WO2020085464A1 - Matériau de conditionnement pour dispositif de stockage d'énergie, son procédé de production et dispositif de stockage d'énergie - Google Patents

Matériau de conditionnement pour dispositif de stockage d'énergie, son procédé de production et dispositif de stockage d'énergie Download PDF

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Publication number
WO2020085464A1
WO2020085464A1 PCT/JP2019/041799 JP2019041799W WO2020085464A1 WO 2020085464 A1 WO2020085464 A1 WO 2020085464A1 JP 2019041799 W JP2019041799 W JP 2019041799W WO 2020085464 A1 WO2020085464 A1 WO 2020085464A1
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Prior art keywords
heat
resin layer
fusible resin
layer
storage device
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PCT/JP2019/041799
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English (en)
Japanese (ja)
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大佑 安田
山下　孝典
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大日本印刷株式会社
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Priority to JP2020501397A priority Critical patent/JP7104137B2/ja
Publication of WO2020085464A1 publication Critical patent/WO2020085464A1/fr

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    • 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
    • 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 disclosure relates to an exterior material for an electricity storage device, a method for manufacturing the same, and an electricity storage device.
  • the exterior material is an indispensable member for sealing the power storage device elements such as electrodes and electrolytes.
  • metal exterior materials have been often used as exterior materials for power storage devices.
  • the inventors of the present disclosure have made earnest studies to solve the above problems.
  • at least a base material layer, a barrier layer, and a heat-fusible resin layer is composed of a laminate provided in this order, the heat-fusible resin layer is composed of a single layer or multiple layers.
  • the heat-fusible resin layer includes at least one layer having a modulus of elasticity of 1300 MPa or more measured by a nanoindentation method with a pushing load of 100 ⁇ N from a cross section in the stacking direction of the laminate. It has been found that the exterior material for a vehicle can exhibit high insulating properties even when minute foreign matter is present in the heat-sealing portion of the heat-sealing resin layer.
  • At least a base material layer, a barrier layer, and a heat-fusible resin layer which is composed of a laminate provided in this order
  • the heat-fusible resin layer is composed of a single layer or multiple layers
  • the heat-fusible resin layer includes at least one layer having a modulus of elasticity of 1300 MPa or more measured by a nanoindentation method with a pushing load of 100 ⁇ N, which is measured from a cross section in the stacking direction of the laminate.
  • FIG. 3 is a schematic diagram showing an example of a cross-sectional structure of a power storage device exterior material of the present disclosure.
  • FIG. 3 is a schematic diagram showing an example of a cross-sectional structure of a power storage device exterior material of the present disclosure.
  • FIG. 3 is a schematic diagram showing an example of a cross-sectional structure of a power storage device exterior material of the present disclosure.
  • FIG. 3 is a schematic diagram showing an example of a cross-sectional structure of a power storage device exterior material of the present disclosure.
  • FIG. 3 is a schematic diagram showing an example of a cross-sectional structure of a power storage device exterior material of the present disclosure. It is a schematic diagram for demonstrating the measuring method of seal strength.
  • the heat-fusible resin layer 4 is composed of a single layer of the first heat-fusible resin layer 41, and the first heat-fusible resin layer 41 covers the surface of the laminate.
  • the illustrated stacking arrangement is illustrated.
  • the heat-fusible resin layer 4 is composed of a plurality of layers (two layers) of a first heat-fusible resin layer 41 and a second heat-fusible resin layer 42,
  • the 1st heat-fusible resin layer 41 has illustrated the laminated structure which comprises the surface of the laminated body.
  • the thickness of the laminate constituting the exterior material 10 for an electricity storage device is not particularly limited, but from the viewpoint of cost reduction, energy density improvement, etc., preferably about 180 ⁇ m or less, about 155 ⁇ m or less. From the viewpoint of maintaining the function of the outer covering material for an electricity storage device of protecting, it is preferably about 35 ⁇ m or more, about 45 ⁇ m or more, about 60 ⁇ m or more, and the preferable range is, for example, about 35 to 180 ⁇ m, about 35 to 155 ⁇ m. , About 45 to 180 ⁇ m, about 45 to 155 ⁇ m, about 60 to 180 ⁇ m, about 60 to 155 ⁇ m.
  • the material forming the base material layer 1 is not particularly limited as long as it has a function as a base material, that is, at least an insulating property.
  • the base material layer 1 can be formed by using, for example, a resin, and the resin may contain an additive described below.
  • the base material layer 1 may be, for example, a resin film made of resin, or may be formed by applying resin.
  • the resin film may be an unstretched film or a stretched film.
  • the stretched film include a uniaxially stretched film and a biaxially stretched film, and a biaxially stretched film is preferable.
  • the stretching method for forming the biaxially stretched film include a sequential biaxial stretching method, an inflation method and a simultaneous biaxial stretching method.
  • the method for applying the resin include a roll coating method, a gravure coating method and an extrusion coating method.
  • Examples of the resin forming the base material layer 1 include resins such as polyester, polyamide, polyolefin, epoxy resin, acrylic resin, fluororesin, polyurethane, silicon resin, and phenol resin, and modified products of these resins.
  • the resin forming the base material layer 1 may be a copolymer of these resins or a modified product of the copolymer. Further, it may be a mixture of these resins.
  • polyester examples include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, and copolyester.
  • copolyester examples include a copolyester having ethylene terephthalate as a main repeating unit.
  • the base material layer 1 may be a single layer or may be composed of two or more layers.
  • the base material layer 1 may be a laminate in which resin films are laminated with an adhesive or the like, or a resin is coextruded into two or more layers. It may be a laminate of the above resin films. Further, a resin film laminate obtained by coextruding a resin into two or more layers may be the unstretched base material layer 1 or may be uniaxially or biaxially stretched to form the base material layer 1.
  • a laminate of two or more resin films in the base material layer 1 include a laminate of a polyester film and a nylon film, a laminate of two or more nylon films, a laminate of two or more polyester films. And the like, and preferably a laminate of a stretched nylon film and a stretched polyester film, a laminate of two or more stretched nylon films, and a laminate of two or more stretched polyester films.
  • the base material layer 1 is a laminate of two resin films, a laminate of a polyester resin film and a polyester resin film, a laminate of a polyamide resin film and a polyamide resin film, or a polyester resin film and a polyamide resin film.
  • a laminated body is preferable, and a laminated body of a polyethylene terephthalate film and a polyethylene terephthalate film, a laminated body of a nylon film and a nylon film, or a laminated body of a polyethylene terephthalate film and a nylon film is more preferable.
  • the polyester resin does not easily discolor when an electrolytic solution adheres to the surface, when the base material layer 1 is a laminate of two or more resin films, the polyester resin film is It is preferably located in the outermost layer.
  • an anchor coat layer may be formed on the resin film and laminated.
  • the anchor coat layer may be the same as the adhesive exemplified in the adhesive layer 2 described later.
  • the thickness of the anchor coat layer is, for example, about 0.01 to 1.0 ⁇ m.
  • additives such as a lubricant, a flame retardant, an antiblocking agent, an antioxidant, a light stabilizer, a tackifier, and an antistatic agent are present on at least one of the surface and the inside of the base material layer 1. Good.
  • the additive only one kind may be used, or two or more kinds may be mixed and used.
  • saturated fatty acid bisamide examples include methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amide, ethylenebisstearic acid amide, ethylenebishydroxystearic acid amide, ethylenebisbehenic acid amide, and hexamethylenebisstearic acid amide.
  • saturated fatty acid bisamide examples include acid amide, hexamethylene bisbehenic acid amide, hexamethylene hydroxystearic acid amide, N, N′-distearyl adipic acid amide and N, N′-distearyl sebacic acid amide.
  • the unsaturated fatty acid bisamide include ethylene bisoleic acid amide, ethylene bis erucic acid amide, hexamethylene bis oleic acid amide, N, N'-dioleyl adipate amide, N, N'-dioleyl sebacic acid amide. And so on.
  • Specific examples of the fatty acid ester amide include stearoamide ethyl stearate.
  • specific examples of the aromatic bisamide include m-xylylenebisstearic acid amide, m-xylylenebishydroxystearic acid amide, N, N'-distearylisophthalic acid amide and the like.
  • the lubricant may be used alone or in combination of two or more.
  • the thickness of the base material layer 1 is not particularly limited as long as it can function as a base material, but is, for example, about 3 to 50 ⁇ m, preferably about 10 to 35 ⁇ m.
  • the thickness of the resin film forming each layer is, for example, 2 to 35 ⁇ m, preferably about 2 to 25 ⁇ m.
  • the adhesive layer 2 is formed of an adhesive that can bond the base material layer 1 and the barrier layer 3 together.
  • the adhesive used for forming the adhesive layer 2 is not limited, and may be any of a chemical reaction type, a solvent volatilization type, a heat melting type, a heat pressure type and the like. Further, it may be a two-component curing type adhesive (two-component adhesive), a one-component curing type adhesive (one-component adhesive), or a resin that does not undergo a curing reaction.
  • the adhesive layer 2 may be a single layer or a multilayer.
  • the adhesive component contained in the adhesive include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, polyesters such as copolyester; polyether; polyurethane; epoxy resin; Phenol resin; nylon 6, nylon 66, nylon 12, polyamide such as copolyamide; polyolefin resin such as polyolefin, cyclic polyolefin, acid modified polyolefin, acid modified cyclic polyolefin; polyvinyl acetate; cellulose; (meth) acrylic resin; Polyimide; Polycarbonate; Amino resin such as urea resin and melamine resin; Rubber such as chloroprene rubber, nitrile rubber and styrene-butadiene rubber; Silicone resin, etc.
  • adhesive components may be used alone or in combination of two or more.
  • a polyurethane adhesive is preferable.
  • the resin serving as the adhesive component may be used in combination with an appropriate curing agent to enhance the adhesive strength.
  • the curing agent is selected from polyisocyanates, polyfunctional epoxy resins, oxazoline group-containing polymers, polyamine resins, acid anhydrides, etc. depending on the functional groups of the adhesive component.
  • the polyurethane adhesive examples include a polyurethane adhesive containing a base compound containing a polyol compound and a curing agent containing an isocyanate compound.
  • a polyurethane adhesive containing a base compound containing a polyol compound and a curing agent containing an isocyanate compound.
  • a two-component curing type polyurethane adhesive containing a polyol such as a polyester polyol, a polyether polyol and an acrylic polyol as a main component and an aromatic or aliphatic polyisocyanate as a curing agent.
  • the polyol compound it is preferable to use a polyester polyol having a hydroxyl group at the side chain in addition to the hydroxyl group at the terminal of the repeating unit. Since the adhesive layer 2 is made of a polyurethane adhesive, excellent resistance to the electrolytic solution is imparted to the exterior material for an electricity storage device, and the base layer 1 is prevented from peeling off even when the electrolytic solution adhere
  • the adhesive layer 2 may contain other components as long as it does not impair the adhesiveness, and may contain a colorant, a thermoplastic elastomer, a tackifier, a filler, or the like. Since the adhesive layer 2 contains the coloring agent, the exterior material for the electricity storage device can be colored. Known colorants such as pigments and dyes can be used as the colorant. Moreover, only one type of colorant may be used, or two or more types may be mixed and used.
  • colorants for example, carbon black is preferable in order to make the exterior material of the electricity storage device have a black appearance.
  • the average particle diameter of the pigment is not particularly limited and may be, for example, about 0.05 to 5 ⁇ m, preferably about 0.08 to 2 ⁇ m.
  • the average particle size of the pigment is the median size measured by a laser diffraction / scattering particle size distribution measuring device.
  • the content of the pigment in the adhesive layer 2 is not particularly limited as long as the exterior material for the electricity storage device is colored, and is, for example, about 5 to 60% by mass, preferably 10 to 40% by mass.
  • the thickness of the adhesive layer 2 is not particularly limited as long as the base material layer 1 and the barrier layer 3 can be adhered, but examples thereof include about 1 ⁇ m or more and about 2 ⁇ m or more, and about 10 ⁇ m or less and about 5 ⁇ m or less.
  • the preferable range is about 1 to 10 ⁇ m, about 1 to 5 ⁇ m, about 2 to 10 ⁇ m, about 2 to 5 ⁇ m.
  • the colored layer is a layer provided between the base material layer 1 and the barrier layer 3 as needed (not shown).
  • a coloring layer may be provided between the base material layer 1 and the adhesive layer 2 and between the adhesive layer 2 and the barrier layer 3. Further, a colored layer may be provided outside the base material layer 1. By providing the colored layer, the exterior material for the electricity storage device can be colored.
  • the coloring layer can be formed, for example, by applying an ink containing a coloring agent to the surface of the base material layer 1, the surface of the adhesive layer 2, or the surface of the barrier layer 3.
  • a coloring agent such as pigments and dyes can be used as the colorant.
  • only one type of colorant may be used, or two or more types may be mixed and used.
  • coloring agent contained in the coloring layer are the same as those described in the section of [Adhesive layer 2].
  • the barrier layer 3 is a layer that suppresses at least entry of moisture.
  • the barrier layer 3 examples include a metal foil having a barrier property, a vapor deposition film, a resin layer, and the like.
  • the vapor deposition film examples include a metal vapor deposition film, an inorganic oxide vapor deposition film, a carbon-containing inorganic oxide vapor deposition film, and the like
  • the resin layer includes polyvinylidene chloride, polymers containing chlorotrifluoroethylene (CTFE) as a main component or tetra
  • CTFE chlorotrifluoroethylene
  • TFE fluoroethylene
  • fluorine-containing resins such as polymers having a fluoroalkyl unit as a main component
  • ethylene vinyl alcohol copolymers examples include ethylene vinyl alcohol copolymers.
  • barrier layer 3 a resin film provided with at least one of the vapor deposition film and the resin layer may be used.
  • a plurality of barrier layers 3 may be provided.
  • the barrier layer 3 preferably includes a layer made of a metal material. Specific examples of the metal material forming the barrier layer 3 include aluminum alloys, stainless steels, titanium steels, and steel plates. When used as metal foils, at least one of aluminum alloy foils and stainless steel foils is included. It is preferable.
  • the aluminum alloy foil is, from the viewpoint of improving the formability of the exterior material for an electricity storage device, for example, more preferably a soft aluminum alloy foil composed of an annealed aluminum alloy or the like, and from the viewpoint of further improving the formability. Therefore, the aluminum alloy foil containing iron is preferable.
  • the content of iron is preferably 0.1 to 9.0 mass%, and more preferably 0.5 to 2.0 mass%. When the content of iron is 0.1% by mass or more, it is possible to obtain the exterior material for an electricity storage device having more excellent moldability. When the content of iron is 9.0% by mass or less, a more flexible outer packaging material for an electricity storage device can be obtained.
  • the soft aluminum alloy foil for example, an aluminum alloy having a composition specified by JIS H4160: 1994 A8021H-O, JIS H4160: 1994 A8079H-O, JIS H4000: 2014 A8021P-O, or JIS H4000: 2014 A8079P-O.
  • Foil can be mentioned. If necessary, silicon, magnesium, copper, manganese, etc. may be added.
  • the softening can be performed by annealing treatment or the like.
  • examples of stainless steel foils include austenite-based, ferrite-based, austenite-ferrite-based, martensite-based, and precipitation-hardening-based stainless steel foils. Further, from the viewpoint of providing an exterior material for an electricity storage device having excellent moldability, the stainless steel foil is preferably made of austenitic stainless steel.
  • austenitic stainless steel forming the stainless steel foil examples include SUS304, SUS301, and SUS316L, and among these, SUS304 is particularly preferable.
  • the thickness of the barrier layer 3 may be at least a function as a barrier layer that suppresses the infiltration of moisture, and is, for example, about 9 to 200 ⁇ m.
  • the thickness of the barrier layer 3 is, for example, preferably about 85 ⁇ m or less, more preferably about 50 ⁇ m or less, further preferably about 40 ⁇ m or less, particularly preferably about 35 ⁇ m or less, and preferably about 10 ⁇ m or more, more preferably
  • the thickness may be about 20 ⁇ m or more, more preferably about 25 ⁇ m or more.
  • the preferable range of the thickness is about 10 to 85 ⁇ m, about 10 to 50 ⁇ m, about 10 to 40 ⁇ m, about 10 to 35 ⁇ m, about 20 to 85 ⁇ m, 20 to 50 ⁇ m.
  • the barrier layer 3 is composed of an aluminum alloy foil, the above range is particularly preferable.
  • the thickness of the stainless steel foil is preferably about 60 ⁇ m or less, more preferably about 50 ⁇ m or less, further preferably about 40 ⁇ m or less, and further preferably about 30 ⁇ m or less, particularly preferably about 25 ⁇ m or less, preferably about 10 ⁇ m or more, more preferably about 15 ⁇ m or more, and a preferable thickness range is about 10 to 60 ⁇ m, about 10 to 50 ⁇ m, about 10 to For example, about 40 ⁇ m, about 10 to 30 ⁇ m, about 10 to 25 ⁇ m, about 15 to 60 ⁇ m, about 15 to 50 ⁇ m, about 15 to 40 ⁇ m, about 15 to 30 ⁇ m, about 15 to 25 ⁇ m.
  • the barrier layer 3 when the barrier layer 3 is a metal foil, it is preferable to provide a corrosion resistant film on at least the surface opposite to the base material layer in order to prevent dissolution and corrosion.
  • the barrier layer 3 may have a corrosion resistant coating on both sides.
  • the corrosion-resistant film means, for example, hot water conversion treatment such as boehmite treatment, chemical conversion treatment, anodization treatment, plating treatment with nickel or chromium, and corrosion prevention treatment for coating a coating agent on the surface of the barrier layer.
  • a barrier layer having corrosion resistance for example, acid resistance, alkali resistance, etc.
  • the corrosion-resistant coating specifically means a coating that improves the acid resistance of the barrier layer (acid-resistant coating), a coating that improves the alkali resistance of the barrier layer (alkali-resistant coating), and the like.
  • the treatment for forming the corrosion resistant film one type may be performed, or two or more types may be combined and performed. Further, not only one layer but also multiple layers can be formed. Further, among these treatments, the hydrothermal conversion treatment and the anodizing treatment are treatments for dissolving the surface of the metal foil with a treatment agent to form a metal compound having excellent corrosion resistance. Note that these processes may be included in the definition of the chemical conversion process.
  • the barrier layer 3 when the barrier layer 3 has a corrosion resistant film, the barrier layer 3 includes the corrosion resistant film.
  • the corrosion-resistant coating is used to prevent delamination between the barrier layer (for example, aluminum alloy foil) and the base material layer during the molding of the exterior material for the electricity storage device, and to prevent hydrogen fluoride generated by the reaction between the electrolyte and water.
  • the barrier layer for example, aluminum alloy foil
  • Dissolution and corrosion of the surface of the barrier layer especially when the barrier layer is an aluminum alloy foil, prevents the aluminum oxide present on the surface of the barrier layer from dissolving and corroding, and the adhesiveness (wettability) of the surface of the barrier layer
  • the effect of preventing delamination between the base material layer and the barrier layer during heat sealing, and preventing delamination between the base material layer and the barrier layer during molding are examples of the barrier layer and the base material layer during heat sealing.
  • Various types of corrosion-resistant films formed by chemical conversion treatment are known, and are mainly at least one of phosphates, chromates, fluorides, triazine thiol compounds, and rare earth oxides. And a corrosion resistant film containing the like.
  • Examples of the chemical conversion treatment using a phosphate or chromate include chromate chromate treatment, chromate phosphoric acid treatment, phosphoric acid-chromate treatment, chromate treatment, and the like.
  • Examples of the compound include chromium nitrate, chromium fluoride, chromium sulfate, chromium acetate, chromium oxalate, chromium diphosphate, acetyl acetate chromate, chromium chloride, potassium chromium sulfate and the like.
  • examples of the phosphorus compound used for these treatments include sodium phosphate, potassium phosphate, ammonium phosphate, polyphosphoric acid, and the like.
  • examples of the chromate treatment include etching chromate treatment, electrolytic chromate treatment, coating type chromate treatment and the like, and coating type chromate treatment is preferable.
  • the inner layer side of the barrier layer eg, aluminum alloy foil
  • a well-known method such as an alkali dipping method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method, and an acid activation method.
  • a degreasing treatment is performed by a treatment method, and thereafter, a phosphate metal such as Cr (chromium) phosphate, Ti (titanium) phosphate, Zr (zirconium) phosphate, Zn (zinc) phosphate, etc.
  • a treatment liquid such as water, alcohol solvents, hydrocarbon solvents, ketone solvents, ester solvents, ether solvents can be used, and water is preferable.
  • Examples of the resin component used at this time include polymers such as phenol resins and acrylic resins, and aminated phenol polymers having repeating units represented by the following general formulas (1) to (4) are used. Examples include the chromate treatment used. In the aminated phenol polymer, the repeating units represented by the following general formulas (1) to (4) may be contained alone or in any combination of two or more. Good.
  • Acrylic resin must be polyacrylic acid, acrylic acid methacrylic acid ester copolymer, acrylic acid maleic acid copolymer, acrylic acid styrene copolymer, or their derivatives such as sodium salt, ammonium salt, amine salt, etc. Is preferred.
  • polyacrylic acid derivatives such as ammonium salt, sodium salt, or amine salt of polyacrylic acid.
  • polyacrylic acid means a polymer of acrylic acid.
  • the acrylic resin is also preferably a copolymer of acrylic acid and a dicarboxylic acid or a dicarboxylic acid anhydride, an ammonium salt of a copolymer of acrylic acid and a dicarboxylic acid or a dicarboxylic acid anhydride, a sodium salt, Alternatively, it is also preferably an amine salt. Only one type of acrylic resin may be used, or two or more types may be mixed and used.
  • X represents a hydrogen atom, a hydroxy 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 hydroxy 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 linear or branched alkyl groups having 1 to 4 carbon atoms such as tert-butyl group.
  • examples of the hydroxyalkyl group represented by X, R 1 and R 2 include, for example, hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group and 3-hydroxypropyl group.
  • An alkyl group is mentioned.
  • the alkyl group and the hydroxyalkyl group represented by X, R 1 and R 2 may be the same or different.
  • X is preferably a hydrogen atom, a hydroxy group or a hydroxyalkyl group.
  • the number average molecular weight of the aminated phenol polymer having the repeating units represented by the general formulas (1) to (4) is, for example, preferably about 500 to 1,000,000, and more preferably about 1,000 to 20,000. More preferable.
  • the aminated phenol polymer is produced by, for example, polycondensing a phenol compound or a naphthol compound with formaldehyde to produce a polymer having a repeating unit represented by the general formula (1) or (3), and then formaldehyde. And an amine (R 1 R 2 NH) to introduce a functional group (—CH 2 NR 1 R 2 ) into the polymer obtained above.
  • the aminated phenol polymer is used alone or in combination of two or more.
  • the corrosion resistant film is formed by a coating type corrosion prevention treatment in which a coating agent containing at least one selected from the group consisting of rare earth element oxide sols, anionic polymers and cationic polymers is applied.
  • a thin film is used.
  • the coating agent may further contain phosphoric acid or phosphate, and a cross-linking agent that cross-links the polymer.
  • fine particles of rare earth element oxide for example, particles having an average particle diameter of 100 nm or less
  • the rare earth element oxide include cerium oxide, yttrium oxide, neodymium oxide, and lanthanum oxide, and cerium oxide is preferable from the viewpoint of further improving the adhesiveness.
  • the rare earth element oxides contained in the corrosion resistant coating may be used alone or in combination of two or more.
  • various solvents such as water, alcohol solvents, hydrocarbon solvents, ketone solvents, ester solvents, ether solvents can be used, and water is preferable.
  • the cationic polymer include polyethyleneimine, an ionic polymer complex composed of a polymer having polyethyleneimine and a carboxylic acid, a primary amine-grafted acrylic resin obtained by graft-polymerizing a primary amine on an acrylic main skeleton, polyallylamine or a derivative thereof. , Aminated phenol and the like are preferable.
  • the anionic polymer is preferably poly (meth) acrylic acid or a salt thereof, or a copolymer containing (meth) acrylic acid or a salt thereof as a main component.
  • the cross-linking agent is at least one selected from the group consisting of a compound having any one of an isocyanate group, a glycidyl group, a carboxyl group and an oxazoline group, and a silane coupling agent.
  • the phosphoric acid or phosphate is preferably condensed phosphoric acid or condensed phosphate.
  • a dispersion of fine particles of metal oxide such as aluminum oxide, titanium oxide, cerium oxide, and tin oxide or barium sulfate in phosphoric acid is applied to the surface of the barrier layer, Examples include those formed by performing a baking treatment at a temperature of not less than ° C.
  • the corrosion-resistant film may have a laminated structure in which at least one of a cationic polymer and an anionic polymer is further laminated, if necessary.
  • a cationic polymer and an anionic polymer include those mentioned above.
  • composition of the corrosion resistant film can be performed using, for example, time-of-flight secondary ion mass spectrometry.
  • the amount of the corrosion resistant film formed on the surface of the barrier layer 3 in the chemical conversion treatment is not particularly limited, but, for example, when the coating type chromate treatment is performed, the chromic acid compound per 1 m 2 of the surface of the barrier layer 3 is used.
  • the chromic acid compound per 1 m 2 of the surface of the barrier layer 3 is used.
  • the phosphorus compound is, for example, about 0.5 to 50 mg, preferably about 1.0 to 40 mg in terms of phosphorus, and aminated phenol polymer.
  • the thickness of the corrosion-resistant film is not particularly limited, but from the viewpoint of the cohesive force of the film and the adhesion with the barrier layer or the heat-fusible resin layer, it is preferably about 1 nm to 20 ⁇ m, more preferably 1 nm to 100 nm. Degree, and more preferably about 1 nm to 50 nm.
  • the thickness of the corrosion-resistant coating can be measured by observation with a transmission electron microscope or a combination of observation with a transmission electron microscope and energy dispersive X-ray spectroscopy or electron beam energy loss spectroscopy.
  • composition of the corrosion-resistant coating using time-of-flight secondary ion mass spectrometry for example, at least one secondary ion consisting of Ce, P, and O (eg, Ce 2 PO 4 + , CePO 4 ⁇ , etc. Species) or, for example, a peak derived from a secondary ion of Cr, P, and O (for example, at least one of CrPO 2 + , CrPO 4 ⁇ ).
  • the chemical conversion treatment is performed by applying a solution containing a compound used for forming a corrosion-resistant film to the surface of the barrier layer by a bar coating method, a roll coating method, a gravure coating method, a dipping method, or the like, and then applying the temperature of the barrier layer. Is heated to about 70 to 200 ° C.
  • the barrier layer may be 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 before the barrier layer is subjected to the chemical conversion treatment. By performing the degreasing treatment in this way, the chemical conversion treatment of the surface of the barrier layer can be performed more efficiently.
  • the heat-fusible resin layer 4 corresponds to the innermost layer, and has a function of sealing the electricity storage device element by heat-sealing the heat-fusible resin layer during assembly of the electricity storage device. It is a layer (sealant layer) that exerts its effect.
  • the heat-fusible resin layer 4 is configured by a single layer or a plurality of layers, and among the heat-fusible resin layers 4, the first heat-fusible resin layer 41. Form the surface of the laminate. Therefore, when assembling the electricity storage device, the first heat-fusible resin layer 41 is heat-sealed to seal the electricity storage device element.
  • the heat fusible resin layer 4 When the heat fusible resin layer 4 is composed of a single layer, the heat fusible resin layer 4 constitutes the first heat fusible resin layer 41. 1 and 2, the heat-fusible resin layer 4 is composed of a single layer of the first heat-fusible resin layer 41, and the first heat-fusible resin layer 41 covers the surface of the laminate. The illustrated stacking arrangement is illustrated.
  • the heat-fusible resin layer 4 is composed of a plurality of layers, at least the first heat-fusible resin layer 41 and the second heat-bondable resin layer 41 are arranged in this order from the front surface side of the laminate forming the exterior material 10 for an electricity storage device.
  • the heat-fusible resin layer 42 is provided.
  • the heat-fusible resin layer 4 is composed of a plurality of layers (two layers) of a first heat-fusible resin layer 41 and a second heat-fusible resin layer 42.
  • the heat-fusible resin layer 41 shows the laminated structure which comprises the surface of a laminated body.
  • the heat-fusible resin layer 4 is composed of a plurality of layers, the heat-fusible resin layer 4 is further added to the first heat-fusible resin layer 41 and the second heat-fusible resin layer 42.
  • a third heat-fusible resin layer, a fourth heat-fusible resin layer, etc. may be provided on the barrier layer 3 side of the second heat-fusible resin layer 42.
  • the heat-fusible resin layer 4 is composed of multiple layers, the heat-fusible resin layer 4 is composed of two layers of a first heat-fusible resin layer 41 and a second heat-fusible resin layer 42. Is preferably provided.
  • the heat-fusible resin layer has a modulus of elasticity of 1300 MPa or more measured by a nanoindentation method with a pushing load of 100 ⁇ N from the cross section in the stacking direction of the stack. Is provided in at least one layer.
  • the elastic modulus is 1300 MPa or more, so that even when a minute foreign substance is present in the heat-sealing portion of the heat-sealing resin layer, high insulation is exhibited. be able to.
  • the heat-fusible resin layer 4 includes at least one layer having a high elastic modulus of 1300 MPa or more, even if the heat-fusible resin layer 4 is heat-sealed in a place where a minute foreign substance exists, the heat-fusible resin layer Can be effectively prevented from becoming thin.
  • the elastic modulus is preferably 1500 MPa or more, more preferably 1800 MPa or more, further preferably 2000 MPa or more, and preferably 3000 MPa or less, more preferably 2800 MPa or less, further preferably Is less than 2500 MPa, and a preferable range is about 1300 to 3000 MPa, about 1300 to 2800 MPa, about 1300 to 2500 MPa, about 1500 to 3000 MPa, about 1500 to 2800 MPa, about 1500 to 2500 MPa, about 1800 to 3000 MPa, 1800 to 2800 MPa. Approx. 1800 to 2500 MPa, 2000 to 3000 MPa, 2000 to 2800 MPa, 2000 to 2600 MPa It is.
  • the above elastic modulus is preferable.
  • the elastic modulus of the first heat-fusible resin layer 41 is about 2000 to 2500 MPa.
  • the elastic modulus of the second heat-fusible resin layer 42 is preferably about 2000 to 2600 MPa.
  • the elastic modulus of the second heat-fusible resin layer 42 is It is preferably larger than the elastic modulus of the adhesive resin layer 41.
  • At least one of the first heat-fusible resin layer 41 and the second heat-fusible resin layer 42 of the heat-fusible resin layer 4 preferably satisfies the elastic modulus.
  • the elastic modulus is the elastic modulus of the first heat-fusible resin layer 41.
  • the heat-fusible resin layer 4 has the second heat-fusible resin layer 42
  • at least the first heat-fusible resin layer 41 and the second heat-fusible resin layer 42 It is preferable that one has the elastic modulus, and it is more preferable that both the first heat-fusible resin layer 41 and the second heat-fusible resin layer 42 have the elastic modulus.
  • the elastic modulus is higher than that of the first heat-fusible resin layer 41.
  • Layer 42 is preferably larger.
  • the elastic modulus of the heat-fusible resin layer 4 can be adjusted by, for example, the molecular weight, melting point, softening point, molecular weight distribution, crystallinity, etc. of the resin forming the layer having the elastic modulus.
  • the elastic modulus of the heat-fusible resin layer is measured by the indentation method as follows.
  • the elastic modulus is measured using a nano indenter (TriboIndenter TI950 manufactured by HYSITRON).
  • a regular triangular pyramid (Birkovich type) indenter (TI-0039 manufactured by HYSITRON) having a diamond tip at its tip is used.
  • TI-0039 manufactured by HYSITRON a regular triangular pyramid (Birkovich type) indenter having a diamond tip at its tip is used.
  • At room temperature (25 ° C.) each outer packaging material for an electricity storage device is cut in the stacking direction to expose the cross section of the heat-fusible resin layer.
  • the elastic modulus when the indenter is pressed in the direction perpendicular to the cross section of the layer to be measured of the heat-fusible resin layer is measured.
  • the measurement condition is a load control method, and the pushing load is constant at 100 ⁇ N (loading from 0 to 100 ⁇ N in 10 seconds, holding 100 ⁇ N for 5 seconds, and unloading from 100 to 0 ⁇ N in 10 seconds).
  • the resin forming the layer having the elastic modulus in the heat-fusible resin layer 4 is not particularly limited as long as it is heat-fusible and has the elastic modulus.
  • the resin forming the layer having the above-mentioned elastic modulus will be described by taking the resin that constitutes the first heat-fusible resin layer 41 as an example. As described above, if at least one of the heat-fusible resin layers 4 satisfies the elastic modulus, the first heat-fusible resin layer 41 does not form the elastic modulus layer. May be.
  • the resin forming the first heat-fusible resin layer 41 is preferably a resin containing a polyolefin skeleton such as polyolefin or acid-modified polyolefin.
  • the fact that the resin forming the first heat-fusible resin layer 41 contains a polyolefin skeleton can be analyzed by, for example, infrared spectroscopy, gas chromatography mass spectrometry, or the like.
  • infrared spectroscopy gas chromatography mass spectrometry, or the like.
  • a peak derived from maleic acid is detected in the vicinity of the wave number of 1760 cm -1 and near the wave number 1780 cm -1.
  • the first heat-fusible resin layer 41 is a layer composed of a maleic anhydride-modified polyolefin
  • a peak derived from maleic anhydride is detected when measured by infrared spectroscopy.
  • the degree of acid modification is low, the peak may be too small to be detected. In that case, it can be analyzed by nuclear magnetic resonance spectroscopy.
  • polystyrene resin examples include polyethylene such as low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene; ethylene- ⁇ olefin copolymers; homopolypropylene, block copolymers of polypropylene (for example, propylene and Examples thereof include polypropylene block copolymers) and polypropylene random copolymers (for example, random copolymers of propylene and ethylene); propylene- ⁇ -olefin copolymers; ethylene-butene-propylene terpolymers. Of these, polypropylene is preferred.
  • the polyolefin resin is a copolymer, it may be a block copolymer or a random copolymer. These polyolefin resins may be used alone or in combination of two or more.
  • the polyolefin may be a cyclic polyolefin.
  • the cyclic polyolefin is a copolymer of an olefin and a cyclic monomer, and examples of the olefin constituting the cyclic polyolefin include ethylene, propylene, 4-methyl-1-pentene, styrene, butadiene and isoprene.
  • the cyclic monomer which is a constituent monomer of the cyclic polyolefin include cyclic alkenes such as norbornene; cyclic dienes such as cyclopentadiene, dicyclopentadiene, cyclohexadiene and norbornadiene. Among these, cyclic alkenes are preferable, and norbornene is more preferable.
  • Acid-modified polyolefin is a polymer modified by block or graft polymerization of polyolefin with an acid component.
  • the acid-modified polyolefin the above-mentioned polyolefin, a copolymer obtained by copolymerizing the above-mentioned polyolefin with a polar molecule such as acrylic acid or methacrylic acid, or a polymer such as a cross-linked polyolefin can be used.
  • the acid component used for acid modification include carboxylic acids such as maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, and itaconic anhydride, or anhydrides thereof.
  • the acid-modified polyolefin may be an acid-modified cyclic polyolefin.
  • the acid-modified cyclic polyolefin is a polymer obtained by copolymerizing some of the monomers constituting the cyclic polyolefin instead of the acid component, or by block-polymerizing or graft-polymerizing the acid component with respect to the cyclic polyolefin. is there.
  • the acid-modified cyclic polyolefin is the same as described above.
  • the acid component used for the acid modification is the same as the acid component used for the modification of the polyolefin.
  • Preferred acid-modified polyolefins include polyolefins modified with carboxylic acids or their anhydrides, polypropylene modified with carboxylic acids or their anhydrides, maleic anhydride-modified polyolefins, maleic anhydride-modified polypropylenes.
  • the first heat-fusible resin layer 41 may be formed of one type of resin alone, or may be formed of a blend polymer in which two or more types of resins are combined.
  • the first heat-fusible resin layer 41 preferably contains polyolefin.
  • the heat-fusible resin layer 4 includes the first heat-fusible resin layer 41 and the second heat-fusible resin layer 42 in the exterior material 10 for an electricity storage device of the present disclosure, the surface is formed. It is preferable that the first heat-fusible resin layer 41 contains polyolefin and the second heat-fusible resin layer 42 contains acid-modified polyolefin.
  • the adhesive layer 5 when the adhesive layer 5 is provided, the first heat-fusible resin layer 41 constituting the surface contains polyolefin, and the adhesive layer 5 is acid-modified. It preferably contains a polyolefin.
  • the adhesive layer 5 contains an acid-modified polyolefin
  • the first heat-fusible resin layer contains a polyolefin
  • the second heat-fusible resin layer contains a polyolefin. More preferably, the first heat-fusible resin layer contains polypropylene, and the second heat-fusible resin layer contains polypropylene.
  • the first heat-fusible resin layer 41 may contain a lubricant and the like, if necessary.
  • a lubricant When the first heat-fusible resin layer 41 contains a lubricant, the moldability of the exterior material for an electricity storage device can be improved.
  • the lubricant is not particularly limited, and known lubricants can be used.
  • the lubricant may be used alone or in combination of two or more.
  • the lubricant is not particularly limited, but an amide lubricant is preferable. Specific examples of the lubricant include those exemplified for the base material layer 1. The lubricant may be used alone or in combination of two or more.
  • the amount of the lubricant is not particularly limited, but is preferably 10 to 50 mg / m from the viewpoint of enhancing the moldability of the exterior material for an electricity storage device. About 2 and more preferably about 15 to 40 mg / m 2 .
  • the lubricant present on the surface of the first heat-fusible resin layer 41 may be one in which the lubricant contained in the resin forming the first heat-fusible resin layer 41 is exuded, or the first heat-meltable resin
  • the surface of the adhesive resin layer 41 may be coated with a lubricant.
  • the thickness of the first heat-fusible resin layer 41 is not particularly limited as long as the heat-fusible resin layer has a function of heat-sealing and sealing the electricity storage device element.
  • the thickness of the first heat-fusible resin layer 41 is preferably about 100 ⁇ m or less, about 85 ⁇ m or less, about 60 ⁇ m or less, and 5 ⁇ m or more, 10 ⁇ m or more, 20 ⁇ m or more, 30 ⁇ m or more, 40 ⁇ m or more.
  • the preferable range is about 5 to 100 ⁇ m, about 5 to 85 ⁇ m, about 5 to 60 ⁇ m, about 10 to 100 ⁇ m, about 10 to 85 ⁇ m, about 10 to 60 ⁇ m, about 20 to 100 ⁇ m, about 20 to 85 ⁇ m, about 20 to 60 ⁇ m. , About 30 to 100 ⁇ m, about 30 to 85 ⁇ m, about 30 to 60 ⁇ m, about 40 to 100 ⁇ m, about 40 to 85 ⁇ m, about 40 to 60 ⁇ m.
  • the thickness of the first heat fusible resin layer 41 is preferably about 100 ⁇ m.
  • about 85 ⁇ m or less, about 60 ⁇ m or less, about 25 ⁇ m or less, and 5 ⁇ m or more, 10 ⁇ m or more, 20 ⁇ m or more, 30 ⁇ m or more, 40 ⁇ m or more, and a preferable range is about 5 to 100 ⁇ m, 5 to 85 ⁇ m.
  • the thickness of the first heat-fusible resin layer 41 is preferably Is about 85 ⁇ m or less, about 60 ⁇ m or less, about 25 ⁇ m or less, and 5 ⁇ m or more, 10 ⁇ m or more, 20 ⁇ m or more, 30 ⁇ m or more, 40 ⁇ m or more, and a preferable range is about 5 to 85 ⁇ m or about 5 to 60 ⁇ m.
  • the resin forming the second heat-fusible resin layer 42 has a polyolefin skeleton such as polyolefin or acid-modified polyolefin. Resins containing are preferred. These resins are the same as the resins described for the first heat-fusible resin layer 41.
  • the fact that the resin forming the second heat-fusible resin layer 42 contains a polyolefin skeleton can be analyzed by, for example, infrared spectroscopy, gas chromatography mass spectrometry, or the like.
  • the first heat-fusible resin layer 41 and the resin forming the second heat-fusible resin layer 42 may be the same or different, but preferably different.
  • the fact that the resins forming the first heat-fusible resin layer 41 and the second heat-fusible resin layer 42 are different means that the types of the resins are different, hardness, melting point, softening point, crystallinity, etc. And the case where the physical properties of are different.
  • the resin constituting the second heat-fusible resin layer is an acid-modified polyolefin and the resin constituting the first heat-fusible resin layer is a polyolefin
  • the types of resins are different.
  • the resin forming the first heat-fusible resin layer and the second heat-fusible resin layer are both polyolefins, but the hardness of each layer is different.
  • the second heat-fusible resin layer 42 preferably contains polyolefin.
  • the 2 heat-fusible resin layer 42 preferably contains a polyolefin.
  • the exterior material 10 for an electricity storage device of the present disclosure in the case where the heat-fusible resin layer 4 includes the first heat-fusible resin layer 41 and the second heat-fusible resin layer 42.
  • the first heat-fusible resin layer 41 forming the surface contains a polyolefin
  • the second heat-fusible resin layer 42 is an acid-modified polyolefin. It is preferable to include.
  • the thickness of the second heat-fusible resin layer 42 is not particularly limited as long as the heat-fusible resin layer 4 has a function of heat-sealing and sealing the electricity storage device element.
  • the thickness of the second heat-fusible resin layer 42 is preferably larger than the thickness of the first heat-fusible resin layer 41.
  • a resin that easily flows at a high temperature is preferably used so that the heat-fusible property is excellent.
  • the MFR, melting point, molecular weight, etc. of the first heat-fusible resin layer 41 can be adjusted appropriately.
  • the projecting portion A has end points A1 and A2, and these end points A1 and A2 tend to be the origins of cracks in the structure. Therefore, when the heat-fusible resin layer 4 largely protrudes inside the heat-bonded portion to form a protruding portion, the insulating property due to the cracks is likely to decrease.
  • the thickness of the second heat-fusible resin layer 42 is preferably about 100 ⁇ m or less, about 85 ⁇ m or less, about 60 ⁇ m or less, and 5 ⁇ m or more. 10 ⁇ m or more, 20 ⁇ m or more, 30 ⁇ m or more, 40 ⁇ m or more, and a preferable range is about 5 to 100 ⁇ m, about 5 to 85 ⁇ m, about 5 to 60 ⁇ m, about 10 to 100 ⁇ m, about 10 to 85 ⁇ m, about 10 to 60 ⁇ m.
  • the heat-fusible resin layer 4 includes, in addition to the first heat-fusible resin layer 41 and the second heat-fusible resin layer 42, a third heat-fusible resin layer and a fourth heat-fusible resin layer.
  • Other heat-fusible resin layers such as the above may be provided on the barrier layer 3 side of the second heat-fusible resin layer 42.
  • the resin forming the other heat-fusible resin layer the same resins as those described for the first heat-fusible resin layer 41 are exemplified.
  • the thickness of each of the other heat-fusible resin layers is the same as the thickness described for the second heat-fusible resin layer 42.
  • the total thickness of the heat-fusible resin layer 4 is preferably about 100 ⁇ m or less, about 85 ⁇ m or less, about 60 ⁇ m or less, and 5 ⁇ m or more, 10 ⁇ m or more, 20 ⁇ m or more, 30 ⁇ m or more, 40 ⁇ m or more,
  • the preferred range is about 5 to 100 ⁇ m, about 5 to 85 ⁇ m, about 5 to 60 ⁇ m, about 10 to 100 ⁇ m, about 10 to 85 ⁇ m, about 10 to 60 ⁇ m, about 20 to 100 ⁇ m, about 20 to 85 ⁇ m, about 20 to 60 ⁇ m, Examples thereof include about 30 to 100 ⁇ m, about 30 to 85 ⁇ m, about 30 to 60 ⁇ m, about 40 to 100 ⁇ m, about 40 to 85 ⁇ m, and about 40 to 60 ⁇ m.
  • the temperature difference T 2 is divided by the temperature difference T 1.
  • the value (ratio T 2 / T 1 ) obtained by the above is more preferably, for example, 0.60 or more, further preferably 0.70 or more.
  • a factor that causes a large change in the width of the extrapolation melting start temperature and the extrapolation melting end temperature of the melting peak is that the low molecular weight resin contained in the resin forming the first heat-fusible resin layer is Is dissolved in the electrolytic solution by contact with the electrolytic solution, and the width of the extrapolation melting start temperature and the extrapolation melting end temperature of the melting peak of the first heat-fusible resin layer after contact with the electrolytic solution is in contact with the electrolytic solution. It may be smaller than before.
  • a low molecular weight resin contained in the resin constituting the first heat-fusible resin layer There is a method of adjusting the ratio of.
  • a differential scanning calorimetry is used to obtain a DSC curve for the resin used for the first heat-fusible resin layer of each of the above-mentioned outer casing materials for electricity storage devices. From the obtained DSC curve, the temperature difference T 1 between the extrapolation melting start temperature and the extrapolation melting end temperature of the melting peak temperature of the first heat-fusible resin layer is measured.
  • the resin used for the first heat-fusible resin layer has a lithium hexafluorophosphate concentration of 1 mol / l and a volume ratio of ethylene carbonate, diethyl carbonate and dimethyl carbonate of 1: After being left to stand for 72 hours in an electrolytic solution which is a 1: 1 solution, it is sufficiently dried.
  • a differential scanning calorimetry (DSC) is used to obtain a DSC curve for the dried polypropylene.
  • the temperature difference T 2 between the extrapolation melting start temperature and the extrapolation melting end temperature of the melting peak temperature of the first heat-fusible resin layer after drying is measured from the obtained DSC curve.
  • the test sample was held at ⁇ 50 ° C. for 10 minutes, then heated up to 200 ° C. at a heating rate of 10 ° C./minute (first time), held at 200 ° C. for 10 minutes, and then cooled down.
  • the temperature was lowered to ⁇ 50 ° C. at ⁇ 10 ° C./min, the temperature was kept at ⁇ 50 ° C. for 10 minutes, then the temperature was raised to 200 ° C. at a temperature rising rate of 10 ° C./min (second time), and the temperature was kept at 200 ° C. for 10 minutes.
  • the DSC curve when heating up to 200 ° C. for the second time is used. Further, when measuring the temperature difference T 1 and the temperature difference T 2 , of the melting peaks appearing in the range of 120 to 160 ° C. in the respective DSC curves, the melting peak with the largest difference in the input of heat energy is analyzed. To do. Even if there are two or more peaks that overlap each other, only the melting peak that maximizes the difference in heat energy input is analyzed.
  • the extrapolation melting start temperature means the starting point of the melting peak temperature, and the melting point that maximizes the difference between the straight line extending the low temperature (65 to 75 ° C) side baseline to the high temperature side and the input of heat energy
  • the temperature at the intersection of the curve on the low temperature side of the peak and the tangent line drawn at the point where the slope is maximum is used.
  • the extrapolation melting end temperature means the end point of the melting peak temperature, and the high temperature side of the melting peak where the difference in the input of thermal energy is the maximum from the straight line extending the high temperature (170 ° C) side baseline to the low temperature side.
  • the first heat-fusible resin is in contact with the first heat-fusible resin layer in a high temperature environment, and the first heat-fusible resin is adhered to the first heat-fusible resin layer.
  • the value obtained by dividing the temperature difference T 2 by the temperature difference T 1 is preferably 0.60 or more, more preferably 0.70 or more, still more preferably 0.75 or more, and the preferable range is about 0.60 to 1.0, 0.70 to 1 It may be about 0.0 or about 0.75 to 1.0.
  • the upper limit is 1.0, for example. In order to set such a ratio T 2 / T 1 , for example, the type, composition, molecular weight, etc. of the resin forming the first heat-fusible resin layer 41 are adjusted.
  • of the temperature difference T 2 and the temperature difference T 1 is, for example, about 15 ° C. or less, preferably about 10 ° C. or less. More preferably, it is about 8 ° C. or lower, further preferably about 7.5 ° C.
  • a preferable range is about 0 to 15 ° C., about 0 to 10 ° C., about 0 to 8 ° C., 0 to 7.5. °C about 1 to 15 °C about 1 to 10 °C about 1 to 8 °C about 1 to 7.5 °C about 2 to 15 °C about 2 to 10 °C about 2 to 8 °C about 2 to 7
  • the temperature is about 0.5 ° C., about 5 to 15 ° C., about 5 to 10 ° C., about 5 to 8 ° C., about 5 to 7.5 ° C.
  • is, for example, 0 ° C., 1 ° C., 2 ° C., 5 ° C.
  • for example, the type, composition, molecular weight, etc. of the resin forming the first heat-fusible resin layer 41 are adjusted.
  • the temperature difference T 1 is preferably about 29 to 38 ° C, more preferably about 32 to 36 ° C.
  • the temperature difference T 2 is preferably about 17 to 30 ° C, more preferably about 26 to 29 ° C. In order to set such temperature differences T 1 and T 2 , for example, the type, composition, molecular weight, etc. of the resin forming the first heat-fusible resin layer 41 are adjusted.
  • the adhesive layer 5 is provided between the barrier layer 3 (or the corrosion resistant film) and the heat-fusible resin layer 4 as needed in order to firmly bond them. It is a layer.
  • the adhesive layer 5 is formed of a resin that can bond the barrier layer 3 and the heat-fusible resin layer 4.
  • the resin used for forming the adhesive layer 5 for example, the same resins as those exemplified for the adhesive layer 2 can be used.
  • the resin used to form the adhesive layer 5 preferably contains a polyolefin skeleton, and examples thereof include the polyolefins and the acid-modified polyolefins described above as the first heat-fusible resin layer 41.
  • the fact that the resin constituting the adhesive layer 5 contains a polyolefin skeleton can be analyzed by, for example, infrared spectroscopy, gas chromatography mass spectrometry, etc., and the analysis method is not particularly limited.
  • the resin constituting the adhesive layer 5 is analyzed by infrared spectroscopy, it is preferable to detect a peak derived from maleic anhydride.
  • a peak derived from maleic acid is detected in the vicinity of the wave number of 1760 cm -1 and near the wave number 1780 cm -1.
  • the degree of acid modification is low, the peak may be too small to be detected. In that case, it can be analyzed by nuclear magnetic resonance spectroscopy.
  • the adhesive layer 5 can be formed of a thermoplastic resin or a cured product of a thermosetting resin, and is preferably formed of a thermoplastic resin.
  • the adhesive layer 5 preferably contains an acid-modified polyolefin.
  • an acid-modified polyolefin a polyolefin modified with a carboxylic acid or an anhydride thereof, a polypropylene modified with a carboxylic acid or an anhydride thereof, a maleic anhydride modified polyolefin, and a maleic anhydride modified polypropylene are particularly preferable.
  • the adhesive layer 5 is a resin composition containing an acid-modified polyolefin and a curing agent. It is more preferable that the cured product is.
  • Preferred examples of the acid-modified polyolefin include those mentioned above.
  • the first heat-fusible resin layer 41 forming the surface contains polyolefin, and the adhesive layer 5 is It preferably contains an acid-modified polyolefin.
  • the adhesive layer 5 is a cured product of a resin composition containing an acid-modified polyolefin and at least one selected from the group consisting of a compound having an isocyanate group, a compound having an oxazoline group, and a compound having an epoxy group. It is preferable that the cured product is a resin composition containing an acid-modified polyolefin and at least one selected from the group consisting of a compound having an isocyanate group and a compound having an epoxy group.
  • the adhesive layer 5 preferably contains at least one selected from the group consisting of polyurethane, polyester, and epoxy resin, and more preferably contains polyurethane and epoxy resin.
  • the polyester for example, an amide ester resin is preferable.
  • the amide ester resin is generally produced by the reaction of a carboxyl group and an oxazoline group.
  • the adhesive layer 5 is more preferably a cured product of a resin composition containing at least one of these resins and the acid-modified polyolefin.
  • unreacted compounds such as a compound having an isocyanate group, a compound having an oxazoline group, and a curing agent such as an epoxy resin remain in the adhesive layer 5, the presence of the unreacted substance is determined by, for example, infrared spectroscopy, It can be confirmed by a method selected from Raman spectroscopy, time-of-flight secondary ion mass spectrometry (TOF-SIMS), and the like.
  • the adhesive layer 5 is at least selected from the group consisting of an oxygen atom, a heterocycle, a C ⁇ N bond, and a C—O—C bond. It is preferably a cured product of a resin composition containing one type of curing agent.
  • the curing agent having a heterocycle include a curing agent having an oxazoline group and a curing agent having an epoxy group.
  • examples of the curing agent having a C—O—C bond include a curing agent having an oxazoline group, a curing agent having an epoxy group, and polyurethane.
  • the fact that the adhesive layer 5 is a cured product of a resin composition containing these curing agents means, for example, gas chromatography mass spectrometry (GCMS), infrared spectroscopy (IR), time-of-flight secondary ion mass spectrometry (TOF). -SIMS), X-ray photoelectron spectroscopy (XPS) and the like.
  • GCMS gas chromatography mass spectrometry
  • IR infrared spectroscopy
  • TOF time-of-flight secondary ion mass spectrometry
  • -SIMS X-ray photoelectron spectroscopy
  • the compound having an isocyanate group is not particularly limited, but from the viewpoint of effectively enhancing the adhesiveness between the barrier layer 3 and the adhesive layer 5, a polyfunctional isocyanate compound is preferable.
  • the polyfunctional isocyanate compound 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 pentane diisocyanate (PDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and polymerization or nurate thereof. And the like, and their mixtures and copolymers with other polymers. Moreover, an adduct body, a burette body, an isocyanurate body, etc. are mentioned.
  • the content of the compound having an isocyanate group in the adhesive layer 5 is preferably in the range of 0.1 to 50% by mass, and 0.5 to 40% by mass in the resin composition constituting the adhesive layer 5. It is more preferable to be in the range. Thereby, the adhesiveness between the barrier layer 3 and the adhesive layer 5 can be effectively enhanced.
  • the compound having an oxazoline group is not particularly limited as long as it is a compound having an oxazoline skeleton.
  • Specific examples of the compound having an oxazoline group include those having a polystyrene main chain and those having an acrylic main chain. Examples of commercially available products include Epocros series manufactured by Nippon Shokubai Co., Ltd.
  • the proportion of the compound having an oxazoline group in the adhesive layer 5 is preferably in the range of 0.1 to 50% by mass, and in the range of 0.5 to 40% by mass in the resin composition constituting the adhesive layer 5. Is more preferable. Thereby, the adhesiveness between the barrier layer 3 and the adhesive layer 5 can be effectively enhanced.
  • Examples of compounds having an epoxy group include epoxy resins.
  • the epoxy resin is not particularly limited as long as it is a resin that can form a crosslinked structure by an epoxy group existing in the molecule, and a known epoxy resin can be used.
  • the weight average molecular weight of the epoxy resin is preferably about 50 to 2000, more preferably about 100 to 1000, and further preferably about 200 to 800.
  • the weight average molecular weight of the epoxy resin is a value measured by gel permeation chromatography (GPC), which is measured under the condition that polystyrene is used as a standard sample.
  • the epoxy resin examples include a glycidyl ether derivative of trimethylolpropane, bisphenol A diglycidyl ether, modified bisphenol A diglycidyl ether, novolac glycidyl ether, glycerin polyglycidyl ether, and polyglycerin polyglycidyl ether.
  • the epoxy resin may be used alone or in combination of two or more.
  • the proportion of the epoxy resin in the adhesive layer 5 is preferably in the range of 0.1 to 50% by mass, and in the range of 0.5 to 40% by mass in the resin composition constituting the adhesive layer 5. Is more preferable. Thereby, the adhesiveness between the barrier layer 3 and the adhesive layer 5 can be effectively enhanced.
  • the polyurethane is not particularly limited, and known polyurethane can be used.
  • the adhesive layer 5 may be, for example, a cured product of two-component curing type polyurethane.
  • the proportion of polyurethane in the adhesive layer 5 is preferably in the range of 0.1 to 50% by mass, and more preferably in the range of 0.5 to 40% by mass in the resin composition constituting the adhesive layer 5. More preferable. Thereby, the adhesiveness between the barrier layer 3 and the adhesive layer 5 can be effectively enhanced in an atmosphere in which a component such as an electrolytic solution that induces corrosion of the barrier layer exists.
  • the adhesive layer 5 is a cured product of a resin composition containing at least one selected from the group consisting of a compound having an isocyanate group, a compound having an oxazoline group, and an epoxy resin, and the acid-modified polyolefin.
  • the acid-modified polyolefin functions as a main agent, and the compound having an isocyanate group, the compound having an oxazoline group, and the compound having an epoxy group each function as a curing agent.
  • the total thickness of the adhesive layer 5 and the heat-fusible resin layer 4 is preferably about 50 ⁇ m or more, more preferably about 60 ⁇ m or more, further preferably about 70 ⁇ m. It is above, and preferably about 120 ⁇ m or less, more preferably about 100 ⁇ m or less, and the preferable range is about 50 to 120 ⁇ m, about 50 to 100 ⁇ m, about 60 to 120 ⁇ m, about 60 to 100 ⁇ m, about 70 to 120 ⁇ m. , 70 to 100 ⁇ m.
  • a preferable ratio between the thickness of the first heat-fusible resin layer 41 and the thickness of the second heat-fusible resin layer 42 is the second with the thickness of the first heat-fusible resin layer 41 being 1.0.
  • the thickness of the heat-fusible resin layer 42 is preferably about 1.5 to 6.0, more preferably about 1.7 to 5.5, and even more preferably about 2.0 to 5.0.
  • the preferable ratio of the thickness of the adhesive layer 5, the thickness of the first heat-fusible resin layer 41, and the thickness of the second heat-fusible resin layer 42 is the thickness of the first heat-fusible resin layer 41.
  • the thickness of the adhesive layer 5 is preferably about 0.5 to 3.0 and the thickness of the second heat-fusible resin layer 42 is preferably about 1.5 to 6.0. More preferably, the thickness of the second heat-fusible resin layer 42 is about 1.7 to 5.5, and the thickness of the adhesive layer 5 is about 1.0 to More preferably, it is about 2.0, and the thickness of the second heat-fusible resin layer 42 is about 2.0 to 5.0.
  • the thickness of the first heat-fusible resin layer 41 is 1.0.
  • the thickness of the second heat-fusible resin layer 42 include 2.0, 2.7, 3.0, 4.0, 5.0, 6.0.
  • the thickness of the adhesive layer 5 is 1.0
  • the thickness of the second heat-fusible resin layer 42 is 2.0
  • the thickness of the adhesive layer 5 is 1.7.
  • the heat-fusible resin layer 42 has a thickness of 2.7, the adhesive layer 5 has a thickness of 1.3, and the second heat-fusible resin layer 42 has a thickness of 3.0. And the thickness of the second heat-fusible resin layer 42 is 5.0.
  • the thickness of the adhesive layer 5 may be larger than the thickness of the first heat-fusible resin layer 41 from the viewpoint of enhancing the insulating property of the heat-fusible resin layer 4.
  • the heat fusible resin layer 4 is composed of a single layer of the first heat fusible resin layer 41, and the adhesive layer 5 is provided between the barrier layer 3 and the first heat fusible resin layer 41.
  • the thickness of the adhesive layer 5 is preferably larger than the thickness of the first heat-fusible resin layer 41.
  • a resin that easily flows at a higher temperature than the adhesive layer 5 is preferably used so as to have excellent heat-fusible properties.
  • the first heat-fusible resin layer 41 that is a part of the heat-fusible resin layer 4 and is made of a resin that easily flows.
  • the insulating property of the exterior material for the electricity storage device can be improved.
  • the MFR, melting point, molecular weight, etc. of the first heat-fusible resin layer 41 can be adjusted appropriately.
  • the heat-fusible resin layer 4 includes the first heat-fusible resin layer 41 and the second heat-fusible resin layer 42 in the power storage device exterior material 10 of the present disclosure
  • the power storage device exterior is provided.
  • the thickness of the second heat-fusible resin layer 42 is preferably larger than the thickness of the adhesive layer 5. Since the second heat-fusible resin layer 42 has a better moisture barrier property than the adhesive layer 5 that contributes to adhesion, by providing such a thickness relationship, the moisture barrier of the exterior material for an electricity storage device can be improved. It is possible to improve the sex.
  • the thickness of the second heat-fusible resin layer 42 is larger than the thickness of the adhesive layer 5, and the thickness of the adhesive layer 5 is It is preferably larger than the thickness of the 1 heat-fusible resin layer 41.
  • the thickness of the adhesive layer 5 is preferably about 60 ⁇ m or less, about 50 ⁇ m or less, about 40 ⁇ m or less, about 30 ⁇ m or less, about 20 ⁇ m or less, about 10 ⁇ m or less, about 8 ⁇ m or less, about 5 ⁇ m or less, about 3 ⁇ m or less, and , Preferably about 0.1 ⁇ m or more, about 0.5 ⁇ m or more, about 5 ⁇ m or more, about 10 ⁇ m or more, about 20 ⁇ m or more, and the thickness range is preferably about 0.1 to 60 ⁇ m, 0.1.
  • 0.1 to 40 ⁇ m 1 to 50 ⁇ m, 0.1 to 40 ⁇ m, 0.1 to 30 ⁇ m, 0.1 to 20 ⁇ m, 0.1 ⁇ m to 10 ⁇ m, 0.1 to 8 ⁇ m, 0.1 to 5 ⁇ m, 0.1 ⁇ 3 ⁇ m, 0.5-60 ⁇ m, 0.5-50 ⁇ m, 0.5-40 ⁇ m, 0.5-30 ⁇ m, 0.5-20 ⁇ m, 0.5 ⁇ m-10 ⁇ m, 0.5- About 8 ⁇ m, 0.5 to 5 ⁇ m, 0.5-3 ⁇ m, 5-60 ⁇ m, 5-50 ⁇ m, 5-40 ⁇ m, 5-30 ⁇ m, 5-20 ⁇ m, 5 ⁇ m-10 ⁇ m, 5-8 ⁇ m, 10-60 ⁇ m,
  • the thickness is about 10 to 50 ⁇ m, about 10 to 40 ⁇ m, about 10 to 30 ⁇ m, and about 10 to 20 ⁇ m.
  • the adhesive exemplified in the adhesive layer 2 or a cured product of an acid-modified polyolefin and a curing agent it is preferably about 1 to 10 ⁇ m, more preferably 1 ⁇ m or more and less than 10 ⁇ m, and further preferably 1 To about 8 ⁇ m, more preferably about 1 to 5 ⁇ m, further preferably about 1 to 3 ⁇ m.
  • the resin exemplified in the first heat-fusible resin layer 41 it is preferably about 2 to 60 ⁇ m, about 2 to 50 ⁇ m, about 10 to 60 ⁇ m, about 10 to 50 ⁇ m, about 20 to 60 ⁇ m, 20. It is about 50 ⁇ m.
  • the adhesive layer 5 is composed of a thermoplastic resin, and the thickness of the thermoplastic resin is preferably about 2 to 60 ⁇ m, about 2 to 50 ⁇ m, about 10 to 60 ⁇ m, about 10 to 50 ⁇ m, 20. The thickness is about 60 to 60 ⁇ m and about 20 to 50 ⁇ m.
  • the adhesive layer 5 is a cured product of the adhesive exemplified in the adhesive layer 2 or a resin composition containing an acid-modified polyolefin and a curing agent, for example, the resin composition is applied and cured by heating or the like. As a result, the adhesive layer 5 can be formed.
  • the heat-fusible resin layer 4 and the adhesive layer 5 can be formed by extrusion molding, for example.
  • the power storage device exterior material 10 of the present disclosure includes the adhesive layer 5, the second heat-fusible resin layer 42, and the first heat-fusible resin layer 41, for example, the adhesive layer 5;
  • the first heat-fusible resin layer 41 and the second heat-fusible resin layer 42 can be laminated by coextrusion molding. That is, the adhesive layer 5, the second heat-fusible resin layer 42, and the first heat-fusible resin layer 41 can be coextruded resin layers.
  • an adhesive layer having a thickness of about 20 to 60 ⁇ m is sequentially provided from the barrier layer 3 side.
  • a first heat-fusible resin layer 41 having a thickness of 20 to 50 ⁇ m are laminated; an adhesive layer 5 having a thickness of about 20 to 60 ⁇ m and a first heat-fusible property of 20 to 40 ⁇ m
  • Lamination structure in which a heat-fusible resin layer 41 is laminated an adhesive layer 5 having a thickness of about 5 to 20 ⁇ m, a second heat-fusible resin layer 42 having a thickness of about 40 to 80 ⁇ m, and a thickness of 5 to 25 ⁇ m
  • an adhesive layer 5 having a thickness of about 5 to 20 ⁇ m
  • a second heat-fusible resin layer 42 having a thickness of about 40 to 80 ⁇ m, and a thickness of 5 to 25 ⁇ m
  • a laminated structure in which the first heat-fusible resin layer 41 is laminated is used.
  • the adhesive layer 5 has a logarithmic decrement ⁇ E at 120 ° C. in the rigid pendulum measurement of, for example, 0.22 or less, 0.20 or less, further 0.18 or less, and even more than 0.1. It is preferably 14 or less, more preferably 0.13 or less.
  • the logarithmic decay rate ⁇ E at 120 ° C. is, for example, 0.22 or less, 0.20 or less, further 0.18 or less, further 0.14 or less, further 0.13 or less.
  • the insulating property of the heat-fusible resin layer 4 can be improved.
  • the logarithmic decrement at 120 ° C in the rigid pendulum measurement is an index showing the hardness of the resin in a high temperature environment of 120 ° C, and the smaller the logarithmic decrement, the higher the resin hardness. Due to the high hardness of the adhesive layer 5 at a high temperature of 120 ° C., the effect is that the heat-fusible resin layer 4 becomes thin even when heat-bonded in the presence of minute foreign matter in the heat-bonded portion. It is suppressed, and high insulation can be exhibited. In the rigid pendulum measurement, the damping rate of the pendulum when the temperature of the resin is raised from a low temperature to a high temperature is measured.
  • the edge portion is brought into contact with the surface of the measurement target object, and the pendulum movement is performed in the left-right direction to impart vibration to the measurement target object.
  • the logarithmic decrement in a high temperature environment of 120 ° C. is, for example, 0.22 or less, 0.20 or less, further 0.18 or less, further 0.14 or less, further 0.
  • ⁇ E [ln (A1 / A2) + ln (A2 / A3) + ... ln (An / An + 1)] / n A: amplitude n: wave number
  • the logarithmic attenuation rate ⁇ E at 120 ° C. is, for example, about 0.10 to 0.22, 0.10 to About 0.20, preferably about 0.10 to 0.18, more preferably about 0.10 to 0.16, further preferably about 0.10 to 0.14, further preferably 0.10 to 0.13.
  • the degree can be mentioned.
  • the type, composition, molecular weight, etc. of the resin forming the adhesive layer 5 are adjusted.
  • the initial amplitude was 0.3 degree
  • the temperature was from 30 ° C to 200 ° C.
  • a rigid pendulum physical property test is performed on the adhesive layer 5 at a temperature rising rate of 3 ° C./min in the range.
  • the adhesive layer for measuring the logarithmic decay rate ⁇ E the exterior material for an electricity storage device was immersed in 15% hydrochloric acid to dissolve the base material layer and the barrier layer, and only the adhesive layer and the heat-fusible resin layer were formed. Allow the sample to dry sufficiently before measurement.
  • the exterior material for an electricity storage device is acquired from the electricity storage device and the logarithmic attenuation rate ⁇ E of the adhesive layer 5 is measured, a sample is cut out from the top surface portion where the exterior material for the electricity storage device is not stretched by molding and is used as a measurement target.
  • the exterior material for an electricity storage device of the present disclosure is, if necessary, on the base material layer 1 (base material layer 1 for the purpose of at least one of improvement in designability, electrolytic solution resistance, scratch resistance, moldability, etc.).
  • the surface coating layer 6 may be provided on the side opposite to the barrier layer 3).
  • the surface coating layer 6 is a layer located on the outermost layer side of the exterior material for an electricity storage device when the electricity storage device is assembled using the exterior material for an electricity storage device.
  • the surface coating layer 6 can be formed of a resin such as polyvinylidene chloride, polyester, polyurethane, acrylic resin, or epoxy resin.
  • the resin forming the surface coating layer 6 is a curable resin
  • the resin may be either a one-component curing type or a two-component curing type, but is preferably a two-component curing type.
  • the two-component curing type resin include two-component curing type polyurethane, two-component curing type polyester, and two-component curing type epoxy resin. Among these, two-component curing type polyurethane is preferable.
  • the two-component curing type polyurethane includes, for example, a polyurethane containing a base compound containing a polyol compound and a curing agent containing an isocyanate compound.
  • a polyurethane containing a base compound containing a polyol compound and a curing agent containing an isocyanate compound.
  • Preferred is a two-component curing type polyurethane having a polyol such as a polyester polyol, a polyether polyol, and an acrylic polyol as a main agent and an aromatic or aliphatic polyisocyanate as a curing agent.
  • the polyol compound it is preferable to use a polyester polyol having a hydroxyl group at the side chain in addition to the hydroxyl group at the terminal of the repeating unit. Since the surface coating layer 6 is formed of polyurethane, excellent electrolytic solution resistance is imparted to the exterior material for an electricity storage device.
  • the surface coating layer 6 is provided on at least one of the surface and the inside of the surface coating layer 6 depending on the surface coating layer 6 and the functionality to be provided on the surface thereof, if necessary, and the above-mentioned lubricant or anti-reflective agent. It may contain additives such as a blocking agent, a matting agent, a flame retardant, an antioxidant, a tackifier, and an antistatic agent. Examples of the additive include fine particles having an average particle diameter of about 0.5 nm to 5 ⁇ m. The average particle diameter of the additive is a median diameter measured by a laser diffraction / scattering type particle diameter distribution measuring device.
  • the additive may be an inorganic substance or an organic substance.
  • the shape of the additive is not particularly limited, and examples thereof include spherical shape, fibrous shape, plate shape, amorphous shape, and scale shape.
  • the additive include talc, silica, graphite, kaolin, montmorillonite, mica, hydrotalcite, silica gel, zeolite, aluminum hydroxide, magnesium hydroxide, zinc oxide, magnesium oxide, aluminum oxide, neodymium oxide, antimony oxide.
  • Titanium oxide, cerium oxide, calcium sulfate, barium sulfate, calcium carbonate, calcium silicate, lithium carbonate, calcium benzoate, calcium oxalate, magnesium stearate, alumina, carbon black, carbon nanotubes, high melting point nylon, acrylate resin examples include crosslinked acrylic, crosslinked styrene, crosslinked polyethylene, benzoguanamine, gold, aluminum, copper and nickel.
  • the additives may be used alone or in combination of two or more.
  • silica, barium sulfate and titanium oxide are preferable from the viewpoint of dispersion stability and cost.
  • the additives may be subjected to various surface treatments such as insulation treatment and high dispersibility treatment on the surface.
  • the method of forming the surface coating layer 6 is not particularly limited, and examples thereof include a method of applying a resin forming the surface coating layer 6.
  • a resin mixed with the additive may be applied.
  • the thickness of the surface coating layer 6 is not particularly limited as long as it exhibits the above-mentioned functions as the surface coating layer 6, and is, for example, about 0.5 to 10 ⁇ m, preferably about 1 to 5 ⁇ m.
  • the method for manufacturing the exterior material for power storage device is not particularly limited as long as a laminate in which each layer of the exterior material for power storage device of the present disclosure is laminated is obtained, and at least a base material.
  • the method includes a step of laminating the layer 1, the barrier layer 3, and the heat-fusible resin layer 4 in this order.
  • the heat-fusible resin layer is configured by a single layer or multiple layers, and the heat-fusible resin layer is a cross section in the laminating direction of the laminate. Therefore, at least one layer having an elastic modulus of 1300 MPa or more measured by the nanoindentation method measured with a pushing load of 100 ⁇ N is provided.
  • the details of the electricity storage device exterior material 10 of the present disclosure are as described above.
  • laminated body A a laminated body in which the base material layer 1, the adhesive layer 2, and the barrier layer 3 are laminated in order
  • laminate A is formed by applying an adhesive used for forming the adhesive layer 2 on the base material layer 1 or on the barrier layer 3 whose surface has been subjected to chemical conversion treatment, if necessary, by a gravure coating method. This can be performed by a dry laminating method in which the barrier layer 3 or the base material layer 1 is laminated and the adhesive layer 2 is cured after being applied and dried by a coating method such as a roll coating method.
  • the heat-fusible resin layer 4 is laminated on the barrier layer 3 of the laminate A.
  • the heat-fusible resin layer 4 is directly laminated on the barrier layer 3
  • the heat-fusible resin layer 4 is laminated on the barrier layer 3 of the laminate A by a method such as a thermal laminating method or an extrusion laminating method. do it.
  • the adhesive layer 5 is provided between the barrier layer 3 and the heat-fusible resin layer 4, for example, (1) the adhesive layer 5 and the heat-fusible resin layer are provided on the barrier layer 3 of the laminate A.
  • Method of laminating by extruding 4 (coextrusion laminating method, tandem laminating method), (2) Separately, a laminated body in which the adhesive layer 5 and the heat-fusible resin layer 4 are laminated is formed, and the laminated body A By a thermal lamination method, or by forming a laminated body in which the adhesive layer 5 is laminated on the barrier layer 3 of the laminated body A, and by using the thermal fusion bonding resin layer 4 and the thermal lamination method.
  • Method of Laminating (3) While pouring the melted adhesive layer 5 between the barrier layer 3 of the laminate A and the heat-fusible resin layer 4 which is formed into a sheet in advance, the adhesive layer 5 is interposed.
  • Method for laminating the laminate A and the heat-fusible resin layer 4 (sandwich lamine (4), (4) the barrier layer 3 of the laminate A is laminated by a solution coating method for forming an adhesive layer 5 with an adhesive, followed by drying, or a baking method. Examples thereof include a method of laminating the heat-fusible resin layer 4 which is previously formed into a sheet shape on the above.
  • the surface coating layer 6 When the surface coating layer 6 is provided, the surface coating layer 6 is laminated on the surface of the base material layer 1 opposite to the barrier layer 3.
  • the surface coating layer 6 can be formed, for example, by applying the above-mentioned resin forming the surface coating layer 6 to the surface of the base material layer 1.
  • the order of the step of laminating the barrier layer 3 on the surface of the base material layer 1 and the step of laminating the surface coating layer 6 on the surface of the base material layer 1 is not particularly limited.
  • the barrier layer 3 may be formed on the surface of the base material layer 1 opposite to the surface coating layer 6.
  • a laminate including the functional resin layer 4 in this order is formed, it may be further subjected to a heat treatment in order to strengthen the adhesiveness of the adhesive layer 2 and the adhesive layer 5 provided as necessary.
  • each layer constituting the laminate may be subjected to surface activation treatment such as corona treatment, blast treatment, oxidation treatment, or ozone treatment, if necessary, to improve the processability.
  • surface activation treatment such as corona treatment, blast treatment, oxidation treatment, or ozone treatment, if necessary, to improve the processability.
  • corona treatment on the surface of the base material layer 1 opposite to the barrier layer 3, it is possible to improve the printability of the ink on the surface of the base material layer 1.
  • the exterior material for an energy storage device is used for a package for hermetically housing an energy storage device element such as a positive electrode, a negative electrode, and an electrolyte. That is, an electricity storage device can be prepared by accommodating an electricity storage device element including at least a positive electrode, a negative electrode, and an electrolyte in a package formed of the electricity storage device exterior material of the present disclosure.
  • an electricity storage device element including at least a positive electrode, a negative electrode, and an electrolyte is used in a state in which a metal terminal connected to each of the positive electrode and the negative electrode is projected to the outside in the exterior material for an electricity storage device of the present disclosure.
  • a flange portion a region where the heat-fusible resin layers are in contact with each other
  • heat-seal and seal the heat-fusible resin layers of the flange portion is provided.
  • the heat-fusible resin portion of the electricity storage device exterior material of the present disclosure is inside (a surface that contacts the electricity storage device element). ), And a package is formed.
  • the exterior material for an electricity storage device of the present disclosure can be suitably used for an electricity storage device such as a battery (including a capacitor, a capacitor, etc.). Further, the exterior material for an electricity storage device of the present disclosure may be used in either a primary battery or a secondary battery, but is preferably a secondary battery.
  • the type of secondary battery to which the exterior material for an electricity storage device of the present disclosure is applied is not particularly limited, and examples thereof include a lithium ion battery, a lithium ion polymer battery, an all-solid-state battery, a lead storage battery, a nickel-hydrogen storage battery, and a nickel-hydrogen storage battery.
  • Examples thereof include a cadmium storage battery, a nickel / iron storage battery, a nickel / zinc storage battery, a silver oxide / zinc storage battery, a metal-air battery, a polyvalent cation battery, a capacitor and a capacitor.
  • a cadmium storage battery a nickel / iron storage battery, a nickel / zinc storage battery, a silver oxide / zinc storage battery, a metal-air battery, a polyvalent cation battery, a capacitor and a capacitor.
  • lithium ion batteries and lithium ion polymer batteries are mentioned as suitable targets to which the exterior material for an electricity storage device of the present disclosure is applied.
  • Example 1 and Comparative Example 1 As a base material layer, a polyethylene terephthalate (PET) film (thickness 12 ⁇ m) and a stretched nylon (ONy) film (thickness 15 ⁇ m) were prepared, and a two-component urethane adhesive (polyol compound and aromatic isocyanate compound) was formed on the PET film. ) was applied (3 ⁇ m) and adhered to the ONy film. An aluminum foil (JIS H4160: 1994 A8021H-O (thickness 40 ⁇ m)) was prepared as a barrier layer.
  • PTT polyethylene terephthalate
  • ONy stretched nylon
  • urethane adhesive polyol compound and aromatic isocyanate compound
  • a two-component urethane adhesive (polyol compound and aromatic isocyanate compound) was applied to one surface of the aluminum foil to form an adhesive layer (thickness 3 ⁇ m) on the barrier layer.
  • the adhesive layer on the barrier layer and the base material layer are laminated by a dry lamination method, and then aging treatment is carried out to produce a laminate of base material layer / adhesive layer / barrier layer. did. Both sides of the aluminum foil are subjected to chemical conversion treatment.
  • the chemical conversion treatment of the aluminum foil is performed by roll coating the both surfaces of the aluminum foil with a treatment liquid consisting of a phenolic resin, a chromium fluoride compound, and phosphoric acid so that the coating amount of chromium is 10 mg / m 2 (dry mass). It was carried out by coating and baking.
  • Base material layer (thickness of 30 ⁇ m including adhesive) / adhesive layer (3 ⁇ m) / barrier layer (40 ⁇ m) / adhesive layer (20 ⁇ m) / second heat-fusible resin layer ( 50 ⁇ m) / first heat-fusible resin layer (10 ⁇ m) were sequentially laminated to obtain an outer packaging material for an electricity storage device.
  • the first heat-fusible resin layer and the second heat-fusible resin layer of Example 1 and Comparative Example 1 respectively have the elastic moduli (elastic moduli measured using a nano indenter) described in Table 1.
  • Have The adhesive layers of Example 1 and Comparative Example 1 each have a logarithmic attenuation rate ⁇ E (value measured using a rigid body pendulum type physical property tester) at 120 ° C. shown in Table 1.
  • Example 2 and Comparative Examples 2 and 3 As a base material layer, a polyethylene terephthalate (PET) film (thickness 12 ⁇ m) and a stretched nylon (ONy) film (thickness 15 ⁇ m) were prepared, and a two-component urethane adhesive (polyol compound and aromatic isocyanate compound) was formed on the PET film. ) was applied (3 ⁇ m) and adhered to the ONy film. An aluminum foil (JIS H4160: 1994 A8021H-O (thickness 40 ⁇ m)) was prepared as a barrier layer.
  • PTT polyethylene terephthalate
  • ONy stretched nylon
  • urethane adhesive polyol compound and aromatic isocyanate compound
  • a two-component urethane adhesive (polyol compound and aromatic isocyanate compound) was applied to one surface of the aluminum foil to form an adhesive layer (thickness 3 ⁇ m) on the barrier layer.
  • the adhesive layer on the barrier layer and the base material layer are laminated by a dry lamination method, and then aging treatment is carried out to produce a laminate of base material layer / adhesive layer / barrier layer. did. Both sides of the aluminum foil are subjected to chemical conversion treatment.
  • the chemical conversion treatment of the aluminum foil is performed by roll coating the both surfaces of the aluminum foil with a treatment liquid consisting of a phenolic resin, a chromium fluoride compound, and phosphoric acid so that the coating amount of chromium is 10 mg / m 2 (dry mass). It was carried out by coating and baking.
  • maleic anhydride modified polypropylene as an adhesive layer (thickness 40 ⁇ m) and random as a first heat-fusible resin layer (thickness 40 ⁇ m)
  • the adhesive layer / first heat-fusible resin layer is laminated on the barrier layer, and the base material layer (thickness 30 ⁇ m including adhesive) / adhesive layer (3 ⁇ m)
  • a barrier material (40 ⁇ m) / adhesive layer (40 ⁇ m) / first heat-fusible resin layer (40 ⁇ m) was laminated in this order to obtain a packaging material for an electricity storage device.
  • the first heat-fusible resin layers of Example 2 and Comparative Examples 2 and 3 each have the elastic modulus shown in Table 1 (elastic modulus measured using a nano indenter).
  • the adhesive layers of Example 2 and Comparative Examples 2 and 3 each have the logarithmic attenuation rate ⁇ E (value measured using a rigid pendulum type physical property tester) at 120 ° C. shown in Table 1. .
  • Example 3 As the base material layer, a polyethylene terephthalate (PET) film (thickness 25 ⁇ m) was used instead of the laminate of the polyethylene terephthalate (PET) film (thickness 12 ⁇ m) and the stretched nylon (ONy) film (thickness 15 ⁇ m). Except for the above, in the same manner as in Example 1, the substrate layer (thickness 25 ⁇ m) / adhesive layer (3 ⁇ m) / barrier layer (40 ⁇ m) / adhesive layer (20 ⁇ m) / second heat-fusible resin layer (50 ⁇ m) ) / First heat-fusible resin layer (10 ⁇ m) was laminated in this order to obtain a packaging material for an electricity storage device.
  • PET polyethylene terephthalate
  • Example 4 As a base material layer, a stretched nylon (ONy) film (thickness: 25 ⁇ m) was used instead of a laminate of a polyethylene terephthalate (PET) film (thickness: 12 ⁇ m) and a stretched nylon (ONy) film (thickness: 15 ⁇ m). Except for the above, in the same manner as in Example 1, the substrate layer (thickness 25 ⁇ m) / adhesive layer (3 ⁇ m) / barrier layer (40 ⁇ m) / adhesive layer (20 ⁇ m) / second heat-fusible resin layer (50 ⁇ m) ) / First heat-fusible resin layer (10 ⁇ m) was laminated in this order to obtain a packaging material for an electricity storage device.
  • PTT polyethylene terephthalate
  • Example 5 Base material in the same manner as in Example 1 except that the thicknesses of the adhesive layer, the first heat-fusible resin layer, and the second heat-fusible resin layer were set to the values shown in Table 2, respectively.
  • An outer packaging material for an electricity storage device in which layers (20 ⁇ m) were sequentially laminated was obtained.
  • Example 6 Base material in the same manner as in Example 1 except that the thicknesses of the adhesive layer, the first heat-fusible resin layer, and the second heat-fusible resin layer were set to the values shown in Table 2, respectively.
  • An outer packaging material for an electricity storage device in which layers (15 ⁇ m) were sequentially laminated was obtained.
  • Example 7 Base material in the same manner as in Example 1 except that the thicknesses of the adhesive layer, the first heat-fusible resin layer, and the second heat-fusible resin layer were set to the values shown in Table 2, respectively.
  • An outer packaging material for an electricity storage device in which layers (15 ⁇ m) were sequentially laminated was obtained.
  • Comparative Example 4 Base material in the same manner as in Comparative Example 1 except that the thicknesses of the adhesive layer, the first heat-fusible resin layer, and the second heat-fusible resin layer were set to the values shown in Table 2, respectively.
  • An outer packaging material for an electricity storage device in which layers (20 ⁇ m) were sequentially laminated was obtained.
  • Comparative Example 5 Base material in the same manner as in Comparative Example 1 except that the thicknesses of the adhesive layer, the first heat-fusible resin layer, and the second heat-fusible resin layer were set to the values shown in Table 2, respectively.
  • An outer packaging material for an electricity storage device in which layers (15 ⁇ m) were sequentially laminated was obtained.
  • Comparative Example 6 Base material in the same manner as in Comparative Example 1 except that the thicknesses of the adhesive layer, the first heat-fusible resin layer, and the second heat-fusible resin layer were set to the values shown in Table 2, respectively.
  • the elastic modulus when the indenter was pressed in the vertical direction was measured for each of the cross sections of the first heat-fusible resin layer and the second heat-fusible resin layer.
  • the measurement conditions were a load control method, and the pushing load was constant at 100 ⁇ N (loading from 0 to 100 ⁇ N in 10 seconds, holding 100 ⁇ N for 5 seconds, and unloading from 100 to 0 ⁇ N in 10 seconds).
  • the results are shown in Tables 1 and 2.
  • ⁇ Measurement of logarithmic attenuation rate ⁇ E of adhesive layer> The outer packaging materials for electricity storage devices of Examples 1 to 4 and Comparative Examples 1 and 2 obtained above were cut into rectangles each having a width (TD: Transverse Direction) of 15 mm and a length (MD: Machine Direction) of 150 mm, and test samples were obtained.
  • the MD of the exterior material for an electricity storage device corresponds to the rolling direction (RD) of the aluminum alloy foil
  • the TD of the exterior material for an electricity storage device corresponds to the TD of the aluminum alloy foil.
  • (RD) can be determined by the rolling pattern.
  • the MD of the exterior material for an electricity storage device cannot be specified due to the rolled grain of the aluminum alloy foil, it can be specified by the following method.
  • the sea-island structure is observed by observing the cross section of the heat-fusible resin layer of the exterior material for an electricity storage device with an electron microscope, and the The direction parallel to the cross section in which the average diameter of the island shape in the direction is maximum can be determined as MD.
  • the angle in the longitudinal direction of the heat-fusible resin layer is changed by 10 degrees from the direction parallel to the longitudinal cross section, and each angle is changed to the direction perpendicular to the longitudinal cross section.
  • the cross-sections are observed with electron micrographs to confirm the sea-island structure.
  • the shape of each individual island is observed in each cross section.
  • a straight line distance connecting the leftmost end in the direction perpendicular to the thickness direction of the heat-fusible resin layer and the rightmost end in the vertical direction is defined as a diameter y.
  • the average of the top 20 diameters y in the descending order of the diameter y of the island shape is calculated.
  • the direction parallel to the cross section in which the average of the diameter y of the island shape is the largest is determined as MD.
  • FIG. 7 shows a schematic diagram for explaining the method of measuring the logarithmic attenuation rate ⁇ E by the rigid pendulum measurement.
  • a rigid pendulum type physical property tester model number: RPT-3000W, manufactured by A & D Co., Ltd.
  • FRB-100 is used for the frame of the pendulum 30
  • RBP-060 is used for the cylindrical cylinder edge 30a at the edge, and cold heat is applied.
  • CHB-100, a vibration displacement detector 32, and a weight 33 were used for the block 31, and the initial amplitude was set to 0.3 degree.
  • the measurement surface (adhesive layer) of the test sample is placed on the cooling / heating block 31 so that the axial direction of the cylindrical cylinder edge 30a with the pendulum 30 is orthogonal to the MD direction of the test sample on the measurement surface. installed. Further, in order to prevent the test sample from floating and warping during the measurement, a tape was attached to a portion of the test sample that does not affect the measurement result and fixed on the cooling / heating block 31. The cylindrical cylinder edge 30a was brought into contact with the surface of the adhesive layer. Next, the cooling block 31 was used to measure the logarithmic decay rate ⁇ E of the adhesive layer in the temperature range of 30 ° C. to 200 ° C. at a temperature rising rate of 3 ° C./min.
  • the adhesive layer the above-mentioned Examples 1 to 4 were used.
  • each of the exterior materials for electricity storage devices of Comparative Examples 1 and 2 was immersed in 15% hydrochloric acid to dissolve the base material layer and the aluminum foil, and a test sample including only the adhesive layer and the heat-fusible resin layer was sufficiently prepared. After drying, the logarithmic decay rate ⁇ E was measured. Table 1 shows the logarithmic decay rate ⁇ E at 120 ° C., respectively.
  • ⁇ E [ln (A1 / A2) + ln (A2 / A3) +. . . + Ln (An / An + 1)] / n A: amplitude n: wave number
  • each of the outer packaging materials for electricity storage devices obtained in the above-described production example was cut to prepare a strip piece having a width of 40 mm and a length of 100 mm, which was used as a test sample (the outer packaging material for electricity storage device 10 ) (FIG. 13A).
  • a stainless wire 11 having a diameter of 25 ⁇ m and a length of 70 mm was arranged in the widthwise center of the aluminum plate 12 having a width of 30 mm, a length of 100 mm and a thickness of 100 ⁇ m (FIG. 13B).
  • the test sample was arranged so that the heat-fusible resin layer side of the test sample and the wire 11 side of the aluminum plate 12 were opposed to each other (FIG. 13C).
  • the center of the test sample in the width direction was made to coincide with the center of the aluminum plate 12 in the width direction.
  • the positive electrode of the tester was connected to the aluminum plate 12, and the negative electrode was connected to the test sample.
  • the alligator clip was sandwiched so as to reach the barrier layer from the base material layer side of the test sample, and the negative pole of the tester and the barrier layer were electrically connected.
  • the tester was prepared to emit a conduction (short circuit) signal when the applied voltage was 100 V and the resistance was 200 M ⁇ or less.
  • FIGS. 10 to 12 show the base material layer 1, the adhesive layer 2, the barrier layer 3, the adhesive layer 5, the first heat-fusible resin layer 41, and the second heat-fusible resin, respectively.
  • the position of layer 42 is indicated.
  • the polypropylene used for the first heat-fusible resin layer has a concentration of lithium hexafluorophosphate of 1 mol / l and a volume ratio of ethylene carbonate, diethyl carbonate and dimethyl carbonate of 1: After being left to stand for 72 hours in an electrolytic solution which is a 1: 1 solution, it was sufficiently dried. Next, a DSC curve was obtained for the dried polypropylene using differential scanning calorimetry (DSC) in accordance with JIS K7121: 2012. Next, the temperature difference T 2 between the extrapolation melting start temperature and the extrapolation melting end temperature of the melting peak temperature of the first heat-fusible resin layer after drying was measured from the obtained DSC curve.
  • DSC differential scanning calorimetry
  • the melting peak with the largest difference in the input of heat energy is analyzed. went. Even when two or more peaks were overlapped with each other, the analysis was performed only on the melting peak that maximizes the difference in input of thermal energy.
  • tensile strength (seal strength) was measured in the same manner except that the electrolytic solution was not injected into the test sample.
  • the maximum tensile strength until the heat-sealed portion is completely peeled off is defined as the sealing strength before contact with the electrolytic solution.
  • the sealing strength before contact with the electrolytic solution is described as the sealing strength when the contact time of the electrolytic solution at 85 ° C. is 0 h.
  • both ends in the x direction of the folded back test sample were sealed by heat sealing (temperature 190 ° C., surface pressure 2.0 MPa, time 3 seconds), and formed into a bag shape having one opening E (FIG. 8c).
  • an electrolyte solution concentration of lithium hexafluorophosphate is 1 mol / l and volume ratio of ethylene carbonate, diethyl carbonate and dimethyl carbonate is 1: 1: 1 from the opening E of the test sample formed in the shape of a bag. 6 g of the solution of No. 1) was injected (FIG. 8 d), and the end of the opening E was sealed by heat sealing (temperature 190 ° C., surface pressure 2.0 MPa, time 3 seconds) (FIG. 8 e).
  • the folded back portion of the bag-shaped test sample was turned down, and the bag was allowed to stand in an environment of a temperature of 85 ° C. for a predetermined storage time (time for contacting with electrolyte solution, 0 hour, 24 hours, 72 hours).
  • the end of the test sample was then cut (Fig. 8e) and all the electrolyte was drained.
  • the electrolytic solution attached to the surface of the heat-fusible resin layer, the upper and lower surfaces of the test sample were sandwiched between metal plates 20 (7 mm width), and the temperature was 190 ° C., the surface pressure was 1.0 MPa, and the time was 3 seconds.
  • the heat-fusible resin layer was heat-fused under the conditions (FIG. 8f).
  • the test sample was cut into a width of 15 mm with a double-edged sample cutter so that the seal strength at a width (x direction) of 15 mm could be measured (Fig. 8f, g).
  • a tensile tester manufactured by Shimadzu Corporation, AGS-xplus (trade name)
  • the tensile strength was measured by peeling the heat-sealed interface under the condition that the distance was 50 mm (FIG. 6).
  • the maximum tensile strength until the heat-sealed portion was completely peeled was taken as the seal strength after contact with the electrolytic solution.
  • Table 4 shows the retention rate (%) of the seal strength after contact with the electrolytic solution, with the seal strength before contacting the electrolytic solution as the standard (100%).
  • the value obtained by dividing the temperature difference T 2 by the temperature difference T 1 was 0.60 or more, and the exterior material for an electricity storage device of Example 2 was not heated in a high temperature environment.
  • the electrolyte is in contact with the fusible resin layer, and even when the thermofusible resin layer is heat-sealed in a state in which the electrolyte is adhered to the heat-fusible resin layer, high sealing strength is obtained by the heat fusion. I know that it will work.
  • Item 1 At least a base material layer, a barrier layer, and a heat-fusible resin layer, which is composed of a laminate provided in this order,
  • the heat-fusible resin layer is composed of a single layer or multiple layers,
  • the heat-fusible resin layer includes at least one layer having a modulus of elasticity of 1300 MPa or more measured by a nanoindentation method, which is measured with an indentation load of 100 ⁇ N, from the cross section in the stacking direction of the laminate, and an exterior for an electricity storage device.
  • Material Item 2.
  • Item 2. The exterior material for an electricity storage device according to Item 1, comprising an adhesive layer between the barrier layer and the heat-fusible resin layer.
  • Item 3 Outer packaging for an electricity storage device according to Item 2, wherein, of the heat-fusible resin layers, the elastic modulus is 1300 MPa or more and the thickness of the layer having the maximum thickness is larger than the thickness of the adhesive layer. Material. Item 4. Item 4. The exterior material for an electricity storage device according to Item 2 or 3, wherein the adhesive layer is made of a thermoplastic resin. Item 5. 5. The outer casing material for an electricity storage device according to any one of Items 2 to 4, wherein the adhesive layer has a logarithmic decrement ⁇ E at 120 ° C. in a rigid body pendulum measurement of 0.22 or less. Item 6.
  • the heat-fusible resin layer comprises a first heat-fusible resin layer and a second heat-fusible resin layer in order from the surface side of the laminate.
  • Item 6. The exterior material for an electricity storage device according to any one of Items 2 to 5, wherein the thickness of the second heat-fusible resin layer is larger than the thickness of the adhesive layer.
  • the heat-fusible resin layer comprises a first heat-fusible resin layer and a second heat-fusible resin layer in order from the surface side of the laminate.
  • the heat-fusible resin layer comprises a first heat-fusible resin layer and a second heat-fusible resin layer in order from the surface side of the laminate.
  • Item 8. The exterior material for an electricity storage device according to any one of Items 1 to 7, wherein the first heat-fusible resin layer and the second heat-fusible resin layer are made of different resins.
  • An adhesive layer is provided between the barrier layer and the heat-fusible resin layer, The heat-fusible resin layer comprises a first heat-fusible resin layer and a second heat-fusible resin layer in order from the surface side of the laminate.
  • the electricity storage device according to any one of Items 1 to 8, wherein the adhesive layer, the first heat-fusible resin layer, and the second heat-fusible resin layer are coextruded resin layers. Exterior material.
  • the heat-fusible resin layer comprises a first heat-fusible resin layer forming the surface of the laminate, The value obtained by measuring the temperature difference T 1 and the temperature difference T 2 of the first heat-fusible resin layer by the following method and dividing the temperature difference T 2 by the temperature difference T 1 is 0.
  • the exterior material for an electricity storage device according to any one of claims 1 to 9, wherein the exterior material is 60 or more.
  • a substrate layer, a barrier layer, and a heat-fusible resin layer are laminated in this order to obtain a laminate
  • the heat-fusible resin layer is composed of a single layer or multiple layers
  • the heat-fusible resin layer includes at least one layer having a modulus of elasticity of 1300 MPa or more measured by a nanoindentation method, which is measured with an indentation load of 100 ⁇ N, from the cross section in the stacking direction of the laminate, and an exterior for an electricity storage device. Method of manufacturing wood.
  • An electricity storage device wherein an electricity storage device element including at least a positive electrode, a negative electrode, and an electrolyte is contained in a package formed of the exterior material for an electricity storage device according to any one of Items 1 to 11.

Landscapes

  • 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

L'invention concerne un matériau de conditionnement pour un dispositif de stockage d'énergie comprenant un stratifié qui comprend, dans l'ordre, au moins une couche de matériau de base, une couche barrière et une couche de résine thermofusible. La couche de résine thermofusible comprend une seule couche ou une pluralité de couches. La couche de résine thermofusible comprend au moins une couche ayant une élasticité d'au moins 1300 MPa à partir d'une section transversale dans la direction de stratification du stratifié, mesurée à l'aide d'un procédé de nano-indentation à l'aide d'une charge d'indentation de 100 µN.
PCT/JP2019/041799 2018-10-24 2019-10-24 Matériau de conditionnement pour dispositif de stockage d'énergie, son procédé de production et dispositif de stockage d'énergie WO2020085464A1 (fr)

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WO2021251501A1 (fr) * 2020-06-12 2021-12-16 大日本印刷株式会社 Matériau extérieur pour dispositif de stockage d'énergie, son procédé de fabrication et dispositif de stockage d'énergie

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WO2023210828A1 (fr) * 2022-04-28 2023-11-02 大日本印刷株式会社 Film adhésif pour borne métallique ainsi que procédé de fabrication de celui-ci, borne métallique avec film adhésif pour borne métallique, matériau d'enveloppe extérieure pour dispositif d'accumulation d'énergie, ensemble comportant un matériau d'enveloppe extérieure pour dispositif d'accumulation d'énergie et un film adhésif pour borne métallique, et dispositif d'accumulation d'énergie ainsi que procédé de fabrication de celui-ci
WO2023210827A1 (fr) * 2022-04-28 2023-11-02 大日本印刷株式会社 Film adhésif pour borne métallique ainsi que procédé de fabrication de celui-ci, borne métallique avec film adhésif pour borne métallique, matériau d'enveloppe extérieure pour dispositif d'accumulation d'énergie, ensemble comportant un matériau d'enveloppe extérieure pour dispositif d'accumulation d'énergie et un film adhésif pour borne métallique, et dispositif d'accumulation d'énergie ainsi que procédé de fabrication de celui-ci

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JP7035538B2 (ja) * 2015-11-30 2022-03-15 大日本印刷株式会社 電池用包装材料、電池、電池用包装材料の製造方法
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JP2014179308A (ja) * 2013-02-18 2014-09-25 Dainippon Printing Co Ltd 電池用包装材料
WO2014178343A1 (fr) * 2013-05-01 2014-11-06 大倉工業株式会社 Matériau de conditionnement de batterie
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JP7024935B1 (ja) * 2020-06-12 2022-02-24 大日本印刷株式会社 蓄電デバイス用外装材、その製造方法、及び蓄電デバイス

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