JP2023055849A - Power storage device exterior material, method for manufacturing the same, and power storage device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a power storage device exterior material which has shielding properties even when the device does not have a metal layer formed of metal.

SOLUTION: A power storage device exterior material is composed of a laminate comprising at least a base material layer and a thermally fusible resin layer sequentially from the outer side. The laminate has a shielding layer and does not have a metal layer formed of metal.

SELECTED DRAWING: None

COPYRIGHT: (C)2023,JPO&INPIT

Description

TECHNICAL FIELD The present disclosure relates to an exterior material for an electricity storage device, a manufacturing method thereof, and an electricity storage device.

Conventionally, various types of electricity storage devices have been developed, and in all electricity storage devices, an exterior material is an indispensable member for sealing electricity storage device elements such as electrodes and electrolytes. Conventionally, metal exterior materials have been frequently used as exterior materials for power storage devices.

On the other hand, in recent years, as the performance of electric vehicles, hybrid electric vehicles, personal computers, cameras, mobile phones, etc. has improved, power storage devices are required to have various shapes, and are required to be thinner and lighter. However, conventionally widely used metallic exterior materials for electric storage devices have the drawback that it is difficult to follow the diversification of shapes and that there is a limit to weight reduction.

Therefore, in recent years, a film-like exterior material that can be easily processed into a variety of shapes and that can achieve thinness and weight reduction has been developed. Laminates have been proposed (see Patent Document 1, for example).

In such an electric storage device exterior material, generally, a recess is formed by cold molding, and an electric storage device element such as an electrode or an electrolytic solution is placed in the space formed by the recess, and a heat-sealing resin is used. By heat-sealing the layers, an electricity storage device in which an electricity storage device element is accommodated inside the exterior material for an electricity storage device can be obtained.

JP 2008-287971 A JP 2015-26528 A

For example, unlike Patent Document 1, Patent Document 2 discloses an exterior material that is thinner and lighter without providing a metal layer.

The inventors of the present disclosure have found that such an exterior material is advantageous from the viewpoint of further weight reduction and thinning of the exterior material, but the transparency of the exterior material is increased by not providing a metal layer, and it is possible to store electricity. The internal structure of the device was grasped, and a new problem was found that it is not desirable from the viewpoint of counterfeit prevention.

Under such circumstances, the main object of the present disclosure is to provide an exterior material for an electricity storage device that has shielding properties even though it does not have a metal layer made of metal.

The inventors of the present disclosure have found that, in order from the outside, at least a base material layer and a laminated body having a heat-fusible resin layer, and an exterior material for an electricity storage device that is formed of a metal and does not have a metal layer, We focused on adopting a configuration that does not provide transparency, which is not assumed in the prior art.

That is, the present disclosure provides inventions in the following aspects.
Consists of a laminate including, in order from the outside, at least a substrate layer and a heat-fusible resin layer,
The laminate has a shielding layer,
The laminate is an exterior material for an electricity storage device, which does not have a metal layer made of metal.

The present disclosure also provides inventions in the following aspects.
An exterior material for an electricity storage device comprising at least a heat-fusible resin layer,
The exterior material for an electricity storage device has a shielding layer,
The exterior material for an electricity storage device is an exterior material for an electricity storage device that does not have a metal layer formed of metal.

Advantageous Effects of Invention According to the present disclosure, it is possible to provide an exterior material for an electricity storage device that has a shielding property without having a metal layer made of metal. Since it does not have a metal layer formed of metal, it is possible to reduce the weight and thickness of the exterior material for an electric storage device. In addition, since it has a shielding property, it is possible to prevent the internal structure of the electricity storage device from being grasped and to prevent counterfeiting. It is possible to carry out the transportation of the outer packaging material, the sealing of the electric storage device element, and the like accurately. Furthermore, if the shielding layer is made black, for example, the power storage device can have a high-class black design. In addition, it is also possible to unify the color black with other electrical components to impart a high-class feeling as a product. Moreover, it is also possible to make the package containing the electricity storage device into a double structure of the inner package and the outer package, and suitably use the exterior material for the electricity storage device of the present disclosure as the inner package. According to the present disclosure, it is also possible to provide a method for manufacturing the exterior material for an electricity storage device, and an electricity storage device using the exterior material for an electricity storage device.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram showing an example of a cross-sectional structure of an exterior material for an electricity storage device of the present disclosure; BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram showing an example of a cross-sectional structure of an exterior material for an electricity storage device of the present disclosure; BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram showing an example of a cross-sectional structure of an exterior material for an electricity storage device of the present disclosure; BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram showing an example of a cross-sectional structure of an exterior material for an electricity storage device of the present disclosure; BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram showing an example of a cross-sectional structure of an exterior material for an electricity storage device of the present disclosure; BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram showing an example of a cross-sectional structure of an exterior material for an electricity storage device of the present disclosure; BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram showing an example of a cross-sectional structure of an exterior material for an electricity storage device of the present disclosure; FIG. 4 is a schematic diagram for explaining a method of housing an electricity storage device element in a package formed by the electricity storage device exterior material of the present disclosure. 1 is a schematic diagram showing an example of a cross-sectional structure of an electricity storage device of the present disclosure; FIG. 1 is a schematic diagram showing an example of a cross-sectional structure of an electricity storage device of the present disclosure; FIG.

The exterior material for an electricity storage device of the present disclosure is composed of a laminate including, in order from the outside, at least a base material layer and a heat-fusible resin layer. The body is characterized in that it does not have a metal layer made of metal. The exterior material for an electricity storage device of the present disclosure has shielding properties even though it does not have a metal layer made of metal.

Hereinafter, the exterior material for an electricity storage device of the present disclosure will be described in detail. In this specification, the numerical range indicated by "-" means "more than" and "less than". For example, the notation of 2 to 15 mm means 2 mm or more and 15 mm or less. Further, the shielding layer means a layer that shields light transmission, and in the power storage device exterior material of the present disclosure, the shielding layer makes it difficult to see the contents. In addition, the metal layer means a layer formed of metal, and examples thereof include metal foil and metal plate. A few millimeters can be mentioned.

1. Laminated Structure and Physical Properties of Electricity Storage Device Exterior Material The electricity storage device exterior material 10 of the present disclosure includes at least a base layer 1 and a heat-fusible resin layer 4, as shown in FIGS. It is composed of a laminate comprising: In the power storage device exterior material 10, the base material layer 1 is the outermost layer, and the heat-fusible resin layer 4 is the innermost layer. When an electricity storage device is assembled using the electricity storage device exterior material 10 and an electricity storage device element, the heat-sealable resin layers 4 of the electricity storage device exterior material 10 face each other, and the peripheral edges are heat-sealed. The electricity storage device element is accommodated in the space formed by . In addition, the exterior material 10 for electrical storage devices of FIG. 7 is a form in which the base material layer 1 contains the 1st base material layer 11 and the 2nd base material layer.

Further, the exterior material 10 for an electricity storage device of the present disclosure may be composed of only the heat-fusible resin layer 4 as shown in FIG. 5, for example.

In the laminate constituting the power storage device exterior material 10 of the present disclosure, at least one layer constitutes a shielding layer S having a shielding property. That is, the shielding layer S included in the laminate may be one layer, or may be two or more layers. As shown, for example, in FIGS. For this purpose, the adhesive layer 2 may be provided if necessary. 1 and 4 show a diagram in which the adhesive layer 2 constitutes the shielding layer S. FIG.

When the layers constituting the power storage device exterior material 10 of the present disclosure are only heat-fusible resin layers, as shown in FIG. do.

As shown in FIG. 2, a colored layer 3 (sometimes referred to as an inner colored layer) may be provided between the substrate layer 1 and the heat-fusible resin layer 4, if necessary. . FIG. 2 shows a diagram in which the colored layer 3 inside the base material layer 1 constitutes the shielding layer S. As shown in FIG. Further, as shown in FIG. 3, a colored layer 3 (sometimes referred to as an outer colored layer) may be provided outside the base material layer 1, if necessary. 3 shows a diagram in which the colored layer 3 outside the base material layer 1 constitutes the shielding layer S. As shown in FIG. The colored layer 3 is preferably provided on at least one surface of the substrate layer 1 (that is, the substrate layer 1 and the colored layer 3 are in contact with each other). This is because the substrate layer is often stiff, and pigments can be easily applied when coating the colored layer, so variations in film thickness can be suppressed and a uniform shielding layer can be formed. It's for.

For example, as shown in FIG. 4, a surface coating layer 6 or the like may be provided on the outer side of the base material layer 1 (the side opposite to the heat-fusible resin layer 4 side), if necessary.

The thickness of the laminate constituting the power storage device exterior material 10 is not particularly limited, but from the viewpoint of cost reduction, energy density improvement, etc., it is, for example, 190 μm or less, preferably about 180 μm or less, and about 170 μm or less. The thickness of the laminate constituting the power storage device exterior material 10 is preferably about 35 μm or more, about 45 μm or more, about 60 μm or more can be mentioned. Further, the preferred range of the laminate constituting the power storage device exterior material 10 is, for example, about 35 to 190 μm, about 35 to 180 μm, about 35 to 170 μm, about 45 to 190 μm, about 45 to 180 μm, and about 45 to 170 μm. , about 60 to 190 μm, about 60 to 180 μm, and about 60 to 170 μm, and particularly preferably about 60 to 170 μm.

In the power storage device exterior material 10, the thickness (total thickness) of the laminate constituting the power storage device exterior material 10 includes the base layer 1, the optionally provided colored layer 3, and the optionally provided adhesive. The ratio of the total thickness of the layer 2, the heat-fusible resin layer 4, and the optionally provided surface coating layer 6 is preferably 90% or more, more preferably 95% or more, and still more preferably 98%. % or more. As a specific example, when the electrical storage device exterior material 10 of the present disclosure includes the base material layer 1, the adhesive layer 2, and the heat-fusible resin layer 4, the laminate constituting the electrical storage device exterior material 10 The ratio of the total thickness of each layer to the thickness (total thickness) is preferably 90% or more, more preferably 95% or more, and still more preferably 98% or more. Further, when the power storage device exterior material 10 of the present disclosure is a laminate including the base material layer 1, the colored layer 3, the adhesive layer 2, and the heat-fusible resin layer 4, the power storage device exterior material The ratio of the total thickness of each of these layers to the thickness (total thickness) of the laminate constituting 10 is, for example, 80% or more, preferably 90% or more, more preferably 95% or more, and further preferably 98% or more. can be done.

The laminate constituting the power storage device exterior material 10 of the present disclosure preferably has a total light transmittance of 20% or less, more preferably 15% or less, as measured in accordance with JIS K7361-1:1997. More preferably 10% or less, more preferably 8% or less. The lower the total light transmittance, the higher the shielding performance of the electrical storage device exterior material 10 can be exhibited. The lower limit of total light transmittance is 0%. The total light transmittance of the exterior material for the power storage device conforms to the measurement method specified in JIS K7361-1: 1997, and is measured using a commercially available spectrophotometer (for example, manufactured by JASCO Corporation, an ultraviolet-visible-near-infrared spectrophotometer V- 670), the transmittance in the visible light region (400 to 700 nm) is measured, and the average value is taken as the total light transmittance. The measurement conditions are a halogen lamp as a light source, a UV/Vis bandwidth of 5.0 nm, a scanning speed of 1000 nm/min, a response of medium, and a data capturing interval of 1.0 nm.

The power storage device exterior material 10 is preferably black. As a result, the power storage device exterior material 10 has a high shielding property and a high anti-counterfeiting effect. In addition, in the manufacturing process of an electricity storage device, it becomes possible to grasp the position with a higher degree of accuracy by the sensor, and it is possible to carry out the transportation of the exterior material 10 for the electricity storage device, the sealing of the electricity storage device element, etc. more accurately. becomes. Furthermore, it is also possible to make the electric storage device and other electrical components black in color to give the product a high-class appearance.

2. Each layer forming the exterior material for the electricity storage device [base layer 1]
In the present disclosure, the base material layer 1 is a layer provided for the purpose of exhibiting a function as a base material of an exterior material for an electric storage device. When the power storage device exterior material 10 has the base material layer 1 , the base material layer 1 is positioned on the outer layer side of the power storage device exterior material.

The material forming the base material layer 1 is not particularly limited as long as it functions as a base material, that is, at least has insulating properties. The base material layer 1 can be formed using, for example, a resin, and the resin may contain additives described later. The base material layer 1 is transparent, and it is preferable to use it by laminating it with the shielding layer S which is composed of a layer different from the base material layer 1. may be configured.

When the substrate layer 1 is formed of resin, the substrate layer 1 may be, for example, a resin film formed of resin, or may be formed by applying resin. The resin film may be an unstretched film or a stretched film. Examples of stretched films include uniaxially stretched films and biaxially stretched films, with biaxially stretched films being preferred. Examples of stretching methods for forming a biaxially stretched film include successive biaxial stretching, inflation, and simultaneous biaxial stretching. Methods for applying the resin include a roll coating method, a gravure coating method, an extrusion coating method, and the like.

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, phenolic resin, and modified products of these resins. Further, the resin forming the base material layer 1 may be a copolymer of these resins or a modified product of the copolymer. Furthermore, it may be a mixture of these resins.

Among these resins, polyesters, polyamides, and polyolefins are preferably used as the resin forming the substrate layer 1 .

Specific examples of polyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, and copolymerized polyester. Examples of copolyester include copolyester having ethylene terephthalate as a main repeating unit. Specifically, copolymer polyester polymerized with ethylene isophthalate with ethylene terephthalate as the main repeating unit (hereinafter abbreviated after polyethylene (terephthalate / isophthalate)), polyethylene (terephthalate / adipate), polyethylene (terephthalate / sodium sulfoisophthalate), polyethylene (terephthalate/sodium isophthalate), polyethylene (terephthalate/phenyl-dicarboxylate), polyethylene (terephthalate/decanedicarboxylate), and the like. These polyesters may be used singly or in combination of two or more.

Further, as the polyamide, specifically, aliphatic polyamide such as nylon 6, nylon 66, nylon 610, nylon 12, nylon 46, copolymer of nylon 6 and nylon 66; terephthalic acid and / or isophthalic acid Hexamethylenediamine-isophthalic acid-terephthalic acid copolymer polyamide such as nylon 6I, nylon 6T, nylon 6IT, nylon 6I6T (I represents isophthalic acid, T represents terephthalic acid) containing structural units derived from, polyamide MXD6 (polymetallic Polyamides containing aromatics such as silylene adipamide); alicyclic polyamides such as polyamide PACM6 (polybis(4-aminocyclohexyl)methane adipamide); Copolymerized polyamides, polyesteramide copolymers and polyetheresteramide copolymers which are copolymers of copolymerized polyamides with polyesters or polyalkylene ether glycols; and polyamides such as these copolymers. These polyamides may be used singly or in combination of two or more.

The substrate layer 1 preferably includes at least one of a polyester film, a polyamide film, and a polyolefin film, preferably includes at least one of a stretched polyester film, a stretched polyamide film, and a stretched polyolefin film, More preferably, at least one of an oriented polyethylene terephthalate film, an oriented polybutylene terephthalate film, an oriented nylon film, and an oriented polypropylene film is included, and the biaxially oriented polyethylene terephthalate film, biaxially oriented polybutylene terephthalate film, and biaxially oriented nylon film , biaxially oriented polypropylene film.

As the polyolefin, a resin containing a polyolefin skeleton such as polyolefin and acid-modified polyolefin is preferable. Polyolefin is preferable from the viewpoint of imparting heat-sealing properties to the outer surface of the substrate layer 1 . A specific example of the polyolefin is the same as the polyolefin exemplified for the heat-fusible resin layer 4 to be described later.

The base material layer 1 may be a single layer, or may be composed of two or more layers. When the substrate layer 1 is composed of two or more layers, the substrate layer 1 may be a laminate obtained by laminating resin films with an adhesive or the like, or may be formed by co-extrusion of resin to form two or more layers. It may also be a laminate of resin films. A laminate of two or more resin films formed by coextrusion of resin may be used as the base material layer 1 without being stretched, or may be used as the base material layer 1 by being uniaxially or biaxially stretched.

For example, when the base material layer 1 is composed of two or more layers, the first base material layer 11 and the second base material layer 12 can be arranged in order from the outside. The first base material layer 11 and the second base material layer 12 may be directly laminated, or may be laminated via an adhesive layer 13 as shown in FIG. When the substrate layer 1 has the first substrate layer 11 and the second substrate layer 12, and the substrate layer 1 is used as the shielding layer S, for example, the first substrate layer 11 and the second substrate At least one of the layers 12 can be a shield layer S. For example, FIG. 7 shows a mode in which the shielding layer S is used as the first base material layer 11 .

Specific examples of the laminate of two or more resin films in the substrate layer 1 include a laminate of a polyester film and a nylon film, a laminate of nylon films of two or more layers, and a laminate of polyester films of two or more layers. etc., preferably a laminate of a stretched nylon film and a stretched polyester film, a laminate of two or more layers of stretched nylon films, and a laminate of two or more layers of stretched polyester films. For example, when the substrate layer 1 is a laminate of two layers of resin films, a laminate of polyester resin films and polyester resin films, a laminate of polyamide resin films and polyamide resin films, or a laminate of polyester resin films and polyamide resin films. A laminate is preferred, and a laminate of polyethylene terephthalate film and polyethylene terephthalate film, a laminate of nylon film and nylon film, or a laminate of polyethylene terephthalate film and nylon film is more preferred. In addition, the polyester resin is resistant to discoloration when, for example, an electrolytic solution adheres to the surface. It is preferably located in the outermost layer.

Further, from the viewpoint of imparting heat-sealability to the outer surface of the substrate layer 1, specific examples of laminates of two or more layers of resin films include laminates of polyolefin and polyester, laminates of polyolefin and polyolefin, Laminates of polyolefins and polyamides are preferred. For example, in the case of a laminate of polyolefin and polyester, a laminate of polypropylene film and polyethylene terephthalate film, a laminate of polypropylene film and polyethylene naphthalate film, a laminate of polypropylene film and polybutylene terephthalate film, and an acid-modified polypropylene film. and a polyethylene terephthalate film, a laminate of an acid-modified polypropylene film and a polyethylene naphthalate film, and a laminate of an acid-modified polypropylene film and a polybutylene terephthalate film. Further, for example, in the case of a laminate of polyolefin and polyolefin, a laminate of polypropylene and polypropylene, a laminate of acid-modified polypropylene and acid-modified polypropylene, and a laminate of acid-modified polypropylene and polypropylene are preferable. In the case of a laminate of polyolefin and polyamide, a laminate of polypropylene and nylon and a laminate of acid-modified polypropylene and nylon are preferred. From the viewpoint of imparting adhesion to metal to the outer surface of the substrate layer 1 , it is preferable to use an acid-modified polyolefin such as acid-modified polypropylene or acid-modified polyethylene as the first substrate layer 11 . As described above, when the outer surface of the base material layer 1 is imparted with adhesiveness to metal, the power storage device exterior body 10 is used as an inner packaging body, and the outer surface of the power storage device exterior material 10 is made of metal. (eg, metal foil, metal can, etc.).

When the substrate layer 1 is a laminate of two or more layers of resin films, the two or more layers of resin films may be laminated via an adhesive. Preferred adhesives are the same as those exemplified for the adhesive layer 2 described later. That is, the adhesive layer 13 can be formed with the same adhesive as the adhesive layer 2 described later. The shielding layer S can also be formed by blending a coloring agent or the like, which will be described later, into the adhesive layer 13 . The method for laminating two or more layers of resin films is not particularly limited, and known methods can be employed. Examples thereof include dry lamination, sandwich lamination, extrusion lamination, thermal lamination, and the like. A lamination method is mentioned. When laminating by dry lamination, it is preferable to use a polyurethane adhesive as the adhesive. At this time, the thickness of the adhesive is, for example, about 2 to 5 μm. Alternatively, an anchor coat layer may be formed on the resin film and laminated. Examples of the anchor coat layer include the same adhesives as those exemplified for the adhesive layer 2 described later. At this time, the thickness of the anchor coat layer is, for example, about 0.01 to 1.0 μm. An anchor coat layer can be used as the adhesive layer 2 or the adhesive layer 13 .

Further, in the present disclosure, the base material layer 1 may be composed of a laminate of a resin layer 1a made of resin and a thin film layer 1b containing at least one of an inorganic oxide and an inorganic nitride. The thin film layer 1b is preferably provided on at least one surface of the resin layer 1a.

The material forming the resin layer 1a is not particularly limited as long as it has insulating properties, and the same resin as the resin forming the substrate layer 1 described above is exemplified.

In the present disclosure, the thin film layer 1b is a layer provided for the purpose of imparting excellent water vapor barrier properties to the exterior material for an electrical storage device while ensuring the insulating properties of the exterior material for the electrical storage device.

The thin film layer 1b preferably has at least one layer of a coating film layer and a vapor deposition layer. The coating layer preferably contains at least one of an inorganic oxide and an inorganic nitride, and at least one of a polyvinyl alcohol-based resin and an ethylene-vinyl alcohol copolymer. Also, the deposited layer preferably contains at least one of an inorganic oxide and an inorganic nitride. The thin film layer 1b preferably contains at least one of an inorganic oxide and an inorganic nitride.

When the thin film layer 1b is formed of a plurality of layers, at least one layer constituting the thin film layer 1b is preferably a coating layer, and it is more preferable to have at least one deposition layer and one coating layer each. . From the same point of view, when at least one of the vapor deposition layer and the coating film layer is provided in plural, the vapor deposition layer and the coating film layer are preferably provided alternately. The vapor deposition layer and the coating film layer will be described in detail below.

[Vapor deposition layer]
The deposited layer preferably contains at least one of an inorganic oxide and an inorganic nitride. Examples of inorganic oxides and inorganic nitrides contained in the deposited layer include silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na ), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y) and other metal oxides or nitrides. Among these, oxides of silicon (Si) or aluminum (Al) are preferred.

Inorganic oxides are represented by MO _x (wherein M represents a metal element, and the value of X varies depending on the metal element) such as SiO _x , AlO _x , and MgO _x . be done.

Further, as the value of X above, silicon (Si) is a number from 0 to 2 (excluding 0), aluminum (Al) is a number from 0 to 1.5 (excluding 0), magnesium (Mg ) is a number from 0 to 1 (excluding 0), calcium (Ca) is a number from 0 to 1 (excluding 0), potassium (K) is a number from 0 to 0.5 (excluding 0) ), tin (Sn) is a number from 0 to 2 (excluding 0), sodium (Na) is a number from 0 to 0.5 (excluding 0), boron (B) is a number from 0 to 1. 5 (excluding 0), titanium (Ti) is a number from 0 to 2 (excluding 0), lead (Pb) is a number from 0 to 1 (excluding 0), zirconium (Zr ) can be a number from 0 to 2 (excluding 0), and yttrium (Y) can be a number from 0 to 1.5 (excluding 0). From the viewpoint of imparting excellent water vapor barrier properties to the power storage device exterior material while ensuring the insulation of the power storage device exterior material, the value of X is preferably silicon (Si) of 1.0 to 2.0. and the number of aluminum (Al) is 0.5 to 1.5.

The thickness of the deposited layer varies depending on the type of inorganic oxide and inorganic nitride, etc., but is in the range of, for example, 5×10 ⁻⁹ to 2×10 ⁻⁶ m, preferably 1×10 ⁻⁸ to 5×10 ⁻⁸ m. can be selected arbitrarily.

Furthermore, when the inorganic oxide is a silicon oxide, it may be a carbon-containing silicon oxide represented by SiO _{x Cy} . In SiO _x C _y , x is preferably a number from 1.5 to 2.2, y is preferably a number from 0.15 to 0.80, and x is a number from 1.7 to 2.1. and y is more preferably a number between 0.39 and 0.47.

Inorganic nitrides are similar to inorganic oxides. In the deposition layer, the inorganic oxides and inorganic nitrides may be contained singly or in combination of two or more.

[Method of Forming Vapor Deposition Layer]
The deposition layer can be preferably formed by chemical vapor deposition, physical vapor deposition, or a combination thereof.

(1) Chemical vapor deposition method (Chemical Vapor Deposition method, CVD method)
Chemical vapor deposition methods utilized in this disclosure include, for example, plasma CVD methods, thermal chemical vapor deposition methods, photochemical vapor deposition methods, and the like. In the plasma CVD method (Plasma Chemical Vapor Deposition method), specifically, a monomer gas for vapor deposition is used as a raw material, and argon gas, helium gas, etc. The deposition layer can be formed by low temperature plasma chemical vapor deposition using an inert gas, oxygen gas or the like as an oxygen supply gas, and using a low temperature plasma generator or the like. As the low-temperature plasma chemical vapor deposition method, for example, a known method such as that described in JP-A-2011-5839 can be employed.

As the low-temperature plasma generator, for example, a generator for high-frequency plasma, pulse wave plasma, microwave plasma, or the like can be used. In the present disclosure, it is desirable to use a high-frequency plasma type generator in order to obtain highly active and stable plasma.

In the low-temperature plasma-enhanced chemical vapor deposition apparatus, the vapor deposition layer is formed in a thin film form on the layer on which the vapor deposition layer is laminated by using plasmatized raw material gas. It becomes a rich continuous layer. Therefore, it exhibits a higher water vapor barrier property than a deposited layer formed by, for example, a vacuum deposition method, and can obtain sufficient water vapor barrier property with a thin film thickness.

(2) Physical vapor deposition method (Physical Vapor Deposition method, PVD method)
Physical vapor deposition methods include, for example, a vacuum deposition method, a sputtering method, an ion plating method, an ion cluster beam method, and the like. The physical vapor deposition method that can be used in the present disclosure is not particularly limited, and for example, a known method such as that described in JP-A-2011-5839 can be employed.

[Coating layer]
In the present disclosure, the coating layer is preferably a layer formed of a coating containing at least one of an inorganic oxide and an inorganic nitride and a water-soluble polymer. The coating layer may be formed, for example, by applying a composition forming the coating layer to the surface of the layer adjacent to the coating layer when laminating each layer of the exterior material for an electric storage device. Alternatively, for example, the composition is separately applied to the substrate surface to form a coating film, as in a transfer method, and the resulting coating film is laminated on the surface of a layer adjacent to the coating film layer. You may The water-soluble polymer preferably contains at least one of a polyvinyl alcohol resin and an ethylene/vinyl alcohol copolymer. The coating layer is preferably formed by applying a vapor barrier composition (gas barrier composition) obtained by polycondensation of an alkoxide and a water-soluble polymer by a sol-gel method. Thereby, the water vapor barrier property of the power storage device exterior material of the present disclosure can be further improved.
(1) Alkoxide The alkoxide that can be used in the water vapor barrier composition has the general formula R ¹ _n M(OR ² ) _m (wherein R ¹ and R ² each independently have 1 to 8 carbon atoms represents an organic group, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n+m represents the valence of M). Alkoxides can be preferably used.

In the present disclosure, as the alkoxide represented by the general formula R ¹ _n M(OR ² ) _m , silicon, zirconium, titanium, aluminum, etc. can be used as the metal atom M, and alkoxysilanes in which M is silicon is preferably used. Also, in the present disclosure, alkoxides of different metal atoms can be used singly or in combination in the same solution.

In the alkoxide represented by the general formula R ¹ _n M(OR ² ) _m , specific examples of the organic group represented by R ¹ include methyl, ethyl, n-propyl, i -propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-octyl group and other alkyl groups. Specific examples of the organic group represented by R ² include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group and the like.

As the alkoxide represented by the general formula R ¹ _n M(OR ² ) _m , at least one kind of partial hydrolyzate of alkoxide and hydrolytic condensate of alkoxide can be used. The partial hydrolyzate does not need to have all of the alkoxy groups hydrolyzed, and may be those in which one or more alkoxy groups are hydrolyzed, or a mixture thereof. , dimers or higher of partially hydrolyzed alkoxides, specifically dimers to hexamers.

(2) Water-soluble polymer The water-soluble polymer preferably contains at least one of a polyvinyl alcohol-based resin and an ethylene/vinyl alcohol copolymer. In the present disclosure, the content of the polyvinyl alcohol-based resin and/or the ethylene/vinyl alcohol copolymer is preferably in the range of 5 to 500 parts by mass with respect to 100 parts by mass of the total amount of the above alkoxides.

In the present disclosure, as the polyvinyl alcohol-based resin, one generally obtained by saponifying polyvinyl acetate can be used. Specific examples of polyvinyl alcohol-based resins include Kuraray Co., Ltd. PVA110 (degree of saponification = 98 to 99%, degree of polymerization = 1100), PVA117 (degree of saponification = 98 to 99%, degree of polymerization = 1700), PVA124 ( degree of saponification = 98 to 99%, degree of polymerization = 2400), PVA135H (degree of saponification = 99.7% or more, degree of polymerization = 3500), RS-110 which is RS polymer manufactured by the same company (degree of saponification = 99% , degree of polymerization = 1000), Kuraray Poval LM-20SO manufactured by the same company (degree of saponification = 40%, degree of polymerization = 2000), Gosenol NM-14 manufactured by Nippon Synthetic Chemical Industry Co., Ltd. (degree of saponification = 99%, polymerization degree = 1400) and Gohsenol NH-18 (degree of saponification = 98 to 99%, degree of polymerization = 1700) and the like can be used.

In the present disclosure, as the ethylene-vinyl alcohol copolymer, a saponified product of a copolymer of ethylene and vinyl acetate, that is, a product obtained by saponifying an ethylene-vinyl acetate random copolymer is used. can be done. Such saponified products include partially saponified products in which several tens of mol % of acetic acid groups remain, to complete saponified products in which only several mol % of acetic acid groups or no acetic acid groups remain. be. Although not particularly limited, from the viewpoint of water vapor barrier properties, it is desirable to use those having a degree of saponification of 80 mol% or more, more preferably 90 mol% or more, and even more preferably 95 mol% or more. The content of repeating units derived from ethylene in the ethylene/vinyl alcohol copolymer (hereinafter also referred to as "ethylene content") is usually 0 to 50 mol%, preferably 20 to 45 mol%. is preferably used. Specific examples of the above ethylene-vinyl alcohol copolymer include EVAL EP-F101 (ethylene content: 32 mol%) manufactured by Kuraray Co., Ltd., Soarnol D2908 (ethylene content: 29 mol%) manufactured by Nippon Synthetic Chemical Industry Co., Ltd. ) etc. can be used.

(3) Silane Coupling Agent In the present disclosure, a silane coupling agent or the like can be added to prepare the water vapor barrier composition that forms the coating layer. In the present disclosure, the silane coupling agent consists of an organosilicon compound having both a hydrolyzable group that reacts with inorganic substances and an organic functional group that reacts with organic substances in one molecule. Examples of hydrolyzable groups that react with inorganic substances include methoxy groups, alkoxy groups such as ethoxy groups, acetoxy groups, and chloro groups. The organic functional group that reacts with an organic substance is preferably a functional group that reacts with a hydroxyl group in a hydroxyl-containing acrylic resin or an isocyanate group in an isocyanate compound, such as an isocyanate group, an amino group, an epoxy group, and a mercapto group. It may also be a vinyl group, a methacryloxy group, or the like.

The organosilicon compound may have an alkyl group or a phenyl group that does not react with either an inorganic substance or an organic substance. It can also be mixed with silicon compounds without organic functional groups, such as compounds with hydrolyzable groups only, such as alkoxysilanes. In the present disclosure, the silane coupling agent may be one type or a mixture of two or more types.

Silane coupling agents used in the present disclosure include N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2 -aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, amino group-containing silane coupling agents such as N-phenyl-3-aminopropyltrimethoxysilane, Epoxy group-containing such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane Silane coupling agents, mercapto group-containing silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane, and isocyanate group-containing agents such as 3-isocyanatopropyltriethoxysilane and 3-isocyanatopropyltrimethoxysilane A silane coupling agent etc. are mentioned.

(4) Preparation of Water Vapor Barrier Composition An alkoxide and a water-soluble polymer (at least one of a polyvinyl alcohol-based resin and an ethylene-vinyl alcohol copolymer) are combined with a sol-gel catalyst, an acid, water and an organic solvent, and If necessary, a silane coupling agent or the like is mixed to prepare a water vapor barrier composition. In preparing the water vapor barrier composition, it is preferable to use water in a proportion of 0.1 to 100 mol per 1 mol of the total molar amount of the above alkoxides. A tertiary amine that is substantially insoluble in water and soluble in an organic solvent, such as N,N-dimethylbenzylamine, is used as the sol-gel catalyst used in the preparation of the water vapor barrier composition. Examples of acids that can be used include mineral acids such as sulfuric acid, hydrochloric acid and nitric acid, and organic acids such as acetic acid and tartaric acid. Furthermore, as the organic solvent, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, etc. can be used.

Further, regarding the water vapor barrier composition, the polyvinyl alcohol resin and/or the ethylene/vinyl alcohol copolymer is preferably dissolved in the coating liquid containing the alkoxide, silane coupling agent, etc. Therefore, the kind of the organic solvent described above is appropriately selected. In the present disclosure, as the ethylene-vinyl alcohol copolymer solubilized in the solvent, for example, one commercially available as Soarnol (manufactured by Nippon Synthetic Chemical Co., Ltd.) can be used.

(5) Method for Forming a Water Vapor Barrier Coating Film The above water vapor barrier composition is applied onto the substrate layer 1 or the deposited layer, and heated to remove the solvent and the alcohol produced by the polycondensation reaction. The condensation reaction is completed and a coating layer is formed. Furthermore, since the hydroxyl groups generated by hydrolysis and the silanol groups derived from the silane coupling agent bond with the hydroxyl groups on the surface of the substrate layer 1 and the vapor deposition layer, the adhesion and adhesion between the vapor barrier coating film and the vapor barrier layer are improved. It has good properties and the like.

By being formed as described above, the coating film layer contains a crystalline linear polymer and has a structure in which a large number of minute crystals are embedded in the amorphous portion. Such a crystal structure is similar to that of a crystalline organic polymer (for example, vinylidene chloride or polyvinyl alcohol), and furthermore, polar groups (OH groups) are partially present in the molecule, and the cohesive energy of the molecule is high. Exhibits good water vapor barrier properties.

In the present disclosure, between the vapor deposition layer and the coating layer, for example, chemical bonds, hydrogen bonds, or coordinate bonds are formed by hydrolysis and co-condensation, and the adhesion between these two layers is improved. , a synergistic effect provides better water vapor barrier properties. Therefore, the thin film layer 1b is preferably a laminate of a vapor deposition layer and a coating film layer.

In the present disclosure, the method for applying the water vapor barrier composition includes, for example, roll coating such as gravure roll coater, spray coating, dipping, brush, bar coating, applicator, and other coating means, once or multiple times. A coating having a dry film thickness of 0.01 to 30 μm, preferably 0.1 to 10 μm can be formed by one application. Furthermore, in a normal environment, 20 to 300 ° C., preferably 20 to 200 ° C., in a temperature environment of 3 seconds to 60 minutes, preferably 10 seconds to 10 minutes, by heating and drying, condensation is performed, and the coating film Layers can be formed.

As a specific example of the thin film layer 1b, for example, a deposited layer containing silicon oxide and a coating film layer containing silicon oxide and a polyvinyl alcohol-based resin are laminated in order on one surface of the resin layer 1a. A layer structure is mentioned. At this time, the silicon oxide is preferably a carbon-containing silicon oxide formed by chemical vapor deposition. Further, the coating film layer containing silicon oxide and polyvinyl alcohol resin is preferably a layer formed by a sol-gel method.

Further, as a specific example of the thin film layer 1b, for example, a deposited layer containing aluminum oxide, a coating layer containing silicon oxide and polyvinyl alcohol-based resin, and an aluminum oxide are formed on one surface of the resin layer 1a. and a coating film layer containing silicon oxide and polyvinyl alcohol-based resin are laminated in this order to form a four-layer structure. At this time, the deposited layer containing aluminum oxide is preferably formed by physical vapor deposition. Further, the coating film layer containing silicon oxide and polyvinyl alcohol resin is preferably a layer formed by a sol-gel method.

The total thickness of the thin film layer 1b is preferably about 0.01 to 30 μm, more preferably about 0.1 to 10 μm.

Additives such as a lubricant, a flame retardant, an antiblocking agent, an antioxidant, a light stabilizer, a tackifier, and an antistatic agent may be present on at least one of the surface and the interior of the substrate layer 1 . Only one type of additive may be used, or two or more types may be mixed and used.

In the present disclosure, it is preferable that a lubricant exists on the surface of the base material layer 1 from the viewpoint of improving the moldability of the exterior material for an electricity storage device. The lubricant is not particularly limited, but preferably includes an amide-based lubricant. Specific examples of amide lubricants include saturated fatty acid amides, unsaturated fatty acid amides, substituted amides, methylolamides, saturated fatty acid bisamides, unsaturated fatty acid bisamides, fatty acid ester amides, and aromatic bisamides. Specific examples of saturated fatty acid amides include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, and hydroxystearic acid amide. Specific examples of unsaturated fatty acid amides include oleic acid amide and erucic acid amide. Specific examples of substituted amides include N-oleyl palmitic acid amide, N-stearyl stearic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl erucic acid amide and the like. Further, specific examples of methylolamide include methylol stearamide. Specific examples of saturated fatty acid bisamides include methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amide, ethylenebisstearic acid amide, ethylenebishydroxystearic acid amide, ethylenebisbehenic acid amide, hexamethylenebisstearin. acid amide, hexamethylenebisbehenamide, hexamethylenehydroxystearic acid amide, N,N'-distearyladipic acid amide, N,N'-distearylsebacic acid amide and the like. Specific examples of unsaturated fatty acid bisamides include ethylenebisoleic acid amide, ethylenebiserucic acid amide, hexamethylenebisoleic acid amide, N,N'-dioleyladipic acid amide, and N,N'-dioleylsebacic acid amide. etc. Specific examples of fatty acid ester amides include stearamide ethyl stearate. Further, specific examples of the aromatic bisamide include m-xylylenebisstearic acid amide, m-xylylenebishydroxystearic acid amide, N,N'-distearylisophthalic acid amide and the like. Lubricants may be used singly or in combination of two or more.

When a lubricant exists on the surface of the base material layer 1, its amount is not particularly limited, but is preferably about 3 mg/m ² or more, more preferably about 4 to 15 mg/m ² , and still more preferably 5 to 14 mg. / m ² degree.

The lubricant present on the surface of the substrate layer 1 may be obtained by exuding the lubricant contained in the resin constituting the substrate layer 1, or by coating the surface of the substrate layer 1 with the lubricant. may

The thickness of the base material layer 1 is not particularly limited as long as it functions as a base material. When the substrate layer 1 is a laminate of two or more resin films, the thickness of each resin film constituting each layer is preferably about 2 to 25 μm.

[Adhesive layer 2]
In the power storage device exterior material 10 of the present disclosure, the adhesive layer 2 is provided between the base material layer 1 and the heat-fusible resin layer 4 as necessary for the purpose of improving the adhesiveness between them. It is a layer that can be In the power storage device exterior material 10 , it is preferable that the adhesive layer 2 is blended with a coloring agent or the like to form the shielding layer S. If a coloring agent is blended into the adhesive that forms the adhesive layer 2 and a shielding layer is formed by one-time coating, it is possible to add a coating of a coloring pigment to the base material layer 1 at locations other than the adhesive layer 2. No need to implement. As a result, the number of steps can be reduced, the production efficiency can be improved, and the risk of contamination by foreign matter can be reduced, compared to the case where the colored layer is provided as the shielding layer. Further, when a colored layer is provided between the base material layer 1 and the adhesive layer 2, the interface strength between the base material layer 1 and the colored layer and between the colored layer and the adhesive layer 2 may decrease. be. Therefore, it is preferable to add a coloring agent to the adhesive layer 2 also from the viewpoint of long-term use.

The adhesive layer 2 is made of an adhesive capable of bonding the base material layer 1 and the heat-fusible resin layer 4 together. The adhesive used to form the adhesive layer 2 is not limited, but may be any of a chemical reaction type, a solvent volatilization type, a hot melt type, a hot pressure type, and the like. Further, it may be a two-liquid curing adhesive (two-liquid adhesive), a one-liquid curing adhesive (one-liquid adhesive), or a resin that does not involve a curing reaction. Further, the adhesive layer 2 may be a single layer or multiple layers.

Specific examples of the adhesive component contained in the adhesive include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, and copolymerized polyester; polyether; polyurethane; epoxy resin; Phenolic resins; polyamides such as nylon 6, nylon 66, nylon 12, and copolymerized polyamides; polyolefin resins such as polyolefins, cyclic polyolefins, acid-modified polyolefins, and acid-modified cyclic polyolefins; polyvinyl acetate; cellulose; (meth)acrylic resins; polyimide; polycarbonate; amino resin such as urea resin and melamine resin; rubber such as chloroprene rubber, nitrile rubber and styrene-butadiene rubber; These adhesive components may be used singly or in combination of two or more. Among these adhesive components, polyurethane adhesives are preferred. In addition, an appropriate curing agent can be used in combination with these adhesive component resins to increase the adhesive strength. The curing agent is selected from among polyisocyanates, polyfunctional epoxy resins, oxazoline group-containing polymers, polyamine resins, acid anhydrides, etc., depending on the functional groups of the adhesive component.

Examples of polyurethane adhesives include polyurethane adhesives containing a first agent containing a polyol compound and a second agent containing an isocyanate compound. Preferred examples include a two-component curing type polyurethane adhesive comprising a polyol such as polyester polyol, polyether polyol, and acrylic polyol as the first agent and an aromatic or aliphatic polyisocyanate as the second agent. Examples of polyurethane adhesives include polyurethane adhesives containing an isocyanate compound and a polyurethane compound obtained by reacting a polyol compound and an isocyanate compound in advance. Examples of polyurethane adhesives include polyurethane adhesives containing a polyurethane compound obtained by reacting a polyol compound and an isocyanate compound in advance and a polyol compound. Examples of polyurethane adhesives include polyurethane adhesives obtained by reacting a polyurethane compound obtained by reacting a polyol compound and an isocyanate compound in advance with moisture in the air and then curing the compound. As the polyol compound, it is preferable to use a polyester polyol having a hydroxyl group in a side chain in addition to the terminal hydroxyl group of the repeating unit. Examples of the second agent include aliphatic, alicyclic, aromatic, and araliphatic isocyanate compounds. Examples of isocyanate compounds include hexamethylene diisocyanate (HDI), xylylene diisocyanate (XDI), isophorone diisocyanate (IPDI), hydrogenated XDI (H6XDI), hydrogenated MDI (H12MDI), tolylene diisocyanate (TDI), and diphenylmethane diisocyanate. (MDI), naphthalene diisocyanate (NDI), and the like. In addition, polyfunctional isocyanate-modified products of one or more of these diisocyanates are also included. Moreover, a polymer (for example, a trimer) can also be used as a polyisocyanate compound. Such multimers include adducts, biurets, nurates and the like. Since the adhesive layer 2 is formed of a polyurethane adhesive, the exterior material for an electric storage device is imparted with excellent electrolyte resistance, and even if the electrolyte adheres to the side surface, the base layer 1 is suppressed from being peeled off. .

Further, the adhesive layer 2 may contain other components as long as they do not impede adhesion, and may contain colorants, thermoplastic elastomers, tackifiers, fillers, and the like. Since the adhesive layer 2 contains a coloring agent, the exterior material for an electric storage device can be colored. The adhesive layer 2 can be used as the shielding layer S if the adhesive layer 2 is colored to such an extent that the exterior material for the electrical storage device can be shielded. Known substances such as pigments and dyes can be used as the colorant. In addition, only one type of colorant may be used, or two or more types may be mixed and used.

The type of pigment is not particularly limited as long as it does not impair the adhesiveness of the adhesive layer 2 . Examples of organic pigments include azo-based, phthalocyanine-based, quinacridone-based, anthraquinone-based, dioxazine-based, indigothioindigo-based, perinone-perylene-based, isoindolenine-based, and benzimidazolone-based pigments. Examples of pigments include carbon black-based, titanium oxide-based, cadmium-based, lead-based, chromium oxide-based, iron-based, and copper-based pigments. be done.

Among the coloring agents, a black coloring agent is preferable, and among the black coloring agents, carbon black is preferable, for example, in order to make the external appearance of the exterior material for an electric storage device black. By using a black colorant to form the black power storage device exterior material 10 , the power storage device exterior material 10 has a high shielding property and a high anti-counterfeiting effect. In addition, in the manufacturing process of an electricity storage device, it becomes possible to grasp the position with a higher degree of accuracy by the sensor, and it is possible to carry out the transportation of the exterior material 10 for the electricity storage device, the sealing of the electricity storage device element, etc. more accurately. becomes. Furthermore, it is also possible to make the electric storage device and other electrical components black in color to give the product a high-class appearance. Carbon black is a more preferable colorant because of its high shielding properties.

The average particle size of the pigment is not particularly limited, and is, for example, approximately 0.05 to 5 μm, preferably approximately 0.08 to 2 μm. Further, the average particle size of carbon black is within the range of 0.161 to 0.221 μm. The average particle size of the pigment is the median size measured with a laser diffraction/scattering particle size distribution analyzer.

The content of the pigment in the adhesive layer 2 is not particularly limited as long as the power storage device exterior material 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 substrate layer 1 and the heat-fusible resin layer 4 can be adhered to each other. Moreover, the thickness of the adhesive layer 2 is, for example, about 10 μm or less, or about 5 μm or less. Moreover, the preferable range of the thickness of the adhesive layer 2 is about 1 to 10 μm, about 1 to 5 μm, about 2 to 10 μm, and about 2 to 5 μm.

[Colored layer 3]
The colored layer 3 is a layer provided between the substrate layer 1 and the heat-fusible resin layer 4 (see FIG. 2) and outside the substrate layer 1 (see FIG. 3) as necessary. When the adhesive layer 2 is provided, a colored layer 3 may be provided between the substrate layer 1 and the adhesive layer 2 . By providing the colored layer 3, the exterior material for an electric storage device can be colored. The colored layer 3 can be used as the shielding layer S if the colored layer 3 is colored to the extent that the shielding property can be imparted to the exterior material for an electric storage device. It is preferable to use the colored layer 3 as the shielding layer S in the power storage device exterior material 10 . The colored layer 3 between the substrate layer 1 and the heat-fusible resin layer 4 may be called an inner colored layer, and the colored layer 3 outside the substrate layer 1 may be called an outer colored layer. The colored layer 3 is preferably provided on at least one surface of the substrate layer 1 (that is, the substrate layer 1 and the colored layer 3 are in contact with each other).

The colored layer 3 can be formed, for example, by applying ink containing a coloring agent to the surface of the substrate layer 1 . Known substances such as pigments and dyes can be used as the colorant. In addition, only one type of colorant may be used, or two or more types may be mixed and used.

Specific examples of the colorant contained in the colored layer 3 are the same as those exemplified in the section [Adhesive layer 2].

The thickness of the colored layer 3 is not particularly limited as long as the electric storage device exterior material 10 is colored, but is, for example, about 1 μm or more, or about 2 μm or more. Moreover, the thickness of the colored layer 3 is, for example, about 10 μm or less, or about 5 μm or less. Moreover, the preferable range of the thickness of the colored layer 3 is about 1 to 10 μm, about 1 to 5 μm, about 2 to 10 μm, and about 2 to 5 μm.

[Heat-fusible resin layer 4]
In the power storage device exterior material of the present disclosure, the heat-fusible resin layer 4 corresponds to the innermost layer, and has the function of sealing the power storage device element by heat-sealing the heat-fusible resin layers to each other when assembling the power storage device. It is a layer (sealant layer) that exhibits The heat-fusible resin layer 4 is transparent, and it is preferable to use it by laminating it with the shielding layer S which is composed of a layer different from the heat-fusible resin layer 4. However, the heat-fusible resin layer 4 may be colored as described above. The shielding layer S may be formed by blending an agent or the like. As described above, the heat-fusible resin layer 4 constitutes the shielding layer S when the power storage device exterior material 10 of the present disclosure is composed only of the heat-fusible resin layer 4 .

The resin constituting the heat-fusible resin layer 4 is not particularly limited as long as it is heat-fusible, but resins containing polyolefin skeletons such as polyolefins and acid-modified polyolefins are preferable. The inclusion of a polyolefin skeleton in the resin constituting the heat-fusible resin layer 4 can be analyzed by, for example, infrared spectroscopy, gas chromatography-mass spectrometry, or the like. Further, when the resin constituting the heat-fusible resin layer 4 is analyzed by infrared spectroscopy, it is preferable that a peak derived from maleic anhydride is detected. For example, when maleic anhydride-modified polyolefin is measured by infrared spectroscopy, peaks derived from maleic anhydride are detected near wavenumbers of 1760 cm ⁻¹ and 1780 cm ⁻¹ . In the case where the heat-fusible resin layer 4 is a layer composed of maleic anhydride-modified polyolefin, a peak derived from maleic anhydride is detected when measured by infrared spectroscopy. However, if the degree of acid denaturation is low, the peak may be too small to be detected. In that case, it can be analyzed by nuclear magnetic resonance spectroscopy.

Specific examples of polyolefins include polyethylenes such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, and linear low-density polyethylene; ethylene-α-olefin copolymers; block copolymers of ethylene), random copolymers of polypropylene (for example, random copolymers of propylene and ethylene); propylene-α-olefin copolymers; ethylene-butene-propylene terpolymers; Among these, polypropylene is preferred. When the polyolefin resin is a copolymer, it may be a block copolymer or a random copolymer. These polyolefin-based resins may be used alone or in combination of two or more.

Also, the polyolefin may be a cyclic polyolefin. A cyclic polyolefin is a copolymer of an olefin and a cyclic monomer. Examples of the olefin, which is a constituent monomer of the cyclic polyolefin, include ethylene, propylene, 4-methyl-1-pentene, styrene, butadiene, and isoprene. be done. Examples of cyclic monomers constituting cyclic polyolefins include cyclic alkenes such as norbornene; cyclic dienes such as cyclopentadiene, dicyclopentadiene, cyclohexadiene and norbornadiene. Among these, cyclic alkenes are preferred, and norbornene is more preferred.

Acid-modified polyolefin is a polymer modified by block polymerization or graft polymerization of polyolefin with an acid component. As the acid-modified polyolefin, the above polyolefin, a copolymer obtained by copolymerizing the above polyolefin with a polar molecule such as acrylic acid or methacrylic acid, or a polymer such as crosslinked polyolefin can be used. Examples of acid components used for acid modification include carboxylic acids such as maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride and itaconic anhydride, and anhydrides thereof.

The acid-modified polyolefin may be an acid-modified cyclic polyolefin. Acid-modified cyclic polyolefin is a polymer obtained by copolymerizing a part of the monomers constituting the cyclic polyolefin in place of the acid component, or by block-polymerizing or graft-polymerizing the acid component to the cyclic polyolefin. be. The acid-modified cyclic polyolefin is the same as described above. The acid component used for acid modification is the same as the acid component used for modification of polyolefin.

Preferred acid-modified polyolefins include carboxylic acid- or anhydride-modified polyolefins, carboxylic acid- or anhydride-modified polypropylenes, maleic anhydride-modified polyolefins, and maleic anhydride-modified polypropylenes.

The heat-fusible resin layer 4 may be formed of one type of resin alone, or may be formed of a blend polymer in which two or more types of resin are combined. Furthermore, the heat-fusible resin layer 4 may be formed of only one layer, or may be formed of two or more layers of the same or different resins.

When at least part of the inner surface of the power storage device exterior material 10 is adhered to a metal (for example, a metal terminal) or the like, the inner surface of the heat-fusible resin layer 4 preferably has adhesiveness to the metal. . In order to impart metal adhesiveness to the inner surface of the heat-fusible resin layer 4, for example, the inner surface of the heat-fusible resin layer 4 is coated with acid-modified polyolefin (acid-modified polypropylene, acid-modified polyethylene, etc.). It is preferable to configure by

Moreover, the heat-fusible resin layer 4 may contain a lubricant or the like as necessary. When the heat-fusible resin layer 4 contains a lubricant, it is possible to improve the moldability of the power storage device exterior material. The lubricant is not particularly limited, and known lubricants can be used. Lubricants may be used singly or in combination of two or more.

The lubricant is not particularly limited, but preferably includes an amide-based lubricant. Specific examples of the lubricant include those exemplified for the base material layer 1 . Lubricants may be used singly or in combination of two or more. By combining two or more types of lubricants, when the power storage device exterior material 10 is cold-molded with a mold, the lubricant is less likely to adhere to the mold due to interaction between the lubricants, and the power storage device can be improved. can suitably enhance the continuous productivity of. The same applies to the case of using a lubricant for the base material layer 1 .

When a lubricant exists on the surface of the heat-sealable resin layer 4, the amount of the lubricant is not particularly limited, but from the viewpoint of improving the moldability of the exterior material for an electricity storage device, the amount is preferably about 10 to 50 mg/m ² . , and more preferably about 15 to 40 mg/m ² .

The lubricant present on the surface of the heat-fusible resin layer 4 may be obtained by exuding the lubricant contained in the resin constituting the heat-fusible resin layer 4 . The surface may be coated with a lubricant.

The thickness of the heat-fusible resin layer 4 is not particularly limited as long as the heat-fusible resin layers are heat-sealed to each other to exhibit the function of sealing the electricity storage device element. About 85 μm or less, more preferably about 15 to 85 μm, more preferably about 35 to 85 μm.

[Surface coating layer 6]
For the purpose of at least one of improving design, electrolyte resistance, scratch resistance, moldability, etc., the exterior material for an electricity storage device of the present disclosure is provided on the base layer 1 (base layer 1 (the side opposite to the heat-fusible resin layer 4 side) may be provided with a surface coating layer 6 . The surface coating layer 6 is a layer positioned on the outermost layer side of the exterior material for an electricity storage device when an electricity storage device is assembled using the exterior material for an electricity storage device. The surface coating layer 6 may form the shielding layer S by blending the above-described coloring agent or the like.

Examples of the surface coating layer 6 include resins such as polyvinylidene chloride, polyester, polyamide, epoxy resin, acrylic resin, fluororesin, polyurethane, silicon resin, phenolic resin, and modified products of these resins. Copolymers of these resins or modified copolymers may also be used. Furthermore, it may be a mixture of these resins. The resin is preferably a curable resin. That is, the surface coating layer 6 is preferably made of a cured product of a resin composition containing a curable resin.

When the resin forming the surface coating layer 6 is a curable resin, the resin may be either a one-component curable type or a two-component curable type, preferably the two-component curable type. Examples of the two-liquid curing resin include two-liquid curing polyurethane, two-liquid curing polyester, and two-liquid curing epoxy resin. Among these, two-liquid curable polyurethane is preferred.

Examples of two-liquid curable polyurethanes include polyurethanes containing a first agent containing a polyol compound and a second agent containing an isocyanate compound. Preferred examples include a two-component curing type polyurethane in which a polyol such as polyester polyol, polyether polyol, or acrylic polyol is used as the first agent and an aromatic or aliphatic polyisocyanate is used as the second agent. Examples of polyurethane include polyurethane containing a polyurethane compound obtained by reacting a polyol compound and an isocyanate compound in advance and an isocyanate compound. Examples of polyurethane include polyurethane containing a polyurethane compound obtained by reacting a polyol compound and an isocyanate compound in advance and a polyol compound. Examples of polyurethanes include polyurethanes obtained by reacting a polyurethane compound obtained by reacting a polyol compound and an isocyanate compound in advance with moisture in the air and the like to cure the compound. As the polyol compound, it is preferable to use a polyester polyol having a hydroxyl group in a side chain in addition to the terminal hydroxyl group of the repeating unit. Examples of the second agent include aliphatic, alicyclic, aromatic, and araliphatic isocyanate compounds. Examples of isocyanate compounds include hexamethylene diisocyanate (HDI), xylylene diisocyanate (XDI), isophorone diisocyanate (IPDI), hydrogenated XDI (H6XDI), hydrogenated MDI (H12MDI), tolylene diisocyanate (TDI), and diphenylmethane diisocyanate. (MDI), naphthalene diisocyanate (NDI), and the like. In addition, polyfunctional isocyanate-modified products of one or more of these diisocyanates are also included. Moreover, a polymer (for example, a trimer) can also be used as a polyisocyanate compound. Such multimers include adducts, biurets, nurates and the like. In addition, the aliphatic isocyanate compound refers to an isocyanate having an aliphatic group and no aromatic ring, and the alicyclic isocyanate compound refers to an isocyanate having an alicyclic hydrocarbon group, and the aromatic isocyanate compound refers to an isocyanate having an aromatic ring. Since the surface coating layer 6 is made of polyurethane, the exterior material for an electric storage device is imparted with excellent electrolyte resistance.

At least one of the surface and the inside of the surface coating layer 6 may be coated with the above-described lubricant or anti-rust agent as necessary depending on the functionality to be provided on the surface coating layer 6 and its surface. Additives such as blocking agents, matting agents, flame retardants, antioxidants, tackifiers and antistatic agents may be included. Examples of the additive include fine particles having an average particle size of about 0.5 nm to 5 μm. The average particle size of the additive is the median size measured with a laser diffraction/scattering particle size distribution analyzer.

Additives may be either inorganic or organic. Also, the shape of the additive is not particularly limited, and examples thereof include spherical, fibrous, plate-like, amorphous, scale-like, and the like.

Specific examples of additives include talc, silica, graphite, kaolin, montmorillonite, mica, hydrotalcite, silica gel, zeolite, aluminum hydroxide, magnesium hydroxide, zinc oxide, magnesium oxide, aluminum oxide, neodymium oxide, and 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 nanotube, high melting point nylon, acrylate resin, Crosslinked acrylic, crosslinked styrene, crosslinked polyethylene, benzoguanamine, gold, aluminum, copper, nickel, and the like. Additives may be used singly or in combination of two or more. Among these additives, silica, barium sulfate, and titanium oxide are preferred from the viewpoint of dispersion stability and cost. In addition, the additive may be subjected to various surface treatments such as insulation treatment and high-dispersion treatment.

A method for forming the surface coating layer 6 is not particularly limited, and an example thereof includes a method of applying a resin for forming the surface coating layer 6 . When adding additives to the surface coating layer 6, a resin mixed with the additives may be applied.

The thickness of the surface coating layer 6 is not particularly limited as long as it exhibits the above functions as the surface coating layer 6, and is, for example, approximately 0.5 to 10 μm, preferably approximately 1 to 5 μm.

3. Method for producing an exterior material for an electricity storage device The method for producing an exterior material for an electricity storage device is not particularly limited as long as a laminate obtained by laminating each layer included in the exterior material for an electricity storage device of the present disclosure is obtained. At least a step of obtaining a laminate in which a substrate layer and a heat-fusible resin layer are laminated, the laminate has a shielding layer, and the laminate is a metal layer formed of metal does not have In addition, when the exterior material for an electricity storage device of the present disclosure is composed of a heat-fusible resin layer, a resin film that constitutes the heat-fusible resin layer is prepared. In addition, when the exterior material for an electricity storage device is composed of two or more layers of heat-fusible resin layers, a resin film in which two or more layers are laminated may be obtained and used as the exterior material for an electricity storage device. Each layer constituting the fusible resin layer can be laminated to form an exterior material for an electricity storage device. When the power storage device exterior material of the present disclosure includes other layers such as a base material layer in addition to the heat-fusible resin layer, a resin film including the other layer is obtained and used for power storage. A step of obtaining a laminate by laminating the heat-fusible resin layer and other layers to form a device exterior material is provided.

An example of the method for manufacturing the exterior material for an electricity storage device of the present disclosure is as follows. First, materials for forming the substrate layer 1, the adhesive layer 2, and the heat-fusible resin layer 4 are prepared. Next, the substrate layer 1 and the heat-fusible resin layer 4 are laminated with the adhesive layer 2 interposed therebetween. Specifically, using an adhesive that forms the adhesive layer 2, the substrate layer 1 and the heat-fusible resin layer 4 are laminated by a dry lamination method or the like to form the substrate layer 1 and the adhesive layer. 2. It is possible to manufacture the exterior material 10 for an electricity storage device in which the heat-fusible resin layers 4 are laminated in this order. When the substrate layer 1 and the heat-fusible resin layer 4 are laminated without the adhesive layer 2 interposed therebetween, the resin constituting the heat-fusible resin layer 4 is melted on the substrate layer 1. The power storage device exterior material 10 can be manufactured by a method such as extrusion. When the colored layer 3 is provided, the colored layer 3 may be formed on the surface of the substrate layer 1 and then laminated with the heat-fusible resin layer 4 . When the surface coating layer 6 is provided, it can be formed, for example, by coating the surface of the substrate layer 1 with the above-mentioned resin composition for forming the surface coating layer 6 and curing the composition.

As described above, in order from the outside, surface coating layer 6 optionally provided / colored layer 3 optionally provided (outer colored layer) / optionally provided substrate layer 1 / optionally provided A laminated body comprising a colored layer 3 (inner colored layer) provided / an adhesive layer 2 provided as necessary / a heat-fusible resin layer 4 is formed. In order to strengthen the properties, it may be further subjected to a heat treatment.

4. Use of Power Storage Device Exterior Material The power storage device exterior material of the present disclosure is used in a packaging body for sealingly housing power storage device elements such as a positive electrode, a negative electrode, and an electrolyte. That is, an electricity storage device can be obtained by housing an electricity storage device element including at least a positive electrode, a negative electrode, and an electrolyte in a package formed by the electricity storage device exterior material of the present disclosure.

Specifically, an electricity storage device element having at least a positive electrode, a negative electrode, and an electrolyte is placed in the exterior material for an electricity storage device of the present disclosure in a state in which metal terminals connected to each of the positive electrode and the negative electrode protrude outward. , covering the periphery of the electricity storage device element so as to form a flange portion (area where the heat-fusible resin layers contact each other), and heat-sealing the heat-fusible resin layers of the flange portion to seal. provides an electricity storage device using an exterior material for an electricity storage device. In addition, when housing an electricity storage device element in a package formed by the electricity storage device exterior material of the present disclosure, the heat-fusible resin portion of the electricity storage device exterior material of the present disclosure is on the inside (surface in contact with the electricity storage device element ) to form a package. The heat-fusible resin layers of the two exterior materials for an electricity storage device may be placed facing each other, and the peripheral edges of the exterior materials for an electricity storage device that have been stacked may be heat-sealed to form a package. As in the example shown in FIG. 8, one electrical storage device outer packaging material may be folded back and overlapped, and the peripheral edges may be heat-sealed to form a package. In the case of folding and stacking, as in the example shown in FIG. 8, the sides other than the folded sides may be heat-sealed to form a package by three-side sealing, or the packages may be folded back so as to form a flange portion. It may be sealed on all sides. Further, in the power storage device exterior material, a recess for housing the power storage device element may be formed by deep drawing or stretch forming. As in the example shown in FIG. 8, one power storage device exterior material may be provided with a recess and the other power storage device exterior material may not be provided with a recess, or the other power storage device exterior material may also be recessed. may be provided.

Further, as shown in FIG. 10, the power storage device exterior material 10 of the present disclosure is a power storage device 30 in which power storage device elements 32 are housed in a container having a double structure of an inner package 10a and an outer package 20. It can be suitably used as the inner package 10a. That is, the power storage device element 32 including at least a positive electrode, a negative electrode, and an electrolyte is housed in the inner package 10a formed by the power storage device exterior material 10 of the present disclosure. By housing inside, the electricity storage device 30 in which the electricity storage device element 32 is housed in the container having the double structure of the inner package 10a body and the outer package 20 is obtained. One or two or more members in which the electricity storage device elements 32 are accommodated in the inner package 10a formed by the power storage device exterior material 10 of the present disclosure are prepared, and the one or two or more members are placed in the outer package. It can be housed in 20 to form an electricity storage device. In FIGS. 8 to 10, each corner is drawn at a right angle, but the angle of each corner and ridgeline is not limited, and each corner and ridgeline may be rounded.

The outer package is not particularly limited, and an exterior material, a metal can, or the like composed of a film-like laminate in which a substrate layer/metal layer/thermal adhesive resin layer are sequentially laminated can be used. .

The power storage device exterior material of the present disclosure can be suitably used for power storage devices such as batteries (including capacitors, capacitors, etc.). Moreover, although the exterior material for an electricity storage device of the present disclosure may be used for either a primary battery or a secondary battery, it is preferably used for a secondary battery. The type of secondary battery to which the power storage device exterior material of the present disclosure is applied is not particularly limited. Cadmium storage batteries, nickel/iron storage batteries, nickel/zinc storage batteries, silver oxide/zinc storage batteries, metal-air batteries, polyvalent cation batteries, capacitors, capacitors, and the like. Among these secondary batteries, lithium ion batteries and lithium ion polymer batteries can be mentioned as suitable targets for application of the power storage device exterior material of the present disclosure.

EXAMPLES The present disclosure will be described in detail below with reference to examples and comparative examples. However, the present disclosure is not limited to the examples.

<Manufacturing exterior materials for power storage devices>
Example 1
A polyethylene terephthalate (PET) film (thickness: 12 μm) was prepared as a base layer. Also, an unstretched polypropylene film (CPP, thickness 50 μm) was prepared as a heat-fusible resin layer. The base material layer and the heat-fusible resin layer are bonded using a two-component urethane adhesive containing carbon black (the average particle size of the carbon black is within the range of 0.161 to 0.221 μm), and the adhesive layer is The substrate layer and the heat-fusible resin layer were adhered via a black adhesive layer by a dry lamination method so that the thickness after curing was 3 μm. A black adhesive layer was used as a shielding layer. Through the above procedure, an exterior material for an electricity storage device was obtained in which the substrate layer/adhesive layer (shielding layer)/heat-fusible resin layer were laminated in this order.

Example 2
A polyethylene terephthalate (PET) film (thickness: 12 μm) was prepared as a base layer. Also, an unstretched polypropylene film (CPP, thickness 50 μm) was prepared as a heat-fusible resin layer. A two-component urethane resin containing carbon black (the average particle size of carbon black is in the range of 0.161 to 0.221 μm, and the content of carbon black is the same as in Example 1.), After curing A black colored layer was formed by coating, drying and curing the surface of one side of the substrate layer so that the thickness of the colored layer was 3 μm. A black colored layer was used as a shielding layer. Next, the side opposite to the colored layer (referred to as the outer colored layer) side of the base layer and the heat-fusible resin layer were bonded using a two-liquid urethane adhesive so that the thickness of the adhesive layer after curing was 3 μm. By bonding the base material layer and the heat-fusible resin layer through the adhesive layer, the outer colored layer (shielding layer) / base layer / adhesive layer / heat-fusible resin layer was laminated in this order to obtain an exterior material for an electricity storage device.

Example 3
A polyethylene terephthalate (PET) film (thickness: 12 μm) was prepared as a base layer. Also, an unstretched polypropylene film (CPP, thickness 50 μm) was prepared as a heat-fusible resin layer. A two-component urethane resin containing carbon black (the average particle size of carbon black is in the range of 0.161 to 0.221 μm, and the content of carbon black is the same as in Example 1.), After curing A black colored layer was formed by coating, drying and curing the surface of one side of the substrate layer so that the thickness of the colored layer was 3 μm. A black colored layer was used as a shielding layer. Next, the colored layer (referred to as the inner colored layer) side of the base material layer and the heat-fusible resin layer are bonded using a two-liquid urethane adhesive so that the adhesive layer has a thickness of 3 μm after curing. Then, the base material layer and the heat-fusible resin layer are adhered via the adhesive layer, and the base material layer/inner colored layer (shielding layer)/adhesive layer/heat-fusible resin layer are laminated in this order. Thus, an exterior material for an electricity storage device was obtained.

Example 4
When the content of carbon black contained in the adhesive layer of Example 1 was set to 100 parts by mass as a reference, the content of carbon black contained in the adhesive layer was set to 50 parts by mass. Similarly, an exterior material for an electricity storage device was obtained in which a substrate layer/adhesive layer (shielding layer)/heat-fusible resin layer were laminated in this order.

Example 5
[Production of base material layer 1]
(1) As the resin layer 1a, a polyethylene terephthalate (PET) film (thickness: 12 μm) subjected to corona treatment was used. A 300 Å-thickness carbon-containing silicon oxide vapor deposition film was formed as a vapor deposition layer on one surface of the resin layer 1a by using a winding-type low-temperature plasma chemical vapor deposition method under the following vapor deposition conditions. .
(Vapor deposition conditions)
Output: 15kW
Vacuum in deposition chamber: 5×10 ⁻² mbar
Processing speed: 200m/min
Gas flow rate: (hexamethyldisiloxane: oxygen gas: He: Ar) = (1.2: 0.5: 0.5: 0.5) [unit: slm]
The unit "slm" indicates the amount per minute in liters.

After that, using a glow discharge plasma generator on the vapor deposition layer surface, using a mixed gas of oxygen gas: argon gas = 7.0: 2.5 (unit: slm) with an output of 9 kW, the mixed gas pressure was 6 × 10 ^- An oxygen/argon mixed gas plasma treatment was performed at ² mbar and a treatment speed of 420 m/min to form a plasma-treated surface in which the surface tension of the evaporated layer surface was increased by 54 dyne/cm or more.

(2) On the other hand, according to the composition shown in Table 1 below, composition a. Preliminarily prepared composition b. was added and stirred to obtain a colorless and transparent water vapor barrier composition.

Next, the steam barrier composition prepared above was coated on the plasma-treated surface formed in (1) above by a gravure roll coating method, and then heat-treated at 150° C. for 60 seconds to obtain a film having a thickness of 0.5. A coating film layer having a thickness of 2 μm (dry state) was formed to obtain a substrate layer 1 in which a resin layer a/vapor-deposited layer/coating film layer were laminated in this order. In addition, in the base material layer 1, the laminated body of a vapor deposition layer and a coating film layer comprises the thin film layer 1b.

(3) Next, the substrate layer 1 thus obtained was mounted on the delivery roll of a take-up type vacuum vapor deposition apparatus. Next, this is fed out, and a glow discharge plasma generator is used for the thin film layer 1b of the base material layer 1, the output is 9 kw, the mixture of oxygen gas: argon gas = 7.0: 2.5 (unit: slm) The oxygen/argon mixed gas plasma treatment was performed using a mixed gas pressure of 6×10 ⁻² mbar and a processing speed of 240 m/min.
(4) The thin film layer 1b side of the base layer and the heat-fusible resin layer are bonded with a two-liquid urethane adhesive containing carbon black (the average particle size of carbon black is in the range of 0.161 to 0.221 μm , and the content of carbon black is 50 parts by mass when the content of carbon black in the adhesive layer of Example 1 is 100 parts by mass. ), and the thickness of the adhesive layer after curing is set to 3 μm, and the base layer and the heat-fusible resin layer are laminated by a dry lamination method to form a black adhesive layer. glued through. A black adhesive layer was used as a shielding layer. By the above procedure, the exterior material for a power storage device, in which the base material layer (resin layer/thin film layer [vapor deposition layer/coating layer])/adhesive layer (shielding layer)/heat-fusible resin layer is laminated in this order, is obtained. Obtained.

Example 6
[Production of base material layer 1]
(1) As the resin layer 1a, a polyethylene terephthalate (PET) film (thickness: 12 μm) having both sides subjected to corona treatment was used. On one surface of the resin layer 1a, an aluminum oxide film having a film thickness of 800 Å was formed under the following vapor deposition conditions using a vacuum vapor deposition method using a roll-type electron beam (EB) heating method using aluminum as a vapor deposition source. A vapor deposition layer was formed. As a result of measuring the X value of AlO _x in the obtained deposited layer, X=0.3.
(Vapor deposition conditions)
Vacuum in deposition chamber: 1×10 ⁻⁴ mbar
Vacuum in winding chamber: 2×10 ⁻² mbar
Electron beam power: 30 kW
Oxygen introduction amount: 8000 sccm
Processing speed: 240m/min
The unit "sccm" indicates the amount per minute in milliliters.

After that, using a glow discharge plasma generator on the vapor deposition layer surface, using a mixed gas of oxygen gas: argon gas = 7.0: 2.5 (unit: slm) with an output of 9 kW, the mixed gas pressure was 6 × 10 ^- An oxygen/argon mixed gas plasma treatment was performed at ² mbar and a treatment speed of 420 m/min to form a plasma-treated surface in which the surface tension of the evaporated layer surface was increased by 54 dyne/cm or more.

(2) On the other hand, according to the composition shown in Table 1 above, composition a. Preliminarily prepared composition b. was added and stirred to obtain a colorless and transparent water vapor barrier composition.

Next, the vapor barrier composition prepared above was coated on the plasma-treated surface of the vapor deposition layer formed in (1) above by a gravure roll coating method, and then heat-treated at 150° C. for 60 seconds to obtain a thick layer. A coating layer of 0.2 μm (dry state) was formed.

(3) Next, the film obtained in (2) above was mounted on the delivery roll of a take-up type vacuum vapor deposition apparatus. Next, this is fed out, and a glow discharge plasma generator is used to apply a mixed gas of oxygen gas: argon gas = 7.0: 2.5 (unit: slm) to the coating layer of the film with an output of 9 kw. , a mixed gas pressure of 6×10 ⁻² mbar, and an oxygen/argon mixed gas plasma treatment at a processing speed of 240 m/min.

(4) After that, on the plasma-treated surface of (3) above, a vacuum deposition method using a winding-type electron beam (EB) heating method using aluminum as a deposition source was used to form a deposited layer under the following deposition conditions. , an aluminum oxide deposition layer having a film thickness of 800 Å was formed. As a result of measuring the X value of AlO _x in the deposited layer, X=0.3.
(Vapor deposition conditions)
Vacuum in deposition chamber: 1×10 ⁻⁴ mbar
Vacuum in winding chamber: 2×10 ⁻² mbar
Electron beam power: 30 kW
Oxygen introduction amount: 8000 sccm
Processing speed: 240m/min

After that, using a glow discharge plasma generator on the vapor deposition layer surface, using a mixed gas of oxygen gas: argon gas = 7.0: 2.5 (unit: slm) with an output of 9 kW, the mixed gas pressure was 6 × 10 ^- An oxygen/argon mixed gas plasma treatment was performed at ² mbar and a treatment speed of 420 m/min to form a plasma-treated surface having an increased surface tension of 54 dyne/cm or more on the deposited film surface.

(5) The steam barrier composition produced in (2) above is coated on the plasma-treated surface formed in (4) above by a gravure roll coating method, and then heat-treated at 150°C for 60 seconds to obtain a thick film. A coating layer of 0.2 μm (dry state) was formed.

(6) Next, the film 1 produced in (5) above was mounted on the delivery roll of a take-up type vacuum vapor deposition apparatus. Next, this is fed out, and a glow discharge plasma generator is used to apply a mixed gas of oxygen gas: argon gas = 7.0: 2.5 (unit: slm) to the surface of the coating layer with an output of 9 kw. , oxygen/argon mixed gas plasma treatment was carried out at a mixed gas pressure of 6×10 ⁻² mbar and a processing speed of 240 m/min to obtain a laminated body of resin layer 1a/thin film layer 1b. The deposited layer/coating layer/deposited layer/coating layer constitute the thin film layer 1b.

Two laminates of the resin layer 1a/thin film layer 1b prepared in the above (1) to (6) were prepared, and a substrate layer 1 was obtained by laminating them. Specifically, a two-component curable urethane adhesive is applied to the thin film layer 1b side of one laminate by a gravure roll coating method (thickness 4 μm in a dry state) to form an adhesive layer, and the other laminate is laminated. It was adhered to the resin layer 1a of the body by dry lamination to obtain a substrate layer 1 having a laminated structure of resin layer 1a/thin film layer 1b/adhesive layer/resin layer 1a/thin film layer 1b. Next, a two-component urethane adhesive containing carbon black (the average particle size of carbon black is in the range of 0.161 to 0.221 μm, and the content of carbon black is When the content of carbon black contained is set to 100 parts by mass as a reference, the content of carbon black contained in the adhesive layer is set to 50 parts by mass.) is used, and after curing the adhesive layer The coating film layer side of the base material layer and the heat-fusible resin layer were adhered via a black adhesive layer by a dry lamination method so that the thickness was 3 μm. A black adhesive layer was used as a shielding layer. By the above procedure, the base layer (resin layer / thin film layer [deposition layer / coating layer / vapor deposition layer / coating layer]) / adhesive layer / base layer (resin layer / thin film layer [deposition layer / coating layer /evaporation layer/coating layer])/adhesive layer/heat-fusible resin layer were laminated in this order to produce an exterior material for an electricity storage device.

Example 7
When the content of carbon black contained in the adhesive layer of Example 1 was set to 100 parts by mass as a reference, the content of carbon black contained in the adhesive layer was set to 33 parts by mass. In the same manner as in Example 1, an exterior material for an electricity storage device was obtained in which a substrate layer/adhesive layer (shielding layer)/heat-fusible resin layer were laminated in this order.

Example 8
When the content of carbon black contained in the adhesive layer of Example 1 was set to 100 parts by mass as a reference, the content of carbon black contained in the adhesive layer was set to 25 parts by mass. In the same manner as in Example 1, an exterior material for an electricity storage device was obtained in which a substrate layer/adhesive layer (shielding layer)/heat-fusible resin layer were laminated in this order.

Example 9
When the content of carbon black contained in the adhesive layer of Example 1 was set to 100 parts by mass as a reference, the content of carbon black contained in the adhesive layer was set to 10 parts by mass. In the same manner as in Example 1, an exterior material for an electricity storage device was obtained in which a substrate layer/adhesive layer (shielding layer)/heat-fusible resin layer were laminated in this order.

Comparative example 1
In the same manner as in Example 1, except that the adhesive layer of Example 1 did not contain carbon black, a base material layer / adhesive layer / heat-fusible resin layer were laminated in this order. I got the cladding.

<Total light transmittance>
The total light transmittance of the exterior material for a power storage device is measured in the visible light region ( 400 to 700 nm), and the average value was taken as the total light transmittance. Measurement conditions were as follows: a halogen lamp was used as the light source, UV/Vis bandwidth: 5.0 nm, scanning speed: 1000 nm/min, response: medium, and data acquisition interval: 1.0 nm. Table 2 shows the results.

<Shielding evaluation>
A sheet of paper was prepared on which the letter "A" was printed in black by a laser printer with Arial font, font size 36, and line thickness of about 1 mm. Under an environment of indoor lighting (300 to 500 lux), a piece of paper bearing the letter "A" was placed under the exterior material for the electricity storage device. The letter "A" was visually observed through the power storage device exterior material from a distance of 30 cm in front of the power storage device exterior material. Regarding the visibility of characters, the shielding property was evaluated according to the following criteria of levels 1 to 5. Table 2 shows the results.
Level 1: Visible.
Level 2: A little difficult to see, but characters can be recognized.
Level 3: It is difficult to see, but the characters can be recognized.
Level 4: It is very difficult to see, but the characters are faintly recognizable.
Level 5: I can't see the letters.

"/" in the laminated structure shown in Table 2 indicates a separation of layers.

The exterior materials for electric storage devices of Examples 1 to 9 do not have a metal layer formed of metal, but have a shielding layer, so even a very simple letter A is shielded and has the effect of making it difficult to see. Therefore, it is considered that the provision of the shielding layer makes it difficult to see the electricity storage device element having a complicated shape, thereby suppressing counterfeiting.

Example 10
A maleic anhydride-modified polypropylene (PPa) film (thickness: 20 μm) containing carbon black (average particle size of carbon black is in the range of 0.161 to 0.221 μm) was prepared as the first substrate layer. A polyethylene naphthalate (PEN) film (thickness: 12 μm) was prepared as the second base material layer. A maleic anhydride-modified polypropylene (PPa) film (thickness: 20 μm) was prepared as a heat-fusible resin layer. Using a two-component urethane adhesive, the thickness of the adhesive layer after curing is 1 μm or less, and the first base layer and the second base layer are laminated via the adhesive layer by a dry lamination method. glued. Further, the second base material layer and the heat-fusible resin layer of the obtained laminate were adhered via the same adhesive layer. A black first substrate layer was used as a shielding layer. Through the above procedure, a power storage device exterior material in which the first substrate layer (shielding layer)/adhesive layer/second substrate layer/adhesive layer/heat-fusible resin layer was laminated in this order was obtained. The PPa of the first base material layer and the heat-fusible resin layer of Example 10 contain two kinds of lubricants, erucic acid amide and behenic acid amide, respectively.

Example 11
First base layer (shielding layer)/adhesive layer/second base layer in the same manner as in Example 10, except that a polyethylene terephthalate (PET) film (thickness: 9 μm) was used as the second base layer. An exterior material for an electric storage device was obtained in which the material layer/adhesive layer/heat-fusible resin layer were laminated in this order. The PPa of the first base material layer and the heat-fusible resin layer of Example 11 contain two types of lubricants, erucamide and behenamide, respectively.

Example 12
First base layer (shielding layer)/adhesive layer/second base layer in the same manner as in Example 10, except that a polyethylene terephthalate (PET) film (thickness: 12 μm) was used as the second base layer. An exterior material for an electric storage device was obtained in which the material layer/adhesive layer/heat-fusible resin layer were laminated in this order. The PPa of the first base material layer and the heat-fusible resin layer of Example 12 contain two types of lubricants, erucamide and behenamide, respectively.

Example 13
First base layer (shielding layer)/adhesive layer/second base layer in the same manner as in Example 10, except that a polyethylene terephthalate (PET) film (thickness: 25 μm) was used as the second base layer. An exterior material for an electric storage device was obtained in which the material layer/adhesive layer/heat-fusible resin layer were laminated in this order. The PPa of the first base material layer and the heat-fusible resin layer of Example 13 contain two types of lubricants, erucamide and behenamide, respectively.

Example 14
Using a maleic anhydride-modified polypropylene (PPa) film (thickness: 30 μm) containing carbon black (average particle size of carbon black is in the range of 0.161 to 0.221 μm) as the first base layer; And, in the same manner as in Example 12, except that a maleic anhydride-modified polypropylene (PPa) film (thickness: 30 μm) was used as the heat-fusible resin layer. Thus, an exterior material for an electric storage device was obtained, in which the agent layer/second base material layer/adhesive layer/heat-fusible resin layer were laminated in this order. The PPa of the first base material layer and the heat-fusible resin layer of Example 14 contain two types of lubricants, erucamide and behenamide, respectively.

Example 15
Using a maleic anhydride-modified polypropylene (PPa) film (thickness: 15 μm) containing carbon black (average particle size of carbon black is in the range of 0.161 to 0.221 μm) as the first base layer; And, in the same manner as in Example 12, except that a maleic anhydride-modified polypropylene (PPa) film (thickness: 15 μm) was used as the heat-fusible resin layer. Thus, an exterior material for an electric storage device was obtained, in which the agent layer/second base material layer/adhesive layer/heat-fusible resin layer were laminated in this order. The PPa of the first base material layer and the heat-fusible resin layer of Example 15 contain two kinds of lubricants, erucamide and behenamide, respectively.

Example 16
As the first base layer, a polypropylene (PP) film (20 μm thick) containing carbon black (the average particle size of carbon black is in the range of 0.161 to 0.221 μm) is used, and heat melting First base layer (shielding layer)/adhesive layer/second base layer in the same manner as in Example 12, except that a polypropylene (PP) film (thickness: 20 μm) was used as the adhesive resin layer. /Adhesive layer/Heat-fusible resin layer were laminated in this order to obtain an exterior material for an electric storage device. The PP of the first base material layer and the heat-fusible resin layer of Example 16 contain two kinds of lubricants, erucamide and behenamide, respectively.

Example 17
The first substrate layer ( Shielding layer)/adhesive layer/second base material layer/adhesive layer/heat-fusible resin layer were laminated in this order to obtain an exterior material for an electricity storage device.

Example 18
First base layer (shielding layer)/adhesive layer in the same manner as in Example 16, except that a maleic anhydride-modified polypropylene (PPa) film (thickness: 20 μm) was used as the heat-fusible resin layer /Second substrate layer/Adhesive layer/Heat-fusible resin layer were laminated in this order to obtain an exterior material for an electricity storage device. PP and PPa of the first base material layer and the heat-fusible resin layer of Example 18 contain two types of lubricants, erucamide and behenamide, respectively.

Example 19
First base layer (shielding layer)/adhesive layer in the same manner as in Example 17, except that a maleic anhydride-modified polyethylene (PEa) film (thickness: 20 μm) was used as the heat-fusible resin layer. /Second substrate layer/Adhesive layer/Heat-fusible resin layer were laminated in this order to obtain an exterior material for an electricity storage device. PPa and PEa of the first base material layer and the heat-fusible resin layer of Example 19 each contained only erucamide as a lubricant.

Example 20
A maleic anhydride-modified polypropylene (PPa) film (thickness: 100 μm) containing carbon black (the average particle size of carbon black is in the range of 0.161 to 0.221 μm) is used as a power storage device consisting only of a heat-fusible resin layer. Used as exterior material for devices. The PPa of the heat-fusible resin layer of Example 20 contains only erucamide as a lubricant.

Example 21
On one side of an unstretched polypropylene (CPP) film (thickness 60 μm) as a second base layer, polypropylene containing carbon black (the average particle size of carbon black is in the range of 0.161 to 0.221 μm) ( PP) film (thickness 20 μm) is melt-extruded, and on the other side of the CPP film, a maleic anhydride-modified polypropylene (PPa) film (thickness 20 μm) is applied as an exterior material for an electricity storage device consisting only of a heat-fusible resin layer. bottom. PP and PPa of the first base material layer and the heat-fusible resin layer of Example 21 each contained only erucamide as a lubricant.

Example 22
A maleic anhydride-modified polypropylene (PPa) film (thickness: 20 μm) was prepared as the first base material layer. A polyethylene terephthalate (PET) film (thickness: 12 μm) was prepared as the second base material layer. A maleic anhydride-modified polypropylene (PPa) film (thickness: 20 μm) was prepared as a heat-fusible resin layer. Using a two-component urethane adhesive containing carbon black (the average particle size of carbon black is in the range of 0.161 to 0.221 μm), the thickness of the adhesive layer after curing is 3 μm. The first base material layer and the second base material layer were adhered via an adhesive layer by a lamination method. Furthermore, the second base material layer and the heat-fusible resin layer of the obtained laminate were dried using a two-component urethane adhesive so that the thickness of the adhesive layer after curing was 1 μm or less. They were adhered through an adhesive layer by a lamination method. A black adhesive layer between the first base layer and the second base layer was used as a shielding layer. Through the above procedure, an exterior material for a power storage device was obtained in which the first substrate layer/adhesive layer (shielding layer)/second substrate layer/adhesive layer/heat-fusible resin layer were laminated in this order. The PPa of the first base material layer and the heat-fusible resin layer of Example 22 contain two types of lubricants, erucic acid amide and behenic acid amide, respectively.

Example 23
Except that a polypropylene (PP) film (20 μm thick) was used as the first base layer and a polypropylene (PP) film (20 μm thick) was used as the heat-sealable resin layer. In the same manner as in Example 22, an exterior material for a power storage device was obtained in which the first substrate layer/adhesive layer (shielding layer)/second substrate layer/adhesive layer/heat-fusible resin layer were laminated in this order. rice field. The PP of the first base material layer and the heat-fusible resin layer of Example 23 contain two kinds of lubricants, erucamide and behenamide, respectively.

Reference example 1
An oriented nylon (ONy) film (thickness: 25 μm) was prepared as a substrate layer. Also, an aluminum (ALM) foil (40 μm thick) was prepared as a barrier layer. Also, maleic anhydride-modified polypropylene (PPa) was prepared as an adhesive layer. Also, polypropylene (PP) was prepared as a heat-fusible resin layer. Using a two-liquid urethane adhesive, the substrate layer and the barrier layer were adhered via the adhesive layer by a dry lamination method so that the adhesive layer had a thickness of 3 μm after curing. Further, an adhesive layer (23 μm thick) and a heat-fusible resin layer (23 μm thick) are melt-extruded on the surface of the barrier layer of the obtained laminate to form a substrate layer/adhesive layer/barrier layer/ An exterior material for an electric storage device was obtained in which an adhesive layer/a heat-fusible resin layer were laminated in this order. The PP of the heat-fusible resin layer of Reference Example 1 contains two kinds of lubricants, erucamide and behenamide. The exterior material for an electricity storage device of Reference Example 1 can be suitably used as an outer package.

For the electrical storage device exterior materials obtained in Examples 10 to 23 and Reference Example 1, the total light transmittance was measured and the shielding properties were evaluated in the same manner as in Examples 1 to 9 and Comparative Example 1, respectively. Table 3 shows the results.

<Continuous battery productivity>
In addition, when the exterior materials for electric storage devices obtained in Examples 1 to 23 and Reference Example 1 were subjected to cold molding using a mold, The exterior materials for electrical storage devices of Examples 1 to 16, 18, 22, and 23 and Reference Example 1 using two types of erucamide and behenamide were lubricants for the substrate layer and/or the heat-fusible resin layer. As compared with Examples 1 to 9, 17, 19 to 21 and Comparative Examples 1 and 7 using only erucamide as a mold, the adhesion of the lubricant to the mold is suppressed, and the frequency of cleaning the mold is reduced. It was reduced, and the continuous productivity of the exterior material for electric storage devices was excellent. In Table 3, evaluation A was given to the examples and comparative examples in which the continuous productivity of the battery was excellent, and evaluation B was given to the cases inferior to evaluation A.

"≦1 μm" described in Table 3 indicates 1 μm or less. In addition, "/" in the laminated structure shown in Table 3 indicates a separation of layers. Also, the numerical value (μm) in parentheses indicates the thickness of the layer.

As described above, the present disclosure provides inventions in the following aspects.
Section 1. An exterior material for an electricity storage device comprising at least a heat-fusible resin layer,
The exterior material for an electricity storage device has a shielding layer,
The exterior material for an electricity storage device is an exterior material for an electricity storage device that does not have a metal layer formed of metal.
Section 2. Item 2. The exterior material for an electricity storage device according to Item 1, wherein the heat-fusible resin layer constitutes a shielding layer.
Item 3. Item 3. The exterior material for an electricity storage device according to Item 1 or 2, which is composed of, in order from the outside, at least a laminate including a substrate layer and the heat-fusible resin layer.
Section 4. Item 4. The exterior material for an electricity storage device according to Item 3, wherein the base layer includes a first base layer and a second base layer in order from the outside.
Item 5. Item 5. The exterior material for an electricity storage device according to Item 3 or 4, wherein the first base material layer constitutes a shielding layer.
Item 6. Item 6. The power storage device exterior material according to any one of Items 1 to 5, wherein the inner surface of the heat-fusible resin layer has adhesiveness to metal.
Item 7. Consists of a laminate including, in order from the outside, at least a substrate layer and a heat-fusible resin layer,
The laminate has a shielding layer,
The laminate is an exterior material for an electricity storage device, which does not have a metal layer made of metal.
Item 8. An adhesive layer is provided between the base material layer and the heat-fusible resin layer,
Item 8. The exterior material for an electricity storage device according to any one of Items 3 to 7, wherein the adhesive layer constitutes the shielding layer.
Item 9. A colored layer is provided between the base material layer and the heat-fusible resin layer,
Item 9. The exterior material for an electricity storage device according to any one of Items 3 to 8, wherein the colored layer constitutes the shielding layer.
Item 10. Having a colored layer on the outside of the base material layer,
Item 10. The exterior material for an electricity storage device according to any one of Items 3 to 9, wherein the colored layer constitutes the shielding layer.
Item 11. Item 11. The power storage device exterior material according to any one of Items 1 to 10, wherein the shielding layer contains a pigment.
Item 12. Item 12. The power storage device exterior material according to Item 11, wherein the pigment is carbon black.
Item 13. Item 13. The exterior material for an electricity storage device according to any one of Items 1 to 12, which is black.
Item 14. Item 14. The exterior material for an electricity storage device according to any one of Items 1 to 13, which has a thin film layer containing at least one of an inorganic oxide and an inorganic nitride.
Item 15. 15. The exterior material for an electric storage device according to any one of Items 1 to 14, wherein the laminate has a total light transmittance of 20% or less as measured in accordance with JIS K7361-1:1997.
Item 16. Used in a container that houses an electricity storage device element having at least a positive electrode, a negative electrode, and an electrolyte,
The container has a double structure of an inner package and an outer package,
Item 16. The exterior material for an electricity storage device according to any one of Items 1 to 15, which is used as the inner package.
Item 17. A step of obtaining a laminate in which at least a substrate layer and a heat-fusible resin layer are laminated in order from the outside,
The laminate has a shielding layer,
A method for manufacturing an exterior material for an electric storage device, wherein the laminate does not have a metal layer formed of metal.
Item 18. 16. An electricity storage device, wherein an electricity storage device element comprising at least a positive electrode, a negative electrode, and an electrolyte is housed in a package formed by the exterior material for an electricity storage device according to any one of Items 1 to 15.
Item 19. An electricity storage device element comprising at least a positive electrode, a negative electrode, and an electrolyte is accommodated in an inner package formed of the exterior material for an electricity storage device according to Item 16,
An electricity storage device, wherein the inner package is further housed in the outer package.

1 Base material layer 2 Adhesive layer 3 Colored layer 4 Heat-fusible resin layer 6 Surface coating layer 10 Exterior material for electric storage device 11 First base material layer 12 Second base material layer 13 Adhesive layer 20 Outer package 30 Electricity storage Device 30a Periphery 31 Metal terminal 32 Storage device element S Shielding layer

Claims (19)

An exterior material for an electricity storage device comprising at least a heat-fusible resin layer,
The exterior material for an electricity storage device has a shielding layer,
The exterior material for an electricity storage device is an exterior material for an electricity storage device that does not have a metal layer formed of metal. The exterior material for an electricity storage device according to claim 1, wherein the heat-fusible resin layer constitutes a shielding layer. 3. The exterior material for an electricity storage device according to claim 1, wherein the exterior material is composed of, in order from the outside, at least a laminate including a substrate layer and the heat-fusible resin layer. The exterior material for an electricity storage device according to claim 3, wherein the base layer includes a first base layer and a second base layer in order from the outside. The exterior material for an electricity storage device according to claim 3 or 4, wherein the first base material layer constitutes a shielding layer. The exterior material for a power storage device according to any one of claims 1 to 5, wherein the inner surface of the heat-fusible resin layer has adhesiveness to metal. Consists of a laminate including, in order from the outside, at least a substrate layer and a heat-fusible resin layer,
The laminate has a shielding layer,
The laminate is an exterior material for an electricity storage device, which does not have a metal layer made of metal. An adhesive layer is provided between the base material layer and the heat-fusible resin layer,
The exterior material for an electricity storage device according to any one of claims 3 to 7, wherein the adhesive layer constitutes the shielding layer. A colored layer is provided between the base material layer and the heat-fusible resin layer,
The exterior material for an electricity storage device according to any one of claims 3 to 8, wherein the colored layer constitutes the shielding layer. Having a colored layer on the outside of the base material layer,
The exterior material for an electricity storage device according to any one of claims 3 to 9, wherein the colored layer constitutes the shielding layer. The power storage device exterior material according to any one of claims 1 to 10, wherein the shielding layer contains a pigment. The exterior material for an electricity storage device according to claim 11, wherein the pigment is carbon black. The exterior material for an electricity storage device according to any one of claims 1 to 12, which is black. The exterior material for a power storage device according to any one of claims 1 to 13, comprising a thin film layer containing at least one of an inorganic oxide and an inorganic nitride. The exterior material for an electric storage device according to any one of claims 1 to 14, wherein the laminate has a total light transmittance of 20% or less as measured in accordance with JIS K7361-1:1997. Used in a container that houses an electricity storage device element having at least a positive electrode, a negative electrode, and an electrolyte,
The container has a double structure of an inner package and an outer package,
The exterior material for an electricity storage device according to any one of claims 1 to 15, which is used as the inner package. A step of obtaining a laminate in which at least a substrate layer and a heat-fusible resin layer are laminated in order from the outside,
The laminate has a shielding layer,
A method for manufacturing an exterior material for an electric storage device, wherein the laminate does not have a metal layer formed of metal. An electricity storage device, wherein an electricity storage device element comprising at least a positive electrode, a negative electrode, and an electrolyte is housed in a package formed of the electricity storage device exterior material according to any one of claims 1 to 15. An electricity storage device element comprising at least a positive electrode, a negative electrode, and an electrolyte is accommodated in an inner package formed by the exterior material for an electricity storage device according to claim 16,
An electricity storage device, wherein the inner package is further housed in the outer package.

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