CN117813719A - All-solid-state battery exterior member and all-solid-state battery - Google Patents
All-solid-state battery exterior member and all-solid-state battery Download PDFInfo
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- CN117813719A CN117813719A CN202280055728.7A CN202280055728A CN117813719A CN 117813719 A CN117813719 A CN 117813719A CN 202280055728 A CN202280055728 A CN 202280055728A CN 117813719 A CN117813719 A CN 117813719A
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- heat
- gas barrier
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- solid
- barrier layer
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
- H01M50/105—Pouches or flexible bags
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/117—Inorganic material
- H01M50/119—Metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/121—Organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
- H01M50/126—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/14—Primary casings; Jackets or wrappings for protecting against damage caused by external factors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sealing Battery Cases Or Jackets (AREA)
Abstract
The invention provides an exterior member for an all-solid-state battery which is free from air leakage and has sufficient insulation. The present invention is directed to an all-solid-state battery package for enclosing a solid-state battery body 5, which includes a base material layer 11, a metal foil layer 12 laminated on the inner surface side of the base material layer 11, and a sealant layer 13 laminated on the inner surface side of the metal foil layer 12. A resin heat-resistant gas barrier layer 21 is provided between the metal foil layer 12 and the sealant layer 13.
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 a high-power battery such as a vehicle-mounted battery, a battery for portable devices such as mobile electronic devices, a battery for storing regenerated energy, and the like.
Background
Since a lithium ion secondary battery that has been largely used in the past uses a liquid electrolyte as an electrolyte, there is a concern that: the separator is broken by the occurrence of leakage and dendrites, and fire or the like due to short-circuiting may occur in some cases.
In contrast, since the all-solid-state battery uses a solid electrolyte, no leakage or dendrite occurs and the separator is not broken. Therefore, there is no concern about ignition or the like caused by breakage of the separator, and attention is paid to safety and the like.
A general all-solid-state battery is configured by enclosing a solid-state battery body such as an electrode active material and a solid electrolyte in an exterior member as a case. In this all-solid battery, as the research of the solid electrolyte progresses, parts of the exterior material that are different from those of the conventional battery using the liquid electrolyte are increasingly displayed, and various exterior materials have been proposed in order to satisfy the performance for the all-solid battery.
The exterior material for an all-solid-state battery includes a metal foil layer and a heat-sealing layer (sealant layer) laminated on the inner side thereof as a basic structure, and is an exterior material in which a solid-state battery body is sealed by heat-sealing the sealant layer.
For example, the casing for an all-solid battery shown in patent document 1 described below has a protective film sandwiched 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. 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. In addition, the exterior material for an all-solid battery shown in patent document 3 uses a sealant layer that absorbs gas as the sealant layer. The exterior material for an all-solid battery shown in patent document 4 is configured by laminating a vapor-deposited film layer on the inner surface of a sealing agent layer.
Prior art literature
Patent literature
Patent document 1: japanese patent No. 6777276
Patent document 2: japanese patent No. 6747636
Patent document 3: japanese patent laid-open No. 2020-187855
Patent document 4: japanese patent laid-open No. 2020-187835
Disclosure of Invention
Problems to be solved by the invention
However, in all solid-state batteries using the exterior material shown in patent documents 1 and 2, there are the following problems: when the solid electrolyte reacts with moisture in the air to generate hydrogen sulfide gas, the hydrogen sulfide gas may leak out.
In addition, the exterior materials shown in patent documents 2 to 4 have the following problems: when the sealant layer is melt-bonded (thermally bonded) at the time of sealing the battery body, the resin constituting the sealant layer is melted and flows out, and the sealant layer becomes partially thinner, so that the protective function of the metal foil layer by the sealant layer may be reduced, resulting in a reduction in insulation properties.
The preferred embodiments of the present invention have been made in view of the above-mentioned and/or other problems occurring in the related art. The preferred embodiments of the present invention enable significant improvements to existing methods and/or apparatus.
The present invention has been made in view of the above-described problems, and an object thereof is to provide an all-solid-state battery exterior material capable of securing sufficient insulation even when a sealant layer is thermally bonded, and capable of preventing leakage of hydrogen sulfide gas or the like generated inside when a battery main body has been sealed, and an all-solid-state battery.
Other objects and advantages of the present invention can be ascertained from the following preferred embodiments.
Means for solving the problems
In order to solve the above problems, the present invention includes the following means.
[1] An all-solid-state battery package for sealing a solid-state battery body, comprising a base layer, a metal foil layer laminated on the inner surface side of the base layer, and a sealant layer laminated on the inner surface side of the metal foil layer,
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 battery according to the above 1, wherein the hydrogen sulfide gas permeability of the heat-resistant gas barrier layer measured in accordance with JIS K7126-1 is set to 15{ cc.mm/(m) 2 D·mpa) } or less.
[3] The exterior member for an all-solid battery according to the aforementioned item 2, wherein the resin constituting the aforementioned heat-resistant gas barrier layer is constituted in the following manner: the original thickness was "da0", and the thickness when pressed at 200℃under 0.2MPa for 5sec was "da1", which satisfies the relation 1. Gtoreq.da 1/da 0. Gtoreq.0.9.
[4] The exterior member for an all-solid battery according to the above 2 or 3, wherein the thickness of the heat-resistant gas barrier layer is set to 3 μm to 50 μm.
[5]The casing for an all-solid battery according to any one of the preceding claims 2 to 4, wherein the sealant layer has a hydrogen sulfide gas permeability of 100{ cc.mm/(m) 2 D·mpa) } or less.
[6] The exterior material for an all-solid battery according to any one of the above 2 to 5, wherein the resin constituting the sealant layer is constituted as follows: the original thickness was "db0", and the thickness when pressed at 200℃under 0.2MPa for 5sec was "db1", satisfying the relation of 0.5. Gtoreq.db1/db 0. Gtoreq.0.1.
[7]The exterior material for an all-solid battery according to any one of the preceding claims 2 to 6, wherein the resin constituting the heat-resistant gas barrier layer has a water vapor permeability of 50 (g/m) as measured in accordance with JIS K7129-1 (humidity sensor method 40 ℃ C. 90% Rh) 2 Day) is below.
[8] The exterior material for an all-solid battery according to any one of the preceding claims 1 to 7, wherein the heat-resistant gas barrier layer is composed of an insulating resin having a melting point 20℃or higher than that of the sealant layer,
the insulation breakdown voltage of the heat-resistant gas barrier layer is 18kV/mm or more.
[9] The exterior material for an all-solid battery according to the above 8, wherein the resin constituting the heat-resistant gas barrier layer has a hot water shrinkage of 2% to 10%.
[10] The exterior member for an all-solid battery according to the preceding item 8 or 9, wherein the resin constituting the aforementioned heat-resistant gas barrier layer is polyamide.
[11] The exterior material for an all-solid battery according to any one of the above 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 disposed so as to be exposed to the inner surface side in the opening.
[12] The exterior material for an all-solid battery according to the above 11, wherein the heat-resistant gas barrier layer is composed of a resin having a melting point higher than that of the sealant layer by 10 ℃ or more.
[13] The exterior material for an all-solid battery according to the above 11 or 12, wherein the thermal conductivity of the resin constituting the heat-resistant gas barrier layer is 0.2W/mK or more.
[14] The exterior member for an all-solid battery according to the aforementioned item 1, wherein a vapor-deposited film is provided between the aforementioned heat-resistant gas barrier layer and the aforementioned sealant layer,
the vapor deposition film is composed of at least one of a metal, a metal oxide, and a metal fluoride.
[15] The exterior material for an all-solid battery according to the above 14, wherein the thickness of the vapor deposited film is set to 5nm to 1000nm.
[16] The exterior member for an all-solid battery according to the preceding claim 14 or 15, wherein an adhesive layer is provided between the heat-resistant gas barrier layer and the sealant layer.
[17] The exterior material for an all-solid battery according to the above 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 battery according to the preceding claim 16 or 17, wherein the vapor-deposited film is provided on a contact surface with the adhesive layer in the heat-resistant gas barrier layer.
[19] The exterior material for an all-solid-state battery according to any one of the preceding claims 1 to 18, wherein the Young's modulus of the heat-resistant gas barrier layer at 90 ℃ is 1GPa or more in both MD and TD.
[20] The exterior material for an all-solid battery according to claim 19, wherein the heat-resistant gas barrier layer has a tensile breaking strength of 100MPa or more in both MD and TD at 90 ℃.
[21] The exterior member for an all-solid battery according to the above 19 or 20, wherein the heat-resistant gas barrier layer has a tensile elongation at break at 90℃of 50% to 200% in both MD and TD.
[22] An all-solid-state battery, wherein the exterior material for all-solid-state battery described in any one of the foregoing items 1 to 21 is filled with a solid-state battery body.
Effects of the invention
According to the exterior material for an all-solid battery of the invention [1], since the heat-resistant gas barrier layer is interposed between the metal foil layer and the sealant layer, leakage of the generated hydrogen sulfide gas to the outside can be reliably prevented. In addition, when the solid-state battery body is sealed by the present exterior material, even if the resin of the sealing material layer is melted and flows out to reduce the insulation properties by the sealing material layer, the heat-resistant gas barrier layer remains, and therefore the insulation properties can be ensured by the heat-resistant gas barrier layer.
According to the exterior material for an all-solid battery of the invention [2], since the hydrogen sulfide gas permeation rate of the heat-resistant gas barrier layer is regulated, the leakage of the hydrogen sulfide gas to the outside can be more reliably prevented.
According to the exterior material for an all-solid-state battery of the inventions [3] and [4], the thickness of the heat-resistant gas barrier layer can be sufficiently ensured when the solid-state battery body is sealed by thermal bonding, and therefore, leakage of the hydrogen sulfide gas can be reliably prevented, and good insulation can be reliably ensured.
According to the exterior material for an all-solid battery of the invention [5], the discharge of the hydrogen sulfide gas can be prevented by the sealant layer, and thus the leakage of the hydrogen sulfide gas can be prevented more reliably.
According to the exterior material for an all-solid battery of the invention [6], when the solid battery main body is sealed by thermal bonding, the thickness of the sealant layer can be ensured to some extent, and therefore, the insulation property and the sealing property can be further improved.
According to the exterior material for an all-solid battery of the invention [7], the invasion of moisture can be prevented, and the generation of hydrogen sulfide gas itself can be suppressed, so that the leakage of hydrogen sulfide gas can be further reliably prevented.
According to the exterior material for an all-solid battery of the invention [8], since the insulation properties of the heat-resistant gas barrier layer are specified, sufficient insulation properties can be reliably ensured even in a high-temperature environment.
According to the exterior material for an all-solid battery of the invention [9], since the hot water shrinkage rate of the heat-resistant gas barrier layer is specified, it is possible to secure high insulation properties and to improve moldability.
According to the exterior material for an all-solid battery of the invention [10], since a general polyamide resin is used as the heat-resistant gas barrier layer, the exterior material can be produced simply and efficiently.
According to the exterior material for an all-solid battery of the invention [11], since the opening portion in which the heat-resistant gas barrier layer is exposed is formed in the portion of the sealant layer corresponding to the solid battery body, heat generated from the solid battery body is not blocked by the sealant layer, and is transmitted to the metal foil layer via the heat-resistant gas barrier layer to dissipate heat, whereby sufficient cooling performance can be ensured.
According to the exterior material for an all-solid battery of the invention [12], since the heat-resistant gas barrier layer has a high melting point, the heat-resistant gas barrier layer can be prevented from flowing out by melting during thermal bonding of the sealant layer, and gas leakage can be further reliably prevented.
According to the exterior material for an all-solid battery of the invention [13], the thermal conductivity of the gas barrier layer is specified, so that the cooling performance can be further improved.
According to the exterior material for an all-solid battery of the inventions [14], [15], since the vapor deposition film is provided between the insulating layer and the sealant layer, a sufficient gas barrier property can be continuously ensured by the vapor deposition film. Therefore, the generation of hydrogen sulfide gas due to the infiltration of moisture in the outside air can be prevented, and even if hydrogen sulfide gas is generated, the leakage of hydrogen sulfide gas to the outside can be reliably prevented by utilizing the gas barrier property of the vapor deposition film.
According to the exterior material for an all-solid battery of the invention [16], since the adhesive layer is provided between the insulating layer and the sealant layer, even if the vapor deposition film is formed between the insulating layer and the sealant layer, the two layers can be reliably adhered and fixed.
According to the exterior material for an all-solid battery of the invention [17], since the vapor deposition film is formed on the outer surface of the sealant layer, the vapor deposition film having gas barrier properties can be disposed further inside, and the barrier properties against moisture can be further improved.
According to the exterior material for an all-solid battery of the invention [18], since the vapor deposition film is formed on the inner surface of the insulating layer, the vapor deposition film is less likely to be damaged by heat due to the heat insulating effect of the adhesive layer when the sealant layer is thermally fused, and the gas barrier property by the vapor deposition film can be reliably ensured.
According to the exterior material for an all-solid battery of the invention [19], since the heat-resistant gas barrier layer having a high young's modulus at a high temperature is used, it is possible to reliably prevent the occurrence of defects such as breakage in the heat-resistant gas barrier layer, even in the entire exterior material, not only at normal temperature but also even in a high-temperature environment.
According to the exterior material for an all-solid-state battery of the inventions [20] and [21], even if the exterior material expands and stretches due to an increase in internal pressure caused by a high temperature in a state where the solid-state battery body has been sealed, breakage of the exterior material can be prevented more reliably.
According to the all-solid-state battery of the invention [22], since the all-solid-state battery using the exterior material of the inventions [1] to [21] is specified, the same effects as above can be obtained.
Drawings
Fig. 1 is a schematic cross-sectional view showing an all-solid battery as an embodiment of the present invention.
Fig. 2 is a schematic cross-sectional view showing an exterior member used in the all-solid battery of the embodiment.
Fig. 3 is a schematic cross-sectional view showing an all-solid-state battery according to modification 1 of the present invention.
Fig. 4 is an exploded cross-sectional view schematically showing the structure of an all-solid-state battery according to modification 1.
Fig. 5 is a schematic cross-sectional view showing an all-solid-state battery according to modification 2 of the present invention.
Fig. 6A is a schematic cross-sectional view showing a 1 st exterior member applicable to the all-solid-state battery of modification 2.
Fig. 6B is a schematic cross-sectional view showing a 2 nd exterior member applicable to the all-solid-state battery of modification 2.
Fig. 6C is a schematic cross-sectional view showing a 3 rd exterior member applicable to the all-solid-state battery of modification 2.
Fig. 7 is a plan view schematically showing a sample for evaluating insulation properties.
Fig. 8 is a sectional view schematically showing the sample for evaluating insulation of fig. 7, and is a sectional view corresponding to a D-D line section of fig. 8.
Detailed Description
Fig. 1 is a schematic cross-sectional view showing an all-solid-state battery as an embodiment of the present invention, and fig. 2 is a schematic cross-sectional view showing an exterior member 1 used in the all-solid-state battery. As shown in both figures, the exterior material 1 constituting the casing of the all-solid battery of the present embodiment is constituted by a laminate such as a laminated sheet.
The outer package 1 includes a base layer 11 disposed on the outermost side, a metal foil layer 12 laminated on the inner surface side of the base layer 11, a heat-resistant gas barrier layer 21 laminated on the inner surface side of the metal foil layer 12, and a sealant layer 13 laminated on the inner surface side of the heat-resistant gas barrier layer 21, and in this embodiment, the layers 11 to 13 and 21 of the outer package 1 are bonded with an adhesive (adhesive layer) by a dry lamination method interposed therebetween. In other words, the outer package 1 of the present embodiment is configured by using a laminate formed of the base material layer 11, the adhesive layer, the metal foil layer 12, the adhesive layer, the heat-resistant gas barrier layer 21, the adhesive layer, and the sealant layer 13.
In the present embodiment, as shown in fig. 1, the solid-state battery body 5 is sealed in a coating manner by the exterior material 1 having the above-described structure, and an all-solid-state battery is manufactured. That is, 2 rectangular cases 1, 1 are stacked up and down with the solid-state battery body 5 interposed therebetween, and the sealant layers 13, 13 at the outer peripheral edge portions of the 2 cases (a pair of cases 1, 1) are bonded and integrated in an airtight state (sealed state) by thermal bonding (heat sealing), whereby an all-solid-state battery in which the solid-state battery body 5 is housed in a pouch-shaped case formed by the cases 1, 1 is produced.
In the all-solid-state battery of the present embodiment, although not shown, tabs are provided for electrical extraction. The tab is configured in the following manner: one end (inner end) of the solid-state battery body 5 is bonded and fixed, and an intermediate portion thereof passes between outer peripheral portions of the 2 outer cases 1, and the other end side (outer end side) is led out to the outside.
In the present embodiment, the case is formed by bonding 2 planar exterior members 1, but not limited thereto, and in the present invention, at least any one of the 2 exterior members may be formed into a tray shape in advance, and the case may be formed by bonding one of the tray-shaped exterior members to the other of the tray-shaped or planar exterior members.
The following describes the detailed structure of the exterior member 1 of the all-solid battery according to the present embodiment.
The base material layer 11 of the exterior material 1 is composed of a film of a heat-resistant resin having a thickness of 5 μm to 50 μm. As the resin constituting the base layer 11, polyamide, polyester (PET, PBT, PEN), polyolefin (PE, PP), or the like can be preferably used.
The thickness of the metal foil layer 12 is set to 5 μm to 120 μm, and has a function of blocking the invasion of oxygen and moisture from the surface (outer surface) side. As the metal foil layer 12, aluminum foil, SUS foil (stainless steel foil), copper foil, nickel foil, or the like can be preferably used. In the present embodiment, terms such as "aluminum", "copper" and "nickel" are used in a meaning that they also include alloys thereof.
Further, when the metal foil layer 12 is subjected to a plating process or the like, the risk of pinholes is reduced, and the function of blocking the intrusion of oxygen and moisture can be further improved.
Further, when the metal foil layer 12 is subjected to a chemical conversion treatment such as a chromate treatment, the corrosion resistance is further improved, and therefore, defects such as chipping can be more reliably prevented from occurring, and the adhesion to the resin can be improved, and the durability can be further improved.
The thickness of the sealant layer 13 is set to 10 μm to 100 μm, and is composed of a film of a heat-bondable (heat-weldable) resin. As the resin constituting the sealant layer 13, a resin selected from the group consisting of polyethylene (LLDPE, LDPE, HDPE), polyolefin such as polypropylene, olefin copolymer, acid modified products thereof, and ionomer, for example, unstretched polypropylene (CPP, IPP) and the like can be preferably used.
When the tab is used for the sealant layer 13 to extract electricity, that is, when sealability, adhesiveness, and the like with the tab are considered, polypropylene resins such as unstretched polypropylene films (CPP, IPP) are preferably used.
The heat-resistant gas barrier layer 21 is made of a film of a resin having heat resistance and insulation properties. As the resin constituting the heat-resistant gas barrier layer 21, polyamide (nylon 6, nylon 66, nylon MXD, etc.), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), cellophane, polyvinylidene chloride, etc. are preferably used.
The heat-resistant gas barrier layer 21 of the present embodiment has good insulation properties, and also has good insulation properties after the solid-state battery body 5 is sealed (after sealing) by the exterior material 1 of the present embodiment by thermal bonding.
In the present embodiment, the resin constituting the heat-resistant gas barrier layer 21 preferably includes a predetermined hydrogen sulfide (H 2 S) gas permeability. Specifically, the heat-resistant gas barrier layer 21 may have a hydrogen sulfide gas permeability of 30{ cc.mm/(m) in the measured value according to JIS K7126-1 2 The resin of D.MPa) } or less, more preferably 15{ cc.mm/(m) 2 D·mpa) } or less. That is, when the hydrogen sulfide gas permeability of the heat-resistant gas barrier layer 21 is set to the above-described specific value or less, the heat-resistant gas barrier layer 21 can prevent the hydrogen sulfide gas from leaking to the outside when the solid electrolyte material reacts with moisture of the outside air to generate the hydrogen sulfide gas. In other words, when the hydrogen sulfide gas permeation rate of the heat-resistant gas barrier layer 21 is large, the generated hydrogen sulfide gas may leak to the outside through the exterior member 1 (heat-resistant gas barrier layer 21), which is not preferable.
For reference, the "D" contained in the unit of hydrogen sulfide gas permeation rate corresponds to "Day (24 hours)".
In the present embodiment, as the resin constituting the heat-resistant gas barrier layer 21, a resin having a water vapor permeability of 50 (g/m) measured in accordance with JIS K7129-1 (humidity sensor method 40 ℃ C. 90% Rh) can be used 2 Per day) or less, more preferably a water vapor permeability of 40 (g/m) 2 Day) the following resins. That is, although hydrogen sulfide gas is generated by the reaction of external moisture passing through the exterior material 1 and the solid electrolyte material, when the water vapor permeability of the heat-resistant gas barrier layer 21 is set to the above-described specific value or less, the penetration of moisture by the heat-resistant gas barrier layer 21 can be prevented, and the gas barrier function of the metal foil layer 12 complements each other, so that the penetration of moisture can be further reliably prevented, the generation of hydrogen sulfide gas itself can be reliably prevented, and the leakage of hydrogen sulfide gas to the outside can be further reliably prevented.
In the present embodiment, the thickness (original thickness) of the heat-resistant gas barrier layer 21 is preferably set 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 permeation of the hydrogen sulfide gas and the water vapor gas can be reliably obtained, and even if the sealant layer 13 is melted and flowed out by the thermal bonding, the heat-resistant gas barrier layer 21 can be reliably used to ensure the insulation property. In other words, if the heat-resistant gas barrier layer 21 is too thin, the effect of suppressing gas permeation and the insulation properties may not be ensured, which is not preferable. On the other hand, if the heat-resistant gas barrier layer 21 is too thick, it is not preferable because the outer package 1 cannot be thinned, and the effect of thickening more than necessary cannot be sufficiently obtained.
In the present embodiment, the resin (resin film) constituting the heat-resistant gas barrier layer 21 is configured such that the original thickness is "da0", and the thickness when pressed under the conditions of 200 ℃ and 0.2MPa and 5sec is "da1", and the residual ratio "da1/da0" is preferably 0.9 or more, that is, such that the relation a of "1 Σ1/da0 Σ0" is satisfied. The relation a corresponds to the following constitution: when the exterior material 1 is thermally bonded, the reduction ratio of the thickness of the heat-resistant gas barrier layer 21 is 10% or less. In the present embodiment, when the above-described relation a is satisfied, even if the exterior material 1 is thermally bonded to seal the solid-state battery body 5, the decrease in the thickness of the heat-resistant gas barrier layer 21 can be suppressed, and a sufficient thickness can be ensured, so that the above-described effect of suppressing gas permeation can be reliably obtained, and the insulation properties by the heat-resistant gas barrier layer 21 can also be reliably obtained.
In the present embodiment, the resin constituting the heat-resistant gas barrier layer 21 is preferably a resin having a melting point higher than that of the resin constituting the sealant layer 13 by 10 ℃ or more, and more preferably by 20 ℃ or more. That is, in the case where the heat-resistant gas barrier layer 21 is made to have a high melting point, even if the sealant layer 13 is melted at the time of thermal bonding of the exterior material 1, the heat-resistant gas barrier layer 21 can be prevented from flowing out of the melt, and therefore, the effect of suppressing gas permeation by the heat-resistant gas barrier layer 21 and the insulation property can be reliably obtained.
In the present embodiment, the insulation breakdown voltage of the heat-resistant gas barrier layer 21 is preferably set to 18kV/mm or more. That is, when the insulation breakdown voltage of the heat-resistant gas barrier layer 21 is a specific value or more, sufficient insulation properties can be reliably ensured. In other words, if the insulation breakdown voltage of the heat-resistant gas barrier layer 21 is too small, sufficient insulation properties may not be ensured.
In the present embodiment, the hot water shrinkage rate of the heat-resistant gas barrier layer 21 is preferably set to 2% to 10%. That is, in the case of this configuration, the heat-resistant gas barrier layer 21 improves the moldability of the exterior material 1, and the high insulation property can be maintained even after the solid-state battery body 5 is sealed by the exterior material 1 by thermal bonding. In other words, when the hot water shrinkage rate of the heat-resistant gas barrier layer 21 is out of the above-described specific range, there is a concern that good insulation properties cannot be ensured, which is not preferable.
In the present embodiment, the hot water shrinkage ratio of the heat-resistant gas barrier layer 21 is the dimensional change ratio in the stretching direction of the test piece before and after immersion in hot water at 95℃for 30 minutes of the resin film test piece (10 cm. Times.10 cm) constituting the heat-resistant gas barrier layer 21. In the present embodiment, the hot water shrinkage ratio may be obtained by the following equation, where the dimension in the stretching direction before the dipping treatment is "X" and the dimension in the stretching direction after the dipping treatment is "Y".
Hot water shrinkage (%) = { (X-Y)/X } ×100
Here, in the present embodiment, as the resin constituting the heat-resistant gas barrier layer 21, a resin having a thermal conductivity of 0.2W/m·k or more is preferably used. That is, in the case of adopting this configuration, the heat conductivity of the heat-resistant gas barrier layer 21 can be sufficiently ensured, and therefore the cooling performance of the solid-state battery body 5 can be further improved.
In the present embodiment, the young's modulus at 90 ℃ of the resin film constituting the heat-resistant gas barrier layer 21 is preferably 1GPa or more, and more preferably 5GPa or more, in both MD as the traveling direction and TD as the direction orthogonal to the MD. That is, by adopting this configuration, it is possible to ensure a predetermined hardness in the heat-resistant gas barrier layer 21 and even in the exterior material 1, not only at normal temperature but also in a high-temperature environment, and therefore it is possible to prevent occurrence of defective portions such as breakage.
In the present embodiment, the Young's modulus of the heat-resistant gas barrier layer 21 at room temperature (25 ℃) is preferably 1.5GPa or more.
In the present embodiment, the tensile breaking strength of the heat-resistant gas barrier layer 21 at 90 ℃ is preferably 100MPa to 400MPa in both MD and TD. That is, in the case of adopting this configuration, even if the internal pressure becomes high due to the expansion of the solid-state battery body 5 at high temperature and the exterior material 1 expands, breakage of the exterior material 1 can be reliably prevented.
In the present embodiment, the heat-resistant gas barrier layer 21 preferably has a tensile elongation at break at 90 ℃ of 50% to 200% in both MD and TD. That is, in the case of adopting this configuration, even if the outer cover 1 expands and stretches due to an increase in the internal pressure at high temperature, breakage of the outer cover 1 can be more reliably prevented.
In the present embodiment, the heat-resistant gas barrier layer 21 preferably has a tensile breaking strength of 150MPa at normal temperature (25 ℃) and a tensile breaking elongation of 50% to 150%.
In the present embodiment, the resin (resin film) constituting the sealant layer 13 is configured such that the original thickness is "db0", and the thickness when pressed at 200 ℃ under 0.2MPa for 5sec is "db1", and the residual ratio "db1/db0" is preferably 0.1 to 0.5, that is, such that the relation B of "0.5 not less than db1/db0 not less than 0.1" is satisfied. The relational expression B corresponds to the following constitution: when the exterior material 1 is thermally bonded, the reduction ratio of the thickness of the sealant layer 13 is 50 to 90%. In the present embodiment, when the above-described relation B is satisfied, the thickness of the sealant layer 13 can be ensured to a certain extent when the exterior material 1 is thermally bonded to seal the solid-state battery body 5, and therefore, the insulation properties by the sealant layer 13 are ensured, and even if the tab and the foreign matter are present, the resin of the sealant layer 13 spreads to the outer peripheral gap thereof, whereby sufficient sealing properties can be reliably obtained.
In the present embodiment, it is preferable to use a hydrogen sulfide gas permeability of 100{ cc.mm/(m) in accordance with JIS K7126-1 2 The resin of d·mpa) } or less constitutes the sealant layer 13 of the exterior material 1. That is, when the hydrogen sulfide gas permeability of the sealant layer 13 is set to the above-described specific value or less, the effect of suppressing the permeation of the hydrogen sulfide gas by the above-described heat-resistant gas barrier layer 21 complements the effect of suppressing the permeation of the hydrogen sulfide gas by the sealant layer 13, and thus the leakage of the hydrogen sulfide gas to the outside can be further reliably prevented.
On the other hand, in the present embodiment, as an adhesive (adhesive layer) for adhering the layers 11 to 13 and 21 of the exterior material 1, a 2-liquid curing type, an energy ray (UV, X-ray, etc.) curing type, or the like curing type may be used, and among them, a urethane type adhesive, an olefin type adhesive, an acrylic type adhesive, an epoxy type adhesive, or the like may be preferably used. The thickness of the adhesive layer 4 is set to 2 μm to 5 μm.
As described above, in the all-solid-state battery of the present embodiment, the heat-resistant gas barrier layer 21 is interposed between the metal foil layer 12 and the sealant layer 13 in the outer package 1, so that the generated hydrogen sulfide gas can be reliably prevented from leaking to the outside. In addition, when the sealing agent layer 13 of the exterior member 1 is thermally bonded at the time of sealing the solid-state battery body 5, even if the resin of the sealing agent layer 13 flows out in a molten state and the insulation property by the sealing agent layer 13 is lowered, the heat-resistant gas barrier layer 21 remains, and therefore the insulation property can be ensured by the heat-resistant barrier layer 21.
Further, in the case where the hydrogen sulfide gas permeability of the heat-resistant gas barrier layer 21 is set to a specific value, the above-described effects can be obtained more reliably.
In addition, in the case where the insulation breakdown voltage of the heat-resistant gas barrier layer 21 is set to a specific value, good insulation properties can be reliably ensured 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, it is possible to reliably prevent occurrence of defects such as breakage in the heat-resistant gas barrier layer 21 and even in the exterior material 1, not only at normal temperature but also in a high-temperature environment, and to provide an all-solid-state battery product excellent in operational reliability particularly in a high-temperature environment.
Fig. 3 is a schematic cross-sectional view showing an all-solid-state battery according to modification 1 of the present invention, and fig. 4 is an exploded view schematically showing the structure of the all-solid-state battery. As shown in the two figures, in this all-solid-state battery, the exterior material 1 includes: a base material layer 11 disposed on the outermost side; a metal foil layer 12 laminated and bonded to the inner surface side of the base material layer 11 via an adhesive layer; a heat-resistant gas barrier layer 21 bonded to the inner surface side of the metal foil layer 12 via an adhesive layer; and a sealant layer 13 laminated and bonded to the inner surface side of the heat-resistant gas barrier layer 21 via an adhesive layer 4.
The sealing agent layer 13 is formed by removing the intermediate portion except the outer peripheral portion thereof to form the opening 15, and is formed only in the outer peripheral portion. The exterior material 1 is configured as follows: the adhesive layer 4 is not present in the opening 15, and the heat-resistant gas barrier layer 21 is exposed to the inside through the opening 15.
In modification 1, 2 (a pair of) cases 1 and 1 each formed in a rectangular shape are stacked up and down with the solid-state battery body 5 interposed therebetween so that the sealant layers 13 in the outer peripheral edge portions of the cases face each other, and the sealant layers 13 and 13 are bonded and integrated in an airtight state (sealed state) by thermal bonding (heat sealing), whereby an all-solid-state battery in which the solid-state battery body 5 is housed in a sealed state in a pouch-shaped case formed by the cases 1 and 1 is produced.
In this all-solid-state battery, the opening 15 of the exterior material 1 is disposed in a portion corresponding to the solid-state battery body 5, and the upper and lower surfaces of the solid-state battery body 5 are disposed so as to face the heat-resistant gas barrier layers 21 of the upper and lower exterior materials 1 through the opening 15.
In the all-solid-state battery according to modification 1, other configurations are similar to those of the all-solid-state battery according to the embodiment described above.
As described above, in the exterior material 1 according to modification 1, the opening 15 is formed in the sealant layer 13. The opening 15 is formed in a portion corresponding to the solid-state battery body 5, and the sealant layer 13 is disposed in a portion corresponding to the heat seal portion (sealing portion).
The adhesive layer 4 is not provided in the opening 15 of the exterior material 1, and the heat-resistant gas barrier layer 21 is exposed (exposed) to the inside through the opening 15, and is disposed so that the heat-resistant gas barrier layer 21 faces the solid-state battery body 5 and, if necessary, at least partially abuts against the solid-state battery body 5 in the state where the all-solid-state battery is manufactured.
In the present embodiment, the opening 15 of the exterior material 1 is formed by cutting out the intermediate portion of the sealant layer 13 laminated over the entire region of the heat-resistant gas barrier layer 21, for example, and the sealant layer 13 having the outer peripheral edge portion formed remains.
That is, in modification 1, when the sealant layer 13 is formed on the heat-resistant gas barrier layer 21, the adhesive agent as the adhesive agent layer 4 is applied by a gravure roll or the like to the inner surface of the resin film as the heat-resistant gas barrier layer 21, and the resin film as the sealant layer 13 is adhered via the adhesive agent layer 4, but when the adhesive agent is applied by a gravure roll or the like to the heat-resistant gas barrier layer 21, an uncoated portion to which no adhesive agent is applied is formed in advance in a region where an opening is to be formed. Then, a resin film for a sealant layer is attached to the heat-resistant gas barrier layer 21 having the adhesive-uncoated portion, and dried. Then, the sealing agent layer of the adhesive non-coated portion is cut off with a resin film by a laser cutter, a hob blade, or the like, to form an opening 15 (1 st forming method).
As the 2 nd forming method, before the adhesive is applied to the heat-resistant gas barrier layer 21, a release paper is attached in a temporarily fixed state to a region of the heat-resistant gas barrier layer 21 where an opening is to be formed, and in this state, the adhesive is applied to the heat-resistant gas barrier layer 21 by a gravure roll or the like, and a resin film for a sealant layer is attached and dried. Then, the resin film for the sealant layer corresponding to the temporary fixing portion of the release paper is cut off together with the adhesive and the release paper by a hob blade or the like, thereby forming the opening portion 15.
As other forming methods, the following methods (other forming methods) and the like can also be considered: before the resin film for a sealing agent layer is bonded to the heat-resistant gas barrier layer 21, a through-hole as the opening 15 is formed in the film in advance, and the resin film for a sealing agent layer with an opening is bonded to the heat-resistant gas barrier layer 21 via an adhesive. However, in this other forming method, it is difficult to uniformly apply the adhesive, and it is difficult to accurately attach the resin film for the sealant layer having the opening portion with good accuracy. Therefore, in modification 1, the above-described 1 st and 2 nd formation methods are preferably employed.
As described above, according to the all-solid-state battery of modification 1, the heat-resistant gas barrier layer 21 is formed between the metal foil layer 12 and the sealant layer 13 in the exterior member 1, and the opening 15 that exposes the heat-resistant gas barrier layer 21 is formed in the portion of the sealant layer 13 corresponding to the solid-state battery body 5, and therefore, heat generated by the solid-state battery body 5 is not blocked by the sealant layer 13, and is transmitted to the metal foil layer 12 via the heat-resistant gas barrier layer 21, thereby dissipating heat. Therefore, sufficient cooling performance can be ensured, and defects caused by high temperature can be reliably prevented.
In the all-solid-state battery according to modification 1, the sealant layer 13 is not present between the solid-state battery body 5 and the metal foil layer 12, but the heat-resistant gas barrier layer 21 having insulation properties is disposed therebetween, so that the insulation properties can be reliably ensured by the heat-resistant gas barrier layer 21.
In the all-solid-state battery according to modification 1, the sealant layer 13 is not formed in the portion of the exterior material 1 corresponding to the solid-state battery body 5, and therefore the space for accommodating the solid-state battery body 5 can be increased (thickened) accordingly. Therefore, in the all-solid-state battery of the present embodiment, compared with the conventional all-solid-state battery, the solid-state battery body 5 of a large size can be housed without changing the external dimensions of the case (the exterior member 1), and therefore, it is possible to achieve a reduction in thickness and a high output and a high capacity.
Fig. 5 is a schematic cross-sectional view showing an all-solid-state battery according to modification 2 of the present invention. As shown in the figure, the exterior material 1 of the all-solid-state battery according to modification 2 includes: a base material layer 11 disposed on the outermost side; a metal foil layer 12 laminated on the inner surface side of the base material layer 11; a heat-resistant gas barrier layer 21 as an insulating layer laminated on the inner surface side of the metal foil layer 12; and a sealant layer 13 laminated on the inner surface side of the heat-resistant gas barrier layer 21. A vapor deposition film (vapor deposition layer) 22 is provided between the heat-resistant gas barrier layer 21 and the sealant layer 13.
In modification 2, as the exterior material 1, the exterior materials 1a to 1c having 3 structures of 1 to 3 can be used.
As shown in fig. 6A, in the 1 st outer package 1a, a resin film for the base material layer 11 is laminated and bonded to the outer surface of a metal foil layer 12 via an adhesive, a resin film for the heat-resistant gas barrier layer 21 is laminated and bonded to the inner surface of the metal foil layer 12 via an adhesive, a vapor deposition film 22 is deposited on the inner surface of the heat-resistant gas barrier layer 21, and a sealant layer 13 of a heat-fusible resin is laminated and bonded to the inner surface of the heat-resistant gas barrier layer 21 via an adhesive layer 4.
As shown in fig. 6B, in the 2 nd casing 1B, the vapor deposition film is not formed on the inner surface of the heat-resistant gas barrier layer 21, and the vapor deposition film 22 is formed on the outer surface of the sealant layer 13, and the vapor deposition surface (outer surface) of the sealant layer 13 is bonded to the inner surface of the heat-resistant gas barrier layer 21 via the adhesive 4, as compared with the 1 st casing 1 a.
As shown in fig. 6C, in the 3 rd exterior part 1C, vapor deposition films 22, 22 are formed on both the inner surface of the heat-resistant gas barrier layer 21 and the outer surface of the sealant layer 13, and the vapor deposition surface (inner surface) of the heat-resistant gas barrier layer 21 and the vapor deposition surface (outer surface) of the sealant layer 13 are bonded via the adhesive layer 4.
In modification 2, as the adhesive constituting the adhesive layer 4 for bonding the heat-resistant gas barrier layer 21 and the sealant layer 13, a 2-liquid curing type, a UV (energy ray) curing type or other curing type may be used, and among them, a urethane type adhesive, an olefin type adhesive, an acrylic type adhesive, an epoxy type adhesive or the like may be preferably used. The thickness of the adhesive layer 4 is set to 2 μm to 5 μm.
In the present embodiment, the heat-resistant gas barrier layer 21 and the sealant layer 13 are bonded to each other by dry lamination or thermal lamination using such an adhesive.
In modification 2, the use of an acid-modified polyolefin adhesive having good adhesion to the vapor deposition film 22 as the adhesive for the adhesive layer 4 can reliably adhere the heat-resistant gas barrier layer 21 to the sealant layer 13, and can effectively prevent interlayer peeling during molding.
In modification 2, the adhesive used for bonding the base material layer 11 and the metal foil layer 12 and the heat-resistant gas barrier layer 21 to each other may be the same as the adhesive used for the adhesive layer 4, and preferably the same thickness is set.
In modification 2, 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 may be at least 1 or more selected from inorganic substances such as aluminum, titanium, and silicon, inorganic oxides such as aluminum oxide, silicon dioxide, and zinc oxide, and metal fluorides such as aluminum fluoride and magnesium fluoride.
In modification 2, the vapor deposition film 22 is formed, whereby the gas barrier property can be further improved. Therefore, the entry of the external gas can be prevented, the generation of the hydrogen sulfide gas itself generated by the reaction of the moisture of the external gas with the solid electrolyte of the solid-state battery body 5 can be prevented, and even if the hydrogen sulfide gas is generated, the leakage of the hydrogen sulfide gas to the outside can be reliably prevented by the gas barrier property of the deposition film 22.
In modification 2, the thickness of the vapor deposition film 22 is preferably set to beOr 5nm to 1000nm, or 0.005 μm to 1 μm. That is, by setting the thickness within this range, good gas barrier properties can be ensured more reliably. In other words, when the thickness of the vapor deposition film 22 is too small, good gas barrier properties cannot be obtained, which is not preferable. Even if the thickness of the vapor deposition film 22 is made thicker than necessary, the effect corresponding to this cannot be obtained, and not only is a large amount of time required to form a thicker vapor deposition film 22, but there is a concern that the production efficiency may be lowered, which is not preferable.
In modification 2, the vapor deposition film 22 can be formed by vapor deposition by dry coating and coating. As the dry coating, a known method such as CVD method or PVD method (sputtering method, ion beam method, etc.) can be used.
In the all-solid-state battery according to modification 2, other configurations are similar to those of the all-solid-state battery according to the embodiment described above.
As described above, according to the all-solid-state battery of modification 2, the vapor-deposited film 22 is provided between the heat-resistant gas barrier layer 21 and the sealant layer 13 in the exterior member 1, and therefore, sufficient gas barrier properties can be obtained by the vapor-deposited film 22. Therefore, the entry of the external gas can be prevented, the generation of the hydrogen sulfide gas itself generated by the reaction of the moisture of the external gas with the solid electrolyte of the solid-state battery body 5 can be prevented, and even if the hydrogen sulfide gas is generated, the leakage of the hydrogen sulfide gas to the outside can be reliably prevented by the gas barrier property of the deposition film 22.
In modification 2, since the adhesive layer 4 is provided between the heat-resistant gas barrier layer 21 and the sealant layer 13, even if the vapor deposition film 22 is formed on the inner surface of the heat-resistant gas barrier layer 21 and the outer surface of the sealant layer 13, the heat-resistant gas barrier layer 21 and the sealant layer 13 can be reliably fixed in close contact with each other, and occurrence of interlayer peeling can be prevented.
In modification 2, when the vapor deposition film 22 is formed on the sealant layer 13 side as in the case of the 2 nd and 3 rd external components 1b and 1c, the vapor deposition film 22 having gas barrier properties can be disposed further inside (on the solid-state battery body 5 side), and therefore the barrier properties against moisture can be further improved.
In modification 2, when the vapor deposition film 22 is formed on the heat-resistant gas barrier layer 21 side as in the case of the 1 st and 3 rd exterior parts 1a and 1c, the thermal insulation effect of the adhesive layer 4 makes it difficult for the vapor deposition film 22 to be broken by heat during the heat welding of the sealant layer 13, and the gas barrier property by the vapor deposition film 22 can be ensured reliably.
Examples
(1) Example 1
TABLE 1
Example 1a ]
(1-1) manufacture of exterior parts
A chemical conversion coating film was formed by applying a chemical conversion treatment solution composed of phosphoric acid, polyacrylic acid (acrylic resin), chromium (III) salt compound, water, and alcohol to both surfaces of an aluminum foil (A8021-O) having a thickness of 40 μm as the metal foil layer 12, and drying the resultant film at 180 ℃. The chromium adhesion amount of the chemical conversion coating was 10mg/m on each side 2 。
Next, a biaxially stretched nylon 6 (ONY-6) film having a thickness of 15 μm was dry laminated (bonded) on one surface (outer surface) of the aluminum foil (metal foil layer 12) subjected to the chemical conversion treatment via a 2-liquid curable urethane adhesive (3 μm) as a base layer 11.
Next, as shown in table 1, a 9 μm thick PET film was bonded to the other surface (inner surface) of the dry laminated aluminum foil via a 2-liquid curable urethane adhesive (3 μm) as a heat-resistant gas barrier resin layer 21.
Next, as shown in table 1, as the sealant layer 13, a 20 μm thick CPP film containing a lubricant (erucamide or the like) was laminated on the inner surface of the above-described dry laminated PET film (heat-resistant gas barrier layer 21) via a 2-liquid cured urethane adhesive (3 μm), and the laminate was sandwiched between a rubber nip roller and a lamination roller heated to 100 ℃ to be pressure-bonded, whereby dry lamination was performed to obtain a laminate constituting the exterior material 1.
The laminate was then wound onto a reel, and after that, aged at 40 ℃ for 10 days, to obtain the exterior sample of example 1 a.
(1-2) H of resin film 2 Determination of S gas permeability etc
The hydrogen sulfide (H) of the PET film (heat-resistant gas barrier layer 21) and CPP film (sealant layer 13) used in producing the exterior material sample of example 1a was measured in accordance with JIS K7126-1 2 S) gas permeability, and further, the water vapor permeability of the PET film was measured in accordance with JIS K7129-1 (humidity sensor method 40 ℃ C. 90% Rh). The results are shown in Table 1.
(1-3) measurement of residual Rate
After 2 sheets of the exterior material samples of example 1a were cut out in a size of 15mm in width by 150mm in length, the pair of samples were stacked with the inner sealant layers of both in contact with each other, and a heat sealing apparatus (TP-701-a) manufactured by ltd. Was used at a heat sealing temperature: 200 ℃, sealing pressure: 0.2MPa (instrument indication pressure), sealing time: under the condition of 2 seconds, heat sealing (heat bonding) was performed by heating one surface, and a residual rate measurement sample of example 1a was obtained.
In the residual rate measurement sample, the sealing portion was fixed with a resin, and the sealing portion was cut so as to have a cross section, and the thickness of the heat-resistant gas barrier layer 21, the sealant layer 13, and the like was obtained by observing the cross section with SEM.
Then, based on the layer thickness after heat sealing and the layer thickness of the exterior material sample before heat sealing, the residual ratio "da1/da0" of the heat-resistant gas barrier layer 21 and the residual ratio "db1/db0" of the sealant layer 13 were measured (see the above-mentioned relational expression A, B). The results are shown in Table 1.
(1-4) measurement of seal Strength
TABLE 2
After 2 sheets of the exterior material samples of example 1a were cut out in a size of 15mm in width by 150mm in length, the pair of samples were stacked with the inner sealant layers of both in contact with each other, and a heat sealing apparatus (TP-701-a) manufactured by ltd. Was used at a heat sealing temperature: 200 ℃, sealing pressure: 0.2MPa (instrument indication pressure), sealing time: under the condition of 2 seconds, heat sealing (heat bonding) was performed by heating one surface, and a sample for evaluating seal strength of example 1a was obtained.
The test piece for evaluating seal strength was T-peeled at a tensile rate of 100 mm/min from each other at the inner sealant layer of the sealing portion by using a Stregle (AGS-5 kNX) manufactured by Shimadzu Access Corporation in accordance with JIS Z0238-1998, and the peel strength at this time was measured as seal strength (N/15 mm width). The results are shown in Table 2.
(1-5) measurement of insulation resistance value (evaluation of insulation Property)
As shown in fig. 7 and 8, the exterior material sample 1 of example 1a was cut out 2 sheets in a size of 100mm in the longitudinal direction and 50mm in the transverse direction. The pair of package samples 1 and 1 are stacked so that the sealant layers 13 are opposed to each other and in contact with each other. On the other hand, in the tab 3 made of aluminum foil 10mm wide and 100 μm thick, tab films (tab films) 31 made of acid-modified polypropylene film 50 μm thick were disposed on both sides thereof, and were disposed so as to be sandwiched between the pair of exterior material samples 1, 1. At this time, a part of the tab 3 is placed between the pair of exterior sample 1, and the remaining part is led out from the edges of the pair of exterior sample 1, 1. The unbonded samples were subjected to heat fusion of sealant layers from both upper and lower surfaces of the exterior sample 1 and 1 by a double-sided heat sealer at a sealing width of 5mm and a temperature of 200℃and a pressure of 0.2MPa for 2 seconds to obtain samples for evaluation of insulation properties.
In the plan view of the insulating property evaluation sample of fig. 7, the heat-bonding portion (heat-sealing portion) 131 is hatched with oblique lines for the sake of easy understanding of the invention. In the cross-sectional view of the insulating property evaluation sample in fig. 8, the heat-resistant gas barrier layer 13 is omitted to facilitate understanding of the structure.
Next, as shown in fig. 7, a part of the resin serving as the base layer 11 was peeled off at the end in the longitudinal direction of the insulation evaluation sample, and the aluminum foil serving as the metal foil layer 12 was partially exposed, and conduction with the aluminum foil (metal foil layer 12) was ensured from the outside at the exposed portion 121.
Then, one terminal of an insulation resistance measuring device (product number "HIOKI3154" manufactured by Nippon Motor Co.) 6 was connected to the metal foil layer 12 in the exposed portion 121 of the insulation evaluation sample, and the other terminal was brought into contact with the tab 3 to form a circuit, and then a voltage was applied between the metal foil layer 12 and the tab 3 at 25V for 5 seconds in the circuit, and the resistance value was measured as an insulation resistance value. The results are shown in Table 2.
(1-6) H of the exterior part 2 S gas permeation evaluation
A copper foil (Cu foil) having a thickness of 9 μm was used instead of the aluminum foil, and the copper foil type exterior material sample 1 of example 1a was produced in the same manner as described above.
The copper foil type package samples were cut into 2 pieces in a size of 30mm×50mm, and the pair of package samples 1 and 1 were stacked so that the sealant layers 13 were opposed to each other, and the package samples were subjected to heat sealing at the heat sealing temperature: 200 ℃, sealing pressure: 0.2MPa (instrument indication pressure), sealing time: under a sealing condition of 2 seconds, 3 sides (3 sides) of the laminated exterior product samples 1 and 1 were sealed to prepare a three-sided envelope. Then, in doingThe three-side bag was sealed (closed) by sandwiching an injection needle between the exterior sample 1 and 1 at 1 side (30 mm side) of the opening, and sealing the opening under the same sealing conditions as described above, and sealing an H of 0.1MPa from the injection needle 2 S gas (needle clamped by 30mm edge).
After the gas is sealed, the needle is pulled out slightly so that the gas does not leak, the inside is heat-sealed again under the same sealing conditions from the tip of the needle, the gas is completely sealed, and then the needle is pulled out, thereby producing a gas sealed bag.
After the gas-sealed bag was left to stand in a constant temperature bath at 40℃for 7 days, the gas was exhausted, and the sealed portion was peeled off to observe the inside. Based on this observation, the case where no change was observed in the Cu foil was evaluated as "o", and the case where discoloration was observed in the sealing portion or the like was evaluated as "x". The results are shown in Table 2.
Example 2a ]
A sample of example 2a was produced and measured (evaluated) in the same manner as in example 1a above, except that a PET film having a thickness of 3 μm was used as the heat-resistant gas barrier layer 21 and a CPP film having a thickness of 30 μm was used as the sealant layer 13. The results are shown in tables 1 and 2.
Example 3a ]
A sample of example 3a was produced and measured (evaluated) in the same manner as in example 1a above, except that a PET film having a thickness of 15 μm was used as the heat-resistant gas barrier layer 21. The results are shown in tables 1 and 2.
Example 4a ]
A sample of example 4a was produced and measured (evaluated) in the same manner as in example 1a above, except that a PET film having a thickness of 25 μm was used as the heat-resistant gas barrier layer 21. The results are shown in tables 1 and 2.
Example 5a ]
A sample of example 5a was produced and measured (evaluated) in the same manner as in example 1a above, except that a film having a thickness of 15 μm was used as the heat-resistant gas barrier layer 21. The results are shown in tables 1 and 2.
Example 6a ]
A sample of example 6a was produced and measured (evaluated) in the same manner as in example 1a above, except that a film having a thickness of 5 μm was used as the heat-resistant gas barrier layer 21. The results are shown in tables 1 and 2.
Example 7a ]
A sample of example 7a was produced and measured (evaluated) in the same manner as in example 1a above, except that a film having a thickness of 40 μm was used as the heat-resistant gas barrier layer 21. The results are shown in tables 1 and 2.
Example 8a ]
A sample of example 8a was produced and measured (evaluated) in the same manner as in example 1a above, except that a CPP film having a thickness of 60 μm was used as the sealant layer 13. The results are shown in tables 1 and 2.
Example 9a ]
A sample of example 9a was produced and measured (evaluated) in the same manner as in example 1a above, except that a HDPE film having a thickness of 60 μm was used as the sealant layer 13. The results are shown in tables 1 and 2.
Example 10a ]
A sample of example 10a was produced and measured (evaluated) in the same manner as in example 1a above, except that an LLDPE film having a thickness of 60 μm was used as the sealant layer 13. The results are shown in tables 1 and 2.
< example 11a >
A sample of example 11a was produced and measured (evaluated) in the same manner as in example 1a above, except that a CPP film having a thickness of 10 μm was used as the sealant layer 13. The results are shown in tables 1 and 2.
Example 12a ]
A sample of example 12a was produced and measured (evaluated) in the same manner as in example 1a above, except that a cellophane film having a thickness of 20 μm was used as the heat-resistant gas barrier layer 21 and a CPP film having a thickness of 10 μm was used as the sealant layer 13. The results are shown in tables 1 and 2.
Comparative example 1a ]
A sample of comparative example 1a was produced and the same measurement (evaluation) was performed in the same manner as in example 1a above, except that the heat-resistant gas barrier layer 21 was not formed. The results are shown in tables 1 and 2.
Comparative example 2a ]
A sample of comparative example 2a was produced and measured (evaluated) in the same manner as in example 1a above, except that the heat-resistant gas barrier layer 21 was not formed and a CPP film having a thickness of 25 μm was used as the sealant layer 13. The results are shown in tables 1 and 2.
Comparative example 3a ]
A sample of comparative example 3a was produced and measured (evaluated) in the same manner as in example 1a above, except that an OPP film having a thickness of 30 μm was used as the heat-resistant gas barrier layer 21. The results are shown in tables 1 and 2.
< general evaluation of example 1 >
From table 2, it was confirmed that the exterior samples of examples 1a to 12a related to the present invention can obtain excellent results in all of the evaluations of insulation and gas permeation.
In contrast, the exterior material samples of comparative examples 1a to 3a, which deviate from the gist of the present invention, do not give good results in the evaluation of gas permeation, and some of them do not give good results in the evaluation of insulation.
(2) Example 2
TABLE 3
< example 1b >
(2-1) manufacture of exterior parts
In an aluminum foil (A8021) having a thickness of 40 μm as the metal foil layer 12-O) is coated on both sides with a chemical conversion treatment solution comprising phosphoric acid, polyacrylic acid (acrylic resin), chromium (III) salt compound, water, and alcohol, and then dried at 180 ℃ to form a chemical conversion coating. The chromium adhesion amount of the chemical conversion coating was 10mg/m on each side 2 。
Next, a biaxially stretched nylon 6 film having a thickness of 15 μm was dry laminated (bonded) on one surface (outer surface) of the aluminum foil (metal foil layer 12) subjected to the chemical conversion treatment via a 2-liquid curable urethane adhesive (3 μm) as a base layer 11.
Next, as shown in Table 3, a stretched film (ONY-6 film) of PA6 having a thickness of 9 μm, a melting point of 225 ℃, an insulation breakdown voltage of 19kV/mm, and a hot water shrinkage of 5% was prepared as the heat-resistant gas barrier layer 21, and a vapor-deposited film of aluminum having a thickness of 20nm was formed on one surface thereof. The non-vapor-deposited surface side of the ONY-6 film with a vapor deposited film was bonded to the other surface (inner surface) of the dry-laminated aluminum foil via a 2-liquid curable urethane adhesive (3 μm).
Next, as shown in table 3, as the sealant layer 13, a CPP film containing a lubricant (erucamide or the like) having a thickness of 20 μm and a melting point of 150 ℃ was laminated on the deposition surface (inner surface) of the above-described dry-laminated ONY-6 film (heat-resistant gas barrier layer 21) via a 2-liquid cured urethane adhesive (3 μm), and the laminate was pressed by sandwiching the film between a rubber nip roller and a lamination roller heated to 100 ℃ to obtain a laminate constituting the exterior material 1.
The laminate was then wound onto a reel, and after that, aged at 40 ℃ for 10 days, to obtain an exterior sample of example 1 b.
(2-2) measurement of insulation breakdown Voltage
In the resin film constituting the heat-resistant gas barrier layer 21 in example 1b, the insulation breakdown voltage was measured in accordance with JIS C2151 in a state before the formation of the vapor deposited film. The results are shown in Table 3.
(2-3) measurement of Hot Water shrinkage
In the resin film constituting the heat-resistant gas barrier layer 21 in example 1, a test piece having a size of 10cm×10cm was cut out, and the test piece was immersed in hot water at 95 ℃ for 30 minutes, and the dimensional change rate in the tensile direction of the test piece before and after the immersion was determined by the following formula.
Hot water shrinkage (%) = { (X-Y)/X } ×100
In the formula, "X" is the dimension in the stretching direction before the dipping treatment, and "Y" is the dimension in the stretching direction after the dipping treatment.
(2-4) measurement of seal Strength
TABLE 4
In the exterior material sample of example 1b, the seal strength was measured in the same manner as in (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 ratio was measured in the same manner as in (1-3) above. The results are shown in Table 4.
(2-6) measurement of insulation resistance value (evaluation of insulation Property)
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 Table 4.
(2-7) evaluation of moldability
The exterior material sample of example 1b was cut into a size of 100mm×100mm to obtain a sample for moldability evaluation. For this sample for formability evaluation, a deep drawing forming test was performed by changing the forming height (drawing depth) by 0.5mm using a deep drawing forming die attached to a 25t press.
Then, the molding height was evaluated as "verygood" when the predetermined moldability was obtained even if it was 7mm or more, and "good" when the predetermined moldability was not obtained in the range of 5mm or more and less than 7mm, and "X" when the predetermined moldability was not obtained in the range of less than 5 mm. The results are shown in Table 4.
(2-8) ONY-6 film H with vapor-deposited film 2 S gas permeation evaluation
For the ONY-6 film with a vapor deposited film used in the exterior sample of example 1b, H was measured according to JIS K7126 2 The permeability of the S gas was measured. The results are shown in Table 4.
< general evaluation of example 2 >
From table 4, it was confirmed that the exterior samples of examples 1b to 13b related to the present invention can obtain excellent results in all the evaluations.
In contrast, the exterior material samples of comparative examples 1b to 3b, which deviate from the gist of the present invention, do not give good results in any of the evaluations.
(3) Example 3
TABLE 5
Example 1c ]
(3-1) manufacture of exterior parts
A chemical conversion coating film was formed by applying a chemical conversion treatment solution composed of phosphoric acid, polyacrylic acid (acrylic resin), chromium (III) salt compound, water, and alcohol to both surfaces of an aluminum foil (A8021-O) having a thickness of 40 μm as the metal foil layer 12, and drying the resultant film at 180 ℃. The chromium adhesion amount of the chemical conversion coating was 10mg/m on each side 2 。
Next, a biaxially stretched nylon 6 (ONY-6) film having a thickness of 15 μm was dry laminated (bonded) on one surface (outer surface) of the aluminum foil (metal foil layer 12) subjected to the chemical conversion treatment via a 2-liquid curable urethane adhesive (3 μm) as a base layer 11.
Next, as shown in table 1, a PET film having a thickness of 9 μm was dry-laminated on the other surface (inner surface) of the dry-laminated aluminum foil via a 2-liquid curable urethane adhesive (3 μm) as a heat-resistant gas barrier layer 21.
Next, a 2-liquid curable urethane 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. In this case, the adhesive is not applied to the rectangular portion, which is the area where the opening is to be formed, but is applied only to the outer peripheral portion (heat-seal portion: remaining portion of the sealant layer) of the opening forming area as the adhesive non-applied area.
Next, as the sealant layer 13, a CPP film containing a lubricant (erucamide or the like) and having a thickness of 40 μm was laminated on the inner surface of the heat-resistant gas barrier layer 21, to which an adhesive was applied only in a necessary portion, and the laminate was sandwiched between a rubber nip roller and a lamination roller heated to 100 ℃ to be pressure-bonded, thereby dry-laminated to obtain a laminate constituting the exterior material 1.
Then, the laminate was wound on a reel, and after that, aged at 40 ℃ for 10 days, the CPP film for the sealant layer was cut off along the outer peripheral edge portion of the adhesive non-coated portion of the aged laminate by a laser cutter, and an opening 15 was formed in the middle portion of the sealant layer 13, to obtain the exterior sample of example 1 c. In the exterior sample, the heat-resistant gas barrier layer 21 is disposed so as to be exposed to the inner surface side through the opening 15.
(3-2) measurement of Water vapor Transmission Rate
The water vapor permeability of the resin film for the heat-resistant gas barrier layer 21 used in the production of the exterior sample of example 1c was measured in accordance with JIS K7129-1 (humidity sensor method 40 ℃ C. 90% Rh). The results are shown in Table 5.
(3-3) determination of thermal conductivity
The thermal conductivity of the resin film for the heat-resistant gas barrier layer 21 used in the production of the exterior sample of example 1c was measured by a heat flow meter method (HFM method) of the steady state method. The results are shown in Table 5.
(3-4) H of resin film 2 Determination of S gas permeability etc
For the heat-resistant gas barrier layer used in the production of the exterior sample of example 1c21, hydrogen sulfide (H) in accordance with JIS K7126-1 2 S) gas permeability is measured. The results are shown in Table 5.
(3-5) evaluation of Cooling Performance (Cooling Effect)
2 exterior samples of example 1c were prepared in a size of 100mm by 100 mm. The opening 15 in the exterior sample was square and had a size of 60mm×60 mm.
The 2 outer package samples were stacked so that the opening 15 side thereof was inside, and the stacked 2 outer package samples were heat sealed at a position 10mm apart from the edge on 3 sides out of 4 sides around the outer package samples by a width of 5mm, to produce a three-sided envelope.
The three-side bag was filled with hot water at 80℃from the opening under a room temperature (25 ℃) temperature environment, and after further insertion of a thermometer, the opening was closed with a large steel clip, and the temperature change of the hot water was measured for 3 minutes. The temperature immediately after the injection of hot water and the temperature after 3 minutes are shown in table 5.
Example 2c ]
A sample of example 2c was produced and measured (evaluated) in the same manner as in example 1c above, except that an ONY-6 film was used as the heat-resistant gas barrier layer 21. The results are shown in Table 5.
Example 3c ]
A sample of example 3c was produced and measured (evaluated) in the same manner as in example 1c above, except that an OPP film (biaxially stretched polypropylene film) was used as the heat-resistant gas barrier layer 21. The results are shown in Table 5.
Comparative example 1c ]
A sample of comparative example 1c was produced and measured (evaluated) in the same manner as in example 1c above except that the sealant layer 13 was formed over the entire inner surface side of the heat-resistant gas barrier layer 21, that is, the opening 15 was not formed in the sealant layer 13. The results are shown in Table 5.
Comparative example 2c ]
A sample of comparative example 2c was produced and the same measurement (evaluation) was performed in the same manner as in comparative example 1c above, except that an ONY-6 film was used as the heat-resistant gas barrier layer 21. The results are shown in Table 5.
Comparative example 3c ]
A sample of comparative example 3c was produced and the same measurement (evaluation) was performed in the same manner as in comparative example 1c, except that an OPP film was used as the heat-resistant gas barrier layer 21. The results are shown in Table 5.
< general evaluation of example 3 >
From table 5, it was confirmed that the exterior samples of examples 1c to 3c related to the present invention were excellent in cooling performance (cooling effect).
In contrast, the exterior material samples of comparative examples 1c to 3c, which deviate from the gist of the present invention, cannot obtain high cooling performance.
(4) Example 4
TABLE 6
Example 1d ]
1. Manufacture of outer parts
A chemical conversion coating film was formed by applying a chemical conversion treatment solution composed of phosphoric acid, polyacrylic acid (acrylic resin), chromium (III) salt compound, water, and alcohol to both surfaces of an aluminum foil (A8021-O) having a thickness of 40 μm as the metal foil layer 12, and drying the resultant film at 180 ℃. The chromium adhesion amount of the chemical conversion coating was 10mg/m on each side 2 。
Next, a biaxially stretched nylon 6 (ONY-6) film having a thickness of 15 μm was dry laminated (bonded) on one surface (outer surface) of the aluminum foil (metal foil layer 12) subjected to the chemical conversion treatment via a 2-liquid curable urethane adhesive (3 μm) as a base layer 11.
Next, as shown in table 6, an OPP film (biaxially oriented polypropylene film) having a thickness of 9 μm was laminated as the insulating layer 21 on the other surface (inner surface) of the dry laminated aluminum foil via a 2-liquid curable urethane adhesive having a thickness of 3 μm.
Next, as the sealant layer 13, a CPP film containing 1000ppm of erucamide (which is a lubricant) and having a thickness of 40 μm was prepared, and an aluminum vapor deposition film having a thickness of 20nm was formed on one surface (outer surface) thereof. The deposition surface (outer surface) of the CPP film with a deposition film was laminated 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, and the laminate was dry laminated by sandwiching a rubber nip roll and a lamination roll heated to 100 ℃.
The laminate was then wound onto a reel, and after that, aged at 40 ℃ for 10 days, to obtain the exterior sample of example 1 d.
In table 6, the bracketed values indicate the thicknesses of the respective layers in μm.
(4-2) measurement of seal Strength
TABLE 7
In the exterior sample of example 1d, the seal strength was measured in the same manner as in (1-4) above. The results are shown in Table 7.
(4-3) evaluation of Water vapor (moisture) permeation of outer Member
The exterior sample of example 1d was cut into 2 pieces in a size of 30mm×50mm, and the pair of exterior samples 1 and 1 were stacked so that the sealant layers 13 were opposed to each other, and the package was subjected to heat sealing at the heat sealing temperature: 200 ℃, sealing pressure: 0.2MPa (instrument indication pressure), sealing time: under a sealing condition of 2 seconds, 3 sides (3 sides) of the laminated exterior product samples 1 and 1 were sealed to prepare a three-sided envelope. Next, calcium chloride of "Mc (g)" (standard 3 g) was added to the three-sided envelope, and then the opening of the three-sided envelope was sealed under the same sealing conditions as described above.
Then, the weight "M0 (g)" immediately after sealing was measured by an electronic balance, and after standing in a constant temperature and humidity tank of 80 ℃ x 90% rh for 7 days, the weight "M1 (g)" after treatment was measured, and the weight change (increase) was confirmed based on the following relational expression. The results are shown in Table 7.
Weight change (%) = (M1-M0)/Mc
(4-4) evaluation of moldability
In the exterior material sample of example 1d, moldability was evaluated in the same manner as in (2-7) above. The results are shown in Table 7.
(4-5) H of the exterior part 2 S gas permeation evaluation
In the exterior material sample of example 1d, the H2S gas permeability was evaluated in the same manner as in (1-6) above. The results are shown in Table 7.
Example 2d ]
As shown in table 6, a sample of example 2d was produced and measured (evaluated) in the same manner as in example 1d above, except that an ONY-6 film having a thickness of 9 μm was used as the insulating layer 21 and a 2-liquid cured urethane adhesive (PU) having a thickness of 2 μm was used as the adhesive. The results are shown in Table 7.
Example 3d ]
As shown in table 6, a sample of example 3d was produced and measured (evaluated) in the same manner as in example 1d above, except that an ONY-6 film having a thickness of 9 μm was used as the insulating layer 21, and a 2-liquid cured urethane adhesive (PU) having a thickness of 2 μm was used as the adhesive, and the thickness of the vapor deposition film 22 was set to 5 nm. The results are shown in Table 7.
Example 4d ]
The sample of example 4d was produced and the same measurement (evaluation) was performed in the same manner as in example 1d above, except that the thickness of the deposited film 22 was 500nm as shown in table 6. The results are shown in Table 7.
Example 5d ]
The sample of example 5d was produced and the same measurement (evaluation) was performed in the same manner as in example 1d above except that the thickness of the deposited film 22 was set to 1000nm as shown in table 6. The results are shown in Table 7.
Example 6d ]
The sample of example 6d was produced and the same measurement (evaluation) was performed in the same manner as in example 1d above, except that the thickness of the deposited film 22 was set to 1200nm as shown in table 6. The results are shown in Table 7.
Example 7d ]
As shown in Table 6, the vapor deposition film 22 was made of aluminum oxide (Al) 20nm thick using a 2-liquid curable urethane adhesive (PU) having a thickness of 2. Mu.m 2 O 3 ) Except for this, the sample of example 7d was prepared in the same manner as in example 1d, and the same measurement (evaluation) was performed. The results are shown in Table 7.
Example 8d ]
As shown in table 6, a sample of example 8d was produced and measured (evaluated) in the same manner as in example 1d above, except that a vapor deposition film 22 of aluminum having a thickness of 20nm was formed on the inner surface of the OPP film for the insulating layer 21, and a 2-liquid cured urethane adhesive (PU) having a thickness of 2 μm was used as an adhesive, and no vapor deposition film was formed on the CPP film for the sealant layer 13. The results are shown in Table 7.
Example 9d ]
The sample of example 9d was produced and measured (evaluated) in the same manner as in example 8d above, except that an ONY-6 film was used as the insulating layer 21, as shown in table 6. The results are shown in Table 7.
Example 10d ]
The sample of example 10d was produced and measured (evaluated) in the same manner as in example 8d above except that the thickness of the deposited film 22 was set to 5nm as shown in table 6. The results are shown in Table 7.
< example 11d >
The sample of example 11d was produced and the same measurement (evaluation) was performed in the same manner as in example 8d above, except that the thickness of the deposited film 22 was set to 1000nm as shown in table 6. The results are shown in Table 7.
Example 12d ]
As shown in table 6, samples of example 12d were produced and measured (evaluated) in the same manner as in example 1d above, except that an aluminum vapor deposition film 22 having a thickness of 20nm was formed on the inner surface of the OPP film for the insulating layer 21. The results are shown in Table 7.
Example 13d ]
As shown in table 6, a sample of example 13d was produced and measured (evaluated) in the same manner as in example 1d above, except that an aluminum vapor deposition film 22 having a thickness of 20nm was formed on the inner surface of an ONY-6 film having a thickness of 9 μm as the insulating layer 21, and a 2-liquid curing urethane adhesive (PU) having a thickness of 2 μm was used as the adhesive. The results are shown in Table 7.
Comparative example 1d ]
As shown in table 6, a sample of comparative example 1 was produced and the same measurement (evaluation) was performed in the same manner as in example 1d above, except that the vapor deposited film 22 was not formed at all and acid-modified polypropylene (acid-modified PP) having a thickness of 2 μm was used as an adhesive. The results are shown in Table 7.
Comparative example 2d ]
As shown in table 6, a sample of comparative example 2d was produced and measured (evaluated) in the same manner as in comparative example 1d except that an ONY-6 film having a thickness of 9 μm was used as the insulating layer 21 and a 2-liquid cured urethane adhesive (PU) having a thickness of 2 μm was used as the adhesive. The results are shown in Table 7.
< general evaluation of example 4 >
From table 7, it was confirmed that the exterior samples of examples 1d to 13d related to the present invention can obtain excellent results in all the evaluations.
In contrast, the exterior material samples of comparative examples 1d and 2d, which deviate from the gist of the present invention, do not give good results in any evaluation.
(5) Example 5
TABLE 8
Example 1e ]
(5-1) manufacture of exterior parts
The exterior sample of example 1e was obtained in the same manner as in example 1 a.
2. Young's modulus, tensile breaking strength and tensile elongation at break
The PET film (heat-resistant gas barrier layer 21) used in the production of the exterior sample of example 1e was measured for Young's modulus at 90℃and tensile breaking strength and tensile breaking elongation in MD and TD, respectively, in accordance with JIS K7127-1999. Specifically, a test piece was produced by cutting a PET film for a heat-resistant gas barrier layer into a size of 15mm in width by 100mm in length, and the test piece was subjected to a tensile test at a tensile rate of 200 mm/min at 90℃in an atmosphere using a Strerograph (AGS-5 kNX) manufactured by Shimadzu corporation, whereby Young's modulus (MPa), tensile breaking strength (MPa) and tensile elongation at break (%) were measured. As shown in table 8, in the PET film for the heat-resistant gas barrier layer of example 1e, young's modulus was 3.6GPa in MD, 3.2GPa in TD, tensile break strength was 190MPa in MD, 210MPa in TD, tensile break elongation was 120% in MD, and 110% in TD.
(5-3) evaluation of high temperature puncture Property
According to JIS Z1707:1997 the puncture strength of the exterior sample of example 1e was measured at 90℃atmosphere. The measurement method (puncture strength test method) is as follows.
A semicircular needle having a diameter of 1.0mm and a tip shape radius of 0.5mm was punched at a speed of 50.+ -.5 mm per minute by fixing a predetermined-sized exterior sample as a test piece, and the maximum stress until penetration of the needle was measured. The number of test pieces was 5, and the average value thereof was used as the puncture strength. The results are shown in Table 8.
(5-4) evaluation of moldability
In the exterior material samples of example 1e, moldability was evaluated in the same manner as in (2-7) above. The results are shown in Table 8.
(5-5) measurement of seal Strength
In the exterior sample of example 1e, the seal strength was measured in the same manner as in (1-4) above. The results are shown in Table 8.
< example 2e >
As the heat-resistant gas barrier layer 21, a young's modulus MD:1.5GPa, TD:1.2GPa, tensile breaking strength MD:210MPa, TD:240MPa, and tensile elongation at break of MD:140%, TD: a sample of example 2e was produced and measured (evaluated) in the same manner as in example 1e above except that a biaxially stretched nylon 6 film (ONY-6 film) of 120% was used. The results are shown in Table 8.
Example 3e ]
A sample of example 3e was produced and measured (evaluated) in the same manner as in example 2e above, except that a film having a thickness of 15 μm was used as the heat-resistant gas barrier layer 21. The results are shown in Table 8.
Example 4e ]
A sample of example 4e was produced and measured (evaluated) in the same manner as in example 2e above, except that a film having a thickness of 25 μm was used as the heat-resistant gas barrier layer 21. The results are shown in Table 8.
Example 5e ]
As the heat-resistant gas barrier layer 21, a young's modulus MD:3.4GPa, TD:3.1GPa, tensile breaking strength is MD:200MPa, TD:220MPa, and tensile elongation at break of MD:130%, TD: a sample of example 5e was produced and measured (evaluated) in the same manner as in example 1e except that a 125% PET film was used. The results are shown in Table 8.
In example 5e, the young's modulus, tensile breaking strength, and tensile breaking elongation of the PET film were different from those of example 1e by changing the crystallinity by adjusting the conditions at the time of film production.
Example 6e ]
As the heat-resistant gas barrier layer 21, a young's modulus MD:1.1GPa, TD:1.6GPa, tensile breaking strength MD:90MPa, TD:160MPa, and a tensile elongation at break of MD:140%, TD: a sample of example 6e was produced and measured (evaluated) in the same manner as in example 1e above except that an 80% biaxially oriented polypropylene film (OPP film) was formed. The results are shown in Table 8.
Example 7e ]
A sample of example 7e was produced and measured (evaluated) in the same manner as in example 1e above, except that a CPP film having a thickness of 10 μm was used as the sealant layer 13. The results are shown in Table 8.
Example 8e ]
A sample of example 8e was produced and measured (evaluated) in the same manner as in example 1e above, except that a CPP film having a thickness of 100 μm was used as the sealant layer 13. The results are shown in Table 8.
Comparative example 1e ]
As the heat-resistant gas barrier layer 21, a young's modulus MD:0.9GPa, TD:1.5GPa, tensile breaking strength MD:80MPa, TD:150MPa, and tensile elongation at break of MD:150%, TD: a sample of comparative example 1e was produced and the same measurement (evaluation) was performed in the same manner as in example 6e above except that an OPP film of 80%. The results are shown in Table 8.
In comparative example 1e, the Young's modulus, tensile breaking strength and tensile breaking elongation of the OPP film were different from those of example 6e by changing the crystallinity by adjusting the conditions at the time of film production.
< general evaluation of example 5 >
From table 8, it was confirmed that the exterior samples of examples 1e to 8e according to the present invention were excellent in puncture properties at 90 ℃.
In contrast, the exterior material sample of comparative example 1, which was out of the gist of the present invention, had poor puncture properties at 90 ℃, and it was considered that the exterior material sample of examples 1e to 8e was likely to have defects such as breakage in a high-temperature environment.
The disclosure of the patent claims 2021-131016 of japanese patent application filed at 2021, 8 and 11, 2021-132355 of japanese patent application filed at 2021, 8 and 16, 2021-132360 of japanese patent application filed at 2021, 8 and 16, 2021-132362 of japanese patent application filed at 2021, 8 and 17, and 2021-132728 of japanese patent application filed at 2021, 8 and 17, which are incorporated herein by reference, are hereby incorporated by reference.
The terms and expressions which have been employed herein are used as terms of description and not of limitation, and there is no intention in the use of such equivalents of the features shown and described herein, it being recognized that various modifications are possible within the scope of the invention claimed.
Industrial applicability
The exterior material for an all-solid battery of the present invention can be suitably used as a material for a case for housing a solid battery body.
Description of the reference numerals
1. 1a, 1b, 1c: outer fitting
11: substrate layer
12: metal foil layer
13: sealant layer
15: an opening part
21: heat-resistant gas barrier layer
22: vapor deposition film
4: adhesive layer
5: solid-state battery body
Claims (22)
1. An all-solid-state battery package for sealing a solid-state battery body, comprising a base layer, a metal foil layer laminated on the inner surface side of the base layer, and a sealant layer laminated on the inner surface side of the metal foil layer,
a resin heat-resistant gas barrier layer is provided between the metal foil layer and the sealant layer.
2. The exterior member for an all-solid battery according to claim 1, wherein the heat-resistant gas barrier layer has a hydrogen sulfide gas permeability of 15{ cc-mm/(m) measured in accordance with JIS K7126-1 2 D·mpa) } or less.
3. The exterior member for an all-solid battery according to claim 2, wherein the resin constituting the heat-resistant gas barrier layer is constituted in the following manner: the original thickness was "da0", and the thickness when pressed at 200℃under 0.2MPa for 5sec was "da1", which satisfies the relation 1. Gtoreq.da 1/da 0. Gtoreq.0.9.
4. The exterior member for an all-solid battery according to claim 2 or 3, wherein the thickness of the heat-resistant gas barrier layer is set to 3 μm to 50 μm.
5. The exterior member for an all-solid-state battery according to any one of claims 2 to 4, wherein the sealant layer has a hydrogen sulfide gas permeability of 100{ cc-mm/(m) 2 D·mpa) } or less.
6. The exterior member for an all-solid battery according to any one of claims 2 to 5, wherein the resin constituting the sealant layer is constituted in such a manner that: the original thickness was "db0", and the thickness when pressed at 200℃under 0.2MPa for 5sec was "db1", satisfying the relation of 0.5. Gtoreq.db1/db 0. Gtoreq.0.1.
7. The exterior member for all-solid-state batteries according to any one of claims 2 to 6, wherein the resin constituting the heat-resistant gas barrier layer has a water vapor permeability of 50 (g/m) as measured in accordance with JIS K7129-1 (humidity sensor method 40 ℃ C. 90% Rh) 2 Day) is below.
8. The exterior member for an all-solid battery according to any one of claims 1 to 7, wherein the heat-resistant gas barrier layer is composed of an insulating resin having a melting point 20 ℃ or higher than that of the sealant layer,
the insulation breakdown voltage of the heat-resistant gas barrier layer is more than 18 kV/mm.
9. The exterior member for an all-solid battery according to claim 8, wherein the resin constituting the heat-resistant gas barrier layer has a hot water shrinkage of 2% to 10%.
10. The exterior member for an all-solid battery according to claim 8 or 9, wherein the resin constituting the heat-resistant gas barrier layer is polyamide.
11. The exterior material for an all-solid battery according to any one of claims 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 disposed so as to be exposed to the inner surface side at the opening.
12. The exterior member for an all-solid battery according to claim 11, wherein the heat-resistant gas barrier layer is composed of a resin having a melting point higher than that of the sealant layer by 10 ℃ or more.
13. The exterior member for an all-solid battery according to claim 11 or 12, wherein a thermal conductivity of a resin constituting the heat-resistant gas barrier layer is 0.2W/m-K or more.
14. The exterior member for an all-solid battery according to claim 1, wherein a vapor deposition film is provided between the heat-resistant gas barrier layer and the sealant layer,
the vapor deposition film is composed of at least one of a metal, a metal oxide, and a metal fluoride.
15. The exterior member for an all-solid battery according to claim 14, wherein the thickness of the vapor deposited film is set to 5nm to 1000nm.
16. The exterior member for an all-solid battery according to claim 14 or 15, wherein an adhesive layer is provided between the heat-resistant gas barrier layer and the sealant layer.
17. The exterior member for an all-solid battery according to claim 16, wherein the vapor-deposited film is provided on a contact surface with the adhesive layer in the sealant layer.
18. The exterior member for an all-solid battery according to claim 16 or 17, wherein the vapor-deposited film is provided on a contact surface with the adhesive layer in the heat-resistant gas barrier layer.
19. The exterior member for an all-solid-state battery according to any one of claims 1 to 18, wherein the heat-resistant gas barrier layer has a young's modulus at 90 ℃ of 1GPa or more in both MD and TD.
20. The exterior member for an all-solid battery according to claim 19, wherein the tensile breaking strength of the heat-resistant gas barrier layer at 90 ℃ is 100MPa or more in both MD and TD.
21. The exterior member for an all-solid battery according to claim 19 or 20, wherein the heat-resistant gas barrier layer has a tensile elongation at break at 90 ℃ of 50% to 200% in both MD and TD.
22. An all-solid-state battery, characterized in that a solid-state battery body is enclosed in the exterior material for all-solid-state batteries according to any one of claims 1 to 21.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021-131016 | 2021-08-11 | ||
| JP2021-132360 | 2021-08-16 | ||
| JP2021-132355 | 2021-08-16 | ||
| JP2021-132362 | 2021-08-16 | ||
| JP2021-132728 | 2021-08-17 | ||
| JP2021132728 | 2021-08-17 | ||
| PCT/JP2022/025347 WO2023017683A1 (en) | 2021-08-11 | 2022-06-24 | Outer package material for all-solid-state batteries, and all-solid-state battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117813719A true CN117813719A (en) | 2024-04-02 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202280055728.7A Pending CN117813719A (en) | 2021-08-11 | 2022-06-24 | All-solid-state battery exterior member and all-solid-state battery |
| CN202280055735.7A Pending CN117813717A (en) | 2021-08-17 | 2022-08-10 | All-solid-state battery exterior member and all-solid-state battery |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202280055735.7A Pending CN117813717A (en) | 2021-08-17 | 2022-08-10 | All-solid-state battery exterior member and all-solid-state battery |
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| Country | Link |
|---|---|
| JP (1) | JPWO2023022088A1 (en) |
| KR (1) | KR20240034810A (en) |
| CN (2) | CN117813719A (en) |
| WO (1) | WO2023022088A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0477276U (en) | 1990-11-20 | 1992-07-06 | ||
| JP2015026438A (en) * | 2013-07-24 | 2015-02-05 | 興人フィルム＆ケミカルズ株式会社 | Battery case packaging material for cold molding |
| TWI691113B (en) * | 2015-07-01 | 2020-04-11 | 日商昭和電工包裝股份有限公司 | Exterior materials for power storage device and power storage device |
| US20220069344A1 (en) | 2019-01-23 | 2022-03-03 | Dai Nippon Printing Co., Ltd. | Exterior material for all-solid-state battery, method for manufacturing same, and all-solid-state battery |
| JP7356257B2 (en) | 2019-05-10 | 2023-10-04 | 共同印刷株式会社 | Laminate sheet for sulfide-based all-solid-state batteries and laminate pack using the same |
| JP2020187835A (en) | 2019-05-10 | 2020-11-19 | 昭和電工パッケージング株式会社 | Outer packaging material for power storage device |
-
2022
- 2022-06-24 CN CN202280055728.7A patent/CN117813719A/en active Pending
- 2022-08-10 JP JP2023542371A patent/JPWO2023022088A1/ja active Pending
- 2022-08-10 KR KR1020247005076A patent/KR20240034810A/en unknown
- 2022-08-10 WO PCT/JP2022/030551 patent/WO2023022088A1/en active Application Filing
- 2022-08-10 CN CN202280055735.7A patent/CN117813717A/en active Pending
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| WO2023022088A1 (en) | 2023-02-23 |
| JPWO2023022088A1 (en) | 2023-02-23 |
| KR20240034810A (en) | 2024-03-14 |
| CN117813717A (en) | 2024-04-02 |
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