WO2023017683A1

WO2023017683A1 - Outer package material for all-solid-state batteries, and all-solid-state battery

Info

Publication number: WO2023017683A1
Application number: PCT/JP2022/025347
Authority: WO
Inventors: 輝利熊木; 大介中嶋
Original assignee: 昭和電工パッケージング株式会社
Priority date: 2021-08-11
Filing date: 2022-06-24
Publication date: 2023-02-16
Also published as: KR20240027809A

Abstract

The present invention provides an outer package material for all-solid-state batteries, the outer package material being free from gas leakage, while exhibiting sufficient insulation performance.　The present invention relates to an outer package material for all-solid-state batteries, the outer package material being used for the purpose of having a solid-state battery main body 5 sealed therein, while being provided with a base material layer 11, a metal foil layer 12 that is superposed on the inner surface of the base material layer 11, and a sealant layer 13 that is superposed on the inner surface of the metal foil layer 12. A heat-resistant gas barrier layer 21, which is formed of a resin, is arranged between the metal foil layer 12 and the sealant layer 13.

Description

Exterior materials for all-solid-state batteries and all-solid-state batteries

The present invention relates to an exterior material for an all-solid-state battery and an all-solid-state battery used as high-power batteries such as batteries for vehicles, batteries for portable devices such as mobile electronic devices, and batteries for storing regenerative energy.

Lithium-ion secondary batteries, which have been widely used in the past, use a liquid electrolyte as the electrolyte, so there is a risk that the separator will be destroyed due to liquid leakage or dentrites, and in some cases, ignition due to short circuit may occur. rice field.

On the other hand, an all-solid-state battery uses a solid electrolyte, so there is no liquid leakage or dendrites, and the separator is not destroyed. Therefore, there is no fear of ignition due to breakage of the separator, and it has attracted much attention from the standpoint of safety.

A normal all-solid-state battery is configured by enclosing a solid-state battery body such as an electrode active material and a solid electrolyte inside an exterior material as a casing. In this all-solid-state battery, as research on solid electrolytes progresses, it has gradually become apparent that the performance required of the exterior material is different from the exterior material of batteries using conventional liquid electrolytes. Various cladding materials have been proposed to meet the performance requirements of the vehicle.

The exterior material for an all-solid-state battery, as a basic structure, includes a metal foil layer and a heat-sealing layer (sealant layer) laminated inside it, and the solid-state battery body is formed by heat-sealing the sealant layer. It is enclosed.

For example, in the all-solid-state battery exterior material shown in Patent Document 1 below, a protective film is interposed between the metal foil layer and the sealant layer, and the hydrogen sulfide gas permeability of the sealant layer is adjusted to a predetermined value. Furthermore, in the all-solid-state battery exterior material disclosed in Patent Document 2, the hydrogen sulfide gas permeability of the sealant layer is adjusted to a predetermined value. In addition, the exterior material for an all-solid-state battery disclosed in Patent Document 3 uses a sealant layer that absorbs gas. Furthermore, the exterior material for an all-solid-state battery disclosed in Patent Document 4 is configured by laminating a deposited film layer on the inner surface of the sealant layer.

Patent No. 6777276 Patent No. 6747636 JP 2020-187855 A Japanese Patent Application Laid-Open No. 2020-187835

However, in the all-solid-state battery using the exterior materials disclosed in Patent Documents 1 and 2, when the solid electrolyte reacts with moisture in the air to generate hydrogen sulfide gas, the hydrogen sulfide gas may leak. I had a problem.

In addition, in the exterior materials shown in Patent Documents 2 to 4, when the sealant layer is melt-bonded (thermally bonded) when the battery body is sealed, the resin constituting the sealant layer melts and flows out, and the sealant layer becomes partially thin. As a result, there is a problem that the function of protecting the metal foil layer by the sealant layer is lowered, and the insulating property may be lowered.

Preferred embodiments of the present invention have been made in view of the above and/or other problems in the related art. Preferred embodiments of the present invention can significantly improve existing methods and/or apparatus.

The present invention has been made in view of the above problems. An object of the present invention is to provide an all-solid-state battery exterior material and an all-solid-state battery that can prevent the leakage of .

Other objects and advantages of the present invention will be apparent from the following preferred embodiments.

In order to solve the above problems, the present invention has the following means.

[1] A total body for encapsulating a solid battery body, comprising a base material layer, a metal foil layer laminated on the inner surface side of the base material layer, and a sealant layer laminated on the inner surface side of the metal foil layer. An exterior material for a solid battery,
An exterior material for an all-solid-state battery, wherein a resin-made heat-resistant gas barrier layer is provided between the metal foil layer and the sealant layer.

[2] The heat-resistant gas barrier layer has a hydrogen sulfide gas permeability measured in accordance with JIS K7126-1 of 15 {cc mm/(m ² D MPa)} or less. The exterior material for all-solid-state batteries described.

[3] The resin constituting the heat-resistant gas barrier layer has an original thickness of "da0" and a thickness of "da1" when pressed under conditions of 200°C, 0.2 MPa, and 5 sec.
1≧da1/da0≧0.9
2. The exterior material for an all-solid-state battery according to the preceding item 2, which is configured to satisfy the relational expression of

[4] The exterior material for an all-solid-state battery according to the preceding item 2 or 3, wherein the heat-resistant gas barrier layer has a thickness of 3 μm to 50 μm.

[5] The sealant layer according to any one of the preceding items 2 to 4, wherein the sealant layer is made of a resin having a hydrogen sulfide gas permeability of 100 {cc mm / (m ² D MPa)} or less. Exterior material for solid-state batteries.

[6] The resin constituting the sealant layer has an original thickness of "db0" and a thickness of "db1" when pressed under the conditions of 200 ° C., 0.2 MPa, 5 sec,
0.5≧db1/db0≧0.1
The exterior material for an all-solid-state battery according to any one of the preceding items 2 to 5, which is configured to satisfy the relational expression.

[7] The resin constituting the heat-resistant gas barrier layer has a water vapor gas permeability of 50 (g/m ² /day) or less as measured according to JIS K7129-1 (moisture sensor method, 40°C, 90% Rh). The exterior material for an all-solid-state battery according to any one of the preceding items 2 to 6.

[8] The heat-resistant gas barrier layer is made of an insulating resin having a melting point higher than that of the sealant layer by 20°C or more,
8. The exterior material for an all-solid-state battery according to any one of the preceding items 1 to 7, wherein the heat-resistant gas barrier layer has a dielectric breakdown voltage of 18 kV/mm or more.

[9] The exterior material for an all-solid-state battery according to the preceding item 8, wherein the resin constituting the heat-resistant gas barrier layer has a hot water shrinkage rate of 2% to 10%.

[10] The exterior material for an all-solid-state battery according to the preceding item 8 or 9, wherein the resin constituting the heat-resistant gas barrier layer is polyamide.

[11] Any one of the preceding items 1 to 10, wherein an opening is provided in a portion of the sealant layer corresponding to the solid battery main body, and the heat-resistant gas barrier layer is arranged to be exposed to the inner surface side in the opening. 1. The exterior material for an all-solid-state battery according to item 1.

[12] The exterior material for an all-solid-state battery according to the preceding item 11, wherein the heat-resistant gas barrier layer is made of a resin having a melting point higher than that of the sealant layer by 10°C or more.

[13] The exterior material for an all-solid-state battery according to the preceding

item

11 or 12, wherein the resin constituting the heat-resistant gas barrier layer has a thermal conductivity of 0.2 W/m·K or more.

[14] A deposited film is provided between the heat-resistant gas barrier layer and the sealant layer,
2. The exterior material for an all-solid-state battery according to 1 above, wherein the vapor-deposited film is composed of at least one of a metal, a metal oxide, and a metal fluoride.

[15] The exterior material for an all-solid-state battery according to the preceding item 14, wherein the vapor deposition film has a thickness of 5 nm to 1000 nm.

[16] The exterior material for an all-solid-state battery according to the preceding item 14 or 15, wherein an adhesive layer is provided between the heat-resistant gas barrier layer and the sealant layer.

[17] The exterior material for an all-solid-state battery according to 16 above, wherein the vapor-deposited film is provided on the contact surface of the sealant layer with the adhesive layer.

[18] The exterior material for an all-solid-state battery according to the preceding item 16 or 17, wherein the vapor-deposited film is provided on the contact surface of the heat-resistant gas barrier layer with the adhesive layer.

[19] The exterior material for an all-solid-state battery according to any one of the preceding items 1 to 18, wherein the heat-resistant gas barrier layer has a Young's modulus of 1 GPa or more in both MD and TD at 90°C.

[20] The exterior material for an all-solid-state battery according to the preceding item 19, wherein the heat-resistant gas barrier layer has a tensile breaking strength of 100 MPa or more at 90°C in both MD and TD.

[21] The exterior material for an all-solid-state battery according to the preceding item 19 or 20, wherein the heat-resistant gas barrier layer has a tensile elongation at break of 50% to 200% in both MD and TD at 90°C.

[22] An all-solid-state battery, wherein a solid-state battery main body is enclosed in the all-solid-state battery exterior material according to any one of the preceding items 1 to 21.

According to the exterior material for an all-solid-state battery of invention [1], since the heat-resistant gas barrier layer is interposed between the metal foil layer and the sealant layer, it is possible to reliably prevent the generated hydrogen sulfide gas from leaking to the outside. Furthermore, when the solid battery body is sealed with this exterior material, the heat-resistant gas barrier layer remains even if the resin of the sealant layer melts and flows out when the sealant layer is thermally bonded, and the insulation performance of the sealant layer is reduced. Therefore, the heat-resistant gas barrier layer can reliably ensure insulation.

According to the exterior material for an all-solid-state battery of invention [2], since the hydrogen sulfide gas permeability of the heat-resistant gas barrier layer is specified, hydrogen sulfide gas can be more reliably prevented from leaking to the outside.

According to the exterior materials for all-solid-state batteries of inventions [3] and [4], when the solid-state battery main body is encapsulated by thermal bonding, a sufficient thickness of the heat-resistant gas barrier layer can be ensured, so that leakage of hydrogen sulfide gas can be prevented. While being able to prevent reliably, a favorable insulation can also be ensured reliably.

According to the exterior material for an all-solid-state battery of invention [5], the sealant layer can also prevent hydrogen sulfide gas from being discharged, so that leakage of hydrogen sulfide gas can be prevented more reliably.

According to the exterior material for an all-solid-state battery of the invention [6], when the solid-state battery body is encapsulated by thermal bonding, the thickness of the sealant layer can be secured to some extent, so that the insulation and sealing performance can be further improved. .

According to the exterior material for an all-solid-state battery of the invention [7], the infiltration of moisture can be prevented, and the generation of hydrogen sulfide gas itself can be suppressed, so that the leakage of hydrogen sulfide gas can be prevented more reliably. can.

According to the exterior material for an all-solid-state battery of invention [8], since the insulation properties of the heat-resistant gas barrier layer are specified, it is possible to ensure sufficient insulation properties even in a high-temperature environment.

According to the exterior material for an all-solid-state battery of invention [9], since the hot water shrinkage rate of the heat-resistant gas barrier layer is specified, it is possible to improve moldability while ensuring high insulation.

According to the exterior material for an all-solid-state battery of invention [10], since a general-purpose polyamide resin is used as the heat-resistant gas barrier layer, it can be manufactured simply and efficiently.

According to the exterior material for an all-solid-state battery of the invention [11], since an opening through which the heat-resistant gas barrier layer is exposed is formed in the portion corresponding to the solid-state battery body in the sealant layer, the heat generated from the solid-state battery body is The heat is transmitted to the metal foil layer through the heat-resistant gas barrier layer without being blocked by the sealant layer, thereby ensuring sufficient cooling performance.

According to the exterior material for an all-solid-state battery of the invention [12], since the heat-resistant gas barrier layer has a high melting point, it is possible to prevent the heat-resistant gas barrier layer from melting and flowing out when the sealant layer is thermally adhered, thereby more reliably preventing gas leakage. can do.

According to the all-solid-state battery exterior material of Invention [13], the heat conductivity of the gas barrier layer is specified, so the cooling performance can be further improved.

According to the exterior materials for all-solid-state batteries of inventions [14] and [15], since the vapor deposition film is provided between the insulating layer and the sealant layer, sufficient gas barrier properties can be continuously ensured by the vapor deposition film. Therefore, it is possible to prevent the generation of hydrogen sulfide gas caused by the infiltration of moisture from the outside air, and furthermore, even if the hydrogen sulfide gas is generated, the gas barrier properties of the deposited film can reliably prevent the hydrogen sulfide gas from leaking to the outside. can be done.

According to the exterior material for an all-solid-state battery of the invention [16], since an adhesive layer is provided between the insulating layer and the sealant layer, even if a vapor deposition film is formed between the insulating layer and the sealant layer, the layers can be reliably separated. It can be tightly fixed.

According to the exterior material for an all-solid-state battery of the invention [17], since the vapor-deposited film is formed on the outer surface of the sealant layer, the gas-barrier vapor-deposited film can be arranged further inside, further improving the barrier property against moisture. be able to.

According to the exterior material for an all-solid-state battery of the invention [18], since a vapor-deposited film is formed on the inner surface of the insulating layer, when the sealant layer is heat-sealed, the heat shielding effect of the adhesive layer prevents heat from Destruction of the deposited film is less likely to occur, and the gas barrier properties of the deposited film can be reliably ensured.

According to the exterior material for an all-solid-state battery of the invention [19], since a heat-resistant gas barrier layer having a high Young's modulus at high temperature is used, the heat-resistant gas barrier layer, and thus the exterior, can be used not only at room temperature but also in a high temperature environment. It is possible to reliably prevent defects such as breakage from occurring in the entire area of the material.

According to the exterior material for an all-solid-state battery of inventions [20] and [21], even if the exterior material expands due to an increase in internal pressure due to high temperature in a state in which the solid-state battery body is enclosed, the exterior material is more reliably damaged. can be prevented.

According to the all-solid-state battery of the invention [22], the all-solid-state battery using the exterior material of the above inventions [1] to [21] is specified, so the same effects as above can be obtained.

FIG. 1 is a schematic cross-sectional view showing an all-solid-state battery that is an embodiment of the invention. FIG. 2 is a schematic cross-sectional view showing an exterior material used in the all-solid-state battery of the embodiment. FIG. 3 is a schematic cross-sectional view showing an all-solid-state battery that is a first modification of the invention. FIG. 4 is an exploded cross-sectional view schematically showing the configuration of the all-solid-state battery of the first modified example. FIG. 5 is a schematic cross-sectional view showing an all-solid-state battery that is a second modification of the invention. FIG. 6A is a schematic cross-sectional view showing a first exterior material applicable to the all-solid-state battery of the second modified example. FIG. 6B is a schematic cross-sectional view showing a second exterior material applicable to the all-solid-state battery of the second modified example. FIG. 6C is a schematic cross-sectional view showing a third exterior material applicable to the all-solid-state battery of the second modification. FIG. 7 is a plan view schematically showing a sample for insulation evaluation. FIG. 8 is a cross-sectional view schematically showing the insulation evaluation sample of FIG. 7, and is a cross-sectional view corresponding to the DD line cross section of FIG.

FIG. 1 is a schematic cross-sectional view showing an all-solid-state battery that is an embodiment of the present invention, and FIG. 2 is a schematic cross-sectional view showing an exterior material 1 used in the all-solid-state battery. As shown in both figures, the exterior material 1 that constitutes the casing of the all-solid-state battery of this embodiment is composed of a laminate such as a laminate sheet.

The exterior material 1 includes a base material layer 11 disposed on the outermost side, a metal foil layer 12 laminated on the inner surface side of the base material layer 11, and a heat-resistant gas barrier layer 21 laminated on the inner surface side of the metal foil layer 12. and a sealant layer 13 laminated on the inner surface side of the heat-resistant gas barrier layer 21. In this embodiment, an adhesive (adhesive layer ). In other words, the exterior material 1 of the present embodiment is composed of a laminate consisting of the base material layer 11/adhesive layer/metal foil layer 12/adhesive layer/heat-resistant gas barrier layer 21/adhesive layer/sealant layer 13. there is

In this embodiment, as shown in FIG. 1, an all-solid-state battery is produced by encapsulating the solid-state battery main body 5 with the exterior material 1 configured as described above so as to cover it. That is, the two rectangular

exterior materials

1, 1 are superimposed one on the other with the solid battery main body 5 interposed therebetween, and the sealant layers 13, 13 at the outer peripheral edges of the two (a pair of)

exterior materials

1, 1 By joining and integrating in an airtight state (sealed state) by thermal bonding (heat sealing), an all-solid-state battery is manufactured in which the solid-state battery main body 5 is housed in a bag-shaped casing made of the

exterior materials

1, 1. It is a thing.

Although not shown, the all-solid-state battery of this embodiment is provided with a tab lead for extracting electricity. One end (inner end) of this tab lead is adhesively fixed to the solid battery main body 5, and the intermediate portion passes between the outer peripheral edges of the two

exterior bodies

1, 1, and the other end side (outer end side) extends to the outside. arranged to be pulled out.

In the present embodiment, the casing is formed by pasting two planar

exterior materials

1, 1 together, but the present invention is not limited to this, and at least one of the two exterior materials may be One of them may be molded in advance into a tray shape, and one tray-shaped exterior material may be attached to the other tray-shaped or planar exterior material to form a casing.

The detailed configuration of the exterior material 1 of the all-solid-state battery of this embodiment will be described below.

The base material layer 11 of the exterior material 1 is composed of a heat-resistant resin film with a thickness of 5 μm to 50 μm. Polyamide, polyester (PET, PBT, PEN), polyolefin (PE, PP), or the like can be suitably used as the resin constituting the base material layer 11 .

The thickness of the metal foil layer 12 is set to 5 μm to 120 μm, and has the function of blocking the intrusion of oxygen and moisture from the surface (outer surface) side. As the metal foil layer 12, aluminum foil, SUS foil (stainless steel foil), copper foil, nickel foil, or the like can be suitably used. In the present embodiment, the terms "aluminum", "copper" and "nickel" are used to include their alloys.

In addition, when the metal foil layer 12 is plated, the risk of pinholes is reduced, and the function of blocking the intrusion of oxygen and moisture can be further improved.

Further, when the metal foil layer 12 is subjected to a chemical conversion treatment such as chromate treatment, the corrosion resistance is further improved, so that defects such as chipping can be prevented more reliably, and adhesion to the resin is improved. The durability can be further improved.

The sealant layer 13 has a thickness of 10 μm to 100 μm, and is made of a thermally adhesive (thermally fusible) resin film. The resin constituting the sealant layer 13 includes polyethylene (LLDPE, LDPE, HDPE), polyolefins such as polypropylene, olefinic copolymers, acid-modified products thereof and ionomers, such as unstretched polypropylene (CPP , IPP) and the like can be preferably used.

As the sealant layer 13, taking into account the use of tab leads to extract electricity, that is, taking into consideration sealing properties and adhesive properties with tab leads, it is preferable to use a polypropylene resin such as unstretched polypropylene film (CPP, IPP). preferable.

The heat-resistant gas barrier layer 21 is composed of a heat-resistant and insulating resin film. Resins constituting the heat-resistant gas barrier layer 21 include polyamide (6-nylon, 66-nylon, MXD nylon, etc.), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), cellophane, poly It is preferable to use vinylidene chloride or the like.

The heat-resistant gas barrier layer 21 of the present embodiment has good insulating properties, and even after the solid battery main body 5 is encapsulated with the exterior material 1 of the present embodiment by thermal bonding (after sealing), the good insulating properties are maintained. It is what you get.

In this embodiment, the resin forming the heat-resistant gas barrier layer 21 preferably has a predetermined hydrogen sulfide (H ₂ S) gas permeability. Specifically, the heat-resistant gas barrier layer 21 is made of a resin having a hydrogen sulfide gas permeability of 30 {cc·mm/(m ² ·D·MPa)} or less, more preferably 15, as measured according to JIS K7126-1. It is preferable to use a resin of {cc·mm/(m ² ·D·MPa)} or less. That is, when the hydrogen sulfide gas permeability of the heat-resistant gas barrier layer 21 is set to the specific value or less, the heat-resistant gas barrier layer 21 prevents the solid electrolyte material from reacting with moisture in the outside air to generate hydrogen sulfide gas. Hydrogen sulfide gas can be prevented from leaking to the outside. In other words, if the hydrogen sulfide gas permeability of the heat-resistant gas barrier layer 21 is too high, the generated hydrogen sulfide gas may leak outside through the exterior material 1 (heat-resistant gas barrier layer 21), which is not preferable.

For reference, "D" included in the unit of hydrogen sulfide gas permeability corresponds to "Day (24h)".

In the present embodiment, the resin constituting the heat-resistant gas barrier layer 21 has a water vapor gas permeability of 50 (g/m ² /day) or less, more preferably 40 (g/m ² /day) or less. That is, hydrogen sulfide gas is generated when external moisture permeates the exterior material 1 and reacts with the solid electrolyte material. In addition to the heat-resistant gas barrier layer 21, the gas barrier function of the metal foil layer 12 can prevent the intrusion of moisture. Therefore, it is possible to more reliably prevent hydrogen sulfide gas from leaking to the outside.

In this embodiment, it is preferable to set the thickness (original thickness) of the heat-resistant gas barrier layer 21 to 3 μm to 50 μm. That is, when the thickness of the heat-resistant gas barrier layer 21 is set within this range, the permeation suppressing effect of the hydrogen sulfide gas and water vapor gas can be reliably obtained. Also, the heat-resistant gas barrier layer 21 can reliably ensure insulation. In other words, if the heat-resistant gas barrier layer 21 is too thin, the gas permeation suppressing action and insulation may not be ensured, which is not preferable. Conversely, if the heat-resistant gas barrier layer 21 is too thick, not only is it impossible to reduce the thickness of the exterior material 1, but the effect of making it thicker than necessary cannot be obtained sufficiently, which is not preferable.

In the present embodiment, the original thickness of the resin (resin film) constituting the heat-resistant gas barrier layer 21 is defined as "da0", and the thickness when pressed under the conditions of 200° C., 0.2 MPa, and 5 sec is defined as "da1". It is preferable to configure so that the survival rate "da1/da0" is 0.9 or more, that is, to satisfy the relational expression A "1≧da1/da0≧0.9". This relational expression A corresponds to a configuration in which the thickness reduction rate of the heat-resistant gas barrier layer 21 is 10% or less when the exterior material 1 is thermally bonded. In this embodiment, when the above relational expression A is satisfied, even if the exterior material 1 is thermally bonded to seal the solid battery main body 5, reduction in the thickness of the heat-resistant gas barrier layer 21 can be suppressed. Since a sufficient thickness can be secured, the gas permeation suppressing action described above can be reliably obtained, and the heat-resistant gas barrier layer 21 can also reliably provide insulation.

In addition, in this embodiment, it is preferable to use a resin that has a melting point higher by 10°C or more, more preferably by 20°C or more, than that of the resin that forms the sealant layer 13, as the resin that forms the heat-resistant gas barrier layer 21. That is, when the heat-resistant gas barrier layer 21 has a high melting point, even if the sealant layer 13 is melted when the exterior material 1 is thermally bonded, the melt-outflow of the heat-resistant gas barrier layer 21 can be prevented. The effect of suppressing gas permeation and insulation can be reliably obtained.

Furthermore, in this embodiment, the heat-resistant gas barrier layer 21 preferably has a dielectric breakdown voltage of 18 kV/mm or more. That is, when the dielectric breakdown voltage of the heat-resistant gas barrier layer 21 is equal to or higher than a specific value, it is possible to ensure sufficient insulation. In other words, if the dielectric breakdown voltage of the heat-resistant gas barrier layer 21 is too low, it may not be possible to ensure sufficient insulation.

Further, in this embodiment, it is preferable to set the hot water shrinkage rate of the heat-resistant gas barrier layer 21 to 2% to 10%. That is, when this configuration is adopted, the moldability of the heat-resistant gas barrier layer 21 and, in turn, the exterior material 1 is improved, and high insulation is maintained even after the solid battery main body 5 is sealed with the exterior material 1 by thermal bonding. can be done. In other words, when the hot water shrinkage ratio of the heat-resistant gas barrier layer 21 deviates from the above specific range, there is a possibility that good insulation cannot be ensured, which is not preferable.

In the present embodiment, the hot water shrinkage rate of the heat-resistant gas barrier layer 21 is measured by testing before and after immersing a resin film test piece (10 cm×10 cm) constituting the heat-resistant gas barrier layer 21 in hot water at 95° C. for 30 minutes. It is the dimensional change rate in the stretching direction of the piece. In this embodiment, the hot water shrinkage ratio can be obtained by the following formula, where "X" is the dimension in the stretching direction before the immersion treatment, and "Y" is the dimension in the stretching direction after the immersion treatment.

Hot water shrinkage (%) = {(XY)/X} x 100
Here, in this embodiment, it is preferable to employ a resin having a thermal conductivity of 0.2 W/m·K or more as the resin constituting the heat-resistant gas barrier layer 21 . That is, when adopting this configuration, the heat transfer property of the heat-resistant gas barrier layer 21 can be sufficiently ensured, so the cooling property of the solid battery main body 5 can be further improved.

In the present embodiment, the resin film that constitutes the heat-resistant gas barrier layer 21 has a Young's modulus at 90° C. that is 1 GPa or more in both the machine direction MD and the direction perpendicular to the MD, and preferably 5 GPa or more. It is preferable to have That is, by adopting this configuration, the heat-resistant gas barrier layer 21 and, in turn, the exterior material 1 can be secured with a predetermined hardness not only at room temperature but also in a high temperature environment, so that defects such as breakage can be prevented. can be prevented.

In this embodiment, the heat-resistant gas barrier layer 21 preferably has a Young's modulus of 1.5 GPa or more at room temperature (25°C).

In addition, in the present embodiment, the heat-resistant gas barrier layer 21 preferably has a tensile breaking strength at 90°C of 100 MPa or more and 400 MPa or less in both MD and TD. That is, when adopting this configuration, even if the internal pressure increases due to the expansion of the solid battery main body 5 at a high temperature and the exterior material 1 expands, damage to the exterior material 1 can be reliably prevented.

Furthermore, in the present embodiment, it is preferable that the heat-resistant gas barrier layer 21 has a structure in which both the tensile elongation at break MD and TD at 90°C are 50% to 200%. That is, when adopting this configuration, even if the exterior material 1 expands and elongates due to an increase in internal pressure at high temperatures, damage to the exterior material 1 can be prevented more reliably.

In this embodiment, the heat-resistant gas barrier layer 21 preferably has a tensile strength at break of 150 MPa and a tensile elongation at break of 50% to 150% at room temperature (25°C).

In the present embodiment, in the resin (resin film) constituting the sealant layer 13, the original thickness is "db0", and the thickness when pressed under the conditions of 200 ° C., 0.2 MPa, 5 sec is "db1". Preferably, the ratio "db1/db0" is 0.1 to 0.5, that is, the relational expression B of "0.5≧db1/db0≧0.1" is satisfied. This relational expression B corresponds to a structure in which the reduction rate of the thickness of the sealant layer 13 is 50 to 90% when the exterior material 1 is thermally bonded. In the present embodiment, when the above relational expression B is satisfied, the thickness of the sealant layer 13 can be secured to some extent when the solid battery main body 5 is sealed by thermally bonding the exterior material 1. Therefore, the sealant layer Even if there are tab leads or foreign matter, the resin of the sealant layer 13 flows into the peripheral gap between them while ensuring the insulation by 13, so that sufficient sealing performance can be reliably obtained.

Here, in the present embodiment, the sealant layer 13 of the exterior material 1 is made of a resin having a hydrogen sulfide gas permeability of 100 {cc·mm/(m ² ·D·MPa)} or less according to JIS K7126-1. is preferred. That is, when the hydrogen sulfide gas permeability of the sealant layer 13 is set to the specific value or less, the heat-resistant gas barrier layer 21 suppresses permeation of hydrogen sulfide gas, and the sealant layer 13 suppresses permeation of hydrogen sulfide gas. Together, it is possible to more reliably prevent hydrogen sulfide gas from leaking to the outside.

On the other hand, in the present embodiment, the adhesive (adhesive layer) for bonding between the layers 11 to 13, 21 of the exterior material 1 is a two-liquid curing type, energy ray (UV, X-ray, etc.) A curing type such as a curing type can be used, and among them, a urethane-based adhesive, an olefin-based adhesive, an acrylic-based adhesive, an epoxy-based adhesive, etc. can be preferably used. Furthermore, the thickness of the adhesive layer 4 is set to 2 μm to 5 μm.

As described above, in the all-solid-state battery of the present embodiment, since the heat-resistant gas barrier layer 21 is interposed between the metal foil layer 12 and the sealant layer 13 in the exterior material 1, the generated hydrogen sulfide gas is prevented from leaking to the outside. It can definitely be prevented. Furthermore, when the sealant layer 13 of the exterior material 1 is heat-bonded to seal the solid battery main body 5, even if the resin of the sealant layer 13 melts and flows out and the insulation performance of the sealant layer 13 is reduced, the heat resistance is reduced. Since the gas barrier layer 21 remains, the heat-resistant barrier layer 21 can reliably ensure insulation.

Further, when the hydrogen sulfide gas permeability of the heat-resistant gas barrier layer 21 is set to a specific value, the above effects can be obtained more reliably.

Also, when the dielectric breakdown voltage of the heat-resistant gas barrier layer 21 is set to a specific value, it is possible to ensure good insulation even in a high-temperature environment.

When the tensile strength at break of the heat-resistant gas barrier layer 21 is set to a specific value, the heat-resistant gas barrier layer 21 and, in turn, the exterior material 1 may be damaged or otherwise damaged not only at room temperature but also at high temperatures. can be reliably prevented, and an all-solid-state battery product having excellent operational reliability especially in a high-temperature environment can be provided.

FIG. 3 is a schematic cross-sectional view showing an all-solid-state battery that is a first modified example of the present invention, and FIG. 4 is an exploded view schematically showing the configuration of the all-solid-state battery. As shown in both figures, in this all-solid-state battery, the exterior material 1 includes a base material layer 11 arranged on the outermost side, and a metal layer laminated and bonded to the inner surface side of the base material layer 11 via an adhesive layer. A foil layer 12, a heat-resistant gas barrier layer 21 laminated and bonded to the inner surface side of the metal foil layer 12 via an adhesive layer, and a heat-resistant gas barrier layer 21 laminated and bonded to the inner surface side of the heat-resistant gas barrier layer 21 via an adhesive layer 4. and a sealant layer 13 .

In addition, the sealant layer 13 has an opening 15 formed by removing the intermediate portion excluding the outer peripheral edge, and is left only on the outer peripheral edge. The exterior material 1 is arranged so that the adhesive layer 4 does not exist in the opening 15 and the heat-resistant gas barrier layer 21 is exposed inside through the opening 15 .

In the first modification, two (a pair of)

exterior materials

1, 1 formed in a rectangular shape are arranged so that the sealant layers 13 at the outer peripheral edges of each other face each other, and the solid battery main body 5 is interposed between them. The sealant layers 13, 13 are joined together in an airtight state (sealed state) by heat bonding (heat sealing), and thus the bag-shaped casing made of the

exterior materials

1, 1 An all-solid-state battery in which the solid-state battery main body 5 is accommodated in a sealed state is manufactured.

In this all-solid-state battery, the opening 15 of the exterior material 1 is arranged in a portion corresponding to the solid-state battery main body 5 , and the upper and lower surfaces of the solid-state battery body 5 are in contact with the heat-resistant gas barrier layers 21 of the upper and lower exterior materials 1 . They are arranged to face each other through the opening 15 .

Other configurations of the all-solid-state battery of the first modification are the same as those of the all-solid-state battery of the above embodiment.

As described above, the exterior material 1 of the first modified example has the openings 15 formed in the sealant layer 13 . The opening 15 is formed in a portion corresponding to the solid battery main body 5, and the sealant layer 13 is arranged in a portion corresponding to the heat seal portion (sealing portion).

In addition, the adhesive layer 4 is not provided in the opening 15 of the exterior material 1, and the heat-resistant gas barrier layer 21 is exposed (exposed) inside through the opening 15. , the heat-resistant gas barrier layer 21 is arranged so as to face the solid battery main body 5, and in some cases, so that at least a part thereof is in contact therewith.

In this embodiment, the opening 15 of the exterior material 1 is formed, for example, by cutting the intermediate portion of the sealant layer 13 laminated on the entire area of the heat-resistant gas barrier layer 21. is a residual formation.

That is, in the first modification, when the sealant layer 13 is formed on the heat-resistant gas barrier layer 21, the inner surface of the resin film serving as the heat-resistant gas barrier layer 21 is coated with an adhesive serving as the adhesive layer 4 using a gravure roll or the like. A resin film as the sealant layer 13 is pasted through the adhesive layer 4. When the adhesive is applied to the heat-resistant gas barrier layer 21 by a gravure roll or the like, the adhesive is applied to the region where the opening is to be formed. An uncoated portion is formed where is not applied. Then, a resin film for a sealant layer is adhered to the heat-resistant gas barrier layer 21 having the adhesive uncoated portion and dried. After that, the resin film for the sealant layer in the adhesive uncoated portion is cut off with a laser cutter, a roll blade, or the like to form the opening 15 (first forming method).

As a second forming method, before the adhesive is applied to the heat-resistant gas barrier layer 21, release paper is temporarily attached to the region where the opening portion is to be formed in the heat-resistant gas barrier layer 21, and the heat-resistant gas barrier layer 21 is attached in that state. Then, an adhesive is applied using a gravure roll or the like, and a resin film for the sealant layer is adhered and dried. After that, the sealant layer resin film corresponding to the release paper temporary fixing portion is cut off together with the adhesive and the release paper with a roll blade or the like to form the opening 15 .

As another forming method, before the sealant layer resin film is adhered to the heat-resistant gas barrier layer 21, through holes are formed in the film as the openings 15, and the sealant layer resin film with the openings is formed. to the heat-resistant gas barrier layer 21 via an adhesive (another forming method). However, with other forming methods, it is difficult to evenly apply the adhesive, and it is difficult to precisely and accurately attach the sealant layer resin film having openings. Therefore, in the first modified example, it is preferable to employ the first and second forming methods.

As described above, according to the all-solid-state battery of the first modification, the heat-resistant gas barrier layer 21 is formed between the metal foil layer 12 and the sealant layer 13 in the exterior material 1, and the sealant layer 13 corresponds to the solid-state battery main body 5. Since the opening 15 through which the heat-resistant gas barrier layer 21 is exposed is formed in the part, the heat generated from the solid battery main body 5 is not blocked by the sealant layer 13 and passes through the heat-resistant gas barrier layer 21 to the metal foil layer. 12 to dissipate the heat. Therefore, sufficient cooling performance can be ensured, and problems due to high temperatures can be reliably prevented.

In addition, in the all-solid-state battery of the first modification, although the sealant layer 13 does not exist between the solid-state battery main body 5 and the metal foil layer 12, the insulating heat-resistant gas barrier layer 21 is arranged therebetween. The heat-resistant gas barrier 21 can reliably ensure insulation.

Furthermore, in the all-solid-state battery of the first modification, the sealant layer 13 is not formed on the portion of the exterior material 1 corresponding to the solid-state battery main body 5, so the space for accommodating the solid-state battery main body 5 is increased accordingly ( thick). Therefore, in the all-solid-state battery of the present embodiment, compared with the conventional all-solid-state battery, the large-sized solid-state battery main body 5 can be accommodated without changing the external dimensions of the casing (the exterior material 1), so the thickness can be reduced. while achieving high output and high capacity.

FIG. 5 is a schematic cross-sectional view showing an all-solid-state battery that is a second modification of the invention. As shown in the figure, the exterior material 1 in the all-solid-state battery of the second modification includes a base material layer 11 arranged on the outermost side, a metal foil layer 12 laminated on the inner surface side of the base material layer 11, a metal A heat-resistant gas barrier layer 21 as an insulating layer laminated on the inner surface side of the foil layer 12 and a sealant layer 13 laminated on the inner surface side of the heat-resistant gas barrier layer 21 are provided. Furthermore, a deposited film (deposited layer) 22 is provided between the heat-resistant gas barrier layer 21 and the sealant layer 13 .

In the second modified example, as the exterior material 1, exterior materials 1a to 1c having first to third configurations can be adopted.

As shown in FIG. 6A, the first exterior material 1a is formed by laminating and bonding a resin film for the base material layer 11 to the outer surface of the metal foil for the metal foil layer 12 via an adhesive. Then, a resin film for the heat-resistant gas barrier layer 21 is laminated and adhered via an adhesive, and a vapor-deposited film 22 is vapor-deposited on the inner surface of the heat-resistant gas barrier layer 21. , a sealant layer 13 of a heat-fusible resin is laminated and adhered via an adhesive layer 4 .

Further, as shown in FIG. 6B, in the second exterior material 1b, the vapor deposition film is not formed on the inner surface of the heat-resistant gas barrier layer 21, and the vapor deposition film 22 is formed on the outer surface of the sealant layer 13, as compared with the first exterior material 1a. The deposition surface (outer surface) of the sealant layer 13 is adhered to the inner surface of the heat-resistant gas barrier layer 21 via the adhesive 4 .

In addition, as shown in FIG. 6C, the third exterior material 1c has

vapor deposition films

22, 22 formed on both the inner surface of the heat-resistant gas barrier layer 21 and the outer surface of the sealant layer 13, and the vapor-deposited surface (inner surface) of the heat-resistant gas barrier layer 21 and the deposition surface (outer surface) of the sealant layer 13 are adhered via the adhesive layer 4 .

In the second modification, as the adhesive constituting the adhesive layer 4 that bonds between the heat-resistant gas barrier layer 21 and the sealant layer 13, a curing type such as a two-liquid curing type or a UV (energy ray) curing type can be used. Among them, urethane-based adhesives, olefin-based adhesives, acrylic-based adhesives, epoxy-based adhesives, etc. can be preferably used. Furthermore, the thickness of the adhesive layer 4 is set to 2 μm to 5 μm.

In this embodiment, such an adhesive is used to bond the heat-resistant gas barrier layer 21 and the sealant layer 13 by dry lamination or heat lamination.

In the second modification, the adhesive layer 4 is made of an acid-modified polyolefin-based adhesive that has good adhesion to the deposited film 22, so that the heat-resistant gas barrier layer 21 and the sealant layer 13 are reliably spaced apart. Adhesion can be achieved, and the occurrence of delamination during molding can be effectively prevented.

In the second modification, the same adhesive as the adhesive layer 4 is used as the adhesive for bonding between the base material layer 11 and the metal foil layer 12 and between the metal foil layer 12 and the heat-resistant gas barrier layer 21. can be preferably used, and it is preferable to set them to similar thicknesses.

Further, in the second modification, the deposited film 22 formed on the inner surface of the heat-resistant gas barrier layer 21 and/or the outer surface of the sealant layer 13 is composed of inorganic substances such as aluminum, titanium and silicon, and inorganic oxides such as alumina, silica and zinc oxide. , aluminum fluoride, magnesium fluoride and the like, at least one of which can be employed.

In the second modification, the gas barrier property can be further improved by forming the vapor deposition film 22 . Therefore, it is possible to prevent the infiltration of outside air, prevent the generation of hydrogen sulfide gas itself caused by the reaction between the moisture of the outside air and the solid electrolyte of the solid battery main body 5, and furthermore, even if the hydrogen sulfide gas is generated, the deposited film can be prevented. The gas barrier property of 22 can reliably prevent hydrogen sulfide gas from leaking to the outside.

In the second modified example, the vapor deposition film 22 preferably has a thickness of 50 Å to 10000 Å, or 5 nm to 1000 nm, or 0.005 μm to 1 μm. That is, by setting the thickness within this range, good gas barrier properties can be ensured more reliably. In other words, if the thickness of the deposited film 22 is too thin, good gas barrier properties cannot be obtained, which is not preferable. Even if the thickness of the vapor deposition film 22 is formed to be thicker than necessary, not only is it not possible to obtain the effect corresponding to the thickness, but also it takes a long time to form the thick vapor deposition film 22, which may lead to a decrease in production efficiency. , unfavorable.

In the second modified example, the deposited film 22 can be formed by depositing and coating by dry coating. Well-known methods such as the CVD method and the PVD method (sputtering method, ion beam method, etc.) can be employed for the dry coating.

Other configurations of the all-solid-state battery of the second modification are the same as those of the all-solid-state battery of the above embodiment.

As described above, according to the all-solid-state battery of the second modification, since the deposited film 22 is provided between the heat-resistant gas barrier layer 21 and the sealant layer 13 in the exterior material 1, sufficient gas barrier properties can be obtained by the deposited film 22. can be done. Therefore, it is possible to prevent the infiltration of outside air, prevent the generation of hydrogen sulfide gas itself caused by the reaction between the moisture of the outside air and the solid electrolyte of the solid battery main body 5, and furthermore, even if the hydrogen sulfide gas is generated, the deposited film can be prevented. The gas barrier property of 22 can reliably prevent hydrogen sulfide gas from leaking to the outside.

In the second modification, since the adhesive layer 4 is provided between the heat-resistant gas barrier layer 21 and the sealant layer 13, even if the vapor-deposited film 22 is formed on the inner surface of the heat-resistant gas barrier layer 21 or the outer surface of the sealant layer 13, , the heat-resistant gas barrier layer 21 and the sealant layer 13 can be securely adhered and fixed, and the occurrence of delamination can be prevented.

Further, in the second modification, when the vapor deposition film 22 is formed on the sealant layer 13 side like the second and third

exterior materials

1b and 1c, the gas barrier vapor deposition film 22 is placed further inside (on the solid battery main body 5 side). ), the barrier properties against moisture can be further improved.

In addition, in the second modified example, when the deposited film 22 is formed on the heat-resistant gas barrier layer 21 side like the first and third

exterior materials

1a and 1c, when the sealant layer 13 is heat-sealed, the adhesive layer Due to the heat shielding action of 4, the vapor deposition film 22 is less likely to be destroyed by heat, and the vapor barrier property of the vapor deposition film 22 can be reliably ensured.

(1) First embodiment

<Example 1a>
(1-1) Preparation of exterior material On both sides of a 40 μm thick aluminum foil (A8021-O) as the metal foil layer 12, phosphoric acid, polyacrylic acid (acrylic resin), chromium (III) salt compound, water After applying a chemical conversion treatment liquid containing alcohol, drying was performed at 180° C. to form a chemical conversion film. The amount of chromium deposited on this chemical conversion film was 10 mg/m ² per side.

Next, on one surface (outer surface) of the chemically treated aluminum foil (metal foil layer 12), a two-liquid curable urethane adhesive (3 μm) was applied as the base layer 11 to form two layers having a thickness of 15 μm. An axially oriented 6 nylon (ONY-6) film was dry laminated.

Next, as shown in Table 1, as the heat-resistant gas barrier resin layer 21, a PET film having a thickness of 9 μm is applied to the other surface (inner surface) of the aluminum foil after the dry lamination, and a two-liquid curing type urethane adhesive (3 μm) is applied. pasted together through

Next, as shown in Table 1, as the sealant layer 13, a 20 μm thick CPP film containing a lubricant (erucamide or the like) is sandwiched between a two-liquid curing urethane adhesive (3 μm) after the dry lamination. Laminate constituting the exterior material 1 by being superimposed on the inner surface of the PET film (heat-resistant gas barrier layer 21) and sandwiched between a rubber nip roll and a lamination roll heated to 100° C. for dry lamination. got

Next, this laminate was wound around a roll shaft and then aged at 40°C for 10 days to obtain an exterior material sample of Example 1a.

(1-2) Measurement of H ₂ S gas permeability of resin film Sulfurization of the PET film (heat-resistant gas barrier layer 21) and CPP film (sealant layer 13) used to prepare the exterior material sample of Example 1a Hydrogen (H ₂ S) gas permeability was measured according to JIS K7126-1, and water vapor gas permeability of PET film was measured according to JIS K7129-1 (moisture sensor method, 40°C 90% Rh). bottom. The results are also shown in Table 1.

(1-3) Measurement of residual rate After cutting two pieces of the exterior material sample of Example 1a into a size of 15 mm in width × 150 mm in length, the pair of samples are brought into contact with each other at the inner sealant layers. In the superimposed state, using a heat sealing device (TP-701-A) manufactured by Tester Sangyo Co., Ltd., heat sealing temperature: 200 ° C., sealing pressure: 0.2 MPa (gauge display pressure), sealing time: 2 seconds Heat-sealing (thermal bonding) was performed by heating one side under the conditions of , to obtain a sample for measuring the residual rate of Example 1a.

In this residual ratio measurement sample, the seal portion was hardened with resin, cut so that the cross section appeared, and the cross section was observed by SEM to determine the thickness of the heat-resistant gas barrier layer 21, the sealant layer 13, and the like.

Based on the layer thickness after heat sealing and the layer thickness of the exterior material sample before heat sealing, the residual rate "da1/da0" of the heat-resistant gas barrier layer 21 and the residual rate "db1/db0" of the sealant layer 13 were measured. (see above relational expressions A and B). The results are also shown in Table 1.

(1-4) Measurement of seal strength

After cutting out two pieces of the exterior material sample of Example 1a to a size of 15 mm in width and 150 mm in length, the pair of samples were superimposed so that the inner sealant layers of each other were in contact with each other. Using a heat sealing device (TP-701-A) manufactured by the company, heat sealing is performed by heating one side under the conditions of heat sealing temperature: 200 ° C, sealing pressure: 0.2 MPa (gauge display pressure), sealing time: 2 seconds (Thermal adhesion) was performed to obtain a sample for seal strength evaluation of Example 1a.

For this seal strength evaluation sample, a strograph (AGS-5kNX) manufactured by Shimadzu Access Co., Ltd. was used in accordance with JIS Z0238-1998, and the seal strength evaluation sample was pulled between the inner sealant layers of the seal portion at a tensile speed of 100 mm. The peel strength at the time of T-shaped peeling was measured at 1/min, and this was defined as the seal strength (N/15 mm width). Table 2 shows the results.

(1-5) Measurement of insulation resistance value (evaluation of insulation)
As shown in FIGS. 7 and 8, two pieces each having a size of 100 mm long×50 mm wide were cut out of the exterior material sample 1 of Example 1a. These pair of

exterior material samples

1, 1 were superimposed so that the sealant layers 13 of each were opposed to each other and were in contact with each other. On the other hand, a tab lead 3 made of aluminum foil with a width of 10 mm and a thickness of 100 μm is sandwiched between the pair of

exterior material samples

1, 1 while a tab film 31 made of an acid-modified polypropylene film with a thickness of 50 μm is placed on both sides thereof. placed like this. At this time, a portion of the tab lead 3 was arranged between the pair of

exterior material samples

1, 1, and the remaining portion was arranged so as to be pulled out from the edges of the pair of

exterior material samples

1, 1. This unbonded sample was heat-sealed between the sealant layers for 2 seconds under conditions of a seal width of 5 mm, 200° C., and 0.2 MPa using a double-sided heating heat sealer from both upper and lower surfaces of the

exterior material samples

1 and 1. Thus, a sample for insulation evaluation was obtained.

In addition, in the plan view of the insulation evaluation sample in FIG. 7, the heat-bonded portion (heat-sealed portion) 131 is hatched with oblique lines in order to facilitate understanding of the invention. In addition, in the cross-sectional view of the insulation evaluation sample in FIG. 8, the illustration of the heat-resistant gas barrier layer 13 is omitted for easy understanding of the structure.

Subsequently, as shown in FIG. 7, at the ends in the length direction of the insulation evaluation sample, the resin as the base material layer 11 is partially peeled off to partially expose the aluminum foil as the metal foil layer 12, and the exposed At the portion 121, electrical continuity with the aluminum foil (metal foil layer 12) was secured from the outside.

Then, one terminal of an insulation resistance measuring device (manufactured by Hioki Electric Co., Ltd.: product number “HIOKI3154”) 6 is connected to the metal foil layer 12 in the exposed portion 121 of the insulation evaluation sample, and the other terminal is brought into contact with the tab lead 3. After forming a circuit, a voltage was applied between the metal foil layer 12 and the tab lead 3 under the conditions of 25 V and 5 seconds in the circuit, and the resistance value was measured to obtain the insulation resistance value. The results are also shown in Table 2.

(1-6) Evaluation of H ₂ S gas permeation of exterior material Instead of the aluminum foil, a copper foil (Cu foil) having a thickness of 9 μm was used in the same manner as above, and the copper foil type exterior material sample 1 of Example 1a was used. was made.

This copper foil-type exterior material sample was cut into two sheets of a size of 30 mm × 50 mm, and these pair of

exterior material samples

1, 1 were superimposed with the sealant layers 13 facing each other, and the superimposed exterior material sample Three sides (three sides) of 1 and 1 were sealed under the following sealing conditions: heat sealing temperature: 200°C, sealing pressure: 0.2 MPa (gauge display pressure), sealing time: 2 seconds to prepare a three-sided bag. After that, at one side (30 mm side) that is the opening of the three-sided bag, the injection needle is sandwiched between the outer

packaging material samples

1 and 1, and the opening is sealed under the same sealing conditions as above, 0.1 MPa of H ₂ S gas is sealed from the injection needle (the injection needle is sandwiched between 30 mm sides).

Once the gas is filled, the needle is pulled out a little to prevent the gas from escaping, and the inside of the tip of the needle is heat-sealed again under the same sealing conditions to completely seal the gas. was made.

After the gas-filled bag was left in a constant temperature bath at 40°C for 7 days, the gas was removed, the sealed part was removed, and the inside was observed. By the observation, those in which no change was observed in the Cu foil were evaluated as "good", and those in which discoloration was observed in the sealing portion or the like were evaluated as "poor". The results are also shown in Table 2.

<Example 2a>
A sample of Example 2a was prepared in the same manner as in Example 1a except that a PET film with a thickness of 3 μm was used as the heat-resistant gas barrier layer 21 and a CPP film with a thickness of 30 μm was used as the sealant layer 13. was measured (evaluated). The results are also shown in Tables 1 and 2.

<Example 3a>
A sample of Example 3a was prepared in the same manner as in Example 1a except that a PET film having a thickness of 15 μm was used as the heat-resistant gas barrier layer 21, and the same measurement (evaluation) was performed. The results are also shown in Tables 1 and 2.

<Example 4a>
A sample of Example 4a was prepared in the same manner as in Example 1a except that a PET film having a thickness of 25 μm was used as the heat-resistant gas barrier layer 21, and the same measurement (evaluation) was performed. The results are also shown in Tables 1 and 2.

<Example 5a>
A sample of Example 5a was prepared in the same manner as in Example 1a except that a film having a thickness of 15 μm was used as the heat-resistant gas barrier layer 21, and the same measurement (evaluation) was performed. The results are also shown in Tables 1 and 2.

<Example 6a>
A sample of Example 6a was prepared in the same manner as in Example 1a except that a film having a thickness of 5 μm was used as the heat-resistant gas barrier layer 21, and the same measurement (evaluation) was performed. The results are also shown in Tables 1 and 2.

<Example 7a>
A sample of Example 7a was prepared in the same manner as in Example 1a except that a film having a thickness of 40 μm was used as the heat-resistant gas barrier layer 21, and the same measurement (evaluation) was performed. The results are also shown in Tables 1 and 2.

<Example 8a>
A sample of Example 8a was prepared in the same manner as in Example 1a except that a CPP film having a thickness of 60 μm was used as the sealant layer 13, and the same measurement (evaluation) was performed. The results are also shown in Tables 1 and 2.

<Example 9a>
A sample of Example 9a was prepared in the same manner as in Example 1a except that an HDPE film having a thickness of 60 μm was used as the sealant layer 13, and the same measurement (evaluation) was performed. The results are also shown in Tables 1 and 2.

<Example 10a>
A sample of Example 10a was prepared in the same manner as in Example 1a except that an LLDPE film having a thickness of 60 μm was used as the sealant layer 13, and the same measurement (evaluation) was performed. The results are also shown in Tables 1 and 2.

<Example 11a>
A sample of Example 11a was prepared in the same manner as in Example 1a except that a CPP film having a thickness of 10 μm was used as the sealant layer 13, and the same measurement (evaluation) was performed. The results are also shown in Tables 1 and 2.

<Example 12a>
A sample of Example 12a was prepared in the same manner as in Example 1a except that a cellophane film with a thickness of 20 μm was used as the heat-resistant gas barrier layer 21, and a CPP film with a thickness of 10 μm was used as the sealant layer 13. was measured (evaluated). The results are also shown in Tables 1 and 2.

<Comparative Example 1a>
A sample of Comparative Example 1a was prepared in the same manner as in Example 1a, except that the heat-resistant gas barrier layer 21 was not formed, and the same measurement (evaluation) was performed. The results are also shown in Tables 1 and 2.

<Comparative Example 2a>
A sample of Comparative Example 2a was prepared in the same manner as in Example 1a except that a CPP film having a thickness of 25 μm was used as the sealant layer 13 without forming the heat-resistant gas barrier layer 21, and the same measurement (evaluation) was performed. did The results are also shown in Tables 1 and 2.

<Comparative Example 3a>
A sample of Comparative Example 3a was prepared in the same manner as in Example 1a except that an OPP film having a thickness of 30 μm was used as the heat-resistant gas barrier layer 21, and the same measurement (evaluation) was performed. The results are also shown in Tables 1 and 2.

<Overview of the first embodiment>
As is clear from Table 2, the cladding material samples of Examples 1a to 12a related to the present invention were able to obtain excellent results in all evaluations of insulation properties and gas permeation.

On the other hand, the exterior material samples of Comparative Examples 1a to 3a, which deviate from the gist of the present invention, did not obtain good results in the evaluation of gas permeation, and also obtained good results in part in the evaluation of insulation properties. I couldn't do it.

(2) Second embodiment

<Example 1b>
(2-1) Preparation of exterior material On both sides of a 40 μm thick aluminum foil (A8021-O) as the metal foil layer 12, phosphoric acid, polyacrylic acid (acrylic resin), chromium (III) salt compound, water After applying a chemical conversion treatment liquid containing alcohol, drying was performed at 180° C. to form a chemical conversion film. The amount of chromium deposited on this chemical conversion film was 10 mg/m ² per side.

Next, on one surface (outer surface) of the chemically treated aluminum foil (metal foil layer 12), a two-liquid curable urethane adhesive (3 μm) was applied as the base layer 11 to form two layers having a thickness of 15 μm. An axially stretched 6 nylon film was dry laminated (laminated).

Next, as shown in Table 3, as the heat-resistant gas barrier layer 21, a stretched PA6 film (ONY-6 film) having a thickness of 9 μm, a melting point of 225° C., a dielectric breakdown voltage of 19 kV/mm, and a hot water shrinkage rate of 5% was prepared. A 20 nm-thick vapor deposition film of aluminum was formed on one side thereof. The non-vapor-deposited surface of the ONY-6 film with the vapor-deposited film was adhered to the other surface (inner surface) of the aluminum foil after the dry lamination via a two-liquid curing urethane adhesive (3 μm).

Next, as shown in Table 3, as the sealant layer 13, a CPP film having a thickness of 20 μm and a melting point of 150° C. containing a lubricant (erucamide or the like) is sandwiched through a two-component curable urethane adhesive (3 μm). It is dry-laminated by superimposing it on the deposition surface (inner surface) of the ONY-6 film (heat-resistant gas barrier layer 21) after dry lamination, sandwiching it between a rubber nip roll and a lamination roll heated to 100 ° C. and pressing it. Thus, a laminate constituting the exterior material 1 was obtained.

Next, this laminate was wound around a roll shaft and then aged at 40°C for 10 days to obtain an exterior material sample of Example 1b.

(2-2) Measurement of Dielectric Breakdown Voltage With respect to the resin film constituting the heat-resistant gas barrier layer 21 in Example 1b, the dielectric breakdown voltage was measured in accordance with JIS C2151 before forming the deposited film. The results are also shown in Table 3.

(2-3) Measurement of Hot Water Shrinkage Ratio From the resin film constituting the heat-resistant gas barrier layer 21 in Example 1, a test piece measuring 10 cm×10 cm was cut out, and the test piece was immersed in hot water at 95° C. for 30 minutes. The dimensional change rate in the stretching direction of the test piece before and after the immersion for 1 minute was determined by the following equation.

Hot water shrinkage (%) = {(XY)/X} x 100
In this formula, "X" is the dimension in the stretching direction before immersion treatment, and "Y" is the dimension in the stretching direction after immersion treatment.

(2-4) Measurement of seal strength

For the exterior material sample of Example 1b, the seal strength was measured in the same manner as in (1-4) above. Table 4 shows the results.

(2-5) Measurement of residual rate The residual rate of the exterior material sample of Example 1b was measured in the same manner as in (1-3) above. Table 4 shows the results.

(2-6) Measurement of insulation resistance value (evaluation of insulation)
The insulation resistance value of the exterior material sample of Example 1b was measured in the same manner as in (1-5) above. The result is shown in 4.

(2-7) Evaluation of Formability The exterior material sample of Example 1b was cut into a size of 100 mm×100 mm to obtain a sample for formability evaluation. A deep drawing test was performed on this formability evaluation sample using a deep drawing mold attached to a 25t press machine while changing the forming height (drawing depth) in increments of 0.5 mm. .

Then, when the predetermined moldability was obtained even if the molding height was 7 mm or more, it was evaluated as "⊚". When the moldability was obtained, it was evaluated as "◯", and when it was less than 5 mm and the predetermined moldability was not obtained, it was evaluated as "x". The results are also shown in Table 4.

(2-8) Evaluation of H ₂ S Gas Permeability of ONY-6 Film with Vapor Deposited Film Based on JIS K7126, H ₂ The S gas permeability was measured. The results are also shown in Table 4.

<General review of the second embodiment>
As is clear from Table 4, the exterior material samples of Examples 1b to 13b related to the present invention were able to obtain excellent results in all evaluations.

On the other hand, the exterior material samples of Comparative Examples 1b to 3b, which deviate from the gist of the present invention, could not obtain good results in any of the evaluations.

(3) Third embodiment

<Example 1c>
(3-1) Preparation of exterior material On both sides of a 40 μm thick aluminum foil (A8021-O) as the metal foil layer 12, phosphoric acid, polyacrylic acid (acrylic resin), chromium (III) salt compound, water After applying a chemical conversion treatment liquid containing alcohol, drying was performed at 180° C. to form a chemical conversion film. The amount of chromium deposited on this chemical conversion film was 10 mg/m ² per side.

Next, as shown in Table 1, a heat-resistant gas barrier layer 21 having a thickness of 9 μm was formed on the other surface (inner surface) of the aluminum foil after the dry lamination via a two-liquid curing type urethane adhesive (3 μm). A PET film was dry laminated.

Next, the inner surface of the PET film as the heat-resistant gas barrier layer 21 was gravure-coated with a two-liquid curing urethane adhesive (3 μm) as the adhesive layer 4 . At this time, adhesive is not applied to the rectangular area where the opening is to be formed, leaving it as an uncoated area, and bonding only to the outer periphery of the opening forming area (heat-sealed area: remaining portion of sealant layer). agent was applied.

Next, as the sealant layer 13, a 40 μm-thick CPP film containing a lubricant (erucamide or the like) is superimposed on the inner surface of the heat-resistant gas barrier layer 21 coated with the above-mentioned adhesive only on the required portions, and the rubber is coated. The laminate was sandwiched between a nip roll and a laminating roll heated to 100° C. and pressed to perform dry lamination, thereby obtaining a laminate constituting the exterior material 1 .

Next, this laminate is wound around a roll shaft and then aged at 40° C. for 10 days. The CPP film for the sealant layer was cut out, and an opening 15 was formed in the intermediate portion of the sealant layer 13 to obtain an exterior material sample of Example 1c. In addition, in this exterior material sample, the heat-resistant gas barrier layer 21 is arranged so as to be exposed to the inner surface side through the opening 15 .

(3-2) Measurement of Water Vapor Permeability JIS K7129-1 (moisture sensor method, 40° C. 90% Rh) was applied to the resin film for the heat-resistant gas barrier layer 21 used to prepare the exterior material sample of Example 1c. The water vapor transmission rate was measured according to. The results are also shown in Table 5.

(3-3) Measurement of Thermal Conductivity The resin film for the heat-resistant gas barrier layer 21 used to prepare the exterior material sample of Example 1c was subjected to thermal conductivity measurement by a steady heat flow meter method (HFM method). was measured. The results are also shown in Table 5.

(3-4). Measurement of H ₂ S Gas Permeability of Resin Film The hydrogen sulfide (H ₂ S) gas permeability of the resin film for the heat-resistant gas barrier layer 21 used to prepare the exterior material sample of Example 1c was measured according to JIS K7126. -1. The results are also shown in Table 5.

(3-5) Evaluation of Cooling Performance (Cooling Effect) Two exterior material samples of Example 1c each having a size of 100 mm×100 mm were prepared. The opening 15 in this exterior material sample is square and has a size of 60 mm×60 mm.

These two exterior material samples are superimposed so that the opening 15 side faces inward, and the two exterior material samples that have been superimposed are placed 10 mm from the edge on three of the four peripheral sides. A 3-sided bag was produced by heat-sealing at the position with a width of 5 mm.

In a room temperature (25°C) temperature environment, pour hot water at 80°C from the opening into the three-sided bag, insert a thermometer, close the opening with an eye clip, and measure the temperature of the hot water for 3 minutes. change was measured. Table 5 also shows the temperature immediately after the injection of hot water and the temperature after 3 minutes in the measurement results.

<Example 2c>
A sample of Example 2c was prepared in the same manner as in Example 1c except that an ONY-6 film was used as the heat-resistant gas barrier layer 21, and the same measurement (evaluation) was performed. The results are also shown in Table 5.

<Example 3c>
A sample of Example 3c was prepared in the same manner as in Example 1c except that an OPP film (biaxially oriented polypropylene film) was used as the heat-resistant gas barrier layer 21, and the same measurement (evaluation) was performed. The results are also shown in Table 5.

<Comparative Example 1c>
A sample of Comparative Example 1c was prepared in the same manner as in Example 1c except that the sealant layer 13 was formed over the entire inner surface of the heat-resistant gas barrier layer 21, that is, the sealant layer 13 did not have the openings 15. was measured (evaluated). The results are also shown in Table 5.

<Comparative Example 2c>
A sample of Comparative Example 2c was prepared in the same manner as in Comparative Example 1c except that an ONY-6 film was used as the heat-resistant gas barrier layer 21, and the same measurement (evaluation) was performed. The results are also shown in Table 5.

<Comparative Example 3c>
A sample of Comparative Example 3c was prepared in the same manner as in Comparative Example 1c except that an OPP film was used as the heat-resistant gas barrier layer 21, and the same measurement (evaluation) was performed. The results are also shown in Table 5.

<Overview of the third embodiment>
As is clear from Table 5, the exterior material samples of Examples 1c to 3c related to the present invention were excellent in cooling properties (cooling effect).

On the other hand, the exterior material samples of Comparative Examples 1c to 3c, which deviate from the gist of the present invention, could not obtain high cooling performance.

(4) Fourth embodiment

<Example 1d>
1. Fabrication of exterior material On both sides of a 40 μm thick aluminum foil (A8021-O) as the metal foil layer 12, a chemical compound consisting of phosphoric acid, polyacrylic acid (acrylic resin), chromium (III) salt compound, water, and alcohol was applied. After applying the treatment liquid, drying was performed at 180° C. to form a chemical conversion film. The amount of chromium deposited on this chemical conversion film was 10 mg/m ² per side.

Next, as shown in Table 6, an insulating layer 21 having a thickness of 9 μm was applied to the other surface (inner surface) of the aluminum foil after the dry lamination via a two-liquid curing type urethane adhesive having a thickness of 3 μm. An OPP film (biaxially oriented polypropylene film) was laminated.

Next, as the sealant layer 13, a CPP film with a thickness of 40 μm containing 1000 ppm of erucamide as a lubricant was prepared, and on one surface (outer surface) thereof, an aluminum deposition film with a thickness of 20 nm was formed. The vapor-deposited surface (outer surface) of the CPP film with the vapor-deposited film is superimposed on the inner surface of the CPP film of the insulating layer 21 via a maleic acid-modified polypropylene adhesive (MAPP) having a thickness of 2 μm as the adhesive layer 4. Then, it was sandwiched between a rubber nip roll and a lamination roll heated to 100° C., and dry-laminated to obtain a laminate constituting the exterior material 1 .

Next, this laminate was wound around a roll shaft and then aged at 40°C for 10 days to obtain an exterior material sample of Example 1d.

In Table 6, the values in parentheses indicate the thickness of each layer, and the unit is μm.

(4-2) Measurement of seal strength

For the exterior material sample of Example 1d, the seal strength was measured in the same manner as in (1-4) above. Table 7 shows the results.

(4-3) Evaluation of Water Vapor (Moisture) Permeability of Exterior Material Two exterior material samples of Example 1d were cut into a size of 30 mm × 50 mm, and these pair of

exterior material samples

1, 1 were attached to each other with the sealant layer 13. The three sides (three sides) of the laminated

exterior material samples

1 and 1 were heat-sealed at a temperature of 200°C, a sealing pressure of 0.2 MPa (gauge display pressure), and a sealing time of 2 seconds. It was sealed under the conditions to prepare a three-sided bag. Subsequently, "Mc (g)" of calcium chloride was added to the three-sided bag (3 g as a guideline), and then the opening of the three-sided bag was sealed under the same sealing conditions as above.

Then, the weight "M0 (g)" immediately after sealing was measured with an electronic balance, and after standing in a constant temperature and humidity chamber of 80 ° C. × 90% Rh for 7 days, the weight "M1 (g)" after processing. was measured and the weight change (increased amount) was confirmed based on the following relational expression. The results are also shown in Table 7.

Weight change (%) = (M1-M0) / Mc
(4-4) Evaluation of formability The formability of the exterior material sample of Example 1d was evaluated in the same manner as in (2-7) above. The results are also shown in Table 7.

(4-5) Evaluation of H ₂ S Gas Permeability of Exterior Material The H2S gas permeability of the exterior material sample of Example 1d was evaluated in the same manner as in (1-6) above. The results are also shown in Table 7.

<Example 2d>
As shown in Table 6, the same as Example 1d above except that a 9 μm thick ONY-6 film was used as the insulating layer 21 and a 2 μm thick two-liquid curing urethane adhesive (PU) was used as the adhesive. Then, a sample of Example 2d was prepared, and the same measurement (evaluation) was performed. The results are also shown in Table 7.

<Example 3d>
As shown in Table 6, a 9 μm thick ONY-6 film is used as the insulating layer 21, a 2 μm thick two-liquid curable urethane adhesive (PU) is used as the adhesive, and the deposited film 22 is 5 nm thick. A sample of Example 3d was prepared in the same manner as in Example 1d except for the above, and the same measurement (evaluation) was performed. The results are also shown in Table 7.

<Example 4d>
As shown in Table 6, a sample of Example 4d was produced in the same manner as in Example 1d except that the thickness of the deposited film 22 was set to 500 nm, and the same measurement (evaluation) was performed. The results are also shown in Table 7.

<Example 5d>
As shown in Table 6, a sample of Example 5d was produced in the same manner as in Example 1d except that the thickness of the deposited film 22 was set to 1000 nm, and the same measurement (evaluation) was performed. The results are also shown in Table 7.

<Example 6d>
As shown in Table 6, a sample of Example 6d was produced in the same manner as in Example 1d except that the thickness of the deposited film 22 was set to 1200 nm, and the same measurement (evaluation) was performed. The results are also shown in Table 7.

<Example 7d>
As shown in Table 6, except that a two-liquid curing type urethane adhesive (PU) having a thickness of 2 μm was used as the adhesive, and the deposited film 22 was made of alumina (Al ₂ O ₃ ) having a thickness of 20 nm, A sample of Example 7d was prepared in the same manner as in 1d, and the same measurement (evaluation) was performed. The results are also shown in Table 7.

<Example 8d>
As shown in Table 6, a 20 nm-thick aluminum deposition film 22 is formed on the inner surface of the OPP film for the insulating layer 21, and a 2-μm-thick two-liquid curing urethane adhesive (PU) is used as the adhesive. Further, a sample of Example 8d was produced in the same manner as in Example 1d except that no deposited film was formed on the CPP film for the sealant layer 13, and the same measurement (evaluation) was performed. The results are also shown in Table 7.

<Example 9d>
As shown in Table 6, a sample of Example 9d was produced in the same manner as in Example 8d except that an ONY-6 film was used as the insulating layer 21, and the same measurement (evaluation) was performed. The results are also shown in Table 7.

<Example 10d>
As shown in Table 6, a sample of Example 10d was produced in the same manner as in Example 8d except that the thickness of the deposited film 22 was set to 5 nm, and the same measurement (evaluation) was performed. The results are also shown in Table 7.

<Example 11d>
As shown in Table 6, a sample of Example 11d was produced in the same manner as in Example 8d except that the thickness of the deposited film 22 was set to 1000 nm, and the same measurement (evaluation) was performed. The results are also shown in Table 7.

<Example 12d>
As shown in Table 6, a sample of Example 12d was prepared in the same manner as in Example 1d above, except that an aluminum vapor deposition film 22 having a thickness of 20 nm was formed on the inner surface of the OPP film for the insulating layer 21. A similar measurement (evaluation) was performed. The results are also shown in Table 7.

<Example 13d>
As shown in Table 6, an aluminum deposition film 22 having a thickness of 20 nm was formed on the inner surface of ONY-6 film having a thickness of 9 μm as the insulating layer 21, and a two-component curable urethane adhesive having a thickness of 2 μm was used as the adhesive. A sample of Example 13d was prepared in the same manner as in Example 1d except that (PU) was used, and the same measurement (evaluation) was performed. The results are also shown in Table 7.

<Comparative Example 1d>
As shown in Table 6, Comparative Example 1 was prepared in the same manner as in Example 1d above, except that an acid-modified polypropylene (acid-modified PP) having a thickness of 2 μm was used as an adhesive without forming any deposited film 22. A sample was prepared and the same measurement (evaluation) was performed. The results are also shown in Table 7.

<Comparative Example 2d>
As shown in Table 6, a 9 μm thick ONY-6 film was used as the insulating layer 21, and a 2 μm thick two-liquid curable urethane adhesive (PU) was used as the adhesive. A sample of Comparative Example 2d was prepared in the same manner, and the same measurement (evaluation) was performed. The results are also shown in Table 7.

<Overview of the fourth embodiment>
As is clear from Table 7, the exterior material samples of Examples 1d to 13d related to the present invention were able to obtain excellent results in all evaluations.

On the other hand, the exterior material samples of Comparative Examples 1d and 2d, which deviate from the gist of the present invention, could not obtain good results in any of the evaluations.

(5) Fifth embodiment

<Example 1e>
(5-1) Fabrication of Exterior Material An exterior material sample of Example 1e was obtained in the same manner as in Example 1a.

2. Measurement of Young's modulus, tensile strength at break and tensile elongation at break Both MD and TD were measured in accordance with JIS K7127-1999 for the PET film (heat-resistant gas barrier layer 21) used to prepare the exterior material sample of Example 1e. , Young's modulus at 90° C., tensile strength at break and tensile elongation at break were measured respectively. That is, a PET film for a heat-resistant gas barrier layer was cut into a size of 15 mm in width and 100 mm in length to prepare a test piece. C. atmosphere, a tensile test was performed at a tensile speed of 200 mm/min to measure Young's modulus (MPa), tensile strength at break (MPa), and tensile elongation at break (%). As shown in Table 8, in the heat-resistant gas barrier layer PET film of Example 1e, the Young's modulus was 3.6 GPa in MD and 3.2 GPa in TD, and the tensile strength at break was 190 MPa in MD and 210 MPa in TD. and the tensile elongation at break is 120% in MD and 110% in TD.

(5-3) Evaluation of high-temperature puncture resistance The puncture strength of the exterior material sample of Example 1e was measured in an atmosphere of 90°C in accordance with JIS Z1707:1997. The measurement method (penetration strength test method) is as follows.

An exterior material sample of a predetermined size is fixed as a test piece, and a semicircular needle with a diameter of 1.0 mm and a tip shape radius of 0.5 mm is pierced at a speed of 50 ± 5 mm per minute, and the maximum stress until the needle penetrates. was measured. The number of test pieces was 5, and the average value was taken as the puncture strength. The results are also shown in Table 8.

(5-4) Evaluation of Formability The moldability of the exterior material sample of Example 1e was evaluated in the same manner as in (2-7) above. The results are also shown in Table 8.

(5-5) Measurement of Seal Strength The seal strength of the exterior material sample of Example 1e was measured in the same manner as in (1-4) above. The results are also shown in Table 8.

<Example 2e>
The heat-resistant gas barrier layer 21 is biaxially oriented with a Young's modulus of MD: 1.5 GPa, TD: 1.2 GPa, a tensile strength at break of MD: 210 MPa, TD: 240 MPa, and a tensile elongation at break of MD: 140%, TD: 120%. A sample of Example 2e was prepared in the same manner as in Example 1e except that a 6 nylon film (ONY-6 film) was used, and the same measurement (evaluation) was performed. The results are also shown in Table 8.

<Example 3e>
A sample of Example 3e was prepared in the same manner as in Example 2e except that a film having a thickness of 15 μm was used as the heat-resistant gas barrier layer 21, and the same measurement (evaluation) was performed. The results are also shown in Table 8.

<Example 4e>
A sample of Example 4e was prepared in the same manner as in Example 2e except that a film having a thickness of 25 μm was used as the heat-resistant gas barrier layer 21, and the same measurement (evaluation) was performed. The results are also shown in Table 8.

<Example 5e>
As the heat-resistant gas barrier layer 21, a PET film having Young's modulus MD: 3.4 GPa, TD: 3.1 GPa, tensile strength at break MD: 200 MPa, TD: 220 MPa, and tensile elongation at break MD: 130%, TD: 125%. A sample of Example 5e was prepared in the same manner as in Example 1e, except that it was used, and the same measurement (evaluation) was performed. The results are also shown in Table 8.

In Example 5e, the Young's modulus, tensile strength at break, and tensile elongation at break of the PET film were made different from those in Example 1e by adjusting the conditions during film production and changing the degree of crystallinity.

<Example 6e>
The heat-resistant gas barrier layer 21 is biaxially stretched with a Young's modulus of MD: 1.1 GPa, TD: 1.6 GPa, a tensile strength at break of MD: 90 MPa, TD: 160 MPa, and a tensile elongation at break of MD: 140%, TD: 80%. A sample of Example 6e was prepared in the same manner as in Example 1e except that a polypropylene film (OPP film) was used, and the same measurement (evaluation) was performed. The results are also shown in Table 8.

<Example 7e>
A sample of Example 7e was prepared in the same manner as in Example 1e except that a CPP film having a thickness of 10 μm was used as the sealant layer 13, and the same measurement (evaluation) was performed. The results are also shown in Table 8.

<Example 8e>
A sample of Example 8e was prepared in the same manner as in Example 1e except that a CPP film having a thickness of 100 μm was used as the sealant layer 13, and the same measurement (evaluation) was performed. The results are also shown in Table 8.

<Comparative Example 1e>
As the heat-resistant gas barrier layer 21, an OPP film having Young's modulus MD: 0.9 GPa, TD: 1.5 GPa, tensile strength at break MD: 80 MPa, TD: 150 MPa, and tensile elongation at break MD: 150%, TD: 80%. A sample of Comparative Example 1e was prepared in the same manner as in Example 6e, except that it was used, and the same measurement (evaluation) was performed. The results are also shown in Table 8.

In Comparative Example 1e, the Young's modulus, tensile strength at break, and tensile elongation at break of the OPP film were made different from those in Example 6e by adjusting the conditions during film production and changing the degree of crystallinity.

<Overview of the fifth embodiment>
As is clear from Table 8, the exterior material samples of Examples 1e to 8e related to the present invention are excellent in puncture resistance at 90 ° C., and it is considered that defects such as breakage are unlikely to occur in high temperature environments. .

On the other hand, the exterior material sample of Comparative Example 1, which deviates from the gist of the present invention, is inferior in piercing resistance at 90° C., and is damaged in a high-temperature environment compared to Examples 1e to 8e. It is thought that such defects are likely to occur.

This application is Japanese Patent Application No. 2021-131016 filed on August 11, 2021, Japanese Patent Application No. 2021-132355 filed on August 16, 2021, 2021 8 Japanese Patent Application No. 2021-132360 filed on August 16, 2021, Japanese Patent Application No. 2021-132362 filed on August 16, 2021 and filed on August 17, 2021 This is accompanied by a priority claim of Japanese Patent Application No. 2021-132728 of the Japanese patent application, and the disclosure content thereof constitutes a part of the present application as it is.

The terms and expressions used herein are used as terms of description and not of limitation, as any equivalent of the features shown and described herein. are not to be excluded, and variations within the claimed scope of the invention are permissible.

The all-solid-state battery exterior material of the present invention can be suitably used as a casing material for housing the solid-state battery main body.

1, 1a, 1b, 1c: exterior material 11: base material layer 12: metal foil layer 13: sealant layer 15: opening 21: heat-resistant gas barrier layer 22: deposited film 4: adhesive layer 5: solid battery body

Claims

A base material layer, a metal foil layer laminated on the inner surface side of the base material layer, and a sealant layer laminated on the inner surface side of the metal foil layer, for enclosing a solid battery main body. As an exterior material,
An exterior material for an all-solid-state battery, wherein a resin-made heat-resistant gas barrier layer is provided between the metal foil layer and the sealant layer.
2. The heat-resistant gas barrier layer according to claim 1, wherein the hydrogen sulfide gas permeability measured in accordance with JIS K7126-1 is set to 15 {cc·mm/(m 2 ·D·MPa)} or less. Exterior material for all-solid-state batteries.
The resin constituting the heat-resistant gas barrier layer has an original thickness of "da0" and a thickness of "da1" when pressed under conditions of 200°C, 0.2 MPa, and 5 sec.
1≧da1/da0≧0.9
3. The exterior material for an all-solid-state battery according to claim 2, which is configured to satisfy the relational expression.
The exterior material for an all-solid-state battery according to claim 2 or 3, wherein the heat-resistant gas barrier layer has a thickness of 3 µm to 50 µm.
The all-solid-state battery according to any one of claims 2 to 4, wherein the sealant layer is made of a resin having a hydrogen sulfide gas permeability of 100 {cc·mm/(m 2 ·D · MPa)} or less. exterior material.
The resin constituting the sealant layer has an original thickness of "db0" and a thickness of "db1" when pressed under the conditions of 200 ° C., 0.2 MPa, 5 sec,
0.5≧db1/db0≧0.1
The exterior material for an all-solid-state battery according to any one of claims 2 to 5, which is configured to satisfy the relational expression.
The resin constituting the heat-resistant gas barrier layer has a water vapor gas permeability of 50 (g/m 2 /day) or less measured according to JIS K7129-1 (moisture sensor method, 40°C, 90% Rh). The exterior material for an all-solid battery according to any one of Items 2 to 6.
The heat-resistant gas barrier layer is made of an insulating resin having a melting point higher than that of the sealant layer by 20° C. or more,
The exterior material for an all-solid-state battery according to any one of claims 1 to 7, wherein the heat-resistant gas barrier layer has a dielectric breakdown voltage of 18 kV/mm or more.
The exterior material for an all-solid-state battery according to claim 8, wherein the resin constituting the heat-resistant gas barrier layer has a hot water shrinkage rate of 2% to 10%.
The exterior material for an all-solid-state battery according to claim 8 or 9, wherein the resin constituting the heat-resistant gas barrier layer is polyamide.
11. The sealant layer according to any one of claims 1 to 10, wherein an opening is provided in a portion corresponding to the solid battery main body, and the heat-resistant gas barrier layer is arranged so as to be exposed to the inner surface side in the opening. 2. The exterior material for an all-solid-state battery according to .
The exterior material for an all-solid-state battery according to claim 11, wherein the heat-resistant gas barrier layer is made of a resin having a melting point higher than that of the sealant layer by 10°C or more.
The exterior material for an all-solid-state battery according to claim 11 or 12, wherein the resin constituting the heat-resistant gas barrier layer has a thermal conductivity of 0.2 W/m·K or more.
A deposited film is provided between the heat-resistant gas barrier layer and the sealant layer,
The exterior material for an all-solid-state battery according to claim 1, wherein the vapor-deposited film is composed of at least one of metal, metal oxide, and metal fluoride.
The exterior material for an all-solid-state battery according to claim 14, wherein the vapor deposition film has a thickness of 5 nm to 1000 nm.
The exterior material for an all-solid-state battery according to claim 14 or 15, wherein an adhesive layer is provided between the heat-resistant gas barrier layer and the sealant layer.
The exterior material for an all-solid-state battery according to claim 16, wherein the vapor-deposited film is provided on the contact surface of the sealant layer with the adhesive layer.
The exterior material for an all-solid-state battery according to claim 16 or 17, wherein the vapor-deposited film is provided on a contact surface of the heat-resistant gas barrier layer with the adhesive layer.
The exterior material for an all-solid-state battery according to any one of claims 1 to 18, wherein the heat-resistant gas barrier layer has a Young's modulus of 1 GPa or more in both MD and TD at 90°C.
The exterior material for an all-solid-state battery according to claim 19, wherein the heat-resistant gas barrier layer has a tensile breaking strength of 100 MPa or more at 90°C in both MD and TD.
The exterior material for an all-solid-state battery according to claim 19 or 20, wherein the heat-resistant gas barrier layer has a tensile elongation at break of 50% to 200% in both MD and TD at 90°C.
An all-solid-state battery, wherein a solid-state battery main body is enclosed in the all-solid-state battery exterior material according to any one of claims 1 to 21.