Valuable metal recovery alloy, valuable metal recovery composition, and valuable metal recovery method

Abstract

The present embodiment relates to a valuable metal recovery alloy, a valuable metal recovery composition, and a valuable metal recovery method. In one embodiment, the valuable metal recovery alloy contains 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, and can satisfy the following formula 1. <Expression 1> 0.02≦[C] / [Ni]≦7 ([C] and [Ni] mean the weight percentages of C and Ni, respectively.)

Description

[Technical field]

[0001] The present embodiment relates to the reuse of waste battery components, more specifically to a method for producing concentrated metals from waste batteries, and 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 secondary batteries, such as batteries from electric vehicles, is becoming a global issue. Secondary batteries, especially lithium-ion batteries, contain fire hazards caused by organic solvents, explosive substances, and heavy metals such as Ni, Co, Mn, and Fe. Among them, Ni, Co, Mn, and Li are valuable metals that are scarce and have utility value. As a result, the recovery and reuse process of lithium-ion batteries after they are discarded has become a very important 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), manganese (Mn) oxides that make up the cathode, and graphite used as the anode, a separator that separates the cathode and anode, and an electrolyte that is poured into the separator. The electrolyte is composed of a solvent and a salt, and the solvent can be a mixture of carbonate organics such as ethylene carbonate and propylene carbonate, and the salt can be LiPF6 (lithium hexafluorophosphate).

[0004] In order to reuse the secondary batteries, such as battery cells, battery modules, and battery packs, black powder containing a mixture of positive and negative electrode materials is extracted from waste batteries through a crushing process, a grinding process, a specific gravity separation process, and a magnetic separation process. The black powder contains some impurities, such as oxides of nickel, cobalt, manganese, lithium, aluminum, and oxygen as positive electrode materials, graphite and its mixture as negative electrode materials, aluminum, and copper. The methods for recovering valuable metals from the black powder are largely divided into wet and dry processes. The wet process produces NiSO4, CoSO4, MnSO4, and Li2CO3 through leaching, solvent extraction, and lithium production. The biggest problems with treating the black powder with the wet process are that the graphite, which is the negative electrode material contained in the black powder, does not dissolve in a strong acid atmosphere, which makes the leaching process time-consuming, and that it is separated together with the graphite, which reduces the recovery rate.

[0005] In addition, the dry process is a process of removing aluminum in the slag from the black powder through a high-temperature dry process, and can produce Ni-Co-Mn-C alloy. The dry process reduces the Ni-Mn-Li-Al-O oxide in the black powder at high temperatures, for example, 1400°C to 1600°C, using graphite and oxygen blowing, and generates CO or CO2 gas, and can remove the Ni-Co-Mn alloy and lithium and aluminum in the slag. The separated Ni-Co-Mn alloy can be subjected to the same wet process. NiSO4, CoSO4, and MnSO4 are produced through the leaching-solvent extraction process in the wet process, and the time required for the leaching process is reduced to about 70% compared to when the black powder is used, because carbon is dissolved in the alloy. However, in this process, valuable metals such as lithium and aluminum are consumed as slag, and the lithium cannot be recovered. In addition, the blowing of oxygen to remove graphite from the black powder introduced into the high-temperature dry process generates excessive carbon dioxide, which may cause environmental problems.

[0006] Therefore, in order to solve the environmental problems, it is necessary to develop a high-temperature melting and reduction process that minimizes the generation of carbon dioxide while minimizing the consumption of lithium, which is a valuable metal, and produces Ni-Co-Mn alloys with a carbon content of 10% or less, and the ratio of alloyed components. Summary of the Invention [Problem to be solved by the invention]

[0007] The technical problem to be solved by the present invention is to provide a valuable metal recovery alloy that minimizes carbon dioxide generation in black powder, provides a high concentration of valuable metals, prevents environmental pollution, and provides a high recovery rate of valuable metals. Another technical problem to be solved by the present invention is to provide a valuable metal recovery composition having the above-mentioned advantages. Another technical problem to be solved by the present invention is to provide a valuable metal recovery method for providing a valuable metal recovery alloy having the above-mentioned advantages. [Means for solving the problem]

[0008] The valuable metal recovery alloy according to one embodiment of the present invention contains 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, and may satisfy the following formula 1. <Expression 1> 0.02≦[C] / [Ni]≦7 ([C] and [Ni] mean the weight percentages of C and Ni, respectively.)

[0009] In one embodiment, the valuable metal may be 70% by weight or more. In one embodiment, the valuable metal may contain 0.01 to 5% by weight of lithium (Li). In one embodiment, the XRD peak value may have at least one diffraction peak at 2θ=44°±1°, 2θ=51.5°±1.5°, and 2θ=75.5°±1.5°.

[0010] In one embodiment, the valuable metal recovery alloy may satisfy the following formula 2: <Expression 2> 0.1 B / I A <0.98 (In the above formula 2, I A is the peak intensity value at 2θ = 44° ± 1°, and I B is the peak intensity value at 2θ=51.5°±1.5°)

[0011] In one embodiment, the valuable metal recovery alloy may include copper (Cu) in an amount of 0.02 wt % or more. In one embodiment, the copper (Cu) may combine with nickel (Ni) in the valuable metal to form an alloy.

[0012] In one embodiment, the valuable metal recovery alloy may include 0.1 to 10 wt% carbon (C). In one embodiment, the valuable metal recovery alloy may include 0.25 to 30 wt% aluminum (Al). In one embodiment, the valuable metal may include at least one of lithium (Li), cobalt (Co), nickel (Ni), aluminum (Al), and manganese (Mn).

[0013] According to another embodiment of the present invention, the valuable metal recovery composition includes a valuable metal recovery alloy and a lithium compound, and the lithium content in the composition is 0.1 to 10 wt %, and the valuable metal content in the lithium-containing composition may be 45 wt % or more. In one embodiment, the valuable metal recovery alloy may satisfy the following formula 1: <Expression 1> 0.02≦[C] / [Ni]≦7 ​([C] and [Ni] mean the weight percentages of C and Ni, respectively.)

[0014] In one embodiment, the lithium compound can be bound to a surface portion of the valuable metal recovery alloy. In one embodiment, the lithium compound bound to a surface portion of the valuable metal recovery alloy can be separated by an external force.

[0015] In one embodiment, the valuable metal recovery composition can include a carbonaceous material. In one embodiment, the valuable metal recovery composition can include 10 to 30 wt% aluminum (Al). In one embodiment, the valuable metal can include at least one of lithium (Li), cobalt (Co), nickel (Ni), aluminum (Al), and manganese (Mn).

[0016] According to another embodiment of the present invention, a valuable metal recovery method includes the steps of preparing a battery or crushed battery material in a cell unit, dry heat treating the battery or crushed battery material, and separating the heat-treated crushed battery material by at least one of particle size separation and magnetic separation, and the step of dry heat treating the crushed battery material involves heat treatment conditions for performing a high-temperature reduction reaction at 900 to 1,800°C without going through a melting step, and the heat treatment conditions satisfy the operating temperature of the following formula 3, and the lithium content is 0.1 to 10 wt% based on 100 wt% of the total composition of a valuable metal recovery composition including a valuable metal recovery alloy and a lithium compound, and the content of valuable metals in the composition including the lithium content is 70 wt% or more, and the valuable metals can be recovered from the remainder, which is an impurity. <Expression 3> 1050≦(1550±250)×exp((-0.0005×[Cu])+(-0.01×[Al]))≦1800 (In formula 3, [Al] is the Al content (wt%) contained in the crushed material, [Cu] is the Cu content (wt%) contained in the crushed material, and the unit of the heat treatment conditions is °C.)

[0017] In one embodiment, the crushed battery material may include aluminum (Al) and copper (Cu). In one embodiment, the aluminum (Al) may be included in an amount of 0.5 to 30 wt %. In one embodiment, the copper (Cu) may be included in an amount of 0.25 wt % or more.

[0018] In one embodiment, the step of separating the heat-treated crushed material by at least one of particle size separation and magnetic separation may include performing magnetic separation first, followed by particle size separation. In one embodiment, the valuable metal recovery alloy may include, based on a total composition of the valuable metal recovery alloy (100 wt%), lithium (Li): 0.1 to 10 wt%, valuable metal: 45 wt% or more, and the remainder being impurities.

[0019] In one embodiment, the method may further include a step of freezing the battery before the step of preparing the crushed battery. In one embodiment, the step of freezing the battery may be performed by cooling the battery at -150°C to -60°C.

[0020] In one embodiment, the freezing of the battery may be performed under a vacuum atmosphere of 100 torr or less, at −60° C. to −20° C. In one embodiment, the dry heat treatment may be performed under at least one atmosphere of a reducing gas and an inert gas. In one embodiment, the average oxygen partial pressure in the dry heat treatment may be 0.01 to 1 atm.

[0021] In one embodiment, the valuable metal content of the valuable metal recovery alloy is enriched by 150 to 500 wt % compared to the valuable metal content of the crushed material. In one embodiment, a lithium compound can be produced in the dry heat treatment step.

[0022] In one embodiment, the lithium compound can be bound to a surface portion of the valuable metal recovery alloy. In another embodiment, the lithium compound bound to a surface portion of the valuable metal recovery alloy can be separated by an external force.

[0023] In one embodiment, the components of the crushed battery material include 5-40 wt% nickel (Ni), 1-15 wt% cobalt (Co), 1-15 wt% manganese (Mn), 0.5-5 wt% lithium (Li), and the balance impurities, and the components of the valuable metal alloy include 10-60 wt% nickel (Ni), 5-20 wt% cobalt (Co), 1-20 wt% manganese (Mn), 3-15 wt% lithium (Li), and the balance impurities. Effect of the Invention

[0024] According to an embodiment of the present invention, there is provided a valuable metal recovery alloy that can minimize carbon dioxide generation and maximize valuable metal recovery by reducing the carbon content from crushed battery material. According to another embodiment of the present invention, there is provided a valuable metal recovery composition having the above advantages. According to another embodiment of the present invention, there is provided a valuable metal recovery method for providing a valuable metal recovery alloy having the above advantages. [Brief description of the drawings]

[0025] [Figure 1] 3 is a photograph of an alloy composition for recovering valuable metals and carbon according to an embodiment of the present invention; [Figure 2a] 1 shows the XRD peaks of a valuable metal recovery alloy according to one embodiment of the present invention. [Figure 2b] This is an enlarged view of the peak intensity values ​​at azimuth angles of 44°±1°, 51.5°±1.5°, and 75.5±1.5°. [Figure 3a] 1 is a photograph of the structure of a valuable metal recovery composition according to one embodiment of the present invention. [Figure 3b] 1 is a photograph of the structure of a valuable metal recovery composition according to one embodiment of the present invention. [Figure 4] 1 is a flow chart of a valuable metal recovery method according to an embodiment of the present invention. [Diagram 5] 2 is a graph showing heat treatment conditions according to weight percent of copper and aluminum in accordance with one embodiment of the present invention. [Figure 6a] 4 illustrates the activity of lithium gas, according to one embodiment of the present invention. [Figure 6b] 1 illustrates the reduction of lithium oxide and gas generation according to one embodiment of the present invention. [Figure 7] 4 is a graph showing a voltage change caused by performing a freezing process of a frozen battery according to an embodiment of the present invention; [Figure 8a] 1 shows the state of a waste battery before and after crushing according to one embodiment of the present invention. [Figure 8b] 1 shows the state of a waste battery before and after crushing according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0026] Terms such as first, second, and third are used to describe various parts, components, regions, layers, and / or sections, but are not limited thereto. These terms are used only to distinguish one part, component, region, layer, or section from another part, component, region, layer, or section. Thus, a first part, component, region, layer, or section described below can be referred to as a second part, component, region, layer, or section without departing from the scope of the present invention. The terminology used herein is merely for the purpose of referring to particular embodiments and is not intended to limit the present invention. As used herein, the singular form includes the plural form unless the phrase clearly indicates otherwise. As used in the specification, the meaning of "comprising" embodies the specified features, regions, integers, steps, operations, elements, and / or components and does not exclude the presence or addition of other features, regions, integers, steps, operations, elements, and / or components. When an element is referred to as being "on" or "on" another element, this means that it is directly on or above the other element, or there may be other elements between them. In contrast, when an element is referred to as being "directly on" another element, there are no other elements between them. Unless otherwise defined, all terms, including technical and scientific terms, used herein have the same meaning as commonly understood by a person of ordinary skill in the art to which the present invention belongs. Terms defined in commonly used dictionaries are additionally interpreted to have a meaning consistent with the relevant technical literature and the currently disclosed content, and are not interpreted in an ideal or very formal sense unless otherwise defined.

[0027] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail, but they are given by way of example only and are not intended to limit the present invention, which is defined only by the scope of the claims set forth below.

[0028] FIG. 1 is a photograph of a valuable metal recovery composition and carbon according to one embodiment of the present invention. Referring to FIG. 1, the valuable metal recovery alloy may contain 45% or more by weight 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 may refer to expensive metal components contained in a battery, and may refer to nickel, cobalt, manganese, aluminum, copper, and lithium. In one embodiment, the valuable metals may be 70% or more by weight.

[0029] In one embodiment, the valuable metal recovery alloy may satisfy the following formula 1: <Expression 1> 0.02≦[C] / [Ni]≦7 ([C] and [Ni] mean the weight percentages of C and Ni, respectively.) The formula 1 is the content ratio of carbon to nickel, and the value of the formula 1 may be 0.02 to 7, specifically, 0.02 to 6, and more specifically, 0.02 to 3. When the content ratio of carbon to nickel satisfies the range of the formula 1, there are advantages in terms of reducing the amount of carbon dioxide generated and the efficiency of the wet reaction. If the value of formula 1 is greater than 7%, the reaction rate is very slow, if the value of formula 1 is greater than 6%, the carbon is saturated in the nickel, so it is difficult to evaluate, and if the value of formula 1 is greater than 3%, the amount of residual alloy remaining after reaction is excessively large. If the value of formula 1 is less than 0.02%, the oxygen ratio increases depending on the oxygen partial pressure state, which induces the loss of lithium described below, and the efficiency of the wet reaction is reduced. In one embodiment, lithium (Li) may be included in the valuable metal in a range of 0.01 to 5 wt %. By satisfying the lithium range, there is an advantage that the Li recovery rate during the Li smelting process can be maximized. If the upper limit of the range is exceeded, there is a problem of a decrease in Ni and Co recovery rates, and if the lower limit of the range is exceeded, there is a problem of an increase in process costs due to a decrease in Li recovery rate during the Li smelting process.

[0030] In one embodiment, the valuable metal recovery alloy may contain copper (Cu) in an amount of 0.02 wt% or more. Specifically, the valuable metal recovery alloy may contain copper in a range of 0.1 to 15 wt%. If the copper content is outside the upper limit of the range, there is a problem of process costs due to an increase in the amount of CuSO4 precipitated during leaching and solvent extraction, and if the copper content is outside the lower limit of the range, there is a problem of an increase in the amount of unreacted material due to the difficulty in producing low melting point Ni-Co-Mn.

[0031] In one embodiment, the copper can combine with nickel (Ni) in the valuable metals to form an alloy. In one embodiment, the nickel can be included in a range of 5 to 40 wt %. If the nickel exceeds the upper limit of the range, there is a problem of a decrease in the leaching rate due to the generation of nickel carbide (Ni3C), and if the nickel exceeds the lower limit of the range, there is a problem of a decrease in the Ni recovery rate during leaching and solvent extraction.

[0032] In one embodiment, the valuable metal recovery alloy may contain carbon (C) in the range of 0.1 to 10 wt%. When the carbon satisfies this range, the recovery rate can be increased and the treatment time in the wet process can be reduced. Specifically, the carbon may be contained in the range of 1 to 7 wt%. If the upper limit of the range is exceeded, the negative electrode material may remain unreacted and may not be fully alloyed, resulting in a problem of remaining in the form of valuable metal oxide in the positive electrode material, whereas if the lower limit of the range is exceeded, there is a problem of loss of lithium due to high temperatures.

[0033] In one embodiment, the valuable metal recovery alloy may contain aluminum (Al) in the range of 0.25 to 30 wt %. If the aluminum content is outside the upper limit of the range, there is a problem of a decrease in Ni and Co recovery rate during the leaching and solvent extraction processes, and if the aluminum content is outside the lower limit of the range, there is a problem of a decrease in Li recovery rate due to the difficulty in producing LiAlO2.

[0034] FIG. 2a shows the XRD peaks of a valuable metal recovery alloy according to one embodiment of the present invention, and FIG. 2b shows a magnified view of the peak intensity values ​​at azimuth angles of 44°±1°, 51.5°±1.5°, and 75.5±1.5°. 2a and 2b, in one embodiment of the present invention, the valuable metal recovery alloy may include at least one of peak intensity values ​​at azimuth angles of 44°±1°, 51.5°±1.5°, and 75.5±1.5°. The valuable metal recovery alloy may have different peak intensity values ​​at the azimuth angles depending on the carbon content value relative to the nickel content in Equation 1. Specifically, the magnitude of the peak intensity value may increase as the carbon content value relative to the nickel content increases. The valuable metal recovery alloy can be confirmed to contain carbon and nickel by including at least one of the peak intensity values ​​of the azimuth angles, and specifically, it can be confirmed that the oxygen content ratio to the nickel is within the range of the present invention.

[0035] In one embodiment, the valuable metal recovery alloy may satisfy the following formula 2: <Expression 2> 0.1 B / I A <0.98 (In the above formula 2, I A is the peak intensity value at 2θ = 44° ± 1°, and I B is the peak intensity value at 2θ=51.5°±1.5°) The formula 2 is derived from the relationship between copper and nickel. By satisfying the formula 2, it is possible to provide an alloy with high valuable metal recovery while minimizing carbon dioxide generation.

[0036] 3a and 3b are photographs of the structure of a valuable metal recovery composition according to one embodiment of the present invention. Referring to Fig. 3a, the valuable metal recovery composition according to one embodiment of the present invention may include a valuable metal recovery alloy and a lithium compound. The above description of the valuable metal recovery alloy may be referred to to the extent that it is not inconsistent. The valuable metal content in the valuable metal recovery composition may include 45 wt%. Specifically, the valuable metal recovery composition may include nickel as a main component, and may include materials such as cobalt, manganese, copper, aluminum, and lithium. ​

[0037] In one embodiment, the lithium content in the composition may be in the range of 0.1 to 10 wt %. Specifically, the lithium content in the composition may be in the range of 8 to 10 wt %. The lithium content in the composition may include the lithium content in the valuable metal recovery alloy as well as the lithium content in the lithium compound. If the upper limit of the range is exceeded, there is a problem that lithium is lost due to the process in which oxygen burns carbon, which is not an oxygen-free reaction, making it impossible to recover lithium from the valuable metals in the battery. If the lower limit of the range is exceeded, there is a problem that the recovery rate of valuable metals is reduced.

[0038] The lithium compound may be, for example, lithium-aluminum oxide. The lithium-aluminum oxide may be a lithium-aluminum compound, for example, lithium-aluminate (LiAl2O3). The lithium-aluminum oxide may be an oxide in which the lithium and aluminum contained in the composition are physically or chemically bonded to each other. For example, when valuable metals are recovered from waste batteries, the valuable metals in the waste batteries exist in the form of oxides, and are reduced by the graphite in the anode material at the process temperature and in an oxygen atmosphere according to the present invention, which will be described later. At this time, the copper current collector is melted and exists in a liquid state, and serves to solidify the reduced valuable metals. The aluminum current collector, which is different from the current collector, partially participates in the reduction reaction with the oxide of the cathode material, and the rest reacts with lithium and may remain as lithium-aluminum oxide.

[0039] 3b, the bonding state of the valuable metal alloy with lithium and aluminum can be seen. In one embodiment, the lithium compound can be bonded to a surface portion of the valuable metal recovery alloy. The lithium compound can be physically or chemically bonded to the lithium contained in the composition, specifically, the lithium disposed on the surface of the valuable metal recovery alloy.

[0040] In one embodiment, the lithium compound partially bonded to the surface of the valuable metal recovery alloy can be separated using a wet process. In another embodiment, the lithium compound 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, but the lithium compound can also be separated at the same time, so that the recovery rate of lithium is high and the amount of lost lithium can be reduced.

[0041] In one embodiment, the valuable metal recovery composition may include a carbon-based material. The carbon-based material may be, for example, carbon (C). The carbon content may be in the range of 1% to 7%. By having the carbon content satisfy the above range, it is advantageous for optimizing the wet treatment of the valuable metal recovery composition. If the carbon content is outside the upper limit of the range, there is a problem of a decrease in the leaching rate due to the generation of nickel carbide (NiC), and if the carbon content is outside the lower limit of the range, there is a problem of a decrease in the recovery rate of valuable metals such as Ni and Co in solvent extraction after the leaching process due to an increase in the content of other impurities such as Si.

[0042] In one embodiment, the valuable metal recovery composition may contain 10 to 30 wt% of aluminum (Al). When the aluminum content satisfies this range, it can form a lithium compound through physical or chemical bonding with lithium, and the lithium compound can be separated later, which is advantageous in increasing the yield of lithium. If the aluminum content is outside the upper limit of the range, excessive generation of Al2(SO4)3 during the leaching and solvent extraction processes increases the costs of the Ni, Co solvent extraction and crystallization processes and reduces the recovery rate of Ni and Co. If the aluminum content is outside the lower limit of the range, insufficient aluminum content causes poor formation of Li-Al-O oxides.

[0043] FIG. 4 is a flow chart of a valuable metal recovery method according to one embodiment of the present disclosure. Referring to FIG. 4, in one embodiment, the valuable metal recovery method may include preparing crushed battery material (S100), dry heat treating the crushed battery material (S200), and separating the heat-treated crushed battery material by at least one of particle size separation and magnetic separation (S300). The valuable metal recovery alloy may be a method for producing an alloy having a high concentration content, and in particular, a method for producing an alloy having a higher concentration content of valuable metals than black powder that has undergone an initial crushing step. In addition, the valuable metal recovery alloy produced by the above-mentioned production method is the same as that of FIG. 1 to the extent that it does not contradict. The step of preparing crushed battery material (S100) is a step of preparing a base material of the crushed battery material by crushing it, or preparing the crushed material itself. The base material of the crushed battery material may include batteries that have reached the end of their life, cathode materials such as scrap, jelly rolls, and slurry that constitute the waste batteries, defective products generated during the manufacturing process, residues in the manufacturing process, and waste batteries such as waste generated during the manufacturing process, for example, waste materials in the manufacturing process of lithium ion batteries. The crushed material itself may be the product itself that has been crushed, such as black powder.

[0044] In one embodiment, the step of preparing a cell-unit battery or crushed battery material (S100) may further include a step of crushing the material that will be the base material of the crushed battery material, if the material that will be the base material of the crushed battery material is crushed to prepare the crushed battery material. The base material of the crushed battery material can be crushed using a crusher. The crushing may include, as a non-limiting example, crushing the waste battery by applying a physical or mechanical force and pulverizing the waste battery into powder. The crushing step may separate impurities that are large in size from impurities such as aluminum (Al), copper (Cu), iron (Fe), and plastic contained in the waste battery. The state in which the large impurities are separated is called black powder, and the crushing step may produce the crushed battery material such as black powder.

[0045] In one embodiment, the battery shredder may include aluminum (Al), manganese (Mn), lithium (Li), copper (Cu), cobalt (Co), nickel (Ni), carbon (C), and the remaining impurities. In one embodiment, the black powder may include 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), and the total of impurities such as iron (Fe) and phosphorus (P) may be 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 according to the oxide of the positive electrode material in the lithium secondary battery when the lithium secondary battery is crushed.

[0046] In one embodiment, the step of crushing the material to be the base material of the battery crushed material may be a crushing method using at least one of shear, compression, and tension. Specifically, the crushing step may be performed by at least one of a hammer mill, a ball mill, and an agitating ball mill. The hammer mill performs at least one of disintegration, punching, and milling, and it is clear that the crushing can be performed using various types of crushing or grinding devices, such as an industrial grinder, as a non-limiting example.

[0047] In one embodiment, the particle size of the crushed battery material may be within 50 mm, specifically within 30 mm. If the particle size is larger than this range, more energy needs to be supplied in the heat treatment step described later, which is uneconomical.

[0048] In one embodiment, a pretreatment step may be further included to prevent explosion or render harmless the base material of the crushed battery material before the step of crushing the material to be the base material of the crushed battery material. By including the pretreatment step, materials that may explode, such as electrolyte, in the base material may be removed, and the base material, such as waste batteries, may be discharged, thereby improving safety during the crushing step and increasing the recovery and productivity of valuable metals. The step of dry heat treating the crushed material (S200) may involve heating the crushed material to a temperature above the melting point by feeding the crushed material into a furnace capable of heating the crushed material to a high temperature. The step of dry heat treating the crushed material (S200) may involve heat treatment conditions for performing a high-temperature reduction reaction without a melting step.

[0049] In one embodiment, the heat treatment conditions may be in the range of 900 to 1,800°C. Specifically, the range may be 1,200 to 1,800°C, more specifically, 1,300 to 1,700°C. If the upper limit of the range is exceeded, there is a problem of lithium being lost due to vaporization, and if the lower limit of the range is exceeded, there is a problem of alloying elements not being sintered and reduced. Within the temperature range, carbon in the crushed material is burned to a minimum, and a reduction reaction can be performed with almost no carbon dioxide generation. A detailed description of this will be given later with reference to FIG. 5.

[0050] In one embodiment, the step of dry heat treating the crushed material (S200) can be performed in an atmosphere of at least one of an inert gas, carbon dioxide, carbon monoxide, and a hydrocarbon gas. The inert gas may include at least one of argon and nitrogen. By performing a reduction reaction of the crushed material in the gas atmosphere, valuable metal recovery alloys containing valuable metals contained in the crushed material can be effectively recovered.

[0051] In one embodiment, a portion of the gas atmosphere may contain impurities including residual oxygen. If the impurities contain a large amount of oxygen, they may combine with components of the crushed material during the reduction reaction to form carbon dioxide, which may be gasified together with lithium and may be difficult to recover.

[0052] In one embodiment, the average oxygen partial pressure in the dry heat treatment step (S200) may be in the range of 0.01 to 1 atm. In particular, if the oxygen partial pressure is higher than this value, there is a problem of lithium loss and large amounts of carbon dioxide being generated in a local high temperature state. If the oxygen partial pressure is lower than the lower limit of this range, there is a problem of a decrease in Li recovery rate due to poor formation of LiAlO2. Specifically, the valuable metal recovery composition may be an alloy of components such as nickel, cobalt, manganese, and lithium-containing oxides in the crushed material in the dry heat treatment step (S200), and may contain valuable metals and 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 impurities, and the detailed description thereof is the same as that of the valuable metal recovery composition described above in FIG. 1 to the extent that it does not contradict.

[0053] The valuable metal recovery composition may include a lithium compound, and the lithium compound may be produced by the reduction reaction. For example, the lithium compound may be lithium aluminate (2LiAlO2), and the reaction formula for this is as follows: [Reaction Scheme 1] Li2O+Al2O3=2LiAlO2

[0054] FIG. 5 is a graph showing heat treatment conditions according to weight percent of copper and aluminum in accordance with one embodiment of the present invention. Referring to FIG. 5, in one embodiment, in the step of dry heat-treating the crushed material (S200), the heat-treatment conditions may satisfy the reference operating temperature of Equation 3 below. <Expression 3> 1050≦(1550±250)×exp((-0.0005×[Cu])+(-0.01×[Al]))≦1800 (In formula 3, [Al] is the Al content (wt%) contained in the crushed material, [Cu] is the Cu content (wt%) contained in the crushed material, and the unit of the heat treatment conditions is °C.) Equation 3 shows the relationship between the upper and lower limits of temperature depending on the content of copper and aluminum. Specifically, based on Equation 3, when copper is added, it has an effect of promoting alloy formation because its melting point is lower than that of nickel, cobalt, and manganese (Ni-Co-Mn). In addition, when aluminum is added, it has an effect of lowering the stabilization temperature when forming a lithium compound, for example, lithium-alumina (LiAlO2). In the formula 3, (1550±250)×exp((−0.0005×[Cu])+(−0.01×[Al])) means the reference operating temperature. In consideration of the copper alloy recovery rate and lithium recovery rate at the reference operating temperature, the maximum and minimum temperature control ranges may be set as (1550±250)×exp((−0.0005×[Cu])+(−0.01×[Al])). In the above formula 3, (1550+250)×exp((−0.0005×[Cu])+(−0.01×[Al])) is the upper limit temperature for preventing lithium from evaporating, and (1550-250)×exp((−0.0005×[Cu])+(−0.01×[Al])) is the lower limit temperature for ensuring the recovery rate through the molten copper alloy.

[0055] In one embodiment, the value of (1550±250)×exp((−0.0005×[Cu])+(−0.01×[Al])) in the formula 3 may be in the range of 1050 to 1800° C. When the value of the formula 3 deviates from the upper limit, there is a problem of a decrease in Li recovery rate due to vaporization of Li due to exposure to high temperature, and there is a problem of deviation from the normal use temperature range of the refractory material. When the value of the formula 3 deviates from the lower limit, there is a problem of inferior valuable metal generation due to a decrease in the reaction between Ni-Co-Mn oxide and carbon in the positive electrode material, and there is a problem of copper not being melted.

[0056] In one embodiment, the aluminum content in the valuable metal recovery composition may be 0.25 to 30 wt %. The more aluminum is added, the lower the stabilization temperature when producing a lithium compound, for example, lithium-alumina (LiAlO2). When the aluminum content is outside the upper limit of the range, Li-Al-O oxides having a high Al2O3 content (LiAl 11 O 17 If the aluminum content is outside the lower limit of the range, the Li-Al-O oxide formation becomes inferior due to the insufficient Al2O3 content.

[0057] 4 again, in one embodiment, a stirring process can be added in the heat treatment furnace. The stirring process can promote the reaction in the heat treatment furnace, which is a high-temperature reduction furnace, and ensure uniformity of the internal temperature by using, for example, a rotor or gas. A valuable metal recovery composition can be recovered by a reduction reaction of the black powder in the heat treatment furnace.

[0058] The step (S300) of separating the heat-treated crushed material by at least one of particle size separation and magnetic separation may separate the heat-treated crushed material, e.g., valuable metal recovery alloys, by at least one of particle size separation and magnetic separation. The particle size separation method is a method of separating particles according to their size or diameter, and may include various methods of separating particles using, for example, a sieve. The magnetic separation method uses a magnetic material to separate particles through contact with the magnetic material, and various types of magnetic separation methods may be applied.

[0059] 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 be a step of separating the heat-treated crushed material 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 considering the difference in specific gravity of each substance, for example, by using 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.

[0060] In one embodiment, the step of separating the heat-treated crushed material by at least one of particle size separation and magnetic separation (S300) includes all of the steps of performing the particle size separation, the magnetic separation, and both the particle size separation and the magnetic separation, thereby separating valuable metal recovery alloys. The step of performing only the particle size separation can recover valuable metal recovery alloys by only particle size separation of valuable metal recovery composition having a particle size of 100 μm to 100 mm or less.

[0061] In the case of the magnetic separation, when the valuable metal recovery composition contains a material having a particle size of 100 μm or less, the valuable metal can be recovered from the valuable metal recovery composition by the magnetic separation alone. Since the particle size of the material having a particle size of 100 μm or less is similar to that of carbon, the recovery rate of valuable metals that would be lost by the particle size separation alone can be increased by the magnetic separation.

[0062] In one embodiment, when the particle size separation and the magnetic separation are performed together, the magnetic separation can be performed first, followed by the particle size separation. By performing the magnetic separation first, it is possible to prevent the loss of valuable metal recovery alloys from the valuable metal recovery composition having a particle size of 100 μm or less.

[0063] 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 the lithium-containing lithium compound. The step of separating the lithium-containing lithium compound may 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). The lithium compound may be, for example, a lithium-containing oxide, and can be separated by applying a physical force. For a detailed description of this, refer to the valuable metal recovery alloy in FIG. 1 to the extent that it does not contradict. In this way, by separating the lithium-containing oxide by applying a physical force, the recovery rate of not only the valuable metal but also lithium can be increased.

[0064] In one embodiment, the method may further include a step of freezing the batteries prior to the step of preparing the crushed battery material (S100). As described above, when the base material of the crushed battery material is the battery itself, the battery itself must be crushed. When a battery is used as the base material of the battery fragments, the battery may be frozen before being crushed into the battery fragments. When the battery is directly crushed, an explosion and a fire may occur due to the electrolyte contained in the battery. Specifically, when a certain pressure is applied to the battery, the separator is physically crushed, and a high current is generated due to a short circuit, which generates a spark, and the electrolyte may ignite due to the spark, which may cause a fire. In the freezing step, the battery is frozen to prevent ignition of the liquid electrolyte contained in the battery, and then the crushing step is performed, so that problems caused by electrolyte ignition do not occur.

[0065] In one embodiment, the freezing of the battery may be performed by cooling the battery to a temperature range of −150° C. to −60° C. If the temperature is outside the upper limit of the temperature range, the voltage remaining inside the battery does not drop to 0 V, which may cause a battery reaction due to a short circuit, and the electrolyte is not completely frozen, which is not appropriate. If the temperature is outside the lower limit of the above temperature range, the electrolyte is sufficiently frozen and the internal voltage of the battery drops to 0 V, so that even if a short circuit occurs due to direct contact between the positive and negative electrodes, no battery reaction occurs, so the battery temperature does not increase and gas generation and combustion of the electrolyte do not occur. In addition, since the electrolyte is in a frozen state, the mobility of lithium ions is very low, so that the current carrying characteristics due to the movement of lithium ions are significantly reduced, and since the electrolyte does not vaporize, flammable gases such as ethylene, propylene, and hydrogen are not generated. If the temperature exceeds the upper limit of the temperature range during freezing of the battery, the voltage remaining inside the battery does not drop to 0V, which may cause a battery reaction due to a short circuit, and the electrolyte is not completely frozen, which is not appropriate. If the temperature exceeds the lower limit of the temperature range, a lot of energy must be supplied for freezing, which is uneconomical.

[0066] In one embodiment, the freezing of the battery may be performed by cooling the battery to a temperature range of -60 to -20°C under a vacuum atmosphere of 100 torr or less. The freezing of the battery may be performed in the temperature range that is a temperature that can suppress evaporation of the electrolyte. The vacuum atmosphere may be, for example, an inert gas, carbon dioxide, nitrogen, water, or a combination thereof. Since the pressure is controlled to a vacuum atmosphere of 100 torr or less, the supply of oxygen is suppressed, thereby preventing the electrolyte from reacting with oxygen, which can prevent an explosion. Furthermore, the vaporization of the electrolyte can be suppressed, so that flammable gases such as ethylene, propylene, and hydrogen are not generated. If the freezing step of the battery is performed in an air atmosphere or at a pressure exceeding 100 torr, a voltage may remain in the battery. Since the electrolyte is not frozen in the temperature range of -60 to -20°C, a short circuit may occur due to the remaining voltage, and a spark may be generated, causing the electrolyte to vaporize and explode.

[0067] As described above, according to one embodiment of the present disclosure, the valuable metals, for example, nickel, cobalt, lithium, and manganese, are enriched by 150 to 500% compared to the contents of the heat-treated crushed battery material, so that the recovery rate of valuable metals is excellent, and the alloy contains less than 10% carbon, so that carbon dioxide generation during post-processing can be suppressed. Thus, an environmentally friendly method for producing a recycled alloy from waste batteries can be provided.

[0068] FIG. 8a shows the lithium gas activity and FIG. 8b shows the lithium oxide reduction and gas generation according to one embodiment of the present invention. Referring to Figure 8a, when dry heat treatment is applied to the crushed material, it can be seen that the activity of lithium gas is excellent at 1,200°C or more, specifically 1,400°C or more. Referring to Figure 8b, it can be seen that the amount of lithium in the alloy increases at 1,200°C or more, specifically 1,400°C or more, the activity of lithium gas is active, and lithium oxide is reduced.

[0069] FIG. 9 is a voltage change graph by performing a freezing process of a frozen battery according to an embodiment of the present invention. 9, the battery pack shows almost the same voltage at a high temperature of about 40° C., room temperature and up to -60° C., so it does not lose its battery characteristics. Next, when the temperature drops from -60 to -70° C., the voltage drops rapidly and becomes 0 at -70° C., so it can be seen that a short circuit should not occur if the battery pack is frozen at -60 to -150° C. Specifically, when the battery is cooled to a temperature range of -150 to -60°C, the voltage that normally remains inside the battery, for example 2V to 3V, drops to almost 0V and converges. As a result, even if a short circuit occurs in which the positive and negative electrodes come into direct contact with each other, no battery reaction occurs, so the battery temperature does not increase and gas generation and combustion of the electrolyte do not occur. EXAMPLES

[0070] In order to describe the present invention in more detail, examples of the present invention are described below. The following examples are merely one embodiment of the present invention, and the present invention is not limited to the following examples.

[0071] <Experimental Example> In the experimental examples of the present disclosure, the carbon content was analyzed by a combustion method using a CS analyzer (LECO Co., Ltd.), and the oxygen content was analyzed by an infrared sensing method using a NO analyzer (LECO Co., Ltd.). In addition, inorganic substances other than the carbon and oxygen were analyzed by ICP wet analysis. In the experimental examples of the present disclosure, particle size analysis was performed using a particle size analyzer to measure particle size, and particle size analysis by material was estimated through component analysis of materials separated by screening.

[0072] 1. Preparation of battery fragments 7a and 7b show the state of waste batteries before and after crushing according to one embodiment of the present invention. 7a and 7b, among the crushed batteries, for example, waste batteries can be utilized. The crushed batteries can be manufactured through a step of crushing the waste batteries.

[0073] 2. Dry heat treatment stage <Amount of alloy recovered by process temperature> Table 1 below shows the process oxygen fraction, amount of crushed NCM, amount of valuable metal alloy recovered, amount of lithium aluminum compound, unreacted material, and process loss at process temperatures of 900, 1000, 1100, 1200, 1300, 1500, 1600, and 1700° C., based on a process oxygen fraction of 0.01 atm and 25 g of copper. The crushed battery material was placed in a heat treatment furnace in an argon (Ar) gas atmosphere within the above temperature range.

[0074] [Table 1]

[0075] From Table 1 above, it can be seen that, under the same amount of crushed NCM and the same process oxygen fraction conditions, the amount of alloyed valuable metals recovered is high at 900°C or higher, specifically 1200°C or higher. Also, from the amount of lithium aluminum compound, it can be seen that lithium aluminum compound is contained in the temperature range of 900 to 1700°C. Specifically, it can be seen that the amount of lithium aluminum compound is large at 1100°C or higher, more specifically 1500°C or higher. This confirms that there is an advantage in that lithium loss is reduced in the above temperature range.

[0076] <Amount of alloy recovered by process oxygen> Table 2 below shows the C / Ni content ratio and the Li ratio in the alloy according to the oxygen partial pressure in the process.

[0077] [Table 2]

[0078] Referring to Table 2 above, the ratio of C / Ni and the ratio of Li in the alloy can be confirmed according to the in-process oxygen partial pressure. It can be confirmed that the higher the amount of oxygen, the higher the temperature in the process reactor rises, which can be judged to be due to the oxidation heat of carbon and oxygen. Looking at Table 2 again, it can be confirmed that the higher the oxygen input amount, the lower the content ratio of C / Ni, but at the same time, the disappearance of lithium (Li) also increases. When the average oxygen partial pressure reaches a level similar to that in the process reactor atmosphere, it can be confirmed that most of the lithium disappears and the graphite that was the negative electrode material also reacts and disappears as carbon dioxide.

[0079] <Amount of alloy recovered according to copper content> Table 3 below shows the amount of alloy products according to the content of copper (Cu) in the crushed waste batteries. After performing particle size separation on the alloy products, the amount of valuable metal alloy recovered according to the copper content in the crushed material was confirmed.

[0080]

Table 3

[0081] Referring to Table 3 above, when copper (Cu) is contained in a large amount, it can be confirmed that nickel (Ni), manganese (Mn), cobalt (Co), and aluminum (Al) that are reduced while being liquefied at 1500 °C are collected together. The lower the copper content, the lower the above-mentioned collection characteristics, and there is a problem that the size of the reduced alloy is very small and it is difficult to perform particle size separation. It can be confirmed that when the copper (Cu) content decreases at a low temperature, the recovery rate recovered by particle size separation or magnetic separation decreases very much. Thereby, it can be confirmed that the appropriate input amount of copper is 0.02% or more.

[0082] <Wet reaction evaluation results according to the C / Ni ratio> FIG. 7a shows the results of evaluating the wet reaction according to the content ratio of carbon to nickel according to one embodiment of the present invention, and FIGS. 7b and 7c are photographs before and after reacting nickel and carbon powder with acid. FIG. 7a is a graph showing the undissolved rate as a result of the wet reaction according to the carbon content ratio to nickel, FIG. 7b is a photograph of nickel and carbon powder before reacting with acid, and FIG. 7c is a photograph of the nickel and carbon powder after reacting with acid. Referring again to Fig. 7a, the results show that the undissolved amount is the amount of alloy that does not react after a certain time in acid for wet reaction, and the undissolved amount is compared using alloys with different carbon to nickel ratios to evaluate the wet reaction according to the carbon to nickel ratio. It can be seen that the undissolved amount increases when the carbon content of the nickel is 3% or more. In particular, as the carbon content of the nickel increases, it can be seen that the undissolved amount is high when it exceeds 6%, and it can be determined that the reaction rate is decreased.

[0083] 3. Separating by at least one of particle size separation and magnetic separation After the high-temperature reaction was completed, contact magnetic separation was performed using a 5000G magnet, and the non-magnetic portion was separated by particle size using a 250μm sieve. The component distribution is shown in Table 4.

[0084] [Table 4]

[0085] In Table 4, it can be seen that Ni, Co, and Mn are mainly concentrated in the magnetic portion, and Cu also forms a solid solution with the concentrated metal components. In addition, the material separated as non-magnetic is composed of coarse lithium aluminate and finely powdered graphite, and can be effectively separated through particle size separation. Approximately 98% of the total Ni and Co present in the battery was in a magnetic alloy and effectively separated, while in the case of Li, more than 70% was found to be distributed in the alloy and lithium aluminate. This is because the Li-NCM alloy, in which the positive active material is reduced, exhibits magnetism, and LiAlO2 oxide is fused to the surface of the magnetic alloy that is melted into droplets and then solidified. In addition, it was confirmed that some LiAlO2 is a material that is formed when the aluminum current collector, which is bonded to the positive electrode material in a plate shape, is oxidized during the reaction with lithium, and that it may exist independently without being fused to the surface of the alloy. LiAlO2 that maintains the shape of the current collector can be separated from the powder graphite through particle size separation.

[0086] In addition, when the particle size separation was performed before the magnetic separation in a different order from the above-mentioned method, and the material separated to 250 μm or more was subjected to additional magnetic separation, the recovery rate of Ni and Co was confirmed to be about 78%, and the recovery rate of Li was confirmed to be at the level of 60%. This indicates that the Ni, Co, and Li contained in the positive active material were lost because the powder-form positive active material, which was simply reduced and could not form droplets, was separated as a powder together with the negative active material through particle size separation. The present invention is not limited to the above-described embodiments, and can be manufactured in various different forms, and a person skilled in the art to which the present invention pertains can understand that the present invention can be embodied in other specific forms without changing the technical concept or essential features of the present invention. Therefore, the above-described embodiments should be understood to be illustrative and not restrictive in all respects.

Claims

1. Based on 100% by weight of the total composition of the alloy, The valuable metals comprise at least 45% by weight, with the remainder being impurities; A valuable metal recovery alloy that satisfies the following formula 1. <Formula 1> 0.02≦[C] / [Ni]≦7 ([C] and [Ni] mean the weight percentages of C and Ni, respectively.)

2. 2. The valuable metal recovery alloy according to claim 1, wherein the valuable metal is 70% by weight or more.

3. The valuable metal recovery alloy according to claim 1, wherein the valuable metal contains 0.01 to 5% by weight of lithium (Li).

4. 2. The valuable metal recovery alloy according to claim 1, having at least one diffraction peak at 2θ = 44° ± 1°, 2θ = 51.5° ± 1.5°, and 2θ = 75.5° ± 1.5° in XRD peak values.

5. The valuable metal recovery alloy according to claim 1, which satisfies the following formula 2. <Formula 2> 0.1<I Ｂ / I Ａ <0.98 (In the above formula 2, I Ａ is the peak intensity value at 2θ = 44° ± 1°, and I Ｂ is the peak intensity value at 2θ=51.5°±1.5°)

6. The valuable metal recovery alloy according to claim 1, wherein the valuable metal recovery alloy contains copper (Cu): 0.02 wt. % or more.

7. The valuable metal recovery alloy according to claim 5, wherein the copper (Cu) combines with nickel (Ni) in the valuable metal to form an alloy.

8. The valuable metal recovery alloy according to claim 1, wherein the valuable metal recovery alloy contains carbon (C): 0.1 to 10 wt %.

9. The valuable metal recovery alloy according to claim 1, wherein the valuable metal recovery alloy contains aluminum (Al): 0.25 to 30 wt. %.

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

11. Valuable metal recovery alloys; and A valuable metal recovery composition containing a lithium compound, The lithium content in the composition is 0.1 to 10 wt. %; A valuable metal recovery composition, wherein the content of valuable metals in the composition containing lithium is 45% by weight or more.

12. The valuable metal recovery composition according to claim 11, wherein the valuable metal recovery alloy satisfies the following formula 1: <Formula 1> 0.02≦[C] / [Ni]≦7 ([C] and [Ni] mean the weight percentages of C and Ni, respectively.)

13. The valuable metal recovery composition according to claim 11, wherein the lithium compound is bound to a surface portion of the valuable metal recovery alloy.

14. The valuable metal recovery composition according to claim 13, wherein the lithium compound bound to the surface portion of the valuable metal recovery alloy is separated by an external force.

15. The valuable metal recovery composition according to claim 11, comprising a carbonaceous material.

16. The valuable metal recovery composition according to claim 11, wherein the valuable metal recovery composition contains 10 to 30% by weight of aluminum (Al).

17. The valuable metal recovery composition according to claim 11, wherein the valuable metal includes at least one of lithium (Li), cobalt (Co), nickel (Ni), aluminum (Al), and manganese (Mn).

18. Providing a battery cell or crushed batteries; subjecting the battery or the crushed material to a dry heat treatment; and separating the heat-treated crushed material by at least one of particle size separation and magnetic separation; The step of dry heat treating the crushed material involves heat treatment conditions of performing a high-temperature reduction reaction at 900 to 1,800 ° C. without going through a melting step, The heat treatment conditions satisfy the standard operating temperature of the following formula 3: A method for recovering valuable metals, comprising the steps of: based on 100% by weight of a total composition of a valuable metal recovery composition containing a valuable metal recovery alloy and a lithium compound, the lithium content is 0.1 to 10% by weight, the content of valuable metals in the composition containing the lithium content is 70% by weight or more, and valuable metals are recovered from the remainder which is an impurity. <Formula 3> 1050≦(1550±250)×exp((-0.0005×[Cu])+(-0.01×[Al]))≦1800 (In formula 3, [Al] is the content (wt%) of Al contained in the crushed material, [Cu] is the content (wt%) of Cu contained in the crushed material, and the unit of the heat treatment condition is ° C.)

19. The method for recovering valuable metals according to claim 18, wherein the crushed battery material contains aluminum (Al) and copper (Cu).

20. The valuable metal recovery method according to claim 18, wherein the aluminum (Al) contains 0.5 to 30% by weight.

21. The valuable metal recovery method according to claim 18, wherein the copper (Cu) content is 0.25% by weight or more.

22. The method for recovering valuable metals according to claim 18, wherein the step of separating the heat-treated crushed material by at least one of particle size separation and magnetic separation comprises performing magnetic separation first and then particle size separation.

23. The valuable metal recovery alloy is, based on the total composition of the valuable metal recovery alloy being 100 wt.%, The valuable metal recovery method according to claim 18, comprising lithium (Li): 0.1 to 10% by weight, valuable metals: 45% by weight or more, and the remainder being impurities.

24. Prior to the step of preparing the crushed battery material, 20. The method for recovering valuable metals according to claim 18, further comprising the step of freezing the battery.

25. The method for recovering valuable metals according to claim 24, wherein the freezing of the battery is carried out by cooling the battery at -150°C to -60°C.

26. The method for recovering valuable metals according to claim 24, wherein the freezing of the battery is performed at a temperature of -60°C to -20°C under a vacuum atmosphere of 100 torr or less.

27. The method for recovering valuable metals according to claim 18, wherein the dry heat treatment is carried out under at least one atmosphere of a reducing gas and an inert gas.

28. The method for recovering valuable metals according to claim 18, wherein the average oxygen partial pressure in the dry heat treatment step is 0.01 to 1 atm.

29. The valuable metal recovery method according to claim 18, wherein the valuable metal content of the valuable metal recovery alloy is concentrated by 150 to 500 wt % compared to the valuable metal content of the crushed material.

30. The method for recovering valuable metals according to claim 18, wherein a lithium compound is produced in the dry heat treatment step.

31. The valuable metal recovery method according to claim 18, wherein the lithium compound is bonded to a surface portion of the valuable metal recovery alloy.

32. 32. The valuable metal recovery composition according to claim 31, wherein the lithium compound bound to the surface portion of the valuable metal recovery alloy is detached by an external force.

33. The components of the crushed battery material include 5-40 wt% nickel (Ni), 1-15 wt% cobalt (Co), 1-15 wt% manganese (Mn), 0.5-5 wt% lithium (Li), and the balance impurities; The valuable metal alloy contains 10 to 60 wt% nickel (Ni), 5 to 20 wt% cobalt (Co), 1 to 20 wt% manganese (Mn), 3 to 15 wt% lithium (Li), and the balance is impurities.

Images