WO2021245562A1 - 正極活物質、正極活物質層、二次電池、電子機器、及び車両 - Google Patents

正極活物質、正極活物質層、二次電池、電子機器、及び車両 Download PDF

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WO2021245562A1
WO2021245562A1 PCT/IB2021/054818 IB2021054818W WO2021245562A1 WO 2021245562 A1 WO2021245562 A1 WO 2021245562A1 IB 2021054818 W IB2021054818 W IB 2021054818W WO 2021245562 A1 WO2021245562 A1 WO 2021245562A1
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Prior art keywords
positive electrode
active material
electrode active
secondary battery
lithium
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English (en)
French (fr)
Japanese (ja)
Inventor
斉藤丞
門馬洋平
三上真弓
落合輝明
吉谷友輔
菊池梓
成田和平
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Semiconductor Energy Laboratory Co Ltd
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Semiconductor Energy Laboratory Co Ltd
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Priority to JP2022529121A priority Critical patent/JP7809057B2/ja
Priority to KR1020227043226A priority patent/KR20230021001A/ko
Priority to US18/007,789 priority patent/US20230246183A1/en
Priority to CN202180040450.1A priority patent/CN115917790A/zh
Publication of WO2021245562A1 publication Critical patent/WO2021245562A1/ja
Anticipated expiration legal-status Critical
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Complex oxides containing cobalt and at least one other metal element
    • C01G51/42—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • 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
    • C01G53/66—Complex oxides containing nickel and at least one other metal element containing alkaline earth metals, e.g. SrNiO3 or SrNiO2
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of 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
    • H01M4/364—Composites as mixtures
    • 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
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • 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
    • C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • 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
    • C01P2006/42—Magnetic 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 invention relates to a secondary battery using a positive electrode active material and a method for producing the same. Or, it relates to a portable information terminal having a secondary battery, a vehicle, or the like.
  • the uniformity of the present invention relates to a product, a method, or a manufacturing method.
  • the invention relates to a process, machine, manufacture, or composition (composition of matter).
  • One aspect of the present invention relates to a semiconductor device, a display device, a light emitting device, a power storage device, a lighting device, an electronic device, or a method for manufacturing the same.
  • the electronic device refers to all devices having a power storage device, and the electro-optical device having the power storage device, the information terminal device having the power storage device, and the like are all electronic devices.
  • a power storage device refers to an element having a power storage function and a device in general.
  • a power storage device also referred to as a secondary battery
  • a lithium ion secondary battery such as a lithium ion secondary battery, a lithium ion capacitor, an electric double layer capacitor, and the like.
  • Lithium-ion secondary batteries which have particularly high output and high energy density, are portable information terminals such as mobile phones, smartphones, or notebook computers, portable music players, digital cameras, medical devices, or hybrid vehicles (HVs), and electric vehicles.
  • HVs hybrid vehicles
  • EVs electric vehicles
  • PSVs plug-in hybrid vehicles
  • Patent Document 1 improvement of the positive electrode active material has been studied in order to improve the cycle characteristics and the capacity of the lithium ion secondary battery (for example, Patent Document 1 and Non-Patent Document 1).
  • Non-Patent Documents 2 to 4 Research on the crystal structure of the positive electrode active material is also being conducted (Non-Patent Documents 2 to 4). Further, the physical properties of fluoride such as fluorite (calcium fluoride) have been studied for a long time (Non-Patent Document 5). Further, research is being conducted to analyze the X-ray diffraction (XRD) of the crystal structure of the positive electrode active material by using ICSD (Inorganic Crystal Structure Database) introduced in Non-Patent Document 6.
  • XRD X-ray diffraction
  • the characteristics required for the power storage device include improvement of safety and long-term reliability in various operating environments.
  • One aspect of the present invention is to provide a positive electrode active material having a large charge / discharge capacity.
  • one of the issues is to provide a positive electrode active material having a high charge / discharge voltage.
  • it is an object to provide a positive electrode active material with less deterioration.
  • it is an object to provide a new positive electrode active material.
  • Another issue is to provide a secondary battery having a large charge / discharge capacity.
  • Another issue is to provide a secondary battery having a high charge / discharge voltage.
  • one of the issues is to provide a secondary battery having high safety or reliability.
  • one of the issues is to provide a secondary battery with less deterioration.
  • one of the issues is to provide a secondary battery having a long life.
  • one of the issues is to provide a new secondary battery.
  • one aspect of the present invention is to provide a novel substance, an active material, a power storage device, or a method for producing the same.
  • One aspect of the present invention is a secondary battery having a layered crystal structure and having a composite oxide containing at least lithium and an oxide containing zirconium in at least a part of the surface of the composite oxide.
  • the configuration disclosed herein is a secondary battery having a positive electrode and a negative electrode, the positive electrode has a positive electrode active material containing lithium and cobalt, and the positive electrode active material is fluorine, zirconium, nickel, magnesium, aluminum. , Titanium, lanthanum, and calcium, the positive electrode active material has a plurality of convex portions, and the convex portions are secondary batteries containing a zirconium compound.
  • the ridges contain polycrystalline zirconium oxide.
  • the convex portion is a zirconium compound, for example, zirconium dioxide or lithium zirconate.
  • Zirconium oxide represented by zirconium dioxide is also called zirconia.
  • the convex portion has crystallinity and contains zirconium oxide in a polycrystalline state.
  • the positive electrode active material disclosed in the present specification may be said to be a granular material in which the surface of the mother particles is coated with child particles (zirconium oxide) in a non-uniform state. Further, the coverage of the child particles is less than 50%, and the surface of the uncoated mother particles is exposed.
  • the convex part of the positive electrode active material does not have a function such as insertion / removal of lithium ions by charging or discharging, deterioration due to many charge / discharge cycles is reduced, and the entire positive electrode active material is used. Since it seems that it contributes to the structure maintenance of the above, the convex part is also regarded as a part of the positive electrode active material, and the convex part is also referred to as a part of the positive electrode active material.
  • the concentration of fluorine in the positive electrode active material is higher in the surface layer portion than in the central portion of the positive electrode active material.
  • This concentration distribution of fluorine is due to the fact that in the method for producing a positive electrode active material, fluorine is added in two steps, that is, after particles containing lithium and cobalt are produced.
  • the positive electrode active material containing fluorine, lithium, zirconium, and cobalt is preferably obtained by a solid phase method or a sol-gel method.
  • a production method for obtaining the above configuration is also one of the present inventions, and one of the configurations is to prepare a first mixture in which a first material, a second material and a third material are mixed.
  • the first material is a halogen compound with lithium and the second material has magnesium and a third, with a fifth step of heating under conditions to make a fifth mixture.
  • the material is a metal oxide having lithium and cobalt
  • the fourth material has nickel
  • the heating is done in an atmosphere with oxygen, the first.
  • the temperature condition is a temperature range of 600 ° C. or more and 950 ° C. or less and a range of 1 hour or more and 100 hours or less
  • the second temperature condition is a temperature range of 600 ° C. or more and 900 ° C. or less and 1 hour or more and 100 hours or less. It is a method for producing a positive electrode active material performed in the following range.
  • the fifth material has aluminum and the sixth material has zirconium.
  • a mixing method for obtaining a first mixture, a second mixture, a third mixture, a fourth mixture, or a fifth mixture a dry mixing method, a wet mixing method, or a solid phase method is used.
  • a sol-gel method, a sputtering method, a mechanochemical method, and a CVD method can be used.
  • a positive electrode active material having a high energy density and a large charge / discharge capacity it is possible to provide a positive electrode active material having a high energy density and a high charge / discharge voltage. Alternatively, it is possible to provide a positive electrode active material with less deterioration. Alternatively, a novel positive electrode active material can be provided. Alternatively, it is possible to provide a secondary battery having a large charge / discharge capacity. Alternatively, it is possible to provide a secondary battery having a high charge / discharge voltage. Alternatively, a safe or reliable secondary battery can be provided. Alternatively, it is possible to provide a secondary battery with less deterioration. Alternatively, a long-life secondary battery can be provided. Alternatively, a new secondary battery can be provided.
  • FIG. 1A is an SEM photographic diagram
  • FIG. 1B is a schematic diagram thereof.
  • 2A is a partially enlarged STEM photograph of the active material
  • FIG. 2B is a Zr mapping image
  • FIG. 2C is an oxygen mapping image
  • FIG. 2D is an aluminum mapping image
  • FIG. 2E is a cobalt mapping image. It is a mapping image.
  • 3A and 3B are diagrams showing electron diffraction of a cross-sectional STEM image.
  • FIG. 4 is a diagram illustrating a method for producing a positive electrode active material.
  • FIG. 5 is a diagram illustrating a method for producing a positive electrode active material.
  • FIG. 6 is a diagram illustrating a method for producing a positive electrode active material.
  • FIG. 4 is a diagram illustrating a method for producing a positive electrode active material.
  • FIG. 7 is a diagram illustrating a method for producing a positive electrode active material.
  • FIG. 8 is a diagram illustrating the crystal structure of the positive electrode active material according to one aspect of the present invention.
  • FIG. 9 is an XRD pattern calculated from the crystal structure.
  • FIG. 10 is a diagram illustrating the crystal structure of the positive electrode active material of the comparative example.
  • FIG. 11 is an XRD pattern calculated from the crystal structure.
  • 12A to 12D are cross-sectional views illustrating an example of a positive electrode of a secondary battery.
  • 13A is an exploded perspective view of the coin-type secondary battery
  • FIG. 13B is a perspective view of the coin-type secondary battery
  • FIG. 13C is a cross-sectional perspective view thereof.
  • FIG. 14A is a diagram showing an example of a cylindrical secondary battery.
  • FIG. 14B shows an example of a cylindrical secondary battery.
  • FIG. 14C is a diagram showing an example of a plurality of cylindrical secondary batteries.
  • FIG. 14D is a diagram showing an example of a power storage system having a plurality of cylindrical secondary batteries.
  • 15A and 15B are diagrams illustrating an example of a secondary battery.
  • FIG. 15C is a diagram showing the inside of the secondary battery.
  • 16A to 16C are diagrams illustrating an example of a secondary battery.
  • 17A and 17B are views showing the appearance of the secondary battery.
  • 18A to 18C are diagrams illustrating a method for manufacturing a secondary battery.
  • FIG. 19A is a diagram showing a configuration example of the battery pack.
  • FIG. 19A is a diagram showing a configuration example of the battery pack.
  • FIG. 19A is a diagram showing a configuration example of the battery pack.
  • FIG. 19A is a diagram showing
  • FIG. 19B is a diagram showing a configuration example of the battery pack.
  • FIG. 19C is a diagram showing a configuration example of the battery pack.
  • 20A and 20B are diagrams illustrating an example of a secondary battery.
  • 21A to 21C are diagrams illustrating an example of a secondary battery.
  • 22A and 22B are diagrams illustrating an example of a secondary battery.
  • FIG. 23A is a perspective view of a battery pack showing one aspect of the present invention.
  • FIG. 23B is a block diagram of the battery pack.
  • FIG. 23C is a block diagram of a vehicle having a motor.
  • 24A to 24D are diagrams illustrating an example of a transportation vehicle.
  • 25A and 25B are diagrams illustrating a power storage device according to an aspect of the present invention.
  • 26A is a diagram showing an electric bicycle.
  • FIG. 26B is a diagram showing a secondary battery of an electric bicycle.
  • FIG. 26C is a diagram illustrating an electric motorcycle.
  • 27A to 27D are diagrams illustrating an example of an electronic device.
  • FIG. 28A is a diagram showing an example of a wearable device.
  • FIG. 28B is a diagram showing a perspective view of the wristwatch type device.
  • FIG. 28C is a diagram illustrating a side surface of a wristwatch-type device.
  • 29A and 29B are graphs showing the cycle characteristics shown in Example 1.
  • 30A and 30B are graphs showing the cycle characteristics shown in Example 1.
  • FIG. 31 is a graph showing the powder resistance shown in Example 1.
  • FIG. 32 is a graph showing the cycle characteristics (maintenance rate of discharge capacity) shown in Example 2.
  • FIG. 33A and 33B are diagrams showing the results of XPS analysis.
  • 34A and 34B are diagrams showing the results of XPS analysis.
  • FIG. 35A is an SEM photographic diagram, and FIG. 35B is a schematic diagram thereof.
  • FIG. 36 is a graph showing the cycle characteristics shown in Example 3.
  • FIG. 37 is a diagram illustrating a method for producing a positive electrode active material.
  • the secondary battery has, for example, a positive electrode and a negative electrode.
  • a positive electrode active material As a material constituting the positive electrode, there is a positive electrode active material.
  • the positive electrode active material is, for example, a substance that undergoes a reaction that contributes to the charge / discharge capacity.
  • the positive electrode active material may contain a substance that does not contribute to the charge / discharge capacity as a part thereof.
  • the positive electrode active material of one aspect of the present invention may be expressed as a positive electrode material, a positive electrode material for a secondary battery, a composite oxide, or the like. Further, in the present specification and the like, it is preferable that the positive electrode active material of one aspect of the present invention has a compound. Further, in the present specification and the like, it is preferable that the positive electrode active material of one aspect of the present invention has a composition. Further, in the present specification and the like, the positive electrode active material according to one aspect of the present invention preferably has a complex.
  • uneven distribution means a phenomenon in which a certain element (for example, B) is spatially unevenly distributed in a solid composed of a plurality of elements (for example, A, B, C).
  • the surface layer portion of particles such as an active material is, for example, a region within 50 nm, more preferably within 35 nm, still more preferably within 20 nm, and most preferably within 10 nm from the surface toward the inside.
  • the surface created by cracks and cracks can also be called the surface.
  • the area deeper than the surface layer is called the inside.
  • the grain boundaries are, for example, a portion where particles are fixed to each other, a portion where the crystal orientation changes inside the particles (including the central portion), a portion containing many defects, and a portion where the crystal structure is disturbed. Etc. Grain boundaries can be said to be one of the surface defects.
  • the vicinity of the grain boundary means a region within 10 nm from the grain boundary.
  • the particle is not limited to a spherical shape (the cross-sectional shape is a circle), and the cross-sectional shape of each particle is an ellipse, a rectangle, a trapezoid, a cone, a quadrangle with rounded corners, and an asymmetry.
  • the shape of the individual particles may be irregular.
  • the Miller index is used for the notation of the crystal plane and the direction.
  • Individual planes indicating crystal planes are represented by (). Crystallographically, the notation of the crystal plane, direction, and space group is crystallographically, but due to the restrictions of the application notation in the present specification, etc., instead of adding a bar above the number, the number is preceded by the number. It may be expressed with a- (minus sign).
  • the layered rock salt type crystal structure of the composite oxide containing lithium and the transition metal has a rock salt type ion arrangement in which cations and anions are alternately arranged, and the transition metal and lithium are present.
  • a crystal structure capable of two-dimensional diffusion of lithium because it is regularly arranged to form a two-dimensional plane.
  • the layered rock salt crystal structure may have a distorted lattice of rock salt crystals.
  • the rock salt type crystal structure means a structure in which cations and anions are alternately arranged. There may be a cation or anion deficiency.
  • a material having a layered rock salt type crystal structure such as lithium cobalt oxide (LiCoO 2 ) has a high discharge capacity and is excellent as a positive electrode active material for a secondary battery.
  • the material having a layered rock salt type crystal structure include a composite oxide represented by LiMO 2.
  • the amount of lithium that can be inserted and removed in the positive electrode active material is indicated by x in the composition formula, for example, x in Li x CoO 2 , or x in Li x MO 2 .
  • Li x CoO 2 in the present specification can be appropriately read as Li x MO 2.
  • x charge capacity / theoretical capacity can be set.
  • LiCoO 2 as a positive electrode active material
  • x 0.8
  • x in Li x CoO 2 is small means, for example, 0.1 ⁇ x ⁇ 0.24.
  • the positive electrode active material will be described with reference to FIGS. 8 to 10.
  • 8 to 10 show a case where cobalt is used as the transition metal of the positive electrode active material.
  • Lithium cobalt oxide (LiCoO 2 ) may have a different crystal structure depending on the Li occupancy x of the lithium site.
  • FIG. 10 shows changes in the crystal structure of the conventional positive electrode active material.
  • the conventional positive electrode active material shown in FIG. 10 is lithium cobalt oxide (LiCoO 2 ) having no additive element A in particular.
  • changes in the crystal structure of lithium cobalt oxide having no additive element A are described in Non-Patent Documents 1 to 3 and the like.
  • lithium occupies the octahedral site, and there are three CoO two layers in the unit cell. Therefore, this crystal structure may be referred to as an O3 type crystal structure.
  • the CoO 2 layer is a structure in which an octahedral structure in which oxygen is coordinated to cobalt is continuous with a plane in a shared ridge state. This may be referred to as a layer composed of an octahedron of cobalt and oxygen.
  • This structure CoO 2 layer is present one layer in the unit cell. Therefore, it may be called O1 type or monoclinic O1 type.
  • This structure can be said to be a structure in which CoO 2 structures such as P-3m1 (O1) and LiCoO 2 structures such as R-3m (O3) are alternately laminated. Therefore, this crystal structure may be referred to as an H1-3 type crystal structure.
  • the H1-3 type crystal structure has twice the number of cobalt atoms per unit cell as the other structures.
  • the c-axis of the H1-3 type crystal structure is shown as a half of the unit cell.
  • the coordinates of cobalt and oxygen in the unit cell are set to Co (0, 0 , 0.42150 ⁇ 0.00016), O 1 (0). , 0, 0.267671 ⁇ 0.00045), O 2 (0, 0, 0.11535 ⁇ 0.00045).
  • O 1 and O 2 are oxygen atoms, respectively.
  • the H1-3 type crystal structure is represented by a unit cell using one cobalt and two oxygens.
  • the O3'type crystal structure of one aspect of the present invention is preferably represented by a unit cell using one cobalt and one oxygen.
  • lithium cobalt oxide When charging and discharging such that x in Li x CoO 2 becomes 0.24 or less are repeated, lithium cobalt oxide has an H1-3 type crystal structure and a discharged state R-3m (O3) structure. Changes in crystal structure (that is, non-equilibrium phase changes) will be repeated between them.
  • the difference in volume is also large.
  • the difference in volume between the H1-3 type crystal structure and the discharged state O3 type crystal structure is 3.0% or more.
  • the continuous structure of two CoO layers such as P-3m1 (O1) of the H1-3 type crystal structure is likely to be unstable.
  • the crystal structure of lithium cobalt oxide collapses when charging and discharging are repeated so that x becomes 0.24 or less.
  • the collapse of the crystal structure causes deterioration of the cycle characteristics. This is because the collapse of the crystal structure reduces the number of sites where lithium can stably exist, and it becomes difficult to insert and remove lithium.
  • Layered rock salt crystals and anions of rock salt crystals have a cubic close-packed structure (face-centered cubic lattice structure).
  • the O3'type crystal structure is also presumed to have a cubic close-packed structure for anions. When they come into contact, there is a crystal plane in which the orientation of the hexagonal close-packed structure composed of anions is aligned.
  • the space group of layered rock salt type crystals and O3'type crystals is R-3m
  • the space group of rock salt type crystals Fm-3m (space group of general rock salt type crystals) and Fd-3m (simplest symmetry).
  • the mirror index of the crystal plane satisfying the above conditions is different between the layered rock salt type crystals and the O3'type crystals and the rock salt type crystals.
  • the orientations of the crystals are substantially the same when the orientations of the cubic close-packed structures composed of anions are aligned. be.
  • TEM transmission electron microscope
  • STEM scanning transmission electron microscope
  • HAADF-STEM high-angle scattering annular dark-field scanning transmission electron microscope
  • ABF-STEM Abbreviations: X-ray diffraction
  • XRD X-ray diffraction
  • electron diffraction neutron diffraction
  • the arrangement of cations and anions can be observed as repetition of bright and dark lines.
  • the angle formed by the repetition of the bright line and the dark line between the crystals is 5 degrees or less, more preferably 2.5 degrees or less. It can be observed. In some cases, light elements such as oxygen and fluorine cannot be clearly observed in the TEM image or the like, but in that case, the alignment of the metal elements can be used to determine the alignment.
  • the theoretical capacity of the positive electrode active material means the amount of electricity when all the lithium that can be inserted and removed from the positive electrode active material is desorbed.
  • the theoretical capacity of LiCoO 2 is 274 mAh / g
  • the theoretical capacity of LiNiO 2 is 274 mAh / g
  • the theoretical capacity of LiMn 2 O 4 is 148 mAh / g.
  • LiCoO 2 and x 1.
  • discharge completed means a state in which the voltage is 3.0 V or 2.5 V or less with a current of 100 mAh / g or less, for example.
  • the charge capacity and / or the discharge capacity used for calculating x in Li x CoO 2 is preferably measured under conditions where there is no influence of short circuit and / or decomposition of the electrolyte. For example, data from a secondary battery with a sudden change in capacity, which appears to be a short circuit, should not be used to calculate x.
  • the discharge rate is a relative ratio of the current at the time of discharge to the battery capacity, and is expressed in the unit C.
  • the current corresponding to 1C is X (A).
  • X (A) When discharged with a current of 2X (A), it is said to be discharged at 2C, and when discharged with a current of X / 5 (A), it is said to be discharged at 0.2C.
  • the charging rate is also the same.
  • When charged with a current of 2X (A) it is said to be charged with 2C, and when charged with a current of X / 5 (A), it is charged with 0.2C. It is said that.
  • Constant current charging refers to, for example, a method of charging with a constant charging rate.
  • Constant voltage charging refers to, for example, a method of charging by keeping the voltage constant when the charging reaches the upper limit voltage.
  • the constant current discharge refers to, for example, a method of discharging with a constant discharge rate.
  • the value in the vicinity of a certain numerical value A means a value of 0.9A or more and 1.1A or less.
  • a lithium metal is used as a counter electrode
  • the secondary battery of one aspect of the present invention is the same.
  • Other materials such as graphite and lithium titanate may be used for the negative electrode.
  • the properties of the positive electrode and the positive electrode active material of one aspect of the present invention such as the crystal structure being less likely to collapse even after repeated charging and discharging, and good cycle characteristics being obtained, are not affected by the material of the negative electrode.
  • the secondary battery of one aspect of the present invention may be charged / discharged with a counterpolar lithium at a voltage higher than a general charging voltage of about 4.7 V, but may be charged / discharged at a lower voltage. You may. When charging / discharging at a lower voltage, it is expected that the cycle characteristics will be further improved as compared with those shown in the present specification and the like.
  • the structure is such that the surface of the positive electrode active material is prevented from reacting with the electrolytic solution and being reduced.
  • the reaction area between the positive electrode active material and the electrolytic solution is reduced, the decomposition of the electrolytic solution or the reduction of the positive electrode active material is suppressed, and the cycle characteristics are improved.
  • FIG. 1 is a TEM photograph of one particle of a positive electrode active material produced by using the sol-gel method shown in the present embodiment.
  • the positive electrode active material 100 which is one particle, has a plurality of convex portions and has various shapes, but one particle of the positive electrode active material 100 having convex portions 101, 102, 103.
  • a schematic diagram is shown in FIG. 1B.
  • FIG. 2A is a STEM photograph measured at an acceleration voltage of 200 kV using an HD-2700 manufactured by Hitachi High-Technologies Corporation.
  • FIG. 2B shows a mapping image of Zr in the vicinity of the region (Area1) of the convex portion 103 in FIG. 2A.
  • FIG. 2C shows a mapping image of oxygen in the vicinity of the region (Area1) of the convex portion 103.
  • FIG. 2D shows a mapping image of aluminum in the vicinity of the region (Area1) of the convex portion 103.
  • FIG. 2E shows a mapping image of cobalt in the vicinity of the region (Area1) of the convex portion 103. From these mapping images, it can be said that there may be a grain boundary between Area1 and Area2.
  • each element carbon, nitrogen, oxygen, fluorine, Zr, Al, Si, Ti, Co, Ni, Cu detected in Area1 and the region Area2 inside the positive electrode active material particles in FIG. 2A , Ga
  • carbon, oxygen, and silicon include those derived from the collodion membrane.
  • Cu includes scattering of mesh and the like.
  • the convex portion 103 has zirconium oxide from these results.
  • the convex portion 103 also contains cobalt. Fluorine, silicon, and Cu contained in the convex portion 103 are contained in a larger amount than the region Area2 inside the positive electrode active material particles. In the region Area2 inside the positive electrode active material particles, cobalt and aluminum are detected in a larger amount than Area1. Further, as can be read from FIG. 2D, the convex portion 103 also contains aluminum. Further, in Area 1 and Area 2, nitrogen, titanium, nickel and gallium have almost the same concentration.
  • the convex portion 103 includes polycrystals. It is also a monoclinic system. The monoclinic system of zirconium oxide is most stable at room temperature.
  • FIGS. 33A, 33B, 34A, and 34B the analysis result of XPS of the obtained positive electrode active material is shown in FIGS. 33A, 33B, 34A, and 34B.
  • XPS analysis results there is a possibility that each peak appears at a position lower than the actual position due to the influence of charging.
  • zirconium exists as ZrO 2 in the convex portion on the surface of the positive electrode active material.
  • X-ray photoelectron spectroscopy can analyze the region from the surface to a depth of 2 nm or more and 8 nm or less (usually about 5 nm), the concentration of each element is quantitatively measured in about half of the surface layer region. Can be analyzed. In addition, narrow scan analysis can be used to analyze the bonding state of elements. The quantification accuracy of XPS is often about ⁇ 1 atomic%, and the lower limit of detection is about 1 atomic% depending on the element.
  • monochromatic aluminum can be used as an X-ray source.
  • the output can be, for example, a 1486.6 eV.
  • the take-out angle may be, for example, 45 °. Under such measurement conditions, it is possible to analyze a region from the surface to a depth of 2 nm or more and 8 nm or less (usually about 5 nm) as described above.
  • Quantera2 manufactured by PHI was used for XPS analysis.
  • the peak showing the binding energy of fluorine and other elements is preferably 682 eV or more and less than 685 eV as shown in FIG. 33B. It is more preferably about 684.3 eV. This is a value different from both the binding energy of lithium fluoride, 685 eV, and the binding energy of magnesium fluoride, 686 eV. That is, when the positive electrode active material of one aspect of the present invention has fluorine, it is preferably a bond other than lithium fluoride and magnesium fluoride.
  • the peak showing the binding energy between magnesium and other elements is preferably 1302 eV or more and less than 1304 eV, preferably about 1303 eV. Is more preferable. This is a value different from the binding energy of 1305 eV of magnesium fluoride, which is close to the binding energy of magnesium oxide. That is, when the positive electrode active material of one aspect of the present invention has magnesium, it is preferably a bond other than magnesium fluoride.
  • Additive elements that are preferably present in large amounts on the surface layer such as magnesium, aluminum and titanium, have concentrations measured by XPS or the like such as ICP-MS (inductively coupled plasma mass spectrometry) or GD-MS (glow discharge mass spectrometry). It is preferably higher than the concentration measured by method) or the like.
  • the concentration of the surface layer portion is higher than the concentration inside.
  • the magnesium concentration is preferably attenuated to 60% or less of the peak at a depth of 1 nm from the peak top. Further, it is preferable that the attenuation is 30% or less of the peak at a depth of 2 nm from the peak top. Processing can be performed by, for example, a FIB (focused ion beam) device.
  • the atomic number of magnesium is preferably 0.4 times or more and 1.5 times or less the atomic number of cobalt.
  • the ratio Mg / Co of the number of atoms of magnesium as analyzed by ICP-MS is preferably 0.001 or more and 0.06 or less.
  • nickel is not unevenly distributed on the surface layer and is distributed over the entire positive electrode active material.
  • the positive electrode active material 100 has an O3'type crystal structure.
  • the change in the crystal structure between the discharged state where x in Li x CoO 2 is 1 and the state where x is 0.24 or less is larger than that of the conventional positive electrode active material. There are few. More specifically, the deviation between the two CoO layers in the state where x is 1 and the state where x is 0.24 or less can be reduced. In addition, it is possible to reduce the change in volume when compared per cobalt atom. Therefore, in the positive electrode active material 100 of one aspect of the present invention, the crystal structure does not easily collapse even if charging and discharging are repeated so that x becomes 0.24 or less, and excellent cycle characteristics can be realized.
  • the positive electrode active material 100 of one aspect of the present invention can have a more stable crystal structure than the conventional positive electrode active material in a state where x in Li x CoO 2 is 0.24 or less. Therefore, the positive electrode active material 100 according to one aspect of the present invention is unlikely to cause a short circuit when x in Li x CoO 2 is maintained in a state of 0.24 or less. This is preferable because the safety is further improved.
  • the difference in volume between the sufficiently discharged state and the charged state with a high voltage is small when compared with the change in the crystal structure and the same number of transition metal atoms.
  • FIG. 8 shows the crystal structure of the positive electrode active material 100 when x in Li x CoO 2 is about 1 and 0.2.
  • the positive electrode active material 100 is a composite oxide having lithium, cobalt as a transition metal, and oxygen.
  • a halogen such as fluorine or chlorine as an additive element.
  • R-3m O3' is attached to FIG. 8 to show this crystal structure.
  • ions such as cobalt, nickel and magnesium occupy the oxygen 6 coordination position.
  • a light element such as lithium may occupy the oxygen 4-coordination position.
  • FIG. 8 it is shown that lithium is present in all lithium sites with an equal probability, but the present invention is not limited to this. It may be unevenly present in some lithium sites, or may have symmetry such as monoclinic O1 (Li 0.5 CoO 2). The distribution of lithium can be analyzed, for example, by neutron diffraction.
  • the O3'type crystal structure is a crystal structure similar to the CdCl 2 type crystal structure, although Li is randomly present between the layers.
  • This crystal structure similar to CdCl type 2 is similar to the crystal structure when lithium nickel oxide is charged to Li 0.06 NiO 2, but is pure lithium cobalt oxide or a layered rock salt type positive electrode active material containing a large amount of cobalt. It is known that usually does not have a CdCl type 2 crystal structure.
  • the change in the crystal structure when a large amount of lithium is removed in a state where x in Li x CoO 2 is 0.24 or less is larger than that of the conventional positive electrode active material. It is suppressed.
  • the discharge state R-3m (O3) there is little deviation of CoO 2 layers in O3 'type crystal structure.
  • the difference in volume per cobalt atom of the same number of O3'-type crystal structures from R-3m (O3) in the discharged state is 2.5% or less, more specifically 2.2% or less, typically 1. It is 8%.
  • the positive electrode active material 100 suppresses changes in the crystal structure when x in Li x CoO 2 is small, that is, when a large amount of lithium is removed, as compared with the conventional positive electrode active material. Has been done.
  • the change in volume when compared per the same number of cobalt atoms is also suppressed. Therefore, the crystal structure of the positive electrode active material 100 does not easily collapse even if charging and discharging are repeated so that x becomes 0.24 or less. Therefore, the positive electrode active material 100 suppresses a decrease in charge / discharge capacity in the charge / discharge cycle.
  • the positive electrode active material 100 since more lithium can be stably used than the conventional positive electrode active material, the positive electrode active material 100 has a large discharge capacity per weight and per volume. Therefore, by using the positive electrode active material 100, a secondary battery having a high discharge capacity per weight and per volume can be manufactured. It was confirmed that the positive electrode active material 100 may have an O3'type crystal structure when x in Li x CoO 2 is 0.15 or more and 0.24 or less, and x exceeds 0.24 and is 0. It is presumed to have an O3'type crystal structure even at .27 or less.
  • the crystal structure is not necessarily limited to the above range of x because it is affected not only by x in Li x CoO 2 but also by the number of charge / discharge cycles, charge / discharge current, temperature, electrolyte, and the like. Therefore, when x in Li x CoO 2 is more than 0.1 and 0.24 or less, the positive electrode active material 100 does not have to have an O3'type crystal structure in all of the internal 100b of the positive electrode active material 100. It may contain other crystal structures or may be partially amorphous. Further, in order to make x in Li x CoO 2 small, it is generally necessary to charge with a high charging voltage.
  • a state in which x in Li x CoO 2 is small can be rephrased as a state in which the battery is charged with a high charging voltage.
  • a charging voltage of 4.6 V or higher based on the potential of lithium metal is a high charging voltage.
  • the charging voltage is expressed with reference to the potential of lithium metal.
  • the positive electrode active material 100 is preferable because it can maintain a crystal structure having symmetry of R-3m O3 even when charged at a high charging voltage, for example, a voltage of 4.6 V or more at 25 ° C. In other words. Further, it can be said that it is preferable because an O3'type crystal structure can be obtained when the battery is charged at a higher charging voltage, for example, a voltage of 4.65 V or more and 4.7 V or less at 25 ° C.
  • the positive electrode active material 100 may have an O3'type crystal structure.
  • the voltage of the secondary battery is lower than the above by the potential of graphite.
  • the potential of graphite is about 0.05 V to 0.2 V with respect to the potential of the potential lithium metal. Therefore, a secondary battery using graphite as the negative electrode active material has the same crystal structure when the voltage is obtained by subtracting the graphite potential from the above voltage.
  • the difference in volume per cobalt atom of the same number of O3 type crystal structures in the discharged state and the O3'type crystal structure is 2.5% or less, more specifically 2.2% or less, which is typical. Is 1.8%.
  • the coordinates of cobalt and oxygen in the unit cell are set to Co (0,0,0.5), O (0,0, x), 0.20 ⁇ . It can be shown within the range of x ⁇ 0.25.
  • a halogen compound such as a fluorine compound
  • lithium cobalt oxide before the heat treatment for distributing magnesium on the surface layer.
  • a halogen compound causes a melting point depression of lithium cobalt oxide. By lowering the melting point, it becomes easy to distribute magnesium on the surface layer at a temperature at which cationic mixing is unlikely to occur. Further, if a fluorine compound is present, it can be expected that the corrosion resistance to hydrofluoric acid generated by the decomposition of the electrolytic solution is improved.
  • the concentration of magnesium contained in the positive electrode active material of one aspect of the present invention is preferably 0.001 times or more and 0.1 times or less the number of atoms of the transition metal, more preferably larger than 0.01 and less than 0.04, and 0. About 0.02 is more preferable.
  • the concentration of magnesium shown here may be, for example, a value obtained by elemental analysis of the entire particles of the positive electrode active material using ICP-MS or the like, or a value of the blending of raw materials in the process of producing the positive electrode active material. May be based.
  • One or more metals selected from, for example, nickel, aluminum, manganese, titanium, vanadium and chromium may be added to lithium cobaltate as a metal other than cobalt (hereinafter referred to as metal Z), and in particular, one or more of nickel and aluminum may be added. It is preferable to add it.
  • metal Z a metal other than cobalt
  • Manganese, titanium, vanadium and chromium may be stable in tetravalent and may have a high contribution to structural stability.
  • the crystal structure of the positive electrode active material according to one aspect of the present invention may become more stable, for example, when x in Li x CoO 2 is 0.24 or less.
  • the metal Z is added at a concentration that does not significantly change the crystallinity of lithium cobalt oxide.
  • the amount is preferably such that the above-mentioned Jahn-Teller effect and the like are not exhibited.
  • transition metals such as nickel and manganese and aluminum are preferably present at cobalt sites, but some may be present at lithium sites.
  • Magnesium is preferably present in lithium sites.
  • Oxygen may be partially replaced with fluorine.
  • the symmetry of the oxygen atom is slightly different between the O3 type crystal structure and the O3'type crystal structure. Specifically, in the O3 type crystal structure, the oxygen atoms are aligned along the (-102) plane shown by the dotted line, whereas in the O3'type crystal structure, the oxygen atoms are strictly aligned in the (-102) plane. Not aligned. This is because in the O3'type crystal structure, tetravalent cobalt increases with the decrease of lithium, the Jahn-Teller strain increases, and the octahedral structure of CoO 6 is distorted. In addition, the repulsion between oxygen in the two layers of CoO became stronger as the amount of lithium decreased.
  • the device and conditions for XRD measurement are not particularly limited.
  • D8 ADVANCE manufactured by Bruker can be used as the measuring device.
  • the measurement conditions are, for example, a CuK ⁇ X radiation source and a powder setting, a sample is sprinkled on a grease-coated silicon non-reflective plate, and the measurement surface can be measured according to the measurement surface required by the apparatus.
  • the pattern of LiCoO 2 (O3) and CoO 2 (O1) is one of the modules of Material Studio (BIOVIA) from the crystal structure information obtained from ICSD (Inorganic Crystal Structure Database) (see Non-Patent Document 6). It was created using the Reflex Powerer Structure.
  • the pattern of the H1-3 type crystal structure was similarly prepared from the crystal structure information described in Non-Patent Document 4.
  • the crystal structure is estimated from the XRD pattern of the positive electrode active material of one aspect of the present invention, and TOPAS ver. 3 (Crystal structure analysis software manufactured by Bruker) was used for fitting, and an XRD pattern was created in the same manner as the others.
  • the positive electrode active material 100 has an O3'type crystal structure when charged at a high voltage, but not all of the particles need to have an O3'type crystal structure. It may contain other crystal structures or may be partially amorphous. However, when the Rietveld analysis is performed on the XRD pattern, the O3'type crystal structure is preferably 50 wt% or more, more preferably 60 wt% or more, still more preferably 66 wt% or more. When the O3'type crystal structure is 50 wt% or more, more preferably 60 wt% or more, still more preferably 66 wt% or more, the positive electrode active material having sufficiently excellent cycle characteristics can be obtained.
  • the O3'type crystal structure is preferably 35 wt% or more, more preferably 40 wt% or more, and 43 wt% or more when Rietveld analysis is performed. Is more preferable.
  • the crystallite size of the O3'-type crystal structure possessed by the particles of the positive electrode active material is reduced to only about 1/20 of that of LiCoO 2 (O3) in the discharged state. Therefore, even under the same XRD measurement conditions as the positive electrode before charging / discharging, a clear peak of the O3'type crystal structure can be confirmed when x in Li x CoO 2 is small.
  • the crystallite size becomes small and the peak becomes broad and small. The crystallite size can be obtained from the half width of the XRD peak.
  • the influence of the Jahn-Teller effect is small.
  • the positive electrode active material of one aspect of the present invention preferably has a layered rock salt type crystal structure and mainly contains cobalt as a transition metal. Further, in the positive electrode active material of one aspect of the present invention, the metal Z described above may be contained in addition to cobalt as long as the influence of the Jahn-Teller effect is small.
  • Step S11 As step S11 of FIG. 4, first, a lithium source and a transition metal M source are prepared as materials for the composite oxide (LiMO 2 ) having lithium, a transition metal M, and oxygen.
  • lithium source for example, lithium carbonate, lithium hydroxide, lithium nitrate, lithium fluoride and the like can be used.
  • the transition metal M it is preferable to use a metal capable of forming a layered rock salt type composite oxide belonging to the space group R-3m together with lithium.
  • a metal capable of forming a layered rock salt type composite oxide belonging to the space group R-3m together with lithium for example, at least one of manganese, cobalt and nickel can be used. That is, as the transition metal M source, only cobalt may be used, only nickel may be used, two types of cobalt and manganese, or two types of cobalt and nickel may be used, and cobalt, manganese, and nickel may be used. 3 types may be used.
  • a metal capable of forming a layered rock salt type composite oxide When a metal capable of forming a layered rock salt type composite oxide is used, it is preferable to use a mixing ratio of cobalt, manganese, and nickel within a range in which a layered rock salt type crystal structure can be obtained. Further, aluminum may be added to these transition metals to the extent that a layered rock salt type crystal structure can be obtained.
  • transition metal M source an oxide, a hydroxide, or the like of the above-mentioned metal exemplified as the transition metal M can be used.
  • cobalt source for example, cobalt oxide, cobalt hydroxide and the like can be used.
  • manganese source manganese oxide, manganese hydroxide or the like can be used.
  • nickel source nickel oxide, nickel hydroxide or the like can be used.
  • aluminum source aluminum oxide, aluminum hydroxide, or the like can be used.
  • Step S12 the above-mentioned lithium source and transition metal M source are mixed.
  • Mixing can be done dry or wet.
  • a ball mill, a bead mill or the like can be used for mixing.
  • zirconia balls it is preferable to use zirconia balls as a pulverizing medium, for example.
  • step S13 the materials mixed above are heated.
  • This step may be referred to as firing or first heating to distinguish it from the subsequent heating step.
  • the heating is preferably performed at 800 ° C. or higher and lower than 1100 ° C., more preferably 900 ° C. or higher and 1000 ° C. or lower, and further preferably about 950 ° C. Alternatively, it is preferably 800 ° C. or higher and 1000 ° C. or lower. Alternatively, it is preferably 900 ° C. or higher and 1100 ° C. or lower. If the temperature is too low, the decomposition and melting of the lithium source and the transition metal M source may be insufficient.
  • the heating time can be, for example, 1 hour or more and 100 hours or less, and preferably 2 hours or more and 20 hours or less. Alternatively, it is preferably 1 hour or more and 20 hours or less. Alternatively, it is preferably 2 hours or more and 100 hours or less.
  • the firing is preferably performed in an atmosphere such as dry air where there is little water (for example, a dew point of ⁇ 50 ° C. or lower, more preferably ⁇ 100 ° C. or lower). For example, it is preferable to heat at 1000 ° C. for 10 hours, raise the temperature to 200 ° C./h, and set the flow rate of the dry atmosphere to 10 L / min. The heated material can then be cooled to room temperature (25 ° C.). For example, it is preferable that the temperature lowering time from the specified temperature to room temperature is 10 hours or more and 50 hours or less.
  • cooling to room temperature in step S13 is not essential. If there is no problem in performing the subsequent steps S41 to S43, the cooling may be performed at a temperature higher than room temperature.
  • step S14 the material calcined above is recovered to obtain a composite oxide (LiMO 2) having lithium, a transition metal M, and oxygen.
  • a composite oxide LiMO 2
  • lithium cobalt oxide, lithium manganate, lithium nickel oxide, lithium cobalt oxide in which part of cobalt is replaced with manganese, lithium cobalt oxide in which part of cobalt is replaced with nickel, or nickel-manganese- Obtain lithium cobalt oxide and the like.
  • step S14 a composite oxide having lithium, a transition metal M and oxygen previously synthesized may be used. In this case, steps S11 to S13 can be omitted.
  • lithium cobalt oxide particles (trade name: CellSeed C-10N) manufactured by Nippon Chemical Industrial Co., Ltd. can be used as the pre-synthesized composite oxide.
  • This has an average particle size (D50) of about 12 ⁇ m, and in impurity analysis by glow discharge mass spectrometry (GD-MS), the magnesium concentration and fluorine concentration are 50 ppm wt or less, and the calcium concentration, aluminum concentration and silicon concentration are 100 ppm wt.
  • lithium cobaltate has a nickel concentration of 150 ppm wt or less, a sulfur concentration of 500 ppm wt or less, an arsenic concentration of 1100 ppm wt or less, and a concentration of other elements other than lithium, cobalt and oxygen of 150 ppm wt or less.
  • lithium cobalt oxide particles (trade name: CellSeed C-5H) manufactured by Nippon Chemical Industrial Co., Ltd. can also be used. This is a lithium cobalt oxide having an average particle size (D50) of about 6.5 ⁇ m and an element concentration other than lithium, cobalt and oxygen in the impurity analysis by GD-MS, which is about the same as or less than C-10N. be.
  • cobalt is used as the metal M
  • pre-synthesized lithium cobalt oxide particles CellSeed C-10N manufactured by Nippon Chemical Industrial Co., Ltd.
  • a halogen source such as a fluorine source or a chlorine source and a magnesium source are prepared as materials for the mixture 902. It is also preferable to prepare a lithium source.
  • fluorine source examples include lithium fluoride (LiF), magnesium fluoride (MgF 2 ), aluminum fluoride (AlF 3 ), titanium fluoride (TiF 4 , TiF 3 ), and cobalt fluoride (CoF 2 , CoF 3 ).
  • chlorine source for example, lithium chloride, magnesium chloride or the like can be used.
  • magnesium source for example, magnesium fluoride, magnesium oxide, magnesium hydroxide, magnesium carbonate and the like can be used.
  • lithium fluoride for example, lithium fluoride or lithium carbonate can be used. That is, lithium fluoride can be used both as a lithium source and as a fluorine source. Magnesium fluoride can be used both as a fluorine source and as a magnesium source.
  • lithium fluoride LiF is prepared as a fluorine source
  • magnesium fluoride (MgF 2 ) is prepared as a fluorine source and a magnesium source.
  • the effect of lowering the melting point is highest.
  • the amount of lithium fluoride increases, there is a concern that the amount of lithium becomes excessive and the cycle characteristics deteriorate.
  • the term "neighborhood" means a value larger than 0.9 times and smaller than 1.1 times the value.
  • a solvent is prepared.
  • a ketone such as acetone, an alcohol such as ethanol and isopropanol, an ether such as diethyl ether, dioxane, acetonitrile, N-methyl-2-pyrrolidone (NMP) and the like can be used. It is more preferable to use an aprotic solvent that does not easily react with lithium. In this embodiment, acetone is used.
  • step S22 the material of the above mixture 902 is pulverized and mixed.
  • Mixing can be done dry or wet, but wet is preferred because it can be pulverized to a smaller size.
  • a ball mill, a bead mill or the like can be used for mixing.
  • zirconia balls it is preferable to use zirconia balls as a pulverizing medium, for example. It is preferable that the mixing and pulverizing steps are sufficiently performed to atomize the mixture 902.
  • step S23 the material mixed and pulverized above is recovered to obtain a mixture 902.
  • the D50 (median diameter) is preferably 600 nm or more and 20 ⁇ m or less, and more preferably 1 ⁇ m or more and 10 ⁇ m or less. Alternatively, it is preferably 600 nm or more and 10 ⁇ m or less. Alternatively, it is preferably 1 ⁇ m or more and 20 ⁇ m or less.
  • the mixture 902 when mixed with a composite oxide having lithium, a transition metal M, and oxygen in a later step, the mixture 902 tends to be uniformly present on the surface of the particles of the composite oxide. ..
  • step S41 the LiMO 2 obtained in step S14 and the mixture 902 are mixed.
  • the mixing in step S41 is preferably milder than the mixing in step S12 so as not to destroy the particles of the composite oxide.
  • the rotation speed is lower or the time is shorter than the mixing in step S12.
  • the dry type is a condition in which the particles are less likely to be destroyed than the wet type.
  • a ball mill, a bead mill or the like can be used for mixing.
  • zirconia balls it is preferable to use zirconia balls as a pulverizing medium, for example.
  • step S42 the material mixed above is recovered to obtain a mixture 903.
  • the present embodiment describes a method of adding a mixture of lithium fluoride and magnesium fluoride to lithium cobalt oxide having few impurities
  • one aspect of the present invention is not limited to this.
  • a starting material of lithium cobalt oxide to which a magnesium source, a fluorine source, or the like is added and calcined may be used. In this case, since it is not necessary to separate the steps of steps S11 to S14 and the steps of steps S21 to S23, it is simple and highly productive.
  • lithium cobalt oxide to which magnesium and fluorine have been added in advance may be used. If lithium cobalt oxide to which magnesium and fluorine are added can be used, the steps up to step S42 can be omitted, which is more convenient.
  • a magnesium source and a fluorine source may be further added to lithium cobalt oxide to which magnesium and fluorine have been added in advance.
  • step S43 the mixture 903 is heated in an atmosphere containing oxygen.
  • This step may be referred to as a first annealing (first temperature condition) in order to distinguish it from other heating steps.
  • the heating is more preferably a heating having an effect of suppressing sticking so that the particles of the mixture 903 do not stick to each other.
  • Examples of the heating having the effect of suppressing sticking include heating while stirring the mixture 903, heating while vibrating the container containing the mixture 903, and the like.
  • the heating temperature in step S43 needs to be higher than the temperature at which the reaction between LiMO 2 and the mixture 902 proceeds.
  • the temperature at which the reaction proceeds here may be any temperature at which mutual diffusion of the elements of LiMO 2 and the mixture 902 occurs. Therefore, it may be lower than the melting temperature of these materials. For example, in salts and oxides, solid phase diffusion occurs from 0.757 times the melting temperature T m (Tanman temperature T d).
  • the temperature is higher than the temperature at which at least a part of the mixture 903 is melted because the reaction proceeds more easily. Therefore, the annealing temperature is preferably equal to or higher than the co-melting point of the mixture 902.
  • the temperature in step S43 is 742 ° C. or higher, which is the co-melting point.
  • the annealing temperature is more preferably 830 ° C. or higher.
  • Mixture 903 has at least fluorine, lithium, cobalt, and magnesium. Further, the mixture 903 has an O3'type crystal structure.
  • the annealing temperature must be equal to or lower than the decomposition temperature of LiMO 2 (1130 ° C. in the case of LiCoO 2). Further, at a temperature near the decomposition temperature, there is a concern about decomposition of LiMO 2, although the amount is small. Therefore, the annealing temperature is preferably 1130 ° C. or lower, more preferably 1000 ° C. or lower, further preferably 950 ° C. or lower, and even more preferably 900 ° C. or lower.
  • the annealing temperature is preferably 500 ° C. or higher and 1130 ° C. or lower, more preferably 500 ° C. or higher and 1000 ° C. or lower, further preferably 500 ° C. or higher and 950 ° C. or lower, and further preferably 500 ° C. or higher and 900 ° C. or lower.
  • 742 ° C. or higher and 1130 ° C. or lower are preferable, 742 ° C. or higher and 1000 ° C. or lower are more preferable, 742 ° C. or higher and 950 ° C. or lower are further preferable, and 742 ° C. or higher and 900 ° C. or lower are further preferable.
  • 830 ° C. or higher and 1130 ° C. or lower are preferable, 830 ° C. or higher and 1000 ° C. or lower are more preferable, 830 ° C. or higher and 950 ° C. or lower are further preferable, and 830 ° C. or higher and 900 ° C. or lower are further preferable.
  • some materials for example LiF, which is a fluorine source, function as a flux.
  • the annealing temperature can be lowered to below the decomposition temperature of LiMO 2 , for example, 742 ° C or higher and 950 ° C or lower, and additives such as magnesium are distributed higher in the surface layer than in the center, resulting in good characteristics.
  • a positive electrode active material can be produced.
  • LiF is lighter than oxygen molecules, LiF can be volatilized and dissipated by heating. In that case, LiF in the mixture 903 decreases and the function as a flux is weakened. Therefore, it is necessary to heat while suppressing the volatilization of LiF. Even if LiF is not used as a fluorine source or the like , Li and F on the surface of LiMO 2 may react with each other to generate LiF and volatilize. Therefore, even if a fluoride having a melting point higher than that of LiF is used, it is necessary to suppress volatilization in the same manner.
  • the mixture 903 in an atmosphere containing LiF, that is, to heat the mixture 903 in a state where the partial pressure of LiF in the heating furnace is high. By such heating, the volatilization of LiF in the mixture 903 can be suppressed.
  • Annealing is preferably performed at an appropriate time.
  • the appropriate annealing time varies depending on conditions such as annealing temperature, particle size and composition of LiMO 2 in step S14. Smaller particles may be more preferred at lower temperatures or shorter times than larger ones.
  • the annealing temperature is preferably, for example, 600 ° C. or higher and 950 ° C. or lower.
  • the annealing time is, for example, preferably 3 hours or more, more preferably 10 hours or more, still more preferably 60 hours or more.
  • the annealing temperature is preferably, for example, 600 ° C. or higher and 950 ° C. or lower.
  • the annealing time is, for example, preferably 1 hour or more and 10 hours or less, and more preferably about 2 hours.
  • the temperature lowering time after annealing is preferably, for example, 10 hours or more and 50 hours or less.
  • an additive source is prepared as step S31.
  • the element possessed by the additive source for example, one or more selected from zirconium, aluminum, nickel, manganese, titanium, vanadium, iron, chromium, niobium, cobalt, arsenic, zinc, silicon, sulfur, phosphorus and boron should be used. Can be done.
  • FIG. 4 describes an example in which a zirconium source is used as an additive source.
  • the source of each additive is preferably an oxide, a hydroxide, a fluoride, an alkoxide or the like.
  • Step S61 the annealed mixture 903 and the additive source are mixed. It may be said that the additive is contained on the surface of the annealed mixture 903.
  • a solid phase method for example, a solid phase method, a sol-gel method, a sputtering method, a mechanochemical method, a CVD method and the like can be used.
  • the solid-phase method and the sol-gel method are preferable because the additive can be easily contained on the surface of the annealed mixture 903 at atmospheric pressure and room temperature.
  • the sol-gel method uses a metal organic compound solution as a starting material, and the solution is a sol in which metal oxides or fine particles of hydroxide are dissolved by hydrolysis and polymerization of the compounds in the solution.
  • the sol-gel method When the sol-gel method is used, first, the alkoxide of the additive source dissolved in alcohol and the annealed mixture 903 are mixed.
  • zirconium (IV) tetrapropoxide can be used.
  • the alcohol for example, isopropanol (2-propanol) can be used.
  • the mixture of the isopropanol solution of zirconium (IV) tetrapropoxide and the annealed mixture 903 is stirred.
  • Stirring can be done, for example, with a magnetic stirrer.
  • the stirring time may be long enough for water in the atmosphere and zirconium (IV) tetrapropoxide to cause a hydrolysis and polycondensation reaction, and can be performed, for example, for 60 hours under room temperature conditions.
  • the precipitate is collected from the mixed solution after the above treatment.
  • filtration, centrifugation, evaporation to dryness, or the like can be applied.
  • it is recovered by evaporation to dryness.
  • it is air-dried at 95 ° C.
  • Step S62 the material dried above is recovered to obtain a mixture 904.
  • Step S63> the mixture 904 synthesized in step S62 is heated.
  • heating of S63 may be referred to as a second annealing (second temperature condition)
  • the holding time at the specified temperature is preferably 50 hours or less, more preferably 2 hours or more and 10 hours or less, and further preferably 1 hour or more and 3 hours or less.
  • the temperature range of the specified temperature is preferably 500 ° C. or higher and 1200 ° C. or lower, and more preferably 800 ° C. or higher and 1000 ° C. or lower.
  • the specified temperature is set to 800 ° C. and the temperature is maintained for 2 hours, the temperature rise is 200 ° C./h, and the flow rate in the dry atmosphere is 10 L / min.
  • Step S64 crushing is performed, and if necessary, mixing is performed.
  • step S66 the material crushed above can be recovered to prepare the positive electrode active material 100. At this time, it is preferable to further sift the recovered particles. By sieving, if the positive electrode active material particles are stuck to each other, this can be eliminated.
  • FIG. 4 a manufacturing method different from that of FIG. 4 will be described with reference to FIGS. 5 to 7. Since there are many parts in common with FIG. 4, the different parts will be mainly described. For the common parts, the explanation of FIG. 4 can be taken into consideration. Although it is indicated that the positive electrode active material 100 is finally obtained in the production flow of FIGS. 4, 5, 6, and 7, it is instructed that the positive electrode active material 100 has the same structure and the same components. However, if the manufacturing process is different, at least a part thereof is different, for example, the particle size, the convex portion, the concentration distribution, the appearance of the particles, and the like are different.
  • step S61 a method for producing the mixture 903 after annealing and a zirconium source as an additive source are described in step S61, but one aspect of the present invention is not limited to this. As shown in steps S32 and S33 of FIGS. 5 to 7, further other additives may be mixed. Crushing may be performed before mixing steps S32 and S33 of FIGS. 5 to 7.
  • the additive for example, one or more selected from nickel, aluminum, manganese, titanium, zirconium, vanadium, iron, chromium, niobium, cobalt, arsenic, zinc, silicon, sulfur, phosphorus and boron can be used.
  • 5 to 7 show an example in which two kinds of an aluminum source as step S32 and a nickel source as step S33 are further used as additives.
  • a method for mixing these additives for example, a solid phase method, a sol-gel method, a sputtering method, a mechanochemical method, a CVD method and the like can be used. Further, a plurality of methods may be used in combination.
  • the nickel source can be mixed in step S61-1, and then the zirconium source and the aluminum source can be mixed in step S61-2.
  • Mixing can be done dry or wet.
  • step S61-1 can be performed by the solid phase method
  • step S61-2 can be performed by the sol-gel method.
  • the sol-gel method aluminum alkoxide is used as the aluminum source
  • zirconium alkoxide is used as the zirconium source. If the following steps S62, S63, and S64 follow the same procedure, the positive electrode active material 100 can be obtained.
  • various additive sources may be mixed with the mixture 902 in step S41.
  • annealing may be performed a plurality of times as steps S53 and S55, and a sticking suppression operation step S54 may be performed between them.
  • the annealing conditions of steps S53 and S55 can take into account the description of step S43. Examples of the sticking suppressing operation include crushing with a pestle, mixing with a ball mill, mixing with a rotating and revolving mixer, sieving, and vibrating a container containing a composite oxide.
  • the positive electrode active material 100 is obtained by crushing and recovering as step S55-2.
  • LiMO 2 and the mixture 902 may be mixed in step S41 and annealed, and then various additive sources may be mixed in step S61. Mixing can be done dry or wet. As for the annealing conditions, the description in step S43 can be taken into consideration. If the following steps S62, S63, and S64 follow the same procedure, the positive electrode active material 100 can be obtained.
  • the concentration of the additive can be increased in the surface layer portion as compared with the central portion of the particles. Further, based on the number of atoms of the transition metal M, the ratio of the number of atoms of the additive element to the reference can be made higher in the surface layer portion than in the central portion. In particular, the concentration of additive elements is high in the convex parts.
  • This embodiment can be used in combination with other embodiments.
  • a lithium ion secondary battery containing the positive electrode active material according to one aspect of the present invention will be described.
  • the secondary battery has at least an exterior body, a current collector, an active material (positive electrode active material or negative electrode active material), a conductive auxiliary agent, and a binder. It also has an electrolytic solution in which a lithium salt or the like is dissolved.
  • a positive electrode, a negative electrode, and a separator are provided between the positive electrode and the negative electrode.
  • the positive electrode has a positive electrode active material layer and a positive electrode current collector.
  • the positive electrode active material layer preferably has the positive electrode active material shown in the first embodiment, and may further have a binder, a conductive auxiliary agent, or the like.
  • FIG. 12A shows an example of a schematic view of a cross section of a positive electrode.
  • the current collector 550 is a metal foil, and a positive electrode is formed by applying a slurry on the metal foil and drying it. After drying, further pressing may be added.
  • the positive electrode has an active material layer formed on the current collector 550.
  • the slurry is a material liquid used to form an active material layer on the current collector 550, and refers to a material liquid containing at least an active material, a binder, and a solvent, preferably further mixed with a conductive auxiliary agent. There is.
  • the slurry may be referred to as an electrode slurry or an active material slurry, a positive electrode slurry may be used when forming a positive electrode active material layer, and a negative electrode slurry may be used when forming a negative electrode active material layer.
  • the conductive auxiliary agent is also called a conductive imparting agent or a conductive material, and a carbon material is used.
  • a conductive imparting agent By adhering the conductive auxiliary agent between the plurality of active materials, the plurality of active materials are electrically connected to each other, and the conductivity is enhanced.
  • adheresion does not only mean that the active material and the conductive auxiliary agent are physically in close contact with each other, but also when a covalent bond occurs, when the active material is bonded by van der Waals force, the active material is used.
  • the concept includes the case where a part of the surface is covered with the conductive auxiliary agent, the case where the conductive auxiliary agent fits into the surface unevenness of the active material, the case where the conductive auxiliary agent is electrically connected even if they are not in contact with each other, and the like.
  • Carbon black is a typical carbon material used as a conductive auxiliary agent.
  • FIG. 12A acetylene black 553 is illustrated as a conductive auxiliary agent.
  • FIG. 12A shows an example in which a second active material 562 having a particle size smaller than that of the positive electrode active material 100 shown in the first embodiment is mixed. By mixing particles of different sizes, a high-density positive electrode active material layer can be obtained, and the charge / discharge capacity of the secondary battery can be increased.
  • the positive electrode active material 100 shown in the first embodiment corresponds to the active material 561 in FIG. 12A.
  • a binder (resin) is mixed in order to fix the current collector 550 such as a metal foil and the active material. Binders are also called binders.
  • the binder is a polymer material, and if a large amount of binder is contained, the ratio of the active material in the positive electrode decreases, and the discharge capacity of the secondary battery becomes small. Therefore, the amount of binder is mixed to the minimum.
  • the region not filled with the active material 561, the second active material 562, and the acetylene black 553 points to voids or binders.
  • FIG. 12A shows an example in which the active material 561 is illustrated as a sphere, the present invention is not particularly limited and may have various shapes.
  • the cross-sectional shape of the active material 561 may be an ellipse, a rectangle, a trapezoid, a cone, a quadrangle with rounded corners, or an asymmetric shape.
  • FIG. 12B shows an example in which the active material 561 is illustrated as various shapes.
  • FIG. 12B shows an example different from FIG. 12A.
  • graphene 554 is used as the carbon material used as the conductive auxiliary agent.
  • Graphene is a carbon material that is expected to be applied in various fields such as field-effect transistors and solar cells using graphene because it has amazing properties electrically, mechanically, or chemically.
  • a positive electrode active material layer having active material 561, graphene 554, and acetylene black 553 is formed on the current collector 550.
  • the weight of the mixed carbon black is 1.5 times or more and 20 times or less, preferably 2 times or more and 9.5 times or less the weight of graphene. It is preferable to do so.
  • the electrode density can be higher than that of the positive electrode using only acetylene black 553 as the conductive auxiliary agent. By increasing the electrode density, the capacity per weight unit can be increased. Specifically, the density of the positive electrode active material layer by weight measurement can be higher than 3.5 g / cc.
  • the positive electrode active material 100 shown in the first embodiment is used for the positive electrode and the mixture of graphene 554 and acetylene black 555 is within the above range, a synergistic effect can be expected for the secondary battery to have a higher capacity. preferable.
  • the electrode density is lower than that of the positive electrode using only graphene as the conductive auxiliary agent, quick charging is possible by setting the mixture of the first carbon material (graphene) and the second carbon material (acetylene black) in the above range. Can be accommodated. Further, when the positive electrode active material 100 shown in the first embodiment is used for the positive electrode and the mixture of graphene 554 and acetylene black 533 is within the above range, the secondary battery becomes more stable and can cope with further rapid charging. A synergistic effect can be expected and is preferable.
  • the energy to be moved increases and the cruising range also decreases.
  • the cruising range can be maintained with almost no change in the total weight of the vehicle equipped with the secondary battery of the same weight.
  • the positive electrode active material 100 shown in the first embodiment As the positive electrode and setting the mixing ratio of acetylene black and graphene to the optimum range, an appropriate gap necessary for high density of electrodes and ion conduction is created. It is possible to obtain an in-vehicle secondary battery having a high energy density and good output characteristics.
  • this configuration is also effective in a portable information terminal, and a secondary battery is provided by using the positive electrode active material 100 shown in the first embodiment as the positive electrode and setting the mixing ratio of acetylene black and graphene to the optimum range. It can be miniaturized and has a high capacity. In addition, by setting the mixing ratio of acetylene black and graphene to the optimum range, it is possible to quickly charge a mobile information terminal.
  • the region not filled with the active material 561, graphene 554, and acetylene black 553 refers to a void or a binder.
  • the voids are necessary for the penetration of the electrolytic solution, but if it is too large, the electrode density will decrease, and if it is too small, the electrolytic solution will not penetrate, and if it remains as a void even after the secondary battery, the energy density will increase. It will drop.
  • the positive electrode active material 100 obtained in the first embodiment As the positive electrode and setting the mixing ratio of acetylene black and graphene to the optimum range, the density of the electrode and the appropriate gap required for ion conduction can be created. Both are possible, and a secondary battery having a high energy density and good output characteristics can be obtained.
  • FIG. 12C illustrates an example of a positive electrode using carbon nanotubes 555 instead of graphene.
  • FIG. 12C shows an example different from FIG. 12B.
  • the carbon nanotube 555 it is possible to prevent the aggregation of carbon black such as acetylene black 555 and enhance the dispersibility.
  • the region not filled with the active material 561, the carbon nanotube 555, and the acetylene black 553 refers to a void or a binder.
  • FIG. 12D is shown as an example of another positive electrode.
  • FIG. 12C shows an example in which carbon nanotubes 555 are used in addition to graphene 554.
  • carbon nanotubes 555 are used in addition to graphene 554.
  • the region not filled with the active material 561, the carbon nanotube 555, the graphene 554, and the acetylene black 555 refers to a void or a binder.
  • a secondary battery can be manufactured by filling the battery.
  • the above configuration shows an example of a secondary battery using an electrolytic solution, but is not particularly limited.
  • a semi-solid battery or an all-solid-state battery can be manufactured by using the positive electrode active material 100 shown in the first embodiment.
  • the semi-solid battery means a battery having a semi-solid material in at least one of an electrolyte layer, a positive electrode, and a negative electrode.
  • the term semi-solid here does not mean that the ratio of solid materials is 50%.
  • Semi-solid means that it has solid properties such as small volume change, but also has some properties close to liquid such as flexibility. As long as these properties are satisfied, it may be a single material or a plurality of materials. For example, a liquid material may be infiltrated into a porous solid material.
  • the polymer electrolyte secondary battery refers to a secondary battery having a polymer in the electrolyte layer between the positive electrode and the negative electrode.
  • Polymer electrolyte secondary batteries include dry (or intrinsic) polymer electrolyte batteries, and polymer gel electrolyte batteries. Further, the polymer electrolyte secondary battery may be referred to as a semi-solid state battery.
  • the semi-solid-state battery becomes a secondary battery having a large charge / discharge capacity. Further, a semi-solid state battery having a high charge / discharge voltage can be used. Alternatively, a semi-solid state battery with high safety or reliability can be realized.
  • the positive electrode active material described in the first embodiment may be mixed with another positive electrode active material.
  • positive electrode active materials include, for example, an olivine-type crystal structure, a layered rock salt-type crystal structure, or a composite oxide having a spinel-type crystal structure.
  • examples thereof include compounds such as LiFePO 4 , LiFeO 2 , LiNiO 2 , LiMn 2 O 4 , V 2 O 5 , Cr 2 O 5 , and MnO 2.
  • lithium nickelate LiNiO 2 or LiNi 1-x M x O 2 (0 ⁇ x ⁇ 1) is added to a lithium-containing material having a spinel-type crystal structure containing manganese such as LiMn 2 O 4 as another positive electrode active material.
  • LiMn 2 O 4 LiMn 2 O 4
  • M Co, Al, etc.
  • a lithium manganese composite oxide that can be represented by the composition formula Lia Mn b Mc Od can be used.
  • the element M a metal element selected from other than lithium and manganese, silicon, and phosphorus are preferably used, and nickel is more preferable.
  • the lithium manganese composite oxide refers to an oxide containing at least lithium and manganese, and includes chromium, cobalt, aluminum, nickel, iron, magnesium, molybdenum, zinc, indium, gallium, copper, titanium, niobium, and silicon. And at least one element selected from the group consisting of phosphorus and the like may be contained.
  • ⁇ Binder> As the binder, for example, it is preferable to use a rubber material such as styrene-butadiene rubber (SBR), styrene-isoprene-styrene rubber, acrylonitrile-butadiene rubber, butadiene rubber, and ethylene-propylene-diene copolymer. Further, fluororubber can be used as the binder.
  • SBR styrene-butadiene rubber
  • fluororubber can be used as the binder.
  • a water-soluble polymer for example, a polysaccharide or the like can be used.
  • a polysaccharide for example, cellulose derivatives such as carboxymethyl cellulose (CMC), methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose and regenerated cellulose, starch and the like can be used. Further, it is more preferable to use these water-soluble polymers in combination with the above-mentioned rubber material.
  • the binder includes polystyrene, methyl polyacrylate, polymethyl methacrylate (polymethyl methacrylate, PMMA), sodium polyacrylate, polyvinyl alcohol (PVA), polyethylene oxide (PEO), polypropylene oxide, polyimide, and polyvinyl chloride.
  • PVA polyvinyl alcohol
  • PEO polyethylene oxide
  • PAN polyacrylonitrile
  • ethylenepropylene diene polymer polyvinylacetate, nitrocellulose and the like are preferably used. ..
  • the binder may be used in combination of a plurality of the above.
  • a material having a particularly excellent viscosity adjusting effect may be used in combination with another material.
  • a rubber material or the like has excellent adhesive strength and elastic strength, but it may be difficult to adjust the viscosity when mixed with a solvent. In such a case, for example, it is preferable to mix with a material having a particularly excellent viscosity adjusting effect.
  • a material having a particularly excellent viscosity adjusting effect for example, a water-soluble polymer may be used.
  • the water-soluble polymer having a particularly excellent viscosity adjusting effect the above-mentioned polysaccharides such as carboxymethyl cellulose (CMC), methyl cellulose, ethyl cellulose, hydroxypropyl cellulose and diacetyl cellulose, cellulose derivatives such as regenerated cellulose, and starch are used. be able to.
  • CMC carboxymethyl cellulose
  • methyl cellulose methyl cellulose
  • ethyl cellulose methyl cellulose
  • hydroxypropyl cellulose and diacetyl cellulose cellulose derivatives such as regenerated cellulose
  • starch cellulose derivatives
  • the cellulose derivative such as carboxymethyl cellulose has higher solubility by using, for example, a salt such as a sodium salt or an ammonium salt of carboxymethyl cellulose, and easily exerts an effect as a viscosity adjusting agent.
  • a salt such as a sodium salt or an ammonium salt of carboxymethyl cellulose
  • the cellulose and the cellulose derivative used as the binder of the electrode include salts thereof.
  • the water-soluble polymer stabilizes its viscosity by being dissolved in water, and can stably disperse an active material and other materials to be combined as a binder, such as styrene-butadiene rubber, in an aqueous solution. Further, since it has a functional group, it is expected that it can be easily stably adsorbed on the surface of the active material. In addition, many cellulose derivatives such as carboxymethyl cellulose have functional groups such as hydroxyl groups and carboxyl groups, and since they have functional groups, the polymers interact with each other and exist widely covering the surface of the active material. There is expected.
  • the immobile membrane is a membrane having no electrical conductivity or a membrane having extremely low electrical conductivity.
  • the battery reaction potential is changed. Decomposition of the electrolytic solution can be suppressed.
  • the passivation membrane suppresses the conductivity of electricity and can conduct lithium ions.
  • a material having high conductivity such as a metal such as stainless steel, gold, platinum, aluminum, and titanium, and an alloy thereof can be used. Further, it is preferable that the material used for the positive electrode current collector does not elute at the potential of the positive electrode. Further, an aluminum alloy to which an element for improving heat resistance such as silicon, titanium, neodymium, scandium, and molybdenum is added can be used. Further, it may be formed of a metal element that reacts with silicon to form silicide.
  • Metallic elements that react with silicon to form silicide include zirconium, titanium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, cobalt, nickel and the like.
  • a foil-like shape, a plate-like shape, a sheet-like shape, a net-like shape, a punching metal-like shape, an expanded metal-like shape, or the like can be appropriately used. It is preferable to use a current collector having a thickness of 5 ⁇ m or more and 30 ⁇ m or less.
  • the negative electrode has a negative electrode active material layer and a negative electrode current collector. Further, the negative electrode active material layer may have a negative electrode active material, and may further have a conductive auxiliary agent and a binder.
  • Niobium electrode active material for example, an alloy-based material, a carbon-based material, or the like can be used.
  • an element capable of performing a charge / discharge reaction by an alloying / dealloying reaction with lithium can be used.
  • a material containing at least one of silicon, tin, gallium, aluminum, germanium, lead, antimony, bismuth, silver, zinc, cadmium, indium and the like can be used.
  • Such elements have a larger capacity than carbon, and silicon in particular has a high theoretical capacity of 4200 mAh / g. Therefore, it is preferable to use silicon as the negative electrode active material. Further, a compound having these elements may be used.
  • an element capable of performing a charge / discharge reaction by an alloying / dealloying reaction with lithium, a compound having the element, and the like may be referred to as an alloy-based material.
  • SiO refers to, for example, silicon monoxide.
  • SiO can also be expressed as SiO x.
  • x preferably has a value of 1 or a value close to 1.
  • x is preferably 0.2 or more and 1.5 or less, and preferably 0.3 or more and 1.2 or less.
  • carbon-based material graphite, easily graphitizable carbon (soft carbon), non-graphitizable carbon (hard carbon), carbon nanotubes, graphene, carbon black and the like may be used.
  • Examples of graphite include artificial graphite and natural graphite.
  • Examples of the artificial graphite include mesocarbon microbeads (MCMB), coke-based artificial graphite, pitch-based artificial graphite and the like.
  • MCMB mesocarbon microbeads
  • the artificial graphite spheroidal graphite having a spherical shape can be used.
  • MCMB may have a spherical shape, which is preferable.
  • MCMB is relatively easy to reduce its surface area and may be preferable.
  • Examples of natural graphite include scaly graphite and spheroidized natural graphite.
  • graphite When lithium ions are inserted into graphite (at the time of forming a lithium-lithium interlayer compound), graphite shows a potential as low as that of lithium metal (0.05 V or more and 0.3 V or less vs. Li / Li +). As a result, the lithium ion secondary battery using graphite can exhibit a high operating voltage. Further, graphite is preferable because it has advantages such as relatively high capacity per unit volume, relatively small volume expansion, low cost, and high safety as compared with lithium metal.
  • titanium dioxide TIM 2
  • lithium titanium oxide Li 4 Ti 5 O 12
  • lithium-graphite interlayer compound Li x C 6
  • niobium pentoxide Nb 2 O 5
  • oxidation Oxides such as tungsten (WO 2 ) and molybdenum oxide (MoO 2 ) can be used.
  • Li 2.6 Co 0.4 N 3 shows a large charge / discharge capacity (900 mAh / g, 1890 mAh / cm 3 ) and is preferable.
  • lithium ions are contained in the negative electrode active material, so that it can be combined with materials such as V 2 O 5 and Cr 3 O 8 which do not contain lithium ions as the positive electrode active material, which is preferable. .. Even when a material containing lithium ions is used as the positive electrode active material, a double nitride of lithium and a transition metal can be used as the negative electrode active material by desorbing the lithium ions contained in the positive electrode active material in advance.
  • a material that causes a conversion reaction can also be used as a negative electrode active material.
  • a transition metal oxide that does not form an alloy with lithium such as cobalt oxide (CoO), nickel oxide (NiO), and iron oxide (FeO)
  • Materials that cause a conversion reaction include oxides such as Fe 2 O 3 , CuO, Cu 2 O, RuO 2 , Cr 2 O 3 , sulfides such as CoS 0.89 , NiS, and CuS, and Zn 3 N 2. , Cu 3 N, Ge 3 N 4 or the like nitride, NiP 2, FeP 2, CoP 3 etc. phosphide, also at the FeF 3, BiF 3 fluoride and the like.
  • the same material as the conductive auxiliary agent and the binder that the positive electrode active material layer can have can be used.
  • the negative electrode current collector preferably uses a material that does not alloy with carrier ions such as lithium.
  • a separator is placed between the positive electrode and the negative electrode.
  • the separator include fibers having cellulose such as paper, non-woven fabrics, glass fibers, ceramics, nylon (polyamide), vinylon (polyvinyl alcohol-based fibers), polyesters, acrylics, polyolefins, synthetic fibers using polyurethane and the like. It is possible to use the one formed by. It is preferable that the separator is processed into a bag shape and arranged so as to wrap either the positive electrode or the negative electrode.
  • the separator may have a multi-layer structure.
  • an organic material film such as polypropylene or polyethylene can be coated with a ceramic material, a fluorine material, a polyamide material, or a mixture thereof.
  • the ceramic material for example, aluminum oxide particles, silicon oxide particles and the like can be used.
  • the fluorine-based material for example, PVDF, polytetrafluoroethylene and the like can be used.
  • the polyamide-based material for example, nylon, aramid (meth-based aramid, para-based aramid) and the like can be used.
  • the oxidation resistance is improved by coating with a ceramic material, deterioration of the separator during high voltage charging / discharging can be suppressed, and the reliability of the secondary battery can be improved. Further, when a fluorine-based material is coated, the separator and the electrode are easily brought into close contact with each other, and the output characteristics can be improved. Coating a polyamide-based material, particularly aramid, improves heat resistance and thus can improve the safety of the secondary battery.
  • a mixed material of aluminum oxide and aramid may be coated on both sides of a polypropylene film.
  • the surface of the polypropylene film in contact with the positive electrode may be coated with a mixed material of aluminum oxide and aramid, and the surface in contact with the negative electrode may be coated with a fluorine-based material.
  • the safety of the secondary battery can be maintained even if the thickness of the entire separator is thin, so that the capacity per volume of the secondary battery can be increased.
  • the electrolytic solution has a solvent and an electrolyte.
  • the solvent of the electrolytic solution is preferably an aprotonic organic solvent, for example, ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate, chloroethylene carbonate, vinylene carbonate, ⁇ -butyrolactone, ⁇ -valerolactone, dimethyl carbonate.
  • DMC diethyl carbonate
  • DEC diethyl carbonate
  • EMC ethylmethyl carbonate
  • methyl formate methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, 1,3-dioxane, 1,4 -Use one of dioxane, dimethoxyethane (DME), dimethyl sulfoxide, diethyl ether, methyl diglyme, acetonitrile, benzonitrile, tetrahydrofuran, sulfolane, sulton, etc., or two or more of these in any combination and ratio. be able to.
  • Ionic liquids normally temperature molten salt
  • Ionic liquids consist of cations and anions, including organic cations and anions.
  • Examples of the organic cation used in the electrolytic solution include aliphatic onium cations such as quaternary ammonium cations, tertiary sulfonium cations, and quaternary phosphonium cations, and aromatic cations such as imidazolium cations and pyridinium cations.
  • anions used in the electrolytic solution monovalent amide anions, monovalent methide anions, fluorosulfonic acid anions, perfluoroalkyl sulfonic acid anions, tetrafluoroborate anions, perfluoroalkyl borate anions, and hexafluorophosphate anions. , Or perfluoroalkyl phosphate anion and the like.
  • LiPF 6 LiClO 4, LiAsF 6 , LiBF 4, LiAlCl 4, LiSCN, LiBr, LiI, Li 2 SO 4, Li 2 B 10 Cl 10, Li 2 B 12 Cl 12 , LiCF 3 SO 3 , LiC 4 F 9 SO 3 , LiC (CF 3 SO 2 ) 3 , LiC (C 2 F 5 SO 2 ) 3 , LiN (CF 3 SO 2 ) 2 , LiN (C 4 F 9)
  • One type of lithium salt such as SO 2 ) (CF 3 SO 2 ), LiN (C 2 F 5 SO 2 ) 2 , lithium bis (oxalate) borate (Li (C 2 O 4 ) 2, LiBOB), or among these Two or more of these can be used in any combination and ratio.
  • the electrolytic solution used in the power storage device it is preferable to use a highly purified electrolytic solution having a small content of granular dust and elements other than the constituent elements of the electrolytic solution (hereinafter, also simply referred to as “impurities”).
  • the weight ratio of impurities to the electrolytic solution is preferably 1% or less, preferably 0.1% or less, and more preferably 0.01% or less.
  • the electrolytic solution includes vinylene carbonate, propane sultone (PS), tert-butylbenzene (TBB), fluoroethylene carbonate (FEC), lithium bis (oxalate) borate (LiBOB), and dinitrile compounds such as succinonitrile and adiponitrile.
  • Additives may be added.
  • the concentration of the additive may be, for example, 0.1 wt% or more and 5 wt% or less with respect to the solvent.
  • a polymer gel electrolyte obtained by swelling the polymer with an electrolytic solution may be used.
  • the secondary battery can be made thinner and lighter.
  • silicone gel silicone gel, acrylic gel, acrylonitrile gel, polyethylene oxide gel, polypropylene oxide gel, fluoropolymer gel and the like can be used.
  • a polymer having a polyalkylene oxide structure such as polyethylene oxide (PEO), PVDF, polyacrylonitrile, etc., and a copolymer containing them can be used.
  • PVDF-HFP which is a copolymer of PVDF and hexafluoropropylene (HFP)
  • the polymer to be formed may have a porous shape.
  • a solid electrolyte having an inorganic material such as a sulfide type or an oxide type, or a solid electrolyte having a polymer material such as PEO (polyethylene oxide) type can be used.
  • PEO polyethylene oxide
  • the positive electrode active material 100 obtained in the first embodiment can also be applied to an all-solid-state battery.
  • an all-solid-state battery having high safety and good characteristics can be obtained.
  • a metal material such as aluminum or a resin material can be used.
  • a film-like exterior body can also be used.
  • a metal thin film having excellent flexibility such as aluminum, stainless steel, copper, and nickel is provided on a film made of a material such as polyethylene, polypropylene, polycarbonate, ionomer, and polyamide, and an exterior is further formed on the metal thin film.
  • a film having a three-layer structure provided with an insulating synthetic resin film such as a polyamide resin or a polyester resin can be used as the outer surface of the body.
  • This embodiment can be used in combination with other embodiments.
  • FIG. 13A is an exploded perspective view of a coin-type (single-layer flat type) secondary battery
  • FIG. 13B is an external view
  • FIG. 13C is a cross-sectional view thereof.
  • Coin-type secondary batteries are mainly used in small electronic devices.
  • FIG. 13A in order to make it easy to understand, a schematic diagram is made so that the overlap (vertical relationship and positional relationship) of the members can be understood. Therefore, FIGS. 13A and 13B do not have a completely matching correspondence diagram.
  • the positive electrode 304, the separator 310, the negative electrode 307, the spacer 322, and the washer 312 are overlapped. These are sealed with a negative electrode can 302 and a positive electrode can 301.
  • the gasket for sealing is not shown.
  • the spacer 322 and the washer 312 are used to protect the inside or fix the position inside the can when crimping the positive electrode can 301 and the negative electrode can 302. Stainless steel or insulating material is used for the spacer 322 and the washer 312.
  • the laminated structure in which the positive electrode active material layer 306 is formed on the positive electrode current collector 305 is referred to as the positive electrode 304.
  • the separator 310 and the ring-shaped insulator 313 are arranged so as to cover the side surface and the upper surface of the positive electrode 304, respectively.
  • the separator 310 has a wider plane area than the positive electrode 304.
  • FIG. 13B is a perspective view of the completed coin-shaped secondary battery.
  • a positive electrode can 301 that also serves as a positive electrode terminal and a negative electrode can 302 that also serves as a negative electrode terminal are insulated and sealed with a gasket 303 that is made of polypropylene or the like.
  • the positive electrode 304 is formed by a positive electrode current collector 305 and a positive electrode active material layer 306 provided in contact with the positive electrode current collector 305.
  • the negative electrode 307 is formed by a negative electrode current collector 308 and a negative electrode active material layer 309 provided in contact with the negative electrode current collector 308.
  • the negative electrode 307 is not limited to the laminated structure, and a lithium metal foil or an alloy foil of lithium and aluminum may be used.
  • the positive electrode 304 and the negative electrode 307 used in the coin-type secondary battery 300 may have the active material layer formed on only one side thereof.
  • the positive electrode can 301 and the negative electrode can 302 metals such as nickel, aluminum, and titanium having corrosion resistance to the electrolytic solution, or alloys thereof or alloys of these with other metals (for example, stainless steel) may be used. can. Further, in order to prevent corrosion due to an electrolytic solution or the like, it is preferable to coat with nickel, aluminum or the like.
  • the positive electrode can 301 is electrically connected to the positive electrode 304
  • the negative electrode can 302 is electrically connected to the negative electrode 307.
  • the negative electrode 307, the positive electrode 304, and the separator 310 are immersed in an electrolytic solution, and as shown in FIG. 13C, the positive electrode 304, the separator 310, the negative electrode 307, and the negative electrode can 302 are laminated in this order with the positive electrode can 301 facing down, and the positive electrode can A coin-shaped secondary battery 300 is manufactured by crimping the 301 and the negative electrode can 302 via the gasket 303.
  • the secondary battery By using the secondary battery, it is possible to obtain a coin-type secondary battery 300 having a high capacity, a high charge / discharge capacity, and excellent cycle characteristics.
  • the separator 310 may not be required.
  • the cylindrical secondary battery 616 has a positive electrode cap (battery lid) 601 on the upper surface and a battery can (exterior can) 602 on the side surface and the bottom surface.
  • the positive electrode cap 601 and the battery can (exterior can) 602 are insulated by a gasket (insulating packing) 610.
  • FIG. 14B is a diagram schematically showing a cross section of a cylindrical secondary battery.
  • the cylindrical secondary battery shown in FIG. 14B has a positive electrode cap (battery lid) 601 on the upper surface and a battery can (outer can) 602 on the side surface and the bottom surface.
  • These positive electrode caps and the battery can (exterior can) 602 are insulated by a gasket (insulating packing) 610.
  • a battery element in which a band-shaped positive electrode 604 and a negative electrode 606 are wound with a separator 605 sandwiched between them is provided inside the hollow cylindrical battery can 602.
  • the battery element is wound around a central axis.
  • One end of the battery can 602 is closed and the other end is open.
  • a metal such as nickel, aluminum, or titanium that is corrosion resistant to an electrolytic solution, or an alloy thereof or an alloy of these and another metal (for example, stainless steel or the like) can be used. ..
  • the battery element in which the positive electrode, the negative electrode, and the separator are wound is sandwiched between a pair of insulating plates 608 and 609 facing each other. Further, a non-aqueous electrolytic solution (not shown) is injected into the inside of the battery can 602 provided with the battery element.
  • the non-aqueous electrolyte solution the same one as that of a coin-type secondary battery can be used.
  • the positive electrode and the negative electrode used in the cylindrical storage battery are wound, it is preferable to form active materials on both sides of the current collector.
  • a cylindrical secondary battery 616 having a high capacity, a high charge / discharge capacity, and excellent cycle characteristics can be obtained.
  • a positive electrode terminal (positive electrode current collecting lead) 603 is connected to the positive electrode 604, and a negative electrode terminal (negative electrode current collecting lead) 607 is connected to the negative electrode 606.
  • a metal material such as aluminum can be used for both the positive electrode terminal 603 and the negative electrode terminal 607.
  • the positive electrode terminal 603 is resistance welded to the safety valve mechanism 613, and the negative electrode terminal 607 is resistance welded to the bottom of the battery can 602.
  • the safety valve mechanism 613 is electrically connected to the positive electrode cap 601 via a PTC element (Positive Temperature Coefficient) 611. The safety valve mechanism 613 disconnects the electrical connection between the positive electrode cap 601 and the positive electrode 604 when the increase in the internal pressure of the battery exceeds a predetermined threshold value.
  • the PTC element 611 is a heat-sensitive resistance element whose resistance increases when the temperature rises, and the amount of current is limited by the increase in resistance to prevent abnormal heat generation.
  • Barium titanate (BaTIO 3 ) -based semiconductor ceramics or the like can be used as the PTC element.
  • FIG. 14C shows an example of the power storage system 615.
  • the power storage system 615 has a plurality of secondary batteries 616.
  • the positive electrode of each secondary battery is in contact with the conductor 624 separated by the insulator 625 and is electrically connected.
  • the conductor 624 is electrically connected to the control circuit 620 via the wiring 623.
  • the negative electrode of each secondary battery is electrically connected to the control circuit 620 via the wiring 626.
  • As the control circuit 620 a charge / discharge control circuit for charging / discharging and a protection circuit for preventing overcharging or overdischarging can be applied.
  • FIG. 14D shows an example of the power storage system 615.
  • the power storage system 615 has a plurality of secondary batteries 616, and the plurality of secondary batteries 616 are sandwiched between the conductive plate 628 and the conductive plate 614.
  • the plurality of secondary batteries 616 are electrically connected to the conductive plate 628 and the conductive plate 614 by wiring 627.
  • the plurality of secondary batteries 616 may be connected in parallel, may be connected in series, or may be connected in parallel and then further connected in series.
  • a plurality of secondary batteries 616 may be connected in parallel and then further connected in series.
  • a temperature control device may be provided between the plurality of secondary batteries 616.
  • the secondary battery 616 When the secondary battery 616 is overheated, it can be cooled by the temperature control device, and when the secondary battery 616 is too cold, it can be heated by the temperature control device. Therefore, the performance of the power storage system 615 is less likely to be affected by the outside air temperature.
  • the power storage system 615 is electrically connected to the control circuit 620 via the wiring 621 and the wiring 622.
  • the wiring 621 is electrically connected to the positive electrode of the plurality of secondary batteries 600 via the conductive plate 628
  • the wiring 622 is electrically connected to the negative electrode of the plurality of secondary batteries 600 via the conductive plate 614.
  • the secondary battery 913 shown in FIG. 15A has a winding body 950 having a terminal 951 and a terminal 952 inside the housing 930.
  • the winding body 950 is immersed in the electrolytic solution inside the housing 930.
  • the terminal 952 is in contact with the housing 930, and the terminal 951 is not in contact with the housing 930 by using an insulating material or the like.
  • the housing 930 is shown separately for convenience, but in reality, the winding body 950 is covered with the housing 930, and the terminals 951 and 952 extend outside the housing 930. It exists.
  • a metal material for example, aluminum or the like
  • a resin material can be used as the housing 930.
  • the housing 930 shown in FIG. 15A may be formed of a plurality of materials.
  • the housing 930a and the housing 930b are bonded to each other, and the winding body 950 is provided in the region surrounded by the housing 930a and the housing 930b.
  • an insulating material such as an organic resin can be used.
  • a material such as an organic resin on the surface on which the antenna is formed it is possible to suppress the shielding of the electric field by the secondary battery 913. If the electric field shielding by the housing 930a is small, an antenna may be provided inside the housing 930a.
  • a metal material can be used as the housing 930b.
  • the wound body 950 has a negative electrode 931, a positive electrode 932, and a separator 933.
  • the wound body 950 is a wound body in which the negative electrode 931 and the positive electrode 932 are overlapped and laminated with the separator 933 interposed therebetween, and the laminated sheet is wound.
  • a plurality of layers of the negative electrode 931, the positive electrode 932, and the separator 933 may be further laminated.
  • the secondary battery 913 having the winding body 950a as shown in FIG. 16 may be used.
  • the winding body 950a shown in FIG. 16A has a negative electrode 931, a positive electrode 932, and a separator 933.
  • the negative electrode 931 has a negative electrode active material layer 931a.
  • the positive electrode 932 has a positive electrode active material layer 932a.
  • a secondary battery 913 having a high capacity, a high charge / discharge capacity, and excellent cycle characteristics can be obtained.
  • the separator 933 has a wider width than the negative electrode active material layer 931a and the positive electrode active material layer 932a, and is wound so as to overlap the negative electrode active material layer 931a and the positive electrode active material layer 932a. Further, it is preferable that the width of the negative electrode active material layer 931a is wider than that of the positive electrode active material layer 932a in terms of safety. Further, the wound body 950a having such a shape is preferable in terms of safety and productivity.
  • the negative electrode 931 is electrically connected to the terminal 951 by ultrasonic bonding or welding or crimping.
  • the terminal 951 is electrically connected to the terminal 911a.
  • the positive electrode 932 is electrically connected to the terminal 952 by ultrasonic bonding, welding or crimping.
  • the terminal 952 is electrically connected to the terminal 911b.
  • the winding body 950a and the electrolytic solution are covered with the housing 930 to form the secondary battery 913.
  • the housing 930 is provided with a safety valve, an overcurrent protection element, or the like.
  • the safety valve is a valve that opens the inside of the housing 930 at a predetermined internal pressure in order to prevent the battery from exploding.
  • the secondary battery 913 may have a plurality of winding bodies 950a. By using a plurality of winding bodies 950a, it is possible to obtain a secondary battery 913 having a larger charge / discharge capacity.
  • Other elements of the secondary battery 913 shown in FIGS. 16A and 16B can take into account the description of the secondary battery 913 shown in FIGS. 15A-15C.
  • FIGS. 17A and 17B an example of an external view of a laminated secondary battery is shown in FIGS. 17A and 17B.
  • 17A and 17B have a positive electrode 503, a negative electrode 506, a separator 507, an exterior body 509, a positive electrode lead electrode 510, and a negative electrode lead electrode 511.
  • FIG. 18A shows an external view of the positive electrode 503 and the negative electrode 506.
  • the positive electrode 503 has a positive electrode current collector 501, and the positive electrode active material layer 502 is formed on the surface of the positive electrode current collector 501. Further, the positive electrode 503 has a region (hereinafter referred to as a tab region) in which the positive electrode current collector 501 is partially exposed.
  • the negative electrode 506 has a negative electrode current collector 504, and the negative electrode active material layer 505 is formed on the surface of the negative electrode current collector 504. Further, the negative electrode 506 has a region where the negative electrode current collector 504 is partially exposed, that is, a tab region.
  • the area and shape of the tab region of the positive electrode and the negative electrode are not limited to the example shown in FIG. 18A.
  • FIG. 18B shows the negative electrode 506, the separator 507, and the positive electrode 503 laminated.
  • FIG. 18B shows the negative electrode 506, the separator 507, and the positive electrode 503 laminated.
  • an example in which five negative electrodes and four positive electrodes are used is shown. It can also be called a laminate consisting of a negative electrode, a separator, and a positive electrode.
  • the tab regions of the positive electrode 503 are joined to each other, and the positive electrode lead electrode 510 is joined to the tab region of the positive electrode on the outermost surface.
  • ultrasonic welding may be used.
  • the tab regions of the negative electrode 506 are bonded to each other, and the negative electrode lead electrode 511 is bonded to the tab region of the negative electrode on the outermost surface.
  • the negative electrode 506, the separator 507, and the positive electrode 503 are arranged on the exterior body 509.
  • the exterior body 509 is bent at the portion shown by the broken line. After that, the outer peripheral portion of the exterior body 509 is joined. For example, thermocompression bonding may be used for joining. At this time, a region (hereinafter referred to as an introduction port) that is not joined to a part (or one side) of the exterior body 509 is provided so that the electrolytic solution 508 can be put in later.
  • an introduction port a region that is not joined to a part (or one side) of the exterior body 509 is provided so that the electrolytic solution 508 can be put in later.
  • the electrolytic solution 508 (not shown) is introduced into the inside of the exterior body 509 from the introduction port provided in the exterior body 509.
  • the electrolytic solution 508 is preferably introduced under a reduced pressure atmosphere or an inert atmosphere.
  • the inlet is joined. In this way, the laminated type secondary battery 500 can be manufactured.
  • a secondary battery 500 having a high capacity, a high charge / discharge capacity, and excellent cycle characteristics can be obtained.
  • Example of battery pack An example of a secondary battery pack according to an aspect of the present invention capable of wireless charging using an antenna will be described with reference to FIG.
  • FIG. 19A is a diagram showing the appearance of the secondary battery pack 531 and is a thin rectangular parallelepiped shape (also referred to as a thick flat plate shape).
  • FIG. 19B is a diagram illustrating the configuration of the secondary battery pack 531.
  • the secondary battery pack 531 has a circuit board 540 and a secondary battery 513.
  • a label 529 is affixed to the secondary battery 513.
  • the circuit board 540 is fixed by the seal 515.
  • the secondary battery pack 531 has an antenna 517.
  • the inside of the secondary battery 513 may have a structure having a wound body or a structure having a laminated body.
  • the control circuit 590 is provided on the circuit board 540. Further, the circuit board 540 is electrically connected to the terminal 514. Further, the circuit board 540 is electrically connected to the antenna 517, one 551 of the positive electrode lead and the negative electrode lead of the secondary battery 513, and the other 552 of the positive electrode lead and the negative electrode lead.
  • circuit system 590a provided on the circuit board 540 and a circuit system 590b electrically connected to the circuit board 540 via the terminal 514.
  • the antenna 517 is not limited to a coil shape, and may be, for example, a linear shape or a plate shape. Further, antennas such as a planar antenna, an open surface antenna, a traveling wave antenna, an EH antenna, a magnetic field antenna, and a dielectric antenna may be used. Alternatively, the antenna 517 may be a flat conductor. This flat plate-shaped conductor can function as one of the conductors for electric field coupling. That is, the antenna 517 may function as one of the two conductors of the capacitor. This makes it possible to exchange electric power not only with an electromagnetic field and a magnetic field but also with an electric field.
  • the secondary battery pack 531 has a layer 519 between the antenna 517 and the secondary battery 513.
  • the layer 519 has a function of being able to shield the electromagnetic field generated by the secondary battery 513, for example.
  • a magnetic material can be used as the layer 519.
  • the secondary battery 400 of one aspect of the present invention has a positive electrode 410, a solid electrolyte layer 420, and a negative electrode 430.
  • the positive electrode 410 has a positive electrode current collector 413 and a positive electrode active material layer 414.
  • the positive electrode active material layer 414 has a positive electrode active material 411 and a solid electrolyte 421.
  • the positive electrode active material 411 the positive electrode active material 100 obtained in the first embodiment is used.
  • the positive electrode active material layer 414 may have a conductive auxiliary agent and a binder.
  • the solid electrolyte layer 420 has a solid electrolyte 421.
  • the solid electrolyte layer 420 is located between the positive electrode 410 and the negative electrode 430, and is a region having neither the positive electrode active material 411 nor the negative electrode active material 431.
  • the negative electrode 430 has a negative electrode current collector 433 and a negative electrode active material layer 434.
  • the negative electrode active material layer 434 has a negative electrode active material 431 and a solid electrolyte 421. Further, the negative electrode active material layer 434 may have a conductive auxiliary agent and a binder.
  • metallic lithium is used for the negative electrode 430
  • the negative electrode 430 without the solid electrolyte 421 can be used as shown in FIG. 20B. It is preferable to use metallic lithium for the negative electrode 430 because the energy density of the secondary battery 400 can be improved.
  • solid electrolyte 421 of the solid electrolyte layer 420 for example, a sulfide-based solid electrolyte, an oxide-based solid electrolyte, a halide-based solid electrolyte, or the like can be used.
  • Sulfide-based solid electrolytes include thiosilicon- based (Li 10 GeP 2 S 12 , Li 3.25 Ge 0.25 P 0.75 S 4, etc.) and sulfide glass (70Li 2 S / 30P 2 S 5 , 30 Li).
  • sulfide crystallized glass Li 7 P 3 S 11 , Li 3.25 P 0.95 S 4 etc.
  • the sulfide-based solid electrolyte has advantages such as having a material having high conductivity, being able to be synthesized at a low temperature, and being relatively soft so that the conductive path can be easily maintained even after charging and discharging.
  • a material having a perovskite-type crystal structure La 2 / 3-x Li 3x TIO 3, etc.
  • a material having a NASICON-type crystal structure Li 1-Y Al Y Ti 2-Y (PO 4)) ) 3 etc.
  • Material with garnet type crystal structure Li 7 La 3 Zr 2 O 12 etc.
  • Material with LISION type crystal structure Li 14 ZnGe 4 O 16 etc.
  • LLZO Li 7 La 3 Zr 2 O etc. 12
  • Oxide glass Li 3 PO 4- Li 4 SiO 4 , 50Li 4 SiO 4 ⁇ 50Li 3 BO 3, etc.
  • Oxide crystallized glass Li 1.07 Al 0.69 Ti 1.46 (PO 4) ) 3 , Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 etc.
  • Oxide-based solid electrolytes have the advantage of being stable in the atmosphere.
  • the halide-based solid electrolyte includes LiAlCl 4 , Li 3 InBr 6 , LiF, LiCl, LiBr, LiI and the like. Further, a composite material in which these halide-based solid electrolytes are filled in the pores of porous aluminum oxide or porous silica can also be used as the solid electrolyte.
  • Li 1 + x Al x Ti 2-x (PO 4 ) 3 (0 [x [1) (hereinafter referred to as LATP) having a NASICON type crystal structure is a secondary battery 400 of one aspect of the present invention, which is aluminum and titanium. Since the positive electrode active material used in the above contains an element that may be contained, a synergistic effect can be expected for improving the cycle characteristics, which is preferable. In addition, productivity can be expected to improve by reducing the number of processes.
  • the NASICON type crystal structure is a compound represented by M 2 (XO 4 ) 3 (M: transition metal, X: S, P, As, Mo, W, etc.), and is MO 6 It refers to having an octahedral and XO 4 tetrahedra are arranged three-dimensionally share vertices structure.
  • the exterior body of the secondary battery 400 of one aspect of the present invention various materials and shapes can be used, but it is preferable that the exterior body has a function of pressurizing the positive electrode, the solid electrolyte layer and the negative electrode.
  • FIG. 21 is an example of a cell that evaluates the material of an all-solid-state battery.
  • FIG. 21A is a schematic cross-sectional view of the evaluation cell.
  • the evaluation cell has a lower member 761, an upper member 762, a fixing screw and a wing nut 764 for fixing them, and is used for an electrode by rotating a pressing screw 763.
  • the evaluation material is fixed by pushing the plate 753.
  • An insulator 766 is provided between the lower member 761 made of a stainless steel material and the upper member 762. Further, an O-ring 765 for sealing is provided between the upper member 762 and the holding screw 763.
  • FIG. 21B is an enlarged perspective view of the periphery of the evaluation material.
  • FIG. 21C As an evaluation material, an example of laminating a positive electrode 750a, a solid electrolyte layer 750b, and a negative electrode 750c is shown, and a cross-sectional view is shown in FIG. 21C.
  • the same reference numerals are used for the same parts in FIGS. 21A to 21C.
  • the electrode plate 751 and the lower member 761 electrically connected to the positive electrode 750a correspond to the positive electrode terminals. It can be said that the electrode plate 753 and the upper member 762 electrically connected to the negative electrode 750c correspond to the negative electrode terminals.
  • the electrical resistance and the like can be measured while pressing the evaluation material through the electrode plate 751 and the electrode plate 753.
  • a package having excellent airtightness for the exterior body of the secondary battery according to one aspect of the present invention For example, a ceramic package or a resin package can be used. Further, when sealing the exterior body, it is preferable to shut off the outside air and perform it in a closed atmosphere, for example, in a glove box.
  • FIG. 22A shows a perspective view of the secondary battery of one aspect of the present invention having an exterior body and a shape different from those of FIG. 21.
  • the secondary battery of FIG. 22A has external electrodes 771 and 772, and is sealed with an exterior body having a plurality of package members.
  • FIG. 22B shows an example of a cross section cut by a broken line in FIG. 22A.
  • the laminate having a positive electrode 750a, a solid electrolyte layer 750b, and a negative electrode 750c includes a package member 770a having an electrode layer 773a provided on a flat plate, a frame-shaped package member 770b, and a package member 770c having an electrode layer 773b provided on a flat plate. It has a sealed structure surrounded by. Insulating materials such as resin materials and ceramics can be used for the package members 770a, 770b, and 770c.
  • the external electrode 771 is electrically connected to the positive electrode 750a via the electrode layer 773a and functions as a positive electrode terminal. Further, the external electrode 772 is electrically connected to the negative electrode 750c via the electrode layer 773b and functions as a negative electrode terminal.
  • an all-solid-state secondary battery having a high energy density and good output characteristics can be realized.
  • This embodiment can be used in combination with other embodiments as appropriate.
  • FIG. 23C shows an example of application to an electric vehicle (EV).
  • EV electric vehicle
  • the electric vehicle is equipped with a first battery 1301a and 1301b as a main drive secondary battery and a second battery 1311 that supplies electric power to the inverter 1312 that starts the motor 1304.
  • the second battery 1311 is also called a cranking battery (also called a starter battery).
  • the second battery 1311 only needs to have a high output, and a large capacity is not required so much, and the capacity of the second battery 1311 is smaller than that of the first batteries 1301a and 1301b.
  • the internal structure of the first battery 1301a may be the winding type shown in FIG. 15A or FIG. 16C, or the laminated type shown in FIG. 17A or FIG. 17B. Further, as the first battery 1301a, the all-solid-state battery of the fifth embodiment may be used. By using the all-solid-state battery of the fifth embodiment for the first battery 1301a, the capacity can be increased, the safety can be improved, and the size and weight can be reduced.
  • first batteries 1301a and 1301b are connected in parallel, but three or more batteries may be connected in parallel. Further, if the first battery 1301a can store sufficient electric power, the first battery 1301b may not be present.
  • the plurality of secondary batteries may be connected in parallel, may be connected in series, or may be connected in parallel and then further connected in series. Multiple secondary batteries are also called assembled batteries.
  • a service plug or a circuit breaker capable of cutting off a high voltage without using a tool is provided, and the first battery 1301a has. It will be provided.
  • the electric power of the first batteries 1301a and 1301b is mainly used to rotate the motor 1304, but 42V in-vehicle parts (electric power steering 1307, heater 1308, defogger 1309, etc.) via the DCDC circuit 1306. Power to. Even if the rear wheel has a rear motor 1317, the first battery 1301a is used to rotate the rear motor 1317.
  • the second battery 1311 supplies electric power to 14V in-vehicle components (audio 1313, power window 1314, lamps 1315, etc.) via the DCDC circuit 1310.
  • first battery 1301a will be described with reference to FIG. 23A.
  • FIG. 23A shows an example in which nine square secondary batteries 1300 are used as one battery pack 1415. Further, nine square secondary batteries 1300 are connected in series, one electrode is fixed by a fixing portion 1413 made of an insulator, and the other electrode is fixed by a fixing portion 1414 made of an insulator.
  • a fixing portion 1413 made of an insulator In the present embodiment, an example of fixing with the fixing portions 1413 and 1414 is shown, but the configuration may be such that the battery is stored in a battery storage box (also referred to as a housing). Since it is assumed that the vehicle is subjected to vibration or shaking from the outside (road surface, etc.), the fixed portions 1413, 1414 and the like. It is preferable to fix a plurality of secondary batteries in a battery storage box or the like. Further, one of the electrodes is electrically connected to the control circuit unit 1320 by the wiring 1421. The other electrode is electrically connected to the control circuit unit 1320 by wiring 1422.
  • control circuit unit 1320 may use a memory circuit including a transistor using an oxide semiconductor.
  • a charge control circuit or a battery control system having a memory circuit including a transistor using an oxide semiconductor may be referred to as a BTOS (Battery operating system or Battery oxide semiconductor).
  • an In-M-Zn oxide (element M is aluminum, gallium, yttrium, copper, vanadium, beryllium, boron, titanium, iron, nickel, germanium, zirconium, molybdenum, lantern, cerium, neodymium). , Hafnium, tantalum, tungsten, magnesium, etc., one or more) and the like may be used.
  • the In-M-Zn oxide applicable as the oxide 530 is preferably CAAC-OS (C-Axls Aligned Crystal Oxide Semiconductor) and CAC-OS (Cloud-Aligned Compound Semiconductor).
  • CAAC-OS is an oxide semiconductor having a plurality of crystal regions, the plurality of crystal regions having the c-axis oriented in a specific direction.
  • the specific direction is the thickness direction of the CAAC-OS film, the normal direction of the surface to be formed of the CAAC-OS film, or the normal direction of the surface of the CAAC-OS film.
  • the crystal region is a region having periodicity in the atomic arrangement. When the atomic arrangement is regarded as a lattice arrangement, the crystal region is also a region in which the lattice arrangement is aligned.
  • the CAAC-OS has a region in which a plurality of crystal regions are connected in the ab plane direction, and the region may have distortion.
  • the strain refers to a region in which a plurality of crystal regions are connected in which the orientation of the lattice arrangement changes between a region in which the lattice arrangement is aligned and a region in which another grid arrangement is aligned. That is, CAAC-OS is an oxide semiconductor that is c-axis oriented and not clearly oriented in the ab plane direction.
  • CAC-OS is, for example, a composition of a material in which elements constituting a metal oxide are unevenly distributed in a size of 0.5 nm or more and 10 nm or less, preferably 1 nm or more and 3 nm or less, or a size close thereto.
  • the metal oxide one or more metal elements are unevenly distributed, and the region having the metal element has a size of 0.5 nm or more and 10 nm or less, preferably 1 nm or more and 3 nm or less, or a size close thereto.
  • the mixed state is also called a mosaic shape or a patch shape.
  • the CAC-OS has a structure in which the material is separated into a first region and a second region to form a mosaic, and the first region is distributed in the film (hereinafter, also referred to as a cloud shape). It is said.). That is, the CAC-OS is a composite metal oxide having a structure in which the first region and the second region are mixed.
  • the atomic number ratios of In, Ga, and Zn with respect to the metal elements constituting CAC-OS in the In-Ga-Zn oxide are expressed as [In], [Ga], and [Zn], respectively.
  • the first region is a region where [In] is larger than [In] in the composition of the CAC-OS film.
  • the second region is a region in which [Ga] is larger than [Ga] in the composition of the CAC-OS film.
  • the first region is a region where [In] is larger than [In] in the second region and [Ga] is smaller than [Ga] in the second region.
  • the second region is a region in which [Ga] is larger than [Ga] in the first region and [In] is smaller than [In] in the first region.
  • the first region is a region containing indium oxide, indium zinc oxide, or the like as a main component.
  • the second region is a region containing gallium oxide, gallium zinc oxide, or the like as a main component. That is, the first region can be rephrased as a region containing In as a main component. Further, the second region can be rephrased as a region containing Ga as a main component.
  • a region containing In as a main component (No. 1) by EDX mapping acquired by using energy dispersive X-ray spectroscopy (EDX: Energy Dispersive X-ray spectroscopy). It can be confirmed that the region (1 region) and the region containing Ga as a main component (second region) have a structure in which they are unevenly distributed and mixed.
  • EDX Energy Dispersive X-ray spectroscopy
  • CAC-OS When CAC-OS is used for a transistor, the conductivity caused by the first region and the insulating property caused by the second region act in a complementary manner to switch the switching function (On / Off function). Can be added to CAC-OS. That is, the CAC-OS has a conductive function in a part of the material and an insulating function in a part of the material, and has a function as a semiconductor in the whole material. By separating the conductive function and the insulating function, both functions can be maximized. Therefore, by using CAC-OS for the transistor, high on-current ( Ion ), high field effect mobility ( ⁇ ), and good switching operation can be realized.
  • Ion on-current
  • ⁇ high field effect mobility
  • Oxide semiconductors have various structures, and each has different characteristics.
  • the oxide semiconductor of one aspect of the present invention has two or more of amorphous oxide semiconductor, polycrystalline oxide semiconductor, a-like OS, CAC-OS, nc-OS, and CAAC-OS. You may.
  • the control circuit unit 1320 may be formed by using a unipolar transistor.
  • a transistor using an oxide semiconductor as a semiconductor layer has an operating ambient temperature wider than that of single crystal Si and is -40 ° C or higher and 150 ° C or lower, and its characteristic change is smaller than that of single crystal even when a secondary battery is heated.
  • the off-current of a transistor using an oxide semiconductor is below the lower limit of measurement regardless of the temperature even at 150 ° C., but the off-current characteristics of a single crystal Si transistor are highly temperature-dependent.
  • the off-current of the single crystal Si transistor increases, and the current on / off ratio does not become sufficiently large.
  • the control circuit unit 1320 can improve the safety. Further, by combining the positive electrode active material 100 obtained in the first embodiment with a secondary battery using the positive electrode, a synergistic effect on safety can be obtained.
  • the secondary battery and the control circuit unit 1320 using the positive electrode active material 100 obtained in the first embodiment as the positive electrode can greatly contribute to the eradication of accidents such as fires caused by the secondary battery.
  • the control circuit unit 1320 using a memory circuit including a transistor using an oxide semiconductor can also function as an automatic control device for a secondary battery for the causes of instability of 10 items such as micro shorts.
  • Functions that eliminate the causes of instability in 10 items include prevention of overcharging, prevention of overcurrent, overheat control during charging, cell balance with assembled batteries, prevention of overdischarge, fuel gauge, and charging according to temperature.
  • Automatic control of voltage and current amount, charge current amount control according to the degree of deterioration, microshort abnormality behavior detection, abnormality prediction related to microshort, etc. are mentioned, and the control circuit unit 1320 has at least one of these functions.
  • the automatic control device for the secondary battery can be miniaturized.
  • the micro short circuit refers to a minute short circuit inside the secondary battery, and does not mean that the positive electrode and the negative electrode of the secondary battery are short-circuited and cannot be charged or discharged. It refers to the phenomenon that a short-circuit current flows slightly in the part. Since a large voltage change occurs in a relatively short time and even in a small place, the abnormal voltage value may affect the subsequent estimation.
  • microshorts due to multiple charging and discharging, the uneven distribution of the positive electrode active material causes local current concentration in a part of the positive electrode and a part of the negative electrode, resulting in a separator. It is said that a micro-short circuit occurs due to the occurrence of a part where it does not function or the generation of a side reaction product due to a side reaction.
  • control circuit unit 1320 not only detects the micro short circuit but also detects the terminal voltage of the secondary battery and manages the charge / discharge state of the secondary battery. For example, in order to prevent overcharging, both the output transistor of the charging circuit and the cutoff switch can be turned off almost at the same time.
  • FIG. 23B an example of the block diagram of the battery pack 1415 shown in FIG. 23A is shown in FIG. 23B.
  • the control circuit unit 1320 includes at least a switch for preventing overcharging, a switch unit 1324 including a switch for preventing overdischarging, a control circuit 1322 for controlling the switch unit 1324, and a voltage measuring unit for the first battery 1301a.
  • the control circuit unit 1320 sets the upper limit voltage and the lower limit voltage of the secondary battery to be used, and limits the upper limit of the current from the outside and the upper limit of the output current to the outside.
  • the range of the lower limit voltage or more and the upper limit voltage or less of the secondary battery is within the voltage range recommended for use, and when it is out of the range, the switch unit 1324 operates and functions as a protection circuit.
  • control circuit unit 1320 can also be called a protection circuit because it controls the switch unit 1324 to prevent over-discharging and over-charging. For example, when the control circuit 1322 detects a voltage that is likely to cause overcharging, the switch of the switch unit 1324 is turned off to cut off the current. Further, a PTC element may be provided in the charge / discharge path to provide a function of cutting off the current in response to an increase in temperature. Further, the control circuit unit 1320 has an external terminal 1325 (+ IN) and an external terminal 1326 ( ⁇ IN).
  • the switch unit 1324 can be configured by combining an n-channel type transistor and a p-channel type transistor.
  • the switch unit 1324 is not limited to a switch having a Si transistor using single crystal silicon, and is not limited to, for example, Ge (germanium), SiGe (silicon germanium), GaAs (gallium arsenide), GaAlAs (gallium aluminum arsenide), and InP (phosphide).
  • the switch unit 1324 may be formed by a power transistor having indium phosphide, SiC (silicon carbide), ZnSe (zinc selenium), GaN (gallium arsenide), GaOx (gallium oxide; x is a real number larger than 0) and the like.
  • the storage element using the OS transistor can be freely arranged by stacking it on a circuit using a Si transistor or the like, integration can be easily performed.
  • the OS transistor can be manufactured by using the same manufacturing apparatus as the Si transistor, it can be manufactured at low cost. That is, a control circuit unit 1320 using an OS transistor can be stacked on the switch unit 1324 and integrated into one chip. Since the occupied volume of the control circuit unit 1320 can be reduced, the size can be reduced.
  • the first batteries 1301a and 1301b mainly supply electric power to a 42V system (high voltage system) in-vehicle device, and the second battery 1311 supplies electric power to a 14V system (low voltage system) in-vehicle device.
  • the second battery 1311 is often adopted because a lead storage battery is advantageous in terms of cost.
  • Lead-acid batteries have a larger self-discharge than lithium-ion secondary batteries, and have the disadvantage of being easily deteriorated by a phenomenon called sulfation.
  • the second battery 1311 as a lithium ion secondary battery, there is an advantage that it is maintenance-free, but if it is used for a long period of time, for example, after 3 years or more, there is a possibility that an abnormality that cannot be discriminated at the time of manufacture occurs.
  • the second battery 1311 for starting the inverter becomes inoperable, the second battery 1311 is lead-acid in order to prevent the motor from being unable to start even if the first batteries 1301a and 1301b have remaining capacity.
  • power is supplied from the first battery to the second battery, and the battery is charged so as to always maintain a fully charged state.
  • a lithium ion secondary battery is used for both the first battery 1301a and the second battery 1311.
  • the second battery 1311 may use a lead storage battery, an all-solid-state battery, or an electric double layer capacitor.
  • the all-solid-state battery of the fifth embodiment may be used.
  • the capacity can be increased, and the size and weight can be reduced.
  • the regenerative energy due to the rotation of the tire 1316 is sent to the motor 1304 via the gear 1305, and is charged from the motor controller 1303 and the battery controller 1302 to the second battery 1311 via the control circuit unit 1321.
  • the first battery 1301a is charged from the battery controller 1302 via the control circuit unit 1320.
  • the first battery 1301b is charged from the battery controller 1302 via the control circuit unit 1320. In order to efficiently charge the regenerative energy, it is desirable that the first batteries 1301a and 1301b can be quickly charged.
  • the battery controller 1302 can set the charging voltage, charging current, and the like of the first batteries 1301a and 1301b.
  • the battery controller 1302 can set charging conditions according to the charging characteristics of the secondary battery to be used and quickly charge the battery.
  • the outlet of the charger or the connection cable of the charger is electrically connected to the battery controller 1302.
  • the electric power supplied from the external charger charges the first batteries 1301a and 1301b via the battery controller 1302.
  • a control circuit may be provided and the function of the battery controller 1302 may not be used, but the first batteries 1301a and 1301b are charged via the control circuit unit 1320 in order to prevent overcharging. Is preferable.
  • the connection cable or the connection cable of the charger is provided with a control circuit.
  • the control circuit unit 1320 may be referred to as an ECU (Electronic Control Unit).
  • the ECU is connected to a CAN (Controller Area Network) provided in the electric vehicle.
  • CAN is one of the serial communication standards used as an in-vehicle LAN.
  • the ECU also includes a microcomputer. Further, the ECU uses a CPU or GPU.
  • External chargers installed in charging stands and the like include 100V outlets, 200V outlets, three-phase 200V and 50kW.
  • the secondary battery of the present embodiment described above has a high-density positive electrode by using the positive electrode active material 100 obtained in the first embodiment. Furthermore, using graphene as a conductive auxiliary agent, even if the electrode layer is thickened to increase the loading amount, the capacity decrease is suppressed and maintaining high capacity is a synergistic effect of the secondary battery with significantly improved electrical characteristics. realizable. It is particularly effective for a secondary battery used in a vehicle, and provides a vehicle having a long cruising range, specifically, a vehicle having a charge mileage of 500 km or more, without increasing the ratio of the weight of the secondary battery to the total weight of the vehicle. be able to.
  • the secondary battery of the present embodiment described above can increase the operating voltage of the secondary battery by using the positive electrode active material 100 described in the first embodiment, and can be used as the charging voltage increases.
  • the capacity can be increased.
  • the positive electrode active material 100 described in the first embodiment as the positive electrode, it is possible to provide a secondary battery for a vehicle having excellent cycle characteristics.
  • the secondary battery shown in any one of FIGS. 14D, 16C, and 23A is mounted on the vehicle, the next generation such as a hybrid vehicle (HV), an electric vehicle (EV), or a plug-in hybrid vehicle (PHV) is installed.
  • HV hybrid vehicle
  • EV electric vehicle
  • PWD plug-in hybrid vehicle
  • a clean energy vehicle can be realized.
  • Secondary batteries can also be mounted on transport vehicles such as planetary explorers and spacecraft.
  • the secondary battery of one aspect of the present invention can be a high-capacity secondary battery. Therefore, the secondary battery of one aspect of the present invention is suitable for miniaturization and weight reduction, and can be suitably used for a transportation vehicle.
  • the automobile 2001 shown in FIG. 24A is an electric vehicle that uses an electric motor as a power source for traveling. Alternatively, it is a hybrid vehicle in which an electric motor and an engine can be appropriately selected and used as a power source for traveling.
  • an example of the secondary battery shown in the fourth embodiment is installed at one place or a plurality of places.
  • the automobile 2001 shown in FIG. 24A has a battery pack 2200, and the battery pack has a secondary battery module to which a plurality of secondary batteries are connected. Further, it is preferable to have a charge control device that is electrically connected to the secondary battery module.
  • the automobile 2001 can charge the secondary battery of the automobile 2001 by receiving electric power from an external charging facility by a plug-in method, a non-contact power feeding method, or the like.
  • the charging method, the connector standard, etc. may be appropriately performed by a predetermined method such as CHAdeMO (registered trademark) or combo.
  • the secondary battery may be a charging station provided in a commercial facility or a household power source.
  • the plug-in technology can charge the power storage device mounted on the automobile 2001 by supplying electric power from the outside. Charging can be performed by converting AC power into DC power via a conversion device such as an ACDC converter.
  • a power receiving device on the vehicle and supply electric power from a ground power transmission device in a non-contact manner to charge the vehicle.
  • this non-contact power supply system by incorporating a power transmission device on the road or the outer wall, it is possible to charge the battery not only while the vehicle is stopped but also while the vehicle is running.
  • the non-contact power feeding method may be used to transmit and receive electric power between two vehicles.
  • a solar cell may be provided on the exterior portion of the vehicle to charge the secondary battery when the vehicle is stopped or running.
  • An electromagnetic induction method or a magnetic field resonance method can be used for such non-contact power supply.
  • FIG. 24B shows a large transport vehicle 2002 having an electrically controlled motor as an example of a transport vehicle.
  • the secondary battery module of the transport vehicle 2002 has, for example, a secondary battery having a nominal voltage of 3.0 V or more and 5.0 V or less as a four-cell unit, and has a maximum voltage of 170 V in which 48 cells are connected in series. Since it has the same functions as those in FIG. 24A except that the number of secondary batteries constituting the secondary battery module of the battery pack 2201 is different, the description thereof will be omitted.
  • FIG. 24C shows, as an example, a large transport vehicle 2003 having a motor controlled by electricity.
  • the secondary battery module of the transport vehicle 2003 has, for example, a maximum voltage of 600 V in which 100 or more secondary batteries having a nominal voltage of 3.0 V or more and 5.0 V or less are connected in series. Therefore, a secondary battery having a small variation in characteristics is required.
  • a secondary battery using the positive electrode active material 100 described in the first embodiment as the positive electrode a secondary battery having stable battery characteristics can be manufactured, and mass production can be performed at low cost from the viewpoint of yield. It is possible. Further, since it has the same functions as those in FIG. 24A except that the number of secondary batteries constituting the secondary battery module of the battery pack 2202 is different, the description thereof will be omitted.
  • FIG. 24D shows, as an example, an aircraft 2004 with an engine that burns fuel. Since the aircraft 2004 shown in FIG. 24D has wheels for takeoff and landing, it can be said to be a part of a transportation vehicle, and a plurality of secondary batteries are connected to form a secondary battery module, which is charged with the secondary battery module. It has a battery pack 2203 including a control device.
  • the secondary battery module of the aircraft 2004 has a maximum voltage of 32V in which eight 4V secondary batteries are connected in series, for example. Since it has the same functions as those in FIG. 24A except that the number of secondary batteries constituting the secondary battery module of the battery pack 2203 is different, the description thereof will be omitted.
  • This embodiment can be used in combination with other embodiments as appropriate.
  • the house shown in FIG. 25A has a power storage device 2612 having a secondary battery, which is one aspect of the present invention, and a solar panel 2610.
  • the power storage device 2612 is electrically connected to the solar panel 2610 via wiring 2611 and the like. Further, the power storage device 2612 and the ground-mounted charging device 2604 may be electrically connected.
  • the electric power obtained by the solar panel 2610 can be charged to the power storage device 2612. Further, the electric power stored in the power storage device 2612 can be charged to the secondary battery of the vehicle 2603 via the charging device 2604.
  • the power storage device 2612 is preferably installed in the underfloor space. By installing it in the underfloor space, the space above the floor can be effectively used. Alternatively, the power storage device 2612 may be installed on the floor.
  • the electric power stored in the power storage device 2612 can also supply electric power to other electronic devices in the house. Therefore, even when the power cannot be supplied from the commercial power supply due to a power failure or the like, the electronic device can be used by using the power storage device 2612 according to one aspect of the present invention as an uninterruptible power supply.
  • FIG. 25B shows an example of the power storage device 700 according to one aspect of the present invention.
  • the power storage device 791 according to one aspect of the present invention is installed in the underfloor space portion 796 of the building 799.
  • the power storage device 791 may be provided with the control circuit described in the sixth embodiment, and safety is achieved by using a secondary battery using the positive electrode active material 100 obtained in the first embodiment as the positive electrode for the power storage device 791. A synergistic effect is obtained.
  • the secondary battery using the control circuit described in the sixth embodiment and the positive electrode active material 100 described in the first embodiment as the positive electrode greatly contributes to the eradication of accidents such as fire by the power storage device 791 having the secondary battery. Can be done.
  • a control device 790 is installed in the power storage device 791, and the control device 790 is connected to a distribution board 703, a power storage controller 705 (also referred to as a control device), a display 706, and a router 709 by wiring. It is electrically connected.
  • Electric power is sent from the commercial power supply 701 to the distribution board 703 via the drop line mounting portion 710. Further, electric power is transmitted to the distribution board 703 from the power storage device 791 and the commercial power supply 701, and the distribution board 703 transfers the transmitted electric power to a general load via an outlet (not shown). It supplies 707 and the power storage system load 708.
  • the general load 707 is, for example, an electric device such as a television or a personal computer
  • the storage system load 708 is, for example, an electric device such as a microwave oven, a refrigerator, or an air conditioner.
  • the power storage controller 705 includes a measurement unit 711, a prediction unit 712, and a planning unit 713.
  • the measuring unit 711 has a function of measuring the amount of electric power consumed by the general load 707 and the power storage system load 708 during one day (for example, from 0:00 to 24:00). Further, the measuring unit 711 may have a function of measuring the electric power of the power storage device 791 and the electric power supplied from the commercial power source 701.
  • the prediction unit 712 is based on the amount of electric power consumed by the general load 707 and the power storage system load 708 during the next day, and the demand consumed by the general load 707 and the power storage system load 708 during the next day. It has a function to predict the amount of electric power.
  • the planning unit 713 has a function of making a charge / discharge plan of the power storage device 791 based on the power demand amount predicted by the prediction unit 712.
  • the amount of electric power consumed by the general load 707 and the power storage system load 708 measured by the measuring unit 711 can be confirmed by the display 706. It can also be confirmed in an electric device such as a television or a personal computer via a router 709. Further, it can be confirmed by a portable electronic terminal such as a smartphone or a tablet via the router 709. In addition, the amount of power demand for each time zone (or every hour) predicted by the prediction unit 712 can be confirmed by the display 706, the electric device, and the portable electronic terminal.
  • This embodiment can be used in combination with other embodiments as appropriate.
  • FIG. 26A is an example of an electric bicycle using the power storage device of one aspect of the present invention.
  • One aspect of the power storage device of the present invention can be applied to the electric bicycle 8700 shown in FIG. 26A.
  • the power storage device of one aspect of the present invention includes, for example, a plurality of storage batteries and a protection circuit.
  • the electric bicycle 8700 includes a power storage device 8702.
  • the power storage device 8702 can supply electricity to the motor that assists the driver. Further, the power storage device 8702 is portable, and FIG. 26B shows a state in which the power storage device 8702 is removed from the bicycle. Further, the power storage device 8702 incorporates a plurality of storage batteries 8701 included in the power storage device according to one aspect of the present invention, and the remaining battery level and the like can be displayed on the display unit 8703. Further, the power storage device 8702 has a control circuit 8704 capable of charging control or abnormality detection of the secondary battery shown as an example in the sixth embodiment. The control circuit 8704 is electrically connected to the positive electrode and the negative electrode of the storage battery 8701.
  • control circuit 8704 may be provided with the small solid secondary batteries shown in FIGS. 22A and 22B.
  • the small solid-state secondary battery shown in FIGS. 22A and 22B in the control circuit 8704, power can be supplied to hold the data of the memory circuit of the control circuit 8704 for a long time.
  • the positive electrode active material 100 obtained in the first embodiment with a secondary battery using the positive electrode, a synergistic effect on safety can be obtained.
  • the secondary battery and the control circuit 8704 using the positive electrode active material 100 obtained in the first embodiment as the positive electrode can greatly contribute to the eradication of accidents such as fires caused by the secondary battery.
  • FIG. 26C is an example of a two-wheeled vehicle using the power storage device of one aspect of the present invention.
  • the scooter 8600 shown in FIG. 26C includes a power storage device 8602, a side mirror 8601, and a turn signal 8603.
  • the power storage device 8602 can supply electricity to the turn signal 8603.
  • the power storage device 8602 containing a plurality of secondary batteries using the positive electrode active material 100 obtained in the first embodiment as the positive electrode can have a high capacity and can contribute to miniaturization.
  • the power storage device 8602 can be stored in the storage under the seat 8604.
  • the power storage device 8602 can be stored in the under-seat storage 8604 even if the under-seat storage 8604 is small.
  • Electronic devices that mount secondary batteries include, for example, television devices (also referred to as televisions or television receivers), monitors for computers, digital cameras, digital video cameras, digital photo frames, mobile phones (mobile phones, mobile phones, etc.).
  • television devices also referred to as televisions or television receivers
  • monitors for computers digital cameras, digital video cameras, digital photo frames, mobile phones (mobile phones, mobile phones, etc.).
  • mobile phone device a portable game machine
  • mobile information terminal a sound reproduction device
  • a large game machine such as a pachinko machine
  • Examples of mobile information terminals include notebook personal computers, tablet terminals, electronic book terminals, and mobile phones.
  • FIG. 27A shows an example of a mobile phone.
  • the mobile phone 2100 includes an operation button 2103, an external connection port 2104, a speaker 2105, a microphone 2106, and the like, in addition to the display unit 2102 incorporated in the housing 2101.
  • the mobile phone 2100 has a secondary battery 2107.
  • the capacity can be increased, and a configuration capable of saving space due to the miniaturization of the housing can be realized. Can be done.
  • the mobile phone 2100 can execute various applications such as mobile phones, e-mails, text viewing and writing, music playback, Internet communication, and computer games.
  • the operation button 2103 can have various functions such as power on / off operation, wireless communication on / off operation, manner mode execution / cancellation, and power saving mode execution / cancellation. ..
  • the function of the operation button 2103 can be freely set by the operating system incorporated in the mobile phone 2100.
  • the mobile phone 2100 can execute short-range wireless communication with communication standards. For example, by communicating with a headset capable of wireless communication, it is possible to make a hands-free call.
  • the mobile phone 2100 is provided with an external connection port 2104, and data can be directly exchanged with another information terminal via a connector. It can also be charged via the external connection port 2104. The charging operation may be performed by wireless power supply without going through the external connection port 2104.
  • the mobile phone 2100 preferably has a sensor.
  • a human body sensor such as a fingerprint sensor, a pulse sensor, a body temperature sensor, a touch sensor, a pressure sensor, an acceleration sensor, or the like is preferably mounted.
  • FIG. 27B is an unmanned aerial vehicle 2300 with a plurality of rotors 2302.
  • the unmanned aerial vehicle 2300 is sometimes called a drone.
  • the unmanned aerial vehicle 2300 has a secondary battery 2301, a camera 2303, and an antenna (not shown), which is one aspect of the present invention.
  • the unmanned aerial vehicle 2300 can be remotely controlled via an antenna.
  • the secondary battery using the positive electrode active material 100 obtained in the first embodiment as the positive electrode has a high energy density and high safety, so that it can be safely used for a long period of time and can be used in an unmanned aircraft 2300. It is suitable as a secondary battery to be mounted.
  • FIG. 27C shows an example of a robot.
  • the robot 6400 shown in FIG. 27C includes a secondary battery 6409, an illuminance sensor 6401, a microphone 6402, an upper camera 6403, a speaker 6404, a display unit 6405, a lower camera 6406 and an obstacle sensor 6407, a moving mechanism 6408, an arithmetic unit, and the like.
  • the microphone 6402 has a function of detecting a user's voice, environmental sound, and the like. Further, the speaker 6404 has a function of emitting sound. The robot 6400 can communicate with the user by using the microphone 6402 and the speaker 6404.
  • the display unit 6405 has a function of displaying various information.
  • the robot 6400 can display the information desired by the user on the display unit 6405.
  • the display unit 6405 may be equipped with a touch panel. Further, the display unit 6405 may be a removable information terminal, and by installing the robot 6400 at a fixed position, charging and data transfer are possible.
  • the upper camera 6403 and the lower camera 6406 have a function of photographing the surroundings of the robot 6400. Further, the obstacle sensor 6407 can detect the presence / absence of an obstacle in the traveling direction when the robot 6400 moves forward by using the moving mechanism 6408. The robot 6400 can recognize the surrounding environment and move safely by using the upper camera 6403, the lower camera 6406 and the obstacle sensor 6407.
  • the robot 6400 includes a secondary battery 6409 according to an aspect of the present invention and a semiconductor device or an electronic component in the internal region thereof.
  • the secondary battery using the positive electrode active material 100 obtained in the first embodiment as the positive electrode has a high energy density and high safety, so that it can be used safely for a long period of time and is mounted on the robot 6400. It is suitable as a secondary battery 6409.
  • FIG. 27D shows an example of a cleaning robot.
  • the cleaning robot 6300 has a display unit 6302 arranged on the upper surface of the housing 6301, a plurality of cameras 6303 arranged on the side surface, a brush 6304, an operation button 6305, a secondary battery 6306, various sensors, and the like.
  • the cleaning robot 6300 is provided with tires, suction ports, and the like.
  • the cleaning robot 6300 is self-propelled, can detect dust 6310, and can suck dust from a suction port provided on the lower surface.
  • the cleaning robot 6300 can analyze an image taken by the camera 6303 and determine the presence or absence of an obstacle such as a wall, furniture, or a step. Further, when an object that is likely to be entangled with the brush 6304 such as wiring is detected by image analysis, the rotation of the brush 6304 can be stopped.
  • the cleaning robot 6300 includes a secondary battery 6306 according to an aspect of the present invention and a semiconductor device or an electronic component in the internal region thereof.
  • the secondary battery using the positive electrode active material 100 obtained in the first embodiment as the positive electrode has a high energy density and high safety, so that it can be safely used for a long period of time and can be used as a cleaning robot 6300. It is suitable as a secondary battery 6306 to be mounted.
  • FIG. 28A shows an example of a wearable device.
  • Wearable devices use a secondary battery as a power source. Further, in order to improve the water resistance of water for the user in daily use or outdoor use, a wearable device capable of wireless charging as well as wired charging in which the connector portion to be connected is exposed is desired.
  • a secondary battery according to one aspect of the present invention can be mounted on the spectacle-type device 4000 as shown in FIG. 28A.
  • the spectacle-type device 4000 has a frame 4000a and a display unit 4000b.
  • By mounting the secondary battery on the temple portion of the curved frame 4000a it is possible to obtain a spectacle-type device 4000 that is lightweight, has a good weight balance, and has a long continuous use time.
  • the secondary battery using the positive electrode active material 100 obtained in the first embodiment as the positive electrode has a high energy density, and can realize a configuration that can cope with space saving accompanying the miniaturization of the housing.
  • a secondary battery which is one aspect of the present invention, can be mounted on the headset type device 4001.
  • the headset-type device 4001 has at least a microphone unit 4001a, a flexible pipe 4001b, and an earphone unit 4001c.
  • a secondary battery can be provided in the flexible pipe 4001b or in the earphone portion 4001c.
  • the secondary battery using the positive electrode active material 100 obtained in the first embodiment as the positive electrode has a high energy density, and can realize a configuration that can cope with space saving accompanying the miniaturization of the housing.
  • the secondary battery according to one aspect of the present invention can be mounted on the device 4002 that can be directly attached to the body.
  • the secondary battery 4002b can be provided in the thin housing 4002a of the device 4002.
  • the secondary battery using the positive electrode active material 100 obtained in the first embodiment as the positive electrode has a high energy density, and can realize a configuration that can cope with space saving accompanying the miniaturization of the housing.
  • the secondary battery according to one aspect of the present invention can be mounted on the device 4003 that can be attached to clothes.
  • the secondary battery 4003b can be provided in the thin housing 4003a of the device 4003.
  • the secondary battery using the positive electrode active material 100 obtained in the first embodiment as the positive electrode has a high energy density, and can realize a configuration that can cope with space saving accompanying the miniaturization of the housing.
  • a secondary battery which is one aspect of the present invention, can be mounted on the belt-type device 4006.
  • the belt-type device 4006 has a belt portion 4006a and a wireless power supply receiving portion 4006b, and a secondary battery can be mounted in the internal region of the belt portion 4006a.
  • the secondary battery using the positive electrode active material 100 obtained in the first embodiment as the positive electrode has a high energy density, and can realize a configuration that can cope with space saving accompanying the miniaturization of the housing.
  • a secondary battery which is one aspect of the present invention, can be mounted on the wristwatch-type device 4005.
  • the wristwatch-type device 4005 has a display unit 4005a and a belt unit 4005b, and a secondary battery can be provided on the display unit 4005a or the belt unit 4005b.
  • the secondary battery using the positive electrode active material 100 obtained in the first embodiment as the positive electrode has a high energy density, and can realize a configuration that can cope with space saving accompanying the miniaturization of the housing.
  • the display unit 4005a can display not only the time but also various information such as an incoming mail or a telephone call.
  • the wristwatch type device 4005 is a wearable device of a type that is directly wrapped around the wrist, a sensor for measuring the pulse, blood pressure, etc. of the user may be mounted. It is possible to manage the health by accumulating data on the amount of exercise and health of the user.
  • FIG. 28B shows a perspective view of the wristwatch-type device 4005 removed from the arm.
  • FIG. 28C shows a state in which the secondary battery 913 is built in the internal region.
  • the secondary battery 913 is the secondary battery shown in the fourth embodiment.
  • the secondary battery 913 is provided at a position overlapping with the display unit 4005a, can have a high density and a high capacity, is compact, and is lightweight.
  • the positive electrode active material 100 obtained in the first embodiment is used for the positive electrode of the secondary battery 913 to have a high energy density and a small size.
  • the secondary battery 913 can be used.
  • This embodiment can be implemented in combination with other embodiments as appropriate.
  • Example 1 In the present embodiment, after producing the positive electrode active material of one aspect of the present invention, a plurality of coin-shaped battery cells were produced and their cycle characteristics were evaluated.
  • the sample prepared in this example will be described. Four samples were prepared under the same conditions and procedures except for the solvent (amount of 2-propanol) in the sol-gel method. The amount of 2-propanol was prepared as 0 ml, 1 ml, 5 ml, and 10 ml.
  • the positive electrode active material of each sample As the positive electrode active material of each sample, the positive electrode active material obtained by the method shown in the first embodiment was used. A positive electrode active material 100 was obtained according to the flow of FIG.
  • LiMO 2 in step S14 a commercially available lithium cobalt oxide (CellSeed C-10N manufactured by Nippon Chemical Industrial Co., Ltd.) having cobalt as a transition metal M and having no particular additive was prepared. Lithium fluoride and magnesium fluoride were mixed with this by a solid phase method in the same manner as in steps S21 to S23, step S41 and step S42. When the number of atoms of cobalt was 100, the amount of lithium fluoride added was 0.33 and the number of magnesium fluoride molecules was 1. This was designated as a mixture 903.
  • annealing was performed in the same manner as in step S43. 30 g of the mixture 903 was placed in a square alumina container, a lid was placed, and the mixture was heated in a muffle furnace. Oxygen gas was introduced by purging the inside of the furnace, and it did not flow during heating. The annealing temperature was 900 ° C. for 20 hours.
  • Nickel hydroxide was added to the composite oxide after heating as step S61-1, and the mixture was dry-mixed.
  • the number of atoms of cobalt was 100, the amount of nickel added was such that the number of atoms of nickel was 0.5.
  • step S61-2 mixing by the sol-gel method was performed.
  • the solvent used for the sol-gel method is prepared.
  • a ketone such as acetone, an alcohol such as ethanol and isopropanol, ether, dioxane, acetonitrile, N-methyl-2-pyrrolidone (NMP) and the like can be used. It is more preferable to use an aprotic solvent that does not easily react with lithium.
  • aluminum alkoxide was used as the metal alkoxide, and in the case of aluminum, for example, when the number of atoms of cobalt was 100, the number of atoms of aluminum was 0.5.
  • zirconium alkoxide or the like such as zirconium isopropoxide can be used.
  • zirconium for example, when the number of atoms of cobalt is 100, the addition was made so that the number of atoms of zirconium was each sample (0.1 at%, 0.25 at%, 0.5 at%, 1 at%).
  • Step S63 which is the heat treatment after the sol-gel method, was set at 850 ° C. for 2 hours.
  • the positive electrode active material 100 obtained in the above steps was used as a sample.
  • Acetylene black was used as the conductive auxiliary agent and mixed to prepare a slurry, and the slurry was applied to an aluminum current collector.
  • a CR2032 type (diameter 20 mm, height 3.2 mm) coin-shaped battery cell was manufactured.
  • Lithium metal was used as the counter electrode.
  • LiPF 6 lithium hexafluorophosphate
  • DEC diethyl carbonate
  • VC vinylene carbonate
  • Polypropylene having a thickness of 25 ⁇ m was used as the separator.
  • the positive electrode can and the negative electrode are those made of stainless steel (SUS) were used.
  • the charging voltage was 4.7V.
  • the measurement temperature was 25 ° C.
  • Charging was CC / CV (0.5C, 0.05Cut), discharging was CC (0.5C, 2.5Vcut), and a 10-minute rest period was provided before the next charging.
  • 1C was set to 200 mA / g.
  • 29A and 29B show the respective cycle characteristics.
  • the vertical axis represents the maintenance rate of the discharge capacity
  • the vertical axis represents the discharge capacity.
  • the decrease in charge / discharge capacity is suppressed even if the sample having a 2-propanol amount of 5 ml and the sample having a high voltage of 4.7 V are repeatedly charged / discharged with a sample of 10 ml. It was shown to be a positive electrode active material.
  • the comparative example is a sample in which the amount of 2-propanol is 0 ml.
  • FIGS. 30A and 30B show the results of performing the same cycle characteristics by changing the ratio of the number of atoms of zirconium to cobalt (0.1 at%, 0.25 at%, 0.5 at%, 1 at%).
  • the vertical axis represents the maintenance rate of the discharge capacity
  • the vertical axis represents the discharge capacity.
  • the decrease in charge / discharge capacity was suppressed even when high voltage charging / discharging of 4.7 V was repeated with a sample having a zirconium content of 0.1 at% and a sample having a zirconium content of 0.25 at%. It was shown to be a positive electrode active material.
  • FIG. 31 shows the results of powder resistance measurement in which the sample was prepared by the same production method as the above-mentioned sample and the ratio of the number of atoms of zirconium to cobalt (0.25 at%, 2 at%) was changed.
  • the powder resistance of the obtained positive electrode active material particles was measured using a powder resistance measuring device (MCP-PD51 manufactured by Mitsubishi Chemical Analytec Co., Ltd.).
  • MCP-PD51 manufactured by Mitsubishi Chemical Analytec Co., Ltd.
  • the positive electrode active material is put into the measurement cell, and pressure is applied from above using a compression rod to compress the powder. At this time, while measuring the pressure and volume, a current is passed through the powder, and the resistance value is measured by the Loresta GP using the 4-probe method.
  • the powder resistance varies depending on the density.
  • Example 2 In the present embodiment, after producing the positive electrode active material of one aspect of the present invention obtained according to the flow shown in FIG. 5, a laminated battery cell having a separator, an electrolytic solution, and a negative electrode is produced. , Its cycle characteristics were evaluated.
  • LiMO 2 in step S14 a commercially available lithium cobalt oxide (CellSeed C-10N manufactured by Nippon Chemical Industrial Co., Ltd.) having cobalt as a transition metal M and having no particular additive was prepared. Lithium fluoride and magnesium fluoride were mixed with this by a solid phase method in the same manner as in steps S21 to S23, step S41 and step S42. When the number of atoms of cobalt was 100, the amount of lithium fluoride added was 0.33 and the number of magnesium fluoride molecules was 1. This was designated as a mixture 903.
  • annealing was performed in the same manner as in step S43. 30 g of the mixture 903 was placed in a square alumina container, a lid was placed, and the mixture was heated in a muffle furnace. Oxygen gas was introduced by purging the inside of the furnace, and it flowed even during heating. The annealing temperature was 850 ° C. for 60 hours.
  • Nickel hydroxide was added to the composite oxide after heating as step S61-1, and the mixture was dry-mixed.
  • the number of atoms of cobalt was 100, the amount of nickel added was such that the number of atoms of nickel was 0.5.
  • step S61-2 mixing by the sol-gel method was performed.
  • the solvent used for the sol-gel method is prepared.
  • a ketone such as acetone, an alcohol such as ethanol and isopropanol, ether, dioxane, acetonitrile, N-methyl-2-pyrrolidone (NMP) and the like can be used. It is more preferable to use an aprotic solvent that does not easily react with lithium.
  • the amount of 2-propanol was 10 ml.
  • aluminum alkoxide was used as the metal alkoxide, and in the case of aluminum, for example, when the number of atoms of cobalt was 100, the number of atoms of aluminum was 0.5.
  • zirconium alkoxide or the like such as zirconium isopropoxide can be used. In the case of zirconium, for example, when the number of atoms of cobalt is 100, the amount of zirconium added is 0.25.
  • the heat treatment in step S63 after performing the sol-gel method was 850 ° C. for 2 hours. Then, the positive electrode active material 100 obtained by crushing and recovering in step S64 was used as a sample.
  • a slurry in which positive electrode active material particles having a plurality of convex portions containing Zr, AB (acetylene black) and PVDF (polyvinylidene fluoride) are mixed in a positive electrode active material: AB: PVDF 95: 3: 2 (weight ratio).
  • the one coated on the current collector (aluminum foil) was used.
  • NMP N-methyl-2-pyrrolidone was used as the solvent for the slurry.
  • a positive electrode was obtained by the above steps.
  • the amount of the positive electrode supported was approximately 20 mg / cm 2 .
  • LiPF 6 lithium hexafluorophosphate
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • VC vinylene carbonate
  • Polypropylene with a thickness of 25 ⁇ m was used for the separator.
  • Graphite is used for the negative electrode, and a slurry in which graphite: carbon nanotube (VGCF (registered trademark)): CMC (carboxymethyl cellulose) thickener: SBR (styrene-butadiene rubber) is mixed in a ratio of 96: 1: 1: 2. Was applied to the current collector (copper foil).
  • VGCF carbon nanotube
  • CMC carboxymethyl cellulose
  • SBR styrene-butadiene rubber
  • Typical values of the vapor-grown carbon fiber are fiber diameter 150 nm, fiber length 10 ⁇ m or more and 20 ⁇ m or less, true density 2.1 g / cm 3 , specific surface area 13 m. It is 2 / g.
  • the fiber diameter refers to the diameter of a perfect circle circumscribing the cut surface, with the cross section in the direction perpendicular to the fiber axis as the cut surface from the image taken two-dimensionally by observing with SEM. ..
  • the true density refers to a density in which only the volume occupied by the substance itself is used as the volume for density calculation.
  • the specific surface area is the surface area per unit mass or the surface area per unit volume of the object.
  • FIG. 32 shows the results of the cycle test of the sample 1 in which the secondary battery was produced in this way.
  • the measurement temperature was 25 ° C.
  • Charging was 4.5V (CCCV, 0.2C, cutoff current 0.1C), and discharging was 3V (CC, 0.2C), and 233 cycles of charging and discharging were performed.
  • the rest time of the cycle test was 1 minute.
  • 1C here was set to 200mA / g in the current value per weight of the positive electrode active material.
  • a comparative example it is the same as that of sample 1 except that a positive electrode active material to which Zr is not added is used.
  • the maximum capacity value of the comparative example was 188 mAh / g, and the capacity retention rate was 91.5% immediately after 233 cycles.
  • Example 3 an SEM photograph of the positive electrode active material obtained under the same conditions as those in Example 1 is shown in FIG. 35A, and a schematic diagram thereof is shown in FIG. 35B.
  • Zirconium at the time of producing the positive electrode active material was added so that the number of atoms of zirconium was 0.25 when the number of atoms of cobalt was 100. Further, as a difference in the process from Example 1, the heating in step S43 was set to 850 ° C. for 60 hours.
  • FIG. 35B and FIG. 1B a common reference numeral is used for the same portion.
  • a half cell was prepared using this same sample, the same cycle test as in Example 1 (charging voltage 4.7 V, cycle test at 25 ° C.) was performed as sample 2, and the obtained cycle characteristics are shown in FIG. 34.
  • the maximum capacity of sample 2 was 223 mAh / g.
  • sample 3 shows the cycle characteristics when zirconium is not added.
  • Sample 3 is a sample in which nickel and aluminum are added by the solid phase method.
  • the maximum capacity of sample 3 was 230 mAh / g.
  • the sample 4 is prepared by following the procedure shown in FIG. 37 for the preparation flow. Although there are many processes in FIG. 37 in common with FIG. 4, zirconium is added by the solid phase method without using the sol-gel method.
  • the maximum capacity of sample 4 was 231 mAh / g, which was the highest value among the three samples.
  • the volume retention rate of sample 4 was lower than that of sample 2, but the maximum capacity was high.
  • Positive electrode active material 101: Convex part, 102: Convex part, 103: Convex part, 300: Secondary battery, 301: Positive electrode can, 302: Negative electrode can, 303: Gasket, 304: Positive electrode, 305: Positive electrode current collection Body, 306: Positive electrode active material layer, 307: Negative electrode, 308: Negative electrode current collector, 309: Negative electrode active material layer, 310: Separator, 312: Washer, 313: Ring-shaped insulator, 322: Spacer, 400: Secondary Battery, 410: Positive electrode, 411: Positive electrode active material, 413: Positive electrode current collector, 414: Positive electrode active material layer, 420: Solid electrolyte layer, 421: Solid electrolyte, 430: Negative electrode, 431: Negative electrode active material, 433: Negative electrode Collector, 434: Negative electrode active material layer, 500: Secondary battery, 501: Positive electrode current collector, 502: Positive electrode active material layer, 503: Positive electrode, 504: Negative electrode

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PCT/IB2021/054818 2020-06-05 2021-06-02 正極活物質、正極活物質層、二次電池、電子機器、及び車両 Ceased WO2021245562A1 (ja)

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US18/007,789 US20230246183A1 (en) 2020-06-05 2021-06-02 Positive electrode active material, positive electrode active material layer, secondary battery, electronic device, and vehicle
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