JP6287236B2 - Power storage device exterior materials - Google Patents

Description

  The present invention relates to an exterior material for an electricity storage device.

  Conventionally, nickel-metal hydride and lead-acid batteries are known as secondary battery and other power storage devices, but the energy density is often low because downsizing of portable devices and installation space are limited. High lithium-ion batteries are attracting attention. Conventionally, metal cans have been used as exterior materials for lithium-ion batteries (hereinafter sometimes referred to simply as “exterior materials”), but they are lightweight, have high heat dissipation, and can be handled at low cost. Many possible multilayer films have been used.

The electrolyte of the lithium ion battery is composed of an aprotic solvent such as propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate, and an electrolyte. As the electrolyte, lithium salts such as LiPF ₆ and LiBF ₄ are used. However, these lithium salts generate hydrofluoric acid by a hydrolysis reaction with moisture. Hydrofluoric acid may cause corrosion of the metal surface of the battery member and decrease of the laminate strength between the respective layers of the exterior material made of the multilayer film.
Therefore, in the exterior material made of a multilayer film, a barrier layer made of aluminum foil or the like is provided inside to prevent moisture from entering from the surface of the multilayer film. For example, a packaging material is known in which a base material layer having heat resistance / first adhesive layer / barrier layer / corrosion prevention treatment layer for preventing corrosion due to hydrofluoric acid / second adhesive layer / sealant layer are sequentially laminated. A lithium ion battery using such an exterior material is also called an aluminum laminate type lithium ion battery.

  As a kind of aluminum laminate type lithium ion battery, a recess is formed in a part of the exterior material by cold molding, and the battery contents such as a positive electrode, a separator, a negative electrode, an electrolyte solution are accommodated in the recess, A device is known in which the remaining portion is folded and the edge portion is sealed by heat sealing. Such a battery is also called an embossed type lithium ion battery. In recent years, for the purpose of increasing the energy density, an embossed type lithium ion battery has also been manufactured in which recesses are formed on both sides of an exterior material to be bonded to accommodate more battery contents.

  The energy density of a lithium ion battery increases as the recesses formed by cold forming become deeper. However, the deeper the recesses to be formed, the easier it is for pinholes and breaks during molding of the exterior material. Then, protecting a metal foil using a stretched film for the base material layer of an exterior material is performed. As described above, the base material layer is usually bonded to the barrier layer via the adhesive layer (see, for example, Patent Document 1).

Japanese Patent No. 3567230

  In the technique of Patent Document 1, a stretched film having a tensile strength and an amount of elongation equal to or greater than a specified value is used to improve moldability. Therefore, there is a limit to improvement in manufacturing efficiency. In addition, there is a limit to cost reduction and thickness reduction by providing an adhesive layer.

  In view of the above circumstances, an object of the present invention is to provide an exterior material for an electricity storage device that can further improve manufacturing efficiency while ensuring suitable moldability and is excellent in cost.

The present invention is a metal foil layer, a coating layer directly formed on the first surface of the metal foil layer and serving as the outermost layer, a corrosion prevention treatment layer formed on the second surface of the metal foil layer, An exterior material for an electricity storage device comprising an adhesive layer formed on the corrosion prevention treatment layer and a sealant layer formed on the adhesive layer , wherein the coating layer is made of urethane acrylate .

The thickness of the coating layer may be 3 μm or more and 30 μm or less .

  According to the packaging material for an electricity storage device of the present invention, it is possible to further improve the production efficiency while ensuring a suitable moldability, and to improve the cost.

It is sectional drawing which shows the exterior | packing material for electrical storage devices which concerns on one Embodiment of this invention.

An embodiment of the present invention will be described with reference to FIG. FIG. 1 is a cross-sectional view showing an electricity storage device exterior material (hereinafter simply referred to as “exterior material”) 1 of the present embodiment.
As shown in FIG. 1, the exterior material 1 includes a metal foil layer 11 that exhibits a barrier function, a coating layer 12 formed on the first surface of the metal foil layer 11, and a second surface of the metal foil layer 11. And a bonding layer 14 and a sealant layer 15 sequentially stacked on the corrosion prevention treatment layer 13. When forming an electrical storage device using the exterior material 1, the coating layer 11 becomes the outermost layer and the sealant layer 15 becomes the innermost layer.

[Coating layer]
The coating layer 12 provides heat resistance in the sealing process when manufacturing the electricity storage device, and plays a role of suppressing the generation of pinholes that can occur during processing and distribution.
The coating layer 12 is formed of a resin, and is formed directly on the first surface of the metal foil layer 11 without using an adhesive or the like. Such a coating layer can be formed by applying or coating a resin material to be a coating layer on the metal foil layer.

  As the resin material for forming the coating layer 12, polyester, fluorine resin, acrylic resin, or the like can be used, and urethane acrylate is particularly preferable. This is because a coating film made of urethane acrylate has suitable spreadability. As a coating solution containing these resin materials, a two-component curable coating solution may be used.

  The thickness of the coating layer 12 is preferably 3 μm to 30 μm, and more preferably 5 μm to 20 μm. Since the covering layer 12 is directly formed on the metal foil layer 11, it is easy to make the structure thinner than the conventional exterior material by setting the thickness of the covering layer to 20 μm or less.

[Metal foil layer]
As the metal foil layer 11, various metal foils such as aluminum and stainless steel can be used, and aluminum foil is preferable from the viewpoint of workability such as moisture resistance and spreadability and cost. A general soft aluminum foil can be used as the aluminum foil. Among these, an aluminum foil containing iron is preferable from the viewpoint of excellent pinhole resistance and extensibility during molding.
0.1-9.0 mass% is preferable and, as for content of iron in the aluminum foil (100 mass%) containing iron, 0.5-2.0 mass% is more preferable. When the iron content is 0.1% by mass or more, the exterior material 1 is excellent in pinhole resistance and spreadability. If the iron content is 9.0% by mass or less, the exterior material 1 is excellent in flexibility.

  The thickness of the metal foil layer 13 is preferably 9 to 200 μm, more preferably 15 to 100 μm, from the viewpoint of barrier properties, pinhole resistance, and workability.

[Corrosion prevention treatment layer]
The corrosion prevention treatment layer 13 serves to suppress the corrosion of the metal foil layer 11 due to the electrolytic solution or hydrofluoric acid generated by the reaction between the electrolytic solution and moisture. Further, it plays a role of increasing the adhesion between the metal foil layer 11 and the adhesive layer 14.
The corrosion prevention treatment layer 13 is preferably a coating film formed by a coating type or immersion type acid resistant corrosion prevention treatment agent. Such a coating film is excellent in the effect of preventing corrosion of the metal foil layer 11 with respect to acid.

As the coating film constituting the corrosion prevention treatment layer 13, for example, a coating film formed by ceriazol treatment with a corrosion prevention treatment agent comprising cerium oxide, phosphate and various thermosetting resins, chromate, phosphate And a coating film formed by a chromate treatment with a corrosion inhibitor comprising a fluoride and various thermosetting resins.
The corrosion prevention treatment layer 13 is not limited to the above-described layer as long as the corrosion resistance of the metal foil layer 11 is sufficiently obtained. For example, a coating film formed by phosphate treatment, boehmite treatment, or the like may be used.

The corrosion prevention treatment layer 13 may be a single layer or a plurality of layers. In addition, an additive such as a silane coupling agent may be added to the corrosion prevention treatment layer 13.
The thickness of the corrosion prevention treatment layer 13 is preferably 10 nm to 5 μm, more preferably 20 to 500 nm, from the viewpoint of the corrosion prevention function and the function as an anchor.
The corrosion prevention treatment layer 13 may be further provided between the coating layer 12 and the metal foil layer 11 according to a required function.

[Adhesive layer]
The adhesive layer 14 is a layer that bonds the metal foil layer 11 on which the corrosion prevention treatment layer 13 is formed and the sealant layer 15. The exterior material 1 is roughly divided into a thermal laminate configuration and a dry laminate configuration depending on the adhesive component forming the adhesive layer 14.
As an adhesive component for forming the adhesive layer 14 in the thermal laminate configuration, an acid-modified polyolefin resin obtained by graft-modifying a polyolefin resin with an acid such as maleic anhydride is preferable. Since the acid-modified polyolefin resin has a polar group introduced into a part of the non-polar polyolefin resin, the non-polar sealant layer 15 formed of a polyolefin resin film or the like and a polar corrosion prevention treatment It is possible to firmly adhere to both of the layers 13. In addition, by using an acid-modified polyolefin resin, resistance to contents such as an electrolytic solution is improved, and even if hydrofluoric acid is generated inside the battery, it is easy to prevent a decrease in adhesion due to deterioration of the adhesive layer 14.
The acid-modified polyolefin resin used for the adhesive layer 14 may be one type or two or more types.

Examples of the polyolefin resin used for the acid-modified polyolefin resin include low density, medium density, and high density polyethylene; ethylene-α olefin copolymer; homo, block or random polypropylene; propylene-α olefin copolymer. Can be mentioned. In addition, a copolymer obtained by copolymerizing polar molecules such as acrylic acid and methacrylic acid with the above-described one, a polymer such as a crosslinked polyolefin, and the like can also be used.
Examples of the acid that modifies the polyolefin-based resin include carboxylic acid, epoxy compound, acid anhydride and the like, and maleic anhydride is preferable.

Examples of the adhesive component of the adhesive layer 14 in the dry laminate configuration include a two-component curable polyurethane adhesive.
In this case, since the adhesive layer 14 in the dry laminate configuration has a highly hydrolyzable bonding portion such as an ester group or a urethane group, the adhesive layer 14 in the thermal laminate configuration is used for applications that require higher reliability. Is preferred.

[Sealant layer]
The sealant layer 15 is a layer that imparts sealing properties by heat sealing in the exterior material 1. Examples of the sealant layer 15 include a resin film made of a polyolefin resin or an acid-modified polyolefin resin obtained by graft-modifying an acid such as maleic anhydride to a polyolefin resin.
Examples of the polyolefin resin include low density, medium density, and high density polyethylene; ethylene-α olefin copolymer; homo, block, or random polypropylene; propylene-α olefin copolymer. These polyolefin resin may be used individually by 1 type, and may use 2 or more types together.
Examples of the acid-modified polyolefin resin include the same as those described in the description of the adhesive layer 14.

The sealant layer 15 may be a single layer film or a multilayer film, and may be selected according to a required function. For example, in terms of imparting moisture resistance, a multilayer film in which a resin such as an ethylene-cyclic olefin copolymer or polymethylpentene is interposed can be used.
The sealant layer 15 may be blended with various additives such as a flame retardant, slip agent, anti-blocking agent, antioxidant, light stabilizer, and tackifier.
10-100 micrometers is preferable and, as for the thickness of the sealant layer 15, 20-60 micrometers is more preferable.

  The exterior material 1 may be one in which the sealant layer 15 is laminated by dry lamination, but from the viewpoint of improving adhesion, the sealant layer 15 is laminated by sandwich lamination using an acid-modified polyolefin resin as the adhesive layer 14. Preferably it is.

[Production method]
Hereinafter, the manufacturing method of the exterior material 1 is demonstrated. However, the following content is an example, and the manufacturing method of the exterior material 1 is not limited to the following content.
As a manufacturing method of the exterior material 1, the method which has the following process (1)-(3) is mentioned, for example.
Step 1: A step of forming a corrosion prevention treatment layer 13 on one surface (second surface) of the metal foil layer 11.
Process 2: The process of arrange | positioning the resin material of a coating layer on the surface (1st surface) on the opposite side to the 2nd surface in the metal foil layer 11, and forming the coating layer 12. FIG.
Process 3: The process of bonding the sealant layer 15 on the corrosion prevention process layer 14 formed in the metal foil layer 11 through the adhesive layer 14.

(Process 1)
A corrosion prevention treatment agent is applied to one surface of the metal foil layer 11 and dried to form a corrosion prevention treatment layer 13. Examples of the anti-corrosion treatment agent include the above-described anti-corrosion treatment agent for ceriazole treatment, anti-corrosion treatment agent for chromate treatment, and the like.
The coating method of the corrosion inhibitor is not particularly limited, and various methods such as gravure coating, reverse coating, roll coating, and bar coating can be employed.

(Process 2)
A resin material to be a coating layer is applied to the first surface of the metal foil layer 11 and dried to form the coating layer 12 on the first surface. The application method is not particularly limited, and various methods such as gravure coating, reverse coating, roll coating, and bar coating can be employed. As a method for curing the coating film, for example, irradiation with ultraviolet rays can be employed.
In step 2, a step such as aging is unnecessary. As a result, the tact time can be shortened and the manufacturing efficiency can be remarkably improved. Furthermore, the cost can be greatly reduced by not using an adhesive or the like.

(Process 3)
An adhesive layer 14 is formed on the corrosion prevention treatment layer 13 of the laminate in which the coating layer 12, the metal foil layer 11, and the corrosion prevention treatment layer 13 are laminated in this order, and a resin film that forms the sealant layer 15 is bonded thereto. The lamination of the sealant layer 15 is preferably performed by sandwich lamination.

The exterior material 1 is obtained by the steps (1) to (3) described above.
In addition, the process sequence of the manufacturing method of the exterior material 1 is not limited to the method of implementing said (1)-(3) sequentially. For example, step (1) may be performed after performing step (2).

  Prepare two finished exterior materials 1 so that the sealant layers 15 face each other, or fold back one exterior material 1 so that the sealant layers 15 face each other, and a tab member or the like to be a power generation element or a terminal inside If it arrange | positions and a periphery is joined by heat seal, the cell of the electrical storage device using the exterior | packing material 1 will be completed.

Although the exterior material of this invention is further demonstrated using an Example and a comparative example, this invention is not limited at all based on the specific content of an Example.
[Materials used]
The materials (thickness in parentheses) used for the production of Examples and Comparative Examples are shown below.
(Coating layer)
Material A-1: Urethane acrylate coating film (ultraviolet cured film) (10 μm)
Material A-2: Urethane acrylate coating film (ultraviolet curable film) (3 μm)
Material A-3: Biaxially stretched nylon film (25 μm)
Material A-4: Biaxially stretched nylon film (15 μm)

(Coating layer side adhesive layer)
Adhesive B-1: Polyester urethane adhesive (5 μm)

(Metal foil layer)
Metal foil C-1: Soft aluminum foil 8079 (Toyo Aluminum Co., Ltd., thickness 40 μm)

(Corrosion prevention treatment layer)
Treatment agent D-1: Treatment agent for coating type ceriazole treatment mainly composed of cerium oxide, phosphoric acid, and acrylic resin.

(Adhesive layer)
Adhesive resin E-1: Polypropylene resin graft-modified with maleic anhydride (trade name “Admer”, manufactured by Mitsui Chemicals)

(Sealant layer)
Film F-1: A film obtained by corona-treating the surface to be the inner surface of an unstretched polypropylene film (thickness: 40 μm).

(Preparation of exterior materials)
Treatment agent D-1 was applied to one surface of metal foil C-1 to be a metal foil layer and dried to form a corrosion prevention treatment layer. Next, in the Examples, the material A-1 (Example 1) and the material A-2 (Example 2) are respectively applied to the surface of the metal foil layer where the corrosion prevention treatment layer is not formed, and ultraviolet rays are applied. The coating layer was formed by curing by irradiation. In the comparative example, the corrosion prevention treatment layer is formed on the metal foil layer by the dry laminating method using the adhesive A-1 for the material A-3 (Comparative Example 1) and the material A-4 (Comparative Example 2), respectively. Bonded to the surface that is not. Thereafter, aging was performed at 60 ° C. for 6 days to form a layer instead of the coating layer. Next, the adhesive resin E-1 is extruded on the corrosion prevention treatment layer side of the obtained laminate by an extrusion device to form an adhesive layer, and the film F-1 is bonded to form a sealant layer by sandwich lamination. did. Then, the obtained laminate, 190 ° C., and thermocompression bonding with 4kg ^/ cm 2, 2m ^/ min conditions.
Through the above steps, exterior materials of Examples 1 and 2 and Comparative Examples 1 and 2 were produced.

[Evaluation of moldability]
The exterior material obtained in each example is cut into a blank shape of 150 mm × 190 mm, cold-molded while changing the molding depth in a molding environment of 23 ° C. and 40% RH (relative humidity), and the moldability is evaluated. did.
A punch having a shape of 100 mm × 150 mm, a punch corner R (RCP) of 1.5 mm, a punch shoulder R (RP) of 0.75 mm, and a die shoulder R (RD) of 0.75 mm was used. Evaluation criteria were performed according to the following.
“◎ (good)”: Deep drawing molding with a molding depth of 6 mm or more is possible without causing breakage or cracking. “◯ (fair)”: Molding depth of 4 mm or more without breaking or cracking “× (insufficient)” that enables deep drawing of less than 6 mm: Breaking or cracking occurs in deep drawing of a molding depth of less than 4 mm

[Evaluation of manufacturing efficiency]
In the formation of the coating layer of each example or a layer replacing the coating layer, the number of days required for production was evaluated. The evaluation criteria were as follows.
“◎ (good)”: The manufacturing process is completed within one day “× (insufficient)”: The manufacturing process takes 5 days or more.

[Examples 1 and 2 and Comparative Examples 1 and 2]
Table 1 shows the configuration of each example and the evaluation results of moldability and production efficiency.

As shown in Table 1, in Example 1 in which a 10 μm thick urethane acrylate coating film was used for the coating layer, good moldability was observed. In Example 2 where the thickness of the coating layer was reduced to 3 μm, sufficient moldability was confirmed.
On the other hand, in Comparative Examples 1 and 2 in which a biaxially stretched nylon film was used to form a layer instead of the coating layer, the film was good in Comparative Example 1 having a film thickness of 25 μm (total film thickness of 30 μm with the coating layer side adhesive layer). Although moldability was obtained, in Comparative Example 2 (total film thickness of 20 μm with the coating layer side adhesive layer) having a film thickness of 15 μm, the moldability deteriorated and was not sufficient. This is considered to be due to an increase in the ratio of the coating layer side adhesive layer that does not contribute to moldability.
Furthermore, in Comparative Examples 1 and 2, since a polyester urethane adhesive was used as the coating layer side adhesive layer, an aging process was required, and the production efficiency was remarkably poor as compared with the Examples.

  From the above, it can be seen that by forming the coating layer directly on the metal foil layer without using an adhesive layer, the production efficiency can be improved and the moldability can be maintained high even if the coating layer is thinned. It was.

  The embodiments and examples of the present invention have been described above. However, the technical scope of the present invention is not limited to the above-described embodiments, and combinations of components may be changed without departing from the spirit of the present invention. Various changes can be added to or deleted from each component.

DESCRIPTION OF SYMBOLS 1 Exterior material 11 for electrical storage devices Metal foil layer 12 Coating layer 13 Corrosion prevention treatment layer 14 Adhesive layer 15 Sealant layer

Claims (2)

A metal foil layer;
A coating layer that is directly formed on the first surface of the metal foil layer and is the outermost layer;
A corrosion prevention treatment layer formed on the second surface of the metal foil layer;
An adhesive layer formed on the corrosion prevention treatment layer;
A sealant layer formed on the adhesive layer;
Equipped with a,
An exterior material for an electricity storage device, wherein the coating layer is made of urethane acrylate .   The packaging material for an electricity storage device according to claim 1, wherein the coating layer has a thickness of 3 μm or more and 30 μm or less.

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