System and method for recovering valuable metals from waste battery

Abstract

Disclosed is a method for recovering valuable metals from a waste battery according to various embodiments of the present invention for realizing the objective described above. The method may include the steps of: performing heat treatment on an object corresponding to a waste lithium ion battery through a heat treatment device; performing a crushing process using a crushing device in correspondence to the object recovered after the heat treatment, to obtain a plurality of recovery bodies; performing a filtering process on the plurality of recovery bodies through a sieving device to obtain a plurality of separation bodies having different particle sizes; performing a leaching process using a leaching device in correspondence to a first one among the plurality of separation bodies to separate lithium carbonate from the first separation body and obtain a valuable metal oxide; performing a pulverizing process on the valuable metal oxide through a pulverization device to refine the valuable metal oxide; obtaining mixed powder from the refined valuable metal oxide through a magnetic separation process using a magnetic separation device; and separating the valuable metal oxide from which the mixed powder has been removed into a plurality of sub-oxides on the basis of the difference in specific gravity between components by using a specific gravity separation device.

Description

System and method for recovering valuable metals from waste batteries

[0001] The present invention relates to a technology for recycling waste resources, and more specifically, to a system and method for improving efficiency and eco-friendliness in terms of equipment, environment, and economy, and for discharging valuable metals recovered from waste batteries by type, thereby increasing the recovery rate and purity of the discharged valuable metals.

[0002]

[0003] As the global movement toward electric vehicles accelerates in line with carbon neutrality declarations, the use of battery packs containing multiple battery cells is increasing, and the need for research on battery recycling methods is also growing.

[0004] Meanwhile, secondary batteries are actively used in portable electronic devices, electric vehicles, and other devices due to their high energy density and minimal self-discharge. Primary batteries are irreversible and non-rechargeable, whereas secondary batteries can be recharged through reversible oxidation and reduction reactions.

[0005] In particular, lithium-ion secondary batteries have a higher energy density than other batteries, allowing for miniaturization and weight reduction, and are used in a variety of applications as medium and large-scale batteries for portable digital devices as well as automobiles and smart grids due to their long lifespan due to high electromotive force and low memory effect.

[0006] As the use of lithium-ion secondary batteries increases, the amount of discarded batteries is also rapidly increasing, and it is estimated that approximately 5.7 million discarded batteries for electric vehicles will be generated before 2040.

[0007] Secondary batteries contain positive electrode recyclable materials including cobalt, nickel, manganese, and lithium, as well as electrode materials such as copper and aluminum, and a liquid electrolyte capable of ion transfer. Therefore, if secondary batteries that have reached the end of their lifespan are discarded as is, valuable metals are lost and waste is discharged into the environment. Therefore, technology to recover valuable metals from secondary batteries that have reached the end of their lifespan is becoming increasingly important in terms of resource conservation and environmental preservation.

[0008] Typically, the process for recovering valuable metals from spent batteries involves a wet process, which involves acid leaching of the raw material and then a multi-step solvent extraction process to recover individual valuable metals, such as nickel, cobalt, and copper. This process is advantageous for small-scale battery processing and yields high-purity materials. However, this method, which separates each valuable metal using solvent extraction, is time-consuming and inefficient when large-scale processing is required. It also generates large amounts of wastewater and waste acid, and can be uneconomical in terms of equipment and costs.

[0009] Accordingly, there may be a demand in the industry for the development of a system that can effectively recover valuable metals from waste batteries in terms of equipment and cost.

[0010] (Prior art literature)

[0011] (Patent Document)

[0012] Republic of Korea Patent Publication No. 10-2011-0116934

[0013]

[0014] Various embodiments of the present invention are intended to solve the above problems, and to provide a system and method for discharging valuable metals recovered from waste batteries by type and increasing the recovery rate of the discharged valuable metals, while having improved efficiency in environmental, facility, and economic aspects.

[0015] The problems to be solved by the present invention are not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the description below.

[0016]

[0017] A method for recovering valuable metals from waste batteries according to various embodiments of the present invention for solving the above-described problems is disclosed. The method may include a step of performing a heat treatment on an object corresponding to a spent lithium ion battery through a heat treatment device, a step of performing a crushing process using a crushing device corresponding to the object recovered after the heat treatment to obtain a plurality of recovered bodies, a step of performing a filtering process on the plurality of recovered bodies through a sieving device to obtain a plurality of separated bodies having different particle sizes, a step of performing a leaching process using a leaching device corresponding to a first separated body among the plurality of separated bodies to separate lithium carbonate (Li2CO3) from the first separated body to obtain a valuable metal oxide, a step of performing a crushing process on the valuable metal oxide through a crushing device to refine it, a step of obtaining a mixed powder from the refined valuable metal oxide through a magnetic separation process using a magnetic separation device, and a step of separating the valuable metal oxide from which the mixed powder has been removed into a plurality of sub-oxides based on a difference in specific gravity between components using a specific gravity separation device.

[0018] In an alternative embodiment, the heat treatment device includes an object input port into which a storage unit containing the object is input, a working unit connected to the object input port and moving the storage unit in a vertical direction, a heating unit provided inside the working unit to heat the object, an object discharge unit located below the working unit to discharge the heated object, and a heating control unit that controls the heating unit, wherein the heating control unit is characterized in that it controls the heating unit based on a preset condition, and the preset condition may include a temperature condition in which a temperature corresponding to the heat treatment is in a range of 875°C to 1100°C.

[0019] In an alternative embodiment, the crushing device includes a conveying unit that conveys the recovered object after the heat treatment in one direction, a crushing unit including a plurality of blades for crushing the heat-treated object conveyed from the conveying unit, and a motor unit that applies power to the crushing unit, and the step of performing the crushing process is characterized in that the plurality of recovered objects are crushed to a preset size, and the preset size may be characterized in that the length of the first side is 2 cm based on a square shape, and the length of the second side different from the first side is 1 cm or more.

[0020] In an alternative embodiment, the sieving device is a device that separates the plurality of recovery bodies by particle size, and includes a recovery body inlet into which the plurality of recovery bodies are input, a sieve portion for separating each of the plurality of recovery bodies, and a plurality of recovery body discharge portions through which each of the plurality of recovery bodies is separated and discharged, and the sieve portion may include a first screen having a plurality of first holes formed therein for passing at least one recovery body among the plurality of recovery bodies, a second screen having a plurality of second holes formed therein for passing at least one recovery body among the plurality of recovery bodies, a screen frame supporting the first screen and the second screen, and a vibration portion for applying vibration to the first screen and the second screen.

[0021] In an alternative embodiment, the size of the first hole is characterized by being larger than the size of the second hole, and the plurality of recovery outlets may include a first recovery outlet for discharging the recovery substance recovered through the first screen, a second recovery outlet for discharging the recovery substance recovered through the second screen, and a third recovery outlet for discharging the recovery substance not recovered through the first screen and the second screen.

[0022] In an alternative embodiment, the leaching device may include a supply tank, a liquid supply portion for supplying liquid into the supply tank, a mixing portion provided inside the supply tank and rotating to mix the liquid and the first separator, a filter portion for filtering a solid material from a mixture corresponding to the liquid and the first separator, and a plurality of leaching discharge portions for discharging each of the solid material and the liquid material constituting the mixture.

[0023] In an alternative embodiment, the first separator is characterized as a separator from which copper and graphite have been removed, and the step of performing a leaching process using a leaching device corresponding to the first separator among the plurality of separators to separate lithium carbonate (Li2CO3) from the first separator and obtain a valuable metal oxide may include a step of obtaining the lithium carbonate by drying a liquid material discharged from the mixture.

[0024] In an alternative embodiment, the crushing device may include a container forming an internal space, balls provided in the container, and a driving unit applying a rotational force to the container, and may be characterized in that the crushing process is performed by causing collision and friction between the precious metal oxide and the balls through rotation of the container.

[0025] In an alternative embodiment, the magnetic separation device includes an oxide inlet into which the finely divided precious metal oxide is introduced, a magnetic field generating unit that generates a magnetic field to obtain the mixed powder from the precious metal oxide, and an oxide discharging unit that discharges the precious metal oxide from which the mixed powder has been removed, wherein the magnetic field generating unit includes a plurality of magnetic field generating modules that generate magnetic fields of different magnitudes, and may be characterized in that the metal powder stage is obtained multiple times by utilizing each magnetic field generating module.

[0026] In an alternative embodiment, the plurality of sub-oxides may include lithium aluminum oxide (LiAlO2), manganese oxide (MnO), and aluminum dross (Al-dross), and the gravity separation device may include a table portion having an inclined surface at a predetermined angle, a vibration supply portion that applies vibration to the table portion, and a plurality of separation discharge portions that are connected to the table portion and discharge each sub-oxide separated by specific gravity.

[0027] Other specific details of the present invention are included in the detailed description and drawings.

[0028]

[0029] According to an embodiment of the present invention, a system and method for recovering valuable metals can be provided that have improved efficiency in terms of equipment and economy, discharges valuable metals recovered from waste batteries by classifying them by type, and increases the recovery rate of the discharged valuable metals.

[0030] The effects of the present invention are not limited to the effects mentioned above, and other effects not mentioned will be clearly understood by those skilled in the art from the description below.

[0031]

[0032] Various aspects are described with reference to the drawings, wherein like reference numerals are used to refer to similar components generally. In the following examples, for purposes of explanation, numerous specific details are set forth to provide a comprehensive understanding of one or more aspects. However, it will be apparent that such aspects may be practiced without these specific details.

[0033] FIG. 1 illustrates an exemplary block diagram of a system for recovering valuable metals from waste batteries according to one embodiment of the present invention.

[0034] FIG. 2 illustrates an overall schematic diagram of a system for recovering valuable metals from waste batteries according to one embodiment of the present invention.

[0035] FIG. 3 is a drawing showing an exemplary flowchart of a method for recovering valuable metals from waste batteries according to one embodiment of the present invention.

[0036] FIG. 4 illustrates an exemplary cross-sectional view of a heat treatment device according to one embodiment of the present invention.

[0037] FIG. 5 illustrates a cross-sectional view of a working section and a discharge section according to one embodiment of the present invention.

[0038] FIG. 6 is a cutaway perspective view illustrating an insertion section according to one embodiment of the present invention.

[0039] FIG. 7 is a drawing showing the object at each of 30 minutes and 40 minutes based on Comparative Example 1 related to one embodiment of the present invention.

[0040] FIG. 8 is a drawing showing the object at each of 30 minutes and 40 minutes based on Comparative Example 2 related to one embodiment of the present invention.

[0041] FIG. 9 is a drawing showing an object at each of 30 minutes and 40 minutes based on Example 1 related to one embodiment of the present invention.

[0042] FIG. 10 is a diagram showing changes in mass and partial pressure of gas according to temperature changes for NCM622 composite pellets related to one embodiment of the present invention.

[0043] FIG. 11 is a drawing showing XRD patterns of an object corresponding to various temperatures related to one embodiment of the present invention.

[0044] FIG. 12 is a diagram showing changes in mass and partial pressure of gas according to temperature changes for NCM811 composite pellets related to one embodiment of the present invention.

[0045] Fig. 13 is a drawing exemplarily showing a shredding device related to one embodiment of the present invention.

[0046] Fig. 14 is a drawing exemplifying a sieving device related to one embodiment of the present invention.

[0047] FIG. 15 is a drawing illustrating an leaching device according to one embodiment of the present invention.

[0048] Fig. 16 is a drawing showing an example of a crushing device related to one embodiment of the present invention.

[0049] Fig. 17 is a drawing exemplarily showing a magnetic separation device related to one embodiment of the present invention.

[0050] Fig. 18 is a drawing exemplifying a gravity separation device related to one embodiment of the present invention.

[0051]

[0052] Various embodiments and / or aspects are now disclosed with reference to the drawings. In the following description, for purposes of explanation, numerous specific details are set forth to provide a thorough understanding of one or more aspects. However, it will be apparent to one skilled in the art that the aspect(s) may be practiced without these specific details. The following description and the accompanying drawings detail specific exemplary aspects of one or more aspects. However, these aspects are exemplary, and any of the various methods within the principles of the various aspects may be utilized, and the description is intended to encompass all such aspects and their equivalents. Specifically, the terms "embodiment," "example," "aspect," and "example" as used herein are not intended to imply that any aspect or design described therein is preferred or advantageous over other aspects or designs.

[0053] Hereinafter, regardless of the drawing numbers, identical or similar components are assigned the same reference numerals, and redundant descriptions thereof are omitted. Furthermore, when describing the embodiments disclosed in this specification, if a detailed description of a related known technology is judged to obscure the gist of the embodiments disclosed in this specification, the detailed description thereof will be omitted. Furthermore, the attached drawings are only intended to facilitate easy understanding of the embodiments disclosed in this specification, and the technical concepts disclosed in this specification are not limited by the attached drawings.

[0054] Although the terms "first," "second," etc. are used to describe various elements or components, these elements or components are not limited by these terms. These terms are merely used to distinguish one element or component from another. Accordingly, it should be understood that a "first element or component" referred to below may also be a "second element or component" within the technical scope of the present invention.

[0055] Unless otherwise defined, all terms (including technical and scientific terms) used herein may be used in their common sense to those of ordinary skill in the art to which the present invention pertains. Furthermore, terms defined in commonly used dictionaries are not to be interpreted ideally or excessively unless explicitly and specifically defined otherwise.

[0056] Furthermore, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or." That is, unless otherwise specified or clear from context, "X employs A or B" is intended to mean either of the natural inclusive permutations. That is, if X employs A; X employs B; or X employs both A and B, "X employs A or B" can apply to any of these cases. Furthermore, the term "and / or" as used herein should be understood to refer to and include all possible combinations of one or more of the associated items listed.

[0057] Additionally, it should be understood that the terms "comprises" and / or "comprising" imply the presence of a given feature and / or component, but do not preclude the presence or addition of one or more other features, components, and / or groups thereof. Furthermore, unless otherwise specified or clear from context to refer to the singular form, the singular form in the specification and claims should generally be construed to mean "one or more."

[0058] When a component is referred to as being "connected" or "connected" to another component, it should be understood that it may be directly connected or connected to that other component, but that there may be other components intervening. Conversely, when a component is referred to as being "directly connected" or "connected" to another component, it should be understood that there are no other components intervening.

[0059] When an element or layer is referred to as being "on" or "on" another element or layer, this includes not only directly on the other element or layer, but also whether or not there are other intervening elements or layers. Conversely, when an element is referred to as being "directly on" or "directly on" the other element or layer, this means that there are no intervening elements or layers.

[0060] Spatially relative terms such as "below," "beneath," "lower," "above," and "upper" may be used to easily describe the relationship between one component or another as depicted in the drawings. Spatially relative terms should be understood to include different orientations of the component during use or operation in addition to the orientation depicted in the drawings.

[0061] The purposes and effects of the present invention, as well as the technical configurations for achieving them, will become clearer with reference to the embodiments described in detail below, along with the accompanying drawings. In describing the present invention, detailed descriptions of known functions or configurations will be omitted if they are deemed to unnecessarily obscure the gist of the invention. Furthermore, the terms described below are defined based on their functions in the present invention and may vary depending on the intentions or practices of the user or operator.

[0062] However, the present invention is not limited to the embodiments disclosed below and can be implemented in various other forms. These embodiments are provided solely to ensure the completeness of the present invention and to fully inform those skilled in the art of the scope of the disclosure. The present invention is defined solely by the scope of the claims. Therefore, such definitions should be based on the contents of this specification.

[0063]

[0064] Figure 1 illustrates a block diagram of a system for recovering valuable metals from waste batteries according to the present invention. Figure 2 illustrates an overall schematic diagram of a system for recovering valuable metals from waste batteries according to one embodiment of the present invention.

[0065] As illustrated in FIG. 1, a system (1000) for recovering valuable metals from waste batteries (hereinafter referred to as the “valuable metal recovery system”) may include a heat treatment device (100), a crushing device (200), a sieving device (300), a leaching device (400), a crushing device (500), a magnetic separation device (600), and a gravity separation device (700). The components of the system for recovering valuable metals from waste batteries illustrated in FIG. 1 are exemplary, and additional components may be present or some of the components illustrated in FIG. 1 may be omitted.

[0066] Referring to FIG. 2, a precious metal recovery system (1000) may include a heat treatment device (100) for heating a spent battery, a crushing device (200) for crushing a result recovered from the heat treatment device (100) into a preset size, a sieving device (300) for separating the result crushed through the crushing device (200) into a plurality of separators according to particle size, a leaching device (400) for performing a leaching process on at least one of the plurality of separators separated through the sieving device (300) to obtain a precious metal oxide, a crushing device (500) for crushing a precious metal oxide, a magnetic separation device (600) for performing a magnetic separation step for classifying a precious metal oxide refined through the crushing device (500), and a gravity separation device (700) for separating a precious metal oxide into a plurality of sub-oxides according to specific gravity. Each device (100, 200, 300, 400, 500, 600 and 700) of the precious metal recovery system (1000) can be combined with each other to perform a unit process for recovering precious metals as a continuous process, and at least one process among each unit process can be performed at least once or can be performed continuously by a plurality of devices.

[0067] In one embodiment, each device constituting the precious metal recovery system (1000) may be designed to perform a unit process in a batch manner. The arrangement between each device may be independent of other devices, and a suitable transport system or logistics system may be combined between these devices to deliver the results of the corresponding unit process.

[0068] In various embodiments, the metal recovery system (1000) may further include a conveying device connecting each device. The conveying device may transport the separated material classified and discharged from the sieving device (300) to the leaching device (400), or may transport the finely divided metal oxides processed in the crushing device to the magnetic separation device (600). This conveying device enables automation of the entire process system, thereby minimizing the input of manpower. A detailed description of the devices constituting the metal recovery system (1000) will be described below with reference to the drawings.

[0069] As illustrated in FIG. 2, the object of the present invention (i.e., a waste battery or a waste lithium ion battery) can sequentially pass through a heat treatment device (100), a crushing device (200), a sieving device (300), a leaching device (400), a crushing device (500), a magnetic separation device (600), and a gravity separation device (700), and valuable metals are recovered according to the results of sequentially passing through each process step. In a specific embodiment, the waste battery heat-treated through a preset heating rate and heat treatment temperature can be crushed into a predetermined size and separated into a plurality of separators through the sieving device (300). In this case, the plurality of separators may mean a first separator, a second separator, and a third separator.

[0070] In a specific embodiment, the first separator may refer to a separator having an intermediate particle size among the crushed objects exceeding a certain size, from which copper and graphite have been removed. The second separator may refer to a crushed object forming a relatively large particle size, from which copper is formed. The third separator may refer to a crushed object forming a relatively small particle size, from which graphite is formed.

[0071] According to an embodiment, the sieving device (300) is configured to classify a target object crushed to a certain size or larger based on the particle size, and as a result, separate the object into a plurality of separated bodies. That is, copper and graphite are obtained based on the classification result of the sieving device (300), and the first separated body from which copper and graphite have been removed is transferred to the leaching device (400).

[0072] The leaching device (400) separates lithium carbonate from the first separator through a leaching process on the delivered first separator. According to an embodiment, the leaching device (400) performs a leaching process related to aqueous leaching treatment using distilled water to separate lithium carbonate (Li2CO3) in a liquid state and a solid valuable metal oxide. The aqueous leaching may utilize a magnetic bar, and the solvent may be distilled water that does not contain impurities. The aqueous leaching time and the ratio of the first separator to the distilled water may be set to optimal conditions in consideration of the reaction between the lithium carbonate and the distilled water. In an embodiment, the higher the ratio of distilled water to the first separator or the longer the aqueous leaching time, the higher the reaction rate of lithium carbonate.

[0073] When the leaching process is performed, lithium carbonate dissolves in water and changes into an aqueous solution, while the first separator remains in a solid powder form. The solution in which the first separator has been stirred can be filtered through a filter, thereby separating lithium carbonate in a liquid state and precious metal oxide in a solid state. A drying process (e.g., spray drying) can be performed on the separated liquid, and as a result of the drying process, lithium carbonate can be recovered in a powder form.

[0074] The solid-state precious metal oxide separated in the leaching process is transferred to a crushing device (500) and can be refined through the crushing process. The refinement of the precious metal oxide may be for the purpose of separating each component constituting the precious metal oxide.

[0075] The finely divided precious metal oxide is transferred to a magnetic separation device (600), and the magnetic separation device (600) obtains a mixed powder through magnetism. The magnetic separation device (600) uses a magnetic field from an electromagnet or a permanent magnet to separate the finely divided precious metal oxide into a mixed powder having magnetism (i.e., a magnetic material) and a non-magnetic material (i.e., a non-magnetic material) from the mixed powder. In one embodiment, the magnetic separation device may include a storage for temporarily storing the residue and a conveyor belt for classifying and transferring the precious metal oxide from the storage into a magnetic material and a non-magnetic material. That is, the magnetic mixed powder is separated from the finely divided precious metal oxide through magnetic separation using the magnetic separation device (600), and the precious metal oxide from which the mixed powder has been removed is transferred to a gravity separation device (700). According to an embodiment, the mixed powder relates to a magnetic metal powder, and may be, for example, Ni-Co powder, but is not limited thereto. In various embodiments, when the waste battery is an NMC battery, the mixed powder obtained in the corresponding process step may be a Ni-Co alloy powder. On the other hand, when the waste battery is an LCO or LFP battery, the mixed powder obtained in the corresponding process step may include at least one of Ni, Co, Fe, Fe-C, and Fe-P. In other words, the type of mixed powder obtained in the corresponding process step may vary depending on the type of waste battery from which valuable metals are recovered.

[0076] The gravity separation device (700) can separate the precious metal oxide from which the mixed powder has been removed into a plurality of sub-oxides through gravity-based separation. In one embodiment, the plurality of sub-oxides may include first to third sub-oxides, and each of the first to third sub-oxides may be related to lithium aluminum oxide (LiAlO2), manganese oxide (MnO), and aluminum dross (Al-dross), respectively. In a specific embodiment, the gravity separation device (700) can separate and discharge the precious metal oxide from which the nickel-cobalt powder has been removed into lithium aluminum oxide (LiAlO2), manganese oxide (MnO), and aluminum dross (Al-dross), respectively, based on their specific gravity.

[0077] That is, as the waste battery sequentially passes through the process steps corresponding to each device of the precious metal recovery system (1000) of the present invention, precious metals are obtained. Specifically, in the sieving process step, graphite and copper are separated and recovered, and in the leaching process step, lithium carbonate can be recovered. In addition, in the magnetic separation process step, a mixed powder related to the magnetic body is obtained, and in the gravity separation process step, a plurality of sub-oxides (e.g., aluminum oxide, manganese oxide, and aluminum dross) are obtained.

[0078] The precious metal recovery system (1000) of the present invention has the advantage of sequentially classifying and obtaining the results through the process sequence described above, and can improve the recovery rate of the material through mutually complementary process steps.

[0079] For example, if the crushing process is omitted and the process proceeds to the sieving process after the heat treatment, the powder mixed from the copper is not easily separated, making it difficult to separate the copper, graphite, and oxides. This can ultimately reduce the recovery rate of copper and graphite, and ultimately affect the recovery rate of cobalt, nickel, aluminum oxide, manganese oxide, and aluminum dross that are ultimately discharged. For another example, if the magnetic separation process is not performed before the gravity separation process for gravity separation, and the magnetic material is not separated from the precious metal oxide, it is difficult to distinguish each oxide by type during gravity separation, and nickel and cobalt may be separated into their respective oxides, which can lower the recovery rate of each metal. The precious metal recovery system (1000) of the present invention can maximize the recovery rate of the precious metal by sequentially going through the aforementioned process steps.

[0080] A more specific description of each device constituting the configuration and system that increases the recovery rate of precious metals through the sequential process order of the precious metal recovery system (1000) of the present invention will be described later with reference to FIGS. 3 to 18.

[0081]

[0082] FIG. 3 is a drawing showing an exemplary flowchart of a method for recovering valuable metals from waste batteries according to one embodiment of the present invention.

[0083] According to one embodiment of the present invention, a method for recovering valuable metals from waste batteries may include the process steps illustrated in FIG. 3. The steps illustrated in FIG. 3 may be rearranged in order as needed, and at least one step may be omitted or added. In other words, the following steps are merely exemplary of the present invention, and the scope of the present invention is not limited thereto.

[0084] According to one embodiment of the present invention, a method for recovering valuable metals from waste batteries may include a step (S100) of performing heat treatment on an object corresponding to a waste lithium ion battery through a heat treatment device (100). A more specific description of the heat treatment device (100) will be described below with reference to FIGS. 4 to 12.

[0085] A heat treatment device (100) may include an object input port (110) into which a storage unit (20) containing an object is input, a work unit connected to the object input port (110) and vertically moving the storage unit (20), a heating unit (130) provided inside the work unit to heat the object, an object discharge unit (150) located at the bottom of the work unit to discharge the heated object, and a heating control unit that controls the heating unit (130).

[0086] A heat treatment device (100) according to the present invention, as illustrated in FIG. 4, is for obtaining necessary raw materials (i.e., valuable metals) by heating a storage unit (20) containing an object corresponding to a waste lithium ion battery, and includes an object input port (110) for waiting to input the storage unit (20) into a work unit, a work unit for positioning the storage unit (20) and performing a heating operation, and an object discharge unit (150) for taking out the storage unit (20) for which the firing operation has been completed from the work unit.

[0087] The target object insertion port (110) includes an insertion section (111) for inserting the storage section (20) into the interior and a waiting section for the storage section (20) inserted into the interior to wait before being inserted into the work section.

[0088] The working section of the present invention is composed of a first working section (121), a second working section (122), and a third working section (123) arranged in the vertical direction.

[0089] The storage unit (20) containing the object is fed into the working unit through the object input port (110), and in this process, a fixed position arrangement and exhaust process for easier firing can be performed.

[0090] The storage unit (20) is moved from the object input port (110) to the work unit, and a vertical heating process is applied while passing through the first work unit (121), the second work unit (122), and the third work unit (123) sequentially.

[0091] The heated storage unit (20) is moved from the work unit to the object discharge unit (150), refined through the injection of a designated gas, cooled through the injection of a cooling gas, and discharged to the outside.

[0092] In the process of processing an object loaded in the storage unit (20) through the above configurations, the heating control unit controls the operation of the object input port (110) and the working unit, and this can be implemented in various ways, such as adjusting the temperature increase speed within the working unit, adjusting the gas partial pressure, and operating the components within the object input port (110) and the object discharge unit (150). Here, the heating control unit can control at least one of the temperature increase speed and the temperature increase time targeting the heating unit.

[0093] The target material input port (110) is connected to the work section and is configured to supply the storage section (20), and includes an insertion section, a waiting section, and a first opening / closing section.

[0094] Referring to Fig. 4, the working section is configured to provide a space for heating an object while the storage section (20) is placed inside. To this end, the working section is formed in a cylindrical shape with vertical openings, and a heating section, a refractory section, and a temperature measuring section (124) are placed inside to induce the object and the storage section (20) to be heated together. In addition, the working section is composed of a first working section (121), a second working section (122), and a third working section (123), which are arranged vertically.

[0095] The first working section (121) provides a space for performing an initial heating process on the storage section (20) introduced from the waiting section. To this end, the first working section (121) is provided with a first internal temperature, and a second working section (122) is provided in the lower direction, and the first working section (121) and the second working section (122) are connected to each other. The second working section (122) is located below the first working section (121) and has a second internal temperature, thereby performing a process of secondary heating the storage section (20). The second working section (122) is connected to the first working section (121) and the third working section (123), respectively. The third working section (123) is provided below the second working section (122), and a process of secondary heating the storage section (20) with the third internal temperature is performed.

[0096] As another embodiment of the present invention, a mooring unit positioned below the third working section (123) may be further included. The mooring unit is configured to temporarily moor the heated object and storage section (20) through the first working section (121) to the third working section (123) to prevent unintended thermal deformation. To this end, the mooring unit is configured in the same form as the first working section (121) to the third working section (123), but does not include a heating section, which will be described later. Therefore, natural cooling can be induced without additional heating of the object and storage section (20).

[0097] The heating unit is a means installed in the work section to heat the object and the storage section (20), and more specifically, it is a configuration for melting the object. To this end, the heating unit may be configured with a SIC heater capable of generating heat at a high temperature, but is not limited thereto. The heating unit may be an induction heating device supplied with high and low frequency power. For example, the heating unit may be configured with an induction heating device using a metal coil such as copper. However, the heating unit is not limited thereto, and may include a suitable heating device (e.g., a furnace or an electric furnace capable of mass processing) capable of stably increasing the temperature and maintaining the temperature.

[0098] According to one embodiment, the heating unit may be provided with a plurality of heating units that perform different temperature controls according to the height of the working unit. The heating unit is composed of a first heating unit (131), a second heating unit (132), and a third heating unit (133), and is respectively disposed inside the first working unit (121), the second working unit (122), and the third working unit (123). Here, the first heating unit (131), the second heating unit (132), and the third heating unit (133) can be independently or integrally driven by a heating control unit to be described later to heat the object and the storage unit (20) to the first internal temperature, the second internal temperature, and the third internal temperature.

[0099] As another embodiment of the present invention, at least one of the first heating unit (131), the second heating unit (132), and the third heating unit (133) may be configured in multiple units and arranged to have a circular arrangement centered on a central axis in the vertical direction of the working unit. Accordingly, it is possible to reduce the amount of heating units used and to create a uniform first internal temperature, second internal temperature, and third internal temperature. In addition, the first heating unit (131), the second heating unit (132), and the third heating unit (133) may be driven independently or integrally by the heating control unit.

[0100] The refractory portion is configured to prevent the heating portion from being deteriorated by the object being heated within the working portion and to prevent rapid changes in internal temperature. To this end, the refractory portion is arranged to surround or be close to the heating portion, as illustrated in Fig. 5. The refractory portion is provided for the first heating portion (131), the second heating portion (132), and the third heating portion (133), and is configured as the first refractory portion (141), the second refractory portion (142), and the third refractory portion (143) depending on the arrangement position.

[0101] The first refractory section (141) is configured to protect the inner direction of the heating section, which is provided in multiple units. Specifically, the first refractory section (141) is positioned in the inner direction toward the central axis of the first working section (121), the second working section (122), and the third working section (123) with respect to the first heating section (131), the second heating section (132), and the third heating section (133). That is, the first refractory section (141) is positioned to correspond to the portions facing inward of the first heating section (131), the second heating section (132), and the third heating section (133), thereby preventing the heating section from being deteriorated by foreign substances during the heating process of the object.

[0102] The second refractory section (142) performs the same role as the first refractory section (141) described above, but is provided to surround the first heating section (131), the second heating section (132), and the third heating section (133). For example, when the first heating section (131) to the third heating section (133) have an arc cross-section, the cross-section of the second refractory section (142) has a shape that accommodates the arc cross-section to surround it. Accordingly, the second refractory section (142) can not only prevent deterioration from foreign substances entering from all directions, but also prevent deterioration due to radiant heat.

[0103] The third refractory section (143) performs the same role as the first refractory section (141) and the second refractory section (142) described above, but is arranged in the outer direction of the first heating section (131), the second heating section (132), and the third heating section (133). Accordingly, it has a horizontal cross-sectional arrangement structure in which the first refractory section (141), the heating section, the second refractory section (142), and the third refractory section (143) are sequentially arranged in order of proximity from the central axis of the working section.

[0104] The temperature measuring unit (124) measures the temperature of the working unit or heating unit, and based on this, the heating control unit, which will be described later, controls the internal temperature of the working unit. To this end, the temperature measuring unit (124) may be located within the working unit. Here, the temperature measuring unit (124) may be installed in combination with a separate deterioration prevention means that is not damaged by high temperatures as a separate temperature sensing means.

[0105] The temperature measuring unit (124) is provided between the first working unit (121) and the second working unit (122), between the second working unit (122) and the third working unit (123), and in the lower direction of the third working unit (123). Accordingly, each temperature measuring unit (124) can measure the internal temperature of the first working unit (121), the second working unit (122), and the third working unit (123).

[0106] As another embodiment of the present invention, the temperature measuring units (124) may be installed in the first working unit (121) to the third working unit (123), and may all have the same installation location. That is, the temperature measuring units (124) installed in the first working unit (121) to the third working unit (123) respectively have the same horizontal distance from the central axis of the working unit and the same vertical separation distance from each other. Accordingly, the occurrence of thermal measurement errors can be minimized when each temperature measuring unit (124) measures the internal temperature of the working unit.

[0107] The object discharge unit (150) is a configuration for discharging the object from the work unit and is located in the lower direction of the work unit. Accordingly, the object input port (110), the work unit, and the object discharge unit (150) are connected to each other and have a vertical heating structure, which has the effect of facilitating the movement of the object and the gas required to heat the object, compared to a conventional horizontal heating structure.

[0108] In addition, in the object discharge unit (150), gas for heating the object is initially injected, and the gas (predetermined gas) moves upward to induce plasticity of the object, and then moves to the object injection port (110) and is discharged.

[0109] The object discharge unit (150) includes a vertical moving unit (151) for taking out the object, a second pressurized moving unit (152) for moving the object under pressure, a gas supply unit (153) for injecting a designated gas, a second opening / closing unit (154) for partitioning an internal space, a second gas discharge unit (155) for ventilating the space partitioned by the second opening / closing unit (154), and a cooling unit (156) for cooling the object.

[0110] The vertical movement unit (151) is configured to move the position of the object from the inside of the work section to the inside of the object discharge section (150), and moves the storage section (20) containing the object and the object in the vertical direction while supporting it. To this end, the vertical movement unit (151) may be configured as a multi-stage support means whose length in the vertical direction can be adjusted using electricity or hydraulic pressure, and the upper end may be configured in the shape of a plate for more solid contact with the storage section (20). After the storage section (20) with the object placed inside is heated by the heating section inside the work section, the storage section (20) moves downward as one unit with the vertical movement unit (151).

[0111] The second pressurized moving part (152) is configured to pressurize and move an object placed in the internal space of the object discharge part (150) and a storage part (20) containing the object, and is provided in the same manner as the first pressurized moving part (111a) described above.

[0112] The gas supply unit (153) is configured to inject a predetermined gas for the purpose of sintering the object into the object discharge unit (150), and is configured as a separate injection means including a pump that induces the movement of a fluid such as a gas, but is not limited thereto. Here, the predetermined gas is provided as at least one of carbon monoxide, carbon dioxide, and argon that can induce heat treatment of the object while creating an inert gas atmosphere.

[0113] The second opening / closing section (154) is configured to divide the internal space of the object discharge section (150) into two or more, and to use each internal space for the purpose of holding the storage section (20) and cooling the storage section (20), and has the same configuration as the first opening / closing section (113) described above.

[0114] By closing the second opening and closing section (154), the interior space of the work section can be divided into a holding space connected to the working section and a post-processing space disconnected from the working section. The gas supply section (153) described above is formed corresponding to the holding space, and the post-processing space can be equipped with a second gas target discharge section (150) and a cooling section (156).

[0115] The second gas discharge unit (155) is configured to ventilate at least one of the partitioned internal spaces of the object discharge unit (150), and may be configured as a discharge module including a discharge pump, but is not limited thereto. When the second opening / closing unit (154) described above is opened, the second gas discharge unit (155) can ventilate all internal spaces of the object discharge unit (150). Additionally, when the second opening / closing unit (154) is closed, the second gas discharge unit (155) can ventilate only the internal air of the post-processing space.

[0116] The cooling unit (156) is configured to cool the object and storage unit (20) placed in the post-processing space, and is configured with a spraying means capable of spraying a gas having a predetermined temperature. The object and storage unit (20) are cooled by air cooling, thereby preventing damage such as unintended cracks. Here, the predetermined temperature is configured to be 50 to 100 degrees Celsius or lower, but may be configured to be a temperature that decreases by 10 degrees Celsius per hour, but is not limited thereto.

[0117] A space is secured between the upper and lower storage sections (20) into which a fixing section (160) can be inserted. The fixing section (160) prevents the vertical position of the storage section (20) containing the object and heated as a whole from being unintentionally changed. To this end, the fixing section (160) is configured in the form of a plate that is positioned downward of the storage section (20) inside the working section and has a structure in which the upper surface is in contact with the lower surface of the storage section (20). In addition, in order to more firmly fix the height of the storage section (20), the fixing sections (160) may be provided in multiple pieces and arranged in a circular arrangement centered on the central axis of the working section.

[0118] The fixing member (160) is additionally provided and arranged in the upper direction of the storage member (20), thereby enabling height fixation with respect to another storage member (20) located in the upper direction. In order to create a structure for easier injection of a designated gas and air circulation within the storage member (20), an insertion plate member (161) is further included, and the insertion plate member (161) further includes a first inlet hole (161a), a second inlet hole (161b), and a fixing auxiliary member (161c). A more detailed description thereof will be provided later.

[0119] The heating control unit controls the operation of the heating unit, and can control the internal temperature of the working unit while connected to a temperature measuring unit (124) that measures the temperature of the heating unit.

[0120] The temperature measuring unit (124) located inside the working unit measures the first temperature, the second temperature and the third temperature corresponding to the first working unit (121), the second working unit (122) and the second working unit (122), respectively, and the heating control unit compares the measured first temperature, the second temperature and the third temperature with the first internal temperature, the second internal temperature and the third internal temperature specified in advance.

[0121] First, the heating control unit compares the second temperature and the second internal temperature, and controls the operation of the second heating unit (132) based on the comparison result.

[0122] When the second temperature is greater than the second internal temperature, the heating control unit calculates the heating rate of the second heating unit (132) and controls the operation of the heating unit to heat the object according to the predetermined optimal heating rate.

[0123] When the second temperature is the same as the second internal temperature, the heating control unit controls the second heating unit (132) to continuously heat the object at the optimal heating rate.

[0124] When the second temperature is lower than the second internal temperature, the heating control unit calculates the heating rate of the second heating unit (132) and controls the operation of the second heating unit (132) so that the calculated heating rate matches the optimal heating rate. Here, after the second heating unit (132) is driven so that the heating rate of the second heating unit (132) is greater than the optimal heating rate for a predetermined time (e.g., 10 seconds), by controlling the heating rate of the second heating unit (132) so that it matches the optimal heating rate, cracking and reduction of the object can be more easily induced.

[0125] After the operation control of the second heating unit (132) based on the comparison of the second temperature and the second internal temperature as described above, the heating control unit controls the operation of the first heating unit (131) in the same manner based on the result of comparing the first temperature and the first internal temperature, and can then control the operation of the third heating unit (133) in the same manner based on the result of comparing the third temperature and the third internal temperature.

[0126] The reason for controlling the internal temperature of the second working section (122) among the first working section (121) to the third working section (123) first is to maximize the thermal efficiency of the second working section (122) where the object is heated and reduced first.

[0127] When the need for preheating of the object is high, the control of the first heating unit (131) is performed after adjusting the internal temperature of the second working unit (122), and when the need for reduction of the object is higher, the control of the third heating unit (133) may be performed first after the control of the second heating unit (132). In various embodiments, the first heating unit (131) may perform temperature control for preheating, and the third heating unit (133) may perform temperature control for reduction. That is, the order of the control of the first heating unit (131) or the control of the third heating unit (133) may vary depending on the input amount and input type of the object.

[0128] By controlling the operation of each heating unit based on the temperature measured for each of the first working unit (121), the second working unit (122), and the third working unit (123), it is possible to prevent the thermal efficiency of the target object from being reduced in advance.

[0129] The heating control unit creates and controls the working environment of the work unit during the process of heating the object to recover valuable metals composed of at least one of cobalt (Co), nickel (Ni), manganese (Mn), and lithium (Li). Specifically, the heating control unit controls the operation of the gas supply unit (153) described above to induce a predetermined gas to be introduced into the interior of the object discharge unit (150). Thereafter, the predetermined gas moves along the work unit located upward from the object discharge unit (150), and during the movement process, it comes into contact with the object to create a reducing gas atmosphere.

[0130] The above-described working section, including the first working section (121) to the third working section (123), heat-treats the object under a pre-specified mixed reducing gas atmosphere, which is determined based on the partial pressure of carbon dioxide and carbon monoxide contained in the pre-specified gas. Here, when carbon monoxide is generated during the heat treatment process targeting the object, the partial pressure within the working section can be set by reflecting the generated carbon monoxide.

[0131] Here, the heating control unit can supply a predetermined gas through the gas supply unit (153) or exhaust the gas through the first gas discharge unit (112c) so that the logarithm of the partial pressure of carbon monoxide divided by the partial pressure of carbon dioxide, log(PCO2 / PCO), falls within a range of -2.15 to 2.5 or less. Specifically, the logarithm based on the division value of the partial pressure between carbon monoxide and carbon dioxide (log(PCO2 / PCO)) falls within a range of -2.15 to 2.5, but is adjusted so that the logarithm decreases as the internal temperature of the working unit increases.

[0132] When the first internal temperature, the second internal temperature or the third internal temperature corresponding to the first working section (121), the second working section (122) and the third working section (123) respectively correspond to at least one of 500 to 600 degrees Celsius, 600 to 700 degrees Celsius, 700 to 800 degrees Celsius, 800 to 900 degrees Celsius and 900 to 1000 degrees Celsius, the heating control unit additionally injects a gas designated in advance through the gas object inlet (110) and the first gas discharge unit (112c) so that the aforementioned logarithmic value falls within at least one of the ranges of 0.45 to 2.50, -0.20 to 2.15, -0.90 to 1.85, -1.55 to 1.60 and -2.15 to 1.40, or Control emissions.

[0133] For example, the heating control unit can suppress carbon generation by adjusting the amount of carbon dioxide included in the designated gas to be sufficiently large during the heat treatment process of the target object, and shorten the heat treatment process time by adjusting the amount of carbon dioxide contained in the designated gas to be sufficiently large.

[0134] When the amount of the injected designated gas is excessive, the heating control unit can open the first gas discharge unit (112c) formed in the object inlet (110) to exhaust it. Before that, in order to minimize the pressure gradient that may occur during the exhaust process of the designated gas in the internal space of the object inlet (110), the exhaust process inside the object inlet (110) by the pressure maintenance unit (112d) may be performed before or in parallel.

[0135] In addition, the present invention may include a method of pretreating an object equipped with a waste lithium ion battery, performing a first heat treatment, separating a valuable metal, and performing a second heat treatment.

[0136] Pretreatment of waste batteries is performed for the purpose of preventing explosion or rendering them harmless, removing foreign substances such as outer cans, etc. For example, used waste batteries are stored in a sealed system and contain substances such as electrolytes inside, so there is a risk of explosion during crushing. Accordingly, process safety can be enhanced and the recovery rate of valuable metals such as copper, nickel, and cobalt can be increased by discharging waste batteries and removing electrolytes. Discharging waste batteries can be performed by immersing the waste batteries in an aqueous solution containing alkali metal or alkaline earth metal ions, but the type of the aqueous solution is not limited thereto.

[0137] Afterwards, the target object can be subjected to the first heat treatment by being placed in the storage unit to be described later and fed into the working unit (120) through the target input port (110). If the working unit (120) has an input port formed on one side and an exhaust port provided on the other side, it can be used without any special restrictions, and it can be configured as a vertical working unit (120) that can be fed and exhausted up and down, or it can also be configured as a working unit of another connected type. The heat source may be a gas burner, a coal burner, a resistance heater, or an IR lamp, but is not limited thereto. Meanwhile, after the first heat treatment is completed, the storage unit can be equipped with targets such as Me (M = Co or Ni, or Mn) or MeO (M = Co or Ni, or Mn) and Li2CO3 and LiAlO2, Graphite (C) and Al, Cu.

[0138] In the first heat treatment process, a designated gas (mixed gas) is introduced into the work section (120), and heat treatment can be performed under a mixed gas atmosphere of carbon monoxide and carbon dioxide. The temperature in the heat treatment process is determined according to the type and shape of the battery, and can be adjusted so that log(PCO2 / PCO) decreases as the heat treatment temperature increases in the heat treatment step. For example, a pouch-type waste battery containing lithium nickel cobalt manganese oxide or lithium cobalt oxide as a cathode active material is heat treated at a temperature of 650 to 850 degrees Celsius, and at this time, the heat treatment can be performed under a mixed reducing gas atmosphere of carbon dioxide and carbon monoxide adjusted so that log(PCO2 / PCO) becomes a value within a range of -1.20 or more and 2.00 or less.

[0139] In addition, when the heat treatment temperature is 500 to 600 degrees Celsius, 600 to 700 degrees Celsius, 700 to 800 degrees Celsius, 800 to 900 degrees Celsius, or 900 to 1,000 degrees Celsius, log(PCO2 / PCO) can be adjusted to have a value within the range of 0.45 to 2.50, -0.20 to 2.15, -0.90 to 1.85, -1.55 to 1.60, or 2.15 to 1.40, respectively (see Table 1). Through this, it is possible to shorten the time required for the heat treatment process while suppressing the generation of carbon due to the input of the mixed gas and the heat treatment.

[0140] [Table 1] Maximum and minimum values ​​of log(PCO2 / PCO) according to heat treatment temperature

[0141]

[0142] After the first heat treatment as described above, a second heat treatment may be performed to remove residual carbon. Here, the internal temperature of the work section (120) is controlled to provide a temperature environment of 700 degrees Celsius or higher. Through this, any remaining carbon can be easily removed, and any carbon monoxide that may be formed can be utilized for the first heat treatment. After the second heat treatment, the target object may be composed of Me (M = Co or Ni, or Mn) or MeO (M = Co or Ni, or Mn), and Li2CO3 and LiAlO2, and Al-dross, Ni-Co alloy powder, Cu, residual carbon, etc.

[0143] After the first and second heat treatments as described above are completed, valuable metals can be recovered according to the physical properties of the target material. The target material composed of magnetic metal is subjected to selective separation using a magnetic field, and in the case of ash, it is classified by particle size through sieving using an airflow classifier, centrifugal principle, vibration, etc. In addition, Li2CO3 and LiAlO2, which are Li-rich phases, can be recovered through a leaching process using water or acid, and the separation process can be performed before or after the second heat treatment according to the purpose. That is, valuable metals can be separated and obtained through at least one of a separation process using classification, a separation process using magnetism, and a separation process using leaching using acid or water.

[0144] Through a series of methods as described above, valuable metals can be recovered in four groups: alloy-type metals containing at least one of nickel, cobalt, and manganese that are magnetic; non-magnetic Al-dross when the outer can (case) of a spent battery is made of aluminum; lithium carbonate recovered using the water leaching method; MnO and LiAlO2; and residual carbon that is not oxidized in the second heat treatment process.

[0145]

[0146] FIG. 6 is a cutaway perspective view illustrating an insertion section according to one embodiment of the present invention.

[0147] The insertion section (111) provides a space for moving the storage section (20) closer to the work section. To this end, the insertion section (111) includes a first pressurized moving section (111a) that pressurizes and moves the storage section (20) and a first guide section (111b) that guides the storage section (20) to a fixed position, and is provided in a box shape that is connected to the standby section through the opening and closing of the first opening and closing section (113).

[0148] The first pressurized moving part (111a) is configured to move the storage part (20), and moves the storage part (20), which has been moved from the outside to the inside of the object insertion port (110), so as to approach the working part. Here, the movement of the storage part (20) is achieved through the push of the first pressurized moving part (111a). To this end, the first pressurized moving part (111a) may be provided with a hydraulic or electric pusher that receives driving force from a separate driving means and pressurizes and moves the pipe part at the end, but is not limited thereto. The first pressurized moving part (111a) may be configured to face from the outside of the insertion section (111) so as to approach the working part for easy pressurized movement of the storage part (20).

[0149] The first guide part (111b) provides a path for more accurate guide movement during the movement of the storage part (20) by the first pressurized moving part (111a). To this end, the first guide part (111b) is formed inside the insertion section (111), protrudes upward from the lower surface of the insertion section (111), and is formed in the longitudinal direction toward the waiting section and the working section.

[0150] The first guide portion (111b) is formed so as to be insertable into the lower guide groove (25b) formed in the body portion (21) of the storage portion (20). Specifically, the cross-sectional shape of the first guide portion (111b) is formed so as to be engageable with the cross-sectional shape of the lower guide groove (25b). Through this, when the first guide portion (111b) is engaged with the lower guide groove (25b), the storage portion (20) can move in the longitudinal direction of the first guide portion (111b).

[0151] As another embodiment of the present invention, the first guide portion (111b) may be configured in a wedge shape with a triangular cross-section. This allows for easier guided movement of the storage portion (20), and prevents the storage portion (20) from being separated from the first guide portion (111b) during the guiding process. Meanwhile, a second guide portion (112b-1) having the same shape as the first guide portion (111b) as described above may be arranged in the upper direction of the moving partition portion (112b) located inside the waiting section.

[0152]

[0153] The heating control unit according to the present invention controls at least one of the heating rate and heating time of the heating unit, thereby inducing activation of a crack phenomenon that subdivides the object.

[0154] The heating control unit stores information related to a predetermined heating rate in advance, and the heating control unit controls the temperature increase rate of the heating unit based on the information related to the heating rate. Here, the heating rate of the heating unit can be confirmed through Comparative Examples 1 and 2 and Example 1 below. In addition, the amount of the target object to be injected, the type of the object to be injected, the heating method of the target object, the heating time, and the analysis method for measuring the optimal heating rate of the heating unit are the same, and the degree of reduction of the target object is compared by changing the heating rate.

[0155] Comparative Example 1

[0156] After placing the object inside the working section, the heating section's heating rate was set to 20 k / min to heat the object, and 30 and 40 minutes after the start of heating the object, samples were recovered from the object and SEM-BSE analysis was performed. The analysis results of Comparative Example 1 above are as shown in Fig. 7 (a) and (b). Here, the operating temperature for recycling the object is set to 850 degrees Celsius, which is equally applied to both Comparative Example 2 and Example 1.

[0157] After 30 minutes from the heating part's temperature rise, in a heating rate environment of 20 k / min, crack information on the target object is weak, as shown in Fig. 7 (a). Correspondingly, as shown in Fig. 7 (b), after 40 minutes, it can be confirmed that the degree of reduction of the target object is also weak.

[0158] Comparative Example 2

[0159] After placing the object inside the working section, the heating section's heating rate was set to 30 k / min to heat the object, and 30 and 40 minutes after the start of heating the object, samples were recovered from the object and SEM-BSE analysis was performed. The analysis results of Comparative Example 2 are as shown in (a) and (b) of Fig. 8.

[0160] As shown in (a) of Fig. 8, after 30 minutes from the temperature increase targeting the object, it can be confirmed that more cracks have occurred in the object compared to Comparative Example 1, and as shown in (b) of Fig. 8, it can be confirmed that more reduction has occurred in the object after 40 minutes.

[0161] Through this, it can be confirmed that when heating an object at a faster temperature increase rate than in Comparative Example 1, the object must sufficiently break to allow a designated gas composed of a reducing gas to be injected into the interior of the object.

[0162] Example 1

[0163] After placing the object inside the working section, the heating section's heating rate is set to 22 K / min to heat the object, and after 30 minutes and 40 minutes, a sample is recovered from the object and SEM-BSE analysis is performed. The analysis results are as shown in (a) and (b) of Fig. 9.

[0164] Referring to (a) of Fig. 9, it can be seen that more cracks occur in the object compared to Comparative Example 1, and that there is no significant difference from Comparative Example 2. In addition, referring to (b) of Fig. 9, it can be seen that more reduction occurs in the object compared to Comparative Example 1, and that the difference from Comparative Example 2 is minimal.

[0165] Through this, it can be confirmed that the optimal heating rate for the target object is configured to be 22 K / min or higher. In Comparative Example 1, the recovery rate of cobalt that can be recovered from the target object is 70%, but in Example 1, the recovery rate of cobalt is confirmed to be 95%.

[0166] The heating control unit controls the temperature increase of the heating unit for a heating time based on the optimal heating rate as described above, thereby inducing the designated gas to easily be reduced by penetrating into the interior of the object.

[0167]

[0168] Hereinafter, with reference to FIGS. 10 to 12, the heating treatment conditions for obtaining valuable metals from waste batteries will be described.

[0169] According to one embodiment of the present invention, a storage unit (20) containing an object can be inserted through the object insertion port (110) of the heat treatment device (100). More specifically, the storage unit (20) can be inserted into the insertion section (111), moved to the work section via the waiting section, and heat treatment is performed in the work section.

[0170] According to various embodiments, the heat treatment device (100) may include a work section that performs a heat treatment operation on a target object. In an embodiment, the work section may be characterized by having a vertical structure that moves each of one or more storage sections in a vertical direction.

[0171] The working unit may include a sensor module for measuring the type and partial pressure of the internal gas.

[0172] In one embodiment, the heat treatment device (100) may be characterized by performing heat treatment on an object based on preset conditions. According to an embodiment, the heating control unit may perform control related to determining a heating temperature within the working unit, adjusting the heating speed, and adjusting the gas partial pressure.

[0173] In one embodiment, the heating control unit may control the heating unit to perform heat treatment on the object based on preset conditions. Here, the preset conditions may include a temperature condition corresponding to the heat treatment, such as a temperature range of 875°C to 1050°C.

[0174] For example, the heating control unit can control the heating unit to maintain the internal temperature of the working unit at 900°C.

[0175] For another example, the heating control unit can control the heating rate of the working unit to 22 K / min or higher. In other words, the heating control unit can induce active reduction of the target object by controlling the temperature increase of the heating unit for a heating time based on the optimal heating rate.

[0176] As another example, the heating control unit may perform heat treatment under a mixed reducing gas atmosphere of carbon dioxide and carbon monoxide adjusted so that log(PCO2 / PCO) is a value within a range of -1.20 or more and 2.00 or less.

[0177] In a specific embodiment, the heating control unit may be characterized by performing a heat treatment on the object based on preset temperature conditions. The preset temperature conditions relate to a temperature range for maximizing the recovery rate of valuable metals, and may mean heat treating the object within a range of 875°C to 1050°C.

[0178] More specifically, if a graph is displayed by performing thermogravimetry (TG) and differential thermogravimetry (DTG) corresponding to an NCM composite pellet, it may be as in Fig. 10. In an embodiment, the NCM composite pellet may mean an NCM622 composite pellet including an NCM622 cathode material and black powder at a ratio of 1.53. Fig. 13 shows experimental values ​​related to the results of thermogravimetry and differential thermogravimetry (DTG) performed using an NCM622 composite pellet as a target.

[0179] In an embodiment, NCM may refer to a cathode material composed of nickel, cobalt, and manganese. The cathode material is a critical factor in determining battery performance. For example, to increase energy density, the energy density of the cathode material must be maximized. Cathode materials that exhibit suitable performance for batteries include nickel, manganese, cobalt, and aluminum. Nickel provides high-capacity characteristics, manganese and cobalt provide stability, and aluminum enhances output characteristics. These cathode materials can be composed by combining mobile materials in various ratios, and the technology for combining cathode active materials is directly related to the competitiveness of battery manufacturers. For example, while a higher nickel content in the cathode material may facilitate increased battery capacity, a higher nickel content also reduces stability. Therefore, ensuring stability while increasing the nickel content is crucial in cathode material technology.

[0180] Meanwhile, two types of cathode materials, NCM and NCA, dominate the market. NCM is the most commonly used cathode material in secondary batteries and can have a layered lattice structure. In NCM, the components of the cathode active material are arranged in a layered structure, and when the battery is charged, lithium ions move between the crystal lattice layers and are stored in the graphite anode active material. This allows for a large amount of lithium ions to be stored between the wide, flat interlayers, offering the advantage of high energy capacity. However, this can compromise stability during high-voltage charging.

[0181] The cathode active material of NCM622 related to Fig. 10 may be composed of 60% nickel, 20% cobalt, and 20% manganese.

[0182] Thermogravimetric analysis may be an analytical method that measures weight changes that occur while a sample (i.e., the subject matter of the present invention (NCM622 composite pellets)) is heated at a constant rate, accompanied by physical and chemical changes. Physical changes such as melting or vaporization may occur at a specific temperature, and chemical changes such as decomposition reactions of substances, oxidation, reduction, and isomerization reactions may occur at high temperatures.

[0183] In the embodiment, heating is preferably performed at a heating rate of 22 K / min to actively reduce NCM622. From the weight curve generated according to the temperature change during sample heating, information on the thermal stability and compositional changes can be obtained, as well as the identification of intermediate products.

[0184] Meanwhile, the maximum curve corresponding to weight loss appears at the inflection point of the curve. However, when multiple reactions overlap, it can be difficult to identify the exact maximum reaction rate value from a complex TG curve. Accordingly, differential thermogravimetric analysis was additionally performed and is additionally shown in Figure 10.

[0185] Differential thermogravimetric analysis (DTG) uses the same equipment as TG, but can be plotted as the first derivative of the TG curve versus time or temperature. Differential thermogravimetric analysis plots the rate of weight loss (i.e., the derivative) of the TG curve against temperature, while the DTG curve can consist of peaks corresponding to each stage of the decomposition reaction. The DTG curve can be plotted with the vertical axis representing the rate of mass loss and the horizontal axis representing the increasing temperature.

[0186] Accordingly, the temperature of the inflection point in TG, which indicates the maximum rate of weight loss, may be the maximum value of the peak in DTG. Furthermore, in the embodiment, the area of ​​the DTG peak may indicate the weight loss rate at each step. In other words, reaction kinetics can be easily examined through differential thermogravimetric analysis.

[0187] In a specific embodiment, a mass reduction occurs as a result of chemical reaction while heating the object (i.e., NCM622 composite pellet), and a mass change occurs as a continuous decomposition reaction occurs. Since this chemical reaction is a temperature-dependent rate process, the mass change does not occur only at a constant temperature, but can occur over a range, as illustrated in FIG. 10.

[0188] Step 1

[0189] LiNi x Mn y Co z O2+ αC -> (2-y) / 4Li2O + xNiO + y / 2LiMn2O4+ z / 3Co3O4+ αCO2(1)

[0190] 12LiMn2O4+ 5C -> 6Li2O + 8Mn3O4+ 5CO 2(g) (2)

[0191] Mn3O4+ 1 / 2C -> 3MnO + 1 / 2CO 2(g) (3)

[0192] Co3O4+ 1 / 2C -> 3CoO + 1 / 2CO 2(g) (4)

[0193]

[0194] In the Step 1 section (0℃ to 875℃) of Fig. 10, a chemical reaction corresponding to the chemical formula above may mainly occur.

[0195] Examining the above reaction formula, it can be confirmed that nickel and manganese undergo a reduction reaction in Step 1, and most of the NCM622 is converted into lithium oxide and manganese oxide. Furthermore, based on the chemical formula above, a theoretical mass loss of 4.8% occurs in Step 1. Correspondingly, the actual experimental results (i.e., Figure 10 (a)) confirmed an actual mass loss of 4.78%.

[0196] In the embodiment, in the Step 1 section, the structure of NCM622 can be gradually transformed from a layered structure to a spinel structure and a rock-salt structure by temperature change.

[0197] Additionally, in the Step 2 section, the Boudouard reaction and indirect reduction of metal oxides can occur by chemical reactions corresponding to the chemical formula below.

[0198] C + CO 2(g) -> 2CO (g) (5)

[0199] MO + CO (g) -> M + CO 2(g) (M=Ni, Co) (6)

[0200] MO + C -> M + CO(g) (M=Ni, Co) (7)

[0201] The Buda reaction involves a redox reaction of a chemically equilibrium mixture of carbon monoxide and carbon dioxide at a given temperature, and may correspond to the chemical formula (5). This Buda reaction can release a large amount of carbon monoxide, which can be utilized in a subsequent indirect reduction process.

[0202] Specifically, a large amount of carbon monoxide (CO) is required for indirect reduction (i.e., the chemical reaction corresponding to chemical formula (6)) to occur. That is, nickel oxide and cobalt oxide can be indirectly reduced to nickel and cobalt and carbon dioxide (CO2) by reacting with carbon monoxide. Looking at Fig. 10 (b), which shows the change in carbon monoxide and carbon dioxide partial pressure according to temperature change, it can be confirmed that the amount of carbon monoxide increases rapidly due to the Buda reaction in the step 2 section. The carbon monoxide released by the Buda reaction generates nickel and cobalt and carbon dioxide through the indirect reduction of metal oxides (i.e., nickel oxide (NiO) and cobalt oxide (CoO)), and it can be confirmed that the amount of carbon monoxide, which had increased rapidly through this reaction, rapidly decreases.

[0203] The chemical formula related to (7) may represent the overall reaction (i.e., the combination of chemical formulae (5) and (6)) considering indirect reduction through acceleration of the Buda reaction.

[0204] In Step 2, as illustrated in Figure 10, a cumulative mass loss of 26.08% occurred along with the generation of carbon monoxide. This suggests that the amount of nickel and cobalt converted by the reaction may be maximized between 875°C and 1050°C. In other words, the optimal temperature for the conversion of metallic nickel and cobalt may be between 875°C and 1050°C.

[0205] According to the embodiment, as can be seen in Fig. 10, when the heat treatment temperature of the target object is less than 875°C, the Buda reaction and the indirect reduction of the metal oxide do not occur, so the conversion into nickel and cobalt cannot be accelerated. Additionally, as can be seen in Fig. 10 (b), the DTG curve shows that when the heat treatment temperature of the target object exceeds 1050°C (the DTG inflection point), the mass reduction rate decreases. This may show that when the heat treatment temperature of the target object exceeds 1050°C, the conversion rate into nickel and cobalt decreases. In other words, in order to accelerate the conversion into nickel and cobalt, it is preferable to perform the heat treatment at a temperature not exceeding 1050°C. In addition, according to the embodiment, if the heat treatment temperature exceeds 1100°C, copper may melt and stick to the pellets, which may cause a rapid drop in the reduction rate. Therefore, the temperature during the heat treatment process should not exceed 1100°C, and more preferably, it should be controlled not to exceed 1050°C to accelerate the conversion into nickel and cobalt.

[0206] According to one embodiment of the present invention, the preset conditions may include a partial pressure increase condition corresponding to a section in which the increase in the partial pressure of carbon monoxide exceeds a predetermined threshold partial pressure change. Referring to (b) of FIG. 10 and chemical formulas (5) and (6), carbon monoxide is required for conversion into nickel and cobalt.

[0207] MO + CO (g) -> M + CO 2(g) (M=Ni, Co) (6)

[0208] Specifically, a chemical reaction such as the chemical formula (6) above may require carbon monoxide. That is, a large amount of carbon monoxide is required for the conversion into nickel and cobalt. This carbon monoxide can be generated through a chemical reaction related to chemical formula (5), namely the Buda reaction.

[0209] C + CO 2(g) -> 2CO (g) (5)

[0210] That is, carbon monoxide increases rapidly in response to the Buddha reaction point, which leads to the formation of nickel and cobalt.

[0211] Accordingly, the heating control unit can perform a heating process on the object based on a temperature corresponding to a section where the increase in the partial pressure of carbon monoxide exceeds a predetermined threshold partial pressure change amount. For example, the heating control unit can perform a heating process on the object based on a temperature section from the point where the change in carbon monoxide rapidly increases (i.e., the point where the increase in the change exceeds a predetermined threshold change amount) to the point where the change in carbon monoxide changes from rising to falling.

[0212] In another embodiment, the preset conditions may include a mass reduction condition corresponding to a section in which the decrease in mass of the object exceeds a predetermined threshold mass reduction amount. Referring to (a) of FIG. 10 and chemical formulas (5) and (6), acceleration of the mass reduction of the object is essential to accelerate the conversion into nickel and cobalt.

[0213] In an embodiment, the amount of mass loss may increase rapidly as the reaction between nickel oxide or cobalt oxide and carbon monoxide becomes more active, generating nickel, cobalt, and carbon dioxide.

[0214] Accordingly, the present invention can perform heat treatment on an object based on a temperature corresponding to a section in which mass is rapidly reduced, with the section in which mass is rapidly reduced as a condition.

[0215] For a specific example, the heating control unit may perform heating processing on the object based on a temperature range from a point in time when the mass of the object rapidly decreases (i.e., a range in which the amount of mass decrease exceeds a predetermined threshold amount of change) to a point in time when the amount of mass decreases (i.e., a range in which the amount of mass decrease is less than or equal to a predetermined threshold amount of change).

[0216] According to one embodiment of the present invention, the preset conditions may include temperature conditions, partial pressure increase conditions, and mass decrease conditions as described above, and the heating control unit may control the heating unit so that heating processing is performed based on a combination of at least two conditions among the preset conditions.

[0217] In Step 3, direct reduction of manganese oxide and evaporation of Li2O can occur by a chemical reaction corresponding to the chemical formula below.

[0218] MnO + C -> Mn + CO (g) (8)

[0219] Li2O -> 2Li(g) + CO(g) (9)

[0220] That is, manganese is generated through the chemical reaction of (8), and lithium is generated through the chemical reaction of (9). According to the example, the additional mass loss in the Step 3 section was confirmed to be 35.53%. It was confirmed that this mass loss was similar to the mass loss of 33.16% according to the TGA experiment (theoretical).

[0221] In addition, in the embodiment, the NCM composite pellets were cooled at different temperatures and the corresponding XRD phase analysis was performed, and the results related thereto are shown in Fig. 11. Fig. 11 is a drawing showing the XRD pattern of the target object corresponding to various temperatures related to one embodiment of the present invention.

[0222] In an embodiment, XRD stands for X-ray Diffraction, which may refer to analyzing a sample using characteristic x-rays generated when high-speed electrons collide with target atoms. XRD may refer to an analysis method that diffracts x-rays onto a desired sample to graphically display internal information about the sample. In other words, it may be an analysis method that can identify which phase is composed of the sample by showing peak values ​​at unique angles for various phases.

[0223] More specifically, XRD can be performed by striking X-rays against a crystal, causing some of them to diffract. In a specific embodiment, as the X-ray tube and detector move, the degree to which the X-rays are diffracted by the sample can be recorded and graphed. In Fig. 11, (a) is a state without separate heat treatment, (b) is 600°C, (c) is 760°C, (d) is 960°C, and (e) is 1500°C.

[0224] Looking at (a) to (e) of Fig. 11, it can be confirmed that nickel is observed at 760°C or higher. That is, nickel is not formed through a chemical reaction at a temperature lower than 760°C. Accordingly, heat treatment at a temperature of at least 760°C or higher is essential for the formation of nickel. In addition, in the embodiment, looking at (b) and (c) of Fig. 11, it can be confirmed that NCM is observed at a temperature of 600°C, but NCM is reduced through a chemical reaction at a temperature of 760°C. That is, LiNi x Mn y Co z The decomposition peak of O2 can be confirmed to be first observed in (c) of Fig. 11.

[0225] In various embodiments, as described above, it can be confirmed that nickel is formed at a temperature of 760°C or higher, but referring to FIG. 10 and chemical formulas (5) and (6), a temperature of 875°C or higher, where carbon monoxide increases rapidly, may be a region where nickel formation is accelerated. The present invention may be characterized in that heat treatment is performed at 875°C or higher to accelerate nickel formation. In other words, when heat treatment is performed at 875°C or higher in response to a spent battery, nickel formation may be accelerated.

[0226] In various embodiments, the XRD results of the reduced pellets after the experiment exposed to temperatures up to 1500°C (i.e., related to (e) of Fig. 11) show that no lithium content is observed in the XRD pattern due to evaporation of Li2O due to the excessively high temperature.

[0227] In one embodiment, when the temperature exceeds 1100°C, copper may melt and stick to the pellets, which may drastically reduce the reduction rate. Therefore, it is preferable to adjust the temperature to a maximum of 1100°C during the heat treatment process.

[0228] In one embodiment, when a thermogravimetric analysis and a differential thermal analysis are performed on an NCM811 composite pellet including an NCM811 cathode material composed of nickel, cobalt, and manganese in different ratios and a black powder in a ratio of 1.53, the results may be as shown in FIG. 12. FIG. 12 shows experimental values ​​related to the results of thermogravimetric analysis and differential thermal gravimetric analysis performed on an NCM811 composite pellet as a target. That is, FIG. 12 is a diagram related to experimental values ​​corresponding to a case where the nickel content is high and the manganese and cobalt contents are low. The NCM811 related to FIG. 12 may be a battery composed of 80% nickel, 10% cobalt, and 10% manganese. The experiment related to FIG. 12 was conducted in the same manner as the experiment related to FIG. 10, except that the NCM622 composite pellet was replaced with the NCM811 composite pellet.

[0229] In the embodiment, nickel is related to high capacity characteristics, and manganese and cobalt are related to improved stability, so in the case of NCM811, it has high capacity characteristics compared to NCM622, but stability may be somewhat lower.

[0230] Looking at Fig. 12, it can be confirmed that the NCM811 composite pellet also undergoes a mass reduction reaction in three stages, similar to the NCM622 composite pellet. In the case of the NCM811 composite pellet, due to the high nickel content and low manganese content, it can be confirmed that the carbon dioxide peak occurs before Step 2, that is, in Step 1. Looking at Fig. 12 (a), it can be confirmed through the peak value of DTG that the reaction is most active in the range of 875℃ to 1000℃. In other words, the transformation into nickel and cobalt can be accelerated in that range. In other words, both NCM622 and NCM811 undergo mass reduction and reaction in three stages, and in particular, the amounts of nickel and cobalt in both composite pellets can be maximized in the range of 875℃ to 1050℃. As described above, for NCM622 and NCM811, the recovery rate was maximized as the transformation of nickel and cobalt was accelerated by the active reactivity in the corresponding temperature range (875°C to 1050°C). These results indicate that the same reaction can occur in batteries with all two-dimensional layered structures, and thus, the results can be equally applied to LIBs (Lithium Ion Batteries) with various layered structures, such as LCO, NMC333, and NCA, to maximize the recovery rate.

[0231] In other words, the optimal temperature for the conversion of metallic nickel and cobalt may be between 875°C and 1050°C. Accordingly, when the target object (i.e., a spent battery) is heat-treated within the range of 875°C to 1050°C, the recovery rate of nickel and cobalt can be maximized.

[0232] That is, the heat treatment device (100) of the present invention can perform heat treatment on an object through the conditions described above (i.e., heating rate conditions and temperature range conditions). When heat treatment is performed through the heating rate conditions and temperature range conditions suggested in the present invention, the recovery rate of valuable metals can be increased, as can be confirmed through the experimental values ​​described above. According to an embodiment, an object heat-treated through the heat treatment device (100) can be transferred to a crushing device (200) and crushed to a size greater than a certain size.

[0233] According to one embodiment of the present invention, a method for recovering valuable metals from waste batteries may include a step (S200) of performing a crushing process using a crushing device (200) corresponding to the recovered object after heat treatment to obtain a plurality of recovered objects.

[0234] In one embodiment, the crushing process for the heat-treated object may be performed by crushing using a crushing device (200) described below, but may also be performed by utilizing a conventional crushing means such as a cutter mixer. That is, the crushing process in the present invention is not limited to being performed by using the configuration of the crushing device described below.

[0235] Referring to Fig. 13, the shredding device (200) may include a transport unit (210), a shredding unit (220), and a motor unit (230). The components of the shredding device (200) described above are exemplary, and additional components may be added, or at least some of the components described above may be omitted.

[0236] In a specific embodiment, the crushing device (200) may include a conveying unit (210) that conveys the recovered object in one direction after heat treatment. As illustrated in FIGS. 2 and 13 , the conveying unit (210) may be positioned close to the object discharge unit (150) of the heat treatment device (100) and serves to convey the discharged object (i.e., the heat-treated object) in one direction. The conveying unit (210) moves the heat-treated object discharged from the object discharge unit (150) to the crushing unit (220).

[0237] In an embodiment, the shredding device (200) may include a shredding unit (220) including a plurality of blades for shredding a heat-treated object delivered from a conveying unit. The shredding unit (220) may include a shredding housing (221) and a plurality of blades (222) provided inside the shredding housing (221), as illustrated in FIG. 13.

[0238] In addition, the shredding device (200) may include a motor unit (230) that applies power to a shredding unit (220). The shredding unit (220) rotates a plurality of blades based on the power applied from the motor, and shredding of an object (i.e., a heat-treated object) is performed through the rotation of the plurality of blades.

[0239] In one embodiment, the step of performing a shredding process may be characterized by causing the plurality of recovery bodies to be shredded to a predetermined size or larger. Here, the predetermined size may mean that, based on a rectangular shape, the length of the first side is 2 cm, and the length of the second side, which is different from the first side, is 1 cm.

[0240] Typically, in the case of pouch, square, or cylindrical batteries, which form the battery, copper foil is configured in a layered or rolled form. Since the copper foil maintains this layered or rolled form even after the heat treatment reaction, powder (e.g., cathode active material) mixed between the copper foils remains, which reduces the recovery rate of valuable metals. In other words, if the powder existing between the copper foils can be easily separated, the recovery rate can be maximized, and the present invention can crush the recovered object after heat treatment to a size greater than a certain size in order to maximize the recovery rate.

[0241] Meanwhile, in order to easily separate the powder located between the copper in a layered form, the heat-treated object needs to be crushed. In this case, if the crushing process for the object is performed too finely, the copper and powder will mix, making separation more difficult. For example, if the object is crushed into small pieces, it will be difficult to separate the copper and powder. Accordingly, when crushing the object, it must be crushed into a preset size. The crushing process in the present invention may not mean a process of crushing the object into small pieces, but a process of cutting the object into a size greater than a certain size, that is, a preset size. In a preferred embodiment, the preset size during the crushing process may be a first side length of 2 cm and a second side length of 1 cm or more based on a square shape. In other words, the object must have a rectangular size of at least 1 x 2 cm. If the size of the object is smaller than the preset size, it will be difficult to separate the recovery bodies related to the graphite, copper, and positive electrode active material that constitute the object, which may ultimately reduce the recovery rate of valuable metals. In particular, when copper is finely pulverized, separation between the copper particles and the recovered particles related to the cathode active material becomes more difficult.

[0242] That is, the crushing device (200) of the present invention can perform a crushing process on the object at a preset size so that each of the recovery bodies constituting the object can be more easily separated in the subsequent sieving process. In other words, the plurality of recovery bodies (i.e., pieces of the object) that are delivered to the sieving device (300) after the crushing process can have a rectangular size of at least 1 x 2 cm or more.

[0243] According to one embodiment of the present invention, a method for recovering valuable metals from waste batteries may include a step (S300) of performing a sieving process on a plurality of recovery bodies through a sieving device (300) to obtain a plurality of separated bodies having different particle sizes.

[0244] According to one embodiment, the sieving device (300) may be a device for separating a plurality of recovery bodies by particle size. The sieving device (300) may separate the object crushed into a preset size by the crushing device (200) into a plurality of separation bodies. The sieving device (300) may perform vibration sieving or may be configured to include a shaking table. The sieving device (300) may separate the plurality of recovery bodies by filtering them by particle size through vibration.

[0245] More specifically, referring to (a) of FIG. 14, the sieving device (300) may include a sieve inlet (310) into which a plurality of sieves are injected, a sieve section (320) for separating each of the plurality of sieves, and a plurality of sieve discharge ports (330) through which each of the plurality of sieves is separated and discharged.

[0246] In an embodiment, the sieve unit (320) may include a first screen (321) having a plurality of first holes formed therein for passing at least one of a plurality of recovery bodies, and a second screen (322) having a plurality of second holes formed therein for passing at least one of a plurality of recovery bodies, as illustrated in (b) of FIG. 14. (b) of FIG. 14 is an exemplary view related to a side surface of the sieve unit (320).

[0247] As illustrated in (b) of FIG. 14, the first screen (321) and the second screen (322) may be configured to include fine holes to have a sieving function. In various embodiments, the size of the first hole formed in the first screen (321) may be characterized as being larger than the size of the second hole formed in the second screen (322). In addition, the first screen (321) may be provided at an upper portion than the second screen. In addition, in the embodiment, the sieving unit (320) may include a screen frame (323) that supports the first screen (321) and the second screen (322).

[0248] According to one embodiment, the sieving device (300) may further include a vibration supply unit (not shown) that supplies vibration to the sieve unit (320), and vibration is applied to the entire sieve unit (320) by the vibration supply unit, and the configuration is such that more accurate filtering is performed by the vibration. That is, the first screen (321) and the second screen (322) of the sieve unit (320) vibrate by the vibration supply unit, and the recovery material can be easily filtered by particle size through the vibration.

[0249] Referring to (b) of FIG. 14 for more detailed explanation, the sieve unit (320) may include a first screen (321) and a second screen (322) supported by a screen frame (323). The first screen (321) includes a relatively larger hole than the second screen (322) and is provided in the upper direction of the second screen. In a specific embodiment, the diameter of the hole formed in the first screen (321) may be 1 cm. Accordingly, when a plurality of recovered bodies crushed to a preset size are delivered, a recovered body (e.g., a second recovered body) having a size of 1 cm x 2 cm among the recovered bodies is filtered out. Meanwhile, the diameter of the hole formed in the second screen (322) located in the lower direction of the first screen (321) may be 0.5 mm. First, among the recovered particles caught by the first screen (321), powders corresponding to medium-sized particles, excluding fine-sized powders (i.e., powders of 0.5 mm or less), are filtered by the second screen (322).

[0250] In an embodiment, the object delivered from the crushing device (200) is separated into a plurality of separators through the sieving device (300). In this case, the plurality of separators may mean a first separator, a second separator, and a third separator.

[0251] In a specific embodiment, the first separator may refer to a separator having an intermediate particle size among the crushed objects exceeding a certain size, from which copper and graphite have been removed. In other words, the first separator is a powder corresponding to the intermediate-sized particles filtered by the second screen (322).

[0252] In the case of the second separator, it may mean copper, which is formed by relatively large particles among the crushed objects. In other words, the second separator is a powder corresponding to the largest particle size that is minimally caught by the first screen (321).

[0253] In the case of the third separator, it may refer to graphite, which is formed by forming relatively small particles among the crushed objects. In other words, the third separator is a powder with a fine particle size that has passed through both the first screen (321) and the second screen (322).

[0254] That is, the sieving device (300) can separate a target object (i.e., a plurality of recovery bodies) that has been crushed to a certain size or larger into a plurality of separation bodies based on the particle size.

[0255] The sieving device (300) can separate and discharge each of a plurality of separated bodies based on particle size through a plurality of recovery body discharge ports (330).

[0256] The plurality of recovery discharge ports (330) may include a first recovery discharge port (331) for discharging the recovery material recovered through the first screen (321), a second recovery discharge port (332) for discharging the recovery material recovered through the second screen (322), and a third recovery discharge port (333) for discharging the recovery material not recovered through the first screen (321) and the second screen (322).

[0257] That is, the recovered material (i.e., copper) filtered through the first screen (321) is discharged as a second separator through the first recovery body discharge port (331), the recovered material (i.e., recovered material from which copper and graphite have been removed) filtered through the second screen (322) is discharged as a first separator through the second recovery body discharge port (332), and the recovered material (i.e., graphite) corresponding to the fine powder that has passed through the first screen (321) and the second screen (322) is discharged as a third separator through the third recovery body discharge port (333).

[0258] According to the classification result of the sieving device (300), copper and graphite are automatically separated and discharged, and the first separated body from which copper and graphite have been removed is transferred to the leaching device (400). In other words, the sieving device (300) uses a plurality of screens to which vibration is applied and a plurality of recovery body discharge ports to separate the recovered bodies that have been crushed (or cut) into preset sizes, thereby recovering copper and graphite, and transfers the first recovery body to an additional process step to recover remaining valuable metals. The first separated body is moved to the leaching device (400) and sequentially undergoes a leaching process, a crushing process, a magnetic separation process, and a gravity separation process, and the remaining valuable metals are recovered according to the following process steps.

[0259] According to one embodiment of the present invention, a method for recovering valuable metals from a spent battery may include a step (S400) of performing a leaching process using a leaching device (400) corresponding to a first separator among a plurality of separators to separate lithium carbonate from the first separator and obtain a valuable metal oxide.

[0260] The leaching device (400) separates lithium carbonate from the first separator through a leaching process on the delivered first separator. According to an embodiment, the leaching device (400) performs a leaching process related to aqueous leaching treatment using distilled water to separate lithium carbonate (Li2CO3) in a liquid state and a solid valuable metal oxide. The aqueous leaching may utilize a magnetic bar, and the solvent may be distilled water that does not contain impurities. The aqueous leaching time and the ratio of the first separator to the distilled water may be set to optimal conditions in consideration of the reaction between the lithium carbonate and the distilled water. In an embodiment, the higher the ratio of distilled water to the first separator or the longer the aqueous leaching time, the higher the reaction rate of lithium carbonate.

[0261] When the leaching process is performed, lithium carbonate dissolves in water and changes into an aqueous solution, while the first separator remains in a solid powder form. The solution in which the first separator has been stirred can be filtered through a filter, thereby separating the lithium carbonate in a liquid state and the precious metal oxide in a solid state. A drying process can be performed on the separated liquid, and as a result of the drying process, the lithium carbonate can be recovered in a powder form.

[0262] The solid-state precious metal oxide separated in the leaching process is transferred to a crushing device (500) and can be refined through the crushing process. The refinement of the precious metal oxide may be for the purpose of separating each component constituting the precious metal oxide.

[0263] In a specific embodiment, the infiltration device (400) may include a supply tank (410), a liquid supply unit (420), a mixing unit (430), a filter unit (440), and a infiltration discharge unit (450). The components of the infiltration device (400) described above are exemplary, and additional components may be added, or at least some of the components described above may be omitted.

[0264] The supply tank (410) of the extraction device (400) may be provided in a cylindrical shape, as shown in FIG. 15, to provide a space for stirring the first separator and the liquid.

[0265] Referring to Fig. 2, the first recovery body discharged through the second recovery body discharge port (332) is moved into the supply tank through a transport device. The leaching device (400) may include a liquid supply unit (420) that supplies liquid into the supply tank (410). That is, the first recovery body separated through the sieving device (300) and the liquid (i.e., distilled water) supplied through the liquid supply unit (420) are stirred inside the supply tank (410).

[0266] In one embodiment, the leaching device (400) may include a mixing unit (430) provided inside the supply tank (410) and configured to mix the liquid and the first separator by rotation. In various embodiments, the leaching device (400) may include a rotating supply unit that applies a rotational force, and the mixing unit (430) may be rotated based on the rotational force applied from the rotating supply unit. The rotating supply unit may include, for example, a motor as a component for generating a driving force. The mixing unit (430) is rotatably provided inside the supply tank (410) and may be driven to rotate by the rotational force applied from the rotating supply unit. The mixing unit (430) may have a stepped shape, as illustrated in FIG. 15, and may be arranged at a preset interval. That is, the distilled water and the first separator are easily stirred by the rotation of the mixing unit (430) having a stepped shape.

[0267] According to one embodiment, the leaching device (400) may include a filter unit (440) that filters a solid material from a mixture corresponding to a liquid and a first separator. The filter unit (440) may have a funnel structure that narrows toward the center and is configured to filter moisture. When the mixing unit (430) rotates, the first separator and distilled water are stirred, and accordingly, lithium carbonate is dissolved in the liquid (i.e., distilled water) and changes into an aqueous solution state. The liquid in which lithium carbonate is dissolved is discharged to the outside of the filter unit (440), and only the first separator in a solid state is filtered by the filter unit (440) and remains. In this case, the first separator in a solid state may be a valuable metal oxide from which lithium carbonate has been removed.

[0268] The reaction formula when lithium carbonate dissolves in distilled water is as follows.

[0269] Li2CO3= Li 2+ + CO3 2-

[0270] Before the reaction, it is in a solid state, and after the reaction, it becomes a liquid state. In the case of NiO, CoO, and MnO, which are precious metal oxides, there is no solubility in water, so when leaching is performed, Li2CO3 dissolves in water and changes into an aqueous solution, while NiO, CoO, and MnO remain in the form of a solid powder.

[0271] That is, the solution in which the first separator is stirred can be filtered by the filter unit, thereby separating lithium carbonate in a liquid state and precious metal oxide in a solid state. A drying process can be performed on the separated liquid, and as a result of the drying process, lithium carbonate can be recovered in the form of a powder.

[0272] As illustrated in FIG. 2, the results separated into lithium carbonate and the first separation body from which lithium carbonate has been removed by the leaching device (400), i.e., each of the valuable metal oxides, can be discharged through each of a plurality of leaching discharge units. In this case, the valuable metal oxide discharged through the first leaching discharge unit is discharged to the crushing device (500) and can be refined by the crushing device (500).

[0273] According to one embodiment of the present invention, a method for recovering valuable metals from waste batteries may include a step (S500) of performing a crushing process on valuable metal oxides through a crushing device (500) to refine them.

[0274] The crushing device (500) is configured to finely crush the precious metal oxide so that magnetic separation can be easily performed. The crushing device (500) can crush the precious metal oxide into a uniform size.

[0275] In the embodiment, the crushing process step is performed to crush the material more finely than the previous crushing process step. Only when the particles are crushed finely in the crushing process step can nickel and cobalt be separated more accurately in the subsequent magnetic separation process step.

[0276] The crushing device (500) may include a container (510), balls (520), and a driving unit. Specifically, the crushing device (500) may include a container (510) forming an internal space, as illustrated in FIG. 16. In addition, the crushing device (500) may include balls (520) provided within the container. The balls may be made of steel or ceramic, and may finely crush the precious metal oxide through collision and friction with the precious metal oxide. In addition, the crushing device (500) may include a driving unit that applies a rotational force to the container. The crushing device (500) performs a crushing process by generating collision and friction between the balls and the precious metal oxide through rotation of the container (510).

[0277] The container (510) can finely pulverize precious metal oxides while maintaining a constant rotation speed and time. According to an embodiment, the size of the pulverized product may vary depending on the size of the ball (520) and the hardness of the material. In addition, as pulverization progresses, the precious metal oxides become smaller and have a high surface area, which may induce chemical reactions or changes in the properties of the material. This pulverizing device (500) has the advantages of high productivity and easy operation.

[0278] Referring to FIG. 2, the finely divided metal oxide is transferred to a magnetic separation device (600) through a crushing device (500).

[0279] According to one embodiment of the present invention, a method for recovering valuable metals from waste batteries may include a step (S600) of obtaining a mixed powder from a refined valuable metal oxide through a magnetic separation process using a magnetic separation device (600).

[0280] According to an embodiment, the mixed powder may be a magnetic metal powder, for example, Ni-Co powder, but is not limited thereto. In various embodiments, when the waste battery is an NMC battery, the mixed powder obtained in the corresponding process step may be a Ni-Co alloy powder. Meanwhile, when the waste battery is an LCO and LFP battery, the mixed powder obtained in the corresponding process step may include at least one of Ni, Co, Fe, Fe-C, and Fe-P. In other words, the type of the mixed powder obtained in the corresponding process step may vary depending on the type of the waste battery from which valuable metals are to be recovered. The magnetic separation device (600) may include an oxide inlet (610), a magnetic field generating unit (620), and an oxide discharge unit (630), as illustrated in FIG. 17. Specifically, the magnetic separation device (600) may include an oxide inlet (610) into which fine valuable metal oxides are introduced. In addition, the magnetic separation device (600) may include a magnetic field generation unit (620) that generates a magnetic field to obtain metal powder from the precious metal oxide. In a specific embodiment, the magnetic field generation unit (620) may be characterized by generating a magnetic field having a strength below a certain level. If the magnetic field generation unit (620) generates an excessively large magnetic field, other non-magnetic materials are excessively attracted together with the magnetic material in the process of separating the magnetic material from the precious metal oxide. Accordingly, it is preferable that the magnetic field generation unit (620) be controlled to generate a magnetic field having a strength below 4000 Gauss.

[0281] The finely divided precious metal oxide is transferred to a magnetic separation device (600), which obtains a mixed powder through magnetism. The magnetic separation device (600) uses a magnetic field from an electromagnet or a permanent magnet to separate the finely divided precious metal oxide into a mixed powder having magnetism and a non-magnetic material. In one embodiment, the magnetic separation device may include a storage for temporarily storing the residue and a conveyor belt for classifying and transferring the precious metal oxide from the storage into magnetic and non-magnetic materials.

[0282] In one embodiment, the magnetic field generation unit (620) may include a plurality of magnetic field generation modules that generate magnetic fields of different magnitudes. The magnetic field generation unit (620) may be characterized in that it obtains metal powder multiple times in each step by utilizing each magnetic field generation module.

[0283] Referring to FIGS. 2 and 17, when the first magnetic field generating module (621) is driven by a roller in the direction of the arrow, a precious metal oxide is transmitted, and when the precious metal oxide falls from the end of the first magnetic field generating module due to a magnetic field by an electromagnet or permanent magnet mounted on the roller, a difference in the falling trajectory occurs between the first precious metal oxide that interacts with the magnetic field and the second precious metal oxide that does not interact with the magnetic field, and thus spatial separation of the first precious metal oxide and the second precious metal containing material that accumulates is achieved, and thereby a magnetic separation step in which these oxides are easily separated can be performed.

[0284] In particular, the magnetic separation device (600) of the present invention further includes a second magnetic field generation module (622) and a third magnetic field generation module (623), as shown in FIG. 2 and FIG. 17, and can repeatedly apply the above-described magnetic separation step multiple times.

[0285] According to one embodiment, the first magnetic field generating module (621), the second magnetic field generating module (622), and the third magnetic field generating module (623) may be characterized by generating magnetic fields of different magnitudes.

[0286] More specifically, as the magnetic separation step progresses, each magnetic field generating module can perform magnetic separation through a higher magnetic field. That is, the second magnetic field generated by the second magnetic field generating module (622) performing the second-stage magnetic separation is controlled to be larger than the first magnetic field generated by the first magnetic field generating module (621) performing the first-stage magnetic separation, and the third magnetic field generated by the third magnetic field generating module (623) performing the third-stage magnetic separation is controlled to be larger than the second magnetic field generated by the second magnetic field generating module (622) performing the second-stage magnetic separation.

[0287] As the magnetic separation step is performed, the separation of the magnetic material through a higher magnetic field may be configured to minimize the entrainment of non-magnetic materials. That is, by gradually increasing the magnetic field step by step, the magnetic material can be gradually separated by size, thereby minimizing the entrainment of non-magnetic materials along with the magnetic material. This enables the recovery of high-purity magnetic materials (e.g., nickel and cobalt) and can increase the recovery rate of multiple sub-oxides (e.g., aluminum oxide, manganese oxide, aluminum dross, etc.) obtained in the subsequent process.

[0288] In a specific embodiment, the first magnetic field generating module (621) may be controlled to generate a magnetic field of 500 Gauss, the second magnetic field generating module (622) may be controlled to generate a magnetic field of 1000 Gauss, and the third magnetic field generating module (623) may be controlled to generate a magnetic field of 2000 Gauss.

[0289] As described above, the magnetic separation device (600) of the present invention can sequentially perform magnetic separation through each magnetic field generating module that generates different magnetic fields, thereby minimizing the classification of non-magnetic materials into magnetic materials (i.e., separation of oxides into mixed powder).

[0290] Through magnetic separation using a magnetic separation device (600), a magnetic mixed powder is separated from the finely divided precious metal oxide, and the precious metal oxide from which the mixed powder has been removed is transferred to a gravity separation device (700). In other words, nickel and cobalt are recovered through the magnetic separation step.

[0291] According to one embodiment of the present invention, a method for recovering valuable metals from waste batteries may include a step (S700) of separating a valuable metal oxide from which mixed powder has been removed into a plurality of sub-oxides based on the difference in specific gravity between components by using a gravity separation device (700).

[0292] According to one embodiment, the gravity separation device (700) may include a table portion (710), a vibration supply portion, and a plurality of separation discharge portions (720).

[0293] Referring to FIG. 18, the table portion (710) of the gravity separation device (700) may be provided to have an inclined surface at a certain angle.

[0294] The vibration supply unit can supply vibration to the table unit (710), and is configured to gradually move the precious metal oxide positioned on the upper surface of the table unit (710) by the supplied vibration.

[0295] A plurality of separation discharge units (720) are connected to the table unit (710) and may be characterized by separating and discharging each of a plurality of sub-oxides separated by specific gravity.

[0296] More specifically, the gravity separation device (700) can separate the precious metal oxide from which the mixed powder has been removed into a plurality of sub-oxides through gravity-based separation. In one embodiment, the plurality of sub-oxides may include first to third sub-oxides, and each of the first to third sub-oxides may be related to lithium aluminum oxide, manganese oxide, and aluminum dross, respectively. That is, the gravity separation device (700) can separate and discharge the precious metal oxide from which the nickel-cobalt powder has been removed into lithium aluminum oxide, manganese oxide, and aluminum dross, respectively, based on their specific gravity.

[0297] Each sub-oxide separated according to specific gravity is automatically classified and discharged through each of a plurality of separation discharge units (720). According to an embodiment, lithium aluminum oxide is discharged through the first separation discharge unit (721), manganese oxide is discharged through the second separation discharge unit (722), and aluminum dross is discharged through the third separation discharge unit (723).

[0298] That is, as the waste batteries sequentially pass through the process steps corresponding to each device of the precious metal recovery system (1000) of the present invention, precious metals are obtained. Specifically, in the sieving process step, graphite and copper are separated and recovered, and in the leaching process step, lithium carbonate can be recovered. In addition, powders related to nickel and cobalt are obtained in the magnetic separation process step, and aluminum oxide, manganese oxide, and aluminum dross are obtained in the gravity separation process step.

[0299] The precious metal recovery system (1000) of the present invention has the advantage of sequentially classifying and obtaining results through the process sequence described above, and can improve the recovery rate of materials through mutually complementary process steps.

[0300] For example, if the crushing process is omitted and the process proceeds to the sieving process after the heat treatment, the powder mixed from the copper is not easily separated, making it difficult to separate the copper, graphite, and oxides. This can ultimately reduce the recovery rate of copper and graphite, and ultimately affect the recovery rate of the magnetic material (e.g., cobalt, nickel) and multiple sub-oxides (e.g., aluminum oxide, manganese oxide, aluminum dross, etc.) that are ultimately discharged. In another example, if the magnetic separation process is not performed before the gravity separation process for gravity separation, and the magnetic material is not separated from the precious metal oxide, it is difficult to distinguish each oxide by type during gravity separation, and nickel and cobalt may be separated into each oxide, which can lower the recovery rate of each metal. The precious metal recovery system (1000) of the present invention can maximize the recovery rate of the precious metal by sequentially going through the aforementioned process steps.

[0301]

[0302] The description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be applied to other embodiments without departing from the scope of the present invention. Therefore, the present invention is not intended to be limited to the embodiments disclosed herein, but is to be construed in the broadest scope consistent with the principles and novel features disclosed herein.

[0303]

[0304] The best mode for carrying out the invention as described above has been described.

[0305]

[0306] The present invention can be utilized in the field of recycling waste batteries.

Claims

1. A method for recovering valuable metals from waste batteries, A step of performing heat treatment on an object corresponding to a waste lithium ion battery through a heat treatment device; A step of obtaining multiple recovered objects by performing a crushing process using a crushing device in response to the recovered object after the above heat treatment; A step of performing a filtration process on the plurality of recovery bodies through a sieving device to obtain a plurality of separated bodies having different particle sizes; A step of performing a leaching process using a leaching device corresponding to a first separator among the plurality of separators to separate lithium carbonate (Li2CO3) from the first separator and obtain a valuable metal oxide; A step of performing a crushing process on the above metal oxide through a crushing device to make it finer; A step of obtaining a mixed powder from the above-mentioned fine metal oxide through a magnetic separation process using a magnetic separation device; and A step of separating the metal oxide from which the mixed powder has been removed into a plurality of sub-oxides based on the difference in specific gravity between the components by using a gravity separation device; including, A method for recovering valuable metals from waste batteries.

2. In paragraph 1, The above heat treatment device, An object insertion port into which the storage unit containing the object is inserted; A working unit connected to the above target object input port and moving the storage unit in a vertical direction; A heating unit provided inside the above working unit to heat the object; An object discharge unit located at the bottom of the above working unit for discharging a heated object; and A heating control unit that controls the above heating unit; Includes, The above heating control unit is characterized in that it controls the heating unit based on preset conditions, The above preset conditions include a temperature condition in which the temperature corresponding to the heat treatment is in the range of 875°C to 1100°C. A method for recovering valuable metals from waste batteries.

3. In paragraph 1, The above shredding device, A conveying unit that conveys the recovered object in one direction after the above heat treatment; A crushing unit including a plurality of blades for crushing the heat-treated object delivered from the above conveying unit; and A motor unit that applies power to the above shredding unit; Includes, The step of performing the above shredding process is: Characterized in that the plurality of recovery bodies are crushed into a preset size. A method for recovering valuable metals from waste batteries.

4. In paragraph 1, The above sieving device is a device that separates the plurality of recovery bodies by particle size. A recovery body inlet into which the above plurality of recovery bodies are injected; A sieve for separating each of the plurality of recovery bodies; and A plurality of recovery bodies are discharged separately from each other, and include a plurality of recovery bodies discharge ports; The above sieve part is, A first screen having a plurality of first holes formed therein for passing at least one of the plurality of recovery bodies; A second screen having a plurality of second holes formed therein for passing at least one of the plurality of recovery bodies; A screen frame supporting the first screen and the second screen; and A vibration unit that applies vibration to the first screen and the second screen; including; A method for recovering valuable metals from waste batteries.

5. In paragraph 4, The size of the first hole is characterized by being larger than the size of the second hole, The above multiple recovery outlets are, A first recovery body discharge port for discharging the recovery body recovered through the first screen; A second recovery body discharge port for discharging the recovered body through the second screen; and A third recovery body discharge port for discharging the recovered body that is not recovered through the first screen and the second screen; A method for recovering valuable metals from waste batteries.

6. In paragraph 1, The above extraction device, supply tank; A liquid supply unit for supplying liquid into the above supply tank; A mixing unit provided inside the above supply tank and mixing the liquid and the first separator through rotation; A filter unit for filtering a solid material from a mixture corresponding to the liquid and the first separator; and A plurality of leaching discharge units each discharging a solid material and a liquid material constituting the mixture; A method for recovering valuable metals from waste batteries.

7. In paragraph 6, The above first separator is characterized in that it is a separator from which copper and graphite have been removed. The step of performing a leaching process using a leaching device corresponding to the first separator among the above plurality of separators to separate lithium carbonate (Li2CO3) from the first separator and obtain a valuable metal oxide is as follows: A step of obtaining lithium carbonate by drying a liquid material discharged from the mixture; comprising; A method for recovering valuable metals from waste batteries.

8. In paragraph 1, The above crushing device, A container that forms an internal space; A ball provided within the above container; and A driving unit that applies rotational force to the above container; A crushing process is performed by causing collision and friction between the ball and the metal oxide through rotation of the container. A method for recovering valuable metals from waste batteries.

9. In paragraph 1, The above magnetic separation device, An oxide inlet into which the above-mentioned finely divided metal oxide is injected; A magnetic field generating unit that generates a magnetic field to obtain the mixed powder from the metal oxide; and It includes an oxide discharge unit that discharges the metal oxide from which the above mixed powder has been removed; The above magnetic field generating unit is, It comprises a plurality of magnetic field generating modules that generate magnetic fields of different sizes, and is characterized in that each magnetic field generating module is used to obtain the metal powder step multiple times. A method for recovering valuable metals from waste batteries.

10. In paragraph 1, The above multiple sub-oxides are, Contains lithium aluminum oxide (LiAlO2), manganese oxide (MnO) and aluminum dross (Al-dross). The above gravity separation device is, A table portion having a slope at a certain angle; A vibration supply unit that applies vibration to the above table unit; and A plurality of separation discharge units connected to the above table section and discharging each sub-oxide separated by specific gravity; A system for recovering valuable metals from waste batteries.

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