WO2014188896A1 - Collecteur et batterie bipolaire - Google Patents

Collecteur et batterie bipolaire Download PDF

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Publication number
WO2014188896A1
WO2014188896A1 PCT/JP2014/062562 JP2014062562W WO2014188896A1 WO 2014188896 A1 WO2014188896 A1 WO 2014188896A1 JP 2014062562 W JP2014062562 W JP 2014062562W WO 2014188896 A1 WO2014188896 A1 WO 2014188896A1
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WO
WIPO (PCT)
Prior art keywords
resin layer
current collector
conductive resin
conductive
negative electrode
Prior art date
Application number
PCT/JP2014/062562
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English (en)
Japanese (ja)
Inventor
佳宏 古川
井上　真一
Original Assignee
日東電工株式会社
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Filing date
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Publication of WO2014188896A1 publication Critical patent/WO2014188896A1/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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/668—Composites of electroconductive material and synthetic 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
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/029—Bipolar electrodes
    • 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 current collector and a bipolar battery, and more particularly to a bipolar battery suitably used for a lithium ion secondary battery and a current collector provided therein.
  • a lithium ion secondary battery is mounted from the viewpoint that high energy density and high output density are required.
  • a positive electrode active material and a negative electrode active material are respectively disposed on both sides of a plurality of current collectors.
  • Bipolar batteries in which an electrolyte layer is disposed between the bodies are being studied.
  • a current collector made of a polymer material, a positive electrode electrically coupled to one surface of the current collector, and a current collector
  • a bipolar battery including an electrode composed of a negative electrode electrically coupled to the other surface of the body and an electrolyte layer disposed between the plurality of electrodes (for example, see Patent Document 1).
  • the electrolyte in the electrolyte layer may pass through the electrode and come into contact with the surface of the current collector, and may further penetrate into the current collector. In that case, a side reaction occurs on the surface and inside of the current collector, resulting in a problem that the current collector deteriorates.
  • An object of the present invention is to provide a current collector that is excellent in durability while reducing the weight of the current collector and improving the output density per unit mass, and a bipolar battery including the current collector.
  • the current collector of the present invention comprises a conductive resin layer containing a resin and a conductive material, and an insulating resin layer formed on one surface in the thickness direction of the conductive resin layer and having a thickness of 1 nm to 1 ⁇ m. Yes.
  • the insulating resin layer contains a polycarbonate resin.
  • the resin contains polyimide and / or polyamideimide.
  • the conductive material contains nickel and / or stainless steel.
  • the bipolar battery of the present invention is a bipolar battery including a plurality of electrodes spaced apart from each other, and an electrolyte layer disposed between the electrodes, wherein at least one of the plurality of electrodes is as described above.
  • the bipolar battery of the present invention is preferably used as a lithium ion secondary battery.
  • the current collector of the present invention includes a conductive resin layer containing a resin and a conductive material, the current collector can be reduced in weight and the output density per unit mass can be improved.
  • the current collector of the present invention includes an insulating resin layer formed on one surface in the thickness direction of the conductive resin layer, side reactions on one surface in the thickness direction of the conductive resin layer can be suppressed. Therefore, the current collector of the present invention is excellent in durability.
  • the bipolar battery of the present invention includes a current collector having excellent durability, it is excellent in durability.
  • FIG. 1 shows a cross-sectional view of a current collector according to an embodiment of the present invention.
  • FIG. 2 shows a cross-sectional view of one embodiment of the bipolar battery of the present invention comprising a plurality of electrodes having the current collector shown in FIG. 3 shows a partially exploded enlarged view of the charge / discharge part of the bipolar battery shown in FIG.
  • the current collector 1 includes a conductive resin layer 6 and an insulating resin layer 19 as shown in FIG.
  • the conductive resin layer 6 is formed in a substantially rectangular substantially flat plate shape.
  • the conductive resin layer 6 is formed from a conductive resin composition containing a resin and a conductive material.
  • the resin examples include a thermoplastic resin and a thermosetting resin.
  • thermoplastic resin examples include rubber resins such as polystyrene-polyisoprene-polystyrene block copolymer rubber (SIBS) and styrene-butadiene copolymer rubber (SBR), such as low density polyethylene (LDPE), high density Olefin resins such as polyethylene (HDPE), linear low density polyethylene (LLDPE), polypropylene (PP), polybutylene, for example, ethylene such as ethylene-vinyl acetate copolymer (EVA), ethylene-vinyl alcohol copolymer Copolymers, for example, polyesters such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), acrylic polymers such as polymethyl acrylate (PMA), polymethyl methacrylate (PMMA), etc., and other polycarbonates Resin (PC), polyether nitrile (PEN), polyimide (PI), polyamide (PA), polyamideimide (PAI), polytetrafluoroethylene
  • thermoplastic resins can be used alone or in combination.
  • thermoplastic resins polyimide and polyamideimide are preferable, and polyamideimide is more preferable from the viewpoint of ion blocking properties.
  • thermosetting resin examples include epoxy resin, thermosetting polyimide, urea resin, melamine resin, unsaturated polyester resin, diallyl phthalate resin, thermosetting silicone resin, thermosetting polyurethane resin, and the like.
  • the resin is preferably a thermoplastic resin.
  • the number average molecular weight of the resin is, for example, 1 ⁇ 10 3 or more, preferably 1 ⁇ 10 4 or more, more preferably 2 ⁇ 10 4 or more, and for example, 1 ⁇ 10 6 or less, preferably 1 ⁇ 10 5 or less, more preferably 5 ⁇ 10 4 or less.
  • the number average molecular weight is measured as a conversion value based on standard polystyrene using gel permeation chromatography.
  • the glass transition point Tg of the resin is, for example, 100 ° C. or higher, preferably 200 ° C. or higher, and 500 ° C. or lower, preferably 400 ° C. or lower.
  • the glass transition point is measured by a dynamic viscoelasticity measuring device (DMA) and differential scanning calorimetry (DSC).
  • DMA dynamic viscoelasticity measuring device
  • DSC differential scanning calorimetry
  • the blending ratio of the resin is, for example, 20% by mass or more, preferably 50% by mass or more, and for example, 99% by mass or less, preferably 90% by mass or less with respect to the conductive resin composition.
  • Examples of the conductive material include metal fillers and carbon fillers.
  • metal forming the metal filler examples include copper, nickel, tin, aluminum, iron, chromium, titanium, gold, silver, platinum, niobium, and alloys thereof (for example, stainless steel).
  • metal metal carbide, metal nitride, metal oxide, etc. are also mentioned.
  • nickel and stainless steel are used, and more preferably nickel is used.
  • Examples of the carbon forming the carbon filler include graphite (graphite), carbon black (furnace black, acetylene black, ketjen black, carbon nanotube) and the like. Preferably, carbon black is used.
  • the conductive material is preferably a metal filler from the viewpoint of the durability of the current collector.
  • These conductive materials can be used alone or in combination.
  • the shape of the conductive material is not particularly limited, and examples thereof include a spherical shape, a scale shape, a flake shape, a dendritic shape, and a lump shape (indefinite shape).
  • the average value of the maximum length of the conductive material is, for example, 0.01 ⁇ m or more, and, for example, 100 ⁇ m or less, preferably 50 ⁇ m or less, more preferably 40 ⁇ m or less.
  • the blending ratio of the conductive material is, for example, 5 parts by mass or more, preferably 10 parts by mass or more, for example, 500 parts by mass or less, preferably 200 parts by mass or less, relative to 100 parts by mass of the resin. More preferably, it is 50 parts by mass or less.
  • the blending ratio of the conductive material is equal to or higher than the lower limit, the conductivity of the conductive resin layer 6 can be ensured.
  • the mixture ratio of a conductive material is below the said upper limit, the weight reduction of the conductive resin layer 6 and by extension, the weight reduction of the electrical power collector 1 can be achieved.
  • the conductive resin composition can contain known additives such as surfactants and polymer dispersants in an appropriate ratio.
  • surfactants include a cationic surfactant and an anionic surfactant.
  • the thickness of the conductive resin layer 6 is, for example, 0.01 ⁇ m or more, preferably 0.1 ⁇ m or more, and, for example, 100 ⁇ m or less, preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less.
  • the current collector 1 When the thickness of the conductive resin layer 6 is equal to or more than the above lower limit, the current collector 1 can be easily handled. When the thickness of the conductive resin layer 6 is equal to or less than the above upper limit, the thickness of the current collector 1 does not become too thick, and the current collector 1 can be easily reduced in size and weight.
  • the volume resistivity of the conductive resin layer 6 is, for example, 0.01 ⁇ cm or more, and for example, 100 ⁇ cm or less, preferably 50 ⁇ cm or less, more preferably 30 ⁇ cm or less.
  • the volume resistivity is measured using a resistivity meter in accordance with JIS K 7194.
  • the insulating resin layer 19 is provided on the entire upper surface of the conductive resin layer 6.
  • the insulating resin layer 19 is formed of an insulating resin, and examples of such an insulating resin include the resins mentioned in the conductive resin layer 6.
  • a thermoplastic resin is used, and more preferably, a polycarbonate resin is used from the viewpoint of obtaining the insulating resin layer 19 as a dense film.
  • These insulating resins can be used alone or in combination.
  • the polycarbonate resin is a polymer having a carbonate bond (carbonic acid ester group) in the main chain, and the basic skeleton has the general formula [—O—R—O—CO—] n (R represents a hydrocarbon group). It is represented by
  • the polycarbonate resin is a polymer obtained by condensation polymerization of a condensation polymerizable monomer containing, for example, a dihydric alcohol and a dialkyl carbonate.
  • the polycarbonate resin is also a polymer obtained by addition polymerization of an addition polymerizable monomer containing a carbonate compound having an ethylenically unsaturated double bond, for example.
  • the polycarbonate resin is preferably a polymer obtained by addition polymerization of addition polymerizable monomers.
  • dihydric alcohol examples include diols such as ethylene glycol, propylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, and benzenediol.
  • dialkyl carbonate examples include dimethyl carbonate, diethyl carbonate, and di (n-propyl) carbonate.
  • Examples of the carbonate compound having an ethylenically unsaturated double bond include vinylene carbonate (vinylene carbonate), vinyl ethyl carbonate (vinyl ethylene carbonate), allyl ethyl carbonate (allyl ethyl carbonate), and the like.
  • vinylene carbonate is used from the viewpoint of obtaining the insulating resin layer 19 as a dense film.
  • the thickness of the insulating resin layer 19 is, for example, 1 nm or more, preferably 3 nm or more, and for example, 1 ⁇ m or less, preferably 800 nm or less. If the thickness of the insulating resin layer 19 is less than the lower limit, side reactions (described later) cannot be suppressed. Moreover, when the thickness of the insulating resin layer 19 exceeds the above upper limit, the conductivity between the insulating resin layer 19 and an active material (described later) cannot be ensured.
  • the conductive resin layer 6 is formed.
  • a conductive resin-containing solution (varnish) is prepared, and then the conductive resin-containing solution is applied on a substrate to form a coating film. , Heat.
  • the conductive resin-containing solution is obtained by blending a resin and a conductive material to prepare a conductive resin composition, and if necessary, blending a solvent.
  • the solvent examples include water and organic solvents.
  • the organic solvent include alcohols such as ethanol, esters such as ethyl acetate, ketones such as methyl ethyl ketone, and N-methyl.
  • nitrogen-containing organic solvents such as pyrrolidone. These solvents can be used alone or in combination.
  • the mixing ratio of the solvent is, for example, 30 parts by mass or more, preferably 90 parts by mass or more, and, for example, 2700 parts by mass or less, preferably 1200 parts by mass or less with respect to 100 parts by mass of the conductive resin composition. It is.
  • the substrate has a substantially flat plate shape, for example, a polyolefin such as polyethylene and polypropylene, a resin material such as a polyester such as polyethylene terephthalate and polyethylene naphthalate, a metal material such as iron, aluminum, and stainless steel, such as silicon. It is formed from a ceramic material such as glass. Preferably, it is formed from glass.
  • Examples of the method for applying the conductive resin-containing solution onto the substrate include a roll coating method, a gravure coating method, a spin coating method, and a bar coating method.
  • the heating temperature is, for example, 30 ° C. or higher, preferably 50 ° C. or higher, and for example, 450 ° C. or lower, preferably 350 ° C. or lower.
  • the heating time is, for example, 0.1 minutes or more, preferably 1 minute or more, and for example, 200 minutes or less, preferably 100 minutes or less.
  • the heating of this coating film can be carried out several times at different temperatures. For example, it is possible to perform second-stage heating in which the second-stage heating temperature and time each exceed the first-stage heating temperature and time, respectively.
  • the heating condition of the first stage is such that the temperature is, for example, 50 ° C. or higher, preferably 70 ° C. or higher, for example, less than 200 ° C., preferably less than 150 ° C., and time Is, for example, 1 minute or more, preferably 5 minutes or more, and for example, 30 minutes or less, preferably 20 minutes or less.
  • the temperature is, for example, 150 ° C. or more, preferably 250 ° C. or more, for example, 420 ° C. or less, preferably 370 ° C. or less
  • the time is, for example, 10 Minutes or more, preferably 20 minutes or more, and for example, 200 minutes or less, preferably 150 minutes or less.
  • the coating film can be dried by heating in the first stage, and the dried coating film can be cured (that is, cured) by heating in the second stage.
  • the conductive resin layer 6 is peeled off from the base material.
  • an insulating resin layer 19 is formed on the entire upper surface of the conductive resin layer 6.
  • the insulating resin layer 19 In order to form the insulating resin layer 19, an insulating resin is applied to the entire upper surface of the conductive resin layer 6.
  • the insulating resin layer 19 may be previously formed from an insulating resin on the upper surface of a base material (not shown), and then the insulating resin layer 19 may be transferred (laminated) to the upper surface of the conductive resin layer 6.
  • a monomer liquid containing a monomer such as a condensation polymerizable monomer and / or an addition polymerizable monomer is prepared, and then the monomer liquid is applied to the entire upper surface of the conductive resin layer 6. Then, a coating film is formed, and then the monomers in the coating film are reacted.
  • a monomer for example, a monomer, a polymerization initiator, and a solvent are mixed.
  • a radical generator may be mentioned.
  • a thermal polymerization initiator that decomposes by heat to generate radicals, for example, by light
  • photopolymerization initiators that decompose to generate radicals.
  • a photopolymerization initiator is used.
  • examples of the polymerization initiator include peroxides, azo compounds, dihalogen compounds, alkylphenone compounds, acylphosphine oxide compounds, and the like.
  • an alkylphenone compound is used.
  • the blending ratio of the polymerization initiator is, for example, 0.01 parts by mass or more, preferably 0.1 parts by mass or more, for example, 10 parts by mass or less, preferably 5 parts by mass with respect to 100 parts by mass of the monomer. It is below mass parts.
  • solvent examples include the organic solvents described above, and preferably alcohols. These solvents can be used alone or in combination.
  • the mixing ratio of the solvent is such that the mass ratio of the monomer to the monomer liquid is, for example, 0.01% by mass or more, preferably 0.1% by mass or more, and for example, 50% by mass or less, preferably 20% by mass. Adjust so that:
  • the monomer liquid is applied to the entire upper surface of the conductive resin layer 6 by the above-described application method. Thereby, a coating film of the monomer liquid is formed.
  • the coating film is irradiated with light such as ultraviolet rays.
  • the dose of light for example, 10 mJ / cm 2 or more, preferably at most 100 mJ / cm 2 or more, and is, for example, 10000 mJ / cm 2 or less, preferably 1000 mJ / cm 2 or less.
  • the coating film is heated.
  • the heating temperature is, for example, 50 ° C. or more, preferably 100 ° C. or more, for example, 200 ° C. or less, preferably 140 ° C. or less
  • the heating time is, for example, 10 seconds or more. It is preferably 1 minute or longer, and for example, 60 minutes or shorter, preferably 30 minutes or shorter.
  • the polymerization initiator contains a photopolymerization initiator and a thermal polymerization initiator, light irradiation and heating are used in combination with the coating film.
  • the insulating resin layer 19 is formed on the entire upper surface of the conductive resin layer 6.
  • the insulating resin layer 19 can also be formed by immersing the conductive resin layer 6 in the monomer solution and applying a potential to the conductive resin layer 6, that is, passing a current through the conductive resin layer 6.
  • the current collector 1 produced in this way can be used as the current collector 1 of various devices. Specifically, the current collector 1 can be used as the current collector 1 of the bipolar battery 7, for example. This bipolar battery 7 can be used as a lithium ion secondary battery.
  • bipolar battery 7 including the current collector 1 shown in FIG. 1 will be described with reference to FIGS.
  • the bipolar battery 7 is a bipolar lithium ion secondary battery, and includes a charging / discharging unit 8 in which a charging / discharging reaction proceeds, and an exterior material 9 that houses the charging / discharging unit 8.
  • the charging / discharging unit 8 is formed in a substantially flat plate shape, and includes a plurality of electrodes 10 provided at intervals from each other, and an electrolyte layer 11 disposed between the electrodes 10.
  • a plurality of electrodes 10 are stacked in the thickness direction, and are formed between two end electrodes 13 formed at one end in the thickness direction (uppermost side) and the other end in the thickness direction (lowermost side). And a plurality of main electrodes 12 arranged.
  • Each of the main electrodes 12 is a bipolar electrode. Specifically, as shown in FIG. 3, a current collector 1 and a positive electrode 14 laminated on the upper surface (one surface in the thickness direction) of the current collector 1 And the negative electrode 15 laminated on the lower surface (the other surface in the thickness direction) of the current collector 1.
  • the current collector 1 includes a conductive resin layer 6 and an insulating resin layer 19 formed on the entire lower surface of the conductive resin layer 6.
  • the positive electrode 14 is a pattern that exposes an end of the conductive resin layer 6 (a peripheral edge in the plane direction perpendicular to the thickness direction), and is formed so as to be in contact with the upper surface of the conductive resin layer 6 over the entire lower surface of the positive electrode 14. Yes.
  • the positive electrode 14 is made of a positive electrode material containing a positive electrode active material as an essential component and a binder as an optional component.
  • the positive electrode active material is not particularly limited as long as it is a positive electrode active material used in a bipolar lithium ion secondary battery, and examples thereof include a lithium compound.
  • the lithium compound include lithium-transition metal composite oxides (lithium-based composite oxides) such as LiCoO 2 , LiNiO 2 , and Li (Ni—Co—Mn) O 2, such as lithium-transition metal phosphate compounds
  • a lithium-transition metal sulfate compound can be used.
  • the positive electrode active material can be used alone or in combination.
  • the positive electrode active material is preferably a lithium-transition metal composite oxide from the viewpoint of capacity and output characteristics.
  • the binder is not particularly limited.
  • the binder can be used alone or in combination.
  • PVdF polyimide
  • styrene / butadiene rubber CMC
  • polypropylene PTFE
  • polyacrylonitrile polyamide
  • the blending ratio of the binder is, for example, 0.5 parts by mass or more, preferably 1 part by mass or more, for example, 15 parts by mass or less, preferably 10 parts by mass with respect to 100 parts by mass of the positive electrode material. Or less.
  • additives such as a conductive additive, an electrolyte salt, and an ion conductive polymer can be added to the positive electrode material at an appropriate ratio.
  • Examples of the conductive aid include the carbon-based filler described above.
  • electrolyte salt examples include lithium salts such as Li (C 2 F 5 SO 2 ) 2 N, LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , and LiCF 3 SO 3 .
  • Examples of the ion conductive polymer include polyalkylene oxides such as polyethylene oxide (PEO) and polypropylene oxide (PPO).
  • polyalkylene oxides such as polyethylene oxide (PEO) and polypropylene oxide (PPO).
  • the above-described positive electrode material is blended in a solvent such as N-methylpyrrolidone (NMP), dimethyl carbonate (DMC), or acetonitrile at an appropriate ratio. To prepare a slurry. Next, the slurry is applied to the upper surface of the conductive resin layer 6, and then the coating film is dried by heating.
  • NMP N-methylpyrrolidone
  • DMC dimethyl carbonate
  • acetonitrile acetonitrile
  • the positive electrode 14 is formed on the upper surface of the conductive resin layer 6 in the pattern described above.
  • the negative electrode 15 is formed so as to be in contact with the lower surface of the insulating resin layer 19 over the entire upper surface of the negative electrode 15 so as to expose the end portion (peripheral end portion in the plane direction) of the insulating resin layer 19. Is formed so as to be the same pattern as the pattern of the positive electrode 14 when projected in the thickness direction. Thereby, the insulating resin layer 19 is interposed between the negative electrode 15 and the conductive resin layer 6.
  • the negative electrode 15 is formed of a negative electrode material containing a negative electrode active material as an essential component and a binder as an optional component.
  • the negative electrode active material is not particularly limited as long as it is a negative electrode active material used in a bipolar lithium ion secondary battery.
  • carbon active materials such as graphite, soft carbon, and hard carbon, lithium-transition metal composite oxides ( For example, Li 4 Ti 5 O 12) , metal active material, and lithium alloy-based negative electrode active material.
  • the negative electrode active material can be used alone or in combination.
  • the negative electrode active material is preferably a carbon active material or a lithium-transition metal composite oxide from the viewpoint of capacity and output characteristics.
  • binder examples include the binder exemplified in the positive electrode material.
  • the blending ratio of the binder is the same as above.
  • the additive exemplified in the positive electrode material can be added to the negative electrode material at an appropriate ratio.
  • the above-described negative electrode material is blended with the above-described solvent in an appropriate ratio to prepare a slurry.
  • the slurry is applied to the lower surface of the insulating resin layer 19, and then the coating film is dried by heating.
  • the negative electrode 15 is formed on the lower surface of the insulating resin layer 19 with the above-described pattern.
  • the plurality of main electrodes 12 are stacked via the plurality of electrolyte layers 11 in the thickness direction. That is, the electrolyte layer 11 is interposed between the plurality of main electrodes 12 adjacent to each other in the thickness direction, and more specifically, the main electrodes 12 and the electrolyte layers 11 are sequentially stacked alternately in the thickness direction. .
  • the positive electrode 14 of one main electrode 12A and the negative electrode 15 of another main electrode 12B adjacent to the one main electrode 12A are disposed to face each other in the thickness direction, and the electrolyte layer 11 is interposed between them.
  • the main electrodes 12 and the electrolyte layers 11 are alternately stacked so as to be sandwiched between them.
  • the electrolyte layer 11 has a substantially flat plate shape and is configured to hold the electrolyte between adjacent main electrodes 12.
  • electrolyte examples include a liquid electrolyte and a solid electrolyte.
  • the liquid electrolyte has a form in which the supporting salt is dissolved in an organic solvent.
  • the organic solvent include carbonate compounds such as ethylene carbonate (EC) and propylene carbonate (PC).
  • the supporting salt include a lithium salt.
  • examples of the solid electrolyte include a gel electrolyte containing an electrolytic solution and an intrinsic solid electrolyte not containing an electrolytic solution.
  • the gel electrolyte is formed by dispersing the above liquid electrolyte in a matrix polymer made of the above ion conductive polymer.
  • the electrolyte layer 11 when the electrolyte layer 11 is formed from a liquid electrolyte or a gel electrolyte, the electrolyte layer 11 can be provided with a separator.
  • the separator include a microporous film made of polyolefin such as polyethylene and polypropylene.
  • the intrinsic solid electrolyte is prepared by dissolving a supporting salt in the above matrix polymer, and does not contain an organic solvent (such as a plasticizer).
  • the positive electrode 14 (specifically, the positive electrode 14 of one main electrode 12A), the electrolyte layer 11, and the negative electrode 15 (the negative electrode 15 sandwiching the positive electrode 14 and the electrolyte layer 11, specifically, the other main electrode 12B).
  • the negative electrode 15 constitutes a single cell layer 23.
  • the bipolar battery 7 is formed by laminating a plurality of single battery layers 23.
  • the current collector 1 is interposed between the unit cell layers 23 adjacent to each other.
  • each of the two terminal electrodes 13 includes a current collector 1 and either a positive electrode 14 or a negative electrode 15 formed on the upper surface or the lower surface of the current collector 1.
  • the terminal electrode 13a on the positive electrode side includes the current collector 1 and the positive electrode 14 laminated on the upper surface thereof, but does not include the negative electrode 15.
  • a positive electrode current collector plate 16 is provided on the lower surface of the terminal electrode 13a on the positive electrode side.
  • the positive electrode current collector plate 16 is integrally provided with a covering portion that covers the lower surface of the terminal electrode 13a on the positive electrode side, and an extending portion that extends from the covering portion in one plane direction (right direction in FIG. 2). Yes.
  • the terminal electrode 13b on the negative electrode side includes the current collector 1 and the negative electrode 15 stacked on the lower surface thereof, but does not include the positive electrode 14.
  • a negative electrode current collector plate 17 is provided on the upper surface of the terminal electrode 13b on the negative electrode side.
  • the negative electrode current collector plate 17 is integrally provided with a covering portion that covers the upper surface of the terminal electrode 13b on the negative electrode side and an extending portion that extends from the covering portion in the other direction of the surface (left direction in FIG. 2). Yes.
  • Examples of the exterior material 9 include a metal case or a bag-like laminate film.
  • a laminate film is used from the viewpoint of achieving high output and excellent cooling performance and mounting the bipolar battery 7 on the EV and / or HEV.
  • Examples of the laminate film include a laminate film having a three-layer structure formed by laminating PP, aluminum, and nylon (polyamide) in this order.
  • the exterior material 9 seals the charge / discharge part 8. On the other hand, the exterior material 9 exposes the free end portions of the extending portions of the positive electrode current collector plate 16 and the negative electrode current collector plate 17, respectively.
  • Such a bipolar battery 7 is mounted on a vehicle such as EV or HEV and used as a driving power source.
  • the bipolar battery 7 can be used as a mounting power source such as an uninterruptible power supply.
  • this electrical power collector 1 is provided with the conductive resin layer 6 containing resin and an electroconductive material, the weight reduction of the electrical power collector 1 can be achieved and the output density per unit mass can be improved.
  • the current collector 1 includes the insulating resin layer 19 formed on one surface in the thickness direction of the conductive resin layer 6, side reactions on one surface in the thickness direction of the conductive resin layer 6 can be suppressed.
  • the electrolyte layer 11 is a liquid electrolyte, if the liquid electrolyte passes through the negative electrode 15 and comes into contact with the current collector 1, a side reaction may occur.
  • the side reaction is a reaction other than the main reaction between the negative electrode active material that brings about the charging action and the electrolyte of the electrolyte layer 11.
  • the bipolar battery 7 is a bipolar lithium ion secondary battery, the current collector 1 And decomposition of the electrolyte of the electrolyte layer 11. This side reaction needs to be suppressed as much as possible because the current collector 1 and the electrolyte layer 11 deteriorate.
  • the insulating resin layer 19 suppresses the side reaction described above, the current density of the current flowing between the current collector 1 and the electrolyte of the electrolyte layer 11 can be reduced. Therefore, the durability of the current collector 1 is improved by the insulating resin layer 19.
  • the insulating resin layer 19 includes a polycarbonate resin
  • the insulating resin layer 19 is obtained as a dense film, and the electrolyte of the electrolyte layer 11 is transmitted through the insulating resin layer 19. Can be suppressed. Therefore, the amount of the electrolyte of the electrolyte layer 11 that contacts the conductive resin layer 6 can be reduced, and side reactions on the surface and inside of the conductive resin layer 6 of the current collector 1 can be suppressed. As a result, the deterioration of the current collector 1 and the electrolyte layer 11 can be suppressed, and the durability of the current collector 1 is improved.
  • the conductive resin layer 6 when the resin contains polyimide and / or polyamideimide, the conductive resin layer 6 exhibits good ion blocking properties. Therefore, permeation of electrolyte ions of the electrolyte layer 11 to the conductive resin layer 6 can be blocked.
  • the corrosion resistance of the current collector 1 is improved, so that the durability of the current collector 1 can be improved. it can.
  • the bipolar battery 7 since the bipolar battery 7 includes the current collector 1 having excellent durability, the bipolar battery 7 has excellent durability.
  • the bipolar battery 7 can be suitably used as a lithium ion secondary battery.
  • the insulating resin layer 19 is formed on the entire upper surface of the conductive resin layer 6.
  • the insulating resin layer 19 It can also be provided on the lower surface.
  • Example 1 (Formation of insulating resin layer) A vinylene carbonate 0.4 mass% ethanol solution (monomer solution) was prepared, and then the ethanol solution was applied to the entire upper surface of the conductive resin layer produced by the method described in Production Example 1 to form a coating film. By irradiating the coating film with ultraviolet rays at 600 mJ / cm 2 , an insulating resin layer having a thickness of 15 nm was formed on the entire upper surface of the conductive resin layer. Thereby, a current collector provided with a conductive resin layer and an insulating resin layer was obtained (see FIG. 1).
  • Example 2 An insulating resin layer having a thickness of 18 nm is formed on the entire upper surface of the conductive resin layer in the same manner as in Example 1 except that an ethanol solution of 10% by weight of vinylene carbonate is used instead of the ethanol solution of 0.4% by weight of vinylene carbonate. And a current collector provided with a conductive resin layer and an insulating resin layer was obtained (see FIG. 1).
  • the conductive resin layer manufactured by the method described in Preparation Example 1 without using an insulating resin layer was used as a current collector.
  • the volume resistivity of the conductive resin layer was determined using a resistivity meter (Loresta MCP-T360, manufactured by Mitsubishi Chemical Corporation) in accordance with JIS K 7194.
  • the conductivity of the conductive resin layer was evaluated as follows. ⁇ : Volume resistivity is 100 ⁇ cm or less ⁇ : Volume resistivity exceeds 100 ⁇ cm (measurement of current density of current collector in negative electrode)
  • the current density of the flowing current was measured in the negative electrode using a three-electrode cell (manufactured by Hosen). Specifically, the current density was measured 5 minutes after the start of voltage application at a constant voltage of 5 mV.
  • the current collector is used for a lithium ion secondary battery.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Secondary Cells (AREA)

Abstract

L'invention concerne un collecteur comprenant: une couche de résine conductrice qui contient une résine et un matériau conducteur; et une couche de résine isolante qui est formée sur une surface de la couche de résine conductrice dans le sens de l'épaisseur et qui présente une épaisseur comprise entre 1 nm et 1 μm (compris).
PCT/JP2014/062562 2013-05-20 2014-05-12 Collecteur et batterie bipolaire WO2014188896A1 (fr)

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JP2013106167A JP2014229387A (ja) 2013-05-20 2013-05-20 集電体およびバイポーラ電池
JP2013-106167 2013-05-20

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Publication number Priority date Publication date Assignee Title
JP6572015B2 (ja) * 2015-06-25 2019-09-04 株式会社日本マイクロニクス 二次電池の製造方法
WO2024070701A1 (fr) * 2022-09-29 2024-04-04 パナソニックＩｐマネジメント株式会社 Batterie secondaire et collecteur de courant d'électrode négative

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JP2003297701A (ja) * 2002-03-29 2003-10-17 Tdk Corp 電気化学デバイスおよび電気化学デバイスの製造方法
JP2004164897A (ja) * 2002-11-11 2004-06-10 Nissan Motor Co Ltd バイポーラ電池
JP2004220894A (ja) * 2003-01-14 2004-08-05 Sumitomo Electric Ind Ltd リチウム二次電池負極部材およびリチウム二次電池
JP2007059206A (ja) * 2005-08-24 2007-03-08 Sony Corp 負極および電池
JP2009230976A (ja) * 2008-03-21 2009-10-08 Sanyo Electric Co Ltd 非水電解質二次電池及びその製造方法
JP2010170832A (ja) * 2009-01-22 2010-08-05 Nissan Motor Co Ltd ポリマーブレンドフィルムを含む電極
JP2013026057A (ja) * 2011-07-22 2013-02-04 Sharp Corp 集電体および非水系二次電池

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003297701A (ja) * 2002-03-29 2003-10-17 Tdk Corp 電気化学デバイスおよび電気化学デバイスの製造方法
JP2004164897A (ja) * 2002-11-11 2004-06-10 Nissan Motor Co Ltd バイポーラ電池
JP2004220894A (ja) * 2003-01-14 2004-08-05 Sumitomo Electric Ind Ltd リチウム二次電池負極部材およびリチウム二次電池
JP2007059206A (ja) * 2005-08-24 2007-03-08 Sony Corp 負極および電池
JP2009230976A (ja) * 2008-03-21 2009-10-08 Sanyo Electric Co Ltd 非水電解質二次電池及びその製造方法
JP2010170832A (ja) * 2009-01-22 2010-08-05 Nissan Motor Co Ltd ポリマーブレンドフィルムを含む電極
JP2013026057A (ja) * 2011-07-22 2013-02-04 Sharp Corp 集電体および非水系二次電池

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TW201445801A (zh) 2014-12-01

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