WO2022018573A1 - 二次電池の作製方法 - Google Patents

二次電池の作製方法 Download PDF

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Publication number
WO2022018573A1
WO2022018573A1 PCT/IB2021/056266 IB2021056266W WO2022018573A1 WO 2022018573 A1 WO2022018573 A1 WO 2022018573A1 IB 2021056266 W IB2021056266 W IB 2021056266W WO 2022018573 A1 WO2022018573 A1 WO 2022018573A1
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WIPO (PCT)
Prior art keywords
positive electrode
secondary battery
negative electrode
active material
electrolyte
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/IB2021/056266
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English (en)
French (fr)
Japanese (ja)
Inventor
山崎舜平
掛端哲弥
石谷哲二
吉富修平
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Semiconductor Energy Laboratory Co Ltd
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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 KR1020237006549A priority Critical patent/KR20230041075A/ko
Priority to JP2022538488A priority patent/JP7696906B2/ja
Priority to US18/004,749 priority patent/US20230261265A1/en
Priority to CN202180061271.6A priority patent/CN116195080A/zh
Publication of WO2022018573A1 publication Critical patent/WO2022018573A1/ja
Anticipated expiration legal-status Critical
Priority to JP2025097901A priority patent/JP2025128306A/ja
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • 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
    • H01M10/04—Construction or manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a secondary battery and a method for manufacturing the secondary battery. Or, it relates to a portable information terminal having a secondary battery, a vehicle, or the like.
  • the uniformity of the present invention relates to a product, a method, or a manufacturing method.
  • the invention relates to a process, machine, manufacture, or composition (composition of matter).
  • One aspect of the present invention relates to a semiconductor device, a display device, a light emitting device, a power storage device, a lighting device, an electronic device, or a method for manufacturing the same.
  • the electronic device refers to all devices having a power storage device, and the electro-optical device having the power storage device, the information terminal device having the power storage device, and the like are all electronic devices.
  • a power storage device refers to an element having a power storage function and a device in general.
  • a power storage device also referred to as a secondary battery
  • a lithium ion secondary battery such as a lithium ion secondary battery, a lithium ion capacitor, an electric double layer capacitor, and the like.
  • Lithium-ion secondary batteries which have particularly high output and high energy density, are mobile information terminals such as mobile phones, smartphones, or notebook computers, portable music players, digital cameras, medical devices, or hybrid vehicles (HVs), and electric vehicles.
  • HVs hybrid vehicles
  • EVs electric vehicles
  • PSVs plug-in hybrid vehicles
  • Lithium-ion secondary batteries have a positive electrode containing a positive electrode active material such as lithium cobalt oxide (LiCoO 2 ) or lithium iron oxide (LiFePO 4 ), and a negative electrode activity such as a carbon material such as graphite capable of storing and releasing lithium. It is composed of a negative electrode containing a substance and an electrolyte containing an organic solvent such as ethylene carbonate (EC) or diethyl carbonate (DEC).
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • the lithium ion secondary battery is required to have high capacity, high performance, and safety in various operating environments.
  • the challenge is to realize a manufacturing method that can automate the manufacturing of secondary batteries. Another issue is to realize a manufacturing method that can efficiently manufacture a secondary battery in a short time. Another issue is to realize a manufacturing method capable of manufacturing a secondary battery with a high yield.
  • Another issue is to provide a method for manufacturing a secondary battery with reduced manufacturing costs.
  • Another issue is to provide a method for manufacturing a secondary battery having high safety or reliability.
  • a secondary battery is often manufactured by a procedure in which a laminated body of a positive electrode, a separator, and a negative electrode is placed in a can or bag-shaped outer body, then an electrolytic solution is injected, and then sealed.
  • lithium ions may easily diffuse outward from the injection port.
  • the number of steps tends to increase, and it may be difficult to accurately adjust the amount of the electrolytic solution to be injected. It can be said that accurately providing the required amount of electrolytic solution for the secondary battery leads to mass production of the secondary battery having uniform characteristics.
  • One of the inventions disclosed herein is to uniformly impregnate any one or more of the positive electrode, the separator, and the negative electrode by dropping a plurality of electrolytes.
  • the laminated body of the positive electrode, the separator, and the negative electrode is sandwiched between the exterior films, and the outer peripheral edge (in the case of a rectangular parallelepiped having a thin three-dimensional shape of the secondary battery, the four sides when viewed from the upper surface) is sealed without a gap.
  • a thin battery also called a laminated type
  • the terminals for external extraction shall be projected to the outside of the exterior film.
  • the lead terminal is provided to pull out the positive electrode or the negative electrode of the secondary battery to the outside of the exterior film.
  • the sealing is performed under reduced pressure at least lower than the atmospheric pressure so as not to mix impurities.
  • the amount of electrolyte of 0.01 cc ⁇ n can be impregnated by dropping at n (n> 1) places, so that the dropping point
  • the total amount of dripping can be precisely controlled.
  • dripping at n (n> 1) points on a flat surface can shorten the time for impregnating the entire positive electrode by dripping at a plurality of positive electrodes as compared with dripping on only one point of the positive electrode. The manufacturing time can be shortened.
  • the viscosity of the electrolyte dropped from the nozzle or the like it is preferable to appropriately adjust the viscosity of the electrolyte dropped from the nozzle or the like. If the viscosity of the entire electrolyte is within the range of 10 mPa ⁇ s or more and 95 mPa ⁇ s or less at room temperature (25 ° C.), the electrolyte can be dropped from the nozzle.
  • a rotary viscometer (TVE-35L from Toki Sangyo) is used for viscosity measurement.
  • an organic solvent or an ionic liquid can be used as the dropping electrolyte.
  • the electrolyte after dropping the electrolyte, it is preferable to seal the electrolyte under reduced pressure. Therefore, in the case of continuous dropping and sealing, it is preferable to use the same chamber or a plurality of connected chambers. For example, after dropping the electrolyte in the first chamber, the electrolyte is transferred to the second chamber without being exposed to the atmosphere, the pressure in the second chamber is reduced, and then the laminate is exteriorized in the second chamber. Sealing with a film is preferable because impurities such as dust are not mixed. Alternatively, the electrolyte may be dropped continuously in the same chamber and sealed with an exterior film, so that the secondary battery can be efficiently manufactured.
  • the chamber for sealing is connected to the vacuum exhaust processing chamber, and can be evacuated to create a vacuum, or after vacuum exhausting, an inert gas can be introduced to create an atmospheric pressure.
  • the vacuum exhaust treatment chamber is equipped with a magnetic levitation type turbo molecular pump, a cryopump, or a dry pump.
  • a magnetic levitation type turbo molecular pump such as a cryopump, or a dry pump.
  • an inert gas such as nitrogen or a rare gas is used as the gas to be introduced.
  • these gases introduced into the apparatus those purified by a gas purifier before being introduced into the apparatus are used.
  • the ionic liquid is preferable because it hardly volatilizes even in a high vacuum.
  • an ionic liquid mixed with an organic solvent may be used as the electrolyte.
  • the degree of vacuum in the chamber shall be lower than about 5 ⁇ 10 -1 Pa.
  • the configuration of the invention disclosed herein is to drop an electrolyte on any one or more of the positive electrode, the negative electrode, and the separator, impregnate the one or more of the positive electrode, the negative electrode, and the separator with the electrolyte, and then reduce the pressure. Then, the laminated body of the positive electrode, the separator, and the negative electrode is sealed with the exterior film.
  • many secondary batteries can be manufactured at one time by using an exterior film having a large area.
  • an exterior film having a large area having an exterior film size of 320 mm ⁇ 400 mm, 370 mm ⁇ 470 mm, 550 mm ⁇ 650 mm, 600 mm ⁇ 720 mm, 680 mm ⁇ 880 mm, 1000 mm ⁇ 1200 mm, 1100 mm ⁇ 1250 mm, 1150 mm ⁇ 1300 mm, etc. It is possible to provide a method for efficiently manufacturing a plurality of secondary batteries from one large-area exterior film.
  • a film also called a laminated film
  • a resin heat-fused resin
  • a metal foil having an adhesive layer on one surface or both surfaces is used. Thermocompression bonding is performed in a state where the first adhesive layer of the first laminated film and the second adhesive layer of the second laminated film are in close contact with each other so that the first adhesive layer and the second adhesive layer are on the inside. By doing so, a sealing area is formed.
  • the sealing material is not limited to thermocompression bonding, and a sealing material may be drawn on the sealing region using a thermosetting resin, an ultraviolet curing resin, or the like.
  • the sealing area has a frame shape or a closed loop shape.
  • a laminated body of a positive electrode, a separator, and a negative electrode is arranged in an area surrounded by a sealing area and sealed. Therefore, the area of the area surrounded by the seal area is at least wider than the area of the positive electrode of the secondary battery.
  • the film used for the exterior of the secondary battery is a metal film (aluminum, stainless steel, nickel steel, gold, silver, copper, titanium, nichrome, iron, tin, tantalum, niobium, molybdenum, zirconium, zinc, etc. (Alloys, etc.), plastic films made of organic materials, hybrid material films containing organic materials (organic resins or fibers, etc.) and inorganic materials (ceramics, etc.), carbon-containing inorganic films (carbon films, graphite films, etc.) A layered film or a laminated film composed of a plurality of these is used.
  • the production method is also characterized by using two exterior films, and the configuration is such that a positive electrode is placed on the first exterior film, the first electrolyte is dropped on the positive electrode, and a separator is placed on the positive electrode.
  • the second electrolyte is dropped on the separator, the negative electrode is placed on the separator, the third electrolyte is dropped on the negative electrode, the laminate of the positive electrode, the separator, and the negative electrode is placed under reduced pressure, and the laminate is placed.
  • It is a method of manufacturing a secondary battery which is sandwiched between them and sealed by using a first exterior film and a second exterior film. Sealing refers to blocking a certain sealed area from the outside air.
  • the first electrolyte, the second electrolyte, and the third electrolyte may use the same material or different materials.
  • the laminated body may be laminated in the order of the positive electrode, the separator, and the negative electrode, or may be laminated in the order of the negative electrode, the separator, and the positive electrode.
  • the separator is used to prevent a short circuit between the positive electrode and the negative electrode, and when the laminated bodies are stacked in order to increase the capacity, one common separator is used by bending in order to reduce the number of parts. It may be configured.
  • the current collectors such as the positive electrode current collector or the negative electrode current collector include metals such as stainless steel, gold, platinum, zinc, iron, nickel, copper, aluminum, titanium, and tantalum, and alloys thereof. It is possible to use a material that does not alloy with carrier ions such as lithium ion. Further, an aluminum alloy to which an element for improving heat resistance such as silicon, titanium, neodymium, scandium, and molybdenum is added can be used. Further, it may be formed of a metal element that reacts with silicon to form silicide.
  • Metallic elements that react with silicon to form silicide include zirconium, titanium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, cobalt, nickel and the like.
  • a foil-like shape, a plate-like shape (sheet-like shape), a net-like shape, a columnar shape, a coil-like shape, a punching metal-like shape, an expanded metal-like shape, or the like can be appropriately used. It is preferable to use a current collector having a thickness of 10 ⁇ m or more and 30 ⁇ m or less.
  • the example of the thin battery has been mainly described above, it is not particularly limited and can be applied to the winding type.
  • the electrolyte may be dropped onto the wound body, or may be dropped before the wound body is formed, that is, before the wound body is wound.
  • the wound body refers to a band-shaped positive electrode, a band-shaped separator, and a band-shaped negative electrode that are stacked in this order and wound while being stacked.
  • the manufacturing process for the secondary battery can be significantly shortened. Therefore, it is possible to provide a method for manufacturing a secondary battery with reduced manufacturing costs. Alternatively, it is possible to realize a manufacturing method capable of efficiently manufacturing the secondary battery in a short time. Alternatively, it is possible to realize a manufacturing method that can automate the manufacturing of the secondary battery. Alternatively, it is possible to realize a manufacturing method capable of manufacturing a secondary battery with a high yield.
  • a manufacturing method for manufacturing a large secondary battery having a relatively large size can be realized.
  • the number of large secondary batteries to be mounted can be reduced as compared with the number of small secondary batteries to be mounted. If the number of large secondary batteries to be mounted can be reduced, individual control becomes easy and the burden on the charge control circuit is reduced.
  • the secondary battery obtained by the manufacturing method disclosed in the present specification can be firmly sealed by a single sealing step, so that the secondary battery can be a highly safe or reliable secondary battery.
  • 6A, 6B, and 6C are views showing the appearance of the secondary battery.
  • 7A and 7B are views showing the appearance of the secondary battery.
  • 8A, 8B, and 8C are diagrams illustrating a method for manufacturing a secondary battery.
  • 9A is a perspective view showing a battery pack
  • FIG. 9B is a block diagram of the battery pack
  • FIG. 9C is a block diagram of a vehicle having a motor.
  • 10A to 10D are diagrams illustrating an example of a transportation vehicle.
  • 11A and 11B are diagrams illustrating a power storage device.
  • 12A, 12B, 12C, 12D, and 12E are perspective views of an electronic device showing an aspect of the present invention.
  • the secondary battery 500 shown in FIG. 1A has an exterior body 509 and a laminated body 512 arranged in the exterior body 509.
  • the laminate 512 has a positive electrode 503, a negative electrode 506, and a separator 507.
  • the positive electrode 503 and the negative electrode 506 are overlapped with each other, and the separator 507 is arranged between them.
  • the positive electrode 503 has a positive electrode current collector 501 and a positive electrode active material layer 502 provided on both sides of the positive electrode current collector 501.
  • the positive electrode active material layer 502 may be provided on only one side of the positive electrode current collector 501.
  • the negative electrode 506 includes a negative electrode current collector 504 and a negative electrode active material layer 505 provided on both sides of the negative electrode current collector 504.
  • the negative electrode active material layer 505 may be provided on only one side of the negative electrode current collector 504.
  • the positive electrode active material layer 502 and the negative electrode active material layer 505 are preferably arranged so as to face each other with the separator 507 interposed therebetween.
  • FIG. 1A shows an example in which a secondary battery has four sets of a positive electrode active material layer 502 and a negative electrode active material layer 505 facing each other with the separator 507 interposed therebetween.
  • the positive electrode 503 has a region (hereinafter referred to as a tab region) in which the positive electrode current collector 501 is partially exposed.
  • the negative electrode 506 has a region where the negative electrode current collector 504 is partially exposed, that is, a tab region.
  • the tab regions are arranged so as to overlap each other.
  • the overlapping tab regions and the positive electrode lead electrodes may be overlapped and joined by ultrasonic welding or the like.
  • the tab regions are arranged so as to overlap each other.
  • the overlapping tab regions and the negative electrode lead electrode may be overlapped and joined by ultrasonic welding or the like.
  • the timing of joining using ultrasonic welding or the like may be appropriately selected by the practitioner, and may be before or after sealing.
  • droplets of the electrolyte 515c at 140 locations (7 columns ⁇ 20 rows) are shown on the negative electrode at equal intervals, but the present invention is not particularly limited and may be appropriately determined by the practitioner.
  • scanning may be performed sequentially while confirming the dropping position with a CCD or the like, and when dropping droplets from a plurality of nozzles at the same time, the dropping processing time can be shortened, which is preferable.
  • Multi-chamfering is a method of manufacturing a plurality of secondary batteries by arranging a plurality of laminated bodies on one large exterior film, manufacturing a secondary battery, and then dividing each laminated body in a plane. It points to. By performing multi-chamfering, the manufacturing time per secondary battery can be shortened.
  • FIG. 2 is a flow for explaining a method for manufacturing a secondary battery according to an aspect of the present invention.
  • FIG. 3 is a cross-sectional view illustrating a method for manufacturing a secondary battery according to an aspect of the present invention, and corresponds to the alternate long and short dash line AB shown in FIG. 1C.
  • step S000 the process is started.
  • step S001 the positive electrode is arranged.
  • the positive electrode is arranged on the exterior film 509b which is the exterior body 509.
  • the exterior film 509b is arranged on the stage 516.
  • the positive electrode, the exterior film, and the stage are all arranged in the chamber, but for the sake of simplicity, the inner wall of the chamber and the like are not shown here.
  • FIG. 3A shows a state in which the positive electrode 503 is arranged on the exterior film 509b and the electrolyte 515a is dropped from the nozzle 514.
  • the electrolyte 515a can be dropped over the entire surface of the positive electrode 503.
  • the electrolyte 515a may be dropped over the entire surface of the positive electrode 503 by moving the stage 516.
  • step S003 the separator 507 is placed so as to be superimposed on the positive electrode 503.
  • step S004 the electrolyte 515b is dropped onto the separator 507.
  • FIG. 3C shows a state in which the electrolyte 515b is dropped onto the separator.
  • step S005 the negative electrode is placed so as to be superimposed on the positive electrode 503 and the separator 507.
  • step S006 the electrolyte 515c is added dropwise.
  • FIG. 3D shows a state in which the electrolyte 515c is dropped onto the negative electrode.
  • the laminated body of the positive electrode, the separator, and the negative electrode can be further laminated.
  • the laminated body 512 shown in FIG. 1A can be produced. It is preferable to drop the electrolyte after arranging the positive electrode, the negative electrode and the separator respectively.
  • the electrolyte may be dropped only in the step of arranging the positive electrode and the negative electrode.
  • the electrolyte may be added dropwise only in the step of arranging the separator.
  • the positive electrode has a positive electrode active material layer and a positive electrode current collector.
  • the positive electrode active material layer has a positive electrode active material, and may have the conductive material and the binder described above.
  • a positive electrode current collector and a negative electrode current collector metals such as stainless steel, gold, platinum, zinc, iron, copper, aluminum and titanium, and alloys thereof have high conductivity and do not alloy with carrier ions such as lithium. Materials can be used.
  • a sheet-like shape, a net-like shape, a punching metal-like shape, an expanded metal-like shape, or the like can be appropriately used. It is preferable to use a current collector having a thickness of 10 ⁇ m or more and 30 ⁇ m or less.
  • a titanium compound may be provided by laminating the current collector on the metal shown above.
  • titanium compounds include titanium nitride, titanium oxide, titanium nitride in which part of nitrogen is replaced with oxygen, titanium oxide in which part of oxygen is replaced with nitrogen, and titanium oxide (TIO x N y , 0 ⁇ x).
  • titanium oxide titanium oxide
  • titanium nitride is particularly preferable because it has high conductivity and a high function of suppressing oxidation.
  • the active material layer such as the positive electrode active material layer and the negative electrode active material layer has a conductive material.
  • a conductive material it is preferable to have a carbon-based material such as a graphene compound, carbon black, graphite, carbon fiber, fullerene, etc., and it is particularly preferable to have a graphene compound.
  • acetylene black (AB) or the like can be used as the carbon black.
  • graphite for example, natural graphite, artificial graphite such as mesocarbon microbeads, or the like can be used.
  • these carbon-based materials may function as an active material.
  • carbon fiber such as mesophase pitch type carbon fiber and isotropic pitch type carbon fiber can be used.
  • carbon fiber carbon nanofiber, carbon nanotube, or the like can be used.
  • the carbon nanotubes can be produced, for example, by a vapor phase growth method.
  • the active material layer may have a metal powder such as copper, nickel, aluminum, silver, or gold, a metal fiber, a conductive ceramic material, or the like 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, and more preferably 1 wt% or more and 5 wt% or less.
  • Particle-like carbon-containing compounds such as carbon black and graphite, or fibrous carbon-containing compounds such as carbon nanotubes
  • the minute space refers to, for example, a region between a plurality of active substances.
  • a carbon-containing compound that easily enters a minute space and a sheet-shaped carbon-containing compound such as graphene that can impart conductivity over multiple particles By using a combination of a carbon-containing compound that easily enters a minute space and a sheet-shaped carbon-containing compound such as graphene that can impart conductivity over multiple particles, the density of the electrodes can be increased and an excellent conductive path can be obtained. Can be formed.
  • the secondary battery obtained by the manufacturing method of one aspect of the present invention can have stability and is effective as an in-vehicle secondary battery. Control becomes complicated when the number of secondary batteries is increased. By using a large secondary battery, the number of secondary batteries can be reduced and the burden on the charge control circuit can be reduced.
  • the active material layer preferably has a binder (not shown).
  • the binder binds or fixes the electrolyte and the active material, for example. Further, the binder can bind or fix an electrolyte and a carbon-based material, an active material and a carbon-based material, a plurality of active materials to each other, a plurality of carbon-based materials, and the like.
  • a rubber material such as styrene-butadiene rubber (SBR), styrene-isoprene-styrene rubber, acrylonitrile-butadiene rubber, butadiene rubber, or ethylene-propylene-diene copolymer as the binder.
  • SBR styrene-butadiene rubber
  • fluororubber can be used as the binder.
  • a water-soluble polymer for example, a polysaccharide or the like can be used.
  • a polysaccharide such as carboxymethyl cellulose (CMC), methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, or regenerated cellulose, or starch or the like can be used. Further, it is more preferable to use these water-soluble polymers in combination with the above-mentioned rubber material.
  • the binder may be used in combination of a plurality of the above.
  • 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, graphene. Includes quantum dots and the like.
  • the graphene compound has carbon, has a flat plate shape, a sheet shape, or the like, and has a two-dimensional structure formed by a carbon 6-membered ring. The two-dimensional structure formed by the carbon 6-membered ring may be called a carbon sheet.
  • the graphene compound may have a functional group. Further, the graphene compound preferably has a bent shape. The graphene compound may also be curled up into carbon nanofibers.
  • graphene oxide means, for example, one having carbon and oxygen, having a sheet-like shape, and having a functional group, particularly an epoxy group, a carboxy group or a hydroxy group.
  • the reduced graphene oxide in the present specification and the like means, for example, a graphene oxide having carbon and oxygen, having a sheet-like shape, and having a two-dimensional structure formed by a carbon 6-membered ring. It may be called a carbon sheet. Although one reduced graphene oxide functions, a plurality of reduced graphene oxides may be laminated.
  • the reduced graphene oxide preferably has a portion having a carbon concentration of more than 80 atomic% and an oxygen concentration of 2 atomic% or more and 15 atomic% or less. By setting such carbon concentration and oxygen concentration, it is possible to function as a highly conductive conductive material even in a small amount. Further, the reduced graphene oxide preferably has an intensity ratio G / D of G band to D band of 1 or more in the Raman spectrum. The reduced graphene oxide having such an intensity ratio can function as a highly conductive conductive material even in a small amount.
  • the graphene compound may be mixed with the material used for forming the graphene compound and used for the active material layer.
  • particles used as a catalyst for forming a graphene compound may be mixed with the graphene compound.
  • the catalyst for forming the graphene compound include particles having silicon oxide (SiO 2 , SiO x (x ⁇ 2)), aluminum oxide, iron, nickel, ruthenium, iridium, platinum, copper, germanium and the like. ..
  • the particles preferably have a D50 of 1 ⁇ m or less, and more preferably 100 nm or less.
  • Negative electrode active materials include materials that can react with carrier ions of secondary batteries, materials that can insert and remove carrier ions, materials that can alloy with metals that become carrier ions, and carrier ions. It is preferable to use a material capable of dissolving and precipitating the metal.
  • the following is an example of a negative electrode active material.
  • a metal or compound having one or more elements selected from silicon, tin, gallium, aluminum, germanium, lead, antimony, bismuth, silver, zinc, cadmium, and indium can be used.
  • an alloy-based compound using such elements for example, Mg 2 Si, Mg 2 Ge , Mg 2 Sn, SnS 2, V 2 Sn 3, FeSn 2, CoSn 2, Ni 3 Sn 2, Cu 6 Sn 5 , Ag 3 Sn, Ag 3 Sb, Ni 2 MnSb, CeSb 3 , LaSn 3 , La 3 Co 2 Sn 7 , CoSb 3 , InSb, SbSn and the like.
  • a material having a low resistance may be used by adding phosphorus, arsenic, boron, aluminum, gallium or the like as impurity elements to silicon.
  • a silicon material predoped with lithium may be used.
  • a predoping method there are methods such as mixing and annealing lithium fluoride, lithium carbonate and the like with silicon, and a mechanical alloy of lithium metal and silicon.
  • lithium is doped by a charge / discharge reaction in combination with an electrode such as lithium metal, and then an electrode that becomes a counter electrode using the doped electrode (for example, a positive electrode with respect to a pre-doped negative electrode). May be combined to produce a secondary battery.
  • silicon nanoparticles can be used as the negative electrode active material.
  • the average diameter of the silicon nanoparticles is, for example, preferably 5 nm or more and less than 1 ⁇ m, more preferably 10 nm or more and 300 nm or less, and further preferably 10 nm or more and 100 nm or less.
  • Silicon nanoparticles may have crystallinity. Further, the silicon nanoparticles may have a crystalline region and an amorphous region.
  • the material having silicon for example, a material represented by SiO x (x is preferably smaller than 2, more preferably 0.5 or more and 1.6 or less) can be used.
  • the negative electrode active material for example, carbon-based materials such as graphite, graphitizable carbon, non-graphitizable carbon, carbon nanotubes, carbon black and graphene compounds can be used.
  • the negative electrode active material for example, an oxide having one or more elements selected from titanium, niobium, tungsten and molybdenum can be used.
  • the negative electrode active material a plurality of metals, materials, compounds, etc. shown above can be used in combination.
  • double nitride of lithium and a transition metal as a negative electrode material, preferably can be combined with the material of V 2 O 5, Cr 3 O 8 or the like which does not contain lithium ions as a positive electrode material. Even when a material containing lithium ions is used as the positive electrode material, a double nitride of lithium and a transition metal can be used as the negative electrode material by desorbing the lithium ions contained in the positive electrode material in advance.
  • a material that causes a conversion reaction can also be used as a negative electrode active material.
  • a transition metal oxide that does not undergo an alloying reaction with lithium such as cobalt oxide (CoO), nickel oxide (NiO), and iron oxide (FeO) may be used as the negative electrode active material.
  • the conversion reaction further includes oxides such as Fe 2 O 3 , CuO, Cu 2 O, RuO 2 , Cr 2 O 3 , sulfides such as CoS 0.89 , NiS, and CuS, Zn 3 N 2 , and Cu 3 N.
  • Examples of the positive electrode active material include a lithium-containing material having an olivine-type crystal structure, a layered rock salt-type crystal structure, and a spinel-type crystal structure.
  • a positive electrode active material having a layered crystal structure as the positive electrode active material according to one aspect of the present invention.
  • Examples of the layered crystal structure include a layered rock salt type crystal structure.
  • M is a metal element, preferably one or more selected from cobalt, manganese, nickel and iron.
  • M is, for example, two or more selected from cobalt, manganese, nickel, iron, aluminum, titanium, zirconium, lantern, copper, and zinc.
  • LiM x O for example a lithium-containing material represented by LiM x O y, LiCoO 2, LiNiO 2, LiMnO 2 , and the like.
  • LiM x O for example, as a lithium-containing material represented by y, LiNi x Co 1-x O 2 NiCo system represented by (0 ⁇ x ⁇ 1), LiNi x Mn 1-x O 2 (0 ⁇ x Examples thereof include the NiMn system represented by ⁇ 1).
  • LiNi x Co y Mn z O 2 (x> 0, y> 0,0.8 ⁇ x + y + z ⁇ 1.2) NiCoMn system represented by (NCM both )
  • NCM both NiCoMn system represented by (NCM both )
  • it is preferable that x, y and z satisfy a value of x: y: z 5: 2: 3 or a vicinity thereof.
  • lithium-containing material having a layered rock salt type crystal structure examples include Li 2 MnO 3 , Li 2 MnO 3- LiMeO 2 (Me is Co, Ni, Mn) and the like.
  • a lithium manganese composite oxide that can be represented by the composition formula Li a Mn b M c Od can be used.
  • the element M a metal element selected from other than lithium and manganese, silicon, and phosphorus are preferably used, and nickel is more preferable.
  • the lithium manganese composite oxide refers to an oxide containing at least lithium and manganese, and includes chromium, cobalt, aluminum, nickel, iron, magnesium, molybdenum, zinc, indium, gallium, copper, titanium, niobium, and silicon. And at least one element selected from the group consisting of phosphorus and the like may be contained.
  • a material having a layered rock salt type crystal structure such as lithium cobalt oxide (LiCoO 2 ) has a high discharge capacity and is excellent as a positive electrode active material for a secondary battery.
  • the material having a layered rock salt type crystal structure include a composite oxide represented by LiMO 2.
  • the metal M contains the metal Me1.
  • the metal Me1 is one or more metals containing cobalt.
  • the metal M can further contain the metal X in addition to the metal Me1.
  • Metal X is one or more metals selected from magnesium, calcium, zirconium, lanthanum, barium, copper, potassium, sodium and zinc.
  • the amount of lithium that can be inserted and removed in the positive electrode active material is indicated by x in the composition formula, for example, x in Li x CoO 2 or x in Li x MO 2 .
  • Li x CoO 2 in the present specification can be appropriately read as Li x MO 2.
  • the fact that x in Li x CoO 2 is small means, for example, 0.1 ⁇ x ⁇ 0.24.
  • the positive electrode active material will be described with reference to FIGS. 4 and 5.
  • the surface layer portion is a region where lithium ions are first released during charging, and is a region where the lithium concentration tends to be lower than that inside. Further, it can be said that the atoms on the surface of the positive electrode active material having the surface layer portion are in a state where some bonds are broken. Therefore, it can be said that the surface layer portion tends to be unstable and the deterioration of the crystal structure tends to start.
  • the surface layer can be made sufficiently stable , even when x in Li x CoO 2 is small, for example, even if x is 0.24 or less, the layered structure consisting of the internal transition metal M and the octahedron of oxygen is made difficult to break. Can be done. Furthermore, it is possible to suppress the displacement of the layer composed of the internal transition metal M and the octahedron of oxygen.
  • the surface layer portion preferably has the additive element A, and more preferably has a plurality of additive elements A. Further, it is preferable that the concentration of one or more selected from the additive element A is higher in the surface layer portion than in the inside. Further, it is preferable that one or more selected from the additive elements A contained in the positive electrode active material have a concentration gradient. Further, it is more preferable that the distribution of the positive electrode active material differs depending on the additive element A. For example, it is more preferable that the depth of the concentration peak from the surface differs depending on the additive element A.
  • the concentration peak here means the maximum value of the concentration at 50 nm or less from the surface layer portion or the surface.
  • magnesium which is one of the additive elements X, is divalent, and magnesium ions are more stable in the lithium site than in the transition metal M site in the layered rock salt type crystal structure, so that they are more likely to enter the lithium site.
  • the presence of magnesium in the lithium site of the surface layer at an appropriate concentration makes it easier to maintain the layered rock salt type crystal structure. It is presumed that this is because the magnesium present in the lithium site functions as a pillar that supports the two CoO layers. Further, the presence of magnesium can suppress the withdrawal of oxygen around magnesium in a state where x in Li x CoO 2 is, for example, 0.24 or less.
  • the presence of magnesium can be expected to increase the density of the positive electrode active material. Further, when the magnesium concentration in the surface layer portion is high, it can be expected that the corrosion resistance to hydrofluoric acid generated by the decomposition of the electrolytic solution is improved.
  • the amount of magnesium contained in the entire positive electrode active material is an appropriate amount.
  • the atomic number of magnesium is preferably 0.001 times or more and 0.1 times or less, more preferably greater than 0.01 times and less than 0.04 times, still more preferably about 0.02 times.
  • the amount of magnesium contained in the entire positive electrode active material referred to here may be a value obtained by performing elemental analysis of the entire positive electrode active material using, for example, GD-MS, ICP-MS, or the like, or the positive electrode active material. It may be based on the value of the composition of the raw materials in the manufacturing process.
  • Aluminum which is one of the additive elements Y, may be present at the transition metal M site in the layered rock salt type crystal structure. Since aluminum is a typical trivalent element and its valence does not change, lithium around aluminum does not easily move during charging and discharging. Therefore, aluminum and the lithium around it function as pillars and can suppress changes in the crystal structure. In addition, aluminum has the effect of suppressing the elution of the surrounding transition metal M and improving the continuous charge resistance. Moreover, since the Al—O bond is stronger than the Co—O bond, it is possible to suppress the withdrawal of oxygen around aluminum. These effects improve thermal stability. Therefore, if aluminum is included as the additive element Y, the safety when used in a secondary battery can be improved. Further, it is possible to obtain a positive electrode active material whose crystal structure does not easily collapse even after repeated charging and discharging.
  • the amount of aluminum contained in the entire positive electrode active material is an appropriate amount.
  • the total number of atoms of aluminum contained in the positive electrode active material is preferably 0.05% or more and 4% or less, preferably 0.1% or more and 2% or less, and 0.3% or more and 1.5% of the atomic number of cobalt. The following are more preferable. Alternatively, it is preferably 0.05% or more and 2% or less. Alternatively, 0.1% or more and 4% or less are preferable.
  • the amount of the entire positive electrode active material referred to here may be, for example, a value obtained by performing elemental analysis of the entire positive electrode active material using GD-MS, ICP-MS, or the like, or may be used to prepare the positive electrode active material. It may be based on the value of the composition of the raw materials in the process.
  • the crystal structure continuously changes from the inside of the layered rock salt type toward the rock salt type or the surface and the surface layer having the characteristics of both the rock salt type and the layered rock salt type.
  • the surface layer having the characteristics of the rock salt type or both the rock salt type and the layered rock salt type and the internal orientation of the layered rock salt type are substantially the same.
  • the anions in the ⁇ 111 ⁇ plane of the cubic crystal structure have a triangular lattice.
  • the layered rock salt type is a space group R-3m and has a rhombohedral structure, but is generally represented by a composite hexagonal lattice to facilitate understanding of the structure, and the layered rock salt type (000l) plane has a hexagonal lattice.
  • the cubic ⁇ 111 ⁇ plane triangular lattice has an atomic arrangement similar to that of the layered rock salt type (000 l) plane hexagonal lattice. It can be said that the orientation of the cubic close-packed structure is aligned when both lattices are consistent.
  • the space group of layered rock salt type crystals and O3'type crystals is R-3m, which is different from the space group Fm-3m of rock salt type crystals (space group of general rock salt type crystals).
  • the mirror index of the crystal plane to be filled is different between the layered rock salt type crystal and the O3'type crystal and the rock salt type crystal.
  • the orientations of the crystals are substantially the same when the orientations of the cubic close-packed structures composed of anions are aligned.
  • TEM Transmission Electron Microscope
  • STEM Sccanning Transmission Electron Microscope, scanning transmission electron microscope
  • HAADF-STEM High Electron Microscope
  • ABF-STEM Annal Bright-Field Scanning Transmission Electron Microscopic, annular bright-field scanning transmission electron microscope
  • electron beam diffraction TEM image and STEM image, etc. It can be judged from the above.
  • XRD X-ray Diffraction, X-ray diffraction
  • neutron diffraction and the like can also be used as judgment materials.
  • x 1 lithium cobalt oxide in Li x CoO 2.
  • the CoO 2 layer is a structure in which an octahedral structure in which oxygen is coordinated to cobalt is continuous with a plane in a shared ridge state. This may be referred to as a layer composed of an octahedron of cobalt and oxygen.
  • This structure CoO 2 layer is present one layer in the unit cell. Therefore, it may be called O1 type or monoclinic O1 type.
  • This structure includes a structure such CoO 2 as trigonal O1 type, and structure of LiCoO 2 as the R-3m O3, but it can be said that are alternately laminated. Therefore, this crystal structure may be referred to as an H1-3 type crystal structure.
  • the H1-3 type crystal structure has twice the number of cobalt atoms per unit cell as the other structures.
  • the c-axis of the H1-3 type crystal structure is shown in a diagram in which the c-axis is halved of the unit cell.
  • the difference in volume per cobalt atom of the same number of O3'-type crystal structures from R-3m (O3) in the discharged state is 2.5% or less, more specifically 2.2% or less, typically 1. It is 8%.
  • the change in the crystal structure when x in Li x CoO 2 is small is suppressed as compared with the conventional positive electrode active material.
  • the change in volume when compared per the same number of cobalt atoms is also suppressed. Therefore, the crystal structure of the positive electrode active material does not easily collapse even if charging and discharging are repeated so that x becomes 0.24 or less. Therefore, the positive electrode active material suppresses a decrease in charge / discharge capacity in the charge / discharge cycle.
  • the positive electrode active material since more lithium can be stably used than the conventional positive electrode active material, the positive electrode active material has a large discharge capacity per weight and volume. Therefore, by using the positive electrode active material, it is possible to manufacture a secondary battery having a high discharge capacity per weight and per volume.
  • the positive electrode active material of one aspect of the present invention is preferable because it can maintain a crystal structure having symmetry of R-3m O3 even when charged at a high charging voltage, for example, a voltage of 4.6 V or more at 25 ° C. In other words. Further, it can be said that it is preferable because an O3'type crystal structure can be obtained when the battery is charged at a higher charging voltage, for example, a voltage of 4.65 V or more and 4.7 V or less at 25 ° C.
  • the voltage of the secondary battery is lower than the above by the potential of graphite.
  • the potential of graphite is about 0.05V to 0.2V with respect to the potential of lithium metal. Therefore, a secondary battery using graphite as the negative electrode active material has the same crystal structure when the voltage is obtained by subtracting the graphite potential from the above voltage.
  • it is preferably 1 ⁇ m or more and 30 ⁇ m or less. Alternatively, it is preferably 2 ⁇ m or more and 100 ⁇ m or less. Alternatively, it is preferably 2 ⁇ m or more and 30 ⁇ m or less. Alternatively, it is preferably 5 ⁇ m or more and 100 ⁇ m or less. Alternatively, it is preferably 5 ⁇ m or more and 40 ⁇ m or less.
  • XRD can analyze the symmetry of the transition metal M such as cobalt contained in the positive electrode active material with high resolution, compare the high crystallinity and the orientation of the crystal, and analyze the periodic strain and crystallite size of the lattice. It is preferable in that sufficient accuracy can be obtained even if the positive electrode obtained by disassembling the secondary battery is measured as it is.
  • the powder XRD can obtain a diffraction peak reflecting the crystal structure inside the positive electrode active material which occupies most of the volume of the positive electrode active material.
  • the positive electrode active material of one aspect of the present invention is characterized in that the change in crystal structure is small when x in Li x CoO 2 is 1 and when x is 0.24 or less.
  • a material in which a crystal structure in which a large change in crystal structure occupies 50% or more when charged at a high voltage is not preferable because it cannot withstand high voltage charging / discharging.
  • the O3'type crystal structure may not be obtained only by adding the additive element A.
  • x in Li x CoO 2 is 0.24 depending on the concentration and distribution of the additive element A.
  • the O3'type crystal structure is 60% or more, and cases where the H1-3 type crystal structure occupies 50% or more.
  • the positive electrode active material in a state where x is small may cause a change in the crystal structure when exposed to the atmosphere.
  • the O3'type crystal structure may change to the H1-3 type crystal structure. Therefore, it is preferable to handle all the samples used for the analysis of the crystal structure in an inert atmosphere such as an argon atmosphere.
  • Whether or not the distribution of the additive element A possessed by a certain positive electrode active material is in the state as described above can be determined by, for example, XPS, energy dispersive X-ray spectroscopy (EDX: Energy Dispersive X-ray Spectroscopy), EPMA. It can be judged by analysis using (electron probe microanalysis) or the like.
  • the crystal structure such as the surface layer portion and the crystal grain boundary can be analyzed by electron diffraction or the like of the cross section of the positive electrode active material.
  • the H1-3 type crystal structure has the coordinates of cobalt and oxygen in the unit cell as Co (0, 0, 0.42150 ⁇ 0.00016), O1 (0, 0, 0.267671 ⁇ 0.00045), It can be expressed as O2 (0, 0, 0.11535 ⁇ 0.00045).
  • O1 and O2 are oxygen atoms, respectively.
  • Which unit cell should be used to represent the crystal structure of the positive electrode active material can be determined, for example, by Rietveld analysis of XRD. In this case, a unit cell having a small GOF (goodness of fit) value may be adopted.
  • the conventional lithium cobaltate When charging and discharging so that x in Li x CoO 2 becomes 0.24 or less are repeated, the conventional lithium cobaltate has an H1-3 type crystal structure and a discharged state R-3m O3 structure. Changes in crystal structure (that is, non-equilibrium phase changes) will be repeated between them.
  • these two crystal structures have a large difference in volume.
  • the difference in volume between the H1-3 type crystal structure and the discharged R-3m O3 type crystal structure exceeds 3.5%, typically 3.9% or more. ..
  • the conventional crystal structure of lithium cobalt oxide collapses.
  • the collapse of the crystal structure causes deterioration of the cycle characteristics. This is because the collapse of the crystal structure reduces the number of sites where lithium can stably exist, and it becomes difficult to insert and remove lithium.
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • EMC ethylmethyl carbonate
  • EMC
  • the electrolyte contains fluorine.
  • the electrolyte containing fluorine for example, an electrolyte having one or more kinds of fluorinated cyclic carbonates and lithium ions can be used.
  • the fluorinated cyclic carbonate can improve the nonflammability and enhance the safety of the lithium ion secondary battery.
  • fluorinated cyclic carbonate fluorinated ethylene carbonate
  • fluorinated ethylene carbonate for example, monofluoroethylene carbonate (fluoroethylene carbonate, FEC, F1EC), difluoroethylene carbonate (DFEC, F2EC), trifluoroethylene carbonate (F3EC), tetrafluoroethylene carbonate (F4EC) ) Etc.
  • FEC fluorinated ethylene carbonate
  • FEC fluoroethylene carbonate
  • F1EC fluoroethylene carbonate
  • DFEC difluoroethylene carbonate
  • F3EC trifluoroethylene carbonate
  • F4EC tetrafluoroethylene carbonate
  • Etc fluorinated ethylene carbonate
  • DFEC has isomers such as cis-4,5 and trans-4,5. It is important to solvate lithium ions using one or more fluorinated cyclic carbonates as the electrolyte and transport them in the electrolyte contained in the electrode during charging and discharging in order
  • the desolvation energy required for the solvated lithium ions to enter the active material particles in the electrolyte contained in the electrode is reduced. If the energy of this desolvation can be reduced, lithium ions can be easily inserted into or desorbed from the active material particles even in a low temperature range. Lithium ions may move in a solvated state, but a hopping phenomenon may occur in which the coordinating solvent molecules are replaced. When the lithium ion is easily desolvated, it is easy to move due to the hopping phenomenon, and the lithium ion may be easily moved.
  • FEC Monofluoroethylene carbonate
  • Tetrafluoroethylene carbonate (F4EC) is represented by the following formula (2).
  • DFEC Difluoroethylene carbonate
  • Ionic liquids normally temperature molten salt
  • Ionic liquids consist of cations and anions, including organic cations and anions.
  • an ionic liquid represented by the following general formula (G1) can be used as the ionic liquid having an imidazolium cation.
  • R 1 represents an alkyl group having 1 or more and 10 or less carbon atoms
  • R 2 to R 4 independently represent a hydrogen atom or an alkyl group having 1 or more and 4 or less carbon atoms.
  • R 5 is 1 to 6 alkyl groups having a carbon number or, represents C, O, Si, N, S, a backbone with two or more selected from atoms P.
  • substituents in the main chain of R 5 may be introduced. Examples of the substituent to be introduced include an alkyl group and an alkoxy group.
  • an ionic liquid represented by the following general formula (G2) may be used.
  • R 6 is mainly composed of an alkyl group having 1 or more and 6 or less carbon atoms, or two or more atoms selected from C, O, Si, N, S, and P atoms.
  • R 7 to R 11 each independently represent a hydrogen atom or an alkyl group having 1 or more and 4 or less carbon atoms.
  • substituents in the main chain of the R 6 may be introduced. Examples of the substituent to be introduced include an alkyl group and an alkoxy group.
  • ionic liquid having a quaternary ammonium cation for example, ionic liquids represented by the following general formulas (G3), (G4), (G5) and (G6) can be used.
  • R 28 to R 31 each independently represent any one of an alkyl group having 1 or more and 20 or less carbon atoms, a methoxy group, a methoxymethyl group, a methoxyethyl group, or a hydrogen atom.
  • R 12 and R 17 each independently represent an alkyl group having 1 or more and 3 or less carbon atoms.
  • R 13 to R 16 each independently represent either a hydrogen atom or an alkyl group having 1 or more and 3 or less carbon atoms.
  • the cation represented by the general formula (G4) there is a 1-methyl-1-propylpyrrolidinium cation and the like.
  • R 18 and R 24 each independently represent an alkyl group having 1 or more and 3 or less carbon atoms.
  • R 19 to R 23 each independently represent a hydrogen atom or an alkyl group having 1 or more and 3 or less carbon atoms.
  • the cation represented by the general formula (G5) there are N-methyl-N-propylpiperidinium cation, 1,3-dimethyl-1-propylpiperidinium cation and the like.
  • n and m are 1 or more and 3 or less.
  • ⁇ is 0 or more and 6 or less, ⁇ is 0 or more and 4 or less when n is 1, ⁇ is 0 or more and 5 or less when n is 2, and ⁇ is 0 or more and 6 or less when n is 3.
  • ⁇ is 0 or more and 6 or less, ⁇ is 0 or more and 4 or less when m is 1, ⁇ is 0 or more and 5 or less when m is 2, and ⁇ is 0 or more and 6 or less when m is 3.
  • ⁇ or ⁇ it means that it is not substituted. Further, the case where both ⁇ and ⁇ are 0 is excluded.
  • X or Y is a linear or side chain alkyl group having 1 or more and 4 or less carbon atoms, a linear or side chain alkoxy group having 1 or more and 4 or less carbon atoms, or a carbon number as a substituent. Represents a linear or side chain alkoxyalkyl group of 1 or more and 4 or less.
  • an ionic liquid represented by the following general formula (G7) can be used.
  • R 25 to R 27 each independently represent a hydrogen atom, an alkyl group having 1 or more and 4 or less carbon atoms, or a phenyl group.
  • R 25 to R 27 a main chain composed of two or more atoms selected from the atoms of C, O, Si, N, S, and P may be used.
  • an ionic liquid represented by the following general formula (G8) can be used.
  • R 32 to R 35 each independently represent a hydrogen atom, an alkyl group having 1 or more and 4 or less carbon atoms, or a phenyl group.
  • R 32 to R 35 a main chain composed of two or more atoms selected from the atoms of C, O, Si, N, S, and P may be used.
  • a ⁇ represented by the general formulas (G1) to (G8) a monovalent amide anion, a monovalent methide anion, a fluorosulfonic acid anion, a perfluoroalkylsulfonic acid anion, a tetrafluoroborate anion, and a perfluoroalkylborate.
  • anions, hexafluorophosphate anions, perfluoroalkyl phosphate anions and the like can be used.
  • the monovalent amide anion for example, one or more of a bis (fluorosulfonyl) amide anion and a bis (trifluoromethanesulfonyl) amide anion can be used.
  • the ionic liquid may also have one or more of the hexafluorophosphate anion and the tetrafluoroborate anion.
  • the anion represented by (FSO 2 ) 2 N ⁇ may be referred to as an FSA anion, and the anion represented by (CF 3 SO 2 ) 2 N ⁇ may be referred to as a TFSA anion.
  • the secondary battery of one aspect of the present invention has, for example, alkali metal ions such as sodium ion and potassium ion, and alkaline earth metal ions such as calcium ion, strontium ion, barium ion, beryllium ion and magnesium ion as carrier ions. ..
  • the electrolyte contains a lithium salt.
  • a lithium salt LiPF 6, LiClO 4, LiAsF 6, LiBF 4, LiAlCl 4, LiSCN, LiBr, LiI, Li 2 SO 4, Li 2 B 10 Cl 10, Li 2 B 12 Cl 12, LiCF 3 SO 3, LiC 4 F 9 SO 3 , LiC (CF 3 SO 2 ) 3 , LiC (C 2 F 5 SO 2 ) 3 , LiN (CF 3 SO 2 ) 2 , LiN (C 4 F 9 SO 2 ) (CF 3 SO 2) ), LiN (C 2 F 5 SO 2 ) 2, etc.
  • electrolyte is a general term including solid, liquid, semi-solid materials and the like.
  • Deterioration is likely to occur at the interface existing in the secondary battery, for example, the interface between the active material and the electrolyte.
  • the secondary battery of one aspect of the present invention by having an electrolyte having fluorine, it is possible to prevent deterioration, typically alteration of the electrolyte or high viscosity of the electrolyte, which may occur at the interface between the active material and the electrolyte. Can be done.
  • the electrolyte having fluorine may be configured to cling to or retain a binder, a graphene compound, or the like.
  • DFEC with two fluorine bonds and F4EC with four bonds have a lower viscosity and are smoother than FEC with one fluorine bond, and the coordination bond with lithium is weak. Therefore, it is possible to reduce the adhesion of highly viscous decomposition products to the active material particles. If highly viscous decomposition products adhere to or cling to the active material particles, it becomes difficult for lithium ions to move at the interface of the active material particles.
  • electrolyte having fluorine is used as a main component, and the electrolyte having fluorine is 5% by volume or more, 10% by volume or more, preferably 30% by volume or more and 100% by volume or less.
  • the main component of the electrolyte means that it is 5% by volume or more of the total electrolyte of the secondary battery. Further, 5% by volume or more of the total electrolyte of the secondary battery referred to here refers to the ratio of the total electrolyte measured at the time of manufacturing the secondary battery. In addition, when disassembling after manufacturing a secondary battery, it is difficult to quantify the proportion of each of the multiple types of electrolytes, but one type of organic compound accounts for 5% by volume or more of the total amount of electrolytes. It can be determined whether or not it exists.
  • an additive such as vinylene carbonate, propane sultone (PS), tert-butylbenzene (TBB), lithium bis (oxalate) borate (LiBOB), or a dinitrile compound such as succinonitrile or adiponitrile is added to the electrolyte, it may be added. good.
  • concentration of the additive may be, for example, 0.1% by volume or more and less than 5% by volume with respect to the entire electrolyte.
  • having a polymer material in which the electrolyte is gelled enhances safety against liquid leakage and the like.
  • Typical examples of the polymer material to be gelled include silicone gel, acrylic gel, acrylonitrile gel, polyethylene oxide gel, polypropylene oxide gel, and fluoropolymer gel.
  • polymer material for example, a polymer having a polyalkylene oxide structure such as polyethylene oxide (PEO), PVDF, polyacrylonitrile, etc., and a copolymer containing them can be used.
  • PEO polyethylene oxide
  • PVDF-HFP which is a copolymer of PVDF and hexafluoropropylene (HFP)
  • the polymer to be formed may have a porous shape.
  • a separator is placed between the positive electrode and the negative electrode.
  • the separator include fibers having cellulose such as paper, non-woven fabrics, glass fibers, ceramics, nylon resin (polyamide), vinylon resin (polyvinyl alcohol-based fiber), polyester resin, acrylic resin, polyolefin resin, and polyurethane resin. It is possible to use the one formed of synthetic fiber or the like using. It is preferable that the separator is processed into a bag shape and arranged so as to wrap either the positive electrode or the negative electrode.
  • the separator may have a multi-layer structure.
  • an organic material film such as polypropylene or polyethylene can be coated with a ceramic material, a fluorine material, a polyamide material, or a mixture thereof.
  • the ceramic material for example, aluminum oxide particles, silicon oxide particles and the like can be used.
  • the fluorine-based material for example, PVDF, polytetrafluoroethylene and the like can be used.
  • the polyamide-based material for example, nylon, aramid (meth-based aramid, para-based aramid) and the like can be used.
  • the oxidation resistance is improved by coating with a ceramic material, deterioration of the separator during high voltage charging / discharging can be suppressed and the reliability of the secondary battery can be improved. Further, when a fluorine-based material is coated, the separator and the electrode are easily brought into close contact with each other, and the output characteristics can be improved. Coating a polyamide-based material, particularly aramid, improves heat resistance and thus can improve the safety of the secondary battery.
  • a mixed material of aluminum oxide and aramid may be coated on both sides of a polypropylene film.
  • the surface of the polypropylene film in contact with the positive electrode may be coated with a mixed material of aluminum oxide and aramid, and the surface in contact with the negative electrode may be coated with a fluorine-based material.
  • the safety of the secondary battery can be maintained even if the thickness of the entire separator is thin, so that the capacity per volume of the secondary battery can be increased.
  • the exterior body of the secondary battery may be a can type using a metal material such as aluminum or a case type using a resin material. Further, a film-like exterior body can also be used.
  • a metal thin film having excellent flexibility such as aluminum, stainless steel, copper, and nickel is provided on a film made of a material such as polyethylene, polypropylene, polycarbonate, ionomer, and polyamide, and an exterior is further formed on the metal thin film.
  • a film having a three-layer structure provided with an insulating synthetic resin film such as a polyamide resin or a polyester resin can be used as the outer surface of the body. Further, it is preferable to use a fluororesin film as the film.
  • This embodiment can be used in combination with other embodiments as appropriate.
  • the secondary battery shown in FIG. 6A has a positive electrode 503, a negative electrode 506, a separator 507, and an exterior body 509.
  • the exterior body 509 is sealed by the seal region 513.
  • the positive electrode 503, the negative electrode 506, and the separator 507 are laminated and arranged inside the exterior body 509.
  • a positive electrode lead electrode 510 is bonded to the positive electrode 503.
  • the positive electrode lead electrode 510 is exposed to the outside of the exterior body 509.
  • the negative electrode lead electrode 511 is bonded to the negative electrode 506, and the negative electrode lead electrode 511 is exposed to the outside of the exterior body 509.
  • FIG. 8A shows an external view of the positive electrode 503.
  • the positive electrode 503 has a positive electrode current collector 501, and the positive electrode active material layer 502 is formed on the surface of the positive electrode current collector 501. Further, the positive electrode 503 has a region (hereinafter referred to as a tab region) in which the positive electrode current collector 501 is partially exposed.
  • FIG. 8B shows an external view of the negative electrode 506.
  • the negative electrode 506 has a negative electrode current collector 504, and the negative electrode active material layer 505 is formed on the surface of the negative electrode current collector 504. Further, the negative electrode 506 has a region where the negative electrode current collector 504 is partially exposed, that is, a tab region.
  • the area or shape of the tab region of the positive electrode and the negative electrode is not limited to the examples shown in FIGS. 8A and 8B.
  • FIG. 8C is a diagram illustrating joining of lead electrodes.
  • the negative electrode 506, the separator 507, and the positive electrode 503 are laminated.
  • FIG. 8C shows the negative electrode 506, the separator 507, and the positive electrode 503 laminated.
  • the laminate composed of the negative electrode, the separator, and the positive electrode has 5 sets of negative electrodes and 4 sets of positive electrodes.
  • the tab regions of the positive electrode 503 are bonded to each other, and the positive electrode lead electrode 510 is bonded to the tab region of the positive electrode on the outermost surface.
  • ultrasonic welding may be used.
  • the tab regions of the negative electrode 506 are bonded to each other, and the negative electrode lead electrode 511 is bonded to the tab region of the negative electrode on the outermost surface.
  • FIG. 6B shows an example in which the end portions are folded on two sides of the side surface of the exterior body 509.
  • the strength of the exterior body 509 can be increased.
  • FIG. 6C shows an example of folding three sides.
  • FIG. 7A shows an example in which the positive electrode lead electrode 510 and the negative electrode lead electrode 511 are arranged on the same side, but the positive electrode lead electrode 510 and the negative electrode lead electrode 511 are shown on different sides, for example, FIG. 7A. It may be arranged on the upper and lower sides respectively.
  • FIG. 7B shows an example in which the left side and the right side of the exterior body 509 are folded in FIG. 7A.
  • This embodiment can be used in combination with other embodiments as appropriate.
  • the electric vehicle is provided with a first battery 1301a and 1301b as a main drive secondary battery and a second battery 1311 for supplying electric power to the inverter 1312 for starting the motor 1304.
  • the second battery 1311 is also called a cranking battery (starter battery).
  • the second battery 1311 only needs to have a high output, and a large capacity is not required so much, and the capacity of the second battery 1311 is smaller than that of the first batteries 1301a and 1301b.
  • the first battery 1301a a secondary battery using the method for manufacturing a secondary battery shown in the first embodiment can be used.
  • first batteries 1301a and 1301b are connected in parallel, but three or more batteries may be connected in parallel. Further, if the first battery 1301a can store sufficient electric power, the first battery 1301b may not be present.
  • the plurality of secondary batteries may be connected in parallel, may be connected in series, or may be connected in parallel and then further connected in series. Multiple secondary batteries are also called assembled batteries.
  • a service plug or a circuit breaker capable of cutting off a high voltage without using a tool is provided, and the first battery 1301a has. It will be provided.
  • the electric power of the first batteries 1301a and 1301b is mainly used to rotate the motor 1304, but 42V in-vehicle parts (electric power steering 1307, heater 1308, defogger 1309, etc.) via the DCDC circuit 1306. Power to. Even if the rear wheel has a rear motor 1317, the first battery 1301a is used to rotate the rear motor 1317.
  • the second battery 1311 supplies electric power to 14V in-vehicle parts (audio 1313, power window 1314, lamps 1315, etc.) via the DCDC circuit 1310.
  • first battery 1301a will be described with reference to FIG. 9A.
  • FIG. 9A shows an example in which nine square secondary batteries 1300 are used as one battery pack 1415. Further, nine square secondary batteries 1300 are connected in series, one electrode is fixed by a fixing portion 1413 made of an insulator, and the other electrode is fixed by a fixing portion 1414 made of an insulator.
  • a fixing portion 1413 made of an insulator In the present embodiment, an example of fixing with the fixing portions 1413 and 1414 is shown, but the configuration may be such that the battery is stored in a battery storage box (also referred to as a housing). Since it is assumed that the vehicle is vibrated or shaken from the outside (road surface or the like), it is preferable to fix a plurality of secondary batteries in a battery accommodating box or the like by fixing portions 1413 and 1414. Further, one of the electrodes is electrically connected to the control circuit unit 1320 by the wiring 1421. The other electrode is electrically connected to the control circuit unit 1320 by wiring 1422.
  • control circuit unit 1320 may use a memory circuit including a transistor using an oxide semiconductor.
  • a charge control circuit or a battery control system having a memory circuit including a transistor using an oxide semiconductor may be referred to as a BTOS (Battery operating system or Battery oxide semiconductor).
  • the control circuit unit 1320 detects the terminal voltage of the secondary battery and manages the charge / discharge state of the secondary battery. For example, in order to prevent overcharging, both the output transistor of the charging circuit and the cutoff switch can be turned off almost at the same time.
  • FIG. 9B An example of the block diagram of the battery pack 1415 shown in FIG. 9A is shown in FIG. 9B.
  • the control circuit unit 1320 includes at least a switch for preventing overcharging, a switch unit 1324 including a switch for preventing overdischarging, a control circuit 1322 for controlling the switch unit 1324, and a voltage measuring unit for the first battery 1301a.
  • the upper limit voltage and the lower limit voltage of the secondary battery to be used are set, and the upper limit of the current from the outside or the upper limit of the output current to the outside is limited.
  • the range of the lower limit voltage or more and the upper limit voltage or less of the secondary battery is within the voltage range recommended for use, and if it is out of the range, the switch unit 1324 operates and functions as a protection circuit.
  • control circuit unit 1320 can also be called a protection circuit because it controls the switch unit 1324 to prevent over-discharging or over-charging. For example, when the control circuit 1322 detects a voltage that is likely to cause overcharging, the switch of the switch unit 1324 is turned off to cut off the current. Further, a PTC element may be provided in the charge / discharge path to provide a function of cutting off the current in response to an increase in temperature. Further, the control circuit unit 1320 has an external terminal 1325 (+ IN) and an external terminal 1326 ( ⁇ IN).
  • the switch unit 1324 can be configured by combining an n-channel type transistor or a p-channel type transistor.
  • the switch unit 1324 is not limited to a switch having a Si transistor using single crystal silicon, and is not limited to, for example, Ge (germanium), SiGe (silicon germanium), GaAs (gallium arsenide), GaAlAs (gallium aluminum arsenide), and InP (phosphide).
  • the switch unit 1324 may be formed by a power transistor having indium phosphide, SiC (silicon carbide), ZnSe (zinc selenium), GaN (gallium nitride), GaOx (gallium oxide; x is a real number larger than 0) and the like.
  • the storage element using the OS transistor can be freely arranged by stacking it on a circuit using a Si transistor or the like, integration can be easily performed.
  • the OS transistor can be manufactured by using the same manufacturing apparatus as the Si transistor, it can be manufactured at low cost. That is, it is also possible to stack the control circuit unit 1320 using the OS transistor on the switch unit 1324 and integrate them into one chip. Since the occupied volume of the control circuit unit 1320 can be reduced, the size can be reduced.
  • the first batteries 1301a and 1301b mainly supply electric power to 42V system (high voltage system) in-vehicle devices, and the second battery 1311 supplies electric power to 14V system (low voltage system) in-vehicle devices.
  • the second battery 1311 is often adopted because a lead storage battery is advantageous in terms of cost.
  • the second battery 1311 may use a lead storage battery or an all-solid-state battery or an electric double layer capacitor.
  • the regenerative energy due to the rotation of the tire 1316 is sent to the motor 1304 via the gear 1305, and is charged from the motor controller 1303 or the battery controller 1302 to the second battery 1311 via the control circuit unit 1321.
  • the first battery 1301a is charged from the battery controller 1302 via the control circuit unit 1320.
  • the first battery 1301b is charged from the battery controller 1302 via the control circuit unit 1320. In order to efficiently charge the regenerative energy, it is desirable that the first batteries 1301a and 1301b can be quickly charged.
  • the battery controller 1302 can set the charging voltage, charging current, and the like of the first batteries 1301a and 1301b.
  • the battery controller 1302 can set charging conditions according to the charging characteristics of the secondary battery to be used and quickly charge the battery.
  • the outlet of the charger or the connection cable of the charger is electrically connected to the battery controller 1302.
  • the electric power supplied from the external charger charges the first batteries 1301a and 1301b via the battery controller 1302.
  • a control circuit may be provided and the function of the battery controller 1302 may not be used, but the first batteries 1301a and 1301b are charged via the control circuit unit 1320 in order to prevent overcharging. Is preferable.
  • the connection cable or the connection cable of the charger is provided with a control circuit.
  • the control circuit unit 1320 may be referred to as an ECU (Electronic Control Unit).
  • the ECU is connected to a CAN (Control Area Area Network) provided in the electric vehicle.
  • CAN is one of the serial communication standards used as an in-vehicle LAN.
  • the ECU also includes a microcomputer. Further, the ECU uses a CPU or a GPU.
  • the automobile 2001 shown in FIG. 10A is an electric vehicle that uses an electric motor as a power source for traveling. Alternatively, it is a hybrid vehicle in which an electric motor and an engine can be appropriately selected and used as a power source for traveling.
  • the automobile 2001 shown in FIG. 10A has a battery pack 2200, and the battery pack has a secondary battery module to which a plurality of secondary batteries are connected. Further, it is preferable to have a charge control device that is electrically connected to the secondary battery module.
  • the automobile 2001 can be charged by receiving electric power from an external charging facility by a plug-in method, a non-contact power supply method, or the like to the secondary battery of the automobile 2001.
  • the charging method or the standard of the connector may be appropriately performed by a predetermined method such as CHAdeMO (registered trademark) or a combo.
  • the secondary battery may be a charging station provided in a commercial facility or a household power source.
  • the plug-in technology can charge the power storage device mounted on the automobile 2001 by supplying electric power from the outside. Charging can be performed by converting AC power into DC power via a conversion device such as an ACDC converter.
  • a power receiving device on the vehicle and supply power from a ground power transmission device in a non-contact manner to charge the vehicle.
  • this non-contact power supply system by incorporating a power transmission device on the road or the outer wall, charging can be performed not only while the vehicle is stopped but also while the vehicle is running. Further, power may be transmitted and received between two vehicles by using this contactless power feeding method. Further, a solar cell may be provided on the exterior portion of the vehicle to charge the secondary battery when the vehicle is stopped or running. An electromagnetic induction method or a magnetic field resonance method can be used for such non-contact power supply.
  • FIG. 10C shows, as an example, a large transport vehicle 2003 having a motor controlled by electricity.
  • the secondary battery module of the transport vehicle 2003 has, for example, a maximum voltage of 600 V in which 100 or more secondary batteries of 3.5 V or more and 4.7 V or less are connected in series. Therefore, a secondary battery having a small variation in characteristics is required.
  • the method for manufacturing a secondary battery shown in the first embodiment it is possible to manufacture a secondary battery having stable battery characteristics, and mass production is possible at low cost from the viewpoint of yield. Further, since it has the same functions as those in FIG. 10A except that the number of secondary batteries constituting the secondary battery module of the battery pack 2202 is different, the description thereof will be omitted.
  • FIG. 10D shows, as an example, an aircraft 2004 having an engine that burns fuel. Since the aircraft 2004 shown in FIG. 10D has wheels for takeoff and landing, it can be said to be a part of a transportation vehicle, and a plurality of secondary batteries are connected to form a secondary battery module, which is charged with the secondary battery module. It has a battery pack 2203 including a control device.
  • the secondary battery module of the aircraft 2004 has a maximum voltage of 32V in which eight 4V secondary batteries are connected in series, for example. Since it has the same functions as in FIG. 10A except that the number of secondary batteries constituting the secondary battery module of the battery pack 2203 is different, the description thereof will be omitted.
  • This embodiment can be used in combination with other embodiments as appropriate.
  • the house shown in FIG. 11A has a power storage device 2612 having a secondary battery having stable battery characteristics and a solar panel 2610 by using the method for manufacturing the secondary battery shown in the first embodiment.
  • the power storage device 2612 is electrically connected to the solar panel 2610 via wiring 2611 and the like. Further, the power storage device 2612 and the ground-mounted charging device 2604 may be electrically connected.
  • the electric power obtained by the solar panel 2610 can be charged to the power storage device 2612. Further, the electric power stored in the power storage device 2612 can be charged to the secondary battery of the vehicle 2603 via the charging device 2604.
  • the power storage device 2612 is preferably installed in the underfloor space. By installing it in the underfloor space, the space above the floor can be effectively used. Alternatively, the power storage device 2612 may be installed on the floor.
  • the electric power stored in the power storage device 2612 can also supply electric power to other electronic devices in the house. Therefore, even when the power cannot be supplied from the commercial power supply due to a power failure or the like, the electronic device can be used by using the power storage device 2612 as an uninterruptible power supply.
  • FIG. 11B shows an example of the power storage device 700 according to one aspect of the present invention.
  • a large power storage device 791 obtained by the method for manufacturing a secondary battery shown in the first embodiment is installed in the underfloor space portion 796 of the building 799.
  • a control device 790 is installed in the power storage device 791, and the control device 790 is connected to a distribution board 703, a power storage controller 705 (also referred to as a control device), a display 706, and a router 709 by wiring. It is electrically connected.
  • Electric power is sent from the commercial power supply 701 to the distribution board 703 via the drop line mounting portion 710. Further, electric power is transmitted to the distribution board 703 from the power storage device 791 and the commercial power supply 701, and the distribution board 703 transfers the transmitted electric power to a general load via an outlet (not shown). It supplies 707 and the power storage system load 708.
  • the power storage controller 705 has a measurement unit 711, a prediction unit 712, and a planning unit 713.
  • the measuring unit 711 has a function of measuring the amount of electric power consumed by the general load 707 and the power storage system load 708 during one day (for example, from 0:00 to 24:00). Further, the measuring unit 711 may have a function of measuring the electric power of the power storage device 791 and the electric power supplied from the commercial power source 701.
  • the prediction unit 712 is based on the amount of electric power consumed by the general load 707 and the power storage system load 708 during the next day, and the demand consumed by the general load 707 and the power storage system load 708 during the next day. It has a function to predict the amount of electric power.
  • the planning unit 713 has a function of making a charge / discharge plan of the power storage device 791 based on the power demand amount predicted by the prediction unit 712.
  • the amount of electric power consumed by the general load 707 and the power storage system load 708 measured by the measuring unit 711 can be confirmed by the display 706. It can also be confirmed in an electric device such as a television or a personal computer via a router 709. Further, it can be confirmed by a portable electronic terminal such as a smartphone or a tablet via the router 709. Further, the amount of power demand for each time zone (or every hour) predicted by the prediction unit 712 can be confirmed by the display 706, the electric device, and the portable electronic terminal.
  • This embodiment can be used in combination with other embodiments as appropriate.
  • the personal computer 2800 shown in FIG. 12A has a housing 2801, a housing 2802, a display unit 2803, a keyboard 2804, a pointing device 2805, and the like.
  • a secondary battery 2806 is provided inside the housing 2801, and a secondary battery 2807 is provided inside the housing 2802.
  • a touch panel is applied to the display unit 2803.
  • the personal computer 2800 can be used as a tablet terminal by removing the housing 2801 and the housing 2802 and using only the housing 2802.
  • a flexible display is applied to the display unit 2803 of the housing 2802.
  • a large-sized secondary battery obtained by the method for manufacturing a secondary battery shown in the first embodiment is applied to the secondary battery 2807.
  • a bendable secondary battery can be obtained by using a flexible film for the exterior body.
  • the housing 2802 can be bent and used.
  • a part of the display unit 2803 can also be used as a keyboard.
  • housing 2802 can be folded so that the display unit 2803 is on the inside as shown in FIG. 12D, or the housing 2802 can be folded so that the display unit 2803 is on the outside as shown in FIG. 12E.
  • This embodiment can be used in combination with other embodiments as appropriate.
  • the crystal plane and the direction are indicated by the Miller index.
  • the notation of the crystal plane and direction is to add a superscript bar to the number, but in the present specification etc., due to the limitation of the application notation, instead of adding a bar above the number,-(minus) before the number. It may be expressed with a sign).
  • the individual orientation indicating the direction in the crystal is []
  • the aggregate orientation indicating all equivalent directions is ⁇ >
  • the individual plane indicating the crystal plane is ()
  • the aggregate plane having equivalent symmetry is ⁇ . Express each with.
  • segregation refers to a phenomenon in which a certain element (for example, B) is spatially unevenly distributed in a solid composed of a plurality of elements (for example, A, B, C).
  • the rock salt type crystal structure means a structure in which cations and anions are alternately arranged. There may be a cation or anion deficiency.
  • the angle formed by the repetition of the bright line and the dark line between the crystals is 5 degrees or less, more preferably 2.5 degrees or less. It can be observed. In some cases, light elements such as oxygen and fluorine cannot be clearly observed in the TEM image or the like, but in that case, the alignment of the metal elements can be used to determine the alignment.
  • the charging depth when all the insertable and desorbable lithium is inserted is 0, and the charging depth when all the insertable and desorbable lithium contained in the positive electrode active material is desorbed is 1. And.
  • a non-equilibrium phase change means a phenomenon that causes a non-linear change in a physical quantity.
  • an unbalanced phase change occurs before and after the peak in the dQ / dV curve obtained by differentiating the capacitance (Q) with the voltage (V) (dQ / dV), and the crystal structure changes significantly. ..
  • the secondary battery has, for example, a positive electrode and a negative electrode.
  • a positive electrode active material As a material constituting the positive electrode, there is a positive electrode active material.
  • the positive electrode active material is, for example, a substance that undergoes a reaction that contributes to the charge / discharge capacity.
  • the positive electrode active material may contain a substance that does not contribute to the charge / discharge capacity as a part thereof.

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  • Condensed Matter Physics & Semiconductors (AREA)
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  • Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
PCT/IB2021/056266 2020-07-24 2021-07-13 二次電池の作製方法 Ceased WO2022018573A1 (ja)

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US18/004,749 US20230261265A1 (en) 2020-07-24 2021-07-13 Method for fabricating secondary battery
CN202180061271.6A CN116195080A (zh) 2020-07-24 2021-07-13 二次电池的制造方法
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JP2010010095A (ja) * 2008-06-30 2010-01-14 Panasonic Corp 非水電解液および非水電解液二次電池
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