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WO2025135713A1 - Stabilisateur de batterie et système de stabilisation de batterie - Google Patents

Stabilisateur de batterie et système de stabilisation de batterie Download PDF

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Publication number
WO2025135713A1
WO2025135713A1 PCT/KR2024/020450 KR2024020450W WO2025135713A1 WO 2025135713 A1 WO2025135713 A1 WO 2025135713A1 KR 2024020450 W KR2024020450 W KR 2024020450W WO 2025135713 A1 WO2025135713 A1 WO 2025135713A1
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WO
WIPO (PCT)
Prior art keywords
battery
temperature
shreds
weight
waste battery
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.)
Pending
Application number
PCT/KR2024/020450
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English (en)
Korean (ko)
Inventor
이주승
박종력
김학
김천
신용목
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Posco Holdings Inc
Original Assignee
Posco Holdings Inc
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Filing date
Publication date
Application filed by Posco Holdings Inc filed Critical Posco Holdings Inc
Publication of WO2025135713A1 publication Critical patent/WO2025135713A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4207—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells for several batteries or cells simultaneously or sequentially
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using 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 waste batteries, a battery stabilization device and a battery stabilization system.
  • lithium secondary batteries which are the main raw materials of said waste batteries, organic solvents, explosive substances, and heavy metals such as Ni, Co, Mn, and Fe are contained, but in the case of Ni, Co, Mn, and Li, they have high scarcity value as valuable metals, and the recovery and recycling process after the lithium secondary batteries are discarded is emerging as an important research field.
  • a lithium secondary battery mainly consists of copper and aluminum used as a current collector, Li, Ni, Co, Mn-containing oxides constituting a cathode material, and graphite utilized as an anode material, and includes a separator separating the cathode material and the anode material, and an electrolyte injected into the separator.
  • the solvent and salt used as the electrolyte are mainly a mixture of carbonate organic substances such as ethylene carbonate and propylene carbonate, and LiPF 6 is used as a representative salt.
  • waste battery recycling process that crushes the waste batteries to produce intermediate materials such as waste battery shreds or black powder, and then recovers valuable metals through a post-process.
  • the waste battery in the waste battery recycling process, generally has a voltage in the range of 3.0 to 3.2 V in a fully discharged state per cell, and a voltage close to 4 V in a fully charged state, although this may vary depending on the number of times the battery has been used or its condition. Therefore, modules or packs in which tens to hundreds of cells are connected have a considerable amount of energy in this residual voltage, and thus, when physically disassembling the waste battery by applying an external shock, safety related to explosion or electric shock of the battery becomes an issue.
  • the salt used in the brine discharge contains a large amount of substances such as Na, K, Cl, Mg, and Ca.
  • Cl in particular is partially removed during the high-temperature heat treatment process, but the black powder, which is a powder in the form of a mixture of oxides of Ni-Co-Mn-Li-O and C obtained by further processing the shredded material or shredded material of the waste battery to remove Al, Cu, and a part of the separator, contains impurities such as Na, K, and Mg, which causes a problem of reducing the recovery rate during the extraction process using acid leaching in the subsequent process of the battery recycling process.
  • a battery stabilization device that stably removes electrolyte from waste battery shreds, thereby reducing the content of impurities and preventing fire.
  • a battery stabilization system that stably removes electrolyte from waste battery shreds, thereby reducing the content of impurities and preventing fire.
  • a battery stabilization device includes an input unit for inputting a sagger into which waste battery shreds are input, a transport unit for transporting the sagger into which the waste battery shreds are input, a first stabilization unit for stabilizing the waste battery shreds at a temperature of 30° C. or lower, a second stabilization unit for stabilizing the waste battery shreds passing through the first stabilization unit at a temperature of 30 to 150° C., and a discharge unit for discharging the stabilized waste battery shreds, wherein the sagger may include a hot air inlet for supplying heat to the waste battery shreds.
  • the first stabilizing unit may include a compressor. In one embodiment, the first stabilizing unit may include at least one weight and temperature measuring unit for measuring the weight of the waste battery shreds.
  • the weight and temperature measuring unit may include a first weight and temperature measuring unit disposed between the input port and the first stabilizing unit, a second weight and temperature measuring unit disposed between the first stabilizing unit and the second stabilizing unit, and a third weight and temperature measuring unit disposed between the second stabilizing unit and the discharge unit.
  • the second stabilizing unit includes an intermediate stabilizing unit and a high-temperature stabilizing unit, and the intermediate stabilizing unit may heat the waste battery shreds in a range of 30 to 120° C., and the high-temperature stabilizing unit may heat the waste battery shreds in a range of 120 to 150° C.
  • the hot air inlet is arranged in the shape of a cylinder, a triangular prism, a square prism, or a polygonal prism, and can emit heat through the outer surface of the shape.
  • the hot air inlet includes a plurality of hot air inlets, and the spacing between the plurality of hot air inlets can be 35 to 45% based on the horizontal length of the saga.
  • the height of the hot air inlet can be from 25% to 50% of the height of the saga. In one embodiment, the height of the hot air inlet can be from 25% to 50% of the height of the saga.
  • the saga may have a structure with an open upper surface.
  • the saga may include a housing surrounding a side of the saga, and may include a mesh portion and a sealing portion disposed below the mesh portion.
  • a battery stabilization treatment system may include a first step of controlling a tap density of waste battery shreds, a second step of measuring a first weight as an initial weight and a first temperature as an initial temperature of the waste battery shreds, a third step of stabilizing the waste battery shreds at a temperature of 30° C.
  • the first step can control the tap density of the waste battery shreds to 200 to 1,400 kg/m 3 .
  • the fifth step can be performed when the first weight and the first temperature of the waste battery shreds measured in the second step and the second weight and the second temperature of the waste battery shreds measured in the fourth step satisfy the following equations 1 and 2.
  • Second temperature - First temperature ⁇ 25 °C
  • the seventh step can be performed.
  • the size of the unit waste battery shreds based on the long axis, which is the longest axis among the horizontal, vertical, and height directions, is 100 mm or less.
  • Figure 2 illustrates a Sagger according to one embodiment of the present invention.
  • Figure 4 shows the change in voltage of a battery according to cooling temperature according to one embodiment of the present invention.
  • Figures 9a to 9c are photographs showing the temperature measurement process of a waste battery and the temperature trend of the shredded material according to the SOC conditions.
  • FIG. 11 is a graph showing the temperature of waste battery shreds over time in low-temperature stabilization, intermediate stage, and high-temperature stabilization stages according to one embodiment of the present invention.
  • Figure 12 is a graph showing the self-heating of battery waste inside a transport vessel.
  • Figure 14 shows the weight reduction ratio (%) of the electrolyte in the shredded waste according to the heat treatment temperature of 150°C after high-temperature stabilization treatment of the shredded waste battery.
  • Figure 15 shows the temperature and weight reduction according to the tap density of battery shreds.
  • Figure 16 shows a graph of the heating rate according to the spacing of hot air inlets.
  • Figure 17 shows a graph of temperature versus time according to the spacing of the hot air inlet and the spacing of the sealing part.
  • first, second, and third, etc. are used to describe, but are not limited to, various parts, components, regions, layers, and/or sections. These terms are only used to distinguish one part, component, region, layer, or section from another part, component, region, layer, or section. Thus, a first part, component, region, layer, or section described below may be referred to as a second part, component, region, layer, or section without departing from the scope of the present invention.
  • FIG. 1A is a perspective view of a battery stabilization device according to one embodiment of the present invention
  • FIG. 1B is a schematic diagram of a battery stabilization device according to one embodiment of the present invention.
  • a battery stabilization device is a device for stabilizing waste battery waste, and may include an inlet section, a transport section, a first stabilization section, a second stabilization section, a weight and temperature measurement section, and a discharge section.
  • the inlet may be a member into which waste battery shreds are fed.
  • the waste battery shreds may be a result of shredding waste batteries.
  • the transport unit may be a member for transporting the saga into which the waste battery shreds have been inserted within the battery stabilization device.
  • the transport unit may be a member for guiding the saga including the waste battery shreds to be discharged through the first stabilization unit and the second stabilization unit to the discharge unit.
  • the transport unit may be a structure arranged in the form of a conveyor belt, for example.
  • the first stabilizing unit can perform stabilization of the waste battery shreds at a low temperature. Specifically, the first stabilizing unit can perform stabilization of the waste battery shreds by transporting the waste battery shreds while being accommodated in the saga and applying hot air to the saga.
  • the first stable portion may include a first heater portion at the bottom.
  • the first heater portion may supply heat to the bottom of the saga.
  • the first heater portion may supply hot air to the saga to heat the waste battery shreds disposed within the saga.
  • the first stabilizing unit can stabilize the waste battery shreds at a temperature of 30° C. or lower. More specifically, the first stabilizing unit can be a member in which the waste battery shreds self-heat and are stabilized. The first stabilizing unit can prevent a problem in which sudden heat generation occurs and a fire may occur when the SoC (State of Charge), which indicates the remaining capacity of the waste battery shreds, is 30% or higher.
  • SoC State of Charge
  • the first stabilizer may include a high-temperature air dryer for supplying air with minimized moisture.
  • the first stabilizer may be a member that supplies dry air from which moisture has been removed while maintaining a temperature of 5 to 20° C., specifically 5 to 15° C.
  • the heater may be a device that creates dry air.
  • the first stabilizer may include a compressor.
  • the compressor may be a screw compressor for forming dry air.
  • the compressor may form a pressure of less than 10 bar.
  • the first stabilizing unit may further include a first vibrating unit. Specifically, the first vibrating unit may be controlled to vibrate and disperse the battery shreds when the first stabilizing unit applies hot air to the battery shreds, thereby allowing heat to be applied evenly to the battery shreds.
  • the second stabilizing unit can perform stabilization of the waste battery shreds at high temperatures. Specifically, the second stabilizing unit can perform stabilization of the waste battery shreds by transporting the waste battery shreds while being accommodated in the saga, and applying hot air to the saga to volatilize the high-temperature volatile electrolyte that has not been volatilized in the first stabilizing unit.
  • the second stable portion may include a second heater portion at the bottom.
  • the second heater portion may supply heat to the bottom of the saga.
  • the second heater portion may supply hot air to the saga to heat the waste battery shreds disposed within the saga.
  • the second stabilizing member may be a member that stabilizes the waste battery shreds at a temperature of 30 to 150° C.
  • the second stabilizing member heats the waste battery shreds in the aforementioned temperature range, thereby volatilizing the electrolyte in the waste battery shreds, thereby reducing the weight of the waste battery shreds and decreasing the tap density.
  • the second stabilizing unit may include an intermediate stabilizing unit and a high temperature stabilizing unit.
  • the intermediate stabilizing unit may be a step of heating the waste battery shreds at a temperature lower than that of the high temperature stabilizing unit.
  • the intermediate stabilizing unit may be a member that performs stabilization of the waste battery shreds at a temperature of 30 to 120° C. Since the second stabilizing unit includes the intermediate stabilizing unit, the temperature of the waste battery shreds can be gradually increased to stably volatilize the electrolyte within the waste battery shreds.
  • the high-temperature stabilizing unit may be a member that performs stabilization of the waste battery shreds at a temperature of 120 to 150° C. As the high-temperature stabilizing unit is performed in the above-described range, high-temperature heat may be applied to the waste battery shreds that have been stabilized through the low-temperature stabilization treatment step to volatilize the remaining electrolyte.
  • the second stabilizing unit may further include a second vibrating unit.
  • the first vibrating unit may be controlled to vibrate and disperse the battery shreds when the second stabilizing unit applies hot air to the battery shreds, thereby allowing heat to be applied evenly to the battery shreds.
  • first stabilizer and the second stabilizer may be arranged in a horizontal or stacked structure.
  • the second stabilizer may be stacked on the first stabilizer, and may be arranged subsequent to the first stabilizer on the same line.
  • the first stabilizing member and the second stabilizing member can apply heat to the battery shreds placed within the saga as the saga moves.
  • the weight and temperature measuring member can be a member that measures the weight of the waste battery shreds. Specifically, the weight and temperature measuring member can measure the weight and temperature of the waste battery shreds with devices such as a load cell, a TC, and a thermal imaging camera.
  • the battery stabilization device may include a weight and temperature measuring unit.
  • the weight and temperature measuring unit may include a first weight and temperature measuring unit positioned between the inlet and the first stabilizing unit, a second weight and temperature measuring unit positioned between the first stabilizing unit and the second stabilizing unit, and a third weight and temperature measuring unit positioned between the second stabilizing unit and the discharge unit.
  • the first weight and temperature measuring unit can measure the initial weight and tap density of the waste battery shreds.
  • the first weight and temperature measuring unit can measure the initial weight and tap density of the waste battery shreds.
  • the first weight and temperature measuring unit can be a member that measures the initial weight and temperature of the waste battery shreds to determine whether or not to proceed with the subsequent stabilization treatment.
  • the first weight and temperature measuring unit may be a member that determines whether the temperature of the waste battery shreds is -20 to 10° C. and whether the weight of the waste battery shreds is similar to the weight of the waste battery before shredding.
  • the first weight and temperature measuring unit may be a member that determines whether the weight of the waste battery shreds is 31.75 to 32.25 kg.
  • the waste battery shreds When the temperature and weight of the waste battery shreds are within the above-mentioned ranges, the waste battery shreds can be moved to the first stable section along the transport section. When the temperature and weight of the waste battery shreds are outside the above-mentioned ranges, particularly when the temperature decrease is large due to initial heat generation after shredding, the movement of the waste battery shreds to the first stable section can be prevented in consideration of problems such as fire occurrence in the waste battery shreds.
  • the second weight and temperature measuring unit may be a member that measures the temperature and weight of the waste battery shreds that have passed through the first stabilizing unit. Specifically, the second weight and temperature measuring unit may be a member that determines whether the temperature of the waste battery shreds that have passed through the first stabilizing unit is 10 to 35° C. and whether the weight of the waste battery shreds is 30.65 to 31.15 kg. When the temperature and weight of the waste battery shreds are within the above-described ranges, the waste battery shreds may be moved to the second stabilizing unit along the transport unit. When the temperature and weight of the waste battery shreds are outside the above-described ranges, the movement to the second stabilizing unit may be prevented in consideration of problems such as a fire outbreak in the waste battery shreds.
  • the third weight and temperature measuring unit may be a member that measures the temperature and weight of the waste battery shreds that have passed through the second stabilizing unit. Specifically, the third weight and temperature measuring unit may be a member that determines whether the temperature of the waste battery shreds that have passed through the second stabilizing unit is 100° C. or less and whether the weight of the waste battery shreds is 29.85 kg or less. When the temperature and weight of the waste battery shreds are within the above-described range, the waste battery shreds can be discharged through the discharge unit. When the temperature and weight of the waste battery shreds are outside the above-described range, the waste battery shreds can be prevented from being discharged through the discharge unit in consideration of problems such as the occurrence of a fire.
  • the discharge unit may be a member through which the waste battery shreds that have passed through the second stabilization unit are discharged to a subsequent process.
  • the discharge unit may be a member through which the stabilized waste battery shreds are discharged to a subsequent process. More specifically, the discharge unit discharges the battery shreds to a subsequent process, and the receiving unit that receives the shreds discharged by the battery shreds may be returned to the shredder.
  • the ratio of the sealed portion may be 30 to 80%, specifically, 35 to 70%, and more specifically, 60 to 70%, based on 100% of the height of the saga.
  • a battery stabilization system includes a first step of controlling a tap density of waste battery shreds, a second step of measuring a first weight as an initial weight and a first temperature as an initial temperature of the waste battery shreds, a third step of stabilizing the waste battery shreds at a temperature of 30° C.
  • the first step of controlling the tap density of the waste battery shredded material may be a step of controlling the tap density of the waste battery shredded material to 200 to 1,400 kg/m 3 .
  • the first step may be a step of controlling the tap density of the waste battery shredded material to 500 to 1,000 kg/m 3 .
  • the tap density of the unit waste battery shredder calculated by the above-described method is 200 to 600 kg/ m3 . Specifically, the tap density can be 240 to 400 kg/ m3 .
  • the above tap density exceeds the upper limit, there is a risk of fire due to instantaneous heat generation by the short circuit of the densely stacked pieces of shredded material, and there is a problem of reduced stabilization processing capacity due to the narrow space through which the electrolyte can escape to the outside. If the above tap density exceeds the lower limit, there is a problem of many gaps between the shredded material and the volume is large, requiring an additional pressurization process to transport it to the post-process.
  • the method may include a step of controlling the unit waste battery shreds constituting the waste battery shreds to satisfy the following conditions 1 and 2.
  • the above layered structure is a laminated structure having 1 or more layers and 7 or fewer layers.
  • the size of the unit waste battery shreds based on the long axis, which is the longest axis among the horizontal, vertical, and height directions, is 100 mm or less.
  • the above layered structure includes, for example, one of anode-separator-cathode, anode-separator, separator-anode, separator-cathode, and cathode-separator, and for example, anode-separator-cathode-separator-anode-separator-cathode may have a three-layered layered structure.
  • the unit waste battery shredder may have a predetermined thickness in the thickness direction since at least one or more layers are laminated.
  • the above condition 1 may mean that the layered structure of the unit waste battery shredder including a separator having a positive or negative electrode laminated on at least one surface is controlled in the step of shredding into a layered structure of 1 or more layers and 7 or fewer layers.
  • the layered structure may be a laminated structure having 1 or more layers and 7 or fewer layers.
  • the layered structure may be a laminated structure having 1 or more layers and 5 or fewer layers.
  • the temperature rise amount of the shredded material can be minimized and the heating time can be appropriately taken. If the layered structure is laminated thicker than the upper limit of the above range, the temperature rise amount excessively increases and the heating time also increases, which causes a problem of combustion.
  • the size of the unit waste battery shreds may be controlled in the shredding step to be 100 mm or less, specifically 50 mm or less. If the maximum size of the waste battery shreds is greater than 100 mm, the temperature of the heat generated due to instability as the waste battery shreds are shredded may rise to a temperature range of 120° C., which is the average vaporization temperature of the electrolyte, and thus a problem in stability, such as a fire, may occur.
  • the step of crushing the waste battery may be included.
  • the step of controlling the proportion of the unit waste battery crushed material satisfying the above conditions 1 and 2 to be 90% or more, specifically 95% or more, of the total volume of the waste battery crushed material may be further included.
  • this may correspond to controlling the proportion of the unit waste battery crushed material having a laminated structure exceeding 7 layers to be 10% or less of the total volume of the waste battery crushed material.
  • the proportion of the unit waste battery crushed material having a laminated structure exceeding 7 layers may be controlled to be 5% or less of the total volume of the waste battery crushed material.
  • the step of crushing the waste battery may refer to a process of applying an impact or pressure to the battery so that a part of the battery falls off from the battery.
  • the step of crushing the waste battery may refer to a process of crushing the battery, a process of cutting the battery, a process of compressing the battery, and a combination thereof.
  • the step of crushing may include any process that can destroy the battery to obtain small-sized fragments.
  • the step of crushing the battery may include any process of compressing the frozen battery or destroying the battery by applying an external force, such as a shear force or a tensile force.
  • the step of crushing the battery may be performed, for example, using a crusher.
  • the step of crushing the battery may be performed at least once. Specifically, the step of crushing may be performed at least once, either continuously or discontinuously.
  • the step of crushing the battery can be performed under conditions of supplying an inert gas, carbon dioxide, nitrogen, water, or a combination thereof, or under vacuum conditions of 100 torr or less.
  • an inert gas carbon dioxide, nitrogen, water, or a combination thereof
  • vacuum conditions 100 torr or less.
  • the process of freezing the battery is performed by cooling in a temperature range of -60 to -20° C.
  • the supply of oxygen can be suppressed, preventing the electrolyte from reacting with oxygen, thereby preventing an explosion caused thereby, and vaporization of the electrolyte can be suppressed, so that flammable gases such as ethylene, propylene, or hydrogen cannot be generated.
  • the recovery time required to lower the temperature of the waste battery shreds to a range of 20 to 50° C. in the shredding step may be 200 minutes or less. Specifically, the recovery time required to lower the temperature of the waste battery shreds to a range of 35 to 45° C. may be 200 minutes or less.
  • the second step of measuring the first weight, which is the initial weight of the waste battery shreds, and the first temperature, which is the initial temperature may be a step of measuring the initial weight and the initial temperature of the shredded waste battery shreds.
  • the initial weight of the waste battery shreds may be controlled to 30.65 to 31.15 kg.
  • the initial temperature of the waste battery shreds may be controlled to 10 to 35° C.
  • the surface of the unit waste battery shredder may include a combustion region and a top region.
  • the combustion region means an area where at least a portion of the surface of the unit waste battery shredder is burned, and the top region means a top region on the surface where there are no combustion traces.
  • the area ratio of the combustion portion to the top portion on the surface of the unit waste battery shredded material may be 30% or less.
  • the area ratio of the combustion portion to the top portion may be 30% or less.
  • the waste battery shredder is recovered from a waste battery and includes impurities, and the impurities may include, in weight %, Na, Ca, Mg, and K.
  • the waste battery shredder may be a shred residue or black powder manufactured through a process of recovering and crushing the waste battery, which is a pretreatment process of a waste battery recycling process.
  • the waste battery shredder includes impurities, and the impurities may include, in weight %, Na: 0.4 % or less (excluding 0 %), Ca: 0.03 % or less (excluding 0 %), Mg: 0.02 % or less, and K: 0.02 % or less.
  • Sodium (Na) is a homologous element in the post-process of recovering valuable metals from the spent battery shreds, and has the side effect of lowering the recovery of lithium or increasing the cost in the causticization process by partially reacting sodium instead of lithium in the lithium hydroxide forming process.
  • the spent battery shreds may contain 0.4 wt% or less of sodium, and specifically, may contain 0.1 wt% or less of sodium.
  • the waste battery may include a step of freezing.
  • the step of freezing the waste battery may satisfy the following equation 1.
  • W means the weight of the battery, for example, the weight of a battery pack, a single battery, or a combination thereof.
  • the minimum cooling time means the external cooling temperature, which is the cooling temperature applied to the battery, for example, the target temperature for cooling the electrolyte inside the battery.
  • the step of freezing the waste battery has the advantage of being able to perform subsequent processes stably by cooling the electrolyte inside the battery by performing the step for a time longer than the minimum cooling time.
  • the step of freezing the waste battery has the problem that if the battery is frozen for a time shorter than the minimum cooling time, the electrolyte may not be cooled, which may cause a risk of fire when crushed.
  • the step of freezing the above-mentioned waste battery is performed at a temperature sufficient to freeze the electrolyte contained in the battery.
  • the step of freezing may be performed at a temperature range of, for example, -150 to -20°C. More specifically, the temperature range may be -150 to -50°C, and more specifically, -80 to -60°C.
  • the voltage remaining slightly inside the battery for example, about 2 V to 3 V, is lowered to close to 0 V, so that even if a short circuit occurs in which the positive and negative electrodes are in direct contact, a battery reaction does not occur, so the battery temperature does not increase, and gas generation and combustion of the electrolyte do not occur.
  • the electrolyte since the electrolyte is in a frozen state or a state in which vaporization is suppressed, the mobility of lithium ions is very low, so that the conduction characteristics according to the movement of lithium ions can be significantly reduced, and since vaporization of the electrolyte does not occur, flammable gases such as ethylene, propylene, and hydrogen can not be generated.
  • the battery processing method has the advantage of preventing the risk of fire that may occur in the battery crushing process by including a freezing step before crushing a battery such as a lithium secondary battery.
  • the waste battery shreds can be moved to the first stable section along the transport section.
  • the movement to the first stable section can be prevented in consideration of problems such as the occurrence of a fire in the waste battery shreds.
  • the above low-temperature stabilization treatment step may be a step of stabilizing the crushed waste battery fragments at a temperature of 30° C. or lower.
  • the third step of stabilizing the waste battery fragments at a temperature of 30° C. or lower may be a step of slowly transporting the waste battery fragments in a low-temperature state while removing the electrolyte.
  • the low-temperature stabilization treatment step may be a step in which the shredded waste battery shreds self-heat and are stabilized. More specifically, there is a difference in self-heating of the shreds depending on the condition of the SoC (State of Charge) indicating the remaining capacity of the battery.
  • SoC State of Charge
  • the low-temperature stabilization treatment step may be a preliminary step for stabilizing the battery at a temperature of 10° C or lower to minimize the aforementioned fire risk.
  • the third step which is a low-temperature stabilization step, can be performed for 6 to 24 hours. If the low-temperature stabilization treatment step is outside the upper limit of the above-mentioned time range, the fire risk is minimized, but there is a problem that the manufacturing lead time is lengthened and productivity is reduced. If the low-temperature stabilization treatment step is outside the lower limit of the above-mentioned time range, the electrolyte may not be removed sufficiently safely, which may lead to a problem of a post-process fire.
  • the fourth step of measuring the second weight and the second temperature of the waste battery shreds that have gone through the third step is a step of measuring the weight and temperature of the waste battery shreds that have gone through the low-temperature stabilization step.
  • the third step may be a step of determining whether the waste battery shreds that have gone through the low-temperature stabilization are suitable for high-temperature stabilization.
  • the fifth step which is a high-temperature stabilization step, can be performed.
  • the above equations 1 and 2 represent the weight reduction (%) and temperature difference between the low-temperature stabilized waste battery shreds and the initial waste battery shreds. Specifically, the equation 1 represents the weight reduction after the low-temperature stabilization treatment, and the equation 2 represents the temperature difference before and after the low-temperature stabilization.
  • the waste battery shreds have the advantage of not causing a fire and smoothly evaporating the electrolyte even if a high-temperature stabilization step is performed.
  • the waste battery shreds that have undergone a low-temperature stabilization step cannot perform the subsequent high-temperature stabilization step, and the fourth step, which is a low-temperature stabilization step, can be continued until the conditions of the equations 1 and 2 are satisfied.
  • the fifth step of stabilizing the spent battery shreds that have gone through the fourth step at a temperature of 30 to 150° C. may be a high-temperature stabilization step of the spent battery shreds at a temperature higher than that of the low-temperature stabilization step.
  • the high-temperature stabilization step may be a step of applying high-temperature heat to the spent battery shreds that have been stabilized through the low-temperature stabilization step to volatilize the electrolyte within the spent battery shreds.
  • the intermediate stabilization step can be performed at a temperature higher than the low temperature stabilization treatment step and lower than the high temperature stabilization treatment step. In one embodiment, the intermediate stabilization treatment step can be performed at 30 to 120 °C. In one embodiment, the intermediate stabilization treatment step can be performed by a multi-stage heat treatment. The intermediate stabilization treatment steps can be sequentially performed at 30 to 60 °C, 60 to 90 °C, and 90 to 120 °C.
  • the temperature of the spent battery shreds can be gradually increased to stably volatilize the electrolyte within the spent battery shreds.
  • the high temperature stabilization step may be performed at 120 to 150° C.
  • the high temperature stabilization step may be a step of applying high temperature heat to the spent battery shreds stabilized through the low temperature stabilization step to volatilize the electrolyte within the spent battery shreds.
  • the above high-temperature stabilization step exceeds the upper limit of the above-mentioned temperature range, there is a problem of fire occurrence. If the above high-temperature stabilization step exceeds the lower limit of the above-mentioned temperature range, there is a problem of the electrolyte in the waste battery shreds not being sufficiently volatilized.
  • the high temperature stabilization step can be performed for 5 to 12 hours. If the high temperature stabilization step is outside the upper limit of the above-mentioned time range, there is a problem with productivity due to an increase in manufacturing lead time. If the high temperature stabilization step is outside the lower limit of the above-mentioned time range, there is a problem that the electrolyte is not sufficiently removed, which may cause a fire in the subsequent process.
  • the above equations 3 and 4 represent the weight reduction (%) and the temperature difference between the spent battery shreds that have undergone high-temperature stabilization and the spent battery shreds before performing the high-temperature stabilization step.
  • a subsequent process such as a high-temperature reduction process
  • the electrolyte in the spent battery shreds is volatilized
  • a fire does not occur and the subsequent process can be performed with stability.
  • the above equations 3 and 4 are not satisfied, there is a problem in that a fire occurs due to the electrolyte in the spent battery shreds when performing the subsequent process, making it difficult to perform the process.
  • the spent battery shreds can continuously perform the 6th step, which is the high-temperature stabilization step, until the above equations 3 and 4 are satisfied.
  • Figure 4 shows the change in voltage of a battery according to cooling temperature according to one embodiment of the present invention.
  • FIG. 5 is a graph showing the relationship among battery weight, external cooling temperature, and cooling time according to one embodiment of the present invention.
  • a battery processing method can derive a minimum cooling time for cooling a battery in the step of freezing a battery.
  • the minimum cooling time is related to the battery weight, the external cooling temperature, and the target temperature.
  • the target temperature is set to -70° C. and the battery weights are 2.5 kg (A), 10 kg (B), 20 kg (C), and 50 kg (D), respectively.
  • the external cooling temperature and the minimum cooling time are shown.
  • the electrolyte of the battery starts cooling after a predetermined time and the voltage becomes 0 V.
  • a minimum maintenance time is required to sufficiently cool the inside, specifically the electrolyte, when cooling the battery.
  • the battery weight and time for cooling are required.
  • the minimum time required for cooling can be confirmed by using the external cooling temperature for refrigeration, the target temperature, and the battery weight to cool the battery.
  • Table 1 lists the minimum cooling time based on battery weight and external cooling temperature.
  • Table 2 compares the fire occurrence status of the examples and comparative examples according to the same battery weight, external cooling temperature, and minimum freezing time according to 6a to 6d. The determination of the fire occurrence status was made as follows: if fire occurrence was observed after battery crushing, “O”; otherwise, “X”.
  • a standard for stabilizing the shredded material is set by measuring how much the temperature of the shredded material rises.
  • Figure 7 is a graph of temperature over time of a shredded material according to one embodiment of the present invention.
  • the temperature change over time was confirmed. Specifically, after shredding a battery that had gone through a freezing step, the 20 mm-sized shredded materials among the generated shredded materials were placed in the air and the temperature change over time was measured using a cooling method using air. In the case of 20 mm-sized shredded materials, it can be confirmed that the maximum ignition temperature is approximately 65°C. It can be confirmed that this is lower than the average vaporization temperature of the electrolyte, which is 120°C.
  • Table 3 below shows the temperature increase amount measured according to the size of the crushed material.
  • Average shred size (mm) 10 20 50 100 150 Temperature increase [°C] 30 50 65 90 110 140
  • the crushed material was maintained at a room temperature of 30°C for about 3 hours based on an average crushed material size of 20 mm, and at this time, it was confirmed that the increased temperature of the crushed material had dropped to the room temperature level.
  • the stabilization time for fragments less than 100 mm, there is no problem if the holding time is within several minutes, but for fragments greater than 100 mm, the stabilization time must be at least 3 hours.
  • Table 4 below shows the temperature rise according to the layered structure in a unit battery shredder according to one embodiment of the present invention, as measured by a thermal imaging camera.
  • the size of the shredded material was measured based on the long axis among the long and short axes of the shredded material.
  • the battery with SoC 0% was crushed in a frozen state, and the initial temperature started at about -60°C and increased to a maximum temperature of about 30°C, and the battery with SOC 30% was confirmed to rise to 60°C.
  • the maximum temperature trend according to the SOC condition caused a fire during stabilization when it was 80% or higher.
  • the weight loss ratio after reheating the shredded material was confirmed by reheating the unit battery shredded material that had gone through the high-temperature stabilization treatment step to 150 °C and then checking the weight loss ratio before and after heating.
  • Stability was indicated as ⁇ if a fire occurred during the battery crushing process, and ⁇ if no fire occurred.
  • the low-temperature stabilization treatment of the example was performed in the range of 10 to 25°C for 6 to 12 hours, and the high-temperature stabilization treatment was performed in the range of 130 to 150°C for 6 to 12 hours.
  • the weight loss after reheating the shredded material it can be confirmed that it is 1.0% or less, and since the weight loss after reheating the shredded material satisfies 1.0% or less, it was confirmed that the electrolyte reduction amount is large and stability in the post-process is secured.

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  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
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Abstract

La présente invention concerne un stabilisateur de batterie et un système de stabilisation de batterie, et comprend : une unité d'entrée pour entrer une casette dans lequel un matériau broyé de batterie usagée a été chargé ; une unité de transport pour transporter la casette dans laquelle le matériau broyé de batterie usagée a été chargé ; une première unité de stabilisation pour stabiliser le matériau broyé de batterie usagée à une température inférieure ou égale à 30 °C ; une seconde unité de stabilisation pour stabiliser, à une température de 30 °C à 150 °C, le matériau broyé de batterie usagée qui a traversé la première unité de stabilisation ; et une unité de décharge pour décharger le matériau broyé de batterie usagée stabilisé, la casette comprenant une entrée d'air chaud pour fournir de la chaleur au matériau broyé de batterie usagée.
PCT/KR2024/020450 2023-12-18 2024-12-16 Stabilisateur de batterie et système de stabilisation de batterie Pending WO2025135713A1 (fr)

Applications Claiming Priority (2)

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KR10-2023-0185223 2023-12-18
KR1020230185223A KR20250094445A (ko) 2023-12-18 2023-12-18 배터리 안정화 장치 및 배터리 안정화 시스템

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WO2025135713A1 true WO2025135713A1 (fr) 2025-06-26

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20060101683A (ko) * 2005-03-21 2006-09-26 리메텍(주) 폐건전지의 코발트 건식 분리방법
KR20200077108A (ko) * 2018-12-20 2020-06-30 동우 화인켐 주식회사 리튬이차전지 재생공정을 위한 전처리 방법
KR102516186B1 (ko) * 2022-09-27 2023-03-30 주식회사 이알 폐리튬이온배터리 진공 열분해 장치
KR20230088040A (ko) * 2021-12-10 2023-06-19 주식회사 에코비트프리텍 전기차 배터리 재활용 방법
WO2023163336A1 (fr) * 2022-02-28 2023-08-31 (주)에코프로머티리얼즈 Système de traitement thermique pour le recyclage écologique des batteries usagées

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20060101683A (ko) * 2005-03-21 2006-09-26 리메텍(주) 폐건전지의 코발트 건식 분리방법
KR20200077108A (ko) * 2018-12-20 2020-06-30 동우 화인켐 주식회사 리튬이차전지 재생공정을 위한 전처리 방법
KR20230088040A (ko) * 2021-12-10 2023-06-19 주식회사 에코비트프리텍 전기차 배터리 재활용 방법
WO2023163336A1 (fr) * 2022-02-28 2023-08-31 (주)에코프로머티리얼즈 Système de traitement thermique pour le recyclage écologique des batteries usagées
KR102516186B1 (ko) * 2022-09-27 2023-03-30 주식회사 이알 폐리튬이온배터리 진공 열분해 장치

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