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WO2025127687A1 - Composition de récupération de métal de valeur et procédé de récupération de métal de valeur - Google Patents

Composition de récupération de métal de valeur et procédé de récupération de métal de valeur Download PDF

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Publication number
WO2025127687A1
WO2025127687A1 PCT/KR2024/020216 KR2024020216W WO2025127687A1 WO 2025127687 A1 WO2025127687 A1 WO 2025127687A1 KR 2024020216 W KR2024020216 W KR 2024020216W WO 2025127687 A1 WO2025127687 A1 WO 2025127687A1
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Prior art keywords
battery
alloy
valuable metal
lithium
metal recovery
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English (en)
Korean (ko)
Inventor
박종력
박중길
김완이
한상우
이주승
박준용
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Posco Holdings Inc
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Posco Holdings Inc
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Publication of WO2025127687A1 publication Critical patent/WO2025127687A1/fr
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • 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
    • C22B1/02—Roasting 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • 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
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • 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 a composition for recovering valuable metals from waste batteries and a method for recovering valuable metals from waste batteries.
  • 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. From the black alloy thus obtained, materials such as valuable metal alloys, lithium oxide, and graphite can be recovered by material. At this time, the valuable metal alloy in the form of a metal is coated with lithium aluminate or lithium oxide, and the black alloys are finally turned into raw materials through additional processes such as leaching.
  • the carbon content and carbon shape in the recovered valuable metal alloy vary depending on the size of the valuable metal alloy, and the efficiency of the wet refining process using acid or base can be increased and the cost of the process can be reduced.
  • the technical problem to be solved by the present invention is to provide a composition for recovering valuable metals, which can increase the efficiency of the process and reduce the cost of the process when utilizing valuable metal alloy raw materials obtained from waste batteries by putting them into a wet refining process using acid or base.
  • Another technical problem to be solved by the present invention is to provide a method for recovering valuable metals for producing a composition for recovering valuable metals having the aforementioned advantages.
  • a composition for recovering valuable metals comprises a valuable metal recovery alloy including a carbon layer and a lithium compound, wherein the carbon layer is disposed on at least a portion of a surface and an interior of the valuable metal recovery alloy, and the content of carbon (C) in the carbon layer may be 60 wt% or more based on 100 wt% of the carbon layer.
  • the lithium compound can be bonded to at least a portion of a surface area of the valuable metal recovery alloy.
  • the carbon layer is disposed on the surface of the valuable metal recovery alloy, and the total amount of Ni, Co, and Mn in the carbon layer can be 50 wt% based on 100 wt% of the carbon layer.
  • the carbon layer is disposed inside the valuable metal recovery alloy, and the carbon layer can be disposed as a carburized layer in a band shape on a cross-section of the valuable metal recovery alloy.
  • the belt-shaped carbon layer may have a ratio of a major axis to a minor axis of 2 or greater.
  • the lithium compound may include lithium oxide.
  • the lithium oxide may include lithium aluminum oxide.
  • the valuable metal may include at least one of lithium (Li), cobalt (Co), nickel (Ni), aluminum (Al), and manganese (Mn).
  • a method for recovering valuable metals may include a step of preparing a battery or battery scrap in a cell unit, a step of dry heat treating the battery or the scrap in a temperature range of 1,100 to 1,800° C. without going through a melting step, and a cooling step of cooling the resultant of the dry heat treatment at a cooling rate of 10 to 50° C./minute or less.
  • the high temperature reduction reaction step may be performed in an atmosphere having an oxygen content of 5% or less.
  • the step of separating the resultant product after the cooling step by at least one of particle size separation and magnetic separation may be included.
  • the step of separating the resultant product after the cooling step by at least one of particle size separation and magnetic separation may be performed prior to the magnetic separation and then the particle size separation.
  • the resultant product obtained from the step of dry heat treating the shredded material may separate a lithium compound bound to a portion of the surface of the valuable metal recovery alloy by an external force.
  • the step of preparing the cell-unit battery or battery shredded material may include a step of preprocessing the cell-unit battery or battery shredded material.
  • a composition for recovering valuable metals includes a carbon layer in a valuable metal alloy, so that the alloy particles are easily crushed by an external force in a post-process, a wet refining process, thereby reducing the diameter of the alloy and simultaneously increasing the specific surface area, thereby improving the reactivity to sulfuric acid leaching.
  • the carbon layer is disposed on the surface or inside of the valuable metal alloy, making it easy to selectively leach lithium from lithium oxide on the surface of the alloy.
  • a method for recovering valuable metals can provide a method for producing a composition for recovering valuable metals having the aforementioned advantages by controlling heat treatment and cooling conditions.
  • FIG. 1 is a SEM photograph of a unit metal recovery composition constituting a metal recovery composition 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 3 and 4 show SEM photographs of the valuable metal alloy of the present invention.
  • Figure 5 shows an SEM photograph of a cross-section of a valuable metal alloy of the present invention.
  • Figures 6 to 8 are EPMA analysis results according to comparative examples of the present invention.
  • 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.
  • FIG. 1 is a SEM photograph of a unit metal recovery composition constituting a metal recovery composition according to one embodiment of the present invention.
  • the composition for recovering valuable metals (100) may include a core portion (110) including a valuable metal and a shell portion (120) disposed on at least a portion of the core portion (110).
  • the unit composition for recovering valuable metals (100) may be composed of a metal such as a valuable metal such as Ni, Co, or Mn in the core portion (110), and an oxide including lithium may be combined and disposed on the core portion (110).
  • the core portion (110) includes a valuable metal recovery alloy, and the valuable metal recovery alloy may include 45 wt% or more of the valuable metal and the remainder being impurities based on 100 wt% of the total composition of the alloy.
  • the valuable metal recovery alloy may include at least one of valuable metals such as nickel (Ni), cobalt (Co), manganese (Mn), lithium (Li), carbon (C), aluminum (Al), and copper (Cu) and the remainder being impurities.
  • the valuable metal may mean an expensive metal component included in a battery, and may mean nickel, cobalt, manganese, aluminum, copper, and lithium.
  • the valuable metal may be 70 wt% or more.
  • lithium (Li) among the above metals may be included in a range of 0.01 to 5 wt %. Since the lithium satisfies the above range, there is an advantage in that the Li recovery rate can be maximized during the Li refining process. 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 refining process.
  • the valuable metal recovery alloy may contain copper (Cu) in an amount of 0.02 wt% or more.
  • the valuable metal recovery alloy may contain copper (Cu) in a range of 0.1 to 15 wt%.
  • the content of the copper is outside the upper limit of the range, there is a problem of process cost due to an increase in the amount of CuSO 4 precipitation in leaching and solvent extraction, and when the content of the copper is outside the lower limit of the range, it is difficult to produce low-melting-point Ni-Co-Mn, resulting in a problem of an increase in the amount of unreacted materials.
  • the copper may be combined with nickel (Ni) among the valuable metals to form an alloy.
  • the nickel may be included in a range of 5 to 40 wt%. When the nickel is outside the upper limit of the range, there is a problem of a decrease in the leaching rate due to the formation of nickel carbide (Ni 3 C), and when the nickel is outside the lower limit of the range, there is a problem of a decrease in the Ni recovery rate in leaching and solvent extraction.
  • 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 valuable 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 valuable metal recovery alloy may include a carbon layer in at least a portion of the region.
  • the carbon layer may be disposed on the surface or inside of the valuable metal recovery alloy.
  • the carbon layer may be formed in a process in which carbon of graphite included in the negative electrode material in the spent battery is carburized in the valuable metal alloy.
  • the above-mentioned valuable metal recovery alloy includes the carbon layer, the alloy particles can be easily crushed by an external force in a future wet refining process, thereby reducing the diameter and increasing the specific surface area, thereby improving the reactivity to sulfuric acid leaching.
  • the above-mentioned valuable metal alloy includes the carbon layer, there is an advantage in that selective leaching is easy when lithium of lithium oxide on the alloy surface is pre-leached.
  • the content of carbon (C) in the carbon layer may be 60 wt% or more based on 100 wt% of the carbon layer. Specifically, the content of carbon may be 60 to 98 wt%, specifically, the content of carbon may be 70 to 95 wt%, and more specifically, 75 to 94 wt%.
  • the valuable metal alloy particles are easily crushed by an external force during wet refining in the subsequent process, thereby reducing the diameter and increasing the specific surface area, thereby improving the reactivity to sulfuric acid leaching and facilitating the pre-leaching of lithium.
  • the carbon layer may be arranged inside the valuable metal recovery alloy. Specifically, when looking at the cross-section of the valuable metal recovery alloy, the carbon layer may be arranged as a band-shaped carburized layer on the cross-section of the valuable metal recovery alloy.
  • the band-shaped carburized layer may be formed by carbon precipitating at the alloy grain boundary.
  • the carburized layer is a state in which the carbon, which is graphite used as a reducing agent as the anode oxide, is excessively heated to a high temperature under a reducing atmosphere condition, and the carbon is carburized on the surface of the anode and combines with oxygen to be reduced to CO and CO2 .
  • the carbon which is graphite used as a reducing agent as the anode oxide
  • the carbon is carburized on the surface of the anode and combines with oxygen to be reduced to CO and CO2 .
  • the amount of carbon carburized in the anode increases, and this is because the solubility of carbon that can dissolve in the anode increases as the reduction temperature increases, so the amount of carburization increases.
  • the carbon is carburized, the melting point decreases, and even if the temperature increases further after the carbon is saturated, the melting point does not decrease further.
  • the saturated carbon begins to precipitate on the surface of the particles during the cooling process, the saturated solubility decreases again, and the carbon precipitated on the surface of the particles thus exists in the form of a band at the grain boundary of the alloy particle.
  • the cooling rate is slow, most of the carbon in the carbon layer is precipitated at the grain boundary, and if the cooling rate is very fast, the reduced anode and carbon become a solid solution or are precipitated in the form of dots inside the particles.
  • the belt-shaped carburized layer may have a ratio of the major axis to the minor axis of 2 or more. Specifically, the ratio may be 10 or more. Specifically, the minor axis of the belt-shaped carburized layer refers to the thickness of the carburized layer, and the major axis of the belt-shaped carburized layer refers to the grain boundary of the positive electrode alloy. If the ratio is less than 2 to 10, the cooling rate is slow, so that a precipitated dot-shaped carburized layer is generated, and the effect intended for the present invention cannot be obtained.
  • the above-mentioned belt-shaped carburized layer satisfies the above-mentioned ratio, there is an advantage in that it facilitates the penetration of carbon into the alloy, thereby improving the reactivity to sulfuric acid leaching in a future wet smelting process. If the ratio of the major axis to the minor axis of the above-mentioned belt-shaped carburized layer is outside the above-mentioned range, there is a problem in that the above-mentioned effect is not expressed.
  • the lithium in the metal recovery composition (10) is not reduced to form an alloy, unlike Ni, Co, and Mn, and can be combined with the Al component in the battery to form lithium oxide.
  • the metal recovery composition (10) may include a shell portion (120) disposed on a core portion (110).
  • the shell portion (120) may be lithium oxide disposed on the core portion (110).
  • the lithium oxide may include, for example, lithium-aluminum oxide.
  • the lithium-aluminum oxide may be a lithium-aluminum compound.
  • the lithium-aluminum oxide may be formed by combining lithium and aluminum contained in the composition into an oxide by physically or chemically bonding with each other.
  • the lithium oxide may include LiAlO 2 , Li 5 AlO 4 , Li 2 CO 3 , and LiF.
  • the LiAlO 2 , Li 5 AlO 4 , and Li 2 CO 3 correspond to lithium oxides reacted during a high-temperature reduction reaction of the battery waste, and LiF may be a lithium oxide detected by the electrolyte residual amount depending on the degree of pretreatment.
  • the lithium compound can include XRD peaks having 2 ⁇ 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°, 70.0 to 72.0°, 19.5 to 20.2°, 21.6 to 22.2°, 24.0 to 26.0°, 27.0 to 29.0°, 34.0 to 36.0°, 37.0 to 39.0°, 38.2 to 39.5°, 44.0 to 46.0°, 64.5 to 66.5°, and 77.77 to 79.77°.
  • 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 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°.
  • the LiF composition can include XRD peaks of at least one of 38.2 to 39.5°, 44.0 to 46.0°, 64.5 to 66.5°, and 77.77 to 79.77°.
  • the valuable metal recovery composition (10) has an XRD peak value of at least one of LiAlO 2 , Li 5 AlO 4 , Li 2 CO 3 , and LiF, and it can be confirmed that a lithium compound is attached and arranged on a core portion including the valuable metal.
  • the lithium compound partially bonded to the surface of the valuable metal recovery alloy can be separated by utilizing a wet process.
  • the lithium compound can be separated from the valuable metal recovery alloy by mechanical or physical external force. In this way, not only can the valuable metal recovery alloy be recovered from the valuable metal recovery composition (10), 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 metal recovery composition (10) may include a carbon-based material.
  • the carbon-based material may be, for example, a carbon (C) element.
  • the content of the carbon may be in the range of 1% to 7%.
  • the composition for recovering valuable metals (10) may contain 10 to 30 wt % of aluminum (Al).
  • Al aluminum
  • a lithium compound can be formed through physical or chemical bonding with lithium, and as the lithium compound is separated in the future, there is an advantage in that the yield of lithium can be increased.
  • the unit price metal recovery composition (100) includes aluminum (Al), and the aluminum (Al) may have a concentration gradient that gradually increases from the interface of the core portion (110) and the shell portion (120) toward the shell portion (120).
  • the concentration gradient of aluminum (Al) increases toward the shell portion (120) because an oxide including aluminum is attached to the core portion (110) including the price metal alloy.
  • a method for recovering valuable metals may include a step of preparing battery shreds, a step of dry heat-treating the shreds, and a cooling step of cooling the resultant of the dry heat treatment.
  • a method for producing an alloy having a high concentration content of a valuable metal recovery alloy in particular, it may be a method for producing an alloy having a higher concentration content of valuable metals compared to a black powder that has undergone an initial crushing step.
  • the valuable metal recovery composition and the valuable metal recovery alloy produced through the above production method are the same as long as they do not contradict the aforementioned Fig. 1.
  • the step of preparing battery shreds is a step of preparing a material that serves as a parent material of battery shreds by shredding, or preparing the material itself after the shredding is completed.
  • the parent material of the battery shreds may include waste batteries such as scrap, jelly rolls, and slurry constituting the waste batteries, defective products generated during the manufacturing process, residues within the manufacturing process, and debris generated during the manufacturing process, for example, waste materials within the manufacturing process of lithium ion batteries.
  • the material itself after the shredding may be a product itself after the shredding is completed, for example, black powder.
  • the step of preparing a battery or battery shreds in a unit cell manner may further include a step of shredding the material that is the parent material of the battery shreds when the material is prepared by shredding the material.
  • the parent material of the battery shreds may be obtained as a shredder by using a shredder.
  • the shredding may include, as a non-limiting example, crushing the waste battery by applying physical or mechanical force and pulverizing the waste battery into fine powder.
  • the crushing step may separate some large impurities, such as aluminum (Al), copper (Cu), iron (Fe), and plastic, from among the impurities included in the waste battery.
  • a state in which the large impurities are separated is called black powder, and the crushing step may produce battery shreds such as black powder.
  • the battery shredder is for recovering valuable metals from waste batteries and may have a layered structure including a separator having a cathode or anode laminated on at least one surface.
  • the layered structure may include a configuration in which the cathode or anode is included on one surface or both surfaces of the separator based on the separator. More specifically, the number of layers of the layered structure may correspond to the number of separators.
  • the above layered structure includes, for example, one of anode-separator-cathode, anode-separator, separator-anode, separator-cathode, and cathode-separator, and for example, anode-separator-cathode-separator-anode-separator-cathode may have a three-layered layered structure.
  • the battery shredder may have a predetermined thickness in the thickness direction since at least one or more layers are laminated.
  • the battery shreds may satisfy the following condition 1.
  • the above layered structure may be a laminated structure having 1 or more layers and 7 or fewer layers.
  • the above battery shreds may have a layered structure having a laminated structure of 1 to 7 layers.
  • the layered structure may have a layered structure of 1 to 5 layers.
  • the above layered structure can minimize the temperature rise of the shredded material and take an appropriate heating time by being laminated within the above range. If the above layered structure is laminated thicker than the upper limit of the above range, the temperature rise excessively increases and the heating time also increases, which causes a problem of causing a fire by combustion.
  • the battery shreds may satisfy the following condition 2.
  • the size of the above battery shreds may be 100 mm or less based on the longest axis among the length, width, and height directions.
  • the battery shreds may have a size of 100 mm or less based on the longitudinal axis. Specifically, the size of the battery shreds may be 50 mm or less. If the size of the battery shreds is excessively large, there is a problem that the temperature of the battery shreds themselves may rise to 100° C. or more, which may lead to a high possibility of a fire occurring.
  • the battery scrap may include aluminum (Al), manganese (Mn), lithium (Li), copper (Cu), cobalt (Co), nickel (Ni), carbon (C) and residual impurities.
  • the black powder includes 5 to 40 wt% of nickel (Ni), 1 to 20 wt% of cobalt (Co), 1 to 15 wt% of manganese (Mn), 0.5 to 5 wt% of lithium (Li), 10 to 70 wt% of carbon (C), 0.0001 to 20 wt% of aluminum (Al), and 0.0001 to 20 wt% of copper (Cu), and the sum of impurities such as iron (Fe) and phosphorus (P) may be less than 10 wt%.
  • the components of the above black powder may vary depending on the ratio of nickel, cobalt, and manganese, and the nickel, cobalt, and manganese may be controlled by the positive electrode oxide in the lithium secondary battery when the lithium secondary battery is crushed.
  • the step of crushing the material that is the parent material of the battery shredder may be a crushing method using at least one of shear, compression, and tensile force.
  • the crushing step may be performed by, for example, at least one of a hammer mill, a ball mill, and a stirred ball mill.
  • the hammer mill may perform at least one of the steps of disintegration, punching, and milling, and it is clear that the crushing may be performed by utilizing various types of crushing or crushing devices, for example, an industrial crusher, as a non-limiting example.
  • the particle size of the battery shreds may be within 50 mm, specifically within 30 mm. If it is larger than the above range, there is an uneconomical problem because more energy is required in the heat treatment step described later.
  • a pretreatment step may be further included prior to the step of crushing the material that is the parent material of the battery shredder.
  • a pretreatment step may be further included to prevent explosion or render harmless the parent material of the battery shredder.
  • substances that may explode, such as electrolytes, in the parent material are removed, and by discharging the parent material, such as waste batteries, when the crushing step is performed, safety can be improved and the recovery and productivity of valuable metals can be increased.
  • a step of freezing the battery may be included before crushing the above-mentioned battery shreds.
  • an explosion and fire may occur due to the electrolyte contained in the battery. Specifically, when a specific pressure is applied to the battery, the separator is physically crushed, and a high current is formed due to a short circuit, which generates a spark, and the spark may ignite the electrolyte, which may cause a fire.
  • the step of freezing the battery above is to freeze the battery to suppress ignition of the liquid electrolyte contained within the battery, and then perform the crushing process, so that problems due to ignition of the electrolyte do not occur.
  • the step of freezing the battery may be performed by cooling to a temperature in the range of -150° C. to -60° C. If the temperature exceeds the upper limit of the temperature range, the voltage remaining inside the battery may not be reduced to 0 V, which may cause a battery reaction due to a short circuit, and the electrolyte may not be completely frozen, which is not appropriate.
  • the electrolyte When the lower limit of the above temperature range is exceeded, the electrolyte is sufficiently frozen, the internal voltage of the battery is also lowered to 0 V, and even if a short circuit occurs in which the positive and negative electrodes are in direct contact, a battery reaction does not occur, so the battery temperature does not increase, and gas generation and combustion of the electrolyte do not occur.
  • the electrolyte since the electrolyte is in a frozen state, the mobility of lithium ions is very low, so that the conduction characteristics according to the movement of lithium ions can be significantly reduced, and since vaporization of the electrolyte does not occur, flammable gases such as ethylene, propylene, and hydrogen may not be generated.
  • the step of freezing the above battery if the temperature exceeds the upper limit of the above temperature range, the voltage remaining inside the battery will not decrease to 0 V, which may cause a battery reaction due to a short circuit, and the electrolyte will not be completely frozen, which is not appropriate. If the temperature exceeds the lower limit of the above temperature range, there is an uneconomical problem because a lot of energy must be invested for freezing.
  • the step of freezing the battery can be performed by cooling to a temperature range of -60 to -20° C. under a vacuum atmosphere condition of 100 torr or less.
  • the step of freezing the battery can be performed at the temperature range that is capable of suppressing vaporization of the electrolyte.
  • the vacuum atmosphere can be, for example, an inert gas, carbon dioxide, nitrogen, water, or a combination thereof.
  • the process is performed by controlling the pressure to a vacuum atmosphere of 100 torr or less, the supply of oxygen is suppressed, thereby preventing the electrolyte from reacting with oxygen, preventing an explosion caused by this, and suppressing the vaporization of the electrolyte, thereby preventing the generation of flammable gases such as ethylene, propylene, and hydrogen.
  • the electrolyte In the step of freezing the above battery, if carried out in an air atmosphere or at a pressure exceeding 100 torr, there is a problem that voltage may remain within the battery, and since the electrolyte is not in a frozen state in the temperature range of -60 to -20°C, the electrolyte may vaporize and explode due to a spark generated when a short circuit occurs due to the remaining voltage.
  • the preprocessing step may include a step of forcibly discharging the waste battery or the battery shreds.
  • the forced discharging step is a step of lowering the voltage of the waste battery or the battery shreds, and when the shredding step is performed, stability can be increased and the recovery and productivity of valuable metals can be increased.
  • the forced discharging step may perform, for example, salt water discharge or electric discharge.
  • the step of dry heat treating the above crushed material may include placing the crushed material in a heating furnace capable of raising the temperature to a temperature higher than the melting point.
  • the step of dry heat treating the above crushed material may involve heat treatment conditions that perform a high-temperature reduction reaction without going through a melting step.
  • the heat treatment conditions may involve heat treatment conditions in a range of 1,100 to 1,800° C. Specifically, the range may be performed in a range of 1,150 to 1,400° C., and more specifically, 1,200 to 1,400° C. If the upper limit of the range is exceeded, there is a problem of loss due to lithium vaporization, and if the lower limit of the range is exceeded, there is a problem of excessive occurrence of flake formation due to failure to proceed with sintering and reduction of alloy elements. In the above temperature range, the reduction reaction can be performed in a state where carbon in the shredded material is minimally burned and carbon dioxide is hardly generated.
  • the step of dry heat treating the crushed material may be performed in a gas atmosphere of at least one of an inert gas, carbon dioxide, carbon monoxide, and a hydrocarbon gas.
  • the inert gas it may include, for example, at least one of argon and nitrogen.
  • a portion of the gas atmosphere may contain impurities including residual oxygen. If the content of oxygen among the impurities is high, it may form carbon dioxide by combining with the components of the shredded material during the reduction reaction process, and thus, there is a problem that it is difficult to recover by being gasified together with lithium.
  • the oxygen content in the dry heat treatment step may be 5% or less. Specifically, the oxygen content may be 1% or less, more specifically, 0.1% or less. Specifically, when the partial pressure of the oxygen is outside the above-mentioned range, there is a problem of lithium loss and a large amount of carbon dioxide being generated in a local high-temperature state.
  • a composition for recovering valuable metals which alloys components such as nickel, cobalt, manganese and lithium-containing oxides in the crushed material, and may include valuable metals and residual impurities.
  • the composition for recovering valuable metals may include, for example, aluminum (Al), manganese (Mn), lithium (Li), copper (Cu), cobalt (Co), nickel (Ni), carbon (C) and residual impurities, and a detailed description thereof is the same as that of the composition for recovering valuable metals described above in FIG. 1 as long as it is not contradictory.
  • the above-described metal recovery composition may include a lithium compound, and the lithium compound may be prepared by the reduction reaction.
  • the aluminum content in the metal recovery composition may be 0.25 to 30 wt %.
  • a stirring process can be added within the heat treatment furnace.
  • a stirring process can be added within the heat treatment furnace.
  • the stirring process can secure the uniformity of the internal temperature and promote the reaction within the heat treatment furnace, which is a high-temperature reduction furnace, by utilizing, for example, a rotating body or gas.
  • the valuable metal recovery composition can be recovered by the reduction reaction of the black powder within the heat treatment furnace.
  • the cooling step of cooling the dry heat-treated result may be a step of cooling the dry heat-treated result to assist in leaching the carbon layer in the metal alloy.
  • the cooling step may be a step of controlling the speed and shape of precipitation of carburized carbon along the grain boundaries during the reduction process of the cathode material.
  • the cooling step of cooling the dry heat treated resultant can be performed at a rate in the range of 10 to 50 °C/min. Specifically, the cooling step can be performed at a rate in the range of 20 to 30 °C/min.
  • the cooling step lowers the temperature at the aforementioned cooling rate, there is an advantage in that the precipitated carbon is stably precipitated in a band shape at the grain boundary of the positive electrode alloy, and as the cooling step is performed outside the aforementioned speed range, there is a problem in that the carbon is precipitated in a dot shape inside the particle or in a plane shape at the grain boundary based on the cross-section of the particle.
  • the method may further include a step of separating the resultant product after the cooling step by at least one of particle size separation and magnetic separation.
  • the step of separating may separate the resultant product after the cooling step, for example, the valuable metal recovery composition, by at least one of particle size separation and magnetic separation.
  • the particle size separation method may separate the product according to the size or diameter of the particles, and may include various methods, for example, using a sieve.
  • the magnetic separation method may separate the particles by using a magnetic body and contacting the magnetic body, and various types of magnetic separation methods may be applied.
  • the step of separating the resultant product that has gone through the cooling step by at least one of particle size separation and magnetic separation may be a step of separating by at least one of particle size separation, magnetic separation, and specific gravity difference separation.
  • the specific gravity difference separation is a method of separating particles by considering the difference in specific gravity of each material, and for example, by utilizing a specific solvent, particles can be separated based on the size of the specific gravity of the particles corresponding to the specific solvent, and various types of specific gravity difference separation methods can be applied.
  • the step of separating the cooled crushed material by at least one of particle size separation and magnetic separation includes all of the steps of performing the particle size separation, the magnetic separation, and the particle size separation and the magnetic separation together, thereby separating the valuable metal recovery alloy.
  • the step of performing only the particle size separation can recover the valuable metal recovery alloy only by particle size separation of the valuable metal recovery composition having a particle diameter of 100 ⁇ m to 100 mm or less.
  • the composition for recovering valuable metals includes a material having a particle size of 100 ⁇ m or less
  • the valuable metal can be recovered from the composition for recovering valuable metals by the magnetic separation alone.
  • the material having a particle size of 100 ⁇ m or less since the particle size is similar to that of carbon, the recovery rate of the valuable metal lost by the particle size separation alone can be increased by the magnetic separation.
  • the magnetic separation when the particle size separation and the magnetic separation are performed together, the magnetic separation may be performed first, and then the particle size separation may be performed. By performing the magnetic separation first, the loss of the valuable metal recovery alloy from the valuable metal recovery composition having a particle size of 100 ⁇ m or less can be prevented.
  • the step of separating the cooled crushed material by at least one of particle size separation and magnetic separation may further include the step of separating the valuable metal alloy and the lithium compound containing lithium disposed on the valuable metal.
  • the step of separating the lithium compound containing lithium may be performed before or after the step of separating the cooled crushed material by at least one of particle size separation and magnetic separation.
  • the lithium compound may be, for example, a lithium-containing oxide, and may be separated by a physical external force.
  • a lithium-containing oxide for a detailed description thereof, reference may be made to the composition for recovering valuable metals of Fig. 1, within a range that is not contradictory. In this way, by separating the lithium-containing oxide by a physical external force, the recovery rate of not only the valuable metal but also lithium can be increased.
  • a cell, module, or pack which is a spent battery of an electric vehicle, containing 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.
  • a shredder device After freezing the spent battery at -30°C or lower, the spent battery is shredded, and the spent battery is shredded under inert gas conditions using a shredder device so that the longest length or width of the spent battery 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. After the reduction process, the reduction resultant was cooled under a cooling rate of 25° C./min, and then a composition for recovering valuable metals was obtained.
  • FIG. 1 is a SEM photograph of a composition for recovering valuable metals according to one embodiment of the present invention.
  • FIGS. 2a and 2b show XRD analysis results of a composition for recovering valuable metals according to one embodiment.
  • composition for recovering valuable metals is arranged such that a lithium compound, specifically, lithium oxide, is combined on a valuable metal recovery alloy.
  • This structure may be expressed by performing the reduction process described above.
  • a composition for recovering valuable metals was obtained under the same conditions as in Example 1, except that the cooling rate was 3°C/min.
  • a composition for recovering valuable metals was obtained under the same conditions as Example 1, except that the reduction temperature was 1,100°C or lower.
  • a composition for recovering valuable metals was obtained under the same conditions as Example 1, except that the cooling temperature in the cooling step was 100°C/min.
  • FIGS 3 and 4 show SEM photographs of the valuable metal alloy of the present invention.
  • FIGS. 3 and 4 are SEM photographs that can confirm the shape within a valuable metal alloy according to one embodiment of the present invention.
  • Tables 1 and 2 below show the results of observing the surface of the precious metal alloy in Spectrum 1 and Spectrum 2 using SEM and measuring the component contents using EDAX.
  • Spectrum 1 and Spectrum 2 are defined as follows, and the component contents were measured using the following method.
  • Area 1 (Spectrum 1) : The gray area in Figs. 3 and 4, which are SEM images of the alloy of precious metals, represents the carbon layer.
  • Region 2 (Spectrum 2) : The bright-colored region in Figs. 3 and 4, which are SEM images of the precious metal alloy, represents a compound containing lithium, specifically lithium aluminate (LiAlO 2 ).
  • Example 1 has a carbon content of 76 to 92% in the area 1 portion. This confirms that the surface of the valuable metal recovery alloy in the valuable metal recovery composition manufactured according to the example of the present invention is attached with graphite, or that the carbon content includes a region with a high graphite content due to graphite precipitated during the cooling process. In this way, it was confirmed that the comparative example in which the oxygen concentration during the reduction process and the cooling speed during the cooling step are not within the scope of the present invention had a low graphite content and thus could not form a carbon layer. In contrast, Example 1 has the advantage of including a carbon layer, so that the alloy particles can be easily pulverized by an external force in the wet refining process, and lithium of the lithium oxide can be pre-leached.
  • Figure 5 shows an SEM photograph of a cross-section of a valuable metal alloy of the present invention.
  • Figure 5 is a SEM photograph of a cross-section of a metal alloy according to one embodiment of the present invention, and the components are measured using EDAX. Specifically, Spectrum 1 and Spectrum 2 represent carbon, Spectrum 3 represents a lithium compound combined with Al, and Spectrum 4 represents an NCM alloy.
  • Table 3 shows the results of observing the cross-sections of the precious metal alloys in Zone 1, Zone 2, Zone 3, and Zone 4 using SEM photographs and measuring the component contents using EDAX.
  • FIGS. 6 to 8 are EPMA analysis results according to the comparative examples of the present invention.

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Abstract

La présente invention concerne une composition de récupération de métal de valeur et un procédé de récupération d'un métal de valeur. La composition de récupération de métal de valeur comprend : un alliage de récupération de métal de valeur comprenant une couche de carbone ; et un composé de lithium, la couche de carbone étant disposée sur au moins des parties de la surface et à l'intérieur de l'alliage de récupération de métal de valeur, et la teneur en carbone (C) dans la couche de carbone étant d'au moins 60 % en poids par rapport à 100 % en poids de la couche de carbone.
PCT/KR2024/020216 2023-12-15 2024-12-10 Composition de récupération de métal de valeur et procédé de récupération de métal de valeur Pending WO2025127687A1 (fr)

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Citations (5)

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Publication number Priority date Publication date Assignee Title
KR100796369B1 (ko) * 2007-04-26 2008-01-21 주식회사 리싸이텍코리아 폐리튬이온전지로부터 유가금속 및 재생플라스틱의회수방법
JP2021031762A (ja) * 2019-08-29 2021-03-01 住友金属鉱山株式会社 有価金属を回収する方法
KR20220148201A (ko) * 2020-03-06 2022-11-04 도와 에코 시스템 가부시키가이샤 리튬 이온 이차전지에 포함되는 유가 금속 농축 방법
JP2023013656A (ja) * 2021-07-16 2023-01-26 住友金属鉱山株式会社 有価金属の製造方法
KR20230094567A (ko) * 2021-12-21 2023-06-28 포스코홀딩스 주식회사 유가 금속 회수 합금, 유가 금속 회수 조성물, 및 유가 금속 회수 방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100796369B1 (ko) * 2007-04-26 2008-01-21 주식회사 리싸이텍코리아 폐리튬이온전지로부터 유가금속 및 재생플라스틱의회수방법
JP2021031762A (ja) * 2019-08-29 2021-03-01 住友金属鉱山株式会社 有価金属を回収する方法
KR20220148201A (ko) * 2020-03-06 2022-11-04 도와 에코 시스템 가부시키가이샤 리튬 이온 이차전지에 포함되는 유가 금속 농축 방법
JP2023013656A (ja) * 2021-07-16 2023-01-26 住友金属鉱山株式会社 有価金属の製造方法
KR20230094567A (ko) * 2021-12-21 2023-06-28 포스코홀딩스 주식회사 유가 금속 회수 합금, 유가 금속 회수 조성물, 및 유가 금속 회수 방법

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