Method for dry sorting waste batteries

Abstract

The present invention relates to a method for dry sorting waste batteries, the method comprising: a step for preparing a raw material valuable metal product (VM) by performing a high-temperature reduction reaction on crushed waste batteries; a classification step for primarily crushing the raw material valuable metal product and then separating same by particle size; and a step for secondarily crushing and then air-classifying the valuable metal product separated by particle size in the classification step, wherein a large-diameter valuable metal product (LM) having a particle size of 100 ㎛ or more and a small-diameter valuable metal product (SM) having a particle size of less than 100 ㎛ may be separated in the classification step.

Description

Dry sorting method for waste batteries

[0001] The present invention relates to a method for recovering valuable metals from waste batteries, specifically a method for recovering valuable metals from waste batteries using a dry method.

[0002] This application claims priority to Korean Patent Application No. 10-2024-0190810, filed on December 19, 2024, the entire contents of which are incorporated herein by reference.

[0003] Globally, there has recently been a trend of transitioning EV batteries from the more affordable NCM type to the LFP type, with their utilization in mass-market EVs increasing. Therefore, the present invention aims to provide a method for recovering valuable metals by material type from waste NCM and waste LFP batteries, as well as NCM and LFP scraps.

[0004] Conventionally, a method is used in which a pretreatment (upper process) process is used to produce Black Mass by discharging, crushing, heat treatment, classification, and iron removal of LFP batteries, just like in NCM systems, and the Black Mass is fed into a lower process of wet smelting to recover valuable metals.

[0005] Although valuable metals and resources were recovered by material type through a wet separation process using water, the use of water raises concerns about wastewater generation and potential loss of some Li due to dissolution in the water. Additionally, the dehydration and drying processes consume a significant amount of energy, and maintaining the wet separation process smoothly may be difficult in water-scarce regions or areas where temperatures drop below the freezing point.

[0006] When Black Mass, in which all valuable metals and resources are mixed, is fed into wet smelting in this manner, the efficiency of the process decreases, the amount of various reagents such as sulfuric acid increases, and the solvent extraction process to increase purity becomes more complex.

[0007] The present invention aims to provide a dry sorting method for recovering valuable metals and resources by material from high-temperature reduced materials obtained by reducing waste batteries and scrap in a reducing atmosphere of 800°C or higher.

[0008] One objective of the present invention is to provide a method for recovering valuable metal resources from waste batteries in an economical and environmentally friendly manner using a dry method.

[0009] Another objective of the present invention is to provide a method for separating and recovering valuable metals by type from waste batteries.

[0010] A method for recovering valuable metals according to one embodiment of the present invention comprises: a step of preparing a raw valuable metal product (VM) by subjecting crushed waste batteries to a high-temperature reduction reaction; a classification step of first crushing the raw valuable metal product and then separating it into a large-particle valuable metal product (LM) and a small-particle valuable metal product (SM); and a step of secondarily crushing the large-particle valuable metal product (LM) and the small-particle valuable metal product (SM), respectively, and then performing air-stream classification; wherein the average particle size (D50) of the large-particle valuable metal product (LM) L ) is tens of μm to several mm, and the average particle size (D50) of the small-particle valuable metal product (SM) S ) is tens of nm to tens of μm, and the average particle size (D50) of the large-diameter valuable metal product (LM) is L ) is the average particle size (D50) of the small-particle valuable metal product (SM) S It could be larger than ).

[0011] The above large particle size valuable metal product (LM) may be subjected to secondary crushing and then air stream classification to separate the high-density large particle size valuable metal product (HLM) and the low-density large particle size valuable metal product (LLM).

[0012] A further step of separating the high-density large-diameter valuable metal product (HLM) into a magnetic large-diameter valuable metal product (MLM) and a non-magnetic large-diameter valuable metal product (NLM) using a magnetic separator can be performed.

[0013] The above magnetic separation is performed using a dry magnetic separator, and the above magnetic separation may be performed with a magnetic force of 1,000 to 3,000 Gauss.

[0014] The increase rate of the iron (Fe) element content of the magnetic large particle valuable metal product (MLM) relative to the raw material valuable metal product (VM) may be 85% or more.

[0015] The increase rate of the lithium (Li) element content of the mixed valuable metal product (MXLM), composed of the non-magnetic large-particle valuable metal product (NLM) and the low-density large-particle valuable metal product (LLM), relative to the raw material valuable metal product (VM) may be 110% or more.

[0016] The above small particle size valuable metal product (SM) may be subjected to secondary crushing and then air stream classification to separate the high-density small particle size valuable metal product (HSM) and the low-density small particle size valuable metal product (LSM).

[0017]

[0018] The increase rate of the copper (Cu) element content of the high-density, small-particle, valuable metal product (HSM) relative to the raw material valuable metal product (VM) may be 110% or more.

[0019] The increase rate of the carbon (C) element content of the low-density, small-particle, valuable metal product (LSM) relative to the above raw material valuable metal product (VM) may be 155% or more.

[0020] The above primary grinding may be performed using one or more types of equipment selected from a rod mill, ball mill, pin mill, and impact mill.

[0021] The above secondary grinding may be performed using one or more types of equipment selected from a Tower Mill, Attrition Mill, Impact Mill, and Jet Mill.

[0022] The average particle size of the pulverized material obtained by secondary grinding of the above large-diameter metal product (LM) may be 30.0 to 50.0 μm.

[0023] The average particle size of the small particle size crushed material obtained by secondary crushing of the above small particle size valuable metal product may be 10.0 to 30.0 μm.

[0024] The step of preparing a valuable metal product by high-temperature reduction reaction of the above-mentioned crushed waste battery material may be to heat-treat the above-mentioned crushed waste battery material at a temperature of 800°C or higher.

[0025] The above waste battery may include a positive active material containing one or more of iron (Fe), phosphorus (P), nickel (Ni), manganese (Mn), or cobalt (Co).

[0026] A method for recovering valuable metals according to one embodiment of the present invention utilizes a dry method, thereby suppressing lithium (Li) loss due to water usage and having the advantage of not generating wastewater.

[0027] A method for recovering valuable metals according to one embodiment of the present invention has the advantage of being able to separate and recover valuable metals by type from waste batteries.

[0028]

[0029] Figure 1 schematically illustrates the flow of a dry sorting process for waste batteries according to one embodiment of the present invention.

[0030] Figure 2 shows the results of SEM-DEX analysis of the valuable metal recovery composition according to Preparation Example 1.

[0031] Figures 3 and 4 respectively show the SEM-EDX analysis results for a non-magnetic material and a magnetic material according to Example 1.

[0032] Figures 5 and 6 respectively show SEM images of a high-density small-particle material and a low-density small-particle material different from Example 1.

[0033] 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 solely to distinguish one part, component, region, layer, or section from another part, component, region, layer, or section. Accordingly, the first part, component, region, layer, or section described below may be referred to as the second part, component, region, layer, or section without departing from the scope of the present invention.

[0034] The technical terms used herein are for the reference of specific embodiments only and are not intended to limit the invention. The singular forms used herein include plural forms unless phrases clearly indicate otherwise. As used in the specification, the meaning of "comprising" specifies certain characteristics, areas, integers, steps, actions, elements, and / or components, and does not exclude the presence or addition of other characteristics, areas, integers, steps, actions, elements, and / or components.

[0035] When it is stated that one part is "above" or "on" another part, it may be directly above or on the other part, or other parts may be involved in between. In contrast, when it is stated that one part is "directly above" another part, no other parts are interposed in between.

[0036] Additionally, % in this specification means weight % unless otherwise specified.

[0037] Unless otherwise defined, all terms used herein, including technical and scientific terms, have the same meaning as generally understood by those skilled in the art to which this invention pertains. Terms defined in commonly used dictionaries are further interpreted to have meanings consistent with relevant technical literature and the present disclosure, and are not interpreted in an ideal or highly formal sense unless otherwise defined.

[0038] In this specification, the term “combination(s) of these” described in the Markush-type expression means one or more mixtures or combinations selected from the group consisting of the components described in the Markush-type expression, and means including any one or more selected from the group consisting of said components.

[0039] Hereinafter, embodiments of the present invention are described in detail so that those skilled in the art can easily implement the invention. However, the present invention may be embodied in various different forms and is not limited to the embodiments described herein.

[0040]

[0041] Figure 1 schematically illustrates the flow of a dry sorting process for waste batteries according to one embodiment of the present invention.

[0042] Referring to FIG. 1, a dry sorting method for waste batteries according to one embodiment of the present invention may include: a step of preparing a raw material valuable metal product (VM) by reacting crushed waste batteries at a high temperature reduction reaction; a classification step of first crushing the raw material valuable metal product and then separating it by particle size; and a step of secondarily crushing the valuable metal product separated by particle size in the classification step and then classifying it by air stream.

[0043]

[0044] First, a step is performed to prepare a raw material valuable metal product (VM) by high-temperature reduction reaction of the crushed waste battery material.

[0045] In the present invention, the step of preparing a raw material valuable metal product (VM) by high-temperature reduction reaction of waste battery crushed material may include the step of preparing a waste battery, the step of crushing the waste battery to obtain waste battery crushed material, and the step of heat-treating the waste battery crushed material at high temperature in a reducing atmosphere to obtain a raw material valuable metal product (VM).

[0046] In the step of preparing the waste battery, the waste battery may be, for example, a lithium secondary battery separated from a vehicle, a secondary battery separated from an electronic device such as a mobile phone, camera, or laptop, specifically, a lithium secondary battery. Specifically, the waste battery may be a lithium secondary battery comprising one or more types of positive active materials among NCM-based positive active materials or LFP-based positive active materials.

[0047] In one embodiment of the present invention, in the step of preparing the waste battery, the battery may include lithium (Li), aluminum (Al), and copper (Cu). As lithium, aluminum, and copper coexist within the waste battery, the lithium, aluminum, and copper may be arranged as a material in which they are physically and / or chemically bonded in the product generated after the waste battery processing.

[0048] The step of crushing the waste battery may refer to a process of applying impact or pressure to the waste battery so that a portion of the waste battery detaches from the waste battery. In one embodiment, the step of crushing the waste battery may refer to a process of cutting the waste battery, a process of compressing the waste battery, a process of crushing the waste battery, and any combination thereof. Specifically, the crushing step may include any process that destroys the battery to obtain small-sized crushed material.

[0049] In one embodiment, the step of crushing the waste battery may include all processes of compressing the prepared waste battery or destroying the waste battery by applying an external force such as shear force or tensile force. The step of crushing the waste battery may be carried out, for example, using a crusher.

[0050] In one embodiment, the step of crushing the waste battery may be performed at least once. Specifically, the crushing step may be performed at least once, either continuously or discontinuously.

[0051] In one embodiment, the step of crushing the waste battery may be carried out under conditions of supplying an inert gas, carbon dioxide, nitrogen, water, or a combination thereof, or under vacuum conditions of 100 torr or less. When carried out under the aforementioned conditions, the supply of oxygen can be suppressed to prevent the electrolyte from reacting with oxygen, thereby preventing explosions caused by this, and the vaporization of the electrolyte can be suppressed, which can reduce the amount of flammable gases such as ethylene, propylene, or hydrogen generated, thus ensuring safety.

[0052]

[0053] The step of obtaining a raw material valuable metal product (VM) by high-temperature heat treatment of the above-mentioned crushed waste battery material in a reducing atmosphere may be a step of loading the above-mentioned crushed waste battery material into a furnace and heat-treating it in a reducing atmosphere to form a valuable metal product in powder form.

[0054] In the present invention, the valuable metal may refer to expensive metal components included in the battery, and may refer to nickel, cobalt, manganese, aluminum, copper, iron, and lithium.

[0055] In the present invention, the reducing atmosphere may be a gas atmosphere comprising one or more selected from carbon monoxide (CO) gas, hydrocarbon (CH₄) gas, hydrogen (H₂) gas, and low concentration oxygen (O₂), nitrogen (N₂), and argon (Ar).

[0056] In the case of low-concentration oxygen (O2) in the present invention, the process may be carried out in a gas atmosphere where the oxygen concentration is in the range of 0.1 to 2.0 vol%. Specifically, the process may be carried out in a gas atmosphere where the oxygen concentration is in the range of 0.4 to 1.2 vol%.

[0057] If the oxygen concentration exceeds the upper limit of the aforementioned range, as the oxygen concentration increases, the reaction Li2O + C + O2(g) = Li2CO3 is promoted, but simultaneously, there is a problem in that LiAlO2 and Li5AlO4 decrease. Specifically, if the oxygen concentration exceeds the upper limit of the aforementioned range, carbon dioxide is excessively formed during the reduction reaction process and is gasified and lost along with lithium, or the generation of Li2CO3(s) becomes excessive, making recovery by acid leaching difficult. If the oxygen concentration exceeds the lower limit of the aforementioned range, there is a problem in that the lithium recovery rate decreases.

[0058] In one embodiment, the step of high-temperature heat treatment of the battery crushed material may be performed in a range of 600 to 1,500 ℃. Specifically, the high-temperature heat treatment step may be performed in a range of 800 to 1,500 ℃, more specifically in a range of 1,100 to 1,500 ℃, and even more specifically in a range of 1,300 to 1,500 ℃. As the temperature rises, the step of high-temperature heat treatment of the battery crushed material produces Li5AlO4 due to the reaction LiAlO2(s) + 2Li2CO3(s) = Li5AlO4 + 2CO2(g), but the LiF(g) vaporization reaction is promoted, so when performed in the aforementioned range, the yield of lithium can be improved.

[0059] If the value exceeds the upper limit of the above range, there is a problem of lithium loss due to lithium vaporization. Specifically, if the value exceeds the upper limit of the above range, the LiF(g) vaporization reaction is excessively accelerated, leading to a problem where the lithium recovery rate decreases due to the loss of lithium.

[0060] If the value exceeds the lower limit of the above range, the sintering and reduction of alloying elements do not proceed smoothly, and a stabilized lithium-containing compound cannot be formed. Consequently, there is a problem in that it is difficult to recover the stabilized compound during future lithium compound recovery. Specifically, if the value exceeds the lower limit of the above range, MnO among the Li-containing Ni, Co, and Mn oxides in the cathode material does not dissociate. Instead, MnAl2O4 is generated due to the reaction MnO(s) + 2Al(s) + 3 / 2O2 = MnAl2O4(s), which reduces the lithium concentration within the lithium compound and consequently lowers the lithium recovery rate.

[0061] In the present invention, by heat-treating the waste battery at the temperature in the reducing atmosphere, there is an advantage of effectively thermally decomposing and removing residual organic matter present in the waste battery and reducing metal elements to effectively separate them by material.

[0062] In the present invention, the valuable metal product (VM) may vary depending on the type of positive electrode active material included in the waste battery, and specifically may include Li compounds, Cu, graphite (C), and other valuable metals or valuable metal compounds. For example, in the case of a waste battery containing an NCM-based positive electrode active material, it may mainly include an NCM alloy, a Li compound, Cu, and graphite, and in the case of a waste battery containing an LFP positive electrode active material, it may mainly include a lithium compound, Cu, and graphite.

[0063]

[0064] Next, a classification step can be performed to first crush the raw material valuable metal product and then separate it by particle size.

[0065] The classification step of first crushing the above-mentioned raw material valuable metal product and then separating it by particle size may include a step of first crushing the valuable metal product obtained by the above-mentioned high-temperature reduction reaction to form a first crushed product, and a classification step of separating the first crushed product by particle size.

[0066] In the step of forming a primary crushed product by primary crushing the above valuable metal product, the primary crushing can be performed using a crushing equipment that uses impact force, utilizing one or more types of equipment selected from a rod mill, ball mill, pin mill, and impact mill, so that the maximum particle size becomes 1 to 2 mm or less.

[0067] By grinding to the above average particle size, particles in which valuable metals and valuable resources are physically aggregated and bonded together through partial melting during the reduction process of high-temperature heat treatment in a reducing atmosphere are ground, thereby improving the degree of liberation of each material and increasing the separation efficiency in the subsequent separation process.

[0068] If the average particle size of the pulverized product after pulverization is less than 1 mm, the following problems may occur. For example, when spherical alloy particles such as ductile NCM compounds and FeP are stretched by external force, Cu metal or other materials may be physically bonded or embedded in the stretched plane of the alloy, which may result in a decrease in sorting efficiency during the subsequent sorting stage.

[0069] When the average particle size of the pulverized product after pulverization is greater than 2 mm, the degree of separation of individual materials decreases, and the proportion of materials existing as a single composition decreases, which may lead to a problem where the separation efficiency in the subsequent separation stage decreases and the impurity content in the final material recovered by separation increases.

[0070]

[0071] The classification step for separating the primary crushed product by particle size may be a classification step for separating the primary crushed product into a large particle size valuable metal product (LM) and a small particle size valuable metal product (SM).

[0072] Specifically, the material crushed through a primary crusher is processed using a particle size separator such as a vibrating screen to obtain an average particle size (D50 L Large-diameter valuable metal products (LM) with a particle size ranging from tens of µm to several mm and an average particle size (D50 S ) can be separated into small particle size valuable metal products (SM) ranging from a few nm to several tens of μm.

[0073] In the present invention, the average particle size (D50) of the large-diameter metal product (LM) L ) is the average particle size (D50) of the small-particle valuable metal product (SM) S It could be larger than ).

[0074] In the present invention, the average particle size (D50) of the large-diameter metal product (LM) L ) can be tens of µm to several mm, and specifically 50 µm to several 2 mm.

[0075] In the present invention, the large-particle valuable metal product (LM) refers to a valuable metal product remaining at the top of a screen when separated using a screen having a predetermined mesh size, and the small-particle valuable metal product (SM) refers to a valuable metal product that has passed through the screen.

[0076] In the present invention, the separation criteria of the particle size separator can be adjusted according to the degree of individual separation in which particles of NCM compounds, FeP alloys, Li compounds, LiP, Cu, and graphite contained in the primary ground material exist as independent particles. Specifically, the mesh size of the screen can be adjusted within the range of 32㎛ to 150㎛. For example, if the proportion of Li compounds and LP (lithium phosphorus compounds) existing as independent particles larger than 100㎛ in the primary ground is high, a 150㎛ screen can be used, and if the proportion of particles significantly smaller than 100㎛ is high, a 32㎛ screen can be used. However, the present invention is not limited thereto.

[0077] In the present invention, through the classification step, at least 55% of the copper (Cu) element, at least 80% of the iron (Fe) element, and at least 75% of the aluminum (Al) element in the raw material valuable metal product are contained in the large particle size (LM), and at least 75% of the carbon (C) element in the raw material valuable metal product may be contained in the small particle size (SM).

[0078] In the present invention, the large particle size valuable metal product (LM) can be further crushed and then air-stream classified to separate the high-density large particle size valuable metal product (HLM) and the low-density large particle size valuable metal product (LLM).

[0079] In the present invention, the secondary grinding can be performed using one or more types of equipment selected from a Tower Mill, an Attrition Mill, an Impact Mill, and a Jet Mill, and specifically, it can be performed using one or more types of equipment selected from an Impact Mill and a Jet Mill. By grinding using the above equipment, the problem of the quality of the final product being degraded due to excessively high heat generation caused by alloy particles during the dry grinding process can be prevented.

[0080] In the present invention, the large particle size valuable metal product (LM) can be further ground to form a secondary large particle size ground product (LMc) having an average particle size of 30.0 to 50.0 μm.

[0081] When secondary grinding is performed as described above, there is an advantage in that the degree of separation by composition is improved in the subsequent airflow classification stage.

[0082] The above secondary large particle size crushed material (LMc) can be separated into high-density large particle size valuable metal products (HLM) and low-density large particle size valuable metal products (LLM) through air stream classification.

[0083] In the present invention, airflow classification of the secondary large particle size crushed material (LMc) can be performed at an airflow speed of 2 to 15 m / s.

[0084] As described above, airflow classification offers the advantage of being able to select materials with improved separation by composition.

[0085] In the present invention, a further step of separating the high-density, large-diameter valuable metal product (HLM) into a magnetic, large-diameter valuable metal product (MLM) and a non-magnetic, large-diameter valuable metal product (NLM) using a magnetic separator can be performed.

[0086] Here, the magnetic separator may be a dry magnetic separator, and the magnetic strength may be 1,000 to 3,000 Gauss. Specifically, in the case of an NCM positive electrode active material, a dry magnetic separator having a magnetic strength of 1,000 to 3,000 Gauss may be used, and in the case of an LFP positive electrode active material, a magnetic separator having a magnetic strength of 2,000 to 3,000 Gauss may be used.

[0087] If the strength of the magnetic force is below the above range, the recovery rate of NCM alloys and FeP alloys recovered as magnetic products is low and may be lost as non-magnetic products. If the strength of the magnetic force exceeds the above range, the recovery rate of non-magnetic products containing Li, such as Li compounds and LP (lithium phosphorus compounds), is low and may be lost as magnetic products.

[0088] Therefore, in the present invention, when the magnetic force is applied within the above range, there is an advantage in being able to separate materials with improved separation efficiency according to composition.

[0089] In the present invention, the increase rate of the iron (Fe) element content of the magnetic large particle valuable metal product (MLM) with respect to the raw material valuable metal product (VM) may be 85% or more, and specifically 100%.

[0090] In the present invention, the increase rate of the lithium (Li) element content of the mixed valuable metal product (MXLM), composed of the non-magnetic large-particle valuable metal product (NLM) and the low-density large-particle valuable metal product (LLM), relative to the raw material valuable metal product (VM) may be 110% or more, and specifically 200% or more, or 300% or more.

[0091]

[0092] In the present invention, the small particle size valuable metal product (SM) can be secondarily crushed and then air stream classification can be performed.

[0093] The secondary grinding of the above-mentioned small-sized metal product (SM) can be performed using one or more pieces of equipment selected from impact mills. By grinding using the above-mentioned equipment, the problem of the quality of the final product being degraded due to excessive heat generation by alloy particles during the dry grinding process can be prevented.

[0094] In the present invention, the small particle size valuable metal product (SM) can be further crushed to form a secondary small particle size crushed product (SMc) having an average particle size of 10.0 to 30.0 μm.

[0095] When secondary grinding is performed as described above, there is an advantage in that the degree of separation by composition is improved in the subsequent airflow classification stage.

[0096] The above 22nd small particle size crushed material (SMc) can be separated into high-density small particle valuable metal products (HSM) and low-density small particle valuable metal products (LSM) through air stream classification.

[0097] In the present invention, airflow classification of the secondary small particle size crushed material (SMc) can be performed at an airflow speed of 0.2 to 5 m / s.

[0098] As described above, airflow classification offers the advantage of being able to select materials with improved separation by composition.

[0099] In the present invention, the increase rate of the copper (Cu) element content of the high-density, small-particle, valuable metal product (HSM) relative to the raw material valuable metal product (VM) may be 110% or more, and specifically 200% or more.

[0100] In the present invention, the increase rate of the carbon (C) element content of the low-density, small-particle, valuable metal product (LSM) with respect to the raw material valuable metal product (VM) may be 155% or more, and specifically 160% or more.

[0101]

[0102] The embodiments of the present invention will be described in more detail below through examples. However, the following examples are merely preferred embodiments of the present invention, and the present invention is not limited by the following examples.

[0103]

[0104] <Preparation Example 1> (Preparation of Raw Material Valuable Metal Product (VM))

[0105] A cell, module, or pack of a waste electric vehicle battery is prepared, comprising a lithium-ion cathode material, a graphite anode material, an aluminum current collector, a separator, an electrolyte, and a copper current collector. The cathode material contains an LFP cathode active material. The waste battery is frozen at a temperature of -30°C or lower and then shredded. Here, the waste battery is shredded under inert gas conditions using a shredder device so that the longest length between the width and length is 100 mm or less.

[0106] After obtaining a valuable metal recovery composition by the method described above, a reduction process was performed by heat-treating the crushed battery material at a temperature ranging from 1,000 to 1,400°C under conditions of an oxygen partial pressure of 0.5%. After undergoing the reduction process, the reduction product was cooled under conditions of a cooling rate of 25°C / min, and a valuable metal recovery composition was obtained.

[0107] Figure 2 shows the results of SEM-DEX analysis of the above valuable metal recovery composition.

[0108] Table 1 below shows the components and content of the composition for recovering valuable metals produced by the method described above.

[0109] The components and content in Table 1 below were measured by quantitative analysis methods using (ICP-OES) equipment and C / S analysis equipment.

[0110] Li(wt%)Al(wt%)Cu(wt%)Fe(wt%)P(wt%)C(wt%)Others(wt%) Preparation Example 12.6 17.8 15.97 19.03 12.44 26.19 15.96

[0111] <Preparation Example 2> (Classification after primary crushing of raw material valuable metal product (VM))

[0112] 2 kg of the raw material valuable metal product (VM) prepared in Manufacturing Example 1 above was loaded into a 20 L capacity Rod Mill and crushed for 30 minutes to obtain a crushed product.

[0113] Using a screen with a mesh size of 100 μm, the above-mentioned crushed material was separated into a large-sized valuable metal product (LM) remaining at the top of the screen and a small-sized valuable metal product (SM) that passed through the screen.

[0114] The composition and content of the above-described separated large-particle valuable metal products (LM) and small-particle valuable metal products (SM) were measured by quantitative analysis using an (ICP-OES) instrument and a C / S analysis instrument, and are shown in Table 2.

[0115] LiAlCuFePC Other Large Particle Size Valuable Metal Product (LM) Component (wt%) 3.78 11.2 11 7.96 30.4 31 8.75 4.2 13.67 Recovery Rate (%) 80.4 47 9.8 96 2.5 88.86 83.75 8.91 Small Particle Size Valuable Metal Product (SM) Component (wt%) 1.1 5 3.5 31 3.4 84.77 4.5 55 3.7 18.82 Recovery Rate (%) 19.5 6 20.1 13 7.5 11 14 16.25 91.09

[0116] <Comparative Example 1> (Large-diameter magnetic separation)

[0117] The large-diameter metal product (LM) of Preparation Example 2 above was separated into non-magnetic and magnetic materials using a magnetic separator with a magnetic field strength of 2000 to 3000 Gauss, and each component and content was measured by quantitative analysis using an ICP-OES instrument and a C / S analysis instrument, and is shown in Table 3.

[0118] LiAlCuFePC Other Magnetic Material Components (wt%) 1.76 6.28 1.41 2.3 0.71 1.23 2.8 2.2 2.61 Recovery Rate (%) 2.4.61 3.31 3.21 767.32 49.38 1.48 Non-magnetic Material Components (wt%) 4.09 1.44 1.23 61 0.05 1.43 4.34 6.33 Recovery Rate (%) 5.0.48 5.0.35 2.4.86 1.9.45 40.44 6.85

[0119] <Comparative Example 2> (Small particle size airflow classification)

[0120] The small particle size valuable metal product (SM) of Preparation Example 2 above was separated into high-density and low-density materials by airflow separation at an air velocity of 1.5 m / s, and each component and content was measured by quantitative analysis using an (ICP-OES) instrument and a C / S analysis instrument, and is shown in Table 4.

[0121] LiAlCuFePC Other High Specific Gravity Components (wt%) 1.15 3.44 30.45 10.41 1.43 21.13 2.02 Recovery Rate (%) 6.22 6.64 30.29 8.83 2.22 15.5 Low Specific Gravity Components (wt%) 2.95 5.09 8.36 4.36 4.317 0.54.48 Recovery Rate (%) 18.69 11.79 304.417.96 61.71

[0122] <Example 1>

[0123] The large-diameter valuable metal product (LM) of Preparation Example 2 above was separated into a high-density large-diameter valuable metal product (HLM) and a low-density large-diameter valuable metal product (LLM) by airflow separation at an air speed of 8 m / s.

[0124] The above high-density large-diameter valuable metal product (HLM) was separated into a non-magnetic large-diameter valuable metal product (NLM) and a magnetic large-diameter valuable metal product (MLM) using a magnetic separator with a magnetic force of 2000 to 3000 Gauss.

[0125] The results of SEM-EDX analysis for the above non-magnetic large-diameter valuable metal products (NLM) and magnetic large-diameter valuable metal products (MLM) are shown in Figures 3 and 4, respectively.

[0126] The components and content of the above magnetic large-particle valuable metal product (MLM) material and the mixture of the above non-magnetic large-particle valuable metal product (NLM) and low-density large-particle valuable metal product (LLM) were measured by quantitative analysis using an ICP-OES instrument and a C / S analysis instrument, and are shown in Table 5.

[0127] Referring to Figures 3 and 4 and Tables 3 and 5, it can be seen that the magnetic material of Example 1 had high Fe and P content, and the mixture of non-magnetic large-diameter valuable metal product (NLM) and low-density large-diameter valuable metal product (LLM) had a relatively high Li element content.

[0128] In addition, compared to Comparative Example 1, in which the large-diameter valuable metal product (LM) of Example 1 was not subjected to secondary grinding and airflow classification, the magnetic large-diameter valuable metal product (MLM) has higher Fe and P content, and the mixture of the non-magnetic large-diameter valuable metal product (NLM) and low-density large-diameter valuable metal product (LLM) of Example 1 has a higher Li content compared to the non-magnetic material of Comparative Example 1.

[0129]

[0130] The small particle size valuable metal product (SM) of Preparation Example 2 above was ground in a jet mill at a pressure of 5 bar and a flow rate of 800 m / s, and separated into a high-density small particle size valuable metal product (HSM) and a low-density small particle size valuable metal product (LSM) by air flow separation at an air speed of 2.0 m / s.

[0131] SEM images of the high-density, small-particle, valuable metal product (HSM) and the low-density, small-particle, valuable metal product (LSM) are shown in Figures 5 and 6, respectively.

[0132] In addition, the components and content of the high-density, small-particle, valuable metal products (HSM) and low-density, small-particle, valuable metal products (LSM) were measured using quantitative analysis methods such as ICP-OES equipment and C / S analysis equipment, and are shown in Table 5.

[0133] Referring to Figures 5 and 6 and Tables 4 and 5, it can be seen that the high-density, small-particle, valuable metal product (HSM) has a high Cu element content, and the low-density, small-particle, valuable metal product (LSM) has a high C element content.

[0134] In addition, compared to Comparative Example 2, in which the small particle size valuable metal product (SM) of Example 1 was not subjected to secondary grinding and airflow classification, it can be confirmed that the Cu content in the high-density material is higher, and the C content in the low-density material of Example 1 is higher than that in the low-density material of Comparative Example 2.

[0135] LiAlCuFePC Other Magnetic Material Components (wt%) 1.05 3.45 5.26 4.32 16.66 7.62 2.66 Recovery Rate (%) 12.88 15.05 9.64 83.66 57.15 13.03 Non-magnetic Large Particle Valuable Metal Product (NLM) + Low Specific Gravity Large Particle Valuable Metal Product (LLM) Components (wt%) 8.05 17.16.71 2.61 4.39 3.23 8.71 Recovery Rate (%) 72.55 54.48 22.53.69 36.25 2.94 High Specific Gravity Small Particle Valuable Metal Product (HSM) Component (wt%) 0.0 1 4.7 8 4 2.3 7.1 5 0.1 5 5.3 4 0.31 Recovery Rate (%) 0.1 1 6.8 6 2.4 3 1 1.1 2 0.4 1 7.32 Low Specific Gravity Small Particle Size Valuable Metal Product (LSM Component (wt%) 2.0 2 5.3 7 5.0 8 1.3 6 3.0 9 7 6.4 6.68 Recovery Rate (%) 14.4 6 1 3.6 7 5.4 3 1.5 3 6.1 8 7 6.45

[0136] The present invention is not limited to the above embodiments and can be manufactured in various different forms, and those skilled in the art will understand that the invention can be implemented in other specific forms without changing the technical concept or essential features of the invention. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive.

Claims

1. A step of preparing a raw material valuable metal product (VM) by subjecting crushed waste batteries to a high-temperature reduction reaction; A classification step of first crushing the above raw material valuable metal product and then separating it into a large-particle valuable metal product (LM) and a small-particle valuable metal product (SM); The method includes the step of secondarily crushing the large-particle valuable metal product (LM) and the small-particle valuable metal product (SM), respectively, and then classifying them by air stream. The average particle size (D50) of the above large-diameter metal product (LM) L ) is tens of μm to several mm, and the average particle size (D50) of the small-particle valuable metal product (SM) S ) is several nm to tens of µm, and The average particle size (D50) of the above large-diameter metal product (LM) L ) is the average particle size (D50) of the small-particle valuable metal product (SM) S That which is greater than ) Dry sorting method for waste batteries.

2. In Paragraph 1, The method involves secondary crushing of the above large-diameter valuable metal product (LM) and then performing air stream classification to separate the high-density large-diameter valuable metal product (HLM) and the low-density large-diameter valuable metal product (LLM). Dry sorting method for waste batteries.

3. In Paragraph 2, The step of further separating the high-density large-diameter valuable metal product (HLM) into a magnetic large-diameter valuable metal product (MLM) and a non-magnetic large-diameter valuable metal product (NLM) using a magnetic separator, Dry sorting method for waste batteries.

4. In Paragraph 3, The above magnetic separation utilizes a dry magnetic separator, Dry sorting method for waste batteries.

5. In Paragraph 4, The above magnetic separation is performed with a magnetic force of 1,000 to 3,000 Gauss, Dry sorting method for waste batteries.

6. In Paragraph 3, The increase rate of the iron (Fe) element content of the magnetic large-particle valuable metal product (MLM) with respect to the raw material valuable metal product (VM) is 85% or more, Dry sorting method for waste batteries.

7. In Paragraph 3, The increase rate of the lithium (Li) element content of the mixed valuable metal product (MXLM), composed of the non-magnetic large-diameter valuable metal product (NLM) and the low-density large-diameter valuable metal product (LLM), with respect to the raw valuable metal product (VM) is 110% or more. Dry sorting method for waste batteries.

8. In Paragraph 1, The method comprises secondary crushing of the above-mentioned small-particle valuable metal product (SM) and then performing air stream classification to separate the high-density small-particle valuable metal product (HSM) and the low-density small-particle valuable metal product (LSM). Dry sorting method for waste batteries.

9. In Paragraph 8, The copper (Cu) element content increase rate of the high-density, small-particle, valuable metal product (HSM) relative to the above-mentioned raw material valuable metal product (VM) is 110% or more, Dry sorting method for waste batteries.

10. In Paragraph 8, The carbon (C) element content increase rate of the low-density, small-particle, valuable metal product (LSM) with respect to the above-mentioned raw material valuable metal product (VM) is 155% or more, Dry sorting method for waste batteries.

11. In Paragraph 1, The above primary grinding is performed using one or more types of equipment selected from a rod mill, ball mill, pin mill, and impact mill, Dry sorting method for waste batteries.

12. In Paragraph 1, The above secondary grinding is performed using one or more types of equipment selected from a Tower Mill, Attrition Mill, Impact Mill, and Jet Mill. Dry sorting method for waste batteries.

13. In Paragraph 1, The average particle size of the pulverized material obtained by secondary grinding of the above large-diameter valuable metal product (LM) is 30.0 to 50.0 μm, Dry sorting method for waste batteries.

14. In Paragraph 1, The average particle size of the small particle size crushed material obtained by secondary crushing the above small particle size valuable metal product is 10.0 to 30.0 μm, Dry sorting method for waste batteries.

15. In Paragraph 1, The step of preparing a valuable metal product by subjecting the above-mentioned crushed waste battery to a high-temperature reduction reaction is, The above-mentioned crushed waste battery is heat-treated at a temperature of 800℃ or higher. Dry sorting method for waste batteries.

16. In Paragraph 1, The above waste battery comprises a positive active material containing one or more of iron (Fe), phosphorus (P), nickel (Ni), manganese (Mn), or cobalt (Co). Dry sorting method for waste batteries.

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