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WO2025142544A1 - Matériau actif d'électrode positive régénéré, batterie secondaire au lithium-ion le contenant, et procédé de production de matériau actif d'électrode positive régénéré - Google Patents

Matériau actif d'électrode positive régénéré, batterie secondaire au lithium-ion le contenant, et procédé de production de matériau actif d'électrode positive régénéré Download PDF

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WO2025142544A1
WO2025142544A1 PCT/JP2024/044152 JP2024044152W WO2025142544A1 WO 2025142544 A1 WO2025142544 A1 WO 2025142544A1 JP 2024044152 W JP2024044152 W JP 2024044152W WO 2025142544 A1 WO2025142544 A1 WO 2025142544A1
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positive electrode
active material
electrode active
lithium
regenerated
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Japanese (ja)
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利洋 鎌田
稔彦 八幡
信 小澤
雅俊 東海林
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Fujifilm Corp
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Fujifilm Corp
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    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/52—Reclaiming serviceable parts of waste cells or batteries, e.g. recycling

Definitions

  • the positive electrode of a lithium ion secondary battery generally has a positive electrode active material layer, which contains positive electrode active material particles capable of absorbing or releasing lithium ions during charging and discharging.
  • the positive electrode active material layer is usually formed by preparing a slurry (composition) containing components of the positive electrode active material layer, such as the positive electrode active material, applying the slurry, and drying the slurry.
  • the positive electrode active material is an important material that determines the battery capacity, but it is known that it deteriorates with long-term operation of lithium-ion secondary batteries.
  • Patent Document 1 discloses a method of hydrothermally reacting an electrode material in a lithium-deficient state in a solution containing lithium ions, and as a specific example, discloses heating an electrode material containing LiCoO2 in about 4 M lithium hydroxide at 100 to 300° C. for 12 to 48 hours.
  • Patent Document 2 discloses a method for electrochemical alkalization of an electrochemically active material, which comprises the step of adding the electrochemically active material to a solution containing a reducing agent and an alkali metal salt in a solvent to produce an alkalized electrochemically active material, and describes the use of a redox couple as the reducing agent.
  • the present invention aims to provide a regenerated positive electrode active material obtained by replenishing lithium with a lithium-deficient positive electrode active material generated during the use of a lithium ion secondary battery, and by reusing the regenerated positive electrode active material as the positive electrode active material of a lithium ion secondary battery, a lithium ion secondary battery that exhibits excellent discharge capacity even when exposed to high temperatures can be obtained, and a lithium ion secondary battery including the regenerated positive electrode active material.
  • Another objective of the present invention is to provide a method for producing the regenerated positive electrode active material.
  • the ratio of the peak intensity in the region of 528 eV or more and less than 530 eV to the peak intensity in the region of 530 eV or more and less than 535 eV is 0.005 or less.
  • the lithium-deficient positive electrode active material (a) is an active material represented by Li 1- xM 1 PO 4 , where x represents the amount of lithium deficiency, 0 ⁇ x ⁇ 1, and M 1 represents at least one element selected from Fe, Mn, and Co.
  • a lithium ion secondary battery comprising the regenerated positive electrode active material according to any one of [1] to [3].
  • a method for producing a regenerated positive electrode active material comprising: mixing a lithium-deficient positive electrode active material (a), a lithium compound (b), and a reducing agent (c) in a molar ratio of (b) to (c) of 0.13 ⁇ (b)/(c) ⁇ 2.80, thereby replenishing lithium to (a) to obtain a regenerated positive electrode active material.
  • the lithium-deficient positive electrode active material (a) is a positive electrode active material represented by Li 1- xM 1 PO 4 , where x represents the amount of lithium deficiency, 0 ⁇ x ⁇ 1, and M 1 represents at least one element selected from Fe, Mn, and Co.
  • the regenerated positive electrode active material of the present invention suppresses the formation of an oxide film that accompanies relithiation, and by incorporating it into a lithium ion secondary battery, the resulting lithium ion secondary battery can exhibit excellent discharge capacity even when exposed to high temperatures.
  • the lithium ion secondary battery of the present invention exhibits excellent discharge capacity even when exposed to high temperatures, even though it uses a regenerated positive electrode active material.
  • a regenerated positive electrode active material of the present invention can be obtained that suppresses the formation of an oxide film that accompanies relithiation, and by incorporating it into a lithium ion secondary battery, the resulting lithium ion secondary battery can exhibit excellent discharge capacity even when exposed to high temperatures.
  • FIG. 1 is a vertical cross-sectional view showing a schematic diagram of a basic layered structure of an embodiment of a lithium ion secondary battery according to the present invention.
  • a numerical range expressed using “to” means a range including the numerical values before and after “to” as the lower and upper limits.
  • the term “secondary battery” refers to a device in general in which ions move between positive and negative electrodes via an electrolyte by charging and discharging, and energy is stored and released at the positive and negative electrodes. That is, the term “secondary battery” in the present invention includes both batteries and capacitors (e.g., lithium ion capacitors). When the ions are lithium ions, it becomes a lithium ion secondary battery.
  • Secondary batteries can be broadly divided into aqueous secondary batteries and nonaqueous secondary batteries according to the electrolyte used, and in the present invention, nonaqueous secondary batteries are preferred.
  • aqueous secondary battery refers to a secondary battery using an aqueous electrolyte as an electrolyte.
  • nonaqueous secondary battery refers to a nonaqueous electrolyte secondary battery and an all-solid-state secondary battery.
  • nonaqueous electrolyte secondary battery refers to a secondary battery using a nonaqueous electrolyte as an electrolyte.
  • nonaqueous electrolyte refers to an electrolyte that does not substantially contain water.
  • electrolyte that does not substantially contain water means that the “nonaqueous electrolyte” may contain a small amount of water within a range that does not impede the effects of the present invention.
  • the "nonaqueous electrolyte” has a water concentration of 200 ppm (by mass) or less, preferably 100 ppm or less, and more preferably 20 ppm or less. Note that it is practically difficult to make the nonaqueous electrolyte completely anhydrous, and it usually contains 1 ppm or more of water.
  • the regenerated positive electrode active material of the present invention is a regenerated positive electrode active material obtained by replenishing lithium to a lithium-deficient positive electrode active material (a).
  • the lithium-deficient positive electrode active material (a) means a positive electrode active material in a state in which at least a part of the chemical equivalent of lithium derived from the elemental composition of the compound is deficient, and the amount of lithium is less than the chemical equivalent.
  • the amount of lithium (molar amount) of the lithium-deficient positive electrode active material (a) is preferably 0.1 to 0.9 times, more preferably 0.2 to 0.8 times, and even more preferably 0.3 to 0.7 times the amount of lithium (molar amount) of the positive electrode active material in which lithium is not deficient.
  • the ratio (I B /I A ) of the peak intensity (I B ) in the region of 528 eV or more and less than 530 eV to the peak intensity (I A ) in the region of 530 eV or more and less than 535 eV is 0.005 or less.
  • the peak in the region of 530 eV or more and less than 535 eV is a peak derived from the positive electrode active material (e.g., LiFePO 4 ), and the peak in the region of 528 eV or more and less than 530 eV is a peak derived from an oxide film formed on the surface of the positive electrode active material (e.g., an Fe 2 O 3 film formed on LiFePO 4 ). Therefore, the ratio of the peak intensities of these peaks (I B /I A ) being 0.005 or less means that no oxide film is formed on the surface of the regenerated positive electrode active material, or that even if an oxide film is formed, the amount of the oxide film is small.
  • the method of XPS measurement will be described in the Examples below.
  • the regenerated positive electrode active material of the present invention is used as the positive electrode active material of a lithium ion secondary battery, it is possible to obtain a lithium ion secondary battery with an excellent discharge capacity retention rate.
  • the lithium-deficient positive electrode active material (a) which is the raw material of the regenerated positive electrode active material of the present invention is derived from a metal oxide which is usually used as a positive electrode active material of a lithium ion secondary battery.
  • lithium-containing transition metal oxides are often used as positive electrode active materials (see, for example, JP 2023-106633 A).
  • (MA) lithium-containing transition metal oxides having a layered rock salt structure (MB) lithium-containing transition metal oxides having a spinel structure, (MC) lithium-containing transition metal phosphate compounds, (MD) lithium-containing transition metal halide phosphate compounds, and (ME) lithium-containing transition metal silicate compounds are mentioned.
  • lithium-containing transition metal phosphate compounds are preferred, and among them, lithium-containing transition metal phosphate compounds having an olivine structure are preferred.
  • lithium-containing transition metal phosphate compounds having an olivine structure include iron phosphates such as LiFePO 4 and Li 3 Fe 2 (PO 4 ) 3 .
  • the lithium-deficient positive electrode active material (a) is preferably a positive electrode active material containing a lithium-containing transition metal phosphate compound, and is preferably a positive electrode active material represented by Li1 - xM1PO4 (x represents the amount of lithium deficiency, 0 ⁇ x ⁇ 1 , and M1 represents at least one element selected from Fe, Mn, and Co). M1 is preferably an element selected from Fe and Mn, and more preferably Fe.
  • a positive electrode active material not deficient in lithium (a positive electrode active material containing a chemical equivalent of lithium) corresponding to the lithium-deficient positive electrode active material (a) expressed by Li 1- xM 1 PO 4 is a positive electrode active material expressed by LiM 1 PO 4. When Li is completely deficient due to charging and discharging, the positive electrode active material becomes a positive electrode active material expressed by M 1 PO 4 .
  • the lithium-deficient positive electrode active material (a) can be obtained by recovering the positive electrode active material from a used lithium ion secondary battery. The recovery method will be described later.
  • the relithiation rate of the regenerated positive electrode active material is preferably 0.80 or more, more preferably 0.90 or more, more preferably 0.93 or more, more preferably 0.95 or more, more preferably 0.97 or more, and more preferably 0.99 or more.
  • the relithiation rate can be determined by the method described in the Examples.
  • the recycled positive electrode active material may be the recycled positive electrode active material alone, or may contain a trace amount of binder and/or conductive additive that was not removed by the regeneration process in addition to the recycled positive electrode active material.
  • the recycled positive electrode active material usually contains a trace amount of binder and/or conductive additive, and in this case, the whole material including the trace amount of binder and/or conductive additive is the "recycled positive electrode active material" of the present invention.
  • this positive electrode active material is a recycled product (i.e., a recycled positive electrode active material).
  • a 5 mg sample of the dried regenerated positive electrode active material was placed in a sample pan for a simultaneous thermogravimetric and differential thermal analyzer (TGA-50H (trade name), manufactured by Shimadzu Corporation) and set in the apparatus, and the mass was measured under the following conditions.
  • Gas flow rate Nitrogen 50 ml/min Measurement conditions: After standing at 25°C for 2 hours, the sample was heated to 600°C at a rate of 5°C/min under a nitrogen atmosphere, and then left at 600°C for 1 hour.
  • the mass reduction amount (% by mass) calculated by the following formula can be regarded as the binder content (% by mass) in the regenerated positive electrode active material.
  • Mass loss (mass%) 100 ⁇ [(mass after standing at 25° C. for 2 hours) ⁇ (mass after standing at 600° C. for 1 hour)]/(mass after standing at 25° C. for 2 hours)
  • the content of the conductive assistant in the regenerated positive electrode active material is preferably 0.5 mass % or less.
  • the content of the conductive assistant in the regenerated positive electrode active material can be determined by using energy dispersive X-ray spectroscopy (SEM-EDX).
  • SEM-EDX energy dispersive X-ray spectroscopy
  • the regenerated positive electrode active material is applied to a conductive double-sided tape attached to a sample stage to prepare a sample, and the regenerated positive electrode active material is observed by SEM at an acceleration voltage of 1.5 kV using a field emission scanning electron microscope (FE-SEM: Field Emission Scanning Electron Microscope) (manufactured by JEOL, JSM 7100F (trade name)).
  • FE-SEM Field Emission Scanning Electron Microscope
  • An elemental analysis is performed by automatic detection using an energy dispersive X-ray spectroscope (EDX: Energy Dispersive X-ray Spectroscope) (manufactured by Thermo Fisher Scientific, Noran System 7 type (trade name)).
  • EDX Energy Dispersive X-ray Spectroscope
  • the mass ratio of the carbon amount to the total amount of elements detected by automatic detection is the C amount (mass%) of the regenerated positive electrode active material. Since the regenerated positive electrode active material is a metal oxide, this amount of C can be regarded as the amount of conductive additive.
  • the particle size of the regenerated positive electrode active material is not particularly limited. For example, it can be 0.1 to 50.0 ⁇ m, preferably 0.5 to 30.0 ⁇ m, more preferably 1.0 to 20.0 ⁇ m, more preferably 2.0 to 10.0 ⁇ m, and even more preferably 2.0 to 6.0 ⁇ m.
  • the particle size of the regenerated positive electrode active material is the volume-based median diameter D50 in water obtained by dispersing the regenerated positive electrode active material in water and measuring it with a laser diffraction/scattering type particle size distribution measuring device (for example, Particle LA-960V2 manufactured by HORIBA).
  • the lithium ion secondary battery of the present invention contains the regenerated positive electrode active material of the present invention as a positive electrode active material, and is otherwise similar to a normal secondary battery.
  • a lithium ion secondary battery in which the electrode active material layer does not contain an electrolyte is referred to as a first embodiment
  • a lithium ion secondary battery in which the electrode active material layer contains an electrolyte is referred to as a second embodiment.
  • the first form of the lithium ion secondary battery which is a preferred embodiment of the present invention, has a configuration including a positive electrode, a negative electrode, and a separator disposed between the positive electrode and the negative electrode.
  • the positive electrode has a positive electrode current collector and a positive electrode active material layer in contact with the positive electrode current collector
  • the negative electrode has a negative electrode current collector and a negative electrode active material layer in contact with the negative electrode current collector.
  • the positive electrode active material layer is formed using the recycled positive electrode active material of the present invention.
  • the first form of the lithium ion secondary battery of the present invention functions as a secondary battery by charging and discharging, by filling the space between the positive electrode and the negative electrode with a non-aqueous electrolyte.
  • FIG. 1 is a cross-sectional view showing a schematic of a laminated structure of a general lithium ion secondary battery 10 of the first embodiment, including a working electrode when the battery is operated.
  • the lithium ion secondary battery 10 has a laminated structure having, in this order, a negative electrode collector 1, a negative electrode active material layer 2, a separator 3, a positive electrode active material layer 4, and a positive electrode collector 5, as seen from the negative electrode side.
  • the space between the negative electrode active material layer 2 and the positive electrode active material layer 4 is filled with a non-aqueous electrolyte (not shown), and is separated by the separator 3.
  • the separator 3 has pores, and in a normal battery use state, it functions as a positive/negative electrode separator that insulates between the positive and negative electrodes while allowing the electrolyte and ions to pass through the pores.
  • electrons (e ⁇ ) are supplied to the negative electrode side through an external circuit during charging, and at the same time, lithium ions (Li + ) move from the positive electrode through the electrolyte and are accumulated in the negative electrode.
  • the lithium ions (Li + ) stored in the negative electrode are returned to the positive electrode side through the electrolyte, and electrons are supplied to the operating part 6.
  • a light bulb is used as the operating part 6, and this is turned on by discharging.
  • the electrode active material layer is formed in a slurry state containing the electrode active material and the electrolyte. Therefore, the electrode active material layer is a layer using a slurry (suspension, dispersion) in which the electrode active material is dispersed in a non-aqueous electrolyte, and the configuration is different from that of the first embodiment of the lithium ion secondary battery.
  • a coating liquid in which an electrode active material is dispersed in a medium not containing an electrolyte is prepared, the coating liquid is applied to a current collector to form a coating film, and the coating film is dried to form a thin-film electrode active material layer.
  • a binder is usually blended into the coating liquid, and a hard electrode active material layer in which the electrode active material particles are firmly bound to each other is formed.
  • the electrode active material layer is in the state of a hard solid particle layer as a whole, and is not a slurry layer.
  • the electrode active material layer is an electrode slurry layer formed by dispersing solid particles containing an electrode active material and a conductive assistant in a non-aqueous electrolyte solution obtained by dissolving a lithium salt (electrolyte) in a non-aqueous solvent.
  • the electrode slurry layer functions as an electrode active material layer, strong binding between the electrode active material particles is not required, and therefore the electrode slurry layer usually does not contain a binder. Except for the fact that the electrode active material layer is an electrode slurry layer and that the electrode slurry layer is in contact with the separator, the basic layer structure of the quasi-solid lithium ion secondary battery is the same as the layer structure shown in FIG. 1.
  • the lithium ion secondary battery of the present invention comprises the regenerated positive electrode active material of the present invention as the positive electrode active material
  • the materials and components such as the conductive assistant, positive electrode current collector, negative electrode active material, negative electrode current collector, and separator are not particularly limited. These materials and components can be appropriately applied from those used in ordinary secondary batteries.
  • the method for producing a regenerated positive electrode active material of the present invention includes mixing a lithium-deficient positive electrode active material (a), a lithium compound (b), and a reducing agent (c) in a molar ratio of the lithium compound (b) to the reducing agent (c) of 0.13 ⁇ (b)/(c) ⁇ 2.80, thereby replenishing lithium to the lithium-deficient positive electrode active material (a) to obtain a regenerated positive electrode active material.
  • This method is a method for replenishing lithium to the lithium-deficient positive electrode active material (a) using the lithium compound (b) as a lithium source.
  • the regenerated positive electrode active material of the present invention can be efficiently produced under relatively mild conditions while suppressing the formation of an oxide film.
  • a preferred embodiment of the manufacturing method of the present invention includes mixing the lithium-deficient positive electrode active material (a) with a treatment solution containing the lithium compound (b) and the reducing agent (c) in the above molar ratio in a solvent, and replenishing lithium. This mixing is preferably performed by heating.
  • the relithiation reaction of the lithium-deficient positive electrode active material (a) is a so-called hydrothermal reaction when the solvent contains water.
  • the relithiated regenerated positive electrode active material can be recovered from the reaction solution by a conventional solid-liquid separation method such as filtration.
  • the production method of the present invention may further include recovering the lithium-deficient positive electrode active material (a), washing and calcining the resulting regenerated positive electrode active material, and the like.
  • the method for recovering the lithium-deficient positive electrode active material (a) is not particularly limited as long as it is possible to recover the lithium-deficient positive electrode active material from a used lithium ion secondary battery.
  • the lithium-deficient positive electrode active material (a) can be recovered, for example, by immersing the positive electrode removed from the lithium ion secondary battery in a solvent, separating the current collector and the positive electrode active material by an external stimulus such as ultrasonic treatment, and removing the current collector, and then obtaining the lithium-deficient positive electrode active material (a) as solid particles in the remaining suspension.
  • the positive electrode removed from the lithium ion secondary battery is washed, dried, and further immersed in a solvent, and then ultrasonically treated, and the current collector is removed from the resulting suspension, and the precipitate is recovered by centrifugation and dried.
  • the solvent used for the immersion and ultrasonic treatment may be appropriately selected, and examples thereof include N-methylpyrrolidone (NMP), N-ethylpyrrolidone, and N,N-dimethylformamide.
  • NMP N-methylpyrrolidone
  • NMP N-ethylpyrrolidone
  • N,N-dimethylformamide a solvent capable of dissolving the binder
  • the immersion is preferably performed for a time period during which the components constituting the positive electrode active material layer, particularly a binder, are sufficiently compatible with the solvent when the binder is included.
  • the immersion time is preferably 10 minutes or more, and also preferably 20 minutes or more. Since the recovery effect does not change even if the immersion is performed for a long time, the immersion time is preferably 20 minutes to 1 hour.
  • the immersion may be performed at room temperature or with heating.
  • the conditions of the ultrasonic treatment are not particularly limited as long as the positive electrode current collector can be separated from the positive electrode and the solid particles constituting the positive electrode active material layer (solid particles mainly composed of the positive electrode active material) can be obtained in a suspended state in the solvent.
  • the ultrasonic treatment can be performed for 10 to 60 minutes.
  • the centrifugation may be performed at 2000 to 4000 rpm for 5 to 30 minutes, as long as the lithium-deficient positive electrode active material (a) can be recovered as a precipitate from the suspension.
  • Drying is an operation for removing the solvent from the recovered lithium-deficient positive electrode active material (a). Drying conditions can be, for example, 80 to 200° C. and 5 to 24 hours. Alternatively, drying under reduced pressure may be used.
  • the above immersion, ultrasonic treatment, and centrifugation can remove most of the binder and conductive aid.
  • a small amount of the binder and/or conductive aid usually remains. Therefore, the lithium-deficient positive electrode active material (a) that has undergone these steps usually contains a small amount of the binder and/or conductive aid.
  • the molar ratio of the lithium compound (b) and the reducing agent (c) used in the relithiation of the lithium-deficient positive electrode active material (a) is preferably 0.25 ⁇ (b)/(c) ⁇ 2.50, more preferably 0.35 ⁇ (b)/(c) ⁇ 2.45, even more preferably 0.35 ⁇ (B)/(C) ⁇ 2.40, and still more preferably 0.50 ⁇ (b)/(c) ⁇ 2.30, from the viewpoints of suppressing the formation of an oxide film and increasing the relithiation rate of the regenerated positive electrode active material.
  • the amount of the lithium compound (b) is not particularly limited, and from the viewpoint of suppressing the formation of an oxide film and increasing the relithiation rate of the obtained regenerated positive electrode active material, it is preferably 1 molar equivalent or more (1 mole or more of lithium atoms of the lithium compound (b) per mole of lithium deficiency) relative to the lithium deficiency amount (mol) of the lithium-deficient positive electrode active material (a), more preferably 2 molar equivalents or more, more preferably 5 molar equivalents or more, more preferably 10 molar equivalents or more, and even more preferably 15 molar equivalents or more.
  • the upper limit is practically 400 molar equivalents, preferably 380 molar equivalents or less, more preferably 300 molar equivalents or less, and even more preferably 200 molar equivalents or less. Therefore, the amount of the lithium compound (b) to be blended is preferably 1 to 400 molar equivalents relative to the amount of lithium deficiency (mol), more preferably 2 to 400 molar equivalents, more preferably 5 to 400 molar equivalents, still more preferably 10 to 380 molar equivalents, still more preferably 15 to 300 molar equivalents, and still more preferably 15 to 200 molar equivalents.
  • the amount of lithium deficiency in the lithium-deficient positive electrode active material (a) can be calculated from the lithium deficiency rate (%) of the lithium-deficient positive electrode active material (a).
  • the lithium deficiency rate can be measured by the method described in the Examples.
  • the reaction between the lithium-deficient positive electrode active material (a), the lithium compound (b), and the reducing agent (c) is preferably carried out in a pressure-resistant container. This is because the pressure inside the container may become high during the reaction.
  • the above filtration can be carried out by a normal filtration process as long as the solid particles can be recovered from the treatment liquid, and is preferably carried out by vacuum filtration.
  • the rotation speed during centrifugation is not particularly limited, but is preferably 1000 to 5000 rpm, more preferably 1500 to 4000 rpm, and even more preferably 1800 to 3000 rpm.
  • the time during centrifugation is not particularly limited, but is preferably 1 to 10 minutes, and more preferably 2 to 8 minutes.
  • the washed solid particles are preferably further dried, for example, by keeping them at 120° C. for 24 hours.
  • the calcination can be carried out after the relithiation treatment.
  • the calcination may be carried out after the washing treatment.
  • the crystallinity of the regenerated positive electrode active material can be controlled.
  • the firing is preferably carried out at 400° C. or higher, more preferably at 500° C. or higher, and even more preferably at 550° C. or higher.
  • the upper limit of the firing temperature is practically 900° C. or lower, and preferably 650° C. or lower. Therefore, the firing temperature is preferably 400 to 900° C., more preferably 500 to 900° C., even more preferably 500 to 650° C., and even more preferably 550 to 650° C.
  • LiFePO4 lithium iron phosphate
  • AB acetylene black
  • PVdF polyvinylidene fluoride
  • NMP N-methylpyrrolidone
  • the binder was used in an amount of 6 parts by mass relative to 100 parts by mass of the positive electrode active material.
  • the positive electrode slurry P1 was applied to one side of a positive electrode current collector (aluminum foil) having a thickness of 12 ⁇ m to a thickness of 125 ⁇ m, and the dispersion medium was removed at 240° C. Thereafter, the positive electrode was pressed with a pressure of 3.2 t using a roll press machine to obtain a sheet-shaped positive electrode consisting of the positive electrode current collector and the positive electrode active material layer.
  • the thickness of this positive electrode was about 80 ⁇ m.
  • Negative Electrode As a negative electrode active material, 95.7 parts by mass of artificial graphite (UF-G5 (trade name), manufactured by Showa Denko K.K., average particle size (average particle size converted into sphere) 3 ⁇ m), 4.3 parts by mass of acetylene black (AB) (Li-100 (trade name), manufactured by Denka Co., Ltd.) as a conductive assistant, NMP, styrene-butadiene copolymer (SBR) as a binder, and carboxymethyl cellulose (CMC) as a thickener were mixed to obtain a negative electrode slurry N1 (concentration of components insoluble in the solvent: 70.6% by mass).
  • U-G5 artificial graphite
  • AB acetylene black
  • SBR styrene-butadiene copolymer
  • CMC carboxymethyl cellulose
  • the binder was used in an amount of 1 part by mass relative to 100 parts by mass of the negative electrode active material, and the thickener was used in an amount of 1 part by mass relative to 100 parts by mass of the negative electrode active material.
  • a negative electrode slurry N1 was applied to one side of a negative electrode current collector (copper foil) having a thickness of 12 ⁇ m to a thickness of 120 ⁇ m, and the dispersion medium was removed at 240 ° C. Thereafter, the negative electrode was pressed with a pressure of 2 t using a roll press machine to obtain a sheet-shaped negative electrode consisting of a negative electrode current collector and a negative electrode active material layer.
  • the thickness of the negative electrode active material layer of this negative electrode was about 80 ⁇ m.
  • the obtained positive electrode and negative electrode were laminated via a separator (thickness 20 ⁇ m) manufactured by W-SCOPE to form a laminate consisting of a positive electrode collector-positive electrode active material layer-separator-negative electrode active material layer-negative electrode collector.
  • An aluminum tab was attached to the end of the positive electrode collector, and a nickel tab was attached to the end of the negative electrode collector by ultrasonic welding.
  • a battery assembly was prepared by housing this laminate in a laminate container. After injecting nonaqueous electrolyte 1 with the inlet open, the inlet was sealed to close the case, and a lithium ion secondary battery was obtained.
  • Example 23> A positive electrode slurry P2 was prepared in the same manner as in 2. Preparation of a positive electrode above, except that lithium manganese phosphate (LiMnPO 4 ) was used instead of lithium iron phosphate as the positive electrode active material, and a positive electrode was obtained. A lithium ion secondary battery was produced in the same manner as in 4. Battery production above, except that this positive electrode was used.
  • LiMnPO 4 lithium manganese phosphate
  • Example 2> 1 Preparation of Positive Electrode Slurry P3 99.9 parts by mass of lithium iron phosphate, 0.1 parts by mass of Ketjen Black (Carbon ECP (trade name), manufactured by Lion) as a conductive assistant, and non-aqueous electrolyte 1 were mixed for 90 seconds at 1250 rpm in a centrifugal planetary mixer (Thinky Corporation, Awatori Rentaro (trade name)) to obtain positive electrode slurry P3. The amount of non-aqueous electrolyte 1 in the positive electrode slurry P3 was 22.9 mL per 100 g of the total positive electrode active material and conductive assistant in the positive electrode slurry P3.
  • negative electrode slurry N3 98.2 parts by mass of artificial graphite (UF-G30 (trade name), manufactured by Showa Denko K.K.), 1.8 parts by mass of carbon black (LITX300 (trade name), manufactured by CABOT Corporation) as a conductive assistant, and non-aqueous electrolyte 1 were mixed for 90 seconds at 1250 rpm in a centrifugal planetary mixer (manufactured by Thinky Corporation, Awatori Rentaro (trade name)) to obtain negative electrode slurry N3.
  • the amount of non-aqueous electrolyte 1 in the negative electrode slurry N3 was 37.7 mL per 100 g of the total of the negative electrode active material and conductive assistant in the negative electrode slurry N3.
  • a quasi-solid secondary battery was prepared with reference to JP-A 2016-500465 (Examples 10 and 11). Details are shown below.
  • the positive electrode slurry P3 was applied onto an aluminum foil positive electrode current collector to a thickness of 500 ⁇ m and an area of 80 cm 2 to form a positive electrode consisting of the positive electrode current collector and a positive electrode active material layer.
  • the negative electrode slurry N3 was applied onto a copper foil negative electrode current collector to a thickness of 500 ⁇ m and an area of 85 cm 2 to form a negative electrode consisting of the negative electrode current collector and a negative electrode active material layer.
  • a separator manufactured by W-SCOPE was cut to have an area of 90 cm 2 .
  • a separator was laminated on the negative electrode so that the negative electrode was inside the size of the separator, and a positive electrode was laminated on top of that so that the negative electrode was inside the size of the negative electrode, thereby producing a laminate of the negative electrode current collector-negative electrode active material layer (slurry)-separator-positive electrode active material layer (slurry)-positive electrode current collector.
  • the production of the laminate was completed in about 1 minute to prevent the volatilization of the non-aqueous electrolyte 1.
  • Tabs were ultrasonically welded to the positive electrode slurry uncoated portion of the aluminum foil and to the negative electrode slurry uncoated portion of the copper foil of this laminate, and the laminate was wrapped in aluminum laminate and sealed with a vacuum sealer to produce a lithium ion secondary battery (quasi-solid secondary battery) for evaluation tests.
  • Each of the obtained lithium ion secondary batteries was charged and discharged as follows to form a lithium-deficient positive electrode active material (a) in each positive electrode active material layer.
  • the obtained lithium ion secondary battery was charged at 0.1 C using a charge/discharge evaluation device (TOSCAT-3000 (product name), manufactured by Toyo Systems Co., Ltd.) until the voltage reached 3.6 V, and then discharged until the voltage reached 2.0 V. This cycle was counted as one charge/discharge, and charge/discharge was performed 200 times. Thereafter, charge/discharge was further repeated under the same conditions until each positive electrode active material had the lithium deficiency rate shown in Table 1.
  • TOSCAT-3000 product name
  • the lithium-deficient positive electrode active material (a) was recovered as follows. The lithium ion secondary battery after the charge and discharge was disassembled, and the positive electrode was taken out. The taken-out positive electrode was washed with dimethyl carbonate (DMC) and then dried. The dried positive electrode was immersed in NMP for 30 minutes, and then ultrasonically treated in NMP for 20 minutes to dissolve the binder, and the current collector was separated and taken out to obtain a suspension containing a lithium-deficient positive electrode active material (a).
  • DMC dimethyl carbonate
  • the suspension was centrifuged at 3500 rpm for 5 minutes to collect the precipitate, and dried at 120 ° C. for 12 hours. In this way, a lithium-deficient positive electrode active material (a) was obtained.
  • the conductive assistant did not precipitate in the above centrifugation, and the conductive assistant and the lithium-deficient positive electrode active material (a) could be separated.
  • the lithium deficiency rate was calculated from the molar ratio of Fe to Li obtained by ICP-OES measurement, except for Example 23, where the lithium deficiency rate was calculated from the molar ratio of Mn to Li.
  • the lithium-deficient positive electrode active material (a) contains a transition metal element other than Fe and Mn, the lithium deficiency rate can be determined in the same manner.

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Abstract

L'invention concerne : un matériau actif d'électrode positive régénéré obtenu par rechargement de lithium dans un matériau actif d'électrode positive déficient en lithium (a), ledit matériau actif d'électrode positive régénéré ayant un spectre de noyau d'oxygène 1s, tel que mesuré à l'aide de XPS, dans lequel le rapport de l'intensité de pic dans la région d'au moins 528 eV mais inférieure à 530 eV à l'intensité de pic dans la région d'au moins 530 eV mais inférieure à 535 eV est de 0,0005 ou moins ; une batterie secondaire au lithium-ion contenant le matériau actif d'électrode positive régénéré ; et un procédé de production d'un matériau actif d'électrode positive régénéré, ledit procédé comprenant le mélange du matériau actif d'électrode positive déficient en lithium (a), d'un composé de lithium (b) et d'un agent réducteur (c) à des proportions telles que 0,13 ≤ (b)/(c) ≤ 2,80 (rapport molaire) pour obtenir le matériau actif d'électrode positive régénéré.
PCT/JP2024/044152 2023-12-26 2024-12-13 Matériau actif d'électrode positive régénéré, batterie secondaire au lithium-ion le contenant, et procédé de production de matériau actif d'électrode positive régénéré Pending WO2025142544A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010212250A (ja) * 1999-04-06 2010-09-24 Sony Corp 正極活物質の製造方法及び非水電解質二次電池の製造方法
WO2021114747A1 (fr) * 2019-12-09 2021-06-17 贝特瑞（天津）纳米材料制造有限公司 Procédé de régénération sélective par oxydo-réduction à partir de déchets de lithium fer phosphate, lithium fer phosphate régénéré et batterie au lithium-ion
JP7201133B2 (ja) * 2020-07-07 2023-01-10 Dic株式会社 電池用活物質、電池用複合活物質、及び二次電池
CN116525819A (zh) * 2023-07-03 2023-08-01 国网浙江省电力有限公司湖州供电公司 一种基于氮掺杂再生废旧磷酸铁锂正极材料的制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010212250A (ja) * 1999-04-06 2010-09-24 Sony Corp 正極活物質の製造方法及び非水電解質二次電池の製造方法
WO2021114747A1 (fr) * 2019-12-09 2021-06-17 贝特瑞（天津）纳米材料制造有限公司 Procédé de régénération sélective par oxydo-réduction à partir de déchets de lithium fer phosphate, lithium fer phosphate régénéré et batterie au lithium-ion
JP7201133B2 (ja) * 2020-07-07 2023-01-10 Dic株式会社 電池用活物質、電池用複合活物質、及び二次電池
CN116525819A (zh) * 2023-07-03 2023-08-01 国网浙江省电力有限公司湖州供电公司 一种基于氮掺杂再生废旧磷酸铁锂正极材料的制备方法

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