WO2022090862A1 - セパレータおよび二次電池、ならびにセパレータの作製方法 - Google Patents

セパレータおよび二次電池、ならびにセパレータの作製方法 Download PDF

Info

Publication number
WO2022090862A1
WO2022090862A1 PCT/IB2021/059588 IB2021059588W WO2022090862A1 WO 2022090862 A1 WO2022090862 A1 WO 2022090862A1 IB 2021059588 W IB2021059588 W IB 2021059588W WO 2022090862 A1 WO2022090862 A1 WO 2022090862A1
Authority
WO
WIPO (PCT)
Prior art keywords
secondary battery
separator
positive electrode
less
active material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/IB2021/059588
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
荻田香
石谷哲二
吉富修平
田中文子
村椿将太郎
小國哲平
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Semiconductor Energy Laboratory Co Ltd
Original Assignee
Semiconductor Energy Laboratory Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Semiconductor Energy Laboratory Co Ltd filed Critical Semiconductor Energy Laboratory Co Ltd
Priority to CN202180072598.3A priority Critical patent/CN116457997A/zh
Priority to US18/029,779 priority patent/US20240097278A1/en
Priority to KR1020237017332A priority patent/KR20230096010A/ko
Priority to JP2022558372A priority patent/JP7813717B2/ja
Publication of WO2022090862A1 publication Critical patent/WO2022090862A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/52—Separators
    • 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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/443—Particulate material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the uniform state of the present invention relates to a product, a method, or a manufacturing method.
  • the invention relates to a process, machine, manufacture, or composition (composition of matter).
  • One aspect of the present invention relates to a semiconductor device, a display device, a light emitting device, a power storage device, a lighting device, an electronic device, or a method for manufacturing the same.
  • the electronic device refers to all devices having a power storage device, and the electro-optical device having the power storage device, the information terminal device having the power storage device, and the like are all electronic devices.
  • a power storage device refers to an element and a device having a power storage function in general.
  • a power storage device also referred to as a secondary battery
  • a lithium ion secondary battery such as a lithium ion secondary battery, a lithium ion capacitor, an electric double layer capacitor, and the like.
  • Lithium-ion secondary batteries which have particularly high output and high energy density, are portable information terminals such as mobile phones, smartphones, or notebook computers, portable music players, digital cameras, medical devices, or hybrid vehicles (HVs), and electric vehicles.
  • HVs hybrid vehicles
  • EVs electric vehicles
  • PSVs plug-in hybrid vehicles
  • Improvement of the separator is being considered in order to improve the thermal, electrochemical safety, and performance of the lithium-ion secondary battery at the same time.
  • Patent Document 1 discloses a method for producing a composite porous separator membrane having an organic substance and an inorganic substance.
  • One aspect of the present invention is to provide a secondary battery with less deterioration. Alternatively, one aspect of the present invention is to provide a highly safe secondary battery. Alternatively, one aspect of the present invention is to provide a separator having excellent properties. Alternatively, one aspect of the present invention is to provide a separator that realizes a highly safe secondary battery. Alternatively, one aspect of the present invention is to provide a novel separator. Another object of the present invention is to provide a method for producing a separator that realizes a highly safe secondary battery. Alternatively, one aspect of the present invention is an object to provide a method for producing a novel separator.
  • One aspect of the present invention is a separator in which a polymer porous membrane and a layer having a ceramic-based material containing metal oxide fine particles are laminated, and the film thickness of the layer having a ceramic-based material is 1 ⁇ m or more and 100 ⁇ m or less.
  • one aspect of the present invention is a separator having a layer having a ceramic-based material having a density of 0.1 g / cm 3 or more and 2 g / cm 3 or less.
  • one aspect of the present invention is a separator in which the porosity of the polymer porous membrane is 20% by volume or more and 90% by volume or less.
  • one aspect of the present invention is a separator in which the weight per unit area of the porous polymer membrane is 4 g / m 2 or more and 20 g / m 2 or less, preferably 5 g / m 2 or more and 12 g / m 2 or less. ..
  • one aspect of the present invention is a separator containing one or more of magnesium oxide, aluminum oxide, titanium oxide, silicon oxide, magnesium hydroxide, aluminum hydroxide, and titanium hydroxide in the metal oxide fine particles.
  • one aspect of the present invention is a separator in which magnesium hydroxide is contained in the metal oxide fine particles.
  • one aspect of the present invention is a separator having an average particle size of metal oxide fine particles of 0.01 ⁇ m or more and 50 ⁇ m or less.
  • one aspect of the present invention is a separator in which a layer having a ceramic-based material is in contact with one surface of a polymer porous membrane.
  • one aspect of the present invention is a separator in which a polymer porous membrane and a layer having a plurality of ceramic-based materials containing metal oxide fine particles are laminated, and the layer having a plurality of ceramic-based materials is a polymer porous membrane. It is a separator having a thickness of 1 ⁇ m or more and 100 ⁇ m or less, and a polymer porous film having a thickness of 4 ⁇ m or more and 50 ⁇ m or less.
  • one aspect of the present invention is a separator having a layer having a ceramic-based material having a density of 0.1 g / cm 3 or more and 2 g / cm 3 or less.
  • one aspect of the present invention is a separator in which the porosity of the polymer porous membrane is 20% by volume or more and 90% by volume or less.
  • one aspect of the present invention is a separator in which the weight per unit area of the porous polymer membrane is 4 g / m 2 or more and 20 g / m 2 or less, preferably 5 g / m 2 or more and 12 g / m 2 or less. Is.
  • one aspect of the present invention is a separator containing one or more of magnesium oxide, aluminum oxide, titanium oxide, silicon oxide, magnesium hydroxide, aluminum hydroxide, and titanium hydroxide in the metal oxide fine particles.
  • one aspect of the present invention is a separator in which magnesium hydroxide is contained in the metal oxide fine particles.
  • one aspect of the present invention is a separator having an average particle size of metal oxide fine particles of 0.01 ⁇ m or more and 50 ⁇ m or less.
  • one aspect of the present invention is a separator in which a layer having a ceramic-based material is in contact with one surface of a polymer porous membrane.
  • one aspect of the present invention is a secondary battery having a positive electrode, a negative electrode, the separator described above sandwiched between the positive electrode and the negative electrode, and an electrolyte.
  • the electrolyte is arranged inside the pores of the polymer porous membrane.
  • one aspect of the present invention is a first step of mixing a ceramic material containing metal oxide fine particles with a first solvent to prepare a first mixture, a first mixture, and a first binder.
  • the second step of mixing the second solvent to make the second mixture and the second step of mixing the second mixture, the second binder, and the third solvent to make the third mixture.
  • the polymer porous membrane coated with the third mixture is more preferably heated at 60 ° C. or higher and 200 ° C. or lower and dried.
  • the porosity of the polymer porous membrane refers to the ratio of the volume of the pores occupying the polymer porous membrane.
  • the porosity of the layer having the ceramic material refers to the ratio of the volume of the pores occupying the layer having the ceramic material. Density can be determined from thickness, weight, and area.
  • the porosity of the layer having a ceramic material is, for example, 50% by volume or more.
  • a secondary battery with less deterioration Further, according to one aspect of the present invention, it is possible to provide a highly safe secondary battery. Further, according to one aspect of the present invention, it is possible to provide a separator having excellent properties. Further, according to one aspect of the present invention, it is possible to provide a separator that realizes a highly safe secondary battery. Further, according to one aspect of the present invention, a novel separator can be provided. Further, according to one aspect of the present invention, it is possible to provide a method for producing a separator that realizes a highly safe secondary battery. Further, according to one aspect of the present invention, it is possible to provide a method for producing a novel separator.
  • FIG. 1A to 1D are examples of cross-sectional views of a secondary battery.
  • 2A to 2D are examples of cross-sectional views of the secondary battery.
  • FIG. 3 is a flow chart showing an example of a method for producing a separator coated with a ceramic material.
  • FIG. 4 is a diagram showing a method for producing a material.
  • FIG. 5 is an example of a process cross-sectional view showing one aspect of the present invention.
  • FIG. 6 is a diagram illustrating the crystal structure of the positive electrode active material.
  • FIG. 7 is a diagram illustrating the crystal structure of the positive electrode active material.
  • 8A and 8B are views showing an example of the appearance of the secondary battery.
  • 9A and 9B are diagrams illustrating a method for manufacturing a secondary battery.
  • FIGS. 10A and 10B are diagrams illustrating a method for manufacturing a secondary battery.
  • FIG. 11 is a diagram showing an example of the appearance of the secondary battery.
  • FIG. 12 is a top view showing an example of a secondary battery manufacturing apparatus.
  • FIG. 13 is a cross-sectional view showing an example of a method for manufacturing a secondary battery.
  • 14A to 14C are perspective views showing an example of a method for manufacturing a secondary battery.
  • 14D is a cross-sectional view corresponding to FIG. 14C.
  • 15A to 15F are perspective views showing an example of a method for manufacturing a secondary battery.
  • FIG. 16 is a cross-sectional view showing an example of a secondary battery.
  • FIG. 17A is a diagram showing an example of a secondary battery.
  • 17B and 17C are views showing an example of a method for producing a laminated body.
  • 18A to 18C are diagrams showing an example of a method for manufacturing a secondary battery.
  • 19A and 19B are cross-sectional views showing an example of a laminated body.
  • FIG. 19C is a cross-sectional view showing an example of a secondary battery.
  • 20A and 20B are diagrams showing an example of a secondary battery.
  • FIG. 20C is a diagram showing the inside of the secondary battery.
  • 21A to 21C are views showing an example of a secondary battery.
  • FIG. 22A is a perspective view showing an example of a battery pack.
  • FIG. 22B is a block diagram showing an example of a battery pack.
  • FIG. 22C is a block diagram showing an example of a vehicle having a motor.
  • 23A to 23E are views showing an example of a transportation vehicle.
  • 24A is a diagram showing an electric bicycle
  • FIG. 24B is a diagram showing a secondary battery of the electric bicycle
  • FIG. 24C is a diagram illustrating an electric motorcycle.
  • 25A and 25B are diagrams showing an example of a power storage device.
  • 26A to 26E are views showing an example of an electronic device.
  • 27A to 27H are diagrams illustrating an example of an electronic device.
  • 28A to 28C are diagrams illustrating an example of an electronic device.
  • FIG. 29 is a diagram illustrating an example of an electronic device.
  • 30A to 30C are diagrams illustrating an example of an electronic device.
  • 31A to 31C are diagrams showing an example of an electronic device.
  • FIG. 32 is a diagram showing the measurement results of the cobalt solution concentration by the atomic absorption spectroscopy.
  • 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.
  • the surface layer portion of the particles of the active material or the like is preferably, for example, a region within 50 nm, more preferably 35 nm or less, still more preferably 20 nm or less from the surface.
  • 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 of the composite oxide containing lithium and the transition metal is the space group R-3m, and although it is not a spinel type crystal structure, ions such as cobalt and magnesium are contained.
  • 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 at random 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 Li 0.06 NiO 2 , but it is simply pure lithium cobalt oxide or a layered rock salt type positive electrode containing a large amount of cobalt. It is known that active materials usually do not 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 angle formed by the repetition of the bright line and the dark line between the crystals is ⁇ 5 degrees or less, more preferably ⁇ 2.5 degrees or less. You can observe the situation. In some cases, light elements such as oxygen and fluorine cannot be clearly observed in the TEM image, but in that case, the alignment of the metal elements can be used to determine the alignment.
  • the theoretical capacity of the positive electrode active material means the amount of electricity when all the lithium that can be inserted and removed from the positive electrode active material is desorbed.
  • the theoretical capacity of LiCoO 2 is 274 mAh / g
  • the theoretical capacity of LiNiO 2 is 274 mAh / g
  • the theoretical capacity of LiMn 2 O 4 is 148 mAh / g.
  • discharge completed as used herein means a state in which the voltage is 2.5 V (vs.
  • the discharge voltage drops sharply by the time the discharge voltage reaches 2.5 V, so it is assumed that the discharge is completed under the above conditions.
  • a non-equilibrium phase change means a phenomenon that causes a non-linear change in a physical quantity.
  • an unbalanced phase change occurs before and after the peak in the dQ / dV curve obtained by differentiating the capacitance (Q) with the voltage (V) (dQ / dV), and the crystal structure changes significantly. ..
  • 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 discharge rate is the relative ratio of the current at the time of discharge to the battery capacity, and is expressed in the unit C.
  • the current corresponding to 1C is X (A).
  • X (A) When discharged with a current of 2X (A), it is said to be discharged at 2C, and when discharged with a current of X / 5 (A), it is said to be discharged at 0.2C.
  • the charging rate is also the same.
  • When charged with a current of 2X (A) it is said to be charged with 2C, and when charged with a current of X / 5 (A), it is charged with 0.2C. It is said that it was.
  • Constant current charging refers to, for example, a method of charging with a constant charging rate.
  • Constant voltage charging refers to, for example, a method of charging by keeping the voltage constant when the charging reaches the upper limit voltage.
  • the constant current discharge refers to, for example, a method of discharging with a constant discharge rate.
  • the 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 503 has a positive electrode active material layer 502 and a positive electrode current collector 501, and the positive electrode active material layer 502 has a positive electrode active material 561, a conductive auxiliary material, and a binder.
  • FIG. 1B is an enlarged view of the region 502a of the positive electrode active material layer 502, and shows an example in which acetylene black 553 and graphene 554 are used as the conductive auxiliary agents. The details of the positive electrode will be described later.
  • 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 auxiliary agent, and a binder (not shown).
  • FIG. 1D is an enlarged view of the region 505a of the negative electrode active material layer 505, and shows an example in which acetylene black 556 and graphene 557 are used as the conductive auxiliary agents. The details of the negative electrode will be described later.
  • the binder for example, it is preferable to use a rubber material such as styrene-butadiene rubber (SBR), styrene-isoprene-styrene rubber, acrylonitrile-butadiene rubber, butadiene rubber, or ethylene-propylene-diene copolymer. Further, fluororubber can be used as the binder.
  • SBR styrene-butadiene rubber
  • fluororubber can be used as the binder.
  • a water-soluble polymer for example, a polysaccharide or the like can be used.
  • a polysaccharide for example, cellulose derivatives such as carboxymethyl cellulose (CMC), methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose and regenerated cellulose, starch and the like can be used. Further, it is more preferable to use these water-soluble polymers in combination with the above-mentioned rubber material.
  • the binder includes polystyrene, methyl polyacrylate, 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 a material having a particularly excellent viscosity adjusting effect with a rubber material.
  • a material having a particularly excellent viscosity adjusting effect for example, a water-soluble polymer may be used.
  • water-soluble polymer having a particularly excellent viscosity-adjusting effect examples include the above-mentioned polysaccharides such as carboxymethyl cellulose (CMC), methyl cellulose, ethyl cellulose, hydroxypropyl cellulose and diacetyl cellulose, cellulose derivatives such as regenerated cellulose, and starch. Can be used.
  • CMC carboxymethyl cellulose
  • methyl cellulose methyl cellulose
  • ethyl cellulose methyl cellulose
  • hydroxypropyl cellulose hydroxypropyl cellulose
  • diacetyl cellulose cellulose derivatives such as regenerated cellulose
  • starch starch
  • 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 Since the water-soluble polymer has a functional group, it easily adheres stably to the surface of active substances and the like. When the water-soluble polymer is adsorbed on the surface of the active material or the like, the particles of the active material or the like repel each other electrostatically, and the active material or the like can be stably dispersed.
  • many cellulose derivatives such as carboxymethyl cellulose have functional groups such as hydroxyl groups and carboxyl groups, and because they have functional groups, polymers interact with each other and exist widely covering the surface of the active material. It is expected that excessive decomposition of the electrolytic solution will be suppressed.
  • the binder that covers the surface of the active material or is in contact with the surface forms a film
  • it is expected to play a role as a passivation film and suppress the decomposition of the electrolytic solution.
  • a passivation film is formed on the surface of the active material, decomposition of the electrolytic solution can be suppressed at the battery reaction potential.
  • 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 auxiliary 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. ..
  • the positive electrode current collector 501 and the negative electrode current collector 504 metals such as stainless steel, gold, platinum, zinc, iron, copper, aluminum, and titanium, and alloys thereof and the like, which are highly conductive and are alloyed with carrier ions such as lithium.
  • a material that does not change can be used.
  • 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.
  • the graphene or 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, the volume of the active material occupied in the positive electrode or the negative electrode can be increased. It is possible to increase the capacity of the secondary battery.
  • 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 or the like can be used 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, 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.
  • FIG. 1C1 shows an enlarged view of the region 507a 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.
  • FIG. 1C2 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 on the positive electrode side and the surface layer portion of the surface on the negative electrode side.
  • 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 polymer film having polypropylene, polyethylene or the like is coated with a ceramic material, a fluorine material, a polyamide material, or a mixture thereof can be used.
  • an oxide having a metal or a hydroxide can be used as the ceramic material.
  • the oxide or hydroxide having a metal for example, magnesium oxide, titanium oxide, aluminum oxide, silicon oxide, magnesium hydroxide, aluminum hydroxide, titanium hydroxide and the like can be used.
  • the titanium oxide either a material having a rutile type structure or a material having an anatase type structure can be used, but a material having an anatase type structure may be more preferable.
  • the metal oxide that can be used as a ceramic material may be fine particles.
  • coating of the ceramic material on the polymer film for example, coating with particles, coating with a thin film, or the like can be adopted.
  • fluorine-based material for example, PVdF, polytetrafluoroethylene, or the like can be used.
  • polyamide-based material for example, nylon, aramid (meth-based aramid, para-based aramid) and the like can be used.
  • the oxidation resistance is improved, so that deterioration of the separator during high voltage charging / discharging can be suppressed and the reliability of the secondary battery can be improved.
  • the separator and the electrode are easily brought into close contact with each other, and the output characteristics can be improved.
  • the polymer film is coated with a polyamide-based material, particularly aramid, the heat resistance is improved, so that the safety of the secondary battery can be improved.
  • the surface area of the ceramic material is preferably, for example, 10 m 2 / g or more.
  • the specific surface area can be measured by a gas adsorption method or the like.
  • both sides of a film having polypropylene may be coated with a mixed material of one or more ceramic materials selected from magnesium hydroxide and titanium oxide and a binder such as PVdF.
  • the surface of the polypropylene film in contact with the positive electrode is coated with a mixed material of one or more ceramic materials selected from magnesium hydroxide and titanium oxide and a binder such as PVdF, and the surface in contact with the negative electrode is coated with a fluoromaterial.
  • FIG. 2A shows a separator 507 having a polymer porous membrane 521 and a layer 522 having a ceramic-based material coated with the polymer porous membrane 521.
  • the polymer porous membrane 521 is made of a membrane similar to the polymer membrane 581 with holes shown in FIG. 1C1.
  • FIG. 2C1 shows an enlarged view of the region 521a as an example of the polymer porous membrane 521 of the separator 507. In this example, the same structure as the region 507a of the separator 507 shown in FIG. 1C1 is shown.
  • FIG. 2C2 shows an enlarged view of the region 521b as another example of the polymer porous membrane 521 of the separator 507. In this example, the same structure as the region 507b of the separator 507 shown in FIG. 1C2 is shown.
  • the safety of the secondary battery can be maintained even if the thickness of the entire separator is thin, so that the capacity per volume of the secondary battery can be increased.
  • ionic liquids are flame-retardant.
  • an ionic liquid is used as the electrolyte and the separator is impregnated with the ionic liquid, a secondary battery that is hard to burn can be realized.
  • the slurry can be prepared, for example, by mixing a ceramic-based material with a solvent and a binder. At this time, mixing may be carried out in a state of high viscosity. Kneading and mixing the materials in a highly viscous state is sometimes called kneading.
  • the binder the binder described in the preparation of the active material layer can be applied.
  • a ceramic material and a solvent are prepared.
  • a plurality of ceramic materials may be used in combination.
  • the solvent may be, for example, one or more of N-methylpyrrolidone (NMP), water, methanol, ethanol, acetone, tetrahydrofuran (THF), dimethylformamide (DMF), and dimethyl sulfoxide (DMSO).
  • NMP N-methylpyrrolidone
  • THF tetrahydrofuran
  • DMF dimethylformamide
  • DMSO dimethyl sulfoxide
  • Mixing may be performed using a kneader.
  • a kneading machine for example, a rotation / revolution mixer can be used.
  • step S22 the ceramic material prepared in step S21 and the solvent are kneaded to obtain a mixture in step S23.
  • step S24 a binder and a solvent are added to the mixture obtained in step S23, and they are kneaded in step S25 to obtain a mixture in step S26. Binders are preferably added in small portions to prevent agglomeration.
  • step S25 for example, kneading the mixture, binder, and solvent obtained in step S23 as a mixture having a solid content ratio of 50% or more and 80% or less is preferable because it can be mixed with high viscosity.
  • the solid content ratio refers to the ratio of solids (here, ceramic materials and binders) in the mixture.
  • step S27 a binder and a solvent are added to the mixture obtained in step S26, and they are kneaded in step S28 to obtain a slurry in step S29.
  • the solid content ratio of the prepared slurry is preferably 30%.
  • step S30 the prepared slurry is applied onto the polymer material.
  • a blade method, a printing method, or the like may be used for coating. Further, a continuous coating machine or the like may be used for coating.
  • step S31 a polymer material coated with the slurry can be obtained.
  • step S32 the solvent is evaporated from the slurry applied on the polymer material by a method such as ventilation drying or vacuum drying.
  • the solvent may be evaporated using, for example, warm air or hot air at 30 ° C. or higher and 160 ° C. or lower.
  • the atmosphere is not particularly limited.
  • a separator coated with a ceramic-based material can be produced in step S33.
  • the positive electrode active material examples include an olivine-type crystal structure, a layered rock salt-type crystal structure, and a composite oxide having a spinel-type crystal structure.
  • the positive electrode active material examples include compounds such as LiFePO 4 , LiFeO 2 , LiNiO 2 , LiMn 2 O 4 , V 2 O 5 , Cr 2 O 5 , and MnO 2 .
  • a lithium manganese composite oxide that can be represented by the composition formula Li a Mn b M c Od can be used.
  • the metal M a metal element selected from other than lithium and manganese, silicon, and phosphorus are preferably used, and nickel is more preferable.
  • the lithium manganese composite oxide refers to an oxide containing at least lithium and manganese, and includes chromium, cobalt, aluminum, nickel, iron, magnesium, molybdenum, zinc, indium, gallium, copper, titanium, niobium, and silicon. And at least one element selected from the group consisting of phosphorus and the like may be contained.
  • the positive electrode active material is repeatedly charged and discharged, a side reaction occurs in which a transition metal such as cobalt elutes into the electrolytic solution.
  • a transition metal such as cobalt
  • cobalt ions eluted from the positive electrode active material adhere to the surface of the negative electrode, and cobalt is deposited to thicken the film on the surface of the negative electrode.
  • the separator according to one aspect of the present invention can adsorb cobalt, it is expected that the concentration of cobalt eluted in the electrolytic solution can be reduced. Therefore, it is possible to suppress the thickening of the coating film on the negative electrode surface and suppress the deterioration of the secondary battery.
  • step S11 a composite oxide having lithium, a transition metal, and oxygen is used as the composite oxide 801.
  • a composite oxide having lithium, a transition metal and oxygen can be synthesized by heating a lithium source or a transition metal source in an oxygen atmosphere.
  • the transition metal source it is preferable to use a metal capable of forming a layered rock salt type composite oxide belonging to the space group R-3m together with lithium.
  • a metal capable of forming a layered rock salt type composite oxide belonging to the space group R-3m together with lithium for example, at least one of manganese, cobalt and nickel can be used.
  • aluminum may be used in addition to these transition metals. That is, as the transition metal source, only a cobalt source may be used, only a nickel source may be used, two types of a cobalt source and a manganese source, or two types of a cobalt source and a nickel source may be used.
  • the heating temperature at this time is preferably higher than that of step S17, which will be described later. For example, it can be performed at 1000 ° C. This heating process may be referred to as firing.
  • the main components of lithium, transition metals and composite oxides having oxygen, cobalt-containing materials and positive electrode active materials are lithium, cobalt, nickel, manganese, aluminum and oxygen, and elements other than the above main components are impurities.
  • the total impurity concentration is preferably 10,000 ppmw (parts per million weight) or less, and more preferably 5000 ppmw or less.
  • the total concentration of impurities of transition metals such as titanium and arsenic is preferably 3000 ppmw or less, and more preferably 1500 ppmw or less.
  • lithium cobalt oxide particles (trade name: CellSeed C-10N) manufactured by Nippon Chemical Industrial Co., Ltd. can be used as the pre-synthesized lithium cobalt oxide.
  • This has an average particle size (D50) of about 12 ⁇ m, and in impurity analysis by glow discharge mass spectrometry, magnesium concentration and fluorine concentration are 50 ppmw or less, calcium concentration, aluminum concentration and silicon concentration are 100 ppmw or less, and nickel concentration is 150 ppmw or less.
  • Lithium cobaltate having a sulfur concentration of 500 ppmw or less, an arsenic concentration of 1100 ppmw or less, and a concentration of other elements other than lithium, cobalt and oxygen of 150 ppmw or less.
  • the composite oxide 801 of step S11 preferably has a layered rock salt type crystal structure with few defects and strains. Therefore, it is preferable that the composite oxide has few impurities. High impurities in composite oxides with lithium, transition metals and oxygen are likely to result in defective or strained crystal structures.
  • fluoride 802 is prepared.
  • Fluoride includes lithium fluoride (LiF), magnesium fluoride (MgF 2 ), aluminum fluoride (AlF 3 ), titanium fluoride (TiF 4 ), cobalt fluoride (CoF 2 , CoF 3 ), and nickel fluoride.
  • the fluoride 802 may be any as long as it functions as a fluorine source.
  • Fluorine (F 2 ), Fluorocarbon, Sulfur Fluoride, Oxygen Fluoride (OF 2 , O 2 F 2 , O 3 F 2 , O 4 F 2 ). , O 2 F) and the like may be used and mixed in the atmosphere in the heating step described later.
  • the fluoride 802 is a compound having a metal X
  • it can also be used as a compound 803 (a compound having a metal X) described later.
  • LiF lithium fluoride
  • LiF is preferred because it has a cation in common with LiCoO 2 . Further, LiF has a relatively low melting point of 848 ° C. and is easily melted in the annealing step described later, which is preferable.
  • compound 803 is a compound having a metal X.
  • step S13 compound 803 is prepared.
  • a fluoride, an oxide, a hydroxide, or the like of the metal X can be used, and it is particularly preferable to use a fluoride.
  • magnesium when magnesium is used as the metal X, MgF 2 or the like can be used as the compound 803. Magnesium can be placed in high concentrations near the surface of the cobalt-containing material.
  • a material having a metal other than cobalt and a metal other than metal X may be mixed.
  • a material having a metal other than cobalt and having a metal other than metal X for example, a nickel source, a manganese source, an aluminum source, an iron source, a vanadium source, a chromium source, a niobium source, a titanium source and the like can be mixed.
  • step S11, step S12 and step S13 may be freely changed.
  • step S14 the materials prepared in steps S11, S12 and S13 are mixed and pulverized.
  • Mixing can be done dry or wet, but wet is preferred because it can be pulverized to a smaller size.
  • a solvent a ketone such as acetone, an alcohol such as ethanol and isopropanol, ether, dioxane, acetonitrile, N-methyl-2-pyrrolidone (NMP) and the like can be used. It is more preferable to use an aprotic solvent that does not easily react with lithium. In this embodiment, acetone is used.
  • a ball mill, a bead mill, or the like can be used for mixing.
  • a ball mill it is preferable to use, for example, zirconia balls as a medium. It is preferable that the mixing and pulverizing steps are sufficiently performed to atomize the mixture 804.
  • step S15 the material mixed and pulverized above is recovered, and in step S16, the mixture 804 is obtained.
  • D50 is preferably 600 nm or more and 20 ⁇ m or less, and more preferably 1 ⁇ m or more and 10 ⁇ m or less.
  • step S17 the mixture 804 is heat-treated (also referred to as annealing).
  • the heating temperature in step S17 is more preferably equal to or higher than the temperature at which the mixture 804 melts. Further, the heating temperature is preferably lower than the decomposition temperature (1130 ° C.) of LiCoO 2 .
  • a cobalt-containing material 808 having good cycle characteristics can be produced.
  • LiF and MgF 2 are used as the fluoride 802
  • the co-melting point of LiF and MgF 2 is around 742 ° C. Therefore, when the annealing temperature of S17 is 742 ° C. or higher, the reaction with LiCoO 2 is promoted and LiMO 2 is considered to be generated.
  • the annealing temperature is preferably 742 ° C or higher, more preferably 820 ° C or higher.
  • the annealing temperature is preferably 742 ° C or higher and 1130 ° C or lower, and more preferably 742 ° C or higher and 1000 ° C or lower. Further, 820 ° C. or higher and 1130 ° C. or lower are preferable, and 820 ° C. or higher and 1000 ° C. or lower are more preferable.
  • LiF which is a fluoride
  • the volume inside the heating furnace is larger than the volume of the container and lighter than oxygen, it is expected that LiF will volatilize and the production of LiMO 2 will be suppressed when the LiF in the mixture 804 decreases. Therefore, it is necessary to heat while suppressing the volatilization of LiF.
  • the annealing temperature is lowered to less than the decomposition temperature of LiCoO 2 (1130 ° C), specifically 742 ° C or higher and 1000 ° C or lower.
  • the temperature can be lowered to the above level, and the production of LiMO 2 can be efficiently promoted. Therefore, a cobalt-containing material having good properties can be produced, and the annealing time can be shortened.
  • FIG. 5 shows an example of the annealing method in S17.
  • the heating furnace 120 shown in FIG. 5 has a space inside the heating furnace 102, a hot plate 104, a heater portion 106, and a heat insulating material 108. It is more preferable to arrange the lid 118 on the container 116 and anneal it. With this configuration, the space 119 composed of the container 116 and the lid 118 can be filled with an atmosphere containing fluoride. During annealing, if the state is maintained by covering the space 119 so that the concentration of gasified fluoride is not constant or reduced, fluorine and magnesium can be contained in the vicinity of the particle surface. Since the space 119 has a smaller volume than the space 102 in the heating furnace, a small amount of fluoride volatilizes to create an atmosphere containing fluoride.
  • the reaction system can have a fluoride-containing atmosphere without significantly impairing the amount of fluoride contained in the mixture 804. Therefore, LiMO 2 can be efficiently generated. Further, by using the lid 118, the mixture 804 can be easily and inexpensively annealed in an atmosphere containing fluoride.
  • the valence of Co (cobalt) in LiCoO 2 produced according to one aspect of the present invention is approximately trivalent.
  • Cobalt can be divalent and trivalent. Therefore, in order to suppress the reduction of cobalt, the atmosphere of the heating furnace space 102 preferably contains oxygen, and the ratio of oxygen to nitrogen in the atmosphere of the heating furnace space 102 is more preferably equal to or higher than the atmosphere atmosphere. It is more preferable that the oxygen concentration in the atmosphere of the furnace space 102 is equal to or higher than the atmosphere. Therefore, it is necessary to introduce an atmosphere containing oxygen into the space inside the heating furnace.
  • all cobalt atoms do not have to be trivalent because a cobalt atom having a magnesium atom nearby may be more stable if it is divalent.
  • a step of creating an atmosphere containing oxygen and a step of installing a container 116 containing the mixture 804 in the heating furnace space 102 are performed before heating.
  • the mixture 804 can be annealed in an atmosphere containing oxygen and fluoride.
  • the method of creating an atmosphere containing oxygen in the heating furnace space 102 is not particularly limited, but as an example, a method of introducing oxygen gas or a gas containing oxygen such as dry air after exhausting the heating furnace space 102, and Examples thereof include a method of inflowing oxygen gas or a gas containing oxygen such as dry air for a certain period of time. Above all, it is preferable to introduce oxygen gas (oxygen substitution) after exhausting the space 102 in the heating furnace.
  • the atmosphere in the heating furnace space 102 may be regarded as an atmosphere containing oxygen.
  • the annealing in step S17 is preferably performed at an appropriate temperature and time.
  • the appropriate temperature and time vary depending on the conditions such as the particle size and composition of the composite oxide 801 in step S11. Smaller particles may be more preferred at lower temperatures or shorter times than larger ones. It has a step of removing the lid after annealing S17.
  • the annealing time is preferably, for example, 3 hours or more, and more preferably 10 hours or more.
  • the annealing time is preferably, for example, 1 hour or more and 10 hours or less, and more preferably about 2 hours.
  • the temperature lowering time after annealing is preferably, for example, 10 hours or more and 50 hours or less.
  • step S18 the material annealed above is recovered, and in step S19, a cobalt-containing material 808 is obtained.
  • a material having a layered rock salt type crystal structure such as lithium cobalt oxide (LiCoO 2 ) has a high discharge capacity and is excellent as a positive electrode active material for a secondary battery.
  • Examples of the material having a layered rock salt type crystal structure include a composite oxide represented by LiMO 2 .
  • the metal M includes the metals listed above. Further, the metal M can further include the metal X mentioned above in addition to the metal mentioned above.
  • the positive electrode active material will be described with reference to FIGS. 6 and 7.
  • the positive electrode active material produced according to one aspect of the present invention can reduce the displacement of the CoO 2 layer in repeated charging and discharging of a high voltage. Furthermore, the change in volume can be reduced. Therefore, the compound can realize excellent cycle characteristics. In addition, the compound can have a stable crystal structure in a high voltage state of charge. Therefore, the compound may not easily cause a short circuit when it is maintained in a high voltage charge state. In such a case, safety is further improved, which is preferable.
  • the difference in crystal structure and the difference in volume per the same number of transition metal atoms between a fully discharged state and a state charged at a high voltage are small.
  • the positive electrode active material of one aspect of the present invention has lithium, the metal M mentioned above, oxygen, and titanium. Further, the positive electrode active material according to one aspect of the present invention preferably has a halogen such as fluorine or chlorine.
  • the concentration of the element such as metal M has a gradient in each region such as the surface layer portion, the inside, and the first region in the surface layer portion. That is, for example, at the boundary of each region, the concentration of each element does not change sharply, but changes with a gradient.
  • the metal M for example, aluminum, nickel, or the like can be used in addition to cobalt and magnesium.
  • aluminum and nickel each have, for example, a concentration gradient in each region, such as the surface layer, the interior, and the first region in the surface layer.
  • the positive electrode active material of one aspect of the present invention has a first region.
  • the first region includes a region inside the particle surface. Further, at least a part of the surface layer portion may be included in the first region.
  • the first region is preferably represented by a layered rock salt type structure, and the region is represented by the space group R-3m.
  • the first region is a region having lithium and metal M.
  • An example of the crystal structure before and after charging / discharging in the first region is shown in FIG.
  • the surface layer portion of the positive electrode active material of one aspect of the present invention has magnesium and oxygen in addition to or in place of the region represented by the layered rock salt type structure described in FIG. 6 and the like below, and the layered rock salt. It may have a crystal represented by a structure different from the mold structure.
  • 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. Therefore, this structure is referred to as an O3'type crystal structure in the present specification and the like.
  • lithium may 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. Further, in both the O3 type crystal structure and the O3'type crystal structure, it is preferable that magnesium is dilutely present between the CoO 2 layers, that is, in the lithium site. Further, halogens such as fluorine may be randomly and dilutely present at the oxygen sites.
  • 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 Li 0.06 NiO 2 , but is pure lithium cobalt oxide or a layered rock salt type positive electrode active material containing a large amount of cobalt. It is known that this crystal structure is not usually taken.
  • the change in the crystal structure when charging at a high voltage and a large amount of lithium is separated 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. 6, there is almost no deviation of the CoO2 layer in these crystal structures.
  • the first region has high structural stability even when the charging voltage is high.
  • a voltage of about 4.6 V with respect to the potential of the lithium metal results in an H1-3 type crystal structure
  • the positive electrode active material of one aspect of the present invention has a charging voltage of about 4.6 V.
  • the crystal structure of R-3m (O3) can be maintained.
  • Even at a higher charging voltage for example, a voltage of about 4.65 V to 4.7 V with respect to the potential of the lithium metal, the positive electrode active material of one aspect of the present invention can have an O3'type crystal structure.
  • H1-3 type crystals may finally be observed in the positive electrode active material of one aspect of the present invention.
  • the positive electrode active material of one embodiment 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.
  • the charging voltage is increased, for example, a region where the O3'type crystal structure can be obtained even 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'type crystal structure.
  • the crystal structure does not easily collapse even if charging and discharging are repeated at a high voltage.
  • the difference in volume per cobalt atom of the same number of O3 type crystal structures in the discharged state and the O3'type crystal structure is 2.5% or less, more specifically 2.2. % Or less.
  • 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 times 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 a value obtained by performing elemental analysis of the entire particles of the positive electrode active material using, for example, ICP-MS or the like, or may be a blending of raw materials in the process of producing the positive electrode active material. It may be based on the value of the ratio.
  • the average particle size (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 crystal structure of the positive electrode active material according to one aspect of the present invention is analyzed by XRD or the like. Further detailed analysis can be performed by using a combination of measurement such as XRD and other analysis methods.
  • 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. 7 is lithium cobalt oxide (LiCoO 2 ) to which the metal X is not added.
  • the crystal structure of lithium cobalt oxide shown in FIG. 7 changes as the occupancy rate x in Li x CoO 2 changes.
  • 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 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 O3'type crystal structure has an O3 structure compared to the H1-3 type structure. Indicates that the change from is small. It is more preferable to use which unit cell to express the crystal structure of the positive electrode active material. For example, in the Rietveld analysis of XRD, the GOF (goodness of fit) value should be selected to be smaller. Just do it.
  • the conventional lithium cobaltate When charging and discharging are repeated so that the occupancy rate x in Li x CoO 2 becomes 0.24 or less, the conventional lithium cobaltate has an H1-3 type crystal structure and R-3m (O3) in a discharged state.
  • the change in the crystal structure that is, the non-equilibrium phase change is repeated between the structure and the structure.
  • 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.
  • Niobium electrode active material for example, an alloy-based material, a carbon-based material, or the like can be used.
  • an element capable of performing a charge / discharge reaction by an alloying / dealloying reaction with lithium can be used.
  • a material containing at least one of silicon, tin, gallium, aluminum, germanium, lead, antimony, bismuth, silver, zinc, cadmium, indium and the like can be used.
  • Such elements have a larger capacity than carbon, and silicon in particular has a high theoretical capacity of 4200 mAh / g. Therefore, it is preferable to use silicon as the negative electrode active material. Further, a compound having these elements may be used.
  • an element capable of performing a charge / discharge reaction by an alloying / dealloying reaction with lithium, a compound having the element, and the like may be referred to as an alloy-based material.
  • SiO refers to, for example, silicon monoxide.
  • SiO can also be expressed as SiO x .
  • x preferably has a value of 1 or a value close to 1.
  • x is preferably 0.2 or more and 1.5 or less, and preferably 0.3 or more and 1.2 or less.
  • carbon-based material graphite, easily graphitizable carbon (soft carbon), non-graphitizable carbon (hard carbon), carbon nanotubes, graphene, carbon black, etc. may be used.
  • Examples of graphite include artificial graphite and natural graphite.
  • Examples of the artificial graphite include mesocarbon microbeads (MCMB), coke-based artificial graphite, pitch-based artificial graphite and the like.
  • MCMB mesocarbon microbeads
  • the artificial graphite spheroidal graphite having a spherical shape can be used.
  • MCMB may have a spherical shape, which is preferable.
  • MCMB is relatively easy to reduce its surface area and may be preferable.
  • Examples of natural graphite include scaly graphite and spheroidized natural graphite.
  • Graphite exhibits a potential as low as lithium metal when lithium ions are inserted into graphite (during the formation of a lithium-graphite intercalation compound) (0.05V or more and 0.3V or less vs. Li / Li + ).
  • the lithium ion secondary battery using graphite can exhibit a high operating voltage.
  • graphite is preferable because it has advantages such as relatively high capacity per unit volume, relatively small volume expansion, low cost, and high safety as compared with lithium metal.
  • titanium dioxide TIM 2
  • lithium titanium oxide Li 4 Ti 5 O 12
  • lithium-graphite interlayer compound Li x C 6
  • niobium pentoxide Nb 2 O 5
  • Oxides such as tungsten (WO 2 ) and molybdenum oxide (MoO 2 ) can be used.
  • Li 2.6 Co 0.4 N 3 shows a large charge / discharge capacity (900 mAh / g, 1890 mAh / cm 3 ) and is preferable.
  • lithium ions are contained in the negative electrode active material, so that it can be combined with materials such as V 2 O 5 and Cr 3 O 8 which do not contain lithium ions as the positive electrode active material, which is preferable. .. Even when a material containing lithium ions is used as the positive electrode active material, a double nitride of lithium and a transition metal can be used as the negative electrode active material by desorbing the lithium ions contained in the positive electrode active material in advance.
  • a material that causes a conversion reaction can also be used as a negative electrode active material.
  • a transition metal oxide that does not form an alloy with lithium such as cobalt oxide (CoO), nickel oxide (NiO), and iron oxide (FeO) may be used as the negative electrode active material.
  • oxides such as Fe 2 O 3 , CuO, Cu 2 O, RuO 2 , Cr 2 O 3 and sulfides such as CoS 0.89 , NiS and CuS, Zn 3 N 2 , Cu 3 N, Ge 3 N 4 , etc., sulphides such as NiP 2 , FeP 2 , CoP 3 , etc., and fluorides such as FeF 3 , BiF 3 etc. also occur.
  • the same material as the conductive auxiliary agent and the binder that the positive electrode active material layer can have can be used.
  • the negative electrode current collector preferably uses a material that does not alloy with carrier ions such as lithium.
  • electrolyte examples include ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate, chloroethylene carbonate, vinylene carbonate, ⁇ -butyrolactone, ⁇ -valerolactone, dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl.
  • EMC 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 and the like, or two or more of these can be used in any combination and ratio.
  • the electrolyte contains fluorine.
  • the electrolyte containing fluorine for example, an electrolyte having one or more kinds of fluorinated cyclic carbonates and lithium ions can be used.
  • the fluorinated cyclic carbonate can improve the nonflammability and enhance the safety of the lithium ion secondary battery.
  • fluorinated cyclic carbonate fluorinated ethylene carbonate
  • fluorinated ethylene carbonate for example, monofluoroethylene carbonate (fluoroethylene carbonate, FEC, F1EC), difluoroethylene carbonate (DFEC, F2EC), trifluoroethylene carbonate (F3EC), tetrafluoroethylene carbonate (F4EC) ) Etc.
  • DFEC has isomers such as cis-4,5 and trans-4,5. It is important to solvate lithium ions using one or more fluorinated cyclic carbonates as the electrolyte and transport them in the electrolyte contained in the electrode during charging and discharging in order to operate at a low temperature. If the fluorinated cyclic carbonate is contributed to the transport of lithium ions during charging and discharging rather than as a small amount of additive, it is possible to operate at a low temperature.
  • the desolvation energy required for the lithium ions solvated in the electrolyte contained in the electrode to enter the active material particles is reduced. If the energy of this desolvation can be reduced, lithium ions can be easily inserted into or desorbed from the active material particles even in a low temperature range. Lithium ions may move in a solvated state, but a hopping phenomenon may occur in which the coordinating solvent molecules are replaced. When it becomes easy to desolvate lithium ions, it becomes easy to move due to the hopping phenomenon, and it may become easy to move lithium ions.
  • a plurality of solvated lithium ions form clusters in the electrolyte and may move in the negative electrode, between the positive electrode and the negative electrode, in the positive electrode, and the like.
  • FEC Monofluoroethylene carbonate
  • Tetrafluoroethylene carbonate (F4EC) is represented by the following formula (2).
  • DFEC Difluoroethylene carbonate
  • Ionic liquids normally temperature molten salt
  • the internal region temperature rises due to an internal short circuit of the secondary battery, overcharging, or the like.
  • Ionic liquids consist of cations and anions, including organic cations and anions.
  • organic cation examples include aliphatic onium cations such as quaternary ammonium cations, tertiary sulfonium cations, and quaternary phosphonium cations, and aromatic cations such as imidazolium cations and pyridinium cations.
  • a monovalent amide anion a monovalent methide anion, a fluorosulfonic acid anion, a perfluoroalkyl sulfonic acid anion, a tetrafluoroborate anion, a perfluoroalkyl borate anion, a hexafluorophosphate anion, or a perfluoro Examples thereof include alkyl phosphate anions.
  • 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 4 or less carbon atoms
  • R 2 to R 4 independently represent a hydrogen atom or an alkyl group having 1 or more and 4 or less carbon atoms.
  • 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 . Examples of the substituent to be introduced include an alkyl group and an alkoxy group.
  • cation represented by the general formula (G1) 1-ethyl-3-methylimidazolium cation, 1-butyl-3-methylimidazolium cation, 1-methyl-3- (propoxyethyl) imidazolium cation, Examples thereof include 1-hexyl-3-methylimidazolium cation.
  • 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.
  • the cation represented by the general formula (G4) there is a 1-methyl-1-propylpyrrolidinium cation and the like.
  • 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.
  • the cation represented by the general formula (G5) there are N-methyl-N-propylpiperidinium cation, 1,3-dimethyl-1-propylpiperidinium cation and the like.
  • 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 the hexfluorophosphate anion and the 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 secondary battery of one aspect of the present invention is, for example, one of alkali metal ions such as sodium ion and potassium ion, and alkaline earth metal ions such as calcium ion, strontium ion, barium ion, beryllium ion and magnesium ion. It has the above as a carrier ion.
  • alkali metal ions such as sodium ion and potassium ion
  • alkaline earth metal ions such as calcium ion, strontium ion, barium ion, beryllium ion and magnesium ion. It has the above as a carrier ion.
  • the electrolyte contains a lithium salt.
  • Lithium salts include, for example, LiPF 6 , LiClO 4 , LiAsF 6 , LiBF 4 , LiAlCl 4 , LiSCN, LiBr, LiI, Li 2 SO 4 , Li 2 B 10 Cl 10 , Li CF 3 SO 3 , LiCF 3 SO 3 .
  • LiC 4 F 9 SO 3 , LiC (CF 3 SO 2 ) 3 , LiC (C 2 F 5 SO 2 ) 3 , LiN (CF 3 SO 2 ) 2 , LiN (C 4 F 9 SO 2 ) (CF 3 SO 2 ) ), LiN (C 2 F 5 SO 2 ) 2 , etc. can be used.
  • the electrolyte is a general term including a solid, liquid, or semi-solid electrolyte material.
  • Deterioration is likely to occur at the interface existing in the secondary battery, for example, the interface between the active material and the electrolyte.
  • an electrolyte having fluorine it is possible to prevent deterioration, typically alteration of the electrolyte or high viscosity of the electrolyte, which may occur at the interface between the active material and the electrolyte. Can be done. DFEC with two fluorine bonds and F4EC with four fluorine bonds have lower viscosities and weaker coordination bonds with lithium than FECs with one fluorine bond. Therefore, it is possible to reduce the adhesion of highly viscous decomposition products to the active material particles.
  • lithium ions If highly viscous decomposition products adhere to or cling to the active material particles, it becomes difficult for lithium ions to move at the interface of the active material particles.
  • an electrolyte having fluorine When lithium ions are solvated with an electrolyte having fluorine, the formation of decomposition products on the surface of the active material (positive electrode active material or negative electrode active material) is alleviated. Further, by using an electrolyte having fluorine, it is possible to prevent the generation and growth of dendrites by preventing the adhesion of decomposition products.
  • electrolyte having fluorine is used as a main component, and the electrolyte having fluorine is 5% by volume or more, 10% by volume or more, preferably 30% by volume or more and 100% by volume or less.
  • the main component of the electrolyte means that it is 5% by volume or more of the total electrolyte of the secondary battery. Further, 5% by volume or more of the total electrolyte of the secondary battery referred to here refers to the ratio of the total electrolyte measured at the time of manufacturing the secondary battery. In addition, when disassembling after manufacturing a secondary battery, it is difficult to quantify the proportion of each of the multiple types of electrolytes, but one type of organic compound accounts for 5% by volume or more of the total amount of electrolytes. It can be determined whether or not it exists.
  • an electrolyte having fluorine By using an electrolyte having fluorine, it is possible to realize a secondary battery that can operate in a wide temperature range, specifically, -40 ° C or higher and 150 ° C or lower, preferably -40 ° C or higher and 85 ° C or lower.
  • an additive such as vinylene carbonate, propane sultone (PS), tert-butylbenzene (TBB), lithium bis (oxalate) borate (LiBOB), or a dinitrile compound such as succinonitrile or adiponitrile is added to the electrolyte, it may be added. good.
  • concentration of the additive may be, for example, 0.1% by volume or more and less than 5% by volume with respect to the entire electrolyte.
  • the electrolyte may have one or more aprotic organic solvents such as ⁇ -butyrolactone, acetonitrile, dimethoxyethane, and tetrahydrofuran.
  • aprotic organic solvents such as ⁇ -butyrolactone, acetonitrile, dimethoxyethane, and tetrahydrofuran.
  • having a polymer material in which the electrolyte is gelled enhances safety against liquid leakage and the like.
  • Typical examples of the polymer material to be gelled include silicone gel, acrylic gel, acrylonitrile gel, polyethylene oxide gel, polypropylene oxide gel, and fluoropolymer gel.
  • the polymer material for example, a polymer having a polyalkylene oxide structure such as polyethylene oxide (PEO), PVdF, polyacrylonitrile and the like, and a copolymer containing them can be used.
  • a polymer having a polyalkylene oxide structure such as polyethylene oxide (PEO), PVdF, polyacrylonitrile and the like, and a copolymer containing them
  • PVdF-HFP which is a copolymer of PVdF and hexafluoropropylene (HFP)
  • the polymer material to be formed may have a porous shape.
  • a metal material such as aluminum and / or a resin material can be used. Further, a film-like exterior body can also be used.
  • a metal thin film having excellent flexibility such as aluminum, stainless steel, copper, and nickel is provided on a film made of a material such as polyethylene, polypropylene, polycarbonate, ionomer, and polyamide, and an exterior is further formed on the metal thin film.
  • a film having a three-layer structure provided with an insulating synthetic resin film such as a polyamide resin or a polyester resin can be used as the outer surface of the body.
  • This embodiment can be used in combination with other embodiments as appropriate.
  • the secondary battery 500 shown in FIGS. 8A and 8B 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.
  • FIG. 9A 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.
  • the negative electrode 506, the separator 507, and the positive electrode 503 are laminated.
  • 9B 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.
  • the laminated negative electrode 506, separator 507, and positive electrode 503 can also be referred to as a laminate composed 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. 8A was manufactured.
  • the secondary battery 500 shown in FIG. 8B 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. 11 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. 12 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 room 571 is a room for charging a positive electrode, a separator, a negative electrode, an exterior body, and the like into 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 placed on the stage 591 of the processing chamber 573, and then the positive electrode 503 is placed on the exterior body 509b (FIGS. 14A and 14B).
  • the electrolyte 515a is dropped from the nozzle 594 onto the positive electrode 503 (FIGS. 14C and 14D).
  • 14D is a cross section corresponding to the alternate long and short dating line AB in FIG. 14C.
  • 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.
  • 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. 15A).
  • the electrolyte 515b is dropped onto the separator 507 using the nozzle 594 (FIG. 15B).
  • the negative electrode 506 is placed on the separator 507 (FIG. 15C).
  • 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. 15D). After that, the laminated body 512 shown in FIG.
  • the 13 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. 15E and 15F).
  • 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. 11 shows an example in which the exterior body 509 is sealed on four sides (sometimes called a four-sided seal), as shown in FIGS. 8A and 8B, it is sealed on three sides (called a three-sided seal). In some cases).
  • a laminated secondary battery 600 can be manufactured.
  • FIG. 16 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. 16 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.
  • the 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. 17A 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, as shown in FIG. 16, 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 placed 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. 18B 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. 19C An example of a cross-sectional view of a secondary battery according to another aspect of the present invention is shown in FIG. 19C.
  • the secondary battery 560 shown in FIG. 19C is manufactured by using the laminated body 130 shown in FIG. 19A and the laminated body 131 shown in FIG. 19B.
  • the laminated body 130, the laminated body 131, and the separator 507 are excerpted and shown in order to clarify the figure.
  • 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. 20 and 21.
  • the secondary battery shown here can be called a winding type secondary battery or the like.
  • the secondary battery 913 shown in FIG. 20A 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. 20A 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. 21A may be used.
  • the winding body 950a shown in FIG. 21A 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. 22C 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. 22A.
  • FIG. 22A 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. 22B An example of the block diagram of the battery pack 1415 shown in FIG. 22A is shown in FIG. 22B.
  • 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 cutting off the current in response to an increase in temperature. Further, the control circuit unit 1320 has an external terminal 1325 (+ IN) and an external terminal 1326 ( ⁇ IN).
  • the switch unit 1324 can be configured by combining 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.
  • FIGS. 23A to 23E show transportation vehicles using the secondary battery of one aspect of the present invention.
  • the automobile 2001 shown in FIG. 23A 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.
  • When installing the secondary battery in the vehicle install the secondary battery in one or more places.
  • the vehicle 2001 shown in FIG. 23A has the battery pack 1415 shown in FIG. 22A.
  • 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. 23B 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. 23A 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. 23C 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. 23D shows, as an example, an aircraft 2004 having an engine that burns fuel. Since the aircraft 2004 shown in FIG. 23D has wheels for takeoff and landing, it can be said to be a part of a transportation vehicle, and is a battery including a secondary battery module configured by connecting a plurality of secondary batteries and a charge control device. It has a pack 2203.
  • 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. 23A 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. 23E 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. 23E, 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. 24A 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. 24A.
  • the power storage device 2102 shown in FIG. 24B 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. 24B 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 a 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 according to one aspect of the present invention can greatly contribute to the eradication of accidents such as fires caused by the secondary battery.
  • FIG. 24C is an example of a two-wheeled vehicle using a secondary battery according to one aspect of the present invention.
  • the scooter 2300 shown in FIG. 24C 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 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. 25A 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. 25B shows an example of a power storage device according to one aspect of the present invention.
  • a large power storage device 791 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. 26A 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, and a secondary battery 2806 is provided inside the housing 2802.
  • a protection circuit for preventing overcharging and / or overdischarging of the secondary battery 2807 may be electrically connected to the secondary battery 2807.
  • a touch panel is applied to the display unit 2803.
  • the personal computer 2800 can be used as a tablet terminal by removing the housing 2801 and the housing 2802 and using only 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. 26D, or the housing 2802 can be folded so that the display unit 2803 is on the outside as shown in FIG. 26E.
  • FIG. 27A 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. 27B 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. 27C.
  • 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. 27D 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. 27E 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. 27F 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. 27E 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. 27G 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. 27H, 28 and 29 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. 27H, 28 and 29.
  • 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. 27H 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. 27H 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. 28A and 28B show an example of a tablet terminal that can be folded in half.
  • the tablet-type terminal 7600 shown in FIGS. 28A and 28B 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. 28A shows a state in which the tablet-type terminal 7600 is open
  • FIG. 28B 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 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. 28A 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. 28B 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. 28A and 28B 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. 28C 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 shows 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. 28B.
  • 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. 29 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. 29 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. 29 illustrates the 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. 29 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. 29 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. 30A 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. 30A.
  • 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. 30B shows a perspective view of the wristwatch-type device 9005 removed from the arm.
  • FIG. 30C 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. 31A 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. 31B shows an example of a robot.
  • the robot 9400 shown in FIG. 31B 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. 31C shows an example of a flying object.
  • the flying object 9500 shown in FIG. 31C 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.
  • the powdered ceramic material was stirred in the cobalt solution and the concentration of the cobalt solution was measured.
  • a sample cell in which Li metal was immersed in an organic solvent and a sample cell in which a cobalt foil was immersed in an organic solvent were prepared.
  • Two cells were connected and a glass filter was provided between the cells.
  • the glass filter lithium ion conductive glass ceramics (LICGC) manufactured by OHARA Corporation was used.
  • the glass filter is provided to prevent the product produced by electrolysis from being reduced on the counter electrode side.
  • DC 3.6V was applied between the Li metal and the cobalt foil for 20 hours to prepare about 15 mL of a cobalt solution of about 50 ppm.
  • a cobalt solution was added to each ceramic material and stirred. Specifically, put the stirrer in each of 6 5 mL sample bottles, then magnesium oxide (MgO), magnesium hydroxide (Mg (OH) 2 ), alumina (Al 2 O 3 ), boehmite (AlOOH). , Rutyl-type titanium oxide (TiO 2 ), and anatase-type titanium oxide (about 30 mg each) were placed in separate sample bottles. These sample bottles were placed in a glove box, 2 mL of cobalt solution was added to each sample bottle, and the mixture was stirred at room temperature and 300 rpm for about 16 hours.
  • the sample bottle was taken out from the glove box.
  • the stirred suspension was filtered using a membrane filter and separated into a cobalt solution as a filtrate and a ceramic-based material as a filter.
  • the cobalt concentration in the cobalt solution separated from each ceramic material was measured with an atomic absorption spectrometer (ControlAA600, manufactured by Analytical Quiena). The measurement was performed twice for each cobalt-based material and the separated cobalt solution, and the average value was calculated. The measurement result is shown in FIG.
  • the obtained cobalt concentration was 32.55 ppm for the first time, 30.82 ppm for the second time, and 31.69 ppm on average.
  • the first time was 23.40 ppm
  • the second time was 26.72 ppm
  • the average value was 25.06 ppm.
  • the first time was 37.63 ppm
  • the second time was 40.27 ppm
  • the average value was 38.95 ppm.
  • the first time was 40.20 ppm
  • the second time was 43.18 ppm
  • the average value was 41.69 ppm.
  • the first time was 36.56 ppm
  • the second time was 34.59 ppm
  • the average value was 35.58 ppm.
  • the first time was 31.05 ppm
  • the second time was 31.07 ppm
  • the average value was 31.06 ppm.
  • the first time was 40.65 ppm
  • the second time was 41.40 ppm
  • the average value was 41.03 ppm.
  • the first time was 42.97 ppm
  • the second time was 42.40 ppm
  • the average value was 42.69 ppm.
  • a polypropylene separator coated with an MgO layer was produced.
  • the manufacturing method is as follows.
  • MgO was dispersed by first mixing MgO and NMP.
  • 0.2 g of an NMP solution containing 5 wt% PVdF was added to the obtained mixture, and the mixture was mixed by the kneader.
  • 4.24444 g of an NMP solution containing 5 wt% PVdF was added to the obtained mixture, and the mixture was mixed by the kneader.
  • the reason why PVdF was added little by little is to prevent the aggregation of PVdF.
  • the slurry was applied onto a polypropylene separator having a thickness of 20 ⁇ m using a coating device (applicator).
  • a coating device applicator
  • the distance between the coated portion (blade) of the coating device and the coated surface (surface of the polypropylene separator) was set to 40 ⁇ m
  • the coating speed was set to 10 mm / sec.
  • the polypropylene separator coated with the above slurry was dried at 80 ° C. for 30 minutes in a ventilation drying oven.
  • the film thickness of the MgO layer was measured using a micrometer.
  • the film thickness of the separator coated with the MgO layer was 45 ⁇ m to 60 ⁇ m, and the film thickness of the polypropylene separator was 20 ⁇ m. Therefore, the film thickness of the MgO layer was about 25 ⁇ m to 40 ⁇ m.
  • a polypropylene separator coated with two layers of Mg (OH) was produced.
  • the manufacturing method is as follows.
  • Mg (OH) 2 and 2 g of NMP were mixed at 2000 rpm for 3 minutes with a kneader (manufactured by Shinky Co., Ltd., rotating and revolving mixer Awatori Rentaro).
  • the average particle size of the two Mg (OH) particles used was about 7 ⁇ m.
  • a laser diffraction type particle size distribution measuring device (SALD-2200, manufactured by Shimadzu Corporation) was used to measure the average particle size of the two Mg (OH) particles.
  • SALD-2200 manufactured by Shimadzu Corporation
  • the slurry was applied onto a polypropylene separator having a thickness of 20 ⁇ m using a coating device (applicator).
  • a coating device applicator
  • the distance between the coated portion (blade) of the coating device and the coated surface (the surface of the polypropylene separator) was set to 30 ⁇ m, and the coating speed was set to 10 mm / sec.
  • the polypropylene separator coated with the above slurry was dried at 80 ° C. for 30 minutes in a ventilation drying oven.
  • the film thickness of the two layers of Mg (OH) was measured using a micrometer.
  • the film thickness of the separator coated with the two layers of Mg (OH) was 70 ⁇ m to 80 ⁇ m, and the film thickness of the polypropylene separator was 20 ⁇ m. Therefore, the film thickness of the two layers of Mg (OH) was 50 ⁇ m to 60 ⁇ m.
  • the density of the two layers of Mg (OH) was determined as follows. First, a polypropylene separator coated with two layers of Mg (OH) and a polypropylene separator not coated with two layers of Mg (OH) were punched into a circle with a diameter of 18 mm, and then the weight and film thickness were measured. The weight and film thickness of the polypropylene separator coated with the (OH) two layers were 9.271 mg and 75 ⁇ m, respectively, and the weight and film thickness of the polypropylene separator alone were 3.536 mg and 20 ⁇ m, respectively. Therefore, the weight and film thickness of the two layers of Mg (OH) are 5.735 mg and 55 ⁇ m, respectively.
  • the porosity of the two layers of Mg (OH) is a value obtained by dividing the density of the two layers of Mg (OH) by the density of the two layers of Mg (OH) when the porosity is 0 and subtracting it from 1.
  • the density of the two layers of Mg (OH) when the void ratio is 0 is determined to be 2300 mg / cm 3 because the densities of Mg (OH) 2 and PVdF as substances are 2360 mg / cm 3 and 1780 mg / cm 3 , respectively. .. Therefore, the porosity of the two layers of Mg (OH) was about 82.2% by volume.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Ceramic Engineering (AREA)
  • Composite Materials (AREA)
  • Cell Separators (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
PCT/IB2021/059588 2020-10-26 2021-10-19 セパレータおよび二次電池、ならびにセパレータの作製方法 Ceased WO2022090862A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN202180072598.3A CN116457997A (zh) 2020-10-26 2021-10-19 隔离体及二次电池以及隔离体的制造方法
US18/029,779 US20240097278A1 (en) 2020-10-26 2021-10-19 Separator, secondary battery, and a method for manufacturing separator
KR1020237017332A KR20230096010A (ko) 2020-10-26 2021-10-19 세퍼레이터 및 이차 전지, 그리고 세퍼레이터의 제작 방법
JP2022558372A JP7813717B2 (ja) 2020-10-26 2021-10-19 セパレータおよび二次電池

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020-179168 2020-10-26
JP2020179168 2020-10-26

Publications (1)

Publication Number Publication Date
WO2022090862A1 true WO2022090862A1 (ja) 2022-05-05

Family

ID=81383663

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2021/059588 Ceased WO2022090862A1 (ja) 2020-10-26 2021-10-19 セパレータおよび二次電池、ならびにセパレータの作製方法

Country Status (5)

Country Link
US (1) US20240097278A1 (https=)
JP (1) JP7813717B2 (https=)
KR (1) KR20230096010A (https=)
CN (1) CN116457997A (https=)
WO (1) WO2022090862A1 (https=)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119181931B (zh) * 2024-09-04 2025-10-31 宁德新能源科技有限公司 一种二次电池和电子装置

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011190307A (ja) * 2010-03-12 2011-09-29 Teijin Ltd ポリオレフィン微多孔膜、非水系二次電池用セパレータ及び非水系二次電池
WO2012023197A1 (ja) * 2010-08-19 2012-02-23 トヨタ自動車株式会社 リチウムイオン二次電池および該電池用セパレータ
WO2012165624A1 (ja) * 2011-06-03 2012-12-06 富士シリシア化学株式会社 セパレータ、電気化学素子、及びセパレータの製造方法
JP2019523518A (ja) * 2017-06-20 2019-08-22 シェンチェン シニア テクノロジー マテリアル カンパニー リミテッド セラミック・ポリマー複合コーティングリチウムイオン電池用セパレーター及びその製造方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100775310B1 (ko) 2004-12-22 2007-11-08 주식회사 엘지화학 유/무기 복합 다공성 분리막 및 이를 이용한 전기 화학소자

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011190307A (ja) * 2010-03-12 2011-09-29 Teijin Ltd ポリオレフィン微多孔膜、非水系二次電池用セパレータ及び非水系二次電池
WO2012023197A1 (ja) * 2010-08-19 2012-02-23 トヨタ自動車株式会社 リチウムイオン二次電池および該電池用セパレータ
WO2012165624A1 (ja) * 2011-06-03 2012-12-06 富士シリシア化学株式会社 セパレータ、電気化学素子、及びセパレータの製造方法
JP2019523518A (ja) * 2017-06-20 2019-08-22 シェンチェン シニア テクノロジー マテリアル カンパニー リミテッド セラミック・ポリマー複合コーティングリチウムイオン電池用セパレーター及びその製造方法

Also Published As

Publication number Publication date
JPWO2022090862A1 (https=) 2022-05-05
KR20230096010A (ko) 2023-06-29
US20240097278A1 (en) 2024-03-21
CN116457997A (zh) 2023-07-18
JP7813717B2 (ja) 2026-02-13

Similar Documents

Publication Publication Date Title
JP7765384B2 (ja) 負極活物質の作製方法
JP2021093356A (ja) 正極活物質、二次電池、電子機器
WO2022034414A1 (ja) 二次電池、電子機器、車両、及び正極活物質の作製方法
JP2022045353A (ja) 二次電池の作製方法、および二次電池
WO2022123389A1 (ja) 正極、正極の作製方法、二次電池、電子機器、蓄電システムおよび車両
WO2022090843A1 (ja) 二次電池、電子機器および車両
WO2022106950A1 (ja) グラフェン、電極、二次電池、車両および電子機器
WO2021245562A1 (ja) 正極活物質、正極活物質層、二次電池、電子機器、及び車両
WO2022038449A1 (ja) 二次電池、電子機器および車両
WO2021240298A1 (ja) 二次電池および車両
JP7813717B2 (ja) セパレータおよび二次電池
CN115398675A (zh) 正极活性物质、二次电池、电子设备
WO2022038451A1 (ja) 正極活物質の作製方法、および二次電池の作製方法
WO2021240292A1 (ja) 二次電池および二次電池を有する車両
WO2022038454A1 (ja) 正極活物質の作製方法
WO2021152428A1 (ja) 二次電池、携帯情報端末、車両および正極活物質の作製方法
JP2022045263A (ja) 正極活物質、二次電池、二次電池の作製方法、電子機器、及び車両
WO2021191733A1 (ja) 二次電池、電子機器、車両及び二次電池の作製方法
JP2022035302A (ja) 二次電池およびその作製方法、および車両
WO2022130094A1 (ja) 二次電池、電子機器および車両
JP2026074113A (ja) セパレータおよび二次電池
WO2022023865A1 (ja) 二次電池及びその作製方法
KR20230037613A (ko) 비수용매, 이차 전지, 및 이차 전지를 탑재한 차량
WO2023209475A1 (ja) 正極活物質、正極、二次電池、電子機器および車両
WO2024052785A1 (ja) 電池、電子機器、及び車両

Legal Events

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

Ref document number: 21885456

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 18029779

Country of ref document: US

ENP Entry into the national phase

Ref document number: 2022558372

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 202180072598.3

Country of ref document: CN

ENP Entry into the national phase

Ref document number: 20237017332

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21885456

Country of ref document: EP

Kind code of ref document: A1