hereinafter, sometimes referred to as a recovery method of the present invention) is a method of recovering valuable materials from a roasted product obtained by roasting a waste lithium-ion battery. A method for recovering valuable materials from waste lithium-ion batteries,
Step A for obtaining information on the specifications of the waste lithium-ion battery,
Step B of determining a roasting condition including at least one of a roasting temperature range and a roasting time range based on the acquired information on the specification, and roasting the waste lithium ion battery according to the roasting condition;
And causing a computer to execute .

In the recovery method of the present invention, the information about the specifications of the waste lithium-ion battery is acquired, and based on the information, the roasting is performed under the roasting conditions (temperature/time) suitable for the waste lithium-ion battery. Can be recovered without embrittlement.

In the recovery method of the present invention, the information on the specifications in the step A includes information on the outer shape of the waste lithium-ion battery, and the information on the specifications in the step A includes information on the outer shape of the waste lithium-ion battery. In the case of a prismatic type or a cylindrical type, the roasting conditions are such that the upper limit of the roasting temperature range is higher or the upper limit of the roasting time range is longer than in the case where the outer shape is a laminate type. To decide. This is because when the waste lithium-ion battery is a laminate type, the internal electrodes are more easily embrittled when the roasting temperature is higher or the roasting time is longer than when it is a rectangular type or a cylindrical type. Therefore, by determining the roasting temperature or the roasting time based on the information of the outer shape, that is, the information of the square type, the cylindrical type, or the laminating type, in any case, valuable materials such as electrodes can be used while suppressing the embrittlement of the electrodes. Can be recovered.

In the recovery method of the present invention, it is preferable to determine the roasting conditions by referring to a database containing information on the specifications of the waste lithium-ion batteries and optimum roasting conditions based on the specifications of the waste lithium-ion batteries. By creating the above database, determining the optimal roasting conditions for any waste lithium-ion battery by referring to that database, and roasting under the roasting conditions, the embrittlement of valuable materials It can be collected efficiently while preventing it.

On the other hand, the method of creating a database of the present invention is a method of creating a database used in a method of recovering valuable materials from waste lithium-ion batteries,
Steps to obtain information about specifications of waste lithium-ion batteries,
Roasting under a plurality of roasting conditions to two or more waste lithium-ion batteries having the same specifications as the grasped specifications, and determining an optimum roasting condition from the plurality of roasting conditions;
Storing the correspondence relationship between the specifications of the waste lithium-ion battery and the optimum roasting conditions for the specifications in a storage device,
And causing a computer to execute .

By the method of creating a database of the present invention, optimum roasting conditions such as brittleness of electrodes can be found by roasting a plurality of waste lithium ion batteries having the same specifications under different roasting conditions of 2 or more. The roasting conditions are stored in the storage means as a database for each specification of the waste lithium-ion battery. Then, by using the created database, it is possible to determine the optimum roasting conditions of any waste lithium-ion battery and roast it as described above, so it is possible to recover valuable resources more efficiently.

1 is an overall cross-sectional view showing an embodiment of a processing device for a waste lithium-ion battery according to the present invention. 1 is an overall vertical cross-sectional view showing an embodiment of a processing device for a waste lithium-ion battery according to the present invention. It is a figure which shows the container main body of the heat resistant container used for the processing apparatus of FIG. 1 and FIG. 2, (a) is a front view, (b) is a top view, (c) is a bottom view. It is a figure which shows the cover of the heat resistant container used for the processing apparatus of FIG. 1 and FIG. 2, (a) is a front view, (b) is a top view. FIG. 4 is a vertical cross-sectional view showing a state where a heat resistant container is configured by combining the container body of FIG. 3 and the lid of FIG. 4. FIG. 3 is a cross-sectional view showing the heat-resistant container just before being put into the heat treatment furnace in the processing apparatus of FIGS. 1 and 2. FIG. 3 is a vertical cross-sectional view showing a heat-resistant container immediately before being put into a heat treatment furnace in the processing apparatus of FIGS. 1 and 2.

The method for recovering valuable materials from the waste lithium-ion battery of the present invention is a method for recovering valuable materials from the waste lithium-ion battery for recovering valuable materials from the roasted product obtained by roasting the waste lithium-ion battery, Step A of obtaining information about specifications of the waste lithium-ion battery, and determining roasting conditions including at least one of a roasting temperature range and a roasting time range based on the obtained information about the specifications, and according to the roasting conditions. And step B of roasting the waste lithium-ion battery. Each step will be described below.

[Step A]
In step A, information regarding the specifications of the waste lithium-ion battery is acquired. The information on the specifications of the waste lithium-ion battery includes the outer shape, heat resistance of the case, product information, weight, size, nominal voltage, case material, positive electrode material, and the like. In particular, it is preferable that the information regarding the specification is information including the outer shape such as a cylindrical type, a square type, or a laminated type.

[Step B]
In step B, roasting conditions including at least one of a roasting temperature range and a roasting time range are determined based on the acquired information about the specifications, and the waste lithium ion battery is roasted according to the roasting conditions. The information regarding the specifications is roughly classified into a cylindrical type, a square type, and a laminated type in the case of the outer shape. The roasting condition based on the outer shape is preferably determined based on at least one of the following condition 1 and condition 2.
Condition 1: The upper limit of the roasting temperature range is determined so as to be lower in the laminated type than in the rectangular or cylindrical type.
Condition 2: The upper limit of the roasting time range is determined so that the laminate type is shorter than the square type or the cylindrical type.

As described above, the roasting conditions are determined based on the outer shape. In the laminate type, when the roasting temperature is high (or when the roasting time is long), the internal electrodes are easily embrittled, and conversely, the square type or the cylindrical type is used. The reason is that the upper limit of the roasting temperature can be set higher (or the roasting time can be longer) than that of the laminate type. That is, the laminated type has a lower roasting temperature (or shorter roasting time) than the square type or the cylindrical type to suppress the embrittlement of the internal electrodes. Since there is less fear, the roasting temperature is set higher (or the roasting time is longer) than that of the laminate type, and the roasting is efficiently performed.

In order to recover the electrodes inside the waste lithium-ion battery in good condition, it is necessary to prevent the electrodes from melting and integrating with other metals. Since aluminum is mentioned as a simple substance of a low melting point used for a lithium ion battery, a temperature below the melting point (660° C.) of aluminum may be set as the upper limit of the roasting temperature. Further, the lower limit of the roasting temperature is preferably a temperature at which thermal decomposition of various materials sufficiently progresses. The roasting temperature range is preferably 450° C. or higher and lower than 660° C., and the temperature is preferably determined within this range.

For example, in the case of a rectangular type or a cylindrical type, a range of 450° C. or higher and lower than 660° C. can be set, and in the case of a laminate type, a range of 450° C. or higher and 550° C. or lower can be set. By setting the roasting temperature range in this way, even if it is a laminate type, it is possible to efficiently roast the aluminum electrode without embrittlement.

Although the roasting time varies depending on the roasting temperature, it is preferably 3 to 10 hours when roasting at 550° C. in the case of a square type or a cylindrical type. Further, in the case of a laminate type, when roasting at 550° C., it is preferably 3 hours or less.

The above is for determining the roasting conditions based on the information on the specifications of the lithium-ion battery and roasting under those conditions. It is preferable to determine the roasting conditions with reference to a database containing the roasting conditions. By creating such a database and roasting any waste lithium-ion battery under optimal roasting conditions with reference to that database, the valuables can be efficiently collected while preventing embrittlement of the valuables. can do. It is also possible to automatically determine the optimum roasting conditions of an arbitrary waste lithium-ion battery by making full use of the above-mentioned database and an image recognition device, etc.

Next, a method of creating a database used in the recovery method of the present invention as described above will be described. A method of creating a database of the present invention includes a step of grasping information regarding specifications of a waste lithium-ion battery (hereinafter referred to as “step a”) and two or more waste lithium-ion batteries having the same specifications as the grasped specifications. On the other hand, a step of roasting under a plurality of roasting conditions and determining an optimum roasting condition from the plurality of roasting conditions (hereinafter referred to as “step b”), and specifications of the waste lithium-ion battery Storing a correspondence relationship between the specification and the optimum roasting condition in a storage device (hereinafter, referred to as “step c”). Each step will be described below.

[Step a]
In step a, information regarding the specifications of the waste lithium-ion battery is grasped. As mentioned above, the information on the specifications of the waste lithium-ion battery includes the outer shape, heat resistance of the case, product information, weight, size, nominal voltage, case material, positive electrode material, etc. ..

[Step b]
In step b, two or more waste lithium ion batteries having the same specifications as those grasped in step a are roasted under a plurality of roasting conditions, and the optimum roasting conditions are determined from the plurality of roasting conditions. To do. For example, when determining the roasting conditions of a tubular waste lithium-ion battery, prepare a large number of tubular waste lithium-ion batteries, roast under different roasting conditions for each, and suppress embrittlement of the electrode, Find the optimum roasting conditions. Alternatively, a large number of waste lithium-ion batteries of the same product are prepared and roasted under different roasting conditions for each to find the optimum roasting conditions.

[Step c]
A correspondence relationship between the specifications of the waste lithium-ion battery and the optimum roasting conditions for the specifications is stored in a storage device. That is, the waste lithium-ion battery having a predetermined specification is associated with the roasting conditions found in step b, and the corresponding relationship is stored in the storage device. For example, in the case of a prismatic waste lithium-ion battery, roasting conditions such as a roasting temperature of 450° C. or more and less than 660° C. and a roasting time of 3 to 10 hours are associated, and the corresponding relationship is stored in a storage device.

The roasting conditions for each specification of the waste lithium-ion battery obtained as described above are made into a database and stored in the storage means. By using the stored database, it is possible to determine the optimum roasting conditions and roast the arbitrary waste lithium-ion battery by referring to the database, so that valuable resources can be recovered more efficiently. be able to.

Hereinafter, an example of a processing apparatus to which the method for recycling a waste lithium-ion battery of the present invention can be applied will be described.

As shown in FIGS. 1 and 2, a processing device 1 for a waste lithium-ion battery is configured such that a plurality of battery modules in which a plurality of lithium-ion battery cells are arranged are collectively put into a heat-resistant container and subjected to heat treatment. It collects useful metals, and mainly comprises a plurality of heat-resistant containers 2 for storing the lithium-ion battery 50, a heat treatment furnace 3, and a container transfer device 4 for charging and discharging the heat-resistant container 2 into and from the heat treatment furnace 3. .. The processing apparatus 1 is particularly useful when the input amount per container (one batch) in which the amount of heat generated from the battery is high is 50 kg or more, and is particularly useful for a secondary battery in which intense combustion occurs.

As shown in FIGS. 3 to 5, the heat-resistant container 2 is composed of a container body 2A and a lid 2B. The material of the container body 2A and the lid 2B is SS, stainless steel (SUS304) or the like, and has a heat resistant temperature of at least 650°C.

As shown in FIG. 3, the container main body 2A includes an inner cylinder 2a which is opened upward and is formed into a cylindrical shape, and an outer cylinder 2b which is larger in diameter than the inner cylinder 2a and surrounds the inner cylinder 2a. A plurality of wheels 2c arranged on the bottom surfaces of the inner cylinder 2a and the outer cylinder 2b, two handles 2e fixed to the peripheral surface 2d of the outer cylinder 2b, and a hanger protruding from the peripheral surface 2d of the outer cylinder 2b. 2f and.

On the other hand, as shown in FIG. 4, the lid 2B has a cylindrical main body 2n that opens downward, an exhaust pipe 2g that opens to the peripheral surface of the main body 2n and projects obliquely upward, and a ceiling of the main body 2n. It is composed of a handle 2m provided on the surface 2h. The angle formed by the exhaust pipe 2g and the horizontal plane is set to about 45°, but is not limited to this. The direction of the exhaust pipe 2g is set such that the horizontal component of the velocity vector of the combustion gas ejected from the exhaust pipe 2g is in the same direction as the vortex combustion direction of the heat treatment furnace 3. Further, the installation position of the exhaust pipe 2g may be lower than the four gas burners 8 (8A to 8D) and higher than the tip 28a of the exhaust pipe 28 as shown in FIG.

To form the heat-resistant container 2 with the container body 2A and the lid 2B, as shown in FIG. 5, the lower end 2k of the body 2n of the lid 2B is inserted into the groove 2j between the inner cylinder 2a and the outer cylinder 2b of the container body 2A. Is fitted and the groove 2j is filled with glass wool or the like to form a seal, and the lid 2B is attached to the container body 2A in such a state that it can be lifted by a predetermined distance L. By making the lid 2B floatable with respect to the container body 2A, even if the pressure inside the heat-resistant container 2 increases due to the reaction during the heat treatment, the pressure raised by the lid 2B rising is released, and the heat-resistant container 2 Can be prevented from being damaged.

The structure of the heat-resistant container 2 is not limited to the one described above, and any structure may be used as long as it has a structure that allows the lid 2B to float above the container body 2A and release the increased pressure. Can be used.

Further, as long as a plurality of lithium ion batteries 50 can be stored, the heat resistance is excellent, and the exhaust pipe 2g is provided on the upper portion, the lithium ion batteries 50 may not be divided.

Further, a recess (not shown) is formed in the container body 2A of the heat-resistant container 2 to receive and store the melted material such as plastic during the heat treatment to prevent the melted material such as plastic from spilling out from the heat-resistant container 2. May be.

As shown in FIGS. 1 and 2, the heat treatment furnace 3 is a cylindrical vertical furnace in which a furnace wall 7 is made of a steel plate covered with a refractory material, and four gas burners 8 (8A to 8D) are provided. Heated by. Nozzles 11 (11A to 11D) are provided in the vicinity of the gas burner 8, and combustion air A and cooling air A sent via a fan (not shown) are supplied into the furnace. A thermometer 13 and a pressure gauge 14 are provided to measure the temperature and pressure inside the furnace. The thermometer 13 is installed near the hearth 17 of the heat treatment furnace 3 described later so as not to be affected by the gas burner 8 and the exhaust pipe 2g. The number of gas burners 8 and nozzles 11 installed is not limited to four, and may be three or less or five or more.

The hearth 17 of the heat treatment furnace 3 is made of a steel plate covered with a refractory material like the furnace wall 7, and is rotated around a vertical axis by a hearth rotating device 19 equipped with an electric motor (not shown), and a positioning sensor ( It is positioned at a predetermined position (not shown).

On a part of the furnace wall 7 of the heat treatment furnace 3, an opening 7a is formed which is partitioned from the outside by a vertically openable furnace body door 7b. At the position opposite to the opening 7a, the container transporting device 4 is provided for charging the heat-resistant container 2 into the heat-treating furnace 3 through the opening 7a and discharging the heat-resistant container 2 from the heat-treating furnace 3 after going around the heat-treating furnace 3. It is provided.

As shown in FIG. 1, FIG. 2, FIG. 6 and FIG. 7, the container transporting device 4 extends in a direction on the line connecting the opening 7 a of the heat treatment furnace 3 and the center of the heat treatment furnace 3 (left and right direction in FIG. 1 ). , A pusher portion 4a for abutting against the heat-resistant container 2 by the forward rotation of the motor 18 to push the heat-resistant container 2 into the heat treatment furnace 3 and a claw for locking the hanger 2f provided on the outer periphery of the container body 2A of the heat-resistant container 2. 4 c is provided at the tip, and a pull-out portion 4 b for pulling out the heat-resistant container 2 from the inside of the heat treatment furnace 3 by negative rotation of the motor 18 is provided. The pusher portion 4a is arranged directly above the pullout portion 4b.

The heat-resistant container 2 is tangential to the heat-treating furnace 3 (upward and downward in FIG. 1) immediately before being put into the heat-treating furnace 3, that is, when it is located outside the openable furnace door 7b. The slide base 21 is mounted on a slide base 21 which is freely movable to the front side of the furnace body door 7b by a base moving device 22 connected to an end of the slide base 21. Position 1) and a stand 25 located on the outer side of the openable front chamber door 24. The furnace front chamber 23 is separated from the outside by a furnace front chamber door 24 and is separated from the heat treatment furnace 3 by a furnace body door 7b so as to suppress a temperature change when the furnace body door 7b is opened. I have to. Further, by providing the furnace front chamber 23, the atmosphere in the heat treatment furnace 3 can be maintained, and dangerous gas leakage and hot air blowing can be prevented.

When the slide base 21 moves to the stand 25, the heat-resistant container 2 before being heated by a crane (not shown) is placed on the slide base 21 and then conveyed to the furnace front chamber 23 by the base moving device 22. The heat-resistant container 2 after being heated is similarly conveyed from the furnace front chamber 23 to the stand 25 by the base moving device 22, and then automatically moved to the cooling chamber (not shown). The base moving device 22 moves the slide base 21 connected to the tip of the shaft 22b by expanding and contracting the shaft 22b by driving the motor 22a.

As shown in FIGS. 1 and 2, a secondary combustion chamber 27 is provided at a position apart from the heat treatment furnace 3, and the secondary combustion chamber 27 and the heat treatment furnace 3 are connected by an exhaust pipe 28. Further, the exhaust pipe 28 is provided with a fan 29 that sends the unburned gas in the heat treatment furnace 3 to the secondary combustion chamber 27 via the exhaust pipe 28.

The secondary combustion chamber 27 is also heated by the gas burner 34, and combustion air of unburned gas in the secondary combustion chamber 27 is supplied into the secondary combustion chamber 27 via the fan 30. The temperature inside the secondary combustion chamber 27 is measured by the thermometer 32. An exhaust chimney 31 is provided in the secondary combustion chamber 27.

As shown in FIG. 2, the heat treatment furnace 3 side of the exhaust pipe 28 is guided from the center of the ceiling of the heat treatment furnace 3 into the heat treatment furnace 3, and the position of its tip 28 a is the lithium ion battery 50 in the heat resistant container 2. It is set to be lower than the upper surface position of. Here, the position of the tip (lower end) 28a of the exhaust pipe 28 is set to the same position as the height between the third and fourth stages from the top of the lithium ion batteries 50 stacked in the heat-resistant container 2 in four stages. .. In this way, by setting the heat treatment furnace side end 28a of the exhaust pipe 28 lower than the upper surface position of the lithium ion battery 50 in the heat resistant container 2, the hot air flows in the heat treatment furnace 3 from above to below and from below to above. Due to the large convection, the internal battery pack is efficiently carbonized. Therefore, even if a plurality of lithium ion batteries 50 are stacked in the heat-resistant container 2 (four layers in this embodiment), the recycling process can be sufficiently performed, and even if the number of lithium ion batteries 50 to be processed is large. It can be processed in a short time. Further, it can be processed regardless of whether or not the lithium ion battery is discharged.

A damper 33 for adjusting the pressure inside the heat treatment furnace 3 is provided immediately above the heat treatment furnace 3 in the exhaust pipe 28. For example, when the pressure inside the heat treatment furnace 3 increases, the damper 33 opens and the heat treatment furnace 3 The negative pressure inside is maintained. For the damper 33, the butterfly valve or the like shown can be used.

A method for recycling a waste lithium-ion battery using the treatment device 1 for a waste lithium-ion battery having the above configuration will be described.

(1) Information about the specifications of the lithium ion battery 50 is acquired, and the roasting temperature is determined based on the information. That is, if it is a cylindrical type or a rectangular type, it is determined to be 550 to 650° C., and if it is a laminated type, it is determined to be 450 to 550° C.

(2) After performing a pre-purge to discharge the residual gas inside the heat treatment furnace 3 to the outside of the furnace, the gas burner 8 is ignited so that the upper limit of the temperature of the control range of the furnace does not exceed 650° C. The temperature is raised to the temperature determined in 1) and the temperature is kept constant.

(3) The furnace front chamber door 24 is opened and the slide base 21 is advanced to the position of the stand 25 provided outside the furnace front chamber 23 via the base moving device 22. Then, using a crane (not shown), eight used lithium-ion batteries 50 were stored as shown in FIGS. 6 and 7 (in a state in which two sets of four-stage stacks are butted). (Storage) The heat resistant container 2 is placed on the slide base 21 which has been moved to the position of the stand 25.

(4) The slide base 21 is retracted from the position of the stand 25 into the furnace front chamber 23 via the base moving device 22, and the furnace front chamber door 24 is closed.

(5) After opening the furnace body door 7b, the pusher portion 4a of the container carrying device 4 is advanced to put the heat-resistant container 2 into the heat treatment furnace 3. As a result, the heat-resistant container 2 is placed on the hearth 17 of the heat treatment furnace 3 at the 9 o'clock position in FIG.

(6) After retracting the pusher portion 4a of the container transport device 4, the furnace door 7b is closed, and the hearth 17 is rotated leftward by 45° via the hearth rotating device 19. The rotation of 45° is not particularly limited, but for example, by rotating the hearth 17 by 45° every 37.5 minutes, the hearth 17 is set to rotate once in 5 hours. ing.

(7) By repeating the processes of (2) to (6) seven times, as shown in FIG. 1, adjacent heat-resistant containers 2 are spaced at regular intervals on the hearth 17 of the heat treatment furnace 3. In this state, the eight heat-resistant containers 2 are placed in an annular shape.

During the above operation, the heat-resistant container 2 is heated from the outside in the heat-treating furnace 3 while making one revolution, so that the heat-resistant container 2 becomes a reducing atmosphere and is made of the resin of the lithium ion battery 50 stored in the heat-resistant container 2. The plastics such as the case are separated from the material containing useful metals such as lithium, cobalt, nickel and manganese as a carbonized mixture by carbonization. Since the heat-resistant container 2 is heated at a temperature (620° C.) lower than the melting point (660° C.) of aluminum, the aluminum component used in the lithium ion battery 50 does not melt. Further, the electrolytic solution in the battery volatilizes and is discharged into the heat treatment furnace 3 through the exhaust pipe 2g of the heat resistant container 2 together with the gas generated by the thermal decomposition of the combustible substance such as plastic. The two kinds of gas discharged from the exhaust pipe 2g of the heat-resistant container 2 are combustible gases, burn in the heat treatment furnace 3, and are reused as a heat source.

At the time of the heat treatment, the temperature in the heat treatment furnace 3 is controlled by adjusting the oxygen amount of the air supplied through the nozzle 11 so that the flammability released from the exhaust pipe 2g of the heat resistant container 2 into the heat treatment furnace 3 is controlled. The combustion amount of the gas is controlled so that the measured value by the thermometer 13 is within a desired value or range. At this time, since the lid 2B of the heat-resistant container 2 is provided with the exhaust pipe 2g that is open to the peripheral surface of the main body 2n and projects obliquely upward, the organic compound is vigorously burned and the combustion gas is exhausted during the dry distillation of the lithium ion battery 50. Even if the gas is ejected from the tube 2g, the combustion gas is ejected obliquely upward, so that stable eddy combustion inside the heat treatment furnace 3 is not obstructed by the combustion gas, and the thermometer 13 installed near the hearth 17 A typical temperature of the entire furnace can be measured, and stable operation of the heat treatment furnace 3 can be maintained.

On the other hand, when the inside of the heat treatment furnace 3 has a positive pressure, hot gas is ejected from the opening 7a of the heat treatment furnace 3 to the outside of the furnace, which makes it difficult to load and unload the heat resistant container 2 into the heat treatment furnace 3. It is necessary to keep the inside of 3 at a negative pressure. Therefore, the damper 33 is opened and closed according to the measurement value of the pressure gauge 14 to maintain the inside of the heat treatment furnace 3 at a desired value or range. For example, even when the organic compound of the lithium ion secondary battery burns violently and the pressure inside the heat treatment furnace rises sharply during the dry distillation of the lithium ion battery 50, the damper 33 is opened to quickly release the pressure and perform the heat treatment. The negative pressure inside the furnace 3 is maintained. Since the damper 33 is arranged inside the exhaust pipe 28 in the vicinity of the ceiling portion of the heat treatment furnace 3, it is possible to quickly respond to a pressure change inside the heat treatment furnace 3.

The unburned gas in the heat treatment furnace 3 is introduced into the secondary combustion chamber 27 and burns at a temperature (800° C.) higher than the temperature of the heat treatment furnace 3.

(8) When the heat-resistant container 2 makes one round in the heat treatment furnace 3, the furnace body door 7b is opened to advance the pull-out portion 4b of the container transfer device 4 to the position of the heat-resistant container 2, and pull-out as shown in FIG. The claw 4c provided at the tip of the portion 4b is locked to the hanger 2f provided in the heat resistant container 2. Then, the pull-out portion 4b is retracted, the heat resistant container 2 is pulled out from the heat treatment furnace 3, placed on the slide base 21, and the furnace body door 7b is closed.

(9) Next, after opening the furnace front chamber door 24, the slide base 21 on which the heat-treated container 2 that has been subjected to the heat treatment is placed is moved forward to the position of the stand 25 via the base moving device 22. Then, when the furnace front chamber door 24 is half closed in this state and the slide base 21 is returned to the original position, the heat resistant container 2 abuts the half chamber closed front chamber door 24 and is placed on the stand 25. Then, the furnace front chamber door 24 is fully closed.

(10) After that, the heat-resistant container 2 on which the heat treatment has been performed on the slide base 21 that has been moved to the position of the stand 25 is placed on a transfer conveyor (not shown) and conveyed to a cooling chamber (not shown). In (9), the heat-resistant container 2 may be placed on the transfer conveyor and automatically conveyed by contacting the half-closed furnace front chamber door 24. A crane (not shown) is used on the slide base 21 instead of the heat-treated container 2 that has been subjected to the heat treatment, and eight used lithium ion batteries 50 are used. A new heat resistant container 2 in which is stored is installed, and (4) and the following processes are repeated.

Since the hearth rotation device 19 of the heat treatment furnace 3 can freely rotate in the normal direction and the reverse direction, the eight heat-resistant containers 2 on the hearth 17 can be discharged to the outside regardless of the order of charging. That is, by installing a plurality of site holes on the wall surface of the heat treatment furnace 3 and operating the furnace while checking the state of the inside of the furnace, a flame can be seen from the exhaust pipe 2g of the heat resistant container 2 even after a predetermined treatment time has elapsed. In this case, the heat-resistant container 2 charged next is discharged first, so that the processing can be performed without delay. It is expected that various newly developed lithium batteries will behave differently during heat treatment, but the mechanism of the heat treatment furnace 3 that can be freely put in and taken out also supports lithium batteries whose behavior is unknown. An operating method in which the treatment time is finely adjusted is also possible.

The heat-treated container 2 which has been subjected to the heat treatment carried to the cooling chamber is a treatment for crushing and classifying the internal lithium ion battery 50 to remove a carbonized mixture, and then further separating useful metals such as lithium, cobalt, nickel and manganese. Is done. Further, the crushed material of the lithium ion battery 50 is subjected to a magnetic separator to separate it into a magnetic material such as an iron casing and a screw, and a Mick metal composed of copper and aluminum, and the Mick metal is subjected to specific gravity selection to obtain an aluminum lump and a copper lump, After separating into a laminate of copper foil and aluminum foil, it can be further divided into copper foil and aluminum foil by a sorter.

According to the processing apparatus and the processing method of the waste lithium-ion battery configured as described above, the plurality of lithium-ion batteries 50 are stored in the heat-resistant container 2 provided with the exhaust pipe 2g and then placed in the heat treatment furnace 3. Then, the lithium ion battery 50 inside the heat resistant container 2 is dry-distilled by heating from the outside of the heat resistant container 2 to separate the carbonized mixture, so that it can be used as a resin housing of the lithium ion battery 50 or a negative electrode material of the lithium ion battery. The carbon or the like used is separated from the metals containing useful metals as a carbonization mixture. In addition, the heating temperature at that time is set to about 620° C. so that the upper limit of the furnace temperature control range does not exceed 650° C., and aluminum is not melted at a temperature lower than the melting point (660° C.) of aluminum. Therefore, as compared with the case where aluminum is melted out, the treatment for separating the useful metal from the metal containing the useful metal can be easily performed as the subsequent treatment.

At this time, the electrolytic solution in the battery is volatilized, and the volatile gas is discharged from the exhaust pipe 2g of the heat-resistant container 2 into the heat treatment furnace 3, so that the inside of the heat-resistant container 2 naturally becomes a reducing atmosphere, which is different from the conventional technique. Since it is not necessary to introduce a reducing gas or a carbon source into the lithium ion battery 50 and the lithium ion battery 50 is protected by the heat-resistant container 2 in a reducing atmosphere, the risk of exploding the waste lithium ion battery in the heat treatment furnace 3 can be suppressed. You can Further, since flammable substances such as plastic are not burned, temperature runaway can be prevented, and slag formation due to metal oxidation can be suppressed, so that the waste lithium ion battery can be rendered harmless.

Further, since the unburned gas is introduced from the heat treatment furnace 3 into the secondary combustion chamber 27 and burned at a temperature (800° C.) higher than the temperature of the heat treatment furnace 3, generation of odor can be suppressed.

In the present embodiment, the uniform heat treatment is performed by using the heat treatment furnace 3 in which the hearth 17 rotates. However, by heating the heat resistant container 2 from the outside at a temperature lower than the melting point of aluminum, The hearth 17 does not necessarily have to rotate as long as it is a heat treatment furnace that can dry-distill the internal lithium ion battery 50 to separate the carbonized mixture. Further, a plurality of heat-resistant containers 2 are continuously charged into and discharged from the heat treatment furnace 3, but a batch type is also applicable.

Further, the furnace temperature in the heat treatment furnace 3 can be set to 650° C. which is as high as possible within a range in which aluminum is not melted in consideration of the controllable range so that the processing time can be shortened. If the decomposition temperature (300° C.) or higher, the resin material is decomposed and separated from the metal, and is not particularly limited. However, 400° C. or higher, more preferably 500° C. or higher is suitable for the treatment in view of the treatment time.

Further, the heat-resistant container 2 containing the lithium-ion battery 50 is placed in the heat treatment furnace 3 under an oxidizing atmosphere for heat treatment, but it can be applied under a reducing atmosphere or an inert atmosphere.

Further, although the heat treatment furnace 3 using gas as the heat source for the heat treatment is used, various furnaces using electricity or heavy oil as the heat source can also be used. In addition, it is possible to effectively use thermal energy by using exhaust gas from an existing manufacturing facility, for example, a cement burning device as a heat source.

Further, the gas discharged through the exhaust pipe 28 of the heat treatment furnace 3 can be introduced into the preheater of the cement adjusting device at a temperature of 350° C. or higher without being introduced into the secondary combustion chamber 27. As a result, the secondary combustion chamber 27 becomes unnecessary, and the fluoride in the combustion gas can be captured by the cement preparation raw material, and the VOC (volatile organic compound) can also be combusted, and the unburned gas is rendered harmless. You can also According to an experiment in an electric furnace, the concentration of fluoride in the combustion gas can be reduced to about 0.4% and the concentration of hydrogen fluoride to about 0.45% by the cement compounding raw material. There is a reduction effect of about 20 times that when used as an agent.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

[Example 1]
A prismatic waste lithium-ion battery (manufactured by Company A) was subjected to roasting treatment at the temperature and time shown in Table 1 using the waste lithium-ion battery treatment device 1 shown in FIGS. 1 and 2. After the roasting treatment, the metal foils of the positive electrode and the negative electrode were peeled off, and the peeling rate was calculated by the following calculation formula. The calculation results are shown in Table 1.
Peeling rate (%) = (mass of electrode material after roasting and after peeling metal foil)/(weight of electrode material before metal roasting)

[Example 2]
The peeling rate was calculated by performing the same treatment as in Example 1 except that the waste lithium-ion battery was a square-shaped waste lithium-ion battery (manufactured by Company B). The calculation results are shown in Table 1.

[Example 3]
The peeling rate was calculated by performing the same treatment as in Example 1 except that the waste lithium-ion battery was a rectangular waste lithium-ion battery (manufactured by Company C). The calculation results are shown in Table 1.

[Example 4]
The peeling rate was calculated by performing the same treatment as in Example 1 except that the waste lithium-ion battery was a cylindrical waste lithium-ion battery. The calculation results are shown in Table 1.

[Example 5]
The peeling rate was calculated by treating in the same manner as in Example 1 except that the waste lithium-ion battery was a laminated-type waste lithium-ion battery (manufactured by Company D). The calculation results are shown in Table 1.

[Example 6]
The peeling rate was calculated in the same manner as in Example 1 except that the waste lithium-ion battery was a laminated-type waste lithium-ion battery (manufactured by E). The calculation results are shown in Table 1.

[Comparative Examples 1 to 6]
Comparative Examples 1 to 6 were treated in the same manner as in Examples 1 to 6 except that the roasting temperature and time of the waste lithium-ion batteries in Examples 1 to 6 were set as shown in Table 2 below, and the peeling rate was changed. It was calculated. The calculation results are shown in Table 1.

From Table 1 and Table 2, the waste lithium ion batteries (Examples 1 to 4) having a rectangular or cylindrical case shape collect the metal foil at a high peeling rate without embrittlement at a roasting temperature of less than 660°C. We were able to. Also, the laminated type waste lithium ion batteries (Examples 5 and 6) could be recovered without embrittlement up to a roasting temperature of 550° C. and a roasting time of 3 hours. From this, it is understood that the roasting temperature is determined according to the case shape, that is, the strength of the case, and by roasting at that temperature, the metal foil can be efficiently recovered without embrittlement. In all cases, aluminum melted at 660° C. and was integrated with other materials.

1 Waste lithium-ion battery processing device, 2 Heat-resistant container, 2A container body, 2B lid, 2a inner cylinder, 2b outer cylinder, 2c wheel, 2d peripheral surface, 2e handle, 2f hanger, 2g exhaust pipe, 2h ceiling surface, 2j Groove part, 2k lower end, 2m handle, 2n body, 3 heat treatment furnace, 4 container transfer device, 4a pusher part, 4b pullout part, 4c claw, 7 furnace wall, 7a opening, 7b furnace door, 8 (8A to 8D) Gas burner, 11 (11A to 11D) nozzle, 13 thermometer, 14 pressure gauge, 17 hearth, 18 motor, 19 hearth rotating device, 21 slide base, 22 base moving device, 22a motor, 22b shaft, 23 furnace front Chamber, 24 front chamber door, 25 stand, 27 secondary combustion chamber, 28 exhaust pipe, 28a tip, 29 30 fan

Claims (3)

A method of recovering a valuable material from a waste lithium-ion battery, which comprises recovering a valuable material from a roasted product obtained by roasting a waste lithium-ion battery,
Step A for obtaining information on the specifications of the waste lithium-ion battery,
Step B of determining a roasting condition including at least one of a roasting temperature range and a roasting time range based on the acquired information on the specification, and roasting the waste lithium ion battery according to the roasting condition;
Including causing a computer to
The information on the specifications in the step A includes information on the outer shape of the waste lithium-ion battery, and when the outer shape is a prismatic type or a cylindrical type, the upper limit of the roasting temperature range is higher than that when the outer shape is a laminated type. The method of recovering valuables from a waste lithium-ion battery is characterized in that the roasting conditions are determined such that the roasting time becomes higher or the upper limit of the roasting time range becomes longer . In the method of recovering a valuable resource from a waste lithium-ion battery according to claim 1, referring to a database including information about specifications of the waste lithium-ion battery and optimum roasting conditions based on the specifications of the waste lithium-ion battery. A method of recovering valuable materials from a waste lithium-ion battery, characterized by determining roasting conditions. A method of creating a database used in the method for recovering valuable materials from the waste lithium-ion battery according to claim 1 or 2 ,
Steps to obtain information about specifications of waste lithium-ion batteries,
Roasting under a plurality of roasting conditions to two or more waste lithium-ion batteries having the same specifications as the grasped specifications, and determining an optimum roasting condition from the plurality of roasting conditions;
Storing the correspondence relationship between the specifications of the waste lithium-ion battery and the optimum roasting conditions for the specifications in a storage device,
A method of creating a database, comprising causing a computer to execute .