WO2022124310A1

WO2022124310A1 - Power storage device exterior material, method for manufacturing same, and power storage device

Info

Publication number: WO2022124310A1
Application number: PCT/JP2021/044971
Authority: WO
Inventors: 真天野; 一彦横田; 孝典山下
Original assignee: 大日本印刷株式会社
Priority date: 2020-12-07
Filing date: 2021-12-07
Publication date: 2022-06-16
Also published as: JPWO2022124310A1; JP2023055849A; JP7222446B2

Abstract

Provided is a power storage device exterior material which has shielding properties even when the device does not have a metal layer formed of metal.　This 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.

Description

Exterior materials for power storage devices, their manufacturing methods, and power storage devices

This disclosure relates to an exterior material for a power storage device, a manufacturing method thereof, and a power storage device.

Conventionally, various types of power storage devices have been developed, but in all power storage devices, the exterior material is an indispensable member for sealing the power storage device elements such as electrodes and electrolytes. Conventionally, a metal exterior material has been widely used as an exterior material for a power storage device.

On the other hand, in recent years, with the improvement of high performance of electric vehicles, hybrid electric vehicles, personal computers, cameras, mobile phones, etc., various shapes are required for power storage devices, and thinning and weight reduction are required. However, the metal exterior material for a power storage device, which has been widely used in the past, has a drawback that it is difficult to keep up with the diversification of shapes and there is a limit to weight reduction.

Therefore, in recent years, as an exterior material for a power storage device that can be easily processed into various shapes and can be made thinner and lighter, it is in the form of a film in which a base material layer / a metal layer / a heat-sealing resin layer is sequentially laminated. Laminates have been proposed (see, for example, Patent Document 1).

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

Japanese Unexamined Patent Publication No. 2008-287971 Japanese Unexamined Patent Publication No. 2015-26528

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

Although the inventors of the present disclosure have advantages in such an exterior material from the viewpoint of further weight reduction and thinning of the exterior material, the transparency of the exterior material is enhanced by not providing the metal layer, and the storage capacity is increased. The internal structure of the device was grasped, and we found a new problem that it was not desirable from the viewpoint of anti-counterfeiting.

Under such circumstances, the main object of the present disclosure is to provide an exterior material for a power storage device, which has a shielding property even though it does not have a metal layer formed of a metal.

The inventors of the present disclosure, in order from the outside, in an exterior material for a power storage device, which is composed of a laminate having at least a base material layer and a heat-sealing resin layer and does not have a metal layer formed of metal. We focused on adopting a configuration that is not expected in the prior art, that is, it does not impart transparency.

That is, the present disclosure provides the inventions of the following aspects.
From the outside, it is composed of a laminate having at least a base material layer and a heat-sealing resin layer.
The laminated body has a shielding layer and has a shielding layer.
The laminate is an exterior material for a power storage device that does not have a metal layer formed of metal.

The present disclosure also provides inventions of the following aspects.
At least, it is an exterior material for a power storage device provided with a heat-sealing resin layer.
The exterior material for a power storage device has a shielding layer and has a shielding layer.
The exterior material for a power storage device is an exterior material for a power storage device that does not have a metal layer formed of metal.

According to the present disclosure, it is possible to provide an exterior material for a power storage device that has a shielding property even though it does not have a metal layer formed of a metal. Since it does not have a metal layer formed of metal, the exterior material for a power storage device can be made lighter and thinner. In addition, since it has a shielding property, it is possible to prevent the internal structure of the power storage device from being grasped and forged, and further, in the manufacturing process of the power storage device, it is possible to grasp the position by the sensor with high accuracy, and the power storage device can be grasped. It is possible to accurately transport the exterior material and seal the power storage device element. Further, if the shielding layer is made black, for example, the power storage device can be made into a black high-class design. In addition, it is possible to give a high-class feeling as a product by unifying it with other electrical components in black. Further, the package for accommodating the power storage device has a double structure of an inner package and an outer package, and the exterior material for the power storage device of the present disclosure can be suitably used as the inner package. According to the present disclosure, it is also possible to provide a method for manufacturing an exterior material for a power storage device and a power storage device using the exterior material for the power storage device.

It is a schematic diagram which shows an example of the cross-sectional structure of the exterior material for a power storage device of this disclosure. It is a schematic diagram which shows an example of the cross-sectional structure of the exterior material for a power storage device of this disclosure. It is a schematic diagram which shows an example of the cross-sectional structure of the exterior material for a power storage device of this disclosure. It is a schematic diagram which shows an example of the cross-sectional structure of the exterior material for a power storage device of this disclosure. It is a schematic diagram which shows an example of the cross-sectional structure of the exterior material for a power storage device of this disclosure. It is a schematic diagram which shows an example of the cross-sectional structure of the exterior material for a power storage device of this disclosure. It is a schematic diagram which shows an example of the cross-sectional structure of the exterior material for a power storage device of this disclosure. It is a schematic diagram for demonstrating the method of accommodating a power storage device element in a package formed by the exterior material for power storage devices of the present disclosure. It is a schematic diagram which shows an example of the cross-sectional structure of the power storage device of this disclosure. It is a schematic diagram which shows an example of the cross-sectional structure of the power storage device of this disclosure.

The exterior material for a power storage device of the present disclosure is composed of a laminate having at least a base material layer and a heat-sealing resin layer in this order from the outside, and the laminate has a shielding layer and is laminated. The body is characterized by having no metal layer formed of metal. The exterior material for a power storage device of the present disclosure has a shielding property even though it does not have a metal layer formed of metal.

Hereinafter, the exterior material for the power storage device disclosed in the present disclosure will be described in detail. In this specification, the numerical range indicated by "-" means "greater than or equal to" and "less than or equal to". 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 exterior material for a power storage device of the present disclosure, the shielding layer makes it difficult to see the contents. The metal layer means a layer formed of metal, and examples thereof include a metal foil and a metal plate. The thickness of the metal foil is, for example, about 10 to 200 μm, and the thickness of the metal plate is, for example, from 200 μm. A few mm is mentioned.

1. 1. Laminated structure and physical properties of exterior material for power storage device The exterior material 10 for power storage device of the present disclosure has at least a base material layer 1 and a heat-sealing resin layer 4 as shown in FIGS. 1 to 4 and 6 to 7, for example. It is composed of a laminated body to be provided. In the exterior material 10 for a power storage device, the base material layer 1 is on the outermost layer side, and the heat-sealing resin layer 4 is on the innermost layer. When assembling a power storage device using the power storage device exterior material 10 and the power storage device element, the peripheral portion is heat-sealed with the heat-sealing resin layers 4 of the power storage device exterior material 10 facing each other. The energy storage device element is housed in the space formed by. The exterior material 10 for a power storage device of FIG. 7 is an embodiment in which the base material layer 1 includes a first base material layer 11 and a second base material layer.

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

In the laminated body constituting the exterior material 10 for a power storage device 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 laminated body may be one layer or two or more layers. As shown in FIGS. 1 to 4 and 6 to 7, for example, the exterior material 10 for a power storage device enhances the adhesiveness between the base material layer 1 and the heat-sealing resin layer 4. The adhesive layer 2 may be provided as needed for the purpose of such things. 1 and 4 show a diagram in which the adhesive layer 2 constitutes the shielding layer S.

When the layer constituting the exterior material 10 for a power storage device of the present disclosure is only a heat-sealing resin layer, as shown in FIG. 5, the heat-sealing resin layer 4 constitutes a shielding layer S having a shielding property. do.

Further, as shown in FIG. 2, a colored layer 3 (sometimes referred to as an inner colored layer) may be provided between the base material layer 1 and the heat-sealing 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. Further, as shown in FIG. 3, a colored layer 3 (sometimes referred to as an outer colored layer) may be provided on the outside of the base material layer 1 if necessary. FIG. 3 shows a diagram in which the colored layer 3 outside the base material layer 1 constitutes the shielding layer S. It is preferable that the colored layer 3 is provided on at least one surface of the base material layer 1 (that is, the base material layer 1 and the colored layer 3 are in contact with each other). This is because the base material layer is often stiff and it is easy to apply the pigment when coating the colored layer, so that the variation in film thickness can be suppressed and a uniform shielding layer can be formed. Because.

Further, for example, as shown in FIG. 4, a surface covering layer 6 or the like may be provided on the outside of the base material layer 1 (the side opposite to the heat-sealing resin layer 4 side), if necessary.

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

In the power storage device exterior material 10, the base material layer 1, the colored layer 3 provided as needed, and the adhesive provided as needed with respect to the thickness (total thickness) of the laminate constituting the power storage device exterior material 10. The ratio of the total thickness of the layer 2, the heat-sealing resin layer 4, and the surface coating layer 6 provided as needed is preferably 90% or more, more preferably 95% or more, still more preferably 98. % Or more. As a specific example, when the exterior material 10 for a power storage device of the present disclosure includes the base material layer 1, the adhesive layer 2, and the heat-sealing resin layer 4, the laminate of the exterior material 10 for the power storage device is included. The ratio of the total thickness of each of these layers to the thickness (total thickness) is preferably 90% or more, more preferably 95% or more, and further preferably 98% or more. Further, even when the exterior material 10 for a power storage device of the present disclosure is a laminated body including a base material layer 1, a colored layer 3, an adhesive layer 2, and a heat-sealing resin layer 4, the exterior material for a power storage device is also included. 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, still more preferably 98% or more. Can be done.

The laminate constituting the exterior material 10 for a power storage device of the present disclosure has a total light transmittance of preferably 20% or less, more preferably 15% or less, as measured in accordance with JIS K7361-1: 1997. It is more preferably 10% or less, still more preferably 8% or less. The lower the total light transmittance, the higher the shielding property of the exterior material 10 for the power storage device. The lower limit of the 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 a commercially available spectrophotometer (for example, an ultraviolet-visible near-infrared spectrophotometer V- made by Nippon Spectral Co., Ltd.). 670) is used to measure the transmittance in the visible light region (400 to 700 nm), and the average value is taken as the total light transmittance. The measurement conditions are a halogen lamp as a light source, UV / Vis bandwidth: 5.0 nm, scanning speed: 1000 nm / min, response: Medium, and data acquisition interval: 1.0 nm.

The exterior material 10 for the power storage device is preferably black. As a result, the exterior material 10 for a power storage device has a high shielding property and a high anti-counterfeiting effect. Further, in the manufacturing process of the power storage device, it is possible to grasp the position by the sensor with higher accuracy, and it is possible to transport the exterior material 10 for the power storage device and to seal the power storage device element more accurately. It becomes. Furthermore, it is possible to unify both the power storage device and other electrical components in black to give a sense of luxury as a product.

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

The material forming the base material layer 1 is not particularly limited as long as it has a function as a base material, that is, at least an insulating property. The base material layer 1 can be formed by using, for example, a resin, and the resin may contain an additive described later. It is preferable that the base material layer 1 is transparent and is used by being laminated with a shielding layer S composed of a layer different from the base material layer 1. May be configured.

When the base material layer 1 is formed of a resin, the base material layer 1 may be, for example, a resin film formed of a resin or may be formed by applying a resin. The resin film may be an unstretched film or a stretched film. Examples of the stretched film include a uniaxially stretched film and a biaxially stretched film, and a biaxially stretched film is preferable. Examples of the stretching method for forming the biaxially stretched film include a sequential biaxial stretching method, an inflation method, and a simultaneous biaxial stretching method. Examples of the method for applying the resin include a roll coating method, a gravure coating method, and an extrusion coating method.

Examples of the resin forming the base material layer 1 include resins such as polyester, polyamide, polyolefin, epoxy resin, acrylic resin, fluororesin, polyurethane, silicon resin, and phenol resin, and modified products of these resins. Further, the resin forming the base material layer 1 may be a copolymer of these resins or a modified product of the copolymer. Further, it may be a mixture of these resins.

Among these, the resin forming the base material layer 1 preferably includes polyester, polyamide, and polyolefin.

Specific examples of the polyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, and copolymerized polyester. Further, examples of the copolymerized polyester include a copolymerized polyester containing ethylene terephthalate as a repeating unit as a main component. Specifically, a copolymer polyester (hereinafter abbreviated after polyethylene (terephthalate / isophthalate)), polyethylene (terephthalate / adipate), polyethylene (terephthalate / terephthalate /), which polymerizes with ethylene isophthalate using ethylene terephthalate as a repeating unit. (Sodium sulfoisophthalate), polyethylene (terephthalate / sodium isophthalate), polyethylene (terephthalate / phenyl-dicarboxylate), polyethylene (terephthalate / decandicarboxylate) and the like can be mentioned. These polyesters may be used alone or in combination of two or more.

Specific examples of the polyamide include an aliphatic polyamide such as nylon 6, nylon 66, nylon 610, nylon 12, nylon 46, and a copolymer of nylon 6 and nylon 66; terephthalic acid and / or isophthalic acid. Hexamethylenediamine-isophthalic acid-terephthalic acid copolymerized polyamide such as nylon 6I, nylon 6T, nylon 6IT, nylon 6I6T (I stands for isophthalic acid, T stands for terephthalic acid), polyamide MXD6 (polymethaki Aroma-containing polyamides such as silylene adipamide); alicyclic polyamides such as polyamide PACM6 (polybis (4-aminocyclohexyl) methaneadipamide); further lactam components and isocyanate components such as 4,4'-diphenylmethane-diisocyanate. Examples thereof include a copolymerized polyamide, a polyesteramide copolymer or a polyether esteramide copolymer which is a copolymer of a copolymerized polyamide and a polyester or a polyalkylene ether glycol; and a polyamide such as these copolymers. These polyamides may be used alone or in combination of two or more.

The base material layer 1 preferably contains at least one of a polyester film, a polyamide film, and a polyolefin film, and preferably contains at least one of a stretched polyester film, a stretched polyamide film, and a stretched polyolefin film. It is more preferable to contain at least one of a stretched polyethylene terephthalate film, a stretched polybutylene terephthalate film, a stretched nylon film, and a stretched polypropylene film, preferably a biaxially stretched polyethylene terephthalate film, a biaxially stretched polybutylene terephthalate film, and a biaxially stretched nylon film. , It is more preferable to contain at least one of the biaxially stretched polypropylene films.

Further, as the polyolefin, a resin containing a polyolefin skeleton such as a polyolefin or an acid-modified polyolefin is preferable. Polyolefins are preferable from the viewpoint of imparting heat-sealing properties to the outer surface of the base material layer 1. Specific examples of the polyolefin include the same polyolefins exemplified in the heat-sealing resin layer 4 described later.

The base material layer 1 may be a single layer or may be composed of two or more layers. When the base material layer 1 is composed of two or more layers, the base material layer 1 may be a laminated body in which a resin film is laminated with an adhesive or the like, or the resin is co-extruded to form two or more layers. It may be a laminated body of the resin film. Further, the laminated body of the resin film obtained by co-extruding the resin into two or more layers may be used as the base material layer 1 without being stretched, or may be uniaxially stretched or biaxially stretched as the base material layer 1.

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 used in this 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. 7. When the base material layer 1 has the first base material layer 11 and the second base material layer 12, and the base material layer 1 is the shielding layer S, for example, the first base material layer 11 and the second base material At least one of the layers 12 can be a shielding layer S. For example, FIG. 7 shows an embodiment in which the first base material layer 11 is used as the shielding layer S.

As a specific example of the laminated body of two or more layers of resin film in the base material layer 1, a laminated body of a polyester film and a nylon film, a laminated body of two or more layers of nylon film, and a laminated body of two or more layers of polyester film. And the like, preferably a laminated body of a stretched nylon film and a stretched polyester film, a laminated body of two or more layers of stretched nylon film, and a laminated body of two or more layers of stretched polyester film. For example, when the base material layer 1 is a laminate of two layers of resin film, a laminate of polyester resin film and polyester resin film, a laminate of polyamide resin film and polyamide resin film, or a laminate of polyester resin film and polyamide resin film. A laminate is preferable, and a laminate of a polyethylene terephthalate film and a polyethylene terephthalate film, a laminate of a nylon film and a nylon film, or a laminate of a polyethylene terephthalate film and a nylon film is more preferable. Further, since the polyester resin is difficult to discolor when the electrolytic solution adheres to the surface, for example, when the base material layer 1 is a laminate of two or more resin films, the polyester resin film is the base material layer 1. It is preferably located in the outermost layer.

Further, from the viewpoint of imparting heat fusion property to the outer surface of the base material layer 1, specific examples of the laminate of two or more layers of resin film include a laminate of polyolefin and polyester, and a laminate of polyolefin and polyolefin. A laminate of polyolefin and polyamide is preferred. For example, in the case of a laminate of polypropylene and polyester, a laminate of a polypropylene film and a polyethylene terephthalate film, a laminate of a polypropylene film and a polyethylene naphthalate film, a laminate of a polypropylene film and a polybutylene terephthalate film, an acid-modified polypropylene film. A laminate of the polyethylene terephthalate film and the polyethylene terephthalate film, a laminate of the acid-modified polypropylene film and the polyethylene naphthalate film, and a laminate of the acid-modified polypropylene film and the polybutylene terephthalate film are preferable. 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 preferable. From the viewpoint of imparting adhesiveness to the metal to the outer surface of the base material layer 1, it is preferable to use an acid-modified polyolefin such as acid-modified polypropylene or acid-modified polyethylene as the first base material layer 11. As described above, when the outer surface of the base material layer 1 is provided with adhesiveness to metal, the outer surface of the power storage device 10 is used as the inner packaging, and the outer surface of the outer surface of the power storage device 10 is made of metal. It can be suitably adhered to an outer package made of (for example, metal foil, metal can, etc.).

When the base material layer 1 is a laminated body of two or more layers of resin films, the two or more layers of resin films may be laminated via an adhesive. As the preferable adhesive, the same adhesives as those exemplified in the adhesive layer 2 described later can be mentioned. That is, the adhesive layer 13 can be formed by the same adhesive as that exemplified in the adhesive layer 2 described later. The adhesive layer 13 may be mixed with a colorant or the like, which will be described later, to form the shielding layer S. The method for laminating two or more layers of resin films is not particularly limited, and known methods can be adopted. Examples thereof include a dry laminating method, a sandwich laminating method, an extrusion laminating method, a thermal laminating method, and the like, and a dry laminating method is preferable. The laminating method can be mentioned. When laminating by the dry laminating method, it is preferable to use a polyurethane adhesive as the adhesive. At this time, the thickness of the adhesive may be, for example, about 2 to 5 μm. Further, 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 in the adhesive layer 2 described later. At this time, the thickness of the anchor coat layer may be, for example, about 0.01 to 1.0 μm. The 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 formed of a 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 the surface of at least one side of the resin layer 1a.

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

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

The thin film layer 1b preferably has at least one of the coating film layer and the vapor deposition layer. The coating film 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. Further, the thin-film deposition 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, it is preferable that at least one layer constituting the thin film layer 1b is a coating film layer, and it is more preferable to have at least one layer each of the vapor deposition layer and the coating film layer. .. From the same viewpoint, when a plurality of the vapor-deposited layer and the coating film layer are provided, it is preferable that the vapor-deposited layer and the coating film layer are provided alternately. Hereinafter, the vapor deposition layer and the coating film layer will be described in detail.

[Embedded layer]
The thin-film deposition layer preferably contains at least one of an inorganic oxide and an inorganic nitride. Examples of the inorganic oxide and the inorganic nitride contained in the vapor deposition layer include silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), and sodium (Na). ), Oxides or nitrides of metals such as boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y). Among these, an oxide of silicon (Si) or aluminum (Al) is preferable.

Inorganic oxides are represented by MO _X such as SiO _X , AlO _X , MgO _X , etc. (However, in the formula, M represents a metal element, and the value of X has a different range depending on the metal element). Will be done.

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

The thickness of the thin-film deposition layer varies depending on the type of inorganic oxide and inorganic nitride, but is, for example, in the range of 5 × 10 ^-9 to 2 × 10 ^-6 m, preferably 1 × 10 ^-8 to 5 × 10 ^-8 m. It can be selected arbitrarily within.

Further, when the inorganic oxide is a silicon oxide, it may be a carbon-containing silicon oxide represented by SiO _x _Cy . In SiO _x _Cy , x is preferably a number of 1.5 to 2.2, y is preferably a number of 0.15 to 0.80, and x is a number of 1.7 to 2.1. It is more preferable that y is a number of 0.39 to 0.47.

The same applies to inorganic nitrides as to inorganic oxides. In the vapor-filmed layer, the inorganic oxide and the inorganic nitride may be contained individually by one type, or may be contained in a combination of two or more types.

[Method of forming a thin-film deposition layer]
The formation of the thin-film deposition layer can preferably be carried out by a chemical vapor deposition method, a physical vapor deposition method, or a combination thereof.

(1) Chemical Vapor Deposition Method (CVD Method)
The chemical vapor deposition method used in the present disclosure includes, for example, a plasma CVD method, a thermochemical vapor deposition method, a photochemical vapor deposition method, 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 on the surface of the surface to be vaporized of the layer to be laminated with the vapor deposition layer, and argon gas, helium gas or the like is used as a carrier gas. The vapor deposition layer can be formed by using the inert gas of the above, further using oxygen gas or the like as the oxygen supply gas, and using the low temperature plasma chemical vapor deposition method using a low temperature plasma generator or the like. As the low temperature plasma chemical vapor deposition method, for example, a known method as described in JP-A-2011-5839 can be adopted.

As the low temperature plasma generator, for example, a generator such as high frequency plasma, pulse wave plasma, microwave plasma, etc. can be used. In the present disclosure, it is desirable to use a generator by a high frequency plasma method in order to obtain a highly active and stable plasma.

In the low-temperature plasma chemical vapor deposition apparatus, the thin-film deposition layer is formed in the form of a thin film on the layer on which the vapor-film deposition layer is laminated by using the plasma-generated raw material gas, so that it is dense, has few gaps, and is flexible. It becomes a rich continuous layer. Therefore, it exhibits a higher water vapor barrier property than, for example, a vapor deposition layer formed by a vacuum vapor deposition method or the like, and a sufficient water vapor barrier property can be obtained with a thin film thickness.

(2) Physical Vapor Deposition Method (PVD Method)
The physical vapor deposition method includes, for example, a vacuum vapor 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 as described in JP-A-2011-5839 can be adopted.

[Coating film layer]
In the present disclosure, the coating film layer is preferably a layer formed by a coating film containing at least one of an inorganic oxide and an inorganic nitride and a water-soluble polymer. The coating film layer may be formed, for example, by applying a composition forming the coating film layer to the surface of the layer adjacent to the coating film layer when laminating each layer of the exterior material for a power storage device. Further, for example, as in the transfer method, the composition is separately applied to the surface of the substrate to form a coating film, and the obtained coating film is laminated on the surface of a layer adjacent to the coating film layer to form a coating film. You may. The water-soluble polymer preferably contains at least one of a polyvinyl alcohol-based resin and an ethylene / vinyl alcohol copolymer. The coating layer is preferably formed by applying a water vapor barrier composition (gas barrier composition) obtained by polycondensing an alkoxide and a water-soluble polymer by a sol-gel method. Thereby, the water vapor barrier property of the exterior material for the power storage device of the present disclosure can be further improved.
(1) Alkoxide As an alkoxide that can be used in the water vapor barrier composition, the general formula R ¹ _n M (OR ² ) _m (in the formula, R ¹ and R ² each independently have 1 to 8 carbon atoms. Represents an organic group of, 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). Alkoxide 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 or the like can be used as the metal atom M, and M is silicon, an alkoxysilane. It is preferable to use. Further, in the present disclosure, alkoxides of single or two or more different metal atoms can be mixed and used in the same solution.

Further, in the alkoxide represented by the above general formula R ¹ _n M (OR ² ) _m , specific examples of the organic group represented by R ¹ include, for example, a methyl group, an ethyl group, an n-propyl group, and 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 can be mentioned. Specific examples of the organic group represented by R ² include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group and the like.

As the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , at least one or more of a partial hydrolyzate of the alkoxide and a hydrolyzed condensate of the alkoxide can be used, and the above alkoxide can be used. As the partial hydrolyzate, not all of the alkoxide groups need to be hydrolyzed, and one or more of them may be hydrolyzed, or a mixture thereof, and further, as a condensate of hydrolysis. , A dimer or more of a partially hydrolyzed alkoxide, specifically, a dimer of 2 to 6 alkoxide is used.

(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 alkoxide.

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

Further, 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 tens of mol% of acetic acid groups remain, and complete saponified products in which only a few mol% of acetic acid groups remain or no acetic acid groups remain. To. Although not particularly limited, from the viewpoint of water vapor barrier property, it is desirable to use one having a saponification degree of 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more. The content of the repeating unit derived from ethylene in the above ethylene / vinyl alcohol copolymer (hereinafter, also referred to as “ethylene content”) is usually 0 to 50 mol%, preferably 20 to 45 mol%. It is preferable to use. Specific examples of the above ethylene / vinyl alcohol copolymer include Kuraray Co., Ltd., EVAL EP-F101 (ethylene content; 32 mol%), Nippon Synthetic Chemical Industry Co., Ltd., Soanol D2908 (ethylene content; 29 mol%). ) Etc. can be used.

(3) Silane Coupling Agent In the present disclosure, a silane coupling agent or the like can also be added to prepare a water vapor barrier composition that forms a coating film layer. In the present disclosure, the silane coupling agent comprises an organic silicon compound having both a hydrolyzing group that reacts with an inorganic substance and an organic functional group that reacts with an organic substance in one molecule. Examples of the hydrolyzing group that reacts with the inorganic substance include an alkoxy group such as a methoxy group and an ethoxy group, an acetoxy group and a chloro group. Further, as the organic functional group that reacts with an organic substance, a functional group that reacts with a hydroxyl group in a hydroxyl group-containing acrylic resin or an isocyanate group of an isocyanate compound is preferable, and examples thereof include an isocyanate group, an amino group, an epoxy group and a mercapto group. Further, it may be a vinyl group, a methacrylic acid 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 a silicon compound having no organic functional group, for example, a compound such as alkoxysilane having only a hydrolyzing group. In the present disclosure, the silane coupling agent may be one kind or a mixture of two or more kinds.

Examples of the silane coupling agent used in the present disclosure include N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, and N- (2). -Amino group-containing silane coupling agents such as -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, Contains epoxy groups such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane Silane coupling agent, mercapto group-containing silane coupling agent such as 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanuspropyltriethoxysilane, 3-isocyanuppropyltrimethoxysilane and other isocyanate groups Examples thereof include a silane coupling agent.

(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 mixed with a sol-gel method 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. For the preparation of the water vapor barrier composition, it is preferable to use water in a ratio of 0.1 to 100 mol with respect to 1 mol of the total molar amount of the above alkoxide. As the sol-gel method catalyst used in the preparation of the water vapor barrier composition, a tertiary amine which is substantially insoluble in water and soluble in an organic solvent, for example, N, N-dimethylbenzylamine is used. Further, as the acid, for example, mineral acids such as sulfuric acid, hydrochloric acid and nitrate, and organic acids such as acetic acid and tartrate acid and the like can be used. Further, as the organic solvent, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol and the like can be used.

Further, with respect to the water vapor barrier composition, the polyvinyl alcohol-based resin and / or the ethylene / vinyl alcohol copolymer is preferably in a state of being dissolved in a coating liquid containing the above-mentioned alkoxide, silane coupling agent and the like. Therefore, the type of the above organic solvent is appropriately selected. In the present disclosure, as the ethylene / vinyl alcohol copolymer solubilized in the solvent, for example, one commercially available as Soanol (manufactured by Nippon Synthetic Chemistry Co., Ltd.) can be used.

(5) Method for forming a water vapor barrier coating film When the above water vapor barrier composition is applied on the base material layer 1 or the vapor deposition layer and heated to remove the solvent and the alcohol generated by the polycondensation reaction, the weight is increased. The condensation reaction is completed and a coating layer is formed. Further, since the hydroxyl group generated by hydrolysis and the silanol group derived from the silane coupling agent are bonded to the hydroxyl group on the surface of the base material layer 1 and the vapor deposition layer, the adhesion and adhesion between the vapor deposition layer and the water vapor barrier coating film are adhered. Good sex and the like.

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

In the present disclosure, for example, chemical bonds, hydrogen bonds, coordination bonds, etc. by hydrolysis / cocondensation are formed between the two layers of the vapor deposition layer and the coating film layer, and the adhesion between these two layers is improved. Due to the synergistic effect, better water vapor barrier property is exhibited. Therefore, it is preferable that the thin film layer 1b is a laminate of a thin-film deposition layer and a coating film layer.

In the present disclosure, as a method of applying the above-mentioned water vapor barrier composition, for example, once or more than once by a roll coat such as a gravure roll coater, a spray coat, a dipping, a brush, a bar coat, an applicator or the like. With a single application, a coating film having a dry film thickness of 0.01 to 30 μm, preferably 0.1 to 10 μm can be formed. Further, condensation is performed by heating and drying in a normal environment at a temperature of 20 to 300 ° C., preferably 20 to 200 ° C. for 3 seconds to 60 minutes, preferably 10 seconds to 10 minutes to obtain a coating film. Layers can be formed.

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

Specific examples of the thin film layer 1b include, for example, a vapor-deposited layer containing an aluminum oxide, a coating layer containing a silicon oxide and a polyvinyl alcohol-based resin, and an aluminum oxide on one surface of the resin layer 1a. A four-layer structure in which a vapor-deposited layer containing silicon oxide and a coating film layer containing a silicon oxide and a polyvinyl alcohol-based resin are laminated in this order can be mentioned. At this time, the thin-film deposition layer containing the aluminum oxide is preferably formed by the physical vapor deposition method. Further, the coating film layer containing the silicon oxide and the polyvinyl alcohol-based resin is preferably a layer formed by the 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 lubricants, flame retardants, antiblocking agents, antioxidants, light stabilizers, tackifiers, and antistatic agents may be present on at least one of the surface and the inside of the base material layer 1. Only one type of additive may be used, or two or more types may be mixed and used.

In the present disclosure, from the viewpoint of enhancing the moldability of the exterior material for the power storage device, it is preferable that the lubricant is present on the surface of the base material layer 1. The lubricant is not particularly limited, but an amide-based lubricant is preferable. Specific examples of the amide-based lubricant include saturated fatty acid amides, unsaturated fatty acid amides, substituted amides, methylol amides, saturated fatty acid bisamides, unsaturated fatty acid bisamides, fatty acid ester amides, aromatic bisamides and the like. Specific examples of the saturated fatty acid amide include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxystearic acid amide and the like. Specific examples of unsaturated fatty acid amides include oleic acid amides and erucic acid amides. Specific examples of the substituted amide include N-oleyl palmitate amide, N-stearyl stearyl amide, N-stearyl oleate amide, N-oleyl stealic acid amide, N-stearyl erucate amide and the like. Specific examples of the trimethylolamide include trimethylolstearic acid amide. Specific examples of saturated fatty acid bisamides include methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, ethylene bisstearic acid amide, ethylene bishydroxystearic acid amide, ethylene bisbechenic acid amide, and hexamethylene bisstearate. Examples thereof include acid amides, hexamethylene bisbechenic acid amides, hexamethylene hydroxystearic acid amides, N, N'-distealyl adipic acid amides, N, N'-distearyl sebasic acid amides and the like. Specific examples of unsaturated fatty acid bisamides include ethylene bisoleic acid amides, ethylene biserukaic acid amides, hexamethylene bisoleic acid amides, N, N'-diorail adipic acid amides, and N, N'-diorail sevacinic acid amides. And so on. Specific examples of the fatty acid ester amide include stearoamide ethyl stearate and the like. Specific examples of the aromatic bisamide include m-xylylene bisstearic acid amide, m-xylylene bishydroxystearic acid amide, and N, N'-distearylisophthalic acid amide. The lubricant may be used alone or in combination of two or more.

When the lubricant is present on the surface of the base material layer 1, the abundance thereof is not particularly limited, but is preferably about 3 mg / m ² or more, more preferably about 4 to 15 mg / m ² , and further preferably 5 to 14 mg. About / m ² is mentioned.

The lubricant existing on the surface of the base material layer 1 may be one in which the lubricant contained in the resin constituting the base material layer 1 is exuded, or one in which the lubricant is applied to the surface of the base material layer 1. May be.

The thickness of the base material layer 1 is not particularly limited as long as it functions as a base material, but for example, it may be about 3 to 50 μm, preferably about 10 to 35 μm. When the base material layer 1 is a laminate of two or more resin films, the thickness of the resin films constituting each layer is preferably about 2 to 25 μm, respectively.

[Adhesive layer 2]
In the exterior material 10 for a power storage device of the present disclosure, the adhesive layer 2 is provided between the base material layer 1 and the heat-sealing resin layer 4 as necessary for the purpose of enhancing the adhesiveness. It is a layer to be. In the exterior material 10 for a power storage device, it is preferable to add a colorant or the like to the adhesive layer 2 to form a shielding layer S. If a colorant is mixed with the adhesive forming the adhesive layer 2 and a shielding layer is formed by one coating, a coating of the coloring pigment on the base material layer 1 can be added to a portion other than the adhesive layer 2. There is no need to carry out. Then, as compared with the case where the colored layer is provided as the shielding layer, the number of steps is reduced, the production efficiency is improved, and the risk of foreign matter contamination is reduced. Further, when the 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, from the viewpoint of long-term use, it is preferable to add a colorant to the adhesive layer 2.

The adhesive layer 2 is formed by an adhesive capable of adhering the base material layer 1 and the heat-sealing resin layer 4. The adhesive used for forming the adhesive layer 2 is not limited, but may be any of a chemical reaction type, a solvent volatile type, a heat melting type, a thermal pressure type and the like. Further, it may be a two-component curable adhesive (two-component adhesive), a one-component curable adhesive (one-component adhesive), or a resin that does not involve a curing reaction. Further, the adhesive layer 2 may be a single layer or a multilayer.

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 resin; Polyethylene such as nylon 6, nylon 66, nylon 12, copolymerized polyamide; Polyethylene resin such as polyolefin, cyclic polyolefin, acid-modified polyolefin, acid-modified cyclic polyolefin; Polyvinyl acetate; Cellulose; (Meta) acrylic resin; Polyethylene; polycarbonate; amino resin such as urea resin and melamine resin; rubber such as chloroprene rubber, nitrile rubber and styrene-butadiene rubber; silicone resin and the like can be mentioned. These adhesive components may be used alone or in combination of two or more. Among these adhesive components, a polyurethane adhesive is preferable. In addition, the resin as an adhesive component can be used in combination with an appropriate curing agent to increase the adhesive strength. As the curing agent, an appropriate one is selected from polyisocyanate, polyfunctional epoxy resin, oxazoline group-containing polymer, polyamine resin, acid anhydride and the like, depending on the functional group of the adhesive component.

Examples of the polyurethane adhesive include a polyurethane adhesive containing a first agent containing a polyol compound and a second agent containing an isocyanate compound. Preferred are two-component curable polyurethane adhesives in which a polyol such as a polyester polyol, a polyether polyol, and an acrylic polyol is used as a first agent, and an aromatic or aliphatic polyisocyanate is used as a second agent. Examples of the polyurethane adhesive include a polyurethane adhesive in which a polyol compound and an isocyanate compound are reacted in advance, and a polyurethane adhesive containing the isocyanate compound. Examples of the polyurethane adhesive include a polyurethane adhesive in which a polyol compound and an isocyanate compound are reacted in advance, and a polyurethane adhesive containing the polyol compound. Examples of the polyurethane adhesive include a polyurethane adhesive obtained by reacting a polyurethane compound in which a polyol compound and an isocyanate compound are previously reacted with water such as in the air to cure the polyurethane adhesive. As the polyol compound, it is preferable to use a polyester polyol having a hydroxyl group in the side chain in addition to the hydroxyl group at the end of the repeating unit. Examples of the second agent include aliphatic, alicyclic, aromatic, and aromatic aliphatic isocyanate compounds. Examples of the isocyanate-based compound include hexamethylene diisocyanate (HDI), xylylene diisocyanate (XDI), isophorone diisocyanate (IPDI), hydride XDI (H6XDI), hydride MDI (H12MDI), tolylene diisocyanate (TDI), and diphenylmethane diisocyanate. (MDI), naphthalenediocyanate (NDI) and the like can be mentioned. Moreover, a polyfunctional isocyanate modified product from one kind or two or more kinds of these diisocyanates can be mentioned. Further, a multimer (for example, a trimer) can be used as the polyisocyanate compound. Examples of such a multimer include an adduct body, a biuret body, a nurate body and the like. Since the adhesive layer 2 is formed of a polyurethane adhesive, excellent electrolytic solution resistance is imparted to the exterior material for a power storage device, and even if the electrolytic solution adheres to the side surface, the base material layer 1 is suppressed from peeling off. ..

Further, the adhesive layer 2 may contain a colorant, a thermoplastic elastomer, a tackifier, a filler and the like, as long as the adhesiveness is not impaired, the addition of other components is permitted. Since the adhesive layer 2 contains a colorant, the exterior material for a power storage device can be colored. If the adhesive layer 2 is colored to such an extent that the exterior material for the power storage device can be provided with a shielding property, the adhesive layer 2 can be a shielding layer S. As the colorant, known ones such as pigments and dyes can be used. Further, as the colorant, only one kind may be used, or two or more kinds 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, anthracinone-based, dioxazine-based, indigothioindigo-based, perinone-perylene-based, isoindrenine-based, and benzimidazolone-based pigments, which are inorganic. Examples of the pigment include carbon black-based, titanium oxide-based, cadmium-based, lead-based, chromium oxide-based, iron-based, and copper-based pigments, and other examples include fine powder of mica (mica) and fish scale foil. Be done.

Among the colorants, for example, in order to make the appearance of the exterior material for a power storage device black, a black colorant is preferable, and among the black colorants, carbon black is preferable. By using a black colorant to form a black exterior material 10 for a power storage device, the exterior material 10 for a power storage device having a high shielding property and a high anti-counterfeiting effect can be obtained. Further, in the manufacturing process of the power storage device, it is possible to grasp the position by the sensor with higher accuracy, and it is possible to transport the exterior material 10 for the power storage device and to seal the power storage device element more accurately. It becomes. Furthermore, it is possible to unify both the power storage device and other electrical components in black to give a sense of luxury as a product. Carbon black is a more preferable colorant in terms of high shielding property.

The average particle size of the pigment is not particularly limited, and examples thereof include about 0.05 to 5 μm, preferably about 0.08 to 2 μm. The average particle size of carbon black is in the range of 0.161 to 0.221 μm. The average particle size of the pigment is the median diameter measured by the laser diffraction / scattering type particle size distribution measuring device.

The content of the pigment in the adhesive layer 2 is not particularly limited as long as the exterior material for the power storage device is colored, and examples thereof include about 5 to 60% by mass, preferably 10 to 40% by mass.

The thickness of the adhesive layer 2 is not particularly limited as long as the base material layer 1 and the heat-sealing resin layer 4 can be adhered to each other, but is, for example, about 1 μm or more and about 2 μm or more. The thickness of the adhesive layer 2 is, for example, about 10 μm or less and about 5 μm or less. 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 base material layer 1 and the heat-sealing resin layer 4 (see FIG. 2) and outside the base material layer 1 (see FIG. 3) as needed. When the adhesive layer 2 is provided, the colored layer 3 may be provided between the base material layer 1 and the adhesive layer 2. By providing the coloring layer 3, the exterior material for the power storage device can be colored. If the colored layer 3 is colored to such an extent that the exterior material for the power storage device can be provided with a shielding property, the colored layer 3 can be a shielding layer S. In the exterior material 10 for a power storage device, it is preferable that the colored layer 3 is a shielding layer S. The colored layer 3 between the base material layer 1 and the heat-bondable resin layer 4 may be referred to as an inner colored layer, and the outer colored layer 3 of the base material layer 1 may be referred to as an outer colored layer. It is preferable that the colored layer 3 is provided on at least one surface of the base material layer 1 (that is, the base material layer 1 and the colored layer 3 are in contact with each other).

The colored layer 3 can be formed, for example, by applying an ink containing a colorant to the surface of the base material layer 1. As the colorant, known ones such as pigments and dyes can be used. Further, as the colorant, only one kind may be used, or two or more kinds may be mixed and used.

Specific examples of the colorant contained in the color layer 3 include the same as those exemplified in the column of [Adhesive layer 2].

The thickness of the colored layer 3 is not particularly limited as long as the exterior material 10 for the power storage device is colored, but is, for example, about 1 μm or more and about 2 μm or more. The thickness of the colored layer 3 is, for example, about 10 μm or less and about 5 μm or less. The preferred 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-fused resin layer 4]
In the exterior material for a power storage device of the present disclosure, the heat-sealing resin layer 4 corresponds to the innermost layer, and has a function of heat-sealing the heat-sealing resin layers to each other when assembling the power storage device to seal the power storage device element. It is a layer (sealant layer) that exerts. It is preferable that the heat-sealing resin layer 4 is transparent and is used by being laminated with a shielding layer S composed of a layer different from the heat-sealing resin layer 4, but the heat-sealing resin layer 4 is colored as described above. The shielding layer S may be formed by blending an agent or the like. As described above, when the exterior material 10 for a power storage device of the present disclosure is composed of only the heat-sealing resin layer 4, the heat-sealing resin layer 4 constitutes the shielding layer S.

The resin constituting the heat-fusing resin layer 4 is not particularly limited as long as it can be heat-fused, but a resin containing a polyolefin skeleton such as a polyolefin or an acid-modified polyolefin is preferable. The fact that the resin constituting the heat-sealing resin layer 4 contains a polyolefin skeleton can be analyzed by, for example, infrared spectroscopy, gas chromatography-mass spectrometry, or the like. Further, when the resin constituting the heat-sealing 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 in the vicinity of wave number 1760 cm ^-1 and wave number 1780 cm ^-1 . When the heat-sealing 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 become small and may not be detected. In that case, it can be analyzed by nuclear magnetic resonance spectroscopy.

Specific examples of the polyolefin include polyethylene such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, and linear low-density polyethylene; ethylene-α-olefin copolymer; homopolypropylene, block copolymer of polypropylene (for example, with propylene). Polyethylene block copolymers), random copolymers of polypropylene (eg, random copolymers of propylene and ethylene); propylene-α-olefin copolymers; ethylene-butene-propylene tarpolymers and the like. Among these, polypropylene is preferable. When it is a copolymer, the polyolefin resin may be a block copolymer or a random copolymer. One of these polyolefin resins may be used alone, or two or more thereof may be used in combination.

Further, the polyolefin may be a cyclic polyolefin. The cyclic polyolefin is a copolymer of an olefin and a cyclic monomer, and examples of the olefin which is a constituent monomer of the cyclic polyolefin include ethylene, propylene, 4-methyl-1-pentene, styrene, butadiene, and isoprene. Be done. Examples of the cyclic monomer which is a constituent monomer of the cyclic polyolefin include cyclic alkenes such as norbornene; cyclic diene such as cyclopentadiene, dicyclopentadiene, cyclohexadiene, and norbornadiene. Among these, cyclic alkene is preferable, and norbornene is more preferable.

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

The acid-modified polyolefin may be an acid-modified cyclic polyolefin. The acid-modified cyclic polyolefin is a polymer obtained by copolymerizing 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 with the cyclic polyolefin. be. The same applies to the cyclic polyolefin that is acid-modified. The acid component used for acid denaturation is the same as the acid component used for denaturation of the polyolefin.

Preferred acid-modified polyolefins include polyolefins modified with carboxylic acid or its anhydride, polypropylene modified with carboxylic acid or its anhydride, maleic anhydride-modified polyolefin, and maleic anhydride-modified polypropylene.

The heat-sealing resin layer 4 may be formed of one type of resin alone, or may be formed of a blended polymer in which two or more types of resins are combined. Further, the heat-sealing resin layer 4 may be formed of only one layer, but may be formed of two or more layers with the same or different resins.

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

Further, the heat-sealing resin layer 4 may contain a lubricant or the like, if necessary. When the heat-bondable resin layer 4 contains a lubricant, the moldability of the exterior material for a power storage device can be improved. The lubricant is not particularly limited, and a known lubricant can be used. The lubricant may be used alone or in combination of two or more.

The lubricant is not particularly limited, but an amide-based lubricant is preferable. Specific examples of the lubricant include those exemplified in the base material layer 1. The lubricant may be used alone or in combination of two or more. By combining two or more types of lubricants, it is possible to reduce the adhesion of the lubricant to the mold when the exterior material 10 for the power storage device is cold-molded by the mold due to the interaction between the lubricants, and the power storage device. The continuous productivity of the above can be suitably increased. This also applies to the case where a lubricant is used for the base material layer 1.

When the lubricant is present on the surface of the heat-sealing resin layer 4, the amount thereof is not particularly limited, but is preferably about 10 to 50 mg / m ² from the viewpoint of improving the moldability of the exterior material for the power storage device. , More preferably about 15 to 40 mg / m ² .

The lubricant present on the surface of the heat-sealing resin layer 4 may be one in which the lubricant contained in the resin constituting the heat-sealing resin layer 4 is exuded, or the lubricant of the heat-sealing resin layer 4 may be exuded. The surface may be coated with a lubricant.

The thickness of the heat-sealing resin layer 4 is not particularly limited as long as the heat-sealing resin layers have a function of heat-sealing to seal the power storage device element, but is preferably about 150 μm or less, preferably about 150 μm or less. It is about 85 μm or less, more preferably about 15 to 85 μm, still more preferably about 35 to 85 μm.

[Surface coating layer 6]
The exterior material for a power storage device of the present disclosure is above the base material layer 1 (base material layer 1), if necessary, for the purpose of improving at least one of designability, electrolytic solution resistance, scratch resistance, moldability, and the like. The surface coating layer 6 may be provided on the side opposite to the heat-sealing resin layer 4 side). The surface coating layer 6 is a layer located on the outermost layer side of the exterior material for a power storage device when the power storage device is assembled using the exterior material for the power storage device. The surface coating layer 6 may be blended with the above-mentioned colorant or the like to form the shielding layer S.

Examples of the surface coating layer 6 include resins such as polyvinylidene chloride, polyester, polyamide, epoxy resin, acrylic resin, fluororesin, polyurethane, silicon resin, and phenol resin, and modified products of these resins. Further, it may be a copolymer of these resins, or it may be a modified product of the copolymer. Further, it may be a mixture of these resins. The resin is preferably a curable resin. That is, the surface coating layer 6 is preferably composed 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, but is preferably a two-component curable type. Examples of the two-component curable resin include two-component curable polyurethane, two-component curable polyester, and two-component curable epoxy resin. Among these, two-component curable polyurethane is preferable.

Examples of the two-component curable polyurethane include a polyurethane containing a first agent containing a polyol compound and a second agent containing an isocyanate compound. Preferred are two-component curable polyurethanes in which a polyol such as a polyester polyol, a polyether polyol, and an acrylic polyol is used as a first agent, and an aromatic or aliphatic polyisocyanate is used as a second agent. Examples of the polyurethane include a polyurethane compound in which a polyol compound and an isocyanate compound are reacted in advance, and a polyurethane containing an isocyanate compound. Examples of the polyurethane include a polyurethane compound obtained by previously reacting a polyol compound with an isocyanate compound, and a polyurethane containing the polyol compound. Examples of the polyurethane include polyurethane obtained by reacting a polyurethane compound in which a polyol compound and an isocyanate compound are previously reacted with water such as in the air to cure the polyurethane. As the polyol compound, it is preferable to use a polyester polyol having a hydroxyl group in the side chain in addition to the hydroxyl group at the end of the repeating unit. Examples of the second agent include aliphatic, alicyclic, aromatic, and aromatic aliphatic isocyanate compounds. Examples of the isocyanate-based compound include hexamethylene diisocyanate (HDI), xylylene diisocyanate (XDI), isophorone diisocyanate (IPDI), hydride XDI (H6XDI), hydride MDI (H12MDI), tolylene diisocyanate (TDI), and diphenylmethane diisocyanate. (MDI), naphthalenediocyanate (NDI) and the like can be mentioned. Moreover, a polyfunctional isocyanate modified product from one kind or two or more kinds of these diisocyanates can be mentioned. Further, a multimer (for example, a trimer) can be used as the polyisocyanate compound. Examples of such a multimer include an adduct body, a biuret body, a nurate body and the like. The aliphatic isocyanate-based compound refers to an isocyanate having an aliphatic group and no aromatic ring, and the alicyclic isocyanate-based compound refers to an isocyanate having an alicyclic hydrocarbon group, which is an aromatic isocyanate-based compound. Refers to an isocyanate having an aromatic ring. Since the surface coating layer 6 is made of polyurethane, excellent electrolytic solution resistance is imparted to the exterior material for the power storage device.

The surface coating layer 6 is provided on at least one of the surface and the inside of the surface coating layer 6, depending on the functionality and the like to be provided on the surface coating layer 6 and the surface thereof, and if necessary, the above-mentioned lubricant and anti. It may contain additives such as a blocking agent, a matting agent, a flame retardant, an antioxidant, a tackifier, and an antistatic agent. Examples of the additive include fine particles having an average particle diameter of about 0.5 nm to 5 μm. The average particle size of the additive shall be the median diameter measured by the laser diffraction / scattering type particle size distribution measuring device.

The additive may be either an inorganic substance or an organic substance. The shape of the additive is also not particularly limited, and examples thereof include spherical, fibrous, plate-like, amorphous, and scaly shapes.

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, neodium 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 nanotubes, melting point nylon, acrylate resin, Examples thereof include crosslinked acrylic, crosslinked styrene, crosslinked polyethylene, benzoguanamine, gold, aluminum, copper and nickel. The additive may be used alone or in combination of two or more. Among these additives, silica, barium sulfate, and titanium oxide are preferable from the viewpoint of dispersion stability and cost. Further, the additive may be subjected to various surface treatments such as an insulation treatment and a high dispersibility treatment on the surface.

The method for forming the surface coating layer 6 is not particularly limited, and examples thereof include a method of applying a resin for forming the surface coating layer 6. When the additive is blended in the surface coating layer 6, a resin mixed with the additive may be applied.

The thickness of the surface coating layer 6 is not particularly limited as long as it exhibits the above-mentioned functions as the surface coating layer 6, and examples thereof include about 0.5 to 10 μm, preferably about 1 to 5 μm.

3. 3. Method for Manufacturing Exterior Material for Power Storage Device The method for manufacturing the exterior material for power storage device is not particularly limited as long as a laminated body in which each layer of the exterior material for power storage device of the present disclosure is laminated can be obtained, and the method is not particularly limited. At least, it comprises a step of obtaining a laminated body in which a base material layer and a heat-sealing resin layer are laminated, the laminated body has a shielding layer, and the laminated body is a metal layer formed of metal. Does not have. When the exterior material for a power storage device of the present disclosure is composed of a heat-sealing resin layer, a resin film constituting the heat-sealing resin layer is prepared. When the exterior material for a power storage device is composed of two or more heat-sealing resin layers, a resin film in which two or more layers are laminated can be obtained and used as an exterior material for a power storage device, or heat can be obtained. Each layer constituting the fused resin layer can be laminated to form an exterior material for a power storage device. When the exterior material for a power storage device of the present disclosure includes another layer such as a base material layer in addition to the heat-sealing resin layer, a resin film having the other layer is obtained and power storage is performed. It is provided with a step of using it as an exterior material for a device or laminating a heat-sealing resin layer and another layer to obtain a laminated body.

An example of the method for manufacturing the exterior material for the power storage device disclosed in the present disclosure is as follows. First, the materials constituting the base material layer 1, the adhesive layer 2, and the heat-sealing resin layer 4 are prepared. Next, the base material layer 1 and the heat-sealing resin layer 4 are laminated via the adhesive layer 2. Specifically, the base material layer 1 and the adhesive layer are laminated by laminating the base material layer 1 and the heat-sealing resin layer 4 by a dry laminating method or the like using an adhesive that forms the adhesive layer 2. 2. The exterior material 10 for a power storage device, in which the heat-sealing resin layer 4 is laminated in this order, can be manufactured. Further, when the base material layer 1 and the heat-sealing resin layer 4 are laminated without interposing the adhesive layer 2, the resin constituting the heat-sealing resin layer 4 is melted on the base material layer 1. The exterior material 10 for a power storage device can be manufactured by an extruding method or the like. When the colored layer 3 is provided, the colored layer 3 may be formed on the surface of the base material layer 1 and then laminated with the heat-sealing resin layer 4. When the surface coating layer 6 is provided, it can be formed, for example, by applying the above resin composition for forming the surface coating layer 6 to the surface of the base material layer 1 and curing it.

As described above, in order from the outside, the surface coating layer 6 provided as needed / the colored layer 3 (outer colored layer) provided as needed / the base material layer 1 as needed and provided as needed. A laminated body including the colored layer 3 (inner colored layer) / the adhesive layer 2 provided as needed / the heat-sealing resin layer 4 is formed, and the adhesive layer 2 provided as needed is adhered. In order to enhance the property, it may be further subjected to heat treatment.

4. Applications of Exterior Materials for Energy Storage Devices The exterior materials for energy storage devices of the present disclosure are used in packages for sealing and accommodating energy storage device elements such as positive electrodes, negative electrodes, and electrolytes. That is, a power storage device element having at least a positive electrode, a negative electrode, and an electrolyte can be housed in a package formed of the exterior material for a power storage device of the present disclosure to form a power storage device.

Specifically, a power storage device element having at least a positive electrode, a negative electrode, and an electrolyte is provided with the exterior material for the power storage device of the present disclosure in a state where metal terminals connected to each of the positive electrode and the negative electrode are projected outward. , The peripheral edge of the power storage device element is covered so that a flange portion (a region where the heat-sealing resin layers come into contact with each other) can be formed, and the heat-sealing resin layers of the flange portion are heat-sealed and sealed. Provides a power storage device using an exterior material for a power storage device. When the power storage device element is housed in the package formed of the power storage device exterior material of the present disclosure, the heat-sealing resin portion of the power storage device exterior material of the present disclosure is inside (the surface in contact with the power storage device element). ) To form a package. The heat-bondable resin layers of the two exterior materials for power storage devices may be overlapped with each other facing each other, and the peripheral edges of the overlapped exterior materials for power storage devices may be heat-sealed to form a package. As in the example shown in FIG. 8, one exterior material for a power storage device may be folded back and overlapped, and the peripheral edge portion may be heat-sealed to form a package. In the case of folding and overlapping, as shown in the example shown in FIG. 8, the side other than the folded side may be heat-sealed to form a package by a three-way seal, or the package may be folded so that a flange portion can be formed. It may be sealed on all sides. Further, in the exterior material for the power storage device, a recess for accommodating the power storage device element may be formed by deep drawing molding or overhang molding. As shown in the example shown in FIG. 8, it is not necessary to provide a recess in one of the exterior materials for the power storage device and not in the exterior material for the other power storage device, and the other exterior material for the power storage device also has a recess. May be provided.

Further, as shown in FIG. 10, the exterior material 10 for a power storage device of the present disclosure is a power storage device 30 in which a power storage device element 32 is housed in a container having a dual 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 of the exterior material 10 for the power storage device of the present disclosure, and the inner package 10a is further housed in the outer package 20. By accommodating the inside, the electricity storage device 30 in which the energy storage device element 32 is housed in the container having the dual structure of the inner package 10a and the outer package 20 can be obtained. One or two or more members in which the power storage device element 32 is housed are prepared in the inner package 10a formed by the exterior material 10 for the power storage device of the present disclosure, and one or two or more members are housed in the outer package. It can be accommodated in 20 to be a power storage device. Although each corner is drawn at a right angle in FIGS. 8 to 10, the angle of each corner or ridge is not limited, and each corner or ridge may be rounded.

The outer package is not particularly limited, and an exterior material, a metal can, or the like made of a film-like laminate in which a base material layer / a metal layer / a heat-sealing resin layer is sequentially laminated can be used. ..

The exterior material for a power storage device of the present disclosure can be suitably used for a power storage device such as a battery (including a capacitor, a capacitor, etc.). Further, the exterior material for a power storage device of the present disclosure may be used for either a primary battery or a secondary battery, but is preferably used for a secondary battery. The type of the secondary battery to which the exterior material for the power storage device of the present disclosure is applied is not particularly limited, and for example, a lithium ion battery, a lithium ion polymer battery, an all-solid-state battery, a lead storage battery, a nickel / hydrogen storage battery, and a nickel / hydrogen storage battery. Examples thereof include a cadmium storage battery, a nickel / iron storage battery, a nickel / zinc storage battery, a silver oxide / zinc storage battery, a metal air battery, a polyvalent cation battery, a condenser, and a capacitor. Among these secondary batteries, lithium ion batteries and lithium ion polymer batteries can be mentioned as suitable application targets of the exterior materials for power storage devices of the present disclosure.

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 of exterior materials for power storage devices>
Example 1
A polyethylene terephthalate (PET) film (thickness 12 μm) was prepared as a base material layer. Further, an unstretched polypropylene film (CPP, thickness 50 μm) was prepared as a heat-sealing resin layer. 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) is used for the base material layer and the heat-sealing resin layer to form an adhesive layer. The base material layer and the heat-sealing resin layer were adhered to each other via a black adhesive layer by a dry laminating method so that the thickness after curing was 3 μm. The black adhesive layer was used as the shielding layer. By the above procedure, an exterior material for a power storage device in which a base material layer / an adhesive layer (shielding layer) / a heat-sealing resin layer are laminated in this order was obtained.

Example 2
A polyethylene terephthalate (PET) film (thickness 12 μm) was prepared as a base material layer. Further, an unstretched polypropylene film (CPP, thickness 50 μm) was prepared as a heat-sealing resin layer. After curing a two-component urethane resin containing carbon black (the average particle size of carbon black was in the range of 0.161 to 0.221 μm, and the content of carbon black was the same as in Example 1). The black colored layer was formed by applying, drying and curing on one surface of the base material layer so that the thickness of the colored layer was 3 μm. The black colored layer was used as a shielding layer. Next, a two-component urethane adhesive was used for the side of the base material layer opposite to the colored layer (called the outer colored layer) side and the heat-sealing resin layer, and the thickness of the adhesive layer after curing was 3 μm. The base material layer and the heat-sealing resin layer are adhered to each other via the adhesive layer so that the outer colored layer (shielding layer) / base material layer / adhesive layer / heat-sealing resin layer is formed. Obtained an exterior material for a power storage device laminated in this order.

Example 3
A polyethylene terephthalate (PET) film (thickness 12 μm) was prepared as a base material layer. Further, an unstretched polypropylene film (CPP, thickness 50 μm) was prepared as a heat-sealing resin layer. After curing a two-component urethane resin containing carbon black (the average particle size of carbon black was in the range of 0.161 to 0.221 μm, and the content of carbon black was the same as in Example 1). The black colored layer was formed by applying, drying and curing on one surface of the base material layer so that the thickness of the colored layer was 3 μm. The black colored layer was used as a shielding layer. Next, the colored layer (called the inner colored layer) side of the base material layer and the heat-sealing resin layer are made to have a thickness of 3 μm after curing by using a two-component urethane adhesive. Then, the base material layer and the heat-sealing resin layer are adhered to each other via the adhesive layer, and the base material layer / inner colored layer (shielding layer) / adhesive layer / heat-sealing resin layer are laminated in this order. The exterior material for the energy storage device was obtained.

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

Example 5
[Preparation of base material layer 1]
(1) As the resin layer 1a, a corona-treated polyethylene terephthalate (PET) film (thickness 12 μm) was used. Further, using a take-up low-temperature plasma chemical vapor deposition method, a carbon-containing silicon oxide vapor-deposited film having a film thickness of 300 Å was formed on one surface of the resin layer 1a under the following vapor-film deposition conditions. ..
(Evaporation conditions)
Output: 15kW
Vacuum degree in the vapor 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" is the amount per minute expressed in liters.

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

(2) On the other hand, according to the composition shown in Table 1 below, the composition a. A composition prepared in advance in a hydrolyzed solution consisting of ethyl orthosilicate (manufactured by Tama Chemical Co., Ltd.), isopropyl alcohol, 0.5N hydrochloric acid aqueous solution, ion-exchanged water, and a silane coupling agent. An aqueous solution of polyvinyl alcohol was added and stirred to obtain a colorless and transparent water vapor barrier composition.

Next, the plasma-treated surface formed in (1) above was coated with the water vapor barrier composition produced above by a gravure roll coating method, and then heat-treated at 150 ° C. for 60 seconds to obtain a thickness of 0. A coating layer of 2 μm (dry state) was formed, and a base material layer 1 in which the resin layer a / the vapor deposition layer / the coating layer were laminated in this order was obtained. In the base material layer 1, the laminated body of the thin-film deposition layer and the coating film layer constitutes the thin film layer 1b.

(3) Next, the obtained base material layer 1 was mounted on a 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, and a mixture consisting of an output of 9 kW and an oxygen gas: argon gas = 7.0: 2.5 (unit: slm) is used. Using gas, oxygen / argon mixed gas plasma treatment was performed at a mixed gas pressure of 6 × 10 ⁻² mbar and a treatment speed of 240 m / min.
(4) A two-component urethane adhesive containing carbon black on the thin film layer 1b side of the base material layer and the heat-sealing resin layer (the average particle size of carbon black is within the range of 0.161 to 0.221 μm). As for the content of carbon black, the content of carbon black contained in the adhesive layer is 50 parts by mass when the content of carbon black contained in the adhesive layer of Example 1 is 100 parts by mass as a reference. The thickness of the adhesive layer after curing was set to 3 μm, and the base material layer and the heat-sealing resin layer were separated into a black adhesive layer by the dry laminating method. It was glued through. The black adhesive layer was used as the 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 [deposited layer / coating film layer]) / adhesive layer (shielding layer) / heat-sealing resin layer is laminated in this order is obtained. Obtained.

Example 6
[Preparation of base material layer 1]
(1) As the resin layer 1a, a polyethylene terephthalate (PET) film (thickness 12 μm) treated with double-sided corona was used. Using a vacuum vapor deposition method using a take-up electron beam (EB) heating method using aluminum as a vapor deposition source on one surface of the resin layer 1a, aluminum oxide with a film thickness of 800 Å is subjected to the following vapor deposition conditions. A thin-film deposition layer was formed. As a result of measuring the X value of AlO _x in the obtained thin-film deposition layer, X = 0.3.
(Evaporation conditions)
Vacuum degree in the vapor deposition chamber: 1 × 10 ^-4 mbar
Vacuum degree in the take-up chamber: 2 × 10 ^-2 mbar
Electron beam power: 30 kW
Oxygen introduction amount: 8000 sccm
Processing speed: 240m / min
The unit "sccm" is the amount per minute expressed in milliliters.

(2) On the other hand, according to the composition shown in Table 1 above, the composition a. A composition prepared in advance in a hydrolyzed solution consisting of ethyl orthosilicate (manufactured by Tama Chemical Co., Ltd.), isopropyl alcohol, 0.5N hydrochloric acid aqueous solution, ion-exchanged water, and a silane coupling agent. An aqueous solution of polyvinyl alcohol was added and stirred to obtain a colorless and transparent water vapor barrier composition.

Next, the plasma-treated surface of the vapor-film-treated layer formed in (1) above is coated with the water vapor barrier composition produced above by a gravure roll coating method, and then heat-treated at 150 ° C. for 60 seconds to increase the thickness. A coating film layer having a thickness of 0.2 μm (dry state) was formed.

(3) Next, the film obtained in (2) above was mounted on a 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 coating layer of the film, and a mixed gas having an output of 9 kW and an oxygen gas: argon gas = 7.0: 2.5 (unit: slm) is used. , Oxygen / argon mixed gas plasma treatment was performed at a mixed gas pressure of 6 × 10 ⁻² mbar and a treatment speed of 240 m / min.

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

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

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

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

Two laminated bodies of the resin layer 1a / thin film layer 1b produced in the above (1) to (6) were prepared, and a base material layer 1 in which these were laminated was obtained. 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. By adhering to the resin layer 1a of the body by dry laminating, a base material layer 1 having a laminated structure of a resin layer 1a / a thin film layer 1b / an adhesive layer / a resin layer 1a / a thin film layer 1b was obtained. 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 the adhesive layer of Example 1). 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 be 50 parts by mass.) After curing of the adhesive layer. The coating layer side of the base material layer and the heat-sealing resin layer were adhered to each other via a black adhesive layer by a dry laminating method so as to have a thickness of 3 μm. The black adhesive layer was used as the shielding layer. By the above procedure, the base material layer (resin layer / thin film layer [deposited layer / coating layer / vapor deposition layer / coating layer]) / adhesive layer / base material layer (resin layer / thin film layer [deposited layer / coating layer]). / Vapor deposition layer / Coating layer]) / Adhesive layer / Heat-sealing resin layer were laminated in this order to prepare an exterior material for a power storage device.

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

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

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

Comparative Example 1
For a power storage device in which a base material layer / adhesive layer / heat-sealing resin layer is laminated in this order in the same manner as in Example 1 except that the adhesive layer of Example 1 does not contain carbon black. Obtained exterior material.

<Total light transmittance>
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 uses the ultraviolet-visible near-infrared spectrophotometer V-670 manufactured by JASCO Corporation in the visible light region (visible light region). The transmittance was measured at 400 to 700 nm), and the average value was taken as the total light transmittance. The measurement conditions were a halogen lamp as a light source, UV / Vis bandwidth: 5.0 nm, scanning speed: 1000 nm / min, response: Medium, and data acquisition interval: 1.0 nm. The results are shown in Table 2.

<Evaluation of shielding>
We prepared a piece of paper in which the letters of the alphabet "A" with a font of Arial, a font size of 36, and a line thickness of about 1 mm were printed in black with a laser printer. In an environment of indoor lighting (300 to 500 lux), a paper with the letter "A" was placed under the exterior material for the power storage device. The letter "A" was visually observed through the exterior material for the power storage device from a distance of 30 cm in front of the exterior material for the power storage device. Regarding the visibility of characters, the shielding property was evaluated according to the following level 1 to 5 criteria. The results are shown in Table 2.
Level 1: Easy to see.
Level 2: It is a little difficult to see, but the characters can be recognized.
Level 3: It is hard to see, but the characters can be recognized.
Level 4: Very hard to see, but can recognize characters faintly.
Level 5: I can't see the letters.

The "/" in the laminated structure shown in Table 2 indicates the layer division.

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

Example 10
As the first substrate layer, a maleic anhydride-modified polypropylene (PPa) film (thickness 20 μm) containing carbon black (the average particle size of carbon black is in the range of 0.161 to 0.221 μm) was prepared. In addition, a polyethylene naphthalate (PEN) film (thickness 12 μm) was prepared as the second base material layer. Further, a maleic anhydride-modified polypropylene (PPa) film (thickness 20 μm) was prepared as a heat-sealing 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 material layer and the second base material layer are separated through the adhesive layer by the dry laminating method. It was glued. Further, the second base material layer and the heat-sealing resin layer of the obtained laminate were adhered via the same adhesive layer. The black first base material layer was used as a shielding layer. By the above procedure, an exterior material for a power storage device in which the first base material layer (shielding layer) / adhesive layer / second base material layer / adhesive layer / heat-sealing resin layer are laminated in this order was obtained. The PPa of the first base material layer and the heat-sealing resin layer of Example 10 contain two types of lubricants, erucic acid amide and behenic acid amide, respectively.

Example 11
The first base material layer (shielding layer) / adhesive layer / second base layer is the same as in Example 10 except that a polyethylene terephthalate (PET) film (thickness 9 μm) is used as the second base material layer. An exterior material for a power storage device was obtained in which a material layer / an adhesive layer / a heat-sealing resin layer were laminated in this order. The PPa of the first base material layer and the heat-sealing resin layer of Example 11 contain two types of lubricants, erucic acid amide and behenic acid amide, respectively.

Example 12
The first base material layer (shielding layer) / adhesive layer / second base layer is the same as in Example 10 except that a polyethylene terephthalate (PET) film (thickness 12 μm) is used as the second base material layer. An exterior material for a power storage device was obtained in which a material layer / an adhesive layer / a heat-sealing resin layer were laminated in this order. The PPa of the first base material layer and the heat-sealing resin layer of Example 12 contain two kinds of erucic acid amide and behenic acid amide as lubricants, respectively.

Example 13
The first base material layer (shielding layer) / adhesive layer / second base layer is the same as in Example 10 except that a polyethylene terephthalate (PET) film (thickness 25 μm) is used as the second base material layer. An exterior material for a power storage device was obtained in which a material layer / an adhesive layer / a heat-sealing resin layer were laminated in this order. The PPa of the first base material layer and the heat-sealing resin layer of Example 13 contain two types of lubricants, erucic acid amide and behenic acid amide, respectively.

Example 14
A maleic anhydride-modified polypropylene (PPa) film (thickness 30 μm) containing carbon black (the average particle size of carbon black is in the range of 0.161 to 0.221 μm) was used as the first base material layer. The first base material layer (shielding layer) / adhesion is the same as in Example 12, except that a maleic anhydride-modified polypropylene (PPa) film (thickness 30 μm) is used as the heat-sealing resin layer. An exterior material for a power storage device was obtained in which an agent layer / a second base material layer / an adhesive layer / a heat-sealing resin layer were laminated in this order. The PPa of the first base material layer and the heat-sealing resin layer of Example 14 contain two types of lubricants, erucic acid amide and behenic acid amide, respectively.

Example 15
A maleic anhydride-modified polypropylene (PPa) film (thickness 15 μm) containing carbon black (the average particle size of carbon black is in the range of 0.161 to 0.221 μm) was used as the first base material layer. The first base material layer (shielding layer) / adhesion is the same as in Example 12, except that a maleic anhydride-modified polypropylene (PPa) film (thickness 15 μm) is used as the heat-sealing resin layer. An exterior material for a power storage device was obtained in which an agent layer / a second base material layer / an adhesive layer / a heat-sealing resin layer were laminated in this order. The PPa of the first base material layer and the heat-sealing resin layer of Example 15 contain two types of lubricants, erucic acid amide and behenic acid amide, respectively.

Example 16
As the first base material layer, a polypropylene (PP) film (thickness 20 μm) containing carbon black (the average particle size of carbon black is in the range of 0.161 to 0.221 μm) was used, and heat fusion was performed. The first base material layer (shielding layer) / adhesive layer / second base material layer is the same as in Example 12, except that a polypropylene (PP) film (thickness 20 μm) is used as the adhesive resin layer. An exterior material for a power storage device was obtained in which an adhesive layer / a heat-sealing resin layer was laminated in this order. The PP of the first base material layer and the heat-sealing resin layer of Example 16 contains two kinds of erucic acid amide and behenic acid amide as lubricants, respectively.

Example 17
The first base material layer (1st base material layer) in the same manner as in Example 12 except that only the erucic acid amide was used as the lubricant for the PPa of the first base material layer and the heat-sealing resin layer of Example 17, respectively. An exterior material for a power storage device was obtained in which a shielding layer) / an adhesive layer / a second base material layer / an adhesive layer / a heat-sealing resin layer were laminated in this order.

Example 18
The first base material layer (shielding layer) / adhesive layer is the same as in Example 16 except that a maleic anhydride-modified polypropylene (PPa) film (thickness 20 μm) is used as the heat-sealing resin layer. / A second base material layer / an adhesive layer / a heat-sealing resin layer were laminated in this order to obtain an exterior material for a power storage device. The PP and PPa of the first base material layer and the heat-sealing resin layer of Example 18 contain two kinds of erucic acid amide and behenic acid amide as lubricants, respectively.

Example 19
The first base material layer (shielding layer) / adhesive layer is the same as in Example 17, except that a maleic anhydride-modified polyethylene (PEa) film (thickness 20 μm) is used as the heat-sealing resin layer. / A second base material layer / an adhesive layer / a heat-sealing resin layer were laminated in this order to obtain an exterior material for a power storage device. The PPa and PEa of the first base material layer and the heat-sealing resin layer of Example 19 each contain only erucic acid amide as a lubricant.

Example 20
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 stored in a heat-fused resin layer only. Used as an exterior material for devices. The PPa of the heat-bondable resin layer of Example 20 contains only erucic acid amide as a lubricant.

Example 21
Polypropylene containing carbon black (the average particle size of carbon black is in the range of 0.161 to 0.221 μm) on one surface of an unstretched polypropylene (CPP) film (thickness 60 μm) as a second base material layer. A PP) film (thickness 20 μm) is melt-extruded, and a maleic anhydride-modified polypropylene (PPa) film (thickness 20 μm) is placed on the other surface of the CPP film as an exterior material for a power storage device composed of only a heat-sealing resin layer. did. The PP and PPa of the first base material layer and the heat-sealing resin layer of Example 21 each contain only erucic acid amide as a lubricant.

Example 22
A maleic anhydride-modified polypropylene (PPa) film (thickness 20 μm) was prepared as the first base material layer. In addition, a polyethylene terephthalate (PET) film (thickness 12 μm) was prepared as the second base material layer. Further, a maleic anhydride-modified polypropylene (PPa) film (thickness 20 μm) was prepared as a heat-sealing 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), dry the adhesive layer so that the thickness after curing is 3 μm. By the laminating method, the first base material layer and the second base material layer were adhered to each other via the adhesive layer. Further, the second base material layer and the heat-sealing resin layer of the obtained laminate are dried by using a two-component urethane adhesive so that the thickness of the adhesive layer after curing is 1 μm or less. It was adhered via an adhesive layer by a laminating method. The black adhesive layer between the first base material layer and the second base material layer was used as a shielding layer. By the above procedure, an exterior material for a power storage device was obtained in which the first base material layer / adhesive layer (shielding layer) / second base material layer / adhesive layer / heat-sealing resin layer were laminated in this order. The PPa of the first base material layer and the heat-sealing resin layer of Example 22 contain two types of lubricants, erucic acid amide and behenic acid amide, respectively.

Example 23
Implemented except that a polypropylene (PP) film (thickness 20 μm) was used as the first base material layer and a polypropylene (PP) film (thickness 20 μm) was used as the heat-sealing resin layer. Similar to Example 22, an exterior material for a power storage device in which the first base material layer / adhesive layer (shielding layer) / second base material layer / adhesive layer / heat-sealing resin layer are laminated in this order is obtained. rice field. The PP of the first base material layer and the heat-sealing resin layer of Example 23 contain two kinds of erucic acid amide and behenic acid amide as lubricants, respectively.

Reference example 1
A stretched nylon (ONy) film (thickness 25 μm) was prepared as a base material layer. Further, an aluminum (ALM) foil (thickness 40 μm) was prepared as a barrier layer. In addition, maleic anhydride-modified polypropylene (PPa) was prepared as an adhesive layer. Further, polypropylene (PP) was prepared as a heat-sealing resin layer. A two-component urethane adhesive was used, and the thickness of the adhesive layer after curing was set to 3 μm, and the base material layer and the barrier layer were adhered to each other via the adhesive layer by a dry laminating method. Further, an adhesive layer (thickness 23 μm) and a heat-sealing resin layer (thickness 23 μm) are melt-extruded onto the surface of the barrier layer of the obtained laminate to form a base material layer / adhesive layer / barrier layer /. An exterior material for a power storage device was obtained in which an adhesive layer / a heat-sealing resin layer was laminated in this order. The PP of the heat-bondable resin layer of Reference Example 1 contains two types of lubricants, erucic acid amide and behenic acid amide. The exterior material for a power storage device of Reference Example 1 can be suitably used as an outer package.

For the exterior materials for power storage devices obtained in Examples 10 to 23 and Reference Example 1, the total light transmittance was measured and the shielding property was evaluated in the same manner as in Examples 1 to 9 and Comparative Example 1, respectively. The results are shown in Table 3.

<Continuous battery productivity>
Further, when the exterior materials for power storage devices obtained in Examples 1 to 23 and Reference Example 1 were cold-molded using a mold, they were used as lubricants for the base material layer and / or the heat-sealing resin layer. The exterior materials for power storage devices of Examples 1 to 16, 18, 22, 23 and Reference Example 1 using two types of erucic acid amide and behenic acid amide are lubricants for a base material layer and / or a heat-sealing resin layer. As compared with Examples 1 to 9, 17, 19 to 21 and Comparative Examples 1 and 7 using only the erucic acid amide, the adhesion of the lubricant to the mold is suppressed, so that the cleaning frequency of the mold is increased. It was reduced and the continuous productivity of the exterior material for the power storage device was excellent. In Table 3, an example and a comparative example in which the continuous productivity of the battery is superior is evaluated as evaluation A, and a case inferior to the evaluation A is evaluated as evaluation B.

“≦ 1 μm” shown in Table 3 indicates 1 μm or less. Further, "/" in the laminated structure shown in Table 3 indicates a layer delimiter. The numerical value (μm) in () indicates the thickness of the layer.

As described above, the present disclosure provides the inventions of the following aspects.
Item 1. At least, it is an exterior material for a power storage device provided with a heat-sealing resin layer.
The exterior material for a power storage device has a shielding layer and has a shielding layer.
The exterior material for a power storage device is an exterior material for a power storage device that does not have a metal layer formed of metal.
Item 2. Item 2. The exterior material for a power storage device according to Item 1, wherein the heat-sealing resin layer constitutes a shielding layer.
Item 3. Item 2. The exterior material for a power storage device according to

Item

1 or 2, which is composed of a laminate having at least a base material layer and the heat-sealing resin layer in this order from the outside.
Item 4. Item 3. The exterior material for a power storage device, wherein the base material layer includes a first base material layer and a second base material layer in this order from the outside.
Item 5. Item 3. The exterior material for a power storage device according to

Item

3 or 4, wherein the first base material layer constitutes a shielding layer.
Item 6. Item 2. The exterior material for a power storage device according to any one of Items 1 to 5, wherein the inner surface of the heat-sealing resin layer has adhesiveness to a metal.
Item 7. From the outside, it is composed of a laminate having at least a base material layer and a heat-sealing resin layer.
The laminated body has a shielding layer and has a shielding layer.
The laminate is an exterior material for a power storage device that does not have a metal layer formed of metal.
Item 8. An adhesive layer is provided between the base material layer and the heat-sealing resin layer.
Item 6. The exterior material for a power 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-sealing resin layer.
Item 6. The exterior material for a power storage device according to any one of Items 3 to 8, wherein the colored layer constitutes the shielding layer.
Item 10. It has a colored layer on the outside of the base material layer and has a colored layer.
Item 6. The exterior material for a power storage device according to any one of Items 3 to 9, wherein the colored layer constitutes the shielding layer.
Item 11. Item 2. The exterior material for a power storage device according to any one of Items 1 to 10, wherein the shielding layer contains a pigment.
Item 12. Item 12. The exterior material for a power storage device, wherein the pigment is carbon black.
Item 13. Item 2. The exterior material for a power storage device according to any one of Items 1 to 12, which is black.
Item 14. Item 6. The exterior material for a power 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. Item 6. The exterior material for a power storage device according to any one of Items 1 to 14, wherein the total light transmittance of the laminated body measured in accordance with JIS K7361-1: 1997 is 20% or less.
Item 16. Used in containers that house energy storage device elements with 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 6. The exterior material for a power 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 base material layer and a heat-sealing resin layer are laminated is provided in this order from the outside.
The laminated body has a shielding layer and has a shielding layer.
A method for manufacturing an exterior material for a power storage device, wherein the laminate does not have a metal layer formed of metal.
Item 18. A power storage device in which a power storage device element including at least a positive electrode, a negative electrode, and an electrolyte is housed in a package formed of the exterior material for the power storage device according to any one of Items 1 to 15.
Item 19. A power storage device element including at least a positive electrode, a negative electrode, and an electrolyte is housed in an inner package formed of the exterior material for the power storage device according to Item 16.
A power storage device in which the inner package is further housed in the outer package.

1 Base material layer 2 Adhesive layer 3 Colored layer 4 Heat-sealing resin layer 6 Surface coating layer 10 Exterior material for power storage device 11 First base material layer 12 Second base material layer 13 Adhesive layer 20 Outer packaging 30 Power storage Device 30a Peripheral portion 31 Metal terminal 32 Power storage device element S Shielding layer

Claims

At least, it is an exterior material for a power storage device provided with a heat-sealing resin layer.
The exterior material for a power storage device has a shielding layer and has a shielding layer.
The exterior material for a power storage device is an exterior material for a power storage device that does not have a metal layer formed of metal.
The exterior material for a power storage device according to claim 1, wherein the heat-sealing resin layer constitutes a shielding layer.
The exterior material for a power storage device according to claim 1 or 2, which is composed of at least a base material layer and a laminate provided with the heat-sealing resin layer in order from the outside.
The exterior material for a power storage device according to claim 3, wherein the base material layer includes a first base material layer and a second base material layer in this order from the outside.
The exterior material for a power 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-sealing resin layer has adhesiveness to a metal.
From the outside, it is composed of a laminate having at least a base material layer and a heat-sealing resin layer.
The laminated body has a shielding layer and has a shielding layer.
The laminate is an exterior material for a power storage device that does not have a metal layer formed of metal.
An adhesive layer is provided between the base material layer and the heat-sealing resin layer.
The exterior material for a power 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-sealing resin layer.
The exterior material for a power storage device according to any one of claims 3 to 8, wherein the colored layer constitutes the shielding layer.
It has a colored layer on the outside of the base material layer and has a colored layer.
The exterior material for a power storage device according to any one of claims 3 to 9, wherein the colored layer constitutes the shielding layer.
The exterior material for a power storage device according to any one of claims 1 to 10, wherein the shielding layer contains a pigment.
The exterior material for a power storage device according to claim 11, wherein the pigment is carbon black.
The exterior material for a power 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, which has a thin film layer containing at least one of an inorganic oxide and an inorganic nitride.
The exterior material for a power storage device according to any one of claims 1 to 14, wherein the total light transmittance of the laminate measured in accordance with the provisions of JIS K7361-1: 1997 is 20% or less.
Used in containers that house energy storage device elements with 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 a power 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 base material layer and a heat-sealing resin layer are laminated is provided in this order from the outside.
The laminated body has a shielding layer and has a shielding layer.
A method for manufacturing an exterior material for a power storage device, wherein the laminate does not have a metal layer formed of metal.
A power storage device in which a power storage device element including at least a positive electrode, a negative electrode, and an electrolyte is housed in a package formed of the exterior material for the power storage device according to any one of claims 1 to 15.
A power storage device element including at least a positive electrode, a negative electrode, and an electrolyte is housed in an inner package formed of the exterior material for the power storage device according to claim 16.
A power storage device in which the inner package is further housed in the outer package.