WO2021201151A1 - Procédé permettant de désactiver une batterie rechargeable au lithium-ion - Google Patents

Procédé permettant de désactiver une batterie rechargeable au lithium-ion Download PDF

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WO2021201151A1
WO2021201151A1 PCT/JP2021/013974 JP2021013974W WO2021201151A1 WO 2021201151 A1 WO2021201151 A1 WO 2021201151A1 JP 2021013974 W JP2021013974 W JP 2021013974W WO 2021201151 A1 WO2021201151 A1 WO 2021201151A1
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Prior art keywords
ion secondary
secondary battery
lithium ion
lithium
aqueous solution
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PCT/JP2021/013974
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English (en)
Japanese (ja)
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哲也 宇田
勇樹 谷ノ内
章宏 岸本
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国立大学法人京都大学
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Priority to JP2022512651A priority Critical patent/JPWO2021201151A1/ja
Publication of WO2021201151A1 publication Critical patent/WO2021201151A1/fr

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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 method for deactivating a lithium ion secondary battery.
  • lithium-ion secondary batteries contain highly reactive lithium (Li), and it has been reported that they ignite due to improper handling. In the past, hydrogen explosions have also occurred when processing waste lithium-ion secondary batteries in the United States. For this reason, "safe deactivation and dismantling" has become an issue, especially for large lithium-ion secondary batteries used in electric vehicles and the like. At present, it is assumed that waste lithium-ion secondary batteries are incinerated at high temperatures or treated with high-temperature steam, but harmful gases generated by combustion, decomposition, evaporation, etc.
  • Patent Document 1 describes that the waste lithium ion secondary battery is incinerated after being discharged.
  • Patent Document 2 describes that a lithium ion secondary battery is mechanically dry-pulverized in an atmosphere of argon, carbon dioxide or the like.
  • Patent Document 1 At present, as in Patent Document 1, many studies have been conducted on the premise that lithium is inactivated by high-temperature incineration, but in this case, high-temperature incineration equipment is required, and a large-scale processing equipment is required. This is unavoidably unsuitable for distributed treatment in urban areas, and also poses a problem of detoxifying harmful fluorine-containing gas generated by combustion of an organic solvent contained in an electrolytic solution of a lithium ion secondary battery. Further, in the method of Patent Document 1, lithium and graphite are distributed in the slag phase and cannot be recovered.
  • Patent Document 2 is a very dangerous method because the waste lithium ion secondary battery violently ignites and generates heat by dry pulverization even in an atmosphere of argon, carbon dioxide, etc. It cannot be applied to the deactivation treatment of lithium-ion secondary batteries. Therefore, in order to prevent heat generation and generation of harmful gas, in Patent Document 3, the lithium ion secondary battery is cut or crushed in a liquid of water, alcohol, or acid or in an inert gas, and in Patent Document 4, shredder crushed in water. A method has been developed to do this. However, when the lithium ion secondary battery is cut in water and acid without controlling the atmosphere, gas is generated by hydrolysis of an organic solvent such as carbonate contained in the electrolytic solution, and the liquid is stored after deactivation. There is a danger in transportation.
  • the present invention is intended to solve the above problems, and an object of the present invention is to provide a method for easily and safely inactivating a waste lithium ion secondary battery.
  • the present inventors have opened a lithium ion secondary battery in an alkaline aqueous solution, or lithium ions in water under an inert gas atmosphere or a reducing gas atmosphere. It has been found that the waste lithium ion secondary battery can be easily and safely deactivated by opening the secondary battery. Based on these findings, the present inventors further studied and completed the present invention. That is, the present invention includes the following aspects.
  • Item 1 A method of deactivating a lithium-ion secondary battery, (A) A step of opening the lithium ion secondary battery in an alkaline aqueous solution, or (B) a step of opening the lithium ion secondary battery in water under an inert gas atmosphere or a reducing gas atmosphere. How to prepare.
  • Item 2. The method according to Item 1, wherein the amount of the alkaline aqueous solution used in the step (A) and the amount of water used in the step (B) is 10 mL or more with respect to the capacity of 1 Wh of the lithium ion secondary battery.
  • Item 3 The method according to Item 1 or 2, wherein the step (A) is carried out in an inert gas atmosphere or a reducing gas atmosphere.
  • Item 4. The method according to any one of Items 1 to 3, wherein the pH of the alkaline aqueous solution in the step (A) is 10 to 14, and the pH of the water in the step (B) is 6 to 14.
  • the alkaline compound used as the alkaline aqueous solution is at least one selected from the group consisting of calcium hydroxide, calcium oxide, magnesium hydroxide, magnesium oxide, sodium hydroxide, potassium hydroxide and lithium hydroxide. The method according to any one of 4 to 4.
  • Item 6. The method according to any one of Items 1 to 5, wherein in the step (A), the alkaline aqueous solution is lime water.
  • Item 7. The method according to any one of Items 1 to 6, wherein the content of the alkaline compound in the alkaline aqueous solution is larger than the saturation concentration.
  • the step of opening the lithium ion secondary battery is to crush or cut the lithium ion secondary battery, to make a hole penetrating the casing of the lithium ion secondary battery, or to make a casing of the lithium ion secondary battery.
  • Item 2. The method according to any one of Items 1 to 7, which is a step of opening a part or all of the above.
  • Item 9 The method according to any one of Items 1 to 8, wherein the steps (A) and (B) are carried out at 10 to 80 ° C.
  • Item 10. The method according to any one of Items 1 to 9, wherein the timing of completion of deactivation is determined from the state of generation of air bubbles from the opening.
  • Item 11 It is a method of visualizing the deactivation status of lithium-ion secondary batteries.
  • a step of opening the lithium ion secondary battery in an alkaline aqueous solution or
  • B a step of opening the lithium ion secondary battery in water under an inert gas atmosphere or a reducing gas atmosphere.
  • Item 12. It is a method of separating and recovering metal elements from a lithium ion secondary battery.
  • a method comprising a step of deactivating a lithium ion secondary battery by the method according to any one of Items 1 to 11 and then crushing and physically sorting the deactivated lithium ion secondary battery. ..
  • Item 13 The method according to Item 12, wherein at least one selected from the group consisting of lithium, nickel and cobalt is recovered as a solid oxide, and copper and / or aluminum is recovered as a metal.
  • Item 14 A step of sorting a casing with a control substrate by size from the inactivated solid matter of a lithium ion secondary battery and recovering aluminum.
  • Item 12 or 13 comprising a step of recovering at least one selected from the group consisting of copper scraps, aluminum scraps and separator pieces by sieving (1) from the solid matter remaining in the step (A1). The method described in.
  • Item 15 After the step (A2) (A3) A step of recovering a separator piece by sieving (2) from the solid matter remaining in the step (A2), and (A4) Copper scrap and aluminum scrap from the solid matter remaining in the step (A3). Item 14. The method according to Item 14, further comprising a step of separating.
  • Item 16 After the step (A2) (B3) The suspension of the deactivated lithium ion secondary battery is filtered, and at least selected from the group consisting of oxides of lithium, cobalt, nickel and manganese, graphite powder, aluminum hydroxide and calcium fluoride. Item 12. The method according to Item 14, further comprising a step of separating one type.
  • a lithium ion secondary battery deactivating device used to deactivate a lithium ion secondary battery in an alkaline aqueous solution or water.
  • a lithium ion secondary battery deactivating device that is arranged in the chamber and includes a mechanism for opening the lithium ion secondary battery charged into the chamber.
  • Item 18 An openable and closable lid that is placed on the chamber and is formed on the alkaline aqueous solution or water to isolate the closed space from the outside.
  • Item 12. The lithium ion secondary battery deactivating apparatus according to Item 17, further comprising a gas supply unit that supplies an inert gas or a reducing gas to the closed space.
  • Item 19 A vehicle comprising the lithium ion secondary battery deactivating device according to item 17 or 18.
  • Item 20 A lithium ion secondary battery recycling method using the method according to any one of Items 1 to 11.
  • the waste lithium ion secondary battery can be easily and safely deactivated. Therefore, the deactivated product can be transported easily and safely, and the recycling of the waste lithium ion secondary battery can be promoted.
  • the configuration of a general small lithium-ion secondary battery and the raw material price of each member are shown.
  • An example of a method for separating and recovering a metal element from a lithium ion secondary battery is shown.
  • An example of a vehicle in which waste lithium ion secondary batteries can be deactivated on-site (automobile dismantling factory, accident site, etc.) and separated and recovered for each element is shown.
  • the schematic diagram of the lithium ion secondary battery deactivation apparatus of this invention is shown.
  • C) Cross-sectional view It is a photograph explaining the meaning of "no pretreatment", "opening” and “cutting” in this embodiment.
  • Comparative Example 3 the result when the lithium ion secondary battery is cut by the dry type is shown.
  • Example 2 the result when the lithium ion secondary battery was opened in lime water is shown.
  • Test Example 1 the result of analyzing the oxygen concentration and the hydrogen concentration during the deactivation treatment by using gas chromatography (GC) is shown.
  • GC gas chromatography
  • Test Example 1 a flowchart of the deactivation treatment and the element separation treatment of the lithium ion secondary battery is shown. The state of the separated sample is also shown.
  • Test Example 1 a flowchart of the deactivation treatment and the element separation treatment of the lithium ion secondary battery is shown. The recovery rate of the separated samples is also shown.
  • Test Example 2 the ultraviolet-visible absorption spectrum when ethylene carbonate is added to deionized water is shown.
  • Test Example 3 the corrosion behavior of iron balls in lime water, hydrofluoric acid and NaCl aqueous solution is shown.
  • FIG. 1 shows the configuration of a general small lithium ion secondary battery and the raw material price of each member.
  • a casing made of aluminum or the like and having a control substrate appears.
  • the positive electrode active material accounts for about 79% of the total, and all of them contain lithium. That is, considering the recycling efficiency from the lithium ion secondary battery, it is preferable to recover lithium, and it is more preferable to recover the metal elements in the positive electrode active material, particularly nickel and cobalt.
  • the method of deactivating the lithium ion secondary battery of the present invention is (A) A step of opening the lithium ion secondary battery in an alkaline aqueous solution, or (B) a step of opening the lithium ion secondary battery in water under an inert gas atmosphere or a reducing gas atmosphere. Be prepared.
  • the lithium ion secondary battery is opened in neutral or alkaline water or an aqueous solution to form the lithium ion secondary battery. It is possible to gently inactivate the lithium contained. Moreover, in the method of deactivating the lithium ion secondary battery of the present invention, lithium, nickel and cobalt can be recovered as solid oxides, and copper and aluminum can be recovered as metals. Is also useful.
  • the method of deactivating the lithium ion secondary battery of the present invention does not generate toxic gas, can be carried out in a relatively small facility, and can safely disassemble the lithium ion secondary battery. be.
  • the lithium ion secondary battery can be easily and safely disassembled in various places in urban areas such as automobile dismantling sites, and the lithium ion secondary battery can be easily and safely disassembled and transported. be.
  • step (A) Alkaline aqueous solution and water
  • step (B) the lithium ion secondary battery is opened in water under an inert gas atmosphere or a reducing gas atmosphere.
  • the alkaline compound used as the alkaline aqueous solution in the step (A) is not particularly limited as long as it is a compound that exhibits alkalinity (particularly about pH 10 to 14) when dissolved in water, and is, for example, calcium hydroxide, calcium oxide, or water. Examples thereof include magnesium oxide, magnesium oxide, sodium hydroxide, potassium hydroxide and lithium hydroxide. These alkaline compounds may be used alone or in combination of two or more.
  • the alkaline aqueous solution is adopted in the step (A), if the content of the alkaline compound in the alkaline aqueous solution is not more than the saturation concentration, the alkaline compound is consumed by the reaction during the deactivation treatment of the lithium ion secondary battery. Specifically, it will be described in detail below.
  • the carbonate in the lithium ion secondary battery is ethylene carbonate
  • the carbonate is hydrolyzed in water, causing the following reaction.
  • the alkaline compound is calcium hydroxide
  • carbon dioxide reacts with carbon dioxide to form calcium carbonate as follows.
  • the alkaline compound is also consumed in the decomposition reaction of LiPF 6 described later. Therefore, when the content of the alkaline compound in the alkaline aqueous solution is set to the saturation concentration or less, the alkaline compound is consumed by the reaction during the deactivation treatment of the lithium ion secondary battery, and the decomposition reaction of carbonate and LiPF 6 proceeds. It becomes difficult and may not be completely detoxified.
  • step (A) it is preferable that a part of the alkaline compounds is precipitated so that the content of the alkaline compounds in the alkaline aqueous solution is larger than the saturation concentration.
  • the precipitation can be dissolved in the alkaline aqueous solution to replenish the concentration of the alkaline compound.
  • the alkaline compound when calcium hydroxide is used as the alkaline compound, only 0.17 g of calcium hydroxide is dissolved in 100 mL of water at room temperature, but the amount of calcium hydroxide contained in the alkaline aqueous solution is regarded as an excess amount and is dissolved. It is preferable to add, for example, 0.17 to 100 g, particularly 0.4 to 10 g, with respect to 100 mL of water.
  • the pH of the alkaline aqueous solution used in the step (A) is not particularly limited, but 10 to 14 are set from the viewpoint of efficiency, safety, economy, etc. of the deactivation treatment of the lithium ion secondary battery. Preferably, 11 to 13 are more preferable.
  • the water used in the step (B) is not particularly limited, and various types of water such as distilled water, tap water, industrial water, ion-exchanged water, deionized water, pure water, and electrolyzed water can be used.
  • the water used in the step (B) is preferably neutral or alkaline (6 ⁇ pH ⁇ 14).
  • the amount of the alkaline aqueous solution used in the step (A) and the amount of water used in the step (B) is preferably excessive. Specifically, it will be described in detail below.
  • active lithium in a lithium ion secondary battery comes into contact with water and reacts preferentially, and gently deactivates while generating hydrogen.
  • the reaction at this time is the reaction formula: LiC x + yH 2 O ⁇ y / 2H 2 + Li + + yOH - + xC Proceed according to.
  • the flammable organic solvent contained in the electrolytic solution of the lithium ion secondary battery is dissolved in water and diluted, and the oxygen concentration is constant before and after the reaction, that is, oxygen is not generated by the reaction. Since the alkaline aqueous solution or water also functions as a coolant for preventing a rapid temperature rise, ignition and heat generation can be suppressed, which is a safe method. In addition, the excess water in the reaction water (H 2 O) nor insufficient.
  • the amount of the alkaline aqueous solution used in the step (A) and the amount of water used in the step (B) is preferably excessive, and 10 mL or more is used with respect to the capacity of the target lithium ion secondary battery of 1 Wh.
  • 70 mL or more is more preferable, and 130 mL or more is further preferable.
  • the larger the amount of the alkaline aqueous solution used in the step (A) and the amount of water used in the step (B), the better, and the upper limit is not particularly limited. It is not preferable to use water. Therefore, the alkaline aqueous solution or water is preferably 1000 mL or less with respect to the capacity of the target lithium ion secondary battery of 1 Wh. Usually, it is about 50 to 500 mL with respect to a capacity of 1 Wh of the target lithium ion secondary battery.
  • the lithium ion secondary battery is opened by opening the lithium ion secondary battery in neutral or alkaline water or an aqueous solution, thereby forming the lithium ion secondary battery. It is possible to gently inactivate the lithium contained in.
  • the step (A) that is, the alkaline aqueous solution
  • the hydrolysis of the organic solvent such as carbonate is fast as described below. It is possible to shorten the time for gas generation.
  • step (A) that is, when an alkaline aqueous solution is adopted, the reaction is shortened and the generated carbon dioxide is reacted with the alkaline aqueous solution. Since it is easy to capture (when lime water is used as the alkaline aqueous solution, it is easy to immobilize it as calcium carbonate), it is also useful in that the exhaust time can be further shortened.
  • LiPF 6 contained as an electrolyte salt of the electrolytic solution existing in the lithium ion secondary battery is eluted in the treatment liquid during the deactivation treatment of the lithium ion secondary battery. At this time, LiPF 6 is easily hydrolyzed while producing HF.
  • step (A) that is, the alkaline aqueous solution
  • harmful fluoride ions are easily immobilized as salts.
  • fluoride ions can be easily immobilized as calcium fluoride (CaF 2 ) on the spot, and the step of separating fluoride ions can be omitted.
  • step (B) that is, when water is used, it is preferable to use an alkaline aqueous solution in a later step in order to remove the fluoride ions generated. Therefore, even when the step (B), that is, water is adopted, it is preferable to use the alkaline aqueous solution in combination. Therefore, it is preferable to adopt the step (A), that is, the alkaline aqueous solution from the beginning.
  • the step (A) that is, when the alkaline aqueous solution is adopted, the iron-based material is not rusted, so that the lithium ion secondary battery is not used.
  • the deactivation treatment facility, etc. it is possible to use an inexpensive iron-based material even for the members that come into contact with the treatment liquid, and the range of material selection is widened.
  • the atmosphere is not particularly limited. Of these, an inert gas atmosphere such as a nitrogen gas atmosphere and an argon gas atmosphere, and a reducing gas atmosphere such as a hydrogen gas atmosphere are preferable.
  • the step (B) that is, when water is adopted, is under an inert atmosphere such as a nitrogen gas atmosphere or an argon gas atmosphere, or hydrogen.
  • the temperature at which the method for deactivating the lithium ion secondary battery of the present invention is carried out is not particularly limited, and for example, it can be carried out at room temperature. That is, unlike the conventional method, high temperature incinerator is not required, and a simpler and safer method can be used.
  • the temperature at which the method for deactivating the lithium ion secondary battery of the present invention is carried out can be, for example, 10 to 80 ° C, preferably 15 to 45 ° C.
  • the opening treatment of the lithium ion secondary battery is not particularly limited, and various various methods can be adopted. Specifically, crushing or cutting a lithium ion secondary battery, making a hole through the casing of the lithium ion secondary battery, or opening a part or all of the casing of the lithium ion secondary battery. Can be mentioned. In addition, “crushing the lithium ion secondary battery” means breaking and crushing the lithium ion battery. Further, “crushing or cutting a lithium ion secondary battery” does not mean only crushing or cutting only the casing of a lithium ion secondary battery to expose the inside.
  • crushing or cutting a lithium ion secondary battery means crushing or cutting an unspecified position of a lithium ion secondary battery to crush or cut a storage part such as a current collector and a separator arranged in a casing. Or it also means cutting.
  • the number of times the lithium ion secondary battery is crushed or cut is not particularly limited as long as it is once or more, but it is preferably a plurality of times. Further, when the lithium ion secondary battery is crushed or cut a plurality of times, it is preferable to crush or cut the lithium ion secondary batteries at different positions. As a result, it is possible to achieve rapid deactivation and to rapidly proceed with processes such as physical sorting in the process after deactivation.
  • the lithium ion secondary of the present invention is particularly safe.
  • the battery can be deactivated.
  • the deactivation time can be shortened in particular.
  • the conventional dry method of deactivating in air if a method of crushing or cutting the lithium ion secondary battery or making a hole penetrating the casing of the lithium ion secondary battery is adopted, The lithium ion secondary battery ignites or generates heat.
  • the method for deactivating the lithium ion secondary battery of the present invention is adopted, the lithium ion secondary battery can be crushed or cut, or the lithium ion secondary battery can be crushed or cut.
  • the lithium-ion secondary battery can be safely deactivated by making a hole through the casing of the battery.
  • the deactivation is completed when the generation of bubbles is completely stopped.
  • the deactivation may be completed when the bubble generation rate becomes equal to or lower than a predetermined standard.
  • optical means, quantitative means, and the like can be adopted in determining the standard.
  • it may be measured by a spectroscopic device, or may be photographed or visually observed. If it is a measuring means, for example, the volume of bubbles generated within a predetermined time may be measured by collecting the generated bubbles.
  • the lithium ion secondary battery After opening the lithium ion secondary battery, it is preferable to immerse it in an alkaline aqueous solution or water until no bubbles are visually generated.
  • the specific immersion time can be, for example, 10 minutes to 24 hours, particularly 30 minutes to 6 hours.
  • the method of deactivating the lithium ion secondary battery of the present invention does not generate toxic gas and can be performed in a relatively small facility, which is safe. It is possible to disassemble the lithium-ion secondary battery.
  • the lithium ion secondary battery or its crushed product safely deactivated in this way contains metal elements such as lithium, aluminum, copper, nickel, cobalt, and manganese, and is physically sorted or chemically selected. It is possible to separate and collect each of them by various treatments.
  • FIG. 2 shows an example in which the lithium ion secondary battery is deactivated by the cutting treatment using the attritor shown in FIG.
  • the casing with the control board can be sorted by size from the deactivated solids. From here it is possible to recover a lot of aluminum. Then, it can be cut into a desired size (20 mm ⁇ 20 mm in FIG. 2), and then crushed by a ball mill or the like using an iron ball or the like.
  • oxides such as lithium, cobalt, nickel and manganese, graphite powder, aluminum hydroxide, calcium fluoride and the like can be separated by filtering the suspension after the above sieving (1). Can be done. These can be processed in medium-sized smelters specializing in waste lithium-ion secondary battery processed products or in existing smelters. From here, about 70% of lithium, nickel, cobalt and most of them can be recovered.
  • the transportation of large-sized waste lithium-ion secondary batteries to a centralized facility or a smelter can be transformed into a safe and convenient one.
  • the problem of transporting waste lithium-ion secondary batteries, which has been a bottleneck due to the deactivation treatment of lithium-ion secondary batteries at each treatment plant, by setting up treatment plants at dismantling sites of automobiles in various places. Can be solved.
  • a waste lithium ion secondary battery such as a defective vehicle is placed in a chamber of a container soaked with an alkaline aqueous solution or water in advance. Then, the waste lithium ion secondary battery can be cut and crushed by a cutting and crushing unit (for example, a pair of rollers facing the cutting blade), and then each element can be separated from the crushed material.
  • a cutting and crushing unit for example, a pair of rollers facing the cutting blade
  • a lid is provided to cover the upper part of the container so that it can be opened and closed at the part where the waste lithium ion secondary battery is inserted.
  • the upper part of the container is closed by the lid, the space formed on the alkaline aqueous solution or water is sealed with the lid, and a closed space isolated from the outside is formed.
  • an inert gas nitrogen gas
  • the gas supply unit nitrogen generator
  • the closed space is filled with the inert gas, and an inert gas atmosphere is formed.
  • a reducing gas for example, hydrogen gas or the like
  • the vehicle is provided with a single sieve or a plurality of sieves having different mesh sizes, and the crushed material is separated by passing the crushed material together with the alkaline aqueous solution or water in the chamber. Is possible. When a plurality of sieves having different meshes are provided, it is possible to separate the crushed material according to the size. The alkaline aqueous solution or water from which the crushed material has been removed is supplied into the chamber again.
  • the vehicle is equipped with a compressor and a hydrogen storage tank in order to recover the hydrogen generated when lithium is deactivated.
  • the compressor has a function of compressing hydrogen from a closed space and supplying it to a hydrogen storage tank.
  • the vehicle may be provided with a fuel cell that generates electricity using hydrogen.
  • no pretreatment means that the casing is not damaged and the lithium ion secondary battery existing in the casing is not exposed, as shown in the left figure of FIG.
  • opening exists in the casing by cutting off only a part of the casing so as not to damage the lithium ion secondary battery existing in the casing. It means exposing the lithium-ion secondary battery.
  • cutting means cutting the casing together with the lithium ion secondary battery existing in the casing, as shown in the right figure of FIG.
  • the lithium ion secondary battery (3 cm x 4 cm x 0.7 cm; nominal voltage 3.7 V; charging capacity 895 mAh; charged) was newly purchased and charged, and used as a sample.
  • Comparative Example 1 In a glove box with no underwater pretreatment and a nitrogen atmosphere (oxygen concentration: less than 1% by volume), the resin extrapolation of the lithium ion secondary battery was removed, and the deionized water was removed without cutting the casing. 250 mL of the treatment liquid was placed in an air collecting bottle, and the presence or absence of ignition and air bubbles when the lithium ion secondary battery was immersed was confirmed.
  • Comparative Example 2 Calcium hydroxide in a glove box in a nitrogen atmosphere (oxygen concentration: less than 1% by volume) without pretreatment in lime water, with the resin extrapolation of the lithium ion secondary battery removed and the casing not excised. 250 mL (1 g of calcium hydroxide put into the treatment liquid) was put into an air collecting bottle as a treatment liquid in which lime water coexisting with the above was put, and the presence or absence of ignition and air bubbles when the lithium ion secondary battery was immersed was confirmed.
  • Comparative Example 3 Dry cutting In a glove box with a nitrogen atmosphere (oxygen concentration: less than 1% by volume), the resin extrapolation of the lithium ion secondary battery was removed, and the casing was cut by about 1 cm together with the internal lithium ion secondary battery. And confirmed the reactivity. That is, the same method as in Patent Document 2 was performed.
  • Example 1 Opened in water In a glove box with a nitrogen atmosphere (oxygen concentration: less than 1% by volume), the resin extrapolation of the lithium ion secondary battery is removed, and the internal lithium ion secondary battery is not damaged. As described above, a part of the casing (only the side surface) was excised, 250 mL of deionized water was put into an air collecting bottle as a treatment liquid, and the presence or absence of ignition and air bubbles was confirmed.
  • Example 2 Opened in lime water In a glove box in a nitrogen atmosphere (oxygen concentration: less than 1% by volume), the resin extrapolation of the lithium ion secondary battery is removed, and the internal lithium ion secondary battery is damaged. Part of the casing (only the side surface) was excised so that there was no such thing, and 250 mL of lime water in which calcium hydroxide (calcium hydroxide put into the treatment liquid was 1 g) was precipitated was put into an air collecting bottle as a treatment liquid, and ignited and fired. The presence or absence of air bubbles was confirmed.
  • oxygen concentration less than 1% by volume
  • Example 3 Cutting in lime water In a glove box with a nitrogen atmosphere (oxygen concentration: less than 1% by volume), the resin extrapolation of the lithium ion secondary battery is removed, and the casing is about 1 cm together with the internal lithium ion secondary battery. 250 mL of lime water obtained by cutting and precipitating calcium hydroxide (1 g of calcium hydroxide added to the treatment liquid) was placed as a treatment liquid in an air collecting bottle, and the presence or absence of ignition and air bubbles was confirmed.
  • gas containing hydrogen gas was generated from the terminal and the inside of the cell, and deactivation proceeded.
  • the deactivation of the lithium ion secondary battery is completed because bubbles are not generated in about 1 hour without ignition during the reaction.
  • Test Example 1 Deactivation treatment in lime water and deactivation behavior when the lithium ion secondary battery immersed in the element recovery aqueous solution was cut were investigated at 23 to 25 ° C.
  • FIG. 2 shows a flowchart of the deactivation process of the lithium ion secondary battery.
  • the resin extrapolation of the lithium ion secondary battery was removed to expose the aluminum casing.
  • the lithium ion secondary battery installed on the table 2 was immersed. After that, the apparatus was operated, and the lithium ion secondary battery was pressed against the stainless steel blade 3 installed in the chamber 1 with the rotary rod 4 to cut the lithium ion secondary battery. At this time, in order to operate more safely, the drop lid 5 was arranged in the chamber 1. When the lithium ion secondary battery could not be cut by one operation of the device, the device was repeatedly operated to cut the lithium ion secondary battery.
  • the cut lithium-ion secondary battery was left to stand in the treatment liquid until the generation of bubbles was completed, and gas was sampled as appropriate.
  • the sampled gas was analyzed for oxygen concentration and hydrogen concentration by gas chromatography (manufactured by Shimadzu Corporation, GC-8A). The results are shown in FIG.
  • the treatment liquid and the solid matter were carried out from the glove box into the atmosphere, and the solid matter was cut into a size of about 2 cm ⁇ 2 cm by removing the aluminum casing piece by hand. From the casing thus removed, it was possible to recover 86.7% of aluminum as metallic aluminum.
  • the cut solid matter was placed in a polypropylene bottle together with about 20 iron balls (average diameter 0.9 cm) and 100 mL of deionized water, and ball milled for 10 hours.
  • the solid matter crushed in this way was separated by a sieve having a mesh size of 1 mm, and then the solid on the sieve was further separated by magnetic force sorting and sieving with a mesh size of 10 mm to separate iron balls, copper scraps / aluminum scraps, and separator pieces. .. Since a black suspension was collected under the sieve, the black powder and the transparent ball mill liquid were collected by filtering the suspension. A part of these recovered products was sampled and dissolved in a mixed solution of hydrochloric acid and hydrogen peroxide, and the metal elements contained in each were quantified by the ICP-AES method. The results are shown in FIGS. 9 and 10. As a result, it was possible to recover 69% of lithium metal, 99.2% of nickel, and 98.9% of cobalt as solid oxides, and 94.2% of copper as metallic copper.
  • Test Example 2 In the carbonate decomposition aqueous solution in the electrolytic solution, the carbonate contained as the organic solvent of the electrolytic solution existing in the lithium ion secondary battery is hydrolyzed to gradually generate carbon dioxide. Prolonged carbon dioxide generation raises concerns about the safety of storage and transportation of the treatment fluid. As for the expected decomposition reaction at this time, for example, when the carbonate is ethylene carbonate, the following reaction formula is assumed.
  • FIG. 11 shows an ultraviolet-visible absorption spectrum when ethylene carbonate is added to deionized water.
  • Test Example 3 Utilization of iron-based material in lime water treatment In order to examine the use of steel material for equipment materials such as reaction vessels in deactivation treatment of lithium ion secondary batteries in aqueous solution, in various solutions. The corrosion behavior of the iron sample was investigated.
  • the aqueous solution used in this test example was lime water in which calcium hydroxide (10 g of calcium hydroxide was added to the treatment solution) was precipitated, 0.01 mM hydrofluoric acid, and 0.25 M NaCl aqueous solution. used.
  • the NaCl aqueous solution was adopted because salt water is used for the discharge treatment of the lithium ion secondary battery. The results are shown in FIG. 12 and Table 1.
  • an iron-based material such as a steel material can be used as a device material such as a reaction vessel, and the range of material selection is widened. ..

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Abstract

L'invention concerne un procédé permettant de désactiver une batterie rechargeable au lithium-ion, le procédé comprenant (A) une étape d'ouverture de la batterie rechargeable au lithium-ion dans une solution d'eau alcaline ou (B) une étape d'ouverture de la batterie rechargeable au lithium-ion dans de l'eau sous une atmosphère de gaz inerte ou une atmosphère de gaz réducteur. En utilisant ledit procédé, il est possible de désactiver facilement et en toute sécurité des batteries rechargeables au lithium-ion usagées.
PCT/JP2021/013974 2020-03-31 2021-03-31 Procédé permettant de désactiver une batterie rechargeable au lithium-ion WO2021201151A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3128587A1 (fr) * 2021-10-26 2023-04-28 Commissariat A L'energie Atomique Et Aux Energies Alternatives Procédé d’inertage d’accumulateurs électrochimiques, notamment métal-ion, par immersion initiale dans une solution de chlorure de calcium à basse température, puis court-circuitage électrique en vue de leur broyage.

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11260426A (ja) * 1998-03-11 1999-09-24 Asaka Riken Kogyo Kk 非水電解液電池の不活性化装置
US20200078796A1 (en) * 2017-05-30 2020-03-12 Li-Cycle Corp. Process, apparatus, and system for recovering materials from batteries

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11260426A (ja) * 1998-03-11 1999-09-24 Asaka Riken Kogyo Kk 非水電解液電池の不活性化装置
US20200078796A1 (en) * 2017-05-30 2020-03-12 Li-Cycle Corp. Process, apparatus, and system for recovering materials from batteries

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3128587A1 (fr) * 2021-10-26 2023-04-28 Commissariat A L'energie Atomique Et Aux Energies Alternatives Procédé d’inertage d’accumulateurs électrochimiques, notamment métal-ion, par immersion initiale dans une solution de chlorure de calcium à basse température, puis court-circuitage électrique en vue de leur broyage.
EP4175016A1 (fr) * 2021-10-26 2023-05-03 Commissariat à l'énergie atomique et aux énergies alternatives Procédé d'inertage d'accumulateurs électrochimiques, notamment métal-ion, par immersion initiale dans une solution de chlorure de calcium à basse température, puis court-circuitage électrique en vue de leur broyage

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