CN107305930B - Outer packaging material for electricity storage device and electricity storage device - Google Patents

Outer packaging material for electricity storage device and electricity storage device Download PDF

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Publication number
CN107305930B
CN107305930B CN201710252185.9A CN201710252185A CN107305930B CN 107305930 B CN107305930 B CN 107305930B CN 201710252185 A CN201710252185 A CN 201710252185A CN 107305930 B CN107305930 B CN 107305930B
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layer
melting
point
low
thickness
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CN107305930A (en
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永田健祐
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Lishennoco Packaging Co ltd
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Showa Denko Packaging Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/78—Cases; Housings; Encapsulations; Mountings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/117—Inorganic material
    • H01M50/119—Metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/121—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
    • H01M50/133—Thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/06—Coating on the layer surface on metal layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/206—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • 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

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

Abstract

The present invention relates to an outer package for an electricity storage device and an electricity storage device. The outer package for a power storage device of the present invention is configured by: the sealant layer comprises a first low-melting-point layer made of a thermoplastic resin and constituting an outermost layer on the metal foil layer side, a second low-melting-point layer made of a thermoplastic resin and constituting an outermost layer on the side opposite to the metal foil layer side, and a high-melting-point intermediate layer made of a thermoplastic resin and arranged between the first low-melting-point layer and the second low-melting-point layer, wherein the high-melting-point intermediate layer has a melting point of 120 to 180 ℃, the first and second low-melting-point layers have a melting point lower than that of the high-melting-point intermediate layer, the high-melting-point intermediate layer has a thickness of 20 [ mu ] m or more, the high-melting-point intermediate layer has a thickness of "X" and the sealant layer has a thickness of "Y", and when the sealant layer has a thickness of "Y", the relationship of 0.50Y to 0.99Y is satisfied. This can suppress the outflow of the seal layers when the seal layers are thermally welded to each other, and can ensure sufficient insulation in the heat-sealed portion.

Description

Outer packaging material for electricity storage device and electricity storage device
Technical Field
The present invention relates to an outer package for an electricity storage device, and an electricity storage device that is externally packaged with the outer package, the electricity storage device including: batteries, capacitors (capacitors) used in portable devices such as smart phones, tablet computers, etc.; the present invention is used for batteries, capacitors, and the like in hybrid vehicles, electric vehicles, wind power generation, solar power generation, and night power storage applications.
Background
In recent years, with the reduction in thickness and weight of mobile electronic devices such as smartphones and tablet personal computer terminals, a laminate (laminate outer packaging material) formed of a heat-resistant resin layer/adhesive layer/metal foil layer/adhesive layer/thermoplastic resin layer has been used as an outer packaging material for power storage devices such as lithium ion secondary batteries, lithium polymer secondary batteries, lithium ion capacitors (lithium ion capacitors), and electric double layer capacitors mounted on the mobile electronic devices, instead of a conventional metal can (see patent document 1). The laminate (outer packaging material) having the above-described structure is used for outer packaging of a power source for an electric vehicle or the like, a large-sized power source for electric storage, a capacitor, and the like.
Patent document 1: japanese laid-open patent publication No. 2007-161310
Disclosure of Invention
Problems to be solved by the invention
However, the above-described conventional technique (the outer package described in patent document 1) has the following problems. That is, when the battery or the like is externally packed, the seal layers of the external packaging material are thermally welded to each other and sealed, but if foreign matter (electrode active material, electrolyte, or the like) adheres to the surfaces of the seal layers, the heat-sealed portion may be thinned, and it may be difficult to ensure sufficient insulation in the heat-sealed portion. In particular, in the tab (tab) portion, insulation tends to be insufficient, and a short circuit may occur.
The present invention has been made in view of the above-described technical background, and an object of the present invention is to provide an outer package for an electricity storage device, which can suppress the outflow of seal layers when the seal layers are thermally welded to each other, can secure sufficient insulation in a heat-sealed portion, and can secure sufficient sealing strength.
Means for solving the problems
In order to achieve the above object, the present invention provides the following means.
[1] An outer package for an electricity storage device, comprising a metal foil layer and a sealant layer laminated on one surface of the metal foil layer,
the sealing layer comprises: a first low-melting-point layer made of a thermoplastic resin and constituting an outermost layer on the metal foil layer side in the sealant layer, a second low-melting-point layer made of a thermoplastic resin and constituting an outermost layer on the opposite side to the metal foil layer side in the sealant layer, and a high-melting-point intermediate layer made of a thermoplastic resin and disposed between the first low-melting-point layer and the second low-melting-point layer,
the melting point of the high-melting-point middle layer is 120-180 ℃,
the melting point of the first low-melting-point layer and the melting point of the second low-melting-point layer are lower than the melting point of the high-melting-point intermediate layer,
the thickness of the high-melting-point intermediate layer is 20 [ mu ] m or more,
when the thickness of the high-melting-point intermediate layer is defined as "X" and the thickness of the sealing layer is defined as "Y", X is 0.50Y-0.99Y.
[2] The outer package for a power storage device according to item 1 above, wherein the first low-melting-point layer has a thickness of 0.5 μm or more, and the second low-melting-point layer has a thickness of 1 μm or more.
[3] The outer package for a power storage device according to item 1 or 2 above, wherein the melting point of the high-melting-point intermediate layer is higher than the melting point of the first low-melting-point layer by 20 ℃ or more, and the melting point of the high-melting-point intermediate layer is higher than the melting point of the second low-melting-point layer by 20 ℃ or more.
[4] The outer covering material for a power storage device as defined in any one of the aforementioned items 1 to 3, wherein the thermoplastic resin constituting the high-melting-point intermediate layer is an ethylene-propylene block copolymer resin having a weight-average molecular weight in a range of 200,000 to 800,000,
the thermoplastic resin constituting the first low-melting-point layer and the thermoplastic resin constituting the second low-melting-point layer are ethylene-propylene random copolymer resins having a weight-average molecular weight in the range of 10,000 to 200,000.
[5] The outer covering material for a power storage device according to any one of the above items 1 to 4, wherein a heat-resistant resin layer is laminated on the other surface of the metal foil layer via an outer adhesive layer.
[6] An electricity storage device is characterized by comprising:
an electricity storage device main body section; and
the outer packaging material for an electricity storage device according to any one of the aforementioned items 1 to 5,
the power storage device main body is externally coated with the outer coating material.
ADVANTAGEOUS EFFECTS OF INVENTION
In the invention as recited in the aforementioned item [1], since the high-melting-point intermediate layer has a melting point of 120 to 180 ℃ and the low-melting-point layer is present outside the high-melting-point intermediate layer, it is possible to suppress the outflow of the high-melting-point intermediate layer in the heat-sealed portion when the seal layers are heat-sealed to each other, and since the thickness of the high-melting-point intermediate layer is in the relationship of 20 μm or more and 0.50Y X0.99Y, it is possible to suppress the reduction in thickness due to the outflow of the seal layers when the seal layers are heat-sealed to each other, it is possible to ensure sufficient insulation in the heat-sealed portion and to sufficiently prevent the occurrence of short circuits. Further, since the first low-melting-point layer and the second low-melting-point layer having a lower melting point than the melting point of the high-melting-point intermediate layer are disposed on both sides of the high-melting-point intermediate layer, when the sealing layers are heat-welded to each other, heat sealing can be performed satisfactorily without melting the high-melting-point intermediate layer, and sealing and joining can be performed with sufficient sealing strength (sufficient sealing strength can be ensured in the heat-sealed portion).
In the invention as recited in the aforementioned item [2], since the thickness of the first low melting point layer is 0.5 μm or more and the thickness of the second low melting point layer is 1 μm or more, the sealing layers can be sealed with a more sufficient sealing strength (a more sufficient sealing strength can be secured in the heat-sealed portion) when the sealing layers are heat-welded to each other.
In the invention as recited in the aforementioned item [3], since the high-melting-point intermediate layer has a melting point higher than that of the first low-melting-point layer by 20 ℃ or more and the high-melting-point intermediate layer has a melting point higher than that of the second low-melting-point layer by 20 ℃ or more, the outflow of the sealing layers in the heat-sealed portion can be sufficiently suppressed when the sealing layers are heat-welded to each other, and a more sufficient insulation property can be secured in the heat-sealed portion.
In the invention as recited in the aforementioned item [4], since the thermoplastic resin constituting the high-melting-point intermediate layer is an ethylene-propylene block copolymer resin having a weight average molecular weight in the range of 200,000 to 800,000, the outflow of the seal layers in the heat-sealed portion can be more sufficiently suppressed when the seal layers are heat-welded to each other, and the insulation properties in the heat-sealed portion can be further improved. Further, since the thermoplastic resins constituting the first and second low-melting-point layers are each an ethylene-propylene random copolymer resin having a weight average molecular weight in the range of 10,000 to 200,000, when the seal layers are thermally welded to each other, the seal bonding can be performed with a more sufficient seal strength (a more sufficient seal strength can be ensured in the heat seal portion).
In the invention as recited in the aforementioned item [5], since the heat-resistant resin layer is laminated on the other surface of the metal foil layer via the outer adhesive layer, the insulation property on the other surface side of the metal foil layer can be sufficiently ensured, and the physical strength and impact resistance of the exterior material can be improved.
[6] In the invention (power storage device) of (1), there is provided a power storage device that is externally wrapped with an outer covering material, wherein the heat-sealed portions of the outer covering material are bonded with sufficient sealing strength, and sufficient insulation is ensured in the heat-sealed portions.
Drawings
Fig. 1 is a cross-sectional view showing an embodiment of an outer package for a power storage device according to the present invention.
Fig. 2 is a cross-sectional view showing an embodiment of a power storage device formed using the outer package for a power storage device according to the present invention.
Description of the reference numerals
An outer packaging material for an electric storage device
A heat-resistant resin layer (outer layer)
Sealing layer (inner layer)
A metal foil layer
Outer adhesive layer
Inner adhesive layer
A first low melting point layer
A second low melting point layer
A high melting point interlayer
Shaped housing
Electric storage device body section
Electric storage device
Detailed Description
Fig. 1 shows an embodiment of an outer package 1 for a power storage device according to the present invention. This exterior material 1 for a power storage device is used for a lithium ion secondary battery case. The outer package material 1 for a power storage device can be used as a case of a secondary battery by performing forming such as deep drawing and stretch forming. The outer cover 1 for a power storage device may be used in the form of a planar outer cover without being molded (see fig. 2).
In the present embodiment, the outer package 1 for a power storage device includes: the sealing layer (inner layer) 3 is laminated and integrated on one surface of the metal foil layer 4 via the inner adhesive layer 6, and the heat-resistant resin layer (outer layer) 2 is laminated and integrated on the other surface of the metal foil layer 4 via the outer adhesive layer 5.
The sealing layer (thermoplastic resin layer) (inner layer) 3 described above plays a role of: the outer material is provided with excellent chemical resistance even against highly corrosive electrolyte solutions used in lithium ion secondary batteries and the like, and heat sealability is imparted to the outer material.
In the present invention, the sealing layer 3 has a structure including: a first low melting point layer 7 made of a thermoplastic resin constituting an outermost layer of the sealant layer 3 on the metal foil layer 4 side; a second low melting point layer 8 made of a thermoplastic resin and constituting an outermost layer on the side opposite to the metal foil layer side in the sealing layer 3; and a high-melting-point intermediate layer 9 (see fig. 1) made of a thermoplastic resin and disposed between the first low-melting-point layer 7 and the second low-melting-point layer 8, and configured to: the melting point of the high-melting-point intermediate layer 9 is 120 to 180 ℃, the melting point of the first low-melting-point layer 7 and the melting point of the second low-melting-point layer 8 are lower than the melting point of the high-melting-point intermediate layer 9, the thickness of the high-melting-point intermediate layer is 20 μm or more, and when the thickness of the high-melting-point intermediate layer 9 is "X" and the thickness of the sealing layer 3 is "Y", X is 0.50Y-0.99Y.
In the above embodiment, the sealing layer 3 is formed by laminating 3 layers of the first low-melting-point layer 7, the high-melting-point intermediate layer 9, and the second low-melting-point layer 8, but is not particularly limited to such a 3-layer laminated structure, and may be formed by laminating 4 layers, 5 layers, or 6 or more layers as long as the structure includes at least the first low-melting-point layer 7, the high-melting-point intermediate layer 9, and the second low-melting-point layer 8.
The melting point of the high-melting-point intermediate layer 9 must be 120 to 180 ℃. When the temperature is less than 120 ℃, the high-melting-point intermediate layer is likely to flow out in the heat-sealed portion even when the seal layers are heat-sealed to each other, and it is therefore difficult to ensure sufficient insulation in the heat-sealed portion. On the other hand, if the melting point is higher than 180 ℃, the sealing temperature needs to be increased in order to thermally bond the sealing layers to each other, but if the sealing temperature is high, the electrolyte is easily decomposed by the influence of heat. Among them, the melting point of the high-melting-point intermediate layer 9 is preferably 150 to 170 ℃. The heat-sealing temperature at the time of heat-sealing the sealing layers to each other is preferably set to a range of +10 ℃ for the melting point of the high-melting-point intermediate layer 9 and +40 ℃ for the melting point of the high-melting-point intermediate layer 9.
The thickness of the high melting point intermediate layer 9 must be 20 μm or more. If the thickness is less than 20 μm, the thickness of the sealing layer 3 for ensuring sufficient insulation properties cannot be maintained (ensured) after heat sealing. The thickness of the high-melting-point intermediate layer 9 is preferably 20 to 30 μm. In addition, if the thickness of the high melting point intermediate layer 9 is too large, heat conduction at the time of heat sealing is reduced, and sealing and joining may become insufficient, and from this viewpoint, the thickness of the high melting point intermediate layer 9 is preferably set to 40 μm or less.
Further, the following constitution is adopted: when the thickness of the high-melting-point intermediate layer 9 is "X" and the thickness of the sealing layer 3 is "Y", X is 0.50Y-0.99Y. When the thickness X of the high-melting-point intermediate layer 9 is less than 50% of the thickness Y of the sealing layer 3, the low-melting-point layer excessively flows out when the sealing layers are thermally welded to each other, and there is a possibility that the distance of the insulating portion cannot be sufficiently secured after the heat sealing. In addition, when the thickness X of the high-melting-point intermediate layer 9 is 99% or more of the thickness Y of the sealing layer 3, there is a problem that sealing bonding cannot be performed with sufficient sealing strength when the sealing layers are thermally welded to each other. Among them, a structure satisfying the relationship of 0.60 Y.ltoreq.X.ltoreq.0.90Y is preferable.
The preferred composition is: the melting point of the high-melting-point intermediate layer 9 is 20 ℃ or higher than the melting point of the first low-melting-point layer 7, and the melting point of the high-melting-point intermediate layer 9 is 20 ℃ or higher than the melting point of the second low-melting-point layer 8. With such a configuration, the flow-out of the seal layer 3 in the heat-sealed portion can be sufficiently suppressed when the seal layers are heat-sealed to each other. Among them, the preferable constitution is: the melting point of the high-melting-point intermediate layer 9 is 25 to 35 ℃ higher than the melting point of the first low-melting-point layer 7, and the melting point of the high-melting-point intermediate layer 9 is 25 to 35 ℃ higher than the melting point of the second low-melting-point layer 8.
The melting point of the first low melting point layer 7 and the melting point of the second low melting point layer 8 are both preferably in the range of 90 to 140 ℃.
The thermoplastic resin forming the first low-melting-point layer 7, the second low-melting-point layer 8, and the high-melting-point intermediate layer 9 is not particularly limited, and is preferably an unstretched film. The thermoplastic resin is not particularly limited, and at least one thermoplastic resin selected from the group consisting of polyethylene, polypropylene, olefin copolymers, acid-modified products thereof, and ionomers (ionomers) is preferably used.
Among them, the thermoplastic resin constituting the high-melting-point intermediate layer 9 is preferably an ethylene-propylene block copolymer resin having a weight average molecular weight in the range of 200,000 to 800,000. In this case, the flow-out of the seal layers in the heat-sealed portion can be more sufficiently suppressed when the seal layers are heat-welded to each other.
The thermoplastic resin constituting the first low-melting layer 7 and the thermoplastic resin constituting the second low-melting layer 8 are preferably ethylene-propylene random copolymer resins having a weight average molecular weight in the range of 10,000 to 200,000. In this case, the sealing layers can be sealed and joined with a more sufficient sealing strength when the sealing layers are thermally welded to each other. For example, the following configuration can be exemplified: the first low melting point layer 7 is formed of an ethylene-propylene random copolymer resin having a weight average molecular weight of 100,000, and the second low melting point layer 8 is formed of an ethylene-propylene random copolymer resin having a weight average molecular weight of 70,000; the first low-melting-point layer 7 and the second low-melting-point layer 8 are each formed of an ethylene-propylene random copolymer resin having a weight average molecular weight of 120,000.
Further, it is preferable to adopt a configuration in which the thickness of the first low melting point layer 7 is 0.5 μm or more and the thickness of the second low melting point layer 8 is 1 μm or more, and in the case of adopting such a configuration, when the sealing layers are thermally welded to each other, it is possible to perform sealing bonding while securing a more sufficient sealing strength. Among them, the thickness of the first low melting point layer 7 is particularly preferably 1 μm to 10 μm. The thickness of the second low melting point layer 8 is particularly preferably 1 μm to 10 μm.
The thickness (total thickness) of the sealing layer 3 is preferably set to 21 μm to 40 μm. The occurrence of pinholes can be sufficiently prevented by setting the thickness to 21 μm or more, and the amount of resin used can be reduced by setting the thickness to 40 μm or less, thereby enabling cost reduction. Among them, it is particularly preferable to set the thickness of the sealing layer 3 to 25 μm to 35 μm.
The metal foil layer 4 plays a role of imparting gas barrier properties (preventing the intrusion of oxygen and moisture) to the outer wrapper 1. The metal foil layer 4 is not particularly limited, and examples thereof include aluminum foil, SUS foil (stainless steel foil), and copper foil, and aluminum foil is generally used. The thickness of the metal foil layer 4 is preferably 10 μm to 100 μm. By having 10 μm or more, pinholes can be prevented from being generated at the time of rolling at the time of manufacturing the metal foil, and by having 100 μm or less, stress at the time of forming such as stretch forming and drawing can be reduced, and formability can be improved. Among them, the thickness of the metal foil layer 4 is particularly preferably 20 μm to 50 μm.
The metal foil layer 4 is preferably subjected to chemical conversion treatment on at least the inner surface (the surface on the inner pressure-sensitive adhesive layer 6 side). By performing such chemical conversion treatment, corrosion of the surface of the metal foil due to the contents (electrolyte solution of the battery, etc.) can be sufficiently prevented. For example, the metal foil is subjected to a chemical conversion treatment by performing the following treatment. That is, for example, the chemical conversion treatment is performed by applying any one of aqueous solutions 1) to 3) below to the surface of the metal foil subjected to the degreasing treatment and then drying the applied aqueous solution:
1) contains phosphoric acid;
chromic acid; and
an aqueous solution of a mixture of at least 1 compound selected from the group consisting of metal salts of fluoride and non-metal salts of fluoride;
2) contains phosphoric acid;
at least 1 resin selected from the group consisting of acrylic resins, chitosan (chitosan) derivative resins, and phenolic resins; and
an aqueous solution of a mixture of at least 1 compound selected from the group consisting of chromic acid and chromium (III) salts;
3) contains phosphoric acid;
at least 1 resin selected from the group consisting of acrylic resins, chitosan derivative resins, and phenolic resins;
at least one compound selected from the group consisting of chromic acid and chromium (III) salts; and
an aqueous solution of a mixture of at least 1 compound selected from the group consisting of metal salts of fluorides and non-metal salts of fluorides.
The amount of chromium deposited on the chemical conversion coating (per surface) is preferably 0.1mg/m2～50mg/m2Particularly preferably 2mg/m2～20mg/m2。
In the present invention, the heat-resistant resin layer 2 is not an essential constituent layer, but it is preferable to adopt a configuration in which the heat-resistant resin layer 2 is laminated on the other surface of the metal foil layer 4 via an outer pressure-sensitive adhesive layer 5 (see fig. 1). By providing such a heat-resistant resin layer 2, the insulation property on the other surface side of metal foil layer 4 can be sufficiently ensured, and the physical strength and impact resistance of exterior material 1 can be improved.
As the heat-resistant resin constituting the heat-resistant resin layer (outer layer) 2, a heat-resistant resin that does not melt at a heat-sealing temperature when heat-sealing the outer packaging material is performed is used. As the heat-resistant resin, a heat-resistant resin having a melting point higher than the melting point of the high-melting-point intermediate layer 9 constituting the sealing layer 3 by 10 ℃ or more is preferably used, and particularly a heat-resistant resin having a melting point higher than the melting point of the high-melting-point intermediate layer 9 by 20 ℃ or more is preferably used.
The heat-resistant resin layer (outer layer) 2 is not particularly limited, and examples thereof include polyamide films such as nylon films, polyester films, polyolefin films, and the like, and stretched films of these films can be preferably used. Among them, as the heat-resistant resin layer 2, a biaxially stretched polyamide film such as a biaxially stretched nylon film, a biaxially stretched polybutylene terephthalate (PBT) film, a biaxially stretched polyethylene terephthalate (PET) film, a biaxially stretched polyethylene naphthalate (PEN) film, and a biaxially stretched polypropylene film are particularly preferably used. The nylon film is not particularly limited, and examples thereof include a nylon 6 film, a nylon 6, 6 film, and an MXD nylon film. The heat-resistant resin layer 2 may be formed of a single layer, or may be formed of a plurality of layers including a polyester film/a polyamide film (a plurality of layers including a PET film/a nylon film, etc.), for example. In the multilayer structure exemplified above, the polyester film is preferably disposed at a position further outside than the polyamide film, and similarly, the PET film is preferably disposed at a position further outside than the nylon film.
The thickness of the heat-resistant resin layer 2 is preferably 8 to 50 μm. By setting the preferable lower limit value or more, sufficient strength as an outer covering material can be secured, and by setting the preferable upper limit value or less, stress at the time of forming such as stretch forming or drawing can be reduced, and formability can be improved. Among them, the thickness of the heat-resistant resin layer 2 is particularly preferably 12 μm to 25 μm.
The outer pressure-sensitive adhesive layer 5 is not particularly limited, and examples thereof include a polyurethane pressure-sensitive adhesive layer, a polyester polyurethane pressure-sensitive adhesive layer, and a polyether polyurethane pressure-sensitive adhesive layer. The thickness of the outer pressure-sensitive adhesive layer 5 is preferably set to 1 μm to 5 μm. Among them, the thickness of the outer pressure-sensitive adhesive layer 5 is particularly preferably set to 1 μm to 3 μm from the viewpoint of reduction in thickness and weight of the outer covering material.
The inner pressure-sensitive adhesive layer 6 is not particularly limited, and for example, a pressure-sensitive adhesive layer exemplified as the outer pressure-sensitive adhesive layer 5 may be used, but a polyolefin-based pressure-sensitive adhesive that is less likely to swell with an electrolyte solution is preferably used. The thickness of the inner pressure-sensitive adhesive layer 6 is preferably set to 1 to 5 μm. Among them, the thickness of the inner pressure-sensitive adhesive layer 6 is particularly preferably set to 1 μm to 3 μm from the viewpoint of reduction in thickness and weight of the outer covering material.
The thickness of the outer package 1 for a power storage device of the present invention is preferably set to 60 μm to 160 μm.
By molding (deep drawing, stretch forming, etc.) outer package 1 of the present invention, a molded case (battery case, etc.) can be obtained. The outer wrapper 1 of the present invention may be used without molding.
Fig. 2 shows an embodiment of a power storage device 20 configured by using the exterior material 1 of the present invention. The power storage device 20 is a lithium ion secondary battery.
The battery 20 includes: a bare cell (bare cell)21 composed of a positive electrode active material, a negative electrode active material, a separator, and an electrolyte, tabs 22 connected to the positive electrode and the negative electrode, the planar outer cover 1 that is not molded, and a molded case 11 (see fig. 2) having a housing recess 11b formed by molding the outer cover 1. The bare cell 21 and the tab 22 constitute an electric storage device main body 19.
The electric storage device (battery) 20 is configured such that the bare cell 21 and a part of the tab 22 are housed in the housing recess 11b of the molded case 11, the planar outer cover 1 is disposed on the molded case 11, and a heat-sealed portion (heat-sealed portion) is formed by joining (the inner layer 3 of) the peripheral edge portion of the outer cover 1 and (the inner layer 3 of) the sealing peripheral edge portion 11a of the molded case 11 by heat sealing. The distal end portions of the tabs 22 are led out to the outside (see fig. 2).
Examples
Next, specific examples of the present invention will be described, but the present invention is not particularly limited to these examples.
< example 1>
A chemical conversion coating film was formed by applying a chemical conversion treatment solution containing phosphoric acid, polyacrylic acid (acrylic resin), a chromium (III) salt compound, water, and alcohol to both sides of an aluminum foil (annealed aluminum foil of a8021 defined by JIS H4160) 4 having a thickness of 35 μm, and then drying at 180 ℃. The chromium deposition amount on each surface of the chemical conversion coating was 10mg/m2。
Next, a biaxially stretched nylon 6 film (outer layer) 2 having a thickness of 15 μm was dry-laminated (bonded) on one surface of the aluminum foil 4 subjected to the chemical conversion treatment via a two-pack curable urethane adhesive 5.
Then, a first low-melting layer 7 having a thickness of 4.5 μm and made of an ethylene-propylene random copolymer (weight average molecular weight 150,000) having a melting point of 137 ℃, a high-melting intermediate layer 9 having a thickness of 21 μm and made of an ethylene-propylene block copolymer (weight average molecular weight 600,000) having a melting point of 163 ℃, and a second low-melting layer 8 having a thickness of 4.5 μm and made of an ethylene-propylene random copolymer (weight average molecular weight 150,000) having a melting point of 137 ℃ were coextruded in this order by using a T die to obtain a sealing film (first low-melting layer 7/high-melting intermediate layer 9/second low-melting layer 8)3 having a thickness of 30 μm, which was formed by laminating the above 3 layers, and then the first low-melting layer 7 side of the sealing film (inner layer) 3 was laminated on the above-mentioned layer through a two-liquid curable maleic acid-modified polypropylene adhesive (curing agent is a polyfunctional isocyanate) 6, followed by laminating The aluminum foil 4 was dry-laminated by sandwiching it between a rubber nip roll and a laminating roll heated to 100 ℃ and pressure-bonded, and then aged (heated) at 40 ℃ for 5 days to obtain an outer covering material 1 for a power storage device having a thickness of 86 μm, which had the structure shown in FIG. 1.
The details of the high-melting-point intermediate layer (ethylene-propylene block copolymer) are described below, and the high-melting-point intermediate layer is formed from a resin composition containing: 99% by mass of a first elastomer-modified olefinic resin having a melting point of 163 ℃ and a crystal melting enthalpy (Japanese " ルギ one JI crystal melting worker") of 58J/g, and 1% by mass of a second elastomer-modified olefinic resin having a melting point of 144 ℃ and a crystal melting enthalpy of 19J/g. The first elastomer-modified olefinic resin and the second elastomer-modified olefinic resin each contain an elastomer-modified homopolypropylene and/or an elastomer-modified random copolymer. The elastomer-modified random copolymer is an elastomer-modified random copolymer containing propylene and a copolymerizable component other than propylene as a copolymerizable component. As a result of SEM observation (observation using a scanning electron microscope) of only the high-melting-point intermediate layer, it was confirmed that the high-melting-point intermediate layer had a sea-island structure in which the elastomer component was islands.
The term "melting point" mentioned above means a melting peak temperature measured by Differential Scanning Calorimetry (DSC) in accordance with JIS K7121-1987, and the term "crystalline melting enthalpy" means a heat of fusion (crystalline melting enthalpy) measured by Differential Scanning Calorimetry (DSC) in accordance with JIS K7122-1987.
Further, as the two-pack curable maleic acid-modified polypropylene adhesive, 100 parts by mass of maleic acid-modified polypropylene (melting point 80 ℃ C., acid value 10mgKOH/g) as a main component, 8 parts by mass of isocyanurate of hexamethylene diisocyanate (NCO content: 20% by mass) as a curing agent, and a solvent were mixed to prepare an adhesive solution, and the adhesive solution was used so that the amount of solid matter applied was 2g/m2The adhesive solution is applied to the other surface of the aluminum foil 4, heated and dried, and then laminated on the first low melting point layer 7 surface of the sealing film 3.
< example 2>
A sealing film 3 having a thickness of 30 μm was formed by laminating a first low-melting-point layer 7 having a thickness of 3.75 μm and made of a low-density polyethylene (weight-average molecular weight: 80,000) having a melting point of 115 ℃ and an ethylene-propylene block copolymer (weight-average molecular weight: 400,000) having a melting point of 142 ℃ and a high-melting-point intermediate layer 9 having a thickness of 22.5 μm and made of an ethylene-propylene block copolymer (weight-average molecular weight: 400,000) in this order as sealing films, and a sealing film 3 having a thickness of 30 μm was used, and an outer packaging material 1 for an electricity storage device having a thickness of 86 μm was obtained as shown in FIG. 1, except that this sealing film 3 having a thickness of 30 μm was used.
< example 3>
A sealing film 3 having a thickness of 30 μm was formed by laminating a first low-melting-point layer 7 having a thickness of 1.5 μm and formed of an ethylene-propylene random copolymer (weight-average molecular weight: 120,000) having a melting point of 135 ℃, a high-melting-point intermediate layer 9 having a thickness of 27 μm and formed of an ethylene-propylene block copolymer (weight-average molecular weight: 500,000) having a melting point of 161 ℃ and a second low-melting-point layer 8 having a thickness of 1.5 μm and formed of an ethylene-propylene random copolymer (weight-average molecular weight: 120,000) having a melting point of 135 ℃ in this order as a sealing film, and the outer covering material 1 for an electric storage device having a thickness of 86 μm shown in FIG. 1 was obtained by using the sealing film 3 having a thickness of 30 μm in the same manner as in example 1.
< example 4>
A sealing film 3 having a thickness of 30 μm was formed by laminating a first low-melting layer 7 having a thickness of 6 μm and made of an ethylene-propylene random copolymer (weight-average molecular weight of 150,000) having a melting point of 137 ℃, a high-melting intermediate layer 9 having a thickness of 21 μm and made of an ethylene-propylene block copolymer (weight-average molecular weight of 600,000) having a melting point of 163 ℃, and a second low-melting layer 8 having a thickness of 3 μm and made of an ethylene-propylene random copolymer (weight-average molecular weight of 150,000) having a melting point of 137 ℃ in this order as sealing films, and using the sealing film 3 having a thickness of 30 μm, an outer casing 1 for an electric storage device having a thickness of 86 μm as shown in FIG. 1 was obtained in the same manner as in example 1.
< example 5>
A sealing film 3 having a thickness of 30 μm was formed by laminating a first low-melting layer 7 having a thickness of 3 μm and made of an ethylene-propylene random copolymer (weight-average molecular weight of 150,000) having a melting point of 137 ℃, a high-melting intermediate layer 9 having a thickness of 21 μm and made of an ethylene-propylene block copolymer (weight-average molecular weight of 600,000) having a melting point of 163 ℃, and a second low-melting layer 8 having a thickness of 6 μm and made of an ethylene-propylene random copolymer (weight-average molecular weight of 150,000) having a melting point of 137 ℃ in this order as sealing films, and using the sealing film 3 having a thickness of 30 μm, an outer casing 1 for an electric storage device having a thickness of 86 μm as shown in FIG. 1 was obtained in the same manner as in example 1.
< example 6>
A sealing film 3 having a thickness of 30 μm was formed by laminating a first low-melting-point layer 7 having a thickness of 4.5 μm and formed of an ethylene-propylene random copolymer (weight-average molecular weight: 150,000) having a melting point of 137 ℃, a high-melting-point intermediate layer 9 having a thickness of 21 μm and formed of an ethylene-propylene block copolymer (weight-average molecular weight: 400,000) having a melting point of 152 ℃ and a second low-melting-point layer 8 having a thickness of 4.5 μm and formed of an ethylene-propylene random copolymer (weight-average molecular weight: 150,000) having a melting point of 137 ℃ in this order as a sealing film, and the outer cover 1 for an electric storage device having a thickness of 86 μm shown in FIG. 1 was obtained by using the sealing film 3 having a thickness of 30 μm in the same manner as in example 1.
< comparative example 1>
A sealing film 3 having a thickness of 30 μm was formed by laminating a first low-melting layer 7 having a thickness of 10.5 μm and made of an ethylene-propylene random copolymer (weight average molecular weight 140,000) having a melting point of 140 ℃, a high-melting intermediate layer 9 having a thickness of 9 μm and made of an ethylene-propylene block copolymer (weight average molecular weight 600,000) having a melting point of 163 ℃, and a second low-melting layer 8 having a thickness of 10.5 μm and made of an ethylene-propylene random copolymer (weight average molecular weight 140,000) having a melting point of 140 ℃ in this order as sealing films, and an outer package for an electricity storage device having a thickness of 86 μm was obtained in the same manner as in example 1, except that the sealing films 3 having a thickness of 30 μm were used.
< comparative example 2>
A sealing film having a thickness of 30 μm was formed by sequentially laminating a first low-melting layer having a thickness of 15 μm and made of an ethylene-propylene random copolymer (weight average molecular weight of 140,000) having a melting point of 140 ℃ and a high-melting intermediate layer having a thickness of 15 μm and made of an ethylene-propylene block copolymer (weight average molecular weight of 450,000) having a melting point of 156 ℃ as sealing films, and the outer jacket material for an electricity storage device having a thickness of 86 μm was obtained in the same manner as in example 1 except that the sealing film having a thickness of 30 μm was used. In the obtained outer packaging material for a power storage device, the first low melting point layer constitutes the outermost layer on the metal foil layer side in the sealing layer.
< comparative example 3>
A sealing film 3 having a thickness of 30 μm was formed by laminating a first low-melting-point layer 7 having a thickness of 10.5 μm and made of a low-density polyethylene (weight-average molecular weight of 80,000) having a melting point of 115 ℃ and an ethylene-propylene block copolymer (weight-average molecular weight of 400,000) having a melting point of 142 ℃ and a high-melting-point intermediate layer 9 having a thickness of 9 μm and made of an ethylene-propylene block copolymer (weight-average molecular weight of 400,000) in this order as a sealing film, and using this sealing film 3 having a thickness of 30 μm, an outer packaging material for an electricity storage device having a thickness of 86 μm was obtained in the same manner as in example 1.
Figure BDA0001271801550000161
Each of the outer packaging materials for power storage devices obtained by the above-described operations was evaluated by the following measurement method. The results are shown in table 1. In table 1, X/Y means (thickness of high melting point intermediate layer) ÷ (thickness of sealing layer). In table 1, the notation of "> 200M Ω" indicates that the insulation resistance value is a value larger than 200M Ω.
< method for measuring insulation resistance value >
Two rectangular test pieces each having a length of 100mm × a width of 15mm were cut out from the obtained outer packaging material for an electric storage device. The pair of test pieces were stacked with the seal layers in contact with each other, and the seal layers were heat-welded to each other for 2 seconds under a condition of a seal width of 5mm and 0.15MPa using a double-side heating type heat sealer. In examples 1 and 3 to 6 and comparative examples 1 and 2, the heat sealing temperature was set to 180 ℃, and in example 2 and comparative example 3, the heat sealing temperature was set to 160 ℃ (see table 1).
Next, conductive double-sided tapes were attached to both ends of the test piece in the longitudinal direction, respectively, to ensure electrical conduction between them and the aluminum foil layer. A terminal of an insulation resistance measuring device (manufactured by Nichiki Motor Co., Ltd.; product No. HIOKI3154) was connected to the double-sided tape at both ends in the longitudinal direction of the test piece to form a circuit, and a voltage was applied under a condition of 25V for 5 seconds to measure the insulation resistance value.
< method for measuring seal Strength >
The outer packaging material was cut into a long strip having a width of 15mm × a length of 100mm to obtain a test piece. 2 pieces of the above test piece were prepared, and these 2 pieces of test piece were stacked so that the inner layers thereof were positioned inside each other, and then heat-sealed on the entire surface within a range of 15mm in width to form a heat-sealed portion (heat-sealed portion). The heat sealing was performed by single-side heating for 2 seconds under a sealing pressure of 0.2MPa (gauge pressure) using a heat sealing apparatus (TP-701-a) manufactured by stester SANGYO co. The heat sealing temperature was set to 180 ℃ in the test pieces of examples 1 and 3 to 6 and comparative examples 1 and 2, and 160 ℃ in the test pieces of example 2 and comparative example 3, and heat sealing was performed.
Next, the peel strength of the above-mentioned 2 test pieces subjected to heat sealing was measured in accordance with JIS Z0238-1998. The two ends of each of the heat-sealed 2 test pieces, which were to be unsealed portions, were clamped together, and T-peeling (90-degree peeling) was performed at a drawing speed (jig moving speed) of 100 mm/min to measure the peel strength, which was taken as the seal strength (N/15mm width).
As is clear from table 1, in the outer packaging materials for power storage devices of examples 1 to 6 according to the present invention, the insulation resistance value was large, and sufficient insulation was secured in the heat-sealed portion.
On the other hand, in comparative examples 1 and 3 in which X/Y is out of the range defined in the present invention and comparative example 2 in which the second low melting point layer is not provided, the insulation resistance value is small, and sufficient insulation properties cannot be secured.
Industrial applicability
The outer package for a power storage device according to the present invention can be used as an outer package for various power storage devices, and specific examples of the power storage device include:
an electric storage device such as a lithium secondary battery (lithium ion battery, lithium polymer battery, or the like);
lithium ion capacitance;
an electric double layer capacitor; and the like.
In addition to the power storage devices exemplified above, the power storage device according to the present invention includes an all-solid-state battery.
The present application claims priority from Japanese patent application No. 2016-.
The terms and descriptions used herein are used for the purpose of describing embodiments of the present invention and are not intended to be limiting thereof. The present invention also allows any design change within the scope of claims as long as it does not depart from the gist thereof.

Claims (5)

1. An outer package for an electricity storage device, comprising a metal foil layer and a sealant layer laminated on one surface of the metal foil layer,
the sealing layer comprises: a first low-melting-point layer made of a thermoplastic resin and constituting an outermost layer on the metal foil layer side in the sealant layer, a second low-melting-point layer made of a thermoplastic resin and constituting an outermost layer on the opposite side to the metal foil layer side in the sealant layer, and a high-melting-point intermediate layer made of a thermoplastic resin and disposed between the first low-melting-point layer and the second low-melting-point layer,
the melting point of the high-melting-point middle layer is 120-180 ℃,
the melting point of the first low-melting-point layer and the melting point of the second low-melting-point layer are lower than the melting point of the high-melting-point intermediate layer,
the melting point of the high-melting-point middle layer is 25-35 ℃ higher than that of the first low-melting-point layer,
the melting point of the high-melting-point middle layer is 25-35 ℃ higher than that of the second low-melting-point layer,
the thickness of the high-melting-point intermediate layer is 20 [ mu ] m or more,
when the thickness of the high-melting-point intermediate layer is X and the thickness of the sealing layer is Y, the relation that X is more than or equal to 0.50Y and less than or equal to 0.99Y is achieved,
the metal foil layer and the sealing layer are laminated via an inner adhesive layer,
the inner adhesive layer contains a polyolefin adhesive.
2. The electricity storage device exterior material according to claim 1, wherein the first low-melting-point layer has a thickness of 0.5 μm or more, and the second low-melting-point layer has a thickness of 1 μm or more.
3. The outer packaging material for a power storage device according to claim 1 or 2, wherein the thermoplastic resin constituting the high-melting-point intermediate layer is an ethylene-propylene block copolymer resin having a weight-average molecular weight in a range of 200,000 to 800,000,
the thermoplastic resin constituting the first low-melting-point layer and the thermoplastic resin constituting the second low-melting-point layer are ethylene-propylene random copolymer resins having a weight-average molecular weight in the range of 10,000 to 200,000.
4. The outer covering material for a power storage device according to claim 1 or 2, wherein a heat-resistant resin layer is laminated on the other surface of the metal foil layer through an outer adhesive layer.
5. An electricity storage device is characterized by comprising:
an electricity storage device main body section; and
the outer packaging material for a power storage device according to any one of claims 1 to 4,
the power storage device main body is externally coated with the outer coating material.
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