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WO2025135425A1 - Matériaux récupérés à partir de batteries usagées et procédé de récupération de métaux de valeur - Google Patents

Matériaux récupérés à partir de batteries usagées et procédé de récupération de métaux de valeur Download PDF

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Publication number
WO2025135425A1
WO2025135425A1 PCT/KR2024/015635 KR2024015635W WO2025135425A1 WO 2025135425 A1 WO2025135425 A1 WO 2025135425A1 KR 2024015635 W KR2024015635 W KR 2024015635W WO 2025135425 A1 WO2025135425 A1 WO 2025135425A1
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Prior art keywords
recovered
lithium
battery
alloy
magnetic
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English (en)
Korean (ko)
Inventor
박종력
김완이
한상우
이주승
박준용
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Posco Holdings Inc
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Posco Holdings Inc
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/005—Preliminary treatment of scrap
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/001—Dry processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C24/00—Alloys based on an alkali or an alkaline earth metal
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Definitions

  • the present invention relates to waste batteries, and to recovery of materials such as valuable metals, lithium oxide, graphite, and copper from waste batteries by a method for processing waste batteries, and a method for recovering valuable metals.
  • lithium secondary batteries which are the main raw materials of said waste batteries, organic solvents, explosive substances, and heavy metals such as Ni, Co, Mn, and Fe are contained, but in the case of Ni, Co, Mn, and Li, they have high scarcity value as valuable metals, and the recovery and recycling process after the lithium secondary batteries are discarded is emerging as an important research field.
  • a lithium secondary battery mainly consists of copper and aluminum used as a current collector, Li, Ni, Co, Mn-containing oxides constituting a cathode material, and graphite utilized as an anode material, and includes a separator separating the cathode material and the anode material, and an electrolyte injected into the separator.
  • the solvent used as a solvent and salt constituting the electrolyte is mainly a mixture of carbonate organic substances such as ethylene carbonate and propylene carbonate, and for example, LiPF 6 is used.
  • lithium secondary batteries are composed of heavy metal materials such as Ni-Co-Mn-Fe, carbon, and other electrolyte materials, among which Ni, Co, Mn, and Li are valuable as valuable metals.
  • Recycling for the purpose of recovery of battery raw materials generally involves dismantling, discharging, crushing, heat treatment, recovery, and wet processes of batteries to recover valuable metals.
  • salt water discharge is performed, and substances such as Na, K, Mg, Ca, and Cl that are introduced at this time are included as impurities in the recovered raw materials.
  • the recovered material forms different products depending on the heat treatment temperature. If heat treated at a temperature below 600°C, it is called black powder and is a powder form in which the oxides of Ni-Co-Mn-Li and carbon of the cathode material are mixed. Since Al and Cu are removed in advance, they may be included in extremely small amounts.
  • the metal oxide is reduced and alloyed by the carbon of the negative electrode material, and a black alloy containing the alloy components, carbon, and other substances is obtained.
  • Research is needed to recover valuable metals, lithium oxide, and graphite by material from the black alloy to increase the recovery rate of valuable metals.
  • a recovered product from a waste battery can be a recovered product that is easy to recycle in a downstream process by efficiently recovering materials such as valuable metals, lithium oxide, and graphite by material from a black alloy obtained from black powder, thereby increasing the recovery rate of valuable metals and graphite.
  • a method for recovering valuable metals is provided to increase the recovery rate of valuable metals from a black alloy obtained from black powder, thereby providing a recovery method that facilitates battery recycling in a downstream process.
  • the recovered material from the spent battery is a material recovered from the spent battery, and may include 20 to 35 wt% of a valuable metal recovery alloy, 25 to 50 wt% of a lithium compound, and the remainder of a graphite-based material, based on 100 wt% of the recovered material.
  • the valuable metal recovery alloy may include Ni, Co, Mn, and impurities.
  • the precious metal recovery alloy may include a total amount of Ni, Co, and Mn of 90 wt% or more, and the remainder being impurities, based on 100 wt% of the entire precious metal recovery alloy. In one embodiment, the precious metal recovery alloy may include 1 to 7 wt% of copper (Cu), based on 100 wt% of the entire precious metal recovery alloy.
  • the precious metal recovery alloy may include nickel (Ni): 50 to 60 wt%, cobalt (Co): 18 to 28 wt%, manganese (Mn): 10 to 20 wt%, and the remainder as impurities, based on 100 wt% of the total precious metal recovery alloy.
  • the lithium compound may include lithium (Li): 10 to 20 wt%, aluminum (Al): 20 to 30 wt%, and the remainder as impurities, based on 100 wt% of the lithium compound.
  • the lithium compound may comprise lithium oxide.
  • the lithium oxide may comprise lithium aluminum oxide.
  • the graphite-based material may comprise carbon (C): 80 to 90 wt %, and the remainder impurities.
  • the graphite-based material can include 13 to 25 wt% copper (Cu).
  • the metal recovery alloy, the lithium compound, and the graphite-based material can each be in powder form.
  • the composition can include at least a portion of the lithium compound disposed on at least a portion of a surface area of the metal-recovery alloy. In one embodiment, the composition can have a core-shell structure.
  • a method for recovering valuable metals relates to a method for recovering valuable metals from a product obtained by subjecting scrap recovered from a spent battery to a reduction heat treatment at a high temperature, the method 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 can be performed in a shear force range of 1 to 5 m/sec based on a tip speed.
  • the crushing step can be performed for 30 to 60 minutes.
  • At least a portion of the product of high-temperature reduction heat treatment of the recovered scrap from the spent battery may include a composition for recovering valuable metals, the composition including a core portion comprising a valuable metal recovery alloy and a shell portion disposed on the core portion and comprising a lithium compound.
  • a recovered material from a spent battery includes a valuable metal recovery alloy, a lithium compound, and a graphite-based material, thereby efficiently recovering materials such as valuable metals, lithium oxide, and graphite by material from a black alloy obtained from black powder, thereby increasing the recovery rate of valuable metals and graphite, and obtaining a recovered material that can be recycled as a cathode material and an anode material in a downstream process.
  • FIGS. 1A to 1C are photographs of valuable metal recovery alloys, lithium compounds, and graphite-based materials recovered from spent batteries according to one embodiment of the present invention.
  • FIG. 2 is a flowchart of a battery processing method according to one embodiment of the present invention.
  • FIGS. 3a and 3b are XRD analysis results of a composition for recovering valuable metals formed after heat treatment according to one embodiment of the present invention.
  • Figure 4 is a SEM photograph of a composition for recovering valuable metals.
  • first, second, and third, etc. are used to describe, but are not limited to, various parts, components, regions, layers, and/or sections. These terms are only used to distinguish one part, component, region, layer, or section from another part, component, region, layer, or section. Thus, a first part, component, region, layer, or section described below may be referred to as a second part, component, region, layer, or section without departing from the scope of the present invention.
  • % in this specification means weight % unless otherwise specified.
  • FIGS. 1A to 1C are photographs of valuable metal recovery alloys, lithium compounds, and graphite-based materials recovered from spent batteries according to one embodiment of the present invention.
  • a recovered product from a waste battery includes 20 to 35 wt% of a valuable metal recovery alloy, 25 to 50 wt% of a lithium compound, and the remainder a graphite-based material, based on 100 wt% of the recovered product.
  • the recovered product from the waste battery may be a recovered product recovered by the battery processing method described later in FIG. 2.
  • the recovered product may be a valuable metal recovery alloy including a valuable metal, a lithium compound including lithium, and the remainder a graphite-based material.
  • the recovered product may include 20 to 35 wt% of a valuable metal recovery alloy, 25 to 50 wt% of a lithium compound, and the remainder of a graphite-based material, based on 100 wt% of the recovered product.
  • the valuable metal recovery alloy including the valuable metal, the lithium compound including lithium, and the graphite-based material including carbon can be recovered in powder form.
  • the valuable metal recovery alloy may be from 20 to 35 wt% based on 100 wt% of the recovered material. Specifically, the valuable metal recovery alloy may be from 25 to 30 wt%.
  • the valuable metal recovery alloy may be a material that includes a valuable metal such as Ni, Co, and Mn.
  • the recovery rate of valuable metals such as Ni, Co, and Mn can be increased by the weight % of the valuable metal recovery alloy in the recovered material satisfying the above-mentioned range. If it exceeds the upper limit of the above-mentioned range, the recovery rate of valuable metals can be increased, but there is an uneconomical problem. If it exceeds the lower limit of the above-mentioned range, there is a problem in that the recovery rate of valuable metals is reduced.
  • the metal recovery alloy may include a total amount of Ni, Co, and Mn of 90 wt% or more, and a remainder of impurities, based on 100 wt% of the total metal recovery alloy.
  • the total amount of Ni, Co, and Mn may include 90 to 96 wt%, and more specifically, 92 to 95 wt%.
  • the recovery rate of the valuable metal can be increased.
  • the total amount of Ni, Co, and Mn in the valuable metal recovery alloy exceeds the above-mentioned range, there is a problem of lack of economic feasibility or low recovery rate of the valuable metal.
  • nickel (Ni) may be included in an amount ranging from 50 to 60 wt% based on 100 wt% of the total weight of the metal recovery alloy. Specifically, nickel may be included in an amount ranging from 52 to 58 wt%.
  • cobalt (Co) may be included in a range of 18 to 28 wt% based on 100 wt% of the total weight of the metal recovery alloy. Specifically, cobalt may be included in a range of 20 to 26 wt%.
  • manganese (Mn) may be included in an amount ranging from 10 to 20 wt% based on 100 wt% of the total weight of the metal recovery alloy.
  • cobalt may be included in an amount ranging from 12 to 18 wt%.
  • the lithium (Li) may be included in a range of 0.01 to 5 wt% based on 100 wt% of the entire metal recovery alloy. Specifically, the lithium may be included in a range of 0.05 to 0.15 wt%.
  • the above lithium can maximize the Li recovery rate during the Li smelting process by satisfying the above range. If it exceeds the upper limit of the above range, there is a problem of reduced Ni and Co recovery rates, and if it exceeds the lower limit of the above range, there is a problem of increased process costs due to reduced Li recovery rates during the Li smelting process.
  • the metal recovery alloy may contain copper (Cu) in a range of 1.0 to 7 wt%. Specifically, the copper may be contained in a range of 3 to 5 wt%.
  • the copper can form an alloy by combining with nickel (Ni) among the valuable metals.
  • the metal recovery alloy may contain carbon (C) in a range of 0.1 to 10 wt%.
  • C carbon
  • the carbon may be contained in a range of 1 to 7 wt%.
  • the metal recovery alloy may contain aluminum (Al) in a range of 0.25 to 30 wt %. If the content of the aluminum is outside the upper limit of the range, there is a problem of reduced Ni and Co recovery rates during the leaching and solvent extraction processes, and if the content of the aluminum is outside the lower limit of the range, it is difficult to produce LiAlO 2 , resulting in a problem of reduced Li recovery rates.
  • Al aluminum
  • the lithium compound may comprise 25 to 50 wt% based on 100 wt% of the recovered material. Specifically, the lithium compound may comprise 30 to 40 wt%. In one embodiment, the lithium compound may be a compound comprising lithium.
  • the lithium compound may comprise lithium oxide, and the lithium oxide may comprise lithium aluminum oxide.
  • the recovery rate of lithium which is one of the valuable metals, can be increased. If the lithium compound exceeds the lower limit of the above-mentioned range, this is because a lot of Li is lost to NCM alloy or graphite, which causes a problem of a decrease in the Li recovery rate, and when recovering Li in the downstream wet smelting process, there is a problem of an increase in the process cost because the Li content of the input raw material is reduced.
  • the lithium compound may be 10 to 20 wt % lithium (Li), based on 100 wt % of the lithium compound. Specifically, the lithium may be 12 to 18 wt %.
  • the content of the lithium is outside the upper limit of the above-mentioned range, this means that lithium does not react with Al to form a lithium compound in the form of LiAlO 2 , but rather the proportion of lithium hydroxide, lithium fluoride, lithium carbonate, etc. is high, which means that methods such as water leaching and acid leaching must be considered in the downstream wet refining process.
  • the content of the lithium is outside the lower limit of the above-mentioned range, this means that most of the lithium compounds were recovered in the form of LiAlO 2 with low water solubility, which means that lithium compounds with high water solubility were dissolved in water during the selection process, which means that lithium must be recovered again from the water used in the selection process.
  • the lithium compound may contain 20 to 30 wt% of aluminum (Al) based on 100 wt% of the lithium compound. Specifically, it may contain 23 to 28 wt%.
  • Al aluminum
  • a lithium compound may be formed through physical or chemical bonding with lithium, thereby increasing the yield of lithium.
  • the lithium compound may have a carbon (C) content of 1 to 7 wt% based on 100 wt% of the lithium compound.
  • the carbon (C) content may be 3 to 5 wt%.
  • the graphite-based material may comprise 25 to 50 wt% based on 100 wt% of the recovered material. Specifically, the graphite-based material may comprise 30 to 40 wt%.
  • the content of the graphite-based material may be such that a large amount of graphite-based material is generated as a high-temperature reduction reaction is performed in a low-oxygen content range that reduces the generation of carbon dioxide. Since the graphite-based material satisfies the above-described range, the recycling yield of the graphite-based material that can be utilized as an anode material can be increased.
  • the graphite material may have a carbon (C) content of 80 to 90 wt% and may include the remainder of impurities.
  • the carbon (C) content may be 83 to 87 wt%.
  • the graphite-based material may have a copper (Cu) content of 13 to 25 wt% based on 100 wt% of the graphite-based material.
  • the copper content may be 15 to 20 wt%.
  • FIG. 2 is a flowchart of a battery processing method according to one embodiment of the present invention.
  • the battery processing method includes the steps of preparing an output product by subjecting shreds recovered from a spent battery to high-temperature reduction heat treatment, the step of magnetically separating the output product, and the step of crushing a magnetic output product among the magnetically separated output products to separate magnetic substances and non-magnetic substances.
  • the battery processing method of the present invention provides a battery processing method capable of increasing the recovery rate of valuable metals by efficiently performing magnetic separation from an output product produced by subjecting shreds recovered from a spent battery to high-temperature reduction heat treatment.
  • the valuable metal of the present invention may mean an expensive metal component included in a battery, and may mean nickel, cobalt, manganese, aluminum, copper, and lithium.
  • the step of preparing a product by high-temperature reduction heat treatment of the recovered shredded material from a used battery includes the steps of preparing a battery, crushing the battery into battery shredded material, and high-temperature heat treatment of the crushed battery shredded material.
  • the battery may be a method for processing various types of batteries including lithium ions, and the battery may be, for example, a lithium secondary battery separated from an automobile, a secondary battery separated from an electronic device such as a mobile phone, a camera, or a laptop, specifically, a lithium secondary battery. More specifically, the battery has an advantage of being environmentally friendly by utilizing a waste battery.
  • the battery in the step of preparing a battery, may include lithium (Li) and aluminum (Al).
  • lithium and aluminum may be arranged as a physically and/or chemically bonded material in the resulting product after battery processing.
  • the step of crushing the battery may refer to a process of applying an impact or pressure to the battery so that a portion of the battery falls off from the battery.
  • the step of crushing the battery may refer to a process of crushing the battery, a process of cutting the battery, a process of compressing the battery, and a combination thereof.
  • the step of crushing may include any process that can destroy the battery to obtain small-sized fragments.
  • the step of crushing the battery may include any process of compressing the prepared battery or applying an external force, such as a shear force or a tensile force, to destroy the battery.
  • the step of crushing the battery may be performed, for example, using a crusher.
  • the step of crushing the battery may be performed at least once. Specifically, the step of crushing may be performed at least once, either continuously or discontinuously.
  • the step of crushing the battery comprises supplying conditions including an inert gas, carbon dioxide, nitrogen, water, or a combination thereof. Or, it can be carried out under vacuum atmosphere conditions of 100 torr or less.
  • conditions including an inert gas, carbon dioxide, nitrogen, water, or a combination thereof.
  • it can be carried out under vacuum atmosphere conditions of 100 torr or less.
  • the electrolyte can be prevented from reacting with oxygen, thereby preventing an explosion caused thereby, and the vaporization of the electrolyte can be suppressed, so that flammable gases such as ethylene, propylene, or hydrogen are not generated.
  • the step of high-temperature heat treating the shredded battery scrap may include putting the battery scrap into a heating furnace capable of raising the temperature to a temperature higher than the melting point of the battery scrap.
  • the battery scrap may include valuable metals such as Ni, Co, Mn, and Li, for example.
  • the high-temperature heat treatment may involve heat treatment conditions that perform a high-temperature reduction reaction without going through a melting step of the battery.
  • the step of high-temperature heat treatment of the battery shreds may be performed in a gas atmosphere of at least one of an inert gas, carbon dioxide, carbon monoxide, hydrocarbon gas, and oxygen.
  • the inert gas it may include, for example, at least one of argon and nitrogen.
  • the step of high-temperature heat treating the Ni, Co, Mn and Li containing battery scrap can be performed in a gas atmosphere including at least one of an inert gas, carbon dioxide, carbon monoxide, and hydrocarbon gas; and oxygen.
  • the gas atmosphere can be performed in a gas atmosphere having an oxygen concentration in a range of 0.1 to 2.0 vol%.
  • the gas atmosphere can be performed in a gas atmosphere having an oxygen concentration in a range of 0.4 to 1.2 vol%.
  • the step of high-temperature heat treating the battery shreds can be performed in a range of 600 to 1,500 °C.
  • the step of high-temperature heat treating can be performed in a range of 900 to 1,500 °C, more specifically, in a range of 1,100 to 1,500 °C, and even more specifically, in a range of 1,300 to 1,500 °C.
  • LiAlO 2 (s) + 2Li 2 CO 3 (s) Li 5 AlO 4 + 2CO 2 (g) reaction generates Li 5 AlO 4 , but the LiF (g) vaporization reaction is promoted, so that when performed in the above-mentioned range, the yield of lithium can be improved.
  • the lower limit of the above range is exceeded, the sintering and reduction of the alloy elements do not proceed smoothly, and a stabilized lithium-containing compound is not formed, which makes it difficult to recover the stabilized compound when recovering the lithium compound in the future.
  • the step of magnetically separating the above-mentioned high-temperature heat-treated product can separate the first magnetic body having magnetism and the first non-magnetic body having non-magnetism by magnetically separating the above-mentioned product.
  • Magnetic separation can separate particles through contact with the magnetic body by utilizing the magnetic body, and various types of magnetic separation methods can be applied.
  • the above first magnetic body may be a composition including Ni, Co, and Mn, which are valuable metals, and specifically, a composition including a core portion and a shell portion disposed on the core portion.
  • the core portion may include a valuable metal recovery alloy.
  • the core portion of the composition for valuable metal recovery may be recovered from a cathode material component in a spent battery.
  • the shell portion is arranged on the core portion and may include a lithium compound.
  • the valuable metals in the waste battery exist in the form of oxides and are reduced by graphite in the negative electrode material through a high-temperature heat treatment process.
  • the copper current collector may melt and exist in a liquid state, thereby performing the function of agglomerating the reduced valuable metals.
  • the copper current collector and the aluminum current collector may perform a partial reduction reaction with the positive electrode oxide and the remainder may react with lithium, so that a compound in the form of an oxide containing lithium may remain. A detailed description thereof will be described later with reference to FIGS. 3A and 3B and FIG. 4.
  • the second non-magnetic material may include at least one of a compound including Li that is not combined with a valuable metal in the magnetic separation step and a graphite material including carbon.
  • the magnetic separation step can be performed in a magnetic strength range of 1,000 to 5,000 Gauss. Specifically, the magnetic separation step can be performed in a magnetic strength range of 2,000 to 3,000 Gauss.
  • the magnetic separation step is performed within the above magnetic strength range, there is an advantage in that valuable metals can be separated efficiently. If the magnetic strength range exceeds the upper limit of the above-mentioned range, even a trace amount of valuable metal is recovered, so the recovery rate increases, but the grade of the recovered valuable metal is lowered and the amount of impurities such as graphite and copper increases, so there is a problem that the process efficiency in the next process, the wet smelting process, is lowered and the processing cost increases. If the magnetic strength range exceeds the lower limit of the above-mentioned range, there is a problem that the recovery rate of valuable metals is lowered, so that the loss of Ni, Co, and Mn increases.
  • the step of separating a magnetic body and a non-magnetic body by crushing a magnetic product among the magnetically separated products may be a step of crushing a magnetically selected first magnetic body.
  • the first magnetic body means a core part including a valuable metal alloy and a compound including lithium disposed on the core part, as described above.
  • the core part and the shell part may be separated from the first magnetic body through a crushing process.
  • the first magnetic body may be separated into a second magnetic body and a second non-magnetic body through the crushing process described above.
  • the second magnetic body means, for example, an NCM alloy including Ni, Co, and Mn
  • the second non-magnetic body may be a compound including lithium, for example, lithium aluminate (LiAlO 2 ).
  • the first magnetic body can be separated into the valuable metal recovery alloy and the lithium-containing compound by a mechanical or physical external force. In this way, not only can the valuable metal recovery alloy be recovered from the valuable metal recovery composition, but also the lithium compound can be separated at the same time, so that the lithium recovery rate is high and the amount of lithium lost can be reduced.
  • the pulverizing step uses equipment that pulverizes using a shear force in the form of a vertical attrition mill, and the RPM of the attrition mill for the vertical attrition mill can be performed in a shear force range of 1 to 5 m/sec based on the Tip Speed. Specifically, the pulverizing step can be performed in a shear force range of 2 to 3 m/sec based on the Tip Speed. Since the pulverizing step is performed in the above-described shear force range, the NCM alloy, which is the core portion of the first magnetic body, is not pulverized, and only the compound including lithium, which is the shell portion disposed on the core portion, can be pulverized into fine powder.
  • Tip Speed Pi ⁇ Impeller Diameter ⁇ RPM/100
  • the shear force exceeds the upper limit of the aforementioned range, there is a problem that after the shell portion of the first magnetic body is separated, the magnetic body core portion inside is pulverized, and since the core portion is a ductile metal, the spherical particles grow into a plate shape during rolling and are then pulverized into smaller particles again. At this time, there is a problem of reduced recovery rate in the process of separating the magnetic body of the core portion and the lithium compound of the shell portion using particle size. If the shear force exceeds the lower limit of the aforementioned range, there is a problem that the lithium compound of the shell portion is not pulverized and is recovered again together with the magnetic body of the core portion.
  • the crushing step can be performed for 20 to 80 minutes. Specifically, the crushing step can be performed for 30 to 60 minutes. As the crushing step is performed within the above-described range, the recovery rate of valuable metals such as Ni, Co, Mn, and Li can be increased.
  • the magnetic body including the core part's magnetic body and the lithium compound of the shell part is excessively crushed, and rolling is performed into a plate shape due to ductility, and the plate-shaped particles are continuously over-pulverized and split again into fine particles, so that the effect of the magnetic force is insufficient in additional magnetic separation.
  • the lower limit of the above-mentioned range is exceeded, there is a problem that the shell part including the lithium compound is not easily separated from the magnetic body of the core-shell structure.
  • a step of further separating by any one of particle size separation, flotation, and magnetic separation may be included.
  • the flotation separation is a method of separating particles by considering the difference in specific gravity of each material, and for example, the particles may be separated based on the size of the specific gravity of the particles corresponding to the specific solvent by utilizing a specific solvent.
  • the valuable metal alloy is separated into particles that are elongated due to the ductile nature of the metal and have a large particle size, and the compound containing lithium can be pulverized into a fine powder form with a small particle size.
  • the first magnetic body can separate a lithium-containing compound having a particle size of less than 70 to 80 ⁇ m and a valuable metal alloy having a particle size of 70 to 80 ⁇ m or more.
  • the core and shell portions separated through the above-described pulverizing step can be subjected to particle size separation based on a particle size of 70 to 80 ⁇ m.
  • the lithium-containing compound, which is the shell portion has a particle size smaller than the aforementioned particle size standard
  • the valuable metal alloy, which is the core portion has a particle size larger than the aforementioned particle size, so that the valuable metal alloy and the lithium-containing compound can be easily separated through particle size separation.
  • the core and shell portions separated through the above-described crushing step may be subjected to magnetic separation.
  • a valuable metal alloy including Co having magnetism and a compound including lithium having no magnetism can be easily separated.
  • the core and shell portions separated through the above-described crushing step may be subjected to flotation separation.
  • the core portion including the precipitated valuable metal and the compound including the floating lithium can be easily separated.
  • the step of separating the first non-magnetic body may include separating the first non-magnetic body having a non-magnetism separated in the first magnetic separation step, which includes graphite.
  • the flotation step may be a step of selecting a flotation material including graphite and a precipitate including valuable metal.
  • the flotation step may be a step of floatation of hydrophobic graphite in the first non-magnetic body and precipitation and separation of a compound including lithium and a particulate valuable metal alloy.
  • a step of magnetically separating the sediment to recover a material including a valuable metal, and crushing the recovered material together with the magnetic output may be performed.
  • a detailed description of the crushing step is as described above.
  • the step of drying the final product may be included.
  • the valuable metal alloy, the compound including lithium, and the graphite may be dried in a powder form.
  • the step of drying the final product can be performed at a temperature in the range of 80 to 200° C. Specifically, the step of drying the final product can be performed at a temperature in the range of 100 to 150° C.
  • drying is performed outside the upper limit of the above temperature range, there is a problem that combustible materials such as graphite are burned. If drying is performed outside the lower limit of the above temperature range, there is a problem that the moisture in the powder-state particles, which are the final product, is not completely dried and a product with a high moisture content is discharged, which increases the amount of acid used in the leaching process of the downstream wet refining process.
  • FIGS. 3a and 3b are XRD analysis results of a composition for recovering valuable metals formed after heat treatment according to one embodiment of the present invention.
  • the composition for recovering valuable metals that has been subjected to reduction heat treatment at a high temperature does not form an alloy by being reduced, such as Ni, Co, and Mn, but combines with the Al component in the battery to form a compound containing lithium, for example, lithium oxide. It can be confirmed that the lithium oxide is formed as, for example, LiAlO 2 , Li 5 AlO 4 , and Li 2 CO 3 .
  • the composition for recovering valuable metals may further include LiF. The LiF may be a result of the remaining amount of electrolyte depending on the degree of pretreatment.
  • LiAlO 2 can include XRD peaks of 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°.
  • Li 5 AlO 4 can include XRD peaks of at least one of 19.5 to 20.2° and 21.6 to 22.2°.
  • the LiAl 5 O 8 composition can include XRD peaks of 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.
  • the LiF composition can include XRD peaks of at least one of 37.5 to 40.2°, 43.9 to 46.5°, and 64.5 to 66.5°.
  • the Li 3 PO 4 composition can include XRD peaks of at least one of 29.2 to 40.1° and 52 to 77.1°.
  • the Li 2 SiO 3 composition can include XRD peaks of 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.
  • the Li 4 SiO 4 composition can include XRD peaks of 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.
  • the Li 2 Si 2 O 5 composition can include XRD peaks of 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°.
  • the Li 2 CO 3 composition can include XRD peaks of 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°.
  • FIG. 4 is a SEM photograph of a composition for recovering valuable metals according to one embodiment of the present invention.
  • the composition for recovering valuable metals includes a core portion and a shell portion disposed on the core portion.
  • the core portion may include a valuable metal recovery alloy.
  • the valuable metal of the present invention may mean an expensive metal component included in a battery, and may mean nickel, cobalt, manganese, aluminum, copper, and lithium.
  • the core portion of the composition for recovering valuable metals may be recovered from a cathode component in a spent battery.
  • the shell portion is arranged on the core portion and may include a lithium compound.
  • the valuable metals in the waste battery exist in the form of oxides and are reduced by graphite in the negative electrode material through a high-temperature heat treatment process.
  • the copper current collector may melt and exist in a liquid state, thereby performing the function of agglomerating the reduced valuable metals.
  • the copper current collector and the aluminum current collector may perform a partial reduction reaction with the positive electrode oxide and the remainder may react with lithium, so that a compound in the form of an oxide containing lithium may remain.
  • the content of lithium (Li) in the lithium compound may be 4 to 35 wt%, specifically 4 to 25 wt%, based on 100 wt% of the total.
  • a composition including a lithium-containing compound having a high lithium content and an excellent lithium recovery rate can be satisfied.
  • the lithium compound can include at least one of LiAlO 2 , Li 5 AlO 4 , LiAl 5 O 8 , Li 2 CO 3 , LiF, Li 3 PO 4 , Li 2 SiO 3 , Li 4 SiO 4 , and Li 2 Si 2 O 5 .
  • the lithium compound can include lithium aluminum oxide.
  • the lithium compound may be, for example, lithium oxide.
  • the lithium-aluminum oxide may be implemented in the form of an oxide in which lithium contained in the composition is physically or chemically bonded.
  • the lithium compound may include lithium aluminum oxide.
  • the content of lithium aluminum oxide may include 45.0 to 97.0 wt% based on 100 wt% of the valuable metal recovery composition. Specifically, the content may be 70 to 90 wt%.
  • the content of the lithium aluminum oxide exceeds the upper limit of the above-mentioned range, there is a problem that highly water-soluble lithium hydroxide, lithium carbonate, lithium fluoride, etc. dissolve in large quantities in water during the sorting process. If the content of the lithium aluminum oxide exceeds the lower limit of the above-mentioned range, it means that most of the lithium compounds are recovered in the form of LiAlO 2 with low water solubility, which means that highly water-soluble lithium compounds dissolve in water during the sorting process, and this causes a problem that lithium must be recovered again from the water used during the sorting process.
  • the lithium compound may include a lithium and silicon-containing oxide.
  • the content of the lithium and silicon-containing oxide may include 2 to 30 wt% based on 100 wt% of the valuable metal recovery composition. Specifically, it may include 10 to 25 wt%. Since the lithium and silicon-containing oxide satisfy the above-mentioned range, there is an advantage in that a stable product can be secured under a high temperature and an appropriate oxygen concentration atmosphere, thereby increasing the real yield of lithium during acid leaching.
  • the content of the lithium and silicon-containing oxides exceeds the upper limit of the above-mentioned range, there is a problem that the productivity of the reactor decreases and the energy cost increases because it means that it has been exposed to the maximum temperature for a long time during the high-temperature reduction reaction. If the content of the lithium and silicon-containing oxides exceeds the lower limit of the above-mentioned range, there is a problem that the recovery rate of lithium decreases because there is insufficient heat energy for lithium to react with aluminum or silicon to produce lithium compounds such as lithium aluminate, or the temperature of the reactor is too high, so that lithium is volatilized and removed.
  • the metal recovery composition can have no more than 10 wt % of silicon (Si), based on 100 wt % of the metal recovery composition.
  • the silicon can be no more than 1.0 wt %, and more specifically, no more than 0.5 wt %.
  • the content of the above silicon (Si) exceeds the upper limit of the above-mentioned range, there is a problem that the process time and cost increase in removing silicon to battery grade in the downstream wet smelting process. If the content of the above silicon (Si) exceeds the lower limit of the above-mentioned range, there is a problem that the remaining weight % of the silicon of the input raw material is dispersed into graphite and lithium compounds, and the process time and cost increase in the refining and refining process of the graphite and lithium compounds.
  • Li 2 CO 3 may be included in an amount of 30% or less based on 100 wt% of the entire composition.
  • the Li 2 CO 3 may be included in an amount of 15.0% or less, more specifically, 5% or less.
  • LiF may be included in an amount of 30 wt% or less based on 100 wt% of the entire composition.
  • the LiF may be included in an amount of 6.5 to 24.0 wt%, more specifically, 6.5 to 15 wt% or less based on 100 wt% of the entire composition.
  • LiF exceeds the upper limit of the above-mentioned range, there is a problem that the pH control is difficult due to the mixing of sulfate ions and fluoride ions during sulfuric acid leaching, thereby reducing the Li recovery rate. If the LiF exceeds the lower limit of the above-mentioned range, there may be a problem that the leaching process time is delayed because Li 2 SiO 3 , Li 4 SiO 4 , and Li 2 Si 2 O 5 , etc. increase, making sulfuric acid leaching difficult.
  • the total content of Li 2 CO 3 and LiF may be 50% or less, based on 100 wt% of the entire composition. Specifically, the total content may be 0.5 to 50%, and more specifically, the content may be 0.5 to 30% or less.
  • the total content exceeds the upper limit of the above-mentioned range, a large amount of compounds that are difficult to recover due to water solubility problems are generated, which makes it difficult to recover Li. If the total content exceeds the lower limit of the above-mentioned range, the compounds such as Li 2 SiO 3 , Li 4 SiO 4 , and Li 2 Si 2 O 5 increase, making sulfuric acid leaching difficult, which causes a problem in that the leaching process time is delayed.
  • Li 3 PO 4 may be included at 10 wt% or less, based on 100 wt% of the entire composition.
  • the Li 3 PO 4 may be included at 5 wt%, specifically, 3 wt% or less, and more specifically, 0.1 to 0.7 wt %, based on 100 wt% of the entire composition.
  • a cell, module, or pack which is a spent electric vehicle battery, is prepared, which includes a positive electrode material containing lithium ions, an anode material of graphite, an aluminum current collector, a separator, an electrolyte, and a copper current collector.
  • the spent battery is frozen at -30°C or lower and then crushed, or after being discharged under salt water discharge or electric discharge conditions, the spent battery is crushed using a shredder device under atmospheric or inert gas conditions so that the longest length or width becomes 100 mm or less.
  • the crushed battery waste was heat-treated at 1,300° C. under an oxygen partial pressure condition of 0.5% to perform a reduction process.
  • a composition for recovering valuable metals comprising a core part including valuable metals as described above and a shell part including a compound containing lithium on the core part, was produced.
  • Table 1 below shows the components and contents of the composition for recovering valuable metals produced by the above-described method.
  • composition for recovering precious metals that had undergone a high-temperature reduction process in the first magnetic separation step was separated into magnetic and non-magnetic substances using a magnetic separator having a magnetic strength of 3000 Gauss.
  • Experimental Example 2_1 in Table 2 below shows the components and contents of magnetic and non-magnetic substances separated by passing through a 3000 Gauss magnetic separator.
  • the non-magnetic material separated through magnetic separation was subjected to flotation using the Denver Sub_A flotation separation equipment of Experimental Example 3_1, with the following methods: 30% ore concentration, 500 rpm impeller rotation speed, 0.1 ml/100 g of kerosene, and 0.1 ml/100 g of MIBC.
  • Table 3 below shows the components and contents of the results obtained through the flotation selection process.
  • the C content of the material floating in Over Flow (O/F) was 92.5%, which is a significant increase compared to the C content of 35.07% in the initial battery shreds and the C content of 75.30% in the raw material separated into non-magnetic substances through magnetic separation and fed into the flotation separator.
  • the C content of the sediment remaining in Under Flow (U/F) was 5.75%, and it can be seen that most of the hydrophobic C was recovered as floating matter.
  • looking at the lithium content ratio of the floating matter and sediment it can be seen that most of the lithium did not float but remained in the sediment, so that C and lithium could be efficiently separated through flotation.
  • the magnetic material that has gone through the magnetic separation step is pulverized using Attrition Mill equipment, which is a vertical stirring mill, at 500 rpm, an impeller tip speed of 2.8 m/sec, a pulverization time of 60 minutes, and a soil content of 30% by weight.
  • Attrition Mill equipment which is a vertical stirring mill, at 500 rpm, an impeller tip speed of 2.8 m/sec, a pulverization time of 60 minutes, and a soil content of 30% by weight.
  • the magnetic material is composed of a core part including a valuable metal and a shell part including a compound including lithium arranged on the core part, and it was confirmed that the core part and the shell part are separated during the pulverization process of the composition for recovering valuable metal.
  • Table 5 shows the components and contents of the resultant product obtained by separating the magnetic material including the core portion and the shell portion and separating the resultant product according to particle size.
  • the shell part in the form of oxides is pulverized during the pulverization process, and the core part, which has ductility, is continuously pulverized inside the pulverizer and rolled into a plate shape, causing the particle size to increase and the thickness to decrease rather than the initial particle size.
  • the shell part is brittle in the form of oxides, the pulverization continues as the pulverization time increases, causing the particle size to decrease. 5.
  • Experimental Example 4_1 which has gone through a crushing step, can be separated by particle size separation using the difference in the crushing characteristics of the core alloy and the shell oxide compound, but it is more preferable to perform a secondary separation through a magnetic selection process with a magnetic strength of 3000 Gauss using the magnetic property of the core alloy. In this case, if separation is performed using magnetic selection, the recovery rate of valuable metals in the core can be further increased compared to particle size separation. If particle size separation is applied, the separation should be performed using a mesh having a mesh size of 75 ⁇ m or 45 ⁇ m, and at this time, the coarse particles are recovered as the NCM alloy part and the fine particles are recovered as Li oxide.
  • the non-magnetic material containing Li, and the graphite separated through the above-described steps were reduced to a moisture content of 30% using a drum-type dehydrator or a centrifugal dehydrator, and then dried to a moisture content of 5% or less through a drying step using hot air at 100 to 200°C, and then recovered.
  • Table 5 below shows the components and contents of the final product recovered through the steps described above.
  • the valuable metal alloy containing Ni, Co, and Mn as main components can be recovered from the magnetic body separated through the magnetic separation, pulverization, and magnetic separation steps, as in Experimental Example 4_1.
  • the lithium compound contains lithium as a main component and can be recovered from the sum of the non-magnetic body separated through the magnetic separation, pulverization, and magnetic separation steps, as in Experimental Example 4_2, and the precipitated material through flotation, as in Experimental Example 3_2.
  • Graphite can be recovered by separating the floating material through flotation, as in Experimental Example 3_1.
  • Table 6 below shows the changes in the components of magnetic and non-magnetic materials according to changes in magnetic strength during the first magnetic selection.
  • Table 7 shows the results of separating the crushed product into magnetic and non-magnetic materials using a 3000 Gauss magnetic separator after the first magnetic separation and crushing of the magnetic material.
  • a vertical stirring ball mill (Attrition Mill) was used as the pulverizer, and the pulverization conditions were RPM 500 (Tip Speed 2.65 m/sec), pulverization container size 1 L, solid content concentration 30%, pulverization time 0 to 90 minutes, and magnetic and non-magnetic bodies were analyzed according to pulverization time.
  • the lithium compound when it exceeds 60 minutes and exceeds 90 minutes, the lithium compound is mostly pulverized and recovered at a high recovery rate of 91% non-magnetically, but the NCM alloy part, which is the core part, is continuously over-pulverized after the shell part is completely removed and rolled into a plate shape due to ductility, and the plate-shaped particles are split again into fine particles due to continuous over-pulverization, and there is a problem that the particles are excessively fine and the influence of the magnetic force on a single particle is minimal. Accordingly, the finely divided NCM alloy part cannot be recovered as a magnetic body even if it is magnetic during magnetic separation, and this results in a decrease again to 85% or less, which is the recovery rate of Ni, Co, and Mn.

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Abstract

Selon la présente invention, des matériaux récupérés à partir de batteries usagées comprennent de 20 à 35 % en poids d'un alliage de récupération de métal de valeur et de 25 à 50 % en poids d'un composé de lithium sur la base de 100 % en poids des matériaux récupérés, le reste comprenant des matériaux à base de graphite.
PCT/KR2024/015635 2023-12-18 2024-10-15 Matériaux récupérés à partir de batteries usagées et procédé de récupération de métaux de valeur Pending WO2025135425A1 (fr)

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CN114381605A (zh) * 2022-03-23 2022-04-22 中南大学 一种综合回收废旧锂离子电池黑粉中有价金属的方法
KR20230094567A (ko) * 2021-12-21 2023-06-28 포스코홀딩스 주식회사 유가 금속 회수 합금, 유가 금속 회수 조성물, 및 유가 금속 회수 방법
KR102561390B1 (ko) * 2023-01-27 2023-08-01 한국지질자원연구원 역부유선별을 이용하여 폐전지의 블랙 파우더로부터 양극재를 회수하는 방법

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KR101883100B1 (ko) * 2017-04-04 2018-07-27 연세대학교 산학협력단 폐전지로부터 유가금속을 회수하는 방법 및 유가금속 회수 시스템
CN110600702A (zh) * 2019-09-18 2019-12-20 上海应用技术大学 以废弃隔膜为原料的核壳结构二次电池用复合材料及其制备与应用
KR20230094567A (ko) * 2021-12-21 2023-06-28 포스코홀딩스 주식회사 유가 금속 회수 합금, 유가 금속 회수 조성물, 및 유가 금속 회수 방법
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KR102561390B1 (ko) * 2023-01-27 2023-08-01 한국지질자원연구원 역부유선별을 이용하여 폐전지의 블랙 파우더로부터 양극재를 회수하는 방법

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