JP7381528B2 - Exterior material for power storage devices and power storage devices - Google Patents

Description

The present invention relates to batteries and capacitors used in mobile devices such as smartphones and tablets, batteries and capacitors used in hybrid vehicles, electric vehicles, wind power generation, solar power generation, and nighttime electricity storage. Regarding exterior materials and power storage devices.

In addition, in this specification and claims, the term "tensile yield strength" refers to a sample width of 15 mm, a distance between gauge lines of 50 mm, and a tensile speed of 100 mm/min in accordance with JIS K7127-1999 (Tensile test method). It means the tensile yield strength (tensile yield strength) obtained by measuring under the following conditions.

Lithium ion secondary batteries are widely used as power sources for, for example, notebook computers, video cameras, mobile phones, and the like. This lithium ion secondary battery has a structure in which a battery main body (a main body including a positive electrode, a negative electrode, and an electrolyte) is surrounded by a case. As this case material (exterior material), for example, one in which an outer layer made of a heat-resistant resin film, an aluminum foil layer, and an inner layer made of a thermoplastic resin film are bonded and integrated in this order is known (Patent Document (see 1).

The power storage device is configured such that the main body of the power storage device is sandwiched between a pair of exterior materials and sealed by fusion bonding (heat sealing) the peripheral edges of the pair of exterior materials. By sufficiently sealing with such heat seal bonding, leakage of the electrolyte can be prevented.

JP2005-22336A

By the way, batteries such as such lithium ion secondary batteries are intended for use in notebook computers, mobile phones, and the like in normal temperature environments.

However, in recent years, with the diversification of uses for lithium-ion secondary batteries, new uses for external use exposed to high-temperature environments, such as use in automobiles, have also increased. .

For example, when used in automobiles, when a car is parked outdoors in the summer, the temperature is quite high, so even batteries such as lithium-ion secondary batteries cannot be kept in such a high temperature environment for a long period of time. It is desired to develop an exterior material that can maintain good sealing properties of the seal portion of the exterior material even when exposed to exposure.

The present invention has been made in view of this technical background, and provides an exterior material for a power storage device and a power storage device that can maintain good sealing performance of the seal portion of the exterior material even when exposed to a high temperature environment for a long period of time. The purpose is to provide.

In order to achieve the above object, the present invention provides the following means.

[1] An exterior material for a power storage device including a heat-resistant resin layer as an outer layer, a sealant layer as an inner layer, and a metal foil layer disposed between these layers,
The sealant layer is composed of one or more layers, and at least the innermost layer of the sealant layer contains an elastomer-modified olefin resin,
The elastomer-modified olefin resin is composed of an olefin-based thermoplastic elastomer-modified homopolypropylene or/and an olefin-based thermoplastic elastomer-modified random copolymer,
The olefinic thermoplastic elastomer-modified random copolymer is an olefinic thermoplastic elastomer modified random copolymer containing propylene as a copolymerization component and a copolymerization component other than propylene. Exterior material for devices.

[2] The exterior material for an electricity storage device according to item 1, wherein the content of the olefin thermoplastic elastomer in the innermost layer is 0.1% by mass or more and less than 20% by mass.

[3] The exterior material for a power storage device according to item 1 or 2, wherein the elastomer-modified olefin resin constituting the innermost layer has a melting point higher than 160°C.

[4] The exterior material for an electricity storage device according to any one of items 1 to 3 above, wherein the sealant film constituting the sealant layer has a tensile yield strength of 3.5 MPa to 15.0 MPa at 80°C.

[5] The sealant layer is composed of a plurality of layers, and a second sealant layer is disposed on the side of the sealant layer closest to the metal foil layer, and the second sealant layer contains a propylene-ethylene random copolymer containing 50% 5. The exterior material for a power storage device according to any one of items 1 to 4 above, which contains at least % by mass and does not contain an elastomer component.

[6] The exterior material for a power storage device according to any one of items 1 to 5, wherein the metal foil layer and the sealant layer are bonded to each other via an adhesive layer.

[7] The exterior material for a power storage device according to item 6, wherein the adhesive layer is made of an adhesive containing an olefin resin having a carboxyl group and a polyfunctional isocyanate compound.

[8] A power storage device main body,
and the exterior material for a power storage device according to any one of the preceding clauses 1 to 7,
An electricity storage device, wherein the electricity storage device main body is covered with the exterior material.

In the invention [1], since at least the innermost layer of the sealant layer of the exterior material contains the above-mentioned specific elastomer-modified olefin resin, the initial sealing strength between the exterior materials is sufficiently ensured even in a high-temperature environment. In addition, sufficient sealing strength can be maintained even if the seal is placed in a high-temperature environment (for example, inside a car in the summer) for a long period of time.

In the invention of [2], the film strength of the sealant layer increases when the content of the olefinic thermoplastic elastomer in the innermost layer of the sealant layer is 0.1% by mass or more and less than 20% by mass. This makes it difficult for damage (tearing) to occur.

In the invention [3], since the melting point of the elastomer-modified olefin resin constituting the innermost layer of the sealant layer is higher than 160°C, it is possible to sufficiently suppress outflow of the sealant layer when heat sealing the exterior material, and the high temperature It also has excellent heat resistance under environmental conditions.

In the invention [4], a sealant film having a tensile yield strength of 3.5 MPa to 15.0 MPa at 80° C. is used in the sealant layer, so that the electricity storage device can be stored in a high-temperature environment (for example, inside a car in the summer) for a long time. Even if it is used for a long period of time, it is possible to prevent the exterior material from bursting due to an increase in internal pressure.

In the invention [5], the second sealant layer closest to the metal foil layer contains 50% by mass or more of the propylene-ethylene random copolymer and does not contain an elastomer component. The adhesion to the side is improved, and even if deformation occurs, delamination is less likely to occur. Furthermore, since the second sealant layer closest to the metal foil layer does not contain an elastomer component, there are no crazes (cracks or gaps) that may occur at the interface between the propylene-ethylene random copolymer and the elastomer component. There is no infiltration of the electrolytic solution into the vicinity of the metal foil layer due to interface separation), and sufficient insulation can be ensured.

In the invention [6], the interlayer adhesive force between the metal foil layer and the sealant layer can be further increased.

In the invention [7], since the adhesive layer is made of an adhesive containing an olefin resin having a carboxyl group and a polyfunctional isocyanate compound, the electrolyte resistance can be further improved.

The invention of [8] provides an exterior material that can sufficiently secure initial sealing strength between exterior materials even in a high-temperature environment and maintain sufficient sealing strength even when left in a high-temperature environment (for example, inside a car in the summer) for a long period of time. A power storage device that is packaged and has excellent high-temperature durability can be provided.

FIG. 1 is a cross-sectional view showing an embodiment of an exterior material for a power storage device according to the present invention. It is a sectional view showing other embodiments of the exterior material for electricity storage devices concerning the present invention. 1 is a cross-sectional view showing an embodiment of a power storage device according to the present invention. FIG. 4 is a perspective view showing the exterior material (planar), the energy storage device main body, and the exterior case (three-dimensional molded body) that constitute the electricity storage device of FIG. 3 in a separated state before being heat-sealed.

FIG. 1 shows an embodiment of an exterior material 1 for a power storage device according to the present invention. This exterior material 1 for a power storage device is used, for example, as an exterior material for a lithium ion secondary battery. The exterior material 1 for the power storage device may be used as an exterior material as it is without being molded, or may be used as the exterior case 10 after being subjected to shaping such as deep drawing or stretch molding. Good (see Figure 4).

The exterior material 1 for a power storage device has a base material layer (outer layer) 2 laminated and integrated on one side of the metal foil layer 4 via a first adhesive layer 5, and the other side of the metal foil layer 4. An inner sealant layer (inner layer) 3 is integrally laminated on the surface via a second adhesive layer 6 (see FIGS. 1 and 2).

In the exterior material 1 of FIG. 1, the inner sealant layer (inner layer) 3 is composed of a single layer (one layer) consisting of a first sealant layer 7. Therefore, the first sealant layer 7 is arranged at the innermost layer (the first sealant layer 7 is the innermost layer).

In the exterior material 1 of FIG. 2, the inner sealant layer (inner layer) 3 includes a first sealant layer 7 as the innermost layer and a second sealant layer 8 disposed closest to the metal foil layer 4. It has a two-layer laminated structure consisting of , with the first sealant layer 7 disposed at the innermost side.

In the present invention, the inner sealant layer (inner layer) 3 has excellent chemical resistance against highly corrosive electrolytes used in lithium ion secondary batteries, etc., and is heat-sealed to the exterior material. It plays the role of giving gender. The sealant layer (inner layer) 3 is made of an unstretched sealant film.

In the present invention, the sealant layer (inner layer) 3 may be formed of one layer, or may be formed of two or more layers, but at least The innermost layer (first sealant layer) 7 contains an elastomer-modified olefin resin.

The elastomer-modified olefin resin (polypropylene block copolymer) is preferably composed of an olefin-based thermoplastic elastomer-modified homopolypropylene or/and an olefin-based thermoplastic elastomer-modified random copolymer; The combination is an olefin-based thermoplastic elastomer modified product of a random copolymer containing "propylene" and "other copolymer components other than propylene" as copolymer components, and the above-mentioned "other copolymer components other than propylene" Examples thereof include, but are not limited to, olefin components such as ethylene, 1-butene, 1-hexene, 1-pentene, and 4-methyl-1-pentene, as well as butadiene. The above-mentioned olefin thermoplastic elastomer is not particularly limited, but includes, for example, EPR (ethylene propylene rubber), propylene-butene elastomer, propylene-butene-ethylene elastomer, and EPDM (ethylene-propylene-diene rubber). Among them, it is preferable to use EPR (ethylene propylene rubber).

Regarding the elastomer-modified olefin resin, the "olefin-based thermoplastic elastomer modification" may be graft polymerization or other modification methods.

The elastomer-modified olefin resin can be produced, for example, by the following reactor-made method. This is just one example, and the material is not particularly limited to those produced by this method.

First, a Ziegler-Natta catalyst, a promoter, propylene, and hydrogen are supplied to a first reactor to polymerize homopolypropylene. The obtained homopolypropylene, containing unreacted propylene and Ziegler-Natta catalyst, is transferred to the second reactor. In the second reactor, propylene and hydrogen are further added to polymerize homopolypropylene. The obtained homopolypropylene containing unreacted propylene and Ziegler-Natta catalyst is transferred to a third reactor. The elastomer-modified olefin resin can be produced by further adding ethylene, propylene, and hydrogen in the third reactor to polymerize ethylene-propylene rubber (EPR), which is a copolymerization of ethylene and propylene. For example, the elastomer-modified olefin resin can be produced by adding a solvent and producing it in the liquid phase, or the elastomer-modified olefin resin can be produced by carrying out the reaction in the gas phase without using a solvent. can.

The content of the olefin thermoplastic elastomer in the innermost layer (first sealant layer) 7 of the sealant layer 3 is preferably 0.1% by mass or more and less than 20% by mass. Furthermore, homopolypropylene (a portion not modified with an olefinic thermoplastic elastomer) or/and the random copolymer (a portion not modified with an olefinic thermoplastic elastomer) in the innermost layer (first sealant layer) 7 of the sealant layer 3 may be used. It is preferable that the content of the non-containing parts) is 80% by mass or more and 99% by mass or less.

The melting point of the elastomer-modified olefin resin constituting the innermost layer (first sealant layer) 7 of the sealant layer 3 is preferably in the range of 160°C to 180°C. It can sufficiently suppress the leakage of the sealant layer 3 when heat-sealing the exterior material, and has excellent heat resistance in high-temperature environments. Among these, the melting point of the elastomer-modified olefin resin constituting the innermost layer (first sealant layer) 7 of the sealant layer 3 is preferably 163°C or higher, particularly preferably in the range of 163°C to 169°C. The melting point is a melting point measured by differential scanning calorimetry (DSC) in accordance with JIS K7121-1987.

The olefinic thermoplastic elastomer component (this component alone) present in the innermost layer (first sealant layer) 7 preferably has a plurality of crystallization temperatures. When the adhesive has a plurality of crystallization temperatures as described above, an effect can be obtained in that the resin (the olefin resin in the innermost layer) is difficult to dissolve during adhesion. In addition, in the case where the crystallization temperature is one that has multiple crystallization temperatures, it is desirable that the lowest crystallization temperature of the multiple crystallization temperatures is in the range of 40°C to 80°C, and more preferably in the range of 40°C to 75°C. It is more desirable that Since the lowest crystallization temperature is 40° C. to 80° C., it is possible to shorten the adhesion time at room temperature (adhesion time during heat sealing). The crystallization temperature is a crystallization temperature (crystallization peak) measured by differential scanning calorimetry (DSC) according to JIS K7121-1987.

The MFR of the olefin thermoplastic elastomer component (this component alone) present in the innermost layer (first sealant layer) 7 is preferably 0.1 g/10 minutes to 1.4 g/10 minutes, and in this case Since the resin (olefin resin in the innermost layer) is less likely to be eluted during heat sealing, greater adhesive strength can be ensured. Among these, it is more preferable that the MFR of the olefinic thermoplastic elastomer component (this component alone) present in the innermost layer (first sealant layer) 7 is 0.1 g/10 minutes to 1.0 g/10 minutes. , 0.1 g/10 minutes to 0.6 g/10 minutes is particularly preferred. Note that the MFR (melt flow rate) is the MFR measured at 230° C. and 2.16 kg in accordance with JIS K7210-1-2014.

The sealant film constituting the sealant layer 3 preferably has a tensile yield strength of 3.5 MPa to 15.0 MPa at 80°C. For example, when the sealant layer 3 is composed of only the first sealant layer 7, it is preferable that the tensile yield strength at 80° C. of the first sealant film is 3.5 MPa to 15.0 MPa, and the sealant When the layer 3 is composed of a laminate of the first sealant layer 7 and the second sealant layer 8, the tensile yield strength at 80° C. of the laminate sealant film is preferably 3.5 MPa to 15.0 MPa. . This also applies when the sealant layer 3 is a multilayer of three or more layers. Since the tensile yield strength at 80° C. of the sealant film constituting the sealant layer 3 is 3.5 MPa to 15.0 MPa, it is possible to use the electricity storage device while being left in a high-temperature environment (for example, inside a car in the summer) for a long period of time. This can prevent the exterior material from bursting due to an increase in internal pressure. Among these, it is particularly preferable that the sealant film constituting the sealant layer 3 has a tensile yield strength of 4 MPa to 12 MPa at 80°C.

The thickness of the innermost layer (first sealant layer) 7 is preferably 30 μm or more, and in this case there is an advantage that the toughness of the first sealant layer 7 can be improved. Among these, the thickness of the innermost layer (first sealant layer) 7 is more preferably 30 μm to 100 μm.

When the second sealant layer 8 is provided, the thickness of the second sealant layer 8 is preferably 3 μm to 60 μm, more preferably 5 μm to 20 μm. Further, when the second sealant layer 8 is provided, the resin forming the second sealant layer 8 is not particularly limited, but examples include propylene-ethylene random copolymer, homopolypropylene, polyethylene In addition, olefin-based thermoplastic elastomer-modified homopolypropylene, olefin-based thermoplastic elastomer-modified random copolymer (random copolymer olefin containing "propylene" as a copolymerization component and "other copolymerization components other than propylene") modified thermoplastic elastomers), etc.

Further, the thickness of the sealant layer 3 is preferably set to 30 μm to 200 μm.

In the present invention, the sealant layer 3 is composed of a plurality of layers, including an innermost layer (first sealant layer) 7 containing the elastomer-modified olefin resin, and a second sealant layer disposed closest to the metal foil layer 4. The second sealant layer preferably contains a propylene-ethylene random copolymer in an amount of 50% by mass or more and does not contain an elastomer component. When such a configuration is adopted, the second sealant layer 8 closest to the metal foil layer 4 contains 50% by mass or more of a propylene-ethylene random copolymer and does not contain an elastomer component. , the adhesion to the metal foil layer side is improved, and even if deformation occurs, delamination is less likely to occur. Furthermore, since the second sealant layer 8 closest to the metal foil layer 4 does not contain an elastomer component, crazes (cracks and gaps that may occur at the interface between the propylene-ethylene random copolymer and the elastomer component) There is no infiltration of the electrolytic solution into the vicinity of the metal foil layer due to interface separation), and sufficient insulation can be ensured. Among these, it is more preferable that the second sealant layer contains 70% by mass or more of a propylene-ethylene random copolymer and does not contain an elastomer component. Here, the structure containing no elastomer component means that the elastomer component is not mixed (blended), and also the elastomer-modified resin is not mixed.

The sealant film constituting the sealant layer (inner layer) 3 is preferably manufactured by a molding method such as multilayer extrusion molding, inflation molding, T-die cast film molding, or the like.

The method of laminating the sealant film constituting the sealant layer (inner layer) 3 on the metal foil layer 4 is not particularly limited, but may include a dry lamination method, a sandwich lamination method (using an adhesive film such as acid-modified polypropylene), etc. Examples include extrusion, sandwich lamination between metal foil and the sealant film, and then heat lamination with hot rolls.

In the present invention, the base layer (outer layer) 2 is preferably formed of a heat-resistant resin layer. As the heat-resistant resin constituting the heat-resistant resin layer 2, a heat-resistant resin that does not melt at the heat-sealing temperature when heat-sealing the exterior material is used. As the heat-resistant resin, it is preferable to use a heat-resistant resin having a melting point higher than the melting point of the sealant layer 3 by 10° C. or more, and it is particularly preferable to use a heat-resistant resin having a melting point higher than the melting point of the sealant layer 3 by 20° C. or more. preferable.

The heat-resistant resin layer (outer layer) 2 is not particularly limited, but includes, for example, polyamide films such as nylon films, polyester films, etc., and stretched films of these are preferably used. Among these, the heat-resistant resin layer 2 may be a biaxially oriented polyamide film such as a biaxially oriented nylon film, a biaxially oriented polybutylene terephthalate (PBT) film, a biaxially oriented polyethylene terephthalate (PET) film, or a biaxially oriented polyethylene terephthalate (PET) film. Particular preference is given to using phthalate (PEN) films. The nylon film is not particularly limited, and examples thereof include 6 nylon film, 6,6 nylon film, MXD nylon film, and the like. Note that the heat-resistant resin layer 2 may be formed of a single layer, or may be formed of a multilayer consisting of a polyester film/polyamide film (a multilayer consisting of a PET film/nylon film, etc.), for example. Also good. In addition, in the case of the multi-layer structure, it is preferable to arrange the polyester film side at the outermost side.

The thickness of the outer layer (base material layer) 2 is preferably 2 μm to 50 μm. When a polyester film is used, the thickness is preferably 5 μm to 40 μm, and when a nylon film is used, the thickness is preferably 15 μm to 50 μm. By setting the value above the preferred lower limit, it is possible to ensure sufficient strength as an exterior material, and by setting the value below the preferred upper limit, the stress during forming such as stretch forming and drawing can be reduced, improving formability. can be done.

In the exterior material for a power storage device according to the present invention, the metal foil layer 4 serves to provide the exterior material 1 with gas barrier properties that prevent oxygen and moisture from entering. The metal foil layer 4 is not particularly limited, and examples thereof include aluminum foil, SUS foil (stainless steel foil), copper foil, etc. Among them, aluminum foil, SUS foil (stainless steel foil) is preferably used. is preferred. The thickness of the metal foil layer 4 is preferably 10 μm to 120 μm. By having a diameter of 10 μm or more, it is possible to prevent pinholes from occurring during rolling when manufacturing metal foil, and by having a diameter of 120 μm or less, stress during forming such as stretch forming and drawing can be reduced, improving formability. be able to.

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 a chemical conversion treatment. By performing such a chemical conversion treatment, corrosion of the metal foil surface by contents (such as battery electrolyte) can be sufficiently prevented. For example, the metal foil is subjected to a chemical conversion treatment by performing the following treatment. That is, for example, 1) phosphoric acid and
chromic acid and
an aqueous solution of a mixture containing at least one compound selected from the group consisting of metal salts of fluoride and non-metal salts of fluoride; 2) phosphoric acid;
At least one resin selected from the group consisting of acrylic resin, chitosan derivative resin, and phenolic resin,
3) an aqueous solution of a mixture containing at least one compound selected from the group consisting of chromic acid and chromium (III) salts; 3) phosphoric acid;
At least one resin selected from the group consisting of acrylic resin, chitosan derivative resin, and phenolic resin,
At least one compound selected from the group consisting of chromic acid and chromium (III) salts,
An aqueous solution of a mixture containing at least one compound selected from the group consisting of metal salts of fluoride and non-metallic salts of fluoride.After coating the aqueous solution of any one of the above 1) to 3), drying By doing so, chemical conversion treatment is performed.

The amount of chromium deposited (per one side) in the chemical conversion film is preferably 0.1 mg/m ² to 50 mg/m ² , particularly preferably 2 mg/m ² to 20 mg/m ² .

The first adhesive layer (outer adhesive layer) 5 is not particularly limited, but includes, for example, a polyurethane polyolefin adhesive layer, a polyurethane adhesive layer, a polyester polyurethane adhesive layer, a polyether polyurethane adhesive layer. etc. The thickness of the first adhesive layer 5 is preferably set to 1 μm to 6 μm. Among these, from the viewpoint of making the exterior material 1 thinner and lighter, it is particularly preferable that the thickness of the first adhesive layer 5 is set to 1 μm to 3 μm.

The second adhesive layer (inner adhesive layer) 6 is not particularly limited, and for example, those exemplified as the first adhesive layer 5 can also be used, but polyolefins that are less swollen by the electrolytic solution can be used. It is preferred to use adhesives based on adhesives. Among these, the second adhesive layer (inner adhesive layer) 6 is particularly preferably formed of an adhesive containing an olefin resin having a carboxyl group and a polyfunctional isocyanate compound. A second adhesive layer can be formed by dry laminating the adhesive. Alternatively, the second adhesive layer (inner adhesive layer) 6 is particularly preferably formed of an olefin resin having a carboxyl group. In this case, the second adhesive layer can be formed by extrusion lamination by melt extrusion of an olefin resin having a carboxyl group. The olefin resin having a carboxyl group is not particularly limited, but includes, for example, maleic acid-modified polypropylene, maleic acid-modified polyethylene, acrylic acid-modified polypropylene, acrylic acid-modified polyethylene, methacrylic acid-modified polypropylene, and methacrylic acid-modified polypropylene. Examples include carboxylic acid-modified olefin resins such as polyethylene, fumaric acid-modified polypropylene, and fumaric acid-modified polyethylene. The thickness of the second adhesive layer 6 is preferably set to 1 μm to 4 μm. Among these, from the viewpoint of reducing the thickness and weight of the exterior material, it is particularly preferable that the thickness of the second adhesive layer 6 is set to 1 μm to 3 μm.

By molding (deep drawing, stretch molding, etc.) the exterior material 1 of the present invention, an exterior case (battery case, etc.) 10 can be obtained (FIG. 4). In addition, the exterior material 1 of the present invention can also be used as it is without being subjected to molding (FIG. 4).

FIG. 3 shows an embodiment of a power storage device 30 configured using the exterior material 1 of the present invention. This power storage device 30 is a lithium ion secondary battery. In this embodiment, as shown in FIGS. 3 and 4, an exterior member 15 is constituted by an exterior case 10 obtained by molding the exterior material 1 and the planar exterior material 1. Thus, an approximately rectangular parallelepiped-shaped power storage device body portion (electrochemical element, etc.) 31 is accommodated in the housing recess of the exterior case 10 obtained by molding the exterior material 1 of the present invention. The exterior material 1 of the present invention is placed on top of the planar exterior material 1 with its sealant layer 3 side facing inward (lower side) without being molded, and the peripheral edge of the sealant layer 3 of the planar exterior material 1 and the exterior The electricity storage device 30 of the present invention is configured by sealing the flange portion (peripheral portion for sealing) 29 of the case 10 with the sealant layer 3 by heat sealing and sealing. ). The inner surface of the housing recess of the exterior case 10 is a sealant layer 3, and the outer surface of the housing recess is a base material layer (outer layer) 2 (see FIG. 4).

In FIG. 3, reference numeral 39 denotes a heat-sealed portion in which the peripheral edge of the exterior material 1 and the flange portion (sealing peripheral edge) 29 of the exterior case 10 are joined (welded). Note that in the power storage device 30, the tip of the tab lead connected to the power storage device main body 31 is led out to the outside of the exterior member 15, but is not shown.

The power storage device main body 31 is not particularly limited, and examples thereof include a battery main body, a capacitor main body, a capacitor main body, and the like.

The width of the heat seal portion 39 is preferably set to 0.5 mm or more. By setting it to 0.5 mm or more, sealing can be performed reliably. Among these, the width of the heat seal portion 39 is preferably set to 3 mm to 15 mm.

Note that in the above embodiment, the exterior member 15 was configured to include the exterior case 10 obtained by molding the exterior material 1 and the planar exterior material 1 (see FIGS. 3 and 4). The combination is not particularly limited to such a combination, and for example, the exterior member 15 may be composed of a pair of planar exterior materials 1, or may be composed of a pair of exterior cases 10. It's okay.

Next, specific examples of the present invention will be described, but the present invention is not particularly limited to these examples.

<Materials used>
(Elastomer modified olefin resin A)
Elastomer-modified olefin resin A consists of EPR-modified homopolypropylene and EPR-modified product of ethylene-propylene random copolymer. The EPR means ethylene-propylene rubber. The content of the elastomer component in the elastomer-modified olefin resin A is 15% by mass. The melting point of the elastomer-modified olefin resin A is 166°C.
(Elastomer modified olefin resin B)
The elastomer-modified olefin resin B consists of a propylene-butene elastomer-modified homopolypropylene and a propylene-butene elastomer modified product of an ethylene-propylene random copolymer. The content of the elastomer component in the elastomer-modified olefin resin B was 18% by mass. The melting point of elastomer-modified olefin resin B is 164°C.
(Elastomer modified olefin resin C)
The elastomer-modified olefin resin C consists of a propylene-butene-ethylene elastomer-modified homopolypropylene and a propylene-butene-ethylene elastomer modified product of an ethylene-propylene random copolymer. The content of the elastomer component in the elastomer-modified olefin resin C was 16% by mass. The melting point of the elastomer-modified olefin resin C is 164°C.

<Example 1>
A chemical conversion treatment solution consisting of phosphoric acid, polyacrylic acid (acrylic resin), chromium (III) salt compound, water, and alcohol was applied to both sides of aluminum foil 4 with a thickness of 35 μm, and then dried at 180°C. , a chemical conversion film was formed. The amount of chromium deposited on this chemical conversion film was 10 mg/m ² per side.

Next, a biaxially stretched 6-nylon film 2 with a thickness of 15 μm was dry laminated on one side of the chemical conversion treated aluminum foil 4 via a two-component curing urethane adhesive (outer adhesive) 5 ( pasted together).

Next, after extruding a sealant film (first sealant layer) 7 with a thickness of 80 μm made of elastomer-modified olefin resin A, a two-component curing type urethane adhesive is applied to one side of the sealant film 7 (3). By overlapping the other side of the dry-laminated aluminum foil 4 via the (inner adhesive layer) 6 and sandwiching it between a rubber nip roll and a laminating roll heated to 100° C. By dry laminating and then aging (heating) at 50° C. for 5 days, an exterior material 1 for a power storage device having the configuration shown in FIG. 1 was obtained.

<Example 2>
A power storage device having the configuration shown in FIG. 1 was manufactured in the same manner as in Example 1, except that a two-component curing type acrylic adhesive 6 was used as the inner adhesive 6 instead of a two-component curing type urethane adhesive. Exterior material 1 for a device was obtained.

<Example 3>
A chemical conversion treatment solution consisting of phosphoric acid, polyacrylic acid (acrylic resin), chromium (III) salt compound, water, and alcohol was applied to both sides of aluminum foil 4 with a thickness of 35 μm, and then dried at 180°C. , a chemical conversion film was formed. The amount of chromium deposited on this chemical conversion film was 10 mg/m ² per side.

Next, a biaxially stretched 6-nylon film 2 having a thickness of 15 μm was dry-laminated (attached) to one surface of the chemical conversion-treated aluminum foil 4 via a two-component curing urethane adhesive 5.

Next, on the other side of the dry laminated aluminum foil 4, a 4 μm thick maleic anhydride modified polypropylene film (inner adhesive layer) 6 and an 8 μm thick propylene-ethylene random copolymer film (second A coextruded sealant layer) 8 and a 72 μm thick elastomer-modified olefin resin A film (first sealant layer) 7 are stacked in this order and placed between a rubber nip roll and a laminating roll heated to 100°C. The exterior material 1 for a power storage device having the configuration shown in FIG. 2 was obtained by dry laminating by sandwiching and crimping, and then aging (heating) at 50° C. for 5 days.

<Example 4>
A chemical conversion treatment solution consisting of phosphoric acid, polyacrylic acid (acrylic resin), chromium (III) salt compound, water, and alcohol was applied to both sides of aluminum foil 4 with a thickness of 35 μm, and then dried at 180°C. , a chemical conversion film was formed. The amount of chromium deposited on this chemical conversion film was 10 mg/m ² per side.

Next, a biaxially stretched 6-nylon film 2 having a thickness of 15 μm was dry-laminated (attached) to one surface of the chemical conversion-treated aluminum foil 4 via a two-component curing urethane adhesive 5.

Next, on the other side of the dry laminated aluminum foil 4, a 4 μm thick maleic anhydride modified polypropylene film (inner adhesive layer) 6 and an 80 μm thick elastomer modified olefin resin A film 3 are coextruded. These are layered in this order, sandwiched between a rubber nip roll and a laminating roll heated to 100°C, and then dry laminated by pressure bonding, and then aged (heated) at 50°C for 5 days. Thus, an exterior material 1 for an electricity storage device having the configuration shown in FIG. 1 was obtained.

<Example 5>
Exterior material 1 for a power storage device having the configuration shown in FIG. 1 was obtained in the same manner as in Example 1 except that elastomer-modified olefin-based resin B was used instead of elastomer-modified olefin-based resin A.

<Example 6>
Exterior material 1 for a power storage device having the configuration shown in FIG. 1 was obtained in the same manner as in Example 1, except that elastomer-modified olefin-based resin C was used instead of elastomer-modified olefin-based resin A.

<Example 7>
A chemical conversion treatment solution consisting of phosphoric acid, polyacrylic acid (acrylic resin), chromium (III) salt compound, water, and alcohol was applied to both sides of aluminum foil 4 with a thickness of 35 μm, and then dried at 180°C. , a chemical conversion film was formed. The amount of chromium deposited on this chemical conversion film was 10 mg/m ² per side.

Next, a biaxially stretched 6-nylon film 2 having a thickness of 15 μm was dry-laminated (attached) to one surface of the chemical conversion-treated aluminum foil 4 via a two-component curing urethane adhesive 5.

Next, a two-component curing type urethane adhesive (inner adhesive layer) 6 is applied to the other side of the dry laminated aluminum foil 4, and then a homopolypropylene film (8 μm thick) ( A coextruded product of the second sealant layer) 8 and the elastomer-modified olefin resin A film (first sealant layer) 7 with a thickness of 72 μm is layered in this order and placed on a rubber nip roll and a laminating roll heated to 100°C. The exterior material 1 for a power storage device having the configuration shown in FIG. 2 was obtained by dry laminating by sandwiching and crimping and then aging (heating) at 50° C. for 5 days.

<Example 8>
The structure shown in FIG. 2 was prepared in the same manner as in Example 7, except that an 8 μm thick propylene-ethylene random copolymer film 8 was used as the second sealant layer 8 instead of an 8 μm thick homopolypropylene film. Exterior material 1 for a power storage device was obtained.

<Example 9>
A power storage device having the configuration shown in FIG. 2 was manufactured in the same manner as in Example 8, except that a two-component curing type acrylic adhesive 6 was used as the inner adhesive 6 instead of a two-component curing type urethane adhesive. Exterior material 1 for a device was obtained.

<Comparative example 1>
An exterior material for a power storage device having the configuration shown in FIG. 1 was obtained in the same manner as in Example 1, except that a propylene-ethylene random copolymer was used in place of the elastomer-modified olefin resin A.

<Comparative example 2>
A chemical conversion treatment solution consisting of phosphoric acid, polyacrylic acid (acrylic resin), chromium (III) salt compound, water, and alcohol was applied to both sides of aluminum foil 4 with a thickness of 35 μm, and then dried at 180°C. , a chemical conversion film was formed. The amount of chromium deposited on this chemical conversion film was 10 mg/m ² per side.

Next, a biaxially stretched 6-nylon film 2 having a thickness of 15 μm was dry-laminated (attached) to one surface of the chemical conversion-treated aluminum foil 4 via a two-component curing urethane adhesive 5.

Next, after applying a two-component curing type acrylic adhesive 6 to the other surface of the dry laminated aluminum foil 4, a 68 μm thick elastomer-modified olefin resin A film (second The coextruded sealant layer) 8 and 12 μm thick propylene-ethylene random copolymer film (first sealant layer) 7 were layered in this order and then placed between a rubber nip roll and a laminating roll heated to 100°C. Dry lamination was carried out by sandwiching and crimping, and then aging (heating) was performed at 50° C. for 5 days to obtain an exterior material for a power storage device having the configuration shown in FIG. 2.

The tensile yield strength (see Table 1) of the sealant film (thickness: 80 μm) 3 used to create the exterior materials of Examples 1 to 9 and Comparative Examples 1 to 2 was determined by the tensile yield strength measured as follows. Yield strength (tensile yield strength).

<Measurement method of tensile yield strength of sealant film>
For unstretched sealant film 3 (thickness 80 μm) prepared in the same manner for separate measurement, a type 2 test piece (length 150 mm or more) was prepared in accordance with JIS K7127-1999 (tensile test method for plastic films). Tensile yield strength I asked for it. The load at the yield point on the SS curve is defined as the tensile yield strength. In addition, after setting the test piece in a tensile test device in a thermostatic chamber set at 80°C, leave it for 1 minute in this 80°C environment, and then conduct the tensile test in an 80°C environment. did. Table 1 shows the results of measuring the tensile yield strength at 80°C.

Although the thickness of the test piece was set to 80 μm for measurement, for example, the used sealant film 3 with a thickness of 64 μm has a second sealant layer with a thickness of 6 μm and a first sealant layer with a thickness of 58 μm. In the case of a two-layer laminated structure, a test piece with a thickness of 80 μm is prepared and measured so that the thickness ratio of the two layers remains unchanged. That is, a test piece having a two-layer laminated structure of a second sealant layer with a thickness of 7.5 μm and a first sealant layer with a thickness of 72.5 μm is prepared and measured. In the case of a laminated structure of three or more layers, a test piece with a thickness of 80 μm is similarly prepared and measured.

Each of the exterior materials for power storage devices obtained as described above was evaluated based on the following measurement method.

<Measurement method of initial seal strength at high temperature>
After cutting out two specimens with a width of 15 mm and a length of 150 mm from the obtained exterior material, these two specimens were placed one on top of the other so that their inner sealant layers were in contact with each other, and the test pieces were placed at Tester Sangyo Co., Ltd. Heat sealing was performed by heating one side using a heat sealing device (TP-701-A) manufactured by Kogyo Co., Ltd. under the conditions of heat sealing temperature: 200°C, sealing pressure: 0.2 MPa (gauge display pressure), and sealing time: 2 seconds. went.

Next, the pair of exterior materials whose inner sealant layers were heat-sealed together as described above was tested in accordance with JIS Z0238-1998 using a Shimadzu Access Strograph (tensile test device) placed in a thermostatic chamber. ) (AGS-5kNX) to measure the peel strength when the outer sealant layer (test specimen) was peeled 90 degrees between the inner sealant layers of the sealed portion at a tensile speed of 100 mm/min, and this was calculated as the seal strength ( N/15mm width). Note that the seal strength at 100°C and the seal strength at 120°C were measured.

In the measurement of seal strength at 100℃, the test specimen was set in a tensile tester in a constant temperature chamber set at 100℃, left undisturbed in this 100℃ environment for 1 minute, and then placed in a 100℃ environment. Measurement was performed using . To measure the seal strength at 120°C, the specimen was set in a tensile tester in a constant temperature chamber set at 120°C, left to stand for 1 minute in this 120°C environment, and then placed in a 120°C environment. Measurement was performed using .

The seal strength at 100°C and the seal strength at 120°C are both 27N/15mm width or more to be passed.

<Seal strength measurement method after 90 days in high temperature environment>
Two pieces of exterior material cut to a size of 200 mm in length x 150 mm in width were placed one on top of the other so that the sealant layers were on the inside facing each other, and the edges of the three sides were heated at 180°C and 0.2 MPa. Heat sealed for 2 seconds. After injecting 10 mL of electrolyte through the opening on the remaining unsealed side, heat-seal the remaining side under the same sealing conditions as above while removing the air inside to create a simulated battery (test body). did. The electrolytic solution was an electrolytic solution in which lithium hexafluorophosphate (LiPF ₆ ) was dissolved at a concentration of 1 mol/L in a mixed solvent containing ethylene carbonate (EC) and dimethyl carbonate (DMC) in an equal volume ratio. liquid was used.

The obtained simulated battery was placed in a constant temperature and humidity chamber manufactured by ESPEC and allowed to stand for 90 days at 80° C. and 90% Rh (exposed to a high temperature and high humidity environment for 90 days).

After the 90 days have passed, take out the simulated battery, open one side to remove the electrolyte, wash the inside with water several times, and then replace the two outer casings to include the sealed parts of the two outer casings. The pair of exterior materials obtained by cutting the overlapping state into a size of 15 mm width x 150 mm length was tested using a Strograph (tensile testing device) manufactured by Shimadzu Access Co., Ltd. (AGS-5kNX) in accordance with JIS Z0238-1998. ) was used to measure the peel strength when the pair of exterior materials were peeled off at 90 degrees between the sealant layers of the sealed portion at a tensile speed of 100 mm/min, and this was defined as the seal strength (N/15 mm width). In addition, the seal strength at 25°C was measured. Those whose seal strength is 27 N/15 mm width or more are considered to be passed.

As is clear from Table 1, the exterior materials for power storage devices according to Examples 1 to 9 according to the present invention are able to secure sufficient initial seal strength even in high-temperature environments, and even when placed in high-temperature environments for long periods of time. Sufficient seal strength can be maintained.

On the other hand, in Comparative Examples 1 and 2, the initial seal strength was insufficient in a high temperature environment, and the seal strength after being placed in a high temperature environment for a long period of time was significantly reduced.

Specific examples of the exterior material for a power storage device manufactured using the sealant film according to the present invention and the exterior material for a power storage device according to the present invention include, for example,
・Used as an exterior material for various power storage devices such as lithium secondary batteries (lithium ion batteries, lithium polymer batteries, etc.), lithium ion capacitors, electric double layer capacitors, etc. Moreover, the electricity storage device according to the present invention includes an all-solid-state battery in addition to the electricity storage device exemplified above.

1...Exterior material for power storage device 2...Heat-resistant resin layer (outer layer)
3...Sealant layer (inner layer)
4...Metal foil layer 5...Outer adhesive layer (first adhesive layer)
6...Inner adhesive layer (second adhesive layer)
7...First sealant layer (innermost layer; innermost sealant layer)
8...Second sealant layer (sealant layer closest to the metal foil layer side)
10... Exterior case for power storage device 15... Exterior member 30... Power storage device 31... Power storage device main body

Claims (7)

An exterior material for a power storage device including a heat-resistant resin layer as an outer layer, a sealant layer as an inner layer, and a metal foil layer disposed between these layers,
The sealant layer is composed of one or more layers, and at least the innermost layer of the sealant layer contains an elastomer-modified olefin resin,
The elastomer-modified olefin resin is composed of an olefin-based thermoplastic elastomer-modified homopolypropylene and an olefin-based thermoplastic elastomer-modified random copolymer,
The olefinic thermoplastic elastomer-modified random copolymer is an olefinic thermoplastic elastomer modified random copolymer containing propylene as a copolymerization component and a copolymerization component other than propylene. Exterior material for devices. The exterior material for a power storage device according to claim 1, wherein the content of the olefin thermoplastic elastomer component in the elastomer-modified olefin resin is 0.1% by mass or more and less than 20% by mass. The exterior material for a power storage device according to claim 1 or 2, wherein the elastomer-modified olefin resin constituting the innermost layer has a melting point higher than 160°C. The exterior material for an electricity storage device according to any one of claims 1 to 3, wherein the sealant film constituting the sealant layer has a tensile yield strength of 3.5 MPa to 15.0 MPa at 80°C. The exterior material for a power storage device according to any one of claims 1 to 4, wherein the metal foil layer and the sealant layer are bonded to each other via an adhesive layer. The exterior material for a power storage device according to claim 5, wherein the adhesive layer is made of an adhesive containing an olefin resin having a carboxyl group and a polyfunctional isocyanate compound. A power storage device main body,
and an exterior material for an electricity storage device according to any one of claims 1 to 6,
An electricity storage device, wherein the electricity storage device main body is covered with the exterior material.

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