WO2022090843A1 - 二次電池、電子機器および車両 - Google Patents

二次電池、電子機器および車両 Download PDF

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Publication number
WO2022090843A1
WO2022090843A1 PCT/IB2021/059381 IB2021059381W WO2022090843A1 WO 2022090843 A1 WO2022090843 A1 WO 2022090843A1 IB 2021059381 W IB2021059381 W IB 2021059381W WO 2022090843 A1 WO2022090843 A1 WO 2022090843A1
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Prior art keywords
secondary battery
active material
positive electrode
electrode active
present
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English (en)
French (fr)
Japanese (ja)
Inventor
栗城和貴
米田祐美子
嵯峨しおり
浅田善治
山崎舜平
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Semiconductor Energy Laboratory Co Ltd
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Semiconductor Energy Laboratory Co Ltd
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Priority to JP2022558368A priority Critical patent/JPWO2022090843A1/ja
Priority to CN202180072722.6A priority patent/CN116457960A/zh
Priority to KR1020237013707A priority patent/KR20230097011A/ko
Priority to US18/248,103 priority patent/US20230378459A1/en
Publication of WO2022090843A1 publication Critical patent/WO2022090843A1/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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • H01M10/446—Initial charging measures
    • 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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M2004/027—Negative electrodes
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • 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

  • One aspect of the present invention relates to a product, a method, or a manufacturing method. Alternatively, one aspect of 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 or an electronic device, or a method for manufacturing the same.
  • the present invention relates to a positive electrode active material that can be used for a secondary battery, a secondary battery, an electronic device having a secondary battery, and a vehicle having a secondary battery.
  • one aspect of the present invention relates to a power storage system having a secondary battery and a battery control circuit.
  • one aspect of the present invention relates to an electronic device having a power storage system and a vehicle.
  • a power storage device refers to an element and a device having a power storage function in general.
  • a storage battery 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.
  • the electronic device refers to all the 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.
  • Lithium-ion secondary batteries which have particularly high output and high energy density, are mobile information terminals such as mobile phones, smartphones, tablets, or notebook computers, portable music players, digital cameras, medical devices, and next-generation clean energy vehicles (hybrid).
  • semiconductor industry such as cars (HV), electric vehicles (EV), plug-in hybrid vehicles (PHV), etc.
  • HV cars
  • EV electric vehicles
  • PHS plug-in hybrid vehicles
  • the characteristics required for lithium-ion secondary batteries include higher energy density, improved cycle characteristics, safety in various operating environments, and improved long-term reliability.
  • Non-Patent Documents 1 to 3 Improvement of the positive electrode active material is being studied with the aim of improving the cycle characteristics and increasing the capacity of the lithium ion secondary battery.
  • Patent Documents 1 to 3 Research on the crystal structure of the positive electrode active material has also been conducted.
  • Non-Patent Document 4 describes the physical characteristics of metal fluoride.
  • X-ray diffraction is one of the methods used for the analysis of the crystal structure of the positive electrode active material.
  • XRD data can be analyzed by using ICSD (Inorganic Crystal Structure Database) introduced in Non-Patent Document 5.
  • One aspect of the present invention is to provide a lithium ion secondary battery having a high capacity and excellent charge / discharge cycle characteristics, and a method for manufacturing the same.
  • one aspect of the present invention is to provide a secondary battery that can be quickly charged and a method for producing the secondary battery.
  • one aspect of the present invention is to provide a high-capacity secondary battery and a method for manufacturing the same.
  • one aspect of the present invention is to provide a secondary battery having excellent charge / discharge characteristics and a method for manufacturing the secondary battery.
  • Another object of the present invention is to provide a secondary battery in which a decrease in capacity is suppressed even when the state of being charged at a high voltage is maintained for a long time, and a method for manufacturing the secondary battery.
  • one aspect of the present invention is to provide a secondary battery having high safety or reliability, and a method for manufacturing the secondary battery.
  • one aspect of the present invention is to provide a secondary battery in which a decrease in capacity is suppressed even at a high temperature, and a method for manufacturing the secondary battery.
  • one aspect of the present invention is to provide a secondary battery having a long life and a method for manufacturing the secondary battery.
  • One aspect of the present invention provides an extremely excellent secondary battery that can be charged quickly, can be used at a high temperature, can increase the charging voltage to increase the energy density, and is safe and has a long life.
  • One of the challenges is to do.
  • One aspect of the present invention is to provide a positive electrode active material for a lithium ion secondary battery having a high capacity and excellent charge / discharge cycle characteristics, and a method for producing the same.
  • one of the problems is to provide a method for producing a positive electrode active material having good productivity.
  • one aspect of the present invention is to provide a positive electrode active material in which a decrease in capacity in a charge / discharge cycle is suppressed by using it in a lithium ion secondary battery.
  • one aspect of the present invention is to provide a positive electrode active material in which elution of transition metals such as cobalt is suppressed even when the state of being charged at a high voltage is maintained for a long time.
  • one aspect of the present invention is to provide a novel substance, active material particles, a power storage device, or a method for producing them.
  • One aspect of the present invention is a secondary battery provided with positive electrode active material particles and an electrolyte, and the surface layer portion of the positive positive active material particles has a current value up to a voltage of 4.5 V in an environment of 60 ° C.
  • the discharge process of current discharge and the discharge process are alternately repeated 150 times or more, and then the lithium cobaltate has an O3 structure after the discharge, and the electrolyte is a secondary battery having an imidazolium cation.
  • the negative electrode has a negative electrode and the negative electrode has graphite. Further, in the above configuration, the negative electrode has a current collector and a negative electrode active material layer on the current collector, and the ratio of graphite to the total weight of the negative electrode active material layer is 50% by weight or more, or 70% by weight. It is preferable that it is 80% by weight or more.
  • the discharge process of current discharge is alternately repeated 10 times or more, more preferably 50 times or more, still more preferably 100 times or more, and then after discharge, lithium cobaltate having an O3 structure is used, and the electrolyte is imidazo. It is a secondary battery having a lithium cation.
  • one aspect of the present invention is a secondary battery including a positive electrode active material and an electrolyte, wherein the positive electrode active material is lithium cobalt oxide having an O3 structure after repeated charging and discharging, and the electrolyte is ,
  • R 1 is an alkyl group having 1 or more and 4 or less carbon atoms
  • R 2 , R 3 and R 4 are independently alkyl atoms having 1 or more and 4 or less carbon atoms. It is a group
  • R5 represents an alkyl group or a main chain composed of two or more selected from atoms of C, O, Si, N, S and P.
  • R 1 represented by the general formula (G1) is one selected from a methyl group, an ethyl group and a propyl group, and one of R 2 , R 3 and R 4 is a hydrogen atom or a methyl group.
  • the other two are hydrogen atoms
  • R 5 is an alkyl group or a main chain composed of two or more selected from C, O, Si, N, S, P atoms
  • a ⁇ is.
  • (FSO 2 ) 2 N ⁇ and (CF 3 SO 2 ) 2 N ⁇ or a mixture of the two is preferred.
  • the sum of the number of carbon atoms of R 1 represented by the general formula (G1), the number of carbon atoms of R 5 and the number of oxygen atoms of R 5 is 7 or less. Is preferable.
  • R 1 represented by the general formula (G1) is a methyl group
  • R 2 is a hydrogen atom
  • the sum of the number of carbon atoms and the number of oxygen atoms of R 5 is 6 or less. Is preferable.
  • the electrolyte is 1-butyl-3-propylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-butyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation. It is preferred to have one or more selected from the lymium cation and the 1-methyl-3- (2-propoxyethyl) imidazolium cation.
  • the electrolyte preferably has a 1-ethyl-3-methylimidazolium cation.
  • one aspect of the present invention is an electronic device having the secondary battery, the display unit, and the sensor according to any one of the above.
  • one aspect of the present invention includes the secondary battery, the electric motor, and the control device according to any one of the above, and the control device has a function of supplying electric power from the secondary battery to the electric motor. Vehicle to have.
  • a lithium ion secondary battery having a high capacity and excellent charge / discharge cycle characteristics, and a method for manufacturing the same. Further, according to one aspect of the present invention, it is possible to provide a secondary battery that can be quickly charged and a method for producing the secondary battery. Further, according to one aspect of the present invention, it is possible to provide a high-capacity secondary battery and a method for manufacturing the same. Further, according to one aspect of the present invention, it is possible to provide a secondary battery having excellent charge / discharge characteristics and a method for manufacturing the secondary battery.
  • a secondary battery in which a decrease in capacity is suppressed even when a state of being charged at a high voltage is held for a long time, and a method for manufacturing the secondary battery. Further, according to one aspect of the present invention, it is possible to provide a secondary battery having high safety or reliability, and a method for manufacturing the secondary battery. Further, according to one aspect of the present invention, it is possible to provide a secondary battery in which a decrease in capacity is suppressed even at a high temperature, and a method for manufacturing the secondary battery. Further, according to one aspect of the present invention, it is possible to provide a secondary battery having a long life and a method for manufacturing the secondary battery.
  • an extremely excellent secondary battery that can be charged quickly, can be used at a high temperature, can increase the charging voltage to increase the energy density, and is safe and has a long life. Can be provided.
  • a positive electrode active material for a lithium ion secondary battery having a high capacity and excellent charge / discharge cycle characteristics, and a method for producing the same. Further, it is possible to provide a method for producing a positive electrode active material having good productivity. Further, according to one aspect of the present invention, it is possible to provide a positive electrode active material in which a decrease in capacity in a charge / discharge cycle is suppressed by using it in a lithium ion secondary battery. Further, according to one aspect of the present invention, it is possible to provide a positive electrode active material in which elution of transition metals such as cobalt is suppressed even when the state of being charged at a high voltage is maintained for a long time.
  • one aspect of the present invention can provide a novel substance, active material particles, a power storage device, or a method for producing them.
  • FIG. 1 is a diagram illustrating a crystal structure of a positive electrode active material.
  • FIG. 2 is a diagram illustrating the crystal structure of the positive electrode active material.
  • FIG. 3 is a schematic cross-sectional view of the positive electrode active material particles.
  • 4A and 4B are diagrams illustrating an example of a method for producing a positive electrode active material according to one aspect of the present invention.
  • 5A to 5C are diagrams illustrating an example of a method for producing a positive electrode active material according to one aspect of the present invention.
  • FIG. 6 is a diagram illustrating an example of a method for producing a positive electrode active material according to one aspect of the present invention.
  • 7A to 7C are diagrams illustrating an example of a method for producing a positive electrode active material according to one aspect of the present invention.
  • 8A, 8B, 8C, and 8D are schematic cross-sectional views of the negative electrode active material particles.
  • 9A, 9B, 9C, and 9D are examples of cross-sectional views of the secondary battery.
  • 10A and 10B are views showing an example of the appearance of the secondary battery.
  • 11A and 11B are diagrams illustrating a method for manufacturing a secondary battery.
  • 12A and 12B are diagrams illustrating a method for manufacturing a secondary battery.
  • FIG. 13 is a diagram showing an example of the appearance of the secondary battery.
  • FIG. 14 is a top view showing an example of a secondary battery manufacturing apparatus.
  • FIG. 15 is a cross-sectional view showing an example of a method for manufacturing a secondary battery.
  • FIG. 16A to 16C are perspective views showing an example of a method for manufacturing a secondary battery.
  • FIG. 16D is a cross-sectional view corresponding to FIG. 16C.
  • 17A to 17F are perspective views showing an example of a method for manufacturing a secondary battery.
  • FIG. 18 is a cross-sectional view showing an example of a secondary battery.
  • FIG. 19A is a diagram showing an example of a secondary battery.
  • 19B and 19C are diagrams showing an example of a method for producing a laminated body.
  • 20A to 20C are views showing an example of a method for manufacturing a secondary battery.
  • 21A and 21B are cross-sectional views showing an example of a laminated body.
  • FIG. 21C is a cross-sectional view showing an example of a secondary battery.
  • FIG. 22A and 22B are diagrams showing an example of a secondary battery.
  • FIG. 22C is a diagram showing the inside of the secondary battery.
  • 23A to 23C are views showing an example of a secondary battery.
  • FIG. 24A is a perspective view showing an example of a battery pack.
  • FIG. 24B is a block diagram showing an example of a battery pack.
  • FIG. 24C is a block diagram showing an example of a vehicle having a motor.
  • 25A to 25E are views showing an example of a transportation vehicle.
  • 26A is a diagram showing an electric bicycle
  • FIG. 26B is a diagram showing a secondary battery of the electric bicycle
  • FIG. 26C is a diagram illustrating an electric motorcycle.
  • 27A and 27B are diagrams showing an example of a power storage device.
  • 28A to 28E are views showing an example of an electronic device.
  • 29A to 29H are diagrams illustrating an example of an electronic device.
  • 30A to 30C are diagrams illustrating an example of an electronic device.
  • FIG. 31 is a diagram illustrating an example of an electronic device.
  • 32A to 32C are diagrams illustrating an example of an electronic device.
  • 33A to 33C are diagrams showing an example of an electronic device.
  • 34A and 34B are diagrams showing the cycle characteristics of the secondary battery.
  • 35A and 35B are diagrams showing the cycle characteristics of the secondary battery.
  • FIG. 36 is a diagram showing the cycle characteristics of the secondary battery.
  • 37A to 37E show cross-sectional SEM images of the negative electrode.
  • 38A to 38E show cross-sectional SEM images of the negative electrode.
  • FIG. 39 shows the measurement result of the cobalt concentration by EDX analysis and the film thickness of the negative electrode coating.
  • 40A to 40D show SEM images of the positive electrode.
  • the crystal plane and the direction are indicated by the Miller index.
  • the notation of the crystal plane and direction is to add a superscript bar to the number, but in the present specification etc., due to the limitation of the application notation, instead of adding a bar above the number,-(minus) before the number. It may be expressed with a code).
  • the individual orientation indicating the direction in the crystal is []
  • the aggregate orientation indicating all equivalent directions is ⁇ >
  • the individual plane indicating the crystal plane is ()
  • the aggregate plane having equivalent symmetry is ⁇ . Express each with.
  • segregation refers to 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 active material means a region from the surface to about 10 nm.
  • the surface created by cracks or cracks can also be called the surface.
  • the area deeper than the surface layer is called the inside.
  • 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.
  • the O3'-type crystal structure (also referred to as a pseudo-spinel-type crystal structure) possessed by the composite oxide containing lithium and a transition metal is a space group R-3m, not a spinel-type crystal structure.
  • it refers to a crystal structure in which ions such as cobalt and magnesium occupy the oxygen 6 coordination position and the arrangement of cations has symmetry similar to that of the spinel type.
  • a light element such as lithium may occupy the oxygen 4-coordination position, and in this case as well, the ion arrangement has symmetry similar to that of the spinel type.
  • the O3'type crystal structure has Li randomly between layers but is similar to the CdCl 2 type crystal structure.
  • This crystal structure similar to CdCl type 2 is similar to the crystal structure when lithium nickel oxide is charged to a charging depth of 0.94 (Li 0.06 NiO 2 ), but contains a large amount of pure lithium cobalt oxide or cobalt. It is known that layered rock salt type positive electrode active materials do not usually have this crystal structure.
  • Layered rock salt crystals and anions of rock salt crystals have a cubic close-packed structure (face-centered cubic lattice structure). It is presumed that the O3'type crystal also has a cubic close-packed structure for anions. When they come into contact, there is a crystal plane in which the cubic close-packed structure composed of anions is oriented in the same direction.
  • 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 (general space group of 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.
  • 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, 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.
  • the present embodiment describes an example of a secondary battery according to an aspect of the present invention.
  • the secondary battery of one aspect of the present invention has extremely stable characteristics even when charged at a high voltage.
  • the secondary battery of one aspect of the present invention can operate stably in a wide temperature range. According to one aspect of the present invention, a secondary battery having remarkably excellent characteristics can be realized.
  • the positive electrode active material of one aspect of the present invention is an oxide having a metal that becomes a carrier ion (hereinafter, element A) and a metal whose valence changes with charging and discharging of a secondary battery (hereinafter, metal M).
  • the element A one or more selected from alkali metals such as lithium, sodium and potassium, and Group 2 elements such as calcium, beryllium and magnesium can be used.
  • the element A is preferably an element that functions as a metal that becomes a carrier ion.
  • a transition metal can be used as the metal M.
  • the positive electrode active material of one aspect of the present invention has, for example, one or more of cobalt, nickel, and manganese as the metal M, and particularly has cobalt.
  • the metal M may have an element such as aluminum which does not change in valence and can have the same valence as the metal M, more specifically, for example, a trivalent main group element.
  • the positive electrode active material of one aspect of the present invention may be represented by the chemical formula AM y O Z (y> 0, z> 0).
  • Lithium cobalt oxide may be referred to as LiCoO 2 .
  • Lithium nickelate may also be referred to as LiNiO 2 .
  • the positive electrode active material of one aspect of the present invention has an element X.
  • Elements such as magnesium, calcium, zirconium, lanthanum, barium, titanium, and yttrium can be used as the element X.
  • elements such as nickel, aluminum, cobalt, manganese, vanadium, iron, chromium and niobium can be used.
  • elements such as copper, potassium, sodium, zinc, chlorine, fluorine, hafnium, silicon, sulfur, phosphorus, boron and arsenic can be used.
  • the element X two or more of the above-mentioned elements may be used in combination.
  • element X may be replaced with the position of element A.
  • the element X may be partially replaced with the position of the metal M, for example.
  • the positive electrode active material of one aspect of the present invention may be represented by the chemical formula A 1-w X w My O Z ( y > 0, z> 0, 0 ⁇ w ⁇ 1). Further, the positive electrode active material according to one aspect of the present invention may be represented by the chemical formula AM y-j X j O Z (y> 0, z> 0, 0 ⁇ j ⁇ y). Further, the positive electrode active material according to one aspect of the present invention has a chemical formula A 1-w X w M y-j X j O Z (y> 0, z> 0, 0 ⁇ w ⁇ 1, 0 ⁇ j ⁇ y). May be represented.
  • the positive electrode active material according to one aspect of the present invention preferably has a halogen in addition to the element X. It is preferable to have a halogen such as fluorine or chlorine. The presence of the halogen in the positive electrode active material of one aspect of the present invention may promote the substitution of element X with the position of element A.
  • the crystal structure of the positive electrode active material becomes unstable, and the characteristics of the secondary battery may deteriorate.
  • a material having a layered crystal structure and the metal A is desorbed from the layers during the charging reaction is used as the positive electrode active material.
  • the charge capacity and the discharge capacity can be increased by increasing the charge voltage.
  • the charging voltage is increased, a large amount of metal A is desorbed from the positive electrode active material, and changes in the crystal structure such as a change in the interlayer distance and a shift in the layer may occur remarkably.
  • the change in the crystal structure due to the insertion and desorption of the metal A is irreversible, the crystal structure may gradually collapse as the charge and discharge are repeated, and the capacity may be significantly reduced due to the charge and discharge cycle.
  • the metal M contained in the positive electrode active material may be easily eluted into the electrolyte.
  • the amount of the metal M in the positive electrode active material decreases, which may lead to a decrease in the capacity of the positive electrode.
  • the metal M is mainly bonded to oxygen. Desorption of oxygen from the positive electrode active material may significantly cause elution of the metal M.
  • a metal salt that becomes a carrier ion and the following solvents such as carbonate are used.
  • Methyl formate Methyl acetate, Ethyl acetate, Methyl propionate, Ethyl propionate, propyl propionate, Methyl butyrate, 1,3-dioxane, 1,4-dioxane, Dimethoxyethane (DME), dimethylsulfoxide, diethyl ether, Aprotic solvents such as methyl diglyme, acetonitrile, benzonitrile, tetrahydrofuran, sulfolane, and sulton are used.
  • DME Dimethoxyethane
  • dimethylsulfoxide diethyl ether
  • Aprotic solvents such as methyl diglyme, acetonitrile, benzonitrile, tetrahydrofuran, sulfolane, and sulton are used.
  • the oxidation number of the metal M contained in the positive electrode active material becomes high during charging, the reactivity of the positive electrode active material increases, and more specifically, it becomes easy to react with an organic solvent, more specifically, a carbonate having a high polarity.
  • an organic solvent more specifically, a carbonate having a high polarity.
  • oxygen in the positive electrode active material is desorbed and the organic solvent is oxidized. When oxygen is desorbed, elution of metal M is likely to occur.
  • FIG. 3 shows a schematic cross-sectional view of the positive electrode active material particles 51.
  • the pits are shown as holes in the pits 54 and 58 in FIG. 3, but the opening shape is not a circle but has a depth, and the cracks are shown as cracks 57 in FIG.
  • FIG. 3 shows a crystal plane 55 as a crystal plane, a recess 52 as a recess, and a barrier membrane 53 and a barrier membrane 56 as a barrier membrane.
  • the positive electrode active material particles have defects, and the defects may change before and after charging and discharging.
  • the positive electrode active material particles are used in a secondary battery, they are chemically or electrochemically eroded by environmental substances (electrolytic solution, etc.) surrounding the positive positive active material particles, or the material deteriorates. There is. This deterioration does not occur uniformly on the surface of the particles, but occurs locally and centrally, and repeated charging and discharging of the secondary battery causes, for example, deep defects from the surface to the inside.
  • pitting corrosion The phenomenon in which defects progress to form holes in the positive electrode active material particles can also be called pitting corrosion, and the holes generated by this phenomenon are also referred to as pits in the present specification.
  • cracks and pits are different. Immediately after the positive electrode active material particles are produced, cracks are present but pits are not present.
  • the pit can be said to be a hole where cobalt and oxygen have escaped by several layers by charging and discharging under high voltage conditions of 4.5 V or higher or high temperature (45 ° C or higher), and the location where cobalt is eluted. It can be said that.
  • a crack refers to a new surface created by applying physical pressure or a crack created by a grain boundary. Cracks may occur due to the expansion and contraction of particles due to charging and discharging. Also, pits may occur from cracks or cavities within the particles.
  • cobalt elutes in lithium cobalt oxide, and a crystal phase different from that of lithium cobalt oxide may be formed on the surface layer portion.
  • one or more of Co 3 O 4 having a spinel structure, Li Co 2 O 4 having a spinel structure, and CoO having a rock salt type structure may be formed.
  • These materials are, for example, materials having a smaller discharge capacity than lithium cobalt oxide or do not contribute to charge / discharge. Therefore, the formation of these materials on the surface layer portion may lead to a decrease in the discharge capacity of the secondary battery.
  • the output characteristics of the secondary battery may be deteriorated and the low temperature characteristics may be deteriorated. Also, these materials may be formed in the vicinity of the pits.
  • the metal M may be eluted from the positive electrode active material, the electrolyte may transport the ions of the metal M, and the metal M may be deposited on the surface of the negative electrode. Further, on the surface of the negative electrode, a film may be formed from the decomposition products of the metal M and the electrolyte. The formation of the film makes it difficult to insert and remove carrier ions into the negative electrode active material, which may lead to deterioration of the rate characteristics, low temperature characteristics, etc. of the secondary battery.
  • the positive electrode active material of one aspect of the present invention can have an O3'structure described later at the time of charging, it can be charged to a deep charging depth. By increasing the charging depth, the capacity of the positive electrode can be increased, so that the energy density of the secondary battery can be increased. Further, even when an extremely high charging voltage is used, charging and discharging can be performed repeatedly.
  • the elution of the metal M is likely to occur because the charging voltage is extremely high, but the elution of the metal M can be suppressed by the electrolyte having a desired ionic liquid. Therefore, it is possible to achieve both a high charging voltage and suppression of elution of the metal M.
  • charging / discharging at a high rate can be realized.
  • excellent charge / discharge characteristics at low temperatures can be realized.
  • the present inventors have extremely excellent characteristics by using the positive electrode active material of one aspect of the present invention and a desired ionic liquid having characteristics suitable for the secondary battery of one aspect of the present invention. We found that the next battery can be realized.
  • the present inventors have found that in the secondary battery of one aspect of the present invention, the generation of pits of the positive electrode active material is suppressed after repeated charging and discharging. Further, it has been found that in the secondary battery of one aspect of the present invention, there is no heterogeneous phase or substantially no heterogeneous phase in the surface layer portion of the positive electrode active material after repeated charging and discharging. More specifically, for example, when the positive electrode active material is lithium cobalt oxide, the surface layer portion of the positive electrode active material has Co 3 O 4 having a spinel structure, LiCo 2 O 4 having a spinel structure, and CoO having a rock salt structure. It was found that it does not exist or does not exist substantially.
  • the secondary battery of one aspect of the present invention after repeated charging and discharging, there is no different phase or substantially no different phase in the vicinity of the pit of the positive electrode active material. More specifically, for example, when the positive electrode active material is lithium cobalt oxide, Co 3 O 4 having a spinel structure, LiCo 2 O 4 having a spinel structure, and CoO having a rock salt structure are located in the vicinity of the pits of the positive electrode active material. It was found that there is no or substantially no. “Substantially nonexistent” does not include, for example, dust adhering to the surface.
  • the present inventors have a thin coating on the surface of the negative electrode active material after repeated charging and discharging, and the film is formed on the surface of the negative electrode active material or the surface of the negative electrode active material. It was found that the amount of metal M detected in the coated film was extremely small.
  • the amount of metal M detected is extremely small in the coating film formed on the surface of the negative electrode active material or the surface of the negative electrode active material, suggesting that the coating film is thin. Therefore, for example, it is possible to realize a secondary battery in which carrier ions easily move in and out of the negative electrode active material, have high output characteristics, and are easily charged and discharged even at a low temperature.
  • the secondary battery of one aspect of the present invention since the elution of the metal M can be suppressed, the decrease in capacity can be suppressed and the collapse of the crystal structure can also be suppressed. Therefore, it is possible to realize an excellent secondary battery in which a decrease in capacity is suppressed even in repeated charging / discharging, holding in a charged state, and holding at a high temperature.
  • the different phase is not substantially formed on the surface of the positive electrode, the decrease in capacity is suppressed and the carrier ions in the positive electrode active material are easily moved in and out. Therefore, it is possible to realize a secondary battery in which a decrease in capacity is suppressed. In addition, it is possible to realize a secondary battery having high output characteristics and easy to charge and discharge even at a low temperature.
  • Ionic liquids have low volatility and flammability, and are stable over a wide temperature range. Since it is difficult to volatilize even at high temperatures, it is possible to suppress the expansion of the secondary battery due to the generation of gas from the electrolytic solution. Therefore, the operation of the secondary battery is stable even at a high temperature. In addition, it has low flammability and is flame-retardant.
  • the organic solvent has a flash point at 50 ° C. or lower.
  • the ionic liquid has low volatility and can be said to be extremely stable up to a temperature lower than the temperature at which a reaction such as decomposition occurs, for example, about 300 ° C.
  • an ionic liquid it is possible to use it at a high temperature, and it is possible to realize a highly safe secondary battery.
  • an ionic liquid it is possible to realize a secondary battery having stable characteristics even at 50 ° C. or higher, 60 ° C. or higher, or 80 ° C. or higher.
  • the secondary battery of one aspect of the present invention can realize good operation in a wide temperature range from low temperature to high temperature.
  • the charging voltage can be increased by using the positive electrode active material in which the irreversible change of the crystal structure is suppressed at a high charging voltage, so that the secondary battery having a high energy density can be used. It can be realized.
  • the secondary battery of one aspect of the present invention can suppress the elution of metal M from the positive electrode active material by using an ionic liquid as the electrolyte, so that even if the secondary battery is repeatedly charged at a high charging voltage, it may be charged. It is possible to suppress the decrease in capacity due to the charge / discharge cycle.
  • the surface layer portion is preferably, for example, a region within 50 nm, more preferably within 35 nm, and even more preferably within 20 nm from the surface.
  • the area deeper than the surface layer is called the inside.
  • Ion liquid is a salt consisting of a combination of cations and anions. Ionic liquids are sometimes referred to as room temperature molten salts.
  • the positive electrode active material of one aspect of the present invention has element X.
  • the element X has a concentration gradient.
  • the element X preferably has a concentration gradient that increases from the inside toward the surface.
  • the concentration gradient of element X can be evaluated using, for example, energy dispersive X-ray spectroscopy (EDX: Energy Dispersive X-ray Spectroscopy).
  • the ionic liquid is stable even at high temperatures.
  • other elements constituting the secondary battery such as a positive electrode active material, a negative electrode active material, an exterior body, etc.
  • change at a high temperature particularly when the change is irreversible
  • the remarkable capacity of the secondary battery is remarkable. May lead to a decline.
  • the secondary battery when the crystal structure of the material constituting the positive electrode active material is irreversibly changed by charging at a high temperature, the secondary battery is significantly deteriorated. For example, the capacity may decrease significantly with the charge / discharge cycle. When the temperature is high and the charging voltage is high, the crystal structure of the positive electrode may become more unstable.
  • the secondary battery of one aspect of the present invention by using a positive electrode active material having a high charging voltage and an extremely stable crystal structure at a high temperature, it is excellent even when the temperature is high and the charging voltage is high. Since the characteristics can be realized, the effect of the ionic liquid can be fully exhibited. That is, the remarkable improvement in characteristics obtained by using the configuration of the secondary battery of one aspect of the present invention is found by the combination with the positive electrode active material of one aspect of the present invention.
  • the positive electrode active material of one aspect of the present invention preferably has an element X, and preferably has a halogen in addition to the element X, as described later.
  • the fact that the positive electrode active material of one aspect of the present invention has element X or a halogen in addition to the element X suggests suppression of the reaction with the ionic liquid on the surface of the positive electrode active material.
  • ionic liquids are extremely stable even at high temperatures.
  • the range of reaction potentials is extremely wide.
  • the configuration of the secondary battery according to one aspect of the present invention for example, it is possible to realize a secondary battery capable of repeatedly charging at a high charging voltage even at a high temperature of 42 ° C. or higher.
  • the environmental temperature is 42 ° C. or higher and the upper limit voltage for charging is graphite as the negative electrode, it is preferably 4.37 or higher, more preferably 4.40 V or higher, still more preferably 4.42 or higher, still more preferably.
  • an excellent secondary battery can be realized even at a higher temperature.
  • it is stable at 42 ° C or higher and 200 ° C or lower, or 42 ° C or higher and 180 ° C or lower, or 42 ° C or higher and 150 ° C or lower, or 42 ° C or higher and 120 ° C or lower, or 42 ° C or higher and 100 ° C or lower, or 42 ° C or higher and 90 ° C or lower.
  • a rechargeable battery that operates can be realized.
  • the secondary battery of one aspect of the present invention has, for example, a discharge capacity of 160 mAh / g or more after discharging a cumulative charge amount of 57,000 mAh / g.
  • the discharge capacity is preferably measured at 0.2C. Further, it is preferable to calculate the cumulative charge amount and the discharge capacity per weight of the positive electrode active material.
  • the charging voltage is 4.5 V
  • the discharge capacity after 300 times of charging is 160 mAh /. It is g or more.
  • the discharge capacity is preferably measured at 0.2C. Further, it is preferable to calculate the cumulative charge amount and the discharge capacity per weight of the positive electrode active material.
  • the secondary battery of one aspect of the present invention is preferably used in combination with a battery control circuit.
  • the battery control circuit preferably has, for example, a function of controlling charging.
  • Charging control refers to, for example, monitoring the parameters of a secondary battery and changing the charging conditions according to the state. Examples of the parameters of the secondary battery to be monitored include the voltage, current, temperature, charge amount, impedance, etc. of the secondary battery.
  • the secondary battery of one aspect of the present invention is preferably used in combination with a sensor.
  • the sensor is, for example, displacement, position, velocity, acceleration, angular velocity, rotation speed, distance, light, liquid, magnetism, temperature, chemical substance, voice, time, hardness, electric field, current, voltage, power, radiation, flow rate, humidity. It is preferable to have a function capable of measuring one or more of tilt, vibration, odor, and infrared rays.
  • the charging is controlled according to the value measured by the sensor.
  • An example of controlling the secondary battery using the temperature sensor will be described later.
  • the positive electrode active material preferably has the element A.
  • the element A one or more selected from alkali metals such as lithium, sodium and potassium, and Group 2 elements such as calcium, beryllium and magnesium can be used.
  • the positive electrode active material carrier ions are desorbed from the positive electrode active material with charging. If the desorption of the element A is large, the capacity of the secondary battery is increased due to the large amount of ions contributing to the capacity of the secondary battery. On the other hand, if the element A is largely desorbed, the crystal structure of the compound contained in the positive electrode active material is likely to collapse. The collapse of the crystal structure of the positive electrode active material may lead to a decrease in the discharge capacity due to the charge / discharge cycle. When the positive electrode active material of one aspect of the present invention has the element X, the collapse of the crystal structure when the carrier ion is desorbed during charging of the secondary battery may be suppressed.
  • the element X For example, a part of the element X is replaced with the position of the element A.
  • Elements such as magnesium, calcium, zirconium, lanthanum, and barium can be used as the element X.
  • an element such as copper, potassium, sodium, or zinc can be used as the element X.
  • two or more of the above-mentioned elements may be used in combination.
  • the positive electrode active material according to one aspect of the present invention preferably has a halogen in addition to the element X. It is preferable to have a halogen such as fluorine or chlorine. The presence of the halogen in the positive electrode active material of one aspect of the present invention may promote the substitution of element X with the position of element A.
  • the positive electrode active material of one aspect of the present invention has the element X, or when it has a halogen in addition to the element X, the electrical conductivity on the surface of the positive electrode active material may be suppressed.
  • the positive electrode active material of one aspect of the present invention has a metal M.
  • the metal M is, for example, a transition metal.
  • the positive electrode active material of one aspect of the present invention has, for example, one or more of cobalt, nickel, and manganese as the metal M, and particularly has cobalt.
  • an element such as aluminum which does not change in valence and can have the same valence as the metal M, more specifically, for example, a trivalent main group element may be present.
  • the element X described above may be substituted at the position of the metal M, for example.
  • the positive electrode active material of one aspect of the present invention is an oxide, the element X may be substituted at the position of oxygen.
  • the positive electrode active material of one aspect of the present invention for example, it is preferable to use a lithium composite oxide having a layered rock salt type crystal structure. More specifically, for example, as a lithium composite oxide having a layered rock salt type crystal structure, a lithium composite oxide having lithium cobalt oxide, lithium nickel oxide, nickel, manganese and cobalt, and a lithium composite oxide having nickel, cobalt and aluminum. , Etc. can be used. Further, these positive electrode active materials are preferably represented by the space group R-3m.
  • the crystal structure may collapse when the charging depth is increased.
  • the collapse of the crystal structure is, for example, a layer shift. If the collapse of the crystal structure is irreversible, the capacity of the secondary battery may decrease due to repeated charging and discharging.
  • the positive electrode active material of one aspect of the present invention has the element X, for example, even if the charging depth is deepened, the displacement of the above layer is suppressed. By suppressing the deviation, it is possible to reduce the change in volume during charging and discharging. Therefore, the positive electrode active material of one aspect of the present invention can realize excellent cycle characteristics. Further, the positive electrode active material according to one aspect of the present invention can have a stable crystal structure in a state of charge with a high voltage. Therefore, the positive electrode active material of one aspect of the present invention may not easily cause a short circuit when the high voltage charge state is maintained. In such a case, safety is further improved, which is preferable.
  • the difference in volume is small when compared with the change in the crystal structure and the same number of transition metal atoms in the state of being sufficiently discharged and the state of being charged at a high voltage.
  • the positive electrode active material of one aspect of the present invention may be represented by the chemical formula AM y O Z (y> 0, z> 0).
  • lithium cobalt oxide may be represented by LiCoO 2 .
  • lithium nickelate may be represented by LiNiO 2 .
  • the positive electrode active material of one aspect of the present invention having the element X when the charging depth is 0.8 or more, it is represented by the space group R-3m, and although it does not have a spinel-type crystal structure, it is a metal M (for example, cobalt).
  • Elements X eg magnesium
  • the cation arrangement may have symmetry similar to the spinel type.
  • This structure is referred to as an O3'type crystal structure in the present specification and the like.
  • a light element such as lithium may occupy the oxygen 4-coordination position, and in this case as well, the ion arrangement has symmetry similar to that of the spinel type.
  • the structure of the positive electrode active material becomes unstable due to the desorption of carrier ions during charging. It can be said that the O3'type crystal structure is a structure capable of maintaining high stability even though carrier ions are desorbed.
  • the O3'type crystal structure has Li randomly between layers but is similar to the CdCl 2 type crystal structure.
  • This crystal structure similar to CdCl type 2 is similar to the crystal structure when lithium nickel oxide is charged to a charging depth of 0.94 (Li 0.06 NiO 2 ), but contains a large amount of pure lithium cobalt oxide or cobalt. It is known that layered rock salt type positive electrode active materials do not usually have this crystal structure.
  • Layered rock salt crystals and anions of rock salt crystals have a cubic close-packed structure (face-centered cubic lattice structure). It is presumed that the O3'type crystal also has a cubic close-packed structure for anions. When they come into contact, there is a crystal plane in which the cubic close-packed structure composed of anions is oriented in the same direction.
  • 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 (general space group of 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.
  • the crystal structure at a charge depth of 0 (discharged state) in FIG. 1 is R-3 m (O3), which is the same as in FIG.
  • the positive electrode active material of one aspect of the present invention shown in FIG. 1 has a crystal structure different from that of the H1-3 type crystal structure (space group R-3m) shown in FIG. 2 when the charging depth is sufficiently charged.
  • This structure is a space group R-3m and is not a spinel-type crystal structure, ions such as cobalt and magnesium occupy the oxygen 6-coordination position, and the arrangement of cations has symmetry similar to that of the spinel-type.
  • the symmetry of the CoO2 layer of this structure is the same as that of the O3 type.
  • this structure is referred to as an O3'type crystal structure or a pseudo-spinel type crystal structure in the present specification and the like.
  • lithium can be present at any lithium site with a probability of about 20%, but the present invention is not limited to this. It may be present only in some specific lithium sites.
  • magnesium is dilutely present between the CoO 2 layers, that is, in the lithium site.
  • halogens such as fluorine are randomly and dilutely present in the oxygen sites.
  • light elements such as lithium may occupy the oxygen 4-coordination position, and in this case as well, the ion arrangement has symmetry similar to that of the spinel type.
  • the O3'type crystal structure has Li randomly between layers but is similar to the CdCl 2 type crystal structure.
  • This crystal structure similar to CdCl type 2 is similar to the crystal structure when lithium nickel oxide is charged to a charging depth of 0.94 (Li 0.06 NiO 2 ), but contains a large amount of pure lithium cobalt oxide or cobalt. It is known that layered rock salt type positive electrode active materials do not usually have this crystal structure.
  • Layered rock salt crystals and anions of rock salt crystals have a cubic close-packed structure (face-centered cubic lattice structure). It is presumed that the O3'type crystal also has a cubic close-packed structure for anions. When they come into contact, there is a crystal plane in which the cubic close-packed structure composed of anions is oriented in the same direction.
  • 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 (general space group of 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.
  • the change in the crystal structure when charged at a high voltage and a large amount of lithium is desorbed is suppressed as compared with the comparative example described later.
  • the comparative example described later For example, as shown by the dotted line in FIG. 1, there is almost no deviation of the CoO2 layer in these crystal structures.
  • the positive electrode active material of one aspect of the present invention has high structural stability even when the charging voltage is high.
  • the positive electrode active material shown in FIG. 2 has an H1-3 type crystal structure at a voltage of about 4.6 V with respect to the potential of the lithium metal, but the positive electrode active material of one aspect of the present invention is the same.
  • the crystal structure of R-3m (O3) can be maintained even at a charging voltage of about 4.6V.
  • the positive electrode active material of one aspect of the present invention can have an O3'type crystal structure. There is.
  • the positive electrode active material of one aspect of the present invention can retain the crystal structure of R-3m (O3), and further.
  • An O3'type crystal structure can be obtained even in a region where the charging voltage is increased, for example, when the voltage of the secondary battery exceeds 4.5 V and is 4.6 V or less.
  • the positive electrode active material of one aspect of the present invention may have an O3'structure.
  • the crystal structure does not easily collapse even if charging and discharging are repeated at a high voltage.
  • the difference in volume per unit cell between the O3 type crystal structure having a charging depth of 0 and the O3'type crystal structure having a charging depth of 0.8 is 2.5% or less, which is more detailed. Is less than 2.2%.
  • the coordinates of cobalt and oxygen in the unit cell are within the range of Co (0,0,0.5), O (0,0,x), 0.20 ⁇ x ⁇ 0.25. Can be indicated by.
  • Magnesium which is randomly and dilutely present between the two CoO layers, that is, at the lithium site, has an effect of suppressing the displacement of the two CoO layers when charged at a high voltage. Therefore, if magnesium is present between the CoO 2 layers, it tends to have an O3'type crystal structure.
  • a halogen compound such as a fluorine compound
  • lithium cobalt oxide before the heat treatment for distributing magnesium throughout the particles.
  • a halogen compound causes a melting point depression of lithium cobalt oxide. By lowering the melting point, it becomes easy to distribute magnesium throughout the particles 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 magnesium concentration is higher than the desired value, the effect on stabilizing the crystal structure may be reduced. It is thought that magnesium enters cobalt sites in addition to lithium sites.
  • the number of atoms of magnesium contained in the positive electrode active material produced by one aspect of the present invention is preferably 0.001 times or more and 0.1 times or less, and more than 0.01 times and less than 0.04 times the number of atoms of cobalt. More preferably, about 0.02 is further 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.
  • the number of atoms of nickel contained in the positive electrode active material of one aspect of the present invention is preferably 7.5% or less, preferably 0.05% or more and 4% or less, and 0.1% or more and 2% or less of the atomic number of cobalt. More preferred.
  • the concentration of nickel 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.
  • the average particle diameter (D50: also referred to as median diameter) is preferably 1 ⁇ m or more and 100 ⁇ m or less, more preferably 2 ⁇ m or more and 40 ⁇ m or less, and further preferably 5 ⁇ m or more and 30 ⁇ m or less.
  • a positive electrode active material exhibits an O3'type crystal structure when charged at a high voltage is determined by XRD, electron diffraction, neutron diffraction, electron spin resonance (ESR), and electron spin resonance (ESR). It can be determined by analysis using nuclear magnetic resonance (NMR) or the like.
  • XRD can analyze the symmetry of transition metals such as cobalt possessed by the positive electrode active material with high resolution, compare the height of crystallinity and the orientation of crystals, and analyze the periodic strain and crystallite size of the lattice. It is preferable in that sufficient accuracy can be obtained even if the positive electrode obtained by disassembling the secondary battery is measured as it is.
  • the positive electrode active material of one aspect of the present invention is characterized in that the crystal structure does not change much between the state of being charged with a high voltage and the state of being discharged.
  • a material in which a crystal structure having a large change from the discharged state occupies 50 wt% or more in a state of being charged at a high voltage is not preferable because it cannot withstand the charging / discharging of a high voltage.
  • the desired crystal structure may not be obtained simply by adding an impurity element. For example, even if lithium cobalt oxide having magnesium and fluorine is common, the O3'type crystal structure becomes 60 wt% or more when charged at a high voltage, and the H1-3 type crystal structure becomes 50 wt% or more.
  • the O3'type crystal structure becomes approximately 100 wt%, and when the predetermined voltage is further increased, an H1-3 type crystal structure may occur. Therefore, it is preferable that the crystal structure of the positive electrode active material according to one aspect of the present invention is analyzed by XRD or the like. By using it in combination with measurement such as XRD, more detailed analysis can be performed.
  • the positive electrode active material charged or discharged at a high voltage may change its crystal structure when exposed to the atmosphere.
  • the O3'type crystal structure may change to the H1-3 type crystal structure. Therefore, it is preferable to handle all the samples in an inert atmosphere such as an atmosphere containing argon.
  • the positive electrode active material shown in FIG. 2 is lithium cobalt oxide (LiCoO 2 ) to which halogen and magnesium are not added by the production method described later.
  • the crystal structure of lithium cobalt oxide shown in FIG. 2 changes depending on the charging depth.
  • the lithium cobalt oxide having a charge depth of 0 has a region having a crystal structure of the space group R-3 m, and three CoO layers are present 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 state of sharing a ridge.
  • the space group P-3m1 has a crystal structure, and one CoO layer is present in the unit cell. Therefore, this crystal structure may be referred to as an O1 type crystal structure.
  • lithium cobalt oxide when the charging depth is about 0.8 has a crystal structure of the space group R-3m.
  • 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.
  • 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 high voltage charging and discharging are repeated.
  • the collapse of the crystal structure causes deterioration of the cycle characteristics. It is considered that this is because the crystal structure collapses, the number of sites where lithium can stably exist decreases, and it becomes difficult to insert and remove lithium.
  • a method for producing a positive electrode active material having lithium, a transition metal, and an element X will be described.
  • Step S11 of FIG. 4A a lithium source and a transition metal source are prepared as materials for lithium and the transition metal.
  • the transition metal source is shown as the M source.
  • lithium source for example, lithium carbonate, lithium fluoride, or the like can be used.
  • transition metal source for example, at least one of manganese, cobalt, and nickel can be used.
  • transition metal source when only cobalt is used, when only nickel is used, when two types of cobalt and manganese are used, when two types of cobalt and nickel are used, or when three types of cobalt, manganese, and nickel are used. May be used.
  • the purity of the material is 3N (99.9%) or higher, preferably 4N (99.99%) or higher, more preferably 4N5 (99.995%) or higher, and even more preferably 5N (99%). .999%) or more.
  • the capacity of the secondary battery can be increased and / or the reliability of the secondary battery can be increased.
  • the transition metal source at this time has high crystallinity.
  • the transition metal source has a single crystal grain.
  • the crystallinity of the transition metal source is, for example, TEM (transmission electron microscope) image, STEM (scanning transmission electron microscope) image, HAADF-STEM (high-angle scattering annular dark-field scanning transmission electron microscope) image, ABF-STEM (circular bright-field). It can be evaluated from a scanning transmission electron microscope) image or the like. Further, the crystallinity of the transition metal source can be evaluated by using XRD, electron diffraction, neutron diffraction or the like. The above-mentioned crystallinity evaluation can be applied not only to the evaluation of the crystallinity of the transition metal source but also to the evaluation of the crystallinity of the primary particles or the secondary particles.
  • step S11 the lithium source, the transition metal source, and the additive element X source may be prepared, and then step S12 may be performed.
  • Additive elements X include magnesium, calcium, zirconium, lantern, barium, titanium, yttrium, nickel, aluminum, cobalt, manganese, vanadium, iron, chromium, niobium, copper, potassium, sodium, zinc, chlorine, fluorine, hafnium, One or more selected from silicon, sulfur, phosphorus, boron and arsenic can be used. Further, as the additive element X, bromine and beryllium may be used in addition to the above elements. However, since bromine and beryllium are elements that are toxic to living organisms, it is preferable to use the above-mentioned additive element X.
  • transition metal source oxides, hydroxides, etc. of the above metals exemplified as transition metals 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, transition metal source, and additive element X source are crushed and mixed.
  • Crushing and mixing can be performed dry or wet.
  • the wording described as crushing may be read as crushing.
  • a ball mill, a bead mill or the like can be used for mixing. When a ball mill is used, it is preferable to use, for example, zirconia balls as a medium.
  • the peripheral speed is preferably 100 mm / s or more and 2000 mm / s or less in order to suppress contamination from media or materials.
  • the peripheral speed may be 838 mm / s (rotation speed 400 rpm, ball mill diameter 40 mm). Further, by using the above-mentioned dehydrated acetone in crushing and mixing, impurities that can be mixed in the material can be reduced.
  • step S13 the materials mixed above are heated.
  • the heating temperature of this step is preferably 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. If the temperature is too low, the decomposition and melting of the lithium source and the transition metal source may be insufficient. On the other hand, if the temperature is too high, defects may occur due to the evaporation of lithium from the lithium source and / or the excessive reduction of the metal used as the transition metal source. For example, when cobalt is used as a transition metal, a defect may occur in which cobalt becomes divalent.
  • 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.
  • the heating is preferably performed in an atmosphere such as dry air with little water (for example, a dew point of ⁇ 50 ° C. or lower, more preferably a dew point of ⁇ 80 ° C. or lower).
  • heating may be performed in an atmosphere with a dew point of ⁇ 93 ° C.
  • it is preferable that the heating is performed in an atmosphere where the impurity concentrations of CH 4 , CO, CO 2 and H 2 are 5 ppb (parts per billion) or less, respectively, because impurities that can be mixed in the material can be suppressed.
  • the temperature rise is 200 ° C./h and the flow rate of the dry air is 10 L / min.
  • the heated material can then be cooled to room temperature.
  • 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.
  • the crucible used for heating in step S13 is preferably made of a material that does not contain impurities.
  • alumina crucible with a purity of 99.9% may be used.
  • step S13 when recovering the material that has been heated in step S13, it is preferable to move the material from the crucible to the mortar and then recover the material because impurities are not mixed in the material. Further, it is preferable that the mortar is also made of a material that does not contain impurities. Specifically, it is preferable to use an alumina mortar having a purity of 90% or more, preferably 99% or more. The same conditions as in step S13 can be applied to the heating steps described later other than step S13.
  • the positive electrode active material 100 can be produced (step S14).
  • the positive electrode active material 100 may be represented as a composite oxide (LiMO 2 ) having lithium, a transition metal, and oxygen.
  • the impurity concentration is low, in other words, the purity is increased. You can get the material that has been made.
  • the positive electrode active material obtained by such a method for producing a positive electrode active material is a material having high crystallinity.
  • the positive electrode active material obtained by the method for producing a positive electrode active material according to one aspect of the present invention can increase the capacity of the secondary battery and / or enhance the reliability of the secondary battery.
  • steps S11 to S14 are performed in the same manner as in FIG. 4A to prepare a composite oxide (LiMO 2 ) having lithium, a transition metal, and oxygen.
  • a composite oxide synthesized in advance may be used as step S14.
  • steps S11 to S13 can be omitted.
  • a high-purity material it is preferable to use a high-purity material.
  • the purity of the material is 99.5% or more, preferably 99.9% or more, and more preferably 99.99% or more.
  • a step for heating may be provided between the step S14 and the next step S20.
  • the heating can, for example, smooth the surface of the composite oxide.
  • the heating may use the same conditions as the atmosphere and temperature of step S33 described later, and the processing time may be shorter than that of step S33.
  • a smooth surface means that there are few irregularities, the surface is rounded as a whole, and the corners are rounded. Further, a state in which there is little foreign matter adhering to the surface is called smooth. Foreign matter is considered to be a cause of unevenness, and it is preferable that foreign matter does not adhere to the surface.
  • an additive element X source is prepared.
  • the material described above can be used.
  • the additive element X a plurality of elements may be used. A case where a plurality of elements are used as the additive element X will be described with reference to FIGS. 5B and 5C.
  • a solid phase method, a liquid phase method including a sol-gel method, a sputtering method, a vapor deposition method, a CVD (chemical vapor deposition) method, a PLD (pulse laser deposition) method, or the like is applied. be able to.
  • a magnesium source (Mg source) and a fluorine source (F source) are prepared. Further, a lithium source may be prepared in combination with the magnesium source and the fluorine source.
  • magnesium source for example, magnesium fluoride, magnesium oxide, magnesium hydroxide, magnesium carbonate and the like can be used.
  • fluorine source examples include lithium fluoride (LiF), magnesium fluoride (MgF 2 ), aluminum fluoride (AlF 3 ), titanium fluoride (TiF 4 ), cobalt fluoride (CoF 2 , CoF 3 ), and fluorine.
  • the fluorine source is not limited to solid, for example, fluorine (F 2 ), carbon fluoride, sulfur fluoride, oxygen fluoride (OF 2 , O 2 F 2 , O 3 F 2 , O 4 F 2 , O 2 F). Etc. may be used to mix the mixture in the atmosphere in the heating step described later. Further, a plurality of fluorine sources may be mixed and used. Among them, lithium fluoride is preferable because it has a relatively low melting point of 848 ° C. and is easily melted in the heating step described later.
  • 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.
  • LiF: MgF 2 65:35 (molar ratio)
  • the effect of lowering the melting point is highest (Non-Patent Document 4).
  • 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 it is preferable to use a protonic solvent such as a ketone such as acetone, an alcohol such as ethanol and isopropanol, ether, dioxane, acetonitrile, N-methyl-2-pyrrolidone (NMP) and the like, which is unlikely to react with lithium.
  • a protonic solvent such as a ketone such as acetone, an alcohol such as ethanol and isopropanol, ether, dioxane, acetonitrile, N-methyl-2-pyrrolidone (NMP) and the like, which is unlikely to react with lithium.
  • step S22 of FIG. 5B the above materials are mixed and crushed.
  • Mixing can be done dry or wet, but wet is preferred because it can be crushed into smaller pieces.
  • a ball mill, a bead mill, or the like can be used for mixing.
  • zirconia balls it is preferable to use, for example, zirconia balls as a medium.
  • the conditions of the ball mill, the bead mill, and the like may be the same as those of step S12.
  • step S23 the material crushed and mixed as described above is recovered to obtain an additive element X source. Since the additive element X source shown in step S23 is formed from a plurality of materials, it may be referred to as a mixture.
  • the D50 (median diameter) of the above mixture is preferably 600 nm or more and 20 ⁇ m or less, and more preferably 1 ⁇ m or more and 10 ⁇ m or less.
  • Such a finely divided mixture tends to uniformly adhere to the surface of the particles of the composite oxide when mixed with the composite oxide having lithium, a transition metal and oxygen in a later step. It is preferable that the mixture is uniformly adhered to the surface of the composite oxide particles because halogen and magnesium are easily distributed in the vicinity of the surface of the composite oxide particles after heating. If there is a region near the surface that does not contain halogen and magnesium, it may be difficult to form the O3'type crystal structure described later in the charged state.
  • step S21 of FIG. 5B a method of mixing two kinds of materials has been illustrated, but the method is not limited thereto.
  • four kinds of materials magnesium source (Mg source), fluorine source (F source), nickel source (Ni source), and aluminum source (Al source)
  • Mg source magnesium source
  • F source fluorine source
  • Ni source nickel source
  • Al source aluminum source
  • a single material i.e. one material, may be used to prepare the additive element X source.
  • 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 S31 of FIG. 5A the LiMO 2 obtained in step S14 and the additive element X source are mixed.
  • the mixing in step S31 is under milder conditions 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 milder condition 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, for example, zirconia balls as a medium.
  • a ball mill using zirconia balls having a diameter of 1 mm is used for mixing at 150 rpm for 1 hour in a dry manner.
  • the mixing is performed in a dry room having a dew point of ⁇ 100 ° C. or higher and ⁇ 10 ° C. or lower.
  • Step S32> Next, in step S32 of FIG. 5A, the materials mixed above are 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 heated may be used.
  • 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 is used, the steps up to step S32 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 S33 the mixture 903 is heated in an atmosphere containing oxygen.
  • the heating is preferably performed so that the particles of the mixture 903 do not stick to each other.
  • the additive is uniformly and evenly added over the entire surface of the particles.
  • the additive may be added unevenly to a part of the surface.
  • the irregularities may increase, and defects such as cracks and / or cracks may increase. It is considered that this is due to the fact that the particles of the mixture 903 adhere to each other, the contact area with oxygen in the atmosphere is reduced, and the path of diffusion of the additive is obstructed.
  • heating by a rotary kiln may be performed.
  • the heating by the rotary kiln can be heated with stirring in either the continuous type or the batch type.
  • the heating may be performed by a roller herring kiln.
  • the heating temperature in step S33 needs to be equal to or higher than the temperature at which the reaction between LiMO 2 and the additive element X source 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 additive element X source occurs. Therefore, it may be possible to lower the melting temperature of these materials. For example, in the case of oxides, solid phase diffusion occurs from 0.757 times the melting temperature T m (Tanman temperature T d ) or more. Therefore, the heating temperature in step S33 may be, for example, 500 ° C. or higher.
  • the reaction is more likely to proceed, which is preferable.
  • the co-melting point of LiF and MgF 2 is around 742 ° C, so that the heating temperature in step S33 is preferably 742 ° C or higher.
  • the heating temperature is more preferably 830 ° C. or higher.
  • the heating temperature needs to be less 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 heating temperature in step S33 is preferably less than 1130 ° C, more preferably 1000 ° C or lower, further preferably 950 ° C or lower, and even more preferably 900 ° C or lower.
  • the heating temperature in step S33 is preferably 500 ° C. or higher and lower than 1130 ° C., 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 lower than 1130 ° C. is preferable, 742 ° C. or higher and 1000 ° C. or lower is more preferable, 742 ° C. or higher and 950 ° C. or lower is further preferable, and 742 ° C. or higher and 900 ° C. or lower is further preferable.
  • 1130 ° C. is preferable, 830 ° C. or higher and 1000 ° C. or lower is more preferable, 830 ° C. or higher and 950 ° C. or lower is further preferable, and 830 ° C. or higher and 900 ° C. or lower is further preferable.
  • some materials for example, LiF, which is a fluorine source, may function as a flux.
  • the heating 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 can be distributed near the surface to produce a positive electrode active material with good characteristics. ..
  • LiF has a lighter specific gravity in a gaseous state than oxygen
  • LiF in the mixture 903 decreases.
  • the function as a flux is weakened. Therefore, it is necessary to heat while suppressing the volatilization of LiF.
  • LiF is not used as a fluorine source or the like, Li and F on the surface of LiMO 2 may react 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.
  • heating by a rotary kiln it is preferable to heat the mixture 903 by controlling the flow rate of the atmosphere containing oxygen in the kiln. For example, it is preferable to reduce the flow rate of the atmosphere containing oxygen, or to purge the atmosphere first and introduce oxygen gas into the kiln, and then the oxygen gas does not flow.
  • the mixture 903 can be heated in an atmosphere containing LiF, for example, by arranging a lid on a container containing the mixture 903.
  • the heating is preferably performed at an appropriate time.
  • the heating time varies depending on conditions such as the heating temperature, the size of the particles of LiMO 2 in step S14, and the composition. Smaller particles may be more preferred at lower temperatures or shorter times than larger particles.
  • the heating temperature is preferably, for example, 600 ° C. or higher and 950 ° C. or lower.
  • the heating time is, for example, preferably 3 hours or more, more preferably 10 hours or more, still more preferably 60 hours or more.
  • the heating temperature is preferably, for example, 600 ° C. or higher and 950 ° C. or lower.
  • the heating 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 heating is preferably, for example, 10 hours or more and 50 hours or less.
  • Step S34 Next, the heated material is recovered to prepare the positive electrode active material 100. At this time, it is preferable to further sift the recovered particles.
  • the positive electrode active material 100 according to one aspect of the present invention can be produced (step S34).
  • steps S11 to S14 are performed in the same manner as in FIG. 4A to prepare a composite oxide (LiMO 2 ) having lithium, a transition metal, and oxygen.
  • step S14 a composite oxide having lithium, a transition metal, and oxygen previously synthesized may be used. In this case, steps S11 to S13 can be omitted.
  • a step for heating may be provided between steps S14 and S20.
  • the heating may use the same conditions as the atmosphere and temperature of step S33 described later, and the processing time may be shorter than that of step S33.
  • Step S20a As step S20a of FIG. 6, an additive element X1 source is prepared.
  • the source of the additive element X1 it can be selected and used from the additive elements X described above.
  • any one or a plurality selected from magnesium, fluorine, and calcium can be preferably used.
  • a configuration using magnesium and fluorine as the additive element X1 is exemplified in FIG. 7A.
  • Step S21 and step S22 included in step S20a shown in FIG. 7A can be produced in the same process as steps S21 and S22 shown in FIG. 5B.
  • a solid phase method including a sol-gel method, a sputtering method, a vapor deposition method, a CVD (chemical vapor deposition) method, a PLD (pulse laser deposition) method, or the like is applied. be able to.
  • Step S23 shown in FIG. 7A is a step of recovering the crushed and mixed material in step S22 shown in FIG. 7A to use the additive element X1 as a source.
  • steps S31 to S33 shown in FIG. 6 can be manufactured in the same process as steps S31 to S33 shown in FIG. 6
  • Step S34a> the material heated in step S33 is recovered to prepare a composite oxide.
  • an additive element X2 source is prepared.
  • the source of the additive element X2 it can be selected and used from the additive elements X described above.
  • any one or a plurality selected from nickel, titanium, boron, zirconium, and aluminum can be preferably used.
  • a configuration in which nickel and aluminum are used as the additive element X2 is exemplified in FIG. 7B.
  • Step S41 and step S42 included in step S40 shown in FIG. 7B can be produced in the same process as steps S21 and S22 shown in FIG. 5B.
  • a solid phase method including a sol-gel method, a sputtering method, a vapor deposition method, a CVD (chemical vapor deposition) method, a PLD (pulse laser deposition) method, or the like is applied. be able to.
  • Step S43 shown in FIG. 7B is a step of recovering the crushed and mixed materials in step S42 shown in FIG. 7B to use the additive element X2 as a source.
  • step S40 shown in FIG. 7C is a modification of step S40 shown in FIG. 7B.
  • a nickel source and an aluminum source are prepared (step S41), and each is independently crushed (step S42a) to prepare a plurality of additive element X2 sources (step S43).
  • a solvent used for the sol-gel method is prepared in addition to the additive element X2 source.
  • a metal alkoxide can be used as the metal source of the sol-gel method, and for example, alcohol can be used as the solvent.
  • aluminum is added aluminum isopropoxide can be used as a metal source, and isopropanol (2-propanol) can be used as a solvent.
  • zirconium zirconium (IV) tetrapropoxide can be used as a metal source, and isopropanol can be used as a solvent.
  • step S51 in FIG. 6 is a step of mixing the composite oxide produced in step S34a and the additive element X2 source produced in step S40.
  • step S51 in FIG. 6 can be processed in the same process as step S31 shown in FIG. 5A.
  • step S52 in FIG. 6 the process can be performed in the same process as step S32 shown in FIG. 5A.
  • the material produced in step S52 of FIG. 6 is the mixture 904.
  • the mixture 904 is a material containing the additive element X2 added in step S40 in addition to the material of the mixture 903.
  • step S53 in FIG. 6 the process can be performed in the same process as step S33 shown in FIG. 5A.
  • Step S54 Next, the heated material is recovered to prepare the positive electrode active material 100. At this time, it is preferable to further sift the recovered particles.
  • the positive electrode active material 100 according to one aspect of the present invention can be produced (step S54).
  • the profile in the depth direction of each element can be changed by separating the steps of introducing the transition metal, the additive element X1 and the additive element X2. It may be possible.
  • the concentration of the additive can be increased near the surface as compared to the inside of the particle.
  • the ratio of the number of atoms of the additive element to the reference can be made higher in the vicinity of the surface than in the inside.
  • a high-purity material is used as the transition metal source used in the synthesis, and a step in which impurities are less mixed in the synthesis is used to thoroughly eliminate the inclusion of impurities in the synthesis, and a desired additive element is used.
  • a controlled positive electrode active material can be obtained.
  • a positive electrode active material having high crystallinity can be obtained.
  • the positive electrode active material obtained by the method for producing a positive electrode active material according to one aspect of the present invention can increase the capacity of the secondary battery and / or enhance the reliability of the secondary battery.
  • the positive electrode active material of one aspect of the present invention is not limited to the materials listed above. Alternatively, as the positive electrode active material of one aspect of the present invention, in addition to the materials listed above, other materials may be mixed and used.
  • the positive electrode active material for example, a composite oxide having a spinel-type crystal structure or the like can be used. Further, for example, a polyanion-based material can be used as the positive electrode active material. Examples of the polyanionic material include a material having an olivine type crystal structure, a pearcon type material, and the like. Further, as the positive electrode active material, for example, a material having sulfur can be used.
  • LiNiO 2 or LiNi 1-x M x O 2 (M Co, Al, etc.
  • a composite oxide having oxygen, a metal A, a metal M, and an element X can be used.
  • Metal A is one or more of Li, Na, Mg
  • metal M is one or more of Fe, Mn, Co, Ni, Ti, V, Nb
  • element X is S, P, Mo, W, As, Si. One or more.
  • a composite material (general formula LiMPO 4 (M is one or more of Fe (II), Mn (II), Co (II), Ni (II)) can be used.
  • M is one or more of Fe (II), Mn (II), Co (II), Ni (II)
  • Typical examples of the general formula LiMPO 4 are LiFePO 4 , LiNiPO 4 , LiCoPO 4 , LiMnPO 4 , LiFe a Ni b PO 4 , LiFe a Co b PO 4 , LiFe a Mn b PO 4 , LiNi a Co b PO 4 .
  • LiNi a Mn b PO 4 (a + b is 1 or less, 0 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 1), LiFe c Ni d Co e PO 4 , LiFe c Ni d Mn e PO 4 , LiNi c Co d Mn e PO 4 (c + d + e is 1 or less, 0 ⁇ c ⁇ 1, 0 ⁇ d ⁇ 1, 0 ⁇ e ⁇ 1), LiFe f Ni g Coh Mn i PO 4 (f + g + h + i is 1 or less, 0 ⁇ f ⁇ 1, 0 ⁇ Lithium compounds such as g ⁇ 1, 0 ⁇ h ⁇ 1, 0 ⁇ i ⁇ 1) can be used.
  • a composite material such as the general formula Li (2-j) MSiO 4 (M is one or more of Fe (II), Mn (II), Co (II), Ni (II), 0 ⁇ j ⁇ 2) is used. Can be used.
  • Typical examples of the general formula Li (2-j) MSiO 4 are Li (2-j) FeSiO 4 , Li (2-j) NiSiO 4 , Li (2-j) CoSiO 4 , Li (2-j) MnSiO.
  • the represented Nacicon-type compound can be used.
  • the pear-con type compound include Fe 2 (MnO 4 ) 3 , Fe 2 (SO 4 ) 3 , Li 3 Fe 2 (PO 4 ) 3 and the like.
  • a perovskite-type fluoride such as NaFeF 3 , FeF 3 , metal chalcogenides (sulfide, selenium, telluride) such as TiS 2 and MoS 2 , and a reverse spinel-type crystal structure such as LiMVO 4 are used.
  • Materials such as oxides, vanadium oxides (V 2 O 5 , V 6 O 13 , LiV 3 O 8 and the like), manganese oxides, organic sulfur compounds and the like may be used.
  • a borate-based material represented by the general formula LiMBO 3 (M is Fe (II), Mn (II), Co (II)) may be used.
  • Materials having sodium include, for example, NaFeO 2 , Na 2/3 [Fe 1/2 Mn 1/2 ] O 2 , Na 2/3 [Ni 1/3 Mn 2/3 ] O 2 , Na 2 Fe 2 (SO). 4 ) 3 , Na 3 V 2 (PO 4 ) 3 , Na 2 FePO 4 F, NaVPO 4 F, NaMPO 4 (M is Fe (II), Mn (II), Co (II), Ni (II)) , Na 2 FePO 4 F, Na 4 Co 3 (PO 4 ) 2 P 2 O 7 , and other sodium-containing oxides may be used as the positive electrode active material.
  • a lithium-containing metal sulfide may be used as the positive electrode active material.
  • Li 2 TiS 3 , Li 3 NbS 4 , and the like can be mentioned.
  • the secondary battery of one aspect of the present invention preferably has an electrolytic solution.
  • the electrolytic solution contained in the secondary battery of one aspect of the present invention preferably contains an ionic liquid and a salt containing a metal as a carrier ion.
  • the metal to be a carrier ion is lithium
  • One type, or two or more of these, can be used in any combination and ratio.
  • Metal salts with anions are preferable because they are highly stable at high temperatures and have high oxidation-reduction resistance.
  • the ionic liquid consists of cations and anions, and contains organic cations and anions.
  • organic cation used in the electrolytic solution include aromatic cations such as imidazolium cation and pyridinium cation, quaternary ammonium cation, tertiary sulfonium cation, and aliphatic onium cation such as quaternary phosphonium cation.
  • monovalent amide anions monovalent methide anions, fluorosulfonic acid anions, perfluoroalkyl sulfonic acid anions, tetrafluoroborate anions, perfluoroalkyl borate anions, and hexafluorophosphate anions.
  • perfluoroalkyl phosphate anion and the like are examples of perfluoroalkyl phosphate anion and the like.
  • the electrolytic solution is, for example, ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate, chloroethylene carbonate, vinylene carbonate, ⁇ -butyrolactone, ⁇ -valerolactone, dimethyl carbonate (DMC), diethyl.
  • EC ethylene carbonate
  • PC propylene carbonate
  • PC butylene carbonate
  • chloroethylene carbonate vinylene carbonate
  • ⁇ -butyrolactone ⁇ -valerolactone
  • DMC dimethyl carbonate
  • diethyl diethyl
  • DEC Ethyl Methyl Carbonate
  • EMC Ethyl Methyl Carbonate
  • Methyl formate Methyl acetate, Ethyl acetate, Methyl propionate, Ethyl propionate, propyl propionate, Methyl butyrate, 1,3-dioxane, 1,4-dioxane, dimethoxyethane (DME), dimethyl sulfoxide, diethyl ether, methyl diglyme, acetonitrile, benzonitrile, tetrahydrofuran, sulfolane, sulton, etc., or an aprotic solvent in which two or more of these are mixed in any combination and ratio. May have.
  • the electrolytic solution contains vinylene carbonate (VC), propane sultone (PS), tert-butylbenzene (TBB), fluoroethylene carbonate (FEC), lithium bis (oxalate) borate (LiBOB), succinonitrile, adiponitrile, etc. Dinitrile compounds and additives such as fluorobenzene, cyclohexylbenzene and biphenyl may be added.
  • the concentration of the material to be added may be, for example, 0.1 wt% or more and 5 wt% or less with respect to the entire solvent.
  • an ionic liquid represented by the following general formula (G1) can be used as the ionic liquid having an imidazolium cation.
  • R 1 represents an alkyl group having 1 or more and 6 or less carbon atoms, and an substituted or unsubstituted aryl group having 6 or more and 13 or less carbon atoms, preferably having 1 or more and 4 or less carbon atoms.
  • R 2 to R 4 independently represent a hydrogen atom or an alkyl group having 1 or more and 6 or less carbon atoms, and a substituted or unsubstituted aryl group having 6 or more and 13 or less carbon atoms, preferably 1.
  • R5 represents an alkyl group of 4 or more
  • R5 represents an alkyl group or a main chain composed of two or more selected atoms of C, O, Si, N, S, and P.
  • a substituent may be introduced into the main chain of R5 .
  • the substituent to be introduced include an alkyl group and an alkoxy group.
  • the main chain of R5 may have a carboxy group.
  • the main chain of R5 may have a carbonyl group.
  • an ionic liquid represented by the following general formula (G2) may be used.
  • R 6 represents an alkyl group or a main chain composed of two or more selected from atoms of C, O, Si, N, S and P, and R 7 to R.
  • Each of 11 independently represents a hydrogen atom or an alkyl group having 1 or more and 4 or less carbon atoms.
  • a substituent may be introduced into the main chain of R6 . Examples of the substituent to be introduced include an alkyl group and an alkoxy group.
  • ionic liquid having a quaternary ammonium cation for example, ionic liquids represented by the following general formulas (G3), (G4), (G5) and (G6) can be used.
  • R 28 to R 31 each independently represent any one of an alkyl group having 1 or more and 20 or less carbon atoms, a methoxy group, a methoxymethyl group, a methoxyethyl group, or a hydrogen atom.
  • R 12 to R 17 each independently represent any one of an alkyl group having 1 or more and 20 or less carbon atoms, a methoxy group, a methoxymethyl group, a methoxyethyl group, or a hydrogen atom.
  • R18 to R24 independently represent any one of an alkyl group having 1 or more and 20 or less carbon atoms, a methoxy group, a methoxymethyl group, a methoxyethyl group, or a hydrogen atom.
  • n and m are 1 or more and 3 or less.
  • ⁇ is 0 or more and 6 or less, ⁇ is 0 or more and 4 or less when n is 1, ⁇ is 0 or more and 5 or less when n is 2, and ⁇ is 0 or more and 6 or less when n is 3.
  • ⁇ is 0 or more and 6 or less, ⁇ is 0 or more and 4 or less when m is 1, ⁇ is 0 or more and 5 or less when m is 2, and ⁇ is 0 or more and 6 or less when m is 3.
  • ⁇ or ⁇ it means that it is not substituted. Further, the case where both ⁇ and ⁇ are 0 is excluded.
  • X or Y is a linear or side chain alkyl group having 1 or more and 4 or less carbon atoms, a linear or side chain alkoxy group having 1 or more and 4 or less carbon atoms, or a carbon number as a substituent. Represents a linear or side chain alkoxyalkyl group of 1 or more and 4 or less.
  • an ionic liquid represented by the following general formula (G7) can be used.
  • R 25 to R 27 each independently represent a hydrogen atom, an alkyl group having 1 or more and 4 or less carbon atoms, or a phenyl group.
  • R 25 to R 27 a main chain composed of two or more selected from the atoms of C, O, Si, N, S, and P may be used.
  • an ionic liquid represented by the following general formula (G8) can be used.
  • R 32 to R 35 each independently represent a hydrogen atom, an alkyl group having 1 or more and 4 or less carbon atoms, or a phenyl group.
  • R 32 to R 35 a main chain composed of two or more atoms selected from the atoms of C, O, Si, N, S, and P may be used.
  • a ⁇ represented by the general formulas (G1) to (G8) a monovalent amide anion, a monovalent methide anion, a fluorosulfonic acid anion, a perfluoroalkylsulfonic acid anion, a tetrafluoroborate anion, and a perfluoroalkylborate.
  • anions, hexafluorophosphate anions, perfluoroalkyl phosphate anions and the like can be used.
  • the monovalent amide anion for example, one or more of a bis (fluorosulfonyl) amide anion and a bis (trifluoromethanesulfonyl) amide anion can be used.
  • the ionic liquid may have one or more of a hexafluorophosphate anion and a tetrafluoroborate anion.
  • the anion represented by (FSO 2 ) 2 N ⁇ may be referred to as an FSA anion, and the anion represented by (CF 3 SO 2 ) 2 N ⁇ may be referred to as a TFSA anion.
  • the ionic liquid represented by the general formula (G1) has an imidazolium cation and an anion represented by A ⁇ .
  • Ionic liquids with imidazolium cations have low viscosities and can be used in a wide temperature range. Further, the ionic liquid having an imidazolium cation is highly stable and has a wide potential window, so that it can be suitably used as an electrolyte for a secondary battery.
  • a salt such as a lithium salt can be mixed with the ionic liquid represented by the general formula (G1) and used as an electrolyte for a secondary battery.
  • the imidazolium cation represented by the general formula (G1) has high oxidation resistance and reduction resistance, and has a wide potential window, so that it is suitable as a solvent used for an electrolyte.
  • the width of the potential at which the electrolyte is not electrolyzed is called a potential window.
  • a positive electrode active material having excellent characteristics even at a high charging voltage can be mounted to increase the charging voltage. Therefore, an excellent secondary battery can be realized by using an ionic liquid having a wide potential window and particularly excellent oxidation resistance.
  • R 1 is a methyl group, an ethyl group or a propyl group
  • one of R 2 , R 3 and R 4 is a hydrogen atom or a methyl group
  • the other two are hydrogen atoms.
  • anion A ⁇ one of (FSA anion) represented by (FSA anion) 2 N ⁇ and anion represented by (CF 3 SO 2 ) 2 N ⁇ ( TFSA anion), or a mixture of two .
  • the metal salt with the amide-based anion represented by (below) is preferable because it has high stability at high temperatures and high oxidation-reduction resistance.
  • LiN (FSO 2 ) 2 or LiN (CF 3 SO 2 ) 2 or a mixture of the two it is possible to realize a secondary battery that is highly stable and can operate at a wide temperature. can.
  • R 1 is a methyl group, an ethyl group or a propyl group
  • one of R 2 , R 3 and R 4 is a hydrogen atom or a methyl group
  • the other two are hydrogen atoms.
  • the structural formulas (111) to (124), the structural formulas (131) to (136), the structural formulas (146) to (155), the structural formulas (156) to (166), and (170). ) Is mentioned. It is preferable to use one selected from these cations. Alternatively, a plurality of cations selected from these cations may be used in combination.
  • the electrolyte of the secondary battery has one or more selected from the cations represented by the structural formulas (111) to (115) and the structural formulas (156) to (162).
  • the viscosity is low and the ionic liquid can be used in a wide temperature range. can. Therefore, it is possible to realize an ionic liquid having particularly high oxidation resistance and extremely high stability.
  • the volume of the ionic liquid represented by the general formula (G1) is preferably larger than the volume of one or more selected from the ionic liquids represented by the general formulas (G2) to (G8), and the general formula (G1) is used. It is more preferable that the volume of the ionic liquid shown is larger than twice the volume of one or more selected from the ionic liquids represented by the general formulas (G2) to (G8).
  • the positive electrode active material of one aspect of the present invention is used, and the electrolytic solution has the ionic liquid shown above, so that the secondary battery is repeatedly used at a high charging voltage. Even in this case, it is possible to suppress a decrease in capacity and realize remarkably excellent characteristics.
  • the negative electrode of one aspect of the present invention has a negative electrode active material. Moreover, it is preferable that the negative electrode of one aspect of the present invention has a conductive agent. Further, it is preferable that the negative electrode of one aspect of the present invention has a binder.
  • Negative negative active materials include materials that can react with carrier ions of secondary batteries, materials that can insert and remove carrier ions, materials that can alloy with metals that become carrier ions, and carrier ions. It is preferable to use a material or the like capable of dissolving and precipitating the metal.
  • the negative electrode active material for example, carbon materials such as graphite, graphitizable carbon, non-graphitizable carbon, carbon nanotubes, carbon black and graphene can be used.
  • the negative electrode active material for example, a material having one or more elements selected from silicon, tin, gallium, aluminum, germanium, lead, antimony, bismuth, silver, zinc, cadmium, and indium can be used.
  • phosphorus, arsenic, boron, aluminum, gallium and the like may be added to silicon as impurity elements to reduce the resistance.
  • the material having silicon for example, a material represented by SiO x (x is preferably smaller than 2, more preferably 0.5 or more and 1.6 or less) can be used.
  • a material having silicon for example, a form having a plurality of crystal grains in one particle can be used.
  • a form having one or a plurality of silicon crystal grains in one particle can be used.
  • the one particle may have silicon oxide around the crystal grain of silicon.
  • the silicon oxide may be amorphous.
  • Li 2 SiO 3 and Li 4 SiO 4 can be used as the compound having silicon.
  • Li 2 SiO 3 and Li 4 SiO 4 may be crystalline or amorphous, respectively.
  • Analysis of compounds having silicon can be performed using NMR, XRD, Raman spectroscopy, or the like.
  • a material that can be used as a negative electrode active material for example, an oxide having one or more elements selected from titanium, niobium, tungsten and molybdenum can be mentioned.
  • the negative electrode active material a plurality of metals, materials, compounds, etc. shown above can be used in combination.
  • the negative electrode active material of one aspect of the present invention may have fluorine in the surface layer portion. Since the negative electrode active material has a halogen on the surface layer portion, it is possible to suppress a decrease in charge / discharge efficiency. In addition, it is considered that the reaction with the electrolyte on the surface of the active material is suppressed. Further, in the negative electrode active material of one aspect of the present invention, at least a part of the surface of the negative electrode active material may be covered with a region containing halogen. The region may be, for example, membranous. Fluorine is particularly preferable as the halogen.
  • the material that can be used as the negative electrode active material described above and the compound having a halogen as the second material are mixed and heat-treated.
  • a material that causes a eutectic reaction with the second material may be mixed.
  • the melting point due to the eutectic reaction is preferably lower than at least one of the melting point of the second material and the melting point of the third material. Since the melting point is lowered by the eutectic reaction, the surface of the first material may be easily covered by the second material and the third material during the heat treatment, and the covering property may be improved.
  • the carrier ions are used. In some cases, it can contribute to charging and discharging.
  • a material having oxygen and carbon can be used.
  • carbonate can be used as the material having oxygen and carbon.
  • an organic compound can be used as the material having oxygen and carbon.
  • hydroxide may be used as the third material.
  • Carbonates, hydroxides, etc. are preferable because many of them are inexpensive and highly safe materials. Further, carbonates, hydroxides and the like may have a co-melting point with a material having a halogen, which is preferable.
  • the second material and the third material A more specific example of the second material and the third material will be described.
  • lithium fluoride when it is mixed with the first material and heated, lithium fluoride does not cover the surface of the first material and aggregates only with lithium fluoride. There is.
  • the coating property of the first material on the surface may be improved by using a material that causes a euphoric reaction with lithium fluoride as the third material.
  • the first material When the first material is heated, a reaction with oxygen in the atmosphere may occur during the heating, and an oxide film may be formed on the surface.
  • heating is performed at a low temperature by causing a eutectic reaction between the material having halogen and the material having oxygen and carbon. Therefore, it is possible to suppress an oxidation reaction or the like on the surface.
  • the negative electrode active material When a carbon material is used as the first material, carbon dioxide is generated by the reaction between the carbon material and oxygen in the atmosphere during heating, and the weight of the first material is reduced. There is a concern that damage to the surface of the material may occur.
  • heating can be performed at a low temperature, so that weight reduction, surface damage, and the like can be suppressed even when a carbon material is used as the first material.
  • graphite is prepared as the first material.
  • the graphite scaly graphite, spheroidized natural graphite, MCMB and the like can be used. Further, the surface of graphite may be coated with a low-crystal carbon material.
  • a material having halogen As the second material, prepare a material having halogen.
  • a halogen compound having a metal A1 can be used.
  • the metal A1 for example, one or more selected from lithium, magnesium, aluminum, sodium, potassium, calcium, barium, lanthanum, cerium, chromium, manganese, iron, cobalt, nickel, zinc, zirconium, titanium, vanadium and niobium shall be used. Can be done.
  • fluoride or chloride can be used as the halogen compound.
  • the halogen contained in the material having a halogen is represented as an element Z.
  • lithium fluoride is prepared as an example.
  • a material having oxygen and carbon for example, a carbonate having the metal A2 can be used.
  • the metal A2 for example, one or more selected from lithium, magnesium, aluminum, sodium, potassium, calcium, barium, lanthanum, cerium, chromium, manganese, iron, cobalt and nickel can be used.
  • lithium carbonate is prepared as an example.
  • the first material, the second material and the third material are mixed to obtain a mixture.
  • an annealing step is performed to obtain a negative electrode active material according to one aspect of the present invention.
  • the annealing step it is preferable to carry out the annealing step in a reducing atmosphere because the oxidation of the surface of the first material and the reaction between the first material and oxygen can be suppressed.
  • a reducing atmosphere for example, it may be carried out in a nitrogen atmosphere or a noble gas atmosphere. Further, two or more kinds of gases of nitrogen and noble gas may be mixed and used. Further, heating may be performed under reduced pressure.
  • the heating temperature is preferably higher than, for example, (M 2-550) [K] and lower than (M 2 +50) [K], and is preferably (M 2 ) . -400) [° C] or higher (M 2 ) [° C] or lower is more preferable.
  • the compound tends to cause solid phase diffusion at a temperature higher than the Tanman temperature.
  • the Tanman temperature is, for example, 0.757 times the melting point of an oxide. Therefore, for example, the heating temperature is preferably 0.757 times or more the co-melting point or higher than the temperature in the vicinity thereof.
  • the heating temperature is preferably equal to or lower than the melting point of the halogen-containing material.
  • the heating temperature is higher than (M 23 ⁇ 0.7) [K], for example (M 2 +50) [K]. ], It is preferably (M 23 ⁇ 0.75) [K] or more (M 2 +20) [K] or less, and (M 23 ⁇ 0.75) [K] or more (M 2 +20). ) [K] or less, preferably higher than M 23 [K] and lower than (M 2 +10) [K], and (M 23 ⁇ 0.8) [K] or more and M 2 [K] or less. It is more preferable that it is (M 23 ) [K] or more, and it is more preferable that it is M 2 [K] or less.
  • the heating temperature is preferably higher than 350 ° C. and lower than 900 ° C., more preferably 390 ° C. or higher and 850 ° C. or lower. It is more preferably 520 ° C. or higher and 910 ° C. or lower, further preferably 570 ° C. or higher and 860 ° C. or lower, and further preferably 610 ° C. or higher and 860 ° C. or lower.
  • the heating time is, for example, preferably 1 hour or more and 60 hours or less, and more preferably 3 hours or more and 20 hours or less.
  • 8A, 8B, 8C and 8D show an example of a cross section of the negative electrode active material 400.
  • the cross section can be observed and analyzed by exposing the cross section by processing.
  • the negative electrode active material 400 shown in FIG. 8A has a region 401 and a region 402.
  • the region 402 is located outside the region 401. Further, it is preferable that the region 402 is in contact with the surface of the region 401.
  • At least a part of the region 402 includes the surface of the negative electrode active material 400.
  • Region 401 is, for example, a region including the inside of the negative electrode active material 400.
  • Region 401 has the first material mentioned above.
  • Region 402 has, for example, element Z, oxygen, carbon, metal A1 and metal A2.
  • the element Z is, for example, fluorine, chlorine or the like.
  • the region 402 may not contain some of the elements Z, oxygen, carbon, metal A1 and metal A2. Alternatively, the concentration of some of the elements Z, oxygen, carbon, metal A1 and metal A2 in region 402 may be low and may not be detected by analysis.
  • the region 402 may be referred to as a surface layer portion of the negative electrode active material 400.
  • the negative electrode active material 400 can have various forms such as one particle, an aggregate of a plurality of particles, and a thin film.
  • Region 401 may be a particle of the first material.
  • the region 401 may be an aggregate of a plurality of particles of the first material.
  • the region 401 may be a thin film of the first material.
  • Region 402 may be part of the particle.
  • the region 402 may be the surface layer portion of the particles.
  • the region 402 may be a part of the thin film.
  • the region 402 may be the upper layer of the thin film.
  • the region 402 may be a coating layer formed on the surface of the particles.
  • the region 402 may be a region having a bond between the element constituting the first material and the element Z.
  • the surface of the first material may be modified with element Z or a functional group having element Z. Therefore, in the negative electrode active material of one aspect of the present invention, a bond between the element constituting the first material and the element Z may be observed.
  • a bond between the element constituting the first material and the element Z may be observed.
  • the first material is graphite and the element Z is fluorine
  • a CF bond may be observed.
  • the first material has silicon and the element Z is fluorine, for example, a Si—F bond may be observed.
  • the region 401 is the graphite particles, and the region 402 is the coating layer of the graphite particles.
  • the region 401 is a region containing the inside of the graphite particles, and the region 402 is a surface layer portion of the graphite particles.
  • Region 402 has, for example, a bond between element Z and carbon. Further, the region 402 has, for example, a bond between the element Z and the metal A1. The region 402 also has, for example, a carbonic acid group.
  • the element Z is detected, and the element Z is preferably detected at a concentration of 1 atomic% or more.
  • the concentration of the element Z can be calculated, for example, assuming that the total concentration of carbon, oxygen, metal A1, metal A2 and element Z is 100%. Alternatively, the value obtained by adding the concentration of nitrogen to the concentration of these elements may be calculated as 100%. Further, the concentration of the element Z is, for example, 60 atomic% or less, or 30 atomic% or less, for example.
  • a peak caused by the bond between the element Z and carbon When analyzing the negative electrode active material 400 by XPS, it is preferable to detect a peak caused by the bond between the element Z and carbon. Further, a peak caused by the bond between the element Z and the metal A1 may be detected.
  • the peak suggesting a carbon-fluorine bond (hereinafter referred to as peak F2) is in the vicinity of 688 eV, for example, an energy range higher than 686.5 eV and lower than 689.5 eV in the F1s spectrum of XPS.
  • peak F1 the peak suggesting the lithium-fluorine bond
  • peak F1 the peak suggesting the lithium-fluorine bond
  • the intensity of the peak F2 is preferably larger than 0.1 times and smaller than 10 times the intensity of the peak F1, for example, 0.3 times or more and 3 times or less.
  • the negative electrode active material 400 When analyzing the negative electrode active material 400 by XPS, it is preferable to see a peak corresponding to a carbonate or a carbonic acid group.
  • the peak position corresponding to the carbonate or carbonic acid group is observed in the vicinity of 290 eV, for example, in the energy range higher than 288.5 eV and lower than 291.5 eV.
  • the region 401 has a region not covered by the region 402. Further, in the example shown in FIG. 8C, the region 402 covering the recessed region on the surface of the region 401 is thicker.
  • the region 401 has the region 401a and the region 401b.
  • the region 401a is a region including the inside of the region 401, and the region 401b is located outside the region 401a. Further, it is preferable that the region 401b is in contact with the region 402.
  • Region 401b is the surface layer portion of region 401.
  • Region 401b has one or more elements of element Z, oxygen, carbon, metal A1 and metal A2 possessed by region 402. Further, in the region 401b, the elements such as element Z, oxygen, carbon, metal A1 and metal A2 possessed by the region 402 have a concentration gradient in which the concentration gradually decreases from the surface or the vicinity of the surface toward the inside. May be good.
  • the concentration of the element Z possessed by the region 401b is higher than the concentration of the element Z possessed by the region 401a. Further, the concentration of the element Z possessed by the region 401b is preferably lower than the concentration of the element Z possessed by the region 402.
  • the oxygen concentration of the region 401b may be higher than the oxygen concentration of the region 401a. Further, the oxygen concentration of the region 401b may be lower than the oxygen concentration of the region 402.
  • the element Z is detected when the negative electrode active material of one aspect of the present invention is measured by an energy dispersive X-ray analysis method using a scanning electron microscope. Further, the concentration of the element Z is preferably 10 atomic% or more and 70 atomic% or less, for example, assuming that the total concentration of the element Z and oxygen is 100 atomic%.
  • the region 402 has, for example, a region having a thickness of 50 nm or less, more preferably 1 nm or more and 35 nm or less, and further preferably 5 nm or more and 20 nm or less.
  • the region 401b has, for example, a region having a thickness of 50 nm or less, more preferably 1 nm or more and 35 nm or less, and further preferably 5 nm or more and 20 nm or less.
  • the region 402 is a region covered with a region having lithium fluoride and a region covered with a region having lithium carbonate with respect to the region 401. , May have. Further, since the region 402 does not hinder the insertion and desorption of lithium, an excellent secondary battery can be realized without reducing the output characteristics of the secondary battery and the like.
  • the secondary battery has an exterior body (not shown), a positive electrode 503, a negative electrode 506, a separator 507, and an electrolyte 508 in which a lithium salt or the like is dissolved.
  • the separator 507 is provided between the positive electrode 503 and the negative electrode 506.
  • the positive electrode of one aspect of the present invention has a positive electrode active material layer.
  • the positive electrode active material layer has a positive electrode active material.
  • the positive electrode active material layer may have a conductive agent, a binder, or the like.
  • the positive electrode of one aspect of the present invention preferably has a current collector, and it is preferable that a positive electrode active material layer is provided on the current collector.
  • the positive electrode 503 has a positive electrode active material layer 502 and a positive electrode current collector 501.
  • the positive electrode active material layer 502 has a positive electrode active material 561, a conductive auxiliary material, and a binder.
  • 9B is an enlarged view of the region 502a shown in FIG. 9A.
  • FIG. 9B shows an example in which acetylene black 553 and graphene 554 are used as the conductive agents.
  • the negative electrode of one aspect of the present invention has a negative electrode active material layer.
  • the negative electrode active material layer has a negative electrode active material.
  • the negative electrode active material layer may have a conductive agent, a binder, or the like.
  • the negative electrode of one aspect of the present invention preferably has a current collector, and it is preferable that a negative electrode active material layer is provided on the current collector.
  • the negative electrode 506 has a negative electrode active material layer 505 and a negative electrode current collector 504. Further, the negative electrode active material layer 505 has a negative electrode active material 563, a conductive agent, and a binder.
  • 9D is an enlarged view of the region 505a shown in FIG. 9A.
  • FIG. 9D shows an example in which acetylene black 556 and graphene 557 are used as the conductive agents.
  • a carbon material, a metal material, a conductive ceramic material, or the like can be used as the conductive agent. Further, a fibrous material may be used as the conductive agent.
  • the content of the conductive agent with respect to the total amount of the active material layer is preferably 1 wt% or more and 10 wt% or less, and more preferably 1 wt% or more and 5 wt% or less.
  • the conductive agent can form a network of electrical conduction in the active material layer.
  • the conductive agent can maintain the path of electrical conduction between the active materials.
  • a graphene compound can be used as the conductive agent. Further, as the conductive agent, natural graphite, artificial graphite such as mesocarbon microbeads, carbon fiber and the like can be used.
  • carbon fiber such as mesophase pitch type carbon fiber and isotropic pitch type carbon fiber can be used.
  • carbon fiber carbon nanofiber, carbon nanotube, or the like can be used.
  • the carbon nanotubes can be produced, for example, by a vapor phase growth method.
  • a carbon material such as carbon black (acetylene black (AB) or the like), graphite particles, graphene, fullerene or the like can be used.
  • metal powders such as copper, nickel, aluminum, silver, and gold, metal fibers, and conductive ceramic materials can be used.
  • the graphene compound is referred to as multi-layer graphene, multi-grafene, multi-layer graphene oxide, multi-layered graphene oxide, multi-oxidized graphene, reduced graphene oxide, reduced multi-layered graphene oxide, reduced multi-layered graphene oxide, graphene quantum dot. Etc. are included.
  • the graphene compound has carbon, has a flat plate-like shape, a sheet-like shape, or the like, and has a two-dimensional structure formed by a carbon 6-membered ring. The two-dimensional structure formed by the carbon 6-membered ring may be called a carbon sheet.
  • the graphene compound may have a functional group. Further, the graphene compound preferably has a bent shape. The graphene compound may also be curled up into carbon nanofibers.
  • the materials described above can be used in combination.
  • graphene oxide has carbon and oxygen, has a sheet-like shape, and has a functional group, particularly an epoxy group, a carboxy group or a hydroxy group.
  • the reduced graphene oxide in the present specification and the like means a graphene oxide having carbon and oxygen, having a sheet-like shape, and having a two-dimensional structure formed by a carbon 6-membered ring. It may be called a carbon sheet. Although one reduced graphene oxide functions, a plurality of reduced graphene oxides may be laminated.
  • the reduced graphene oxide preferably has a portion having a carbon concentration of more than 80 atomic% and an oxygen concentration of 2 atomic% or more and 15 atomic% or less. By setting such carbon concentration and oxygen concentration, it is possible to function as a highly conductive conductive agent even in a small amount.
  • the reduced graphene oxide preferably has an intensity ratio G / D of G band to D band of 1 or more in the Raman spectrum. Graphene oxide reduced at such an intensity ratio can function as a highly conductive conductive agent even in a small amount.
  • the sheet-like graphene compound is dispersed substantially uniformly in the internal region of the active material layer. Since the plurality of graphene compounds are formed so as to partially cover the plurality of granular active substances or to stick to the surface of the plurality of granular active substances, they are in surface contact with each other.
  • graphene compound net By binding a plurality of graphene compounds to each other, a mesh-like graphene compound sheet (hereinafter referred to as graphene compound net or graphene net) can be formed.
  • the graphene net When the active material is covered with graphene net, the graphene net can also function as a binder for binding the active materials to each other. Therefore, since the amount of the binder can be reduced or not used, the ratio of the active material to the electrode volume and the electrode weight can be improved. That is, the charge / discharge capacity of the secondary battery can be increased.
  • graphene oxide as a graphene compound, mix it with an active material to form a layer to be an active material layer, and then reduce the amount. That is, it is preferable that the active material layer after completion has reduced graphene oxide.
  • the graphene compound can be dispersed substantially uniformly in the internal region of the active material layer. In order to volatilize and remove the solvent from the dispersion medium containing uniformly dispersed graphene oxide and reduce the graphene oxide, the graphene compounds remaining in the active material layer partially overlap and are dispersed to the extent that they are in surface contact with each other.
  • the graphene oxide may be reduced, for example, by heat treatment or by using a reducing agent.
  • a reducing agent Unlike granular conductive agents such as acetylene black, which make point contact with active materials, graphene compounds enable surface contact with low contact resistance, so the amount of electrical conductivity in the electrode is smaller than that of ordinary conductive agents. Can be improved. Therefore, the ratio of the active material in the active material layer can be increased. As a result, the discharge capacity of the secondary battery can be increased.
  • 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 one or more selected from cellulose derivatives such as carboxymethyl cellulose (CMC), methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, and regenerated cellulose, and 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, methyl polymethacrylate (polymethylmethacrylate, PMMA), sodium polyacrylate, polyvinyl alcohol (PVA), polyethylene oxide (PEO), polypropylene oxide, polyimide, polyvinyl chloride.
  • PVA polyvinyl alcohol
  • PEO polyethylene oxide
  • PEO polypropylene oxide
  • polyimide polyvinyl chloride.
  • Polytetrafluoroethylene, polyethylene, polypropylene, polyisobutylene, polyethylene terephthalate, nylon, polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), ethylenepropylene diene polymer, polyvinyl acetate, 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.
  • examples of the water-soluble polymer having a particularly excellent viscosity-adjusting effect include the above-mentioned polysaccharides, for example, cellulose derivatives such as carboxymethyl cellulose (CMC), methyl cellulose, ethyl cellulose, hydroxypropyl cellulose and diacetyl cellulose, and regenerated cellulose, and starch.
  • CMC carboxymethyl cellulose
  • methyl cellulose methyl cellulose
  • ethyl cellulose methyl cellulose
  • hydroxypropyl cellulose and diacetyl cellulose regenerated cellulose
  • starch regenerated cellulose
  • 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 its effect as a viscosity adjusting agent.
  • the high solubility can also enhance the dispersibility with the active material and other components when preparing the electrode slurry.
  • 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 the active material and other materials to be combined as a binder, such as styrene-butadiene rubber, can be stably dispersed in the 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 immovable 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.
  • the active material layer can be prepared by mixing an active material, a binder, a conductive agent and a solvent to prepare a slurry, forming the slurry on a current collector, and volatilizing the solvent.
  • the solvent used for the slurry is preferably a polar solvent.
  • a polar solvent for example, one or a mixture of water, methanol, ethanol, acetone, tetrahydrofuran (THF), dimethylformamide (DMF), N-methylpyrrolidone (NMP) and dimethyl sulfoxide (DMSO) can be used. ..
  • a positive electrode current collector and a negative electrode current collector metals such as stainless steel, gold, platinum, zinc, iron, copper, aluminum and titanium, and alloys thereof have high conductivity and do not alloy with carrier ions such as lithium. Materials can be used. 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 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 10 ⁇ m or more and 30 ⁇ m or less.
  • a titanium compound may be provided by laminating on the metal element shown above.
  • titanium compounds include titanium nitride, titanium oxide, titanium nitride in which a part of nitrogen is replaced with oxygen, titanium oxide in which a part of oxygen is replaced with nitrogen, and titanium oxide (TIO x N y , 0 ⁇ x).
  • titanium oxide titanium oxide
  • Ti x N y , 0 ⁇ x titanium oxide
  • titanium oxide titanium oxide
  • the active material layer contains a compound having oxygen
  • the oxidation reaction between the metal element and oxygen can be suppressed.
  • the active material layer contains a compound having oxygen
  • the oxidation reaction between the metal element and oxygen can be suppressed.
  • the active material layer contains a compound having oxygen
  • the oxidation reaction between the metal element and oxygen can be suppressed.
  • Graphene or a graphene compound can be used as graphene 554 and graphene 557.
  • the graphene compound means multi-layer graphene, multi-graphene, graphene oxide, multi-layer graphene oxide, multi-graphene oxide, reduced graphene oxide, reduced multi-layer graphene oxide, reduced multi-graphene oxide, graphene quantum dot. Etc. are included.
  • the graphene compound has carbon, has a flat plate shape, a sheet shape, or the like, and has a two-dimensional structure formed by a carbon 6-membered ring.
  • the two-dimensional structure formed by the carbon 6-membered ring may be called a carbon sheet.
  • the graphene compound may have a functional group. Further, the graphene compound preferably has a bent shape.
  • the graphene compound may also be curled up into carbon nanofibers.
  • graphene or a graphene compound can function as a conductive agent.
  • the plurality of graphenes or graphene compounds can form a three-dimensional conductive path in the positive electrode or the negative electrode to enhance the conductivity of the positive electrode or the negative electrode. Further, since the graphene or graphene compound can cling to the particles at the positive electrode or the negative electrode, it is possible to suppress the collapse of the particles at the positive electrode or the negative electrode and increase the strength of the positive electrode or the negative electrode.
  • graphene or a graphene compound has a thin sheet-like shape and can form an excellent conductive path even if the volume occupied in the positive electrode or the negative electrode is small, it is possible to increase the volume of the active material in the positive electrode or the negative electrode. can. Therefore, the capacity of the secondary battery can be increased.
  • separator 507 for example, one made of paper, non-woven fabric, glass fiber, ceramics or the like can be used. Alternatively, those made of nylon (polyamide), vinylon (polyvinyl alcohol-based fiber), polyester, acrylic, polyolefin, polyurethane, polypropylene, polyethylene and the like can be used. It is preferable that the separator is processed into an envelope shape and arranged so as to wrap either the positive electrode or the negative electrode.
  • a polymer film having, for example, polypropylene, polyethylene, polyimide or the like can be used for the separator 507.
  • Polyimide has good wettability of ionic liquids and may be more preferable as a material for the separator 507.
  • the polymer film having polypropylene, polyethylene, etc. can be produced by a dry method or a wet method.
  • the dry method is a manufacturing method in which a polymer film having polypropylene, polyethylene, polyimide or the like is stretched while being heated to form a gap between crystals and to make fine pores.
  • the wet method is a manufacturing method in which a solvent is mixed with a resin in advance to form a film, and then the solvent is extracted to make holes.
  • the left figure of FIG. 9C shows an enlarged view of the region 507a shown in FIG. 9A as an example of the separator 507 (when manufactured by the wet method).
  • a structure in which a plurality of holes 582 are formed in the polymer film 581 is shown.
  • the right figure of FIG. 9C shows an enlarged view of the region 507b as another example of the separator 507 (when manufactured by the dry method).
  • a structure in which a plurality of holes 585 are formed in the polymer film 584 is shown.
  • the diameter of the hole of the separator may differ between the surface layer portion of the surface facing the positive electrode after charging and discharging and the surface layer portion of the surface facing the negative electrode.
  • the surface layer portion of the separator is preferably, for example, a region within 5 ⁇ m, more preferably within 3 ⁇ m from the surface.
  • the separator may have a multi-layer structure.
  • a structure in which two types of polymer materials are laminated may be used.
  • a structure in which a ceramic-based material, a fluorine-based material, a polyamide-based material, or a mixture thereof is coated on a polymer film having, for example, polypropylene, polyethylene, polyimide, etc. can be used.
  • a structure in which a ceramic-based material, a fluorine-based material, a polyamide-based material, or a mixture thereof is coated on a non-woven fabric can be used.
  • Polyimide has good wettability of ionic liquids and may be more preferable as a material for coating.
  • fluorine-based material for example, PVDF, polytetrafluoroethylene and the like can be used.
  • polyamide-based material for example, nylon, aramid (meth-based aramid, para-based aramid) and the like can be used.
  • Exterior body As the exterior body of the secondary battery, one or more selected from a metal material such as aluminum and a resin material can be used. Further, a film-like exterior body can also be used. As the film, 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 as appropriate.
  • the secondary battery 500 shown in FIGS. 10A and 10B has 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.
  • a cross-sectional structure of the laminated type secondary battery shown in FIG. 10A or the like for example, as shown in FIG. 15 described later, a structure in which a positive electrode, a separator and a negative electrode are laminated and surrounded by an exterior body can be used.
  • FIG. 11A shows an example of the positive electrode 503 and the negative electrode 506.
  • the positive electrode 503 has a positive electrode active material layer 502 on the positive electrode current collector 501. Further, it is preferable that the positive electrode 503 has a tab region where the positive electrode current collector 501 is exposed.
  • the negative electrode 506 has a negative electrode active material layer 505 on the negative electrode current collector 504. Further, it is preferable that the negative electrode 506 has a tab region where the negative electrode current collector 504 is exposed.
  • FIG. 11B shows the negative electrode 506, the separator 507, and the positive electrode 503 laminated.
  • an example in which 5 sets of negative electrodes and 4 sets of 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.
  • 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 516) that is not joined to a part (or one side) of the exterior body 509 is provided so that the electrolyte 508 can be put in later.
  • an introduction port 516 a region that is not joined to a part (or one side) of the exterior body 509 is provided so that the electrolyte 508 can be put in later.
  • the electrolyte 508 is introduced into the exterior body 509 from the introduction port 516 provided in the exterior body 509.
  • the electrolyte 508 is preferably introduced under a reduced pressure atmosphere or an inert atmosphere.
  • the introduction port 516 is joined. In this way, the laminated type secondary battery 500 can be manufactured.
  • the positive electrode lead electrode 510 and the negative electrode lead electrode 511 were led out from the same side to the outside of the exterior body, and the secondary battery 500 shown in FIG. 10A was manufactured.
  • the secondary battery 500 shown in FIG. 10B can also be manufactured by leading the positive electrode lead electrode 510 and the negative electrode lead electrode 511 to the outside of the exterior body from the opposite sides.
  • the secondary battery 600 shown in FIG. 13 has 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.
  • the exterior body 509 is sealed in region 514.
  • the laminated type secondary battery 600 can be manufactured by using, for example, the manufacturing apparatus shown in FIG.
  • the manufacturing apparatus 570 shown in FIG. 14 has a member input chamber 571, a transfer chamber 572, a processing chamber 573, and a member take-out chamber 576.
  • Each room can be configured to be connected to various exhaust mechanisms according to the intended use. Further, each room can be configured to be connected to various gas supply mechanisms according to the intended use.
  • the inert gas is supplied into the manufacturing apparatus 570.
  • As the gas supplied to the inside of the manufacturing apparatus 570 it is preferable to use a gas that has been highly purified by a gas purifier before being introduced into the manufacturing apparatus 570.
  • the member charging chamber 571 is a room for charging a positive electrode, a separator, a negative electrode, an exterior body, and the like into each of the transport chambers 572, the processing chamber 573, and the like in the manufacturing apparatus 570.
  • the transport chamber 572 has a transport mechanism 580.
  • the treatment chamber 573 has a stage and an electrolyte dropping mechanism.
  • the member take-out room 576 is a room for taking out the manufactured secondary battery to the outside of the manufacturing apparatus 570.
  • the procedure for manufacturing the laminated secondary battery 600 is as follows.
  • the exterior body 509b is arranged on the stage 591 of the processing chamber 573, the frame-shaped resin layer 513 is formed on the exterior body 509b, and then the positive electrode 503 is arranged on the exterior body 509b (FIGS. 16A and 16A).
  • FIG. 16B the electrolyte 515a is dropped from the nozzle 594 onto the positive electrode 503 (FIGS. 16C and 16D).
  • FIG. 16D is a cross section corresponding to the alternate long and short dash line AB in FIG. 16C.
  • the description of the stage 591 may be omitted in order to avoid complicating the drawings.
  • the dropping method for example, any one of a dispense method, a spray method, an inkjet method and the like can be used. Further, an ODF (One Drop Fill) method can be used for dropping the electrolyte.
  • ODF One Drop Fill
  • the electrolyte 515a By moving the nozzle 594, the electrolyte 515a can be dropped over the entire surface of the positive electrode 503. Alternatively, the electrolyte 515a may be dropped over the entire surface of the positive electrode 503 by moving the stage 591.
  • the electrolyte is preferably dropped from a position where the shortest distance from the surface to be dropped is greater than 0 mm and 1 mm or less.
  • the viscosity of the electrolyte dropped from the nozzle or the like is in the range of 0.3 mPa ⁇ s or more and 1000 mPa ⁇ s or less at room temperature (25 ° C.), the electrolyte can be dropped from the nozzle.
  • the temperature of the electrolyte is preferably equal to or higher than the melting point of the electrolyte, lower than the boiling point, or lower than the flash point.
  • the separator 507 is placed on the positive electrode 503 so as to overlap the entire surface of the positive electrode 503 (FIG. 17A).
  • the electrolyte 515b is dropped onto the separator 507 using the nozzle 594 (FIG. 17B).
  • the negative electrode 506 is placed on the separator 507 (FIG. 17C).
  • the negative electrodes 506 are arranged so as to overlap each other so as not to protrude from the separator 507 when viewed from above.
  • the electrolyte 515c is dropped onto the negative electrode 506 using the nozzle 594 (FIG. 17D). After that, the laminated body 512 shown in FIG.
  • the 15 can be manufactured by further laminating the laminated body of the positive electrode 503, the separator 507, and the negative electrode 506. Next, the positive electrode 503, the separator 507, and the negative electrode 506 are sealed by the exterior body 509a and the exterior body 509b (FIGS. 17E and 17F).
  • the positive electrode and the negative electrode are arranged so that the positive electrode active material layer and the negative electrode active material layer sandwich the separator.
  • the region where the negative electrode active material layer does not face the positive electrode active material layer is small or absent.
  • the electrolyte has an ionic liquid and the negative electrode active material layer has a region not facing the positive electrode active material layer, the charge / discharge efficiency of the secondary battery may decrease. Therefore, in the secondary battery of one aspect of the present invention, for example, it is preferable that the end portion of the positive electrode active material layer and the end portion of the negative electrode active material layer are aligned as much as possible.
  • the end portion of the positive electrode active material layer is located inside the end portion of the negative electrode active material layer.
  • a plurality of secondary batteries are individually separated by sealing the exterior bodies 509a and 509b in the region 514 so as to surround the active material layer one by one and then dividing the laminated body 512 on the outside of the region 514. be able to.
  • a frame-shaped resin layer 513 is formed on the exterior body 509b.
  • a frame-shaped resin layer 513 is formed on the exterior body 509b.
  • sealing is performed in the region 514 by thermocompression bonding or welding under atmospheric pressure. Further, it is also possible to perform only thermocompression bonding or sealing by welding without performing the above-mentioned sealing by light irradiation.
  • FIG. 13 shows an example in which the exterior body 509 is sealed on four sides (sometimes called a four-sided seal), as shown in FIGS. 10A and 10B, it is sealed on three sides (called a three-sided seal). In some cases).
  • a laminated secondary battery 600 can be manufactured.
  • FIG. 18 shows an example of a cross-sectional view of the laminated body of one aspect of the present invention.
  • the laminated body 550 shown in FIG. 18 is manufactured by arranging one separator between the positive electrode and the negative electrode while bending it.
  • one separator 507 is folded back a plurality of times so as to be sandwiched between the positive electrode active material layer 502 and the negative electrode active material layer 505.
  • the separator 507 is folded back at least 5 times.
  • the separator 507 is not only provided so as to be sandwiched between the positive electrode active material layer 502 and the negative electrode active material layer 505, but also by further bending the extending portion, the plurality of positive electrode 503 and the negative electrode 506 are bundled together with tape or the like. You may try to do it.
  • the electrolyte can be dropped onto the positive electrode 503.
  • the electrolyte can be dropped onto the negative electrode 506.
  • an electrolyte can be dropped onto the separator 507 before the separator is bent or after the separator 507 is bent and overlapped with the negative electrode 506 or the positive electrode 503. .. By dropping the electrolyte on at least one of the negative electrode 506, the separator 507, and the positive electrode 503, the negative electrode 506, the separator 507, or the positive electrode 503 can be impregnated with the electrolyte.
  • the secondary battery 970 shown in FIG. 19A has a laminated body 972 inside the housing 971.
  • the terminal 973b and the terminal 974b are electrically connected to the laminated body 972. At least a part of the terminal 973b and at least a part of the terminal 974b are exposed to the outside of the housing 971.
  • the laminated body 972 As the laminated body 972, a structure in which a positive electrode, a negative electrode, and a separator are laminated can be applied. Further, as the laminated body 972, a positive electrode, a negative electrode, a structure in which a separator is wound, and the like can be applied.
  • the laminated body 972 a laminated body having a structure in which the separator is folded back, which is shown in FIG. 18, can be used.
  • a strip-shaped separator 976 is superposed on the positive electrode 975a, and the negative electrode 977a is superposed on the positive electrode 975a with the separator 976 in between. Then, the separator 976 is folded back and superposed on the negative electrode 977a.
  • the positive electrode 975b is superposed on the negative electrode 977a with the separator 976 in between.
  • the laminated body 972 can be manufactured by folding back the separator and arranging the positive electrode and the negative electrode in order.
  • the structure including the laminated body produced in this way may be referred to as a "spin turn structure".
  • the positive electrode lead electrode 973a is electrically connected to the positive electrode of the laminated body 972.
  • a tab region can be provided on each of the positive electrodes of the laminated body 972, and each tab region and the positive electrode lead electrode 973a can be electrically connected by welding or the like.
  • the negative electrode lead electrode 974a is electrically connected to the negative electrode of the laminated body 972.
  • One laminated body 972 may be arranged inside the housing 971, or a plurality of laminated bodies 972 may be arranged.
  • FIG. 20B shows an example of preparing two sets of laminated bodies 972.
  • the prepared laminated body 972 is housed in the housing 971, the terminals 973b and the terminals 974b are mounted, and the housing 971 is sealed. It is preferable to electrically connect the conductor 973c to each of the positive electrode lead electrodes 973a of the plurality of laminated bodies 972. Further, it is preferable to electrically connect the conductor 974c to each of the negative electrode lead electrodes 974a of the plurality of laminated bodies 972.
  • the terminal 973b is electrically connected to the conductor 973c, and the terminal 974b is electrically connected to the conductor 974c.
  • the conductor 973c may have a conductive region and an insulating region. Further, the conductor 974c may have a region having conductivity and a region having insulation.
  • a metal material for example, aluminum
  • a metal material can be used as the housing 971.
  • a resin material can be used as the housing 971.
  • the safety valve is a valve that releases gas when the inside of the housing 971 reaches a predetermined pressure in order to prevent the battery from exploding.
  • FIG. 21C An example of a cross-sectional view of a secondary battery according to another aspect of the present invention is shown in FIG. 21C.
  • the secondary battery 560 shown in FIG. 21C is manufactured by using the laminated body 130 shown in FIG. 21A and the laminated body 131 shown in FIG. 21B.
  • FIG. 21C in order to clarify the figure, the laminated body 130, the laminated body 131, and the separator 507 are excerpted and shown.
  • the laminate 130 has a positive electrode 503 and a separator 507 having positive electrode active material layers on both sides of a positive electrode current collector, and a negative electrode 506 and a separator 507 having negative electrode active material layers on both sides of a negative electrode current collector.
  • Positive electrode 503 having positive electrode active material layers on both sides of the positive electrode current collector are laminated in this order.
  • the laminate 131 has a negative electrode 506 and a separator 507 having negative electrode active material layers on both sides of the negative electrode current collector, and a positive electrode 503 and a separator 507 having positive electrode active material layers on both sides of the positive electrode current collector.
  • Negative electrodes 506 having negative electrode active material layers on both sides of the negative electrode current collector are laminated in this order.
  • the method for manufacturing a secondary battery according to one aspect of the present invention can be applied when manufacturing a laminated body. Specifically, when laminating the negative electrode 506, the separator 507, and the positive electrode 503 in order to produce the laminated body, the electrolyte is dropped onto at least one of the negative electrode 506, the separator 507, and the positive electrode 503. By dropping a plurality of drops of the electrolyte, the negative electrode 506, the separator 507, or the positive electrode 503 can be impregnated with the electrolyte.
  • the plurality of laminated bodies 130 and the plurality of laminated bodies 131 are covered with the wound separator 507.
  • the electrolyte after arranging the laminated body 130, the electrolyte can be dropped onto the laminated body 130. Similarly, after arranging the laminated body 131, the electrolyte can be dropped onto the laminated body 131. Further, the electrolyte can be dropped onto the separator 507 before the separator 507 is bent or after the separator 507 is bent and overlapped with the laminated body. By dropping a plurality of drops of the electrolyte, the laminate 130, the laminate 131, or the separator 507 can be impregnated with the electrolyte.
  • a secondary battery of another aspect of the present invention will be described with reference to FIGS. 22 and 23.
  • the secondary battery shown here can be called a winding type secondary battery or the like.
  • the secondary battery 913 shown in FIG. 22A has a winding body 950 provided with terminals 951 and terminals 952 inside the housing 930.
  • the winding body 950 is immersed in the electrolyte 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. 22A 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.
  • an electrolyte is dropped onto at least one of the negative electrode 931, the separator 933, and the positive electrode 932. .. That is, it is preferable to drop the electrolyte before turning the laminated sheet. By dropping a plurality of drops of the electrolyte, the negative electrode 931, the separator 933, or the positive electrode 932 can be impregnated with the electrolyte.
  • a secondary battery 913 having a winding body 950a as shown in FIG. 23A may be used.
  • the winding body 950a shown in FIG. 23A 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.
  • 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 from the viewpoint 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.
  • the terminal 951 is electrically connected to the terminal 911a.
  • the positive electrode 932 is electrically connected to the terminal 952.
  • the terminal 952 is electrically connected to the terminal 911b.
  • the winding body 950a and the electrolyte 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 temporarily opened only when the inside of the housing 930 exceeds 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.
  • FIG. 24C shows a block diagram of a vehicle having a motor.
  • 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 referred to as a cranking battery or a starter battery.
  • the second battery 1311 may have a high output and does not require much large capacity, and the capacity of the second battery 1311 is smaller than that of the first batteries 1301a and 1301b.
  • a secondary battery manufactured by using the method for manufacturing a secondary battery according to one aspect of the present invention can be used for one or both of the first batteries 1301a and 1301b.
  • 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 the 42V system (high voltage system) in-vehicle parts (electric power steering 1307, heater 1308) via the DCDC circuit 1306. , Defogger 1309, etc.). 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 system (low voltage system) in-vehicle parts (audio 1313, power window 1314, lamps 1315, etc.) via the DCDC circuit 1310.
  • 14V system low voltage system
  • in-vehicle parts audio 1313, power window 1314, lamps 1315, etc.
  • first battery 1301a will be described with reference to FIG. 24A.
  • FIG. 24A shows an example of a large battery pack 1415.
  • One electrode of the battery pack 1415 is electrically connected to the control circuit unit 1320 by wiring 1421.
  • the other electrode is electrically connected to the control circuit unit 1320 by wiring 1422.
  • the battery pack may be configured by connecting a plurality of secondary batteries in series.
  • 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).
  • the control circuit unit 1320 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. 24B An example of the block diagram of the battery pack 1415 shown in FIG. 24A is shown in FIG. 24B.
  • the control circuit unit 1320 includes a switch unit 1324 including at least a switch for preventing overcharging, a switch for preventing overdischarge, a control circuit 1322 for controlling the switch unit 1324, and a voltage measuring unit for the first battery 1301a. And have.
  • 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, the upper limit of the output current to the outside, and the like.
  • 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 if 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 or 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 interrupting the current as the temperature rises. 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 one or both of 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, for example, Ge (germanium), SiGe (silicon germanium), GaAs (gallium arsenide), GaAlAs (gallium aluminum arsenide), InP (phosphorization).
  • the switch unit 1324 may be formed by a power transistor having (indium), 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 42V system (high voltage system) in-vehicle devices, and the second battery 1311 supplies electric power to 14V system (low voltage system) in-vehicle devices.
  • a lead-acid battery is often used as the second battery 1311 because of its cost advantage.
  • the second battery 1311 may use a lead storage battery, an all-solid-state battery, or an electric double layer capacitor.
  • 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 or 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 a GPU.
  • a next-generation clean energy vehicle such as a hybrid vehicle (HV), an electric vehicle (EV), or a plug-in hybrid vehicle (PHV)
  • HV hybrid vehicle
  • EV electric vehicle
  • PHS plug-in hybrid vehicle
  • agricultural machinery such as electric tractors, motorized bicycles including electric assisted bicycles, motorcycles, electric wheelchairs, electric carts, small or large vessels, submarines, aircraft such as fixed-wing or rotary-wing machines, rockets, artificial satellites, etc.
  • Secondary batteries can also be mounted on transport vehicles such as space explorers, planetary explorers, and spacecraft.
  • the automobile 2001 shown in FIG. 25A 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.
  • the vehicle 2001 shown in FIG. 25A has the battery pack 1415 shown in FIG. 24A.
  • the battery pack 1415 has a secondary battery module.
  • the battery pack 1415 further preferably has a charge control device that is electrically connected to the secondary battery module.
  • the secondary battery module has one or more secondary batteries.
  • the automobile 2001 can be charged by receiving electric power from an external charging facility by a plug-in method, a non-contact power supply method, or the like to the secondary battery of the automobile 2001.
  • the charging method or the standard of the connector may be appropriately performed by a predetermined method such as CHAdeMO (registered trademark) or a combo.
  • the charging device may be a charging station provided in a commercial facility or a household power source.
  • the plug-in technology can charge a secondary battery mounted on an 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 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, charging can be performed not only while the vehicle is stopped but also while the vehicle is running. Further, electric power may be transmitted and received between two vehicles by using this contactless power feeding method. Further, 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. 25B shows a large transport vehicle 2002 having a motor controlled by electricity as an example of a transport vehicle.
  • the secondary battery module of the transport vehicle 2002 has, for example, a secondary battery of 3.5 V or more and 4.7 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. 25A 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. 25C 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 of 3.5 V or more and 4.7 V or less are connected in series. Therefore, a secondary battery having a small variation in characteristics is required.
  • a secondary battery having a small variation in characteristics is required.
  • FIG. 25D shows, as an example, an aircraft 2004 having an engine that burns fuel. Since the aircraft 2004 shown in FIG. 25D 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. 25A 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.
  • FIG. 25E shows a transport vehicle 2005 that transports cargo as an example. It has a motor controlled by electricity, and performs various operations by supplying electric power from the secondary battery constituting the secondary battery module of the battery pack 2204. Further, the transport vehicle 2005 is not limited to being driven and operated by a human as a driver, and can be operated unmanned by CAN communication or the like. Although the forklift is shown in FIG. 25E, the forklift is not particularly limited, and the present invention relates to an industrial machine that can be operated by CAN communication or the like, for example, an automatic transport machine, a work robot, a small construction machine, or the like. A battery pack having a secondary battery can be mounted.
  • FIG. 26A is an example of an electric bicycle using the secondary battery of one aspect of the present invention.
  • the secondary battery of one aspect of the present invention can be applied to the electric bicycle 2100 shown in FIG. 26A.
  • the power storage device 2102 shown in FIG. 26B has, for example, a plurality of secondary batteries and a protection circuit.
  • the electric bicycle 2100 includes a power storage device 2102.
  • the power storage device 2102 can supply electricity to a motor that assists the driver. Further, the power storage device 2102 is portable, and FIG. 26B shows a state in which the power storage device 2102 is removed from the bicycle. Further, the power storage device 2102 contains a plurality of secondary batteries 2101 according to one aspect of the present invention, and the remaining battery level and the like can be displayed on the display unit 2103. Further, the power storage device 2102 has a control circuit 2104 capable of charging control or abnormality detection of the secondary battery, which is shown as an example in one aspect of the present invention. The control circuit 2104 is electrically connected to the positive electrode and the negative electrode of the secondary battery 2101.
  • a small solid-state secondary battery may be provided in the control circuit 2104.
  • the control circuit 2104 By providing the control circuit 2104 with a small solid-state secondary battery, it is possible to supply electric power to hold the data of the memory circuit of the control circuit 2104 for a long time.
  • a synergistic effect on safety can be obtained.
  • the secondary battery and the control circuit 2104 using the positive electrode active material 100 according to one aspect of the present invention 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 a secondary battery of one aspect of the present invention.
  • the scooter 2300 shown in FIG. 26C includes a power storage device 2302, side mirrors 2301, and a turn signal 2303.
  • the power storage device 2302 can supply electricity to the turn signal lamp 2303.
  • the power storage device 2302 containing a plurality of secondary batteries using the positive electrode active material 100 according to one aspect of the present invention can have a high capacity and can contribute to miniaturization.
  • a protection circuit for preventing overcharging and / or overdischarging of the secondary battery may be electrically connected to the secondary battery.
  • the power storage device 2302 can be stored in the storage under the seat 2304.
  • the power storage device 2302 can be stored in the under-seat storage 2304 even if the under-seat storage 2304 is small.
  • the house shown in FIG. 27A has a power storage device 2612 having a secondary battery having stable battery characteristics and a solar panel 2610 by using the method for manufacturing a secondary battery according to one aspect of the present invention.
  • 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 be supplied 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 as an uninterruptible power supply.
  • FIG. 27B shows an example of a power storage device according to one aspect of the present invention.
  • a large power storage device 791 having a secondary battery obtained by the method for manufacturing a secondary battery according to one aspect of the present invention is installed in the underfloor space portion 796 of the building 799.
  • 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 has 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. Further, 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.
  • the secondary battery of one aspect of the present invention can be used, for example, for one or both of an electronic device and a lighting device.
  • the electronic device include a mobile information terminal such as a mobile phone, a smartphone, or a notebook computer, a portable game machine, a portable music player, a digital camera, and a digital video camera.
  • the personal computer 2800 shown in FIG. 28A has a housing 2801, a housing 2802, a display unit 2803, a keyboard 2804, a pointing device 2805, and the like.
  • a secondary battery 2807 is provided inside the housing 2801
  • a secondary battery 2806 is provided inside the housing 2802.
  • a protection circuit for preventing overcharging and / or overdischarging of the secondary batteries 2807 and 2806 may be electrically connected to the secondary batteries 2807 and 2806.
  • a touch panel is applied to the display unit 2803.
  • the personal computer 2800 can be used as a tablet terminal only by removing the housing 2801 and the housing 2802.
  • the large-sized secondary battery obtained by the method for manufacturing a secondary battery according to one aspect of the present invention can be applied to one or both of the secondary battery 2806 and the secondary battery 2807.
  • the shape of the secondary battery obtained by the method for manufacturing a secondary battery according to one aspect of the present invention can be freely changed by changing the shape of the exterior body.
  • the capacity of the secondary batteries can be increased and the usage time of the personal computer 2800 can be lengthened.
  • the weight of the personal computer 2800 can be reduced.
  • a flexible display is applied to the display unit 2803 of the housing 2802.
  • a large-sized secondary battery obtained by the method for manufacturing a secondary battery according to one aspect of the present invention is applied to the secondary battery 2806.
  • a bendable secondary battery can be obtained by using a flexible film for the exterior body. ..
  • the housing 2802 can be bent and used.
  • a part of the display unit 2803 can also be used as a keyboard.
  • housing 2802 can be folded so that the display unit 2803 is on the inside as shown in FIG. 28D, or the housing 2802 can be folded so that the display unit 2803 is on the outside as shown in FIG. 28E.
  • the secondary battery of one aspect of the present invention is applied to a bendable secondary battery, mounted on an electronic device, and incorporated along a curved surface of a house, an inner wall or an outer wall of a building, or an interior or exterior of an automobile. It is possible.
  • FIG. 29A shows an example of a mobile phone.
  • the mobile phone 7400 includes an operation button 7403, an external connection port 7404, a speaker 7405, a microphone 7406, and the like, in addition to the display unit 7402 incorporated in the housing 7401.
  • the mobile phone 7400 has a secondary battery 7407.
  • the secondary battery of one aspect of the present invention for the secondary battery 7407, it is possible to provide a lightweight and long-life mobile phone.
  • a protection circuit for preventing overcharging and / or overdischarging of the secondary battery 7407 may be electrically connected to the secondary battery 7407.
  • FIG. 29B shows a state in which the mobile phone 7400 is curved.
  • the secondary battery 7407 provided inside the mobile phone 7400 is also bent. Further, the state of the bent secondary battery 7407 at that time is shown in FIG. 29C.
  • the secondary battery 7407 is a thin storage battery.
  • the secondary battery 7407 is fixed in a bent state.
  • the secondary battery 7407 has a lead electrode electrically connected to the current collector.
  • the current collector is a copper foil, which is partially alloyed with gallium to improve the adhesion to the active material layer in contact with the current collector, and the reliability of the secondary battery 7407 in a bent state is improved. It has a high composition.
  • FIG. 29D shows an example of a bangle type display device.
  • the portable display device 7100 includes a housing 7101, a display unit 7102, an operation button 7103, and a secondary battery 7104.
  • a protection circuit for preventing overcharging and / or overdischarging of the secondary battery 7104 may be electrically connected to the secondary battery 7104.
  • FIG. 29E shows the state of the bent secondary battery 7104. When the secondary battery 7104 is attached to the user's arm in a bent state, the housing is deformed and the curvature of a part or the whole of the secondary battery 7104 changes.
  • the degree of bending at an arbitrary point of the curve is expressed by the value of the radius of the corresponding circle, which is called the radius of curvature, and the reciprocal of the radius of curvature is called the curvature.
  • a part or all of the main surface of the housing or the secondary battery 7104 changes within the range of the radius of curvature of 40 mm or more and 150 mm or less. High reliability can be maintained as long as the radius of curvature on the main surface of the secondary battery 7104 is in the range of 40 mm or more and 150 mm or less.
  • FIG. 29F shows an example of a wristwatch-type mobile information terminal.
  • the mobile information terminal 7200 includes a housing 7201, a display unit 7202, a band 7203, a buckle 7204, an operation button 7205, an input / output terminal 7206, and the like.
  • the mobile information terminal 7200 can execute various applications such as mobile phones, e-mails, text viewing and creation, music playback, Internet communication, and computer games.
  • the display unit 7202 is provided with a curved display surface, and can display along the curved display surface. Further, the display unit 7202 is provided with a touch sensor and can be operated by touching the screen with a finger or a stylus. For example, the application can be started by touching the icon 7207 displayed on the display unit 7202.
  • the operation button 7205 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 7205 can be freely set by the operating system incorporated in the mobile information terminal 7200.
  • the mobile information terminal 7200 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 information terminal 7200 is provided with an input / output terminal 7206, and data can be directly exchanged with another information terminal via a connector. It is also possible to charge via the input / output terminal 7206. The charging operation may be performed by wireless power supply without going through the input / output terminal 7206.
  • the display unit 7202 of the portable information terminal 7200 has a secondary battery of one aspect of the present invention.
  • the secondary battery of one aspect of the present invention it is possible to provide a lightweight and long-life portable information terminal.
  • a protection circuit for preventing overcharging and / or overdischarging of the secondary battery may be electrically connected to the secondary battery.
  • the secondary battery 7104 shown in FIG. 29E can be incorporated in a curved state inside the housing 7201 or in a bendable state inside the band 7203.
  • the mobile information terminal 7200 has a sensor.
  • a human body sensor such as a fingerprint sensor, a pulse sensor, or a body temperature sensor, a touch sensor, a pressure sensor, an acceleration sensor, or the like is preferably mounted.
  • FIG. 29G shows an example of an armband-shaped display device.
  • the display device 7300 has a display unit 7304 and has a secondary battery according to an aspect of the present invention.
  • a protection circuit for preventing overcharging and / or overdischarging of the secondary battery may be electrically connected to the secondary battery.
  • the display device 7300 can be provided with a touch sensor in the display unit 7304, and can also function as a portable information terminal.
  • the display surface of the display unit 7304 is curved, and display can be performed along the curved display surface. Further, the display device 7300 can change the display status by communication standard short-range wireless communication or the like.
  • the display device 7300 is provided with an input / output terminal, and data can be directly exchanged with another information terminal via a connector. It can also be charged via the input / output terminals.
  • the charging operation may be performed by wireless power supply without going through the input / output terminals.
  • the secondary battery of one aspect of the present invention as the secondary battery of the display device 7300, it is possible to provide a lightweight and long-life display device.
  • FIGS. 29H, 30 and 31 An example of mounting a secondary battery having good cycle characteristics according to one aspect of the present invention in an electronic device will be described with reference to FIGS. 29H, 30 and 31.
  • the secondary battery of one aspect of the present invention as the secondary battery in the electronic device, it is possible to provide a lightweight and long-life product.
  • daily electronic devices include electric toothbrushes, electric shavers, electric beauty devices, etc.
  • the secondary batteries of these products are compact and lightweight, with a stick-shaped shape in consideration of user-friendliness.
  • a large-capacity secondary battery is desired.
  • FIG. 29H is a perspective view of a device also called a cigarette-accommodating smoking device (electronic cigarette).
  • the electronic cigarette 7500 is composed of an atomizer 7501 including a heating element, a secondary battery 7504 for supplying electric power to the atomizer, and a cartridge 7502 including a liquid supply bottle or a sensor.
  • a protection circuit for preventing overcharging and / or overdischarging of the secondary battery 7504 may be electrically connected to the secondary battery 7504.
  • the secondary battery 7504 shown in FIG. 29H has an external terminal so that it can be connected to a charging device.
  • the secondary battery 7504 becomes the tip portion when it is held, it is desirable that the total length is short and the weight is light. Since the secondary battery of one aspect of the present invention has a high capacity and good cycle characteristics, it is possible to provide a compact and lightweight electronic cigarette 7500 that can be used for a long period of time.
  • FIGS. 30A and 30B show an example of a tablet terminal that can be folded in half.
  • the tablet-type terminal 7600 shown in FIGS. 30A and 30B has a housing 7630a, a housing 7630b, a movable portion 7640 connecting the housing 7630a and the housing 7630b, a display unit 7631 having a display unit 7631a and a display unit 7631b, and a switch 7625. It has a switch 7627, a fastener 7629, and an operation switch 7628.
  • FIG. 30A shows a state in which the tablet-type terminal 7600 is open
  • FIG. 30B shows a state in which the tablet-type terminal 7600 is closed.
  • the tablet type terminal 7600 has a storage body 7635 inside the housing 7630a and the housing 7630b.
  • the power storage body 7635 passes through the movable portion 7640 and is provided over the housing 7630a and the housing 7630b.
  • the display unit 7631 can use all or part of the area as the touch panel area, and can input data by touching an image, characters, an input form, or the like including an icon displayed in the area.
  • a keyboard button may be displayed on the entire surface of the display unit 7631a on the housing 7630a side, and information such as characters and images may be displayed on the display unit 7631b on the housing 7630b side.
  • the keyboard may be displayed on the display unit 7631b on the housing 7630b side, and information such as characters and images may be displayed on the display unit 7631a on the housing 7630a side.
  • the keyboard display switching button on the touch panel may be displayed on the display unit 7631, and the keyboard may be displayed on the display unit 7631 by touching the button with a finger or a stylus.
  • touch input can be simultaneously performed on the touch panel area of the display unit 7631a on the housing 7630a side and the touch panel area of the display unit 7631b on the housing 7630b side.
  • the switch 7625 to the switch 7627 may be not only an interface for operating the tablet terminal 7600 but also an interface capable of switching various functions.
  • at least one of the switch 7625 to the switch 7627 may function as a switch for switching the power of the tablet terminal 7600 on and off.
  • at least one of the switch 7625 to the switch 7627 may have a function of switching the display direction such as vertical display or horizontal display, or a function of switching between black and white display and color display.
  • at least one of the switch 7625 to the switch 7627 may have a function of adjusting the brightness of the display unit 7631.
  • the brightness of the display unit 7631 can be optimized according to the amount of external light during use detected by the optical sensor built in the tablet terminal 7600.
  • the tablet terminal 7600 may incorporate not only an optical sensor but also other detection devices such as a gyro, an acceleration sensor, and other sensors that detect tilt.
  • FIG. 30A shows an example in which the display areas of the display unit 7631a on the housing 7630a side and the display unit 7631b on the housing 7630b side are almost the same, but the display areas of the display unit 7631a and the display unit 7631b are particularly different. It is not limited, and one size and the other size may be different, and the display quality may be different. For example, one may be a display panel capable of displaying a higher definition than the other.
  • FIG. 30B shows a tablet-type terminal 7600 closed in half, and the tablet-type terminal 7600 has a charge / discharge control circuit 7634 including a housing 7630, a solar cell 7633, and a DCDC converter 7636. Further, as the storage body 7635, a secondary battery according to one aspect of the present invention is used.
  • the housing 7630a and the housing 7630b can be folded so as to overlap each other when not in use. By folding, the display unit 7631 can be protected, so that the durability of the tablet terminal 7600 can be enhanced. Further, since the storage body 7635 using the secondary battery of one aspect of the present invention has a high capacity and good cycle characteristics, it is possible to provide a tablet-type terminal 7600 that can be used for a long time over a long period of time. In order to enhance safety, a protection circuit for preventing overcharging and / or overdischarging of the secondary battery included in the storage body 7635 may be electrically connected to the secondary battery.
  • the tablet-type terminal 7600 shown in FIGS. 30A and 30B displays various information (still images, moving images, text images, etc.), a calendar, a date, a time, and the like on the display unit. It can have a function, a touch input function for touch input operation or editing of information displayed on a display unit, a function for controlling processing by various software (programs), and the like.
  • Electric power can be supplied to a touch panel, a display unit, a video signal processing unit, or the like by a solar cell 7633 mounted on the surface of the tablet terminal 7600.
  • the solar cell 7633 can be provided on one side or both sides of the housing 7630, and can be configured to efficiently charge the power storage body 7635. If a lithium ion battery is used as the power storage body 7635, there is an advantage that the size can be reduced.
  • FIG. 30C shows the solar cell 7633, the storage body 7635, the DCDC converter 7636, the converter 7637, the switch SW1 to the switch SW3, and the display unit 7631, and the storage body 7635, the DCDC converter 7636, the converter 7637, the switch SW1 to the switch SW3. Is the location corresponding to the charge / discharge control circuit 7634 shown in FIG. 30B.
  • the electric power generated by the solar cell is stepped up or down by the DCDC converter 7636 so as to be a voltage for charging the storage body 7635. Then, when the power from the solar cell 7633 is used for the operation of the display unit 7631, the switch SW1 is turned on, and the converter 7637 boosts or lowers the voltage required for the display unit 7631. Further, when the display is not performed on the display unit 7631, the switch SW1 may be turned off and the switch SW2 may be turned on to charge the power storage body 7635.
  • the storage body 7635 is charged by another power generation means such as a piezoelectric element (piezo element) or a thermoelectric conversion element (Peltier element) without particular limitation. It may be a configuration.
  • a non-contact power transmission module that wirelessly (non-contactly) transmits and receives power for charging, or a configuration performed in combination with other charging means may be used.
  • FIG. 31 shows an example of another electronic device.
  • the display device 8000 is an example of an electronic device using the secondary battery 8004 according to one aspect of the present invention.
  • the display device 8000 corresponds to a display device for receiving TV broadcasts, and includes a housing 8001, a display unit 8002, a speaker unit 8003, a secondary battery 8004, and the like.
  • a protection circuit for preventing overcharging and / or overdischarging of the secondary battery 8004 may be electrically connected to the secondary battery 8004.
  • the secondary battery 8004 according to one aspect of the present invention is provided inside the housing 8001.
  • the display device 8000 can be supplied with electric power from a commercial power source, or can use the electric power stored in the secondary battery 8004. Therefore, even when the power cannot be supplied from the commercial power supply due to a power failure or the like, the display device 8000 can be used by using the secondary battery 8004 according to one aspect of the present invention as an uninterruptible power supply.
  • the display unit 8002 includes a liquid crystal display device, a light emitting device having a light emitting element such as an organic EL element in each pixel, an electrophoresis display device, a DMD (Digital Micromirror Device), a PDP (Plasma Display Panel), and a FED (Field Emission Display). ), Etc., a semiconductor display device can be used.
  • a liquid crystal display device a light emitting device having a light emitting element such as an organic EL element in each pixel
  • an electrophoresis display device a DMD (Digital Micromirror Device), a PDP (Plasma Display Panel), and a FED (Field Emission Display).
  • Etc. a semiconductor display device can be used.
  • the display device includes all information display devices such as those for receiving TV broadcasts, those for personal computers, and those for displaying advertisements.
  • the stationary lighting device 8100 is an example of an electronic device using the secondary battery 8103 according to one aspect of the present invention.
  • the lighting device 8100 includes a housing 8101, a light source 8102, a secondary battery 8103, and the like.
  • a protection circuit for preventing overcharging and / or overdischarging of the secondary battery 8103 may be electrically connected to the secondary battery 8103.
  • FIG. 31 illustrates a case where the secondary battery 8103 is provided inside the ceiling 8104 in which the housing 8101 and the light source 8102 are installed, but the secondary battery 8103 is provided inside the housing 8101. It may have been done.
  • the lighting device 8100 can be supplied with electric power from a commercial power source, or can use the electric power stored in the secondary battery 8103. Therefore, even when the power cannot be supplied from the commercial power supply due to a power failure or the like, the lighting device 8100 can be used by using the secondary battery 8103 according to one aspect of the present invention as an uninterruptible power supply.
  • FIG. 31 illustrates a stationary lighting device 8100 provided on the ceiling 8104
  • the secondary battery according to one aspect of the present invention includes, for example, a side wall 8105, a floor 8106, a window 8107, etc., other than the ceiling 8104. It can be used for a stationary lighting device provided in the above, or it can be used for a tabletop lighting device or the like.
  • an artificial light source that artificially obtains light by using electric power can be used.
  • an incandescent lamp, a discharge lamp such as a fluorescent lamp, an LED, and / or a light emitting element such as an organic EL element can be mentioned as an example of the artificial light source.
  • the air conditioner having the indoor unit 8200 and the outdoor unit 8204 is an example of an electronic device using the secondary battery 8203 according to one aspect of the present invention.
  • the indoor unit 8200 has a housing 8201, an air outlet 8202, a secondary battery 8203, and the like.
  • a protection circuit for preventing overcharging and / or overdischarging of the secondary battery 8203 may be electrically connected to the secondary battery 8203.
  • FIG. 31 illustrates the case where the secondary battery 8203 is provided in the indoor unit 8200, the secondary battery 8203 may be provided in the outdoor unit 8204. Alternatively, the secondary battery 8203 may be provided in both the indoor unit 8200 and the outdoor unit 8204.
  • the air conditioner can be supplied with electric power from a commercial power source, or can use the electric power stored in the secondary battery 8203.
  • the secondary battery 8203 when the secondary battery 8203 is provided in both the indoor unit 8200 and the outdoor unit 8204, the secondary battery 8203 according to one aspect of the present invention is provided even when power cannot be supplied from a commercial power source due to a power failure or the like.
  • the air conditioner can be used by using the power supply as an uninterruptible power supply.
  • FIG. 31 illustrates a separate type air conditioner composed of an indoor unit and an outdoor unit
  • the integrated air conditioner having the functions of the indoor unit and the outdoor unit in one housing is used.
  • the secondary battery according to one aspect of the present invention can also be used.
  • the electric refrigerator / freezer 8300 is an example of an electronic device using the secondary battery 8304 according to one aspect of the present invention.
  • the electric freezer / refrigerator 8300 has a housing 8301, a refrigerator door 8302, a freezer door 8303, a secondary battery 8304, and the like.
  • a protection circuit for preventing overcharging and / or overdischarging of the secondary battery 8304 may be electrically connected to the secondary battery 8304.
  • the secondary battery 8304 is provided inside the housing 8301.
  • the electric refrigerator-freezer 8300 can be supplied with electric power from a commercial power source, or can use the electric power stored in the secondary battery 8304. Therefore, even when the power cannot be supplied from the commercial power source due to a power failure or the like, the electric refrigerator-freezer 8300 can be used by using the secondary battery 8304 according to one aspect of the present invention as an uninterruptible power supply.
  • high-frequency heating devices such as microwave ovens and electronic devices such as electric rice cookers require high electric power in a short time. Therefore, by using the secondary battery according to one aspect of the present invention as an auxiliary power source for assisting the electric power that cannot be covered by the commercial power source, it is possible to prevent the breaker of the commercial power source from tripping when the electronic device is used. ..
  • the power usage rate the ratio of the amount of power actually used (called the power usage rate) to the total amount of power that can be supplied by the commercial power supply source.
  • the secondary battery 8304 can be used as an auxiliary power source to keep the daytime power usage rate low.
  • the cycle characteristics of the secondary battery can be improved and the reliability can be improved. Further, according to one aspect of the present invention, it is possible to obtain a high-capacity secondary battery, thereby improving the characteristics of the secondary battery, and thus reducing the size and weight of the secondary battery itself. can. Therefore, by mounting the secondary battery, which is one aspect of the present invention, in the electronic device described in the present embodiment, it is possible to obtain an electronic device having a longer life and a lighter weight.
  • FIG. 32A shows an example of a wearable device.
  • Wearable devices use a secondary battery as a power source.
  • a wearable device that can be used not only for wired charging but also for wireless charging, where the connector to be connected is exposed, in order to improve splash-proof, water-resistant, or dust-proof performance when the user uses it in daily life or outdoors. Is desired.
  • the secondary battery according to one aspect of the present invention can be mounted on the spectacle-type device 9000 as shown in FIG. 32A.
  • the spectacle-type device 9000 has a frame 9000a and a display unit 9000b.
  • a protection circuit for preventing overcharging and / or overdischarging of the secondary battery may be electrically connected to the secondary battery.
  • the headset type device 9001 can be equipped with a secondary battery which is one aspect of the present invention.
  • the headset-type device 9001 has at least a microphone unit 9001a, a flexible pipe 9001b, and an earphone unit 9001c.
  • a secondary battery can be provided in the flexible pipe 9001b or in the earphone portion 9001c.
  • a protection circuit for preventing overcharging and / or overdischarging of the secondary battery may be electrically connected to the secondary battery.
  • the secondary battery which is one aspect of the present invention can be mounted on the device 9002 which can be directly attached to the body.
  • the secondary battery 9002b can be provided in the thin housing 9002a of the device 9002.
  • a protection circuit for preventing overcharging and / or overdischarging of the secondary battery 9002b may be electrically connected to the secondary battery 9002b.
  • the secondary battery which is one aspect of the present invention can be mounted on the device 9003 which can be attached to clothes.
  • the secondary battery 9003b can be provided in the thin housing 9003a of the device 9003.
  • a protection circuit for preventing overcharging and / or overdischarging of the secondary battery 9003b may be electrically connected to the secondary battery 9003b.
  • the secondary battery which is one aspect of the present invention can be mounted on the belt type device 9006.
  • the belt-type device 9006 has a belt portion 9006a and a wireless power supply receiving portion 9006b, and a secondary battery can be mounted inside the belt portion 9006a.
  • a protection circuit for preventing overcharging and / or overdischarging of the secondary battery may be electrically connected to the secondary battery.
  • a secondary battery which is one aspect of the present invention, can be mounted on the wristwatch type device 9005.
  • the wristwatch-type device 9005 has a display unit 9005a and a belt unit 9005b, and a secondary battery can be provided on the display unit 9005a or the belt unit 9005b.
  • a protection circuit for preventing overcharging and / or overdischarging of the secondary battery may be electrically connected to the secondary battery.
  • the display unit 9005a can display not only the time but also various information such as an incoming mail and / or a telephone call.
  • the wristwatch type device 9005 is a wearable device that is directly wrapped around the wrist, it may be equipped with a sensor that measures the user's pulse, blood pressure, and the like. It is possible to manage the health by accumulating data on the amount of exercise and health of the user.
  • FIG. 32B shows a perspective view of the wristwatch-type device 9005 removed from the arm.
  • FIG. 32C shows a state in which the secondary battery 913 according to one aspect of the present invention is built in the inside.
  • the secondary battery 913 is provided at a position overlapping the display unit 9005a, and is compact and lightweight.
  • FIG. 33A shows an example of a cleaning robot.
  • the cleaning robot 9300 has a display unit 9302 arranged on the upper surface of the housing 9301, a plurality of cameras 9303 arranged on the side surface, a brush 9304, an operation button 9305, a secondary battery 9306, various sensors, and the like.
  • a protection circuit for preventing overcharging and / or overdischarging of the secondary battery 9306 may be electrically connected to the secondary battery 9306.
  • the cleaning robot 9300 is provided with tires, suction ports, and the like.
  • the cleaning robot 9300 is self-propelled, can detect dust 9310, and can suck dust from a suction port provided on the lower surface.
  • the cleaning robot 9300 can analyze the image taken by the camera 9303 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 9304 such as wiring is detected by image analysis, the rotation of the brush 9304 can be stopped.
  • the cleaning robot 9300 includes a secondary battery 9306 according to an aspect of the present invention, and a semiconductor device or an electronic component inside the cleaning robot 9300. By using the secondary battery 9306 according to one aspect of the present invention for the cleaning robot 9300, the cleaning robot 9300 can be made into a highly reliable electronic device with a long operating time.
  • FIG. 33B shows an example of a robot.
  • the robot 9400 shown in FIG. 33B includes a secondary battery 9409, an illuminance sensor 9401, a microphone 9402, an upper camera 9403, a speaker 9404, a display unit 9405, a lower camera 9406 and an obstacle sensor 9407, a moving mechanism 9408, an arithmetic unit, and the like.
  • a protection circuit for preventing overcharging and / or overdischarging of the secondary battery 9409 may be electrically connected to the secondary battery 9409.
  • the microphone 9402 has a function of detecting the user's voice, environmental sound, and the like. Further, the speaker 9404 has a function of emitting sound. The robot 9400 can communicate with the user by using the microphone 9402 and the speaker 9404.
  • the display unit 9405 has a function of displaying various information.
  • the robot 9400 can display the information desired by the user on the display unit 9405.
  • the display unit 9405 may be equipped with a touch panel. Further, the display unit 9405 may be a removable information terminal, and by installing the display unit 9405 at a fixed position of the robot 9400, charging and data transfer are possible.
  • the upper camera 9403 and the lower camera 9406 have a function of photographing the surroundings of the robot 9400. Further, the obstacle sensor 9407 can detect the presence or absence of an obstacle in the traveling direction when the robot 9400 moves forward by using the moving mechanism 9408. The robot 9400 can recognize the surrounding environment and move safely by using the upper camera 9403, the lower camera 9406 and the obstacle sensor 9407.
  • the robot 9400 includes a secondary battery 9409 according to one aspect of the present invention, and a semiconductor device or an electronic component inside the robot 9400.
  • the secondary battery according to one aspect of the present invention for the robot 9400, the robot 9400 can be made into a highly reliable electronic device having a long operating time.
  • FIG. 33C shows an example of a flying object.
  • the flying object 9500 shown in FIG. 33C has a propeller 9501, a camera 9502, a secondary battery 9503, and the like, and has a function of autonomously flying.
  • a protection circuit for preventing overcharging and / or overdischarging of the secondary battery 9503 may be electrically connected to the secondary battery 9503.
  • the image data taken by the camera 9502 is stored in the electronic component 9504.
  • the electronic component 9504 can analyze the image data and detect the presence or absence of an obstacle when moving. Further, the remaining battery level can be estimated from the change in the storage capacity of the secondary battery 9503 by the electronic component 9504.
  • the flying object 9500 includes a secondary battery 9503 according to an aspect of the present invention inside the flying object 9500. By using the secondary battery according to one aspect of the present invention for the flying object 9500, the flying object 9500 can be made into a highly reliable electronic device having a long operating time.
  • This embodiment can be implemented in combination with other embodiments as appropriate.
  • each embodiment can be appropriately combined with the configurations shown in other embodiments to form one aspect of the present invention. Further, when a plurality of configuration examples are shown in one embodiment, the configuration examples can be appropriately combined.
  • the content described in one embodiment is another content (may be a part of the content) described in the embodiment, and / or one or more. It is possible to apply, combine, or replace the contents described in another embodiment (some contents may be used).
  • figure (which may be a part) described in one embodiment is another part of the figure, another figure (which may be a part) described in the embodiment, and / or one or more.
  • figures (which may be a part) described in another embodiment of the above more figures can be formed.
  • the components are classified by function and shown as blocks independent of each other.
  • it is difficult to separate the components for each function and there may be a case where a plurality of functions are involved in one circuit or a case where one function is involved in a plurality of circuits. Therefore, the blocks in the block diagram are not limited to the components described in the specification, and can be appropriately paraphrased according to the situation.
  • the size, the thickness of the layer, or the area is shown in an arbitrary size for convenience of explanation. Therefore, it is not necessarily limited to that scale. It should be noted that the drawings are schematically shown for the sake of clarity, and are not limited to the shapes or values shown in the drawings. For example, it is possible to include variations in the signal, voltage, or current due to noise, or variations in the signal, voltage, or current due to timing deviation.
  • electrode and “wiring” do not functionally limit these components.
  • an “electrode” may be used as part of a “wiring” and vice versa.
  • the terms “electrode” and “wiring” may be used when a plurality of “electrodes”, a plurality of “wiring”, or a plurality of “electrodes” and a plurality of “wiring” are integrally formed. include.
  • voltage and potential can be paraphrased as appropriate.
  • the voltage is a potential difference from a reference potential.
  • the reference potential is a ground voltage
  • the voltage can be paraphrased as a potential.
  • the ground potential does not always mean 0V.
  • the potential is relative, and the potential given to the wiring or the like may be changed depending on the reference potential.
  • a switch is a switch that is in a conducting state (on state) or a non-conducting state (off state) and has a function of controlling whether or not a current flows.
  • the switch means a switch having a function of selecting and switching a path through which a current flows.
  • the channel length means, for example, in the top view of a transistor, a region or a channel where a semiconductor (or a part where a current flows in the semiconductor when the transistor is on) and a gate overlap is formed.
  • the distance between the source and the drain in the area means, for example, in the top view of a transistor, a region or a channel where a semiconductor (or a part where a current flows in the semiconductor when the transistor is on) and a gate overlap is formed. The distance between the source and the drain in the area.
  • the channel width is a source in, for example, a region where a semiconductor (or a portion where a current flows in a semiconductor when a transistor is on) and a gate electrode overlap, or a region where a channel is formed.
  • a and B are connected includes those in which A and B are directly connected and those in which they are electrically connected.
  • the fact that A and B are electrically connected means that when an object having some kind of electrical action exists between A and B, it is possible to exchange electric signals between A and B. It means what is said.
  • a secondary battery according to one aspect of the present invention was produced and evaluated.
  • the positive electrode active material was prepared with reference to the manufacturing method shown in 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 prepared as X1 sources in the same manner as in step S20a, and lithium fluoride and magnesium fluoride were mixed by the solid phase method in the same manner as in step S31.
  • the number of atoms of cobalt was 100, the amount of lithium fluoride was added so that the number of molecules was 0.33 and the number of molecules of magnesium fluoride was 1. As in step S32, this was the mixture 903.
  • step S33 it was annealed in the same manner as in step S33.
  • 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 and aluminum hydroxide were added to the heated composite oxide as step S51 and mixed dry.
  • the number of atoms of cobalt was 100
  • the number of atoms of nickel was 0.5
  • the number of atoms of aluminum was 0.5. This was designated as a mixture 904.
  • step S33 it was annealed in the same manner as in step S33.
  • 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 the flow was performed during heating.
  • the annealing temperature was 850 ° C. for 10 hours.
  • a positive electrode was prepared using the positive electrode active material prepared above.
  • PVDF polyvinylidene fluoride
  • NMP is used as a solvent.
  • the prepared slurry was applied to a current collector to volatilize the solvent.
  • the press was performed at 120 ° C. at 120 kN / m to form a positive electrode active material layer on the current collector to prepare a positive electrode.
  • a 20 ⁇ m thick aluminum foil was used as the current collector.
  • the positive electrode active material layer was provided on one side of the current collector.
  • the loading amount was approximately 10 mg / cm 2 .
  • a negative electrode was prepared using graphite as the negative electrode active material.
  • the degree of polymerization of CMC-Na used was 600 to 800, and the viscosity of the aqueous solution when used as a 1 weight% aqueous solution was in the range of 300 mPa ⁇ s to 500 mPa ⁇ s.
  • VGCF registered trademark
  • -H manufactured by Showa Denko KK, fiber diameter 150 nm, specific surface area 13 m 2 / g
  • fiber diameter 150 nm specific surface area 13 m 2 / g
  • Each of the prepared slurries was applied to a current collector and dried to prepare a negative electrode active material layer on the current collector.
  • a copper foil having a thickness of 18 ⁇ m was used as a current collector.
  • the negative electrode active material layer was provided on both sides or one side of the current collector. The loading amount was approximately 9 mg / cm 2 .
  • a polyimide with a thickness of 23 ⁇ m was used for the separator.
  • one negative electrode having a negative electrode active material layer formed on both sides and two positive electrodes having a positive electrode active material layer formed on one side were prepared.
  • the positive electrode active material layers were arranged so as to face each other with the separator sandwiched between the negative electrode active material layers formed on both sides of the negative electrode.
  • one negative electrode having a negative electrode active material layer formed on one side and one positive electrode having a positive electrode active material layer formed on one side were prepared.
  • the negative electrode active material layer and the positive electrode active material layer were arranged so as to face each other with the separator in between.
  • Leads were joined to the positive electrode and the negative electrode respectively.
  • the laminated body in which the positive electrode, the negative electrode and the separator were laminated was sandwiched between the exterior bodies bent in half, and the laminated body was arranged so that one end of the lead was exposed to the outside of the exterior body. Next, one side of the exterior body was left as an open portion, and the other side was sealed.
  • the film to be the exterior body a film in which a polypropylene layer, an acid-modified polypropylene layer, an aluminum layer, and a nylon layer were laminated in this order was used.
  • the thickness of the film was about 110 n ⁇ m.
  • the film to be the exterior body was bent so that the nylon layer was arranged on the surface arranged on the outside as the exterior body and the polypropylene layer was arranged on the surface arranged on the inside.
  • the thickness of the aluminum layer was about 40 ⁇ m
  • the thickness of the nylon layer was about 25 ⁇ m
  • the total thickness of the polypropylene layer and the acid-modified polypropylene layer was about 45 ⁇ m.
  • electrolytic solution A Two types of electrolytic solutions (hereinafter, electrolytic solution A and electrolytic solution B) were prepared.
  • Electrolyte A was prepared.
  • EMI-FSA represented by the structural formula (G11) was used as the solvent for the electrolytic solution.
  • LiFSA lithium bis (fluorosulfonyl) amide
  • concentration of the lithium salt with respect to the electrolytic solution was 2.15 mol / L.
  • the secondary battery was manufactured by the above process.
  • the secondary battery was sandwiched between two plates, CC charging with a capacity of 15 mAh / g was performed at 0.01 C, rest was performed for 10 minutes, and CC charging with a capacity of 105 mAh / g was performed at 0.1 C. .. Then, the two plates were removed and held at 0 ° C. for 24 hours, and then one side of the exterior body was cut and opened in an argon atmosphere, the gas was released, and resealing was performed.
  • the area of the positive electrode active material layer on the positive electrode was set to 20.493 cm 2 .
  • the amount of the negative electrode active material carried on the negative electrode in each battery cell was adjusted so that the capacity ratio was approximately 75% or more and 85% or less.
  • the capacity ratio is a value indicating the positive electrode capacity with respect to the negative electrode capacity as a percentage.
  • the negative electrode capacity was set to 330 mAh / g based on the weight of the negative electrode active material.
  • the amount of the negative electrode active material supported was calculated by dividing the total amount of the supported negative electrode active material layers in half when the negative electrode active material layers were provided on both sides of the current collector.
  • the areas of the positive electrode and the negative electrode were the same.
  • a cycle test was conducted in an environment of 0 ° C, 25 ° C, 45 ° C, 60 ° C and -20 ° C.
  • Charging was performed at CCCV (0.2C, termination current 0.1C, 4.5V) and discharging was performed at CC (0.2C, 3.0V) in an environment of 0 ° C.
  • the capacity of the secondary battery was calculated based on the weight of the positive electrode active material.
  • the C rate was calculated with 1C as 210 mA / g (per weight of the positive electrode active material) in the secondary battery using the electrolytic solution A.
  • 1C was calculated as 210 mA / g (per weight of the positive electrode active material).
  • the results of the cycle characteristics are shown in FIG. 34A.
  • the initial discharge capacity was 161.3 mAh / g in the electrolytic solution A and 145.5 mAh / g in the electrolytic solution B.
  • Charging was performed at CCCV (0.2C, termination current 0.1C, 4.5V) and discharging was performed at CC (0.2C, 3.0V) in an environment of 25 ° C.
  • the capacity of the secondary battery was calculated based on the weight of the positive electrode active material.
  • the C rate was calculated with 1C as 210 mA / g (per weight of the positive electrode active material) in the secondary battery using the electrolytic solution A.
  • 1C was calculated as 210 mA / g (per weight of the positive electrode active material).
  • the results of the cycle characteristics are shown in FIG. 34B.
  • the maximum value of the discharge capacity in the cycle test was 205.1 mAh / g in the electrolytic solution A and 195.0 mAh / g in the electrolytic solution B.
  • Charging was performed at CCCV (0.5C, termination current 0.2C, 4.5V) and discharging was performed at CC (0.5C, 3.0V) in an environment of 45 ° C.
  • the capacity of the secondary battery was calculated based on the weight of the positive electrode active material.
  • the C rate was calculated with 1C as 210 mA / g (per weight of the positive electrode active material) in the secondary battery using the electrolytic solution A.
  • 1C was calculated as 210 mA / g (per weight of the positive electrode active material).
  • the results of the cycle characteristics are shown in FIG. 35A.
  • the maximum value of the discharge capacity in the cycle test was 201.8 mAh / g in the electrolytic solution A and 201.0 mAh / g in the electrolytic solution B.
  • Charging was performed at CCCV (0.5C, termination current 0.2C, 4.5V) and discharging was performed at CC (0.5C, 3.0V) in an environment of 60 ° C.
  • the capacity of the secondary battery was calculated based on the weight of the positive electrode active material.
  • the C rate was calculated with 1C as 210 mA / g (per weight of the positive electrode active material) in the secondary battery using the electrolytic solution A.
  • 1C was calculated as 210 mA / g (per weight of the positive electrode active material).
  • the results of the cycle characteristics are shown in FIG. 35B.
  • the maximum value of the discharge capacity in the cycle test was 197.2 mAh / g in the electrolytic solution A and 213.9 mAh / g in the electrolytic solution B.
  • Charging was performed at CCCV (0.1C, termination current 0.05C, 4.5V) and discharging was performed at CC (0.1C, 3.0V) in an environment of ⁇ 20 ° C.
  • the capacity of the secondary battery was calculated based on the weight of the positive electrode active material.
  • the C rate was calculated with 1C as 210 mA / g (per weight of the positive electrode active material) in the secondary battery using the electrolytic solution A.
  • 1C was calculated as 210 mA / g (per weight of the positive electrode active material).
  • the results of the cycle characteristics are shown in FIG.
  • the maximum value of the discharge capacity in the cycle test was 112.0 mAh / g in the electrolytic solution A and 87.2 mAh / g in the electrolytic solution B.
  • the secondary battery produced in Example 1 and subjected to a charge / discharge cycle of 150 cycles or more at 60 ° C. was disassembled, and the positive electrode and the negative electrode were observed.
  • a SU8030 manufactured by Hitachi High-Tech was used, and the acceleration voltage was set to 1 kV.
  • the cross section was exposed and observed by processing by ion milling.
  • FIG. 37A shows a cross-sectional SEM photograph of the negative electrode of the secondary battery using the electrolytic solution A.
  • FIG. 37A it was observed that the negative electrode active material layer 905a having graphite 991a was provided on the current collector 904a.
  • An enlarged view of the portion of the square frame 992a shown in FIG. 37A is shown in FIG. 37B
  • an enlarged view of the portion of the frame 993a is shown in FIG. 37C
  • an enlarged view of the portion of the frame 994a is shown in FIG. 37D
  • an enlarged view of the portion of the frame 995a is shown. It is shown in FIG. 37E, respectively.
  • FIG. 38A shows a cross-sectional SEM photograph of the negative electrode of the secondary battery using the electrolytic solution B.
  • FIG. 38A it was observed that the negative electrode active material layer 905b having graphite 991b was provided on the current collector 904b.
  • An enlarged view of the portion of the square frame 992b shown in FIG. 38A is shown in FIG. 38B
  • an enlarged view of the portion of the frame 993b is shown in FIG. 38C
  • an enlarged view of the portion of the frame 994b is shown in FIG. 38D
  • an enlarged view of the portion of the frame 995b is shown. It is shown in FIG. 38E, respectively.
  • EDX analysis was performed at point d2 shown in FIG. 38E.
  • EDX was analyzed at the points shown in the figure. The acceleration voltage at the time of analysis was set to 5 kV.
  • Carbon, nitrogen, oxygen, fluorine and sulfur were detected in the EDX analysis of points a1, b1, c1 and d1. Further, in the EDX analysis of points a1, b1, c1 and d1, magnesium, aluminum and cobalt were below the lower limit of detection. Further, in the EDX analysis of points b1, c1 and d1, copper was detected, and at point a1, copper was below the lower limit of detection. Copper can result from current collectors.
  • Carbon, oxygen, fluorine and phosphorus were detected in the EDX analysis of points a2, b2, c2 and d2.
  • nitrogen, magnesium and aluminum were below the lower limit of detection.
  • copper was detected in the EDX analysis at point d2, and copper was below the lower limit of detection at points a2, b2 and c2. Copper can result from current collectors.
  • Cobalt was also detected in the EDX analysis of points a2, b2 and c2. Further, at point d2, cobalt was below the lower limit of detection. It is suggested that the cobalt detected at points a2, b2 and c2 is due to the cobalt eluted from the positive electrode active material.
  • FIG. 39 shows the thickness of the coating and the cobalt concentration detected by EDX in each measurement region. The thickness of the coating film was measured at 5 points, and the average value was calculated.
  • FIG. 40 shows an SEM photograph.
  • FIG. 40A shows an SEM observation image of the positive electrode of the secondary battery using the electrolytic solution A
  • FIG. 40B shows an SEM observation image of the positive electrode of the secondary battery using the electrolytic solution B.
  • FIG. 40C shows an enlarged view of the region shown by the square frame in FIG. 40A
  • FIG. 40D shows an enlarged view of the region shown by the square frame in FIG. 40B.
  • FIGS. 40C and 40D it was found that the number of pits was small in the positive electrode of the secondary battery using the electrolytic solution A. This suggests that in the configuration of the secondary battery of one aspect of the present invention using the ionic liquid as the electrolytic solution, the elution of cobalt was suppressed and the generation of pits could be suppressed.
  • Positive electrode active material particles 52: Concave, 53: Barrier film, 54: Pit, 55: Crystal plane, 56: Barrier film, 57: Crack, 58: Pit, 100: Positive electrode active material, 130: Laminated body, 131 : Laminated body, 400: Negative electrode active material, 401: Region, 401a: Region, 401b: Region, 402: Region, 500: Secondary battery, 501: Positive electrode current collector, 502: Positive electrode active material layer, 503: Positive electrode, 504: Negative electrode current collector, 505: Negative electrode active material layer, 506: Negative electrode, 507: Separator, 507a: Region, 507b: Region, 508: Electrolyte, 509: Exterior body, 509a: Exterior body, 509b: Exterior body, 510 : Positive electrode lead electrode, 511: Negative electrode lead electrode 512: Laminated body, 513: Resin layer, 514: Region, 515a: Electrolyte, 515b: Electrolyte, 515c:

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