WO2014091542A1 - Corps stratifié pour boîtier externe de batterie - Google Patents

Corps stratifié pour boîtier externe de batterie Download PDF

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Publication number
WO2014091542A1
WO2014091542A1 PCT/JP2012/081977 JP2012081977W WO2014091542A1 WO 2014091542 A1 WO2014091542 A1 WO 2014091542A1 JP 2012081977 W JP2012081977 W JP 2012081977W WO 2014091542 A1 WO2014091542 A1 WO 2014091542A1
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WIPO (PCT)
Prior art keywords
layer
resin
aluminum foil
laminated
polyolefin
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PCT/JP2012/081977
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English (en)
Japanese (ja)
Inventor
宏和 飯塚
邦浩 武井
康宏 金田
智子 堀
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藤森工業株式会社
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Priority to PCT/JP2012/081977 priority Critical patent/WO2014091542A1/fr
Publication of WO2014091542A1 publication Critical patent/WO2014091542A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/78—Cases; Housings; Encapsulations; Mountings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
    • H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
    • H01M50/121—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/78—Cases; Housings; Encapsulations; Mountings
    • H01G11/80—Gaskets; Sealings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
    • H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
    • H01M50/117—Inorganic material
    • H01M50/119—Metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
    • H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
    • H01M50/124—Primary casings, jackets or wrappings of a single cell or a single battery 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
    • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
    • H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
    • H01M50/124—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure
    • H01M50/126—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure comprising three or more layers
    • H01M50/129—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure comprising three or more layers with two or more layers of only organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
    • H01M50/131—Primary casings, jackets or wrappings of a single cell or a single battery characterised by physical properties, e.g. gas-permeability or size
    • H01M50/133—Thickness
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/543—Terminals
    • H01M50/547—Terminals characterised by the disposition of the terminals on the cells
    • H01M50/55—Terminals characterised by the disposition of the terminals on the cells on the same side of the cell
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/543—Terminals
    • H01M50/552—Terminals characterised by their shape
    • H01M50/553—Terminals adapted for prismatic, pouch or rectangular cells
    • 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

Definitions

  • the present invention relates to a laminate for battery exterior used as an exterior material for secondary batteries such as lithium ion batteries and electric double layer capacitors (hereinafter referred to as capacitors).
  • the outer container for storing lithium-ion batteries used in electric vehicles, etc. is a flat bag made by using a laminated body for battery exteriors in which an aluminum foil and a resin film are laminated, or drawn or stretched. A molded container is used to reduce the thickness and weight. As demand grows, the cost of the battery body has become a key point, and battery exterior laminates that are laminated with aluminum foil and resin films that are cheaper than metal containers and have high sealing productivity are attracting attention.
  • the electrolyte solution of a lithium ion battery has the property of being sensitive to moisture and light.
  • a base material layer made of polyamide or polyester and an aluminum foil are laminated on the exterior material for a lithium ion battery, and a polyolefin resin film having a high heat sealability is further laminated on the inside using a heat adhesive resin. It is laminated by the method.
  • the battery exterior laminate is superior in waterproofness and light-shielding property to the dry laminate method using a urethane adhesive, which is a conventional film laminate method, and is used.
  • a mounting container 30 as shown in FIG. 3A is used. That is, a tray-like shape having a recess 31 is formed in advance by using a laminate for battery exterior by drawing or the like, and accessories such as a lithium ion battery (not shown) and an electrode 36 are attached to the recess 31 of the tray.
  • the lid member 33 made of a battery exterior laminate is stacked from above to wrap the battery, and the flange portion 32 of the tray and the four side edges 34 of the lid member 33 are heat-sealed. To seal.
  • the storage container 35 created by the method of placing the battery in the concave portion 31 of the tray the battery can be stored from above, so that the productivity is high.
  • the depth of the tray (hereinafter, the tray depth is sometimes referred to as “throttle”) is 5 to 5 for a conventional small lithium ion battery. It is about 6 mm.
  • the tray depth is sometimes referred to as “throttle”
  • storage containers for large batteries have been demanded more than ever for applications such as for electric vehicles.
  • a deeper drawing tray has to be formed, which increases technical difficulties.
  • the electrolytic solution is decomposed by moisture and strong acid is generated.
  • strong acid generated from the inside of the battery exterior laminate may permeate, and as a result, the aluminum foil may corrode with strong acid and deteriorate.
  • the electrolyte leaks and the battery performance is deteriorated, and the lithium ion battery is ignited.
  • Patent Document 1 describes that the surface of the aluminum foil is subjected to chromate treatment to form a coating film, which has corrosion resistance. Measures to improve are disclosed. However, since the chromate treatment uses chromium, which is a heavy metal, it is problematic from the viewpoint of environmental measures, and chemical conversion treatments other than the chromate treatment are less effective in improving the corrosion resistance.
  • a polyolefin resin film (polyolefin sealant) that has high electrolytic solution resistance and high heat sealability is laminated on one surface of an aluminum foil by thermal lamination using a heat-adhesive resin.
  • an ionomer resin, an EAA resin and a maleic anhydride-modified polyolefin resin are extruded and laminated with a polyolefin sealant by sand lamination, or on the surface where the polyolefin sealant is bonded to the aluminum foil.
  • Examples include a method in which a heat-adhesive resin is multilayered and heat-laminated, and a method in which a heat-adhesive polyolefin dispersion is coated on an aluminum foil and a polyolefin sealant is heat-laminated.
  • the present invention has been made in view of the above circumstances, and the decrease in the laminate strength and delamination between the aluminum foil and the innermost layer due to the deterioration of the electrolyte of the lithium ion battery is reduced, and the high yield is achieved. It aims at providing the laminated body for battery exterior which can manufacture an exterior container by low cost.
  • the present invention introduces a polar group into a base material layer, an aluminum foil, a polypropylene resin, a polyethylene resin, and a polyolefin in a laminate for battery exterior in which an aluminum foil and a resin layer are sequentially laminated.
  • an innermost layer consisting of at least one polyolefin sealant layer selected from the group of resins consisting of polyolefin resins, wherein the polyolefin sealant layer is a single layer or a multilayer, and the polyolefin sealant layer
  • a polyolefin sealant layer containing a heat-adhesive polyolefin resin having an epoxy group is laminated on the interface side with the aluminum foil, and a polyamide resin film layer having a thickness of 10 to 50 ⁇ m as the base material layer on the outer surface of the aluminum foil
  • a laminated body for battery exterior that is a laminated film in which is laminated.
  • the present invention provides a battery exterior laminate in which an aluminum foil and a resin layer are sequentially laminated, and a polar group is formed on at least a base material layer having a polyamide resin film layer, an aluminum foil, a polypropylene resin, a polyethylene resin, and a polyolefin.
  • an innermost layer composed of at least one polyolefin sealant layer selected from the group of resins composed of the introduced polyolefin-based resin, and the polyolefin sealant layer is a single layer or a multilayer, and at least of the aluminum foil
  • a thin film coating layer made of a water-soluble resin or a copolymer resin thereof is laminated on the innermost layer side surface, and contains a thermal adhesive polyolefin resin having an epoxy group on the interface side with the aluminum foil of the polyolefin sealant layer
  • a polyolefin sealant layer is laminated to the aluminum foil and the front And a polyolefin sealant layer to provide a battery exterior laminate which is heat-laminated.
  • the innermost layer side surface of the aluminum foil is laminated with a coating type thin film coating layer made of a water-soluble resin or a copolymer resin thereof, and the thin film coating layer is cross-linked.
  • a coating type thin film coating layer made of a water-soluble resin or a copolymer resin thereof, and the thin film coating layer is cross-linked.
  • the thin film coating layer contains a substance that improves water resistance, moisture resistance and heat resistance and further passivates the surface of aluminum by the crosslinking.
  • the tensile breaking elongation of the laminate measured by the measuring method specified in JIS K7127 is 50% or more in both the MD direction and the TD direction.
  • a polyamide resin film as the outermost layer of the outer packaging material of the battery outer laminate in order to suppress heat resistance, water resistance and whitening phenomenon of the outer packaging material due to leakage of the electrolyte during production.
  • the thin film coating layer has a structure in which water resistance is achieved by crosslinking or amorphization using heat treatment or the like, and moisture permeation from the end face is suppressed.
  • the base material layer and the aluminum foil are bonded with a coating type adhesive such as a urethane-based adhesive.
  • the polyolefin sealant layer becomes a single layer or a multilayer, the thermal adhesiveness having an epoxy group on the aluminum foil interface side It is a polyolefin sealant innermost layer containing a polyolefin resin, and is preferably bonded by heat lamination, and the heat lamination processing speed is preferably 50 m / min or more.
  • the thickness of the innermost layer is 20 ⁇ m or more and 150 ⁇ m or less, and the adhesive strength between the aluminum foil and the innermost layer is measured by a measurement method defined by the peeling measurement method A defined in JIS C6471. It is preferable that it is 10 N / inch or more. This is because the pressure resistance strength of the seat seal portion is maintained, and the thinner the sealant on the end face, the slower the moisture penetration. N / inch corresponds to N / 25.4 mm.
  • the innermost layer composed of a polyolefin sealant layer is laminated via a thin film coating layer laminated on at least one surface of an aluminum foil or without a thin film coating layer, and the polyolefin sealant layer Is a single layer or multiple layers.
  • the polyolefin sealant layer containing a heat-adhesive polyolefin resin having an epoxy group is laminated on the surface of the polyolefin sealant layer on the interface side with the aluminum foil, the adhesive strength between the aluminum foil and the innermost layer composed of the polyolefin sealant layer Is very strong, and after laminating, when it is stored in an oven set in a temperature range from room temperature to 100 ° C., the adhesive strength is significantly increased. For this reason, it is possible to provide an epoch-making exterior body production method that has sufficient performance as a battery exterior material, further reduces production costs, and can reduce costs.
  • the innermost layer is a polypropylene resin, a polyethylene resin, or a resin group comprising a polyolefin resin in which a polar group is introduced into a polyolefin.
  • the base material layer is a layer obtained by laminating at least an aluminum foil and a polyamide resin film by a dry laminating method using a urethane-based adhesive, and when a polyamide resin film having a thickness of 10 to 50 ⁇ m is used, it is drawn. Even in this case, pinholes and delamination do not occur.
  • a storage container for a lithium ion battery manufactured using the laminate for battery exterior according to the present invention will be described as an example, and will be described with reference to FIGS.
  • a battery exterior container 20 created using the battery exterior laminate of the present invention folds the battery exterior laminate 10 to enclose a lithium ion battery 17 and an electrode 18, and further includes a battery.
  • the three side edge portions 19 of the exterior container 20 are heat-sealed to form a bag.
  • the electrode lead wire member 18 is pulled out from the battery outer container 20 as shown in FIG. 3A and 3B show the storage method in the battery storage container of the lithium ion battery manufactured using the electrode lead wire member 18 according to the present invention.
  • the battery outer laminate 10 includes a base material layer 11, an aluminum foil 12, and an innermost layer 13, which are sequentially laminated, and the base material layer 11 and the aluminum foil 12 have an adhesive layer 15.
  • the aluminum foil 12 and the innermost layer 13 are bonded without using an adhesive layer.
  • a thin film coating layer 14 made of a water-soluble resin or a copolymer resin thereof is laminated on at least one surface of the aluminum foil 12.
  • the thin film coating layer 14 includes a substance that crosslinks the thin film coating layer made of a water-soluble resin or a copolymer resin thereof to improve water resistance, moisture resistance, and heat resistance, and further passivates the aluminum surface. Yes.
  • this laminated body 10 for battery exteriors is measured by the measuring method prescribed
  • the tensile elongation at break is the tensile elongation at break obtained when measured at a tensile speed of 50 mm / min according to JIS K7127. If the tensile strength at break of the laminate for battery exterior 10 is 50% or more in both the MD direction and the TD direction, the corner portion may be sufficiently stretched and broken even when the laminate for battery exterior 10 is folded. There is no pinhole because there is no.
  • the base material layer 11 and the aluminum foil 12 are bonded via a urethane adhesive layer 15, and the resin group of the aluminum foil 12, a polypropylene resin, a polyethylene resin, and a polyolefin resin in which a polar group is introduced into polyolefin.
  • a polyolefin sealant layer containing a heat-adhesive polyolefin resin having an epoxy group is laminated on the aluminum foil interface side surface of the polyolefin sealant layer of the innermost layer 13 comprising at least one polyolefin sealant layer selected from the inside. Therefore, it can be bonded by heat lamination.
  • the adhesive strength between the aluminum foil 12 and the innermost layer 13 made of at least one polyolefin sealant layer selected from the resin group consisting of the polyolefin resin in which a polar group is introduced into the polypropylene resin, polyethylene resin, and polyolefin is used. , Measured by the measurement method defined in JIS C6471, and is 10 N / inch or more.
  • the base material layer 11 is not particularly limited as long as it has high mechanical strength.
  • a biaxially stretched polyamide resin film ONy
  • a polyethylene terephthalate (PET) resin film is further laminated on the biaxially stretched polyamide resin film (ONy).
  • the total thickness of the base material layer 11 is preferably 18 to 60 ⁇ m, the thickness of the polyamide resin film is 10 to 50 ⁇ m, and the thickness of the polyethylene terephthalate (PET) resin film is 3 to 16 ⁇ m. Further preferred.
  • the battery outer laminate of the present invention uses a polyethylene terephthalate (PET) resin film as the outermost layer, so that heat resistance, water resistance, and productivity during heat sealing are high. Even if the electrolytic solution adheres to the terephthalate (PET) resin film, the whitening phenomenon does not occur, and if wiped off, the product quality is not affected.
  • PET polyethylene terephthalate
  • the drawability is good and it is possible to prevent delamination between the base material and the aluminum foil in the heat sealing process during bag making.
  • the aluminum foil 12 is an external insulating layer for providing the battery outer container with waterproofness and light shielding properties. Although it does not restrict
  • the water-soluble resin is a resin containing a hydroxyl group, and specifically, a resin obtained by saponifying a polymer of a vinyl ester monomer or a copolymer thereof.
  • the vinyl ester monomers include fatty acid vinyl esters such as vinyl formate, vinyl acetate, and vinyl butyrate, and aromatic vinyl esters such as vinyl benzoate.
  • the thin film coating layer 14 preferably contains an aluminum passivating agent made of a metal fluoride or a derivative thereof.
  • a metal fluoride or a derivative thereof is a substance containing F 2 ⁇ ions that form a passive aluminum fluoride, such as chromium fluoride, iron fluoride, zirconium fluoride, fluorinated zirconate compound, hafnium fluoride. And fluorides such as fluorinated titanic acid compounds.
  • Commercially available products include non-polar polyolefins manufactured by Mitsubishi Chemical, which have polar groups introduced to give adhesion to different materials (trade names: MODIC, Modic), polyamide, EVOH, polyester, metal, polyolefin Can be glued with etc.
  • the thin film coating layer 14 is preferably a chromate treatment solution, among which a metal fluoride or a derivative thereof is used to crosslink a thin film coating layer mainly composed of a hydroxyl group-containing resin or a copolymer resin thereof.
  • a method that includes a material that passivates the surface is desirable. However, even if a metal fluoride or a derivative thereof is not included, the corrosion resistance of the coating layer is improved.
  • the thin film coating layer 14 is preferably water-resistant by crosslinking or amorphization by heat treatment.
  • the pressure resistance of the battery exterior laminate is high. Lithium ion battery from the edge because the pressure resistance can be maintained even if the thickness of at least one polyolefin sealant layer selected from the group consisting of resin and polyolefin resin in which polar groups are introduced into polyolefin is reduced. Moisture penetration into the interior is reduced, and deterioration of the electrolyte of the lithium ion battery over time is reduced, so that the battery product life is extended.
  • the thin film coating layer 14 made of a water-soluble resin or a copolymer resin thereof is laminated on at least one surface of the aluminum foil 12, the aluminum foil 12, the innermost layer 13, When heat laminating, the interlayer adhesion strength is very strong. Therefore, when the tray is formed by drawing or stretch forming using the battery exterior laminate, it is possible to prevent the generation of pinholes and the peeling between the base material layer 11 and the aluminum foil 12. As a result, the occurrence of defects during molding of the storage container is reduced.
  • the resin having a skeleton of polyvinyl alcohol containing hydroxyl groups or a copolymer resin thereof has a low free volume. Since the gas barrier property is high, hydrofluoric acid does not diffuse outside along the innermost layer 13 that also serves as a sealant layer. In addition, even if a small amount of hydrofluoric acid comes into contact with the aluminum surface, the aluminum foil is not attacked by passivation, the interlayer adhesion strength between the aluminum foil and the sealant layer is maintained, the pressure resistance strength retention is increased, and the battery performance is also improved. Does not deteriorate.
  • the thickness of the aluminum foil 12 is 20 to 100 ⁇ m.
  • a thickness of the aluminum foil 12 of 30 to 60 ⁇ m is preferable because sufficient waterproofness and light shielding properties are exhibited and processability is good.
  • the thickness of the thin film coating layer 14 made of a water-soluble resin or a copolymer resin thereof is preferably from 0.1 to 5 ⁇ m, and more preferably from 0.5 to 1 ⁇ m, the performance of wettability and adhesive strength is increased.
  • the innermost layer 13 composed of at least one polyolefin sealant layer selected from the group consisting of a polypropylene resin, a polyethylene resin, and a polyolefin resin in which a polar group is introduced into a polyolefin is a layer mainly containing a polypropylene resin and a polyethylene resin.
  • the innermost layer 13 composed of at least one polyolefin sealant layer selected from the group consisting of polypropylene resin, polyethylene resin, and polyolefin resin in which a polar group is introduced into polyolefin is a layer in contact with the lithium ion battery is as follows.
  • the polypropylene resin or polyethylene resin is excellent in corrosion resistance to the electrolyte solution of the lithium ion battery and has good heat sealability.
  • the heat sealing property is the stability of the seal at a high temperature.
  • the polyolefin resin introduced with the polar group used in the innermost layer 13 is a polypropylene resin having a polar group introduced into polypropylene.
  • at least a polymer obtained by modifying a part of the polypropylene molecule with an epoxy group may be used alone, or the epoxy group may be modified to a part of the molecule on the side of the interface with the innermost aluminum foil.
  • the polypropylene resin may be a homopolymer or a copolymer with ethylene, and the copolymer type may be a random copolymer or a block copolymer.
  • the innermost layer 13 mainly contains a polyethylene resin (not having a polar group introduced), at least as a polyolefin resin introduced with a polar group used for the innermost layer 13, a polyethylene having a polar group introduced into polyethylene is used.
  • Type resin is preferable, and epoxy-modified polyethylene is preferable.
  • a multilayer structure may be used as long as there is polyethylene in which an epoxy group is modified to a part of the molecule on the surface on the interface side with the innermost aluminum foil.
  • the thickness of the innermost layer 13 composed of at least one polyolefin sealant layer selected from the group consisting of polypropylene resin, polyethylene resin, and polyolefin resin in which a polar group is introduced into polyolefin is 20 to 150 ⁇ m. preferable.
  • the innermost layer 13 mainly includes a polypropylene resin or a polypropylene resin into which a polar group is introduced, the corrosion resistance and heat sealability with respect to the electrolytic solution, and a sufficient pressure resistance can be obtained without excessively increasing the thickness to 150 ⁇ m or more. It is preferable because the strength can be maintained.
  • such an innermost layer 13 is a very effective method because it can prevent deterioration of nonaqueous batteries and capacitors by preventing moisture from entering from a heat-sealed cross section.
  • the adhesive layer 15 is a layer that adheres the base material layer 11 and the aluminum foil 12.
  • the adhesive contained in the adhesive layer 15 is not particularly limited as long as the base material layer 11 and the aluminum foil 12 can be bonded, and examples thereof include an epoxy adhesive and a urethane adhesive.
  • the adhesive layer 15 consists of an epoxy-type adhesive agent, a urethane type adhesive agent, etc.
  • the adhesive bond layer 15 can be normally laminated
  • the thickness of the adhesive layer 15 is preferably 3 to 16 ⁇ m.
  • the thickness of the adhesive layer 15 is 2 to 10 ⁇ m because the base material layer 11 and the aluminum foil 12 are bonded with a sufficiently high adhesive force, and the battery exterior laminate 10 is formed by drawing or stretching. In addition, adhesion at the ridge line portion and the deformed portion is maintained, and the base material layer 11 and the aluminum foil 12 do not delaminate.
  • Adhesion with the innermost layer 13 composed of at least one polyolefin sealant layer selected from the inside is that the polyolefin sealant layer is a single layer or a multilayer, and an epoxy group is formed on the interface side surface with the aluminum foil of the innermost layer. Since the modified polyolefin is partly included, it can be bonded by a heat laminating method.
  • the thin film coating layer 14 laminated on the innermost layer side surface of the aluminum foil 12 preferably uses a water-soluble resin containing a hydroxyl group.
  • the polyolefin containing an epoxy group has particularly high adhesive strength and less heat, the thin film coating layer 14 and the innermost layer 13 of the aluminum foil 12 can be bonded by extrusion lamination or heat lamination. .
  • the aluminum foil 12 or its thin film coating layer 14 and the innermost layer 13 can be laminated without an adhesive layer therebetween. Thermal lamination without an adhesive or anchor coating agent is preferred.
  • the tensile breaking elongation of the battery outer laminate 10 used is 50% or more in both the MD direction and the TD direction.
  • the corner portion C is sufficiently stretched, so that it is not broken and no pinhole is generated.
  • the adhesive force between the base material layer 11 and the aluminum foil 12 is sufficiently high and does not yield to the stress during stretching, peeling can be prevented.
  • Measurement method of tensile elongation at break of laminate Measured by the measurement method defined in JIS K7127 “Plastics—Test method of tensile properties—Part 3: Test conditions of film and sheet”.
  • Measurement method of adhesive strength between aluminum foil and innermost layer Measured by peeling measurement method A (90 ° direction peeling) defined in JIS C6471 “Test method for copper-clad laminate for flexible printed wiring board”.
  • ⁇ Measurement method of pinhole rupture rate 50 draw-molded products were formed by cold forming with a predetermined depth within a range of 6 to 10 mm in depth of 50 ⁇ 50 mm in the battery exterior laminate, and visually The presence or absence of pinholes was confirmed.
  • Number of occurrences of delamination during heat sealing 50 draw-formed products by cold forming with a predetermined depth within a range of 50 mm ⁇ 50 mm in depth and 8 mm in depth are formed into a battery exterior laminate, and after heat sealing, 60 The sample was left in a constant temperature and humidity open at 90 ° C. for 48 hours, and then visually checked for the presence of delamination between the base material layer and the aluminum foil.
  • Measurement method of electrolyte strength retention rate Using the produced laminate for battery exterior, a 50 ⁇ 50 mm (heat seal width is 5 mm) bag was made into a four-sided bag, and LiPF 6 was contained at 1 mol / liter in it.
  • a base material layer was prepared by laminating a stretched polyethylene terephthalate (PET) resin film having a thickness of 12 ⁇ m and a stretched polyamide resin film having a thickness of 25 ⁇ m by dry lamination using a urethane adhesive layer having a thickness of 4 ⁇ m.
  • PET polyethylene terephthalate
  • This base material layer and an aluminum foil having a thickness of 40 ⁇ m were laminated via an adhesive layer (thickness: 3 ⁇ m) made of a urethane-based adhesive (containing an epoxy-based adhesive).
  • amorphous polymer having a hydroxyl group-containing polyvinyl alcohol skeleton manufactured by Nippon Synthetic Chemical Co., Ltd., trade name: G polymer resin
  • chromium fluoride (III) An aqueous solution in which 2% by weight was dissolved was applied so that the thickness after drying was 0.5 ⁇ m, a thin film coating layer was laminated, and further heated in an oven at 200 ° C. for crosslinking reaction.
  • each 50 ⁇ m thick epoxy group-modified polyethylene product name; manufactured by Sumitomo Chemical Co., Ltd .; Bond First
  • LLDPE low density polyethylene
  • the polyethylene sealant thus obtained was heat-laminated at a processing speed of 50 m / min and laminated in order to form the innermost layer.
  • the battery outer laminate 10 of Example 1 was produced.
  • the laminate for battery exterior was stored in a hot air oven at 50 ° C. for 48 hours. Test pieces were taken from the battery outer laminate 10 of Example 1 and measured for the tensile breaking elongation in the MD direction and the TD direction.
  • Example 2 A stretched polyamide resin film having a thickness of 25 ⁇ m and an aluminum foil having a thickness of 40 ⁇ m were laminated via an adhesive layer (thickness 3 ⁇ m) made of a urethane adhesive (containing an epoxy adhesive). Moreover, 1% by weight of an amorphous polymer having a polyvinyl alcohol skeleton having a hydroxyl group on the innermost surface of the aluminum foil (trade name: G polymer resin, manufactured by Nippon Synthetic Chemical Co., Ltd.) and chromium fluoride (III) An aqueous solution in which 2% by weight was dissolved was applied so that the thickness after drying was 0.5 ⁇ m, a thin film coating layer was laminated, and further heated in an oven at 200 ° C.
  • a single-layer polyolefin sealant film containing an epoxy group-modified polypropylene having a thickness of 50 ⁇ m [maleic anhydride-modified polypropylene resin (product name / Admer resin, manufactured by Mitsui Chemicals, Inc.)
  • a 1.5 wt% blend compound of a hydroxyl group-containing epoxy compound (Mitsubishi Chemical Co., Ltd., product name / Epicoat 1001) was reacted with the maleic anhydride functional group of the polypropylene resin to produce a polypropylene resin into which an epoxy group was introduced.
  • Example 1 Using a film-forming machine, use a film formed to a thickness of 100 ⁇ m] was obtained in the same manner as in Example 1 except that the laminate 10 for battery exterior was obtained in the same manner as in Example 1 except that the film was thermally laminated at a processing speed of 80 m / min. , Tensile elongation at break, number of delamination during heat sealing, and adhesive strength between aluminum foil and innermost layer was measured. The results are shown in Table 1.
  • a base material layer was prepared by dry laminating a stretched polyethylene terephthalate (PET) resin film having a thickness of 12 ⁇ m and a stretched polyamide resin film having a thickness of 25 ⁇ m with a urethane-based adhesive.
  • PET polyethylene terephthalate
  • This base material layer and an aluminum foil having a thickness of 40 ⁇ m were laminated via an adhesive layer (thickness: 4 ⁇ m) made of a urethane-based adhesive (containing an epoxy-based adhesive).
  • the battery exterior laminate 10 of Comparative Example 1 was obtained in the same manner as in Example 1, and the tensile elongation at break and heat sealing were as follows. The number of delamination occurrences and the adhesive strength between the aluminum foil and the innermost layer were measured. The results are shown in Table 1.
  • Example 3 A base material layer was prepared by dry laminating a stretched polyethylene terephthalate (PET) resin film having a thickness of 12 ⁇ m and a stretched polyamide resin film having a thickness of 25 ⁇ m with a urethane-based adhesive.
  • PET polyethylene terephthalate
  • This base material layer and an aluminum foil having a thickness of 40 ⁇ m were laminated via an adhesive layer (thickness: 4 ⁇ m) made of a urethane-based adhesive (containing an epoxy-based adhesive).
  • a base material layer was prepared by dry laminating a stretched polyethylene terephthalate (PET) resin film having a thickness of 12 ⁇ m and a stretched polyamide resin film having a thickness of 25 ⁇ m with a urethane-based adhesive.
  • PET polyethylene terephthalate
  • This base material layer and an aluminum foil having a thickness of 40 ⁇ m were laminated via an adhesive layer (thickness: 4 ⁇ m) made of a urethane-based adhesive (containing an epoxy-based adhesive).
  • a laminated body 10 for battery exterior of Comparative Example 2 was obtained in the same manner as in Example 1 except that maleic anhydride-modified polyethylene resin was extruded and laminated at a processing speed of 50 m / min and a polyethylene sealant for boil was sanded. The tensile breaking elongation, the number of delamination during heat sealing, and the adhesive strength between the aluminum foil and the innermost layer were measured. The results are shown in Table 1.
  • Examples 1 to 3 were prepared by dissolving 3% by weight of an amorphous polymer having a hydroxyl group-containing polyvinyl alcohol skeleton (G polymer resin manufactured by Nippon Synthetic Chemical Co., Ltd.) and 1% by weight of chromium (III) fluoride. Since the aqueous solution is applied and the thin film coating layer is laminated, the adhesive strength between the aluminum foil and the innermost layer is 10 N / inch or more. That is, the tensile elongation at break exceeded 50% in both the MD and TD directions, and the frequency of delamination during heat sealing became zero. In addition, the electrolyte strength retention was measured using the battery outer laminates of Examples 1 to 3.
  • G polymer resin manufactured by Nippon Synthetic Chemical Co., Ltd. 1% by weight of chromium (III) fluoride. Since the aqueous solution is applied and the thin film coating layer is laminated, the adhesive strength between the aluminum foil and the innermost layer is 10 N / inch or more. That is,
  • the test results show that the electrolyte solution strength retention in the battery exterior laminate of Example 1 is 82%, and the electrolyte solution strength retention in the battery exterior laminate of Example 2 is 84%.
  • the electrolyte solution strength retention in the laminate for battery exterior was 80%.
  • Examples 1 to 3 were also corrosion resistant to the electrolyte solution of the lithium battery.
  • the adhesive strength between the aluminum foil and the innermost layer sealant is a dry laminate using a urethane adhesive
  • the thermal adhesive strength is sufficient and the interlayer strength is 10 N / inch or more.
  • aluminum foil and a sealant film were laminated with a urethane adhesive, delamination occurred after the electrolytic solution treatment.
  • Example 4 An aluminum laminate film was prepared by laminating a polyamide resin film layer having a thickness of 25 ⁇ m on an aluminum foil via a urethane adhesive layer applied at 3 g / m 2 . On the surface of the aluminum laminate film where the aluminum foil is exposed, 1% by weight of an amorphous polymer having a polyvinyl alcohol skeleton having a hydroxyl group (manufactured by Nippon Synthetic Chemical Co., Ltd., trade name: G polymer resin) is used.
  • G polymer resin amorphous polymer having a polyvinyl alcohol skeleton having a hydroxyl group
  • Example 5 Except for changing the thickness of the innermost polyethylene layer to 30 ⁇ m, the battery exterior laminate 10 of Example 5 was obtained in the same manner as in Example 4 to obtain the adhesive strength between the aluminum foil and the innermost layer, during heat sealing. The number of delamination occurrence and the pinhole fracture occurrence rate were measured. The results are shown in Table 2.
  • a base material layer was prepared by laminating a polyethylene terephthalate (PET) resin film having a thickness of 12 ⁇ m and a polyamide resin film layer having a thickness of 25 ⁇ m via a urethane adhesive layer applied at 3 g / m 2 . .
  • PET polyethylene terephthalate
  • This base material layer and the aluminum foil were laminated via a urethane adhesive layer 3 ⁇ m containing an epoxy adhesive.
  • a non-crystalline polymer (product name: G polymer resin, manufactured by Nippon Synthetic Chemical Co., Ltd.) having a skeleton of polyvinyl alcohol having a hydroxyl group on the surface of the aluminum foil opposite to the adhesive surface with the adhesive layer is 1
  • An aqueous solution in which 2% by weight of chromium (III) fluoride is dissolved is applied so that the thickness after drying is 0.5 ⁇ m, and an acid-modified polypropylene heat sealant is applied thereon to 3 g / m. was coated with 2, followed in the polypropylene layer 40 ⁇ m composed of four-layer structure that is thermally laminated at 50 m / min processing speed, to obtain a battery exterior laminate 10 of Comparative example 3.
  • a test piece was taken from the battery outer laminate 10 of Comparative Example 3, and the adhesive strength between the aluminum foil and the innermost layer was measured.
  • the 8 mm deep drawing was performed 50 times, the number of occurrences of pinhole breakage was measured, and the pinhole breakage occurrence rate was obtained.
  • drawing with a depth of 8 mm was performed 50 times, and the number of occurrences of delamination during heat sealing was measured. The results are shown in Table 2.
  • a possible battery exterior laminate can be provided at low cost.
  • SYMBOLS 10 Laminate for battery exterior, 11 ... Base material layer (polyethylene terephthalate (PET) resin film / polyamide resin film), 12 ... Aluminum foil, 13 ... Innermost layer, 14 ... Thin film coating layer, 15 ... Adhesive layer, 17 DESCRIPTION OF SYMBOLS ... Lithium ion battery, 18 ... Electrode, 19 ... Side edge part, 20 ... Battery outer container, 30 ... Battery mounting container, 35 ... Battery storage container.
  • PET polyethylene terephthalate

Abstract

L'invention concerne un corps stratifié pour un boîtier externe de batterie qui est un film stratifié dans lequel : une couche de matériau de base (11), une feuille d'aluminium (12), et une couche la plus interne (13) comprenant une couche de colle à polyoléfine sont stratifiées dans cet ordre, la couche de colle à polyoléfine étant une couche unique ou des multiples couches ; une couche de colle à polyoléfine contenant une résine polyoléfine à adhésion thermique ayant un groupement époxy est stratifiée sur le côté de la couche de colle à polyoléfine qui est une face frontière avec la feuille d'aluminium ; et une couche de film de résine polyamide ayant une épaisseur de 10 à 50 µm est stratifiée sur la face externe de la feuille d'aluminium en tant que couche de matériau de base. De plus, une couche de revêtement en couches minces (14) comprenant une résine hydrosoluble ou une résine copolymère de celle-ci est stratifiée sur au moins la face de couche la plus interne de la feuille d'aluminium (12).
PCT/JP2012/081977 2012-12-10 2012-12-10 Corps stratifié pour boîtier externe de batterie WO2014091542A1 (fr)

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PCT/JP2012/081977 WO2014091542A1 (fr) 2012-12-10 2012-12-10 Corps stratifié pour boîtier externe de batterie

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001057181A (ja) * 1999-06-10 2001-02-27 Toyo Aluminium Kk 電池包装材料用アルミニウム箔及びそれを使用した電池包装材料
JP2007095654A (ja) * 2006-03-23 2007-04-12 Dainippon Printing Co Ltd リチウムイオン電池
JP2010086831A (ja) * 2008-09-30 2010-04-15 Dainippon Printing Co Ltd 電気化学セル用包装材料
JP2012033393A (ja) * 2010-07-30 2012-02-16 Fujimori Kogyo Co Ltd 電池外装用積層体
WO2012063764A1 (fr) * 2010-11-11 2012-05-18 藤森工業株式会社 Procédé de fabrication d'un film de scellement, et film de scellement
JP2013012469A (ja) * 2011-05-31 2013-01-17 Fujimori Kogyo Co Ltd 電池外装用積層体

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001057181A (ja) * 1999-06-10 2001-02-27 Toyo Aluminium Kk 電池包装材料用アルミニウム箔及びそれを使用した電池包装材料
JP2007095654A (ja) * 2006-03-23 2007-04-12 Dainippon Printing Co Ltd リチウムイオン電池
JP2010086831A (ja) * 2008-09-30 2010-04-15 Dainippon Printing Co Ltd 電気化学セル用包装材料
JP2012033393A (ja) * 2010-07-30 2012-02-16 Fujimori Kogyo Co Ltd 電池外装用積層体
WO2012063764A1 (fr) * 2010-11-11 2012-05-18 藤森工業株式会社 Procédé de fabrication d'un film de scellement, et film de scellement
JP2013012469A (ja) * 2011-05-31 2013-01-17 Fujimori Kogyo Co Ltd 電池外装用積層体

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