CN107204406B - Outer packaging material for electricity storage device and electricity storage device - Google Patents

Outer packaging material for electricity storage device and electricity storage device Download PDF

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Publication number
CN107204406B
CN107204406B CN201710147482.7A CN201710147482A CN107204406B CN 107204406 B CN107204406 B CN 107204406B CN 201710147482 A CN201710147482 A CN 201710147482A CN 107204406 B CN107204406 B CN 107204406B
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storage device
layer
heat
power storage
outer package
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CN107204406A (en
Inventor
中嶋大介
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Lishennoco Packaging Co ltd
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Showa Denko Packaging Co Ltd
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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 of a single cell or a single battery
    • H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
    • H01M50/124—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered 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
    • 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
    • B32B15/085—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 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • 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 of a single cell or a single battery
    • H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery 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 of a single cell or a single battery
    • H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery 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 of a single cell or a single battery
    • H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
    • H01M50/124—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure
    • H01M50/126—Primary casings, jackets or wrappings of a single cell or a single battery 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
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • 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
    • B32B2307/558—Impact strength, toughness
    • 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
    • B32B2307/582—Tearability
    • B32B2307/5825—Tear resistant
    • 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
    • B32B2457/10—Batteries
    • 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
    • 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
    • Y02E60/13—Energy storage using capacitors

Abstract

The present invention relates to an outer package for an electricity storage device and an electricity storage device. The outer package (1) for the electricity storage device comprises a heat-resistant resin film layer (2) as an outer layer, a thermoplastic resin layer (3) as an inner layer, and a metal foil layer (4) provided between the two layers, wherein the outer package (1) for the electricity storage device has a failure energy of 1.5J or more, and the heat-resistant resin film (2) has a failure energy of 1.3J or more. With the above configuration, it is possible to provide an outer cover for a power storage device, which is less likely to break or crack when an external impact is applied thereto even if the outer cover is designed to be thin.

Description

Outer packaging material for electricity storage device and electricity storage device
Technical Field
The present invention relates to an outer covering material for an electric storage device such as a battery and a capacitor (capacitor) used in a portable device (portable device) such as a smartphone and a tablet computer, a battery and a capacitor used in an electric storage application of a hybrid vehicle, an electric vehicle, wind power generation, solar power generation, and night power, and an electric storage device that is externally covered with the outer covering material.
In the claims and the description of the present application, the term "energy to failure" means the energy to failure W determined by measuring the mass of a 6.5 kg-and a hemisphere (hemisphere with a radius of 10 mm) having a diameter of 20mm with a hammer dropped naturally from a height of 30cm in an environment at a temperature of 23 ℃ in accordance with JIS K7124-2-1999 (part 2 of the impact test method of plastic films and sheets by the free falling dart method: the instrumental breakdown method) F 。
In the claims and the description of the present application, the "W" should be used for both "energy to break of outer packaging material for power storage device" and "energy to break of heat-resistant resin film F "description (abbreviated description)" but to avoid bothFor the sake of convenience, "energy of destruction of outer package for power storage device" is referred to as "W FT "energy of failure of Heat-resistant resin film" is referred to as "W FS ”。
In addition, in the present specification, the term "aluminum" is used in the meaning of including aluminum and its alloys.
Background
In recent years, with the reduction in thickness and weight of mobile electronic devices such as smartphones and tablet personal computer terminals, a laminate (laminate outer packaging material) formed of a heat-resistant resin layer/an adhesive layer/a metal foil layer/an adhesive layer/a thermoplastic resin layer has been used in place of a conventional metal can as an outer packaging material for an electric storage device such as a lithium ion secondary battery, a lithium polymer secondary battery, a lithium ion capacitor (lithium ion capacitor) or an electric double layer capacitor mounted on the mobile electronic device (see patent document 1). The laminate (outer packaging material) having the above-described structure is used for outer packaging of a power source for an electric vehicle or the like, a large-sized power source for electric storage, a capacitor, and the like.
The laminated outer package material having the above-described configuration has advantages of light weight and good heat radiation property as compared with a metal can, but is inferior to a metal can in impact resistance when subjected to an impact from the outside.
Therefore, in order to improve the impact resistance against the external impact as described above, an outer package having the following configuration has been proposed. That is, a secondary battery has been proposed in which a positive electrode member and a negative electrode member electrically connected to a current collector are laminated via a non-flowable electrolyte, a rigid holding member is in contact with the outer periphery of a battery element containing an ionic metal component, and the outer surface of the battery element is covered with a flexible synthetic resin film and sealed (see patent document 2).
Further, a laminate film exterior battery has been proposed in which an electrode group obtained by laminating a positive electrode and a negative electrode with a separator interposed therebetween is enclosed in an exterior body of a laminate film, and a frame-shaped protective member for protecting the electrode group is provided around the electrode group (see patent document 3).
Patent document 1: japanese laid-open patent publication No. 2007-161310
Patent document 2: japanese patent laid-open No. 2000-195475
Patent document 3: japanese patent laid-open publication No. 2005-259621
Disclosure of Invention
Problems to be solved by the invention
However, the above-described prior art has the following problems. In the secondary battery described in patent document 2, since a rigid holding member is disposed as an additional member between the battery element and the flexible synthetic resin film (outer package), the requirements for reduction in thickness and weight cannot be satisfied sufficiently. That is, there is a problem that the effect of weight reduction by providing the laminate film outer packaging material is impaired or reduced.
In addition, in the laminate film exterior battery described in patent document 3, similarly, a frame-shaped protective member is disposed as an additional member between the electrode group and the laminate film exterior body, and therefore, the requirements for reduction in thickness and weight cannot be satisfied sufficiently. That is, there is a problem that the effect of weight reduction by providing the laminate film outer packaging material is impaired or reduced.
The present invention has been made in view of the background of the related art, and a first object of the present invention is to provide an outer cover for a power storage device, which is less likely to break or crack when an external impact is applied thereto even if the outer cover is designed to be thin.
A second object of the present invention is to provide an outer package for an electricity storage device, which is less likely to break or crack when an external impact is applied thereto even when the outer package is designed to be thin, and which can prevent the outer package from cracking more favorably by selectively causing cohesive failure in a heat-sealed portion (heat-sealed portion).
Means for solving the problems
To achieve the above object, the present invention provides the following strategies.
[1] An outer package for an electricity storage device, comprising a heat-resistant resin film layer as an outer layer, a thermoplastic resin layer as an inner layer, and a metal foil layer provided between the two layers,
the outer package for an electricity storage device has a destruction energy of 1.5J or more,
the heat-resistant resin film has a failure energy of 1.3J or more.
[2] The outer cover for a power storage device described in the aforementioned item 1, wherein the inner layer is formed of a thermoplastic resin layer having a seal-breaking energy of 0.50J or more in a heat-seal bonded state of the thermoplastic resin layers of the outer cover for a power storage device.
[3]The outer package for power storage devices as set forth in the above item 1 or 2, wherein the energy of destruction of the outer package for power storage devices is "W FT ", and" W "represents seal-breaking energy in a state where the thermoplastic resin layers of the outer covering material for an electricity storage device are heat-sealed and joined to each other P When (W) FT /W P )>2.0。
[4] The outer covering material for power storage devices as defined in any one of the above items 1 to 3, wherein the thermoplastic resin layer comprises at least a 3-layer laminate structure in which coating layers comprising an olefinic resin are laminated on both surfaces of an intermediate layer comprising an olefinic resin containing an elastomer component
The intermediate layer has a sea-island structure in which the elastomer component becomes islands.
[5] An electricity storage device is characterized by comprising
A power storage device main body portion, and
the outer covering material for a power storage device as described in any one of the above items 1 to 4,
the power storage device main body is externally coated with the outer coating material.
Effects of the invention
[1] In the invention according to (1), since the outer cover for a power storage device has a structure in which the energy to break is 1.5J or more and the energy to break of the heat-resistant resin film is 1.3J or more, even if the outer cover is made thin and designed to be lightweight (for example, even if the outer cover is designed to be thin at a thickness of 50 μm to 70 μm), the outer cover is less likely to break or crack when an impact from the outside is applied. Therefore, even if an electronic device or the like having the power storage device (in which the device main body is externally packaged with the exterior material of the present invention) receives an impact due to a drop, an impact, or the like, the exterior material is less likely to be broken or cracked, and occurrence of a short circuit of the power storage device can be suppressed. That is, the first object can be achieved.
[2] In the invention as recited in the above, the inner layer is formed of the thermoplastic resin layer having the seal-breaking energy of 0.50J or more in the heat-seal bonded state of the thermoplastic resin layers to the outer covering material for the electricity storage device, and when the electricity storage device receives an impact from the outside, the heat-seal surfaces of the thermoplastic resin layers are easily peeled off by cohesive peeling, whereby the outer covering material can be prevented from being broken or cracked, and therefore, the occurrence of short-circuiting of the electricity storage device can be further suppressed. Namely, the second object can be achieved.
[3]In the invention (2), since (W) is present FT /W P )>2.0, even when a strong impact from the outside is applied to the power storage device, the outer package can be effectively prevented from being broken or ruptured by selectively peeling and cohesive failure from the heat-sealed portion (heat-sealed portion) before the outer package is broken or ruptured, and short circuits between the electrodes of the power storage device can be effectively prevented.
[4] In the invention as described above, since the thermoplastic resin layer has a structure in which the thermoplastic resin layer has at least a 3-layer laminated structure in which the coating layer containing the olefinic resin is laminated on both surfaces of the intermediate layer containing the olefinic resin containing the elastomer component, and the intermediate layer has a sea-island structure in which the elastomer component is islands, when the electric storage device receives an impact from the outside, energy of the impact can be efficiently absorbed by the intermediate layer having the sea-island structure, and thus, when the electric storage device receives an impact from the outside, the outer package is less likely to be broken or cracked.
[5] In the invention (power storage device) of (1), even if the outer package is designed to be thin, the outer package is less likely to be broken or cracked when an external impact is applied thereto, and occurrence of a short circuit can be suppressed.
Drawings
Fig. 1 is a cross-sectional view showing an embodiment of an outer package for a power storage device according to the present invention.
Fig. 2 is a cross-sectional view showing an embodiment of a power storage device formed using the outer package for a power storage device according to the present invention.
Description of the reference numerals
1 … outer packaging material for electricity storage device
2 … Heat-resistant resin film layer (outer layer)
3 … thermoplastic resin layer (inner layer)
4 … Metal foil layer
5 … first adhesive layer
6 … second adhesive layer
11 … moulded case
19 … electric storage device main body part
20 … electric storage device
Detailed Description
Fig. 1 shows an embodiment of an outer package 1 for a power storage device according to the present invention. This exterior material 1 for a power storage device is used for a lithium ion secondary battery case. That is, the outer package 1 for a power storage device can be used as a case of a secondary battery by, for example, deep drawing, bulging, or the like.
The outer package 1 for a power storage device includes: a heat-resistant resin film layer (outer layer) 2 is laminated and integrated on one surface of a metal foil layer 4 via a first pressure-sensitive adhesive layer 5, and a thermoplastic resin layer (inner layer) 3 is laminated and integrated on the other surface of the metal foil layer 4 via a second pressure-sensitive adhesive layer 6.
The outer package 1 for a power storage device according to the present invention is configured to: breaking of the outer packaging material for the electricity storage deviceBad energy W FT 1.5J or more, and a breaking energy W of the heat-resistant resin film FS Is 1.3J or more. Since the outer package 1 for a power storage device of the present invention is configured as described above, even if the outer package is made thin and designed to be lightweight (for example, even if the outer package is designed to be thin at a thickness of 50 μm to 70 μm), the outer package is less likely to be broken or cracked when an external impact is applied thereto. Therefore, even when an electronic device or the like having a power storage device (in which the device main body is externally packaged with the outer package material of the present invention) receives an impact due to a drop, a collision, or the like, the outer package material is less likely to be broken or cracked, and short-circuiting of the power storage device can be suppressed. In the present invention, the energy of destruction W of the outer package for the electricity storage device is FT The energy of destruction W of the outer package for an electricity storage device is required to be 1.5J or more FT Usually 2.5J or less. In the present invention, the heat-resistant resin film has a fracture energy W FS It is required to be 1.3J or more, but the heat-resistant resin film has a breaking energy W of 1.3J or more FS Usually 2.0J or less. The "energy to break of the heat-resistant resin film" is energy to break measured in a state before the heat-resistant resin film is laminated with another layer.
The inner layer 3 is preferably formed of the outer covering material for an electricity storage device, and has seal-breaking energy W in a state where the thermoplastic resin layers are heat-sealed to each other P In this case, when the power storage device receives an impact from the outside, the heat-sealed surfaces of the thermoplastic resin layers are easily peeled off due to cohesive peeling, and thus cracking of the outer cover material can be prevented, and occurrence of a short circuit in the power storage device can be further suppressed. The seal breaking energy W P Preferably 0.50J or more and 1.3J or less.
Further, the outer package 1 for a power storage device according to the present invention is preferably (W) FT /W P )>2.0, even when a strong impact from the outside is applied to the electricity storage device, the outer cover can be broken or broken before the outer cover is brokenBy selectively causing peeling and cohesive failure from the heat-sealed portion (heat-sealed portion), breakage and cracking of the outer package material can be effectively prevented, and occurrence of short circuit between the electrodes of the power storage device can be effectively prevented. Among them, the outer package 1 for a power storage device of the present invention is particularly preferably 4.0>(W FT /W P )>2.0.
As the heat-resistant resin constituting the heat-resistant resin film layer (outer layer) 2, a heat-resistant resin that does not melt at a heat-sealing temperature when heat-sealing the outer packaging material is performed is used. As the heat-resistant resin, a heat-resistant resin having a melting point higher than that of the thermoplastic resin constituting the thermoplastic resin layer 3 by 10 ℃ or more is preferably used, and particularly, a heat-resistant resin having a melting point higher than that of the thermoplastic resin by 20 ℃ or more is preferably used.
The heat-resistant resin layer (outer layer) 2 is not particularly limited, and examples thereof include polyamide films such as nylon films, polyester films, polyolefin films, and the like, and stretched films thereof are preferably used. Among these, 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, a biaxially stretched polyethylene naphthalate (PEN) film, and a biaxially stretched polypropylene film are particularly preferably used. The nylon film is not particularly limited, and examples thereof include a nylon 6 film, a nylon 6,6 film, and an MXD nylon film. The heat-resistant resin layer 2 may be formed as a single layer, or may be formed as a composite layer formed of, for example, a polyester film/polyamide film (e.g., a composite layer formed of a PET film/nylon film). In the composite layer structure exemplified above, the polyester film is preferably disposed outside the polyamide film, and similarly, the PET film is preferably disposed outside the nylon film.
The thickness of the heat-resistant resin layer 2 is preferably 8 to 50 μm. By setting the above-described preferable lower limit or more, sufficient strength can be secured as the outer jacket material, and by setting the above-described preferable upper limit or less, the stress at the time of forming such as bulging or deep drawing can be reduced, and formability can be improved. Among them, the thickness of the heat-resistant resin layer 2 is particularly preferably 12 μm to 25 μm.
The thermoplastic resin layer (thermal adhesive resin layer) (inner layer) 3 plays a role of: the outer packaging material is provided with excellent chemical resistance even against highly corrosive electrolytes used in lithium ion secondary batteries and the like, and heat sealability.
The thermoplastic resin layer 3 is not particularly limited, and is preferably a thermoplastic resin unstretched film layer. The thermoplastic resin unstretched film layer 3 is not particularly limited, and is preferably composed of an unstretched film formed of at least one thermoplastic resin selected from the group consisting of: polyethylene, polypropylene, olefin copolymers, acid-modified products thereof, and ionomers (ionomers). The thermoplastic resin layer 3 may be a single layer or a composite layer.
The thermoplastic resin layer 3 preferably has a structure including at least a 3-layer laminate structure in which coating layers of an olefin-based resin are laminated on both surfaces of an intermediate layer including an olefin-based resin containing an elastomer component, and the intermediate layer has a sea-island structure in which the elastomer component is islands.
The olefin-based resin containing the elastomer component may be a composition in which an elastomer is added (blended) to an olefin-based resin, or an elastomer-modified olefin-based resin in which an elastomer component is chemically bonded to an olefin-based resin skeleton. It is noted that the term "elastomer" is used in a sense of also including a rubber component.
The thickness of the thermoplastic resin layer 3 is preferably set to 10 to 80 μm. By setting the thickness to 10 μm or more, the occurrence of pin holes can be sufficiently prevented, and by setting the thickness to 80 μm or less, the amount of resin used can be reduced, and cost reduction can be achieved. Among them, the thickness of the thermoplastic resin layer 3 is particularly preferably set to 25 μm to 50 μm.
The metal foil layer 4 plays a role of imparting gas barrier properties for preventing oxygen and moisture from entering the outer wrapper 1. The metal foil layer 4 is not particularly limited, and examples thereof include an aluminum foil, a SUS foil (stainless steel) foil, and a copper foil, and an aluminum foil is generally used. The thickness of the metal foil layer 4 is preferably 20 to 100 μm. By setting the thickness to 20 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 100 μm or less, stress during forming such as bulging or deep drawing can be reduced, and formability can be improved. Among them, the thickness of the metal foil layer 4 is particularly preferably 20 μm to 50 μm.
It is preferable that at least the inner surface (the surface on the second adhesive layer 6 side) of the metal foil layer 4 is subjected to chemical conversion treatment. By performing such chemical conversion treatment, corrosion of the metal foil surface by the contents (electrolyte solution of the battery, etc.) can be sufficiently prevented. The metal foil is subjected to a chemical conversion treatment by performing the following treatment, for example. That is, for example, a chemical conversion treatment is performed by applying any one of aqueous solutions 1) to 3) described below to the surface of the degreased metal foil and then drying the applied solution,
1) an aqueous solution comprising a mixture of:
phosphoric acid,
Chromic acid, and
at least 1 compound selected from the group consisting of metal salts of fluoride and non-metal salts of fluoride;
2) an aqueous solution comprising a mixture of:
phosphoric acid,
At least 1 resin selected from the group consisting of acrylic resin, 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 comprising a mixture of:
phosphoric acid,
At least 1 resin selected from the group consisting of acrylic resin, chitosan derivative resin and phenolic resin,
At least 1 compound selected from the group consisting of chromic acid and chromium (III) salt, and
at least 1 compound selected from the group consisting of metal salts of fluoride and non-metal salts of fluoride.
The chemical conversion coating is preferably 0.1mg/m in chromium adhesion amount (per surface) 2 ～50mg/m 2 Particularly preferably 2mg/m 2 ～20mg/m 2 。
The first pressure-sensitive adhesive layer 5 is not particularly limited, and examples thereof include a polyurethane pressure-sensitive adhesive layer, a polyester polyurethane pressure-sensitive adhesive layer, and a polyether polyurethane pressure-sensitive adhesive layer. The thickness of the first adhesive layer 5 is preferably set to 1 μm to 5 μm. Among them, the thickness of the first pressure-sensitive 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 covering material.
The second pressure-sensitive adhesive layer 6 is not particularly limited, and for example, the pressure-sensitive adhesive layer shown as the first pressure-sensitive adhesive layer 5 may be used, and a polyolefin-based pressure-sensitive adhesive which is less likely to swell with an electrolyte solution is preferably used. The thickness of the second adhesive layer 6 is preferably set to 1 μm to 5 μm. Among them, the thickness of the second pressure-sensitive 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 covering material.
By molding (deep drawing, bulging, etc.) the exterior material 1 of the present invention, a molded case (battery case, etc.) can be obtained. The outer cover 1 of the present invention can be used without molding.
Fig. 2 shows an embodiment of a power storage device 20 configured by using the exterior material 1 of the present invention. The power storage device 20 is a lithium ion secondary battery.
The battery 20 includes: an electrolyte 21, a tab (tab lead)22, the planar outer cover 1 which is not molded, and a molded case 11 having a housing recess 11b which is obtained by molding the outer cover 1 (see fig. 2). The power storage device body 19 is composed of the electrolyte 21 and the tab 22.
The battery 20 is configured such that the electrolyte 21 and a part of the tab 22 are accommodated in the accommodation recess 11b of the molded case 11, the planar outer package 1 is disposed on the molded case 11, and a heat-sealed portion (heat-sealed portion) is formed by heat-sealing and joining (the inner layer 3 of) the peripheral edge portion of the outer package 1 and (the inner layer 3 of) the sealing peripheral edge portion 11a of the molded case 11. The distal end portions of the tabs 22 are led out to the outside (see fig. 2).
Examples
Next, specific examples of the present invention will be described, but the present invention is not particularly limited to these examples.
< example 1>
A chemical conversion coating film was formed by applying a chemical conversion treatment solution containing phosphoric acid, polyacrylic acid (acrylic resin), a chromium (III) salt compound, water, and alcohol to both sides of an aluminum foil (annealed aluminum foil of a8021 defined by JIS H4160) 4 having a thickness of 30 μm, and then drying at 180 ℃. The chromium deposition amount on each surface of the chemical conversion coating was 10mg/m 2 。
Next, a biaxially stretched nylon 6 film (outer layer) 2 having a thickness of 12 μm was dry-laminated (bonded) on one surface of the aluminum foil 4 subjected to the chemical conversion treatment with a two-pack curable urethane adhesive 5 interposed therebetween.
Then, a first resin layer having a thickness of 4.5 μm made of an ethylene-propylene random copolymer, a second resin layer having a thickness of 21 μm made of an ethylene-propylene block copolymer, and a first resin layer having a thickness of 4.5 μm made of an ethylene-propylene random copolymer were coextruded using a T die so as to 3-layer laminate in this order to obtain a sealing film (first resin layer/second resin layer/first resin layer) 3 having a thickness of 20 μm obtained by laminating the above 3 layers, and then one first resin layer of the sealing film (inner layer) 3 was laminated on the other surface of the aluminum foil 4 laminated by interposing a two-liquid curable maleic acid-modified polypropylene adhesive (curing agent is a polyfunctional isocyanate) 6 therebetween, and was pressure-bonded by sandwiching between a rubber nip roller and a laminating roller heated to 100 ℃, thus, dry lamination was performed, and then aging (heating) was performed at 40 ℃ for 5 days, thereby obtaining outer package 1 for an electricity storage device having a thickness of 79 μm as shown in fig. 1.
The second resin layer (ethylene-propylene block copolymer) is described in detail, and is formed of a resin composition containing: 99% by mass of a first elastomer-modified olefinic resin having a melting point of 163 ℃ and a crystal melting enthalpy (Japanese "JI Crystal melting エネルギー") of 58J/g, and 1% by mass of a second elastomer-modified olefinic resin having a melting point of 144 ℃ and a crystal melting enthalpy of 19J/g. The first elastomer-modified olefinic resin and the second elastomer-modified olefinic resin each include an elastomer-modified homopolypropylene or/and an elastomer-modified random copolymer. The elastomer-modified random copolymer is an elastomer-modified random copolymer containing propylene and a copolymerization component other than propylene as a copolymerization component. When SEM observation (scanning electron microscope observation) was performed only on the second resin layer, it was confirmed that the second resin layer had a sea-island structure in which the elastomer component was islands.
The above term "melting point" means a melting peak temperature measured by Differential Scanning Calorimetry (DSC) in accordance with JIS K7121-1987, and the term "crystalline melting enthalpy" means a heat of fusion (crystalline melting enthalpy) measured by Differential Scanning Calorimetry (DSC) in accordance with JIS K7122-1987.
As the two-pack curable maleic acid-modified polypropylene adhesive, an adhesive solution (obtained by mixing 100 parts by mass of a maleic acid-modified polypropylene (melting point: 80 ℃ C., acid value: 10mgKOH/g) as a main component, 8 parts by mass of an isocyanurate body of 1, 6-hexamethylene diisocyanate (NCO content: 20 mass%) as a curing agent, and a solvent) was used, and the adhesive solution was applied in such an amount that the solid content was 2g/m 2 The method (3) is applied to the other surface of the aluminum foil 4, heated and dried, and then superimposed on one first resin layer surface of the sealing film 3.
< example 2>
An outer cover 1 for a power storage device having a thickness of 74 μm and having a structure shown in fig. 1 was obtained in the same manner as in example 1, except that an aluminum foil having a thickness of 25 μm (annealed aluminum foil a8021 prescribed in JIS H4160) was used instead of the aluminum foil having a thickness of 30 μm.
< example 3>
An outer cover 1 for an electricity storage device having a thickness of 92 μm and a configuration shown in fig. 1 was obtained in the same manner as in example 1, except that a polyethylene terephthalate film having a thickness of 9 μm was laminated on the outer side of a biaxially stretched nylon 6 film having a thickness of 12 μm via a two-pack curable polyurethane adhesive.
< example 4>
An outer package for an electricity storage device having a thickness of 82 μm was obtained in the same manner as in example 1, except that a biaxially stretched nylon 6 film having a thickness of 15 μm was used instead of the biaxially stretched nylon 6 film having a thickness of 12 μm.
< example 5>
An electricity storage device exterior material having a thickness of 89 μm was obtained in the same manner as in example 2, except that a sealing film having a thickness of 40 μm (first resin layer/second resin layer/first resin layer: 6 μm/28 μm/6 μm) was used instead of the sealing film having a thickness of 30 μm (first resin layer/second resin layer/first resin layer: 4.5 μm/21 μm/4.5 μm). The same resins as in example 2 (example 1) were used as the resins constituting the first resin layer and the second resin layer, respectively.
< comparative example 1>
An outer packaging material for an electricity storage device having a thickness of 69 μm was obtained in the same manner as in example 1, except that an aluminum foil having a thickness of 20 μm (annealed aluminum foil a8021 defined in JIS H4160) was used instead of the aluminum foil having a thickness of 30 μm.
< comparative example 2>
An outer covering material for an electric storage device having a thickness of 79 μm was obtained in the same manner as in example 1, except that a biaxially stretched nylon 6 film having a thickness of 12 μm and a heat shrinkage rate of 3% smaller than that of the biaxially stretched nylon 6 film used in example 1 was used.
< comparative example 3>
An outer packaging material for an electricity storage device having a thickness of 79 μm was obtained in the same manner as in example 4, except that a sealing film made of an ethylene-propylene random copolymer having a thickness of 30 μm was used instead of the sealing film (first resin layer/second resin layer/first resin layer) having a thickness of 30 μm obtained by laminating 3 layers.
TABLE 1
Figure BDA0001244607340000131
The energy of destruction W of the outer package for the electricity storage device obtained in each of the examples and comparative examples described above FT The energy of rupture W of the heat-resistant resin film for outer layer (biaxially stretched Nylon 6 film) used in each of the examples and comparative examples described above FS Seal-breaking energy W of outer package for electricity storage devices of each of the above examples and comparative examples P And (W) FT /W P ) Are shown in Table 1, respectively.
The energy of destruction W of the outer package for power storage devices of each of the examples and comparative examples described above FT The heat-resistant resin film for the outer layer (biaxially stretched nylon 6 film) used in each of the above examples and comparative examples was measured for the fracture energy W in the following manner FS The seal-breaking energy W of the outer packaging materials for the electricity storage devices of the examples and comparative examples was measured as follows P The measurement was carried out in the following manner.
< method for measuring energy of destruction of outer packaging Material >
According to JIS K7124-2-1999 (part 2 of the impact test method of plastic films and sheets by the free falling dart method: the instrumental puncture method), the test piece was pressed with a chuck (clamp) having an inner diameter of 40mm under an environment of 23 ℃ and the destruction energy of the outer package was measured under the condition that a hammer having a mass of 6.5kg and a hemisphere shape corresponding to a diameter of 20mm (hemisphere shape having a radius of 10 mm) was naturally dropped from a height of 30 cm. The measurement was performed using a Toyo Seiki co., ltd. drop weight impact tester (Falling weight graphical impact tester).
< method for measuring energy to destroy Heat-resistant resin film >
According to JIS K7124-2-1999 (part 2 of the impact test method of plastic films and sheets by the free falling dart method: the instrumental puncture method), the test piece was pressed with a chuck (clamp) having an inner diameter of 40mm under an environment of 23 ℃ and the breaking energy of a heat-resistant resin film (biaxially stretched nylon 6 film) was measured under the condition that a hammer having a mass of 6.5kg and a hemisphere shape corresponding to a diameter of 20mm (hemisphere shape having a radius of 10 mm) was naturally dropped from a height of 30 cm. The measurement was performed using a Toyo Seiki co., ltd.
In example 3, since the outer layer was formed of a laminate film (which contained a polyethylene terephthalate film having a thickness of 9 μm/a polyurethane-based adhesive layer having a thickness of 3 μm/a biaxially stretched nylon 6 film having a thickness of 12 μm), the heat-resistant resin film in example 3 was subjected to the measurement of the energy to break of the laminate film (having a thickness of 24 μm) containing a polyethylene terephthalate film having a thickness of 9 μm/a polyurethane-based adhesive layer having a thickness of 3 μm/a biaxially stretched nylon 6 film having a thickness of 12 μm.
< method for measuring seal-breaking energy of outer packaging Material >
The outer packaging material was cut into a short strip having a width of 15mm × a length of 100mm to obtain a test piece. 2 test pieces were prepared, and after the 2 test pieces were stacked so that the inner layers of the test pieces were positioned inward, heat sealing was performed on the entire surface over the entire width of 15mm, thereby forming a heat-sealed portion (heat-sealed portion). The heat sealing was performed by single-side heating for 2 seconds at a heat sealing temperature of 200 ℃ and a sealing pressure of 0.2MPa (gauge pressure) using a heat sealing apparatus (TP-701-A) manufactured by Tester Industry Co.
Next, the peel strength of the 2 heat-sealed test pieces was measured in accordance with JIS Z0238-1998. One end in the longitudinal direction of the heat-sealed 2 test pieces was peeled off at the interface between the inner layers, and the peel strength was measured by peeling 180 degrees at a stretching speed (grip moving rate) of 100 mm/min while sandwiching the peeled end, and this was taken as the seal strength (N/15mm width). In the measurement of the peel strength, graph data of "peel strength (vertical axis)" with respect to "grip displacement (horizontal axis)" was recorded. The area of the lower side of the curve (curve from the start of peeling to the end of peeling) in the graph (graph) of the peel strength (N) against the grip displacement (mm) was calculated to determine the seal rupture energy (J).
The term "peeling completion" means a state in which the inner layers (sealant layers) after thermal bonding are completely peeled from each other after peeling is started (after peeling is started) from one end in the longitudinal direction of the heat-sealed 2 test pieces. At the end of the above peeling, the peel strength was 0.
The performance of each of the outer packaging materials for power storage devices obtained as described above was evaluated by the following evaluation method. The results are shown in Table 1.
< method for evaluating cohesion (cohesion) at peeling interface >
The peeling portion (broken portion) of the inner layer of the outer cover material after the seal rupture energy was measured (after the peeling was completed) was observed on both sides by visual observation, and the presence or absence of whitening on both sides of the peeling portion (broken portion) and the degree of whitening (the stronger the whitening, the greater the cohesive force) were evaluated based on the following criteria.
(criteria for determination)
The case where whitening occurred significantly and the cohesive force was high was evaluated as "o", the case where whitening occurred to some extent and the cohesive force was medium was evaluated as "Δ", and the case where whitening was not observed or whitening was not substantially observed and the cohesive force was low was evaluated as "x".
< impact test method >
In each of the examples, 2 rectangular outer materials were prepared in comparative examples, and a three-dimensional molded article was obtained by deep drawing one outer material, the three-dimensional molded article comprising: the container case is formed in a three-dimensional shape (a substantially rectangular parallelepiped shape with an open upper surface) having a vertical length of 55mm, a horizontal length of 30mm, and a depth of 5.5mm, and a sealing peripheral edge portion having a width of 5mm extending from a peripheral edge of an upper surface opening of the container case toward the outside in the substantially horizontal direction. A battery body part (polypropylene) is put into the concave part of the three-dimensional forming bodyA dummy product prepared) was further injected with 5mL of an electrolytic solution, and then, the peripheral edge portion of the inner layer of the other (another) planar outer covering material (outer covering material not molded) was laminated on the inner layer of the sealing peripheral edge portion of the three-dimensional molded body, and heat-sealed by a metal hot plate heated to 200 ℃ for 2 seconds to form a heat-sealed portion (heat-sealed portion), thereby obtaining a dummy battery. The following electrolytes were used: lithium hexafluorophosphate (LiPF) as electrolyte 6 ) Ethylene Carbonate (EC), dimethyl carbonate (DMC), and Ethyl Methyl Carbonate (EMC) were mixed in an equal volume ratio at a concentration of 1mol/L to obtain a mixed solvent. 10 simulated cells were produced for each of the examples and comparative examples.
Next, a round bar having a diameter of 15mm was placed on the upper surface (flat surface portion) of the dummy cell in a stable state, and then a 9kg ball-shaped metal hammer was dropped on the round bar, and the fracture resistance of the outer jacket material was evaluated based on the following criteria.
(criteria for determination)
Among the … … 10 simulated cells, 0 or 1 cell was broken in the outer package at the center (maximum flat surface) due to the falling of the weight
Of the "Δ" … … 10 simulated batteries, 2 batteries in which the outer jacket was broken at the central portion (maximum flat surface portion) due to dropping of the weight were used
Of the "x" … … 10 simulated batteries, 3 to 10 batteries were broken at the center (maximum flat surface) of the exterior material by dropping the weight.
< comprehensive judgment >
The case where both the evaluation results of the above-described peeling interface were "good" was evaluated as "excellent" (particularly excellent), the case where one of the 2 evaluation results was "good" and the other was "Δ" was evaluated as "good" (excellent), the case where both of the 2 evaluation results were "Δ" was evaluated as "Δ" (substantially good), and the case where at least 1 of the 2 evaluation results was "x" was evaluated as "x" (poor).
As can be seen from table 1, the outer covering materials for power storage devices according to examples 1 to 5 of the present invention were less likely to break or crack at the central portion (maximum flat surface portion) of the outer covering material even when subjected to an external impact, and were less likely to cause a short circuit even when subjected to an external impact. In addition, in the outer package for the electricity storage device of examples 1 to 5 of the present invention, since the degree of whitening at the peeling interface of the heat-sealed portion (heat-sealed portion) is large, the cohesive force at the peeling interface of the heat-sealed portion is high, and therefore, when the electricity storage device receives an impact from the outside, the heat-sealed surfaces of the thermoplastic resin layers of the outer package are easily peeled off by cohesive peeling (peeling and cohesive failure are easily generated selectively in the heat-sealed portion), and thus, the outer package can be more sufficiently prevented from being broken or cracked.
In contrast, comparative example 1, in which the energy to break of the outer package for the power storage device was less than the predetermined range of the present invention, had poor results of the impact test. In comparative example 2 in which the heat-resistant resin film had a failure energy less than the predetermined range of the present invention, the impact test result was poor. In comparative example 3 in which the energy to failure of the outer package for a power storage device was less than the predetermined range of the present invention and the seal failure energy was less than 0.50J, the cohesive force at the peeling interface was low, and the impact test result was also poor.
Industrial applicability
The outer package for a power storage device of the present invention can be used as an outer package for various power storage devices, and specific examples of the power storage device include:
an electric storage device such as a lithium secondary battery (lithium ion battery, lithium polymer battery, or the like);
lithium ion capacitance;
an electric double layer capacitor; and the like. The power storage device according to the present invention includes an all-solid-state battery in addition to the power storage device described above.
The present application claims priority from Japanese patent application No. 2016-.
The terms and descriptions used herein are used for the purpose of describing embodiments of the present invention and are not intended to be limiting thereof. The present invention also allows any design change within the claims as long as it does not depart from the gist thereof.

Claims (4)

1. An outer package for an electricity storage device, comprising a heat-resistant resin film layer as an outer layer, a thermoplastic resin layer as an inner layer, and a metal foil layer provided between the two layers,
the outer package for an electricity storage device has a destruction energy of 1.5J or more,
the heat-resistant resin film has a breaking energy of 1.3J or more,
the thermoplastic resin layer comprises at least a 3-layer laminated structure in which coating layers containing an olefin resin are laminated on both surfaces of an intermediate layer comprising an olefin resin containing an elastomer component,
the intermediate layer has a sea-island structure in which the elastomer component becomes islands,
the seal breaking energy in the heat-seal bonded state of the thermoplastic resin layers is 0.48J or more.
2. The outer package for the power storage device according to claim 1, wherein the inner layer is formed of a thermoplastic resin layer having a seal rupture energy of 0.50J or more in a heat-seal bonded state of the thermoplastic resin layers of the outer package for the power storage device.
3. The outer package for power storage devices according to claim 1 or 2, wherein the energy of destruction of the outer package for power storage devices is W FT W represents seal-breaking energy in a state in which the thermoplastic resin layers of the outer packaging material for an electricity storage device are heat-sealed and bonded to each other P When (W) FT /W P )>2.0。
4. An electricity storage device is characterized by comprising
A power storage device main body portion, and
the outer packaging material for a power storage device according to any one of claims 1 to 3,
the power storage device main body is externally coated with the outer coating material.
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