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WO2024128714A1 - Procédé de prétraitement pour le recyclage d'une batterie secondaire au lithium - Google Patents

Procédé de prétraitement pour le recyclage d'une batterie secondaire au lithium Download PDF

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Publication number
WO2024128714A1
WO2024128714A1 PCT/KR2023/020290 KR2023020290W WO2024128714A1 WO 2024128714 A1 WO2024128714 A1 WO 2024128714A1 KR 2023020290 W KR2023020290 W KR 2023020290W WO 2024128714 A1 WO2024128714 A1 WO 2024128714A1
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WO
WIPO (PCT)
Prior art keywords
lithium secondary
secondary battery
waste
nitrogen
pretreatment method
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2023/020290
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English (en)
Korean (ko)
Inventor
변석현
박상렬
이아름
김현준
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sungeel Hitech Co Ltd
Original Assignee
Sungeel Hitech Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020230177986A external-priority patent/KR102703136B1/ko
Application filed by Sungeel Hitech Co Ltd filed Critical Sungeel Hitech Co Ltd
Publication of WO2024128714A1 publication Critical patent/WO2024128714A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/30—Destroying solid waste or transforming solid waste into something useful or harmless involving mechanical treatment
    • B09B3/35—Shredding, crushing or cutting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F26—DRYING
    • F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
    • F26B17/00—Machines or apparatus for drying materials in loose, plastic, or fluidised form, e.g. granules, staple fibres, with progressive movement
    • F26B17/30—Machines or apparatus for drying materials in loose, plastic, or fluidised form, e.g. granules, staple fibres, with progressive movement with movement performed by rotary or oscillating containers; with movement performed by rotary floors
    • F26B17/32—Machines or apparatus for drying materials in loose, plastic, or fluidised form, e.g. granules, staple fibres, with progressive movement with movement performed by rotary or oscillating containers; with movement performed by rotary floors the movement being in a horizontal or slightly inclined plane
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F26—DRYING
    • F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
    • F26B21/00—Arrangements or duct systems, e.g. in combination with pallet boxes, for supplying and controlling air or gases for drying solid materials or objects
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F26—DRYING
    • F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
    • F26B21/00—Arrangements or duct systems, e.g. in combination with pallet boxes, for supplying and controlling air or gases for drying solid materials or objects
    • F26B21/14—Arrangements or duct systems, e.g. in combination with pallet boxes, for supplying and controlling air or gases for drying solid materials or objects using gases or vapours other than air or steam, e.g. inert gases
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B2101/00—Type of solid waste
    • B09B2101/15—Electronic waste
    • B09B2101/16—Batteries
    • 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 pretreatment method for the lithium secondary battery recycling process for controlling impurities in waste batteries and recovering electrolyte solution.
  • Lithium secondary batteries used in electric vehicles have the same composition as batteries used in small IT devices, and are composed of a cathode, an anode, a separator, and an electrolyte.
  • LiCoO 2 (hereinafter referred to as LCO), which has excellent discharge and high capacity characteristics, is used as the cathode active material for small-sized lithium secondary batteries, and Li[NixAlyCoz]O 2 (NCA) is used as the cathode active material for medium- and large-sized lithium secondary batteries due to its low price and high output. ) and Li[NixCoyMnz]O 2 (NCM), etc. are used.
  • the lithium secondary battery recycling process refers to extracting expensive valuable metals from the cathode active material of waste batteries. Since most valuable metals depend on imports, it is necessary to secure stable materials through the lithium secondary battery recycling process.
  • the present applicant obtained a pretreatment method for the lithium secondary battery recycling process for controlling impurities in waste batteries and recovering electrolyte solution, which solved the above problems, and completed the present invention.
  • the purpose of the present invention is to provide a pretreatment method for the lithium secondary battery recycling process for controlling impurities in waste batteries and recovering electrolyte solution.
  • the pretreatment method for the lithium secondary battery recycling process is to introduce nitrogen into the closed drying furnace, maintain the temperature inside the closed pipe constant, and then apply heat to the shredded material to effectively evaporate the organic substances in the waste battery. By recovering the spent batteries, it is possible to control impurities in the spent batteries.
  • step (a-1) of electrically discharging the waste lithium secondary battery module or waste lithium secondary battery pack to obtain a discharged waste lithium secondary battery module or waste lithium secondary battery pack in the step (a-1) of electrically discharging the waste lithium secondary battery module or waste lithium secondary battery pack to obtain a discharged waste lithium secondary battery module or waste lithium secondary battery pack,
  • the electrical discharge may be short-circuited for 24 hours after discharging for 1.5 to 3 hours.
  • step (a-3) of manufacturing a waste lithium secondary battery cell by cutting the terminal of the waste lithium secondary battery module, and separating the waste lithium secondary battery cell/terminal and plastic,
  • the terminal cutting uses a terminal cutter
  • the terminal cutter may include an insulated terminal cutter, a metal cutter, or a high-speed cutter.
  • step (a-4) of punching the waste lithium secondary battery cell in the step (a-4) of punching the waste lithium secondary battery cell,
  • Physical discharge can be achieved by the above punching.
  • step (a-5) of introducing nitrogen into the closed nitrogen shredder and crushing the punched waste lithium secondary battery cell to obtain shredded material in the step (a-5) of introducing nitrogen into the closed nitrogen shredder and crushing the punched waste lithium secondary battery cell to obtain shredded material,
  • the crushing can be done using a shredder, jaw crusher, or cone crusher.
  • step (a-5) of introducing nitrogen into the closed nitrogen shredder and crushing the punched waste lithium secondary battery cell to obtain shredded material in the step (a-5) of introducing nitrogen into the closed nitrogen shredder and crushing the punched waste lithium secondary battery cell to obtain shredded material,
  • the closed nitrogen shredder can be introduced through a conveyor in a nitrogen atmosphere.
  • step (a-5) of introducing nitrogen into the closed nitrogen shredder and crushing the punched waste lithium secondary battery cell to obtain shredded material in the step (a-5) of introducing nitrogen into the closed nitrogen shredder and crushing the punched waste lithium secondary battery cell to obtain shredded material,
  • the closed nitrogen shredder is a two-stage nitrogen shredder
  • the primary size of the two-stage nitrogen crusher may be 30 to 60 mm in width and 130 to 200 mm in height, and the secondary size may be 15 to 30 mm in width and 20 to 130 mm in height.
  • step (a-6) of introducing nitrogen into a closed drying furnace and heating the obtained shredded material to evaporate organic substances and drying and recovering the waste battery shredded material in the step (a-6) of introducing nitrogen into a closed drying furnace and heating the obtained shredded material to evaporate organic substances and drying and recovering the waste battery shredded material,
  • the nitrogen may pass through a nitrogen shredder, a closed transfer conveyor, and then be introduced into the closed drying furnace.
  • step (a-6) of introducing nitrogen into a closed drying furnace and heating the obtained shredded material to evaporate organic substances and drying and recovering the waste battery shredded material in the step (a-6) of introducing nitrogen into a closed drying furnace and heating the obtained shredded material to evaporate organic substances and drying and recovering the waste battery shredded material,
  • the organic material evaporation is performed in the closed drying furnace into which nitrogen is introduced,
  • the closed drying furnace may be at least one selected from a rotary kiln, a rotary dryer, a tunnel furnace, a box furnace, and a furnace capable of being sealed.
  • step (a-6) of introducing nitrogen into a closed drying furnace and heating the obtained shredded material to evaporate organic substances and drying and recovering the waste battery shredded material in the step (a-6) of introducing nitrogen into a closed drying furnace and heating the obtained shredded material to evaporate organic substances and drying and recovering the waste battery shredded material,
  • Evaporation of the organic material may be performed by indirect heating at a temperature of 100°C to 800°C.
  • step (a-6) of introducing nitrogen into a closed drying furnace and heating the obtained shredded material to evaporate organic substances and drying and recovering the waste battery shredded material in the step (a-6) of introducing nitrogen into a closed drying furnace and heating the obtained shredded material to evaporate organic substances and drying and recovering the waste battery shredded material,
  • step (a-7) of recovering the evaporated organic material in the step (a-7) of recovering the evaporated organic material,
  • the device for recovering the evaporated organic material may be a condenser, cooling tower, refrigerator, heat exchanger, or shell-and-tube heat exchanger.
  • step (a-8) of cooling the obtained dried shreds to room temperature in the step (a-8) of cooling the obtained dried shreds to room temperature,
  • the apparatus for cooling the obtained dried crushed material is carried out in a closed cooling apparatus
  • the closed cooling device may be at least one selected from Rotary Type, Tunnel Type, and Box Type.
  • step (a-8) of cooling the obtained dried shreds to room temperature in the step (a-8) of cooling the obtained dried shreds to room temperature,
  • the cooling may be performed using an indirect cooling method using a refrigerant at a temperature of 15°C to 30°C in the closed cooling device.
  • step (a-8) of cooling the obtained dried shreds to room temperature in the step (a-8) of cooling the obtained dried shreds to room temperature,
  • the waste battery shredded material discharged from the closed cooling device may be discharged at a temperature of 25°C to 40°C.
  • step (a-9) of pulverizing and selecting the obtained shredded material in the step (a-9) of pulverizing and selecting the obtained shredded material,
  • the grinder may be a rod mill, pin mill, ball mill, tube mill, port mill, roller mill, turbo mill, impact mill, cut mill, or tower mill.
  • step (a-9) of pulverizing and selecting the obtained shredded material in the step (a-9) of pulverizing and selecting the obtained shredded material,
  • the size of the pulverized lithium secondary battery waste may be 10 ⁇ m to 15 mm.
  • step (a-9) of pulverizing and selecting the obtained shredded material in the step (a-9) of pulverizing and selecting the obtained shredded material,
  • the separator may be a gravity separator, specific gravity separator, vibration separator, magnetic separator, electrostatic separator, wind separator, flotation separator, or optical separator.
  • step (a-9) of pulverizing and selecting the obtained shredded material in the step (a-9) of pulverizing and selecting the obtained shredded material,
  • waste batteries can be sorted into at least one group selected from cathode active material (Catohde), negative electrode active material (Anode), copper (Cu), and aluminum (Al).
  • step (a-9) of pulverizing and selecting the obtained shredded material in the step (a-9) of pulverizing and selecting the obtained shredded material,
  • the valuable metal powder recovered through the grinding and screening may be a compound of at least one valuable metal selected from lithium, nickel, manganese, cobalt, iron, aluminum, and copper.
  • the waste battery may be at least one lithium secondary battery selected from electric vehicle waste batteries, energy storage system (ESS) waste batteries, electronic product waste batteries, and mobile phone waste batteries.
  • ESS energy storage system
  • the waste battery may include a positive electrode active material (Cathode), a negative electrode active material (Anode), a separator, a copper electrode plate (Cu foil), an aluminum electrode plate (Al foil), and an electrolyte. You can.
  • Cathode positive electrode active material
  • Anode negative electrode active material
  • separator separator
  • Cu foil copper electrode plate
  • Al foil aluminum electrode plate
  • electrolyte electrolyte
  • the present invention provides a pretreatment method for the lithium secondary battery recycling process for controlling impurities in waste batteries and recovering electrolyte, thereby reducing the cost of recycling lithium secondary batteries, increasing the efficiency of the pretreatment process, and increasing the material recycling rate. It can be raised.
  • the present invention can provide an environmentally friendly waste battery pretreatment method by preventing fire and explosion during the crushing and drying process during waste battery pretreatment and recovering evaporated organic compounds in the form of oil, gas, or ash without a combustion device. .
  • Figure 1 is a process flow diagram of a pretreatment method for a lithium secondary battery recycling process according to an embodiment of the present invention.
  • the present invention provides a pretreatment method for the lithium secondary battery recycling process for controlling impurities in waste batteries and recovering electrolyte solution.
  • the pretreatment method for the lithium secondary battery recycling process is to introduce nitrogen into the closed drying furnace, maintain the temperature inside the closed pipe constant, and then apply heat to the shredded material to effectively evaporate the organic substances in the waste battery. By recovering the spent batteries, impurities in the spent batteries can be controlled.
  • the present invention provides a pretreatment method for the lithium secondary battery recycling process for controlling impurities in waste batteries and recovering electrolyte, thereby reducing the cost of recycling lithium secondary batteries, increasing the efficiency of the pretreatment process, and increasing the material recycling rate. there is.
  • the present invention can provide an environmentally friendly waste battery pretreatment method by preventing fire and explosion during the crushing and drying process during waste battery pretreatment and recovering evaporated organic compounds in the form of oil, gas, or ash without a combustion device. .
  • Lithium secondary batteries used in electric vehicles have the same composition as batteries used in small IT devices, and are composed of a cathode, an anode, a separator, and an electrolyte.
  • LiCoO 2 (hereinafter referred to as LCO), which has excellent discharge and high capacity characteristics, is used as the cathode active material for small-sized lithium secondary batteries, and Li[NixAlyCoz]O 2 (NCA) is used as the cathode active material for medium- and large-sized lithium secondary batteries due to its low price and high output. ) and Li[NixCoyMnz]O 2 (NCM), etc. are used.
  • the lithium secondary battery recycling process refers to extracting expensive valuable metals from the cathode active material of waste batteries. Since most valuable metals depend on imports, it is necessary to secure stable materials through the lithium secondary battery recycling process.
  • the present applicant obtained a pretreatment method for the lithium secondary battery recycling process for controlling impurities in waste batteries and recovering electrolyte solution, which solved the above problems, and completed the present invention.
  • the pretreatment method for the lithium secondary battery recycling process is to introduce nitrogen into the closed drying furnace, maintain the temperature inside the closed pipe constant, and then apply heat to the shredded material to remove organic materials from the waste battery. By effectively evaporating and recovering, impurities in the spent batteries can be controlled.
  • step (a-1) of electrically discharging the waste lithium secondary battery module or waste lithium secondary battery pack to obtain a discharged waste lithium secondary battery module or waste lithium secondary battery pack
  • the electrical discharge may be short-circuited for 24 hours after discharging for 1.5 to 3 hours.
  • step (a-3) of manufacturing a waste lithium secondary battery cell by cutting the terminal of the waste lithium secondary battery module and separating the waste lithium secondary battery cell/terminal and plastic,
  • the terminal cutting uses a terminal cutter
  • the terminal cutter may include an insulated terminal cutter, a metal cutter, or a high-speed cutter.
  • Physical discharge can be achieved by the above punching.
  • the discharge process can be completed with the electrical discharge and the physical discharge of the punching.
  • step (a-5) of introducing nitrogen into the closed nitrogen shredder and crushing the punched waste lithium secondary battery cell to obtain shredded material in the step (a-5) of introducing nitrogen into the closed nitrogen shredder and crushing the punched waste lithium secondary battery cell to obtain shredded material,
  • the crushing can be done using a shredder, jaw crusher, or cone crusher.
  • step (a-5) of introducing nitrogen into the closed nitrogen shredder and shredding the punched waste lithium secondary battery cell to obtain shredded material
  • the closed nitrogen shredder can be introduced through a conveyor in a nitrogen atmosphere.
  • the closed nitrogen shredder can continuously receive nitrogen in a closed state.
  • step (a-5) of introducing nitrogen into the closed nitrogen shredder and shredding the punched waste lithium secondary battery cell to obtain shredded material in the step (a-5) of introducing nitrogen into the closed nitrogen shredder and shredding the punched waste lithium secondary battery cell to obtain shredded material,
  • the closed nitrogen shredder is a two-stage nitrogen shredder
  • the primary size of the two-stage nitrogen crusher may be 30 to 60 mm in width and 130 to 200 mm in height, and the secondary size may be 15 to 30 mm in width and 20 to 130 mm in height.
  • the size of the two-stage nitrogen crusher of the closed nitrogen crusher is within the above range, crushing efficiency can be superior, and subsequent heat treatment efficiency can be increased by crushing to increase the surface area.
  • step (a-6) nitrogen is added to the obtained shredded material in a closed drying furnace and heat is applied to evaporate organic substances and dry and recover the waste battery shredded material,
  • the nitrogen may pass through a nitrogen shredder, a closed transfer conveyor, and then be introduced into the closed drying furnace.
  • the nitrogen passes through a nitrogen shredder and a closed transfer conveyor, so when the obtained shredded material is input into a closed drying furnace, the oxygen concentration can be easily controlled.
  • nitrogen is added for the purpose of preventing fire and explosion during the destruction of batteries with some remaining capacity (SOC, state of charge) remaining, and thus oxygen in the facility can be maintained at 0.1 to 10% by volume.
  • step (a-6) nitrogen is added to the obtained shredded material in a closed drying furnace and heat is applied to evaporate organic substances and dry and recover the spent battery shredded material,
  • the organic material evaporation is performed in the closed drying furnace into which nitrogen is introduced,
  • the closed drying furnace may be at least one selected from a rotary kiln, a rotary dryer, a tunnel furnace, a box furnace, and a furnace capable of being sealed.
  • step (a-6) nitrogen is added to the obtained shredded material in a closed drying furnace and heat is applied to evaporate organic substances and dry and recover the waste battery shredded material,
  • Evaporation of the organic material may be performed by indirect heating at a temperature of 100°C to 800°C.
  • the evaporation temperature of the organic material may be preferably 200°C to 700°C, and more preferably 300°C to 600°C.
  • the indirect heating method can suppress rapid temperature rise, increase the evaporation efficiency of organic substances, and facilitate the recovery of dry powder from spent batteries.
  • the pretreatment temperature of the waste battery is maintained uniformly and the organic substances in the waste battery powder are effectively evaporated, enabling recovery of organic substances through an air pollution prevention facility. You can do it.
  • step (a-6) nitrogen is added to the obtained shredded material in a closed drying furnace and heat is applied to evaporate organic substances and dry and recover the spent battery shredded material,
  • the organic material may be a combustible material composed of carbon or hydrogen, moisture, or ash.
  • the organic material may consist of 50 to 95% by weight of the combustible material, 0.5 to 35% by weight of moisture, or 0.2 to 30% by weight of ash.
  • the device for recovering the evaporated organic material may be a condenser, cooling tower, refrigerator, heat exchanger, or shell-and-tube heat exchanger.
  • the device for recovering the evaporated organic material may recover the evaporated organic material due to a temperature difference.
  • a plurality of devices for recovering the evaporated organic material may be used.
  • the evaporated organic material is recovered in the form of oil, gas, or ash through the recovery device, and the respective ratios based on 100% by weight of the evaporated organic material are olefinic compounds (CO, CH4, H2, CO2, C n H n ) may be 10 to 20% by weight of gaseous component, 50 to 70% by weight of liquid component, and 10 to 20% by weight of ash.
  • olefinic compounds CO, CH4, H2, CO2, C n H n
  • the apparatus for cooling the obtained dried crushed material is carried out in a closed cooling apparatus
  • the closed cooling device may be at least one selected from Rotary Type, Tunnel Type, and Box Type.
  • the high temperature of the transport system for shredded products dried at 200°C to 600°C causes frequent replacement of consumables, which also reduces factory operation rate.
  • the cooling may be performed using an indirect cooling method using a refrigerant at a temperature of 15°C to 30°C in the closed cooling device.
  • the waste battery shredded material discharged from the closed cooling device may be discharged at a temperature of 25°C to 40°C.
  • the grinder may be a rod mill, pin mill, ball mill, tube mill, port mill, roller mill, turbo mill, impact mill, cut mill, or tower mill.
  • the size of the pulverized lithium secondary battery waste may be 10 ⁇ m to 15 mm.
  • the particle size of the pulverized lithium secondary battery waste is outside the above range, it may be difficult to control impurities in the waste battery in the pretreatment method for the lithium secondary battery recycling process.
  • the size of the pulverized lithium secondary battery waste may preferably be 15 ⁇ m to 15 mm, and more preferably 20 ⁇ m to 10 mm.
  • the separator may be a gravity separator, specific gravity separator, vibration separator, magnetic separator, electrostatic separator, wind separator, flotation separator, or optical separator.
  • waste batteries can be sorted into at least one group selected from cathode active material (Catohde), negative electrode active material (Anode), copper (Cu), and aluminum (Al).
  • the valuable metal powder recovered through the grinding and screening may be a compound of at least one valuable metal selected from lithium, nickel, manganese, cobalt, iron, aluminum, and copper.
  • the present invention prevents fire and explosion during the crushing and drying process during waste battery pretreatment, recovers evaporated organic compounds in the form of oil, gas, or ash, reduces the consumption of chemicals for the purpose of removing impurities in the wet process, and reduces organic By recovering compounds without a combustion device, an environmentally friendly waste battery pretreatment process can be provided.
  • the waste battery may be at least one lithium secondary battery selected from electric vehicle waste batteries, energy storage system (ESS) waste batteries, electronic product waste batteries, and mobile phone waste batteries.
  • ESS energy storage system
  • the waste battery may include a cathode, a cathode, a separator, a copper foil, an aluminum foil, and an electrolyte.
  • Figure 1 is a process flow diagram of a pretreatment method for a lithium secondary battery recycling process according to an embodiment of the present invention.
  • a waste lithium secondary battery module or a waste lithium secondary battery pack is electrically discharged to obtain a discharged waste lithium secondary battery module or a waste lithium secondary battery pack (S110).
  • waste lithium secondary battery pack is dismantled into a waste lithium secondary battery module (S120).
  • the waste lithium secondary battery module is cut into terminals to manufacture a waste lithium secondary battery cell, and the waste lithium secondary battery cell/terminal and plastic are separated (S130).
  • the dried waste battery shredded material is cooled to room temperature (S180).
  • the obtained shredded material is dried by indirect heating at 500 ° C. in a rotary type dryer, and nitrogen is introduced into the closed drying furnace of the rotary kiln to maintain the oxygen content in the facility below 1% by volume. While doing this, organic substances were evaporated and dried shredded waste batteries were recovered.
  • the dried crushed material was pulverized and selected to recover valuable metal powder.
  • the waste battery of the preparation example was pretreated using the same method as Example 1, except that the pretreatment process for the lithium secondary battery recycling process shown in Table 1 below was used.
  • Waste batteries were pretreated in the same manner as in Example 1, except that nitrogen was not used (atmospheric atmosphere) and the size of the shredded material was 30 mm.
  • the waste battery of the preparation example was pretreated in the same manner as Example 4, except that nitrogen was not used (atmospheric atmosphere).
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 Example 6
  • Example 7 Comparative Example 1 Comparative Example 2 Waste battery type Waste batteries for electric vehicles Waste batteries for electric vehicles Waste batteries for ESS Waste batteries for ESS Waste batteries for electric vehicles Waste batteries for IT Waste batteries for IT Waste batteries for electric vehicles Waste batteries for ESS closed drying furnace rotary kiln rotary kiln rotary kiln Box furnace rotary kiln Box furnace rotary kiln rotary kiln gas atmosphere nitrogen nitrogen nitrogen nitrogen nitrogen nitrogen nitrogen nitrogen atmosphere atmosphere crushing device shredder shredder shredder shredder shredder shredder shredder shredder shredder shredder shredder Shredded material size (mm) 60 30 60 30 50 30 50 30 30 30 Drying temperature (°C) 500 500 500 500 400 500 400 500 500
  • Examples 1 to 4 compared to Comparative Examples 1 and 2, organic materials are evaporated by indirect heating while nitrogen is introduced into the closed drying furnace, so the evaporated organic compounds are oil, gas, or ash.
  • the dried powder can be recovered in the form of a bonsai, and the amount of chemicals used to remove impurities in the wet process has been significantly reduced.
  • Comparative Examples 1 and 2 did not use nitrogen, making it difficult to easily remove organic substances, and the amount of chemicals used to remove impurities in the wet process significantly increased.
  • the organic materials recovered through the pretreatment process for the lithium secondary battery recycling process of Example 1 were analyzed by gas chromatography (GC), and the evaporated organic materials were 210 g of octene oil, carbon monoxide, and methane gas. g and 15 g of batch ash.
  • GC gas chromatography
  • the present invention can be used in the lithium secondary battery recycling industry.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Secondary Cells (AREA)
  • Processing Of Solid Wastes (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

La présente invention concerne un procédé de prétraitement pour le recyclage d'une batterie secondaire au lithium, le procédé comprenant les étapes consistant à : décharger physiquement les blocs-batteries secondaires au lithium usés, puis les démonter et couper les bornes afin d'obtenir des cellules de batteries secondaires au lithium usées, pour ainsi séparer les bornes de cellule et les matières plastiques; perforer les cellules de batteries secondaires au lithium usées; les mettre dans un broyeur à azote fermé et les déchiqueter, puis injecter les produits déchiquetés ainsi générés dans un four de séchage fermé afin de les chauffer tout en injectant de l'azote, pour ainsi évaporer et sécher les matériaux organiques afin de récupérer les matériaux organiques évaporés; refroidir, jusqu'à température ambiante, les produits déchiquetés séchés; et pulvériser et de trier les produits déchiquetés séchés. Le procédé de prétraitement pour le recyclage d'une batterie secondaire au lithium injecte de l'azote dans le four de séchage fermé, maintient constante la température à l'intérieur d'un tube fermé, puis applique de la chaleur aux produits déchiquetés afin d'évaporer et de récupérer efficacement les matériaux organiques des batteries usées, ce qui permet de gérer les impuretés des batteries usées.
PCT/KR2023/020290 2022-12-13 2023-12-11 Procédé de prétraitement pour le recyclage d'une batterie secondaire au lithium Ceased WO2024128714A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20220173870 2022-12-13
KR10-2022-0173870 2022-12-13
KR10-2023-0177986 2023-12-08
KR1020230177986A KR102703136B1 (ko) 2022-12-13 2023-12-08 리튬이차전지 재활용 공정을 위한 전처리 방법

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Citations (9)

* Cited by examiner, † Cited by third party
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