JP2023026915A - Sheath material for all-solid battery, and all-solid battery - Google Patents

Abstract

To provide a sheath material for an all-solid battery capable of continuously ensuring sufficient gas barrier properties.SOLUTION: Provided is a sheath material for an all-solid battery for sealing a solid-state battery main body 5 that comprises: a base material layer 11; a metal foil layer 12 laminated at an inner surface side of the base material layer 11; a resin insulating layer 21 laminated at an inner surface side of the metal foil layer 12; and a sealant layer 13 provided at an inner surface side of the insulating layer 21. A vapor deposition film 22 is provided between the insulating layer 21 and the sealant layer 13. The vapor deposition film 22 is configured by at least any one of metal, metal oxide, and metal fluoride.SELECTED DRAWING: Figure 1

Description

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

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

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

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

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

In such an all-solid-state battery exterior material, outside air enters and the moisture reacts with the solid electrolyte to generate hydrogen sulfide gas, which may leak out. Therefore, it is desired to ensure gas barrier properties. ing.

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

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

However, the exterior materials for all-solid-state batteries disclosed in Patent Literatures 1 and 2 have a problem that the gas barrier property is insufficient and hydrogen sulfide gas may be generated and leak. In addition, since the exterior material for an all-solid-state battery disclosed in Patent Document 3 traps gas, there is a limit to the amount of gas absorption, and it is difficult to ensure gas barrier properties continuously for a long period of time. was there. In addition, in the exterior material for an all-solid-state battery shown in Patent Document 4, when the sealant layer is heat-sealed, the vapor-deposited film layer may also be destroyed, resulting in a decrease in gas barrier properties. It is considered that there is still room for improvement in this respect.

The present invention has been made in view of the above problems, and an object of the present invention is to provide an exterior material for an all-solid-state battery and an all-solid-state battery that can ensure sufficient gas barrier properties continuously for a long period of time.

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

[1] a base material layer, a metal foil layer laminated on the inner surface side of the base material layer, a resin insulating layer laminated on the inner surface side of the metal foil layer, and provided on the inner surface side of the insulating layer An all-solid-state battery exterior material for enclosing a solid-state battery body, comprising a sealant layer coated with
A deposited film is provided between the insulating layer and the sealant layer,
An exterior material for an all-solid-state battery, wherein the vapor-deposited film is composed of at least one of a metal, a metal oxide, and a metal fluoride.

[2] The exterior material for an all-solid-state battery according to the above item 1, wherein the vapor deposition film has a thickness of 5 nm to 1000 nm.

[3] The exterior material for an all-solid-state battery according to [1] or [2] above, wherein an adhesive layer is provided between the insulating layer and the sealant layer.

[4] The exterior material for an all-solid-state battery according to [3] above, wherein the vapor-deposited film is provided on a contact surface of the sealant layer with the adhesive layer.

[5] The exterior material for an all-solid-state battery according to the above item 3 or 4, wherein the deposition film is provided on a contact surface of the insulating layer with the adhesive layer.

[6] An all-solid-state battery, wherein a solid-state battery main body is enclosed in the all-solid-state battery exterior material according to any one of the preceding items 1 to 5.

According to the exterior materials for all-solid-state batteries of the inventions [1] and [2], since the vapor deposition film is provided between the insulating layer and the sealant layer, sufficient gas barrier properties can be continuously ensured by the vapor deposition film. Therefore, it is possible to prevent the generation of hydrogen sulfide gas caused by the infiltration of moisture from the outside air, and even if the hydrogen sulfide gas is generated, it is possible to prevent the hydrogen sulfide gas from leaking to the outside due to the gas barrier properties of the deposited film. .

According to the exterior material for an all-solid-state battery of the invention [3], since an adhesive layer is provided between the insulating layer and the sealant layer, even if a vapor deposition film is formed between the insulating layer and the sealant layer, the layers can be reliably separated. It can be tightly fixed.

According to the exterior material for an all-solid-state battery of the invention [4], since the vapor-deposited film is formed on the outer surface of the sealant layer, the gas-barrier vapor-deposited film can be arranged further inside, further improving the barrier property against moisture. be able to.

According to the exterior material for an all-solid-state battery of the invention [5], since a vapor-deposited film is formed on the inner surface of the insulating layer, when the sealant layer is heat-sealed, the heat shielding effect of the adhesive layer prevents heat from Destruction of the deposited film is less likely to occur, and the gas barrier properties of the deposited film can be reliably ensured.

According to the invention [6], since it specifies an all-solid-state battery using the exterior material of the inventions [1] to [5], the same effect as above can be obtained.

FIG. 1 is a schematic cross-sectional view showing an all-solid-state battery that is an embodiment of the invention. FIG. 2A is a schematic cross-sectional view showing a first exterior material applicable to the all-solid-state battery of the embodiment. FIG. 2B is a schematic cross-sectional view showing a second exterior material applicable to the all-solid-state battery of the embodiment. FIG. 2C is a schematic cross-sectional view showing a third exterior material applicable to the all-solid-state battery of the embodiment.

FIG. 1 is a schematic cross-sectional view showing an all-solid-state battery that is an embodiment of the invention. As shown in the figure, the exterior material 1 that constitutes the casing of the all-solid-state battery of the present embodiment is composed of a laminated body such as a laminate sheet.

The exterior material 1 includes a base material layer 11 arranged on the outermost side, a metal foil layer 12 laminated on the inner surface side of the base material layer 11, and an insulating layer 21 laminated on the inner surface side of the metal foil layer 12. , and a sealant layer 13 laminated on the inner surface side of the insulating layer 21 , and an evaporated film (evaporated layer) 22 is provided between the insulating layer 21 and the sealant layer 13 .

In this embodiment, the solid battery main body 5 is encapsulated so as to be covered with the exterior material 1 to produce an all-solid battery. That is, the two rectangular exterior materials 1, 1 are superimposed one on the other with the solid battery main body 5 interposed therebetween, and the sealant layers 13, 13 at the outer peripheral edges of the two (a pair of) exterior materials 1, 1 By joining and integrating in an airtight state (sealed state) by thermal bonding (heat sealing), an all-solid-state battery is manufactured in which the solid-state battery main body 5 is housed in a bag-shaped casing made of the exterior materials 1, 1. It is a thing.

Although not shown, the all-solid-state battery of the present embodiment is provided with tab leads for extracting electricity. One end (inner end) of this tab lead is adhesively fixed to the solid battery main body 5, and the intermediate portion passes between the outer peripheral edges of the two exterior bodies 1, 1, and the other end side (outer end side) extends to the outside. arranged to be pulled out.

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

In this embodiment, as the exterior material 1, exterior materials 1a to 1c having first to third configurations can be employed.

As shown in FIG. 2A , the first exterior material 1 a has a resin film for the base material layer 11 laminated and bonded to the outer surface of the metal foil for the metal foil layer 12 via an adhesive, and the inner surface of the metal foil layer 12 . Then, a resin film for the insulating layer 21 is laminated and adhered via an adhesive, and a vapor deposition film 22 is vapor-deposited on the inner surface of the insulating layer 21, and an adhesive is applied to the vapor deposition surface, which is the inner surface of the insulating layer 21. A sealant layer 13 made of a heat-fusible resin is laminated and bonded with the layer 4 interposed therebetween.

Further, as shown in FIG. 2B, the second exterior material 1b does not have a vapor deposition film formed on the inner surface of the insulating layer 21, and the vapor deposition film 22 is formed on the outer surface of the sealant layer 13, as compared with the first exterior material 1a. , the deposition surface (outer surface) of the sealant layer 13 is adhered to the inner surface of the insulating layer 21 via the adhesive 4 .

In addition, as shown in FIG. 2C, the third exterior material 1c has vapor deposition films 22, 22 formed on both the inner surface of the insulating layer 21 and the outer surface of the sealant layer 13, and the vapor deposition surface (inner surface) of the insulating layer 21, The deposition surface (outer surface) of the sealant layer 13 is adhered via the adhesive layer 4 .

A detailed configuration of the exterior material 1 (1a to 1c) applied to the all-solid-state battery of the present embodiment will be described below.

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

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

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

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

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

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

The insulating layer (heat-resistant gas barrier layer) 21 is composed of a resin film having heat resistance and insulating properties. As the resin constituting the insulating layer 21, it is preferable to use polyamide (PA6, PA66, MXD, etc.), polyester (PET, PBT, PEN, etc.), cellophane, polyvinylidene chloride, or the like.

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

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

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

Further, in the present embodiment, as the adhesive for the adhesive layer 4, by using an acid-modified polyolefin-based adhesive having good adhesiveness to the deposited film 22, the insulating layer 21 and the sealant layer 13 can be reliably adhered to each other. , the occurrence of delamination during molding can be effectively prevented.

In this embodiment, as the adhesive for bonding between the base material layer 11 and the metal foil layer 12 and between the metal foil layer 12 and the insulating layer 21, the same adhesive as the adhesive for the adhesive layer 4 is preferably used. and preferably set to similar thicknesses.

In the present embodiment, the deposited film 22 formed on the inner surface of the heat-resistant gas barrier layer 21 and/or the outer surface of the sealant layer 13 is composed of metals such as aluminum, titanium and silicone, metal oxides such as alumina, silica and zinc oxide, At least one of metal fluorides such as aluminum fluoride and magnesium fluoride can be employed.

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

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

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

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

Further, in the present embodiment, since the adhesive layer 4 is provided between the insulating layer 21 and the sealant layer 13, even if the vapor deposition film 22 is formed on the inner surface of the insulating layer 21 or the outer surface of the sealant layer 13, the insulating layer 21 and the sealant layer 13 can be securely adhered and fixed, and the occurrence of delamination can be prevented.

Further, in this embodiment, when the vapor deposition film 22 is formed on the sealant layer 13 side as in the second and third exterior materials 1b and 1c, the gas barrier vapor deposition film 22 is positioned further inside (on the solid battery main body 5 side). Since it can be arranged in the space, the barrier property against moisture can be further improved.

Further, in the present embodiment, when the vapor deposition film 22 is formed on the insulating layer 21 side like the first and third exterior materials 1a and 1c, the adhesive layer 4 is formed when the sealant layer 13 is heat-sealed. The heat shielding effect makes it difficult for the deposited film 22 to be destroyed by heat, and the gas barrier property of the deposited film 22 can be reliably ensured.

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

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

Next, as shown in Table 1, an insulating layer 21 having a thickness of 9 μm was applied to the other surface (inner surface) of the aluminum foil after the dry lamination via a two-liquid curing type urethane adhesive having a thickness of 3 μm. An OPP film (biaxially oriented polypropylene film) was laminated.

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

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

In Table 1, the values in parentheses indicate the thickness of each layer, and the unit is μm.

2. Seal strength measurement

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

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

3. Evaluation of Water Vapor (Moisture) Permeability of Exterior Material Two exterior material samples of Example 1 were cut into a size of 30 mm×50 mm, and these pair of exterior material samples 1, 1 were superimposed with the sealant layers 13 facing each other. , The three sides (three sides) of the superimposed exterior material samples 1 and 1 were sealed under the following sealing conditions: heat sealing temperature: 200 ° C., sealing pressure: 0.2 MPa (gauge display pressure), sealing time: 2 seconds 3 A square bag was made. Subsequently, "Mc (g)" of calcium chloride was added to the three-sided bag (3 g as a guideline), and then the opening of the three-sided bag was sealed under the same sealing conditions as above.

Then, the weight "M0 (g)" immediately after sealing was measured with an electronic balance, and after standing in a constant temperature and humidity chamber of 80 ° C. × 90% Rh for 7 days, the weight "M1 (g)" after processing. was measured and the weight change (increased amount) was confirmed based on the following relational expression. The results are also shown in Table 2.

Weight change (%) = (M1-M0) / Mc
4. Evaluation of Formability The exterior material sample of Example 1 was cut into a size of 100 mm×100 mm to obtain a sample for formability evaluation. A deep drawing test was performed on this formability evaluation sample using a deep drawing mold attached to a 25t press machine while changing the forming height (drawing depth) in increments of 0.5 mm. .

When the desired moldability was obtained even when the molding height was 7 mm or more, it was evaluated as "◎". When the moldability was obtained, it was evaluated as "O", and when it was less than 5 mm and the predetermined moldability was not obtained, it was evaluated as "X". The results are also shown in Table 2.

5. Evaluation of H ₂ S Gas Permeability of Exterior Material Instead of the aluminum foil, a copper foil type exterior material sample 1 of Example 1 was produced in the same manner as described above using a copper foil (Cu foil) having a thickness of 9 μm.

This copper foil-type exterior material sample was cut into two sheets of a size of 30 mm × 50 mm, and these pair of exterior material samples 1, 1 were superimposed with the sealant layers 13 facing each other, and the superimposed exterior material sample Three sides (three sides) of 1 and 1 were sealed under the following sealing conditions: heat sealing temperature: 200°C, sealing pressure: 0.2 MPa (gauge display pressure), sealing time: 2 seconds to prepare a three-sided bag. After that, at one side (30 mm side) that is the opening of the three-sided bag, the injection needle is sandwiched between the outer packaging material samples 1 and 1, and the opening is sealed under the same sealing conditions as above, 0.1 MPa of H ₂ S gas is sealed from the injection needle (the injection needle is sandwiched between 30 mm sides).

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

After the gas-filled bag was allowed to stand still in a constant temperature bath at 40° C. for 7 days, the gas was removed, the sealed portion was peeled off, and the inside was observed. According to 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 and the like were evaluated as "X". The results are also shown in Table 2.

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

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

<Example 4>
As shown in Table 1, a sample of Example 4 was prepared in the same manner as in Example 1 except that the thickness of the deposited film 22 was set to 500 nm, and the same measurement (evaluation) was performed. The results are also shown in Table 2.

<Example 5>
As shown in Table 1, a sample of Example 5 was prepared in the same manner as in Example 1 except that the thickness of the deposited film 22 was set to 1000 nm, and the same measurement (evaluation) was performed. The results are also shown in Table 2.

<Example 6>
As shown in Table 1, a sample of Example 6 was produced in the same manner as in Example 1 except that the thickness of the deposited film 22 was set to 1200 nm, and the same measurement (evaluation) was performed. The results are also shown in Table 2.

<Example 7>
As shown in Table 1, except that a two-liquid curing type 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 7 was prepared in the same manner as in Example 1, and the same measurement (evaluation) was performed. The results are also shown in Table 2.

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

<Example 9>
As shown in Table 1, a sample of Example 9 was prepared in the same manner as in Example 8 except that an O—Ny film was used as the insulating layer 21, and the same measurement (evaluation) was performed. The results are also shown in Table 2.

<Example 10>
As shown in Table 1, a sample of Example 10 was produced in the same manner as in Example 8 except that the thickness of the deposited film 22 was set to 5 nm, and the same measurement (evaluation) was performed. The results are also shown in Table 2.

<Example 11>
As shown in Table 1, a sample of Example 11 was produced in the same manner as in Example 8 except that the thickness of the deposited film 22 was set to 1000 nm, and the same measurement (evaluation) was performed. The results are also shown in Table 2.

<Example 12>
As shown in Table 1, a sample of Example 12 was prepared in the same manner as in Example 1 except that an aluminum vapor deposition film 22 having a thickness of 20 nm was formed on the inner surface of the OPP film for the insulating layer 21. A similar measurement (evaluation) was performed. The results are also shown in Table 2.

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

<Comparative Example 1>
As shown in Table 1, a sample of Comparative Example 1 was prepared in the same manner as in Example 1 above, except that no deposited film 22 was formed and acid-modified polypropylene (PP) having a thickness of 2 μm was used as an adhesive. It was produced and the same measurement (evaluation) was performed. The results are also shown in Table 2.

<Comparative Example 2>
As shown in Table 1, a sample of Comparative Example 2 was prepared in the same manner as in Comparative Example 1 above, except that an O—Ny film with a thickness of 9 μm was used as the insulating layer 21 and PU with a thickness of 2 μm was used as the adhesive. It was produced and the same measurement (evaluation) was performed. The results are also shown in Table 2.

<General comments>
As is clear from Table 2, the exterior material samples of Examples 1 to 13 related to the present invention were able to obtain excellent results in all evaluations.

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

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

1, 1a, 1b, 1c: exterior material 11: base material layer 12: metal foil layer 13: sealant layer 21: insulating layer 22: deposited film 4: adhesive layer 5: solid battery body

Claims (6)

A base material layer, a metal foil layer laminated on the inner surface side of the base material layer, a resin insulating layer laminated on the inner surface side of the metal foil layer, and a sealant provided on the inner surface side of the insulating layer An all-solid-state battery outer material for enclosing a solid-state battery body, comprising a layer,
A deposited film is provided between the insulating layer and the sealant layer,
An exterior material for an all-solid-state battery, wherein the vapor-deposited film is composed of at least one of a metal, a metal oxide, and a metal fluoride. 2. The exterior material for an all-solid-state battery according to claim 1, wherein the vapor-deposited film has a thickness of 5 nm to 1000 nm. 3. The exterior material for an all-solid-state battery according to claim 1, wherein an adhesive layer is provided between said insulating layer and said sealant layer. 4. The exterior material for an all-solid-state battery according to claim 3, wherein the vapor-deposited film is provided on a contact surface of the sealant layer with the adhesive layer. 5. The exterior material for an all-solid-state battery according to claim 3, wherein the vapor-deposited film is provided on a contact surface of the insulating layer with the adhesive layer. An all-solid-state battery, wherein a solid-state battery main body is enclosed in the all-solid-state battery exterior material according to any one of claims 1 to 5.

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