WO2016159278A1 - Matériau d'encapsulation pour pile, son procédé de production, et pile - Google Patents

Matériau d'encapsulation pour pile, son procédé de production, et pile Download PDF

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Publication number
WO2016159278A1
WO2016159278A1 PCT/JP2016/060761 JP2016060761W WO2016159278A1 WO 2016159278 A1 WO2016159278 A1 WO 2016159278A1 JP 2016060761 W JP2016060761 W JP 2016060761W WO 2016159278 A1 WO2016159278 A1 WO 2016159278A1
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Prior art keywords
layer
packaging material
base material
battery packaging
metal layer
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PCT/JP2016/060761
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English (en)
Japanese (ja)
Inventor
大佑 安田
山下　力也
山下　孝典
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大日本印刷株式会社
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Priority to JP2017510213A priority Critical patent/JP6881298B2/ja
Publication of WO2016159278A1 publication Critical patent/WO2016159278A1/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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/14—Primary casings; Jackets or wrappings for protecting against damage caused by external factors
    • H01M50/141—Primary casings; Jackets or wrappings for protecting against damage caused by external factors for protecting against humidity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/78—Cases; Housings; Encapsulations; Mountings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/105—Pouches or flexible bags
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/14—Primary casings; Jackets or wrappings for protecting against damage caused by external factors
    • H01M50/145—Primary casings; Jackets or wrappings for protecting against damage caused by external factors for protecting against corrosion
    • 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 battery packaging material, a method for producing the same, and a battery.
  • a concave portion is formed by cold forming, and a battery element such as an electrode or an electrolytic solution is arranged in a space formed by the concave portion, and a heat-fusible resin is provided.
  • a battery element such as an electrode or an electrolytic solution
  • a heat-fusible resin is provided.
  • a battery in which the battery element is accommodated in the battery packaging material is obtained.
  • a film-shaped packaging material has a drawback that it is thinner than a metal packaging material and easily causes pinholes and cracks during molding. When pinholes or cracks occur in battery packaging materials, the electrolyte can penetrate into the metal layer to form metal deposits, which can result in short circuits. It is indispensable for the battery packaging material to have a characteristic that does not easily cause pinholes during molding, that is, excellent moldability.
  • a polyamide resin such as nylon is used as a base material layer to improve moldability.
  • polyester such as polyethylene terephthalate is inferior in moldability compared to nylon and the like
  • the thickness of the metal layer is very thin (for example, 40 ⁇ m or less, further 35 ⁇ m or less), a problem that pinholes and the like are likely to occur in the metal layer during the molding of the battery packaging material occurred.
  • the main object of the present invention is excellent in a battery packaging material comprising a laminate comprising at least a base material layer formed of polyester, a metal layer, and a heat-fusible resin layer in this order. It is another object of the present invention to provide a battery packaging material that has excellent moldability and has excellent insulating properties, and is less prone to pinholes and cracks during molding.
  • the present invention has excellent moldability in a battery packaging material comprising a laminate comprising at least a base material layer, an adhesive layer, a metal layer, and a heat-fusible resin layer in this order. Furthermore, it is a main object to provide a battery packaging material in which curling after molding is effectively suppressed.
  • a metal layer having a thickness of 40 ⁇ m or less is used. Nevertheless, by setting the thickness of the base material layer to 15 ⁇ m or more and 30 ⁇ m or less, it not only has excellent insulating properties, but also becomes a battery packaging material with excellent moldability. I found.
  • the present inventors comprise a laminate comprising at least a base material layer containing polyester, a metal layer, and a heat-fusible resin layer in this order, and the base material layer having a length of 100 mm ⁇ a width of 15 mm Is a tensile force of 50 mm / min at 25 ° C., the displacement when a tensile stress of 15 MPa is applied is 5% or less, and the laminate having a length of 100 mm ⁇ a width of 15 mm is 25 ° C.
  • Battery packaging materials that are pulled at a pulling speed of 50 mm / min and have a displacement of 5% or less when a tensile stress of 40 MPa is applied have excellent moldability, and curling after molding is effectively suppressed. I found out that The present invention has been completed by further studies based on these findings.
  • Item 1 It consists of a laminate comprising at least a base material layer, a metal layer, and a heat-fusible resin layer in this order, The metal layer has a thickness of 40 ⁇ m or less, The base material layer is made of polyester, A battery packaging material, wherein the base material layer has a thickness of 15 ⁇ m or more and 30 ⁇ m or less.
  • Item 2. Item 2. The battery packaging material according to Item 1, wherein the laminate has a thickness of 140 ⁇ m or less.
  • Item 3. Item 3. The battery packaging material according to Item 1 or 2, wherein the base material layer is composed of one layer formed of polyester.
  • the battery packaging material according to Item 1 or 2 wherein the base material layer is composed of a plurality of layers formed of polyester.
  • Item 5. The battery packaging material according to any one of Items 1 to 4, further comprising an acid-resistant film layer on at least one surface of the metal layer.
  • Item 6. Item 6. The battery packaging material according to any one of Items 1 to 5, wherein the metal layer is an aluminum foil.
  • Comprising a step of obtaining a laminate comprising at least a base material layer, a metal layer, and a heat-fusible resin layer in this order;
  • the metal layer one having a thickness of 40 ⁇ m or less,
  • the base material layer is made of polyester and has a thickness of 15 ⁇ m to 30 ⁇ m.
  • At least a base material layer containing polyester, a metal layer, and a laminate comprising a heat-fusible resin layer in this order The substrate layer having a length of 100 mm and a width of 15 mm is pulled at a tensile speed of 50 mm / min at 25 ° C., and the displacement when a tensile stress of 15 MPa is applied is 5% or less,
  • the laminate having a length of 100 mm and a width of 15 mm is a battery packaging material having a displacement of 5% or less when a tensile stress of 40 MPa is applied at 25 ° C. at a tensile rate of 50 mm / min.
  • Item 9 A battery, wherein a battery element comprising at least a positive electrode, a negative electrode, and an electrolyte is accommodated in a package formed of the battery packaging material according to any one of Items 1 to 8.
  • the metal layer has a thickness of 40 ⁇ m or less.
  • the metal layer has a thickness of 40 ⁇ m or less.
  • the battery packaging material of the first aspect of the present invention comprises a laminate comprising at least a base material layer, a metal layer, and a heat-fusible resin layer in this order, and the thickness of the metal layer is 40 ⁇ m or less.
  • the material layer is formed of polyester, and the thickness of the base material layer is 15 ⁇ m or more and 30 ⁇ m or less. Since the battery packaging material according to the first aspect of the present invention has such a configuration, it has not only excellent insulating properties but also excellent moldability.
  • the battery packaging material according to the second aspect of the present invention comprises a laminate comprising at least a base material layer containing polyester, a metal layer, and a heat-fusible resin layer in this order, and has a length of 100 mm ⁇
  • the base material layer having a width of 15 mm is pulled at a tensile speed of 50 mm / min at 25 ° C., and the displacement when a tensile stress of 15 MPa is applied is 5% or less, and the laminate is 100 mm long ⁇ 15 mm wide.
  • the body is characterized by being pulled at a tensile rate of 50 mm / min at 25 ° C. and having a displacement of 5% or less when a tensile stress of 40 MPa is applied. Since the battery packaging material according to the second aspect of the present invention has such a configuration, the battery packaging material has excellent moldability, and curling after molding is effectively suppressed.
  • the battery packaging material of the present invention will be described in detail.
  • the indication of “to” indicating a numerical range indicates that the numerical value is greater than or equal to the numerical value attached to the left side thereof and less than or equal to the numerical value attached to the right side thereof.
  • the notation "" means X or more and Y or less.
  • the battery packaging material is composed of a laminate including at least a base material layer 1, a metal layer 3, and a heat-fusible resin layer 4 in this order.
  • the base material layer 1 is the outermost layer
  • the heat-fusible resin layer 4 is the innermost layer. That is, at the time of battery assembly, the heat-fusible resin layers 4 positioned at the periphery of the battery element are thermally welded to seal the battery element, thereby sealing the battery element.
  • the battery packaging material of the present invention is provided with an adhesive layer 2 between the base material layer 1 and the metal layer 3 as necessary for the purpose of enhancing the adhesion between them. May be. Further, as shown in FIG. 3, the battery packaging material of the present invention is provided with an adhesive layer 5 between the metal layer 3 and the heat-fusible resin layer 4 for the purpose of enhancing the adhesiveness as required. May be provided.
  • the thickness of the laminate constituting the battery packaging material of the present invention is not particularly limited, but is preferably 150 ⁇ m or less from the viewpoint of effectively suppressing a decrease in moldability and insulation while reducing the thickness. More preferably, the thickness is about 110 ⁇ m to 145 ⁇ m. Even when the thickness of the laminate constituting the battery packaging material of the present invention is very thin, for example, 150 ⁇ m or less, according to the first aspect of the present invention, the occurrence of pinholes and the like due to molding is effectively suppressed. In addition, it is possible to effectively suppress a decrease in insulation. Moreover, according to the 2nd aspect of this invention, generation
  • the laminate constituting the battery packaging material according to the second aspect of the present invention has a length of 100 mm ⁇ width of 15 mm, and is pulled at a tensile rate of 50 mm / min at 25 ° C.
  • the displacement when stress is applied is 5% or less.
  • the displacement is preferably about 2% to 4%.
  • each layer forming the battery packaging material [base material layer 1]
  • the base material layer 1 is a layer forming the outermost layer side.
  • the base material layer 1 is made of polyester.
  • the base layer 1 is made of polyester, and the thickness of the base layer 1 is in the range of 15 ⁇ m to 30 ⁇ m. 3, pinholes and cracks are effectively prevented from being generated, and further, the insulation is dramatically improved as compared with the case of using nylon or the like.
  • the battery packaging material is thinned, the moldability is lowered, and conventionally, it has not been considered to use a resin having poor moldability, such as polyester, alone for the base material layer. Therefore, it is surprising that by setting the thickness of the base material layer 1 made of polyester in the above specific range, it becomes a battery packaging material excellent not only in insulation but also in moldability. It was.
  • the details of the mechanism by which excellent moldability is exhibited despite the use of polyester is not clear, but can be considered as follows, for example. That is, in the present invention, when the thickness of the base material layer 1 formed of polyester is set within the specific range, the rapid extension of the metal layer 3 at the time of molding is appropriately controlled by the base material layer 1. As a result, it is considered that the occurrence of pinholes or the like in the metal layer 3 is suppressed.
  • polyester examples include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, polycarbonate, copolymerized polyester mainly composed of ethylene terephthalate, butylene terephthalate as a repeating unit.
  • examples thereof include a copolymer polyester mainly used.
  • the copolymer polyester mainly composed of ethylene terephthalate is a copolymer polyester that polymerizes with ethylene isophthalate mainly composed of ethylene terephthalate (hereinafter, polyethylene (terephthalate / isophthalate)).
  • polyethylene terephthalate / isophthalate
  • polyethylene terephthalate / adipate
  • polyethylene terephthalate / sodium sulfoisophthalate
  • polyethylene terephthalate / sodium isophthalate
  • polyethylene terephthalate / phenyl-dicarboxylate
  • polyethylene terephthalate / decanedicarboxylate
  • a copolymer polyester mainly composed of butylene terephthalate as a repeating unit specifically, a copolymer polyester that polymerizes with butylene isophthalate having butylene terephthalate as a repeating unit (hereinafter referred to as polybutylene (terephthalate / isophthalate)).
  • polybutylene (terephthalate / adipate) polybutylene (terephthalate / sebacate), polybutylene (terephthalate / decanedicarboxylate), polybutylene naphthalate and the like.
  • These polyesters may be used individually by 1 type, and may be used in combination of 2 or more type.
  • polyethylene terephthalate has an advantage that it is excellent in resistance to electrolytic solution and hardly causes whitening or the like due to adhesion of the electrolytic solution, and is preferably used as a material for forming the base material layer 1.
  • the thickness of the base material layer 1 is not particularly limited as long as it is in the range of 15 ⁇ m to 30 ⁇ m. However, the thickness of the battery packaging material is further reduced, and excellent insulation and excellent moldability are achieved. From the viewpoint of securing, more preferably about 20 ⁇ m to 25 ⁇ m. As will be described later, when the base material layer 1 is composed of a plurality of layers and each layer is adhered by an adhesive component such as an adhesive, the thickness of the adhesive component is 1 of the base material layer. Not included in thickness. This is because the adhesive component does not substantially contribute to the improvement of the insulation and moldability of the battery packaging material.
  • the base material layer 1 may be composed of a single layer formed of polyester, or may be composed of a plurality of layers formed of polyester. When the base material layer 1 is composed of a plurality of layers, it is preferably composed of two layers formed of polyester.
  • the base material layer 1 can be preferably composed of a polyester film, particularly preferably a polyethylene terephthalate film.
  • a polyester film particularly preferably a polyethylene terephthalate film.
  • the layers may be laminated via an adhesive component such as an adhesive or an adhesive resin, and the type and amount of the adhesive component used. Is the same as in the case of the adhesive layer 2 described later.
  • the method for laminating two or more polyester films is not particularly limited, and a known method can be employed. Examples thereof include a dry laminating method and a sandwich laminating method, and a dry laminating method is preferable. When laminating by the dry laminating method, it is preferable to use a urethane-based adhesive as the adhesive layer. At this time, the thickness of the adhesive layer is, for example, about 2 ⁇ m to 5 ⁇ m.
  • the substrate layer 1 when the base material layer 1 has a length of 100 mm ⁇ a width of 15 mm, the substrate layer 1 is pulled at a tensile speed of 50 mm / min at 25 ° C., and the displacement when a tensile stress of 15 MPa is applied. 5% or less.
  • the displacement is preferably about 2% to 4%.
  • the thickness of the base material layer 1 is, for example, about 10 ⁇ m to 50 ⁇ m, preferably about 12 ⁇ m to 30 ⁇ m.
  • the base material layer 1 may have low friction in order to improve moldability.
  • the friction coefficient of the surface is not particularly limited, but for example, 1.0 or less can be mentioned.
  • mat treatment, formation of a thin film layer of a lubricant, a combination thereof, and the like can be given.
  • a matting agent is added to the base material layer 1 in advance to form irregularities on the surface, a transfer method by heating or pressurizing with an embossing roll, a surface is mechanically dry or wet blasting, or a file. There is a way to troll.
  • the matting agent include fine particles having a particle size of about 0.5 nm to 5 ⁇ m.
  • the material of the matting agent is not particularly limited, and examples thereof include metals, metal oxides, inorganic substances, and organic substances.
  • the shape of the matting agent is not particularly limited, and examples thereof include a spherical shape, a fiber shape, a plate shape, an indeterminate shape, and a balloon shape.
  • the matting agent examples include talc, silica, graphite, kaolin, montmorilloid, montmorillonite, synthetic mica, hydrotalcite, silica gel, zeolite, aluminum hydroxide, magnesium hydroxide, zinc oxide, magnesium oxide, and aluminum oxide.
  • matting agents may be used individually by 1 type, and may be used in combination of 2 or more type.
  • these matting agents silica, barium sulfate, and titanium oxide are preferable from the viewpoint of dispersion stability and cost.
  • the matting agent may be subjected to various surface treatments such as insulation treatment and high dispersibility treatment on the surface.
  • the thin film layer of the lubricant can be formed by depositing the lubricant on the surface of the base material layer 1 by bleeding out to form a thin layer, or by laminating the lubricant on the base material layer 1.
  • the lubricant is not particularly limited.
  • amide-based lubricant, metal soap, hydrophilic silicone, silicone grafted acrylic, silicone grafted epoxy, silicone grafted polyether, silicone grafted polyester as described below. Block type silicone acrylic copolymer, polyglycerol-modified silicone, paraffin and the like.
  • These lubricants may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the adhesive layer 2 is a layer provided between the base material layer 1 and the metal layer 3 in order to firmly bond them.
  • the adhesive layer 2 is formed of an adhesive capable of bonding the base material layer 1 and the metal layer 3 together.
  • the adhesive used for forming the adhesive layer 2 may be a two-component curable adhesive or a one-component curable adhesive.
  • the bonding mechanism of the adhesive used for forming the adhesive layer 2 is not particularly limited, and may be any of a chemical reaction type, a solvent volatilization type, a heat melting type, a hot pressure type, and the like.
  • adhesive components that can be used to form the adhesive layer 2 include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, polycarbonate, and copolyester; Polyether adhesive; Polyurethane adhesive; Epoxy resin; Phenol resin resin; Polyamide resin such as nylon 6, nylon 66, nylon 12, copolymer polyamide; polyolefin, carboxylic acid modified polyolefin, metal modified polyolefin, etc.
  • Polyolefin resins polyvinyl acetate resins, cellulose adhesives, (meth) acrylic resins, polyimide resins, urea resins, melamine resins and other amino resins, chloroprene rubber, nitrile rubber, - Len rubbers such as butadiene rubber, silicone-based resins.
  • These adhesive components may be used individually by 1 type, and may be used in combination of 2 or more type. Among these adhesive components, a polyurethane adhesive is preferable.
  • the thickness of the adhesive layer 2 is not particularly limited as long as it functions as an adhesive layer.
  • the thickness is about 1 ⁇ m to 10 ⁇ m, preferably about 2 ⁇ m to 5 ⁇ m.
  • the metal layer 3 is a layer that functions as a barrier layer for preventing water vapor, oxygen, light, and the like from entering the battery, in addition to improving the strength of the battery packaging material.
  • Specific examples of the metal constituting the metal layer 3 include aluminum, stainless steel, and titanium, and preferably aluminum.
  • the metal layer 3 can be formed by metal foil, metal vapor deposition, or the like, preferably by metal foil, and more preferably by aluminum foil.
  • annealed aluminum JIS H4160 A8021H-O, JIS H4160 A8079H-O, JIS H4000: It is more preferable to use soft aluminum foil such as 2014 A8021P-O, JIS H4000: 2014 A8079P-O).
  • the thickness of the metal layer 3 is 40 ⁇ m or less. Thereby, in the battery packaging material of this invention, it can be set as a thin thing. From the viewpoint of achieving both formability and insulation while further reducing the thickness of the battery packaging material, the thickness of the metal layer 3 is more preferably 35 ⁇ m or less, and even more preferably about 10 ⁇ m to 35 ⁇ m. On the other hand, in the battery packaging material of the second aspect of the present invention, the thickness of the metal layer 3 is not limited to 40 ⁇ m or less.
  • the thickness of the metal layer 3 is not particularly limited as long as it functions as a barrier layer such as water vapor, but is, for example, about 10 ⁇ m to 50 ⁇ m, preferably about 10 ⁇ m to 40 ⁇ m. it can.
  • the metal layer 3 is preferably provided with an acid-resistant film layer formed by chemical conversion treatment on at least one surface, preferably both surfaces, for the purpose of stabilizing adhesion, preventing dissolution and corrosion.
  • the chemical conversion treatment refers to a treatment for forming an acid-resistant film on the surface of the metal layer.
  • chromic acid compounds such as chromium nitrate, chromium fluoride, chromium sulfate, chromium acetate, chromium oxalate, chromium biphosphate, chromic acetyl acetate, chromium chloride, potassium sulfate chromium, etc.
  • X represents a hydrogen atom, a hydroxyl group, an alkyl group, a hydroxyalkyl group, an allyl group or a benzyl group.
  • R 1 and R 2 are the same or different and each represents a hydroxyl group, an alkyl group, or a hydroxyalkyl group.
  • examples of the alkyl group represented by X, R 1 and R 2 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, Examples thereof include a linear or branched alkyl group having 1 to 4 carbon atoms such as a tert-butyl group.
  • Examples of the hydroxyalkyl group represented by X, R 1 and R 2 include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, 3- C1-C4 straight or branched chain in which one hydroxy group such as hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group is substituted
  • An alkyl group is mentioned.
  • the alkyl group and hydroxyalkyl group represented by X, R 1 and R 2 may be the same or different.
  • X is preferably a hydrogen atom, a hydroxyl group or a hydroxyalkyl group.
  • the number average molecular weight of the aminated phenol polymer having a repeating unit represented by the general formulas (1) to (4) is preferably, for example, 500 to 1,000,000, more preferably about 1,000 to 20,000. preferable.
  • a metal oxide such as aluminum oxide, titanium oxide, cerium oxide, tin oxide, or barium sulfate fine particles dispersed in phosphoric acid is coated.
  • a method of forming a corrosion-resistant treatment layer on the surface of the metal layer 3 by performing a baking treatment at 150 ° C. or higher can be mentioned.
  • a resin layer obtained by crosslinking a cationic polymer with a crosslinking agent may be further formed on the corrosion-resistant treatment layer.
  • examples of the cationic polymer include polyethyleneimine, an ionic polymer complex composed of a polymer having polyethyleneimine and a carboxylic acid, a primary amine graft acrylic resin obtained by graft polymerization of a primary amine on an acrylic main skeleton, and polyallylamine. Or the derivative, aminophenol, etc. are mentioned.
  • these cationic polymers only one type may be used, or two or more types may be used in combination.
  • examples of the crosslinking agent include a compound having at least one functional group selected from the group consisting of an isocyanate group, a glycidyl group, a carboxyl group, and an oxazoline group, and a silane coupling agent. As these crosslinking agents, only one type may be used, or two or more types may be used in combination.
  • chemical conversion treatment only one type of chemical conversion treatment may be performed, or two or more types of chemical conversion processing may be performed in combination. Furthermore, these chemical conversion treatments may be carried out using one kind of compound alone, or may be carried out using a combination of two or more kinds of compounds.
  • chemical conversion treatments chromic acid chromate treatment, chromate treatment combining a chromic acid compound, a phosphoric acid compound, and an aminated phenol polymer are preferable.
  • the amount of the acid-resistant film formed on the surface of the metal layer 3 in the chemical conversion treatment is not particularly limited.
  • a chromic acid compound is present per 1 m 2 of the surface of the metal layer 3.
  • a solution containing a compound used for forming an acid-resistant film is applied to the surface of the metal layer by a bar coating method, a roll coating method, a gravure coating method, an immersion method, or the like, and then the temperature of the metal layer is 70. It is carried out by heating so as to reach about 200 ° C to 200 ° C.
  • the metal layer may be previously subjected to a degreasing treatment by an alkali dipping method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method, or the like. By performing the degreasing treatment in this way, it becomes possible to more efficiently perform the chemical conversion treatment on the surface of the metal layer.
  • the heat-fusible resin layer 4 corresponds to the innermost layer, and is a layer that heat-welds the heat-fusible resin layers together to seal the battery element when the battery is assembled.
  • the resin component used for the heat-fusible resin layer 4 is not particularly limited as long as it can be heat-welded, and examples thereof include polyolefin, cyclic polyolefin, carboxylic acid-modified polyolefin, and carboxylic acid-modified cyclic polyolefin. .
  • polystyrene resin examples include polyethylene such as low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene; homopolypropylene, polypropylene block copolymer (for example, block copolymer of propylene and ethylene), polypropylene And a random copolymer (eg, a random copolymer of propylene and ethylene); an ethylene-butene-propylene terpolymer; and the like.
  • polyethylene and polypropylene are preferable.
  • the cyclic polyolefin is a copolymer of an olefin and a cyclic monomer
  • examples of the olefin that is a constituent monomer of the cyclic polyolefin include ethylene, propylene, 4-methyl-1-pentene, styrene, butadiene, and isoprene. Is mentioned.
  • Examples of the cyclic monomer that is a constituent monomer of the cyclic polyolefin include cyclic alkenes such as norbornene; specifically, cyclic dienes such as cyclopentadiene, dicyclopentadiene, cyclohexadiene, and norbornadiene.
  • cyclic alkene is preferable, and norbornene is more preferable.
  • the carboxylic acid-modified polyolefin is a polymer modified by block polymerization or graft polymerization of the polyolefin with carboxylic acid.
  • Examples of the carboxylic acid used for modification include maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, itaconic anhydride and the like.
  • the carboxylic acid-modified cyclic polyolefin is obtained by copolymerizing a part of the monomer constituting the cyclic polyolefin in place of the ⁇ , ⁇ -unsaturated carboxylic acid or its anhydride, or by ⁇ , ⁇ with respect to the cyclic polyolefin.
  • the cyclic polyolefin to be modified with carboxylic acid is the same as described above.
  • the carboxylic acid used for modification is the same as that used for modification of the acid-modified cycloolefin copolymer.
  • carboxylic acid-modified polyolefin is preferable; carboxylic acid-modified polypropylene is more preferable.
  • the heat-fusible resin layer 4 may be formed of one kind of resin component alone or may be formed of a blend polymer in which two or more kinds of resin components are combined. Furthermore, the heat-fusible resin layer 4 may be formed of only one layer, but may be formed of two or more layers using the same or different resin components.
  • the heat-fusible resin layer 4 may contain a lubricant or the like as necessary.
  • the lubricant is not particularly limited, and a known slip agent can be used, and examples thereof include those exemplified for the base material layer 1 described above.
  • a slip agent may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the content of the slip agent in the heat-fusible resin layer 4 is not particularly limited, and is preferably 0.01% by mass to 0.2% by mass from the viewpoint of improving the moldability and insulation of the electronic packaging material. About 0.05% by mass to 0.15% by mass is preferable.
  • the thickness of the heat-fusible resin layer 4 can be selected as appropriate, but is about 10 ⁇ m to 100 ⁇ m, preferably about 15 ⁇ m to 50 ⁇ m.
  • the adhesive layer 5 is a layer provided between the metal layer 3 and the heat-fusible resin layer 4 as necessary in order to firmly bond them.
  • the adhesive layer 5 is formed of a resin capable of bonding the metal layer 3 and the heat-fusible resin layer 4.
  • the resin used for forming the adhesive layer 5 the adhesive mechanism, the kind of adhesive component, and the like can be the same as the adhesive exemplified in the adhesive layer 2.
  • polyolefin resins such as polyolefin, cyclic polyolefin, carboxylic acid-modified polyolefin, carboxylic acid-modified cyclic polyolefin exemplified in the above-mentioned heat-fusible resin layer 4 can also be used. .
  • the polyolefin is preferably a carboxylic acid-modified polyolefin, and particularly preferably a carboxylic acid-modified polypropylene.
  • the adhesive layer 5 is a cured resin composition containing an acid-modified polyolefin and a curing agent. It may be a thing.
  • Preferred examples of the acid-modified polyolefin include the same carboxylic acid-modified polyolefin and carboxylic acid-modified cyclic polyolefin exemplified in the heat-fusible resin layer 4.
  • the curing agent is not particularly limited as long as it can cure the acid-modified polyolefin.
  • the curing agent include an epoxy curing agent, a polyfunctional isocyanate curing agent, a carbodiimide curing agent, and an oxazoline curing agent.
  • the epoxy curing agent is not particularly limited as long as it is a compound having at least one epoxy group.
  • examples of the epoxy curing agent include epoxy resins such as bisphenol A diglycidyl ether, modified bisphenol A diglycidyl ether, novolac glycidyl ether, glycerin polyglycidyl ether, and polyglycerin polyglycidyl ether.
  • the polyfunctional isocyanate curing agent is not particularly limited as long as it is a compound having two or more isocyanate groups.
  • Specific examples of the polyfunctional isocyanate-based curing agent include isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), those obtained by polymerizing or nurating these, Examples thereof include mixtures and copolymers with other polymers.
  • the carbodiimide curing agent is not particularly limited as long as it is a compound having at least one carbodiimide group (—N ⁇ C ⁇ N—).
  • a polycarbodiimide compound having at least two carbodiimide groups is preferable.
  • the oxazoline-based curing agent is not particularly limited as long as it is a compound having an oxazoline skeleton.
  • Specific examples of the oxazoline-based curing agent include Epocros series manufactured by Nippon Shokubai Co., Ltd.
  • the curing agent may be composed of two or more kinds of compounds.
  • the content of the curing agent in the resin composition forming the adhesive layer 5 is preferably in the range of 0.1% by mass to 50% by mass, and more preferably in the range of 0.1% by mass to 30% by mass. Preferably, it is in the range of 0.1% by mass to 10% by mass.
  • the thickness of the adhesive layer 5 is not particularly limited as long as it functions as an adhesive layer. However, when the adhesive exemplified in the adhesive layer 2 is used, it is preferably 2 ⁇ m to 10 ⁇ m, more preferably 2 ⁇ m to 5 ⁇ m. Is mentioned. Further, when the resin exemplified in the heat-fusible resin layer 4 is used, it is preferably 2 ⁇ m to 50 ⁇ m, more preferably 10 ⁇ m to 40 ⁇ m. In the case of a cured product of an acid-modified polyolefin and a curing agent, the thickness is preferably 30 ⁇ m, more preferably 0.1 ⁇ m to 20 ⁇ m, still more preferably 0.5 ⁇ m to 5 ⁇ m. When the adhesive layer 5 is a cured product of a resin composition containing an acid-modified polyolefin and a curing agent, the adhesive layer 5 can be formed by applying the resin composition and curing it by heating or the like.
  • the base material layer 1 may be formed on the base material layer 1 as necessary (the metal layer of the base material layer 1). If necessary, a surface coating layer (not shown) may be provided on the side opposite to (3).
  • a surface coating layer is a layer located in the outermost layer when a battery is assembled.
  • the surface coating layer can be formed of, for example, polyvinylidene chloride, polyester resin, urethane resin, acrylic resin, epoxy resin, or the like. Of these, the surface coating layer is preferably formed of a two-component curable resin. Examples of the two-component curable resin that forms the surface coating layer include a two-component curable urethane resin, a two-component curable polyester resin, and a two-component curable epoxy resin. Moreover, you may mix
  • Examples of the matting agent include fine particles having a particle size of about 0.5 nm to 5 ⁇ m.
  • the material of the matting agent is not particularly limited, and examples thereof include metals, metal oxides, inorganic substances, and organic substances.
  • the shape of the matting agent is not particularly limited, and examples thereof include a spherical shape, a fiber shape, a plate shape, an indeterminate shape, and a balloon shape.
  • Specific examples of the matting agent include talc, silica, graphite, kaolin, montmorilloid, montmorillonite, synthetic mica, hydrotalcite, silica gel, zeolite, aluminum hydroxide, magnesium hydroxide, zinc oxide, magnesium oxide, and aluminum oxide.
  • These matting agents may be used individually by 1 type, and may be used in combination of 2 or more type. Among these matting agents, silica, barium sulfate, and titanium oxide are preferable from the viewpoint of dispersion stability and cost.
  • the matting agent may be subjected to various surface treatments such as insulation treatment and high dispersibility treatment on the surface.
  • the method for forming the surface coating layer is not particularly limited, and examples thereof include a method of applying a two-component curable resin for forming the surface coating layer on one surface of the base material layer 1.
  • the matting agent may be added to the two-component curable resin, mixed, and then applied.
  • the thickness of the surface coating layer is not particularly limited as long as it exhibits the above function as the surface coating layer, and examples thereof include about 0.5 ⁇ m to 10 ⁇ m, preferably about 1 ⁇ m to 5 ⁇ m.
  • the production method of the battery packaging material according to the first aspect of the present invention is not particularly limited as long as a laminate in which layers of a predetermined composition are laminated is obtained.
  • a step of obtaining a laminate comprising the layer 1, the metal layer 3, and the heat-fusible resin layer 4 in this order.
  • the metal layer 3 having a thickness of 40 ⁇ m or less is used, and the base layer 1 is made of polyester. And having a thickness of 15 ⁇ m to 30 ⁇ m.
  • the method for producing the battery packaging material according to the second aspect of the present invention is not particularly limited as long as a laminated body obtained by laminating each layer having a predetermined composition is obtained.
  • the base material layer 1 the base material layer having a length of 100 mm and a width of 15 mm is tensioned at 25 ° C.
  • the tensile force is 50 mm / min and the displacement when a tensile stress of 15 MPa is applied is 5% or less, and the resulting laminate has a length of 100 mm ⁇ width of 15 mm, the tensile speed at 25 ° C.
  • Tensile at 50 mm / min and the displacement when a tensile stress of 40 MPa is applied is 5% or less. That is, as the base material layer 1, by using the base material layer 1 described in the section of “2. Each layer forming the battery packaging material”, the layers are laminated to produce the battery packaging material of the present invention. be able to.
  • a laminate including the base material layer 1, the adhesive layer 2, and the metal layer 3 in this order (hereinafter may be referred to as “laminate A”) is formed.
  • the layered product A is formed by applying an adhesive used for forming the adhesive layer 2 on the base layer 1 or the metal layer 3 whose surface is subjected to chemical conversion treatment, if necessary, a gravure coating method, After applying and drying by an application method such as a roll coating method, the metal layer 3 or the base material layer 1 can be laminated and the adhesive layer 2 can be cured by a dry laminating method.
  • the heat-fusible resin layer 4 is laminated on the metal layer 3 of the laminate A.
  • the resin component constituting the heat-fusible resin layer 4 is applied to the metal layer 3 of the laminate A by a gravure coating method or a roll coating method. What is necessary is just to apply
  • the adhesive layer 5 is provided between the metal layer 3 and the heat-fusible resin layer 4, for example, (1) the adhesive layer 5 and the heat-fusible resin layer on the metal layer 3 of the laminate A 4 by co-extrusion (coextrusion lamination method), (2) Separately, a laminated body in which the adhesive layer 5 and the heat-fusible resin layer 4 are laminated is formed, and this is formed into a metal layer of the laminated body A (3) Extruding the adhesive for forming the adhesive layer 5 on the metal layer 3 of the laminate A, or drying and baking at a high temperature after solution coating.
  • the surface coating layer is laminated on the surface of the base material layer 1 opposite to the metal layer 3.
  • the surface coating layer can be formed, for example, by applying the above-described resin for forming the surface coating layer to the surface of the base material layer 1.
  • the order of the step of laminating the metal layer 3 on the surface of the base material layer 1 and the step of laminating the surface coating layer on the surface of the base material layer 1 are not particularly limited.
  • the metal layer 3 may be formed on the surface of the base material layer 1 opposite to the surface coating layer.
  • a laminate composed of the heat-fusible resin layer 4 is formed.
  • a hot roll contact type and a hot air type are further provided. You may use for near- or far-infrared type heat processing. Examples of such heat treatment conditions include 150 ° C. to 250 ° C. for 1 minute to 5 minutes.
  • each layer constituting the laminate improves or stabilizes film forming properties, lamination processing, suitability for final processing (pouching, embossing), etc., as necessary. Therefore, surface activation treatment such as corona treatment, blast treatment, oxidation treatment, ozone treatment may be performed.
  • the battery packaging material of the present invention is used as a packaging material for sealing and housing battery elements such as a positive electrode, a negative electrode, and an electrolyte.
  • a battery element including at least a positive electrode, a negative electrode, and an electrolyte is formed using the battery packaging material of the present invention, with the metal terminals connected to each of the positive electrode and the negative electrode protruding outward.
  • a flange portion region where the heat-fusible resin layers are in contact with each other
  • heat-sealing the heat-fusible resin layers of the flange portion to seal the battery
  • the battery packaging material of the present invention is used such that the sealant portion is on the inner side (surface in contact with the battery element).
  • the battery packaging material of the present invention may be used for either a primary battery or a secondary battery, but is preferably a secondary battery.
  • the type of secondary battery to which the battery packaging material of the present invention is applied is not particularly limited.
  • a lithium ion battery, a lithium ion polymer battery, a lead battery, a nickel / hydrogen battery, a nickel / cadmium battery , Nickel / iron livestock batteries, nickel / zinc livestock batteries, silver oxide / zinc livestock batteries, metal-air batteries, polyvalent cation batteries, capacitors, capacitors and the like are suitable applications for the battery packaging material of the present invention.
  • Example 1A-5A and Comparative Example 1A-6A Manufacture of battery packaging materials>
  • a metal layer made of an aluminum foil subjected to chemical conversion treatment on both surfaces was laminated by a dry laminating method. Specifically, a two-component urethane adhesive (a polyol compound and an aromatic isocyanate compound) was applied to one surface of an aluminum foil to form an adhesive layer (thickness 3 ⁇ m) on the metal layer. Subsequently, after laminating the adhesive layer and the base material layer on the metal layer, an aging treatment was carried out at 40 ° C. for 24 hours to prepare a base material layer / adhesive layer / metal layer laminate.
  • a two-component urethane adhesive a polyol compound and an aromatic isocyanate compound
  • the chemical conversion treatment of the aluminum foil used as the metal layer is performed by roll coating a treatment liquid composed of a phenol resin, a chromium fluoride compound, and phosphoric acid so that the coating amount of chromium is 10 mg / m 2 (dry weight).
  • the coating was performed on both surfaces of the aluminum foil by the method and baked for 20 seconds under the condition that the film temperature was 180 ° C. or higher.
  • a two-component urethane adhesive (a polyol compound and an aromatic isocyanate compound) was applied on the metal layer of the laminate to form an adhesive layer on the metal layer.
  • PET / PET has a two-layer structure in which a polyethylene terephthalate layer is bonded via an adhesive layer (two-component urethane adhesive (polyol compound and aromatic isocyanate compound, thickness 3 ⁇ m)).
  • a polyethylene terephthalate layer and a nylon layer are bonded via an adhesive layer (two-component urethane adhesive (polyol compound and aromatic isocyanate compound, thickness 3 ⁇ m) 2
  • an adhesive layer two-component urethane adhesive (polyol compound and aromatic isocyanate compound, thickness 3 ⁇ m) 2
  • the thickness of the base material layer does not include the thickness of the adhesive layer.
  • the thickness of the metal layer is 40 ⁇ m or less, and the thickness of the base material layer is in the range of 15 ⁇ m to 30 ⁇ m even though the base material layer is formed of PET. It can be seen that the battery packaging materials of Examples 1A to 5A are excellent in moldability and insulation. On the other hand, in Comparative Examples 1A to 6A, in which the thickness of the base material layer formed of PET is 9 ⁇ m to 12 ⁇ m, which is thinner than the examples, the moldability and the insulating properties are inferior to those of Examples 1A to 5A. .
  • Example 1B-6B and Comparative Example 1B-5B ⁇ Manufacture of battery packaging materials> Each base material layer in which the displacement due to pulling described later has the values shown in Table 1B was prepared. Next, on each base material layer, the metal layer which consists of aluminum foil which performed the chemical conversion treatment on both surfaces was laminated
  • a two-component urethane adhesive a polyol compound and an aromatic isocyanate compound
  • the chemical conversion treatment of the aluminum foil used as the metal layer is performed by roll coating a treatment liquid composed of a phenol resin, a chromium fluoride compound, and phosphoric acid so that the coating amount of chromium is 10 mg / m 2 (dry weight).
  • the coating was performed on both surfaces of the aluminum foil by the method and baked for 20 seconds under the condition that the film temperature was 180 ° C. or higher.
  • Carboxylic acid-modified polypropylene as the adhesive layer (located on the metal layer side) and random polypropylene film as the heat-fusible resin layer (innermost layer) are coextruded, and the adhesive layer / heat-fusible resin layer is placed on the metal layer.
  • Each battery packaging material was obtained by laminating.
  • the specific layer structure of the laminate is as shown in Table 1B.
  • PET / PET has a two-layer structure in which a polyethylene terephthalate layer is bonded via an adhesive layer (two-component urethane adhesive (polyol compound and aromatic isocyanate compound, thickness 3 ⁇ m)).
  • a polyethylene terephthalate layer and a nylon layer are bonded via an adhesive layer (two-component urethane adhesive (polyol compound and aromatic isocyanate compound, thickness 3 ⁇ m) 2
  • an adhesive layer two-component urethane adhesive (polyol compound and aromatic isocyanate compound, thickness 3 ⁇ m) 2
  • the thickness of the base material layer does not include the thickness of the adhesive layer.
  • Example 1B-5B and Comparative Example 1B-6B Each base material layer used in the battery packaging material of Example 1B-5B and Comparative Example 1B-6B was cut into a rectangle having a length of 100 mm and a width of 15 mm to obtain a test piece. Each test piece was pulled at a tensile rate of 50 mm / min at 25 ° C., and a tensile stress of 15 MPa was measured. An autograph (SHIMAZU AUTOGRAPH AG-X Plus) was used for pulling. The distance between chucks was 30 mm. The results are shown in Table 1B.
  • Example 1B-5B and Comparative Example 1B-6B were cut into rectangles each having a length of 100 mm and a width of 15 mm to obtain test pieces. Each test piece was pulled at a tensile rate of 50 mm / min at 25 ° C., and a tensile stress of 40 MPa was measured. An autograph (SHIMAZU AUTOGRAPH AG-X Plus) was used for pulling. The distance between chucks was 30 mm. The results are shown in Table 1B.
  • FIG. 8 is a graph showing the relationship between the tensile stress (MPa) and the displacement (%) for the test pieces prepared from the battery packaging materials of Examples 1B, 2B, and 6B and Comparative Examples 1B, 4B, and 5B. , 9.
  • Example 1B-6B and Comparative Example 1B-5B were cut to produce strips of length (z direction) 150 mm ⁇ width (x direction) 100 mm, which were used as test samples.
  • a straight mold consisting of a 30 mm x 50 mm rectangular male mold and a female mold with a clearance of 0.5 mm between the male mold and the female mold so that the heat-fusible resin layer 4 side is located on the male mold side.
  • the test sample was placed on the substrate, and the test sample was pressed with a presser pressure (surface pressure) of 0.1 MPa so as to have a molding depth of 6 mm, and cold-molded (drawn one-step molding). The details of the position where the molding is performed are as shown in FIG.
  • ONy is nylon and PET is polyethylene terephthalate.
  • PET / ONy is a two-layer laminate of a polyethylene terephthalate film and a nylon film, and ONy is located on the metal layer side.
  • Each layer of the two-layer laminate is bonded with 3 ⁇ m of a two-component urethane adhesive.
  • the thickness of the base material layer does not include the thickness of the adhesive.
  • ALM means aluminum alloy foil.
  • PP means random polypropylene and PPa means maleic anhydride-modified polypropylene.
  • the numerical value in parentheses means the thickness ( ⁇ m).
  • the adhesive layer (3 ⁇ m) when the base material layer is a two-layer laminate and the adhesive layer (3 ⁇ m) located between the base material layer and the metal layer Description is omitted.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Laminated Bodies (AREA)

Abstract

Le problème décrit par la présente invention est de fournir un matériau d'encapsulation destiné à des piles qui est excellent en termes d'aptitude au formage et de propriété d'isolation. La solution selon l'invention porte sur un matériau d'encapsulation destiné à des piles qui est constitué d'un stratifié comprenant une couche de base, une couche métallique, et une couche de résine pouvant être collée par fusion dans cet ordre, la couche métallique ayant une épaisseur inférieure ou égale à 40 µm, la couche de base étant constituée d'un polyester, et la couche de base ayant une épaisseur de 15 à 30 µm.
PCT/JP2016/060761 2015-03-31 2016-03-31 Matériau d'encapsulation pour pile, son procédé de production, et pile WO2016159278A1 (fr)

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JP7456378B2 (ja) 2018-03-27 2024-03-27 大日本印刷株式会社 電池用包装材料用ポリエチレンテレフタレートフィルム、電池用包装材料、電池用包装材料の製造方法及び電池

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