CN113629326B - Outer packaging material for power storage device, and power storage device - Google Patents
Outer packaging material for power storage device, and power storage device Download PDFInfo
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- CN113629326B CN113629326B CN202110883546.6A CN202110883546A CN113629326B CN 113629326 B CN113629326 B CN 113629326B CN 202110883546 A CN202110883546 A CN 202110883546A CN 113629326 B CN113629326 B CN 113629326B
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- layer
- storage device
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- modified
- elastomer
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- 238000003860 storage Methods 0.000 title claims abstract description 89
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Images
Classifications
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/78—Cases; Housings; Encapsulations; Mountings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G2/00—Details of capacitors not covered by a single one of groups H01G4/00-H01G11/00
- H01G2/10—Housing; Encapsulation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G2/00—Details of capacitors not covered by a single one of groups H01G4/00-H01G11/00
- H01G2/10—Housing; Encapsulation
- H01G2/103—Sealings, e.g. for lead-in wires; Covers
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- 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
-
- 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
- H01M50/183—Sealing members
- H01M50/184—Sealing members characterised by their shape or structure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/54—Yield strength; Tensile strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/16—Capacitors
-
- 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)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Sealing Battery Cases Or Jackets (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Laminated Bodies (AREA)
- Inorganic Chemistry (AREA)
Abstract
The present invention relates to an exterior material for an electric storage device and an electric storage device. The outer packaging material for an electric storage device is configured to include a heat-resistant resin layer (2) as an outer layer, a sealing layer (3) as an inner layer, and a metal foil layer (4) disposed between the two layers, wherein at least the innermost layer (7) of the sealing layer (3) contains an elastomer-modified olefin-based resin that includes an olefin-based thermoplastic elastomer-modified homo-polypropylene or/and an olefin-based thermoplastic elastomer-modified random copolymer that is an olefin-based thermoplastic elastomer-modified copolymer that contains propylene and a copolymer component other than propylene as copolymer components. With this structure, it is possible to provide an outer package for an electric storage device that can maintain the sealing property of the outer package sealing portion satisfactorily even when exposed to a high-temperature environment for a long period of time.
Description
The present application is a divisional application of chinese patent application No.201710554299.9, entitled "outer package for power storage device and power storage device", having a filing date of 2017, 7 and 7.
Technical Field
The present invention relates to an exterior material for a battery or a capacitor (capacitor) used in a portable device such as a smart phone or a tablet pc, and an electrical storage device such as a battery or a capacitor used in a hybrid vehicle, an electric vehicle, wind power generation, solar power generation, or night power storage.
In the present specification and claims, the term "tensile yield strength" means a tensile yield strength measured in accordance with JIS K7127-1999 (tensile test method) under conditions that the sample width is 15mm, the distance between scales is 50mm, and the tensile speed is 100 mm/min.
Background
Lithium ion secondary batteries are widely used as power sources for, for example, notebook computers, video cameras, mobile phones, and the like. As the lithium ion secondary battery, a battery in which a battery body (body including a positive electrode, a negative electrode, and an electrolyte) is surrounded by a case is used. As a material (outer packaging material) for the case, for example, a material having a structure in which an outer layer formed of a heat-resistant resin film, an aluminum foil layer, and an inner layer formed of a thermoplastic resin film are sequentially bonded and integrated is known (see patent document 1).
The power storage device is configured by sandwiching a power storage device main body between a pair of outer packaging materials, and sealing the peripheral edge portions of the pair of outer packaging materials by fusion bonding (heat sealing). By sufficiently sealing with such heat sealing, leakage of the electrolyte can be prevented.
Patent document 1: japanese patent laid-open publication No. 2005-22336
Disclosure of Invention
Problems to be solved by the invention
It is assumed that such batteries such as lithium ion secondary batteries are used in normal temperature environments such as notebook computers and mobile phones.
However, in recent years, with the diversification of the use applications of the lithium ion secondary batteries, new applications, typified by the use in automotive applications, for use outside exposed to high temperature environments have been increasing.
For example, in use in automotive applications, when an automobile is parked outdoors in summer, the temperature becomes extremely high, and therefore, it is also desired to develop an outer packaging material capable of maintaining the sealing property of the sealing portion of the outer packaging material satisfactorily even when exposed to such a high-temperature environment for a long period of time, in a battery such as a lithium ion secondary battery.
The present invention has been made in view of the above-described technical background, and an object thereof is to provide an exterior material for an electric storage device and an electric storage device, which can maintain the sealing property of an exterior material sealing portion satisfactorily even when exposed to a high-temperature environment for a long period of time.
Means for solving the problems
In order to achieve the above object, the present invention provides the following means.
[1] An exterior material for an electric storage device, characterized in that the exterior material for an electric storage device comprises a heat-resistant resin layer as an outer layer, a sealing layer as an inner layer, and a metal foil layer disposed between the two layers,
the sealing layer is formed of 1 layer to a plurality of layers, at least the innermost layer of the sealing layer contains an elastomer-modified olefin-based resin,
the elastomer-modified olefin resin comprises an olefin-based thermoplastic elastomer-modified homo-polypropylene or/and an olefin-based thermoplastic elastomer-modified random copolymer,
the olefin thermoplastic elastomer modified random copolymer is an olefin thermoplastic elastomer modified product of a random copolymer containing propylene and a copolymerization component other than propylene as copolymerization components.
[2] The exterior material for a power storage device according to the above 1, wherein the content of the olefinic thermoplastic elastomer in the innermost layer is 0.1 mass% or more and less than 20 mass%.
[3] The exterior material for an electric storage device according to the preceding item 1 or 2, wherein the melting point of the elastomer-modified olefin resin constituting the innermost layer is 160 ℃ to 180 ℃.
[4] The exterior material for an electric storage device according to any one of the above 1 to 3, wherein the olefinic thermoplastic elastomer component present in the innermost layer has a plurality of crystallization temperatures, and a lowest crystallization temperature among the plurality of crystallization temperatures is 40 ℃ to 80 ℃.
[5] The exterior material for an electrical storage device according to any one of the above 1 to 4, wherein the olefin-based thermoplastic elastomer component present in the innermost layer has an MFR of 0.1g/10 min to 1.4g/10 min.
[6] The exterior material for a power storage device according to any one of the preceding claims 1 to 5, wherein a tensile yield strength at 80 ℃ of a sealing film constituting the sealing layer is 3.5MPa to 15.0MPa.
[7] The outer packaging material for a power storage device according to any one of the preceding claims 1 to 6, wherein the sealing layer is formed of a plurality of layers, and a second sealing layer is disposed on a side closest to the metal foil layer among the sealing layers, the second sealing layer containing 50 mass% or more of the propylene-ethylene random copolymer and not containing an elastomer component.
[8] The outer packaging material for a power storage device according to any one of the preceding claims 1 to 7, wherein the metal foil layer and the sealing layer are bonded via an adhesive layer.
[9] The exterior material for a power storage device according to the aforementioned 8, wherein the adhesive layer is formed of an adhesive containing an olefin resin having a carboxyl group and a polyfunctional isocyanate compound.
[10] An electric storage device is characterized by comprising:
a power storage device main body portion; and
the exterior material for an electrical storage device according to any one of the preceding claims 1 to 9,
the power storage device main body is externally covered with the outer covering material.
ADVANTAGEOUS EFFECTS OF INVENTION
[1] In the present invention, since at least the innermost layer of the sealing layer constituting the outer packaging material contains the above-described specific elastomer-modified olefin resin, the initial sealing strength between the outer packaging materials can be sufficiently ensured even in a high-temperature environment, and the sufficient sealing strength can be maintained even when the packaging material is left in a high-temperature environment (for example, in a vehicle in summer) for a long period of time.
[2] In the present invention, the content of the olefinic thermoplastic elastomer in the innermost layer of the sealing layer is 0.1 mass% or more and less than 20 mass%, whereby the film strength of the sealing layer is increased, and breakage (rupture) starting from the sealing layer is less likely to occur.
[3] In the present invention, since the melting point of the elastomer-modified olefin resin constituting the innermost layer of the sealing layer is 160 to 180 ℃, the outflow of the sealing layer can be sufficiently suppressed when the outer packaging material is heat sealed, and the heat resistance in the above-mentioned high-temperature environment is also excellent.
[4] In the invention, since the minimum crystallization temperature is 40 to 80 ℃, the bonding time at normal temperature (bonding time at heat sealing) can be shortened.
[5] In the invention of (c), the resin (the innermost olefin resin) is not easily eluted at the time of heat sealing, and therefore, a greater adhesive strength can be ensured.
[6] In the present invention, since the sealing film having a tensile yield strength of 3.5 to 15.0MPa at 80 ℃ is used as the sealing layer, even when the power storage device is used in a high-temperature environment (for example, in a vehicle in summer) for a long period of time, cracking of the exterior material due to an increase in internal pressure can be prevented.
[7] In the present invention, the second sealing layer located closest to the metal foil layer is composed of 50 mass% or more of the propylene-ethylene random copolymer and does not contain an elastomer component, and therefore, the adhesion to the metal foil layer is improved, and interlayer peeling is less likely to occur even if deformation occurs. Further, since the second seal layer located closest to the metal foil layer does not contain an elastomer component, the electrolyte does not penetrate into the vicinity of the metal foil layer due to silver (craze) possibly generated at the interface between the propylene-ethylene random copolymer and the elastomer component (cracks, and the interface without gaps is not deviated), and sufficient insulation can be ensured.
[8] In the invention, the interlayer adhesion between the metal foil layer and the sealing layer can be further improved.
[9] In the present invention, since the adhesive layer is formed of an adhesive containing an olefin resin having a carboxyl group and a polyfunctional isocyanate compound, the electrolyte resistance can be further improved.
[10] In the present invention, an electric storage device having excellent high-temperature durability can be provided, which is formed by packaging an exterior material that can sufficiently ensure the initial seal strength between the exterior materials even in a high-temperature environment and can maintain sufficient seal strength even when placed in a high-temperature environment (for example, in a vehicle in summer) for a long period of time.
Drawings
Fig. 1 is a cross-sectional view showing an embodiment of an outer package material for a power storage device according to the present invention.
Fig. 2 is a cross-sectional view showing another embodiment of the outer package material for the power storage device according to the present invention.
Fig. 3 is a cross-sectional view showing an embodiment of the power storage device according to the present invention.
Fig. 4 is a perspective view showing a state before heat-sealing an exterior material (a planar object), a power storage device main body, and an exterior case (a molded body molded into a three-dimensional shape) constituting the power storage device of fig. 3.
Description of the reference numerals
1 … outer packaging material for power storage device
2 … Heat-resistant resin layer (outer layer)
3 … sealing layer (inner layer)
4 … Metal foil layer
5 … outer adhesive layer (first adhesive layer)
6 … inner adhesive layer (second adhesive layer)
7 … first seal layer (innermost layer; innermost seal layer)
8 … second seal layer (seal layer closest to the side of the Metal foil layer)
10 … outer casing for power storage device
15 … outer packing member
30 … electric storage device
31 … Main body of Power storage device
Detailed Description
Fig. 1 shows an embodiment of an outer package 1 for an electric storage device according to the present invention. The outer package 1 for a power storage device is used as an outer package for a lithium ion secondary battery, for example. The outer package material 1 for the power storage device may be used as it is without molding, or may be used as an outer package case 10 by molding such as deep drawing molding or bulging molding (see fig. 4).
The outer package 1 for the power storage device includes the following components: a base material layer (outer layer) 2 is laminated and integrated on one surface of the metal foil layer 4 via a first adhesive layer 5, and an inner sealing layer (inner layer) 3 is laminated and integrated on the other surface of the metal foil layer 4 via a second adhesive layer 6 (see fig. 1 and 2).
In the outer package 1 of fig. 1, the inner seal layer (inner layer) 3 is formed as a single layer (1 layer) formed of the first seal layer 7. Therefore, the first sealing layer 7 is disposed at the innermost side (the first sealing layer 7 is the innermost layer).
In the outer packaging material 1 of fig. 2, the inner sealing layer (inner layer) 3 has a 2-layer structure formed of a first sealing layer 7 as an innermost layer and a second sealing layer 8 disposed on the side closest to the metal foil layer 4, and the first sealing layer 7 is disposed on the innermost side.
In the present invention, the inner seal layer (inner layer) 3 plays the following roles: the outer packaging material is also excellent in chemical resistance against an electrolyte solution or the like having a strong corrosiveness used in lithium ion secondary batteries or the like, and heat sealability is imparted to the outer packaging material. The seal layer (inner layer) 3 is formed of an unstretched seal film.
In the present invention, the sealing layer (inner layer) 3 may be formed of 1 layer or 2 or more layers, and at least the innermost layer (first sealing layer) 7 of the sealing layer (inner layer) 3 may be formed of an elastomer-modified olefin resin.
The elastomer-modified olefin-based resin (polypropylene block copolymer) preferably contains olefin-based thermoplastic elastomer-modified homo-polypropylene and/or olefin-based thermoplastic elastomer-modified random copolymer, which is a random copolymer containing "propylene" and "other copolymerization component than propylene" as copolymerization components, and examples of the "other copolymerization component than propylene" include olefin components such as ethylene, 1-butene, 1-hexene, 1-pentene, 4-methyl-1-pentene, butadiene, and the like, without particular limitation. The olefinic thermoplastic elastomer is not particularly limited, and examples thereof include EPR (ethylene propylene rubber), propylene-butene elastomer, propylene-butene-ethylene elastomer, EPDM (ethylene-propylene-diene rubber) and the like, and among them, EPR (ethylene propylene rubber) is preferably used.
The elastomer-modified olefin resin may be graft polymerized or may be modified in other forms as the "modified olefin-based thermoplastic elastomer".
The elastomer-modified olefin resin can be produced by, for example, the following reactor production method. This represents only 1 example, and is not particularly limited to the production by such a production method.
First, a Ziegler-Natta catalyst, a cocatalyst, propylene and hydrogen are fed into a first reactor to polymerize homopolypropylene. The resulting homo-polypropylene was transferred to a second reactor in a state comprising unreacted propylene and Ziegler-Natta catalyst. Propylene and hydrogen were further added to the second reactor to polymerize the homopolypropylene. The resulting homo-polypropylene was transferred to a third reactor in a state comprising unreacted propylene and Ziegler-Natta catalyst. The elastomer-modified olefin resin can be produced by further adding ethylene, propylene and hydrogen to the third reactor and polymerizing an ethylene-propylene rubber (EPR) formed by copolymerizing ethylene and propylene. For example, the elastomer-modified olefin resin can be produced by adding a solvent to the liquid phase, and the elastomer-modified olefin resin can be produced by reacting the above in the gas phase without using a solvent.
The content of the olefinic thermoplastic elastomer in the innermost layer (first sealing layer) 7 of the sealing layer 3 is preferably 0.1 mass% or more and less than 20 mass%. The content of the homo-polypropylene (the portion not modified with the olefinic thermoplastic elastomer) and/or the random copolymer (the portion not modified with the olefinic thermoplastic elastomer) in the innermost layer (first sealing layer) 7 of the sealing layer 3 is preferably 80 mass% or more and 99 mass% or less.
The melting point of the elastomer-modified olefin resin constituting the innermost layer (first sealing layer) 7 of the sealing layer 3 is preferably in the range of 160 to 180 ℃. The outflow of the sealing layer 3 can be sufficiently suppressed when the outer package material is heat-sealed, and the heat resistance under high-temperature environment is excellent. Among them, the melting point of the elastomer-modified olefin resin constituting the innermost layer (first sealing layer) 7 of the sealing layer 3 is preferably 163 ℃ or higher, and particularly preferably in the range of 163 ℃ to 169 ℃. The above melting point is a melting point measured according to JIS K7121-1987 by Differential Scanning Calorimetry (DSC).
The olefinic thermoplastic elastomer component (only this component) present in the innermost layer (first sealing layer) 7 preferably has a plurality of crystallization temperatures. When the crystallization temperatures are plural as described above, the effect that the resin (the olefin-based resin in the innermost layer) is less likely to be eluted during bonding can be obtained. When the crystal has a plurality of crystallization temperatures, the lowest crystallization temperature among the plurality of crystallization temperatures is preferably in the range of 40 to 80 ℃, more preferably in the range of 40 to 75 ℃. The minimum crystallization temperature is set to 40 to 80 ℃, whereby the bonding time at normal temperature (bonding time at heat sealing) can be shortened. The crystallization temperature is a crystallization temperature (crystallization peak) measured according to JIS K7121-1987 by Differential Scanning Calorimetry (DSC).
The MFR of the olefinic thermoplastic elastomer component (only this component) present in the innermost layer (first seal layer) 7 is preferably 0.1g/10 min to 1.4g/10 min, and in this case, the resin (olefinic resin of the innermost layer) becomes less likely to be eluted during heat sealing, and therefore a greater adhesive strength can be ensured. Among them, the MFR of the olefinic thermoplastic elastomer component (only the component) present in the innermost layer (first seal layer) 7 is more preferably 0.1g/10 min to 1.0g/10 min or less, and particularly preferably 0.1g/10 min to 0.6g/10 min or less. The MFR (melt flow rate) was measured at 230℃and 2.16kg according to JIS K7210-1-2014.
The tensile yield strength of the sealing film constituting the sealing layer 3 at 80℃is preferably 3.5MPa to 15.0MPa. For example, when the seal layer 3 is constituted by only the first seal layer 7, the tensile yield strength of the first seal film at 80 ℃ is preferably 3.5MPa to 15.0MPa, and when the seal layer 3 is constituted by a laminate of the first seal layer 7 and the second seal layer 8, the tensile yield strength of the laminated seal film at 80 ℃ is preferably 3.5MPa to 15.0MPa. When the sealing layer 3 is a multilayer of 3 or more layers, the laminated sealing film preferably has a tensile yield strength of 3.5 to 15.0MPa at 80 ℃. By setting the tensile yield strength at 80 ℃ of the sealing film constituting the sealing layer 3 to 3.5MPa to 15.0MPa as described above, cracking of the exterior material due to an increase in internal pressure can be prevented even when the power storage device is used in a high-temperature environment (for example, in a vehicle in summer) for a long period of time. Of these, the sealing film constituting the sealing layer 3 is particularly preferably 4 to 12MPa in tensile yield strength at 80 ℃.
The thickness of the innermost layer (first sealing layer) 7 is preferably 30 μm or more, and in this case, there is an advantage that the toughness of the first sealing layer 7 can be improved. Among them, the thickness of the innermost layer (first sealing layer) 7 is more preferably 30 μm to 100 μm.
When the second sealing layer 8 is provided, the thickness of the second sealing layer 8 is preferably 3 μm to 60 μm, more preferably 5 μm to 20 μm. In the case of providing the second sealing layer 8, the resin forming the second sealing layer 8 is not particularly limited, and examples thereof include propylene-ethylene random copolymer, homopolypropylene, polyethylene, olefin-based thermoplastic elastomer-modified homopolypropylene, olefin-based thermoplastic elastomer-modified random copolymer (olefin-based thermoplastic elastomer-modified random copolymer of random copolymer containing "propylene" and "other copolymerization component than propylene" as copolymerization components), and the like.
The thickness of the sealing layer 3 is preferably set to 30 μm to 200 μm.
In the present invention, the sealing layer 3 is formed of a plurality of layers, and has an innermost layer (first sealing layer) 7 containing the elastomer-modified olefin resin, and a second sealing layer 8 (see fig. 2) disposed on the side closest to the metal foil layer 4, and the second sealing layer is preferably composed of a propylene-ethylene random copolymer containing 50 mass% or more and containing no elastomer component. In the case of such a structure, the second sealing layer 8 located closest to the metal foil layer 4 is constituted to contain 50 mass% or more of the propylene-ethylene random copolymer and not to contain the elastomer component, and therefore, the adhesion to the metal foil layer side is improved, and even if deformation occurs, interlayer peeling is less likely to occur. Further, since the second seal layer 8 located closest to the metal foil layer 4 does not contain an elastomer component, the electrolyte does not penetrate into the vicinity of the metal foil layer due to silver streaks (cracks or separation of interfaces without gaps) that may occur at the interface between the propylene-ethylene random copolymer and the elastomer component, and sufficient insulation can be ensured. Among these, the second sealing layer is more preferably composed of a propylene-ethylene random copolymer containing 70 mass% or more and not containing an elastomer component. Here, the configuration not containing the elastomer component means that the elastomer component is not mixed (doped) and that the elastomer-modified resin is not mixed.
The sealing film constituting the sealing layer (inner layer) 3 is preferably produced by a molding method such as multilayer extrusion molding, inflation molding, or T-die cast film molding.
The method of laminating the sealing film constituting the sealing layer (inner layer) 3 on the metal foil layer 4 is not particularly limited, and examples thereof include a dry lamination method and a sandwich lamination method (a method of extruding an adhesive film of acid-modified polypropylene or the like, laminating the adhesive film between a metal foil and the sealing film with a sandwich, and then heat-laminating the adhesive film with a heat roll).
In the present invention, the base material layer (outer layer) 2 is preferably formed of a heat-resistant resin layer. As the heat-resistant resin constituting the heat-resistant resin layer 2, a heat-resistant resin that does not melt at the heat-sealing temperature at the time of heat-sealing the outer packaging material is used. The heat-resistant resin is preferably a heat-resistant resin having a melting point of 10 ℃ or higher than the melting point of the sealing layer 3, and particularly preferably a heat-resistant resin having a melting point of 20 ℃ or higher than the melting point of the sealing layer 3.
The heat-resistant resin layer (outer layer) 2 is not particularly limited, and examples thereof include polyamide films such as nylon films, polyester films, and the like, and stretched films of these films can be preferably used. Among them, as the heat-resistant resin layer 2, a biaxially stretched polyamide film such as a biaxially stretched nylon film, a biaxially stretched polybutylene terephthalate (PBT) film, a biaxially stretched polyethylene terephthalate (PET) film, or a biaxially stretched polyethylene naphthalate (PEN) film is particularly preferably used. The nylon film is not particularly limited, and examples thereof include nylon 6 film, nylon 6,6 film, nylon MXD film, and the like. The heat-resistant resin layer 2 may be formed of a single layer, or may be formed of, for example, a plurality of layers including a polyester film/polyamide film (a plurality of layers including a PET film/nylon film, or the like). In the case of the above-described multilayer, the polyester film side may be disposed at the outermost side.
The thickness of the outer layer (base material layer) 2 is preferably 2 μm to 50 μm. The thickness is preferably 5 to 40 μm when a polyester film is used, and is preferably 15 to 50 μm when a nylon film is used. By setting the lower limit value or more, a sufficient strength as an outer package material can be ensured, and by setting the upper limit value or less, stress at the time of molding such as bulge molding or drawing molding can be reduced, and moldability can be improved.
In the outer packaging material for an electric storage device according to the present invention, the metal foil layer 4 plays a role of imparting gas barrier properties (preventing invasion of oxygen and moisture) to the outer packaging material 1. The metal foil layer 4 is not particularly limited, and examples thereof include aluminum foil, SUS foil (stainless steel foil), copper foil, and the like, and among them, aluminum foil and SUS foil (stainless steel foil) are preferably used. The thickness of the metal foil layer 4 is preferably 10 μm to 120 μm. By setting the thickness to 10 μm or more, pinholes can be prevented from being generated during rolling in the production of the metal foil, and by setting the thickness to 120 μm or less, stress during molding such as bulge molding and drawing can be reduced, and moldability can be improved.
In the metal foil layer 4, it is preferable that at least the inner surface (the surface on the second adhesive layer 6 side) is subjected to a chemical conversion treatment. By performing such chemical conversion treatment, corrosion of the metal foil surface due to the content (electrolyte of the battery or the like) can be sufficiently prevented. For example, the metal foil is subjected to a chemical conversion treatment by performing the following treatment. That is, for example, the surface of the metal foil subjected to degreasing treatment is coated with any one of the aqueous solutions of 1) to 3), and then dried, whereby chemical conversion treatment is performed.
1) An aqueous solution of a mixture comprising:
phosphoric acid;
chromic acid; and
at least 1 compound selected from the group consisting of metal salts of fluorides and nonmetallic salts of fluorides,
2) An aqueous solution of a mixture comprising:
phosphoric acid;
at least 1 resin selected from the group consisting of acrylic resin, chitosan (chitosan) derivative resin, and phenolic resin; and
at least 1 compound selected from the group consisting of chromic acid and chromium (III) salts,
3) An aqueous solution of a mixture comprising:
phosphoric acid;
at least 1 resin selected from the group consisting of acrylic resins, chitosan derivative resins, and phenolic resins;
at least one compound selected from the group consisting of chromic acid and chromium (III) salts; and
at least 1 compound selected from the group consisting of metal salts of fluorides and nonmetallic salts of fluorides.
The chemical conversion coating preferably has a chromium deposit (on each side) of 0.1mg/m 2 ～50mg/m 2 Particularly preferably 2mg/m 2 ～20mg/m 2 。
The first adhesive layer (outer adhesive layer) 5 is not particularly limited, and examples thereof include a polyurethane polyolefin adhesive layer, a polyurethane adhesive layer, a polyester polyurethane adhesive layer, and a polyether polyurethane adhesive layer. The thickness of the first adhesive layer 5 is preferably set to 1 μm to 6 μm. Among them, the thickness of the first adhesive layer 5 is particularly preferably set to 1 μm to 3 μm from the viewpoint of reduction in thickness and weight of the outer package 1.
The second adhesive layer (inner adhesive layer) 6 is not particularly limited, and for example, a material exemplified as the first adhesive layer 5 may be used, but a polyolefin adhesive having little swelling due to an electrolyte solution is preferably used. Among them, the second adhesive layer (inner adhesive layer) 6 is preferably formed of an adhesive containing an olefin resin having a carboxyl group and a polyfunctional isocyanate compound. The second adhesive layer can be formed by dry lamination of the adhesives. Alternatively, the second adhesive layer (inner adhesive layer) 6 is preferably formed of an olefin resin having a carboxyl group. In this case, the second adhesive layer can be formed by extrusion lamination by melt extrusion of an olefin resin having a carboxyl group. The above-mentioned olefin resin having a carboxyl group is not particularly limited, and examples thereof include carboxylic acid-modified olefin resins such as maleic acid-modified polypropylene, maleic acid-modified polyethylene, acrylic acid-modified polypropylene, acrylic acid-modified polyethylene, methacrylic acid-modified polypropylene, methacrylic acid-modified polyethylene, fumaric acid-modified polypropylene, fumaric acid-modified polyethylene, and the like. The thickness of the second adhesive layer 6 is preferably set to 1 μm to 4 μm. Among them, the thickness of the second adhesive layer 6 is particularly preferably set to 1 μm to 3 μm from the viewpoint of reduction in thickness and weight of the outer package.
By molding (deep drawing, bulging, etc.) the outer package material 1 of the present invention, an outer package case (battery case, etc.) 10 (fig. 4) can be obtained. The outer package 1 of the present invention may be used as it is without molding (fig. 4).
Fig. 3 shows an embodiment of an electric storage device 30 configured using the outer package 1 of the present invention. The power storage device 30 is a lithium ion secondary battery. In the present embodiment, as shown in fig. 3 and 4, the outer package member 15 is composed of the outer package case 10 obtained by molding the outer package 1, and the planar outer package 1. Then, the power storage device 30 of the present invention is configured by accommodating a power storage device main body portion (electrochemical element or the like) 31 having a substantially rectangular parallelepiped shape in a storage recess of an outer case 10 obtained by molding an outer package 1 of the present invention, disposing the outer package 1 of the present invention above the power storage device main body portion 31 without molding, disposing the sealing layer 3 side thereof to the inner side (lower side), and sealing the peripheral edge portion of the sealing layer 3 of the planar outer package 1 and the sealing layer 3 of a flange portion (sealing peripheral edge portion) 29 of the outer case 10 by heat sealing (see fig. 3 and 4). The surface of the outer case 10 inside the housing recess is a sealing layer 3, and the outer surface of the housing recess is a base material layer (outer layer) 2 (see fig. 4).
In fig. 3, 39 is a heat seal portion formed by joining (welding) a peripheral edge portion of the outer package 1 and a flange portion (sealing peripheral edge portion) 29 of the outer package case 10. In the power storage device 30, the tip portion of the tab connected to the power storage device main body 31 is led out of the outer package member 15, which is not shown in the drawings.
The power storage device main body 31 is not particularly limited, and examples thereof include a battery main body, a capacitor main body, and a capacitor main body.
The width of the heat seal portion 39 is preferably set to 0.5mm or more. When the thickness is 0.5mm or more, sealing can be performed reliably. The width of the heat seal portion 39 is preferably set to 3mm to 15mm.
In the above embodiment, the outer package member 15 is formed of the outer package case 10 obtained by molding the outer package material 1 and the planar outer package material 1 (see fig. 3 and 4), but the outer package member 15 is not particularly limited to such a combination, and may be formed of a pair of planar outer package materials 1, or may be formed of a pair of outer package cases 10, for example.
Examples
Next, specific embodiments of the present invention will be described, but the present invention is not limited to these embodiments in particular.
< Material used >
(elastomer-modified olefin resin A)
The elastomer-modified olefin-based resin A contains an EPR modified product of an EPR modified homo-polypropylene and an ethylene-propylene random copolymer. The EPR mentioned above represents an ethylene-propylene rubber. The content of the elastomer component in the elastomer-modified olefin resin a was 15 mass%. The melting point of the elastomer-modified olefin resin A was 166 ℃.
(elastomer-modified olefin resin B)
The elastomer-modified olefin-based resin B contains a propylene-butene elastomer-modified homo-polypropylene and a propylene-butene elastomer-modified ethylene-propylene random copolymer. The content of the elastomer component in the elastomer-modified olefin resin B was 18 mass%. The melting point of the elastomer-modified olefin-based resin B was 164 ℃.
(elastomer-modified olefin resin C)
The elastomer-modified olefin-based resin C contains a propylene-butene-ethylene elastomer modified body of a propylene-butene-ethylene elastomer modified homo-polypropylene and an ethylene-propylene random copolymer. The content of the elastomer component in the elastomer-modified olefin resin C was 16 mass%. The melting point of the elastomer-modified olefin-based resin C was 164 ℃.
Example 1 >
A chemical conversion treatment solution containing phosphoric acid, polyacrylic acid (acrylic resin), a chromium (III) salt compound, water, and alcohol was applied to both sides of an aluminum foil 4 having a thickness of 35 μm, and then dried at 180 ℃. The chromium adhesion amount of the chemical conversion coating was 10mg/m per one surface 2 。
Subsequently, a biaxially stretched nylon 6 film 2 having a thickness of 15 μm was dry laminated (bonded) on one surface of the aluminum foil 4 subjected to the chemical conversion treatment via a two-component curable urethane adhesive (outer adhesive) 5.
Next, a sealing film (first sealing layer) 7 having a thickness of 80 μm formed of the elastomer-modified olefin-based resin a was extruded, and then the other surface of the dry-laminated aluminum foil 4 was laminated on one surface of the sealing film 7 (3) via a two-liquid-curable urethane-based adhesive (inner adhesive layer) 6, and the laminate was sandwiched between a rubber nip roller and a laminating roller heated to 100 ℃ and pressure-bonded, whereby dry lamination was performed, and then cured (heated) at 50 ℃ for 5 days, thereby obtaining the exterior package 1 for an electric storage device having the structure shown in fig. 1.
Example 2 >
An exterior material 1 for an electric storage device having a structure shown in fig. 1 was obtained in the same manner as in example 1, except that a two-part curing type acrylic adhesive 6 was used as the inner adhesive 6 instead of the two-part curing type urethane adhesive.
Example 3 >
A chemical conversion treatment solution containing phosphoric acid, polyacrylic acid (acrylic resin), a chromium (III) salt compound, water, and alcohol was applied to both sides of an aluminum foil 4 having a thickness of 35 μm, and then dried at 180 ℃. The chromium adhesion amount of the chemical conversion coating was 10mg/m per one surface 2 。
Subsequently, a biaxially stretched nylon 6 film 2 having a thickness of 15 μm was dry-laminated (bonded) on one surface of the aluminum foil 4 on which the chemical conversion treatment was completed via a two-component curable urethane adhesive 5.
Next, a maleic anhydride-modified polypropylene film (inner adhesive layer) 6 having a thickness of 4 μm, a propylene-ethylene random copolymer film (second sealing layer) 8 having a thickness of 8 μm, and an elastomer-modified olefin-based resin a film (first sealing layer) 7 having a thickness of 72 μm were coextruded, and these were sequentially laminated on the other surface of the above-mentioned dry-laminated aluminum foil 4, and by sandwiching it between a rubber nip roller and a lamination roller heated to 100 ℃ and pressure-bonding, dry lamination was performed, and then cured (heated) at 50 ℃ for 5 days, whereby the exterior package 1 for an electric storage device having the structure shown in fig. 2 was obtained.
Example 4 >
A chemical conversion treatment solution containing phosphoric acid, polyacrylic acid (acrylic resin), a chromium (III) salt compound, water, and alcohol was applied to both sides of an aluminum foil 4 having a thickness of 35 μm, and then dried at 180 ℃. The chromium adhesion amount of the chemical conversion coating was 10mg/m per one surface 2 。
Subsequently, a biaxially stretched nylon 6 film 2 having a thickness of 15 μm was dry-laminated (bonded) on one surface of the aluminum foil 4 on which the chemical conversion treatment was completed via a two-component curable urethane adhesive 5.
Next, a maleic anhydride-modified polypropylene film (inner adhesive layer) 6 having a thickness of 4 μm and an elastomer-modified olefin resin a film 3 having a thickness of 80 μm were co-extruded, and these were sequentially laminated on the other surface of the aluminum foil 4 after the above-described dry lamination, and the laminate was sandwiched between a rubber nip roller and a lamination roller heated to 100 ℃ and pressure-bonded to carry out dry lamination, and then cured (heated) at 50 ℃ for 5 days, thereby obtaining an exterior material 1 for an electric storage device having the structure shown in fig. 1.
Example 5 >
An outer package 1 for an electric storage device having the structure shown in fig. 1 was obtained in the same manner as in example 1, except that the elastomer-modified olefin resin B was used instead of the elastomer-modified olefin resin a.
Example 6 >
An outer package 1 for an electric storage device having the structure shown in fig. 1 was obtained in the same manner as in example 1, except that the elastomer-modified olefin resin C was used instead of the elastomer-modified olefin resin a.
Example 7 >
A chemical conversion treatment solution containing phosphoric acid, polyacrylic acid (acrylic resin), a chromium (III) salt compound, water, and alcohol was applied to both sides of an aluminum foil 4 having a thickness of 35 μm, and then dried at 180 ℃. The chromium adhesion amount of the chemical conversion coating was 10mg/m per one surface 2 。
Subsequently, a biaxially stretched nylon 6 film 2 having a thickness of 15 μm was dry-laminated (bonded) on one surface of the aluminum foil 4 on which the chemical conversion treatment was completed via a two-component curable urethane adhesive 5.
Next, a two-liquid curable urethane adhesive (inner adhesive layer) 6 was applied to the other surface of the dry-laminated aluminum foil 4, and then a homo-polypropylene film (second seal layer) 8 having a thickness of 8 μm and an elastomer-modified olefinic resin a film (first seal layer) 7 having a thickness of 72 μm were laminated in this order on the applied surface, and the resultant was sandwiched between a rubber nip roller and a lamination roller heated to 100 ℃ and pressure-bonded to carry out dry lamination, followed by aging (heating) at 50 ℃ for 5 days, thereby obtaining an exterior package material 1 for an electric storage device having the structure shown in fig. 2.
Example 8 >
An outer packaging material 1 for an electric storage device having a structure shown in fig. 2 was obtained in the same manner as in example 7, except that a propylene-ethylene random copolymer film 8 having a thickness of 8 μm was used as the second sealing layer 8 instead of the homopolypropylene film having a thickness of 8 μm.
Example 9 >
An exterior material 1 for an electric storage device having a structure shown in fig. 2 was obtained in the same manner as in example 8, except that a two-part curing type acrylic adhesive 6 was used as the inner adhesive 6 instead of the two-part curing type urethane adhesive.
Comparative example 1 >
An exterior material for an electric storage device having the structure shown in fig. 1 was obtained in the same manner as in example 1, except that a propylene-ethylene random copolymer was used instead of the elastomer-modified olefin resin a.
Comparative example 2 >
A chemical conversion treatment solution containing phosphoric acid, polyacrylic acid (acrylic resin), a chromium (III) salt compound, water, and alcohol was applied to both sides of an aluminum foil 4 having a thickness of 35 μm, and then dried at 180 ℃. The chromium adhesion amount of the chemical conversion coating was 10mg/m per one surface 2 。
Subsequently, a biaxially stretched nylon 6 film 2 having a thickness of 15 μm was dry-laminated (bonded) on one surface of the aluminum foil 4 on which the chemical conversion treatment was completed via a two-component curable urethane adhesive 5.
Next, a two-liquid curable acrylic adhesive 6 was applied to the other surface of the dry-laminated aluminum foil 4, and an elastomer-modified olefin resin a film (second seal layer) 8 having a thickness of 68 μm and a propylene-ethylene random copolymer film (first seal layer) 7 having a thickness of 12 μm were laminated in this order on the coated surface, and the resultant was sandwiched between a rubber nip roller and a lamination roller heated to 100 ℃ and pressure-bonded, and then dry-laminated was performed, followed by aging (heating) at 50 ℃ for 5 days, whereby the outer package for an electric storage device having the structure shown in fig. 2 was obtained.
The tensile yield strength (see table 1) of the sealing films (thickness 80 μm) 3 used to produce the outer packaging materials of examples 1 to 9 and comparative examples 1 to 2 was measured in the following manner.
Method for measuring tensile yield strength of sealing film
A type 2 test piece (length: 150mm or more) was prepared in accordance with JIS K7127-1999 (tensile test method for plastic film) for an unstretched sealing film 3 (thickness: 80 μm) similarly prepared for other measurement, and tensile test was performed at 80℃under conditions of 15mm in specimen width, 100mm in distance between jigs, 50mm in distance between scales and 100 mm/min in tensile speed to obtain tensile yield strength. The load at the yield point in the S-S curve is taken as the tensile yield strength. After the test piece was mounted in a tensile test apparatus in a constant temperature bath set at 80 ℃, the test piece was allowed to stand in an environment of 80 ℃ for 1 minute, and then a tensile test was performed in an environment of 80 ℃. The measurement results of the tensile yield strength at 80℃are shown in Table 1.
The measurement was performed by setting the thickness of the test piece to 80. Mu.m, but for example, when the sealing film 3 having a thickness of 64 μm was a 2-layer laminate structure of the second sealing layer having a thickness of 6 μm and the first sealing layer having a thickness of 58. Mu.m, the measurement was performed by preparing the test piece having a thickness of 80. Mu.m so that the thickness ratio of the 2 layers was not changed. That is, a test piece of a 2-layer laminate structure of a second sealing layer having a thickness of 7.5 μm and a first sealing layer having a thickness of 72.5 μm was prepared and measured. In the case of a laminated structure of 3 or more layers, a test piece having a thickness of 80 μm was produced and measured in the same manner.
The outer packaging material for each power storage device obtained as described above was evaluated by the following measurement method.
< method for measuring initial seal Strength at high temperature >)
After 2 test pieces each having a width of 15mm×a length of 150mm were cut out from the obtained outer package, the 2 test pieces were stacked so that inner seal layers were in contact with each other, and in this state, heat sealing was performed by single-sided heating using a test SANGYO co., ltd. Heat sealing apparatus (TP-701-a) at a heat sealing temperature of 200 c under a sealing pressure of 0.2MPa (gauge pressure) for a sealing time of 2 seconds.
Next, as for a pair of outer packaging materials obtained by heat-sealing and bonding inner seal layers to each other as described above, peel strength at 90 degrees between inner seal layers of a sealed portion of the outer packaging material (test body) was measured as seal strength (N/15 mm width) using a Shimadzu Access Corporation strapath (tensile test apparatus) (AGS-5 kNX) disposed in a constant temperature bath according to JIS Z0238-1998. The seal strength at 100℃and the seal strength at 120℃were measured.
In the measurement of the seal strength at 100 ℃, the test piece was mounted in a tensile test apparatus in a constant temperature tank set at 100 ℃, allowed to stand in the environment at 100 ℃ for 1 minute, and then the measurement was performed in the environment at 100 ℃. For measurement of seal strength at 120 ℃, the test body was mounted in a tensile test apparatus in a constant temperature tank set at 120 ℃, allowed to stand in the 120 ℃ environment for 1 minute, and then measured in the 120 ℃ environment.
The sealing strength at 100℃and the sealing strength at 120℃were both judged as acceptable for the cases of 27N/15mm width or more.
< method for measuring seal Strength after 90 days in high temperature Environment >)
2 pieces of outer packaging material cut into pieces with a length of 200mm by a width of 150mm are stacked so that sealing layers of the outer packaging material are positioned inside and face each other, and 3-side edge portions of the outer packaging material are heat-sealed at 180℃for 2 seconds under 0.2 MPa. From the left unsealed 1-side openingAfter 10mL of the electrolyte was injected, the remaining 1 was heat-sealed while air was drawn under the same sealing conditions as described above, to prepare a simulated battery (test body). The following electrolytes were used as the electrolytes: lithium hexafluorophosphate (LiPF) 6 ) Dissolved in a mixed solvent of Ethylene Carbonate (EC) and dimethyl carbonate (DMC) in an equal volume ratio to give a concentration of 1 mol/L.
The obtained simulated battery was placed in a constant temperature and humidity apparatus made by ESPEC, and allowed to stand at 80℃for 90 days under 90% Rh (exposed to a high temperature and high humidity environment for 90 days).
The above-mentioned simulated battery after 90 days was taken out, the electrolyte was removed by opening 1 side, the inside was washed several times with water, and then, in a state where 2 sheets of outer packaging materials were laminated, the resultant outer packaging materials were cut into a size of 15mm wide by 150mm long so as to include a sealing portion of 2 sheets of outer packaging materials, and the peel strength when the outer packaging materials were peeled off by 90 degrees at a tensile rate of 100 mm/min between the sealing layers of the sealing portion was measured as a seal strength (N/15 mm width) in accordance with JIS Z0238-1998 using a tensile test apparatus (AGS-5 kNX) manufactured by Shimadzu Access Corporation. The seal strength at 25℃was measured. The sealing strength was at least 27N/15mm wide.
As can be seen from table 1, the outer packaging materials for power storage devices according to examples 1 to 9 of the present invention can maintain sufficient initial seal strength even in a high-temperature environment, and can maintain sufficient seal strength even when left in a high-temperature environment for a long period of time.
In contrast, in comparative examples 1 and 2, the initial seal strength in the high-temperature environment was insufficient, and the seal strength after being left in the high-temperature environment for a long period of time was greatly reduced.
Industrial applicability
The exterior material for an electric storage device manufactured using the sealing film according to the present invention and the exterior material for an electric storage device according to the present invention can be used as exterior materials for various electric storage devices, and specific examples of the electric storage device include:
power storage devices such as lithium secondary batteries (lithium ion batteries, lithium polymer batteries, etc.);
lithium ion capacitor;
an electric double layer capacitor; etc.
The power storage device according to the present invention includes not only the above-described power storage device but also an all-solid-state battery.
The present application claims priority from Japanese patent application No. 2016-159935, filed 8/17, the disclosure of which forms a part of this application directly.
The terminology and descriptions used herein are for the purpose of describing embodiments of the invention only, and are not intended to be limiting. The invention is susceptible to any design modification within the scope of the claims without exceeding the gist thereof.
Claims (9)
1. An exterior material for an electric storage device, characterized in that the exterior material for an electric storage device comprises a heat-resistant resin layer as an outer layer, a sealing layer as an inner layer, and a metal foil layer disposed between the two layers,
the sealing layer is formed of 1 layer to a plurality of layers, at least the innermost layer of the sealing layer contains an elastomer-modified olefin-based resin,
the elastomer-modified olefin resin comprises an olefin thermoplastic elastomer-modified homo-polypropylene and an olefin thermoplastic elastomer-modified random copolymer,
the olefin thermoplastic elastomer modified random copolymer is an olefin thermoplastic elastomer modified product of a random copolymer containing propylene and a copolymerization component other than propylene as copolymerization components.
2. The exterior material for a power storage device according to claim 1, wherein the content of the olefinic thermoplastic elastomer in the innermost layer is 0.1 mass% or more and less than 20 mass%.
3. The exterior cover material for an electric storage device according to claim 1 or 2, wherein the melting point of the elastomer-modified olefin resin constituting the innermost layer is 160 ℃ to 180 ℃.
4. The exterior material for an electric storage device according to claim 1 or 2, wherein the olefinic thermoplastic elastomer component present in the innermost layer has a plurality of crystallization temperatures, and a lowest crystallization temperature among the plurality of crystallization temperatures is 40 ℃ to 80 ℃.
5. The exterior material for an electrical storage device according to claim 1 or 2, wherein the olefin-based thermoplastic elastomer component present in the innermost layer has an MFR of 0.1g/10 min to 1.4g/10 min.
6. The exterior material for an electric storage device according to claim 1 or 2, wherein a tensile yield strength of a sealing film constituting the sealing layer at 80 ℃ is 3.5MPa to 15.0MPa.
7. The exterior material for a power storage device according to claim 1 or 2, wherein the metal foil layer and the sealing layer are bonded together via an adhesive layer.
8. The exterior material for a power storage device according to claim 7, wherein the adhesive layer is formed of an adhesive containing an olefin resin having a carboxyl group and a polyfunctional isocyanate compound.
9. An electric storage device is characterized by comprising:
a power storage device main body portion; and
the exterior material for an electrical storage device according to any one of claim 1 to 8,
the power storage device main body is externally covered with the outer covering material.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110883546.6A CN113629326B (en) | 2016-08-17 | 2017-07-07 | Outer packaging material for power storage device, and power storage device |
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| Application Number | Priority Date | Filing Date | Title |
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| JP2016159935 | 2016-08-17 | ||
| JP2016-159935 | 2016-08-17 | ||
| CN202110883546.6A CN113629326B (en) | 2016-08-17 | 2017-07-07 | Outer packaging material for power storage device, and power storage device |
| CN201710554299.9A CN107768553B (en) | 2016-08-17 | 2017-07-07 | Outer packaging material for electricity storage device and electricity storage device |
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| CN202110883546.6A Active CN113629326B (en) | 2016-08-17 | 2017-07-07 | Outer packaging material for power storage device, and power storage device |
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| KR (2) | KR102399127B1 (en) |
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| CN110341260B (en) * | 2018-04-02 | 2021-10-29 | 昭和电工包装株式会社 | Laminate for molded container, and package |
| JP7291494B2 (en) * | 2018-04-02 | 2023-06-15 | 株式会社レゾナック・パッケージング | Laminate for molded container, molded container and package |
| CN108794788A (en) * | 2018-05-16 | 2018-11-13 | 上海恩捷新材料科技股份有限公司 | A kind of flexible package and preparation method thereof |
| JP7324611B2 (en) * | 2018-05-25 | 2023-08-10 | 株式会社レゾナック・パッケージング | Laminate for molded container, molded container and package |
| WO2020004413A1 (en) * | 2018-06-27 | 2020-01-02 | 凸版印刷株式会社 | Outer packaging material for electricity storage devices and electricity storage device using same |
| EP4129653A1 (en) * | 2020-03-26 | 2023-02-08 | Dai Nippon Printing Co., Ltd. | Packaging material for power storage device, method of producing same, and power storage device |
| CN113594593B (en) * | 2021-07-12 | 2023-06-20 | 苏州福斯特光伏材料有限公司 | Design method of aluminum plastic film and aluminum plastic film |
| KR102662513B1 (en) * | 2022-12-30 | 2024-05-03 | 율촌화학 주식회사 | Pouch film for secondary battery with excellent room temperature and high temperature sealing strength where sealant layer yield strength, sealant layer thickness ratio and sealant layer glass transition temperature are controlled, and manufacturing method thereof |
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| JP4431822B2 (en) | 2003-07-04 | 2010-03-17 | 昭和電工パッケージング株式会社 | Packaging material with excellent moldability and packaging container molded using the same |
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| KR20200130869A (en) | 2011-03-29 | 2020-11-20 | 쇼와 덴코 패키징 가부시키가이샤 | Molding packaging material and battery case |
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| JP2016081705A (en) * | 2014-10-16 | 2016-05-16 | 油化電子株式会社 | Laminate film for battery outer packaging and battery |
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| KR102411295B1 (en) | 2022-06-22 |
| CN107768553A (en) | 2018-03-06 |
| JP2021192377A (en) | 2021-12-16 |
| KR20210100582A (en) | 2021-08-17 |
| JP7381528B2 (en) | 2023-11-15 |
| CN113629326A (en) | 2021-11-09 |
| JP2024016165A (en) | 2024-02-06 |
| CN107768553B (en) | 2021-11-16 |
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| KR20220088403A (en) | 2022-06-27 |
| JP6969892B2 (en) | 2021-11-24 |
| TW201807862A (en) | 2018-03-01 |
| KR20180020082A (en) | 2018-02-27 |
| JP2018032616A (en) | 2018-03-01 |
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