WO2022044489A1 - 非水電解質二次電池用正極活物質および非水電解質二次電池 - Google Patents

非水電解質二次電池用正極活物質および非水電解質二次電池 Download PDF

Info

Publication number
WO2022044489A1
WO2022044489A1 PCT/JP2021/022505 JP2021022505W WO2022044489A1 WO 2022044489 A1 WO2022044489 A1 WO 2022044489A1 JP 2021022505 W JP2021022505 W JP 2021022505W WO 2022044489 A1 WO2022044489 A1 WO 2022044489A1
Authority
WO
WIPO (PCT)
Prior art keywords
positive electrode
composite oxide
active material
amount
mol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2021/022505
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
敏信 金井
毅 小笠原
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Panasonic Intellectual Property Management Co Ltd
Original Assignee
Panasonic Intellectual Property Management Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Panasonic Intellectual Property Management Co Ltd filed Critical Panasonic Intellectual Property Management Co Ltd
Priority to EP21860920.4A priority Critical patent/EP4207370A4/en
Priority to JP2022545463A priority patent/JP7745182B2/ja
Priority to CN202180050460.3A priority patent/CN115868042B/zh
Priority to US18/021,462 priority patent/US20230290941A1/en
Publication of WO2022044489A1 publication Critical patent/WO2022044489A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/20—Two-dimensional structures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/76—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by a space-group or by other symmetry indications
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/45—Aggregated particles or particles with an intergrown morphology
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure relates to a positive electrode active material for a non-aqueous electrolyte secondary battery and a non-aqueous electrolyte secondary battery using the positive electrode active material.
  • the positive electrode active material greatly affects the battery performance such as input / output characteristics, capacity, cycle characteristics, and storage characteristics.
  • a lithium transition metal composite oxide containing metal elements such as Ni, Co, Mn, and Al and composed of secondary particles formed by aggregating primary particles is used as the positive electrode active material. .. Since the properties of the positive electrode active material change greatly depending on the composition, particle shape, etc., many studies have been conducted on various positive electrode active materials.
  • Patent Document 1 At least one selected from a sulfuric acid compound, a nitric acid compound, a boric acid compound, and a phosphoric acid compound is fixed to the particle surface of a lithium transition metal composite oxide containing Ni together with tungsten oxide.
  • a method for producing a positive electrode active material in which the composite particles are heat-treated in an oxygen atmosphere is disclosed.
  • Lithium transition metal composite oxides with a high Ni content are expected as positive electrode active materials that contribute to increasing the capacity of batteries, but in non-aqueous electrolyte secondary batteries using this, non-aqueous electrolytes decompose during charge storage. Therefore, there is a problem that gas is easily generated.
  • the technique disclosed in Patent Document 1 has a problem that when the Ni content ratio in the positive electrode active material is increased, cation mixing is likely to occur and the initial capacity is likely to decrease.
  • the positive electrode active material for a non-aqueous electrolyte secondary battery which is one aspect of the present disclosure, contains a lithium transition metal composite oxide containing 80 mol% or more of Ni with respect to the total molar amount of metal elements excluding Li, and is described above.
  • the lithium transition metal composite oxide contains secondary particles formed by agglomeration of primary particles, and at least one element A selected from Ca and Sr is a total of metal elements excluding Li on the surface of the primary particles. It is present in an amount of 1 mol% or less with respect to the molar amount, and is present on the surface of the secondary particles with at least one element B selected from Zr, Ti, Mn, Er, Pr, In, Sn, and Ba. S exists.
  • the non-aqueous electrolyte secondary battery which is one aspect of the present disclosure, includes a positive electrode containing the positive electrode active material, a negative electrode, and a non-aqueous electrolyte.
  • a non-aqueous electrolyte secondary battery using a positive electrode active material having a high Ni content gas generation during charge storage can be suppressed.
  • the positive electrode active material which is one aspect of the present disclosure, for example, a non-aqueous electrolyte secondary battery having a high capacity and excellent storage characteristics can be provided.
  • FIG. 1 is a cross-sectional view of a non-aqueous electrolyte secondary battery which is an example of an embodiment.
  • FIG. 2 is a diagram schematically showing a particle cross section of a lithium transition metal composite oxide constituting a positive electrode active material, which is an example of an embodiment.
  • the lithium transition metal composite oxide having a large amount of Ni is a useful positive electrode active material that contributes to high capacity and high energy density of the battery, but as a trade-off, it is a non-aqueous electrolyte when the battery is charged and stored. There is a problem that the decomposition of the gas is promoted and the amount of gas generated is increased.
  • the present inventors have added at least one of Ca and Sr (element A) to the surface of the primary particles in the lithium transition metal composite oxide (positive electrode active material) having a large amount of Ni.
  • a predetermined amount of at least one (element B) and S selected from Zr, Ti, Mn, Er, Pr, In, Sn, and Ba are present on the surface of the secondary particles to allow the battery to be present. It has been found that gas generation during charge storage is specifically suppressed.
  • the positive electrode active material having a large amount of Ni is likely to undergo a decomposition reaction of the non-aqueous electrolyte due to the activation of the particle surface, especially when the charge rate is high in a high temperature atmosphere. Therefore, in a non-aqueous electrolyte secondary battery using a positive electrode active material having a large amount of Ni, the amount of gas generated during charge storage is large.
  • a stable protective layer is formed on the surface of the secondary particles of the composite oxide by the interaction due to the coexistence of the elements A, B, and S, and the stability of the surface of the active material is improved. It will be improved. As a result, it is considered that the decomposition reaction of the electrolyte on the surface of the active material is suppressed, and the amount of gas generated during charge storage is greatly reduced.
  • the outer body of the battery is not limited to the cylindrical outer can, for example, a square outer can. It may be a can (square battery), a coin-shaped outer can (coin-shaped battery), or an outer body (laminated battery) composed of a laminated sheet including a metal layer and a resin layer. Further, the electrode body may be a laminated electrode body in which a plurality of positive electrodes and a plurality of negative electrodes are alternately laminated via a separator.
  • FIG. 1 is a cross-sectional view of a non-aqueous electrolyte secondary battery 10 which is an example of an embodiment.
  • the non-aqueous electrolyte secondary battery 10 includes a winding type electrode body 14, a non-aqueous electrolyte, and an outer can 16 for accommodating the electrode body 14 and the non-aqueous electrolyte.
  • the electrode body 14 has a positive electrode 11, a negative electrode 12, and a separator 13, and has a wound structure in which the positive electrode 11 and the negative electrode 12 are spirally wound via the separator 13.
  • the outer can 16 is a bottomed cylindrical metal container having an opening on one side in the axial direction, and the opening of the outer can 16 is closed by a sealing body 17.
  • the sealing body 17 side of the battery is on the top, and the bottom side of the outer can 16 is on the bottom.
  • the positive electrode 11, the negative electrode 12, and the separator 13 constituting the electrode body 14 are all strip-shaped long bodies, and are alternately laminated in the radial direction of the electrode body 14 by being wound in a spiral shape.
  • the negative electrode 12 is formed to have a size one size larger than that of the positive electrode 11 in order to prevent the precipitation of lithium. That is, the negative electrode 12 is formed longer than the positive electrode 11 in the longitudinal direction and the width direction (short direction).
  • the two separators 13 are formed at least one size larger than the positive electrode 11, and are arranged so as to sandwich the positive electrode 11, for example.
  • the electrode body 14 has a positive electrode lead 20 connected to the positive electrode 11 by welding or the like, and a negative electrode lead 21 connected to the negative electrode 12 by welding or the like.
  • Insulating plates 18 and 19 are arranged above and below the electrode body 14, respectively.
  • the positive electrode lead 20 extends to the sealing body 17 side through the through hole of the insulating plate 18, and the negative electrode lead 21 extends to the bottom side of the outer can 16 through the outside of the insulating plate 19.
  • the positive electrode lead 20 is connected to the lower surface of the internal terminal plate 23 of the sealing body 17 by welding or the like, and the cap 27, which is the top plate of the sealing body 17 electrically connected to the internal terminal plate 23, serves as the positive electrode terminal.
  • the negative electrode lead 21 is connected to the inner surface of the bottom of the outer can 16 by welding or the like, and the outer can 16 serves as a negative electrode terminal.
  • a gasket 28 is provided between the outer can 16 and the sealing body 17 to ensure the airtightness inside the battery.
  • the outer can 16 is formed with a grooved portion 22 that supports the sealing body 17, with a part of the side surface portion protruding inward.
  • the grooved portion 22 is preferably formed in an annular shape along the circumferential direction of the outer can 16, and the sealing body 17 is supported on the upper surface thereof.
  • the sealing body 17 is fixed to the upper part of the outer can 16 by the grooved portion 22 and the opening end portion of the outer can 16 crimped to the sealing body 17.
  • the sealing body 17 has a structure in which an internal terminal plate 23, a lower valve body 24, an insulating member 25, an upper valve body 26, and a cap 27 are laminated in this order from the electrode body 14 side.
  • Each member constituting the sealing body 17 has, for example, a disk shape or a ring shape, and each member except the insulating member 25 is electrically connected to each other.
  • the lower valve body 24 and the upper valve body 26 are connected at the central portion of each, and an insulating member 25 is interposed between the peripheral portions of each.
  • the positive electrode 11, the negative electrode 12, the separator 13, and the non-aqueous electrolyte will be described in detail, and in particular, the positive electrode active material constituting the positive electrode 11 will be described in detail.
  • the positive electrode 11 has a positive electrode core 30 and a positive electrode mixture layer 31 provided on the surface of the positive electrode core 30.
  • a metal foil stable in the potential range of the positive electrode 11 such as aluminum or an aluminum alloy, a film on which the metal is arranged on the surface layer, or the like can be used.
  • the positive electrode mixture layer 31 contains a positive electrode active material, a conductive material, and a binder, and is preferably provided on both sides of the positive electrode core body 30.
  • a positive electrode mixture slurry containing a positive electrode active material, a conductive material, a binder, and the like is applied onto the positive electrode core 30, the coating film is dried, and then compressed to compress the positive electrode mixture layer 31.
  • the coating film is dried, and then compressed to compress the positive electrode mixture layer 31.
  • Examples of the conductive material contained in the positive electrode mixture layer 31 include carbon materials such as carbon black, acetylene black, ketjen black, graphite, and carbon nanotubes.
  • Examples of the binder contained in the positive electrode mixture layer 31 include fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN), polyimide resins, acrylic resins, and polyolefin resins. can. These resins may be used in combination with cellulose derivatives such as carboxymethyl cellulose (CMC) or salts thereof, polyethylene oxide (PEO) and the like.
  • CMC carboxymethyl cellulose
  • PEO polyethylene oxide
  • FIG. 2 is a diagram schematically showing a particle cross section of a lithium transition metal composite oxide 35 constituting a positive electrode active material, which is an example of an embodiment.
  • the positive electrode active material of the present embodiment contains a lithium transition metal composite oxide 35 (hereinafter referred to as “composite oxide 35”) containing 80 mol% or more of Ni with respect to the total molar amount of metal elements excluding Li. include.
  • the composite oxide 35 preferably further contains at least one selected from Co, Al, and Mn. Further, as shown in FIG. 2, the composite oxide 35 includes secondary particles 37 formed by aggregating the primary particles 36.
  • the composite oxide 35 having a high Ni content is a useful positive electrode active material that contributes to increasing the capacity and energy density of the battery, but it is said that the amount of gas generated during charging and storage of the battery is large.
  • at least one element A selected from Ca and Sr is present on the surface of the primary particle 36, and at least selected from Zr, Ti, Mn, Er, Pr, In, Sn, and Ba.
  • One kind of elements B and S are present on the surface of the secondary particle 37, and by applying this to the positive electrode active material, gas generation during charge storage can be highly suppressed.
  • the positive electrode active material of this embodiment contains the composite oxide 35 as a main component.
  • the main component means the component having the largest mass ratio among the materials constituting the positive electrode active material.
  • the positive electrode mixture layer 31 may contain a composite oxide other than the composite oxide 35 as the positive electrode active material as long as the object of the present disclosure is not impaired, but the ratio of the composite oxide 35 is preferable. Is 50% by mass or more, more preferably 80% by mass or more. In the present embodiment, it is assumed that the positive electrode active material is substantially composed of only the composite oxide 35. Further, the positive electrode active material may be composed of two or more kinds of composite oxides 35 having different compositions from each other.
  • the composite oxide 35 preferably contains other metal elements in addition to Li, Ni, and the above elements A, B, and S.
  • other metal elements include Co, Al, Mn, Nb, W, Fe, Zn, Er, K, Pr, Ca, Ba, Sc, Rb, Ga, In, Sn, Sr and the like. Above all, it is preferable to contain at least one selected from Co, Al, and Mn.
  • the total amount of the other metal elements contained in the composite oxide 35 is preferably 20 mol% or less, more preferably 15 mol% or less, and more preferably 5 mol% or more, based on the total molar amount of the metal elements excluding Li. It is 20 mol% or less.
  • the Ni content of the composite oxide 35 is 80 mol% or more, preferably 85 mol% or more, and more preferably 90 mol% or more with respect to the total molar amount of the metal element excluding Li.
  • the upper limit of the Ni content is, for example, 95 mol%.
  • the suitable composite oxide 35 contains at least one selected from Co, Al, and Mn in an amount of 5 mol% or more and 20 mol% or less in total with respect to the total molar amount of the metal element excluding Li. .. In this case, the structural stability of the composite oxide 35 is improved, which contributes to the improvement of the storage characteristics.
  • the contents of Al and Mn are, for example, 1 mol% or more and 7 mol% or less, respectively.
  • the Co content of the composite oxide 35 may be less than 5 mol% with respect to the total molar amount of the metal element excluding Li, and the composite oxide 35 may not substantially contain Co. Since Co is rare and expensive, the battery manufacturing cost can be reduced by not using Co.
  • the mole fraction of the element contained in the composite oxide 35 is measured by inductively coupled plasma mass spectrometry (ICP-MS).
  • the composite oxide 35 preferably has a layered rock salt structure.
  • the layered rock salt structure of the composite oxide 35 include a layered rock salt structure belonging to the space group R-3m, a layered rock salt structure belonging to the space group C2 / m, and the like.
  • the composite oxide 35 contains the secondary particles 37 formed by aggregating the primary particles 36.
  • the average particle size of the primary particles 36 is, for example, 200 nm or more and 500 nm or less.
  • the average particle size of the primary particles 36 is determined by analyzing the SEM image of the particle cross section observed by a scanning electron microscope (SEM). For example, the positive electrode 11 is embedded in a resin, a cross section is prepared by cross-section polisher (CP) processing, and the cross section is photographed by SEM. From the SEM image, 30 primary particles 36 are randomly selected and the grain boundaries are observed, the major axis (longest diameter) of each of the 30 primary particles 36 is obtained, and the average value thereof is taken as the average particle size.
  • SEM scanning electron microscope
  • the volume-based median diameter (hereinafter referred to as “D50”) of the secondary particles 37 (composite oxide 35) is, for example, 1 ⁇ m or more and 30 ⁇ m or less, preferably 5 ⁇ m or more and 20 ⁇ m or less.
  • D50 means a particle size in which the cumulative frequency is 50% from the smallest particle size in the volume-based particle size distribution, and is also called a median diameter.
  • the particle size distribution of the secondary particles 37 can be measured using a laser diffraction type particle size distribution measuring device (for example, MT3000II manufactured by Microtrac Bell Co., Ltd.) and water as a dispersion medium.
  • At least one element A selected from Ca and Sr is present on the surface of the primary particles 36 constituting the composite oxide 35 in an amount of 1 mol% or less with respect to the total molar amount of the metal element excluding Li. is doing.
  • the element A is present on the surface of the secondary particles 37 and at the particle interface where the primary particles 36 are in contact with each other, and is present on the surface of all the primary particles 36 constituting the secondary particles 37 of the composite oxide 35. It is considered that the element A adheres evenly to the surface of the primary particles 36 in the state of the compound, and the coat layer 36A containing the element A is formed on the surface of the primary particles 36.
  • the element distribution in the particle cross section of the composite oxide 35 can be confirmed by energy dispersive X-ray spectroscopy (TEM-EDX).
  • Element A is not solid-solved with, for example, Ni or the like, and is substantially present only on the surface of the primary particles 36. Element A contributes to the suppression of gas generation by interacting with elements B and S even if it is added in a small amount, but it should be added in an amount of 0.1 mol% or more based on the total molar amount of the metal element excluding Li. And the effect becomes remarkable. On the other hand, when the content of the element A exceeds 3 mol%, the coat layer 36A containing the element A becomes a resistance layer and the discharge capacity decreases.
  • the content of the element A needs to be controlled to 3 mol% or less with respect to the total molar amount of the metal element excluding Li, but more preferably 0.7 mol% or less, and particularly preferably 0.5 mol% or less.
  • the lower limit of the content of element A is preferably 0.15 mol%, more preferably 0.20 mol%, and particularly preferably 0.25 mol, from the viewpoint of achieving both high capacity of the battery and good storage characteristics.
  • % An example of a suitable element A content is 0.20 mol% or more and 1 mol% or less, or 0.25 mol% or more and 0.5 mol% or less.
  • At least one element B and S selected from Zr, Ti, Mn, Er, Pr, In, Sn, and Ba are present on the surface of the secondary particles 37 of the composite oxide 35.
  • the elements B and S may be present on the entire surface of the primary particle 36 including the inside of the secondary particle 37 as in the element A, but are not substantially present inside the secondary particle 37 and are secondary. It is preferably present only on the surface of the particles 37. In this case, the amount of gas generated during charge storage can be efficiently suppressed. It is considered that the elements B and S adhere evenly to the surface of the secondary particles 37 in the state of compounds, and the coat layer 37B containing the elements B and S is formed on the surface of the secondary particles 37.
  • Element B that is not solid-solved with Ni or the like is present on the surface of the secondary particles 37. Even if the element B is added in a small amount, it contributes to the suppression of gas generation by the interaction with the elements A and S, but by adding 0.02 mol% or more with respect to the total molar amount of the metal element excluding Li, it is possible. , The effect becomes remarkable. On the other hand, when the content of the element B exceeds 0.5 mol%, the coat layer 37B containing the element B becomes a resistance layer and the discharge capacity decreases.
  • the content of the element B is preferably 0.02 mol% or more and 0.5 mol% or less, more preferably 0.04 mol% or more, and particularly preferably 0.05 with respect to the total molar amount of the metal element excluding Li. More than mol%.
  • the upper limit of the content of the element B is more preferably 0.5 mol% or less, and particularly preferably 0.3 mol% or less, from the viewpoint of achieving both high capacity of the battery and good storage characteristics.
  • An example of a suitable element B content is 0.02 mol% or more and 0.5 mol% or less, or 0.04 mol% or more and 0.3 mol% or less.
  • the elements B and S are present outside the element A on the surface of the secondary particles 37. That is, in the particle cross section of the composite oxide 35, the elements B and S and the element A are present in layers in this order from the particle surface side.
  • a coat layer 37B containing the elements B and S is formed so as to cover the coat layer 36A containing the element A. A part of the elements B and S may be directly attached to the surface of the secondary particles 37.
  • the composite oxide 35 is prepared by adding 1 g of the composite oxide 35 to a mixed solution of 100 mL of pure water, 1 mL of a 35 mass% hydrochloric acid aqueous solution, 0.05 mL of 46 mass% hydrofluoric acid, and 0.05 mL of 64 mass% nitrate.
  • the filtrate obtained by filtering the mixed solution after addition and stirring for 5 minutes the partial elution amount of element A in the filtrate determined by ICP-MS and 1 g of the composite oxide 35 are completely dissolved.
  • the ratio of the element A to the total elution amount ((partial elution amount / total elution amount) ⁇ 100) is preferably 60% or more, more preferably 65% or more.
  • the partial elution amount measured by this method indicates the abundance of element A on the surface of the composite oxide 35 and its vicinity (the same applies to S and element B).
  • the elution amount ratio of the element A satisfies the condition, it becomes easier to suppress the gas generation during charge storage as compared with the case where the condition is not satisfied.
  • the total elution amount of the composite oxide 35 For the total elution amount of the composite oxide 35, add 200 mg of the composite oxide 35 to a mixed solution of 35% by mass hydrochloric acid 5 mL, 46% by mass hydrofluoric acid 2.5 mL, and 64% by mass nitric acid 2.5 mL. , Pure water is added to the mixed solution heated at about 90 ° C. for 2 hours, and the mixture is adjusted to 100 mL, and the total elution amount is determined by ICP-MS.
  • the composite oxide 35 is prepared by adding 1 g of the composite oxide 35 to a mixed solution of 100 mL of pure water, 1 mL of a 35 mass% hydrochloric acid aqueous solution, 0.05 mL of 46 mass% hydrofluoric acid, and 0.05 mL of 64 mass% nitrate. The same applies to the filtrate obtained by filtering the mixed solution after addition and stirring for 5 minutes, when the partial elution amount of S in the filtrate determined by ICP-MS and 1 g of the composite oxide 35 are completely dissolved.
  • the ratio of S to the total elution amount ((partial elution amount / total elution amount) ⁇ 100) is preferably 50% or more, more preferably 55% or more. When the elution amount ratio of S satisfies the condition, it becomes easier to suppress gas generation during charge storage as compared with the case where the condition is not satisfied.
  • the composite oxide 35 is prepared by adding 1 g of the composite oxide 35 to a mixed solution of 100 mL of pure water, 1 mL of a 35 mass% hydrochloric acid aqueous solution, 0.05 mL of 46 mass% hydrofluoric acid, and 0.05 mL of 64 mass% nitrate.
  • the filtrate obtained by filtering the mixed solution after addition and stirring for 5 minutes the partial elution amount of element B in the filtrate determined by ICP-MS and 1 g of the composite oxide 35 are completely dissolved.
  • the ratio of the element B to the total elution amount ((partial elution amount / total elution amount) ⁇ 100) is preferably 50% or more, more preferably 55% or more.
  • the composite oxide 35 is a mixture of, for example, a first step of obtaining a composite oxide containing a metal element such as Ni or Al, a composite oxide obtained in the first step, a compound containing an element A, and a Li compound. It can be produced through a second step of obtaining a mixture, a third step of firing the mixture, and a fourth step of adding a compound containing an element B and a compound containing S and heat-treating the mixture. In the fourth step, one kind of compound containing the elements B and S may be added.
  • the first step for example, while stirring a solution of a metal salt containing Ni, Al, etc., an alkaline solution such as sodium hydroxide is dropped to bring the pH to the alkaline side (for example, 8.5 to 12.5).
  • an alkaline solution such as sodium hydroxide
  • a composite hydroxide containing a metal element such as Ni or Al is precipitated (co-precipitated).
  • the firing temperature is not particularly limited, but is, for example, 300 ° C. or higher and 600 ° C. or lower.
  • the composite oxide obtained in the first step, the compound containing the element A, and the Li compound are mixed to obtain a mixture.
  • compounds containing element A include Ca (OH) 2 , CaO, CaCO 3 , CaSO 4 , Ca (NO 3 ) 2 , Sr (OH) 2 , Sr (OH) 2.8H 2 O , SrO, SrCO. 3 , SrSO 4 , Sr (NO 3 ) 2 , and the like can be mentioned.
  • examples of the Li compound include Li 2 CO 3 , LiOH, Li 2 O 2 , Li 2 O, LiNO 3 , LiNO 2 , Li 2 SO 4 , LiOH / H 2 O, LiH, LiF and the like.
  • the mixing ratio of the composite oxide obtained in the first step and the Li compound is, for example, a ratio in which the molar ratio of the metal element excluding Li: Li is in the range of 1: 0.98 to 1: 1.1. It is preferable to do so.
  • another metal raw material may be added as needed.
  • the other metal raw material is an oxide containing a metal element other than the metal element constituting the composite oxide obtained in the first step.
  • the mixture obtained in the second step is calcined in an oxygen atmosphere.
  • a coat layer 36A containing the element A is formed on the surface of the primary particles 36.
  • the heating rate at 450 ° C. or higher and 680 ° C. or lower is 1.0 ° C./min or higher and 5.5 ° C./min or lower, and the maximum temperature reached is 700 ° C. or higher and 850 ° C. or lower.
  • the rate of temperature rise from 680 ° C. to the maximum temperature reached is, for example, 0.1 ° C./min or more and 3.5 ° C./min or less.
  • the holding time of the maximum reached temperature may be 1 hour or more and 10 hours or less.
  • a compound containing elements B and S is mixed with the composite oxide after firing, and the mixture is heat-treated.
  • a coat layer 37B containing the elements B and S is formed on the surface of the secondary particles 37.
  • the composite oxide after firing obtained in the third step may be washed with water by a conventionally known method. After washing with water, the compound containing the elements B and S may be added while the powder of the composite oxide is moist, and then heat treatment (drying) may be performed.
  • the compound containing the elements B and S may be added in a powder state, or may be added in a state of being dissolved or dispersed in water.
  • Examples of compounds containing elements B and S include zirconium sulfate, titanium sulfate, manganese sulfate, erbium sulfate, placeodium sulfate, indium sulfate, tin sulfate, barium sulfate and the like.
  • a compound containing the element B and a compound containing S may be added, respectively.
  • the heat treatment temperature is, for example, 150 ° C. or higher and 300 ° C. or lower in a vacuum atmosphere.
  • the negative electrode 12 has a negative electrode core body 40 and a negative electrode mixture layer 41 provided on the surface of the negative electrode core body 40.
  • a metal foil stable in the potential range of the negative electrode 12 such as copper, a film on which the metal is arranged on the surface layer, or the like can be used.
  • the negative electrode mixture layer 41 contains a negative electrode active material and a binder, and is preferably provided on both sides of the negative electrode core 40.
  • a negative electrode mixture slurry containing a negative electrode active material, a conductive material, a binder, and the like is applied to the surface of the negative electrode core 40, the coating film is dried, and then compressed to compress the negative electrode mixture layer 41. Can be produced by forming on both sides of the negative electrode core 40.
  • the negative electrode mixture layer 41 contains, for example, a carbon-based active material that reversibly occludes and releases lithium ions as the negative electrode active material.
  • Suitable carbon-based active materials are natural graphite such as scaly graphite, massive graphite and earthy graphite, and graphite such as artificial graphite such as massive artificial graphite (MAG) and graphitized mesophase carbon microbeads (MCMB).
  • a Si-based active material composed of at least one of Si and a Si-containing compound may be used, or a carbon-based active material and a Si-based active material may be used in combination.
  • the conductive material contained in the negative electrode mixture layer 41 carbon materials such as carbon black, acetylene black, ketjen black, and graphite can be used as in the case of the positive electrode 11.
  • the binder contained in the negative electrode mixture layer 41 fluororesin, PAN, polyimide, acrylic resin, polyolefin or the like can be used as in the case of the positive electrode 11, but styrene-butadiene rubber (SBR) is used. Is preferable.
  • the negative electrode mixture layer preferably further contains CMC or a salt thereof, polyacrylic acid (PAA) or a salt thereof, polyvinyl alcohol (PVA) and the like. Above all, it is preferable to use SBR in combination with CMC or a salt thereof, PAA or a salt thereof.
  • a porous sheet having ion permeability and insulating property is used as the separator 13.
  • the porous sheet include a microporous thin film, a woven fabric, and a non-woven fabric.
  • the material of the separator 13 polyethylene, polypropylene, polyolefin such as a copolymer of ethylene and ⁇ -olefin, cellulose and the like are suitable.
  • the separator 13 may have either a single-layer structure or a laminated structure.
  • a heat-resistant layer containing inorganic particles, a heat-resistant layer made of a highly heat-resistant resin such as an aramid resin, polyimide, or polyamide-imide may be formed on the surface of the separator 13.
  • the non-aqueous electrolyte includes, for example, a non-aqueous solvent and an electrolyte salt dissolved in the non-aqueous solvent.
  • a non-aqueous solvent for example, esters, ethers, nitriles such as acetonitrile, amides such as dimethylformamide, and a mixed solvent of two or more of these can be used.
  • the non-aqueous solvent may contain a halogen-substituted product in which at least a part of hydrogen in these solvents is substituted with a halogen atom such as fluorine.
  • halogen substituent examples include a fluorinated cyclic carbonate ester such as fluoroethylene carbonate (FEC), a fluorinated chain carbonate ester, and a fluorinated chain carboxylic acid ester such as methyl fluoropropionate (FMP).
  • FEC fluoroethylene carbonate
  • FMP fluorinated chain carboxylic acid ester
  • esters examples include cyclic carbonate esters such as ethylene carbonate (EC), propylene carbonate (PC) and butylene carbonate, dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC) and methylpropyl carbonate.
  • cyclic carbonate esters such as ethylene carbonate (EC), propylene carbonate (PC) and butylene carbonate, dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC) and methylpropyl carbonate.
  • GBL ⁇ -butyrolactone
  • VL ⁇ -valerolactone
  • MP propyl acetate
  • EP methyl propionate
  • ethers examples include 1,3-dioxolane, 4-methyl-1,3-dioxolane, tetrahydrofuran, 2-methyltetrahexyl, propylene oxide, 1,2-butylene oxide, 1,3-dioxane, 1,4.
  • -Cyclic ethers such as dioxane, 1,3,5-trioxane, furan, 2-methylfuran, 1,8-cineole, crown ether, 1,2-dimethoxyethane, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether , Dihexyl ether, ethyl vinyl ether, butyl vinyl ether, methyl phenyl ether, ethyl phenyl ether, butyl phenyl ether, pentyl phenyl ether, methoxy toluene, benzyl ethyl ether, diphenyl ether, dibenzyl ether, o-dimethoxybenzene, 1,2-diethoxy Chain ethers such as ethane, 1,2-dibutoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl
  • the electrolyte salt is preferably a lithium salt.
  • lithium salts include LiBF 4 , LiClO 4 , LiPF 6 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , LiSCN, LiCF 3 SO 3 , LiCF 3 CO 2 , Li (P (C 2 O 4 ) F 4 ), LiPF 6-x (C n F 2n + 1 ) x (1 ⁇ x ⁇ 6, n is 1 or 2 ), LiB 10 Cl 10 , LiCl, LiBr, LiI, chloroborane lithium, lower aliphatic carboxylate lithium, Li 2B 4 O 7 , borates such as Li (B (C 2 O 4 ) F 2 ), LiN (SO 2 CF 3 ) 2 , LiN (C 1 F 2l + 1 SO 2 ) (C m F 2m + 1 SO 2 ) ⁇ l , M is an integer of 0 or more ⁇ and other imide salts.
  • lithium salt these may be used alone or in combination of two or more.
  • LiPF 6 is preferably used from the viewpoint of ionic conductivity, electrochemical stability, and the like.
  • concentration of the lithium salt is, for example, 0.8 mol or more and 1.8 mol or less per 1 L of the non-aqueous solvent.
  • vinylene carbonate, propane sultone-based additive and the like may be added.
  • the above lithium transition metal composite oxide was used as the positive electrode active material.
  • a positive electrode active material, acetylene black, and polyvinylidene fluoride were mixed at a predetermined solid content mass ratio, and N-methyl-2-pyrrolidone (NMP) was used as a dispersion medium to prepare a positive electrode mixture slurry.
  • NMP N-methyl-2-pyrrolidone
  • a positive electrode mixture slurry was applied onto a positive electrode core made of aluminum foil, the coating film was dried and compressed, and then cut to a predetermined electrode size to obtain a positive electrode.
  • Ethylene carbonate (EC), ethylmethyl carbonate (EMC), and dimethyl carbonate (DMC) were mixed in a predetermined volume ratio. LiPF 6 was added to the mixed solvent to obtain a non-aqueous electrolytic solution.
  • test cell non-aqueous electrolyte secondary battery
  • the positive electrode to which the aluminum positive electrode lead is attached and the negative electrode to which the nickel negative electrode lead is attached are spirally wound through a polyethylene separator and molded into a flat shape to form a wound electrode body.
  • This electrode body was housed in an exterior body made of an aluminum laminate, and after injecting the non-aqueous electrolytic solution, the opening of the exterior body was sealed to prepare a test cell for evaluation.
  • Example 2 A test cell was prepared in the same manner as in Example 1 except that the amount of calcium hydroxide added was changed in the synthesis of the positive electrode active material, and the amount of gas generated and the like were evaluated.
  • Example 3 In the synthesis of the positive electrode active material, a test cell was prepared in the same manner as in Example 1 except that titanium sulfate was added instead of zirconium sulfate, and the amount of gas generated and the like were evaluated.
  • Example 4 In the synthesis of the positive electrode active material, a composite oxide containing Ni and Al (molar ratio of Ni and Al is 94: 6) was used instead of the composite oxide containing Ni, Co and Al. , A test cell was prepared in the same manner as in Example 1, and the amount of gas generated and the like were evaluated.
  • Example 5 In the synthesis of the positive electrode active material, except that the composite oxide containing Ni and Mn (molar ratio of Ni and Mn is 94: 6) was used instead of the composite oxide containing Ni, Co and Al. , A test cell was prepared in the same manner as in Example 1, and the amount of gas generated and the like were evaluated. The evaluation results are shown in Table 2. The gas generation amount is a relative value with the gas generation amount of the test cell of Comparative Example 5 described later as 100.
  • Example 6 In the synthesis of the positive electrode active material, a test cell was prepared in the same manner as in Example 1 except that strontium hydroxide was added instead of calcium hydroxide, and the amount of gas generated and the like were evaluated. The evaluation results are shown in Table 2.
  • the gas generation amount is a relative value with the gas generation amount of the test cell of Comparative Example 5 described later as 100.
  • Example 7 In the synthesis of the positive electrode active material, instead of the composite oxide containing Ni, Co, Al, the composite oxide containing Ni, Co, Al (molar ratio of Ni, Co, Al is 83: 14: 3). A test cell was prepared in the same manner as in Example 1 except that the above was used, and the amount of gas generated and the like were evaluated. The evaluation results are shown in Table 3. The gas generation amount is a relative value with the gas generation amount of the test cell of Comparative Example 7 described later as 100.
  • Example 1 A test cell was prepared in the same manner as in Example 1 except that zirconium sulfate was not added in the synthesis of the positive electrode active material, and the amount of gas generated and the like were evaluated.
  • Comparative Example 2 A test cell was prepared in the same manner as in Comparative Example 1 except that the amount of calcium hydroxide added was changed in the synthesis of the positive electrode active material, and the amount of gas generated and the like were evaluated.
  • Example 3 A test cell was prepared in the same manner as in Example 1 except that calcium hydroxide and zirconium sulfate were not added in the synthesis of the positive electrode active material, and the amount of gas generated and the like were evaluated.
  • Example 7 A test cell was prepared in the same manner as in Example 7 except that zirconium sulfate was not added in the synthesis of the positive electrode active material, and the amount of gas generated and the like were evaluated.
  • ⁇ Comparative Example 8> In the synthesis of the positive electrode active material, a test cell was prepared in the same manner as in Comparative Example 1 except that zirconium oxide was added instead of zirconium sulfate, and the amount of gas generated and the like were evaluated.
  • Examples 8 to 10> In the synthesis of the positive electrode active material, a test cell was prepared in the same manner as in Example 1 except that the amount of calcium hydroxide added was changed so that the amount of element A was as shown in Table 4, and the amount of gas generated and the like were determined. Evaluation was performed.
  • the gas generation amount is a relative value with the gas generation amount of the test cell of Comparative Example 1 as 100.
  • Examples 11 to 14> In the synthesis of the positive electrode active material, a test cell was prepared in the same manner as in Example 1 except that the amount of zirconium sulfate added was changed so that the elements B and S were the amounts shown in Table 4, and the amount of gas generated, etc. was evaluated.
  • the gas generation amount is a relative value with the gas generation amount of the test cell of Comparative Example 1 as 100.
  • Non-aqueous electrolyte secondary battery 11 Positive electrode 12 Negative electrode 13 Separator 14 Electrode body 16 Exterior can 17 Sealing body 18, 19 Insulation plate 20 Positive electrode lead 21 Negative electrode lead 22 Grooving part 23 Internal terminal plate 24 Lower valve body 25 Insulation member 26 Upper valve Body 27 Cap 28 Gasket 30 Positive electrode core 31 Positive electrode mixture layer 35 Lithium transition metal composite oxide (composite oxide) 36 Primary particles 36A, 37B Coat layer 37 Secondary particles 40 Negative electrode core 41 Negative electrode mixture layer

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)
PCT/JP2021/022505 2020-08-25 2021-06-14 非水電解質二次電池用正極活物質および非水電解質二次電池 Ceased WO2022044489A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP21860920.4A EP4207370A4 (en) 2020-08-25 2021-06-14 POSITIVE ELECTRODE ACTIVE MATERIAL FOR SECONDARY CELL WITH ANHYDROUS ELECTROLYTE AND SECONDARY CELL WITH ANHYDROUS ELECTROLYTE
JP2022545463A JP7745182B2 (ja) 2020-08-25 2021-06-14 非水電解質二次電池用正極活物質および非水電解質二次電池
CN202180050460.3A CN115868042B (zh) 2020-08-25 2021-06-14 非水电解质二次电池用正极活性物质和非水电解质二次电池
US18/021,462 US20230290941A1 (en) 2020-08-25 2021-06-14 Positive-electrode active material for nonaqueous-electrolyte secondary cell, and nonaqueous-electrolyte secondary cell

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020141799 2020-08-25
JP2020-141799 2020-08-25

Publications (1)

Publication Number Publication Date
WO2022044489A1 true WO2022044489A1 (ja) 2022-03-03

Family

ID=80353063

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/022505 Ceased WO2022044489A1 (ja) 2020-08-25 2021-06-14 非水電解質二次電池用正極活物質および非水電解質二次電池

Country Status (5)

Country Link
US (1) US20230290941A1 (https=)
EP (1) EP4207370A4 (https=)
JP (1) JP7745182B2 (https=)
CN (1) CN115868042B (https=)
WO (1) WO2022044489A1 (https=)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021039239A1 (ja) * 2019-08-30 2021-03-04 パナソニック株式会社 非水電解質二次電池用正極活物質、及び非水電解質二次電池
CN121617948A (zh) * 2026-02-02 2026-03-06 天津师范大学 层状氧化物材料及其制备方法、正极材料、正极片、钠离子电池

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006302880A (ja) * 2005-03-23 2006-11-02 Matsushita Electric Ind Co Ltd リチウムイオン二次電池およびその製造法
JP2006351378A (ja) * 2005-06-16 2006-12-28 Matsushita Electric Ind Co Ltd リチウムイオン二次電池
JP2007018985A (ja) * 2005-07-11 2007-01-25 Matsushita Electric Ind Co Ltd リチウムイオン二次電池
JP2010040383A (ja) 2008-08-06 2010-02-18 Sony Corp 正極活物質の製造方法および正極活物質

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113224271B (zh) * 2020-01-21 2022-04-22 宁德新能源科技有限公司 正极材料和包含所述正极材料的电化学装置及电子装置
KR102392379B1 (ko) * 2020-06-30 2022-04-29 삼성에스디아이 주식회사 니켈계 리튬 금속 복합 산화물, 그 제조방법 및 이를 포함하는 양극을 함유한 리튬이차전지

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006302880A (ja) * 2005-03-23 2006-11-02 Matsushita Electric Ind Co Ltd リチウムイオン二次電池およびその製造法
JP2006351378A (ja) * 2005-06-16 2006-12-28 Matsushita Electric Ind Co Ltd リチウムイオン二次電池
JP2007018985A (ja) * 2005-07-11 2007-01-25 Matsushita Electric Ind Co Ltd リチウムイオン二次電池
JP2010040383A (ja) 2008-08-06 2010-02-18 Sony Corp 正極活物質の製造方法および正極活物質

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4207370A4

Also Published As

Publication number Publication date
CN115868042B (zh) 2025-08-26
JP7745182B2 (ja) 2025-09-29
EP4207370A4 (en) 2024-06-12
EP4207370A1 (en) 2023-07-05
CN115868042A (zh) 2023-03-28
JPWO2022044489A1 (https=) 2022-03-03
US20230290941A1 (en) 2023-09-14

Similar Documents

Publication Publication Date Title
JP7696122B2 (ja) 非水電解質二次電池用正極活物質および非水電解質二次電池
JP7721542B2 (ja) 非水電解質二次電池用正極及び非水電解質二次電池
JPWO2019163483A1 (ja) 非水電解質二次電池
WO2022130982A1 (ja) 非水電解質二次電池用正極、及び非水電解質二次電池
CN114287073A (zh) 非水电解质二次电池用正极活性物质和非水电解质二次电池
WO2022070649A1 (ja) 非水電解質二次電池用正極活物質、及び非水電解質二次電池
JPWO2020174794A1 (ja) 非水電解質二次電池用正極活物質、及び非水電解質二次電池
WO2021181973A1 (ja) 非水電解質二次電池
JP7745182B2 (ja) 非水電解質二次電池用正極活物質および非水電解質二次電池
WO2020262100A1 (ja) 非水電解質二次電池用正極活物質、非水電解質二次電池、及び非水電解質二次電池用正極活物質の製造方法
JP7843471B2 (ja) 非水電解質二次電池用正極、及び非水電解質二次電池
US12473209B2 (en) Positive electrode active material for nonaqueous electrolyte secondary batteries, and nonaqueous electrolyte secondary battery
WO2022138381A1 (ja) 非水電解質二次電池用正極活物質及び非水電解質二次電池
US20260045491A1 (en) Positive electrode active material for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery
WO2023176503A1 (ja) 非水電解質二次電池
CN119384734A (zh) 非水电解质二次电池用正极活性物质、非水电解质二次电池用正极活性物质的制造方法和非水电解质二次电池
US20230155126A1 (en) Positive electrode active material for nonaqueous electrolyte secondary batteries, and nonaqueous electrolyte secondary battery
JP2013137939A (ja) 非水電解質二次電池
US20170047608A1 (en) Rechargeable lithium battery including same
CN116601786A (zh) 非水电解质二次电池用正极活性物质和非水电解质二次电池
EP4550463A1 (en) Positive electrode active material for nonaqueous electrolyte secondary batteries, and nonaqueous electrolyte secondary battery
US20250192234A1 (en) Non-aqueous electrolyte secondary battery
WO2025070166A1 (ja) 非水電解質二次電池
WO2023100748A1 (ja) 非水電解質二次電池
WO2023100766A1 (ja) 非水電解質二次電池

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21860920

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2022545463

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2021860920

Country of ref document: EP

Effective date: 20230327

WWG Wipo information: grant in national office

Ref document number: 202180050460.3

Country of ref document: CN