WO2023156868A1 - 二次電池 - Google Patents

二次電池 Download PDF

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Publication number
WO2023156868A1
WO2023156868A1 PCT/IB2023/050942 IB2023050942W WO2023156868A1 WO 2023156868 A1 WO2023156868 A1 WO 2023156868A1 IB 2023050942 W IB2023050942 W IB 2023050942W WO 2023156868 A1 WO2023156868 A1 WO 2023156868A1
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WO
WIPO (PCT)
Prior art keywords
negative electrode
secondary battery
positive electrode
spacer
battery
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/IB2023/050942
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English (en)
French (fr)
Japanese (ja)
Inventor
浅田善治
栗城和貴
米田祐美子
伊藤春志
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 DE112023001021.8T priority Critical patent/DE112023001021T5/de
Priority to KR1020247030099A priority patent/KR20240154563A/ko
Priority to US18/838,429 priority patent/US20250167359A1/en
Priority to CN202380020016.6A priority patent/CN118715644A/zh
Priority to JP2024500690A priority patent/JPWO2023156868A1/ja
Publication of WO2023156868A1 publication Critical patent/WO2023156868A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • H01G11/74—Terminals, e.g. extensions of current collectors
    • H01G11/76—Terminals, e.g. extensions of current collectors specially adapted for integration in multiple or stacked hybrid or EDL capacitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H01G11/10—Multiple hybrid or EDL capacitors, e.g. arrays or modules
    • H01G11/12—Stacked hybrid or EDL capacitors
    • 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
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • 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
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/105—Pouches or flexible bags
    • 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
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/121—Organic 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
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
    • 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
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/172—Arrangements of electric connectors penetrating the casing
    • H01M50/174—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells
    • H01M50/178—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells for pouch or flexible bag cells
    • 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
    • H01M50/471—Spacing elements inside cells other than separators, membranes or diaphragms; Manufacturing processes thereof
    • H01M50/474—Spacing elements inside cells other than separators, membranes or diaphragms; Manufacturing processes thereof characterised by their position inside the cells
    • 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
    • H01M50/471—Spacing elements inside cells other than separators, membranes or diaphragms; Manufacturing processes thereof
    • H01M50/477—Spacing elements inside cells other than separators, membranes or diaphragms; Manufacturing processes thereof characterised by their shape
    • 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
    • H01M50/471—Spacing elements inside cells other than separators, membranes or diaphragms; Manufacturing processes thereof
    • H01M50/48—Spacing elements inside cells other than separators, membranes or diaphragms; Manufacturing processes thereof characterised by the material
    • H01M50/486—Organic 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
    • H01M50/489—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
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/531—Electrode connections inside a battery casing
    • H01M50/533—Electrode connections inside a battery casing characterised by the shape of the leads or tabs
    • 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
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/531—Electrode connections inside a battery casing
    • H01M50/54—Connection of several leads or tabs of plate-like electrode stacks, e.g. electrode pole straps or bridges
    • 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
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/543—Terminals
    • H01M50/547—Terminals characterised by the disposition of the terminals on the cells
    • H01M50/55—Terminals characterised by the disposition of the terminals on the cells on the same side of the cell
    • 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
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/543—Terminals
    • H01M50/552—Terminals characterised by their shape
    • H01M50/553—Terminals adapted for prismatic, pouch or rectangular cells
    • H01M50/557—Plate-shaped terminals
    • 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
    • H01G11/74—Terminals, e.g. extensions of current collectors
    • 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
    • H01G11/78—Cases; Housings; Encapsulations; Mountings
    • H01G11/82—Fixing or assembling a capacitive element in a housing, e.g. mounting electrodes, current collectors or terminals in containers or encapsulations
    • 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

  • One aspect of the present invention relates to a product, method, or manufacturing method. Alternatively, one aspect of the invention relates to a process, machine, manufacture, or composition of matter. One embodiment of the present invention relates to semiconductor devices, display devices, light-emitting devices, power storage devices, lighting devices, electronic devices, or manufacturing methods thereof.
  • electro-optical device refers to all devices having a power storage device, and electro-optical devices having a power storage device, information terminal devices having a power storage device, and the like are all electronic devices.
  • the power storage device refers to general elements and devices having a power storage function.
  • power storage devices such as lithium ion secondary batteries (also referred to as secondary batteries), lithium ion capacitors, and electric double layer capacitors.
  • lithium-ion secondary batteries As secondary batteries, various power storage devices such as lithium-ion secondary batteries, lithium-ion capacitors, and air batteries are being actively developed.
  • lithium-ion secondary batteries which have high output and high energy density, are widely used in portable information terminals such as mobile phones, smart phones, tablets, and notebook computers, portable music players, digital cameras, medical equipment, and clean energy vehicles (hybrid vehicles). HV), electric vehicles (EV), plug-in hybrid vehicles (PHV), etc.), agricultural machinery, motorized bicycles including electric assisted bicycles, motorcycles, electric wheelchairs, electric carts, ships, submarines, aircraft, rockets, satellites , spacecraft, planetary probes, or spacecraft.
  • the demand for lithium-ion secondary batteries has rapidly expanded in line with the development of the semiconductor industry, and they have become indispensable in the modern information society as a source of rechargeable energy.
  • the wearable device has a curved shape along the curved surface of the body or curves according to the movement of the body. Therefore, it is preferable that the secondary battery mounted on the wearable device also has flexibility, like the display and other housings.
  • the secondary battery can be deformed when it is mounted, the utilization efficiency of the internal space of the device can be improved, so the secondary battery is flexible. It is preferred to have
  • Patent Document 1 discloses an electrochemical device (for example, a secondary battery, a capacitor, etc.) that is covered with a metal laminate and has a structure that can be easily bent and maintained in a bent state. disclosed.
  • a flexible material such as a laminate film is used as an outer package, and a positive electrode lead and a negative electrode lead are provided to extract the positive electrode and the negative electrode from the outer package.
  • the positive electrode lead and the negative electrode lead are sandwiched and fixed between the exterior bodies.
  • the positive electrode lead is connected to a positive electrode tab (a part of the positive electrode current collector) provided on the positive electrode
  • the negative electrode lead is connected to a negative electrode tab (a part of the negative electrode current collector) provided on the negative electrode.
  • the positive electrode tab and the negative electrode tab have a shape in which a part of the current collector protrudes from each electrode. Therefore, the positive electrode tab and the negative electrode tab are more likely to cause deterioration such as cracking and breakage than the main portion of each electrode.
  • Patent Document 1 when the positive electrode lead and the negative electrode lead are connected to the ends of the secondary battery in the bending direction, the stress due to the deformation of the secondary battery is applied to the positive electrode lead connection portion and the negative electrode lead connection portion. easy to concentrate on. For this reason, for example, repeated deformation (such as bending and stretching) of an electronic device equipped with the secondary battery may cause cracking or breakage at the positive electrode lead connection portion and the negative electrode lead connection portion.
  • Patent Document 2 a secondary battery having an internal structure for reducing the stress applied to the lead connection portion due to deformation of the secondary battery is being studied.
  • Patent Document 2 a secondary battery having an internal structure for reducing the stress applied to the lead connection portion due to deformation of the secondary battery is being studied.
  • a secondary battery when a flexible secondary battery is used in a low-pressure environment such as outer space, the volume of the secondary battery expands due to the difference in pressure from the production environment of the secondary battery.
  • a secondary battery is manufactured using an electrolyte containing an ionic liquid and in a low pressure environment (also referred to as a reduced pressure environment).
  • a low pressure environment also referred to as a reduced pressure environment.
  • the sealing of the exterior body of the secondary battery is performed in a low pressure environment of 1000 Pa or less.
  • an object of one embodiment of the present invention is to provide a secondary battery having a structure in which deterioration of a positive electrode or a negative electrode, particularly a positive electrode lead connection portion or a negative electrode lead connection portion, can be suppressed.
  • an object of one embodiment of the present invention is to provide a method for manufacturing a secondary battery having a structure in which deterioration of a positive electrode or a negative electrode, particularly a positive electrode lead connection portion or a negative electrode lead connection portion, can be suppressed.
  • a structure is provided that can reduce stress applied to the positive electrode lead connection portion or the negative electrode lead connection portion when the secondary battery is bent.
  • an outer package enclosing a positive electrode, a negative electrode, a separator, a first spacer, and a second spacer; a positive electrode lead and a negative electrode lead extending from the inside to the outside of a space enclosed by the outer package;
  • the positive electrode has a first portion coated with the positive electrode active material and a second portion where the positive electrode current collector is exposed
  • the negative electrode has a second portion coated with the negative electrode active material 3 and a fourth portion where the negative electrode current collector is exposed, the first portion, the third portion, and the separator overlap each other in the laminated portion, and the positive electrode lead is disposed in the laminated portion. and the negative electrode lead is connected to the fourth portion at a position overlapping with the laminated portion.
  • the second spacer is in contact with the exterior body, and has a region sandwiched between the laminate portion and the second portion, a region sandwiched between the laminate portion and the fourth portion, and a second spacer.
  • a secondary battery comprising a spacer and a connected region.
  • the height of the first spacer is equal to or greater than the sum of the height of the laminate, the height of the second spacer, the height of the second portion, and the height of the positive electrode lead. is preferred.
  • the height of the first spacer is equal to or greater than the sum of the height of the laminated portion, the height of the second spacer, the height of the fourth portion, and the height of the negative electrode lead. is preferred.
  • the second portion may have a curved portion between the connection portion with the positive electrode lead and the laminated portion, and the curved portion may have a region in contact with the second spacer. preferable.
  • the fourth portion may have a curved portion between the connection portion with the negative electrode lead and the laminated portion, and the curved portion may have a region in contact with the second spacer. preferable.
  • the first spacer and the second spacer preferably have flexibility, and the first spacer preferably has higher elasticity than the second spacer.
  • the outer package has a region on the inner side of the space enclosed by the outer package that contacts the flexible film, and the laminate has a flexible film at the other end of the laminate. preferably has a region that contacts the adhesive film.
  • the flexible film is preferably insulating.
  • the flexible film has polyimide and has a region where the polyimide and the other end of the laminated portion are in contact.
  • the exterior body has a concave portion and a convex portion.
  • a secondary battery having a structure in which deterioration of a positive electrode or a negative electrode, particularly a positive electrode lead connection portion or a negative electrode lead connection portion, can be suppressed.
  • a method for manufacturing a secondary battery having a structure in which deterioration of a positive electrode or a negative electrode, particularly a positive electrode lead connection portion or a negative electrode lead connection portion, can be suppressed can be provided.
  • a secondary battery with a novel structure can be provided. More specifically, it is possible to provide a flexible secondary battery with a novel structure. Alternatively, according to one embodiment of the present invention, a novel power storage device, an electronic device including a novel secondary battery, or the like can be provided.
  • FIG. 1A and 1B are perspective views illustrating configuration examples of secondary batteries.
  • FIG. 2A is a top view for explaining a configuration example of a secondary battery
  • FIGS. 2B and 2C are cross-sectional views for explaining a configuration example of the secondary battery.
  • FIG. 3A is a top view illustrating a configuration example of a secondary battery
  • FIGS. 3B to 3D are cross-sectional views illustrating configuration examples of the secondary battery.
  • FIG. 4A is a top view illustrating a configuration example of a secondary battery
  • FIGS. 4B to 4D are cross-sectional views illustrating configuration examples of the secondary battery.
  • 5A to 5C are cross-sectional views illustrating configuration examples of secondary batteries.
  • 6A and 6B are cross-sectional views illustrating configuration examples of secondary batteries.
  • FIG. 7A to 7C are perspective views illustrating an example of manufacturing a secondary battery.
  • 8A to 8C are perspective views illustrating an example of manufacturing a secondary battery.
  • 9A and 9B are perspective views illustrating an example of manufacturing a secondary battery.
  • FIG. 10 is a perspective view illustrating an example of manufacturing a secondary battery.
  • FIG. 11 is a diagram for explaining a film processing method.
  • 12A to 12E are diagrams for explaining a film processing method.
  • 13A and 13B are diagrams for explaining a film processing method.
  • 14A and 14B are diagrams illustrating an electronic device of one embodiment of the present invention.
  • 15A and 15B are diagrams illustrating an electronic device of one embodiment of the present invention.
  • 16A to 16D illustrate an electronic device of one embodiment of the present invention.
  • FIG. 17A to 17D illustrate an electronic device of one embodiment of the present invention.
  • 18A to 18C are diagrams illustrating electronic devices of one embodiment of the present invention.
  • 19A to 19C are diagrams illustrating electronic devices of one embodiment of the present invention.
  • FIG. 20A is a perspective view showing an example of a battery pack.
  • FIG. 20B is a block diagram showing an example of a battery pack.
  • FIG. 20C is a block diagram showing an example of a vehicle having a motor.
  • 21A to 21E are diagrams showing an example of a transportation vehicle.
  • 22A is a diagram showing an electric bicycle
  • FIG. 22B is a diagram showing a secondary battery of the electric bicycle
  • FIG. 22C is a diagram explaining an electric motorcycle.
  • 23A and 23B are diagrams illustrating an example of a power storage device.
  • 24A to 24D are diagrams showing an example of space equipment.
  • Electrically connected includes the case of being connected via "something that has some kind of electrical action".
  • something having some kind of electrical action is not particularly limited as long as it enables transmission and reception of electrical signals between connection objects.
  • parallel refers to a state in which two straight lines are arranged at an angle of -10° or more and 10° or less. Therefore, the case of ⁇ 5° or more and 5° or less is also included.
  • substantially parallel refers to a state in which two straight lines are arranged at an angle of -30° or more and 30° or less.
  • perpendicular means a state in which two straight lines are arranged at an angle of 80° or more and 100° or less. Therefore, the case of 85° or more and 95° or less is also included.
  • substantially perpendicular or substantially perpendicular means a state in which two straight lines are arranged at an angle of 60° or more and 120° or less.
  • the particle size of the particles can be measured, for example, by laser diffraction particle size distribution measurement, and can be expressed as D50.
  • D50 is the particle size when the integrated amount occupies 50% of the integrated particle amount curve of the particle size distribution measurement result, that is, the median diameter.
  • the measurement of particle size is not limited to laser diffraction particle size distribution measurement, and when the measurement is below the lower limit of laser diffraction particle size distribution measurement, analysis such as SEM (scanning electron microscope) or TEM (transmission electron microscope) is used.
  • the cross-sectional diameter of the particles may be measured by As a method for measuring the particle size when the cross-sectional shape of the particle is not circular, for example, the cross-sectional area of the particle is measured by image processing or the like, and the particle size can be calculated as the diameter of a circle having this area.
  • FIGS. 1 to 6 are used to describe a flexible secondary battery (sometimes referred to as a flexible battery, a bendable battery, or a bendable battery) according to one embodiment of the present invention. A configuration example will be described.
  • FIG. 1A to 5C show schematic diagrams of a secondary battery 10 of one embodiment of the present invention.
  • FIG. 1A is a perspective view of a secondary battery 10.
  • FIG. 1B is a perspective view showing the internal structure of secondary battery 10 in the dashed line portion of FIG. 1A.
  • FIG. 1A is a schematic diagram of a flexible secondary battery 10, showing a state in which the secondary battery 10 is curved in one direction.
  • the secondary battery 10 has an exterior body 50 , and a positive electrode lead 21 and a negative electrode lead 31 extending from the inside to the outside of the space enclosed by the exterior body 50 .
  • FIG. 1B shows the internal structure of the secondary battery 10 in the broken line portion of FIG. 1A.
  • the secondary battery 10 has a laminate 60 inside.
  • the laminate 60 has a positive electrode 20 , a negative electrode 30 , a separator 40 , a positive electrode lead 21 , a negative electrode lead 31 , first spacers 55 and second spacers 56 .
  • the laminate 60 has a laminated portion 61 in which the positive electrode 20, the negative electrode 30, and the separator 40 are laminated. , are connected at a connecting portion 26 located at a position overlapping with the laminated portion 61 .
  • a portion of the negative electrode 30 protruding from the laminated portion 61 and the negative electrode lead 31 are connected at a connecting portion 36 that overlaps the laminated portion 61 .
  • the first spacer 55 of the laminated body 60 is located in a region surrounded by the laminated portion 61, the positive lead 21, and the negative lead 31.
  • the second spacer 56 has a first region sandwiched between the connecting portion 26 and the laminated portion 61 and has a second region sandwiched between the connecting portion 36 and the laminated portion 61 .
  • the second spacer 56 has a region connected to the first spacer 55 via a connecting portion 57 at a position between the first region and the second region.
  • FIG. 2A is a top view of secondary battery 10
  • FIG. 2B is a cross-sectional view showing a cross section taken along dashed-dotted line A1-A2 shown in FIG. 2A
  • FIG. 2C is dashed-dotted line B1-B2 shown in FIG. 2A. It is sectional drawing which shows the cut surface in between.
  • the secondary battery 10 shown in FIG. 2A has an exterior body 50 and a sealing portion 51 of the exterior body 50 .
  • an example in which one side of the exterior body 50 is bent and the other three sides have the sealing portions 51 is shown.
  • Such sealing is sometimes referred to as a three-way sealing.
  • a four-sided sealing structure in which four sides of the exterior body are sealed may be employed.
  • the first spacer 55 is located in a region surrounded by the laminated portion 61, the positive electrode lead 21, the negative electrode lead 31, and the sealing portion 51 when viewed from above. This region is also called a region having the first spacers 55 .
  • One end of the laminated portion 61 is in contact with the region having the first spacer 55 , and the other end has a region in contact with the flexible film 58 .
  • FIG. 2B is a cross-sectional view showing a cross-section along the dashed-dotted line A1-A2 shown in FIG. 2A.
  • the sealing portion 51 of the exterior body 50 has a region for sealing with the negative electrode lead 31 sandwiched therebetween.
  • the sealing portion 51 of the exterior body 50 has a region for sealing with the positive electrode lead 21 sandwiched therebetween.
  • the positive electrode lead 21 and the negative electrode lead 31 extend from the interior of the exterior body 50 to the exterior.
  • the negative electrode lead 31 and the negative electrode 30 are connected at the connecting portion 36 inside the outer package 50 .
  • the negative electrode 30 does not have an active material layer at the connection portion 36 and both sides of the negative electrode current collector are exposed, so that the plurality of negative electrodes 30 and the negative electrode lead 31 can be connected.
  • the negative electrode 30 has a negative electrode active material layer in the laminated portion 61 .
  • FIG. 3A is a top view of the negative electrode 30, and FIGS. 3B and 3C are cross-sectional views of the negative electrode 30.
  • FIG. 3B and 3C are cross-sectional views of the negative electrode 30.
  • the negative electrode 30 has a negative electrode current collector exposed portion 34 and a negative electrode active material coated portion 35 .
  • FIG. 3B is a cross-sectional view taken along dashed-dotted line C1-C2 shown in FIG. 3A.
  • the negative electrode 30 has a negative electrode active material layer 33 on the negative electrode current collector 32 in the negative electrode active material coated portion 35 . Both surfaces of the negative electrode current collector 32 are exposed at the negative electrode current collector exposed portion 34 .
  • FIG. 3C is an example in which the negative electrode active material layer 33 is provided at a position different from that in FIG. 3B.
  • the negative electrode 30 shown in FIGS. 3B and 3C can be used as the negative electrode 30 in the cross-sectional view shown in FIG. 2B.
  • the negative electrode current collector exposed portion 34 refers to a region where both surfaces of the negative electrode current collector 32 are exposed, and the back surface (opposite surface) of the negative electrode current collector 32 in the region having the negative electrode active material layer 33 . , or not the sides. Further, even when it is in contact with the electrolyte inside the secondary battery, it is referred to as the negative electrode current collector exposed portion 34 .
  • FIG. 4A is a top view of the positive electrode 20
  • FIGS. 4B and 4C are cross-sectional views of the positive electrode 20.
  • FIG. 4A is a top view of the positive electrode 20
  • FIGS. 4B and 4C are cross-sectional views of the positive electrode 20.
  • FIG. 4A is a top view of the positive electrode 20
  • FIGS. 4B and 4C are cross-sectional views of the positive electrode 20.
  • the positive electrode 20 has a positive electrode current collector exposed portion 24 and a positive electrode active material coated portion 25 .
  • FIG. 4B is a cross-sectional view taken along dashed-dotted line D1-D2 shown in FIG. 4A.
  • the positive electrode 20 has a positive electrode active material layer 23 on a positive electrode current collector 22 in a positive electrode active material coated portion 25 . Both surfaces of the positive electrode current collector 22 are exposed at the positive electrode current collector exposed portion 24 .
  • FIG. 4C is an example in which the positive electrode active material layer 23 is provided at a position different from that in FIG. 4B. 4B and 4C can be used as the positive electrode 20 in the cross-sectional view shown in FIG. 2B.
  • the positive electrode current collector exposed portion 24 refers to a region where both surfaces of the positive electrode current collector 22 are exposed, and the back surface (opposite surface) of the positive electrode current collector 22 in the region having the positive electrode active material layer 23 . , or not the sides. In addition, even when it is in contact with the electrolyte inside the secondary battery, it is referred to as the positive electrode current collector exposed portion 24 .
  • the positive electrode 20, the negative electrode 30, and the separator 40 are stacked in the stacking portion 61.
  • the positive electrode active material layer 23 of the positive electrode 20 and the negative electrode active material layer 33 of the negative electrode 30 are laminated so as to face each other with the separator 40 interposed therebetween.
  • the cross-sectional view shown in FIG. 2B shows an example in which each of the positive electrode 20 and the negative electrode 30 is a single-sided coating electrode having an active material layer on one side of the current collector.
  • the laminated portion 61 refers to a portion where the positive electrode active material coated portion 25, the negative electrode active material coated portion 35, and the separator are stacked. It can also be said that the positive electrode active material coating portion 25, the negative electrode active material coating portion 35, and the separator overlap each other in the laminated portion.
  • the positive electrode current collector exposed portion 24 and the negative electrode current collector exposed portion 34 are sometimes referred to as projecting portions of the laminated portion 61 .
  • the position of the first spacer 55 is indicated by a dashed line.
  • the first spacer 55 has a region that contacts the exterior body 50 .
  • the first spacer 55 contacts the exterior body 50 at a position surrounded by the laminated portion 61 , the positive electrode lead 21 , the negative electrode lead 31 and the sealing portion 51 .
  • the second spacer 56 is provided at a position sandwiched between the laminated portion 61 and the negative electrode current collector exposed portion 34 .
  • first spacer 55 and the second spacer 56 shown in FIG. can be configured to reduce the stress applied to the connection portion 36 that connects the .
  • FIG. 2C is a cross-sectional view showing a cut surface between the dashed-dotted line B1-B2 shown in FIG. 2A.
  • One end of laminate 61 contacts a region having first spacer 55 (FIG. 2B), and the other end has a region contacting flexible film 58 (FIG. 2C).
  • the secondary battery 10 Although it is not essential for the secondary battery 10 to have the flexible film 58 at this position, having the flexible film 58 at this position improves the slidability between the laminated portion 61 and the exterior body 50. It is preferable to have a flexible film 58 because it allows for
  • FIG. 5A to 5C are cross-sectional views showing the inside of the secondary battery 10.
  • FIG. 5A is a cross-sectional view showing a cross-section of the laminate 60 taken along the dashed line X1-X2 shown in FIG. 2A
  • FIG. 5B is a cross-sectional view showing a cross-section of the laminate 60 taken along the dashed line Y1-Y2 shown in FIG. 2A
  • FIG. 5C is a cross-section showing a cross-section of the laminate 60 taken along the dashed-dotted line Z1-Z2 shown in FIG. 2A. It is a diagram.
  • the layered body 60 has a layered portion 61 in which the positive electrode 20, the negative electrode 30, and the separator 40 are layered.
  • the negative electrode 30 has a negative electrode current collector exposed portion 34 and a negative electrode active material coating portion 35
  • the positive electrode 20 has a positive electrode current collector exposed portion 24 and a positive electrode active material coated portion 35 . and a substance coating portion 25 .
  • the positive electrode active material coated portion 25, the negative electrode active material coated portion 35, and the separator have regions that overlap each other.
  • the negative electrode 30 is connected to the negative electrode lead 31 at the connecting portion 36 .
  • the connection portion 36 is provided in the negative electrode current collector exposed portion 34 shown in FIG. 3A.
  • the negative electrode current collector exposed portion 34 has a curved portion between the connecting portion 36 and the laminated portion 61 , and the connecting portion 36 overlaps the laminated portion 61 in a cross-sectional view.
  • the second spacer 56 preferably has a region sandwiched between the negative electrode current collector exposed portion 34 and the laminated portion 61 and is in contact with part of the curved portion of the negative electrode current collector exposed portion 34 as shown in FIG. 5A. .
  • the second spacer 56 has a region that is not sandwiched between the negative electrode current collector exposed portion 34 and the laminated portion 61 and a region that is not sandwiched between the positive electrode current collector exposed portion 24 and the laminated portion 61 . , and has a region connected to the first spacer 55 via the connection portion 57 .
  • the positive electrode 20 is connected to the positive electrode lead 21 at the connecting portion 26 .
  • the connection portion 26 is provided in the positive electrode current collector exposed portion 24 shown in FIG. 4A.
  • the positive electrode current collector exposed portion 24 has a curved portion between the connecting portion 26 and the laminated portion 61 , and the connecting portion 26 overlaps the laminated portion 61 in a cross-sectional view.
  • the second spacer 56 preferably has a region sandwiched between the positive electrode current collector exposed portion 24 and the laminated portion 61 and is in contact with part of the curved portion of the positive electrode current collector exposed portion 24 as shown in FIG. 5C. .
  • the second spacer 56 has a region sandwiched between the negative electrode current collector exposed portion 34 and the laminated portion 61 , a region sandwiched between the positive electrode current collector exposed portion 24 and the laminated portion 61 , and the connecting portion 57 . It has a region connected to the first spacer 55 at the bottom.
  • the laminated portion 61 is connected to the first spacer 55 via the second spacer 56 and the connecting portion 57 .
  • the first spacer 55 since the first spacer 55 has a region in contact with the exterior body 50 as described with reference to FIG. It is connected to the exterior body 50 via 55 .
  • the secondary battery 10 can be provided with a location other than the positive electrode lead 21 and the negative electrode lead 31 where the exterior body 50 and the laminated portion 61 are fixed, and the secondary battery 10 can be curved. It is possible to suppress the deterioration of the positive electrode lead 21, the negative electrode lead 31, the connection portion 26, the connection portion 36, and the peripheral portion thereof.
  • the height of the first spacer 55 is the height of the laminated portion 61, the height of the second spacer 56, the height of the connecting portion 26 or the connecting portion 36, the height of the positive electrode lead 21 or the negative electrode lead 31, It is preferable that the height is equal to or greater than the sum of The height of the first spacer 55 is the height of the laminated portion 61, the height of the second spacer 56, the height of the connecting portion 26 or the connecting portion 36, the height of the positive electrode lead 21 or the negative electrode lead 31,
  • the total height is preferably 2.0 times or less, more preferably 1.5 times or less, more preferably 1.3 times or less, more preferably 1.2 times or less, and more preferably 1.1 times or less. preferable.
  • first spacer 55 and the second spacer 56 insulating materials such as resin (polyolefin resin, polyimide resin, polyamide resin, acrylic resin, siloxane resin, epoxy resin, phenol resin, etc.), glass, amorphous compound, ceramics, etc., may be used. materials can be used. Among them, it is particularly preferable to use a polyolefin resin having insulating properties and appropriate elasticity. As for the elasticity of the first spacer 55 and the second spacer 56 , it is preferable that the elasticity of the first spacer 55 is higher than the elasticity of the second spacer 56 .
  • the second spacers 56 are easier to deform than the first spacers 55 . This is because the second spacer 56 is provided at a position in contact with the positive electrode tab and the negative electrode tab, so if the elasticity of the second spacer 56 is high, the positive electrode tab and the negative electrode tab are likely to crack and deteriorate. because of fear.
  • elasticity refers to the property of an object whose shape or volume has been changed by an external force to restore its original state when the force is removed.
  • High elasticity means that the external force required to deform the object is large.
  • first spacer and the second spacer have a cylindrical shape
  • the shape is not limited to this.
  • the first spacer and the second spacer may have a hollow pipe-like shape, a rectangular parallelepiped shape, a spherical shape, or a polyhedral shape having heptahedrons or more.
  • the shape may be a combination of these shapes.
  • FIG. 6A is a cross-sectional view showing the cross section of the laminate 60 between the dashed-dotted lines X1-X2 shown in FIG. 5A, with the positions of the first spacers 55 added with broken lines.
  • FIG. 6B is a diagram for explaining how the structure shown in FIG. 6A changes when the secondary battery 10 is bent.
  • FIG. 6A is the same as FIG. 5A, the description is omitted.
  • FIG. 6B is a diagram showing a case in which secondary battery 10 is bent in the direction indicated by the solid arrow.
  • the negative electrode 30 can move (also referred to as being able to deform) in the direction indicated by the dashed arrow.
  • the first spacer 55 has a region in contact with the exterior body 50, so that a space for the negative electrode 30 to move as shown in FIG. 5A is maintained inside the exterior body 50. becomes.
  • the second spacer 56 may have a function as a fulcrum for deformation of the negative electrode 30, and it may be possible to stably deform the negative electrode 30 shown in FIG. 5A.
  • FIG. 7A is a schematic perspective view showing a laminated structure.
  • FIG. 7A shows an example in which four positive electrodes 20 and four negative electrodes 30 are used, and two separators 40 are used.
  • the positive electrode 20 and the negative electrode 30 are single-sided coated electrodes described in FIGS. 3B, 3C, 4B, and 4C. positioned so as to be sandwiched between Similarly, when two negative electrodes 30 are in contact with each other, they are stacked so that the negative electrode current collectors 32 are in contact with each other.
  • FIG. 7B shows how the positive electrode 20, the negative electrode 30, and the separator 40 are stacked. Note that the separator 40 is not shown in FIGS. 7B and 7C for clarity.
  • the separator 40 After the separator 40 is folded back, it is preferable to bond the peripheral portion and mold it into a bag shape.
  • a separator 40 even if the pair of positive electrode current collectors 22 are misaligned, electrical shorting between the positive electrode and the negative electrode can be suppressed.
  • a double-sided coated electrode shown in FIG. 4D may be used instead of stacking two sheets of the negative electrode 30 so that the negative electrode current collectors 32 are in contact with each other.
  • a double coated electrode as shown in FIG. 4D may be used.
  • the current collectors of the same polarity slide against each other, which is preferable because the stress applied to the current collector itself when the battery is bent can be alleviated. .
  • connection of the negative electrode 30 and the negative electrode lead 31 and the connection of the positive electrode 20 and the positive electrode lead 21 are performed.
  • the negative lead 31 is connected to the negative electrode 30 at the connecting portion 36
  • the positive lead 21 is connected to the positive electrode 20 at the connecting portion 26 .
  • For the connection for example, ultrasonic welding or the like can be used.
  • the positive electrode 20 and the negative electrode 30 are bent so that the connection portion 26 and the connection portion 36 overlap one surface of the laminated portion 61 .
  • the second spacer 56 is provided so as to be sandwiched between the connection portion 26 or the connection portion 36 and the laminated portion 61 .
  • An adhesive may be used to fix the insulating film 45, or an insulating film having an adhesive layer may be used.
  • a film-shaped resin can be used as the insulating film 45 .
  • resins that can be used include polyimide resins, polyamide resins, acrylic resins, siloxane resins, epoxy resins, and phenol resins.
  • adhesion layer which has a silicone resin etc.
  • the manufacturing process shown in FIG. 8A can be easily performed, and workability is improved in subsequent processes, which is preferable.
  • FIG. 8B is a schematic perspective view of the laminate 60 shown in FIG. 8A viewed from another angle.
  • the first spacer 55 is connected to the second spacer 56 via a connecting portion 57, as shown in FIG. 8C.
  • the connection between the first spacer 55 and the second spacer 56 may be performed after the step shown in FIG. 8A, but is preferably performed in advance from the viewpoint of workability.
  • an exterior body 50 is prepared as shown in FIG. 9A.
  • the dashed lines shown in the drawing indicate the bending lines for the three-way sealing structure.
  • the details of the film that can be used for the exterior body 50 will be described later.
  • flexible films 58 and 59 are attached to the exterior body 50 as shown in FIG. 9B.
  • the flexible film 58 is preferably attached so as to include the above-described fold line so as to be in the position shown in FIG. 2C.
  • An adhesive may be used for attachment, or a flexible film having an adhesive layer may be used.
  • the flexible film 59 is attached so as to overlap with the connecting portion 26 and the connecting portion 36 .
  • a structure in which the flexible film 58 and the flexible film 59 are not attached may be employed, or a structure in which the flexible film 58 is attached and the flexible film 59 is not attached may be employed.
  • a film-like resin for example, can be used as the flexible film 58 and the flexible film 59 .
  • resins that can be used include polyimide resins, polyamide resins, acrylic resins, siloxane resins, epoxy resins, and phenol resins.
  • the manufacturing process shown in FIG. 9B can be easily performed, and workability is improved in subsequent processes, which is preferable.
  • the exterior body 50 is folded in two, the laminated body 60 is placed in between, and the exterior body is sealed leaving an open portion for injecting the electrolyte.
  • an electrolyte is injected from one side left as an open portion, and the periphery of the exterior body 50 is sealed under a reduced pressure environment.
  • the reduced pressure environment is preferably 50000 Pa or less, more preferably 40000 Pa or less, 30000 Pa or less, 20000 Pa or less, 10000 Pa or less, 5000 Pa or less, or 1000 Pa or less.
  • an impregnation treatment may be performed to facilitate the impregnation of the electrolyte into the pores of the electrodes and separators.
  • decompression treatment also referred to as evacuation treatment
  • decompression treatment may be performed multiple times.
  • the environmental pressure (pressure value in the differential pressure gauge) in the decompression process can be set to ⁇ 60 kPa or less.
  • the environmental pressure in the decompression process is preferably -80 kPa or less or -100 kPa or less.
  • Sealing of the outer body can be performed at the same environmental pressure following the depressurization process described above. Alternatively, the sealing may be performed at an environmental pressure different from that of the depressurization process.
  • the depressurization process may be performed at an environmental pressure of -100 kPa, and the exterior body may be sealed at a pressure environment of -80 kPa.
  • the secondary battery 10 of one embodiment of the present invention illustrated in FIG. 1A and the like can be manufactured.
  • the negative electrode has a negative electrode active material layer and a negative electrode current collector.
  • the negative electrode active material layer may have a negative electrode active material, and may further have a conductive material and a binder.
  • a metal foil can be used as the current collector.
  • a negative electrode can be formed by applying a slurry onto a metal foil and drying it. In addition, you may add a press after drying. The negative electrode is obtained by forming an active material layer on a current collector.
  • a slurry is a material liquid used to form an active material layer on a current collector, and refers to a liquid containing an active material, a binder, and a solvent, and preferably further mixed with a conductive material.
  • the slurry may be called electrode slurry or active material slurry, and may be called negative electrode slurry when forming a negative electrode active material layer.
  • a carbon material or an alloy material can be used as the negative electrode active material.
  • carbon materials examples include graphite (natural graphite, artificial graphite), graphitizable carbon (soft carbon), non-graphitizable carbon (hard carbon), carbon fiber (carbon nanotube), graphene, carbon black, and the like. can.
  • Graphite includes artificial graphite and natural graphite.
  • artificial graphite include mesocarbon microbeads (MCMB), coke-based artificial graphite, and pitch-based artificial graphite.
  • MCMB mesocarbon microbeads
  • spherical graphite having a spherical shape can be used as the artificial graphite.
  • MCMB may have a spherical shape and are preferred.
  • MCMB is also relatively easy to reduce its surface area and may be preferred.
  • natural graphite include flake graphite and spherical natural graphite.
  • Graphite exhibits a potential as low as that of lithium metal when lithium ions are inserted into graphite (at the time of formation of a lithium-graphite intercalation compound) (0.05 V or more and 0.3 V or less vs. Li/Li + ). Accordingly, a lithium-ion battery using graphite can exhibit a high operating voltage. Furthermore, graphite is preferable because it has advantages such as relatively high capacity per unit volume, relatively small volume expansion, low cost, and high safety compared to lithium metal.
  • Non-graphitizable carbon can be obtained, for example, by firing synthetic resins such as phenolic resins and plant-derived organic substances.
  • the non-graphitizable carbon contained in the negative electrode active material of the lithium ion battery of one embodiment of the present invention has a (002) plane spacing of 0.34 nm or more and 0.50 nm or less as measured by X-ray diffraction (XRD). , and more preferably 0.35 nm or more and 0.42 nm or less.
  • an element capable of undergoing charge/discharge reaction by alloying/dealloying reaction with lithium can be used as the negative electrode active material.
  • materials containing at least one of silicon, tin, gallium, aluminum, germanium, lead, antimony, bismuth, silver, zinc, cadmium, indium, etc. can be used.
  • Such an element has 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 for the negative electrode active material.
  • Compounds containing these elements may also be used.
  • elements capable of undergoing charge-discharge reactions by alloying/dealloying reactions with lithium, compounds containing such elements, and the like are sometimes referred to as alloy-based materials.
  • SiO refers to silicon monoxide, for example.
  • SiO can be represented as SiO x .
  • x preferably has a value of 1 or close to 1.
  • x is preferably 0.2 or more and 1.5 or less, more preferably 0.3 or more and 1.2 or less.
  • titanium dioxide TiO2
  • lithium titanium oxide Li4Ti5O12
  • lithium -graphite intercalation compound LixC6
  • niobium pentoxide Nb2O5
  • oxide Oxides such as tungsten (WO 2 ) and molybdenum oxide (MoO 2 ) can be used.
  • Li 2.6 Co 0.4 N 3 exhibits a large discharge capacity (900 mAh/g, 1890 mAh/cm 3 ) and is preferred.
  • 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 that do not contain lithium ions as the positive electrode active material, which is preferable.
  • materials such as V 2 O 5 and Cr 3 O 8 that do not contain lithium ions as the positive electrode active material, which is preferable.
  • a composite nitride of lithium and a transition metal can be used as the negative electrode active material by preliminarily desorbing the lithium ions contained in the positive electrode active material.
  • a material that causes a conversion reaction can also be used as the negative electrode active material.
  • transition metal oxides such as cobalt oxide (CoO), nickel oxide (NiO), and iron oxide (FeO) that do not form an alloy with lithium may be used as the negative electrode active material.
  • oxides such as Fe2O3 , CuO, Cu2O , RuO2 and Cr2O3 , sulfides such as CoS0.89 , NiS and CuS, and Zn3N2 , Cu 3 N, Ge 3 N 4 and other nitrides, NiP 2 , FeP 2 and CoP 3 and other phosphides, and FeF 3 and BiF 3 and other fluorides.
  • negative electrode active material can be used from among the above negative electrode active materials, it is also possible to use a combination of multiple types. For example, a combination of a carbon material and silicon or a combination of a carbon material and silicon monoxide can be used.
  • the negative electrode may be a negative electrode that does not have a negative electrode active material at the end of the production of the battery.
  • the negative electrode without a negative electrode active material for example, a negative electrode having only a negative electrode current collector at the end of battery production, lithium ions desorbed from the positive electrode active material by charging the battery are deposited on the negative electrode current collector.
  • a negative electrode deposited as lithium metal to form a negative electrode active material layer can be used.
  • a battery using such a negative electrode is sometimes called a negative electrode-free (anode-free) battery, a negative electrode-less (anode-less) battery, or the like.
  • the negative electrode current collector may have a film for uniform deposition of lithium.
  • a film for uniform deposition of lithium for example, a solid electrolyte having lithium ion conductivity can be used.
  • the solid electrolyte a sulfide-based solid electrolyte, an oxide-based solid electrolyte, a polymer-based solid electrolyte, or the like can be used.
  • a polymer solid electrolyte is suitable as a film for uniform deposition of lithium because it is relatively easy to form a uniform film on the negative electrode current collector.
  • a metal film forming an alloy with lithium can be used as a film for uniformizing deposition of lithium.
  • a magnesium metal film for example, can be used as the metal film forming an alloy with lithium. Since lithium and magnesium form a solid solution in a wide composition range, it is suitable as a film for uniform deposition of lithium.
  • a negative electrode current collector having unevenness can be used.
  • the concave portions of the negative electrode current collector become cavities in which lithium contained in the negative electrode current collector is easily deposited, so that when lithium is deposited, it is suppressed to form a dendrite shape. can do.
  • ⁇ Binder> As the binder, it is preferable to use rubber materials such as styrene-butadiene rubber (SBR), styrene-isoprene-styrene rubber, acrylonitrile-butadiene rubber, butadiene rubber, and ethylene-propylene-diene copolymer. Fluororubber can also be used as the binder.
  • SBR styrene-butadiene rubber
  • styrene-isoprene-styrene rubber acrylonitrile-butadiene rubber
  • butadiene rubber butadiene rubber
  • Fluororubber can also be used as the binder.
  • the binder it is preferable to use, for example, a water-soluble polymer.
  • Polysaccharides for example, can be used as the water-soluble polymer.
  • cellulose derivatives such as carboxymethyl cellulose (CMC), methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, regenerated cellulose, starch, and the like can be used. Further, it is more preferable to use these water-soluble polymers in combination with the aforementioned rubber material.
  • Binders may be used in combination with more than one of the above.
  • a material having a particularly excellent viscosity adjusting effect may be used in combination with another material.
  • rubber materials are excellent in adhesive strength and elasticity, but on the other hand, it may be difficult to adjust the viscosity when they are mixed with a solvent. In such a case, for example, it is preferable to mix with a material having a particularly excellent viscosity-adjusting effect.
  • a water-soluble polymer may be used as a material having a particularly excellent viscosity-adjusting effect.
  • the aforementioned polysaccharides such as carboxymethyl cellulose (CMC), methyl cellulose, ethyl cellulose, hydroxypropyl cellulose and diacetyl cellulose, cellulose derivatives such as regenerated cellulose, or starch are used. be able to.
  • solubility of cellulose derivatives such as carboxymethyl cellulose is increased by making them into salts such as sodium salts or ammonium salts of carboxymethyl cellulose, making it easier for them to exert their effects as viscosity modifiers.
  • the higher solubility also allows for better dispersibility with the active material or other constituents when preparing the electrode slurry.
  • cellulose and cellulose derivatives used as binders for electrodes also include salts thereof.
  • the water-soluble polymer stabilizes the viscosity by dissolving it in water, and can stably disperse the active material and other materials combined as a binder, such as styrene-butadiene rubber, in the aqueous solution.
  • a binder such as styrene-butadiene rubber
  • it since it has a functional group, it is expected to be stably adsorbed on the surface of the active material.
  • many cellulose derivatives such as carboxymethyl cellulose are materials having functional groups such as hydroxyl groups or carboxyl groups, and due to the presence of functional groups, the macromolecules interact with each other, and the surface of the active material can be widely covered. Be expected.
  • the binder that covers or contacts the surface of the active material forms a film
  • it is expected to play a role as a passive film and suppress the decomposition of the electrolyte.
  • the "passive film” is a film with no electrical conductivity or a film with extremely low electrical conductivity.
  • WHEREIN The decomposition
  • the conductive material is also called a conductive agent or a conductive aid, and a carbon material is used.
  • a conductive agent or a conductive aid
  • a carbon material is used.
  • Active material layers such as the positive electrode active material layer and the negative electrode active material layer preferably contain a conductive material.
  • Examples of the conductive material include carbon black such as acetylene black and furnace black, graphite such as artificial graphite and natural graphite, carbon fiber such as carbon nanofiber and carbon nanotube, and graphene compound. More than one species can be used.
  • carbon fibers for example, carbon fibers such as mesophase pitch-based carbon fibers and isotropic pitch-based carbon fibers can be used.
  • Carbon nanofibers, carbon nanotubes, or the like can be used as carbon fibers.
  • Carbon nanotubes can be produced, for example, by vapor deposition.
  • the graphene compound refers to graphene, 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, and graphene. Including quantum dots, etc.
  • a graphene compound refers to a compound that contains carbon, has a shape such as a plate shape or a sheet shape, and has a two-dimensional structure formed of six-membered carbon rings. The two-dimensional structure formed by the six-membered carbon rings may be called a carbon sheet.
  • the graphene compound may have functional groups.
  • the graphene compound preferably has a bent shape.
  • the graphene compound may be rolled up like carbon nanofibers.
  • the active material layer may have metal powder or metal fiber such as copper, nickel, aluminum, silver, gold, etc., conductive ceramics material, etc. as a conductive material.
  • the content of the conductive material with respect to the total amount of the active material layer is preferably 1 wt% or more and 10 wt% or less, more preferably 1 wt% or more and 5 wt% or less.
  • the graphene compound Unlike a granular conductive material such as carbon black that makes point contact with the active material, the graphene compound enables surface contact with low contact resistance. It is possible to improve the electrical conductivity with Therefore, the ratio of the active material in the active material layer can be increased. Thereby, the discharge capacity of the battery can be increased.
  • Particulate carbon-containing compounds such as carbon black, graphite, etc., or fibrous carbon-containing compounds such as carbon nanotubes, easily enter minute spaces.
  • a minute space refers to, for example, a region between a plurality of active materials.
  • ⁇ Current collector> As the current collector, metals such as stainless steel, gold, platinum, zinc, iron, copper, aluminum, and titanium, and alloys thereof, which are highly conductive and do not alloy with carrier ions such as lithium, can be used. .
  • the shape of the current collector can be appropriately used such as a sheet shape, a mesh shape, a punching metal shape, an expanded metal shape, and the like.
  • a resin current collector can be used as the current collector.
  • resins such as polyolefin (polypropylene, polyethylene, etc.), nylon (polyamide), polyimide, vinylon, polyester, acrylic, polyurethane, etc., and particulate or fibrous conductive materials (also called conductive fillers) can be used.
  • the conductive material of the resin current collector one or more of conductive carbon materials and metal materials such as aluminum, titanium, stainless steel, gold, platinum, zinc, iron, and copper can be used.
  • the conductive carbon material for example, any one of carbon black such as acetylene black and furnace black, graphite such as artificial graphite and natural graphite, carbon fiber such as carbon nanofiber and carbon nanotube, graphene and graphene compound, or Two or more kinds can be used.
  • an antioxidant such as a hindered phenol-based material.
  • carbon fibers for example, carbon fibers such as mesophase pitch-based carbon fibers and isotropic pitch-based carbon fibers can be used.
  • Carbon nanofibers, carbon nanotubes, or the like can be used as carbon fibers.
  • Carbon nanotubes can be produced, for example, by vapor deposition.
  • the particle size of the conductive material contained in the resin current collector can have an average particle size of 10 nm or more and 10 ⁇ m or less, preferably 30 nm or more and 5 ⁇ m or less.
  • a current collector having a thickness of 5 ⁇ m or more and 30 ⁇ m or less.
  • the negative electrode current collector it is preferable to use a material that does not alloy with carrier ions such as lithium.
  • the positive electrode has a positive electrode active material layer and a positive electrode current collector.
  • the positive electrode active material layer contains a positive electrode active material and may further contain at least one of a conductive material and a binder.
  • As the positive electrode current collector, conductive material, and binder those described in [Negative electrode] can be used.
  • a metal foil for example, can be used as the current collector.
  • the positive electrode can be formed by applying a slurry onto a metal foil and drying it. In addition, you may add a press after drying.
  • the positive electrode is obtained by forming an active material layer on a current collector.
  • a slurry is a material liquid used to form an active material layer on a current collector, and refers to a liquid containing an active material, a binder, and a solvent, and preferably further mixed with a conductive material. Note that the slurry may be called an electrode slurry or an active material slurry, and may be called a positive electrode slurry when forming a positive electrode active material layer.
  • any one or more of a composite oxide having a layered rock salt structure, a composite oxide having an olivine structure, and a composite oxide having a spinel structure can be used.
  • any one or more of lithium cobaltate, nickel-cobalt-lithium manganate, nickel-cobalt-lithium aluminum oxide, and nickel-manganese-lithium aluminum oxide can be used as the composite oxide having a layered rock salt structure.
  • the composition formula can be represented as LiM1O 2 (M1 is one or more selected from nickel, cobalt, manganese, and aluminum), but the coefficients of the composition formula are not limited to integers.
  • lithium cobaltate to which magnesium and fluorine are added can be used as lithium cobaltate.
  • the composite oxide having an olivine structure one or more of lithium iron phosphate, lithium manganese phosphate, lithium cobalt phosphate, and lithium iron manganese phosphate can be used.
  • the composition formula can be expressed as LiM2PO 4 (M2 is one or more selected from iron, manganese, and cobalt), but the coefficients of the composition formula are not limited to integers.
  • a composite oxide having a spinel structure such as LiMn 2 O 4 can be used.
  • electrolytes examples of electrolytes are described below.
  • a liquid electrolyte also referred to as an electrolytic solution
  • electrolyte containing a solvent and an electrolyte dissolved in the solvent
  • the electrolyte is not limited to a liquid electrolyte (electrolytic solution) that is liquid at room temperature, and a solid electrolyte can also be used.
  • an electrolyte (semi-solid electrolyte) containing both a liquid electrolyte that is liquid at room temperature and a solid electrolyte that is solid at room temperature can be used.
  • a solid electrolyte or a semi-solid electrolyte is used for a bendable battery, the flexibility of the battery can be maintained by providing a structure in which a part of the laminate inside the battery contains the electrolyte.
  • Ionic liquids consist of cations and anions, including organic cations and anions.
  • Organic cations include aliphatic onium cations such as quaternary ammonium, tertiary sulfonium, and quaternary phosphonium cations, and aromatic cations such as imidazolium and pyridinium cations.
  • a monovalent amide anion a monovalent methide anion, a fluorosulfonate anion, a perfluoroalkylsulfonate anion, a tetrafluoroborate anion, a perfluoroalkylborate anion, a hexafluorophosphate anion, or a perfluoro Alkyl phosphate anions and the like are included.
  • carrier ions are, for example, alkali metal ions such as lithium ions, sodium ions, and potassium ions, alkaline earth metal ions such as calcium ions, strontium ions, barium ions, beryllium ions, and magnesium ions.
  • alkali metal ions such as lithium ions, sodium ions, and potassium ions
  • alkaline earth metal ions such as calcium ions, strontium ions, barium ions, beryllium ions, and magnesium ions.
  • the electrolyte contains a lithium salt.
  • Lithium salts such as LiPF6 , LiClO4 , LiAsF6, LiBF4 , LiAlCl4 , LiSCN , LiBr, LiI , Li2SO4 , Li2B10Cl10 , Li2B12Cl12 , LiCF3SO3 , LiC4F9SO3 , LiC ( CF3SO2 ) 3 , LiC( C2F5SO2 ) 3 , LiN( CF3SO2 ) 2 , LiN ( C4F9SO2 ) ( CF3SO2 ), LiN(C 2 F 5 SO 2 ) 2 and the like can be used.
  • Examples of the organic solvent described in this embodiment include ethylene carbonate (EC), ethylmethyl carbonate (EMC), and dimethyl carbonate (DMC), and these ethylene carbonate, ethylmethyl carbonate, and dimethyl carbonate
  • EC ethylene carbonate
  • EMC ethylmethyl carbonate
  • DMC dimethyl carbonate
  • EC ethylene carbonate
  • EMC ethylmethyl carbonate
  • DMC dimethyl carbonate
  • x: y: 100-x-y (where 5 ⁇ x ⁇ 35 and 0 ⁇ y ⁇ 65.) can be used.
  • the electrolytic solution has a low content of particulate matter or elements other than constituent elements of the electrolytic solution (hereinafter also simply referred to as "impurities") and is highly purified.
  • the weight ratio of impurities to the electrolytic solution is preferably 1% or less, preferably 0.1% or less, and more preferably 0.01% or less.
  • VC vinylene carbonate
  • PS propane sultone
  • TB tert-butylbenzene
  • FEC fluoroethylene carbonate
  • LiBOB lithium bis(oxalate)borate
  • dinitrile compounds of succinonitrile or adiponitrile may be added.
  • concentration of the additive may be, for example, 0.1 wt % or more and 5 wt % or less with respect to the solvent.
  • the electrolyte has a polymeric material that can be gelled, which increases safety against liquid leakage and the like.
  • gelled polymer materials include silicone gel, acrylic gel, acrylonitrile gel, polyethylene oxide gel, polypropylene oxide gel, and fluoropolymer gel.
  • polymers having a polyalkylene oxide structure such as polyethylene oxide (PEO), PVDF, polyacrylonitrile, etc., and copolymers containing them can be used.
  • PVDF-HFP which is a copolymer of PVDF and hexafluoropropylene (HFP)
  • the formed polymer may also have a porous geometry.
  • separator When the electrolyte includes an electrolytic solution, a separator is placed between the positive and negative electrodes.
  • separators include fibers containing cellulose such as paper, non-woven fabrics, glass fibers, ceramics, or synthetic materials using nylon (polyamide), polyimide, vinylon (polyvinyl alcohol fiber), polyester, acrylic, polyolefin, and polyurethane. Those formed of fibers or the like can be used. It is preferable that the separator be processed into a bag shape and arranged so as to enclose either the positive electrode or the negative electrode.
  • the separator may have a multilayer structure.
  • an organic material film such as polypropylene or polyethylene can be coated with a ceramic material, a fluorine material, a polyamide material, a polyimide material, or a mixture thereof.
  • the ceramic material for example, aluminum oxide particles, silicon oxide particles, or the like can be used.
  • PVDF, polytetrafluoroethylene, or the like can be used as the fluorine-based material.
  • polyamide-based material for example, nylon, aramid (meta-aramid, para-aramid) and the like can be used.
  • Coating with a ceramic material improves oxidation resistance, so it is possible to suppress the deterioration of the separator during high-voltage charging and discharging and improve the reliability of the battery.
  • the separator and the electrode are more likely to adhere to each other, and the output characteristics can be improved.
  • Coating with a polyamide-based material, particularly aramid improves heat resistance and thus improves the safety of the battery.
  • both sides of a polypropylene film may be coated with a mixed material of aluminum oxide and aramid.
  • a polypropylene film may be coated with a mixed material of aluminum oxide and aramid on the surface thereof in contact with the positive electrode, and coated with a fluorine-based material on the surface thereof in contact with the negative electrode.
  • the safety of the battery can be maintained even if the overall thickness of the separator is thin, so the capacity per unit volume of the battery can be increased.
  • Metal materials such as aluminum, stainless steel, and titanium, or resin materials can be used for the exterior body of the battery.
  • a film-like exterior body can also be used.
  • the film for example, a film made of a material such as polyethylene, polypropylene, polycarbonate, ionomer, or polyamide is provided with a highly flexible metal thin film or metal foil made of aluminum, stainless steel, titanium, copper, nickel, or the like.
  • a film having a three-layer structure in which an insulating synthetic resin film such as a polyamide-based resin or a polyester-based resin is provided on a metal thin film as the outer surface of the exterior body can be used.
  • a film having such a multilayer structure can be called a laminate film.
  • the laminate film may be called an aluminum (aluminum) laminate film, a stainless steel laminate film, a titanium laminate film, a copper laminate film, a nickel laminate film, or the like.
  • the material or thickness of the metal layer of the laminate film may affect the flexibility of the battery. It is preferable to use, for example, an aluminum laminate film having a polypropylene layer, an aluminum layer, and nylon as an exterior body used for a battery that is excellent in flexibility (bendable).
  • the thickness of the aluminum layer is preferably 50 ⁇ m or less, more preferably 40 ⁇ m or less, more preferably 30 ⁇ m or less, and more preferably 20 ⁇ m or less. If the aluminum layer is thinner than 10 ⁇ m, pinholes in the aluminum layer may degrade the gas barrier properties, so the thickness of the aluminum layer is preferably 10 ⁇ m or more.
  • a graphene sheet may be used instead of the metal layer.
  • a graphene sheet a multilayer graphene sheet with a thickness of 100 nm or more and 30 ⁇ m or less, preferably 200 nm or more and 20 ⁇ m or less can be used. Since the graphene sheet is flexible and the distance between graphene layers is 0.34 nm and it has gas barrier properties, it is suitable as a film used for the outer packaging of a secondary battery.
  • a laminate film can be used as the laminate film.
  • a metal film having a heat seal layer on one side or both sides can be used.
  • the adhesive layer can use a heat-fusible resin film containing polypropylene, polyethylene, or the like.
  • an aluminum laminate film is used, which has a nylon resin on the front surface of the aluminum foil, and a lamination of an acid-resistant polypropylene film and a polypropylene film on the rear surface of the aluminum foil.
  • the film is embossed. As a result, a film having an uneven shape can be produced.
  • the film has a visible wavy pattern by having a plurality of uneven portions.
  • FIG. 11 is a cross-sectional view showing an example of embossing.
  • embossing is a type of press work, and refers to a process in which an embossing roll having an uneven surface is brought into pressure contact with a film to form unevenness corresponding to the unevenness of the embossing roll on the film.
  • the embossing roll is a roll having a pattern engraved on its surface.
  • FIG. 11 is an example of embossing on both sides of the film. Also, it is a method of forming a film having a convex portion having a top portion on one surface side.
  • FIG. 11 shows the film 90 sandwiched between an embossing roll 95 in contact with one surface of the film and an embossing roll 96 in contact with the other surface, and the film 90 being sent out in a film traveling direction 91. showing.
  • a pattern is formed on the film surface by pressure or heat.
  • a pattern may be formed on the film surface by both pressure and heat.
  • a metal roll, a ceramic roll, a plastic roll, a rubber roll, an organic resin roll, a wood roll, or the like can be used as the embossing roll as appropriate.
  • embossing is performed using an embossing roll 96 that is an embossing roll with a male handle and an embossing roll 95 with a female handle.
  • the male handle embossing roll 96 has a plurality of protrusions 96a.
  • the projections correspond to the projections formed on the film to be processed.
  • the female handle embossing roll 95 has a plurality of protrusions 95a.
  • the adjacent projections 95a form recesses that fit into the projections formed on the film by the projections 96a provided on the embossing roll 96 with a male handle.
  • the convex part and the flat part can be continuously formed. As a result, a pattern can be formed on the film 90 .
  • FIGS. 12A to 12E a film having a plurality of projections with a shape different from that of FIG. 11 will be described with reference to FIGS. 12A to 12E.
  • embossing with various cross-sectional shapes shown in FIGS. 12A to 12E can be performed.
  • FIG. 12A is a cross-sectional schematic diagram of an embossing having a wavy shape
  • FIGS. 12B to 12E are modifications of FIG. 12A
  • 12B and 12C are diagrams showing an example of forming the wavy shape in steps
  • FIG. 12D is a diagram showing an example of forming the wavy shape into a rectangular shape
  • FIG. It is a figure which shows the example formed by the valley shape and the peak shape of a trapezoid.
  • FIGS. 13A and 13B are bird's-eye views showing the finished shape when the embossing shown in FIGS. 11 to 12E is performed twice while changing the direction of the film 90.
  • a film with the embossed shape shown (which can be referred to as a cross-corrugated shape) can be obtained.
  • the film 81a having a cross-wave shape shown in FIG. 13A shows an outer shape used when a single film 81a is used to manufacture a secondary battery, and can be used by being folded in two along the dashed line.
  • the film 81b and the film 81c can be overlapped and used.
  • the embossed shapes shown in FIGS. 13A and 13B may be produced by a production method other than the above production method. For example, by setting the shape of the embossing roll to a twill pattern, an embossed shape similar to the embossed shape shown in FIGS. 13A and 13B can be obtained in one embossing process.
  • the film can be processed without being cut, it is excellent in mass productivity.
  • the film may be processed by pressing against the film a pair of embossing plates having an uneven surface, for example, without being limited to the processing using the embossing rolls. At this time, one side of the embossed plate may be flat, and may be processed in multiple steps.
  • the exterior body on one surface and the exterior body on the other side of the secondary battery have the same embossed shape.
  • the configuration of the battery is not limited to this.
  • the secondary battery can have an embossed shape on one surface of the secondary battery and a non-embossed shape on the other surface of the secondary battery.
  • the exterior body on one side of the secondary battery and the exterior body on the other side may have different embossed shapes.
  • An electronic device 6500 shown in FIG. 14A is a mobile information terminal that can be used as a smartphone.
  • the electronic device 6500 has at least a first housing 6501a, a second housing 6501b, a hinge section 6519, a first display section 6502a, a power button 6503, a button 6504, a speaker 6505, and a microphone 6506.
  • the first display portion 6502a has a touch panel function.
  • the first housing 6501a and the second housing 6501b are connected via a hinge portion 6519.
  • the electronic device 6500 can be bent at the hinge portion 6519 .
  • FIG. 14B is a schematic cross-sectional view including the end of the housing 6501 (6501a, 6501b) on the microphone 6506 side.
  • a light-transmitting protective member 6510 is provided on the display surface side of the housing 6501 (6501a, 6501b).
  • An optical member 6512, a touch sensor panel 6513, a printed circuit board 6517, and a first battery 6518a are arranged.
  • a display panel 6511, an optical member 6512, and a touch sensor panel 6513 are fixed to the protective member 6510 with an adhesive layer (not shown).
  • a portion of the display panel 6511 is folded back in a region outside the first display portion 6502a, and the FPC 6515 is connected to the folded portion.
  • An IC6516 is mounted on the FPC6515.
  • the FPC 6515 is connected to terminals provided on the printed circuit board 6517 .
  • a flexible display can be applied to the display panel 6511.
  • a flexible display includes a plurality of light-emitting elements that are formed using a plurality of flexible films and are arranged in a matrix.
  • an EL element also referred to as an EL device
  • Examples of light-emitting substances that EL devices have include substances that emit fluorescence (fluorescent materials), substances that emit phosphorescence (phosphorescent materials), inorganic compounds (quantum dot materials, etc.), and substances that exhibit heat-activated delayed fluorescence (heat-activated delayed fluorescence (TADF) material) and the like.
  • LEDs such as micro LED, can also be used as a light emitting element.
  • the display panel 6511 can be provided to overlap with the first housing 6501a, the second housing 6501b, and the hinge portion 6519, and the display panel 6511 can be folded at the hinge portion 6519. becomes possible.
  • the internal space of the housing 6501 (6501a, 6501b) can be effectively used, and an extremely lightweight electronic device can be realized.
  • the display panel 6511 is extremely thin, the thickness of the electronic device can be reduced and the first battery 6518a with a large capacity can be mounted.
  • the electronic device 6500 has a configuration in which a second battery 6518b is provided inside the cover portion 6520 in order to use a large-capacity battery. are electrically connected.
  • the flexible battery of one embodiment of the present invention can be applied to the first battery 6518a and the second battery 6518b.
  • the battery can be provided in a position overlapping with the first housing 6501a, the second housing 6501b, and the hinge portion 6519, and the battery can be bent at the hinge portion 6519. Become.
  • part of the electronic device 6500 can be folded to be downsized and highly portable.
  • Device 6500 can be implemented.
  • FIG. 15A is a perspective view showing a state in which the dotted line portion in FIG. 14A is folded.
  • the electronic device 6500 can be folded in two, and the first display portion 6502a and the second battery 6518b can be repeatedly folded.
  • FIG. 15A has a configuration in which a second display portion 6502b is provided in a portion where the cover portion 6520 is slid by folding. Even when the display is folded in two, the user can easily confirm the time display or notification display of mail reception by visually recognizing the second display portion 6502b.
  • FIG. 15B schematically illustrates a cross-sectional state of the cover portion when the electronic device 6500 is folded.
  • the inside of housing 6501 (6501a, 6501b) is not shown for simplification.
  • the hinge part 6519 can also be called a connection part, and is not limited to the example of the structure in which a plurality of columnar bodies are connected, and can have various forms. In particular, it is preferable to have a mechanism for bending the first display portion 6502a and the second battery 6518b without extending or contracting them.
  • the second battery 6518b is illustrated inside the cover portion 6520, a plurality of batteries may be provided. Further, the inside of the cover portion 6520 may have a charging control circuit or a wireless charging circuit for the second battery 6518b.
  • the cover part 6520 is partly fixed to the housing 6501 (6501a, 6501b), and the part overlapping the hinge part 6519 and the part overlapping the second display part 6502b by bending and sliding are not fixed.
  • the cover part 6520 does not have to be fixed to the housing 6501 (6501a, 6501b), and may be detachable.
  • the electronic device 6500 can be used by removing the cover portion 6520 and using the first battery 6518a. Further, by charging the attached/detached second battery 6518b, the first battery 6518a can be replenished when the second battery 6518b is reconnected to the first battery 6518a. Therefore, the cover part 6520 can also be used as a mobile battery.
  • 15A and 15B show an example in which the display surface of the first display portion 6502a is folded inward, but it is not particularly limited, and depending on the configuration of the hinge portion 6519, it may be folded outward. It may also be possible to fold it in two.
  • the flexible battery of one embodiment of the present invention has high reliability against repeated deformation, and thus can be suitably used for such foldable (also called foldable) devices.
  • This embodiment can be implemented by appropriately combining at least part of it with other embodiments described herein.
  • FIG. 3 An example of mounting the secondary battery 10 of one embodiment of the present invention in an electronic device will be described.
  • electronic devices that implement batteries include television devices (also called televisions or television receivers), monitors for computers, digital cameras, digital video cameras, digital photo frames, mobile phones (mobile phones, mobile phones (also referred to as a device), portable game machines, personal digital assistants, sound reproduction devices, and large game machines such as pachinko machines.
  • Portable information terminals include notebook personal computers, tablet terminals, electronic book terminals, mobile phones, and the like.
  • FIG. 16A shows an example of a mobile phone.
  • a mobile phone 2100 includes a display unit 2102 incorporated in a housing 2101, operation buttons 2103, an external connection port 2104, a speaker 2105, a microphone 2106, and the like. Note that the mobile phone 2100 has a battery 2107 . Since the battery 2107 is bendable, it can be mounted in a bendable region of the mobile phone 2100 .
  • the mobile phone 2100 can execute various applications such as mobile phone, e-mail, reading and creating text, playing music, Internet communication, and computer games.
  • the operation button 2103 can have various functions such as time setting, power on/off operation, wireless communication on/off operation, manner mode execution/cancellation, and power saving mode execution/cancellation.
  • the operating system installed in the mobile phone 2100 can freely set the functions of the operation buttons 2103 .
  • the mobile phone 2100 is capable of performing standardized short-range wireless communication. For example, by intercommunicating with a headset capable of wireless communication, hands-free communication is also possible.
  • the mobile phone 2100 has an external connection port 2104, and can directly exchange data with other information terminals via connectors. Also, charging can be performed via the external connection port 2104 . Note that the charging operation may be performed by wireless power supply without using the external connection port 2104 .
  • the mobile phone 2100 preferably has a sensor.
  • a sensor for example, a fingerprint sensor, a pulse sensor, a body sensor such as a body temperature sensor, a touch sensor, a pressure sensor, an acceleration sensor, or the like is preferably mounted.
  • FIG. 16B is an unmanned aerial vehicle 2300 having multiple rotors 2302 .
  • Unmanned aerial vehicle 2300 may also be referred to as a drone.
  • Unmanned aerial vehicle 2300 has a battery 2301, a camera 2303, and an antenna (not shown), which is an aspect of the present invention.
  • Unmanned aerial vehicle 2300 can be remotely operated via an antenna.
  • the battery 2301 is bendable and can also be mounted on bend areas of the unmanned aerial vehicle 2300 .
  • FIG. 16C shows an example of a robot.
  • a robot 6400 shown in FIG. 16C includes a battery 6409, an illumination sensor 6401, a microphone 6402, an upper camera 6403, a speaker 6404, a display unit 6405, a lower camera 6406, an obstacle sensor 6407, a moving mechanism 6408, an arithmetic device, and the like.
  • the battery 6409 is bendable and can also be mounted on bendable areas of the robot 6400 .
  • the microphone 6402 has a function of detecting the user's speech and environmental sounds. Also, the speaker 6404 has a function of emitting sound. Robot 6400 can communicate with a user using microphone 6402 and speaker 6404 .
  • the display unit 6405 has a function of displaying various information.
  • the robot 6400 can display information desired by the user on the display unit 6405 .
  • the display portion 6405 may include a touch panel. Further, the display unit 6405 may be a detachable information terminal, and by installing it at a fixed position of the robot 6400, charging and data transfer are possible.
  • the upper camera 6403 and the lower camera 6406 have the function of imaging the surroundings of the robot 6400.
  • the obstacle sensor 6407 can detect the presence or absence of an obstacle in the direction in which the robot 6400 moves forward using the movement mechanism 6408 .
  • the robot 6400 uses an upper camera 6403, a lower camera 6406, and an obstacle sensor 6407 to recognize the surrounding environment and can move safely.
  • a robot 6400 includes a battery 6409 according to one embodiment of the present invention and a semiconductor device or an electronic component in its internal region.
  • FIG. 16D shows an example of a cleaning robot.
  • the cleaning robot 6300 has a display unit 6302 arranged on the upper surface of a housing 6301, a plurality of cameras 6303 arranged on the side surfaces, a brush 6304, an operation button 6305, a battery 6306, various sensors, and the like.
  • the cleaning robot 6300 is equipped with tires, a suction port, and the like.
  • the cleaning robot 6300 can run by itself, detect dust 6310, and suck the dust from a suction port provided on the bottom surface.
  • the battery 6306 is bendable and can also be mounted in bendable areas of the cleaning robot 6300 .
  • the cleaning robot 6300 can analyze the image captured by the camera 6303 and determine the presence or absence of obstacles such as walls, furniture, or steps. Further, when an object such as wiring that is likely to get entangled in the brush 6304 is detected by image analysis, the rotation of the brush 6304 can be stopped.
  • the cleaning robot 6300 includes a battery 6306, which is one embodiment of the present invention, and a semiconductor device or an electronic component in its internal area.
  • FIG. 17A shows an example of a wearable device.
  • Wearable devices use flexible batteries as power sources.
  • wearable devices that can be charged not only by wires with exposed connectors but also by wireless charging are being developed. Desired.
  • the flexible battery that is one embodiment of the present invention can be mounted on a spectacles-type device 4000 as shown in FIG. 17A.
  • the glasses-type device 4000 has a frame 4000a and a display section 4000b.
  • the spectacles-type device 4000 that is lightweight, has a good weight balance, and can be used continuously for a long time can be obtained.
  • a flexible battery can be bent and can be mounted on a curved portion.
  • the headset device 4001 can be equipped with a battery that is one embodiment of the present invention.
  • the headset type device 4001 has at least a microphone section 4001a, a flexible pipe 4001b, and an earphone section 4001c.
  • a battery can be provided in the flexible pipe 4001b or in the earphone portion 4001c. The battery is bendable and can be mounted on curved sections.
  • the flexible battery which is one embodiment of the present invention can be mounted on the device 4002 that can be attached directly to the body.
  • a flexible battery 4002b can be provided within a thin housing 4002a of the device 4002. FIG.
  • a flexible battery can be bent and can be mounted on a curved portion.
  • the flexible battery that is one embodiment of the present invention can be mounted on the device 4003 that can be attached to clothes.
  • a flexible battery 4003b can be provided in a thin housing 4003a of the device 4003.
  • FIG. A flexible battery can be bent and can be mounted on a curved portion.
  • the belt-type device 4006 can be equipped with a flexible battery that is one embodiment of the present invention.
  • the belt-type device 4006 has a belt portion 4006a and a wireless power supply receiving portion 4006b, and a flexible battery can be mounted in the inner region of the belt portion 4006a.
  • a flexible battery can be bent and can be mounted on a curved portion.
  • the wristwatch-type device 4005 can be equipped with a flexible battery that is one embodiment of the present invention.
  • a wristwatch-type device 4005 has a display portion 4005a and a belt portion 4005b, and a flexible battery can be provided in the display portion 4005a or the belt portion 4005b.
  • a flexible battery can be bent and can be mounted on a curved portion.
  • the display unit 4005a can display not only the time but also various information such as incoming e-mails or phone calls.
  • the wristwatch-type device 4005 is a type of wearable device that is directly wrapped around the arm, it may be equipped with a sensor that measures the user's pulse, blood pressure, and the like. It is possible to accumulate data on the amount of exercise and health of the user and manage the health.
  • FIG. 17B shows a perspective view of the wristwatch-type device 4005 removed from the arm.
  • FIG. 17C shows a state in which a flexible battery 913 is built in the inner region.
  • the flexible battery 913 is provided so as to overlap with the display portion 4005a, can have high density and high capacity, and is small and lightweight.
  • Flexible battery 913 can be bent and can be mounted on a curved portion.
  • FIG. 17D shows an example of wireless earphones. Although a wireless earphone having a pair of main bodies 4100a and 4100b is illustrated here, they are not necessarily a pair.
  • the main bodies 4100a and 4100b have a driver unit 4101, an antenna 4102, and a flexible battery 4103.
  • a display portion 4104 may be provided.
  • Flexible battery 4103 can be bent and can be mounted on a curved portion.
  • the case 4110 has a flexible battery 4111. Moreover, it is preferable to have a board on which circuits such as a wireless IC and a charging control IC are mounted, and a charging terminal. Further, it may have a display portion, buttons, and the like. Flexible battery 4111 can be bent and can be mounted on a curved portion.
  • the main bodies 4100a and 4100b can wirelessly communicate with other electronic devices such as smartphones. As a result, sound data and the like sent from other electronic devices can be reproduced by the main bodies 4100a and 4100b. Also, if the main bodies 4100a and 4100b have microphones, the sound acquired by the microphones can be sent to another electronic device, and the sound data processed by the electronic device can be sent back to the main bodies 4100a and 4100b for reproduction. As a result, it can be used as a translator, for example.
  • the flexible battery 4103 of the main body 4100a can be charged from the flexible battery 4111 of the case 4110.
  • Flexible battery 4111 and flexible battery 4103 can be bent and can be mounted on a curved portion.
  • FIG. 18A to 18C show examples of spectacle-type devices different from the above.
  • FIG. 18A is a perspective view of the eyewear device 5000.
  • FIG. 18C is a perspective view of the eyewear device 5000.
  • the glasses-type device 5000 has a function as a so-called mobile information terminal, and can execute various programs and reproduce various contents by connecting to the Internet.
  • the glasses-type device 5000 has a function of displaying augmented reality content in AR mode.
  • the glasses-type device 5000 may also have a function of displaying virtual reality content in VR mode.
  • the glasses-type device 5000 may have a function of displaying content of alternative reality (SR) or mixed reality (MR).
  • SR alternative reality
  • MR mixed reality
  • a spectacles-type device 5000 includes a housing 5001, an optical member 5004, a wearing tool 5005, a light blocking section 5007, earphones 5008, and the like.
  • the housing 5001 preferably has a cylindrical shape.
  • the spectacles-type device 5000 has a configuration that can be worn on the user's head.
  • the housing 5001 of the spectacles-type device 5000 is worn on the user's head above the peripheral line of the head passing through the eyebrows and ears.
  • a housing 5001 is fixed to an optical member 5004 .
  • the optical member 5004 is fixed to the mounting fixture 5005 via the light shielding portion 5007 or via the housing 5001 .
  • the glasses-type device 5000 has a display device 5021, a reflector 5022, a flexible battery 5024, and a system section.
  • the display device 5021 , the reflector 5022 , the flexible battery 5024 , and the system section are each preferably provided inside the housing 5001 .
  • the system unit can include a control unit, a storage unit, a communication unit, a sensor, and the like, which the glasses-type device 5000 has. Further, it is preferable that the system section is provided with a charging circuit, a power supply circuit, and the like.
  • the flexible battery 5024 can be bent and can be mounted on curved sections.
  • FIG. 18B shows each part of the spectacles-type device 5000 in FIG. 18A.
  • FIG. 18B is a schematic diagram for explaining the details of each part of the spectacles-type device 5000 shown in FIG. 18A.
  • a flexible battery 5024, a system section 5026, and a system section 5027 are provided along the tube in a tube-shaped housing 5001.
  • FIG. A system unit 5025 is provided along the flexible battery 5024 and the like.
  • the housing 5001 preferably has a shape of a curved cylinder.
  • the flexible battery 5024 can be efficiently arranged in the housing 5001, the space in the housing 5001 can be efficiently used, and the flexible battery 5024 can be used. In some cases, the volume of battery 5024 can be increased.
  • the housing 5001 has, for example, a cylindrical shape, and has a shape such that the axis of the cylinder follows, for example, a part of an approximately elliptical shape.
  • the cross section of the tube is, for example, substantially elliptical.
  • the cross section of the tube has, for example, a part that is elliptical.
  • a portion having an elliptical cross-section is positioned on the side facing the head when the device is worn.
  • the cross section of the cylinder may have a portion that is partially polygonal (triangular, quadrangular, pentagonal, etc.).
  • the housing 5001 is curved along the user's forehead. Further, the housing 5001 is arranged, for example, along the forehead.
  • the housing 5001 may be configured by combining two or more cases. For example, a configuration in which an upper case and a lower case are combined can be used. Further, for example, it is possible to adopt a configuration in which an inner case (the side to be worn by the user) and an outer case are combined. Moreover, it is good also as a structure which combined three or more cases.
  • an electrode can be provided in the part that touches the forehead, and the electroencephalogram can be measured by the electrode.
  • an electrode may be provided in a portion that touches the forehead, and information such as sweat of the user may be measured by the electrode.
  • a plurality of flexible batteries 5024 may be arranged inside the housing 5001 .
  • the flexible battery 5024 is preferable because it can have a shape that follows a curved cylinder.
  • the flexible battery has flexibility, it is possible to increase the degree of freedom of arrangement inside the housing.
  • a flexible battery 5024, a system unit, and the like are arranged inside the cylindrical housing.
  • the system section is configured on, for example, a plurality of circuit boards.
  • a plurality of circuit boards and flexible batteries are connected using connectors, wiring, and the like. Since the flexible battery has flexibility, it can be arranged while avoiding connectors, wiring, and the like.
  • the flexible battery 5024 may be provided inside the mounting tool 5005, for example, in addition to the inside of the housing 5001.
  • 19A to 19C show examples of head-mounted devices.
  • 19A and 19B show a head-mounted device 5100 having a band-like attachment 5105, and the head-mounted device 5100 is connected via a cable 5120 to a terminal 5150 shown in FIG. 19C.
  • FIG. 19A shows a state in which the first portion 5102 is closed
  • FIG. 19B shows a state in which the first portion 5102 is opened.
  • the first portion 5102 has a shape that covers not only the front but also the sides of the face when closed. As a result, the field of view of the user can be shielded from external light, thereby enhancing the sense of realism and immersion. For example, depending on the content displayed, the user's sense of fear can be heightened.
  • a wearing tool 5105 has a band-like shape. As a result, it is less likely to shift than the configuration shown in FIG. 19A, etc., and is suitable for enjoying content with a relatively large amount of exercise, such as attractions.
  • a flexible battery 5107 or the like may be built in the occipital region of the wearing tool 5105 .
  • the center of gravity of the head-mounted device 5100 can be adjusted, and the feeling of wearing can be improved. can.
  • a flexible battery 5108 having flexibility may be arranged inside the band-shaped wearing tool 5105 .
  • the example shown in FIG. 19A shows an example in which two flexible batteries 5108 are arranged inside the mounting tool 5105 .
  • a flexible battery having flexibility it is possible to form a shape along a curved band shape, which is preferable.
  • the wearing tool 5105 also has a portion 5106 that covers the user's forehead or forehead. By having the portion 5106, it is possible to make it more difficult to shift.
  • electrodes can be provided in the portion 5106 or the portion of the housing 5101 that touches the forehead, and electroencephalograms can be measured using the electrodes.
  • FIG. 20C shows a block diagram of a vehicle with a motor.
  • the electric vehicle is provided with first batteries 1301a and 1301b as secondary batteries for main driving, and a second battery 1311 that supplies power to an inverter 1312 that starts the motor 1304 .
  • the second battery 1311 is also called cranking battery or starter battery.
  • the second battery 1311 only needs to have a high output and does not need a large capacity so much, and the capacity of the second battery 1311 is smaller than that of the first batteries 1301a and 1301b.
  • one or both of the first batteries 1301a and 1301b can be a secondary battery manufactured using the method for manufacturing a secondary battery according to one embodiment of the present invention.
  • first batteries 1301a and 1301b are connected in parallel
  • three or more batteries may be connected in parallel.
  • the first battery 1301a can store sufficient electric power
  • the first battery 1301b may be omitted.
  • a large amount of electric power can be extracted by forming a battery pack including a plurality of secondary batteries.
  • a plurality of secondary batteries may be connected in parallel, may be connected in series, or may be connected in series after being connected in parallel.
  • a plurality of secondary batteries is also called an assembled battery.
  • a secondary battery for vehicle has a service plug or a circuit breaker that can cut off high voltage without using a tool in order to cut off power from a plurality of secondary batteries.
  • the power of the first batteries 1301a and 1301b is mainly used to rotate the motor 1304, but it is also used to power 42V (high voltage) vehicle components (electric power steering 1307, heater 1308) via a DCDC circuit 1306. , defogger 1309).
  • the first battery 1301a is also used to rotate the rear motor 1317 when the rear wheel has the rear motor 1317 .
  • the second battery 1311 supplies power to 14V system (low voltage system) in-vehicle components (audio 1313, power window 1314, lamps 1315, etc.) via the DCDC circuit 1310.
  • 14V system low voltage system
  • in-vehicle components audio 1313, power window 1314, lamps 1315, etc.
  • the internal structure of the first battery 1301a may be the stacked type shown in FIG. 1 and the like, or the wound type shown in FIG. 9 and the like.
  • FIG. 20A shows an example in which nine square secondary batteries 1300 are used as one battery pack 1415 . Also, nine square secondary batteries 1300 are connected in series, one electrode is fixed by a fixing portion 1413 made of an insulator, and the other electrode is fixed by a fixing portion 1414 made of an insulator. In this embodiment mode, an example of fixing by fixing portions 1413 and 1414 is shown; Since it is assumed that the vehicle is subject to vibration or shaking from the outside (road surface, etc.), it is preferable to fix a plurality of secondary batteries using fixing portions 1413 and 1414, a battery housing box, or the like.
  • One electrode is electrically connected to the control circuit portion 1320 through a wiring 1421 .
  • the other electrode is electrically connected to the control circuit section 1320 by wiring 1422 .
  • control circuit portion 1320 may use a memory circuit including a transistor using an oxide semiconductor.
  • a charge control circuit or a battery control system including a memory circuit including a transistor using an oxide semiconductor is sometimes called 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 charging/discharging state of the secondary battery. For example, both the output transistor of the charging circuit and the cut-off switch can be turned off almost simultaneously to prevent overcharging.
  • FIG. 20B An example of a block diagram of the battery pack 1415 shown in FIG. 20A is shown in FIG. 20B.
  • the control circuit unit 1320 includes a switch unit 1324 including at least a switch for preventing overcharge and a switch for preventing overdischarge, a control circuit 1322 for controlling the switch unit 1324, and a voltage measurement 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 or the upper limit of the output current to the outside. The range from the lower limit voltage to the upper limit voltage of the secondary battery is within the voltage range recommended for use.
  • the control circuit unit 1320 controls the switch unit 1324 to prevent over-discharging or over-charging, it can also be called a protection circuit.
  • control circuit 1322 detects a voltage that is likely to cause overcharging
  • the switch of the switch section 1324 is turned off to cut off the current.
  • a PTC element may be provided in the charging/discharging path to provide a function of interrupting the current according to the temperature rise.
  • the control circuit section 1320 also has an external terminal 1325 (+IN) and an external terminal 1326 (-IN).
  • the switch section 1324 can be configured by combining one or both of an n-channel transistor and a p-channel transistor.
  • the switch unit 1324 is not limited to a switch having a Si transistor using single crystal silicon. indium), SiC (silicon carbide), ZnSe (zinc selenide), GaN (gallium nitride), GaOx (gallium oxide; x is a real number greater than 0), or the like.
  • a memory element using an OS transistor can be freely arranged by stacking it on a circuit using a Si transistor or the like, integration can be easily performed.
  • an OS transistor can be manufactured using a manufacturing apparatus similar to that of a Si transistor, it can be manufactured at low cost. That is, the control circuit portion 1320 using an OS transistor can be stacked on the switch portion 1324 and integrated into one chip. Since the volume occupied by the control circuit section 1320 can be reduced, miniaturization is possible.
  • the first batteries 1301a and 1301b mainly supply power to 42V system (high voltage system) in-vehicle equipment, and the second battery 1311 supplies power to 14V system (low voltage system) in-vehicle equipment.
  • a lead-acid battery is often adopted as the second battery 1311 because of its cost advantage.
  • the second battery 1311 may use a lead-acid battery, an all-solid battery, or an electric double layer capacitor.
  • regenerated energy from the rotation of the tire 1316 is sent to the motor 1304 via the gear 1305 and charged to the second battery 1311 via the control circuit section 1321 from the motor controller 1303 or the battery controller 1302 .
  • the battery controller 1302 charges the first battery 1301 a through the control circuit unit 1320 .
  • the battery controller 1302 charges the first battery 1301b through the control circuit unit 1320 . In order to efficiently charge the regenerated energy, it is desirable that the first batteries 1301a and 1301b be capable of rapid charging.
  • the battery controller 1302 can set the charging voltage and charging current 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 perform rapid charging.
  • the outlet of the charger or the connection cable of the charger is electrically connected to the battery controller 1302 .
  • Electric power supplied from an external charger charges the first batteries 1301 a and 1301 b via the battery controller 1302 .
  • Some chargers are provided with a control circuit and do not use the function of the battery controller 1302, but the first batteries 1301a and 1301b are charged via the control circuit unit 1320 to prevent overcharging. is preferred.
  • the connection cable or the connection cable of the charger is provided with the control circuit.
  • the control circuit section 1320 is sometimes called an ECU (Electronic Control Unit).
  • the ECU is connected to a CAN (Controller Area Network) provided in the electric vehicle.
  • CAN is one of serial communication standards used as an in-vehicle LAN.
  • the ECU includes a microcomputer.
  • 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 ships, submarines, aircraft such as fixed or rotary wing aircraft, rockets, artificial satellites
  • a secondary battery can also be mounted on a transportation vehicle such as a space probe, a planetary probe, or a spacecraft.
  • a vehicle 3001 shown in FIG. 21A is an electric vehicle that uses an electric motor as a power source for running. Alternatively, it is a hybrid vehicle in which an electric motor and an engine can be appropriately selected and used as power sources for running. When a secondary battery is installed in a vehicle, the secondary battery is installed at one or more locations.
  • the automobile 3001 shown in FIG. 21A has the battery pack 1415 shown in FIG. 20A.
  • Battery pack 1415 has a secondary battery module. It is preferable that the battery pack 1415 further includes a charging control device electrically connected to the secondary battery module.
  • a secondary battery module has a single or a plurality of secondary batteries.
  • the vehicle 3001 can be charged by receiving power from an external charging facility by a plug-in system or a contactless power supply system to the secondary battery of the vehicle 3001 .
  • the charging method or the standard of the connector may be appropriately performed by a predetermined method such as CHAdeMO (registered trademark) or Combo.
  • the charging device may be a charging station provided in a commercial facility, or may be a household power source.
  • plug-in technology can charge a secondary battery mounted on the automobile 3001 with power supplied 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 can be mounted on a vehicle, and power can be supplied from a power transmission device on the ground in a contactless manner for charging.
  • this non-contact power supply system it is possible to charge the vehicle not only while the vehicle is stopped but also while the vehicle is running by installing a power transmission device on the road or the outer wall.
  • power may be transmitted and received between two vehicles.
  • a solar panel may be provided on the exterior of the vehicle to charge the secondary battery while the vehicle is stopped or running. An electromagnetic induction method or a magnetic resonance method can be used for such contactless power supply. Solar panels are sometimes called solar modules.
  • FIG. 21B shows a large transport vehicle 3002 with electrically controlled motors as an example of a transport vehicle.
  • the secondary battery module of the transportation vehicle 3002 has a maximum voltage of 170 V, which is formed by connecting 48 cells in series with four secondary batteries each having a voltage of, for example, 3.5 V or more and 4.7 V or less. Except for the number of secondary batteries forming the secondary battery module of the battery pack 3201, the function is the same as that of FIG. 21A, so the description is omitted.
  • FIG. 21C shows, as an example, a large transport vehicle 3003 with electrically controlled motors.
  • the secondary battery module of the transportation vehicle 3003 has a maximum voltage of 600 V, for example, a hundred or more secondary batteries of 3.5 V or more and 4.7 V or less connected in series. Therefore, a secondary battery with small variations in characteristics is required.
  • a secondary battery having stable battery characteristics can be manufactured, and mass production is possible at low cost in terms of yield. 21A except that the number of secondary batteries constituting the secondary battery module of the battery pack 3202 is different, description thereof is omitted.
  • FIG. 21D shows an aircraft 3004 having an engine that burns fuel as an example. Since the aircraft 3004 shown in FIG. 21D has wheels for takeoff and landing, it can be said to be a type of transportation vehicle, and a secondary battery module is configured by connecting a plurality of secondary batteries, and the secondary battery module and charging control are performed. and a battery pack 3203 containing a device.
  • the secondary battery module of aircraft 3004 has a maximum voltage of 32V, for example, eight 4V secondary batteries connected in series. Except for the number of secondary batteries forming the secondary battery module of the battery pack 3203, the function is the same as that of FIG. 21A, so the description is omitted.
  • FIG. 21E shows a transport vehicle 3005 that transports cargo as an example. It has a motor controlled by electricity, and performs various operations by supplying power from a secondary battery that constitutes a secondary battery module of the battery pack 3204 . Further, the transportation vehicle 3005 is not limited to being operated by a human as a driver, and can be operated unmanned by CAN communication or the like. Although FIG. 21E shows a forklift, the present invention is not particularly limited, and can be applied to industrial machines that can be operated by CAN communication, such as automatic transporters, work robots, or small construction machines. A battery pack having a secondary battery can be mounted.
  • FIG. 22A is an example of an electric bicycle using the secondary battery of one embodiment of the present invention.
  • the secondary battery of one embodiment of the present invention can be applied to the electric bicycle 3100 illustrated in FIG. 22A.
  • a power storage device 3102 illustrated in FIG. 22B includes, for example, a plurality of secondary batteries and a protection circuit.
  • the electric bicycle 3100 has a power storage device 3102 .
  • the power storage device 3102 can supply electricity to a motor that assists the driver.
  • the power storage device 3102 is portable, and is shown removed from the bicycle in FIG. 22B.
  • the power storage device 3102 includes a plurality of secondary batteries 3101 of one embodiment of the present invention, and the remaining battery level and the like can be displayed on the display portion 3103 .
  • the power storage device 3102 also includes a control circuit 3104 capable of controlling charging of the secondary battery or detecting an abnormality, which is an example of one embodiment of the present invention.
  • the control circuit 3104 is electrically connected to the positive and negative electrodes of the secondary battery 3101 .
  • a small solid secondary battery may be provided in the control circuit 3104 . By providing a small solid secondary battery in the control circuit 3104, power can be supplied to hold data in the memory circuit included in the control circuit 3104 for a long time.
  • FIG. 22C is an example of a motorcycle using the secondary battery of one embodiment of the present invention.
  • the power storage device 3302 can supply electricity to the turn signal lights 3303 .
  • the power storage device 3302 can be stored in the storage 3304 under the seat.
  • the power storage device 3302 can be stored in the under-seat storage 3304 even if the under-seat storage 3304 is small.
  • the house illustrated in FIG. 23A includes a power storage device 2612 including a secondary battery with stable battery characteristics and a solar panel 2610 by using a method for manufacturing a secondary battery according to one embodiment of the present invention.
  • the power storage device 2612 is electrically connected to the solar panel 2610 through a wiring 2611 or the like. Alternatively, the power storage device 2612 and the ground-mounted charging device 2604 may be electrically connected.
  • a power storage device 2612 can be charged with power obtained from the solar panel 2610 . Electric power stored in power storage device 2612 can be used to charge a secondary battery of vehicle 2603 via charging device 2604 .
  • Power storage device 2612 is preferably installed in the underfloor space. By installing in the space under the floor, the space above the floor can be effectively used. Alternatively, power storage device 2612 may be installed on the floor.
  • the power stored in the power storage device 2612 can also be supplied to other electronic devices in the house. Therefore, the use of the power storage device 2612 as an uninterruptible power supply makes it possible to use the electronic device even when power cannot be supplied from a commercial power supply due to a power failure or the like.
  • FIG. 23B illustrates an example of a power storage device according to one embodiment of the present invention. As shown in FIG. 23B, in an underfloor space 796 of a building 799, a large power storage device 791 obtained by a method for manufacturing a secondary battery according to one embodiment of the present invention is installed.
  • a control device 790 is installed in the power storage device 791, and the control device 790 is connected to the distribution board 703, the power storage controller 705 (also referred to as a control device), the display 706, and the router 709 by wiring. electrically connected.
  • Electric power is sent from the commercial power source 701 to the distribution board 703 via the service wire attachment portion 710 . Electric power is sent to the distribution board 703 from the power storage device 791 and the commercial power supply 701, and the distribution board 703 distributes the sent power to the general load via an outlet (not shown). 707 and power storage system load 708 .
  • a general load 707 is, for example, an electrical device such as a television or a personal computer
  • a power storage system load 708 is, for example, an electrical device such as a microwave oven, refrigerator, or 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 a day (for example, from 00:00 to 24:00).
  • the measurement unit 711 may also have a function of measuring the amount of power in the power storage device 791 and the amount of power supplied from the commercial power source 701 .
  • the prediction unit 712 predicts the demand to be consumed by the general load 707 and the storage system load 708 during the next day based on the amount of power consumed by the general load 707 and the storage system load 708 during the day. It has a function of predicting power consumption.
  • the planning unit 713 also has a function of planning charging and discharging of the power storage device 791 based on the amount of power demand predicted by the prediction unit 712 .
  • the amount of power consumed by the general load 707 and the power storage system load 708 measured by the measurement unit 711 can be confirmed by the display 706 . Also, it can be checked on an electric device such as a television or a personal computer via the router 709 . In addition, it can be confirmed by a mobile electronic terminal such as a smart phone or a tablet via the router 709 . In addition, it is possible to check the amount of power demand for each time period (or for each hour) predicted by the prediction unit 712 by using the display 706, the electric device, and the portable electronic terminal.
  • FIG. 24A shows a satellite 6800 as an example of space equipment.
  • a satellite 6800 has a body 6801 , a solar panel 6802 , an antenna 6803 and a secondary battery 6805 .
  • Solar panels are sometimes called solar modules.
  • a secondary battery 6805 may be provided in the satellite 6800 so that the satellite 6800 can operate even when the generated power is low.
  • the artificial satellite 6800 can generate a signal.
  • the signal is transmitted via antenna 6803 and can be received by, for example, a receiver located on the ground or other satellite.
  • a receiver located on the ground or other satellite.
  • the position of the receiver that received the signal can be determined.
  • artificial satellite 6800 can constitute, for example, a satellite positioning system.
  • the artificial satellite 6800 can be configured to have a sensor.
  • artificial satellite 6800 can have a function of detecting sunlight that hits and is reflected by an object provided on the ground.
  • the artificial satellite 6800 can have a function of detecting thermal infrared rays emitted from the earth's surface by adopting a configuration having a thermal infrared sensor.
  • artificial satellite 6800 can function as an earth observation satellite, for example.
  • FIG. 24B shows a probe 6900 having a solar sail (also called a solar sail) as an example of space equipment.
  • the spacecraft 6900 has a fuselage 6901 , a solar sail 6902 and a secondary battery 6905 .
  • solar sail 6902 When photons emitted from the sun hit the surface of solar sail 6902 , momentum is transferred to solar sail 6902 . Therefore, the surface of the solar sail 6902 should have a highly reflective thin film and preferably face the direction of the sun.
  • the solar sail 6902 is in a small folded state until it goes out of the atmosphere, and expands into a large sheet of thin film outside the earth's atmosphere (outer space) as shown in FIG. 24B. Therefore, it is preferable to use the bendable secondary battery of one embodiment of the present invention as the secondary battery 6905 mounted on the solar sail 6902 .
  • FIG. 24C shows a spacecraft 6910 as an example of space equipment.
  • Spacecraft 6910 has fuselage 6911 , solar panels 6912 and secondary battery 6913 .
  • the secondary battery 6913 the secondary battery of one embodiment of the present invention can be used.
  • Airframe 6911 may, for example, have pressurized and unpressurized chambers. The pressurized chamber may be designed so that a passenger can get in. Electric power generated when the solar panel 6912 is irradiated with sunlight can charge the secondary battery 6913 . Note that the solar panel 6912 and the secondary battery 6913 may each have flexibility.
  • a flexible solar panel 6912 is preferable because the solar panel 6912 can be provided in a curved shape on the outer surface of the fuselage 6911 .
  • the use of a flexible secondary battery 6913 is preferable because the secondary battery 6913 can be provided in a curved shape inside the solar panel 6912 (inside the body 6911).
  • the flexible secondary battery 6913 the flexible secondary battery 10 described with reference to FIG. 1 and the like can be used.
  • FIG. 24D shows a rover 6920 as an example of space equipment.
  • the probe 6920 has a fuselage 6921 and a secondary battery 6923 .
  • the rover 6920 may have solar panels 6922 .
  • the secondary battery 6923 the secondary battery of one embodiment of the present invention can be used.
  • the rover 6920 may be designed to allow crew members to board. Electric power generated by irradiating the solar panel 6912 with sunlight may be charged in the secondary battery 6923, or electric power generated by other power sources such as a fuel cell, a radioactive isotope thermoelectric converter, and the like may be used.
  • the secondary battery 6923 may be charged. Note that the solar panel 6922 and the secondary battery 6923 may each have flexibility.
  • a flexible solar panel 6922 is preferable because the solar panel 6922 can be provided in a curved shape on the outer surface of the fuselage 6921 .
  • the secondary battery 6923 can be provided in a curved shape inside the solar panel 6922 (inside the body 6921), which is preferable.
  • the flexible secondary battery 6923 the flexible secondary battery 10 described with reference to FIG. 1 and the like can be used.
  • Example 1 a secondary battery of one embodiment of the present invention was manufactured, and battery performance was evaluated.
  • the test cell A manufactured based on the manufacturing method exemplified in the first embodiment, and the test cell B, the comparison cell C, and the comparison cell D manufactured by partially changing the configuration of the test cell A will be described. do.
  • a positive electrode was produced using lithium cobaltate as a positive electrode active material.
  • the prepared slurry was applied to a current collector, and the solvent was volatilized. Thereafter, pressing was performed at 120° C. and 120 kN/m to form a positive electrode active material layer on the current collector, thereby producing a positive electrode.
  • a 20 ⁇ m thick aluminum foil was used as a current collector.
  • the positive electrode active material layer was provided on one side of the current collector. The loading was approximately 10 mg/cm 2 .
  • a negative electrode was produced using graphite as a negative electrode active material.
  • the degree of polymerization of CMC-Na used was 600 to 800, and the aqueous solution viscosity when used as a 1 weight % aqueous solution was a value in the range of 300 mPa ⁇ s to 500 mPa ⁇ s.
  • VGCF registered trademark
  • VGCF-H manufactured by Showa Denko K.K., fiber diameter 150 nm, specific surface area 13 m 2 /g), which is vapor-grown carbon fiber, was used as the conductive material.
  • Each prepared slurry was applied to a current collector and dried to form a negative electrode active material layer on the current collector.
  • a copper foil having a thickness of 18 ⁇ m was used as a current collector.
  • the negative electrode active material layer was provided on both sides or one side of the current collector. The loading was approximately 9 mg/cm 2 .
  • test cell A Eight sheets each of the above positive electrode and negative electrode were prepared.
  • the positive electrode used was a pair of positive electrodes covered with a bag-shaped separator after the surfaces opposite to the coated surface were overlapped.
  • a polyimide separator having a thickness of 24 ⁇ m was used as the separator.
  • FIG. 7A a positive electrode covered with a separator and a negative electrode were laminated.
  • FIG. 7C leads were joined to the current collector exposed portions (also referred to as tab portions) of the positive electrode and the negative electrode by ultrasonic bonding.
  • a polyimide tape was attached as an insulating film to a portion of the negative electrode.
  • a first spacer 55 and a second spacer 56 were prepared, and the first spacer and the second spacer were connected using a polyimide tape as a connecting portion.
  • Cylindrical hollow (tubular) electron beam cross-linked soft polyolefin resin was used as the first spacer and the second spacer.
  • the tab portions of the positive electrode and the negative electrode were curved so as to overlap with the laminated portion, and a first spacer and a second spacer were provided.
  • an embossed aluminum laminate film was used so that the pitch of the embossed pattern was about 1.7 mm and the height difference between the protrusions and the recesses was about 0.5 mm.
  • the laminated body was sandwiched between the exterior bodies, and the exterior bodies were sealed leaving a portion into which the electrolytic solution was injected as an open portion.
  • the electrolytic solution was injected from the one side left as the open portion.
  • EMI-FSA lithium bis(fluorosulfonyl)amide
  • LiFSA lithium bis(fluorosulfonyl)amide
  • test cell A was produced through the above steps.
  • test cell B was produced.
  • Test cell B was fabricated under the same conditions as test cell A, except that the configuration of test cell A did not include the second spacer.
  • the test cell B has a structure in which the tab portions of the positive electrode and the negative electrode are curved so as to overlap with the laminated portion, and the first spacer 55 is provided, but the second spacer 56 is not provided.
  • Comparative cell C was produced. Comparative cell C was fabricated under the same conditions as test cell A, except that it was configured without the first spacer in test cell A. In other words, the comparative cell C has a configuration in which the tab portions of the positive electrode and the negative electrode are curved so as to overlap with the laminated portion, and the second spacer 56 is provided, but the first spacer 55 is not provided.
  • Comparative cell D was produced. Comparative cell D was fabricated under the same conditions as test cell A, except that the second spacer 56 of test cell A was not provided and the tab portions of the positive and negative electrodes were not curved. That is, the comparative cell D has a configuration in which the tab portions of the positive electrode and the negative electrode do not overlap the laminated portion, and the first spacer 55 is provided, but the second spacer 56 is not provided.
  • test cell A test cell B
  • comparative cell C comparative cell D were aged.
  • CC charging was performed at 0.01 C in an environment of 25 ° C. until the charging capacity reached 15 mAh / g, followed by a rest for 10 minutes, and CC charging at 0.1 C to a charging capacity of 105 mAh / g. (120 mAh/g in total). Then, after being held at 60° C. for 24 hours, one side of the exterior body was cut and opened in an argon atmosphere, gas was removed, and resealing was performed. Re-sealing after degassing was performed in a reduced pressure environment of -95 kPa (pressure value measured by a differential pressure gauge) or less.
  • the bending test apparatus has a columnar support extending in the depth direction and having a curvature radius of 40 mm directly below the central portion where the secondary battery is installed.
  • the testing device has an arm extending in the left-right direction.
  • a tip portion of the arm is mechanically connected to the holding plate.
  • the holding plate By moving the tip portion of the arm up and down, the holding plate can be bent along the support.
  • a bending test of a secondary battery is performed in a state in which the secondary battery is sandwiched between two holding plates. Therefore, by moving the tip portion of the arm up and down, the secondary battery can be bent along the columnar support. Specifically, by lowering the tip portion of the arm, the secondary battery can be bent with a radius of curvature of 40 mm.
  • the secondary battery is in a curved state with a curvature radius of 150 mm at the position where the tip portion of the arm is raised.
  • each bending was performed at intervals of 2 seconds.
  • charge-discharge characteristics were measured at 25° C. after removing the secondary battery from the bending tester.
  • the charge/discharge conditions were a rate of 0.2C, the upper limit voltage of charge/discharge was 4.2V, and the lower limit voltage was 3.0V.
  • the measurement temperature was 25°C.
  • the discharge capacity (mAh/g) was a value per weight of the positive electrode active material.
  • 1C is the current density at which the weight of the positive electrode active material is 135 mA/g.
  • Table 1 shows the results of the bending test performed on test cell A.
  • Table 2 shows the results of the bending test performed on the test cell B.
  • Table 3 shows the results of a bending test performed on the comparative cell C.
  • Table 4 shows the results of a bending test performed on the comparative cell D.
  • the number of times of bending described in the first column of Tables 1 to 4 indicates the total number of times of bending in the bending test, and after reaching the total number of times of bending, it was removed from the bending tester and a charge-discharge test was performed. The discharge capacity at this time is shown in the second column of Tables 1 to 4. After the charge/discharge test, it was attached to the bending tester again and the bending test was continued. Note that the retention rate in the third column is a value calculated assuming that the discharge capacity in the charge/discharge test performed before the bending test is 100%.
  • test cell A of this example no rapid decrease in discharge capacity was observed in the bending test up to 45000 times, and a rapid decrease in discharge capacity was observed after the 50000 times bending test.
  • the rapid decrease in discharge capacity in the bending test from 45,001 times to 50,000 times corresponds to a decrease in capacity of one electrode.
  • the positive electrode tab portion), the negative electrode lead connection portion (negative electrode tab portion), and their peripheral portions are considered to have suffered significant deterioration (breakage of the electrode, etc.).
  • breakage of the electrode, etc. breakage of the electrode, etc.
  • test cell A which is an example of the secondary battery of one embodiment of the present invention, was able to withstand repeated bending as many as 45000 times.
  • test cell B of this example no rapid decrease in discharge capacity was observed in the bending test up to 20,000 times, and a rapid decrease in discharge capacity was observed after the 25,000 bending test. there is Therefore, although the test cell B was inferior to the test cell A, it was found to have good bending resistance.
  • the discharge capacity abruptly decreased in the bending test up to 6000 times, and the resistance to repeated bending was low.
  • the second cell of one embodiment of the present invention is compared.
  • Test cell A an example of a secondary battery, was able to withstand a very large number of bends.
  • Test cell A which is an example of a secondary battery of one embodiment, was able to withstand a very large number of bends.
  • the tab portions of the positive electrode and the negative electrode are curved so as to overlap with the laminated portion, and that the structure having the first spacer 55 has high resistance to repeated bending.
  • the tab portions of the positive electrode and the negative electrode are curved so as to overlap with the laminated portion, and the first spacer 55 and the second spacer 56 are provided, the effect of remarkably high resistance to repeated bending can be confirmed. did it.
  • 10 Secondary battery, 20: Positive electrode, 21: Positive electrode lead, 22: Positive electrode current collector, 23: Positive electrode active material layer, 24: Positive electrode current collector exposed portion, 25: Positive electrode active material coated portion, 26: Connection Part, 30: Negative electrode, 31: Negative electrode lead, 32: Negative electrode current collector, 33: Negative electrode active material layer, 34: Negative electrode current collector exposed part, 35: Negative electrode active material coating part, 36: Connection part, 40: separator, 45: insulating film, 50: exterior body, 51: sealing portion, 55: spacer, 56: spacer, 57: connection portion, 58: flexible film, 59: flexible film, 60: laminate, 61: Laminated part

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Secondary Cells (AREA)
  • Connection Of Batteries Or Terminals (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
PCT/IB2023/050942 2022-02-18 2023-02-03 二次電池 Ceased WO2023156868A1 (ja)

Priority Applications (5)

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DE112023001021.8T DE112023001021T5 (de) 2022-02-18 2023-02-03 Sekundärbatterie
KR1020247030099A KR20240154563A (ko) 2022-02-18 2023-02-03 이차 전지
US18/838,429 US20250167359A1 (en) 2022-02-18 2023-02-03 Secondary battery
CN202380020016.6A CN118715644A (zh) 2022-02-18 2023-02-03 二次电池
JP2024500690A JPWO2023156868A1 (https=) 2022-02-18 2023-02-03

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CN118658952A (zh) * 2024-08-05 2024-09-17 比亚迪股份有限公司 一种弯曲电池和用电设备

Citations (3)

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Publication number Priority date Publication date Assignee Title
JP2015233004A (ja) * 2014-05-16 2015-12-24 株式会社半導体エネルギー研究所 二次電池を備えた電子機器
US20160329546A1 (en) * 2015-05-06 2016-11-10 Samsung Electronics Co., Ltd. Cell structure for secondary battery and secondary battery having the cell structure
JP2018006336A (ja) * 2016-06-22 2018-01-11 株式会社半導体エネルギー研究所 電池、及び電池の作製方法

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JP2004241250A (ja) 2003-02-05 2004-08-26 Tdk Corp 電気化学デバイス
JP7296249B2 (ja) 2019-05-16 2023-06-22 三井化学株式会社 熱可塑性ポリウレタン樹脂

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JP2015233004A (ja) * 2014-05-16 2015-12-24 株式会社半導体エネルギー研究所 二次電池を備えた電子機器
US20160329546A1 (en) * 2015-05-06 2016-11-10 Samsung Electronics Co., Ltd. Cell structure for secondary battery and secondary battery having the cell structure
JP2018006336A (ja) * 2016-06-22 2018-01-11 株式会社半導体エネルギー研究所 電池、及び電池の作製方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118658952A (zh) * 2024-08-05 2024-09-17 比亚迪股份有限公司 一种弯曲电池和用电设备

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DE112023001021T5 (de) 2024-11-28
KR20240154563A (ko) 2024-10-25

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