WO2009157263A1 - Batterie secondaire lithium-ion - Google Patents

Batterie secondaire lithium-ion Download PDF

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Publication number
WO2009157263A1
WO2009157263A1 PCT/JP2009/059274 JP2009059274W WO2009157263A1 WO 2009157263 A1 WO2009157263 A1 WO 2009157263A1 JP 2009059274 W JP2009059274 W JP 2009059274W WO 2009157263 A1 WO2009157263 A1 WO 2009157263A1
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WIPO (PCT)
Prior art keywords
resin
layer
separator
secondary battery
ion secondary
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PCT/JP2009/059274
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English (en)
Japanese (ja)
Inventor
直人 西村
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シャープ株式会社
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Priority to JP2010517822A priority Critical patent/JP5371979B2/ja
Publication of WO2009157263A1 publication Critical patent/WO2009157263A1/fr

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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
    • 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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/429—Natural polymers
    • H01M50/4295—Natural cotton, cellulose or wood
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/463—Separators, membranes or diaphragms characterised by their shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a lithium ion secondary battery.
  • the lithium ion secondary battery of the present invention is suitable as a large-capacity lithium ion secondary battery used in, for example, a hybrid electric vehicle, an uninterruptible power supply, a load leveling storage battery system, and a power storage battery system.
  • a large-capacity lithium-ion secondary battery (hereinafter also simply referred to as a battery) generates more heat when the internal short circuit occurs than a small lithium-ion secondary battery for portable device power supply. Therefore, the separator between adjacent positive and negative electrodes (hereinafter, collectively referred to as electrodes) is thermally melted, and the internal short circuit is expanded. As a result, there is a problem that a large amount of heat is released to the surroundings, and a large amount of gas may be ejected.
  • Patent Document 1 Japanese Patent Laid-Open No. 10-340740
  • Patent Document 2 Japanese Patent Laid-Open No. 9-120842
  • the former publication describes a battery having a structure in which electrode groups in a battery are alternately folded in a mountain fold and a valley, and a heat dissipation sheet is arranged between the electrodes in the valley fold. It is said that the heat dissipation in the battery can be improved by having such a structure.
  • the current collector constituting the electrode is one in which a metal foil is attached to both surfaces of a heat-resistant insulating film. In such a current collector, it is said that the heat generated at the location where the internal short circuit occurs does not spread to adjacent electrodes.
  • the positive electrode and the negative electrode are laminated via a resin separator, and at least one of the positive electrode and the negative electrode has a metal layer on both surfaces of a resin layer as a core material.
  • a lithium ion secondary battery comprising an electric body and an electrode active material layer on the metal layer, wherein the resin separator is made of a resin having a softening point higher than that of the resin constituting the core material.
  • the resin separator at that position contracts, and the ion conduction between the positive and negative electrodes is interrupted, and at the same time, the current collector is held. Since the resin layer is also contracted, the metal layer on the surface is mechanically broken, and the electrode itself is also in an insulating state. According to this configuration, even if the battery causes an internal short circuit, both the separator and the current collector have a function of interrupting current, so that the probability of large heat generation can be significantly reduced. As a result, a high-capacity battery with higher safety can be provided.
  • the resin layer can be flowed to the line as a base substrate when manufacturing the battery, so that the productivity is improved and it can be manufactured at low cost.
  • Structure battery can be provided.
  • the lithium ion secondary battery of this invention has the structure which laminated
  • the resin separator is made of a resin having a softening point higher than that of the resin constituting the core material.
  • the separator and the current collector can be provided with a function of interrupting current. Therefore, even if the battery causes an internal short circuit, the probability of large heat generation can be significantly reduced.
  • the current collector is preferably provided with both the positive electrode and the negative electrode from the viewpoint of further enhancing the function of blocking current and from the viewpoint of ease of production.
  • the resin constituting the resin separator that can be used in the present invention is made of a resin having the same temperature or a higher softening point than the resin constituting the resin layer. From the viewpoint of further enhancing the function of interrupting current, the resin constituting the resin separator is preferably made of a resin having a higher softening point than the resin constituting the resin layer.
  • the softening point of the resin constituting the resin separator is preferably 120 to 220 ° C., more preferably 140 to 180 ° C., from the viewpoint of providing a function of interrupting current.
  • the softening point of the resin constituting the resin layer is preferably 110 to 190 ° C., more preferably 120 to 170 ° C., from the viewpoint of providing a function of interrupting current.
  • the resin constituting the resin separator preferably has a softening point that is 10 to 100 ° C. higher than that of the resin that constitutes the resin layer from the viewpoint of further enhancing the function of interrupting the current, and is 20 to 80 ° C. higher softening. It is more preferable to have a point.
  • any resin having different softening points may be selected from various resins as the resin constituting the resin separator and the resin constituting the resin layer.
  • resins for example, polyethylene (softening point: about 100 ° C. to 120 ° C.), polypropylene (softening point: about 140 ° C. to 145 ° C.), a mixture of polyethylene and polypropylene, polyester (softening point: about 200 ° C.
  • polyethylene terephthalate (Softening point: about 180 ° C), polybutylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate, polyvinyl chloride, polystyrene, AS resin, ABS resin, polyamide, polyaramid, 6-nylon, 66-nylon, cellulose resin, etc. Appropriate ones are selected.
  • the softening point said here means the temperature which softens and begins to deform
  • it means a value obtained by placing a sample of about 100 ⁇ m square on a temperature-controlled heating stainless steel plate, observing the softened to molten state with a magnifier of about 50 times, and measuring the temperature at which the softening starts. To do.
  • the resin constituting the resin layer used for the electrode and the resin separator are made of the same resin.
  • the resin separator and the resin layer may be a series of resin layers.
  • Such a series of resin layers includes a region where a positive electrode is formed, a region where a negative electrode is formed, and a region which serves as a separator between these regions, and these three regions are folded in a folding screen at the boundary between them. And if it laminates
  • the resin layer can be flowed on the line as a base substrate, so that productivity can be improved and a battery having a structure that can be manufactured at low cost can be provided.
  • the resin layer used for the electrode and the resin constituting the resin separator have the same softening point.
  • the battery shown in FIG. 1 is a battery in which a negative electrode, a separator, and a positive electrode are simply laminated.
  • the battery shown in FIG. 1 can be formed as follows. First, the metal layer 2 for the negative electrode current collector is installed on both surfaces of the resin layer 3. A negative electrode active material layer 1 is formed on the metal layer 2 by a coating method leaving a part of the metal layer 2 to obtain a negative electrode. Next, the metal layer 6 for a positive electrode current collector is provided on both surfaces of the resin layer 3. A positive electrode active material layer 5 is formed on the metal layer 6 by a coating method leaving a part of the metal layer 6 to obtain a positive electrode.
  • a negative electrode lead 4 for taking out current to an external circuit is attached by welding to a portion where the negative electrode active material layer 1 is not formed on the metal layer 2.
  • the positive electrode lead 7 is attached to the positive electrode.
  • a resin separator 8 is placed on the negative electrode, and a positive electrode is placed thereon so that the positive electrode lead 7 does not come into contact with the negative electrode lead 4, and the resin separator 8 is placed thereon.
  • a negative electrode in order to obtain a laminate. After lamination, if necessary, it is fixed with tape so that the laminate does not shift.
  • FIG. 3 is a schematic plan view of the laminated body of FIG. 1 as viewed from the direction perpendicular to the laminated surface.
  • a lithium ion secondary battery is obtained by putting the obtained laminate into a bag made of an outer can or a resin film and injecting the electrolytic solution and then sealing.
  • FIG. 2 shows a battery using a resin separator and a series of resin layers as a resin layer.
  • the battery shown in FIG. 2 can be formed as follows. First, the negative electrode current collector metal layer 2 and the positive electrode current collector metal layer 6 are sequentially formed on both surfaces of the series of resin layers 9 with portions serving as separators interposed therebetween. Next, a part of the negative electrode active material layer 1 is formed on the metal layer 2 by a coating method, and a part of the positive electrode active material layer 5 is formed on the metal layer 6 by a coating method. Next, the negative electrode lead 4 for taking out an electric current to the external circuit is attached to the part of the metal layer 2 where the negative electrode active material layer 1 is not formed by welding. Similarly, the positive electrode lead 7 is attached to the positive electrode.
  • a negative electrode, a separator, and a positive electrode are laminated in a folding screen to obtain a laminate. Thereafter, the laminate is fixed with tape as necessary. Instead of fixing with a tape, all the positive and negative electrode unformed portions of the series of resin layers 9 may be fixed together by heat fusion with a sealer.
  • FIG. 2 as in FIG. 1, two units of positive electrode, separator, and negative electrode are stacked.
  • a lithium ion secondary battery is obtained by putting the obtained laminate into a bag made of an outer can or a resin film and injecting the electrolytic solution and then sealing.
  • FIG. 4 shows a battery having the same configuration as that of FIG. 1 except that a metal foil is used instead of a resin layer for the current collector on the positive electrode side.
  • the battery shown in FIG. 4 can be formed as follows. First, the metal layer 2 for the negative electrode current collector is placed on both surfaces of the resin layer 3, and the negative electrode active material layer 1 is partially formed on the resin layer 3 by a coating method to obtain a negative electrode. Next, the positive electrode active material layer 5 is partially formed on both surfaces of the metal foil 10 by a coating method to obtain a positive electrode. A negative electrode lead 4 for taking out current to an external circuit is attached by welding to a portion of the metal layer 2 where the negative electrode active material layer 1 is not formed.
  • the positive electrode lead 7 is attached to the portion of the metal foil 10 where the positive electrode active material layer 5 is not formed in the same manner as the negative electrode.
  • a resin separator 8 is placed on the negative electrode, and a positive electrode is placed thereon so that the positive electrode lead 7 does not come into contact with the negative electrode lead 4, and the resin separator 8 is placed thereon.
  • a negative electrode in order to obtain a laminate. After lamination, if necessary, it is fixed with tape so that the laminate does not shift.
  • FIG. 4 as in FIG. 1, two units of positive electrode, separator, and negative electrode are stacked.
  • a lithium ion secondary battery is obtained by putting the obtained laminate into a bag made of an outer can or a resin film and injecting the electrolytic solution and then sealing.
  • metal foil is used on the positive electrode side, but metal foil may be used on the negative electrode side.
  • the resin separator a known porous layer used as a separator of a lithium ion secondary battery can be suitably used.
  • the porous layer has many through micropores.
  • an insulating thin film having a high ion permeability and a predetermined mechanical strength can be used.
  • the resin constituting the separator is selected from olefin polymers, fluorine polymers, cellulose polymers, polyimide, polyamide (nylon), and polyester resins.
  • glass fiber may be used.
  • the resin is preferably an olefin polymer, more preferably polypropylene, polyethylene, a mixture of polypropylene and polyethylene, or a mixture of polypropylene and polyperfluoroethylene.
  • the separator As a form of the separator, a nonwoven fabric, a woven fabric, or a porous film is used.
  • a single layer porous film of polypropylene or polyethylene and a laminated porous film composed of a polypropylene layer and a polyethylene layer are preferable.
  • the porous film can be formed by making a nonporous film porous. Examples of the pore forming method include known methods such as a stretching method (dry method) or an extraction method (wet method).
  • the separator has an air permeability of 30 seconds / 100 cc or more from the viewpoint of functioning the battery.
  • the air permeability is more preferably 50 seconds / 100 cc or more, and most preferably 100 seconds / 100 cc or more.
  • the air permeability is preferably 1000 seconds / 100 cc or less, more preferably 900 seconds / 100 cc or less, and most preferably 800 seconds / 100 cc or less.
  • the air permeability means a value measured according to JIS P8117: 1998.
  • the separator preferably has a maximum pore diameter of 0.02 to 3 ⁇ m. Further, it preferably has a porosity of 30 to 85%. By having these maximum pore diameter and porosity, the capacity characteristics of the battery can be improved.
  • the maximum pore diameter means a value measured by SEM observation, and the porosity means a value calculated by the following formula from the area S, thickness d and weight m of one side of the separator and specific gravity r of the forming material. To do.
  • the thickness of the separator is preferably 5 ⁇ m or more, more preferably 8 ⁇ m or more, and most preferably 10 ⁇ m or more from the viewpoint of mechanical strength, performance, and the like. On the other hand, from the same viewpoint, it is preferably 100 ⁇ m or less, more preferably 40 ⁇ m or less, and most preferably 30 ⁇ m or less.
  • the resin layer used for the electrode is a fine fiber layer mainly composed of ultrafine fibers and / or pulp fibers having a fiber diameter of 10 ⁇ m or less, and fiber reinforcement that reinforces the fine fiber layer.
  • a nonwoven fabric having a thickness of 100 ⁇ m or less including a layer can be used.
  • the nonwoven fabric includes the fine fiber layer, the short-circuit prevention property of the battery can be further improved.
  • the nonwoven fabric provided with the fiber reinforcement layer has high strength, it is easier to manufacture the battery.
  • the ultrafine fibers constituting the fine fiber layer are preferably 10 ⁇ m or less, more preferably 6 ⁇ m or less, still more preferably 3 ⁇ m or less, and particularly preferably 1 ⁇ m or less from the viewpoint of improving short circuit prevention and electrolyte retention. have.
  • the lower limit of the fiber diameter of the ultrafine fiber is not particularly limited as long as the fiber can be produced, but is preferably 0.1 ⁇ m or more.
  • the fiber diameter refers to the diameter when the cross-sectional shape of the fiber is circular, and means the diameter of a circle having the same area as the cross-sectional area otherwise.
  • the resin constituting the ultrafine fiber is not particularly limited as long as it is not affected by the electrolytic solution.
  • polyolefin resins such as polyethylene, polypropylene, poly-4-methylpentene-1
  • polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate, 6-nylon, 66-nylon, all It can be composed of one type or two or more types, such as a polyamide-based resin such as aromatic polyamide, or a cellulose-based resin.
  • the ultrafine fibers composed of two or more kinds of resins having different melting points are suitable as a resin layer because the ultrafine fibers are not easily detached from the fine fiber layer by fusing.
  • the arrangement of two or more kinds of resins include arrangements such as a core-sheath shape (including an eccentric shape), a bonded shape, a sea-island shape, an orange shape, and a multilayer laminated shape in the fiber cross section. Of these arrangements, a core-sheath or sea-island arrangement having a wide fusion area is preferable.
  • the fiber length of the ultrafine fibers is not particularly limited, but is preferably 1 to 15 mm, more preferably 2 to 10 mm from the viewpoint of preventing the ultrafine fibers from falling off the fine fiber layer.
  • a pulp-like fiber may be used instead of the above-mentioned ultrafine fiber, or a pulp-like fiber may be added to the above-mentioned ultrafine fiber. Since this pulp-like fiber is a fiber in which countless fine fibers (fibrils) are generated from one fiber by mechanical shearing force or the like, the short circuit prevention property of the resin layer and the retention property of the electrolyte can be improved. From the viewpoint of improving short circuit prevention and retention, the freeness of this pulp-like fiber is preferably 600 mlCSF or less, more preferably 400 mlCSF or less, and even more preferably 300 mlCSF or less.
  • the lower limit of the freeness of the pulp-like fiber is not particularly limited, but is preferably 50 mlCSF or more from the viewpoint of productivity.
  • This “freeness” refers to a value measured by a JIS P8121 Canadian standard freeness tester.
  • resin which comprises a pulp-like fiber will not be specifically limited if it is not attacked by electrolyte solution. Examples of such a resin include one kind or a combination of plural kinds of resins similar to the ultrafine fibers.
  • the nonwoven fabric constituting the resin layer includes the fine fiber layer and the fiber reinforcing layer as described above. However, as long as the thickness is 100 ⁇ m or less, the fine fiber layer and the fiber reinforcing layer need to be one layer at a time. Alternatively, two or more layers may be provided.
  • the thickness of the nonwoven fabric is preferably 100 ⁇ m or less from the viewpoint of producing a battery having low internal resistance and suitable for high-rate discharge. Moreover, since internal resistance can be made low, so that the thickness of a nonwoven fabric becomes thin, it is more preferable that it is 40 micrometers or less, and it is still more preferable that it is 30 micrometers or less.
  • the thickness is preferably 15 ⁇ m or more.
  • the “thickness” in the present invention is randomly selected by the measuring method of JIS C2111 5.1 (1) using an outer micrometer (0 to 25 mm) defined in JIS B 7502: 1994. The arithmetic average value of 10 points
  • the tensile strength of the nonwoven fabric is preferably 40 N / 50 mm width or more from the viewpoint of battery manufacturability. Further, from the same viewpoint, it is more preferably 45 N / 50 mm width or more, and further preferably 50 N / 50 mm width or more.
  • the upper limit of tensile strength is not specifically limited, From a viewpoint of the availability of a nonwoven fabric, it is about 100 N / 50mm width.
  • Tensile strength was fixed to a tensile strength tester (Orientec Tensilon UTM-III-100) with a separator cut into a strip with a width of 50 mm (chuck distance: 100 mm), and the speed was 300 mm / min. The tensile strength at the time of cutting and cutting is measured three times, and the arithmetic average value is said.
  • the porosity of the nonwoven fabric is preferably 35 to 60%. Since the porosity is as high as 35% or more and the nonwoven fabric structure is used, a battery suitable for high-rate discharge can be manufactured with low internal resistance. Moreover, if the porosity is 60% or less, a nonwoven fabric having the above-described tensile strength can be easily obtained, and short-circuiting hardly occurs. A more preferable porosity is 40 to 55%, and a still more preferable porosity is 42 to 50%. The porosity is a value obtained by the following formula.
  • Porosity (P) ⁇ 1 ⁇ W / (T ⁇ d) ⁇ ⁇ 100
  • W means the basis weight (g / m 2 ) of the nonwoven fabric
  • T means the thickness ( ⁇ m) of the nonwoven fabric
  • d means the mass average density (g / cm 3 ) of the material constituting the nonwoven fabric.
  • the average pore diameter of the nonwoven fabric is preferably 15 ⁇ m or less, more preferably 12 ⁇ m or less, and still more preferably 8 ⁇ m or less, from the viewpoint of improving short circuit prevention.
  • the lower limit of the average pore diameter is not particularly limited, but is preferably 1 ⁇ m.
  • the average pore diameter means an average flow pore diameter measured by a bubble point method using a porometer (Polometer, manufactured by Coulter). If the resin layer is used, a short circuit is unlikely to occur and a battery suitable for increasing the capacity can be configured. Moreover, since the resin layer has the above-described strength, a current collector for a battery can be obtained by providing a metal layer on both surfaces thereof.
  • Examples of the method for producing the current collector include the following methods. A method of laminating a foil-like metal layer using an adhesive such as urethane resin on both sides of the resin layer, and a method of forming a metal layer on both sides of the resin layer by a sputtering method, a vacuum deposition method or an ion plating method And a method of forming a metal thin film on both surfaces of the resin layer by sputtering, vacuum deposition or ion plating, and then forming a metal layer on the metal thin film by gradient electroplating.
  • a method of laminating a foil-like metal layer using an adhesive such as urethane resin on both sides of the resin layer and a method of forming a metal layer on both sides of the resin layer by a sputtering method, a vacuum deposition method or an ion plating method
  • a method of forming a metal thin film on both surfaces of the resin layer by sputtering, vacuum deposition or ion plating and then
  • the metal layer may be a metal layer selected from copper, nickel, iron, aluminum, zinc, gold, platinum and the like.
  • the positive electrode current collector is preferably aluminum from the viewpoint of high oxidation resistance
  • the negative electrode current collector is preferably copper from the viewpoint that it is difficult to alloy with lithium.
  • the thickness of the metal layer varies depending on the type of metal to be formed, but is preferably in the range of 0.5 to 5 ⁇ m. If it is thinner than 0.5 ⁇ m, the strength of the metal layer itself may be lowered, and the internal resistance of the battery may be increased. On the other hand, if it is thicker than 5 ⁇ m, a useless volume may be generated in the battery, and the cost for forming the metal layer may be increased. In addition, when the use of the battery is for power storage, charge / discharge performance at a high rate is not required as much as for lithium ion secondary batteries for portable devices and electric vehicles. Therefore, the thickness of the metal layer can be set to 1 to 2 ⁇ m. When the application is for portable devices or electric vehicles, the thickness of the metal layer can be 2 to 20 ⁇ m.
  • the electrode active material layer is a positive electrode active material layer in the positive electrode and a negative electrode active material layer in the negative electrode.
  • the positive electrode active material in the positive electrode active material layer include an oxide containing lithium. Specifically, LiCoO 2 , LiNiO 2 , LiFeO 2 , LiMnO 2 , LiMn 2 O 4 , compounds in which transition metals in these oxides are partially substituted with other metal elements, and the like are used. Among them, in normal use, it is preferable to use a positive electrode active material that can utilize 80% or more of the lithium amount possessed by the positive electrode for the battery reaction, thereby improving the safety of the battery against accidents such as overcharging. It becomes possible.
  • a positive electrode active material a compound having a spinel structure such as LiMn 2 O 4 or an olivine structure represented by LiMPO 4 (M is at least one element selected from Co, Ni, Mn, and Fe) is used. And the like.
  • a positive electrode active material containing Mn and / or Fe is preferable from the viewpoint of cost.
  • LiFePO 4 is preferable from the viewpoint of safety and charging voltage. LiFePO 4 is excellent in safety because all oxygen is bonded to phosphorus by a strong covalent bond, and oxygen is not easily released due to a temperature rise. In addition, since it contains phosphorus, it can be expected to have an anti-inflammatory effect.
  • Examples of the negative electrode active material in the negative electrode active material layer include natural graphite, particulate (eg, scale-like, lump-like, fiber-like, whisker-like, spherical, crushed, etc.) artificial graphite, mesocarbon microbeads, and mesophase pitch.
  • Highly crystalline graphite represented by graphitized products such as powder and isotropic pitch powder, non-graphitizable carbon such as resin-fired charcoal, etc. can be used as the negative electrode active material, and these can also be used as a mixture It doesn't matter.
  • an alloy-based negative electrode active material having a large capacity such as a tin oxide or a silicon-based negative electrode active material, can be used.
  • the graphitic carbon material is preferable in that the potential flatness of the charge / discharge reaction is high and the potential is close to the dissolution and precipitation potential of metallic lithium, so that high energy density can be achieved. Furthermore, a graphite powder material having amorphous carbon attached to the surface is preferable in that it can suppress the decomposition reaction of the nonaqueous electrolyte accompanying charge / discharge and reduce gas generation in the battery.
  • the average particle size of the graphitic carbon material as the negative electrode active material is preferably 2 to 50 ⁇ m, and more preferably 5 to 30 ⁇ m.
  • the negative electrode active material may pass through the pores of the separator, and the negative electrode active material that passes through may cause the battery to be short-circuited.
  • the specific surface area of the graphitic carbon material is preferably 1 ⁇ 100m 2 / g, 2 ⁇ 20m 2 / g is more preferable.
  • an average particle diameter and a specific surface area are the values measured using BELSORP18 by Nippon Bell Co., Ltd.
  • the active material layer of each of the positive electrode and the negative electrode may contain a conductive agent, a binder, a filler, a dispersant, an ionic conductive agent, a pressure enhancer, and other various additives.
  • the conductive agent is not particularly limited as long as it is an electron conductive material that does not cause a chemical change in the battery.
  • natural graphite scale-like graphite, scale-like graphite, earth-like graphite, etc.
  • graphite such as artificial graphite
  • carbon blacks such as acetylene black, ketjen black, channel black, furnace black, lamp black and thermal black
  • Conductive fibers such as phase-grown graphite fiber (VGCF), carbon fiber and metal fiber
  • metal powders such as copper, nickel, aluminum and silver
  • conductive whiskers such as zinc oxide and potassium titanate
  • titanium oxide examples thereof include organic conductive materials such as conductive metal oxides and polyphenylene derivatives. These materials may be used alone or in combination.
  • acetylene black, VGCF, or a combination of graphite and acetylene black is particularly preferable.
  • the addition amount of the conductive agent is not particularly limited, but is preferably 1 to 50 parts by weight, particularly preferably 2 to 20 parts by weight, based on 100 parts by weight of the positive or negative electrode active material.
  • a polysaccharide As the binder, one kind of a polysaccharide, a thermoplastic resin and a polymer having rubber elasticity or a mixture thereof can be used.
  • Preferred examples include starch, polyvinyl alcohol, carboxymethylcellulose, hydroxypropylcellulose, regenerated cellulose, diacetylcellulose, polyvinylchloride, polyvinylpyrrolidone, polytetrafluoroethylene, polyvinylidene fluoride (PVDF), polyethylene, polypropylene, ethylene-propylene- Examples include diene terpolymer (EPDM), sulfonated EPDM, styrene butadiene rubber (SBR), polybutadiene, fluorine rubber, and polyethylene oxide.
  • EPDM diene terpolymer
  • SBR sulfonated EPDM
  • SBR styrene butadiene rubber
  • fluorine rubber and polyethylene oxide.
  • the compound containing a functional group which reacts with lithium like a polysaccharide as a binder, it is preferable to add a compound like an isocyanate group and to deactivate the functional group, for example.
  • the amount of the binder added is not particularly limited, but is preferably 1 to 50 parts by weight, particularly preferably 2 to 20 parts by weight, based on 100 parts by weight of the positive or negative electrode active material.
  • the distribution of the binder in the mixture (in the mixture of the active material and various additives) may be uniform or non-uniform, but is preferably uniform.
  • the filler is not particularly limited as long as it is made of a material that does not cause a chemical change in the battery. Examples thereof include olefin polymers such as polypropylene and polyethylene, and fibers such as glass and carbon.
  • the addition amount of the filler is not particularly limited, but is preferably 0 to 30 parts by weight with respect to 100 parts by weight of the positive electrode or negative electrode active material.
  • a lithium ion secondary battery usually contains a non-aqueous electrolyte.
  • Nonaqueous electrolytes include nonaqueous electrolytes, gel electrolytes, and the like.
  • the nonaqueous electrolytic solution includes a solvent, an electrolyte salt, and the like.
  • Non-aqueous electrolyte solvents include cyclic carbonates such as propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate, dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate, dipropyl carbonate, etc.
  • Chain carbonates ⁇ -butyrolactone (hereinafter sometimes abbreviated as GBL), lactones such as ⁇ -valerolactone, furans such as tetrahydrofuran and 2-methyltetrahydrofuran, diethyl ether, 1,2-dimethoxyethane 1,2-diethoxyethane, ethoxymethoxyethane, dioxane and the like ethers, dimethyl sulfoxide, sulfolane, methyl sulfolane, acetonitrile, methyl formate, methyl acetate and the like.
  • these solvents can be used alone or as a mixture of two or more thereof.
  • the solvent preferably contains at least ⁇ -butyrolactone (GBL).
  • GBL has the properties of having both a high dielectric constant and a low viscosity, and has excellent oxidation resistance, high boiling point, low vapor pressure, and high flash point. Therefore, it is suitable as a solvent for non-aqueous electrolyte of a large battery that requires very high safety compared to a small battery.
  • the content of GBL in the solvent is preferably 50 to 80%, more preferably 60 to 70% in terms of volume fraction. If GBL is less than 50%, the safety of large batteries may be reduced. On the other hand, if it exceeds 80%, the permeability of the electrolytic solution to not only the electrode but also other members constituting the battery, such as a separator, is lowered, and the performance of the battery is lowered.
  • electrolyte salt examples include lithium borofluoride (LiBF 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium trifluoromethanesulfonate (LiCF 3 SO 3 ), lithium trifluoroacetate (LiCF 3 COO), lithium bis (trifluoro) Examples thereof include lithium salts such as romethanesulfone) imide (LiN (CF 3 SO 2 ) 2 ). These electrolyte salts can be used alone or in admixture of two or more.
  • the salt concentration of the nonaqueous electrolyte is preferably 0.5 to 3 mol / L.
  • the gel electrolyte is obtained by holding the electrolytic solution in the polymer matrix.
  • a polymer matrix a polymer having a basic structure of a copolymer of polyethylene oxide and polypropylene oxide and a compound having a polyfunctional acrylate at the terminal is crosslinked.
  • Gel electrolytes using such cross-linked polymers are referred to as chemical cross-linked gels.
  • a gel electrolyte (physically cross-linked gel) in which the polymer is dissolved in a solvent, dried, and then impregnated with an electrolytic solution can also be used.
  • a chemically crosslinked gel is preferable. This is because the solid cross-linking gel has a stronger cross-linking structure, so that the non-aqueous electrolyte oozes out from the gel and the reliability of the battery is increased.
  • the battery of the present invention is usually held in a battery case.
  • the battery case (exterior material) is preferably a metal can such as a can made of iron, stainless steel, aluminum or the like. Moreover, you may use the film which laminated aluminum with resin.
  • the shape of the battery case may be any of a cylindrical shape, a rectangular tube shape, a thin flat tube shape, etc., but in the case of a large-sized lithium secondary battery, it is often used as an assembled battery, so a rectangular shape or a thin flat shape is preferable. .
  • the present invention can be suitably used for a battery having a large capacity of about 4 Ah or more.
  • Example 1 Polyethylene porous film having a thickness of 25 ⁇ m, a width of 220 mm, a length of 340 mm, and a porosity of 55% (Asahi Kasei PE microporous film, softening temperature of 120 ° C., air permeability of 330 seconds / 100 cc, maximum pore size of 0.1 ⁇ m
  • the copper layer (thickness 1 ⁇ m) which is the metal layer 2 for the negative electrode current collector, is formed on both surfaces of the resin layer 3 by vacuum evaporation, and natural graphite (flat graphite made by Osaka Gas Chemical Company, average
  • an aluminum layer (thickness 1 ⁇ m), which is a metal layer 6 for the positive electrode current collector, is formed on both surfaces of the same resin layer 3 as the negative electrode by a vacuum deposition method, and a spinel structure LiMn 2 O 4 is formed on the positive electrode active layer.
  • Denka Black by Denki Kagaku Kogyo Co., Ltd. was used for acetylene black.
  • a nickel negative electrode lead 4 for taking out current to an external circuit was attached to the portion of the obtained negative electrode metal layer 2 where the negative electrode active material layer 1 was not formed by welding.
  • the positive electrode lead 7 made of aluminum was attached to the positive electrode.
  • a resin separator 8 is placed on the negative electrode, and the positive electrode is placed thereon so that the positive electrode lead 7 does not come into contact with the negative electrode lead 4, and the separator 8 is placed thereon, and the negative electrode is called thereon.
  • a laminate was obtained.
  • the separator 8 the same resin layer 3 as that of the negative electrode was used. Furthermore, it fixed with the Kapton tape so that a laminated body might not shift
  • Non-woven fabric made of polyethylene terephthalate having a thickness of 50 ⁇ m, a width of 220 mm, a length of 1700 mm and a porosity of 60% (Mitsui Chemicals Syntex, softening temperature 180 ° C., air permeability 180 seconds / 100 cc, average pore diameter 1 ⁇ m, fiber diameter 0.
  • the copper layer was formed by vacuum evaporation and gradient electroplating, and the aluminum layer was formed by vacuum evaporation. Moreover, the width and length of both layers were 210 mm in width and 330 mm in length, respectively.
  • a negative electrode using graphite (OMAC, manufactured by Osaka Gas Chemical Co., Ltd., average particle size 10 ⁇ m, specific surface area 2 m 2 / g) having amorphous carbon attached on the metal layer 2 for the negative electrode current collector.
  • olivine structure LiFePO 4 as the positive electrode active material
  • a positive electrode was obtained by coating with a thickness of 70 ⁇ m.
  • VGCF-H manufactured by Showa Denko KK was used for VGCF, and the same PVDF as in Example 1 was used for PVDF.
  • a nickel negative electrode lead 4 for taking out current to an external circuit was attached to the portion of the obtained negative electrode metal layer 2 where the negative electrode active material layer 1 was not formed by welding.
  • the positive electrode lead 7 made of aluminum was attached to the positive electrode. Thereafter, the negative electrode, separator, and positive electrode were folded in a folding screen to obtain a laminate. Further, the active material layer non-formed parts at both ends of both poles and the separator were all fixed together by heat fusion with a sealer.
  • the battery of Example 1 was charged to a battery voltage of 4.2 V at a constant current of 400 mA, charged at a constant voltage of 4.2 V for 3 hours, and then discharged to a battery voltage of 3 V at a constant current of 800 mA. The battery capacity at that time was 3950 mAh.
  • the battery of Example 2 was charged to a battery voltage of 3.8 V at a constant current of 400 mA, then charged at a constant voltage of 3.8 V for 3 hours, and then discharged to a battery voltage of 2.4 V at a constant current of 800 mA. went.
  • the battery capacity at that time was 4030 mAh.
  • the battery capacity after repeating the above charge / discharge test 1000 times was 3100 mAh for the battery of Example 1 and 3250 mAh for the battery of Example 2.
  • Example 1 and Example 2 were each subjected to a nail penetration test in a fully charged state.
  • the surface temperature of the battery of Example 1 rose to 70 ° C., but then the temperature gradually decreased and dropped to room temperature. Neither ignition nor smoke was seen.
  • the surface temperature of the battery of Example 2 increased to 60 ° C., but then gradually decreased to room temperature. Neither ignition nor smoke was seen.
  • the lithium ion secondary battery in which the positive and negative electrodes, in which the electrode active material is applied to the current collector having the metal layers on both sides of the resin layer, are laminated via the resin separator is used for power storage. It was found that even in repeated charge and discharge tests, good performance was exhibited and the safety was excellent.
  • Example 3 Resin layer 3 composed of a polyethylene porous film (PE microporous film made by Celgard, softening temperature 120 ° C., air permeability 170 seconds / 100 cc) having a thickness of 25 ⁇ m, a width of 220 mm, a length of 340 mm, and a porosity of 79%
  • the same PVDF as in Example 1 was used.
  • an aluminum layer (thickness 1 ⁇ m), which is a metal layer 6 for the positive electrode current collector, is formed on both surfaces of the same resin layer 3 as the negative electrode by a vacuum deposition method, and a spinel structure LiMn 2 O 4 is formed on the positive electrode active layer.
  • a nickel negative electrode lead 4 for taking out current to an external circuit was attached to the portion of the obtained negative electrode metal layer 2 where the negative electrode active material layer 1 was not formed by welding.
  • the positive electrode lead 7 made of aluminum was attached to the positive electrode.
  • a polyamide porous film (Nippon Vilene non-woven fabric, softening temperature 220 ° C., air permeability 150 sec / 100 cc) having a thickness of 35 ⁇ m, a width of 225 mm, a length of 345 mm and a porosity of 65% is formed on the negative electrode.
  • the positive electrode lead 7 is placed so that the positive electrode lead 7 does not come into contact with the negative electrode lead 4, and the separator 8 is stacked thereon, and the negative electrode is stacked thereon.
  • a laminate was obtained. Furthermore, it fixed with the Kapton tape so that a laminated body might not shift
  • Example 4 Nonwoven fabric made of polyester having a thickness of 25 ⁇ m, a width of 220 mm, a length of 340 mm, and a porosity of 59% (Nippon Vilene nonwoven fabric, softening temperature 200 ° C., air permeability 150 seconds / 100 cc, average pore diameter 1 ⁇ m, fiber diameter 0.5 ⁇ m
  • the same PVDF as in Example 1 was used.
  • PVDF 90: 5: 5 (weight ratio)
  • the same PVDF and acetylene black as Example 1 were used.
  • a nickel negative electrode lead 4 for taking out current to an external circuit was attached by welding to a portion of the negative electrode metal layer 2 where the negative electrode active material layer 1 was not formed.
  • the positive electrode lead 7 made of aluminum was attached to the positive electrode.
  • a polyethylene terephthalate nonwoven fabric film having a thickness of 40 ⁇ m, a width of 220 mm, a length of 340 mm and a porosity of 80% (Mitsui Chemicals Syntex, softening temperature of 220 ° C., air permeability of 140 seconds / 100 cc,
  • a resin separator 8 having an average pore diameter of 1 ⁇ m, a fiber diameter of 0.9 ⁇ m, a fiber length of 1 mm, and a tensile strength of 50 N / 50 mm is placed, and a positive electrode is placed thereon so that the positive electrode lead 7 does not contact the negative electrode lead 4.
  • a laminate 8 was obtained by laminating the separator 8 thereon and a negative electrode thereon. Furthermore, it fixed with the Kapton tape so that a laminated body might not shift
  • Example 1 Copper layer which is metal layer 2 for negative electrode current collector on the surface of resin layer 3 made of polyethylene porous film (PE microporous film manufactured by Asahi Kasei Co., Ltd., softening temperature 120 ° C.) having a thickness of 25 ⁇ m and a porosity of 60%
  • a current collector was obtained by forming (thickness: 1 ⁇ m) by a vacuum deposition method. As shown in FIG. 5, the end of the current collector was sandwiched between clips 11, and an iron wire 12 having a diameter of 1 mm was pressed onto the metal layer 2. Copper wire 13 is soldered to iron wire 12 and iron clip 11. When a constant current of 15 A was continuously passed between the copper wires 13 for 3 minutes, the current stopped flowing. When the iron wire was removed and the current collector was observed, a hole with a diameter of about 1.5 mm was found. This result indicates that the current collecting function is lost due to softening or melting of the resin layer of the current collector during abnormal heat generation.

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Abstract

L'invention porte sur une batterie secondaire lithium-ion dans la structure de laquelle une électrode positive et une électrode négative sont laminées à travers un séparateur de résine. Au moins l'électrode positive ou l'électrode négative est composée d'un collecteur dont les deux côtés d'une couche de résine servant de base de noyau sont recouverts d’une couche métallique sur lesquelles sont formées des couches de matériau actives d'électrode. Le séparateur de résine est composé d'une résine dont le point de ramollissement est égal ou supérieur à celui de la résine constituant la base de noyau.
PCT/JP2009/059274 2008-06-23 2009-05-20 Batterie secondaire lithium-ion WO2009157263A1 (fr)

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JP2012185938A (ja) * 2011-03-03 2012-09-27 Sharp Corp 非水系二次電池
JP2014067667A (ja) * 2012-09-27 2014-04-17 Mitsubishi Paper Mills Ltd リチウムイオン二次電池セパレータ用不織布基材
JP2016532261A (ja) * 2013-08-12 2016-10-13 ソルヴェイ（ソシエテ アノニム） 固体複合フルオロポリマーセパレータ
CN112335092A (zh) * 2018-06-29 2021-02-05 远景Aesc能源元器件有限公司 锂离子二次电池
CN112335091A (zh) * 2018-06-29 2021-02-05 远景Aesc能源元器件有限公司 锂离子二次电池
JP2022526744A (ja) * 2019-05-31 2022-05-26 寧徳時代新能源科技股▲分▼有限公司 正極集電体、正電極シート、電気化学装置及び装置
JP2022531162A (ja) * 2019-05-31 2022-07-06 寧徳時代新能源科技股▲分▼有限公司 複合集電体、電極シート及び電気化学装置
CN114843666A (zh) * 2016-12-28 2022-08-02 大日本印刷株式会社 电池用包装材料用铝合金箔、电池用包装材料和电池
JP7123221B1 (ja) 2021-06-18 2022-08-22 ソフトバンク株式会社 製造方法、プログラム、製造システム、積層集電体、電池、移動体、及び飛行体
WO2024012564A1 (fr) * 2022-07-14 2024-01-18 扬州纳力新材料科技有限公司 Collecteur de courant composite en aluminium, son procédé de préparation et son utilisation
WO2024011535A1 (fr) * 2022-07-14 2024-01-18 扬州纳力新材料科技有限公司 Collecteur de courant composite en aluminium, son procédé de préparation et son utilisation

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JPH09213338A (ja) * 1996-01-30 1997-08-15 Shin Kobe Electric Mach Co Ltd 電池及びリチウムイオン二次電池
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Cited By (17)

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Publication number Priority date Publication date Assignee Title
JP2012185938A (ja) * 2011-03-03 2012-09-27 Sharp Corp 非水系二次電池
JP2014067667A (ja) * 2012-09-27 2014-04-17 Mitsubishi Paper Mills Ltd リチウムイオン二次電池セパレータ用不織布基材
JP2016532261A (ja) * 2013-08-12 2016-10-13 ソルヴェイ（ソシエテ アノニム） 固体複合フルオロポリマーセパレータ
CN114843666A (zh) * 2016-12-28 2022-08-02 大日本印刷株式会社 电池用包装材料用铝合金箔、电池用包装材料和电池
CN112335092A (zh) * 2018-06-29 2021-02-05 远景Aesc能源元器件有限公司 锂离子二次电池
CN112335091A (zh) * 2018-06-29 2021-02-05 远景Aesc能源元器件有限公司 锂离子二次电池
CN112335091B (zh) * 2018-06-29 2023-10-27 远景Aesc能源元器件有限公司 锂离子二次电池
CN112335092B (zh) * 2018-06-29 2023-10-13 株式会社Aesc 日本 锂离子二次电池
JP7357690B2 (ja) 2019-05-31 2023-10-06 寧徳時代新能源科技股▲分▼有限公司 複合集電体、電極シート及び電気化学装置
JP7344309B2 (ja) 2019-05-31 2023-09-13 寧徳時代新能源科技股▲分▼有限公司 正極集電体、正電極シート、電気化学装置及び装置
JP2022531162A (ja) * 2019-05-31 2022-07-06 寧徳時代新能源科技股▲分▼有限公司 複合集電体、電極シート及び電気化学装置
JP2022526744A (ja) * 2019-05-31 2022-05-26 寧徳時代新能源科技股▲分▼有限公司 正極集電体、正電極シート、電気化学装置及び装置
WO2022265102A1 (fr) * 2021-06-18 2022-12-22 ソフトバンク株式会社 Procédé de fabrication, programme, système de fabrication, collecteur multicouche, batterie, corps mobile et véhicule de vol
JP2023000600A (ja) * 2021-06-18 2023-01-04 ソフトバンク株式会社 製造方法、プログラム、製造システム、積層集電体、電池、移動体、及び飛行体
JP7123221B1 (ja) 2021-06-18 2022-08-22 ソフトバンク株式会社 製造方法、プログラム、製造システム、積層集電体、電池、移動体、及び飛行体
WO2024012564A1 (fr) * 2022-07-14 2024-01-18 扬州纳力新材料科技有限公司 Collecteur de courant composite en aluminium, son procédé de préparation et son utilisation
WO2024011535A1 (fr) * 2022-07-14 2024-01-18 扬州纳力新材料科技有限公司 Collecteur de courant composite en aluminium, son procédé de préparation et son utilisation

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