Valuable metal recovery composition and valuable metal recovery method

Abstract

This embodiment relates to a valuable metal recovery composition comprising at least one unit valuable metal recovery composition, wherein the unit valuable metal recovery composition comprises a core portion containing a valuable metal and a shell portion disposed on at least a part of the core portion, the shell portion contains an oxide containing lithium, and the proportion of unit valuable metal recovery compositions having an average particle size (D50) of more than 4000 μm is 70% or less of the total valuable metal recovery composition.

Description

[Technical Field]

[0001] This embodiment relates to the reuse of waste battery components, more specifically to a method for producing concentrated metals from waste batteries, and even more specifically to a valuable metal recovery alloy, a valuable metal recovery composition, and a valuable metal recovery method. [Background technology]

[0002] The problem of disposing of used batteries, such as those from electric vehicles, is a global concern. Used batteries, particularly lithium-ion batteries, contain organic solvents that pose fire hazards, explosive materials, and heavy metals like Ni, Co, Mn, and Fe. Of these, Ni, Co, Mn, and Li are valuable metals with scarcity and potential applications. Therefore, the recovery and reuse process after the disposal of lithium-ion batteries is a critical issue.

[0003] A secondary battery is mainly composed of copper (Cu) and aluminum (Al) used as a current collector, lithium (Li), nickel (Ni), cobalt (Co), and manganese (Mn)-containing oxides as the cathode material, and graphite used as the anode material. It also consists of a separator plate that separates the cathode material and the anode material, and an electrolyte injected into the separator plate. The electrolyte may consist of a solvent and a salt, and the solvent can be a mixture of carbonate organic substances such as ethylene carbonate and propylene carbonate, and the salt can be, for example, LiPF6 (Lithium hexafluorophosphate).

[0004] For the reuse of the secondary batteries, such as battery cells, battery modules, and battery packs, used batteries are subjected to crushing, grinding, specific gravity separation, and magnetic separation processes to extract black powder, which is a mixture of positive and negative electrode materials. The black powder contains, for example, oxides of nickel, cobalt, manganese, lithium, aluminum, and oxygen as positive electrode materials, and graphite and its mixtures as negative electrode materials, along with some impurities such as aluminum and copper.

[0005] The method for recovering valuable metals from the aforementioned black powder can be broadly divided into wet and dry processes. The wet process involves leaching, solvent extraction, and lithium production to produce NiSO4, CoSO4, MnSO4, and Li2CO3. The biggest problems when processing the black powder in the wet process are that the graphite, which is the negative electrode material contained in the black powder, does not dissolve in a strongly acidic atmosphere, resulting in a long leaching time and a decrease in the actual yield due to separation along with the graphite.

[0006] Furthermore, the dry process involves removing aluminum from the slag through a high-temperature dry process using the black powder, thereby producing a Ni-Co-Mn-C alloy. The dry process can be carried out at high temperatures, for example, 1400°C to 1600°C, utilizing graphite and oxygen blowing to reduce the Ni-Mn-Li-Al-O oxide in the black powder at high temperatures, generating CO or CO2 gas, while removing lithium and aluminum from the slag along with the Ni-Co-Mn alloy. The separated Ni-Co-Mn alloy can then undergo a wet process. Through the leaching-solvent extraction process within the wet process, NiSO4, CoSO4, and MnSO4 are produced, and since carbon is dissolved in the alloy, the time required for the leaching process is reduced to approximately 70% of the time required when using the black powder.

[0007] However, in the aforementioned process, not only are the valuable metals lithium and aluminum consumed in the slag, but the lithium becomes impossible to recover. Furthermore, the blowing of oxygen to remove graphite from the black powder introduced into the high-temperature dry process can generate excessive amounts of carbon dioxide, causing environmental problems.

[0008] Therefore, in order to solve the aforementioned environmental problems, it is necessary to develop a high-temperature melting reduction process and alloying component ratio that can be manufactured with a carbon content of 10% or less in the Ni-Co-Mn alloy, while minimizing the generation of carbon dioxide and the consumption of lithium, which is a valuable metal. [Overview of the project] [Problems that the invention aims to solve]

[0009] The technical problem that the present invention aims to solve is to provide a valuable metal recovery composition that provides a valuable metal recovery alloy that minimizes the generation of carbon dioxide in black powder, increases the degree of concentration of valuable metals, prevents environmental pollution, and provides a high recovery rate of valuable metals.

[0010] Another technical problem that the present invention aims to solve is to provide a method for recovering valuable metals to provide a valuable metal recovery alloy having the aforementioned advantages. [Means for solving the problem]

[0011] According to one embodiment of the present invention, the valuable metal recovery composition relates to a valuable metal recovery composition comprising at least one unit valuable metal recovery composition, wherein the unit valuable metal recovery composition comprises a core portion containing a valuable metal and a shell portion disposed in at least a part of the core portion, the shell portion contains an oxide containing lithium, and the proportion of unit valuable metal recovery compositions in which the average particle size (D50) of the valuable metal recovery composition exceeds 4000 μm may be 70% or less of the total valuable metal recovery composition. In one embodiment, the valuable metal recovery composition can satisfy the following formula 1.

[0012] <Expression 1> 2.4 ≤ [Ni] / [Co] ≤ 4.5

[0013] (In formula 1 above, [Ni] and [Co] represent the weight percentages of Ni and Co, respectively.)

[0014] In one embodiment, the unit valuable metal recovery composition may contain aluminum (Al), and the aluminum (Al) may have a concentration gradient that gradually increases from the interface between the core portion and the shell portion toward the shell portion. In one embodiment, the XRD peak may include at least one of the following 2θ values: 20.5~21.5°, 29.0~29.5°, 31.5~32.0°, 32.2~33.0°, 60.5~61.5°, 70.0~72.0°, 19.5~20.2°, 21.6~22.2°, 24.0~26.0°, 27.0~29.0°, 34.0~36.0°, 37.0~39.0°, 38.2~39.5°, 44.0~46.0°, 64.5~66.5°, and 77.77~79.77°.

[0015] In one embodiment, the lithium-containing oxide may include at least one of LiAlO2, Li5AlO4, Li2CO3, and LiF. In one embodiment, the valuable metal recovery composition may satisfy the following formula 2.

[0016] <Expression 2> 0.1 ≤ I A / I B ≤1.5

[0017] (In the above formula 2, I A This is the peak intensity value of the LiAlO2 product at 2θ = 21° ± 0.5°, and I B (This is the peak intensity value of the LiAlO2 product at 2θ = 32.6° ± 0.4°)

[0018] In one embodiment, the ratio of the unit valuable metal recovery composition having an average particle size (D50) of the valuable metal recovery composition of 500 μm or more and less than 4000 μm may be 30% or more in 100% of the total valuable metal recovery composition. In one embodiment, the thickness of the shell portion of the unit valuable metal recovery composition having an average particle size (D50) of the valuable metal recovery composition of 500 μm or more may be 30 to 1100 μm.

[0019] In one embodiment, the thickness of the shell portion of the unit valuable metal recovery composition having an average particle size (D50) of the valuable metal recovery composition of 250 μm or more and less than 500 μm may be 5 to 450 μm. In one embodiment, the thickness of the shell portion of the unit valuable metal recovery composition having an average particle size (D50) of the valuable metal recovery composition of 150 μm or more and less than 250 μm may be 3.5 to 160 μm.

[0020] In one embodiment, the shell portion bonded to the core portion can be separated by an external force. In one embodiment, the valuable metal can include at least one of lithium (Li), cobalt (Co), nickel (Ni), aluminum (Al), and manganese (Mn).

[0021] A valuable metal recovery method according to another embodiment of the present invention includes a step of preparing a battery or battery crushed material in cell units, a step of subjecting the battery or the crushed material to dry heat treatment, and a step of separating the heat-treated crushed material by at least one of particle size separation and magnetic separation. The step of subjecting the crushed material to dry heat treatment can be performed under heat treatment conditions in which a high-temperature reduction reaction is performed in a temperature range of 1,150 to 1,800 °C and an inert atmosphere containing 1% or less of oxygen without passing through a melting step.

[0022] In one embodiment, in the step of preparing the battery crushed material, the battery crushed material satisfies the following Conditions 1 and 2.

[0023] <Condition 1> The layered structure is a laminated structure of 1 or more to 7 or less layers.

[0024] <Condition 2> Based on the long axis, which is the longest axis among the horizontal, vertical, and height directions, the size of the crushed unit battery is 100 mm or less.

[0025] In one embodiment, in the step of separating the heat-treated crushed material by at least one of particle size separation and magnetic separation, magnetic separation can be performed first and then particle size separation. In one embodiment, the lithium compound bonded to a part of the surface of the valuable metal recovery alloy can be separated by an external force.

Advantages of the Invention

[0026] According to one embodiment of the present invention, it is to provide a valuable metal recovery alloy that can minimize carbon dioxide generation and maximize valuable metal recovery by reducing the carbon content from battery crushed material.

[0027] According to another embodiment of the present invention, it is to provide a valuable metal recovery method for providing a valuable metal recovery alloy having the above advantages.

Brief Description of the Drawings

[0028] [Figure 1] SEM photograph of the unit valuable metal recovery composition constituting the valuable metal recovery composition according to one embodiment of the present invention. [Figure 2] Flowchart regarding the valuable metal recovery method according to one embodiment of the present invention. [Figure 3a] Showing battery crushed material according to one embodiment of the present invention. [Figure 3b] Showing battery crushed material according to one embodiment of the present invention. [Figure 4a] Showing the XRD analysis results of the composition for valuable metal recovery according to one embodiment. [Figure 4b] Showing the XRD analysis results of the composition for valuable metal recovery according to one embodiment. [Figure 5a] Showing the SEM-EDS analysis results of the composition for valuable metal recovery according to one embodiment. [Figure 5b] The results of SEM-EDS analysis of a valuable metal recovery composition according to one embodiment are shown. [Figure 5c] The results of SEM-EDS analysis of a valuable metal recovery composition according to one embodiment are shown. [Figure 6] This shows the particle size distribution of the core portion within a valuable metal recovery composition according to one embodiment. [Modes for carrying out the invention]

[0029] The terms first, second, and third are used to describe various parts, components, regions, layers, and / or sections, but are not limited to these. These terms are used to distinguish one part, component, region, layer, or section from another part, component, region, layer, or section. Accordingly, the first part, component, region, layer, or section described below may be referred to as the second part, component, region, layer, or section without departing from the scope of the invention.

[0030] The technical terms used herein are for the sole purpose of referring to specific embodiments and are not intended to limit the invention. The singular form used herein also includes plural forms unless the wording clearly indicates otherwise. The meaning of “including” as used in this specification embodies a particular characteristic, area, integer, stage, operation, element, and / or component, and does not exclude the presence or addition of other characteristics, areas, integers, stages, operations, elements, and / or components.

[0031] When we say that one part is "on top of" another part, it means that it is either directly above the other part, or that another part may be in between them. In contrast, when we say that one part is "directly above" another part, there is no other part in between them.

[0032] Unless otherwise defined, all terms used herein, including technical and scientific terms, have the same meaning as those generally understood by a person of ordinary skill in the art to which this invention pertains. Terms defined in commonly used dictionaries are further interpreted to have meanings consistent with the relevant technical literature and the present disclosures, and are not interpreted in their ideal or highly formal sense unless otherwise defined.

[0033] Embodiments of the present invention will be described in detail below. However, these are presented as examples only, and the present invention is not limited thereto, but is defined solely within the scope of the claims described below.

[0034] Figure 1 is an SEM image of a unit valuable metal recovery composition that constitutes a valuable metal recovery composition according to one embodiment of the present invention.

[0035] Referring to Figure 1, the valuable metal recovery composition 10 may include at least one unit valuable metal recovery composition 100. The unit valuable metal recovery composition 100 may include a core portion 110 containing a valuable metal, and a shell portion 120 disposed on at least a part of the core portion 110. Specifically, the unit valuable metal recovery composition 100 may consist of a metal such as Ni, Co, or Mn in the core portion 110, and an oxide containing lithium may be bonded and disposed on the core portion 110.

[0036] The core portion 110 includes a valuable metal recovery alloy, which may contain 45% by weight or more of valuable metals and the remainder being impurities, based on 100% by weight of the total composition of the alloy. The valuable metal recovery alloy may contain at least one of valuable metals such as nickel (Ni), cobalt (Co), manganese (Mn), lithium (Li), carbon (C), aluminum (Al), and copper (Cu), and the remainder being impurities. In this specification, valuable metals mean expensive metallic components contained in a battery, and refer to nickel, cobalt, manganese, aluminum, copper, and lithium. In one embodiment, the valuable metals may be 70% by weight or more.

[0037] In one embodiment, the lithium (Li) in the valuable metal can be contained in a range of 0.01 to 5% by weight. The advantage of this is that the Li recovery rate can be maximized during the Li smelting process if the lithium content falls outside the upper limit of the range. If the lithium content falls outside the upper limit, there is a problem of reduced recovery rates for Ni and Co. If the lithium content falls outside the lower limit of the range, there is a problem of reduced Li recovery rates during the Li smelting process and increased process costs.

[0038] In one embodiment, the valuable metal recovery alloy may contain 0.02% by weight or more of copper (Cu). Specifically, the valuable metal recovery alloy may contain copper in the range of 0.1 to 15% by weight. If the copper content falls outside the upper limit of the range, there is a problem of increased process costs due to the increased amount of CuSO4 precipitated during leaching and solvent extraction. If the copper content falls outside the lower limit of the range, there is a problem of increased unreacted material due to the difficulty in producing low-melting-point Ni-Co-Mn.

[0039] In one embodiment, the copper can combine with nickel (Ni) in the valuable metal to form an alloy. In one embodiment, the nickel can be present in a range of 5 to 40% by weight. If the nickel exceeds the upper limit of the range, there is a problem of reduced leaching rate due to the formation of nickel carbide (Ni3C), and if the nickel exceeds the lower limit of the range, there is a problem of reduced Ni recovery rate in leaching and solvent extraction.

[0040] In one embodiment, the valuable metal recovery alloy may contain carbon (C) in the range of 0.1 to 10% by weight. By satisfying this range of carbon, the actual yield can be increased and the processing time in the wet process can be reduced. Specifically, the carbon may be contained in the range of 1 to 7% by weight.

[0041] If the value falls outside the upper limit of the aforementioned range, it means that the negative electrode material remains in an unreacted state, resulting in poor alloying and the material remaining in the form of a valuable metal oxide within the positive electrode material. If the value falls outside the lower limit of the aforementioned range, it means that lithium may be lost due to high temperatures.

[0042] In one embodiment, the valuable metal recovery alloy may contain aluminum (Al) in the range of 0.25 to 30% by weight. If the aluminum content falls outside the upper limit of the range, there is a problem of reduced Ni and Co recovery rates during the leaching and solvent extraction process. If the aluminum content falls outside the lower limit of the range, there is a problem of reduced Li recovery rates due to difficulty in LiAlO2 formation.

[0043] In one embodiment, the unit valuable metal recovery composition 100 in the valuable metal recovery composition 10 can satisfy the following formula 1.

[0044] <Expression 1> 2.4 ≤ [Ni] / [Co] ≤ 4.5

[0045] (In formula 1 above, [Ni] and [Co] represent the weight percentages of Ni and Co, respectively.)

[0046] Formula 1 represents the nickel content ratio to cobalt. The fact that Formula 1 satisfies the range described above has the advantage that the recovered valuable metal recovery composition 10 can be used in materials such as NCM cathode material.

[0047] If Equation 1 falls outside the upper limit of the range mentioned above, there is a problem that the efficiency of magnetic separation decreases due to a decrease in the Co content. If Equation 1 falls outside the lower limit of the range mentioned above, it means that an abnormal reduction reaction and the resulting metal droplets have been formed, and in this case, there is a problem that the recovery rate of Ni decreases.

[0048] In one embodiment, the proportion of unit valuable metal recovery composition 100 in which the average particle size (D50) of the valuable metal recovery composition 100 exceeds 4000 μm may be 70% or less of 100% of the total valuable metal recovery composition 10. Specifically, the proportion may be 67% or less, more specifically 65% ​​or less, and even more specifically 2.5 to 50%.

[0049] If the ratio falls outside the upper limit, it means that the reduction reaction for the formation of the metal droplets in the core 110 was insufficient, which leads to a problem of a sharp decrease in the metal recovery rate. If the ratio falls outside the lower limit, there is a problem of a decrease in the leaching rate of the metal droplets by wet smelting due to an increase in metal droplets having a particle size similar to graphite.

[0050] In one embodiment, the proportion of unit valuable metal recovery composition 100 having an average particle size (D50) of 500 μm or more and less than 4000 μm may be 30% or more of the total valuable metal recovery composition 10. Specifically, the proportion may be 31.9% or more, more specifically 45.0 to 95%, and even more specifically 58.1 to 92.0%.

[0051] In one embodiment, the lithium in the valuable metal recovery composition 10, unlike Ni, Co, and Mn, cannot be reduced to form an alloy, but can combine with the Al component in the battery to form lithium oxide.

[0052] In one embodiment, the valuable metal recovery composition 10 may include a shell portion 120 disposed on a core portion 110. The shell portion 120 may be a lithium oxide disposed on the core portion 110.

[0053] The lithium oxide may include, for example, lithium-aluminum oxide. The lithium-aluminum oxide may be a lithium-aluminum compound. In the lithium-aluminum oxide, the lithium and aluminum contained in the composition can be bonded together by physical or chemical bonding to each other in an oxide.

[0054] In one embodiment, the lithium oxide may include LiAlO2, Li5AlO4, Li2CO3, and LiF. LiAlO2, Li5AlO4, and Li2CO3 are lithium oxides that react in the high-temperature reduction reaction process of battery waste, and LiF may be a lithium oxide detected by the electrolyte residue depending on the degree of pretreatment.

[0055] In one embodiment, the XRD peak may include at least one of the following 2θ ranges: 20.5–21.5°, 29.0–29.5°, 31.5–32.0°, 32.2–33.0°, 60.5–61.5°, 70.0–72.0°, 19.5–20.2°, 21.6–22.2°, 24.0–26.0°, 27.0–29.0°, 34.0–36.0°, 37.0–39.0°, 38.2–39.5°, 44.0–46.0°, 64.5–66.5°, and 77.77–79.77°.

[0056] In one embodiment, LiAlO2 may include at least one of the following XRD peaks: 20.5–21.5°, 29.0–29.5°, 31.5–32.0°, 32.2–33.0°, 60.5–61.5°, and 70.0–72.0°. Li5AlO4 may include at least one of the following XRD peaks: 19.5–20.2° and 21.6–22.2°.

[0057] The Li2CO3 composition can include at least one of 24.0 - 26.0°, 27.0 - 29.0°, 34.0 - 36.0°, and 37.0 - 39.0° in the XRD peak. The LiF composition can include at least one of 38.2 - 39.5°, 44.0 - 46.0°, 64.5 - 66.5°, and 77.77 - 79.77° in the XRD peak.

[0058] As described above, the valuable metal recovery composition 10 has an XRD peak value of at least one of LiAlO2, Li5AlO4, Li2CO3, and LiF, and it can be confirmed that lithium oxide is adhered and disposed on the core part containing valuable metals.

[0059] In one embodiment, the valuable metal recovery composition 10 can satisfy the intensity ratio of I A / I B with the following formula 2.

[0060] <Formula 2> 0.1 ≦ I A / I B ≦ 1.5

[0061] (In the above formula 2, I A is the peak intensity value at 2θ = 21° ± 0.5° of the LiAlO2 product, and I B is the peak intensity value at 2θ = 32.6° ± 0.4° of the LiAlO2 product)

[0062] The above formula 2 is a relational formula for the ratio of the peak intensity value at a specific angle of LiAlO2, which is a lithium oxide in the composition containing a lithium-containing compound that is a reactant generated through the high-temperature reduction reaction described later. The formula 2 can satisfy 0.1 - 1.5, specifically 0.3 - 1.5, and more specifically 0.7 - 1.3.

[0063] When the lower limit value of the above range is exceeded in the formula 2, Al2O3 is high in LiAl7O 11There is a problem in that an excessive amount of phase is generated, which leads to a low Li leaching rate and a decrease in lithium recovery rate. If the value of equation 2 falls outside the upper limit of the range mentioned above, a large amount of Li2O is generated, and as the temperature rises, the lithium vaporizes, which leads to a decrease in lithium recovery rate.

[0064] In one embodiment, the lithium oxide partially bonded to the surface of the valuable metal recovery alloy can be separated using a wet process. In another embodiment, the lithium oxide can be separated from the valuable metal recovery alloy by mechanical or physical external force. In this way, not only can the valuable metal recovery alloy be recovered from the valuable metal recovery composition 10, but the lithium compound can also be separated at the same time, resulting in a high lithium recovery rate and a reduction in the amount of lithium lost.

[0065] In one embodiment, the valuable metal recovery composition 10 may contain a carbon-based substance. The carbon-based substance may be, for example, the element carbon (C). The carbon content may be in the range of 1% to 7%. A carbon content within this range offers advantages in optimizing the wet processing of the valuable metal recovery composition.

[0066] If the carbon content falls outside the upper limit of the range, there is a problem of reduced leaching rate due to the formation of nickel carbide (Ni3C). If the carbon content falls outside the lower limit of the range, the content of other impurities such as Si increases, leading to a problem of reduced recovery rates of valuable metals such as Ni and Co in solvent extraction after the leaching process.

[0067] In one embodiment, the valuable metal recovery composition 10 may contain 10 to 30% by weight of aluminum (Al). The advantage of the aluminum content being within this range is that it can form lithium compounds through physical or chemical bonding with lithium, and the subsequent separation of these lithium compounds can increase the lithium yield.

[0068] If the aluminum content falls outside the upper limit of the range, excessive Al2(SO4)3 is produced in the leaching and solvent extraction steps, leading to increased costs in the Ni, Co solvent extraction and crystallization steps, and a decrease in the recovery rate of Ni and Co. If the aluminum content falls outside the lower limit of the range, insufficient aluminum content leads to a decrease in the production of Li-Al-O oxide.

[0069] In one embodiment, the unit valuable metal recovery composition 100 contains aluminum (Al), and the concentration of aluminum (Al) may have a gradually increasing gradient from the interface between the core portion 110 and the shell portion 120 toward the shell portion 120. The reason why the concentration gradient of aluminum (Al) increases toward the shell portion 120 is that an oxide containing aluminum adheres to the core portion 110 which contains a valuable metal alloy.

[0070] In one embodiment, the thickness of the shell portion 120 of the unit valuable metal recovery composition 100, in which the average particle size (D50) of the valuable metal recovery composition 100 exceeds 500 μm, may be 30 to 1100 μm. Specifically, the thickness may be 30 to 1000 μm, and more specifically, 30 to 950 μm.

[0071] In one embodiment, the thickness of the shell portion 120 of the unit valuable metal recovery composition 100, which is greater than 250 μm but less than 500 μm, may be 5 to 450 μm. Specifically, the thickness may be 10 to 400 μm.

[0072] In one embodiment, the thickness of the shell portion 120 of the unit valuable metal recovery composition 100, which is greater than 150 μm but less than 250 μm, may be 3.5 to 160 μm. Specifically, the thickness may be 5 to 150 μm.

[0073] If the thickness of the shell portion 120 falls outside the upper limit within the aforementioned average particle size range, there is a problem that the shell portion is excessively formed, leading to a decrease in the leaching rate of lithium oxide in subsequent processes. If the thickness of the shell portion 120 falls outside the lower limit within the aforementioned average particle size range, there is a problem that the recovery rate decreases because separation between the metal droplets and lithium oxide is not easy during magnetic separation.

[0074] Figure 2 is a flowchart of a valuable metal recovery method according to one embodiment of the present invention.

[0075] Referring to Figure 2, in one embodiment, the valuable metal recovery method may include the steps of preparing battery crushed material (S100), dry heat treating the crushed material (S200), and separating the heat-treated crushed material by at least one of particle size separation and magnetic separation (S300). As a method for producing an alloy with a high concentration content of the valuable metal recovery alloy, it may be a method for producing an alloy in which the concentration content of the valuable metal is higher than that of the black powder that has gone through the initial crushing stage. Furthermore, the valuable metal recovery alloy produced by the above manufacturing method is identical to that shown in Figure 1 above, to the extent that it is not inconsistent with the above.

[0076] The step of preparing the battery shredded material (S100) is the step of either shredding and preparing a material that will become the base material of the battery shredded material, or preparing the material itself after the shredding is complete. The base material of the battery shredded material can include waste materials in the manufacturing process of a lithium-ion battery, such as batteries that have reached the end of their lifespan, scrap, jelly rolls, and cathode materials such as slurry that make up the waste battery, defective products produced during the manufacturing process, residues inside the manufacturing process, and generated fragments. The material itself after the shredding is complete can be the shredded product itself, such as black powder.

[0077] In one embodiment, the step of preparing a battery or battery shredder in cell units (S100) may further include a step of crushing a material that will become the base material of the battery shredder, if the base material of the battery shredder is to be crushed. The base material of the battery shredder can be crushed using a crusher to obtain a pulverized product. The crushing is a non-limiting example and may include breaking the waste battery by applying physical or mechanical force and crushing it into a fine powder. The crushing step can separate some larger impurities in the composition contained in the waste battery, such as aluminum (Al), copper (Cu), iron (Fe), and plastic. The state in which the larger impurities have been separated is called black powder, and battery shredder such as black powder can be produced through the crushing step.

[0078] In one embodiment, the battery shredder is for recovering valuable metals from waste batteries and may be a layered structure including a separation membrane on which a positive or negative electrode is laminated on at least one surface. Specifically, the layered structure may include a configuration in which a positive or negative electrode is included on one or both surfaces of the separation membrane, with respect to the separation membrane. More specifically, the number of layers in the layered structure may correspond to the number of separation membranes.

[0079] The layered structure includes, for example, one of the following: positive electrode-separator-negative electrode, positive electrode-separator, separator-positive electrode, separator-negative electrode, and negative electrode-separator. For example, positive electrode-separator-negative electrode-separator-positive electrode-separator-negative electrode may have a three-layered structure. Specifically, the battery shredder can have a predetermined thickness in the thickness direction by stacking at least one layer.

[0080] In one embodiment, the battery shredder can satisfy the following condition 1. <Condition 1> The layered structure may be a laminated structure of 1 to 7 layers.

[0081] The battery shredder may have a layered structure having one to seven layers. Specifically, the layered structure may have one to five layers. By stacking the layers within the aforementioned range, the temperature rise of the shredder can be minimized and the heating time can be appropriately controlled. If the layered structure is stacked to a thickness exceeding the upper limit of the aforementioned range, the temperature rise will increase excessively, and the heating time will also increase, leading to combustion and potentially causing a fire.

[0082] In one embodiment, the battery shredder can satisfy the following condition 2.

[0083] <Condition 2> The size of the crushed battery material may be 100 mm or less, based on the longest axis among the horizontal, vertical, and height directions.

[0084] In one embodiment, the battery shredder may have a size of 100 mm or less based on its long axis. Specifically, the size of the battery shredder may be 50 mm or less. If the size of the battery shredder is excessively large, there is a problem that the temperature of the battery shredder itself may rise to 100°C or higher, which could cause a fire.

[0085] In one embodiment, the surface of the battery shredder may include a burnt portion and a top portion. The burnt portion means an area on the surface of the battery shredder where at least a portion has been burned, and the top portion means the top portion of the surface where there are no burn marks.

[0086] In one embodiment, the area ratio of the combustion area to the top surface of the crushed battery can be 30% or less. By keeping the area ratio of the combustion area to the top surface at 30% or less, the possibility of the crushed battery burning and causing a fire can be prevented. If the area ratio of the combustion area to the top surface exceeds 30%, there is a risk that the crushed battery will burn and cause a fire accompanied by smoke.

[0087] In one embodiment, the combustion portion may be located at the periphery of the surface of the battery shredder. The top portion may be located near the center of the surface of the battery shredder. The combustion portion refers to an area that exhibits a darker color compared to the top portion.

[0088] In one embodiment, the battery fragments may include aluminum (Al), manganese (Mn), lithium (Li), copper (Cu), cobalt (Co), nickel (Ni), carbon (C), and residual impurities. In one embodiment, the black powder may contain 5-40 wt% nickel (Ni), 1-20 wt% cobalt (Co), 1-15 wt% manganese (Mn), 0.5-5 wt% lithium (Li), 10-70 wt% carbon (C), 0.0001-20 wt% aluminum (Al), and 0.0001-20 wt% copper (Cu), with the total amount of impurities such as iron (Fe) and phosphorus (P) being less than 10 wt%. The composition of the black powder may vary depending on the ratio of nickel, cobalt, and manganese, and the nickel, cobalt, and manganese can be adjusted by the cathode material oxide of the lithium secondary battery when the lithium secondary battery is crushed.

[0089] In one embodiment, the step of crushing the material that will become the base material of the battery shredder may be a crushing method utilizing at least one of shear, compression, and tensile forces. Specifically, the crushing step may be performed by at least one of a hammer mill, a ball mill, and a stirring ball mill, for example. The hammer mill may perform at least one of disassembly, punching, and milling, and this is a non-limiting example, and it is clear that a wide variety of crushing or grinding equipment, such as industrial grinders, can be used for grinding.

[0090] In one embodiment, the particle size of the battery fragments can be within 50 mm, specifically within 30 mm. If the particle size is larger than this range, a greater energy supply is required in the heat treatment stage described later, which is uneconomical.

[0091] In one embodiment, a pretreatment step may be further included before the step of crushing the material that will become the base material of the battery shreds, in order to prevent explosion or detoxify the base material of the battery shreds. By including the pretreatment step, explosive substances such as electrolyte in the base material can be removed, and the base material, such as a waste battery, can be discharged, thereby increasing safety during the crushing step and improving the recovery of valuable metals and productivity.

[0092] The step of dry heat treatment of the crushed material (S200) involves placing the crushed material into a heating furnace (Furnace) capable of raising the temperature to a high level, thereby raising the temperature of the crushed material to a level above its melting point. The step of dry heat treatment of the crushed material (S200) may involve heat treatment conditions that carry out a high-temperature reduction reaction without going through a melting step.

[0093] In one embodiment, the heat treatment conditions can be carried out within the range of 1,150 to 1,800°C. Specifically, the range can be 1,150 to 1,400°C, and more specifically, 1,200 to 1,400°C. If the temperature is outside the upper limit of the range, there is a problem of loss due to lithium vaporization, and if it is outside the lower limit of the range, there is a problem that sintering and reduction of the alloying elements do not occur, and excessive flake formation occurs. Within the temperature range, the carbon in the crushed material can be burned to a minimum, and the reduction reaction can be carried out in a state where carbon dioxide generation is almost zero.

[0094] In one embodiment, the step of dry heat treatment of the crushed material (S200) can be carried out under a gas atmosphere of at least one of an inert gas, carbon dioxide, carbon monoxide, and hydrocarbon gas. In the case of the inert gas, for example, at least one of argon and nitrogen can be included. By carrying out the reduction reaction of the crushed material under the gas atmosphere, a valuable metal recovery alloy containing valuable metals as components contained in the crushed material can be effectively recovered.

[0095] In one embodiment, a portion of the gas atmosphere may contain impurities, including residual oxygen. If the oxygen content in the impurities is high, it may combine with components of the crushed material during the reduction reaction to form carbon dioxide, which can lead to the problem of gasification together with lithium and difficulty in recovery.

[0096] In one embodiment, the oxygen content in the dry heat treatment step (S200) may be 1% or less. Specifically, the oxygen content may be 0.1% or less. Specifically, if the partial pressure of oxygen exceeds the range described above, there is a problem of lithium loss and the generation of large amounts of carbon dioxide in localized high-temperature conditions.

[0097] Specifically, the valuable metal recovery composition, which is an alloy of components such as nickel, cobalt, manganese, and lithium-containing oxides in the crushed material during the dry heat treatment step (S200), may contain valuable metals and residual impurities. The valuable metal recovery composition may contain, for example, aluminum (Al), manganese (Mn), lithium (Li), copper (Cu), cobalt (Co), nickel (Ni), carbon (C), and residual impurities, and a detailed explanation thereof is the same as that of the valuable metal recovery composition described above in Figure 1, to the extent that it is not inconsistent.

[0098] The valuable metal recovery composition may contain a lithium compound, which can be produced by the reduction reaction. In one embodiment, the aluminum content in the valuable metal recovery composition may be 0.25 to 30% by weight. The more aluminum added, the lower the stabilization temperature during the formation of the lithium compound, for example, lithium-alumina (LiAlO2).

[0099] If the aluminum content falls outside the upper limit of the range, Li-Al-O oxide (LiAl) has a high Al2O3 content. 11 O 17 The formation of ) leads to a problem of reduced Li recovery rate. If the aluminum content falls outside the lower limit of the range, there is a problem that the formation of Li-Al-O oxide is poor due to insufficient Al2O3 content.

[0100] In one embodiment, a stirring step can be added to the heat treatment furnace. This stirring step can be carried out, for example, by using a rotating body or gas to promote the reaction in the heat treatment furnace, which is a high-temperature reduction furnace, and to ensure uniformity of the internal temperature. A valuable metal recovery composition can be recovered by the reduction reaction of black powder in the heat treatment furnace.

[0101] The step (S300) of separating the heat-treated crushed material by at least one of particle size separation and magnetic separation allows for the separation of the heat-treated crushed material, such as a valuable metal recovery alloy, by at least one of particle size separation and magnetic separation. The particle size separation method separates the particles by size or diameter and can include a variety of methods, such as using a sieve. The magnetic separation method can utilize a magnetic material to separate particles through contact with the magnetic material, and a variety of magnetic separation methods can be applied.

[0102] In one embodiment, the step (S300) of separating the heat-treated crushed material by at least one of particle size separation and magnetic separation may be a step of separating by at least one of particle size separation, magnetic separation, and specific gravity difference separation. The specific gravity difference separation is a method of separating particles by taking into account the difference in specific gravity of different substances, and for example, by utilizing a specific solvent, particles can be separated based on the magnitude of the specific gravity of the particles corresponding to the specific solvent, and various types of specific gravity difference separation methods can be applied.

[0103] In one embodiment, the step (S300) of separating the heat-treated crushed material by at least one of particle size separation and magnetic separation includes the steps of performing particle size separation, magnetic separation, and both particle size separation and magnetic separation, thereby enabling the separation of the valuable metal recovery alloy. In the step of performing only particle size separation, the valuable metal recovery alloy can be recovered by particle size separation alone from a valuable metal recovery composition with a particle size of 100 μm to 100 mm or less.

[0104] In the case of magnetic separation, if the valuable metal recovery composition contains a substance with a particle size of 100 μm or less, the valuable metal can be recovered from the valuable metal recovery composition by magnetic separation alone. In the case of the substance with a particle size of 100 μm or less, since its particle size is similar to that of carbon, the recovery rate of valuable metals that would be lost by particle size separation alone can be increased through magnetic separation.

[0105] In one embodiment, when both particle size separation and magnetic separation are performed, the magnetic separation can be performed first, followed by the particle size separation. By performing the magnetic separation first, the loss of the valuable metal recovery alloy from the valuable metal recovery composition with particles smaller than 100 μm can be prevented.

[0106] In one embodiment, the step of separating the heat-treated crushed material by at least one of particle size separation and magnetic separation (S300) may further include a step of separating it from lithium-containing lithium compounds. The step of separating it from lithium-containing lithium compounds can be performed before or after the step of separating the heat-treated crushed material by at least one of particle size separation and magnetic separation (S300).

[0107] The lithium compound may be, for example, a lithium-containing oxide, which can be separated by physical force. A detailed explanation of this can be found in the valuable metal recovery composition shown in Figure 1, to the extent that it is consistent with the description. In this way, by separating the lithium-containing oxide by physical force, the recovery rate of not only the valuable metal but also the lithium can be increased.

[0108] In one embodiment, the step of freezing the battery may be further included before the step of preparing the battery shredded material (S100). As explained above, if the base material of the battery shredded material is the battery itself, it must be crushed.

[0109] When a battery is used as the base material for the crushed battery material, the process may include a step of freezing the battery before crushing the crushed battery material. If the battery is crushed directly, an explosion and fire may occur due to the electrolyte contained within the battery. Specifically, when a certain pressure is applied to the battery, the separator is physically crushed, a high current is formed due to a short circuit, a spark is generated, and this spark can cause the electrolyte to ignite, resulting in a fire.

[0110] The step of freezing the battery involves freezing the battery to suppress the ignition of the liquid electrolyte contained within it, and then carrying out the crushing process, thus preventing problems caused by electrolyte ignition.

[0111] In one embodiment, the step of freezing the battery can be carried out by cooling in the range of -150°C to -60°C. If the temperature is outside the upper limit of the above temperature range, the voltage remaining inside the battery may not drop to 0V, a battery reaction due to a short circuit may occur, and the electrolyte will not be completely frozen, which is not appropriate.

[0112] If the temperature falls outside the lower limit of the aforementioned temperature range, the electrolyte is sufficiently frozen, and the internal voltage of the battery drops to 0V. Therefore, even if a short circuit occurs where the positive and negative electrodes are in direct contact, no battery reaction takes place, and the battery temperature does not rise, thus preventing the generation of electrolyte gas and combustion. Furthermore, because the electrolyte is frozen, the mobility of lithium ions is very low, which significantly reduces the current-carrying characteristics due to lithium ion movement. Since the electrolyte does not vaporize, it does not generate flammable gases such as ethylene, propylene, and hydrogen.

[0113] If the temperature exceeds the upper limit of the temperature range during the freezing stage of the battery, the voltage remaining inside the battery will not drop to 0V, which may cause a short circuit and battery reaction, and the electrolyte will not be completely frozen, making it unsuitable. If the temperature exceeds the lower limit of the temperature range, a large amount of energy must be supplied for freezing, which is uneconomical.

[0114] In one embodiment, the step of freezing the battery can be carried out by cooling it in a temperature range of -60 to -20°C under a vacuum atmosphere of 100 torr or less. The step of freezing the battery can be carried out in the temperature range that suppresses the vaporization of the electrolyte. The vacuum atmosphere may be, for example, an inert gas, carbon dioxide, nitrogen, water, or a combination thereof.

[0115] By performing the process in a vacuum atmosphere with controlled pressure of 100 torr or less, oxygen supply is suppressed, preventing the electrolyte from reacting with oxygen and thus preventing explosions. Furthermore, vaporization of the electrolyte is suppressed, thus preventing the generation of flammable gases such as ethylene, propylene, and hydrogen.

[0116] When freezing the battery, if the process is carried out in an air atmosphere or under a pressure exceeding 100 torr, some voltage may remain inside the battery. Since the electrolyte is not frozen at a temperature range of -60 to -20°C, a spark generated when a short circuit occurs due to the remaining voltage can vaporize the electrolyte and cause an explosion.

[0117] Thus, according to one embodiment of the present invention, it is possible to provide a method for manufacturing an environmentally friendly waste battery recovery alloy that has excellent recovery rates for valuable metals, such as nickel, cobalt, lithium, and manganese, by having a concentration of 150 to 500% compared to the constituent content of the heat-treated battery crushed material, and that contains less than 10% carbon, thereby suppressing the generation of carbon dioxide in subsequent processes. [Examples]

[0118] To illustrate the present invention in more detail, embodiments of the present invention are described below. The embodiments described below are merely one example of the present invention, and the present invention is not limited to these embodiments.

[0119] <Example of experiment> In the experimental examples of the present invention, carbon content was measured using a combustion method with a CS analyzer (LECO). Oxygen content was measured using an infrared sensing method with an NO analyzer (LECO). In addition, inorganic substances other than carbon and oxygen were analyzed for their components through ICP wet analysis.

[0120] In the experimental examples of the present invention, particle size measurement was performed by estimating the particle size of each substance through particle size analysis using a particle size analyzer and component analysis of substances separated by screening.

[0121] 1. Preparing the battery fragments Figures 3a and 3b show battery fragments according to one embodiment of the present invention.

[0122] Figures 3a and 3b show that the battery shredder has a layered structure in which the positive electrode, negative electrode, and separation membrane are stacked in order. Specifically, it can be confirmed that the layered structure of the battery shredder consists of at least one layer, and the size of the battery shredder is 100 mm or less. The size of the battery shredder refers to the length of the long axis among the width, length, and height of the battery shredder.

[0123] 2. Dry heat treatment stage <Components of the composition for recovering valuable metals by a high-temperature reduction process> The battery fragments shown in Figures 3a and 3b can be heat-treated at a temperature of 1100°C or higher, which is higher than the melting point of Cu, and with an oxygen content of less than 1%. Because carbon is present in the negative electrode active material, it reacts with the oxygen partially present in the gas to produce CO gas, and a reducing atmosphere can be formed. As a result, the metal oxides in the positive electrode active material are reduced, ultimately forming a metal core.

[0124] Table 1 below shows the component range of the magnetic material when the crushed battery material shown in Figures 3a and 3b is subjected to a high-temperature reduction reaction within the temperature and oxygen content ranges shown in Table 1 below and then magnetically separated. Specifically, the magnetic material shows the component range of the magnetic material including the recovered valuable metal alloy. In this case, the raw material used was NCM622, and it was confirmed that it was formed so that the ratio of Ni, Co, and Mn in the battery was close to the initial composition ratio of 6:2:2. Furthermore, the recovered alloy with a Ni / Co weight ratio in the range of 3.0±1.6 contains impurities of Na: 2 wt% or less, K: 0.1 wt% or less, Ca: 0.7 wt% or less, and Mg: 0.5 wt% or less.

[0125] [Table 1]

[0126] As seen in Table 1 above, it was confirmed that the high-temperature reduction process satisfies the requirement of an oxygen content of less than 1%, and that the heat treatment is performed at a temperature range above the melting point of copper, resulting in a Ni / Co weight ratio of 2.4 to 4.5 and a high content of valuable metals.

[0127] <XRD analysis results of compositions for recovering valuable metals by high-temperature reduction process> Figures 4a and 4b show the results of XRD analysis of a valuable metal recovery composition according to one embodiment.

[0128] Figures 4a and 4b show the XRD analysis results of a valuable metal recovery composition obtained by heat-treating the battery fragments at a temperature of 1,200°C or higher and with an oxygen content of less than 1%. Specifically, it was confirmed that the lithium component, unlike Ni, Co, and Mn, could not be reduced to form an alloy, but instead combined with the Al component in the waste battery to form lithium oxide. Specifically, it was confirmed that the lithium oxide was formed as LiAlO2, Li5AlO4, and Li2CO3, and that LiF was also detected depending on the electrolyte residue.

[0129] <SEM-EDS analysis results of compositions for recovering valuable metals by high-temperature reduction process> Figures 5a to 5c show the SEM-EDS analysis results of a valuable metal recovery composition according to one embodiment.

[0130] From Figures 5a to 5c, LineScan component analysis results for the metal core and the lithium oxide surrounding the metal core show that the Al content is negligible in the metal core, but is detected in large quantities in the lithium oxide surrounding the core. XRD analysis confirmed that this is not Al2O3, but rather LiAlO2 or Li5AlO4.

[0131] <Particle size distribution of compositions for recovering valuable metals by high-temperature reduction process> Figure 6 shows the particle size distribution of a valuable metal recovery composition according to one embodiment.

[0132] Figure 6 shows that the composition for recovering valuable metals, specifically the composition including the core and shell components, has the particle size distribution shown in Table 2 below.

[0133] Table 2 below shows the particle size distribution of a valuable metal recovery composition formed by heat treatment temperature in a high-temperature reduction process under conditions where the oxygen concentration is 1% or less, specifically including metal droplets and oxides formed around them. The particle size distribution means that the average particle size (D50) of the composition including the core and the oxides formed around the core falls within the range shown in Table 2 below. The particle size distribution was determined by weight after sorting by particle size using screen vibration sorting equipment.

[0134] [Table 2]

[0135] As can be seen in Table 2 above, the proportion of magnetic material in the total reactant remained at approximately 50% as the heat treatment temperature increased from 1,100°C to 1,400°C, showing no significant difference. However, examining the particle size distribution of particles larger than 4,000 μm in the magnetic material, it can be seen that it decreases sharply to 66.8%, 38.0%, and 3.1% as the heat treatment temperature increases. This is because at 1,100°C, the reduction of the cathode material oxide is insufficient, allowing the existing bulky structure (flake type) of the crushed material to be maintained. These flake-type reactants, which exist as large particles of 4,000 μm or more, decreased as the temperature increased. As the heat treatment temperature increases, the reduction of the cathode material oxide increases, and alloying becomes easier. The distribution ratio of micron particles with a particle size between 250 μm and 4,000 μm increases to 31.9%, 58.1%, and 92.0% with increasing temperature. Specifically, at a low heat treatment temperature of 1,100°C, materials with a particle size of 4,000 μm or larger account for the highest proportion. This is because the reduced metal components are not completely melted, preventing the formation of droplets (metal cores), and instead maintaining a flake form that preserves the shape of large-grained fragments.

[0136] In contrast, as the heat treatment temperature increases, the amount of coarse particles larger than 4,000 μm decreases, while the amount of particles smaller than that increases. However, at a high temperature of 1,400°C, there are fewer coarse particles that maintain a flake-like fragment shape, and a larger proportion of particles with lower particle sizes. This confirms that the metal reduced at high temperatures melts sufficiently, resulting in a high proportion of particles that can form droplets.

[0137] Thus, we confirmed that the larger the particle size distribution of the heat-treated product, with particle sizes ranging from 250 μm to less than 4,000 μm, the more coarse droplets there are, which are easier to form into droplets. This makes magnetic separation in subsequent processes easier, resulting in a higher recovery rate of valuable metals and lithium. Furthermore, the thickness of the lithium oxide surrounding the metal core varies depending on the particle size of the metal droplets.

[0138] <Thickness range of lithium oxide according to particle size of compositions for recovering valuable metals by high-temperature reduction process> Table 3 below shows the range of lithium oxide thickness surrounding the metal core, according to the particle size of the metal droplets described in Table 2 above.

[0139] The thickness of the lithium oxide was measured using a scanning electron microscope (SEM) for an area of ​​1900 μm × 2500 μm.

[0140] [Table 3]

[0141] Table 3 shows that the thickness of the lithium oxide was greater in the range where the particle size distribution of metal droplets was 500 μm or more. This confirms that when the distribution of metal droplets with large particle sizes constitutes the majority of the particle size distribution of the overall composition, the lithium oxide is thicker, magnetic separation of the metal core is easier, and lithium can be easily recovered by recovering the lithium oxide adhering to the surface of the metal core.

[0142] The present invention is not limited to the embodiments described above, and can be manufactured in a variety of different forms. Those with ordinary skill in the art to which the invention pertains should understand that it can be implemented in other specific forms without altering the technical idea or essential features of the invention. Therefore, it should be understood that the embodiments described above are illustrative and not limiting in all respects.

Claims

1. This relates to a valuable metal recovery composition comprising at least one or more unit valuable metal recovery compositions, The unit valuable metal recovery composition is, Core portion containing valuable metals; and The core portion includes a shell portion which is disposed in at least a part of the core portion, The aforementioned shell portion contains an oxide containing lithium, A valuable metal recovery composition in which the proportion of the unit valuable metal recovery composition having an average particle size (D50) exceeding 4000 μm is 70% or less of the total valuable metal recovery composition.

2. A valuable metal recovery composition according to claim 1, satisfying the following formula 1. <Formula 1> 2.4≦[Ni] / [Co]≦4.5 (In formula 1 above, [Ni] and [Co] represent weight percentages of Ni and Co, respectively.)

3. The aforementioned unit valuable metal recovery composition contains aluminum (Al), The valuable metal recovery composition according to claim 1, wherein the aluminum (Al) has a concentration gradient that gradually increases from the interface between the core portion and the shell portion toward the shell portion.

4. The valuable metal recovery composition according to claim 1, wherein the XRD peaks include at least one of the following 2θ values: 20.5–21.5°, 29.0–29.5°, 31.5–32.0°, 32.2–33.0°, 60.5–61.5°, 70.0–72.0°, 19.5–20.2°, 21.6–22.2°, 24.0–26.0°, 27.0–29.0°, 34.0–36.0°, 37.0–39.0°, 38.2–39.5°, 44.0–46.0°, 64.5–66.5°, and 77.77–79.77°.

5. The lithium-containing oxide is LiAlO ２ Li ５ AlO ４ Li ２ CO ３ The valuable metal recovery composition according to claim 1, comprising at least one of , and LiF.

6. A valuable metal recovery composition according to claim 1, satisfying the following formula 2. <Formula 2> 0.1≦I Ａ / I Ｂ ≦1.5 (In the above formula 2, I Ａ is the peak intensity value of the LiAlO ２ product at 2θ = 21° ± 0.5°, and I Ｂ is the peak intensity value of the LiAlO ２ product at 2θ = 32.6° ± 0.4°)

7. The valuable metal recovery composition according to claim 1, wherein the proportion of unit valuable metal recovery compositions having an average particle size (D50) of 500 μm or more and less than 4000 μm is 30% or more of the total valuable metal recovery composition.

8. The valuable metal recovery composition according to claim 1, wherein the average particle size (D50) of the valuable metal recovery composition is 500 μm or more, and the thickness of the shell portion of the unit valuable metal recovery composition is 30 to 1100 μm.

9. The valuable metal recovery composition according to claim 1, wherein the average particle size (D50) of the valuable metal recovery composition is 250 μm or more and less than 500 μm, and the thickness of the shell portion of the unit valuable metal recovery composition is 5 to 450 μm.

10. The valuable metal recovery composition according to claim 1, wherein the average particle size (D50) of the valuable metal recovery composition is 150 μm or more and less than 250 μm, and the thickness of the shell portion of the unit valuable metal recovery composition is 3.5 to 160 μm.

11. The valuable metal recovery composition according to claim 1, wherein the shell portion bonded to the core portion is separated by an external force.

12. The valuable metal recovery composition according to claim 1, wherein the valuable metal comprises at least one of lithium (Li), cobalt (Co), nickel (Ni), aluminum (Al), and manganese (Mn).

13. The stage of preparing individual battery cells or battery fragments; A step of dry heat treatment of the battery or the crushed material; and The step includes separating the heat-treated crushed material by at least one of particle size separation and magnetic separation, The step of dry heat treatment of the crushed material is a method for recovering valuable metals, in which heat treatment conditions are performed to carry out a high-temperature reduction reaction in an inert atmosphere containing 1% or less oxygen and a temperature range of 1,150 to 1,800°C, without going through a melting step.

14. In the stage of preparing the aforementioned battery shredder, The method for recovering valuable metals according to claim 13, wherein the battery shredder satisfies the following conditions 1 and 2. <Condition 1> The layered structure is a laminated structure consisting of one to seven layers. <Condition 2> The size of the unit battery shredded material is 100 mm or less, with respect to the longest axis among the horizontal, vertical, and height directions.

15. The method for recovering valuable metals according to claim 13, wherein the step of separating the heat-treated crushed material by at least one of particle size separation and magnetic separation is to perform magnetic separation first, followed by particle size separation.

16. The method for recovering valuable metals according to claim 13, wherein the lithium compound bonded to a portion of the surface of the valuable metal recovery alloy is separated by an external force.

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