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WO2024166762A1 - Procédé de recyclage pour batteries secondaires au lithium-ion - Google Patents

Procédé de recyclage pour batteries secondaires au lithium-ion Download PDF

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Publication number
WO2024166762A1
WO2024166762A1 PCT/JP2024/003037 JP2024003037W WO2024166762A1 WO 2024166762 A1 WO2024166762 A1 WO 2024166762A1 JP 2024003037 W JP2024003037 W JP 2024003037W WO 2024166762 A1 WO2024166762 A1 WO 2024166762A1
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Prior art keywords
ion secondary
lithium
positive electrode
active material
electrode active
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English (en)
Japanese (ja)
Inventor
朝嗣 仲本
篤史 佐野
由美子 尾崎
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TDK Corp
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TDK Corp
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • 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

Definitions

  • the present invention relates to a method for recycling lithium ion secondary batteries.
  • This application claims priority based on Japanese Patent Application No. 2023-015843, filed on February 6, 2023, the contents of which are incorporated herein by reference.
  • Lithium-ion secondary batteries are also widely used as a power source for mobile devices such as mobile phones and laptops, as well as hybrid cars.
  • lithium-ion secondary batteries contain valuable metals, attempts are being made to recollect and recycle these metals.
  • One method of recycling lithium-ion secondary batteries is known as the solvent extraction method.
  • used lithium-ion secondary batteries are heat-treated and crushed to obtain a powder (hereafter referred to as "black mass"), which is then immersed in acid to extract the valuable metals as elements.
  • waste lithium-ion secondary batteries contain impurity metals such as iron and copper. If the positive electrode active material is regenerated while still containing impurity metals, the impurity metals eluted from the positive electrode due to an electrochemical reaction will be electrolytically deposited on the negative electrode, causing a short circuit in the lithium-ion secondary battery. For this reason, there is a demand to remove impurity metals when recycling lithium-ion secondary batteries.
  • Patent Document 1 describes a method of separating impurity metals from the post-leaching solution of acid leaching of black mass by combining specific extractants.
  • Patent Document 2 describes a method of separating the valuable metal cobalt from the impurity metal copper by solvent extraction.
  • Patent Documents 1 and 2 dissolve the positive electrode active material contained in the black mass and extract the valuable metal as an element.
  • the methods described in Patent Documents 1 and 2 require a process of constructing a new positive electrode active material from the extracted elements in order to reuse the valuable metal as an active material, and therefore cannot be said to be efficient.
  • the positive electrode active material does not contain valuable metals such as cobalt and nickel, such as lithium iron phosphate (LiFePO 4 )
  • the process of dissolving the positive electrode active material once and then regenerating it is not economical.
  • This disclosure has been made in consideration of the above problems, and aims to provide a method for recycling lithium-ion secondary batteries that can efficiently remove impurities contained in the positive electrode active material.
  • the method for recycling lithium ion secondary batteries according to the first aspect includes the steps of: immersing the black mass obtained by heat-treating and pulverizing the lithium ion secondary batteries in an aqueous ferric chloride solution to prepare a mixed solution; filtering the mixed solution to extract the dissolved residue; mixing the washed and dried dissolved residue with a lithium compound; and heating the mixture in an inert atmosphere at a temperature of 400°C or higher and 900°C or lower.
  • the concentration of the aqueous ferric chloride solution may be 1% or more and 50% or less.
  • the temperature of the aqueous ferric chloride solution may be 20°C or higher and 120°C or lower.
  • the lithium-ion secondary battery may contain lithium iron phosphate as a positive electrode active material.
  • the step of preparing the mixed solution may include a step of physically separating the black mass and removing a portion of the black mass.
  • the method for recycling lithium-ion secondary batteries according to the above embodiment can efficiently remove impurities contained in the positive electrode active material.
  • FIG. 2 is a flow diagram of a method for recycling a lithium-ion secondary battery according to the present embodiment.
  • FIG. 2 is a schematic diagram of an example of a lithium ion secondary battery to be collected in the recycling method for lithium ion secondary batteries according to the embodiment.
  • FIG. 2 is a flow diagram of a characteristic part of the recycling method for lithium ion secondary batteries according to the embodiment of the present invention. 1 shows X-ray diffraction results of black mass before and after a Li addition step in a recycling method for a lithium ion secondary battery according to an embodiment of the present invention.
  • FIG. 1 is a flow diagram of a method for recycling lithium ion secondary batteries.
  • the method for recycling lithium ion secondary batteries according to this embodiment includes, for example, a recovery step S1, a discharge step S2, a decomposition step S3, a heat treatment step S4, a crushing step S5, a sieving step S6, an impurity removal step S7, and a regeneration step S8.
  • the method for recycling lithium ion secondary batteries according to this embodiment includes a predetermined impurity removal step S7.
  • FIG. 2 is a schematic diagram of an example of a lithium ion secondary battery to be collected in the lithium ion secondary battery recycling method according to this embodiment.
  • the lithium ion secondary battery 100 comprises a power generating element 40, an exterior body 50, and a non-aqueous electrolyte (not shown).
  • the exterior body 50 covers the periphery of the power generating element 40.
  • the power generating element 40 is connected to the outside by a pair of terminals 60, 62 connected to the power generating element 40.
  • the non-aqueous electrolyte is contained in the exterior body 50.
  • FIG. 2 a case where one power generating element 40 is contained in the exterior body 50 is illustrated, but multiple power generating elements 40 may be stacked.
  • the lithium ion secondary battery 100 may be of any type, such as a cylindrical type, a square type, a laminate type, or a button type.
  • the power generating element 40 comprises a separator 10, a positive electrode 20, and a negative electrode 30.
  • the positive electrode 20 has, for example, a positive electrode current collector 22 and a positive electrode active material layer 24.
  • the positive electrode active material layer 24 is in contact with at least one surface of the positive electrode current collector 22.
  • the positive electrode collector 22 is, for example, a conductive plate material.
  • the positive electrode collector 22 is, for example, a thin metal plate made of aluminum, copper, nickel, titanium, stainless steel, etc.
  • the positive electrode active material layer 24 contains, for example, a positive electrode active material.
  • the positive electrode active material layer 24 may contain a conductive additive and a binder as necessary.
  • the positive electrode active material can be an electrode active material that can reversibly absorb and release ions, remove and insert ions (intercalation), or dope and dedope ions with their counter anions (e.g., PF 6 ⁇ ). Lithium, magnesium, etc. can be used as the ion.
  • Ti5O12 LiNixCoyAlzO2
  • the recycling method of the lithium ion secondary battery according to this embodiment is useful.
  • the solvent extraction method in which the positive electrode active material is dissolved once is not suitable when lithium iron phosphate is the positive electrode active material.
  • the solvent extraction method decomposes the positive electrode active material once and extracts a predetermined metal as an element. Valuable metals such as cobalt and nickel can be extracted as elements to obtain cost profitability, but when the positive electrode active material is lithium iron phosphate that does not contain valuable metals such as cobalt and nickel, it is difficult to obtain cost profitability.
  • the recycling method of the lithium ion secondary battery according to this embodiment does not decompose the positive electrode active material much and can be directly reused, so that cost profitability can be obtained even when the positive electrode active material is lithium iron phosphate.
  • the conductive additive increases the electronic conductivity between the positive electrode active materials.
  • the conductive additive is, for example, carbon powder, carbon nanotubes, carbon material, metal powder, a mixture of carbon material and metal powder, or conductive oxide.
  • the carbon powder is, for example, carbon black, acetylene black, ketjen black, etc.
  • the metal powder is, for example, copper, nickel, stainless steel, iron, etc.
  • the binder in the positive electrode active material layer 24 bonds the positive electrode active materials together. Any known binder can be used.
  • the negative electrode 30 has, for example, a negative electrode current collector 32 and a negative electrode active material layer 34.
  • the negative electrode active material layer 34 is in contact with at least one surface of the negative electrode current collector 32.
  • the negative electrode collector 32 is, for example, a conductive plate material.
  • the negative electrode collector 32 can be the same as the positive electrode collector 22.
  • the negative electrode active material layer 34 contains a negative electrode active material and a binder.
  • the negative electrode active material layer 34 may contain a conductive additive as necessary.
  • the negative electrode active material may be any compound capable of absorbing and releasing ions, and may be any negative electrode active material used in known lithium ion secondary batteries.
  • the negative electrode active material may be, for example, metallic lithium, a lithium alloy, a carbon material, or a material capable of alloying with lithium.
  • the carbon material may be, for example, graphite (natural graphite, artificial graphite), carbon nanotubes, non-graphitizable carbon, easily graphitizable carbon, low-temperature fired carbon, or the like capable of absorbing and releasing ions.
  • the material capable of alloying with lithium includes, for example, silicon, tin, zinc, lead, and antimony.
  • the material capable of alloying with lithium may be, for example, these simple metals, or alloys or oxides containing these elements.
  • the material capable of alloying with lithium may also be a composite in which at least a portion of the surface is coated with a conductive material (for example, a carbon material) or the like.
  • the conductive additive and binder used in the negative electrode active material layer 34 can be the same as those used in the positive electrode active material layer 24.
  • the separator 10 is sandwiched between the positive electrode 20 and the negative electrode 30.
  • the separator 10 isolates the positive electrode 20 and the negative electrode 30, and prevents a short circuit between the positive electrode 20 and the negative electrode 30.
  • the separator 10 spreads in-plane along the positive electrode 20 and the negative electrode 30. Lithium ions can pass through the separator 10.
  • the separator 10 has, for example, an electrically insulating porous structure.
  • the separator 10 is, for example, a monolayer or laminate of a polyolefin film.
  • the separator 10 may be a stretched film of a mixture of polyethylene, polypropylene, or the like.
  • the separator 10 may be a fibrous nonwoven fabric made of at least one constituent material selected from the group consisting of cellulose, polyester, polyacrylonitrile, polyamide, polyethylene, and polypropylene.
  • the separator 10 may be, for example, a solid electrolyte.
  • the separator 10 may be an inorganic coated separator.
  • the electrolyte is sealed in the exterior body 50 and is impregnated into the power generating element 40.
  • the non-aqueous electrolyte contains, for example, a non-aqueous solvent and an electrolyte salt.
  • the electrolyte salt is dissolved in the non-aqueous solvent.
  • a known electrolyte can be used as the electrolyte.
  • the electrolyte contains, for example, a non-aqueous solvent and an electrolyte salt.
  • the exterior body 50 seals the power generating element 40 and the non-aqueous electrolyte inside.
  • the exterior body 50 prevents the non-aqueous electrolyte from leaking out and prevents moisture from entering the lithium-ion secondary battery 100 from the outside.
  • the exterior body 50 has a metal foil 52 and a resin layer 54 laminated on each side of the metal foil 52.
  • the exterior body 50 is, for example, a metal laminate film in which the metal foil 52 is coated on both sides with a polymer film (resin layer 54).
  • the metal foil 52 is, for example, aluminum foil.
  • the resin layer 54 is, for example, a polymer film such as polypropylene.
  • the terminals 60 and 62 are connected to the negative electrode 30 and the positive electrode 20, respectively.
  • the terminal 62 connected to the positive electrode 20 is a positive electrode terminal
  • the terminal 60 connected to the negative electrode 30 is a negative electrode terminal.
  • the terminals 60 and 62 are responsible for electrical connection to the outside.
  • the terminals 60 and 62 are formed from a conductive material such as aluminum, nickel, or copper.
  • the discharging step S2 discharges the residual charge of the lithium ion secondary battery 100.
  • the discharging step S2 is performed to increase the stability of the work of the disassembly step S3.
  • the discharging step S2 does not need to be performed if the environment is one in which safety can be ensured.
  • the discharging step S2 can be performed by a known method.
  • the decomposition step S3 is performed.
  • the positive electrode 20 is removed from the lithium ion secondary battery 100.
  • the black mass is a sample that is to be sorted after the heat treatment step S4 and the crushing step S5.
  • the decomposition step S3 does not have to be performed. By omitting the decomposition step S3, the effort and cost can be reduced.
  • a heat treatment step S4 is performed.
  • the heat treatment step S4 at least the positive electrode active material layer 24 is heat treated.
  • the heat treatment is, for example, a firing treatment. If the decomposition step S3 is performed, the positive electrode active material layer 24 or the positive electrode 20 may be fired. If the decomposition step S3 is not performed, the entire lithium ion secondary battery 100 may be fired.
  • the heat treatment step S4 is carried out at a temperature of 300°C or higher.
  • the temperature of the heat treatment step is preferably 300°C or higher and lower than 800°C, and more preferably 400°C or higher and lower than 650°C.
  • the electrolyte is thermally decomposed and rendered harmless, and combustible materials such as the separator 10 and binder are thermally decomposed.
  • the crushing step S5 is performed.
  • the heat-treated sample is crushed.
  • the heat-treated sample is crushed to become black mass.
  • Crushing can be performed by a known method.
  • the crushing step S5 is performed, for example, with a crushing device such as a biaxial crusher or a hammer mill.
  • the positive electrode collector 22 and the negative electrode collector 32 are malleable, and when the crushing step S5 is performed, they tend to become particles of 1 mm or more.
  • the positive electrode active material and the negative electrode active material are subjected to the crushing step S5, they tend to become particles of less than 1 mm.
  • a sieving step S6 is performed.
  • the average particle size of the sample after the heat treatment is set to 100 ⁇ m or less.
  • the sieving step S6 for example, particles of 1 mm or more originating from the positive electrode collector 22 and the negative electrode collector 32 can be removed.
  • the impurity removal step S7 described below can be performed more efficiently, but the sieving step S6 is not necessarily required.
  • FIG. 3 is a flow diagram of a characteristic part of the lithium ion secondary battery recycling method according to this embodiment.
  • Figure 3 is a flow diagram showing an example of the impurity removal step S7 in detail.
  • impurities are, for example, impurity metals such as copper and iron, carbon, etc.
  • the impurity removing step S7 includes, for example, a wet classification step S71, a floating step S72, a magnetic separation step S73, a mixed liquid preparation step S74, a filtration step S75, an electrolysis step S76, a heat treatment step S77, and a Li addition step S78.
  • the impurity removal step S7 may include a step of physically separating a part of the black mass.
  • the physical separation here refers to a material selection method that does not involve a chemical reaction.
  • the physical separation may be a wet classification step S71, a floating step S72, a magnetic separation step S73, or a dry classification step such as wind separation.
  • the black mass is immersed in a solvent to perform classification.
  • the solvent is, for example, water or an organic solvent.
  • By performing the wet classification process S71 it is possible to remove a portion of the carbon from the black mass.
  • By performing the wet classification process S71 it is possible to reduce the carbon in the black mass to, for example, 20 wt % or less.
  • the wet classification process S71 does not have to be performed.
  • the black mass after the wet classification step S71 is immersed in a solvent to separate the black mass based on specific gravity.
  • a solvent for example, components that float on the solvent are separated from components that settle in the solvent.
  • the carbon in the black mass can be reduced to, for example, 10 wt % or less.
  • the floating step S72 does not have to be performed.
  • the magnetic separation step S73 magnetic separation is performed. For example, by bringing a magnet or the like close to the black mass or the suspended slurry, the magnetic material is attracted to the magnet or the like.
  • the positive electrode active material is a lithium iron phosphate compound
  • the lithium iron phosphate compound which is a magnetic material
  • the carbon in the black mass can be reduced to, for example, 5 wt % or less.
  • the magnetic separation step S73 does not have to be performed.
  • the black mass is immersed in an aqueous solution of ferric chloride (FeCl 3 ) to prepare a mixed solution.
  • ferric chloride FeCl 3
  • metal impurities contained in the black mass are dissolved in the solution.
  • the mixed solution preparation step S74 is performed for the purpose of removing impurities, particularly metal impurities.
  • the immersion time of the black mass is, for example, 60 minutes or more, and preferably 120 minutes or more.
  • the stirring speed is, for example, 200 rpm or more and 1000 rpm or less, preferably 400 rpm or more and 800 rpm or less, and more preferably 600 rpm.
  • the mixture is stirred, for example, using a stirrer.
  • the concentration of ferric chloride in the aqueous ferric chloride solution is, for example, 1% or more and 50% or less, preferably 10% or more and 40% or less, more preferably 20% or more and 40% or less, and even more preferably 30% or more and 40% or less.
  • concentration of ferric chloride the easier it is to remove impurities from the black mass.
  • the temperature of the aqueous ferric chloride solution is, for example, 20°C or higher and 120°C or lower, preferably 25°C or higher and 100°C or lower, more preferably 25°C or higher and 80°C or lower, and even more preferably 60°C or higher and 80°C or lower.
  • the mixed liquid is filtered.
  • the mixed liquid is filtered, and the dissolved residue is extracted and washed.
  • the positive electrode active material is almost insoluble in the ferric chloride aqueous solution, but impurity metals such as Cu contained in the black mass are dissolved in the ferric chloride aqueous solution. Therefore, the positive electrode active material contained in the black mass is contained in the dissolved residue. The impurity metals are also contained in the filtrate.
  • electrolysis step S76 electrolysis is performed by applying a voltage to the solution containing the dissolved residue. By performing electrolysis step S76, impurity metals remaining in the dissolved residue can be further separated. Electrolysis step S76 does not have to be performed.
  • the dissolved residue is subjected to heat treatment.
  • the heat treatment is carried out in a low-oxygen atmosphere by bringing the dissolved residue (black mass) into contact with metallic zirconium.
  • the carbon components contained in the black mass react with the metallic zirconium, and some of the carbon components are removed from the black mass.
  • the heat treatment temperature is, for example, 600°C or higher and 1000°C or lower, and preferably 800°C or higher and 900°C or lower. If the heat treatment temperature in the heat treatment step S77 is too high, the structure of the positive electrode active material contained in the black mass may be destroyed. If the heat treatment temperature in the heat treatment step S77 is too low, the efficiency of removing carbon from the black mass decreases.
  • the low-oxygen atmosphere is an atmosphere with a lower oxygen concentration than the air, for example, an inert atmosphere or a vacuum.
  • the inert gas is, for example, nitrogen, argon, or helium.
  • the low-oxygen atmosphere in the heat treatment step S77 is preferably an argon or helium atmosphere, and particularly preferably an argon atmosphere. If the inert gas is nitrogen, a nitriding reaction of the zirconium metal also occurs, reducing the efficiency of removing carbon components from the black mass by the zirconium metal.
  • the carbon contained in the dissolved residue reacts with metallic zirconium to form zirconium carbide. Carbon contained in the dissolved residue is consumed in the carbonization of zirconium, and carbon is removed from the dissolved residue.
  • the carbon in the black mass can be reduced to, for example, 2 wt% or less. The heat treatment step S77 does not have to be performed.
  • the dried dissolved residue is mixed with a lithium compound and heated in an inert atmosphere at a temperature of 400° C. to 900° C.
  • the lithium compound is, for example, Li 2 CO 3 , LiOH, Li 2 O, LiCl, or LiHCO 3 .
  • the black mass was immersed in an FeCl 3 aqueous solution having a concentration of 20% at a temperature of 80° C. for 2 hours, and the dissolved residue (before the Li addition step) after filtration and the dissolved residue (after the Li addition step) after adding Li 2 CO 3 to the dissolved residue and heating at 700° C. in a nitrogen atmosphere were structurally analyzed by the X-ray diffraction method.
  • Li addition step S78 Li 0.05 FePO 4 was used, but after the Li addition step S78, LiFePO 4 was used.
  • Li addition step S78 Li was added to the dissolved residue, and the positive electrode active material was regenerated.
  • the regeneration process S8 is carried out.
  • the positive electrode active material regenerated from the black mass is reused in the lithium ion secondary battery.
  • the method for recycling lithium ion secondary batteries according to this embodiment can remove impurity metals from the black mass by immersing the black mass in an aqueous solution of ferric chloride, with little decomposition of the positive electrode active material. Furthermore, the method for recycling lithium ion secondary batteries according to this embodiment can recover the positive electrode active material while maintaining its crystal structure, allowing the positive electrode active material to be reused.
  • Example 1 First, a lithium ion secondary battery using lithium iron phosphate as a positive electrode active material was collected and discharged. Next, the collected lithium ion secondary battery was heat-treated at 600°C. Then, the heat-treated sample was crushed and sieved to prepare a black mass with an average particle size of 5 ⁇ m. The composition of the black mass was analyzed by inductively coupled plasma emission spectrometry and combustion-infrared absorption spectrometry. The black mass contained 5% by mass of Li, 30% by mass of C, 0.90% by mass of Al, 12% by mass of P, 19% by mass of Fe, 0.12% by mass of Cu, and 33% by mass of other components.
  • the black mass was then immersed in a 10% aqueous solution of ferric chloride at 25°C for 120 minutes.
  • the aqueous solution of ferric chloride to which the black mass had been added was stirred at a stirring speed of 600 rpm.
  • the mixture was filtered and the dissolved residue was extracted.
  • the Cu concentration in the dissolved residue was then measured using inductively coupled plasma atomic emission spectrometry. As a result, the Cu concentration in the dissolved residue was found to be 112 ppm.
  • the ratio of the weight of the dissolved residue (weight after treatment) to the weight of the black mass before immersion in the aqueous solution of ferric chloride (weight before treatment) was calculated to be 0.89.
  • Examples 2 and 3 differ from Example 1 in that the temperature of the aqueous ferric chloride solution was changed.
  • the temperature of the aqueous ferric chloride solution was set to 60° C.
  • the temperature of the aqueous ferric chloride solution was set to 80° C.
  • Other conditions were the same as in Example 1, and the Cu concentrations of the dissolved residues in Examples 2 and 3 were measured.
  • the ratio of the post-treatment weight to the pre-treatment weight was calculated.
  • Examples 4 to 6 Each of Examples 4 to 6 differs from each of Examples 1 to 3 in that the concentration of ferric chloride in the aqueous ferric chloride solution was 20%. The other conditions were the same as in Example 1, and the Cu concentrations of the dissolved residues of Examples 4 to 6 were measured. In addition, the ratio of the post-treatment weight to the pre-treatment weight was calculated.
  • Examples 7 to 9 Each of Examples 7 to 9 differs from each of Examples 1 to 3 in that the ferric chloride concentration of the ferric chloride aqueous solution was 30%. The other conditions were the same as in Example 1, and the Cu concentrations of the dissolved residues of Examples 7 to 9 were measured. In addition, the ratio of the post-treatment weight to the pre-treatment weight was calculated.
  • Examples 10 to 12 Each of Examples 10 to 12 differs from each of Examples 1 to 3 in that the concentration of ferric chloride in the aqueous ferric chloride solution was 40%. The other conditions were the same as in Example 1, and the Cu concentrations of the dissolved residues of Examples 10 to 12 were measured. The ratio of the post-treatment weight to the pre-treatment weight was also calculated.
  • Examples 1 to 3 differ from Examples 1 to 3 in that the solution in which the black mass was immersed was a 1% aqueous nitric acid solution, rather than an aqueous ferric chloride solution.
  • the other conditions were the same as in Example 1, and the Cu concentrations of the dissolved residues of Comparative Examples 1 to 3 were measured. The ratio of the post-treatment weight to the pre-treatment weight was also calculated.
  • Comparative Examples 4 to 6 Each of Comparative Examples 4 to 6 differs from each of Comparative Examples 1 to 3 in that the nitric acid concentration of the nitric acid aqueous solution was 5%. The other conditions were the same as in Example 1, and the Cu concentrations of the dissolved residues of Comparative Examples 4 to 6 were measured. In addition, the ratio of the post-treatment weight to the pre-treatment weight was calculated.
  • Comparative Examples 7 to 9 Each of Comparative Examples 7 to 9 differs from each of Comparative Examples 1 to 3 in that the nitric acid concentration of the nitric acid aqueous solution was 10%. The other conditions were the same as in Example 1, and the Cu concentrations of the dissolved residues of Comparative Examples 7 to 9 were measured. In addition, the ratio of the post-treatment weight to the pre-treatment weight was calculated.
  • the impurity (Cu) concentration in the dissolved residue was lower in Examples 1 to 12 compared to Comparative Examples 1 to 9. This is believed to be because the impurities dissolved in the filtrate and were properly separated from the dissolved residue. Furthermore, in Examples 1 to 12, the ratio of post-treatment weight to pre-treatment weight was small, and the weight did not fluctuate significantly due to treatment. In other words, it can be said that this treatment selectively removed Cu, an impurity metal, and maintained the positive electrode active material.
  • Examples 4-1 to 4-4 Next, in Examples 4-1 to 4-4, the black mass was classified and treated in the same manner as in Example 4, and the Cu concentration in the dissolved residue was measured by inductively coupled plasma atomic emission spectrometry.
  • Example 4 the black mass before immersion in the ferric chloride aqueous solution was mixed with an organic solvent to form a slurry, and classified using a special classification device that uses a microfiltration membrane.
  • the classification diameter was 20 ⁇ m
  • the classification diameter was 15 ⁇ m
  • the classification diameter was 10 ⁇ m
  • the classification diameter was 5 ⁇ m.
  • the black mass of each particle size obtained was treated in the same way as in Example 4, and the Cu concentration of the dissolved residue was measured. The results are shown in Table 2.
  • a positive electrode slurry was applied to one side of an aluminum foil having a thickness of 15 ⁇ m.
  • the positive electrode slurry was prepared by mixing a positive electrode active material, a conductive assistant, a binder, and a solvent.
  • the positive electrode active material was LiFePO 4 extracted from black mass.
  • the conductive assistant was carbon black and carbon nanotubes.
  • the binder was polyvinylidene fluoride (PVDF).
  • the solvent was N-methyl-2-pyrrolidone. 97 parts by mass of the positive electrode active material, 1 part by mass of the conductive assistant, 2 parts by mass of the binder, and 70 parts by mass of the solvent were mixed to prepare a positive electrode slurry.
  • the amount of the positive electrode active material carried in the positive electrode active material layer after drying was 25 mg/cm 2.
  • the solvent was removed from the positive electrode slurry in a drying furnace to prepare a positive electrode active material layer.
  • the positive electrode active material layer was pressed with a roll press to prepare a positive electrode.
  • a negative electrode slurry was prepared.
  • the negative electrode slurry was prepared by mixing a negative electrode active material, a conductive additive, a binder, and a solvent.
  • Graphite was used as the negative electrode active material.
  • Carbon black and carbon nanotubes were used as the conductive additive.
  • Polyvinylidene fluoride (PVDF) was used as the binder.
  • the mass ratio of the negative electrode active material, conductive additive, and binder was 89.5:2.4:8.1.
  • the negative electrode slurry was applied to one side of a copper foil having a thickness of 10 ⁇ m and dried.
  • the amount of the negative electrode active material carried in the negative electrode active material layer after drying was set to 2.5 mg/cm 2.
  • the negative electrode active material layer was pressed with a roll press and then fired in a nitrogen atmosphere at 300° C. or higher for 5 hours to prepare a negative electrode.
  • an electrolyte solution was prepared.
  • FEC fluoroethylene carbonate
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • additives for improving output, gas suppression additives, additives for improving cycle characteristics, additives for improving safety performance, etc. were added to the electrolyte solution.
  • LiPF 6 was used as the electrolyte salt. The concentration of LiPF 6 was 1 mol/L.
  • the prepared negative and positive electrodes were laminated with a separator (porous polyethylene sheet) between them so that the positive and negative active material layers faced each other to obtain a laminate.
  • This laminate was inserted into an exterior body of aluminum laminate film and heat sealed except for one peripheral location to form a closed portion. Finally, the above electrolyte was injected into the exterior body, and the remaining location was sealed with heat sealing while reducing the pressure using a vacuum sealer, to produce a lithium-ion secondary battery. After fabrication, the lithium-ion secondary battery was left to stand for 24 hours.
  • the initial discharge capacity and cycle characteristics of the lithium ion secondary battery thus produced were determined.
  • the cycle characteristics were determined using a secondary battery charge/discharge tester (manufactured by Hokuto Denko Corporation).
  • the battery was charged at a constant current charge rate of 2C (a current value at which charging is completed in 30 minutes when constant current charging is performed at 25°C) until the battery voltage reached 4.2V, and discharged at a constant current discharge rate of 0.5C until the battery voltage reached 2.5V.
  • the discharge capacity after the end of charging and discharging was detected, and the battery capacity Q1 before the cycle test was determined.
  • the battery capacity Q1 before the cycle test corresponds to the initial capacity of the lithium ion secondary battery.
  • the battery whose battery capacity Q1 was calculated above was charged again using a secondary battery charge/discharge tester at a constant current charge rate of 2C until the battery voltage reached 4.2V, and discharged at a constant current discharge rate of 0.5C until the battery voltage reached 2.5V.
  • the above charge/discharge was counted as one cycle, and 500 cycles of charge/discharge were performed. Thereafter, the discharge capacity after 500 cycles of charge/discharge was detected, and the battery capacity Q2 after 500 cycles was calculated.
  • the lithium ion secondary batteries using the positive electrode active materials regenerated from the black mass of Examples 1 to 12 operated normally.
  • the lithium ion secondary batteries using the positive electrode active materials regenerated from the black mass of Comparative Examples 1 to 9 did not operate normally. This is believed to be due to a short circuit occurring between the positive and negative electrodes due to Cu remaining as an impurity.
  • the present invention makes it possible to provide a method for recycling lithium-ion secondary batteries that can efficiently remove impurities contained in the positive electrode active material.

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Abstract

L'invention concerne un procédé de recyclage pour batteries secondaires au lithium-ion, qui comprend : une étape consistant à immerger, dans une solution aqueuse de chlorure ferrique, une masse noire obtenue par le traitement thermique et le broyage de batteries secondaires au lithium-ion, pour préparer une solution de mélange ; une étape consistant à filtrer la solution de mélange pour extraire un résidu de dissolution ; et une étape consistant à mélanger le résidu de dissolution, qui a été lavé et séché, avec un composé de lithium, et à chauffer le mélange résultant sous une condition de température de 400 à 900 °C dans une atmosphère inerte.
PCT/JP2024/003037 2023-02-06 2024-01-31 Procédé de recyclage pour batteries secondaires au lithium-ion Ceased WO2024166762A1 (fr)

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Citations (3)

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CN112678791A (zh) * 2020-12-25 2021-04-20 湖南邦普循环科技有限公司 一种磷酸铁锂废料中锂的回收方法及其应用
CN115148483A (zh) * 2022-07-28 2022-10-04 中国科学院生态环境研究中心 利用废旧磷酸铁锂电池制备LiFe5O8磁性材料的方法

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US20180261894A1 (en) * 2012-04-04 2018-09-13 Worcester Polytechnic Institute Method and apparatus for recycling lithium iron phosphate batteries
CN112678791A (zh) * 2020-12-25 2021-04-20 湖南邦普循环科技有限公司 一种磷酸铁锂废料中锂的回收方法及其应用
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