Recyclate and valuable metal recovery process from spent batteries

Abstract

The present invention relates to a recyclate recovered from spent batteries, the recyclate comprising, based on 100% by weight of the recyclate, 20 to 35% by weight of a valuable metal recyclate alloy, 25 to 50% by weight of a lithium compound and the balance of a graphite-based substance.

Description

Technical Field

[0001] This invention relates to waste batteries, and more particularly to a method for recovering recyclables and valuable metals from waste batteries, wherein the recyclables are valuable metals, lithium oxides, graphite, copper, and other materials recovered through the waste battery processing method. Background Technology

[0002] With the increasing global demand for electric vehicles, the disposal of waste batteries generated by these vehicles has become a social problem. Lithium-ion batteries, the main raw material for these waste batteries, contain organic solvents, explosive substances, and heavy metals such as Ni, Co, Mn, and Fe. However, Ni, Co, Mn, and Li are valuable metals with significant scarcity value, making the recycling and reuse of discarded lithium-ion batteries an important research area.

[0003] Specifically, a lithium secondary battery mainly consists of copper and aluminum as current collectors, Li, Ni, Co, and Mn-containing oxides constituting the positive electrode material, and graphite as the negative electrode material. It also includes a separator for separating the positive and negative electrode materials and an electrolyte injected into the separator. The solvents and salts used to constitute the electrolyte are primarily a mixture of carbonate organic compounds such as ethylene carbonate, propylene carbonate, and, for example, LiPF6.

[0004] As mentioned above, lithium secondary batteries are composed of heavy metals such as Ni-Co-Mn-Fe, carbon, and other electrolytes, among which Ni, Co, Mn, and Li are valuable metals.

[0005] The reuse of recycled battery materials generally involves disassembling, discharging, crushing, heat treatment, recycling, and hydrometallurgical processes to recover valuable metals. For the discharge process, brine discharge is performed, during which substances such as Na, K, Mg, Ca, and Cl are included as impurities in the recovered materials.

[0006] After heat treatment, the recovered material is called black powder when heat-treated at temperatures below 600°C. It is in powder form and contains a mixture of Ni-Co-Mn-Li oxides and carbon from the anode material. As for Al and Cu, since they have been removed beforehand, they may contain very small amounts.

[0007] When the black powder is heat-treated at a high temperature above 1000°C, the metal oxide is reduced and alloyed by the carbon in the negative electrode material, thereby obtaining a black alloy containing the alloy components, carbon, and other substances. Therefore, it is necessary to conduct research to recover valuable metals, lithium oxides, and graphite from the black alloy according to their material composition, thereby improving the recovery rate of valuable metals. Summary of the Invention

[0008] Technical problems to be solved According to one embodiment of the present invention, the recyclables from waste batteries can be as follows: valuable metals, lithium oxides and graphite are effectively recovered from black alloys obtained from black powder, thereby improving the recovery rate of valuable metals and graphite and facilitating battery reuse in the next process.

[0009] The valuable metal recycling method according to another embodiment of the present invention aims to provide a recycling method that improves the recovery rate of valuable metals from black alloys obtained from black powder, facilitating battery reuse in subsequent processes.

[0010] Technical solution According to one embodiment of the present invention, the recyclable material recovered from waste batteries may contain, by weight 100%, 20 to 35% of a valuable metal recovery alloy, 25 to 50% of a lithium compound, and the balance being graphitic material. In one embodiment, the valuable metal recovery alloy may contain Ni, Co, Mn, and impurities.

[0011] In one embodiment, the valuable metal recycled alloy may contain a total content of 90% or more of Ni, Co, and Mn, and the balance being impurities, based on 100% by weight of the total valuable metal recycled alloy. In one embodiment, the valuable metal recycled alloy may contain 1 to 7% by weight of copper (Cu) based on 100% by weight of the total valuable metal recycled alloy.

[0012] In one embodiment, the valuable metal recycling alloy, based on 100% by weight of total valuable metal recycled alloy, may contain 50 to 60% by weight of nickel (Ni), 18 to 28% by weight of cobalt (Co), 10 to 20% by weight of manganese (Mn), and the balance being impurities. In one embodiment, the lithium compound, based on 100% by weight of lithium compound, may contain 10 to 20% by weight of lithium (Li), 20 to 30% by weight of aluminum (Al), and the balance being impurities.

[0013] In one embodiment, the lithium compound may comprise lithium oxide. In one embodiment, the lithium oxide may comprise lithium aluminum oxide. In one embodiment, the graphitic material may comprise 80 to 90% by weight of carbon (C) and the balance being impurities.

[0014] In one embodiment, the graphitic material may contain 13 to 25% by weight of copper (Cu). In one embodiment, the valuable metal recycling alloy, the lithium compound, and the graphitic material may each be in powder form.

[0015] In one embodiment, at least a portion of the lithium compound may comprise a composition disposed in at least a portion of the surface of the valuable metal recycling alloy. In one embodiment, the composition may have a core-shell structure.

[0016] According to another embodiment of the present invention, a method for recovering valuable metals relates to a method for recovering valuable metals from a product obtained by reducing heat treatment of shredded material recovered from waste batteries at high temperature, comprising: a step of magnetically separating the heat-treated product into a first magnetic body and a first non-magnetic body; and a step of crushing the first magnetic body, wherein the crushing step may be carried out within a shear force range of 1 to 5 m / s based on a tip speed.

[0017] In one embodiment, the pulverizing step can be carried out for 30 to 60 minutes.

[0018] In one embodiment, at least a portion of the product from the reduction heat treatment of the shredded material recovered from waste batteries at high temperature may contain a valuable metal recycling composition, the valuable metal recycling composition comprising: a core containing a valuable metal recycling alloy; and a shell disposed on the core and containing a lithium compound.

[0019] Beneficial effects According to one embodiment of the present invention, the recyclables from waste batteries include valuable metal recovery alloys, lithium compounds, and graphite-like substances. Valuable metals, lithium oxides, and graphite are effectively recovered from black alloys obtained from black powder, thereby improving the recovery rate of valuable metals and graphite. In the next process, recyclables that can be reused as positive and negative electrode materials can be obtained. Attached Figure Description

[0020] Figures 1a to 1c This is a photograph of valuable metal recovery alloys, lithium compounds, and graphite-like substances recovered from waste batteries according to an embodiment of the present invention.

[0021] Figure 2This is a flowchart of a battery processing method according to an embodiment of the present invention.

[0022] Figure 3a and Figure 3b The results are XRD analysis of a valuable metal recycling composition formed after heat treatment according to an embodiment of the present invention.

[0023] Figure 4 This is an SEM image of a composition for recycling valuable metals. Detailed Implementation

[0024] The terms "first," "second," "third," etc., are used to describe parts, components, regions, layers, and / or segments, but these parts, components, regions, layers, and / or segments should not be limited by these terms. These terms are only used to distinguish one part, component, region, layer, or segment from another. Therefore, without departing from the scope of the invention, the first part, component, region, layer, or segment described below can also be described as a second part, component, region, layer, or segment.

[0025] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the invention. Unless the context clearly indicates otherwise, the singular forms used herein are intended to include the plural forms as well. The word "comprising" as used in the specification can specifically refer to a feature, domain, integer, step, action, element, and / or component, but does not exclude the presence or addition of other features, domains, integers, steps, actions, elements, and / or components.

[0026] If one part is described as being on top of another part, then other parts may exist directly on top of or in between the other part. If one part is described as being directly on top of another part, then no other parts exist in between.

[0027] Furthermore, % in this specification represents weight percentage, unless otherwise stated.

[0028] Although not otherwise defined, all terms used herein (including technical and scientific terms) have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Terms defined in dictionaries should be interpreted as having the same meaning as disclosed in relevant technical literature and herein, and should not be interpreted in an idealized or overly formal sense.

[0029] Embodiments of the present invention will be described in detail below. However, the following embodiments are given by way of example only, and the present invention is not limited to the following embodiments; the present invention is defined only by the scope of the claims.

[0030] Figures 1a to 1cThis is a photograph of valuable metal recovery alloys, lithium compounds, and graphite-like substances recovered from waste batteries according to an embodiment of the present invention.

[0031] Reference Figures 1a to 1c According to one embodiment of the present invention, the recyclables recovered from waste batteries, based on 100% by weight of the recyclables, comprise 20 to 35% by weight of valuable metal recycling alloys, 25 to 50% by weight of lithium compounds, and the balance being graphite-like materials. The recyclables recovered from waste batteries can be obtained through... Figure 2 The battery processing method shown in the diagram recovers the recycled materials. Specifically, the recycled materials may be valuable metal recovery alloys containing valuable metals, lithium compounds containing lithium, and residual graphite-like materials.

[0032] In one embodiment, the recyclable material may contain 20 to 35% by weight of a valuable metal recovery alloy, 25 to 50% by weight of a lithium compound, and the balance being graphitic material, per 100% by weight. The valuable metal recovery alloy containing the valuable metal, the lithium compound containing lithium, and the carbon-containing graphitic material can be recovered in powder form using the battery processing method described below.

[0033] In one embodiment, the valuable metal recycling alloy may be 20 to 35% by weight per 100% of the recycled material. Specifically, the valuable metal recycling alloy may be 25 to 30% by weight. The valuable metal recycling alloy may be a substance containing valuable metals such as Ni, Co, and Mn.

[0034] Since the weight percentage of valuable metal alloys in the recovered materials meets the aforementioned range, it has the advantage of improving the recovery rate of valuable metals such as Ni, Co, and Mn. If the upper limit of the aforementioned range is exceeded, although the recovery rate of valuable metals can be improved, it becomes uneconomical. If the lower limit of the aforementioned range is exceeded, the recovery rate of valuable metals will decrease.

[0035] In one embodiment, the valuable metal recycling alloy may contain a total content of more than 90% by weight of Ni, Co, and Mn, and the balance being impurities, based on 100% by weight of the total valuable metal recycling alloy. Specifically, the total content of Ni, Co, and Mn is 90 to 96% by weight, more specifically 92 to 95% by weight.

[0036] If the total content of Ni, Co, and Mn in the valuable metal recovery alloy meets the aforementioned range, the recovery rate of the valuable metal can be improved. If the total content of Ni, Co, and Mn in the valuable metal recovery alloy exceeds the aforementioned range, it is not economical or the recovery rate of the valuable metal is low.

[0037] In one embodiment, nickel (Ni) may comprise 50 to 60% by weight of the total 100% by weight of the valuable metal recycled alloy. Specifically, nickel may comprise 52 to 58% by weight.

[0038] If the nickel content exceeds the upper limit of the aforementioned range, there is a problem of nickel carbide (Ni3C) formation leading to a decrease in leaching rate. If the nickel content exceeds the lower limit of the aforementioned range, there is a problem of a decrease in Ni recovery rate during leaching and solvent extraction.

[0039] In one embodiment, cobalt (Co) may comprise 18 to 28% by weight of the total 100% valuable metal recycled alloy. Specifically, cobalt may comprise 20 to 26% by weight.

[0040] If the cobalt content exceeds the upper limit of the aforementioned range, there is a problem of cobalt carbide formation leading to a decrease in the leaching rate. If the cobalt content exceeds the lower limit of the aforementioned range, there is a problem of decreased Co recovery rate during leaching and solvent extraction.

[0041] In one embodiment, manganese (Mn) may comprise 10 to 20% by weight of 100% of the total valuable metal recycled alloy. Specifically, cobalt may comprise 12 to 18% by weight.

[0042] If the manganese content exceeds the upper limit of the aforementioned range, there is a problem of manganese carbide formation leading to a decrease in the leaching rate. If the manganese content exceeds the lower limit of the aforementioned range, there is a problem of decreased Mn recovery rate in leaching and solvent extraction.

[0043] In one embodiment, lithium (Li) may comprise 0.01 to 5% by weight of 100% of the total valuable metal recycled alloy. Specifically, the lithium may comprise 0.05 to 0.15% by weight.

[0044] Since the lithium falls within the specified range, it has the advantage of maximizing Li recovery in the Li refining process. If the upper limit of the range is exceeded, the recovery rates of Ni and Co decrease; if the lower limit of the range is exceeded, the Li recovery rate in the Li refining process decreases, leading to increased process costs.

[0045] In one embodiment, copper (Cu) may comprise 1.0 to 7% by weight of the valuable metal recycling alloy. Specifically, the copper may comprise 3 to 5% by weight.

[0046] If the copper content exceeds the upper limit of the range, there is a problem of increased process cost due to increased CuSO4 precipitation during leaching and solvent extraction. If the copper content exceeds the lower limit of the range, it is difficult to generate low-melting-point Ni-Co-Mn, resulting in an increase in the amount of unreacted matter. In one embodiment, the copper can be combined with nickel (Ni) in the valuable metal to form an alloy.

[0047] In one embodiment, for a valuable metal recycling alloy, carbon (C) may comprise from 0.1 to 10% by weight. Because the carbon meets this range, the yield can be improved, and the processing time in the hydrometallurgical process can be reduced. Specifically, the carbon may comprise from 1 to 7% by weight.

[0048] If the upper limit of the range is exceeded, the negative electrode material will remain in an unreacted state, alloying cannot proceed normally, and there is a problem of valuable metal oxides remaining in the positive electrode material. If the lower limit of the range is exceeded, there is a possibility of lithium loss due to high temperature.

[0049] In one embodiment, for the valuable metal recycling alloy, aluminum (Al) may be present in the range of 0.25 to 30% by weight. If the aluminum content exceeds the upper limit of the range, there is a problem of decreased Ni and Co recovery rates in the leaching and solvent extraction processes; if the aluminum content exceeds the lower limit of the range, it is difficult to generate LiAlO2, resulting in a decrease in Li recovery rate.

[0050] In one embodiment, the lithium compound may contain 25 to 50% by weight of 100% of the recycled material. Specifically, the lithium compound may contain 30 to 40% by weight. In one embodiment, the lithium compound may be a lithium-containing compound. For example, the lithium compound may contain lithium oxide, which may contain lithium aluminum oxide.

[0051] Since the lithium compound meets the aforementioned range, the recovery rate of lithium, one of the valuable metals, can be improved. If the lithium compound exceeds the lower limit of the aforementioned range, it means that a large amount of Li is lost due to NCM alloys or graphite, resulting in a decrease in Li recovery rate. When recovering Li in the subsequent wet refining process, the low Li content of the added raw material leads to increased process costs.

[0052] In one embodiment, for the lithium compound, lithium (Li) may be 10 to 20% by weight, based on 100% by weight of the lithium compound. Specifically, the lithium may be 12 to 18% by weight.

[0053] If the lithium content exceeds the upper limit of the aforementioned range, it means that lithium has not reacted with Al to form lithium compounds in the form of LiAlO2, and the proportions of lithium hydroxide, lithium fluoride, and lithium carbonate are relatively high. This raises the issue of needing to consider water leaching and acid leaching methods in the subsequent wet refining process. If the lithium content exceeds the lower limit of the aforementioned range, it means that most of the lithium compounds are recovered in the form of LiAlO2, which has low water solubility. This indicates that the highly water-soluble lithium compounds have dissolved in water during the screening process, thus requiring the recovery of lithium from the water used in the screening process.

[0054] In one embodiment, for the lithium compound, aluminum (Al) may be 20 to 30% by weight, based on 100% by weight of the lithium compound. Specifically, it may be 23 to 28% by weight. Since the aluminum content meets the aforementioned range, the lithium yield can be improved by forming a lithium compound through physical or chemical combination with lithium.

[0055] If the aluminum content exceeds the upper limit of the range, excessive Al2(SO4)3 will be generated during the leaching and solvent extraction processes, leading to increased costs in Ni and Co solvent extraction and crystallization processes, as well as decreased Ni and Co recovery rates. If the aluminum content exceeds the lower limit of the range, insufficient aluminum content will result in poor formation of Li-Al-O oxides.

[0056] In one embodiment, for the lithium compound, the carbon (C) content may range from 1 to 7% by weight, based on 100% by weight of the lithium compound. Specifically, the carbon (C) content may be from 3 to 5% by weight. Since the carbon content meets this range, it offers the advantage of optimizing the wet processing of valuable metal recovery compositions.

[0057] If the carbon content exceeds the upper limit of the range, there is a problem of nickel carbide (Ni3C) formation leading to a decrease in leaching rate. If the carbon content exceeds the lower limit of the range, there is a problem of decreased recovery rate of valuable metals such as Ni and Co in solvent extraction after leaching due to increased content of other impurities such as Si.

[0058] In one embodiment, the graphitic material may contain 25 to 50% by weight of 100% recycled material. Specifically, the graphitic material may contain 30 to 40% by weight. Regarding the content of the graphitic material, a large amount of graphitic material can be generated by conducting a high-temperature reduction reaction within a low-oxygen content range that reduces carbon dioxide generation. Since the graphitic material meets the aforementioned range, the recycling yield of graphitic material suitable as a negative electrode material can be improved.

[0059] If the graphitic material exceeds the upper limit of the aforementioned range, the graphite content becomes excessive, leading to a decrease in the recovery rate of valuable metals. If the graphitic material exceeds the lower limit of the aforementioned range, the graphite recovery rate is low.

[0060] In one embodiment, for graphitic materials, the carbon (C) content is 80 to 90% by weight, and may include the balance of impurities. The carbon (C) content may be 83 to 87% by weight. Since the carbon content meets the aforementioned range, high-purity carbon-containing graphite can be obtained.

[0061] If the carbon content exceeds the upper limit of the aforementioned range, there is a problem of decreased recovery rate of valuable metals. If the carbon content exceeds the lower limit of the aforementioned range, there is a problem of low graphite recovery rate.

[0062] In one embodiment, for graphite materials, the copper (Cu) content may be 13 to 25% by weight per 100% of the graphite material. Specifically, the copper content may be 15 to 20% by weight. If the copper content exceeds the upper limit of the aforementioned range, there is a problem of increased acid usage required to remove Cu during the process of refining graphite into high-purity graphite.

[0063] Figure 2 This is a flowchart of a battery processing method according to an embodiment of the present invention.

[0064] Reference Figure 2 The battery processing method includes the following steps: preparing a product from crushed material recovered from waste batteries by high-temperature reduction heat treatment; magnetically separating the product; and pulverizing the magnetically separated product to separate it into magnetic and non-magnetic components. This invention provides a battery processing method that uses high-temperature reduction heat treatment on crushed material recovered from waste batteries, effectively separating the resulting product magnetically, thereby improving the recovery rate of valuable metals. The valuable metals in this invention can refer to high-valence metal components contained in the battery, and can specifically refer to nickel, cobalt, manganese, aluminum, copper, and lithium.

[0065] The steps for preparing the product of high-temperature reduction heat treatment of shredded material from waste batteries include: preparing the battery; crushing the battery into battery shreds; and subjecting the crushed battery shreds to high-temperature heat treatment.

[0066] In the battery preparation step, the battery can be any type of lithium-ion battery, such as a lithium secondary battery separated from a car, or a secondary battery separated from electronic devices such as mobile phones, cameras, and laptops; specifically, it can be a lithium secondary battery. More specifically, because the battery utilizes waste batteries, it has the advantage of being environmentally friendly.

[0067] In one embodiment, during the battery preparation step, the battery may contain lithium (Li) and aluminum (Al). Because lithium and aluminum coexist in the battery, the lithium and aluminum in the products generated after battery processing may exist as physically and / or chemically combined substances.

[0068] The battery crushing step can refer to a process that applies impact or pressure to the battery, causing a portion of the battery to detach. In one embodiment, the battery crushing step can refer to all processes of pulverizing the battery, cutting the battery, compressing the battery, and combinations thereof. Specifically, the crushing step can include all processes capable of destroying the battery to obtain small fragments.

[0069] In one embodiment, the battery crushing step may include all processes of compressing the prepared battery or applying external forces such as shearing or tensile forces to destroy the battery. For example, the battery crushing step may be carried out using a crusher.

[0070] In one embodiment, the battery breaking step may be performed at least once. Specifically, the breaking step may be performed continuously or discontinuously at least once.

[0071] In one embodiment, the battery breaking step can be carried out under conditions of supplying an inert gas, carbon dioxide, nitrogen, water, or a combination thereof, or under vacuum conditions below 100 Torr. If carried out under the aforementioned conditions, by suppressing the oxygen supply, the reaction between the electrolyte and oxygen can be prevented, thus preventing an explosion. Furthermore, the vaporization of the electrolyte can be suppressed, thereby avoiding the generation of flammable gases such as ethylene, propylene, or hydrogen.

[0072] The step of subjecting the broken battery fragments to high-temperature heat treatment involves placing the fragments in a furnace capable of heating them to a temperature above their melting point. For example, the broken battery fragments may contain valuable metals such as Ni, Co, Mn, and Li. This high-temperature heat treatment may include a high-temperature reduction reaction of the battery, eliminating the need for a melting step.

[0073] In one embodiment, the high-temperature heat treatment step of the battery fragments can be carried out in an environment of at least one gas selected from inert gas, carbon dioxide, carbon monoxide, hydrocarbon gas, and oxygen. For example, the inert gas may include at least one of argon and nitrogen. Because the reduction reaction of the fragments is carried out in this gas environment, it has the advantage of increasing the recovery rate of valuable metal elements contained in the battery fragments.

[0074] In one embodiment, the high-temperature heat treatment of the battery fragments containing Ni, Co, Mn, and Li can be performed in an oxygen-containing gas environment, consisting of at least one of an inert gas, carbon dioxide, carbon monoxide, and hydrocarbon gas. In one embodiment, the treatment can be performed in a gas environment with an oxygen concentration ranging from 0.1 to 2.0 vol%. Specifically, it can be performed in a gas environment with an oxygen concentration ranging from 0.4 to 1.2 vol%.

[0075] If the oxygen concentration exceeds the upper limit of the aforementioned range, the reaction Li₂O + C + O₂(g) = Li₂CO₃ is promoted as the oxygen concentration increases, but there is also a problem of reduced LiAlO₂ and Li₅AlO₄. Specifically, if the oxygen concentration exceeds the upper limit of the aforementioned range, excessive carbon dioxide is formed during the reduction reaction, which vaporizes and is lost along with lithium, or excessive Li₂CO₃(s) is generated, making it difficult to recover by acid leaching. If the oxygen concentration exceeds the lower limit of the aforementioned range, the lithium recovery rate decreases.

[0076] In one embodiment, the high-temperature heat treatment step of the battery fragments can be carried out in the range of 600 to 1500°C. Specifically, the high-temperature heat treatment step can be carried out in the range of 900 to 1500°C, more specifically 1100 to 1500°C, and more specifically 1300 to 1500°C. The high-temperature heat treatment step of the battery fragments generates Li5AlO4 due to the reaction LiAlO2(s) + 2Li2CO3(s) = Li5AlO4 + 2CO2(g) as the temperature rises, but promotes the gasification reaction of LiF(g). When carried out within the aforementioned range, the lithium yield can be improved.

[0077] If the upper limit of the range is exceeded, there is a problem of lithium loss due to lithium vaporization. Specifically, if the upper limit of the range is exceeded, there is a problem of lithium loss and decreased lithium recovery rate due to excessive promotion of the LiF(g) vaporization reaction.

[0078] If the lower limit of the range is exceeded, the sintering and reduction of alloying elements cannot proceed smoothly, and a stable lithium-containing compound will not be formed. This leads to difficulties in recovering the stable compound during subsequent lithium recycling. Specifically, if the lower limit of the range is exceeded, MnO in the lithium-containing Ni, Co, and Mn oxides in the cathode material will not dissociate. Instead, MnAl2O4 will be generated due to the reaction MnO(s) + 2Al(s) + 3 / 2O2 = MnAl2O4(s). This reduces the lithium concentration in the lithium compound, resulting in a decrease in lithium recovery rate.

[0079] The step of magnetically separating the product after the high-temperature heat treatment can magnetically separate the product to separate the first magnetic body with magnetism and the first non-magnetic body with non-magnetism. For magnetic separation, a magnetic body can be used to separate particles through contact with the magnetic body, and various magnetic separation methods can be employed.

[0080] The first magnetic material is a composition comprising valuable metals Ni, Co, and Mn. Specifically, it may be a composition comprising a core and a shell disposed on the core. The core may comprise a recycled valuable metal alloy. The core of the composition for recycling valuable metals may be recycled from the positive electrode material components of spent batteries.

[0081] The shell portion is disposed on the core portion and may contain lithium compounds. Specifically, when valuable metals are recovered from waste batteries, the valuable metals in the waste batteries exist in the form of oxides. Through a high-temperature heat treatment process, these metals are reduced under the action of graphite in the negative electrode material. At this time, the copper current collector melts and exists in a liquid phase, which can play a role in aggregating the reduced valuable metals. The copper current collector and the aluminum current collector undergo a partial reduction reaction with the oxide of the positive electrode material, and the remainder reacts with lithium, possibly leaving lithium-containing compounds in the form of oxides. A detailed explanation of this is provided in... Figure 3a and Figure 3b and Figure 4 Further explanation will follow.

[0082] The second nonmagnetic body may contain at least one of a lithium-containing compound and a carbon-containing graphite material, wherein the lithium is lithium that has not been bonded to a valuable metal during the magnetic separation step.

[0083] In one embodiment, the magnetic separation step can be performed within a magnetic field strength range of 1000 to 5000 Gauss. Specifically, the magnetic separation step can be performed within a magnetic field strength range of 2000 to 3000 Gauss.

[0084] Performing the magnetic separation step within the aforementioned magnetic strength range offers the advantage of effectively separating valuable metals. If the magnetic strength range exceeds the upper limit, even trace amounts of valuable metals will be recovered, increasing the recovery rate. However, the grade of the recovered valuable metals will decrease, with increased contamination from impurities such as graphite and copper. This leads to reduced process efficiency and increased processing costs in the subsequent wet refining process. Conversely, if the magnetic strength range exceeds the lower limit, the recovery rate of valuable metals will decrease, resulting in increased losses of Ni, Co, and Mn.

[0085] The step of separating the magnetic product from the magnetically separated product into magnetic and non-magnetic bodies by crushing it can be a step of crushing the first magnetic body after magnetic separation. As mentioned above, the first magnetic body refers to a core containing a valence metal alloy and a lithium-containing compound disposed on the core. For the first magnetic body, the core and the shell can be separated by the crushing process. Specifically, for the first magnetic body, by the aforementioned crushing process, it can be separated into a second magnetic body and a second non-magnetic body. For example, the second magnetic body refers to an NCM alloy containing Ni, Co, and Mn, and the second non-magnetic body is a lithium-containing compound, such as lithium aluminate (LiAlO2).

[0086] In one embodiment, the first magnetic material can be separated into the valuable metal recovery alloy and the lithium-containing compound by mechanical or physical force. As described above, not only can the valuable metal recovery alloy be recovered from the valuable metal recovery composition, but the lithium compound can also be separated simultaneously, thus achieving a high lithium recovery rate and reducing lithium loss.

[0087] In one embodiment, the pulverization step utilizes a device employing shear force in the form of a vertical stirring mill. For this mill, the pulverization can be carried out within a shear force range of 1 to 5 m / s based on the impeller tip velocity (RPM). Specifically, the pulverization step can be carried out within a shear force range of 2 to 3 m / s. Because the pulverization step is carried out within the aforementioned shear force range, the core of the first magnetic material (i.e., the NCM alloy) will not be pulverized; only the shell portion (i.e., the lithium-containing compound) disposed on the core will be pulverized into fine powder.

[0088] At this point, the blade tip velocity can be calculated using the following formula.

[0089] Blade tip velocity = Pi × impeller diameter × RPM / 100 In one embodiment, if the shear force exceeds the upper limit of the aforementioned range, the shell of the first magnetic body is separated and crushed together with the internal magnetic core. Since the core is a malleable metal, a problem arises where spherical particles enlarge into flakes during crushing, requiring further crushing into smaller particles. In this case, the recovery rate decreases during the separation of the magnetic core and the lithium compound in the shell based on particle size. If the shear force exceeds the lower limit of the aforementioned range, the lithium compound in the shell is not crushed and is recycled again along with the magnetic core.

[0090] In one embodiment, the pulverization step can be performed for 20 to 80 minutes. Specifically, the pulverization step can be performed for 30 to 60 minutes. Because the pulverization step is performed within the aforementioned range, the recovery rate of valuable metals such as Ni, Co, Mn, and Li can be improved.

[0091] If the upper limit of the aforementioned range is exceeded in the pulverization step, the magnetic material containing the core and shell of the lithium compound is excessively pulverized, crushed into flakes due to its malleability. Due to continued over-pulverization, the flake particles further break into fine powder particles, resulting in insufficient magnetic force during further magnetic separation. If the lower limit of the aforementioned range is exceeded in the pulverization step, the shell of the lithium-containing compound is difficult to separate from the core-shell magnetic material.

[0092] In one embodiment, following the pulverization step, a further separation step may be included, using any one of particle size separation, flotation, and magnetic separation. Flotation is a method of separating particles that takes into account differences in specific gravity between different substances; for example, particles may be separated using a specific solvent based on the particle size corresponding to the specific gravity of that solvent.

[0093] For the first magnetic material, when the core and shell are separated via the pulverization step, due to the ductility of metals, the valuable metal alloy particles are elongated or separated into larger particle sizes, while the lithium-containing compound can be pulverized into fine powder with smaller particle sizes. Specifically, the first magnetic material can be separated into lithium-containing compounds with particle sizes less than 70 to 80 μm and valuable metal alloys with particle sizes greater than 70 to 80 μm.

[0094] In one embodiment, the core and shell portions separated via the pulverization step can be separated by particle size based on a particle size of 70 to 80 μm. The lithium-containing compound in the shell portion has a particle size smaller than the aforementioned particle size standard, while the valuable metal alloy in the core portion has a particle size larger than the aforementioned particle size. Through particle size separation, the valuable metal alloy and the lithium-containing compound can be easily separated.

[0095] In another embodiment, the core and shell portions separated via the crushing step can be magnetically separated. This magnetic separation allows for the easy separation of magnetic cobalt-containing valuable metal alloys and non-magnetic lithium-containing compounds.

[0096] In yet another embodiment, the core and shell separated by the pulverizing step can be floated. This flotation allows for the easy separation of the core containing valence metals and the floating lithium-containing compound.

[0097] In one embodiment, the process may include a step of flotation of a first nonmagnetic body. As a graphite-containing nonmagnetic body, the first nonmagnetic body separated in the first magnetic separation step can be separated.

[0098] In one embodiment, the flotation step may be a step of screening graphite-containing floating matter and precipitates containing valuable metals. Specifically, the flotation step may be a step of floating hydrophobic graphite in the first non-magnetic body and separating lithium-containing compounds and particulate valuable metal alloys after precipitation.

[0099] In one embodiment, the following steps may be performed: magnetically separating the precipitate to recover substances containing valence metals, and pulverizing the recovered substances together with the magnetic product. A detailed description of the pulverization step is as described above.

[0100] In one embodiment, after the step of pulverizing the magnetic products in the magnetic separation process to separate them into magnetic and non-magnetic substances, a step of drying the final product may be included. Through this drying step, valuable metal alloys, lithium-containing compounds, and graphite can be dried into powder form.

[0101] In one embodiment, the drying step of the final product can be performed in the range of 80 to 200°C. Specifically, the drying step of the final product can be performed in the range of 100 to 150°C.

[0102] If drying is performed beyond the upper limit of the temperature range, there is a risk of combustion of flammable materials such as graphite. If drying is performed beyond the lower limit of the temperature range, the moisture in the powdered particles of the final product will not be completely dried, resulting in a product with high moisture content. This could lead to an increase in the amount of acid used in the leaching process of the subsequent wet refining process.

[0103] Figure 3a and Figure 3b The results are XRD analysis of a valuable metal recycling composition formed after heat treatment according to an embodiment of the present invention.

[0104] Reference Figure 3a and Figure 3b For compositions used in the recovery of valuable metals after high-temperature reduction heat treatment, it has been confirmed that Ni, Co, Mn, etc., are reduced without forming alloys, instead combining with the Al component in the battery to form lithium-containing compounds such as lithium oxides. These lithium oxides have been confirmed to form, for example, LiAlO2, Li5AlO4, and Li2CO3. In one embodiment, the composition for recovering valuable metals may further contain LiF. The LiF content may be determined based on the residual electrolyte content according to the degree of pretreatment.

[0105] In one embodiment, for LiAlO2, the XRD peak value may include at least one of 20.5 to 21.5°, 29.0 to 29.5°, 31.5 to 32.0°, 32.2 to 33.0°, 60.5 to 61.5°, and 70.0 to 72.0°. For Li5AlO4, the XRD peak value may include at least one of 19.5 to 20.2° and 21.6 to 22.2°.

[0106] For LiAl5O8 compositions, the XRD peak values ​​may include at least one of 15.0 to 17.4°, 24.2 to 26.1°, 31.4 to 33.1°, 36.2 to 40.3°, 46.1 to 47.3°, 61.1 to 63.4°, and 66.2 to 68.7°. For LiF compositions, the XRD peak values ​​may include at least one of 37.5 to 40.2°, 43.9 to 46.5°, and 64.5 to 66.5°.

[0107] For the Li3PO4 composition, the XRD peak value may include at least one of 29.2 to 40.1° and 52 to 77.1°. For the Li2SiO3 composition, the XRD peak value may include at least one of 17.7 to 20.1°, 26.1 to 29.5°, 32.2 to 36.2°, and 37.6 to 39.7°. For the Li4SiO4 composition, the XRD peak value may include at least one of 16.2 to 18.3°, 21.4 to 25.2°, 34.2 to 39.7°, and 59.2 to 63.4°.

[0108] For the Li2Si2O5 composition, the XRD peak value may include at least one of 16.2 to 18.3°, 21.4 to 25.2°, 34.2 to 39.7°, and 59.2 to 63.4°. For the Li2CO3 composition, the XRD peak value may include at least one of 24.0 to 26.0°, 27.0 to 29.0°, 34.0 to 36.0°, and 37.0 to 39.0°.

[0109] Figure 4 This is an SEM image of a composition for recycling valuable metals according to an embodiment of the present invention.

[0110] Reference Figure 4 According to one embodiment of the present invention, a valuable metal recycling composition comprises a core and a shell disposed on the core. The core may comprise a valuable metal recycling alloy. The valuable metal of the present invention may refer to high-valence metal components contained in a battery, and may refer to nickel, cobalt, manganese, aluminum, copper, and lithium. The core of the valuable metal recycling composition may be recovered from the positive electrode material components of a waste battery.

[0111] The shell portion is disposed on the core portion and may contain lithium compounds. Specifically, when recovering valuable metals from waste batteries, the valuable metals in the waste batteries exist in the form of oxides. Through a high-temperature heat treatment process, these metals are reduced under the action of graphite in the negative electrode material. At this time, the copper current collector melts and exists in a liquid phase, which can play a role in aggregating the reduced valuable metals. The copper current collector and the aluminum current collector undergo a partial reduction reaction with the oxide of the positive electrode material, and the remainder reacts with lithium, possibly leaving lithium-containing compounds in the form of oxides.

[0112] In one embodiment, the lithium (Li) content in the lithium compound is 4 to 35% by weight, specifically 4 to 25% by weight, based on a total weight of 100%. Since the lithium content in the lithium compound meets the aforementioned range, the higher lithium content satisfies the requirement of including a lithium-containing compound with excellent lithium recovery. If the Li content exceeds the upper limit of the aforementioned range, the Li₂O content becomes higher, and due to water solubility issues, a large amount of difficult-to-recover compounds are generated, leading to a decrease in lithium recovery. Conversely, if the Li content exceeds the lower limit of the aforementioned range, the lithium recovery rate decreases, rendering the composition impractical.

[0113] In one embodiment, the lithium compound may comprise at least one of LiAlO2, Li5AlO4, LiAl5O8, Li2CO3, LiF, Li3PO4, Li2SiO3, Li4SiO4, and Li2Si2O5. In another embodiment, the lithium compound may comprise lithium aluminum oxide.

[0114] The lithium compound may be, for example, a lithium oxide. The lithium-aluminum oxide may be realized in oxide form through the physical or chemical bonding of lithium contained in the composition.

[0115] In one embodiment, the lithium compound may comprise lithium aluminum oxide. Specifically, the content of lithium aluminum oxide may be 45.0 to 97.0% by weight, based on 100% by weight of the valuable metal recycling composition. Specifically, the content may be 70 to 90% by weight.

[0116] If the content of lithium aluminum oxide exceeds the upper limit of the aforementioned range, there is a problem that highly water-soluble lithium hydroxide, lithium carbonate, lithium fluoride, etc., will dissolve in large quantities in water during the screening process. If the content of lithium aluminum oxide exceeds the lower limit of the aforementioned range, most of the lithium compounds will be recovered in the form of low water-soluble LiAlO2, indicating that highly water-soluble lithium compounds have dissolved in water during the screening process. This leads to the need to recover lithium again from the water used in the screening process.

[0117] In one embodiment, the lithium compound may comprise a lithium- and silicon-containing oxide. Specifically, the content of the lithium- and silicon-containing oxide may be 2 to 30% by weight per 100% of the valuable metal recovery composition. Specifically, it may comprise 10 to 25% by weight. Since the lithium- and silicon-containing oxide meets the aforementioned range, a stable product is ensured under high temperature and appropriate oxygen concentration conditions, which has the advantage of improving the actual lithium recovery rate during acid leaching.

[0118] If the content of the lithium and silicon oxides exceeds the upper limit of the aforementioned range, it indicates that the high-temperature reduction reaction is exposed to the highest temperature for an extended period, reducing the productivity of the reactor and increasing energy costs. If the content of the lithium and silicon oxides exceeds the lower limit of the aforementioned range, there is insufficient sufficient thermal energy required for the reaction of lithium with aluminum or silicon to form lithium compounds such as lithium aluminates, or the reactor temperature is too high, causing lithium volatilization and resulting in a reduced lithium recovery rate.

[0119] In one embodiment, for a valuable metal recycling composition, silicon (Si) may be less than 10% by weight per 100% of the valuable metal recycling composition. Specifically, the silicon may be less than 1.0% by weight, and more specifically, less than 0.5% by weight.

[0120] If the silicon (Si) content exceeds the upper limit of the aforementioned range, there is an increase in the process time and cost required for silicon removal to the battery grade in the subsequent wet refining process. If the silicon (Si) content exceeds the lower limit of the aforementioned range, the remaining silicon (by weight%) in the added raw materials disperses into graphite and lithium compounds, resulting in increased process time and cost for the purification and refining processes of graphite and lithium compounds.

[0121] In one embodiment, the Li2CO3 content may be less than 30% based on 100% by weight of the total composition. The Li2CO3 content may be less than 15.0%, more specifically less than 5%. Because the Li2CO3 content meets the aforementioned range, it has the advantage of preventing the large-scale formation of compounds that are difficult to recover due to water solubility issues.

[0122] In one embodiment, the LiF content may be less than 30% by weight per 100% of the total composition. More specifically, the LiF content may be from 6.5% to 24.0% by weight per 100% of the total composition, and more specifically, from 6.5% to less than 15% by weight. Because the LiF content meets the aforementioned range, it has the advantage of preventing the formation of large quantities of compounds that are difficult to recover due to water solubility issues.

[0123] If the LiF value exceeds the upper limit of the aforementioned range, the mixing of sulfate and fluoride ions during sulfuric acid leaching will make it difficult to adjust the pH, resulting in a decrease in lithium recovery rate. If the LiF value exceeds the lower limit of the aforementioned range, the levels of Li₂SiO₃, Li₄SiO₄, and Li₂Si₂O₅ will become higher, making sulfuric acid leaching difficult and potentially causing delays in the leaching process.

[0124] In one embodiment, the combined content of Li₂CO₃ and LiF, based on 100% by weight of the total composition, may be less than 50%. Specifically, the combined content may be from 0.5% to 50%. More specifically, the content may be from 0.5% to less than 30%.

[0125] If the total content exceeds the upper limit of the aforementioned range, a large amount of compounds that are difficult to recover due to water solubility will be generated, resulting in difficulties in recovering Li. If the total content exceeds the lower limit of the aforementioned range, the levels of compounds such as Li₂SiO₃, Li₄SiO₄, and Li₂Si₂O₅ will increase, making sulfuric acid leaching difficult and causing delays in the leaching process.

[0126] Since the total content of Li2CO3 and LiF meets the aforementioned range, it prevents the generation of large amounts of compounds that are difficult to recover due to water solubility issues. By appropriately adjusting the high temperature and oxygen concentration, a large amount of stable compounds with excellent leaching rates in sulfuric acid are generated, which has the advantage of improving lithium recovery efficiency.

[0127] In one embodiment, Li3PO4 may be contained at least 10% by weight, based on 100% by weight of the total composition. Specifically, the Li3PO4 may be contained at least 5% by weight, more specifically at least 3% by weight, and more specifically at 0.1 to 0.7% by weight, based on 100% by weight of the total composition. Since the Li3PO4 content meets the aforementioned range, it is possible to prevent the presence of PO4 during acid leaching. 3- The leaching behavior caused by pH changes due to anions and the formation of LiOH during impurity removal lead to a decrease in lithium recovery. Since the Li3PO4 content meets the aforementioned range, it can prevent the degradation of lithium recovery due to PO4 content during acid leaching. 3- The leaching behavior caused by pH changes due to anions and the generation of LiOH during impurity removal lead to a decrease in lithium recovery rate.

[0128] Preferred embodiments and comparative examples of the present invention are described below. However, the following embodiments are merely preferred embodiments of the present invention, and the present invention is not limited to the following embodiments.

[0129] <Experimental Example 1> 1. Steps for preparing valuable metal recycling compositions Prepare battery cells, battery modules, or battery packs from spent electric vehicle batteries, comprising lithium-ion positive electrode materials, graphite negative electrode materials, aluminum current collectors, separators, electrolytes, and copper current collectors. The batteries are crushed using the following method: the spent batteries are frozen at a temperature below -30°C and then crushed, or discharged under salt water discharge or electrical discharge conditions, and then crushed using crushing equipment under atmospheric or inert gas conditions into lengths where the longest horizontal and vertical length is less than 100 mm.

[0130] After obtaining the valuable metal recycling composition by the aforementioned method, the crushed battery fragments are heat-treated at 1300°C under an oxygen partial pressure of 0.5% to perform a reduction process. After the reduction process, a valuable metal recycling composition is generated as described above, consisting of a core containing valuable metal and a shell containing a lithium compound on the core.

[0131] Table 1 below shows the composition and content of the valuable metal recycling composition produced by the aforementioned method.

[0132] The components and contents in Table 1 below were determined by quantitative analysis methods using ICP-OES equipment and C / S analysis equipment.

[0133] Table 1

[0134] 2. One-step magnetic separation For compositions used for recycling valuable metals that have undergone a high-temperature reduction process, magnetic and non-magnetic materials are separated using a magnetic separator with a magnetic strength of 3000 Gauss.

[0135] Table 2 below shows the composition and content of magnetic and non-magnetic materials separated by a magnetic separator with a speed of 3000 gauss.

[0136] Table 2

[0137] As confirmed in Table 2 above, as shown in Experimental Example 2_1, the magnetic material separated by magnetic separation contains NCM metals, which are valuable metals, with high contents of Li, Ni, Co, and Mn. As shown in Experimental Example 2_2, the non-magnetic particles separated by magnetic separation consist of mostly separated Li and Al particles and graphite particles, with a high C content.

[0138] 3_1. Flotation Steps As shown in Experiment 2_2, non-magnetic substances separated by magnetic separation were floated using the following method: using the Denver Sub_A flotation equipment of Experiment 3_1, flotation was carried out under the conditions of ore liquor concentration of 30%, impeller speed of 500 rpm, kerosene concentration of 0.1 ml / 100 g, and MIBC concentration of 0.1 ml / 100 g.

[0139] Through the flotation process, lightweight graphite powder floats to the top of the device, where it is separated to recover the graphite.

[0140] Table 3 below shows the composition and content of the results after the flotation process.

[0141] Table 3

[0142] As shown in Table 3, the carbon content of the material floating due to overflow (O / F) is 92.5%, which is significantly higher than the initial battery fragments (35.07%) and the raw material fed into the flotation machine after separation of non-magnetic materials by magnetic separation (75.30%). Furthermore, the carbon content of the precipitate remaining due to underflow (U / F) is 5.75%, indicating that most of the hydrophobic carbon is recovered as floating matter. Further, the lithium content ratio between floating matter and precipitate shows that most lithium does not float and remains as precipitate, allowing for effective separation of carbon and lithium through flotation. Additionally, the precipitate has a high aluminum content, indicating that most lithium remains in the precipitate as LiAlO2. Furthermore, Cu does not float and mostly remains as precipitate, with a content of 18.04%.

[0143] 4. Crushing and Secondary Magnetic Separation Steps 2_1. The magnetic material after the magnetic separation step is pulverized using the following method: pulverization is performed using a vertical stirring mill at 500 rpm, an impeller tip speed of 2.8 m / s, a pulverization time of 60 minutes, and a solids content of 30% by weight. For the magnetic material, as previously mentioned, it has been confirmed that a valuable metal recovery composition consisting of a core containing a valuable metal and a shell containing a lithium compound disposed on the core can separate the core and the shell through the pulverization process.

[0144] Table 5 below shows the composition and content of the resulting material obtained by separating the magnetic body containing the core and the shell and separating it by particle size.

[0145] Table 4

[0146] As confirmed in Table 5 above, in order to separate the alloy core containing valence metals and lithium compounds from the product after the pulverization process, a magnetic separator at 3000 gauss was used to separate magnetic and non-magnetic materials. Experimental Example 4_1, which showed a valence metal core, had excessive Ni, Co, and Mn content. Experimental Example 4_2, which was confirmed to be separated into non-magnetic materials, was the product from which the lithium-containing shell was pulverized, resulting in a high lithium content. During the pulverization process, the shell, in oxide form, of the product recovered as a magnetic product in magnetic separation is pulverized, while the ductile core is continuously crushed into flakes inside the pulverizer, resulting in a particle size larger than the initial particle size and a thinner thickness. On the other hand, the shell, being in oxide form, is brittle, and its particle size gradually decreases as pulverization time increases and pulverization continues.

[0147] 5. Secondary separation step For Experiment 4_1, which has undergone a pulverization step, particle size separation can also be achieved by utilizing the difference in pulverization characteristics between the core alloy and the shell oxide compound. However, it is more ideal to utilize the magnetic properties of the core alloy by performing a secondary screening process using magnetic separation at a magnetic force of 3000 Gauss. In this case, if magnetic separation is used, the recovery rate of valuable metals in the core will further increase compared to particle size separation. If particle size separation is used, a sieve with a screen size of 75 μm or 45 μm is required. In this case, coarse particles are recovered as the NCM alloy portion, and fine particles are recovered as lithium oxide.

[0148] 6. Drying Steps For the magnetic materials containing Ni, Co, and Mn, the non-magnetic materials containing Li, and graphite separated by the aforementioned steps, the moisture content is reduced to 30% using a drum dehydrator or centrifugal dehydrator, and then dried to below 5% using hot air at 100 to 200°C, and then recovered.

[0149] Table 5 below shows the composition and content of the final product recovered through the aforementioned steps.

[0150] Table 5

[0151] Referring to Table 5 above, for valuable metal alloys whose main components are Ni, Co, and Mn, as shown in Experimental Example 4_1, they can be recovered from the magnetic material separated by magnetic separation, crushing, and magnetic separation steps. Lithium compounds, whose main component is lithium, can be recovered from the total amount of non-magnetic material separated by magnetic separation, crushing, and magnetic separation steps as shown in Experimental Example 4_2, and the material precipitated by flotation as shown in Experimental Example 3_2. For graphite, as shown in Experimental Example 3_1, it can be recovered by separating the floating material by flotation. As described above, through the aforementioned battery processing method, valuable metal alloys containing valuable metals such as Ni, Co, and Mn can be recovered, while lithium compounds with high lithium content can be separated, thereby improving the recovery rate of valuable metals Li, Ni, Co, and Mn. Furthermore, by separately separating graphite, the recovery rate of graphite that can be used as a negative electrode material can be improved.

[0152] <Experimental Example 2>: Based on the changes in the composition of magnetic and non-magnetic materials according to changes in magnetic strength. Table 6 below shows the compositional changes of magnetic and non-magnetic materials during a single magnetic separation, based on variations in magnetic force.

[0153] Table 6

[0154] Referring to Table 6 above, based on the changes in the composition of magnetic and non-magnetic materials during a single magnetic separation, the NCM cathode material recovered as a magnetic product under weak magnetic intensities of 500 and 1000 Gauss (G) has a higher grade, but the recovery rate (Dist.) is below 90%, indicating a low recovery rate and reduced Li content and recovery rate. However, when the magnetic intensity is above 2000 Gauss, it can be confirmed that most of the NCM cathode material is recovered as a magnetic product.

[0155] <Experimental Example 3>: After controlling the pulverization conditions, secondary magnetic separation was performed. Table 7 below shows the results of pulverizing the magnetic material after one magnetic separation and then separating the pulverized product into magnetic and non-magnetic materials using a 3000 Gauss magnetic separator.

[0156] At this time, a vertical stirring ball mill was used as the pulverizer. The pulverizing conditions were 500 RPM (blade tip speed of 2.65 m / s), 1L pulverizing container size, 30% solids concentration, and 0 to 90 minutes of pulverizing time. Magnetic and non-magnetic materials were analyzed according to the pulverizing time.

[0157] Table 7

[0158] As shown in Table 7, during the initial 10 minutes of crushing, only a portion of the lithium compounds encasing the NCM alloy were crushed. The recovery rates of the NCM alloy portion, which was recovered as a magnetic material, were only 86% for Ni, 87% for Co, and 85% for Mn. However, when the crushing time reached 30 to 60 minutes, the recovery rates of Ni, Co, and Mn exceeded 90%. Furthermore, when the crushing time exceeded 60 minutes and reached 90 minutes, most of the lithium compounds were crushed into non-magnetic materials and recovered at a high recovery rate of 91%. The NCM alloy portion, which served as the core, was completely crushed into flakes due to its ductility after the shell was completely detached. Due to continuous over-crushing, the flake particles further split into fine powder particles, which became excessively fine, resulting in negligible influence of magnetic force on individual particles. Therefore, even if the micronized NCM alloy portion was magnetic during magnetic separation, it could not be recovered as a magnetic material, thus confirming that the recovery rates of Ni, Co, and Mn dropped below 85% again.

[0159] The preferred embodiments have been described in detail above, but the scope of the present invention is not limited to the above embodiments. Various modifications and improvements made by those skilled in the art using the basic concepts defined in the claims also fall within the scope of the present invention.

Claims

1. A recyclable material recovered from waste batteries, wherein, The recycled material is a substance recovered from waste batteries. Based on 100% by weight of the recycled material, it contains 20 to 35% by weight of valuable metal recycled alloys, 25 to 50% by weight of lithium compounds, and the balance of graphitic materials.

2. The recyclable material recovered from waste batteries according to claim 1, wherein, The valuable metal recycling alloy contains Ni, Co, Mn, and impurities.

3. The recyclable material recovered from waste batteries according to claim 2, wherein, The total value of the recycled metal alloy is calculated as 100% by weight, and the recycled metal alloy contains a total content of more than 90% by weight of Ni, Co and Mn, and the balance is impurities.

4. The recyclable material recovered from waste batteries according to claim 3, wherein, The total value of the recycled metal alloy is 100% by weight, including 1 to 7% by weight of copper (Cu).

5. The recyclable material recovered from waste batteries according to claim 3, wherein, The valuable metal recycling alloy comprises 50 to 60% by weight of nickel (Ni), 18 to 28% by weight of cobalt (Co), 10 to 20% by weight of manganese (Mn), and the balance being impurities, based on a total of 100% by weight of the valuable metal recycling alloy.

6. The recyclable material recovered from waste batteries according to claim 1, wherein, The lithium compound comprises 10 to 20% by weight of lithium (Li), 20 to 30% by weight of aluminum (Al), and the balance being impurities, based on 100% by weight of the lithium compound.

7. The recyclable material recovered from waste batteries according to claim 1, wherein, The lithium compound comprises lithium oxide.

8. The recyclable material recovered from waste batteries according to claim 7, wherein, The lithium oxide comprises lithium aluminum oxide.

9. The recyclable material recovered from waste batteries according to claim 1, wherein, The graphitic material contains 80 to 90% by weight of carbon (C) and the balance being impurities.

10. The recyclable material recovered from waste batteries according to claim 1, wherein, The graphitic material contains 13 to 25% by weight of copper (Cu).

11. The recyclable material recovered from waste batteries according to claim 1, wherein, The valuable metal recycling alloy, the lithium compound, and the graphitic material are each in powder form.

12. The recyclable material recovered from waste batteries according to claim 1, wherein, At least a portion of the lithium compound comprises a composition disposed in at least a portion of the surface of the valuable metal recycling alloy.

13. The recyclable material recovered from waste batteries according to claim 12, wherein, The composition has a core-shell structure.

14. A method for recovering valuable metals, comprising: a method for recovering valuable metals from the product of reducing heat treatment at high temperature on crushed material recovered from waste batteries, the method comprising: The step of magnetically separating the heat-treated product into a first magnetic body and a first non-magnetic body; The step of crushing the first magnetic material. The pulverizing step is carried out within a shear force range of 1 to 5 m / s based on the blade tip velocity.

15. The method for recovering valuable metals according to claim 14, wherein, The pulverizing step is carried out for 30 to 60 minutes.

16. The method for recovering valuable metals according to claim 14, wherein, At least a portion of the product obtained by subjecting the shredded material recovered from waste batteries to high-temperature reduction heat treatment contains a valuable metal recovery composition, the valuable metal recovery composition comprising: The core, which contains a valuable metal recycled alloy; and A shell portion disposed on the core portion and containing a lithium compound.

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