CN111063833A - Outer casing for electricity storage device and method for manufacturing same - Google Patents
Outer casing for electricity storage device and method for manufacturing same Download PDFInfo
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- CN111063833A CN111063833A CN201910913266.8A CN201910913266A CN111063833A CN 111063833 A CN111063833 A CN 111063833A CN 201910913266 A CN201910913266 A CN 201910913266A CN 111063833 A CN111063833 A CN 111063833A
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- heat
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- lubricant
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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
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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
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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
- H01M50/183—Sealing members
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- 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
Abstract
The present invention relates to an outer casing for an electric storage device and a method for manufacturing the same. An outer casing (10) for an electricity storage device is formed from a molded casing of an outer casing (1), wherein the outer casing (1) is formed from a heat-resistant resin layer (2) as an outer layer, a heat-fusible resin layer (3) as an inner layer, and a metal foil layer disposed between the two layers (2), (3). The heat-fusible resin layer (3) contains a lubricant, and the content of the lubricant in the heat-fusible resin layer (3) is 200ppm to 7000 ppm. The amount of the lubricant in the outer surface (2a) of the heat-resistant resin layer (2) is less than 0.1 [ mu ] g/cm2. The wetting tension of the outer surface (2a) of the heat-resistant resin layer (2) is 33mN/m or more.
Description
Technical Field
The present invention relates to an exterior body for a battery, a capacitor, and an electricity storage device such as a battery and a capacitor used for portable devices such as smartphones and tablet computers, and for use in storage of electric power in hybrid vehicles, electric vehicles, wind power generation, solar power generation, and night power, and a method for manufacturing the exterior body.
In the present specification and claims, the term "wetting tension" refers to a wetting index (surface tension) measured in accordance with JIS K6768-1999.
Background
In recent years, with the reduction in thickness and weight of mobile electronic devices such as smartphones and tablet personal computer terminals, laminates composed of a heat-resistant resin layer/adhesive layer/metal foil layer/adhesive layer/thermoplastic resin layer (inner sealant layer) have been used in place of conventional metal cases as exterior materials for electric storage devices such as lithium ion secondary batteries, lithium polymer secondary batteries, lithium ion capacitors, and electric double layer capacitors mounted on the mobile electronic devices. Further, the laminated body (outer package) having the above-described structure is often used for outer packaging of a power source for an electric vehicle or the like, a large power source for electric storage, a capacitor, and the like. The laminate is subjected to bulging molding and deep drawing molding to be molded into a three-dimensional shape such as a substantially rectangular parallelepiped shape. By forming the battery into such a three-dimensional shape, a storage space for storing the power storage device main body can be secured.
In order to form a three-dimensional shape in a good state without generating a pinhole, a crack, or the like, it is required to improve the slidability of the surface of the inner seal layer. As a material for improving the sliding property of the surface of the inner seal layer to ensure good moldability, a material having a structure in which an anti-blocking agent (AB agent) is contained in the inner seal layer is known (see patent document 1).
Furthermore, the following solutions are proposed: forming a coating layer of a lubricant on the surface of the heat-resistant resin layer (i.e., the outer surface of the heat-resistant resin layer) further improves moldability, and molding with a deep molding depth is performed (see patent document 2).
Documents of the prior art
Patent document 1: japanese laid-open patent publication No. 2001-266811
Patent document 2: japanese patent No. 6222183
Disclosure of Invention
Problems to be solved by the invention
However, batteries that are externally packaged with an exterior material are often housed in a case together with other electronic circuits and the like. In this case, the battery is fixed by attaching a tape to the outer surface of the battery exterior material so that the battery does not contact other electronic circuits, but there is a problem as follows: the lubricant is present on the outer surface of the outer covering material, and the adhesion of the tape (the tape is easily peeled) cannot be sufficiently obtained. That is, from the viewpoint of improving moldability, it is desirable that a lubricant be present on the outer surface of the outer jacket material, but on the other hand, from the viewpoint of ensuring tape adhesion, it is necessary to avoid the presence of a lubricant on the outer surface of the outer jacket material.
The present invention has been made in view of the above-described technical background, and an object thereof is to provide an outer casing for an electricity storage device having an outer layer with good tape adhesion and a good molding state, and a method for manufacturing the outer casing.
Means for solving the problems
In order to achieve the above object, the present invention provides the following means.
[1] An outer casing for an electricity storage device, which is formed from a molded casing of an outer casing, the outer casing including: a heat-resistant resin layer as an outer layer, a heat-fusible resin layer as an inner layer, and a metal foil layer disposed between the two layers,
the heat-fusible resin layer contains a lubricant, the content of the lubricant in the heat-fusible resin layer is 200ppm to 7000ppm,
the amount of the lubricant in the outer surface of the heat-resistant resin layer is less than 0.1. mu.g/cm2，
The wetting tension of the outer surface of the heat-resistant resin layer is 33mN/m or more.
[2] The outer casing for an electricity storage device according to the above item 1, wherein the molded casing has a molding depth of 3mm or more.
[3] The outer casing for an electricity storage device according to item 1 or 2 above, wherein the heat-fusible resin layer is formed of a laminate of a plurality of heat-fusible resin films, and the heat-fusible resin film is formed of an acrylic resin containing propylene as a main component.
[4] A method for manufacturing an outer casing for an electricity storage device, comprising the steps of:
a step of laminating an outer covering material comprising a heat-resistant resin layer as an outer layer, a heat-fusible resin layer containing a lubricant as an inner layer, and a metal foil layer disposed between the two layers in a roll form so that the heat-fusible resin layer is in contact with the heat-resistant resin layer to obtain a roll body,
a step of obtaining an outer casing for an electricity storage device by drawing out the outer casing from the roll body and molding the drawn-out outer casing, and
and a treatment step of performing corona treatment or flame treatment on the outer surface of the outer layer of the outer casing for the electricity storage device.
ADVANTAGEOUS EFFECTS OF INVENTION
With respect to the aforementioned item 1, since the amount of the lubricant in the outer surface of the heat-resistant resin layer is less than 0.1. mu.g/cm2And the wetting tension of the outer surface is 33mN/m or more, so that an outer casing (molded casing) having good adhesive tape adhesion can be obtained in which the fixing adhesive tape sufficiently adheres to the outer surface of the outer layer. Further, since the lubricant content in the heat-fusible resin layer is 200ppm to 7000ppm, an appropriate amount of the lubricant is transferred to the outer surface of the outer layer, and thus a housing case which is not subjected to pinholes or cracks and can be molded satisfactorily can be provided.
In the above item 2, even when deep molding is performed to a molding depth of 3mm or more, an outer shell can be obtained which has excellent tape adhesion.
In the aforementioned item 3, since the movement of the lubricant in the heat-fusible resin layer is easily controlled, the outer shell can be obtained in a more favorable molded state.
In the above item 4, since the outer surface of the outer layer is subjected to corona treatment or flame treatment, the lubricant on the outer surface of the outer layer can be removed and the wettability of the outer surface can be improved, so that the tape adhesion to the outer surface of the outer layer can be significantly improved.
Drawings
Fig. 1 is a cross-sectional view showing an outer package for an electricity storage device (before molding) according to an embodiment of the present invention.
Fig. 2 is a perspective view showing an example of an outer casing for an electricity storage device molded from the outer material of fig. 1.
Detailed Description
An outer case 10 for an electric storage device according to an embodiment of the present invention is formed of a molded case of an outer case 1, and the outer case 1 includes a heat-resistant resin layer 2 as an outer layer, a heat-fusible resin layer 3 as an inner layer, and a metal foil layer 4 disposed between the two layers 2 and 3, that is, the outer case 10 is a case molded into a container shape by the outer case 1.
The heat-fusible resin layer 3 contains a lubricant, and the content of the lubricant in the heat-fusible resin layer 3 is 200ppm to 7000 ppm. The amount of the lubricant in the outer surface 2a of the heat-resistant resin layer 2 is less than 0.1. mu.g/cm2And the wetting tension of the outer surface 2a of the heat-resistant resin layer 2 is 33mN/m or more.
Hereinafter, the outer surface 2a of the heat-resistant resin layer 2 is also referred to as an outer surface 2a of the outer layer 2.
According to the present embodiment, since the amount of the lubricant in the outer surface 2a of the heat-resistant resin layer (outer layer) 2 is less than 0.1. mu.g/cm2Since the wetting tension of the outer surface 2a is 33mN/m or more, a good tape adhesion can be obtained in which the fixing tape sufficiently adheres to the outer surface 2a of the outer layer 2. Further, since the lubricant content in the heat-fusible resin layer 3 is 200ppm to 7000ppm, an appropriate amount of lubricant is transferred to the outer surface 2a of the outer layer 2 at the time of molding, and thus a good-moldable outer case without generating pin holes or breakage can be provided.
The content of the lubricant in the heat-fusible resin layer 3 is preferably 500ppm to 6000ppm, and more preferably 800ppm to 4000 ppm.
The amount of the lubricant in the outer surface 2a of the above heat-resistant resin layer 2 (after corona treatment or after flame treatment) needs to be less than 0.1. mu.g/cm2. Is 0.1 mu g/cm2In the above case, the adhesive tape adhesiveness is reduced. The amount of the lubricant in the outer surface 2a of the heat-resistant resin layer 2 is preferably 0.08. mu.g/cm2Hereinafter, more preferably 0.06. mu.g/cm2The following.
The wetting tension of the outer surface 2a of the heat-resistant resin layer 2 needs to be 33mN/m or more. When the amount is less than 33mN/m, the adhesive tape adhesiveness is lowered. Among these, the wetting tension of the outer surface 2a of the heat-resistant resin layer 2 is preferably 45mN/m or more, more preferably 45mN/m to 59mN/m, and particularly preferably 50mN/m to 59 mN/m.
In the present embodiment, outer package 1 has the following structure: a heat-resistant resin layer (outer layer) 2 is integrally laminated on one surface (upper surface) of the metal foil layer 4 via an outer adhesive layer (1 st adhesive layer) 5, and a heat-fusible resin layer (inner layer) 3 is integrally laminated on the other surface (lower surface) of the metal foil layer 4 via an inner adhesive layer (2 nd adhesive layer) 6 (see fig. 1).
An example of a method for manufacturing the outer case 10 for an electric storage device according to the present embodiment will be described below.
An exterior material 1 is prepared, which includes a heat-resistant resin layer 2 as an outer layer, a heat-fusible resin layer 3 containing a lubricant as an inner layer, and a metal foil layer 4 disposed between the two layers 2 and 3.
The amount of the lubricant in the outer surface 2a of the heat-resistant resin layer 2 of the exterior material 1 (i.e., before the corona treatment or before the flame treatment) is not limited. It is particularly preferred that the amount of the lubricant is 0.1. mu.g/cm2～1.0μg/cm2Within the range of (1). Less than 0.1 mug/cm2In the case, it tends to be difficult to obtain sufficient moldability. Greater than 1.0 mug/cm2Then, there is the following tendency: even if corona treatment or flame treatment is performed, the lubricant on the outer surface 2a of the heat-resistant resin layer 2 cannot be sufficiently removed, and the tape adhesion is reduced.
The content of the lubricant in heat-fusible resin layer 3 of outer cover 1 (i.e., before corona treatment or before flame treatment) is preferably set to 100ppm to 6000 ppm.
Next, the exterior material 1 is stacked in a roll shape so that the heat-sealable resin layer 3 and the heat-resistant resin layer 2 are in contact with each other, thereby obtaining a roll body. Since the heat-fusible resin layer 3 is stacked in a roll shape so as to be in contact with the heat-resistant resin layer 2, the lubricant of the heat-fusible resin layer 3 is transferred to the outer surface 2a of the heat-resistant resin layer 2.
Next, the outer package 1 is pulled out from the roll, and the pulled-out outer package 1 is molded so that the heat-resistant resin layer 2 of the outer package 1 becomes an outer layer of the outer package 10, thereby obtaining the outer package 10. Since the lubricant is already present on the outer surface 2a of the heat-resistant resin layer 2 by the transfer, the molding can be performed in a good state (molding defects such as pinholes and cracks do not exist in the molded article). Examples of the molding method include: deep drawing forming, bulging forming, embossing forming and the like. In fig. 2, reference numeral "29" denotes a flange portion of the outer case 10.
Next, corona treatment or flame treatment is performed on the outer surface 2a of the heat-resistant resin layer (outer layer) 2 of the outer case 10 for an electric storage device (treatment step). By performing corona treatment or flame treatment on the outer surface 2a of the outer layer 2 in this way, the lubricant on the outer surface 2a of the outer layer 2 can be removed, and the wettability of the outer surface 2a can also be improved, so that the tape adhesion of the outer surface 2a of the outer layer 2 can be significantly improved. Removing the lubricant from the outer surface 2a of the outer layer 2 by performing the corona treatment or the flame treatment so that the amount of the lubricant in the outer surface 2a of the outer layer 2 is less than 0.1. mu.g/cm2. Among them, the amount of the lubricant in the outer surface 2a of the outer layer 2 is preferably set to 0.08. mu.g/cm2Hereinafter, it is particularly preferably 0.06. mu.g/cm2The following. Further, by performing corona treatment or flame treatment on the outer surface 2a of the outer layer 2, the wetting tension of the outer surface 2a of the outer layer 2 can be set to 33mN/m or more.
As described above, the above-described outside layer 2 may be formed of the heat-resistant resin layer 2. 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 when heat-sealing the outer packaging material 1 is performed is used. As the heat-resistant resin, a heat-resistant resin having a melting point higher by 10 ℃ or more than that of the heat-fusible resin constituting the heat-fusible resin layer 3 is preferably used, and particularly a heat-resistant resin having a melting point higher by 20 ℃ or more than that of the heat-fusible resin is preferably used.
The heat-resistant resin layer (outer layer) 2 is a member mainly having a function of ensuring good formability, that is, a function of preventing breakage due to necking of the aluminum foil during forming.
The heat-resistant resin layer (outer layer) 2 is not particularly limited, and examples thereof include a stretched polyamide film such as a stretched nylon film, a stretched polyester film, and the like. 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, each having a hot water shrinkage ratio of 0.1% to 12%, is preferably used. As the heat-resistant resin layer 2, a heat-resistant resin biaxially stretched film stretched by a simultaneous biaxial stretching method is preferably used.
The nylon is not particularly limited, and examples thereof include nylon 6, and nylon MXD.
The heat-resistant resin layer 2 may be formed of a single layer (a single stretched film), or may be formed of a plurality of layers including, for example, a stretched polyester film/a stretched polyamide film (a plurality of layers including a stretched PET film/a stretched nylon film, etc.).
The thickness of the heat-resistant resin layer 2 is preferably 7 to 50 μm. By setting the value to be equal to or higher than the preferable lower limit value, sufficient strength as outer package 1 can be secured, and by setting the value to be equal to or lower than the preferable upper limit value, stress at the time of bulging forming or at the time of drawing forming can be reduced, and formability can be improved.
The metal foil layer 4 serves to impart gas barrier properties (oxygen and moisture intrusion prevention) to the outer wrapper 1. The metal foil layer 4 is not particularly limited, and examples thereof include aluminum foil, SUS foil, Cu foil, Ni foil, Ti foil, and the like, and aluminum foil is generally 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 forming such as bulging forming and drawing forming can be reduced, and formability can be improved. Among them, the thickness of the metal foil layer 4 is particularly preferably 10 μm to 80 μm.
The metal foil layer 4 is preferably subjected to chemical conversion treatment at least on the inner surface (the surface on the side of the heat-fusible resin layer 3). By performing such chemical conversion treatment, corrosion of the surface of the metal foil due to 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, the chemical conversion treatment is performed by applying any one of aqueous solutions 1) to 3) below to the surface of the metal foil after the degreasing treatment and then drying the applied aqueous solution:
1) containing phosphoric acid,
Chromic acid, and
an aqueous solution of a mixture of at least one compound selected from the group consisting of metal salts of fluoride and non-metal salts of fluoride;
2) containing phosphoric acid,
At least one resin selected from the group consisting of acrylic resins, chitosan derivative resins and phenolic resins, and
an aqueous solution of a mixture of at least one compound selected from the group consisting of chromic acid and chromium (III) salts;
3) containing phosphoric acid,
At least one 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
an aqueous solution of a mixture of at least one compound selected from the group consisting of metal salts of fluorides and non-metal salts of fluorides.
The amount of chromium deposited (per surface) is preferably 0.1mg/m for the chemical conversion coating2～50mg/m2Particularly preferably 2mg/m2～20mg/m2。
The heat-sealable resin layer (inner layer) 3 has excellent chemical resistance to an electrolyte solution or the like, which is highly corrosive to lithium ion secondary batteries or the like, and also has a function of imparting heat sealability to the outer wrapper 1.
The resin constituting the heat-fusible resin layer 3 is not particularly limited, and examples thereof include polyethylene, polypropylene, ionomers, Ethylene Ethyl Acrylate (EEA), ethylene methyl acrylate (EAA), ethylene methyl methacrylate resin (EMMA), ethylene-vinyl acetate copolymer resin (EVA), maleic anhydride-modified polypropylene, and maleic anhydride-modified polyethylene.
The thickness of the heat-sealable resin layer 3 is preferably set to 10 μm to 100. mu.m. The thickness of 10 μm or more ensures sufficient heat seal strength, and the thickness and weight reduction are facilitated by setting the thickness to 100 μm or less. Among them, the thickness of the heat-fusible resin layer 3 is more preferably set to 10 μm to 80 μm. The heat-fusible resin layer 3 is preferably formed of a heat-fusible resin unstretched film, and the heat-fusible resin layer 3 may be a single layer or a plurality of layers.
The heat-fusible resin layer 3 is preferably formed of a laminate of a plurality of heat-fusible resin films, and the heat-fusible resin film is preferably formed of an acrylic resin containing propylene as a main component. In this case, since the movement of the lubricant in the heat-fusible resin layer 3 is easily controlled, the outer case 10 having a more favorable molded state can be obtained.
The lubricant is not particularly limited, and examples thereof include saturated fatty acid amides, unsaturated fatty acid amides, substituted amides, methylol amides, saturated fatty acid bisamides, unsaturated fatty acid bisamides, fatty acid ester amides, and aromatic bisamides.
The saturated fatty acid amide is not particularly limited, and examples thereof include lauramide, palmitamide, stearamide, behenamide, and hydroxystearamide. The unsaturated fatty acid amide is not particularly limited, and examples thereof include oleamide, erucamide and the like.
The substituted amide is not particularly limited, and examples thereof include N-oleyl palmitamide, N-octadecyl stearamide, N-octadecyl oleamide, N-oleyl stearamide, and N-octadecyl erucamide. The methylolamide is not particularly limited, and examples thereof include methylolstearylamide.
The saturated fatty acid bisamide is not particularly limited, and examples thereof include methylenebisstearamide, ethylenebisdecanamide, ethylenebislauramide, ethylenebisstearamide, ethylenebishydroxystearamide, ethylenebisbehenamide, hexamethylenebisstearamide, hexamethylenebisbehenamide, hexamethylenehydroxystearamide, N '-dioctadecyladipamide, and N, N' -dioctadecylsebacamide.
The unsaturated fatty acid bisamide is not particularly limited, and examples thereof include ethylene bisoleamide, ethylene biserucamide, hexamethylene bisoleamide, N '-dioleyl sebacamide, and N, N' -dioleyl adipamide.
The fatty acid ester amide is not particularly limited, and examples thereof include stearyl stearate (stearylamido stearate). The aromatic bisamide is not particularly limited, and examples thereof include m-xylylene bisstearamide, m-xylylene bishydroxystearamide, and N, N' -dioctadecyl isophthalamide.
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 4 having a thickness of 40 μm, and then drying at 180 ℃. The chemical conversion coating had a chromium deposit amount of 10mg/m per surface2。
Next, a biaxially stretched nylon 6 film 2 having a thickness of 25 μm was dry-laminated (bonded) on one surface of the chemically converted aluminum foil 4 via a 2-liquid curable urethane adhesive layer 5.
Then, a sealing film (inner layer) 3 was obtained by co-extrusion using a T die in such a manner that a 1 st unstretched film having a thickness of 4.5 μm (comprising an ethylene-propylene random copolymer, 1000ppm of behenamide and 3000ppm of silica particles (antiblocking agent)), a 2 nd unstretched film having a thickness of 21 μm (comprising an ethylene-propylene block copolymer and 1000ppm of erucamide), and a 1 st unstretched film having a thickness of 4.5 μm (comprising an ethylene-propylene random copolymer, 1000ppm of behenamide and 3000ppm of silica particles (antiblocking agent)) were laminated in this order, and then the 1 st unstretched film surface of the sealing film 3 was laminated on the other surface of the aluminum foil 4 after dry lamination via an olefin adhesive layer 6 (having a thickness of 2 μm), and the sealing film was pressure-bonded by sandwiching the film between a rubber nip roll and a lamination roll heated to 100 ℃, thus, dry lamination was performed, followed by aging (heating) at 40 ℃ for 10 days, thereby obtaining an outer package 1 for an electric storage device having the configuration shown in fig. 1.
The obtained outer packaging material 1 was cut to obtain a sheet having a length of 200mm × a width of 200 mm. The sheet was molded into a length of 150mm, a width of 150mm and a depth of 5mm by using a press molding machine to obtain a container-shaped molded article (pressing speed: 20spm, crease-resist pressure: 1.60 mPa). The outer surface of the outer layer of the obtained molded article was subjected to corona treatment (voltage 12kV, treatment time 0.1s), to obtain an outer casing 10 for an electric storage device shown in fig. 2.
< example 2 >
An outer casing 10 for an electricity storage device shown in fig. 2 was obtained by using a T die and co-extruding a first unstretched film (1 film comprising an ethylene-propylene random copolymer, 2000ppm of behenamide and 3000ppm of silica particles (anti-blocking agent)) having a thickness of 4.5 μm, a second unstretched film (2 film comprising an ethylene-propylene block copolymer and 2000ppm of erucamide) having a thickness of 21 μm, and a first unstretched film (1 film comprising an ethylene-propylene random copolymer, 2000ppm of behenamide and 3000ppm of silica particles (anti-blocking agent)) having a thickness of 4.5 μm in this order as a sealing film 3, and using this sealing film 3, the same operation as in example 1 was carried out.
< example 3 >
As the sealing film 3, a sealing film 3 was obtained by coextrusion using a T die in such a manner that a 1 st unstretched film (comprising an ethylene-propylene random copolymer, 5000ppm of behenamide and 3000ppm of silica particles (antiblocking agent)) having a thickness of 4.5 μm, a 2 nd unstretched film (comprising an ethylene-propylene block copolymer and 5000ppm of erucamide) having a thickness of 21 μm, and a 1 st unstretched film (comprising an ethylene-propylene random copolymer, 5000ppm of behenamide and 3000ppm of silica particles (antiblocking agent)) having a thickness of 4.5 μm were laminated in this order, and Flame Treatment (Flame Treatment) was performed instead of corona Treatment using this sealing film 3, in the same manner as in example 1, an outer case 10 for an electric storage device shown in fig. 2 was obtained.
< example 4 >
An outer casing 10 for an electricity storage device shown in fig. 2 was obtained in the same manner as in example 1, except that the outer surface of the outer layer was wiped with an ethanol-impregnated nonwoven fabric before corona treatment after molding.
< comparative example 1 >
An outer casing for an electric storage device was obtained in the same manner as in example 1 except that a 1 st unstretched film (comprising an ethylene-propylene random copolymer, 1000ppm of behenamide and 3000ppm of silica particles (anti-blocking agent)) having a thickness of 4.5 μm, a 2 nd unstretched film (comprising an ethylene-propylene block copolymer and 1000ppm of erucamide) having a thickness of 21 μm, and a 1 st unstretched film (comprising an ethylene-propylene random copolymer, 1000ppm of behenamide and 3000ppm of silica particles (anti-blocking agent)) having a thickness of 4.5 μm were laminated in this order and coextruded through a T-die to obtain a sealing film 3, and this sealing film was used without corona treatment.
< comparative example 2 >
An outer casing for an electric storage device was obtained in the same manner as in example 1 except that a 1 st unstretched film (comprising an ethylene-propylene random copolymer, 400ppm of behenamide and 3000ppm of silica particles (anti-blocking agent)) having a thickness of 4.5 μm, a 2 nd unstretched film (comprising an ethylene-propylene block copolymer and 400ppm of erucamide) having a thickness of 21 μm, and a 1 st unstretched film (comprising an ethylene-propylene random copolymer, 400ppm of behenamide and 3000ppm of silica particles (anti-blocking agent)) having a thickness of 4.5 μm were laminated in this order and coextruded using a T die to obtain a sealing film 3, and this sealing film was used without corona treatment.
< comparative example 3 >
An outer casing for an electric storage device was obtained in the same manner as in example 1 except that a 1 st unstretched film (comprising an ethylene-propylene random copolymer, 100ppm of behenamide and 3000ppm of silica particles (anti-blocking agent)) having a thickness of 4.5 μm, a 2 nd unstretched film (comprising an ethylene-propylene block copolymer and 100ppm of erucamide) having a thickness of 21 μm, and a 1 st unstretched film (comprising an ethylene-propylene random copolymer, 100ppm of behenamide and 3000ppm of silica particles (anti-blocking agent)) having a thickness of 4.5 μm were laminated in this order and coextruded through a T-die to obtain a sealing film 3, and this sealing film was used without corona treatment.
< comparative example 4 >
An outer casing for an electricity storage device was obtained in the same manner as in example 1 except that a 1 st unstretched film (comprising an ethylene-propylene random copolymer, 9000ppm of behenamide and 3000ppm of silica particles (anti-blocking agent)) having a thickness of 4.5 μm, a 2 nd unstretched film (comprising an ethylene-propylene block copolymer and 9000ppm of erucamide) having a thickness of 21 μm, and a 1 st unstretched film (comprising an ethylene-propylene random copolymer, 9000ppm of behenamide and 3000ppm of silica particles (anti-blocking agent)) having a thickness of 4.5 μm were laminated in this order by co-extrusion using a T die to obtain a sealing film 3, and this sealing film was used without corona treatment.
[ Table 1]
With respect to the outer casing for an electric storage device obtained in the above manner, the amount of the lubricant present on the outer surface of the outer layer was evaluated, the wetting tension (wetting index) of the outer surface of the outer layer was measured, and the moldability, the appearance, and the tape adhesion were evaluated.
< evaluation method of amount of lubricant present on outer surface of outer layer >
2 rectangular test pieces each having a length of 100mm × a width of 100mm were cut out from each outer casing 10 for an electric storage device, and these 2 test pieces were stacked so that the outer layers were positioned inside, and the peripheral edge portions of the outer surfaces of the outer layers were heat-sealed at a heat-sealing temperature of 250 ℃ with a seal width of 5mm, thereby producing a bag. Acetone was injected into the inner space of the bag body in an amount of 1ml using a syringe, left for 3 minutes in a state where the inner surface of the bag body was in contact with acetone, and then the acetone in the bag body was extracted. The amount of the lubricant (unit: μ g/cm) present on the outer surface 2a of the outer layer 2 of the outer jacket 10 was determined by measuring and analyzing the amount of the component contained in the extracted acetone by gas chromatography2)。
< method for measuring wetting tension >
The wetting index (surface tension) of the outer surface of the outer layer of the outer jacket for each power storage device was measured in accordance with JIS K6768-1999.
< moldability evaluation method >
The outer packaging material 1 was molded by a press molding machine to have a length of 150mm, a width of 150mm and a depth of 5mm to obtain a molded article, and the molded article obtained at this time was visually inspected to evaluate that no cracks or pinholes were generated at all as "○" and that cracks or pinholes were generated as "x".
< method of evaluating appearance >
By visually inspecting the surface of the obtained outer case 10, the case where white powder was generated on the surface of the inner layer was evaluated as "x", and the case where white powder was not generated on the surface of the inner layer was evaluated as "○".
< method for evaluating adhesion of adhesive tape >
Rectangular test pieces of 145mm in length × 145mm in width were collected from the largest surface of each exterior case for an electric storage device. After a tape having a width of 5mm × a length of 100mm was attached to the outer surface of the outer layer of the test piece, the tape was subjected to a load by a roller having a weight of 2kg while the roller was reciprocated 5 times. Followed by standing in a room at 25 ℃ for 1 hour. Next, the test piece was clamped and fixed by one chuck and the adhesive tape was clamped and fixed by the other chuck by using STROGRAPH AGS-5kNX manufactured by Shimadzu according to JIS K6854-3(1999), and the peel strength at 180 ℃ was measured. The tape adhesion was evaluated from the peel strength based on the following criteria.
(criteria for determination)
◎ "(acceptable) … peel strength of 6N/5mm or more
○ "(pass) … peel strength of 5N/5mm or more and less than 6N/5mm
"×" … peel strength was less than 5N/5 mm.
As is clear from the table, the outer cases of examples 1 to 3 of the present invention were able to be molded well and also had good tape adhesion. In contrast, comparative examples 1 to 4, which deviate from the specified range of the present invention, had poor evaluation values for at least one of "moldability", "appearance", and "tape adhesion". In comparative example 3, the evaluation result of moldability failure was that the tape adhesion could not be evaluated.
The present application claims priority from japanese patent application No. 2018-195019 filed on 2018, 10, 16, the disclosure of which directly forms part of the present application.
The terms and expressions which have been employed herein are used as terms of description and not of limitation, and there is no intention, in the use of such terms and expressions, of excluding any equivalents of the features shown and described, it being recognized that various modifications are possible within the scope of the invention claimed.
Industrial applicability
The outer casing for an electric storage device according to the present invention can be used as an outer casing for various electric storage devices, and specific examples thereof include:
● electric storage devices such as lithium secondary batteries (lithium ion batteries, lithium polymer batteries, etc.);
● a lithium ion capacitor;
● electric double layer capacitance;
● all-solid-state battery;
and so on.
Claims (4)
1. An outer casing for an electricity storage device, which is formed from a molded casing of an outer casing material that includes a heat-resistant resin layer as an outer layer, a heat-fusible resin layer as an inner layer, and a metal foil layer disposed between the two layers,
the heat-fusible resin layer contains a lubricant, the content of the lubricant in the heat-fusible resin layer is 200ppm to 7000ppm,
the amount of the lubricant in the outer surface of the heat-resistant resin layer is less than 0.1 [ mu ] g/cm2，
The heat-resistant resin layer has an outer surface wetting tension of 33mN/m or more.
2. The exterior casing for a power storage device according to claim 1, wherein a molding depth of the molded casing is 3mm or more.
3. The exterior casing for an electricity storage device according to claim 1 or 2, wherein the heat-fusible resin layer is formed of a laminate of a plurality of heat-fusible resin films, and the heat-fusible resin films are formed of an acrylic resin containing propylene as a main component.
4. A method for manufacturing an outer casing for an electricity storage device, comprising the steps of:
a step of laminating an outer covering material, which comprises a heat-resistant resin layer as an outer layer, a heat-fusible resin layer containing a lubricant as an inner layer, and a metal foil layer disposed between the two layers, in a roll shape so that the heat-fusible resin layer is in contact with the heat-resistant resin layer, thereby obtaining a roll body;
a step of obtaining an outer casing for an electricity storage device by drawing out the outer casing from the roll body and molding the drawn-out outer casing, and
and a treatment step of subjecting the outer surface of the outer layer of the outer casing for an electric storage device to corona treatment or flame treatment.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018195019A JP7217870B2 (en) | 2018-10-16 | 2018-10-16 | Outer case for power storage device |
| JP2018-195019 | 2018-10-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111063833A true CN111063833A (en) | 2020-04-24 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201910913266.8A Pending CN111063833A (en) | 2018-10-16 | 2019-09-25 | Outer casing for electricity storage device and method for manufacturing same |
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| Country | Link |
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| JP (2) | JP7217870B2 (en) |
| CN (1) | CN111063833A (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2023038255A (en) | 2023-03-16 |
| JP2020064739A (en) | 2020-04-23 |
| JP7393569B2 (en) | 2023-12-06 |
| JP7217870B2 (en) | 2023-02-06 |
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