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WO2024128714A1 - Pretreatment method for lithium secondary battery recycling - Google Patents

Pretreatment method for lithium secondary battery recycling 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
Other languages
French (fr)
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/en
Application filed by Sungeel Hitech Co Ltd filed Critical Sungeel Hitech Co Ltd
Publication of WO2024128714A1 publication Critical patent/WO2024128714A1/en
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)
  • Processing Of Solid Wastes (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Secondary Cells (AREA)

Abstract

The present invention relates to a pretreatment method for lithium secondary battery recycling, comprising the steps of: physically discharging waste lithium secondary battery packs, and then dismantling same and cutting terminals so as to manufacture waste lithium secondary battery cells, thereby separating out cell terminals and plastics; punching the waste lithium secondary battery cells; putting same into a closed nitrogen shredder and shredding same, and then injecting the shredded products generated thereby into a closed drying furnace so as to heat same while injecting nitrogen, thereby evaporating and drying organic materials so that the evaporated organic materials are recovered; cooling, to room temperature, the dried shredded products; and pulverizing and sorting the dried shredded products. The pretreatment method for a lithium secondary battery recycling injects nitrogen into the closed drying furnace, maintains the temperature inside a closed tube to be constant, and then applies heat to the shredded products so as to effectively evaporate and recover organic materials of the waste batteries, thereby controlling impurities of the waste batteries.

Description

리튬이차전지 재활용 공정을 위한 전처리 방법Pretreatment method for lithium secondary battery recycling process

본 발명은 폐전지의 불순물 제어와 전해액 회수를 위한 리튬이차전지 재활용 공정을 위한 전처리 방법에 관한 것이다The present invention relates to a pretreatment method for the lithium secondary battery recycling process for controlling impurities in waste batteries and recovering electrolyte solution.

국내 전기자동차 보급은 2018년 누적 기준 약 5.7만대이며 대한민국 정부는"2030년 국가 로드맵"을 통해 2030년까지 300만대로 확대할 계획으로, 향후 전기 자동차에서 발생되는 폐전지의 규모 역시 크게 증가할 것으로 예상된다. Domestic electric vehicle distribution is approximately 57,000 units as of 2018, and the Korean government plans to expand it to 3 million units by 2030 through the “2030 National Roadmap,” and the volume of waste batteries generated from electric vehicles is expected to increase significantly in the future. It is expected.

전기자동차에 사용되는 리튬이차전지는 소형 IT기기에 사용되는 전지와 구성이 동일하며, 양극활물질(Cathode), 음극활물질(Anode), 분리막(Separator), 전해질 (Electrolyte) 등으로 구성되어 있다.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.

소형 리튬이차전지의 양극활물질로는 우수한 방전 및 고용량 특성을 가진 LiCoO2(이하 LCO)가 사용되고 있고, 중·대형 리튬이차 전지용 양극활물질은 저렴한 가격과 고출력의 장점으로 Li[NixAlyCoz]O2(NCA) 및 Li[NixCoyMnz]O2(NCM) 등이 사용되고 있다.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.

일반적으로, 리튬이차전지 재활용 공정은 폐전지의 양극활물질로부터 고가의 유가금속을 추출하는 것을 말하며, 대부분의 유가금속은 수입에 의존하고 있어, 리튬이차전지 재활용 공정으로 안정적인 재료 확보가 필요하다.In general, 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.

이러한 리튬이차전지 재활용 공정에서 배터리 건조 공정을 수행하여 전처리하고 있다. In this lithium secondary battery recycling process, a battery drying process is performed for pretreatment.

종래의 건조 진행 시 장치 내 화재 발생으로 인하여 내부 온도의 불균일성이 발생하고, 이에 따른 Cu는 취성이 증가하고, Al은 산화되어 불순물 (Cu, Al 등)이 다량 혼입되는 문제점이 있다.During conventional drying, a fire occurs within the device, resulting in non-uniformity of internal temperature, resulting in increased brittleness of Cu and oxidation of Al, which causes a large amount of impurities (Cu, Al, etc.) to be mixed.

또한, 열처리 온도를 낮추는 경우 배터리 내부 유기성 물질이 제거되지 않는 문제점이 있다.Additionally, there is a problem in that organic substances inside the battery are not removed when the heat treatment temperature is lowered.

그리고, 기존 공정에는 1차 연소 후 2차 연소를 통해 발생하는 가스(탄화수소)를 CO2로 배출하여 탄소중립 및 친환경 관점에서 불리한 면이 있다.In addition, the existing process is disadvantageous from a carbon neutral and eco-friendly perspective because gas (hydrocarbons) generated through secondary combustion after primary combustion is emitted as CO 2 .

본 출원인은 각고의 노력과 여러 연구를 통하여 상기 문제점들을 해결한 폐전지의 불순물 제어와 전해액 회수를 위한 리튬이차전지 재활용 공정을 위한 전처리 방법을 획득하여 본 발명을 완성하게 되었다.Through hard work and various studies, 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.

따라서, 본 발명의 목적은 폐전지의 불순물 제어와 전해액 회수를 위한 리튬이차전지 재활용 공정을 위한 전처리 방법을 제공하는 데 있다. Therefore, 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.

본 발명이 해결하고자 하는 과제는 이상에서 언급한 과제들로 제한되지 않으며, 언급되지 않은 또 다른 과제들은 이하의 기재로부터 당업자에게 명확하게 이해될 수 있을 것이다.The problems to be solved by the present invention are not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

상기 과제를 해결하기 위해, 본 발명의 일 측면에 따르면, In order to solve the above problem, according to one aspect of the present invention,

리튬이차전지 재활용 공정을 위한 전처리 방법으로,As a pretreatment method for the lithium secondary battery recycling process,

(a-1) 폐리튬이차전지 모듈 또는 폐리튬이차전지 팩을 전기적 방전시켜 방전된 폐리튬이차전지 모듈 또는 폐리튬이차전지 팩을 수득하는 단계;(a-1) electrically discharging a waste lithium secondary battery module or a waste lithium secondary battery pack to obtain a discharged waste lithium secondary battery module or a waste lithium secondary battery pack;

(a-2) 상기 폐리튬이차전지 팩을 폐리튬이차전지 모듈로 해체하는 단계; (a-2) dismantling the waste lithium secondary battery pack into a waste lithium secondary battery module;

(a-3) 상기 폐리튬이차전지 모듈을 단자컷팅하여 폐리튬이차전지 셀을 제조하고, 상기 폐리튬이차전지 셀/단자 및 플라스틱을 분리하는 단계;(a-3) 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;

(a-4) 상기 폐리튬이차전지 셀을 펀칭하는 단계;(a-4) punching the waste lithium secondary battery cell;

(a-5) 밀폐형 질소 파쇄기에 질소를 투입하고, 상기 펀칭된 폐리튬이차전지 셀을 파쇄하여 파쇄물을 수득하는 단계;(a-5) introducing nitrogen into a closed nitrogen shredder and crushing the punched waste lithium secondary battery cell to obtain shredded material;

(a-6) 상기 수득된 파쇄물을 폐쇄형 건조로에 질소를 투입하며 열을 가하여 유기성 물질을 증발시키고 파쇄물을 건조하는 단계;(a-6) adding nitrogen to the obtained crushed material in a closed drying furnace and applying heat to evaporate the organic substances and dry the crushed material;

(a-7) 상기 증발된 유기성 물질을 회수하는 단계;(a-7) recovering the evaporated organic material;

(a-8) 상기 수득된 건조 파쇄물을 상온까지 냉각하는 단계; 및(a-8) cooling the obtained dried crushed material to room temperature; and

(a-9) 상기 수득된 파쇄물을 분쇄 및 선별하는 단계;를 포함하고, (a-9) pulverizing and selecting the obtained crushed material;

상기 리튬이차전지 재활용 공정을 위한 전처리 방법은 상기 폐쇄형 건조로에 질소를 투입하고, 상기 폐쇄형 관 내부의 온도를 일정하게 유지한 후 상기 파쇄물에 열을 가하여, 상기 폐전지의 유기성 물질을 효과적으로 증발시켜 회수함으로써, 상기 폐전지의 불순물 제어를 가져오는The 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.

리튬이차전지 재활용 공정을 위한 전처리 방법을 제공한다.Provides a pretreatment method for the lithium secondary battery recycling process.

본 발명의 일 실시예에 따르면, 상기 (a-1) 폐리튬이차전지 모듈 또는 폐리튬이차전지 팩을 전기적 방전시켜 방전된 폐리튬이차전지 모듈 또는 폐리튬이차전지 팩을 수득하는 단계에서,According to one embodiment of the present invention, 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,

상기 전기적 방전은 1.5 ~ 3 시간 방전한 후 24 시간 쇼트할 수 있다.The electrical discharge may be short-circuited for 24 hours after discharging for 1.5 to 3 hours.

본 발명의 일 실시예에 따르면, 상기 (a-3) 폐리튬이차전지 모듈을 단자컷팅하여 폐리튬이차전지 셀을 제조하고, 상기 폐리튬이차전지 셀/단자 및 플라스틱을 분리하는 단계에서,According to one embodiment of the present invention, in the 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,

상기 단자커팅은 단자컷팅기를 사용하고,The terminal cutting uses a terminal cutter,

상기 단자컷팅기를 이용하여 상기 폐리튬이차전지 셀/단자 및 플라스틱을 분리하며,Separate the waste lithium secondary battery cells/terminals and plastic using the terminal cutter,

상기 단자컷팅기는 절연단자컷팅기, 금속컷팅기, 또는 고속절단기를 포함할 수 있다.The terminal cutter may include an insulated terminal cutter, a metal cutter, or a high-speed cutter.

본 발명의 일 실시예에 따르면, 상기 (a-4) 폐리튬이차전지 셀을 펀칭하는 단계에서, According to an embodiment of the present invention, in the step (a-4) of punching the waste lithium secondary battery cell,

상기 펀칭으로 물리적 방전할 수 있다.Physical discharge can be achieved by the above punching.

본 발명의 일 실시예에 따르면, 상기 (a-5) 밀폐형 질소 파쇄기에 질소를 투입하고, 상기 펀칭된 폐리튬이차전지 셀을 파쇄하여 파쇄물을 수득하는 단계에서,According to one embodiment of the present invention, 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,

상기 파쇄는 슈레더, 조크러셔(jaw crusher), 또는 콘크러셔(cone crusher)를 사용할 수 있다.The crushing can be done using a shredder, jaw crusher, or cone crusher.

본 발명의 일 실시예에 따르면, 상기 (a-5) 밀폐형 질소 파쇄기에 질소를 투입하고 상기 펀칭된 폐리튬이차전지 셀을 파쇄하여 파쇄물을 수득하는 단계에서,According to one embodiment of the present invention, 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,

상기 밀폐형 질소 파쇄기는 질소분위기의 컨베이어를 통해 투입될 수 있다.The closed nitrogen shredder can be introduced through a conveyor in a nitrogen atmosphere.

본 발명의 일 실시예에 따르면, 상기 (a-5) 밀폐형 질소 파쇄기에 질소를 투입하고 상기 펀칭된 폐리튬이차전지 셀을 파쇄하여 파쇄물을 수득하는 단계에서,According to one embodiment of the present invention, 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,

상기 밀폐형 질소 파쇄기는 2단 질소 파쇄기이고,The closed nitrogen shredder is a two-stage nitrogen shredder,

상기 2단 질소 파쇄기의 1차 크기는 가로 30~60 mm와 세로 130~200 mm 이고, 2차 크기는 가로 15~30 mm와 세로 20~130 mm 일 수 있다.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.

본 발명의 일 실시예에 따르면, 상기 (a-6) 수득된 파쇄물을 폐쇄형 건조로에 질소를 투입하며 열을 가하여 유기성 물질을 증발시키고 폐전지 파쇄물을 건조 회수하는 단계에서,According to one embodiment of the present invention, 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,

상기 질소는 질소 슈레더를 거쳐 밀폐형 이송컨베이어를 통과하여 상기 폐쇄형 건조로에 투입될 수 있다.The nitrogen may pass through a nitrogen shredder, a closed transfer conveyor, and then be introduced into the closed drying furnace.

본 발명의 일 실시예에 따르면, 상기 (a-6) 수득된 파쇄물을 폐쇄형 건조로에 질소를 투입하며 열을 가하여 유기성 물질을 증발시키고 폐전지 파쇄물을 건조 회수하는 단계에서,According to one embodiment of the present invention, 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,

상기 유기성 물질 증발은 질소가 투입된 상기 폐쇄형 건조로에서 수행되고,The organic material evaporation is performed in the closed drying furnace into which nitrogen is introduced,

상기 폐쇄형 건조로는 로터리 킬른(rotary kiln), 로터리 드라이어(rotary dryer), 터널로(Tunnel furnace), 대차로(box furnace) 및 밀폐구조가 가능한 로(furnace) 중에서 선택된 적어도 어느 하나일 수 있다.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.

본 발명의 일 실시예에 따르면, 상기 (a-6) 수득된 파쇄물을 폐쇄형 건조로에 질소를 투입하며 열을 가하여 유기성 물질을 증발시키고 폐전지 파쇄물을 건조 회수하는 단계에서,According to one embodiment of the present invention, 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,

상기 유기성 물질의 증발은 100 ℃ 내지 800 ℃의 온도에서 간접 가열방식으로 수행될 수 있다.Evaporation of the organic material may be performed by indirect heating at a temperature of 100°C to 800°C.

본 발명의 일 실시예에 따르면, 상기 (a-6) 수득된 파쇄물을 폐쇄형 건조로에 질소를 투입하며 열을 가하여 유기성 물질을 증발시키고 폐전지 파쇄물을 건조 회수하는 단계에서,According to one embodiment of the present invention, 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,

상기 유기성 물질은 탄소 또는 수소로 구성된 가연물질, 수분, 또는 회분재일 수 있다.The organic material may be a combustible material composed of carbon or hydrogen, moisture, or ash.

본 발명의 일 실시예에 따르면, 상기 (a-7) 증발된 유기성 물질을 회수하는 단계에서,According to one embodiment of the present invention, in the step (a-7) of recovering the evaporated organic material,

상기 증발된 유기성 물질을 회수하는 장치는 응축기, 쿨링타워, 냉동기, 열교환기 또는 다관식 열교환기일 수 있다.The device for recovering the evaporated organic material may be a condenser, cooling tower, refrigerator, heat exchanger, or shell-and-tube heat exchanger.

본 발명의 일 실시예에 따르면, 상기 (a-8) 수득된 건조 파쇄물을 상온까지 냉각하는 단계에서,According to one embodiment of the present invention, in the step (a-8) of cooling the obtained dried shreds to room temperature,

상기 수득된 건조 파쇄물을 냉각하는 장치는 폐쇄형 냉각 장치에서 수행되고,The apparatus for cooling the obtained dried crushed material is carried out in a closed cooling apparatus,

상기 폐쇄형 냉각 장치는 Rotary Type, Tunnel Type, 및 Box Type 중에서 선택된 적어도 어느 하나일 수 있다. The closed cooling device may be at least one selected from Rotary Type, Tunnel Type, and Box Type.

본 발명의 일 실시예에 따르면, 상기 (a-8) 수득된 건조 파쇄물을 상온까지 냉각하는 단계에서,According to one embodiment of the present invention, in the step (a-8) of cooling the obtained dried shreds to room temperature,

상기 냉각은 상기 폐쇄형 냉각 장치에서 15 ℃ 내지 30 ℃ 의 온도에서 냉매를 활용한 간접냉각방식으로 수행될 수 있다.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.

본 발명의 일 실시예에 따르면, 상기 (a-8) 수득된 건조 파쇄물을 상온까지 냉각하는 단계에서,According to one embodiment of the present invention, in the step (a-8) of cooling the obtained dried shreds to room temperature,

상기 폐쇄형 냉각장치에서 배출되는 폐전지 파쇄물은 25 ℃ 내지 40 ℃ 로 배출될 수 있다.The waste battery shredded material discharged from the closed cooling device may be discharged at a temperature of 25°C to 40°C.

본 발명의 일 실시예에 따르면, 상기 (a-9) 수득된 파쇄물을 분쇄 및 선별하는 단계에서, According to one embodiment of the present invention, in the step (a-9) of pulverizing and selecting the obtained shredded material,

상기 분쇄기는 로드밀, 핀밀, 볼밀, 튜브밀, 포트밀, 롤러밀, 터보밀, 임펙트밀, 컷밀 또는 타워밀 일 수 있다.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.

본 발명의 일 실시예에 따르면, 상기 (a-9) 수득된 파쇄물을 분쇄 및 선별하는 단계에서, According to one embodiment of the present invention, in the step (a-9) of pulverizing and selecting the obtained shredded material,

분쇄된 리튬이차전지 폐기물의 크기는 10 ㎛ 내지 15 mm 일 수 있다.The size of the pulverized lithium secondary battery waste may be 10 ㎛ to 15 mm.

본 발명의 일 실시예에 따르면, 상기 (a-9) 수득된 파쇄물을 분쇄 및 선별하는 단계에서, According to one embodiment of the present invention, in the step (a-9) of pulverizing and selecting the obtained shredded material,

상기 선별기는 중력선별기, 비중선별기, 진동선별기, 자력선별기, 정전선별기, 풍력선별기, 부유선별기, 또는 광학선별기 일 수 있다.The separator may be a gravity separator, specific gravity separator, vibration separator, magnetic separator, electrostatic separator, wind separator, flotation separator, or optical separator.

본 발명의 일 실시예에 따르면, 상기 (a-9) 수득된 파쇄물을 분쇄 및 선별하는 단계에서, According to one embodiment of the present invention, in the step (a-9) of pulverizing and selecting the obtained shredded material,

상기 선별로 폐전지를 양극활물질(Catohde), 음극활물질(Anode), 구리(Cu), 및 알루미늄(Al) 중에서 선택된 적어도 어느 그룹으로 선별할 수 있다. Through the above sorting, 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).

본 발명의 일 실시예에 따르면, 상기 (a-9) 수득된 파쇄물을 분쇄 및 선별하는 단계에서, According to one embodiment of the present invention, in the step (a-9) of pulverizing and selecting the obtained shredded material,

상기 분쇄 및 선별로 회수한 유가 금속 분말은 리튬, 니켈, 망간, 코발트, 철, 알루미늄, 및 구리 중에서 선택된 적어도 어느 하나의 유가금속의 화합물 일 수 있다.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.

본 발명의 일 실시예에 따르면, 상기 폐전지는 전기자동차 폐전지, 에너지저장장치(ESS) 폐전지, 전자제품 폐전지, 및 휴대폰 폐전지 중에서 선택된 적어도 어느 하나의 리튬이차전지 일 수 있다.According to one embodiment of the present invention, 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.

본 발명의 일 실시예에 따르면, 상기 폐전지는 양극활물질(Cathode), 음극활물질(Anode), 분리막(Separator), 구리 극판(Cu foil), 알루미늄 극판(Al foil) 및 전해질 (Electrolyte)을 포함할 수 있다.According to one embodiment of the present invention, 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.

본 발명에 따르면, 본 발명은 폐전지의 불순물 제어와 전해액 회수를 위한 리튬이차전지 재활용 공정을 위한 전처리 방법을 제공하므로, 리튬이차전지 재활용 비용이 절감되고, 전처리 공정 효율이 높고, 물질 재활용율을 높일 수 있다.According to 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, 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.

또한, 본 발명은 폐전지 전처리 중 파쇄, 건조 공정 내 화재 및 폭발을 방지하고 증발된 유기성 화합물을 연소장치 없이 오일, 가스, 또는 회분재 형태로 회수함으로써 친환경적인 폐전지 전처리 방법을 제공할 수 있다. In addition, 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. .

본 발명의 효과는 상기한 효과로 한정되는 것은 아니며, 본 발명의 상세한 설명 또는 특허청구범위에 기재된 발명의 구성으로부터 추론 가능한 모든 효과를 포함하는 것으로 이해되어야 한다.The effects of the present invention are not limited to the effects described above, but should be understood to include all effects that can be inferred from the configuration of the invention described in the detailed description or claims of the present invention.

도 1은 본 발명의 일 실시예에 따른 리튬이차전지 재활용 공정을 위한 전처리 방법의 공정흐름도이다.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.

이하 첨부된 도면을 참조하면서 본 발명에 따른 바람직한 실시예를 상세히 설명하기로 한다.Hereinafter, preferred embodiments according to the present invention will be described in detail with reference to the attached drawings.

본 발명의 이점 및 특징, 그리고 그것을 달성하는 방법은 첨부된 도면과 함께 상세하게 후술되어 있는 실시예들을 참조하면 명확해질 것이다.The advantages and features of the present invention and how to achieve it will become clear by referring to the embodiments described in detail below along with the accompanying drawings.

그러나 본 발명은 이하에 개시되는 실시예들에 의해 한정되는 것이 아니라 서로 다른 다양한 형태로 구현될 것이며, 단지 본 실시예들은 본 발명의 개시가 완전하도록 하며, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게 발명의 범주를 완전하게 알려주기 위해 제공되는 것이며, 본 발명은 청구항의 범주에 의해 정의될 뿐이다.However, the present invention is not limited to the embodiments disclosed below, but will be implemented in various different forms. These embodiments only serve to ensure that the disclosure of the present invention is complete and are within the scope of common knowledge in the technical field to which the present invention pertains. It is provided to fully inform those who have the scope of the invention, and the present invention is only defined by the scope of the claims.

또한, 본 발명을 설명함에 있어 관련된 공지 기술 등이 본 발명의 요지를 흐리게 할 수 있다고 판단되는 경우 그에 관한 자세한 설명은 생략하기로 한다.Additionally, in describing the present invention, if it is determined that related known techniques may obscure the gist of the present invention, detailed description thereof will be omitted.

이하, 본 발명을 상세히 설명한다. Hereinafter, the present invention will be described in detail.

리튬이차전지 재활용 공정을 위한 전처리 방법Pretreatment method for lithium secondary battery recycling process

본 발명은 폐전지의 불순물 제어와 전해액 회수를 위한 리튬이차전지 재활용 공정을 위한 전처리 방법을 제공한다.The present invention provides a pretreatment method for the lithium secondary battery recycling process for controlling impurities in waste batteries and recovering electrolyte solution.

리튬이차전지 재활용 공정을 위한 전처리 방법으로,As a pretreatment method for the lithium secondary battery recycling process,

(a-1) 폐리튬이차전지 모듈 또는 폐리튬이차전지 팩을 전기적 방전시켜 방전된 폐리튬이차전지 모듈 또는 폐리튬이차전지 팩을 수득하는 단계;(a-1) electrically discharging a waste lithium secondary battery module or a waste lithium secondary battery pack to obtain a discharged waste lithium secondary battery module or a waste lithium secondary battery pack;

(a-2) 상기 폐리튬이차전지 팩을 폐리튬이차전지 모듈로 해체하는 단계; (a-2) dismantling the waste lithium secondary battery pack into a waste lithium secondary battery module;

(a-3) 상기 폐리튬이차전지 모듈을 단자컷팅하여 폐리튬이차전지 셀을 제조하고, 상기 폐리튬이차전지 셀/단자 및 플라스틱을 분리하는 단계;(a-3) 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;

(a-4) 상기 폐리튬이차전지 셀을 펀칭하는 단계;(a-4) punching the waste lithium secondary battery cell;

(a-5) 밀폐형 질소 파쇄기에 질소를 투입하고, 상기 펀칭된 폐리튬이차전지 셀을 파쇄하여 파쇄물을 수득하는 단계;(a-5) introducing nitrogen into a closed nitrogen shredder and crushing the punched waste lithium secondary battery cell to obtain shredded material;

(a-6) 상기 수득된 파쇄물을 폐쇄형 건조로에 질소를 투입하며 열을 가하여 유기성 물질을 증발시키고 파쇄물을 건조하는 단계;(a-6) adding nitrogen to the obtained crushed material in a closed drying furnace and applying heat to evaporate the organic substances and dry the crushed material;

(a-7) 상기 증발된 유기성 물질을 회수하는 단계;(a-7) recovering the evaporated organic material;

(a-8) 상기 수득된 건조 파쇄물을 상온까지 냉각하는 단계; 및(a-8) cooling the obtained dried crushed material to room temperature; and

(a-9) 상기 수득된 파쇄물을 분쇄 및 선별하는 단계;를 포함하고, (a-9) pulverizing and selecting the obtained crushed material;

상기 리튬이차전지 재활용 공정을 위한 전처리 방법은 상기 폐쇄형 건조로에 질소를 투입하고, 상기 폐쇄형 관 내부의 온도를 일정하게 유지한 후 상기 파쇄물에 열을 가하여, 상기 폐전지의 유기성 물질을 효과적으로 증발시켜 회수함으로써, 상기 폐전지의 불순물 제어를 가져올 수 있다.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.

본 발명은 폐전지의 폐전지의 불순물 제어와 전해액 회수를 위한 리튬이차전지 재활용 공정을 위한 전처리 방법을 제공하므로, 리튬이차전지 재활용 비용이 절감되고, 전처리 공정 효율이 높고, 물질 재활용율을 높일 수 있다.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.

또한, 본 발명은 폐전지 전처리 중 파쇄, 건조 공정 내 화재 및 폭발을 방지하고 증발된 유기성 화합물을 연소장치 없이 오일, 가스, 또는 회분재 형태로 회수함으로써 친환경적인 폐전지 전처리 방법을 제공할 수 있다. In addition, 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. .

국내 전기자동차 보급은 2018년 누적 기준 약 5.7만대이며 대한민국 정부는"2030년 국가 로드맵"을 통해 2030년까지 300만대로 확대할 계획으로, 향후 전기 자동차에서 발생되는 폐전지의 규모 역시 크게 증가할 것으로 예상된다. Domestic electric vehicle distribution is approximately 57,000 units as of 2018, and the Korean government plans to expand it to 3 million units by 2030 through the “2030 National Roadmap,” and the volume of waste batteries generated from electric vehicles is expected to increase significantly in the future. It is expected.

전기자동차에 사용되는 리튬이차전지는 소형 IT기기에 사용되는 전지와 구성이 동일하며, 양극활물질(Cathode), 음극활물질(Anode), 분리막(Separator), 전해질 (Electrolyte) 등으로 구성되어 있다.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.

소형 리튬이차전지의 양극활물질로는 우수한 방전 및 고용량 특성을 가진 LiCoO2(이하 LCO)가 사용되고 있고, 중·대형 리튬이차 전지용 양극활물질은 저렴한 가격과 고출력의 장점으로 Li[NixAlyCoz]O2(NCA) 및 Li[NixCoyMnz]O2(NCM) 등이 사용되고 있다.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.

일반적으로, 리튬이차전지 재활용 공정은 폐전지의 양극활물질로부터 고가의 유가금속을 추출하는 것을 말하며, 대부분의 유가금속은 수입에 의존하고 있어, 리튬이차전지 재활용 공정으로 안정적인 재료 확보가 필요하다.In general, 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.

이러한 리튬이차전지 재활용 공정에서 배터리 건조 공정을 수행하여 전처리하고 있다. In this lithium secondary battery recycling process, a battery drying process is performed for pretreatment.

종래의 건조 진행 시 장치 내 화재 발생으로 인하여 내부 온도의 불균일성이 발생하고, 이에 따른 Cu는 취성이 증가하고, Al은 산화되어 불순물 (Cu, Al 등)이 다량 혼입되는 문제점이 있다.During conventional drying, a fire occurs within the device, resulting in non-uniformity of internal temperature, resulting in increased brittleness of Cu and oxidation of Al, which causes a large amount of impurities (Cu, Al, etc.) to be mixed.

또한, 열처리 온도를 낮추는 경우 배터리 내부 유기성 물질이 제거되지 않는 문제점이 있다.Additionally, there is a problem in that organic substances inside the battery are not removed when the heat treatment temperature is lowered.

그리고, 기존 공정에는 1차 연소 후 2차 연소를 통해 발생하는 가스(탄화수소)를 CO2로 배출하여 탄소중립 및 친환경 관점에서 불리한 면이 있다.In addition, the existing process is disadvantageous from a carbon neutral and eco-friendly perspective because gas (hydrocarbons) generated through secondary combustion after primary combustion is emitted as CO 2 .

본 출원인은 각고의 노력과 여러 연구를 통하여 상기 문제점들을 해결한 폐전지의 불순물 제어와 전해액 회수를 위한 리튬이차전지 재활용 공정을 위한 전처리 방법을 획득하여 본 발명을 완성하게 되었다.Through hard work and various studies, 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.

여기서, 상기 리튬이차전지 재활용 공정을 위한 전처리 방법은 상기 폐쇄형 건조로에 질소를 투입하고, 상기 폐쇄형 관 내부의 온도를 일정하게 유지한 후 상기 파쇄물에 열을 가하여, 상기 폐전지의 유기성 물질을 효과적으로 증발시켜 회수함으로써, 상기 폐전지의 불순물 제어를 가져올 수 있다.Here, 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.

그리고, 상기 (a-1) 폐리튬이차전지 모듈 또는 폐리튬이차전지 팩을 전기적 방전시켜 방전된 폐리튬이차전지 모듈 또는 폐리튬이차전지 팩을 수득하는 단계에서,And, 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,

상기 전기적 방전은 1.5 ~ 3 시간 방전한 후 24 시간 쇼트할 수 있다.The electrical discharge may be short-circuited for 24 hours after discharging for 1.5 to 3 hours.

여기서, 상기 전기적 방전 시간이 상기 범위 내인 경우, 방전 효율이 우수할 수 있다.Here, when the electrical discharge time is within the above range, discharge efficiency may be excellent.

또한, 상기 (a-3) 폐리튬이차전지 모듈을 단자컷팅하여 폐리튬이차전지 셀을 제조하고, 상기 폐리튬이차전지 셀/단자 및 플라스틱을 분리하는 단계에서,In addition, in the 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,

상기 단자커팅은 단자컷팅기를 사용하고,The terminal cutting uses a terminal cutter,

상기 단자컷팅기를 이용하여 상기 폐리튬이차전지 셀/단자 및 플라스틱을 분리하며,Separate the waste lithium secondary battery cells/terminals and plastic using the terminal cutter,

상기 단자컷팅기는 절연단자컷팅기, 금속컷팅기, 또는 고속절단기를 포함할 수 있다.The terminal cutter may include an insulated terminal cutter, a metal cutter, or a high-speed cutter.

그리고, 상기 (a-4) 폐리튬이차전지 셀을 펀칭하는 단계에서, And, in the step (a-4) of punching the waste lithium secondary battery cell,

상기 펀칭으로 물리적 방전할 수 있다.Physical discharge can be achieved by the above punching.

여기서, 상기 전기적 방전과 상기 펀칭의 물리적 방전으로 방전 공정을 완성할 수 있다.Here, the discharge process can be completed with the electrical discharge and the physical discharge of the punching.

또한, 상기 (a-5) 밀폐형 질소 파쇄기에 질소를 투입하고, 상기 펀칭된 폐리튬이차전지 셀을 파쇄하여 파쇄물을 수득하는 단계에서,In addition, 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,

상기 파쇄는 슈레더, 조크러셔(jaw crusher), 또는 콘크러셔(cone crusher)를 사용할 수 있다.The crushing can be done using a shredder, jaw crusher, or cone crusher.

그리고, 상기 (a-5) 밀폐형 질소 파쇄기에 질소를 투입하고 상기 펀칭된 폐리튬이차전지 셀을 파쇄하여 파쇄물을 수득하는 단계에서,And, 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,

상기 밀폐형 질소 파쇄기는 질소분위기의 컨베이어를 통해 투입될 수 있다.The closed nitrogen shredder can be introduced through a conveyor in a nitrogen atmosphere.

여기서, 상기 밀폐형 질소 파쇄기는 밀폐 상태에서 연속적으로 질소를 공급받을 수 있다.Here, the closed nitrogen shredder can continuously receive nitrogen in a closed state.

또한, 상기 (a-5) 밀폐형 질소 파쇄기에 질소를 투입하고 상기 펀칭된 폐리튬이차전지 셀을 파쇄하여 파쇄물을 수득하는 단계에서,In addition, 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,

상기 밀폐형 질소 파쇄기는 2단 질소 파쇄기이고,The closed nitrogen shredder is a two-stage nitrogen shredder,

상기 2단 질소 파쇄기의 1차 크기는 가로 30~60 mm와 세로 130~200 mm 이고, 2차 크기는 가로 15~30 mm와 세로 20~130 mm 일 수 있다.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.

여기서, 상기 밀폐형 질소 파쇄기의 상기 2단 질소 파쇄기의 크기가 상기 범위 내인 경우, 파쇄 효율이 월등할 수 있고, 파쇄하여 표면적을 높여 후속 열처리 효율을 높일 수 있다.Here, when 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.

그리고, 상기 (a-6) 수득된 파쇄물을 폐쇄형 건조로에 질소를 투입하며 열을 가하여 유기성 물질을 증발시키고 폐전지 파쇄물을 건조 회수하는 단계에서,In the 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,

상기 질소는 질소 슈레더를 거쳐 밀폐형 이송컨베이어를 통과하여 상기 폐쇄형 건조로에 투입될 수 있다.The nitrogen may pass through a nitrogen shredder, a closed transfer conveyor, and then be introduced into the closed drying furnace.

여기서, 상기 질소는 질소 슈레더를 거쳐 밀폐형 이송컨베이어를 통과하기에 폐쇄형 건조로에 상기 수득된 파쇄물이 투입되는 경우, 산소 농도를 용이하게 제어할 수 있다.Here, 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.

이때, 상기 질소는 일부 잔존용량(SOC, State of Charge) 잔류 배터리의 파쇄 중 화재, 폭발 방지를 목적으로 질소를 투입하며, 이에 따라 설비 내 산소는 0.1 ~ 10 부피%로 유지할 수 있다.At this time, 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.

또한, 상기 (a-6) 수득된 파쇄물을 폐쇄형 건조로에 질소를 투입하며 열을 가하여 유기성 물질을 증발시키고 폐전지 파쇄물을 건조 회수하는 단계에서,In addition, in the 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,

상기 유기성 물질 증발은 질소가 투입된 상기 폐쇄형 건조로에서 수행되고,The organic material evaporation is performed in the closed drying furnace into which nitrogen is introduced,

상기 폐쇄형 건조로는 로터리 킬른(rotary kiln), 로터리 드라이어(rotary dryer), 터널로(Tunnel furnace), 대차로(box furnace) 및 밀폐구조가 가능한 로(furnace) 중에서 선택된 적어도 어느 하나일 수 있다.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.

그리고, 상기 (a-6) 수득된 파쇄물을 폐쇄형 건조로에 질소를 투입하며 열을 가하여 유기성 물질을 증발시키고 폐전지 파쇄물을 건조 회수하는 단계에서,In the 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,

상기 유기성 물질의 증발은 100 ℃ 내지 800 ℃의 온도에서 간접 가열방식으로 수행될 수 있다.Evaporation of the organic material may be performed by indirect heating at a temperature of 100°C to 800°C.

여기서, 상기 유기성 물질의 증발 온도가 상기 범위를 벗어나는 경우, 유기성 물질의 증발 효율이 감소하고, 폐전지 건조 분말의 회수가 어려울 수 있다.Here, when the evaporation temperature of the organic material is outside the above range, the evaporation efficiency of the organic material decreases, and recovery of the spent battery dry powder may be difficult.

이때, 상기 유기성 물질의 증발 온도는 바람직하게는 200 ℃ 내지 700 ℃ 일 수 있고, 보다 바람직하게는 300 ℃ 내지 600 ℃ 일 수 있다.At this time, the evaporation temperature of the organic material may be preferably 200°C to 700°C, and more preferably 300°C to 600°C.

또한, 상기 유기성 물질을 증발할 때, 상기 폐쇄성 관에 질소를 투입하여 유기성 물질을 증발시킴에 의해, 상기 유기성 물질을 화재, 폭발 없이 증발시킬 수 있다.In addition, when evaporating the organic material, nitrogen is introduced into the closed pipe to evaporate the organic material, so that the organic material can be evaporated without fire or explosion.

그리고, 상기 간접 가열방식은 급격한 온도 상승을 억제하여 유기성 물질의 증발 효율이 증가하고, 폐전지 건조 분말의 회수가 용이할 수 있다.In addition, 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.

또한, 상기 폐쇄성 관에 질소를 투입하여 유기성 물질을 증발시킴에 의해, 폐전지의 전처리 온도를 균일하게 유지하여 폐전지 분말 내 유기성 물질을 효과적으로 증발시킴으로써, 대기방지시설을 통한 유기성 물질의 회수를 가능하게 할 수 있다.In addition, by evaporating organic substances by injecting nitrogen into the closed pipe, 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.

그리고, 상기 폐쇄성 관에 질소를 투입하여 유기성 물질을 증발시킴에 의해, 다음의 문제점을 해결할 수 있다.Also, by introducing nitrogen into the closed tube to evaporate organic substances, the following problems can be solved.

즉, 기존 파쇄 공정과 건조 공정에서는 완전 방전이 되지 않은 셀의 화재, 폭발 가능성으로 인한 작업 안전성이 떨어지며, 내부 화재 발생 시 공정 내 물질이 설계된 온도 이상(1,000 ℃ 이상)으로 건조되어 양극재 외 원치 않는 불순물들의 혼입이 이루어지고 습식 공정에서 이를 제어하기 위한 약품 소모량이 증가한다.In other words, in the existing crushing and drying processes, work safety is reduced due to the possibility of fire or explosion in cells that are not fully discharged, and in the event of an internal fire, the materials in the process are dried above the designed temperature (over 1,000 ℃), causing waste other than the cathode material to be destroyed. Unexpected impurities are mixed and the amount of chemicals consumed to control them increases in the wet process.

또한, 상기 (a-6) 수득된 파쇄물을 폐쇄형 건조로에 질소를 투입하며 열을 가하여 유기성 물질을 증발시키고 폐전지 파쇄물을 건조 회수하는 단계에서,In addition, in the 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,

상기 유기성 물질은 탄소 또는 수소로 구성된 가연물질, 수분, 또는 회분재일 수 있다.The organic material may be a combustible material composed of carbon or hydrogen, moisture, or ash.

여기서, 상기 유기성 물질 100 중량%에 대하여 상기 가연물질 50 ~ 95 중량%, 수분 0.5 ~ 35 중량%, 또는 회분재 0.2 ~ 30 중량%로 구성될 수 있다.Here, based on 100% by weight of the organic material, it 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.

또한, 상기 (a-7) 증발된 유기성 물질을 회수하는 단계에서,In addition, in the step (a-7) of recovering the evaporated organic material,

상기 증발된 유기성 물질을 회수하는 장치는 응축기, 쿨링타워, 냉동기, 열교환기 또는 다관식 열교환기일 수 있다.The device for recovering the evaporated organic material may be a condenser, cooling tower, refrigerator, heat exchanger, or shell-and-tube heat exchanger.

여기서, 상기 증발된 유기성 물질을 회수하는 장치는 온도 차이에 의해 증발된 유기성 물질을 회수할 수 있다.Here, the device for recovering the evaporated organic material may recover the evaporated organic material due to a temperature difference.

이때, 상기 증발된 유기성 물질을 회수하는 장치는 복수개를 사용할 수 있다.At this time, a plurality of devices for recovering the evaporated organic material may be used.

그리고, 상기 증발된 유기성 물질은 상기 회수 장치를 통해 오일, 가스, 또는 회분재 형태로 회수되며, 상기 증발된 유기성 물질 100 중량%에 대하여 각각의 비율은 상기 오일이 올레핀계 화합물(CO, CH4, H2, CO2, CnHn)로 가스상성분 10~20중량%, 액상성분 50~70 중량%, 회분 10~20 중량% 일 수 있다.In addition, 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.

또한, 상기 (a-8) 수득된 건조 파쇄물을 상온까지 냉각하는 단계에서In addition, in the step (a-8) of cooling the obtained dried crushed material to room temperature,

상기 수득된 건조 파쇄물을 냉각하는 장치는 폐쇄형 냉각 장치에서 수행되고,The apparatus for cooling the obtained dried crushed material is carried out in a closed cooling apparatus,

상기 폐쇄형 냉각 장치는 Rotary Type, Tunnel Type, 및 Box Type 중에서 선택된 적어도 어느 하나일 수 있다.The closed cooling device may be at least one selected from Rotary Type, Tunnel Type, and Box Type.

여기서, 상기 폐쇄성 냉각 장치에 건조 파쇄물을 투입하여 상온까지 냉각시킴에 의해, 다음의 문제점을 해결할 수 있다.Here, the following problems can be solved by adding dried shredded material to the closed cooling device and cooling it to room temperature.

즉, 200 ℃ 내지 600 ℃에서 건조된 파쇄품의 이송 시스템이 높은 온도로 인해 소모품 교환이 잦게 되며, 공장 가동률도 저하시킨다.In other words, 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.

여기서, 상기 (a-8) 수득된 건조 파쇄물을 상온까지 냉각하는 단계에서,Here, in the step of cooling the dried crushed material obtained in (a-8) to room temperature,

상기 냉각은 상기 폐쇄형 냉각 장치에서 15 ℃ 내지 30 ℃ 의 온도에서 냉매를 활용한 간접냉각방식으로 수행될 수 있다.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.

또한, 상기 (a-8) 수득된 건조 파쇄물을 상온까지 냉각하는 단계에서,In addition, in the step (a-8) of cooling the obtained dried crushed material to room temperature,

상기 폐쇄형 냉각장치에서 배출되는 폐전지 파쇄물은 25 ℃ 내지 40 ℃ 로 배출될 수 있다.The waste battery shredded material discharged from the closed cooling device may be discharged at a temperature of 25°C to 40°C.

그리고, 상기 (a-9) 수득된 파쇄물을 분쇄 및 선별하는 단계에서, And, in the step (a-9) of pulverizing and selecting the obtained shredded material,

상기 분쇄기는 로드밀, 핀밀, 볼밀, 튜브밀, 포트밀, 롤러밀, 터보밀, 임펙트밀, 컷밀 또는 타워밀 일 수 있다.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.

또한, 상기 (a-9) 수득된 파쇄물을 분쇄 및 선별하는 단계에서, In addition, in the step (a-9) of grinding and selecting the obtained shredded material,

분쇄된 리튬이차전지 폐기물의 크기는 10 ㎛ 내지 15 mm 일 수 있다.The size of the pulverized lithium secondary battery waste may be 10 ㎛ to 15 mm.

여기서, 상기 분쇄된 리튬이차전지 폐기물의 입도가 크기가 상기 범위를 벗어나는 경우, 상기 리튬이차전지 재활용 공정을 위한 전처리 방법에서 폐전지의 불순물 제어가 어려울 수 있다.Here, when 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.

이때, 상기 분쇄된 분쇄된 리튬이차전지 폐기물의 크기는 바람직하게는 15 ㎛ 내지 15 mm 일 수 있고, 보다 바람직하게는 20 ㎛ 내지 10 mm 일 수 있다.At this time, the size of the pulverized lithium secondary battery waste may preferably be 15 ㎛ to 15 mm, and more preferably 20 ㎛ to 10 mm.

그리고, 상기 (a-9) 수득된 파쇄물을 분쇄 및 선별하는 단계에서, And, in the step (a-9) of pulverizing and selecting the obtained shredded material,

상기 선별기는 중력선별기, 비중선별기, 진동선별기, 자력선별기, 정전선별기, 풍력선별기, 부유선별기, 또는 광학선별기 일 수 있다.The separator may be a gravity separator, specific gravity separator, vibration separator, magnetic separator, electrostatic separator, wind separator, flotation separator, or optical separator.

또한, 상기 (a-9) 수득된 파쇄물을 분쇄 및 선별하는 단계에서, In addition, in the step (a-9) of grinding and selecting the obtained shredded material,

상기 선별로 폐전지를 양극활물질(Catohde), 음극활물질(Anode), 구리(Cu), 및 알루미늄(Al) 중에서 선택된 적어도 어느 그룹으로 선별할 수 있다. Through the above sorting, 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).

그리고, 상기 (a-9) 수득된 파쇄물을 분쇄 및 선별하는 단계에서, And, in the step (a-9) of pulverizing and selecting the obtained shredded material,

상기 분쇄 및 선별로 회수한 유가 금속 분말은 리튬, 니켈, 망간, 코발트, 철, 알루미늄, 및 구리 중에서 선택된 적어도 어느 하나의 유가금속의 화합물 일 수 있다.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.

따라서, 본 발명은 폐전지 전처리 중 파쇄, 건조 공정 내 화재 및 폭발을 방지하고 증발된 유기성 화합물을 오일, 가스, 또는 회분재 형태로 회수함으로써 습식공정에서의 불순물 제거 목적 약품 소모량을 감소시키고, 유기성 화합물을 연소장치 없이 회수함으로써 친환경적인 폐전지 전처리 공정을 제공할 수 있다.Therefore, 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.

그리고, 상기 폐전지는 전기자동차 폐전지, 에너지저장장치(ESS) 폐전지, 전자제품 폐전지, 및 휴대폰 폐전지 중에서 선택된 적어도 어느 하나의 리튬이차전지일 수 있다.In addition, 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.

또한, 상기 폐전지는 양극활물질(Cathode), 음극활물질(Anode), 분리막(Separator), 구리 극판(Cu foil), 알루미늄 극판(Al foil) 및 전해질 (Electrolyte)을 포함할 수 있다.Additionally, the waste battery may include a cathode, a cathode, a separator, a copper foil, an aluminum foil, and an electrolyte.

도 1은 본 발명의 일 실시예에 따른 리튬이차전지 재활용 공정을 위한 전처리 방법의 공정흐름도이다. 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.

도 1을 참조하면, 폐리튬이차전지 모듈 또는 폐리튬이차전지 팩을 전기적 방전시켜 방전된 폐리튬이차전지 모듈 또는 폐리튬이차전지 팩을 수득한다(S110). Referring to FIG. 1, 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).

그 후, 상기 폐리튬이차전지 팩을 폐리튬이차전지 모듈로 해체한다(S120). Afterwards, the waste lithium secondary battery pack is dismantled into a waste lithium secondary battery module (S120).

그런 다음, 상기 폐리튬이차전지 모듈을 단자컷팅하여 폐리튬이차전지 셀을 제조하고, 상기 폐리튬이차전지 셀/단자 및 플라스틱을 분리한다(S130). Then, 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).

그 후, 상기 폐리튬이차전지 셀을 펀칭한다(S140). Afterwards, the waste lithium secondary battery cell is punched (S140).

그런 다음, 밀폐형 질소 파쇄기에 질소를 투입하고, 상기 펀칭된 폐리튬이차전지 셀을 파쇄하여 파쇄물을 수득한다(S150).Then, nitrogen is introduced into a closed nitrogen shredder, and the punched waste lithium secondary battery cell is shredded to obtain shredded material (S150).

그 후, 상기 수득된 파쇄물을 폐쇄형 건조로에 질소를 투입하며 열을 가하여 유기성 물질을 증발시키고 폐전지 건조 파쇄물을 회수한다(S160).Afterwards, nitrogen is added to the obtained shredded material in a closed drying furnace and heat is applied to evaporate organic substances and recover the dried shredded waste battery (S160).

그 후, 상기 증발된 유기성 물질을 회수한다(S170).Afterwards, the evaporated organic material is recovered (S170).

그 후, 상기 폐전지 건조 파쇄물을 상온까지 냉각한다(S180)Afterwards, the dried waste battery shredded material is cooled to room temperature (S180).

그런 다음, 상기 상온의 건조 파쇄물을 분쇄 및 선별하여 유가 금속 분말을 회수한다(S190)Then, the dried shredded material at room temperature is pulverized and selected to recover valuable metal powder (S190)

이하에서, 실시예를 통하여 본 발명을 보다 상세히 설명한다. 그러나, 하기의 실시예는 본 발명을 더욱 구체적으로 설명하기 위한 것으로서, 본 발명의 범위가 하기의 실시예에 의하여 한정되는 것은 아니다. 하기의 실시예는 본 발명의 범위 내에서 당업자에 의해 적절히 수정, 변경될 수 있다.Below, the present invention will be described in more detail through examples. However, the following examples are intended to illustrate the present invention in more detail, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

<준비예> <Preparation example>

분리막, 전해액, 바인더 등을 포함한 유기성 물질이 20 ~ 30 중량% 정도인 전기자동차용 리튬이차전지, ESS용 리튬이차전지 및 IT 용 리튬이차전지 폐기물을 폐전지로 준비하였다.Waste from lithium secondary batteries for electric vehicles, lithium secondary batteries for ESS, and lithium secondary batteries for IT, which contain about 20 to 30% by weight of organic materials including separators, electrolytes, binders, etc., were prepared as waste batteries.

<실시예> <Example>

<실시예 1> 리튬이차전지 재활용 공정을 위한 전처리 공정<Example 1> Pretreatment process for lithium secondary battery recycling process

하기 표 1의 리튬이차전지 재활용 공정을 위한 전처리 공정으로 준비예의 전기자동차용 리튬이차전지 1 kg을 방전시켜 방전된 리튬이차전지 폐기물을 수득하였다. As a pretreatment process for the lithium secondary battery recycling process shown in Table 1 below, 1 kg of the lithium secondary battery for an electric vehicle of the preparation example was discharged to obtain discharged lithium secondary battery waste.

그 후, 밀폐형 파쇄기에 질소를 투입하고 상기 방전된 리튬이차전지 폐기물을 슈레더를 이용하여 60 mm 정도로 파쇄하여 파쇄물을 수득하였다.Afterwards, nitrogen was introduced into a closed shredder, and the discharged lithium secondary battery waste was shredded to about 60 mm using a shredder to obtain shredded material.

그런 다음, 상기 수득된 파쇄물을 로터리 타입 건조기로 500 ℃로 간접 가열하는 방식으로 건조하며, 상기 로터리 킬른(rotary kiln)의 폐쇄형 건조로에 질소를 투입하여 설비내 산소 함량을 1 부피% 이하로 유지하면서 유기성 물질을 증발시키고 폐전지 건조 파쇄품을 회수하였다.Then, 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.

그 후, 상기 증발된 유기성 물질을 응축기로 회수하였다.Afterwards, the evaporated organic material was recovered with a condenser.

그런 다음, 고온의 건조 파쇄품을 냉각하여 상온까지 냉각시켰다.Then, the hot dry shredded product was cooled to room temperature.

그 후, 건조 파쇄물을 분쇄 및 선별하여 유가금속 분말을 회수하였다.Afterwards, the dried crushed material was pulverized and selected to recover valuable metal powder.

그리고, 상기 폐전지 건조 유가금속 분말 내 Cu 함량과 Al 함량을 각각 분석하였다.In addition, the Cu content and Al content in the dried valuable metal powder from the waste battery were analyzed, respectively.

<실시예 2 ~ 실시예 7> 리튬이차전지 재활용 공정을 위한 전처리 공정<Example 2 to Example 7> Pretreatment process for lithium secondary battery recycling process

하기 표 1의 리튬이차전지 재활용 공정을 위한 전처리 공정을 사용하는 것을 제외하고 실시예 1과 동일한 방법을 사용하여 준비예의 폐전지를 전처리 하였다. 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.

<비교예 1> 리튬이차전지 재활용 공정을 위한 전처리 공정<Comparative Example 1> Pretreatment process for lithium secondary battery recycling process

질소를 사용하지 않는 것(대기 분위기)과 파쇄물 크기(30 mm)를 제외하고는 실시예 1과 동일한 방법으로 폐전지를 전처리 하였다. 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.

<비교예 2> 리튬이차전지 재활용 공정을 위한 전처리 공정<Comparative Example 2> Pretreatment process for lithium secondary battery recycling process

질소를 사용하지 않는 것(대기 분위기)을 제외하고는 실시예 4와 동일한 방법으로 준비예의 폐전지를 전처리 하였다. The waste battery of the preparation example was pretreated in the same manner as Example 4, except that nitrogen was not used (atmospheric atmosphere).

공정process 실시예 1Example 1 실시예 2Example 2 실시예 3Example 3 실시예 4Example 4 실시예 5Example 5 실시예 6Example 6 실시예 7Example 7 비교예 1Comparative Example 1 비교예 2Comparative Example 2 폐전지타입Waste battery type 전기자동차용 폐전지Waste batteries for electric vehicles 전기자동차용 폐전지Waste batteries for electric vehicles ESS용 폐전지Waste batteries for ESS ESS용 폐전지Waste batteries for ESS 전기자동차용 폐전지Waste batteries for electric vehicles IT용 폐전지Waste batteries for IT IT용 폐전지Waste batteries for IT 전기자동차용 폐전지Waste batteries for electric vehicles ESS용 폐전지Waste batteries for ESS 폐쇄형 건조로 closed drying furnace 로터리 킬른rotary kiln 로터리 킬른rotary kiln 로터리 킬른rotary kiln 로터리 킬른rotary kiln Box furnaceBox furnace 로터리 킬른rotary kiln Box furnaceBox furnace 로터리 킬른rotary kiln 로터리 킬른rotary kiln 가스분위기gas atmosphere 질소nitrogen 질소nitrogen 질소nitrogen 질소nitrogen 질소nitrogen 질소nitrogen 질소nitrogen 대기atmosphere 대기atmosphere 파쇄장치crushing device 슈레더shredder 슈레더shredder 슈레더shredder 슈레더shredder 슈레더shredder 슈레더shredder 슈레더shredder 슈레더shredder 슈레더shredder 파쇄물 크기(mm)Shredded material size (mm) 6060 3030 6060 3030 5050 3030 5050 3030 3030 건조온도(℃)Drying temperature (℃) 500500 500500 500500 500500 400400 500500 400400 500500 500500 가열방식Heating method 간접가열indirect heating 간접가열indirect heating 간접가열indirect heating 간접가열indirect heating 간접가열indirect heating 간접가열indirect heating 간접가열indirect heating 간접가열indirect heating 간접가열indirect heating 유기성 물질 회수장치Organic material recovery device 응축기condenser 응축기condenser 응축기condenser 응축기condenser 열교환기heat exchanger 응축기condenser 냉동기freezer 응축기condenser 응축기condenser 건조분말 내 Cu 함량
(중량%)Cu content in dry powder
(weight%) 0.90.9 0.70.7 1.21.2 1One 1One 0.90.9 1.21.2 33 44 건조분말 내 Al 함량(중량%)Al content in dry powder (% by weight) 0.50.5 0.40.4 0.80.8 0.70.7 0.70.7 0.60.6 0.50.5 55 66

<평가예> <Evaluation example>

<평가예 1> 리튬이차전지 재활용 공정을 위한 전처리 공정 평가 - 화재 및 폭발<Evaluation Example 1> Evaluation of pretreatment process for lithium secondary battery recycling process - Fire and explosion

상기 실시예 1 ~ 실시예 4는 상기 비교예 1 및 비교예 2에 비하여, 상기 폐쇄형 건조로에 질소를 투입하면서 간접가열 방식으로 유기성 물질을 증발시키므로, 설비 가동시 화재 및 폭발이 발생하지 않았다.In Examples 1 to 4, compared to Comparative Examples 1 and 2, organic materials were evaporated through indirect heating while nitrogen was introduced into the closed drying furnace, so no fire or explosion occurred during facility operation.

그러나, 상기 비교예 1 및 비교예 2는 설비 내 산소의 함량이 많아 설비 가동시 화재 및 폭발 위험성이 현저하였다.However, in Comparative Examples 1 and 2, the oxygen content in the equipment was high, so there was a significant risk of fire and explosion when the equipment was in operation.

<평가예 2> 리튬이차전지 재활용 공정을 위한 전처리 공정 평가 - 습식 공정에서의 불순물 제거 목적 약품 사용량<Evaluation Example 2> Evaluation of pretreatment process for lithium secondary battery recycling process - Amount of chemical used for removal of impurities in wet process

상기 실시예 1 ~ 실시예 4는 상기 비교예 1 및 비교예 2에 비하여, 상기 폐쇄형 건조로에 질소를 투입하면서 간접가열 방식으로 유기성 물질을 증발시키므로, 증발된 유기성 화합물은 오일, 가스, 또는 회분재 형태로 회수가 가능하고 건조된 분말은 습식공정에서 불순물을 제거하기 위한 약품사용량이 현저하게 감소하였다.In 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.

그러나, 상기 비교예 1 및 상기 비교예 2는 질소를 사용하지 않아, 유기성 물질을 용이하게 제거하기 어려워, 습식공정에서의 불순물 제거 목적 약품 사용량이 현저히 증가하였다.However, 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.

<분석예> 리튬이차전지 재활용 공정을 위한 전처리 공정에 의해 회수된 유기성 물질<Analysis example> Organic materials recovered through the pretreatment process for the lithium secondary battery recycling process

상기 실시예 1의 리튬이차전지 재활용 공정을 위한 전처리 공정에 의해 회수된 유기성 물질을 기체 크로마토그래피(GC, Gas Chromatography)로 분석하였고, 상기 증발된 유기성 물질은 옥텐 오일 210 g, 일산화탄소 및 메탄 가스 75 g 및 회분재 15 g 이였다.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.

지금까지 본 발명에 따른 리튬이차전지 재활용 공정을 위한 전처리 방법에 관한 구체적인 실시예에 관하여 설명하였으나, 본 발명의 범위에서 벗어나지 않는 한도 내에서는 여러 가지 실시 변형이 가능함은 자명하다.So far, specific embodiments of the pretreatment method for the lithium secondary battery recycling process according to the present invention have been described, but it is obvious that various implementation modifications are possible without departing from the scope of the present invention.

그러므로 본 발명의 범위는 설명된 실시예에 국한되어 정해져서는 안 되며, 후술하는 특허청구범위뿐만 아니라 이 특허청구범위와 균등한 것들에 의해 정해져야 한다.Therefore, the scope of the present invention should not be limited to the described embodiments, but should be determined by the claims and equivalents thereof as well as the claims described later.

즉, 전술된 실시예는 모든 면에서 예시적인 것이며, 한정적인 것이 아닌 것으로 이해되어야 하며, 본 발명의 범위는 상세한 설명보다는 후술될 특허청구범위에 의하여 나타내어지고, 그 특허청구범위의 의미 및 범위 그리고 그 등가 개념으로부터 도출되는 모든 변경 또는 변형된 형태가 본 발명의 범위에 포함되는 것으로 해석되어야 한다.That is, the above-described embodiments should be understood in all respects as illustrative and not restrictive, and the scope of the present invention is indicated by the claims to be described later rather than the detailed description, and the meaning and scope of the claims and All changes or modified forms derived from the equivalent concept should be construed as falling within the scope of the present invention.

본 발명은 리튬이차전지 재활용 산업에 이용될 수 있다. The present invention can be used in the lithium secondary battery recycling industry.

Claims (22)

리튬이차전지 재활용 공정을 위한 전처리 방법으로,As a pretreatment method for the lithium secondary battery recycling process, (a-1) 폐리튬이차전지 모듈 또는 폐리튬이차전지 팩을 전기적 방전시켜 방전된 폐리튬이차전지 모듈 또는 폐리튬이차전지 팩을 수득하는 단계;(a-1) electrically discharging a waste lithium secondary battery module or a waste lithium secondary battery pack to obtain a discharged waste lithium secondary battery module or a waste lithium secondary battery pack; (a-2) 상기 폐리튬이차전지 팩을 폐리튬이차전지 모듈로 해체하는 단계; (a-2) dismantling the waste lithium secondary battery pack into a waste lithium secondary battery module; (a-3) 상기 폐리튬이차전지 모듈을 단자컷팅하여 폐리튬이차전지 셀을 제조하고, 상기 폐리튬이차전지 셀/단자 및 플라스틱을 분리하는 단계;(a-3) 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; (a-4) 상기 폐리튬이차전지 셀을 펀칭하는 단계;(a-4) punching the waste lithium secondary battery cell; (a-5) 밀폐형 질소 파쇄기에 질소를 투입하고, 상기 펀칭된 폐리튬이차전지 셀을 파쇄하여 파쇄물을 수득하는 단계;(a-5) introducing nitrogen into a closed nitrogen shredder and crushing the punched waste lithium secondary battery cell to obtain shredded material; (a-6) 상기 수득된 파쇄물을 폐쇄형 건조로에 질소를 투입하며 열을 가하여 유기성 물질을 증발시키고 파쇄물을 건조하는 단계; (a-6) adding nitrogen to the obtained crushed material in a closed drying furnace and applying heat to evaporate the organic substances and dry the crushed material; (a-7) 상기 증발된 유기성 물질을 회수하는 단계;(a-7) recovering the evaporated organic material; (a-8) 상기 수득된 건조 파쇄물을 상온까지 냉각하는 단계; 및(a-8) cooling the obtained dried crushed material to room temperature; and (a-9) 상기 수득된 파쇄물을 분쇄 및 선별하는 단계;를 포함하고, (a-9) pulverizing and selecting the obtained crushed material; 상기 리튬이차전지 재활용 공정을 위한 전처리 방법은 상기 폐쇄형 건조로에 질소를 투입하고, 상기 폐쇄형 관 내부의 온도를 일정하게 유지한 후 상기 파쇄물에 열을 가하여, 상기 폐전지의 유기성 물질을 효과적으로 증발시켜 회수함으로써, 상기 폐전지의 불순물 제어를 가져오는The 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. 리튬이차전지 재활용 공정을 위한 전처리 방법.Pretreatment method for lithium secondary battery recycling process. 제 1 항에 있어서, According to claim 1, 상기 (a-1) 폐리튬이차전지 모듈 또는 폐리튬이차전지 팩을 전기적 방전시켜 방전된 폐리튬이차전지 모듈 또는 폐리튬이차전지 팩을 수득하는 단계에서,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, 상기 전기적 방전은 1.5 ~ 3 시간 방전한 후 24 시간 쇼트하는 것을 특징으로 하는The electrical discharge is characterized in that it is discharged for 1.5 to 3 hours and then short-circuited for 24 hours. 리튬이차전지 재활용 공정을 위한 전처리 방법.Pretreatment method for lithium secondary battery recycling process. 제 1 항에 있어서,According to claim 1, 상기 (a-3) 폐리튬이차전지 모듈을 단자컷팅하여 폐리튬이차전지 셀을 제조하고, 상기 폐리튬이차전지 셀/단자 및 플라스틱을 분리하는 단계에서,In the 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, 상기 단자커팅은 단자컷팅기를 사용하고,The terminal cutting uses a terminal cutter, 상기 단자컷팅기를 이용하여 상기 폐리튬이차전지 셀/단자 및 플라스틱을 분리하며,Separate the waste lithium secondary battery cells/terminals and plastic using the terminal cutter, 상기 단자컷팅기는 절연단자컷팅기, 금속컷팅기, 또는 고속절단기를 포함하는 것을 특징으로 하는The terminal cutter is characterized in that it includes an insulated terminal cutter, a metal cutter, or a high-speed cutter. 리튬이차전지 재활용 공정을 위한 전처리 방법.Pretreatment method for lithium secondary battery recycling process. 제 1 항에 있어서,According to claim 1, 상기 (a-4) 폐리튬이차전지 셀을 펀칭하는 단계에서, In the step (a-4) of punching the waste lithium secondary battery cell, 상기 펀칭으로 물리적 방전하는 것을 특징으로 하는 Characterized by physical discharge through the punching 리튬이차전지 재활용 공정을 위한 전처리 방법.Pretreatment method for lithium secondary battery recycling process. 제 1 항에 있어서, According to claim 1, 상기 (a-5) 밀폐형 질소 파쇄기에 질소를 투입하고, 상기 펀칭된 폐리튬이차전지 셀을 파쇄하여 파쇄물을 수득하는 단계에서,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, 상기 파쇄는 슈레더, 조크러셔(jaw crusher), 또는 콘크러셔(cone crusher)를 사용하는 것을 특징으로 하는The crushing is characterized by using a shredder, jaw crusher, or cone crusher. 리튬이차전지 재활용 공정을 위한 전처리 방법.Pretreatment method for lithium secondary battery recycling process. 제 1 항에 있어서, According to claim 1, 상기 (a-5) 밀폐형 질소 파쇄기에 질소를 투입하고 상기 펀칭된 폐리튬이차전지 셀을 파쇄하여 파쇄물을 수득하는 단계에서,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, 상기 밀폐형 질소 파쇄기는 질소분위기의 컨베이어를 통해 투입되는 것을 특징으로 하는The closed nitrogen shredder is characterized in that it is introduced through a conveyor in a nitrogen atmosphere. 리튬이차전지 재활용 공정을 위한 전처리 방법.Pretreatment method for lithium secondary battery recycling process. 제 1 항에 있어서, According to claim 1, 상기 (a-5) 밀폐형 질소 파쇄기에 질소를 투입하고 상기 펀칭된 폐리튬이차전지 셀을 파쇄하여 파쇄물을 수득하는 단계에서,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, 상기 밀폐형 질소 파쇄기는 2단 질소 파쇄기이고,The closed nitrogen shredder is a two-stage nitrogen shredder, 상기 2단 질소 파쇄기의 1차 크기는 가로 30~60 mm와 세로 130~200 mm 이고, 2차 크기는 가로 15~30 mm와 세로 20~130 mm 인 것을 특징으로 하는The primary size of the two-stage nitrogen crusher is 30 to 60 mm in width and 130 to 200 mm in height, and the secondary size is 15 to 30 mm in width and 20 to 130 mm in height. 리튬이차전지 재활용 공정을 위한 전처리 방법.Pretreatment method for lithium secondary battery recycling process. 제 1 항에 있어서, According to claim 1, 상기 (a-6) 수득된 파쇄물을 폐쇄형 건조로에 질소를 투입하며 열을 가하여 유기성 물질을 증발시키고 폐전지 파쇄물을 건조 회수하는 단계에서,In the 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, 상기 질소는 질소 슈레더를 거쳐 밀폐형 이송컨베이어를 통과하여 상기 폐쇄형 건조로에 투입되는 것을 특징으로 하는The nitrogen passes through a nitrogen shredder, a closed transfer conveyor, and is then introduced into the closed drying furnace. 리튬이차전지 재활용 공정을 위한 전처리 방법.Pretreatment method for lithium secondary battery recycling process. 제 1 항에 있어서, According to claim 1, 상기 (a-6) 수득된 파쇄물을 폐쇄형 건조로에 질소를 투입하며 열을 가하여 유기성 물질을 증발시키고 폐전지 파쇄물을 건조 회수하는 단계에서,In the 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, 상기 유기성 물질 증발은 질소가 투입된 상기 폐쇄형 건조로에서 수행되고,The organic material evaporation is performed in the closed drying furnace into which nitrogen is introduced, 상기 폐쇄형 건조로는 로터리 킬른(rotary kiln), 로터리 드라이어(rotary dryer), 터널로(Tunnel furnace), 대차로(box furnace) 및 밀폐구조가 가능한 로(furnace) 중에서 선택된 적어도 어느 하나인 것을 특징으로 하는 The closed drying furnace is characterized in that it is at least one selected from a rotary kiln, a rotary dryer, a tunnel furnace, a box furnace, and a furnace capable of a sealed structure. doing 리튬이차전지 재활용 공정을 위한 전처리 방법.Pretreatment method for lithium secondary battery recycling process. 제 1 항에 있어서, According to claim 1, 상기 (a-6) 수득된 파쇄물을 폐쇄형 건조로에 질소를 투입하며 열을 가하여 유기성 물질을 증발시키고 폐전지 파쇄물을 건조 회수하는 단계에서,In the 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, 상기 유기성 물질의 증발은 100 ℃ 내지 800 ℃의 온도에서 간접 가열방식으로 수행되는 것을 특징으로 하는 Characterized in that the evaporation of the organic material is carried out by indirect heating at a temperature of 100 ℃ to 800 ℃. 리튬이차전지 재활용 공정을 위한 전처리 방법.Pretreatment method for lithium secondary battery recycling process. 제 1 항에 있어서, According to claim 1, 상기 (a-6) 수득된 파쇄물을 폐쇄형 건조로에 질소를 투입하며 열을 가하여 유기성 물질을 증발시키고 폐전지 파쇄물을 건조 회수하는 단계에서,In the 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, 상기 유기성 물질은 탄소 또는 수소로 구성된 가연물질, 수분, 또는 회분재인 것을 특징으로 하는 The organic material is characterized in that it is a combustible material composed of carbon or hydrogen, moisture, or ash. 리튬이차전지 재활용 공정을 위한 전처리 방법.Pretreatment method for lithium secondary battery recycling process. 제 1 항에 있어서, According to claim 1, 상기 (a-7) 증발된 유기성 물질을 회수하는 단계에서,In the step (a-7) of recovering the evaporated organic material, 상기 증발된 유기성 물질을 회수하는 장치는 응축기, 쿨링타워, 냉동기, 열교환기 또는 다관식 열교환기인 것을 특징으로 하는 The device for recovering the evaporated organic material is a condenser, cooling tower, refrigerator, heat exchanger, or shell-and-tube heat exchanger. 리튬이차전지 재활용 공정을 위한 전처리 방법.Pretreatment method for lithium secondary battery recycling process. 제 1 항에 있어서, According to claim 1, 상기 (a-8) 수득된 건조 파쇄물을 상온까지 냉각하는 단계에서,In the step (a-8) of cooling the obtained dried crushed material to room temperature, 상기 수득된 건조 파쇄물을 냉각하는 장치는 폐쇄형 냉각 장치에서 수행되고,The apparatus for cooling the obtained dried crushed material is carried out in a closed cooling apparatus, 상기 폐쇄형 냉각 장치는 Rotary Type, Tunnel Type, 및 Box Type 중에서 선택된 적어도 어느 하나인 것을 특징으로 하는 The closed cooling device is characterized in that at least one selected from Rotary Type, Tunnel Type, and Box Type. 리튬이차전지 재활용 공정을 위한 전처리 방법.Pretreatment method for lithium secondary battery recycling process. 제 1 항에 있어서, According to claim 1, 상기 (a-8) 수득된 건조 파쇄물을 상온까지 냉각하는 단계에서,In the step (a-8) of cooling the obtained dried shreds to room temperature, 상기 냉각은 상기 폐쇄형 냉각 장치에서 15 ℃ 내지 30 ℃ 의 온도에서 냉매를 활용한 간접냉각방식으로 수행되는 것을 특징으로 하는The cooling is characterized in that it is performed by indirect cooling using a refrigerant at a temperature of 15 ℃ to 30 ℃ in the closed cooling device. 리튬이차전지 재활용 공정을 위한 전처리 방법.Pretreatment method for lithium secondary battery recycling process. 제 1 항에 있어서, According to claim 1, 상기 (a-8) 수득된 건조 파쇄물을 상온까지 냉각하는 단계에서,In the step (a-8) of cooling the obtained dried crushed material to room temperature, 상기 폐쇄형 냉각장치에서 배출되는 폐전지 파쇄물은 25 ℃ 내지 40 ℃로 배출되는 것을 특징으로 하는The waste battery shredded material discharged from the closed cooling device is characterized in that it is discharged at a temperature of 25 ℃ to 40 ℃. 리튬이차전지 재활용 공정을 위한 전처리 방법.Pretreatment method for lithium secondary battery recycling process. 제 1 항에 있어서, According to claim 1, 상기 (a-9) 수득된 파쇄물을 분쇄 및 선별하는 단계에서, In the step (a-9) of grinding and selecting the obtained shredded material, 상기 분쇄기는 로드밀, 핀밀, 볼밀, 튜브밀, 포트밀, 롤러밀, 터보밀, 임펙트밀, 컷밀 또는 타워밀인 것을 특징으로 하는The crusher is characterized in that it is a rod mill, pin mill, ball mill, tube mill, port mill, roller mill, turbo mill, impact mill, cut mill, or tower mill. 리튬이차전지 재활용 공정을 위한 전처리 방법.Pretreatment method for lithium secondary battery recycling process. 제 1 항에 있어서, According to claim 1, 상기 (a-9) 수득된 파쇄물을 분쇄 및 선별하는 단계에서, In the step (a-9) of grinding and selecting the obtained shredded material, 분쇄된 리튬이차전지 폐기물의 크기는 10 ㎛ 내지 15 mm 인 것을 특징으로 하는The size of the pulverized lithium secondary battery waste is 10 ㎛ to 15 mm. 리튬이차전지 재활용 공정을 위한 전처리 방법.Pretreatment method for lithium secondary battery recycling process. 제 1 항에 있어서, According to claim 1, 상기 (a-9) 수득된 파쇄물을 분쇄 및 선별하는 단계에서, In the step (a-9) of grinding and selecting the obtained shredded material, 상기 선별기는 중력선별기, 비중선별기, 진동선별기, 자력선별기, 정전선별기, 풍력선별기, 부유선별기, 또는 광학선별기인 것을 특징으로 하는The separator is characterized in that it is a gravity separator, specific gravity separator, vibration separator, magnetic separator, electrostatic separator, wind separator, flotation separator, or optical separator. 리튬이차전지 재활용 공정을 위한 전처리 방법.Pretreatment method for lithium secondary battery recycling process. 제 1 항에 있어서, According to claim 1, 상기 (a-9) 수득된 파쇄물을 분쇄 및 선별하는 단계에서, In the step (a-9) of grinding and selecting the obtained shredded material, 상기 선별로 양극활물질(Cathode), 음극활물질(Anode), 구리(Cu), 및 알루미늄(Al) 중에서 선택된 적어도 어느 그룹으로 선별하는 것을 특징으로 하는Characterized in that the selection is performed on at least one group selected from a cathode active material (Cathode), a negative electrode active material (Anode), copper (Cu), and aluminum (Al). 리튬이차전지 재활용 공정을 위한 전처리 방법.Pretreatment method for lithium secondary battery recycling process. 제 1 항에 있어서, According to claim 1, 상기 (a-9) 수득된 파쇄물을 분쇄 및 선별하는 단계에서, In the step (a-9) of grinding and selecting the obtained shredded material, 상기 분쇄 및 선별로 회수한 유가 금속 분말은 리튬, 니켈, 망간, 코발트, 철, 알루미늄, 및 구리 중에서 선택된 적어도 어느 하나의 유가금속의 화합물인 것을 특징으로 하는 The valuable metal powder recovered by grinding and screening is a compound of at least one valuable metal selected from lithium, nickel, manganese, cobalt, iron, aluminum, and copper. 리튬이차전지 재활용 공정을 위한 전처리 방법.Pretreatment method for lithium secondary battery recycling process. 제 1 항에 있어서, According to claim 1, 상기 폐전지는 전기자동차 폐전지, 에너지저장장치(ESS) 폐전지, 전자제품 폐전지, 및 휴대폰 폐전지 중에서 선택된 적어도 어느 하나의 리튬이차전지인 것을 특징으로 하는 The waste battery is 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. 리튬이차전지 재활용 공정을 위한 전처리 방법.Pretreatment method for lithium secondary battery recycling process. 제 1 항에 있어서, According to claim 1, 상기 폐전지는 양극활물질(Cathode), 음극활물질(Anode), 분리막(Separator), 구리 극판(Cu foil), 알루미늄 극판(Al foil) 및 전해질 (Electrolyte)을 포함하는 것을 특징으로 하는 The waste battery is characterized in that it contains 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. 리튬이차전지 재활용 공정을 위한 전처리 방법.Pretreatment method for lithium secondary battery recycling process.
PCT/KR2023/020290 2022-12-13 2023-12-11 Pretreatment method for lithium secondary battery recycling Ceased WO2024128714A1 (en)

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KR1020230177986A KR102703136B1 (en) 2022-12-13 2023-12-08 Pre-treatment method for lithium secondary battery recycling process
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JP2013080595A (en) * 2011-10-03 2013-05-02 Dowa Eco-System Co Ltd Method for recovering valuable from lithium ion secondary battery
JP2015170480A (en) * 2014-03-07 2015-09-28 松田産業株式会社 Method for recovering valuable materials from lithium ion secondary batteries
KR101803859B1 (en) * 2017-08-09 2017-12-04 주식회사 현대특수로 apparatus for recycling metal of battery
KR101830312B1 (en) * 2017-09-21 2018-02-21 성일하이텍㈜ Firing apparatus for battery
JP2022049364A (en) * 2020-09-16 2022-03-29 Ｄｏｗａエコシステム株式会社 Method for recovering valuable materials from lithium ion secondary battery
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KR102447931B1 (en) * 2022-01-04 2022-09-28 (주)에코프로머티리얼즈 How to recycle waste batteries in an eco-friendly way
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KR20010107009A (en) * 2000-05-24 2001-12-07 곽영훈 Valuable metal extraction method from the exhausted li-ion secondary battery
JP2013080595A (en) * 2011-10-03 2013-05-02 Dowa Eco-System Co Ltd Method for recovering valuable from lithium ion secondary battery
JP2015170480A (en) * 2014-03-07 2015-09-28 松田産業株式会社 Method for recovering valuable materials from lithium ion secondary batteries
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JP2022049364A (en) * 2020-09-16 2022-03-29 Ｄｏｗａエコシステム株式会社 Method for recovering valuable materials from lithium ion secondary battery
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