KR20240027809A - Exterior materials for all-solid-state batteries and all-solid-state batteries - Google Patents

Abstract

Provided is an exterior material for an all-solid-state battery that does not leak gas and has sufficient insulation properties. The present invention provides a solid battery comprising a base layer 11, a metal foil layer 12 laminated on the inner surface of the base layer 11, and a sealant layer 13 laminated on the inner surface of the metal foil layer 12. The target is the exterior material for an all-solid-state battery to enclose the main body (5). Between the metal foil layer 12 and the sealant layer 13, a heat-resistant gas barrier layer 21 made of resin is provided.

Description

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

The present invention relates to exterior materials and all-solid-state batteries for all-solid-state batteries 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.

Since lithium ion secondary batteries, which have been widely used in the past, use a liquid electrolyte as an electrolyte, there is a risk that the separator may be destroyed due to liquid leakage or generation of dendrites, and in some cases, ignition due to short circuit may occur.

In contrast, since the all-solid-state battery is a battery using a solid electrolyte, liquid leakage or dendrites do not occur and the separator is not destroyed. Therefore, there is no concern about ignition due to destruction of the separator, and it is attracting great attention in terms of safety, etc.

A typical all-solid-state battery is comprised of a solid battery body, such as an electrode active material or a solid electrolyte, encapsulated inside an exterior material serving as a casing. In this all-solid-state battery, as research on solid electrolytes progresses, the performance obtained from the exterior material is gradually becoming different from that of the exterior material of batteries using conventional liquid electrolytes, and the performance for all-solid-state batteries is gradually increasing. Various exterior materials have been proposed to meet these requirements.

The exterior material for an all-solid-state battery has a basic structure that includes a metal foil layer and a heat-sealing layer (sealant layer) laminated on the inside, and the solid-state battery body is encapsulated by heat-sealing the sealant layer.

For example, the exterior material for an all-solid-state battery shown in Patent Document 1 below has a protective film interposed between a metal foil layer and a sealant layer, and the hydrogen sulfide gas permeability of the sealant layer is adjusted to a predetermined value. Additionally, in the exterior material for an all-solid-state battery shown in Patent Document 2, the hydrogen sulfide gas permeability of the sealant layer is adjusted to a predetermined value. Additionally, the exterior material for an all-solid-state battery shown in Patent Document 3 is used as a sealant layer to absorb gas. Additionally, the exterior material for an all-solid-state battery shown in Patent Document 4 is composed of a vapor-deposited film layer laminated on the inner surface of a sealant layer.

Japanese Patent No. 6777276 Japanese Patent No. 6747636 Japanese Patent Laid-open No. 2020-187855 Japanese Patent Laid-open No. 2020-187835

However, in the all-solid-state battery using the exterior material shown in Patent Documents 1 and 2, there is a problem that when the solid electrolyte reacts with moisture in the air and hydrogen sulfide gas is generated, the hydrogen sulfide gas may leak.

Additionally, in the packaging materials shown in Patent Documents 2 to 4, when the sealant layer is melted and bonded (thermal bonded) at the time of encapsulating the battery body, the resin constituting the sealant layer melts and flows out, and the sealant layer becomes partially thin, resulting in sealant There is a problem that the protective function for the metal foil layer is reduced, which may lead to a decrease in insulation properties.

Preferred embodiments of the present invention have been made in consideration of the above-mentioned and/or other problems in the related art. Preferred embodiments of the present invention are those that can significantly improve existing methods and/or devices.

The present invention was made in consideration of the above-mentioned problems, and it is possible to secure sufficient insulation even by heat-sealing the sealant layer, and also prevents leakage of hydrogen sulfide gas generated inside when the battery body is sealed. The purpose is to provide an exterior material for an all-solid-state battery and an all-solid-state battery that can be used.

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

In order to solve the above problems, the present invention is provided with the following means.

[1] An exterior material for an all-solid-state battery for encapsulating a solid-state battery body, comprising a base layer, a metal foil layer laminated on the inner surface of the base layer, and a sealant layer laminated on the inner surface of the metal foil layer,

An exterior material for an all-solid-state battery, characterized in that a heat-resistant gas barrier layer made of resin is provided between the metal foil layer and the sealant layer.

[2] The exterior material for an all-solid-state battery according to the preceding paragraph 1, wherein the heat-resistant gas barrier layer has a hydrogen sulfide gas permeability measured in accordance with JIS K7126-1 set to 15{cc·mm/(m2·D·MPa)} or less.

[3] The original thickness of the resin constituting the heat-resistant gas barrier layer is set to “da0”, and the thickness when pressurized under the conditions of 200°C, 0.2 MPa, and 5 sec is set to “da1”.

1≥da1/da0≥0.9

The exterior material for an all-solid-state battery according to the preceding paragraph 2, which is configured to satisfy the relational expression.

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

[5] The exterior material for an all-solid-state battery according to any one of the preceding paragraphs 2 to 4, wherein the sealant layer is made of a resin with a hydrogen sulfide gas permeability of 100{cc·mm/(m2·D·MPa)} or less.

[6] The original thickness of the resin constituting the sealant layer is set to “db0”, and the thickness when pressed under the conditions of 200°C, 0.2 MPa, and 5 sec is set to “db1”.

0.5≥db1/db0≥0.1

The exterior material for an all-solid-state battery according to any one of the preceding paragraphs 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/m2/day) or less as measured in accordance with JIS K7129-1 (humidity sensor method 40°C 90% Rh). The exterior material for an all-solid-state battery according to any one of 2 to 6.

[8] The heat-resistant gas barrier layer is made of an insulating resin with a melting point of 20°C or more higher than that of the sealant layer,

The heat-resistant gas barrier layer is an exterior material for an all-solid-state battery according to any one of the preceding paragraphs 1 to 7, wherein the heat-resistant gas barrier layer has an insulation 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 thermal 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] The battery according to any one of the preceding paragraphs 1 to 10, wherein an opening is provided in a portion of the sealant layer corresponding to the solid battery body, and the heat-resistant gas barrier layer is arranged to be exposed on the inner surface through the opening. Exterior material for solid-state batteries.

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

[13] The exterior material for an all-solid-state battery according to 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 vapor deposition 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 the preceding paragraph 1, wherein the deposited film is composed of at least one of metal, metal oxide, and metal fluoride.

[15] The exterior material for an all-solid-state battery according to item 14, wherein the thickness of the deposited film is set to 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 packaging material for an all-solid-state battery according to item 16, wherein the vapor-deposited film is provided on a contact surface of the sealant layer with the adhesive layer.

[18] The exterior material for an all-solid-state battery according to item 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.

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

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

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

[22] An all-solid-state battery, characterized in that the solid-state battery body is encapsulated in the exterior material for an all-solid-state battery according to any one of the preceding paragraphs 1 to 21.

According to the exterior material for an all-solid-state battery of invention [1], since a 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. In addition, when sealing the solid battery body with this packaging material, when the sealant layer is heat-sealed, the resin of the sealant layer melts and flows out, and even if the insulation property of the sealant layer deteriorates, the heat-resistant gas barrier layer remains. , insulation can be reliably secured by the heat-resistant gas barrier layer.

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, leakage of hydrogen sulfide gas to the outside can be more reliably prevented.

According to the exterior material for an all-solid-state battery of inventions [3] and [4], when the solid battery body is encapsulated by thermal bonding, a sufficient thickness of the heat-resistant gas barrier layer can be secured, thereby reliably preventing hydrogen sulfide gas from leaking. In addition to being able to do this, good insulation properties can also be ensured.

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

According to the exterior material for an all-solid-state battery of invention [6], when the solid battery main body is encapsulated by heat sealing, the thickness of the sealant layer can be secured to a certain extent, and thus the insulation and sealing properties can be further improved.

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

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, sufficient insulation properties can be reliably secured even in a high-temperature environment.

According to the exterior material for an all-solid-state battery of invention [9], since the thermal water shrinkage rate of the heat-resistant gas barrier layer is specified, formability can be improved while ensuring high insulation properties.

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 invention [11], an opening through which the heat-resistant gas barrier layer is exposed is formed in the portion of the sealant layer corresponding to the solid battery body, so that heat generated from the solid battery body is transmitted to the sealant layer. By dissipating heat by transferring it to the metal foil layer through the heat-resistant gas barrier layer without being blocked, sufficient cooling properties can be ensured.

According to the exterior material for an all-solid-state battery of invention [12], since the heat-resistant gas barrier layer has a high melting point, melting and outflow of the heat-resistant gas barrier layer can be prevented during thermal bonding of the sealant layer, and gas leakage can be more reliably prevented. It can be prevented.

According to the exterior material for an all-solid-state battery of invention [13], since the thermal conductivity of the gas barrier layer is specified, cooling properties can be further improved.

According to the exterior material for an all-solid-state battery of inventions [14] [15], a vapor-deposited film is provided between the insulating layer and the sealant layer, and therefore sufficient gas barrier properties can be continuously secured by the vapor-deposited film. For this reason, it is possible to prevent the generation of hydrogen sulfide gas caused by intrusion of external moisture, and even if hydrogen sulfide gas is generated, leakage of hydrogen sulfide gas to the outside can be reliably prevented due to the gas barrier property of the deposited film.

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 two layers can be reliably fixed in close contact.

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 placed further inside, and the barrier against moisture can be further improved.

According to the exterior material for an all-solid-state battery of 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-insulating effect of the adhesive layer prevents the destruction of the vapor-deposited film due to heat. This makes it less likely to occur, and gas barrier properties can be reliably secured by the vapor-deposited film.

According to the exterior material for an all-solid-state battery of the invention [19], since a heat-resistant gas barrier layer with a high Young's modulus at high temperature is used, even in a high-temperature environment, not limited to room temperature, the heat-resistant gas barrier layer and, by extension, the entire exterior material are damaged, etc. The occurrence of defective parts can be reliably prevented.

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

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

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

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

This exterior material 1 includes a base material layer 11 disposed on the outermost side, a metal foil layer 12 laminated on the inner side of the base layer 11, and a heat-resistant gas barrier laminated on the inner side of the metal foil layer 12. It has a layer 21 and a sealant layer 13 laminated on the inner surface of the heat-resistant gas barrier layer 21, and in the present embodiment, between each layer 11 to 13, 21 of the exterior material 1. is bonded through an adhesive (adhesive layer) using a dry lamination method. In other words, the exterior material 1 of this embodiment is a laminate composed of base material layer 11/adhesive layer/metal foil layer 12/adhesive layer/heat-resistant gas barrier layer 21/adhesive layer/sealant layer 13. It is composed by.

In this embodiment, as shown in FIG. 1, an all-solid-state battery is manufactured by encapsulating the solid-state battery body 5 to cover it with the exterior material 1 of the above-described configuration. That is, the two square-shaped exterior materials 1, 1 are overlapped top and bottom through the solid battery body 5, and the sealant layers 13, 13 of the outer peripheral edges of the two (pair of) exterior materials 1, 1 are formed. ) are joined together in an airtight state (encapsulated state) by thermal bonding (heat sealing), thereby producing an all-solid-state battery in which the solid-state battery body (5) is housed in a bag-shaped casing made of the exterior materials (1, 1). will be.

In the all-solid-state battery of this embodiment, although not shown, a tab lead is provided for extracting electricity. One end (inner end) of this tab lead is adhesively fixed to the solid-state battery body 5, the middle part 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. It is arranged as much as possible.

In addition, in the present embodiment, the casing is formed by bonding two planar exterior materials 1, 1 together, but the casing is not limited to this, and in the present invention, at least one of the two exterior materials 1, 1 is molded into a tray shape in advance. Then, one tray-shaped exterior material may be bonded to the other tray-shaped or flat exterior material to form a casing.

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

The base material layer 11 of the exterior material 1 is made of a heat-resistant resin film with a thickness of 5 μm to 50 μm. As the resin constituting this base material layer 11, polyamide, polyester (PET, PBT, PEN), polyolefin (PE, PP), etc. can be suitably used.

The thickness of the metal foil layer 12 is set to 5 μm to 120 μm, and has a function of blocking the intrusion of oxygen and moisture from the surface (outer surface) side. As this metal foil layer 12, aluminum foil, SUS foil (stainless steel foil), copper foil, nickel foil, etc. can be suitably used. Additionally, in this embodiment, the terms “aluminum,” “copper,” and “nickel” are used to include their alloys.

Additionally, if plating treatment or the like is performed on the metal foil layer 12, the risk of pinholes occurring is reduced, and the function of blocking the intrusion of oxygen or moisture can be further improved.

In addition, if the metal foil layer 12 is subjected to chemical conversion treatment such as chromate treatment, the corrosion resistance is further improved, and defects such as defects can be more reliably prevented from occurring, and adhesion to the resin is improved. This can further improve durability.

The sealant layer 13 has a thickness set to 10 μm to 100 μm and is made of a film of heat-sealable (heat-sealable) resin. Resins constituting this sealant layer 13 include polyethylene (LLDPE, LDPE, HDPE), polyolefins such as polypropylene, olefin-based copolymers, acid-modified products and ionomers thereof, for example, non-stretched resins. Polypropylene (CPP, IPP), etc. can be used appropriately.

As the sealant layer 13, considering that electricity is extracted using a tab lead, that is, considering sealing or adhesiveness with the tab lead, non-oriented polypropylene film (CPP, IPP), etc. It is preferable to use polypropylene-based resin.

The heat-resistant gas barrier layer 21 is made of a resin film having heat resistance and insulating properties. Resins constituting this heat-resistant gas barrier layer 21 include polyamides (6-nylon, 66-nylon, MXD nylon, etc.), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate ( It is preferable to use PEN), cellophane, polyvinylidene chloride, etc.

The heat-resistant gas barrier layer 21 of the present embodiment has good insulating properties, and has good insulation properties even after the solid battery main body 5 is sealed by thermal bonding with the exterior material 1 of the present embodiment. This is to obtain insulation.

In this embodiment, the resin constituting 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 a resin with a hydrogen sulfide gas permeability of 30{cc·mm/(㎡·D·MPa)} or less in measurements based on JIS K7126-1, more preferably 15{ cc·mm/(㎡·D·MPa)} It is better to make it with the following resin. That is, when the hydrogen sulfide gas permeability of the heat-resistant gas barrier layer 21 is set to the above-mentioned specific value or less, when hydrogen sulfide gas is generated by the reaction between the solid electrolyte material and moisture in the external air, the hydrogen sulfide gas is generated by the heat-resistant gas barrier layer 21. It can prevent gas from leaking to the outside. In other words, if the hydrogen sulfide gas permeability of the heat-resistant gas barrier layer 21 is too large, the generated hydrogen sulfide gas may pass through the exterior material 1 (heat-resistant gas barrier layer 21) and leak to the outside, which is not desirable. not.

Also, for reference, “D” included in the unit of hydrogen sulfide gas permeability corresponds to “Day (24h).”

In addition, in this embodiment, the resin constituting the heat-resistant gas barrier layer 21 has a water vapor gas permeability of 50 (g/m2/day) measured in accordance with JIS K7129-1 (humidity sensor method 40°C 90% Rh). It is better to adopt the following, more preferably 40 (g/m2/day) or less. In other words, hydrogen sulfide gas is generated when external moisture penetrates the exterior material 1 and reacts with the solid electrolyte material. When the water vapor gas permeability of the heat-resistant gas barrier layer 21 is set to the above-mentioned specific value or less, the heat-resistant gas barrier layer 21 reacts with the solid electrolyte material. In addition to preventing the intrusion of moisture by the gas barrier layer 21, the gas barrier function of the metal foil layer 12 is also compatible with each other, so that the intrusion of moisture can be prevented more reliably, preventing the generation of hydrogen sulfide gas itself. This can be reliably prevented, and furthermore, 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 to this range, the above-described effect of suppressing the transmission of hydrogen sulfide gas and water vapor gas can be reliably obtained, and the sealant layer 13 is melted and leaked by thermal bonding. Even so, insulation can be reliably secured by the heat-resistant gas barrier layer 21. In other words, if the heat-resistant gas barrier layer 21 is too thin, there is a risk that the gas permeation suppressing effect and insulation properties cannot be secured, which is not preferable. Conversely, if the heat-resistant gas barrier layer 21 is too thick, not only can the exterior material 1 not be made thinner, but the effect of making it thicker than necessary is not fully obtained, which is not desirable.

In addition, in this embodiment, the original thickness of the resin (resin film) constituting the heat-resistant gas barrier layer 21 is set to “da0”, and the thickness when pressurized under the conditions of 200°C, 0.2 MPa, and 5 sec is set to “da1.” ”, it is desirable to configure it so that the residual ratio “da1/da0” is 0.9 or more, that is, to satisfy the relational expression (A) of “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 heat-bonded. In the present embodiment, when the above relational expression (A) is satisfied, even if the solid battery body 5 is sealed by thermally bonding the exterior material 1, the thickness of the heat-resistant gas barrier layer 21 is not reduced. Since this can be suppressed and a sufficient thickness can be ensured, the above-mentioned gas permeation suppressing effect can be reliably obtained, and the insulation provided by the heat-resistant gas barrier layer 21 can also be reliably obtained.

In addition, in this embodiment, it is desirable to employ a resin constituting the heat-resistant gas barrier layer 21 that has a melting point of at least 10°C higher than that of the resin constituting the sealant layer 13, and more preferably at least 20°C higher. do. That is, when the heat-resistant gas barrier layer 21 is set to a high melting point, even if the sealant layer 13 is melted when heat-sealing the exterior material 1, it is impossible to prevent the melt and outflow of the heat-resistant gas barrier layer 21. Therefore, the gas permeation suppression effect and insulation properties of the heat-resistant gas barrier layer 21 can be reliably obtained.

In addition, in this embodiment, it is preferable that the heat-resistant gas barrier layer 21 has an insulation breakdown voltage of 18 kV/mm or more. That is, when the dielectric breakdown voltage of the heat-resistant gas barrier layer 21 is above a certain value, sufficient insulation can be reliably secured. In other words, if the dielectric breakdown voltage of the heat-resistant gas barrier layer 21 is too small, there is a risk that sufficient insulation may not be secured.

Additionally, in this embodiment, it is preferable to set the thermal water shrinkage rate of the heat-resistant gas barrier layer 21 to 2% to 10%. That is, when this configuration is adopted, the formability of the heat-resistant gas barrier layer 21 and, by extension, the packaging material 1 is improved, and after encapsulating the solid battery main body 5 with the packaging material 1 by thermal bonding, Also, high insulation properties can be maintained. In other words, if the thermal water shrinkage rate of the heat-resistant gas barrier layer 21 deviates from the above-mentioned specific range, there is a risk that good insulation may not be secured, which is not preferable.

In this embodiment, the thermal water shrinkage rate of the heat-resistant gas barrier layer 21 is measured before and after immersion when a test piece (10 cm x 10 cm) of the resin film constituting the heat-resistant gas barrier layer 21 is immersed in hot water at 95°C for 30 minutes. is the rate of dimensional change in the stretching direction of the test piece. In this embodiment, the thermal shrinkage rate can be obtained from the following equation, with the dimension in the stretching direction before immersion treatment being "X" and the dimension in the stretching direction after immersion treatment being "Y".

Thermal shrinkage rate (%)={(X-Y)/X}×100

Here, in this embodiment, it is preferable to employ a resin constituting the heat-resistant gas barrier layer 21 with a thermal conductivity of 0.2 W/m·K or more. That is, when this configuration is adopted, the heat conduction properties of the heat-resistant gas barrier layer 21 can be sufficiently secured, and therefore the cooling properties of the solid battery body 5 can be further improved.

In this embodiment, the resin film constituting the heat-resistant gas barrier layer 21 has a Young's modulus at 90°C of 1 GPa or more for both MD, which is the flow direction, and TD, which is the direction orthogonal to MD, and preferably 5 GPa or more. It is desirable. In other words, by adopting this configuration, a predetermined hardness can be secured in the heat-resistant gas barrier layer 21 and, by extension, the exterior material 1 even in a high-temperature environment, not limited to room temperature, thereby preventing the occurrence of defective parts such as breakage. You can prevent it from happening.

In addition, in this embodiment, it is preferable that the Young's modulus of the heat-resistant gas barrier layer 21 at room temperature (25°C) is 1.5 GPa or more.

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

In addition, in this embodiment, it is preferable that the heat-resistant gas barrier layer 21 adopts a configuration in which the tensile elongation at rupture at 90°C is 50% to 200% in both MD and TD. In other words, when this configuration is adopted, damage to the exterior material 1 can be more reliably prevented even if the exterior material 1 expands and expands due to an increase in internal pressure under high temperature.

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

In addition, in this embodiment, the original thickness of the resin (resin film) constituting the sealant layer 13 is set to “db0”, and the thickness when pressurized under the conditions of 200°C, 0.2 MPa, and 5 sec is set to “db1”. Therefore, it is preferable to configure the residual ratio "db1/db0" to be 0.1 to 0.5, that is, to satisfy the relational expression (B) of "0.5≥db1/db0≥0.1". This relational expression (B) corresponds to the configuration that the thickness reduction rate of the sealant layer 13 is 50 to 90% when the exterior material 1 is heat-bonded. In this 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 body 5 is sealed by thermally bonding the exterior material 1. Therefore, the insulation of the sealant layer 13 is ensured, and even if tab leads or foreign substances are present, the resin of the sealant layer 13 flows into the outer circumferential gap between them, thereby ensuring sufficient sealing properties.

Here, in this embodiment, the sealant layer 13 of the exterior material 1 is made of a resin that conforms to JIS K7126-1 and has a hydrogen sulfide gas permeability of 100{cc·mm/(m2·D·MPa)} or less. desirable. That is, when the hydrogen sulfide gas permeability of the sealant layer 13 is set to the above-mentioned specific value or less, the hydrogen sulfide gas permeation suppression effect by the heat-resistant gas barrier layer 21 described above is prevented by the hydrogen sulfide gas permeability of the sealant layer 13. The permeation-inhibiting effects of are combined to more reliably prevent hydrogen sulfide gas from leaking to the outside.

Meanwhile, in this embodiment, the adhesive (adhesive layer) for attaching each layer 11 to 13, 21 of the exterior material 1 includes a two-component curing type, an energy ray (UV, X-ray, etc.) curing type, etc. Curing types can be used, and among them, urethane-based adhesives, olefin-based adhesives, acrylic-based adhesives, epoxy-based adhesives, etc. can be used appropriately. Additionally, 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 this 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 not exposed to the outside. Leakage can be reliably prevented. In addition, when sealing the solid battery body 5, when the sealant layer 13 of the exterior material 1 is heat-sealed, the resin of the sealant layer 13 melts and flows out, and the insulation property of the sealant layer 13 deteriorates. Even if this is done, since the heat-resistant gas barrier layer 21 remains, insulation can be reliably secured by the heat-resistant barrier layer 21.

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

Additionally, when the dielectric breakdown voltage of the heat-resistant gas barrier layer 21 is set to a specific value, good insulation can be reliably secured even in a high-temperature environment.

In addition, when the tensile breaking strength of the heat-resistant gas barrier layer 21 is set to a specific value, defects such as breakage will occur in the heat-resistant gas barrier layer 21 and, by extension, the exterior material 1 even in a high temperature environment, not limited to room temperature. This can be reliably prevented, and an all-solid-state battery product with 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 modification of the present invention, and FIG. 4 is an exploded view schematically showing the structure of the all-solid-state battery. As shown in both figures, in this all-solid-state battery, the exterior material 1 consists of a base layer 11 disposed on the outermost side and a metal foil layer laminated and bonded to the inner side of the base layer 11 through an adhesive layer. (12) and a heat-resistant gas barrier layer (21) laminated and bonded to the inner side of the metal foil layer (12) through an adhesive layer, and to the inner side of the heat-resistant gas barrier layer (21) through an adhesive layer (4). It is provided with a sealant layer 13 that is laminated and bonded.

Additionally, the middle portion of the sealant layer 13 excluding the outer peripheral edge is removed to form an opening 15, and the sealant layer 13 remains only at the outer peripheral edge. This 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 on the inside through the opening 15.

In the first modification, two pieces (a pair) of exterior materials 1, 1 formed in a square shape have the sealant layers 13 on their outer peripheral edges facing each other, so that the upper and lower surfaces are formed through the solid battery body 5. By overlapping with each other, the sealant layers 13, 13 are joined and integrated in an airtight state (sealed state) by thermal bonding (heat sealing), thereby forming a solid battery body within the bag-shaped casing made of the exterior material 1, 1. (5) An all-solid-state battery accommodated in a sealed state is manufactured.

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

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

As already stated, in the exterior material 1 of the first modification example, an opening 15 is formed in the sealant layer 13. This opening 15 is formed in a portion corresponding to the solid battery main body 5, and the sealant layer 13 is disposed 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 to the inside through the opening 15, thereby producing an all-solid-state battery. In this state, the heat-resistant gas barrier layer 21 is arranged to face the solid battery main body 5, and in some cases, at least a portion of it faces the solid battery body 5.

In this embodiment, the opening 15 of the exterior material 1 is formed, for example, by cutting the middle part of the sealant layer 13 laminated over the entire heat-resistant gas barrier layer 21, and the outer peripheral edge. The sealant layer 13 remains formed.

That is, in the first modification, when the sealant layer 13 is formed on the heat-resistant gas barrier layer 21, an adhesive as the adhesive layer 4 is applied to the inner surface of the resin film as the heat-resistant gas barrier layer 21 using a gravure roll or the like. is applied and a resin film as the sealant layer 13 is attached through the adhesive layer 4. When the adhesive is applied to the heat-resistant gas barrier layer 21 using a gravure roll or the like, an opening is formed. An uncoated area is created where no adhesive is applied in the planned area. Then, the resin film for the sealant layer is attached to the heat-resistant gas barrier layer 21 having the adhesive uncoated portion and dried. Thereafter, the resin film for the sealant layer in the adhesive uncoated area is cut with a laser cutter, roll knife, etc. to form the opening 15 (first forming method).

As a second forming method, before applying the adhesive to the heat-resistant gas barrier layer 21, release paper is temporarily fixed to the area where the opening is planned to be formed in the heat-resistant gas barrier layer 21, and is held in that state. An adhesive is applied to the heat-resistant gas barrier layer 21 using a gravure roll or the like, and a resin film for the sealant layer is attached and dried. Thereafter, the resin film for the sealant layer corresponding to the temporary fixing part of the release paper is cut along with the adhesive and the release paper using a roll knife or the like to form an opening 15.

As another formation method, before attaching the resin film for a sealant layer to the heat-resistant gas barrier layer 21, a through-hole as an opening 15 is formed in the film, and the resin film for a sealant layer having the opening is formed into the heat-resistant gas barrier layer. (21) A method of attaching through an adhesive (another forming method) is also considered. However, in these other forming methods, it is difficult to apply the adhesive evenly and it is difficult to accurately attach the resin film for the sealant layer having openings with high precision. Therefore, in the first modification, 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 is formed. Since the opening 15 through which the heat-resistant gas barrier layer 21 is exposed is formed in the portion corresponding to the solid battery body 5 in ), the heat generated from the solid battery body 5 is transmitted through the sealant layer 13. Heat is dissipated by being transmitted to the metal foil layer 12 through the heat-resistant gas barrier layer 21 without being blocked. Therefore, sufficient cooling properties can be secured, and malfunctions due to high temperatures can be reliably prevented.

In addition, in the all-solid-state battery of the first modification, the sealant layer 13 does not exist between the solid battery body 5 and the metal foil layer 12, but a heat-resistant gas barrier layer 21 with insulation is provided therebetween. Because of this arrangement, insulation can be reliably secured by the heat-resistant gas barrier 21.

In addition, in the all-solid-state battery of the first modification, since the sealant layer 13 is not formed in the portion of the packaging material 1 corresponding to the solid battery body 5, it is difficult to accommodate the solid battery body 5 to that extent. The space for this can be made larger (thicker). Therefore, in the all-solid-state battery of this embodiment, compared to a conventional all-solid-state battery, a large-sized solid-state battery body 5 can be accommodated without changing the external dimensions of the casing (exterior material 1), While reducing the thickness, it is possible to achieve higher output and higher capacity.

Figure 5 is a schematic cross-sectional view showing an all-solid-state battery, which is a second modification of the present 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 disposed on the outermost side, and a metal foil layer 12 laminated on the inner side of the base layer 11. and a heat-resistant gas barrier layer 21 as an insulating layer laminated on the inner surface of the metal foil layer 12, and a sealant layer 13 laminated on the inner surface of the heat-resistant gas barrier layer 21. Additionally, a vapor deposition film (deposited layer) 22 is provided between the heat-resistant gas barrier layer 21 and the sealant layer 13.

In the second modification, as the exterior material 1, exterior materials 1a to 1c having the first to third three 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 layer 11 to the outer surface of the metal foil for the metal foil layer 12 through an adhesive, and On the inner surface, a resin film for the heat-resistant gas barrier layer 21 is laminated and bonded to the inner surface of the heat-resistant gas barrier layer 21, and a vapor-deposited film 22 is deposited on the inner surface of the heat-resistant gas barrier layer 21. ) A sealant layer 13 of heat-sealable resin is laminated and bonded to the inner surface of the evaporation surface through an adhesive layer 4.

In addition, as shown in FIG. 6B, compared to the first exterior material 1a, the second exterior material 1b does not have a deposition film formed on the inner surface of the heat-resistant gas barrier layer 21, and a deposited film is formed on the outer surface of the sealant layer 13. The deposited film 22 is formed, and the deposited 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.

Also, as shown in FIG. 6C, the third exterior material 1c has vapor-deposited films 22 and 22 formed on the inner surface of the heat-resistant gas barrier layer 21 and the outer surface of the sealant layer 13, and the heat-resistant gas barrier layer The deposition surface (inner surface) of (21) and the deposition surface (outer surface) of the sealant layer (13) are bonded through the adhesive layer (4).

In the second modification, as the adhesive constituting the adhesive layer 4 for bonding between the heat-resistant gas barrier layer 21 and the sealant layer 13, a curing type such as a two-component 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 appropriately used. Additionally, 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 addition, in the second modification, an acid-modified polyolefin-based adhesive having good adhesion to the vapor deposition film 22 is used as the adhesive for the adhesive layer 4, thereby forming a bond between the heat-resistant gas barrier layer 21 and the sealant layer 13. can be firmly adhered to each other, and the occurrence of delamination during molding can be effectively prevented.

In addition, in the second modification, as an adhesive for bonding between the base layer 11 and the metal foil layer 12 and between the metal foil layer 12 and the heat-resistant gas barrier layer 21, the adhesive of the adhesive layer 4 The same adhesive can be used appropriately, and it is desirable to set it to the same thickness.

Additionally, in the second modification, the vapor deposition 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 made of inorganic materials such as aluminum, titanium, silicon, alumina, silica, zinc oxide, etc. Among inorganic oxides and metal fluorides such as aluminum fluoride and magnesium fluoride, at least one type can be adopted.

In the second modification example, the gas barrier property can be further improved by forming the vapor deposition film 22. For this reason, it is possible to prevent the intrusion of external air and the generation of hydrogen sulfide gas itself, which is generated by the reaction between moisture in the external air and the solid electrolyte of the solid battery main body 5, and also prevent the generation of hydrogen sulfide gas itself even if hydrogen sulfide gas is generated. , the gas barrier properties of the deposited film 22 can reliably prevent hydrogen sulfide gas from leaking to the outside.

In the second modification, the thickness of the deposited film 22 is preferably set to 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 secured more reliably. In other words, if the thickness of the deposited film 22 is too thin, good gas barrier properties cannot be obtained and this is not desirable. Even if the thickness of the deposition film 22 is formed thicker than necessary, not only can an appropriate effect not be obtained, but it also requires a lot of time to form the thick deposition film 22, which may lead to a decrease in production efficiency. Not desirable.

In the second modification, the deposited film 22 can be formed by depositing and coating by dry coating. As dry coating, known methods such as CVD method and PVD method (sputtering method, ion beam method, etc.) can be adopted.

Other configurations of the all-solid-state battery of this 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 vapor deposition film 22 is provided between the heat-resistant gas barrier layer 21 and the sealant layer 13 in the exterior material 1, the vapor deposition film 22 Sufficient gas barrier properties can be obtained through this. For this reason, it is possible to prevent the intrusion of external air, and prevent the generation of hydrogen sulfide gas itself, which is generated by the reaction between moisture in the external air and the solid electrolyte of the solid battery body 5, and also prevent the generation of hydrogen sulfide gas itself even if hydrogen sulfide gas is generated. , the gas barrier properties of the deposited film 22 can reliably prevent hydrogen sulfide gas from leaking to the outside.

In addition, in the second modification, since the adhesive layer 4 is provided between the heat-resistant gas barrier layer 21 and the sealant layer 13, the inner surface of the heat-resistant gas barrier layer 21 and the sealant layer 13 Even if the vapor deposition film 22 is formed on the outer surface, the heat-resistant gas barrier layer 21 and the sealant layer 13 can be tightly fixed and the occurrence of delamination can be prevented.

Additionally, in the second modification example, when forming the vapor deposition film 22 on the sealant layer 13 side as in the case of the second and third exterior materials 1b and 1c, the gas barrier vapor deposition film 22 is formed on the inner side (solid battery). Since it can be placed on the main body 5 side, the barrier property against moisture can be further improved.

In addition, in the second modification example, when forming the vapor deposition film 22 on the heat-resistant gas barrier layer 21 side as in the first and third exterior materials 1a and 1c, when the sealant layer 13 is heat-sealed, Due to the heat shielding effect of the adhesive layer 4, it is difficult for the vapor-deposited film 22 to be destroyed by heat, and the gas barrier property of the vapor-deposited film 22 can be reliably secured.

Example

(1) First embodiment

[Table 1]

<Example 1a>

(1-1) Production of exterior materials

After applying a chemical treatment liquid consisting of phosphoric acid, polyacrylic acid (acrylic resin), chromium (III) salt compound, water, and alcohol to both sides of an aluminum foil (A8021-O) with a thickness of 40 μm as the metal foil layer 12, Drying was performed at 180°C to form a chemical conversion film. The chromium adhesion amount of this chemical conversion film was 10 mg/m2 per side.

Next, a two-component curing type urethane-based adhesive (3 μm) is applied to one surface (outer surface) of the chemically treated aluminum foil (metal foil layer 12) to form a biaxial layer with a thickness of 15 μm as a base material layer 11. Stretched 6 nylon (ONY-6) film was dry laminated (laminated).

As shown in Table 1, as the heat-resistant gas barrier resin layer 21, a 9 μm thick PET film was applied to the other side (inner surface) of the dry laminated aluminum foil with a two-component curing type urethane-based adhesive (3 μm). ) was met through.

Next, as shown in Table 1, as the sealant layer 13, a 20㎛ thick CPP film containing a lubricant (erucic acid amide, etc.) was laminated through a two-component curing type urethane-based adhesive (3㎛). The outer surface of the PET film (heat-resistant gas barrier layer 21) is overlaid on the inner surface of the PET film (heat-resistant gas barrier layer 21), sandwiched between a rubber nip roll and a laminate roll heated to 100°C, and then dry laminated by compression to form the exterior material 1. A laminate was obtained.

Next, this laminate was wound on 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, etc. of resin film

The hydrogen sulfide (H ₂ S) gas permeability of the PET film (heat-resistant gas barrier layer 21) and the CPP film (sealant layer 13) used to produce the exterior material sample of Example 1a was measured in accordance with JIS K7126-1. , Additionally, the water vapor gas permeability of the PET film was measured based on JIS K7129-1 (humidity sensor method 40°C 90% Rh). The results are also shown in Table 1.

(1-3) Measurement of residual rate

After cutting out two pieces of the exterior material sample of Example 1a with a size of 15 mm in width Using (TP-701-A), heat sealing (thermal bonding) was performed by heating on one side under the conditions of heat seal temperature: 200°C, actual pressure: 0.2 MPa (gauge display pressure), and actual time: 2 seconds. A sample for measuring the residual rate of Example 1a was obtained.

In this sample for measurement of residual ratio, the seal portion was hardened with resin, cut to reveal a cross section, and the cross section was observed with SEM to determine the thicknesses of the heat-resistant gas barrier layer 21, the sealant layer 13, etc.

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

(1-4) Measurement of yarn strength

[Table 2]

After cutting out two pieces of the exterior material sample of Example 1a with a size of 15 mm in width Using (TP-701-A), heat sealing (thermal bonding) was performed by heating on one side under the conditions of heat seal temperature: 200°C, actual pressure: 0.2 MPa (gauge display pressure), and actual time: 2 seconds. A sample for evaluating the yarn strength of Example 1a was obtained.

Regarding this sample for yarn strength evaluation, in accordance with JIS Z0238-1998, using a Strograph (AGS-5kNX) manufactured by Shimadzu Access, the sample for yarn strength evaluation was stretched between the inner sealant layers of the yarn portion at a tensile speed of 100 mm/mm. The peeling strength when peeled in a T shape was measured, and this was taken as the thread strength (N/15 mm width). The results are shown in Table 2.

(1-5) Measurement of insulation resistance value (evaluation of insulation)

As shown in FIGS. 7 and 8, the exterior material sample 1 of Example 1a was cut into two pieces measuring 100 mm long and 50 mm wide. These pairs of exterior material samples 1, 1 were overlapped so that their sealant layers 13 were opposed to each other and were in contact. Meanwhile, a tab lead 3 made of aluminum foil with a width of 10 mm and a thickness of 100 μm was disposed on both sides of the tab film 31 made of an acid-modified polypropylene film with a thickness of 50 μm, and the pair of exterior material samples were placed. It was arranged to fit between (1, 1). At this time, a part of the tab lead 3 is disposed between the pair of exterior material samples 1, 1, and the remaining part is arranged to be drawn outward from the edge of the pair of exterior material samples 1, 1. did. This non-bonded sample was heat-sealed with a double-sided heating type heat sealer on both the top and bottom sides of the exterior material sample (1, 1) for 2 seconds under the conditions of a seal width of 5 mm, 200°C, and 0.2 MPa, and the insulation properties were obtained. Samples for evaluation were obtained.

In addition, in the top view of the sample for insulation evaluation in FIG. 7, in order to facilitate understanding of the invention, the thermal bonding portion (heat seal portion) 131 is hatched with a diagonal line. In addition, in the cross-sectional view of the sample for insulation evaluation in FIG. 8, description of the heat-resistant gas barrier layer 13 is omitted to make the structure easier to understand.

Subsequently, as shown in FIG. 7, at the longitudinal end of the insulation evaluation sample, a portion of the resin as the base material layer 11 is peeled off to partially expose the aluminum foil as the metal foil layer 12, and the exposed portion 121 is formed. , 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 connected to After contacting the tab lead 3 to form a circuit, voltage was applied between the metal foil layer 12 and the tab lead 3 in the circuit under the conditions of 25 V and 5 seconds, and the resistance value was measured to determine 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 aluminum foil, a copper foil-shaped exterior material sample 1 of Example 1a was produced in the same manner as above using copper foil (Cu foil) with a thickness of 9 μm.

This copper foil-shaped exterior material sample was cut into two pieces with a size of 30 mm Seal the 3 sides of (1, 1) under the conditions of heat seal temperature: 200℃, seal pressure: 0.2 MPa (gauge display pressure), seal time: 2 seconds to create a 3-way pocket (3 flaps).袋) was produced. After that, a needle is inserted between the exterior material samples (1, 1) at one side (side of 30 mm), which is the opening of the three-way pocket, and the opening is sealed (sealed) under the same sealing conditions as above, and the needle is discharged from the needle. Enclose 0.1 MPa of H ₂ S gas (the needle is inserted from a side of 30 mm).

Once the gas was encapsulated, the needle was pulled out slightly to prevent the gas from escaping, and the inside of the tip of the needle was heat-sealed again under the same seal conditions to completely encapsulate the gas. After that, the needle was removed to create a gas encapsulation bag.

After the gas-sealed bag was left standing in a constant temperature bath at 40°C for 7 days, the gas was degassed, the sealed portion was removed, and the interior was observed. Based on the observation, those in which no change was observed in the Cu foil were evaluated as “○”, and those in which discoloration was observed in the sealing portion etc. were evaluated as “×”. The results are also shown in Table 2.

<Example 2a>

A sample of Example 2a was produced in the same manner as 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. and performed the same measurement (evaluation). The results are shown in Table 1 and Table 2.

<Example 3a>

A sample of Example 3a was produced in the same manner as Example 1a except that a PET film with 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 shown in Table 1 and Table 2.

<Example 4a>

A sample of Example 4a was produced in the same manner as Example 1a except that a PET film with 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 shown in Table 1 and Table 2.

<Example 5a>

A sample of Example 5a was produced in the same manner as Example 1a above except that a film with 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 shown in Table 1 and Table 2.

<Example 6a>

A sample of Example 6a was produced in the same manner as Example 1a except that a film with 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 shown in Table 1 and Table 2.

<Example 7a>

A sample of Example 7a was produced in the same manner as Example 1a except that a film with 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 shown in Table 1 and Table 2.

<Example 8a>

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

<Example 9a>

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

<Example 10a>

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

<Example 11a>

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

<Example 12a>

A sample of Example 12a was produced in the same manner as 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. and performed the same measurement (evaluation). The results are shown in Table 1 and Table 2.

<Comparative example 1a>

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

<Comparative example 2a>

A sample of Comparative Example 2a was produced in the same manner as Example 1a except that the heat-resistant gas barrier layer 21 was not formed and a CPP film with a thickness of 25 μm was used as the sealant layer 13, and the same measurement (evaluation) was performed. was done. The results are shown in Table 1 and Table 2.

<Comparative Example 3a>

A sample of Comparative Example 3a was produced in the same manner as Example 1a except that an OPP film with 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 shown in Table 1 and Table 2.

<General review of the first embodiment>

As is clear from Table 2, the exterior material samples of Examples 1a to 12a according to the present invention were able to obtain excellent results in all evaluations of insulation and gas permeation.

On the other hand, the exterior material samples of Comparative Examples 1a to 3a, which deviated from the gist of the present invention, did not yield good results in the evaluation of gas permeation, and good results were not obtained in some cases in the evaluation of insulation.

(2) Second embodiment

[Table 3]

<Example 1b>

(2-1) Production of exterior materials

After applying a chemical treatment liquid consisting of phosphoric acid, polyacrylic acid (acrylic resin), chromium (III) salt compound, water, and alcohol to both sides of an aluminum foil (A8021-O) with a thickness of 40 μm as the metal foil layer 12, Drying was performed at 180°C to form a chemical conversion film. The chromium adhesion amount of this chemical conversion film was 10 mg/m2 per side.

Next, a two-component curing type urethane-based adhesive (3 μm) is applied to one surface (outer surface) of the chemically treated aluminum foil (metal foil layer 12) to form a biaxial layer with a thickness of 15 μm as a base material layer 11. Stretched 6 nylon film was dry laminated (laminated).

As shown in Table 3 below, as the heat-resistant gas barrier layer 21, a stretched film (ONY-6 film) made of PA6 with a thickness of 9 μm, a melting point of 225° C., a dielectric breakdown voltage of 19 kV/mm, and a hydrothermal shrinkage rate of 5%. was prepared, and a vapor-deposited film of aluminum with a thickness of 20 nm was formed on one side of it. The non-deposited side of the ONY-6 film with the vapor-deposited film was bonded to the other side (inner surface) of the dry-laminated aluminum foil through a two-component curing type urethane-based adhesive (3 μm).

As shown in Table 3, as the sealant layer 13, a CPP film with a thickness of 20 μm and a melting point of 150°C containing a lubricant (erucic acid amide, etc.) is mixed with a two-component curing type urethane-based adhesive (3 μm). By overlapping the deposition surface (inner surface) of the dry laminated ONY-6 film (heat-resistant gas barrier layer 21) and sandwiching it between a rubber nip roll and a laminate roll heated to 100° C. Dry lamination was performed to obtain a laminate constituting the exterior material 1.

Next, this laminate was wound on 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

In the resin film constituting the heat-resistant gas barrier layer 21 in Example 1b, the dielectric breakdown voltage was measured in the state before forming the vapor deposition film, based on JIS C2151. The results are also shown in Table 3.

(2-3) Measurement of thermal shrinkage rate

A test piece with a size of 10 cm The rate of dimensional change in the stretching direction was obtained from the following equation.

Thermal shrinkage rate (%)={(X-Y)/X}×100

In this formula, “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.

(2-4) Measurement of yarn strength

[Table 4]

In the exterior material sample of Example 1b, the yarn strength was measured in the same manner as (1-4) above. The results are shown in Table 4.

(2-5) Measurement of residual rate

In the exterior material sample of Example 1b, the residual rate was measured in the same manner as (1-3) above. The results are shown in Table 4.

(2-6) Measurement of insulation resistance value (evaluation of insulation)

In the exterior material sample of Example 1b, the insulation resistance value was measured in the same manner as in (1-5) above. The results are shown in 4.

(2-7) Evaluation of formability

The exterior material sample of Example 1b was cut into a size of 100 mm x 100 mm to obtain a sample for evaluating formability. For this sample for moldability evaluation, a deep drawing molding test was performed using a mold for deep drawing molding attached to a 25t press machine and changing the molding height (drawing depth) in 0.5 mm units.

Also, if the desired moldability was obtained even if the molding height was 7 mm or more, it was evaluated as "◎". If the mold height was 7 mm or more, the desired moldability could not be obtained, but the mold height was within the range of 5 mm or more and less than 7 mm. When moldability was obtained, it was evaluated as “○”, and when the desired formability was not obtained at less than 5 mm, it was evaluated as “×”. The results are also shown in Table 4.

(2-8) Evaluation of H ₂ S gas permeation of ONY-6 film with deposited film

For the ONY-6 film with a vapor-deposited film used in the exterior material sample of Example 1b, the permeability of H ₂ S gas was measured in accordance with JIS K7126. 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 according to the present invention were able to obtain excellent results in all evaluations.

In contrast, the exterior material samples of Comparative Examples 1b to 3b, which deviated from the gist of the present invention, could not obtain good results in any of the evaluations.

(3) Third embodiment

[Table 5]

<Example 1c>

(3-1) Production of exterior materials

After applying a chemical treatment liquid consisting of phosphoric acid, polyacrylic acid (acrylic resin), chromium (III) salt compound, water, and alcohol to both sides of an aluminum foil (A8021-O) with a thickness of 40 μm as the metal foil layer 12, Drying was performed at 180°C to form a chemical conversion film. The chromium adhesion amount of this chemical conversion film was 10 mg/m2 per side.

Next, a two-component curing type urethane-based adhesive (3 μm) is applied to one surface (outer surface) of the chemically treated aluminum foil (metal foil layer 12) to form a biaxial layer with a thickness of 15 μm as a base material layer 11. Stretched 6 nylon (ONY-6) film was dry laminated (laminated).

As shown in Table 1 below, a two-component curing type urethane-based adhesive (3 μm) is applied to the other side (inner surface) of the aluminum foil after dry lamination to form a heat-resistant gas barrier layer 21 with a thickness of 9 μm. PET film was dry laminated.

Next, a two-component curing type urethane-based adhesive (3 μm) as the adhesive layer 4 was gravure-coated on the inner surface of the PET film as the heat-resistant gas barrier layer 21. At this time, the adhesive was not applied to the square-shaped part that was the area where the opening was scheduled to be formed, but was treated as an adhesive-uncoated area, and the adhesive was applied only to the outer peripheral part of the opening formation area (heat seal portion: the remaining portion of the sealant layer).

Next, as the sealant layer 13, a CPP film with a thickness of 40 μm containing a lubricant (erucic acid amide, etc.) is overlapped on the inner surface of the heat-resistant gas barrier layer 21 on which the adhesive is applied only to the required portion, Dry lamination was performed by sandwiching and pressing a rubber nip roll between a laminate roll heated to 100°C to obtain a laminate constituting the exterior material 1.

Next, this laminate is wound on a roll shaft, and then aged at 40°C for 10 days. The aged laminate is cut into a CPP film for the sealant layer using a laser cutter along the outer peripheral edge of the adhesive uncoated area. was cut, and an opening 15 was formed in the middle portion of the sealant layer 13 to obtain an exterior material sample of Example 1c. Additionally, in this exterior material sample, the heat-resistant gas barrier layer 21 is disposed to be exposed on the inner side through the opening 15.

(3-2) Measurement of water vapor transmission rate

For the resin film for the heat-resistant gas barrier layer 21 used when producing the exterior material sample of Example 1c, the water vapor transmission rate was measured in accordance with JIS K7129-1 (humidity sensor method 40°C 90% Rh). The results are also shown in Table 5.

(3-3) Measurement of thermal conductivity

The thermal conductivity of the resin film for the heat-resistant gas barrier layer 21 used when producing the exterior material sample of Example 1c was measured by the normal heat flow meter method (HFM method). The results are also shown in Table 5.

(3-4) Measurement of H ₂ S gas permeability of resin film, etc.

For the resin film for the heat-resistant gas barrier layer 21 used when producing the exterior material sample of Example 1c, hydrogen sulfide (H ₂ S) gas permeability was measured in accordance with JIS K7126-1. The results are also shown in Table 5.

(3-5) Evaluation of cooling performance (cooling effect)

Two samples of the exterior material of Example 1c measuring 100 mm × 100 mm were prepared. Additionally, the opening 15 in this exterior material sample was square and had a size of 60 mm x 60 mm.

These two exterior material samples are overlapped face to face so that the opening 15 side is on the inside, and the two overlapped exterior material samples are hit with a width of 5 mm at a position 10 mm from the edge on three of the four surrounding sides. A three-way pocket was created by threading.

In a temperature environment of room temperature (25°C), 80°C hot water is injected from the opening into the three-way bag, a thermometer is inserted, the opening is closed with a bulldog clip, and the temperature change of the hot water is measured for 3 minutes. Measured. The measurement results show the temperature immediately after hot water injection and the temperature after 3 minutes in Table 5.

<Example 2c>

A sample of Example 2c was produced in the same manner as Example 1c above except that 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 produced in the same manner as Example 1c above 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>

The sample of Comparative Example 1c was prepared in the same manner as Example 1c except that the sealant layer 13 was formed on the entire inner surface of the heat-resistant gas barrier layer 21, that is, the opening 15 was not formed in the sealant layer 13. was produced and the same measurement (evaluation) was performed. The results are also shown in Table 5.

<Comparative example 2c>

A sample of Comparative Example 2c was produced in the same manner as Comparative Example 1c above except that 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 produced in the same manner as Comparative Example 1c above, 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.

<General evaluation of the third embodiment>

As is clear from Table 5, the exterior material samples of Examples 1c to 3c according to the present invention had excellent cooling properties (cooling effect).

In contrast, the exterior material samples of Comparative Examples 1c to 3c, which deviated from the gist of the present invention, could not obtain high cooling performance.

(4) Fourth embodiment

[Table 6]

<Example 1d>

1. Production of exterior materials

After applying a chemical treatment liquid consisting of phosphoric acid, polyacrylic acid (acrylic resin), chromium (III) salt compound, water, and alcohol to both sides of an aluminum foil (A8021-O) with a thickness of 40 μm as the metal foil layer 12, Drying was performed at 180°C to form a chemical conversion film. The chromium adhesion amount of this chemical conversion film was 10 mg/m2 per side.

Next, a two-component curing type urethane-based adhesive (3 μm) is applied to one surface (outer surface) of the chemically treated aluminum foil (metal foil layer 12) to form a biaxial layer with a thickness of 15 μm as a base material layer 11. Stretched 6 nylon (ONY-6) film was dry laminated (laminated).

As shown in Table 6, an OPP film with a thickness of 9 μm is applied as the insulating layer 21 through a two-component curing urethane adhesive with a thickness of 3 μm on the other side (inner surface) of the aluminum foil after dry lamination. (Biaxially stretched polypropylene film) was glued together.

Next, as the sealant layer 13, a CPP film with a thickness of 40 μm containing 1000 ppm of erucic acid amide as a lubricant was prepared, and a vapor-deposited aluminum film with a thickness of 20 nm was formed on one side (outer surface) of the film. The deposition surface (outer surface) of the CPP film with the vapor deposition film is overlapped with the inner surface of the CPP film of the insulating layer 21 through a maleic acid-modified polypropylene adhesive (MAPP) with a thickness of 2 μm as the adhesive layer 4. , dry lamination was performed by sandwiching and pressing between a rubber nip roll and a laminate roll heated to 100°C to obtain a laminate constituting the exterior material 1.

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

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

(4-2) Measurement of yarn strength

[Table 7]

In the exterior material sample of Example 1d, the yarn strength was measured in the same manner as (1-4) above. The results are shown in Table 7.

(4-3) Evaluation of water vapor (moisture) permeability of exterior materials

The exterior material sample of Example 1d was cut into two pieces with a size of 30 mm A three-way bag was produced by sealing three sides (three sides) of (1, 1) under the conditions of heat seal temperature: 200°C, seal pressure: 0.2 MPa (gauge display pressure), and seal time: 2 seconds. Subsequently, “Mc(g)” of calcium chloride was added to the three-chambered bag (target: 3g), and then the opening of the three-chambered bag was sealed under the same seal conditions as above.

Then, the weight "M0(g)" immediately after bagging was measured with an electronic balance, left in a constant temperature and humidity chamber at 80°C amount of increase) was confirmed based on the following relational formula. The results are also shown in Table 7.

Weight change (%)=(M1-M0)/Mc

(4-4) Evaluation of formability

For the exterior material sample of Example 1d, formability was evaluated in the same manner as (2-7) above. The results are also shown in Table 7.

(4-5) Evaluation of H ₂ S gas permeation of exterior material

In the exterior material sample of Example 1d, H ₂ S gas permeability was evaluated in the same manner as (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 ONY-6 film with a thickness of 9 μm was used as the insulating layer 21 and a two-component curing urethane adhesive (PU) with a thickness of 2 μm was used as the adhesive. 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, an ONY-6 film with a thickness of 9 μm was used as the insulating layer 21 and a two-component curing type urethane adhesive (PU) with a thickness of 2 μm was used as the adhesive, and the thickness of the deposited film 22 was A sample of Example 3d was produced in the same manner as Example 1d above except that the thickness was set to 5 nm, 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 Example 1d except that the thickness of the deposited film 22 was 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 Example 1d except that the thickness of the deposited film 22 was 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 Example 1d except that the thickness of the deposited film 22 was 1200 nm, and the same measurement (evaluation) was performed. The results are also shown in Table 7.

<Example 7d>

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

<Example 8d>

As shown in Table 6, a vapor-deposited film 22 of aluminum with a thickness of 20 nm was formed on the inner surface of the OPP film for the insulating layer 21, and a two-component curing type urethane adhesive (PU) with a thickness of 2 μm was used as an adhesive. A sample of Example 8d was produced in the same manner as Example 1d except that no vapor deposition 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 Example 8d except that 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 Example 8d except that the thickness of the deposited film 22 was 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 Example 8d except that the thickness of the deposited film 22 was 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 produced in the same manner as Example 1d except that an aluminum vapor deposition film 22 with a thickness of 20 nm was formed on the inner surface of the OPP film for the insulating layer 21. and performed the same measurement (evaluation). The results are also shown in Table 7.

<Example 13d>

As shown in Table 6, a vapor-deposited film 22 of aluminum with a thickness of 20 nm was formed on the inner surface of an ONY-6 film with a thickness of 9 μm as an insulating layer 21, and a two-component curing type urethane with a thickness of 2 μm was formed as an adhesive. A sample of Example 13d was produced in the same manner as Example 1d except for using an adhesive (PU), and the same measurement (evaluation) was performed. The results are also shown in Table 7.

<Comparative example 1d>

As shown in Table 6, the sample of Comparative Example 1 was prepared in the same manner as Example 1d, except that the vapor deposition film 22 was not formed at all and acid-modified polypropylene (acid-modified PP) with a thickness of 2 μm was used as an adhesive. was produced and the same measurement (evaluation) was performed. The results are also shown in Table 7.

<Comparative example 2d>

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

<General evaluation of the fourth embodiment>

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

In contrast, the exterior material samples of Comparative Examples 1d and 2d, which deviated from the gist of the present invention, could not obtain good results in any of the evaluations.

(5) Fifth embodiment

[Table 8]

<Example 1e>

(5-1) Production of exterior materials

In the same manner as Example 1a, an exterior material sample of Example 1e was obtained.

2. Measurement of Young's modulus, tensile strength at break and tensile elongation at break

For the PET film (heat-resistant gas barrier layer 21) used when producing the exterior material sample of Example 1e, Young's modulus, tensile strength at break, and tensile elongation at break at 90°C for both MD and TD in accordance with JIS K7127-1999. were measured respectively. That is, the PET film for the heat-resistant gas barrier layer was cut into a size of 15 mm in width x 100 mm in length to produce a test piece, and the test piece was subjected to a 90°C atmosphere using a Strograph (AGS-5kNX) manufactured by Shimadzu Corporation. 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 PET film for the heat-resistant gas barrier layer of Example 1e, the Young's modulus was 3.6 GPa in MD and 3.2 GPa in TD, the tensile breaking strength was 190 MPa in MD and 210 MPa in TD, and the tensile strength at break was 190 MPa in MD and 210 MPa in TD. The elongation at break is 120% in MD and 110% in TD.

(5-3) Evaluation of high temperature stone magnetism

The puncture strength of the exterior material sample of Example 1e was measured under a 90°C atmosphere in accordance with JIS Z1707:1997. The measurement method (impact strength test method) is as follows.

An exterior material sample of a predetermined size was fixed as a test piece, a semicircular needle with a diameter of 1.0 mm and a tip radius of 0.5 mm was pierced at a speed of 50 ± 5 mm per minute, and the maximum stress until the needle penetrated 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

For the exterior material sample of Example 1e, formability was evaluated in the same manner as in (2-7) above. The results are also shown in Table 8.

(5-5) Measurement of yarn strength

In the exterior material sample of Example 1e, the yarn strength was measured in the same manner as (1-4) above. The results are also shown in Table 8.

<Example 2e>

The heat-resistant gas barrier layer 21 has a Young's modulus of MD: 1.5 GPa and TD: 1.2 GPa, a tensile strength at break of MD: 210 MPa and TD: 240 MPa, and a tensile elongation at break of MD: 140% and TD: 120%. A sample of Example 2e was produced in the same manner as Example 1e except that an axially stretched 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 produced in the same manner as Example 2e except that a film with 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 produced in the same manner as Example 2e except that a film with 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>

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

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

<Example 6e>

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

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

<General evaluation of the fifth embodiment>

As is clear from Table 8, the exterior material samples of Examples 1e to 8e according to the present invention are excellent in magnetic resistance at 90°C and are thought to be unlikely to cause defects such as breakage in a high temperature environment.

On the other hand, the exterior material sample of Comparative Example 1, which deviates from the gist of the present invention, is inferior to the magnetic resistance at 90°C, and it is thought that defective parts such as breakage are more likely to occur in a high temperature environment compared to those of Examples 1e to 8e. .

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, and Japanese Patent Application No. 2021-132355 filed on August 16, 2021. Patent Application No. 2021-132360, Japanese Patent Application No. 2021-132362 filed on August 16, 2021, and Japanese Patent Application No. 2021-132728 filed on August 17, 2021. and the disclosed content constitutes a part of the present application.

The terms and expressions used herein are for the purpose of description and are not to be construed as limiting, nor are they intended to exclude any equivalents of the features shown and stated herein, and are intended to cover a variety of issues within the claimed scope of the invention. It should be recognized that transformation is also allowed.

[Industrial applicability]

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

1, 1a, 1b, 1c: exterior material
11: Base layer
12: Metal foil layer
13: Sealant layer
15: opening
21: Heat-resistant gas barrier layer
22: deposition film
4: Adhesive layer
5: Solid battery body

Claims (22)

An exterior material for an all-solid-state battery for encapsulating a solid-state battery body, comprising a base material layer, a metal foil layer laminated on the inner surface of the base layer, and a sealant layer laminated on the inner surface of the metal foil layer,
An exterior material for an all-solid-state battery, characterized in that a heat-resistant gas barrier layer made of resin is provided between the metal foil layer and the sealant layer. According to paragraph 1,
The heat-resistant gas barrier layer is an exterior material for an all-solid-state battery, characterized in that the hydrogen sulfide gas permeability measured in accordance with JIS K7126-1 is set to 15{cc·mm/(㎡·D·MPa)} or less. According to paragraph 2,
The original thickness of the resin constituting the heat-resistant gas barrier layer is set to “da0”, and the thickness when pressurized under the conditions of 200°C, 0.2 MPa, and 5 sec is set to “da1”.
1≥da1/da0≥0.9
An exterior material for an all-solid-state battery, characterized in that it is configured to satisfy the relational expression of . According to paragraph 2 or 3,
The exterior material for an all-solid-state battery, characterized in that the heat-resistant gas barrier layer has a thickness of 3㎛ to 50㎛. According to any one of claims 2 to 4,
The sealant layer is an exterior material for an all-solid-state battery, wherein the sealant layer is made of a resin with a hydrogen sulfide gas permeability of 100{cc·mm/(㎡·D·MPa)} or less. According to any one of claims 2 to 5,
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, and 5 sec.
0.5≥db1/db0≥0.1
An exterior material for an all-solid-state battery, characterized in that it is configured to satisfy the relational expression of . According to any one of claims 2 to 6,
The resin constituting the heat-resistant gas barrier layer is an exterior material for an all-solid-state battery, characterized in that the water vapor gas permeability measured in accordance with JIS K7129-1 (humidity sensor method 40°C 90% Rh) is 50 (g/m2/day) or less. . According to any one of claims 1 to 7,
The heat-resistant gas barrier layer is made of an insulating resin with a melting point higher than that of the sealant layer by 20°C or more,
The heat-resistant gas barrier layer is an exterior material for an all-solid-state battery, characterized in that the breakdown voltage is 18 kV/mm or more. According to clause 8,
The exterior material for an all-solid-state battery, characterized in that the resin constituting the heat-resistant gas barrier layer has a thermal water shrinkage rate of 2% to 10%. According to clause 8 or 9,
An exterior material for an all-solid-state battery, characterized in that the resin constituting the heat-resistant gas barrier layer is polyamide. According to any one of claims 1 to 10,
An exterior material for an all-solid-state battery, 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 on the inner surface through the opening. According to clause 11,
An exterior material for an all-solid-state battery, wherein the heat-resistant gas barrier layer is made of a resin with a melting point that is 10°C or more higher than that of the sealant layer. According to claim 11 or 12,
The exterior material for an all-solid-state battery, characterized in that the resin constituting the heat-resistant gas barrier layer has a thermal conductivity of 0.2 W/m·K or more. According to paragraph 1,
A vapor deposition film is provided between the heat resistant gas barrier layer and the sealant layer,
An exterior material for an all-solid-state battery, wherein the deposited film is composed of at least one of metal, metal oxide, and metal fluoride. According to clause 14,
An exterior material for an all-solid-state battery, characterized in that the thickness of the deposited film is set to 5 nm to 1000 nm. According to claim 14 or 15,
An exterior material for an all-solid-state battery, characterized in that an adhesive layer is provided between the heat-resistant gas barrier layer and the sealant layer. According to clause 16,
An exterior material for an all-solid-state battery, characterized in that the deposition film is provided on a contact surface of the sealant layer with the adhesive layer. According to claim 16 or 17,
An exterior material for an all-solid-state battery, characterized in that the deposition film is provided on a contact surface of the heat-resistant gas barrier layer with the adhesive layer. According to any one of claims 1 to 18,
The heat-resistant gas barrier layer is an exterior material for an all-solid-state battery, characterized in that the Young's modulus at 90°C is 1 GPa or more in both MD and TD. According to clause 19,
The heat-resistant gas barrier layer is an exterior material for an all-solid-state battery, characterized in that the tensile breaking strength at 90°C is 100 MPa or more in both MD and TD. According to claim 19 or 20,
The heat-resistant gas barrier layer is an exterior material for an all-solid-state battery, characterized in that the tensile elongation at rupture at 90°C is 50% to 200% in both MD and TD. An all-solid-state battery, characterized in that the solid-state battery main body is encapsulated in the exterior material for an all-solid-state battery according to any one of claims 1 to 21.

Images