JP6036880B2 - Exterior materials for lithium-ion batteries - Google Patents

Description

  The present invention relates to a packaging material for a lithium ion battery.

  BACKGROUND ART Lithium ion batteries that can be ultra-thin and miniaturized have been actively developed as batteries for use in mobile terminal devices such as mobile phones and laptop computers, video cameras, satellites, electric vehicles, and the like. As an exterior material for lithium ion batteries (hereinafter, sometimes simply referred to as “exterior material”), a metal can type that is obtained by press-molding a metal plate or the like and processed into a cylindrical shape or a rectangular parallelepiped shape. There are two types of laminate film type using aluminum foil (for example, a structure such as a base material layer / aluminum foil layer / adhesive resin layer / sealant layer). When a metal can is used as the exterior material, there are many restrictions on the shape of the battery itself. On the other hand, a laminate film type exterior material using an aluminum foil is attracting attention because it can be freely selected in shape and can be further reduced in weight.

  Laminate film type exterior materials using aluminum foil are roughly classified into two types depending on the type of adhesive layer between the aluminum foil layer and the sealant layer. That is, it can be broadly divided into a dry laminate configuration using an adhesive for dry laminate for the adhesive layer and a thermal laminate configuration using a thermoplastic material such as acid-modified polyolefin resin for the adhesive layer. The exterior material having a dry laminate structure is used for consumer applications such as portable devices that require particularly excellent moldability. Moreover, the exterior material of the heat laminate structure is used for large-scale applications such as electric vehicles, satellites, submarines, and electric bicycles that require higher reliability.

  As a form of a lithium ion battery using a laminate film type exterior material using an aluminum foil, the exterior material is deep-drawn by cold forming to form a recess, and the battery contents are stored in the recess to heat. The sealing form is widely used. In this embodiment, a deeper concave portion formed by cold forming can accommodate more battery contents, resulting in higher energy density. Thus, conventionally, a polyamide film having excellent moldability has been used as the base material layer of the exterior material. However, since the polyamide film does not have sufficient scratch resistance, the surface of the exterior material is scratched by the handling during the production of the exterior material and the assembly of the lithium ion battery, and the vibration when the lithium ion battery is laminated. May occur.

  On the other hand, in the lithium ion battery, as the battery contents, together with the positive electrode material, the negative electrode material, and the separator, an aprotic solvent having penetrating power such as propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate is used. An electrolyte layer made of an electrolytic solution in which an electrolyte (lithium salt) is dissolved or a polymer gel impregnated with the electrolytic solution is contained. When the solvent having the osmotic force passes through the sealant layer, the laminate strength between the aluminum foil layer and the sealant layer is lowered, and the electrolyte may leak out in the end. In a form in which a plurality of lithium ion batteries are stacked and used, the electrolyte solution leaking from one lithium ion battery may adhere to the exterior material of another lithium ion battery. Therefore, when a base material layer is a polyamide film, there exists a possibility that a base material layer may melt | dissolve with electrolyte solution and an aluminum foil layer may corrode.

  Therefore, in recent years, for the purpose of protecting the polyamide film, a laminated film in which a polyester film such as a polyethylene terephthalate (PET) film is laminated on the outside of the polyamide film is used as a base material layer (for example, Patent Documents 1 and 2). . However, when a laminated film is used for the base material layer, there is a problem that moldability of the exterior material is lowered.

JP 2004-327039 A JP 2002-56824 A

  An object of this invention is to provide the exterior material for lithium ion batteries which used the laminated | multilayer film for the base material layer, and has the outstanding moldability.

The present invention employs the following configuration in order to solve the above problems.
[1] In a lithium ion battery exterior material in which at least a metal foil layer, a corrosion prevention treatment layer, an adhesive resin layer, and a sealant layer are sequentially laminated on one surface of a base material layer,
The base material layer comprises a laminated film in which a plurality of biaxially stretched films are laminated,
The biaxially stretched films adjacent to each other in the laminated film are laminated via an adhesive for dry lamination,
Adhesives for the dry lamination is a polyester polyol, a main agent selected from polyether polyols and acrylic polyols, Ri polyurethane adhesive der of two-component curable exerting aromatic or aliphatic isocyanate as a curing agent ,
The biaxially stretched film is biaxially stretched in the 0 degree direction and the 90 degree direction,
An exterior material for a lithium ion battery, wherein the adjacent biaxially stretched films in the laminated film satisfy the following condition (1) .
(1) Tensile strength out of the 45 degree direction and 135 degree direction with respect to the stretching direction of one biaxially stretched film, the direction having the largest tensile strength, and the 45 degree direction and 135 degree direction with respect to the stretching direction of the other biaxially stretched film Are stacked so that the direction in which they are small is aligned.
[2] The exterior material for a lithium ion battery according to [1], wherein the base material layer is a laminated film in which a biaxially stretched polyester film and a biaxially stretched polyamide film are laminated.
[3] The exterior material for a lithium ion battery according to [1] or [2], wherein the outermost layer of the base material layer is a biaxially stretched polyester film.
[4] The exterior material for a lithium ion battery according to any one of [1] to [3], wherein the thickness of the base material layer is 6 to 40 μm.
[5] The packaging material for a lithium ion battery according to any one of [1] to [4], wherein a molding improvement layer that improves moldability is provided between the metal foil layer and the base material layer.
[6] The outer packaging material for a lithium ion battery according to any one of [1] to [5], wherein the metal foil layer is a layer made of a soft aluminum foil subjected to an annealing treatment.
[7] The lithium ion battery according to any one of [1] to [6], wherein the corrosion prevention treatment layer is a layer formed by a method using a sol of a rare earth element-based oxide having an average particle size of 100 nm or less. Exterior material.
[8] The exterior packaging material for a lithium ion battery according to any one of [1] to [6], wherein the corrosion prevention treatment layer is a layer formed by a coating-type chromate treatment.
[9] The external packaging material for a lithium ion battery according to any one of [1] to [8], wherein the adhesive resin layer contains maleic anhydride-modified polypropylene, and the sealant layer is made of a polypropylene film.

  The lithium ion battery exterior material of the present invention uses a laminated film for the base material layer and has excellent moldability.

It is sectional drawing which showed an example of the exterior material for lithium ion batteries of this invention. It is sectional drawing which showed the other example of the exterior material for lithium ion batteries of this invention.

Hereinafter, an example of an embodiment of the outer packaging material for a lithium ion battery of the present invention will be shown and described in detail.
[First Embodiment]
As shown in FIG. 1, an exterior material 1 for a lithium ion battery of the present embodiment (hereinafter referred to as “exterior material 1”) has an adhesive layer 12 and a metal foil layer 13 on one surface of a base material layer 11. , A laminate in which the corrosion prevention treatment layer 14, the adhesive resin layer 15, and the sealant layer 16 are sequentially laminated.

(Base material layer 11)
The base material layer 11 imparts heat resistance in a sealing process when manufacturing a lithium ion battery, and plays a role of suppressing generation of pinholes that may occur during molding processing and distribution. In particular, in the case of an exterior material for a large-sized lithium ion battery, scratch resistance, chemical resistance, insulation, and the like can be imparted.
The base material layer 11 is made of a laminated film in which a first biaxially stretched film 11A and a second biaxially stretched film 11B are laminated. By using a laminated film as the base material layer 11, a base material layer having properties such as moldability, heat resistance, insulation, flexibility, scratch resistance, chemical resistance, and the like can be obtained.

The biaxially stretched film used for the base material layer 11 is preferably a biaxially stretched polyester film, a biaxially stretched polyamide film, or a biaxially stretched polypropylene film.
As a combination of the first biaxially stretched film 11A and the second biaxially stretched film 11B, a combination of a biaxially stretched polyester film and a biaxially stretched polyamide film is preferable. That is, the base material layer 11 is preferably a laminated film in which a biaxially stretched polyester film and a biaxially stretched polyamide film are laminated. The biaxially stretched polyamide film is excellent in terms of moldability, pinhole resistance, insulation, flexibility, bending strength and the like. The biaxially stretched polyester film is excellent in terms of rigidity, scratch resistance, chemical resistance and the like.

As for base material layer 11, it is preferred that the outermost layer is a biaxially stretched polyester film. That is, the first biaxially stretched film 11A is preferably a biaxially stretched polyester film.
As the base material layer 11, a biaxially stretched polyester film is formed from the outermost layer side from the viewpoint that a base material layer 11 having excellent moldability, heat resistance, insulation, flexibility, electrolytic solution resistance, and scratch resistance can be easily obtained. In particular, a laminated film in which a biaxially stretched polyamide film is laminated, that is, a laminated film in which the first biaxially stretched film 11A is a biaxially stretched polyester film and the second biaxially stretched film 11B is a biaxially stretched polyamide film. preferable.

The first biaxially stretched film 11A and the second biaxially stretched film 11B in the base material layer 11 are laminated so as to satisfy the following condition (1). Thereby, the exterior material 1 which has the outstanding moldability is obtained.
(1) The 45 degree direction with respect to the stretching direction of the first biaxially stretched film 11A and the direction having a higher tensile strength among the 135 degree directions, and the 45 degree direction with respect to the stretching direction of the second biaxially stretched film 11B and the 135 degree direction. Are laminated so that the directions in which the tensile strength is small are aligned.
The tensile strength in the present invention means the tensile strength until breaking in each direction. The tensile strength is measured in accordance with JIS K7127, using a type 5 punching die and measuring a tensile strength of 300 mm / min.

  The biaxially stretched film varies in mechanical strength depending on the direction, and has anisotropy in tensile strength and ease of elongation. That is, when the tensile strength is measured in four directions of 0 degree, 45 degrees, 90 degrees, and 135 degrees with respect to the stretching direction of the biaxially stretched film, the tensile strengths in these four directions are usually different. When the present inventors examined in detail, it turned out that especially the anisotropy of the tensile strength of a 45 degree direction and a 135 degree direction has influenced the moldability of an exterior material greatly. In the packaging material 1, the adjacent first biaxially stretched film 11A and the second biaxially stretched film 11B in the laminated film are laminated so as to satisfy the condition (1), so that the direction of 45 degrees with respect to the stretching direction. Since the anisotropy of the tensile strength in the direction of 135 degrees is relaxed and the anisotropy as the base material layer 11 is reduced, excellent moldability is obtained.

The biaxially stretched film used for the base material layer 11 may contain additives such as a flame retardant, a lubricant, an antiblocking agent, an antioxidant, a light stabilizer, and a tackifier.
Examples of the lubricant include fatty acid amides (oleic acid amide, erucic acid amide, stearic acid amide, behenic acid amide, ethylene bisoleic acid amide, ethylene biserucic acid amide, etc.) and the like.
As the anti-blocking agent, various filler-based anti-blocking agents such as silica are preferable.
An additive may be used individually by 1 type and may use 2 or more types together.

The first biaxially stretched film 11A and the second biaxially stretched film 11B in the base material layer 11 are provided with an adhesive for dry lamination from the viewpoint of excellent adhesion and economic efficiency of the biaxially stretched films. Are preferably laminated.
As an adhesive for dry lamination, a two-component curing type polyurethane adhesive in which a bifunctional or higher aromatic or aliphatic isocyanate is allowed to act as a curing agent on a main component such as polyester polyol, polyether polyol, and acrylic polyol. Is preferred.
The polyurethane adhesive is subjected to aging for 4 days or more after application, for example, at 40 ° C., whereby the reaction between the hydroxyl group of the main agent and the isocyanate group of the curing agent proceeds to enable strong adhesion. 1-10 are preferable and, as for the molar ratio (NCO / OH) of the isocyanate group which the hardening | curing agent has with respect to the hydroxyl group which a main ingredient has, 2-5 are more preferable.

  As for the thickness of the base material layer 11, 6-40 micrometers is preferable. When the thickness of the base material layer 11 is 6 μm or more, the pinhole resistance and the insulation are improved. If the thickness of the base material layer 11 is 40 μm or less, the moldability is improved.

(Adhesive layer 12)
The adhesive layer 12 is a layer that bonds the base material layer 11 and the metal foil layer 13 together.
As the adhesive constituting the adhesive layer 12, the dry laminating adhesives mentioned for the lamination in the laminated film of the base material layer 11 can be used, and the preferred embodiments are also the same.
The thickness of the adhesive layer 12 is preferably 1 to 10 μm and more preferably 3 to 7 μm from the viewpoints of adhesive strength, followability, workability, and the like.

(Metal foil layer 13)
As the metal foil layer 13, 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.
As the aluminum foil, for example, a known soft aluminum foil can be used, and an aluminum foil containing iron is preferable from the viewpoint of pinhole resistance and spreadability at the time of molding. 0.1-9.0 mass% is preferable and, as for content of iron in aluminum foil (100 mass%), 0.5-2.0 mass% is more preferable. If the iron content is at least the lower limit, pinhole resistance and spreadability are improved. If the iron content is less than or equal to the upper limit, flexibility is improved.
Moreover, as an aluminum foil, the soft aluminum foil which performed annealing treatment from the point which can provide the extensibility at the time of shaping | molding is further more preferable.

The thickness of the metal foil layer 13 is preferably 9 to 200 μm and more preferably 15 to 150 μm from the viewpoint of barrier properties, pinhole resistance, and workability.
A particularly preferred metal foil layer 13 is an annealed soft aluminum foil having a thickness of 15 to 150 μm. Specifically, 8021 material and 8079 material are preferable according to JIS standards.

The aluminum foil used for the metal foil layer 13 is preferably subjected to a degreasing treatment from the viewpoint of resistance to electrolytic solution. Further, from the viewpoint of simplifying the production process, an aluminum foil whose surface is not etched is preferable.
The degreasing treatment is roughly classified into a wet type and a dry type, and the dry type is preferable from the viewpoint of simplifying the manufacturing process.
Examples of the dry type degreasing treatment include a method of performing a degreasing treatment by increasing the treatment time in the step of annealing the aluminum foil. In the annealing treatment performed to soften the aluminum foil, sufficient electrolytic solution resistance can be obtained even with a degreasing treatment performed simultaneously. In addition to the degreasing treatment, frame treatment, corona treatment and the like can be mentioned. Furthermore, a degreasing process in which contaminants are oxidatively decomposed and removed by active oxygen generated by irradiation with ultraviolet rays having a specific wavelength may be employed.

  Examples of the wet type degreasing treatment include acid degreasing and alkali degreasing. Examples of the acid used for acid degreasing include inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid, and hydrofluoric acid. These acids may be used individually by 1 type, and may use 2 or more types together. As an alkali used for alkali degreasing, sodium hydroxide etc. are mentioned as a thing with a high etching effect, for example. Moreover, what mix | blended weak alkali type and surfactant is mentioned. The wet type degreasing treatment is performed by an immersion method or a spray method.

(Corrosion prevention treatment layer 14)
The corrosion prevention treatment layer 14 serves to firmly adhere the metal foil layer 13 and the adhesive resin layer 15 and to protect the metal foil layer 13 from the electrolytic solution and hydrofluoric acid generated from the electrolytic solution.
The corrosion prevention treatment layer 14 can be formed by, for example, a hydrothermal alteration treatment, an anodizing treatment, a chemical conversion treatment, or a combination of these treatments.
Examples of the hydrothermal modification treatment include boehmite treatment obtained by immersing aluminum foil in boiling water to which triethanolamine is added. Examples of the anodizing treatment include alumite treatment. Examples of the chemical conversion treatment include various chemical conversion treatments including a chromate treatment, a zirconium treatment, a titanium treatment, a vanadium treatment, a molybdenum treatment, a calcium phosphate treatment, a strontium hydroxide treatment, a cerium treatment, a ruthenium treatment, or a mixed layer thereof. Further, these chemical conversion treatments are not limited to wet types, and application types in which these treatment agents are mixed with resin components can also be applied.
As described above, among these corrosion prevention treatments, the coating type chromate treatment is preferable from the viewpoint of waste liquid treatment while maximizing the curing thereof.

  In addition to the chemical conversion treatment described above, the corrosion prevention treatment layer 14 can be formed only by a pure coating technique. As such a method, a sol of a rare earth element-based oxide such as cerium oxide having an average particle diameter of 100 nm or less is used as a material that has an aluminum corrosion prevention effect (inhibitor effect) and is also suitable from an environmental viewpoint. The method using is mentioned. By using this method, it is possible to impart an effect of preventing corrosion of a metal foil such as an aluminum foil even by a general coating method.

(Adhesive resin layer 15)
The adhesive resin layer 15 is a layer that bonds the sealant layer 16 and the metal foil layer 13 on which the corrosion prevention treatment layer 14 is formed.
The resin constituting the adhesive resin layer 15 varies greatly depending on the manufacturing method. When the sealant layer 16 and the metal foil layer 13 on which the corrosion prevention treatment layer 14 is formed are bonded by dry lamination, the same adhesive composition as that used for the adhesive layer 12 can be used. In this case, in order to suppress swelling due to the electrolytic solution and hydrolysis due to hydrofluoric acid, it is necessary to design the composition such as using a main component having a skeleton that is difficult to hydrolyze and improving the crosslinking density as an adhesive to be used. is there.

For example, as a technique for improving the crosslinking density, there may be mentioned a method using dimer fatty acid, dimer fatty acid ester or hydrogenated product, dimer fatty acid reduced glycol, dimer fatty acid ester or hydrogenated reduced glycol. Dimer fatty acids are those obtained by dimerizing various unsaturated fatty acids, and examples of their structures include acyclic, monocyclic, polycyclic, and aromatic ring types. The polybasic acid which is a raw material of the polyester polyol used as an adhesive for forming the adhesive resin layer 15 is not particularly limited. Moreover, the fatty acid which is a starting material of a dimer fatty acid is not specifically limited. Moreover, you may introduce | transduce such a dibasic acid used with a normal polyester polyol by using such a dimer fatty acid as an essential component.
As a curing agent for the main agent, an isocyanate compound that can also be used as a chain extender of a polyester polyol can be used. As a result, the crosslink density of the adhesive coating film is increased, leading to improvements in solubility and swelling properties, and an increase in the urethane group concentration is also expected to improve the substrate adhesion.

When the sealant layer 16 and the metal foil layer 13 on which the corrosion prevention treatment layer 14 is formed are bonded by thermal lamination, an acid-modified polyolefin resin obtained by graft-modifying a polyolefin resin with an acid is preferable. 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. The polyolefin resin may be used alone or in combination of two or more. Examples of the acid to be graft-modified include carboxylic acid, epoxy compound, acid anhydride and the like, and maleic anhydride is preferable.
As the resin constituting the adhesive resin layer 15, a polyolefin resin is graft-modified with maleic anhydride from the viewpoint that the adhesion between the sealant layer 16 and the metal foil layer 13 can be easily maintained even when the electrolytic solution penetrates. Maleic acid-modified polyolefin resin is preferable, and maleic anhydride-modified polypropylene is particularly preferable.

When the adhesive resin layer 15 is formed by extrusion molding, the adhesive resin is easily oriented in the MD direction (machine direction) due to stress or the like generated during extrusion molding. In this case, an elastomer may be blended in the adhesive resin layer 15 from the viewpoint of relaxing anisotropy.
Examples of the elastomer blended in the adhesive resin layer 15 include olefin-based elastomers and styrene-based elastomers. The average particle size of the elastomer to be blended is preferably 200 nm or less from the viewpoint of improving the compatibility with the adhesive resin and improving the effect of relaxing the anisotropy of the adhesive resin layer 15. In addition, the said average particle diameter is measured by taking the photograph which expanded the cross section of the elastomer composition with an electron microscope, and measuring the average particle diameter of the disperse | distributed crosslinked rubber component by image analysis.
These elastomers may be used alone or in combination of two or more.

  When mix | blending the said elastomer with the adhesive resin layer 15, 1-25 mass% is preferable and, as for the compounding quantity of the said elastomer in the adhesive resin layer 15 (100 mass%), 10-20 mass% is more preferable. If the blending amount of the elastomer is not less than the lower limit, compatibility with the adhesive resin is improved, and the effect of relaxing the anisotropy of the adhesive resin layer 15 is improved. If the blending amount of the elastomer is equal to or less than the upper limit value, it is easy to suppress the adhesive resin layer 15 from being swollen by the electrolytic solution.

The adhesive resin layer 15 may be formed using a dispersion type adhesive resin liquid in which the adhesive resin is dispersed in an organic solvent.
1-40 micrometers is preferable and, as for the thickness of the adhesive resin layer 15, 5-20 micrometers is more preferable.

(Sealant layer 16)
The sealant layer 16 is an inner layer of the exterior material 1 and is a layer that is thermally welded when the battery is assembled. That is, the sealant layer 16 is a layer made of a heat-weldable film.
Examples of the film component constituting the sealant layer 16 include polyolefin resins and acid-modified polyolefin resins obtained by graft-modifying polyolefin resins with maleic anhydride or the like. Among these, polyolefin resins are preferable and polypropylene is particularly preferable from the viewpoint of excellent water vapor barrier properties and easy formation of a battery form without being crushed excessively by heat sealing. Examples of the polypropylene include the polypropylene exemplified in the adhesive resin layer 15.
The sealant layer 16 may be formed of a film in which the various resins described above are mixed.
The sealant layer 16 may be a single layer film or a multilayer film.

  When a film formed by extrusion molding is used as the sealant layer 16, since there is an orientation tendency in the extrusion direction of the film, an elastomer may be added to the sealant layer 16 in order to reduce anisotropy due to the orientation. . Thereby, it becomes easy to suppress that the sealant layer 16 whitens when cold-molding the exterior material 1 to form a recess.

As an elastomer mix | blended with the sealant layer 16, the same thing as what was mentioned as an elastomer mix | blended with the adhesive resin layer 15 can be used, and a preferable form is also the same.
When the sealant layer 16 is a laminated film, the elastomer may be blended only in one of the layers, or may be blended in all the layers. For example, when the sealant layer 16 has a three-layer structure of random polypropylene / block polypropylene / random polypropylene, the elastomer may be blended only in the block polypropylene layer, or may be blended only in the random polypropylene layer. You may mix | blend with both the layer of this, and the layer of block polypropylene.

  The sealant layer 16 may contain a lubricant for the purpose of imparting slipperiness. Thereby, when forming a recessed part in the cladding | exterior_material 1 by cold forming, it becomes easy to prevent the part which becomes a side and a corner | angular part of a recessed part with a high extending | stretching ratio in the cladding | exterior_material 1 from extending more than necessary. Therefore, it becomes easy to prevent the metal foil layer 13 and the adhesive resin layer 15 from being peeled off, and the sealant layer 16 and the adhesive resin layer 15 from being broken or whitened due to cracks.

  When a lubricant is blended in the sealant layer 16, the blending amount of the lubricant in the sealant layer 16 (100% by mass) is preferably 0.001% by mass to 0.5% by mass. When the blending amount of the lubricant is 0.001% by mass or more, an effect of suppressing the whitening of the sealant layer 16 during cold molding is easily obtained. If the blending amount of the lubricant is 0.5% by mass or less, it is easy to suppress the lubricant from bleeding on the laminate surface with the other layers other than the surface of the outer packaging material 1 to reduce the adhesion strength.

  As the adhesive resin layer 15 and the sealant layer 16, the adhesive resin layer 15 preferably contains maleic anhydride-modified polypropylene, and the sealant layer 16 is preferably made of a polypropylene film. This makes it easy to maintain the adhesive force between the sealant layer 16 and the metal foil layer 13 even when the electrolytic solution penetrates, and to easily form a battery configuration without excessively crushing the heat seal layer 16 with heat seal. .

(Production method)
Hereinafter, the manufacturing method of the exterior material 1 is demonstrated. However, the manufacturing method of the exterior material 1 is not limited to the method described below.
As a manufacturing method of the exterior material 1, the method which has the following process (I-1)-(IV-1) is mentioned, for example.
(I-1) A step of forming a corrosion prevention treatment layer 14 on the metal foil layer 13.
(II-1) A step of laminating the first biaxially stretched film 11A and the second biaxially stretched film 11B to form the base material layer 11 made of a laminated film.
(III-1) The process of bonding the base material layer 11 through the adhesive bond layer 12 on the opposite side to the side in which the corrosion prevention process layer 14 in the metal foil layer 13 was formed.
(IV-1) A step of bonding the sealant layer 16 to the corrosion prevention treatment layer 14 side of the metal foil layer 13 via the adhesive resin layer 15.

Step (I-1):
A corrosion prevention treatment agent is applied to one surface of the metal foil layer 13 and dried, cured, and baked to form the corrosion prevention treatment layer 14. Examples of the corrosion prevention treatment agent include a corrosion prevention treatment agent for coating type chromate treatment.
The method for applying the corrosion inhibitor is not particularly limited, and examples thereof include gravure coating, gravure reverse coating, roll coating, reverse roll coating, die coating, bar coating, kiss coating, and comma coating.
The metal foil layer 13 may be an untreated metal foil or a metal foil that has been degreased by a wet type or a dry type.

Step (II-1):
The first biaxially stretched film 11A and the second biaxially stretched film are bonded together using an adhesive for dry laminating to form a base material layer 11 made of a laminated film.
Examples of the method of laminating the biaxially stretched film include techniques such as dry lamination, non-solvent lamination, and wet lamination.
In step (II-1), an aging treatment may be performed in the range of room temperature to 100 ° C. in order to promote adhesion.

Step (III-1):
The base material layer 11 is bonded to the side of the metal foil layer 13 opposite to the side on which the corrosion prevention treatment layer 14 is formed, using an adhesive that forms the adhesive layer 12.
Examples of the bonding method include dry lamination, non-solvent lamination, wet lamination, and the like.
In step (III-1), an aging (curing) treatment may be performed in the range of room temperature to 100 ° C. to promote adhesion.

Step (IV-1):
On the side of the corrosion prevention treatment layer 14 of the laminate in which the base material layer 11, the adhesive layer 12, the metal foil layer 13, and the corrosion prevention treatment layer 14 are laminated in this order, a sealant is formed via an adhesive resin that forms the adhesive resin layer 15. Layer 16 is bonded together. Examples of the method for laminating the sealant layer 16 include a dry process and a wet process.
In the case of the dry process, an adhesive resin is extruded and laminated on the corrosion prevention treatment layer 14 of the laminate, and a film for forming a sealant layer 16 obtained by an inflation method or a cast method is laminated. Thereafter, heat treatment (aging treatment, thermal lamination, etc.) may be performed for the purpose of improving the adhesion between the corrosion prevention treatment layer 14 and the adhesive resin layer 15.
In addition, a multilayer film in which the adhesive resin layer 15 and the sealant layer 16 are laminated by an inflation method or a cast method, and the multilayer resin film is laminated on the laminate by thermal lamination, whereby the adhesive resin layer 15 is formed. Alternatively, the sealant layer 16 may be laminated.

  In the case of a wet process, a dispersion type adhesive resin solution of an adhesive resin such as an acid-modified polyolefin resin is applied on the corrosion prevention treatment layer 14 of the laminate, and the solvent is volatilized at a temperature equal to or higher than the melting point of the adhesive resin. After the adhesive resin is melted and softened and baked, the sealant layer 16 is laminated by a heat treatment such as thermal lamination.

The exterior material 1 is obtained by the steps (I-1) to (IV-1) described above.
In addition, the manufacturing method of the exterior material 1 is not limited to the method of implementing the said process (I-1)-(IV-1) sequentially. For example, step (I-1) may be performed after performing step (II-1).
Moreover, you may perform a process (II-1) and a process (III-1) simultaneously. Moreover, you may perform a process (III-1) after performing a process (IV-1). Further, the formation of the corrosion prevention treatment layer 14 may be performed in-line at the time of extrusion lamination for laminating the sealant layer 16. Moreover, you may provide a corrosion prevention process layer on both surfaces of a metal foil layer.

[Second Embodiment]
Next, a lithium ion battery exterior material 2 (hereinafter referred to as “exterior material 2”), which is another example of the lithium ion battery exterior material of the present invention, will be described. In the exterior material 2, the same parts as those of the exterior material 1 are denoted by the same reference numerals and description thereof is omitted.
As shown in FIG. 2, the packaging material 2 of the present embodiment has an adhesive layer 12, a molding improvement layer 17, a metal foil layer 13, a corrosion prevention treatment layer 14, and an adhesive resin layer on one surface of the base material layer 11. 15 is a laminate in which the sealant layer 16 is sequentially laminated.

(Molding improvement layer 17)
The molding improvement layer 17 is a layer that improves the adhesion between the base material layer 11 and the metal foil layer 13 and improves the moldability of the exterior material 2. Examples of the molding improvement layer 17 include a layer containing at least one of the following resin (A) and coupling agent (B).
Resin (A): Polyolefin resin, polyether resin, polyester resin, polyurethane resin, polyvinyl resin, polystyrene resin, polyacrylic resin, polyamide resin, phenolic resin, melamine resin, epoxy resin One or more resins selected from the group consisting of unsaturated polyester resins, silicone resins, polysulfone resins, polycarbonate resins, polyallyl resins, and ionomer resins.
Coupling agent (B): One or more coupling agents selected from the group consisting of silane coupling agents, titanate coupling agents, aluminate coupling agents, and zirconate coupling agents.
The resin (A) may be a modified product thereof. Further, the molding improving layer 17 may be a layer containing either one of the resin (A) and the coupling agent (B), or a layer containing both the resin (A) and the coupling agent (B). It may be.

Examples of the polyolefin resin used for the molding improvement layer 17 include polyethylene, polypropylene, polybutene, α-polyolefin, and polymethylpentene.
Examples of polyether resins include polyether ketone and polyether ether ketone.
Examples of the polyester resin include polyethylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate, polybutylene terephthalate, and polybutylene naphthalate.
Examples of the polyurethane resin include poly-n-butyl isocyanate, poly-n-hexyl isocyanate, and 2-6-polyurethane.
Examples of the polyvinyl resin include ethylene / vinyl acetate copolymer, polyvinyl chloride, styrene vinyl, and vinyl acetate.
Examples of polystyrene resins include styrene / acrylonitrile copolymers, acrylonitrile / butadiene / styrene resins, and impact-resistant polystyrene.
Examples of the polyacrylic resin include polymethyl methacrylate, ethylene / methyl methacrylate copolymer, and polycarboxylic acid.
Examples of the phenolic resin include random novolak type, high ortho novolak type, alkali resol type, ammonia resol type, benzyl ether resol type resin and the like.
Examples of the polyamide resin include nylon 6, nylon 11, nylon 12, nylon 66, nylon 610, nylon 612, and the like.
Examples of melamine resins include guanamine and aniline.
Examples of the epoxy resin include resins of glycidyl ester type, glycidyl amine type, and cycloaliphatic type.
Examples of the unsaturated polyester resin include orthophthalic acid, isophthalic acid, terephthalic acid, dicyclo, fatty saturated acid, and bisphenol resins.
Examples of the silicone resin include polydimethylsiloxane, polydiethylsiloxane, and polymethylphenylsiloxane.
Examples of the polysulfone-based resin include polyether sulfone, polysulfone, polyallyl sulfone, and allyl polyphenyl sulfone.
Polycarbonate resins include polytetramethylene carbonate, polypentamethylene carbonate, polyhexamethylene carbonate, and the like.
Examples of polyallyl resins include polyallylamine, polyallylamide, polyallyl ether, polyallyl ether ketone, and the like.
Examples of the ionomer resin include those obtained by polymerizing an ethylene-based, styrene-based or elastomer-based resin or an ethylene carboxylic acid copolymer with an ion source such as Na, K, Li, or Zn.

Examples of the silane coupling agent used for the molding improvement layer 17 include trimethoxysilane, tetramethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, glycidoxypropyltrimethoxysilane, and the like.
Examples of titanate coupling agents include trimethoxy titanate, tetramethoxy titanate, tetrapropoxy titanate, chlorotrimethoxy titanate, methyl triethoxy titanate, diethyl diethoxy titanate, and phenyl trimethoxy titanate.
Examples of the aluminate coupling agent include trimethoxy aluminate, triethoxy aluminate, tripropoxy aluminate, and tetraethoxy aluminate.
Examples of the zirconate coupling agent include trimethoxy zirconate, tetramethoxy zirconate, tetrapropoxy zirconate, chlorotriethoxy zirconate, ethyl trimethoxy zirconate, and phenyl trimethoxy zirconate.

Since the molding material 17 is provided between the base material layer 11 and the metal foil layer 13, the exterior material 2 increases the adhesion strength between the base material layer 11 and the metal foil layer 13. Even when tensile and compressive stress is applied to the exterior material 2, sufficient adhesion between the base material layer 11 and the metal foil layer 13 can be secured. Thereby, the outstanding moldability is obtained. That is, by suppressing the peeling between the base material layer 11 and the metal foil layer 13, it is possible to suppress the metal foil layer 13 from being broken or a pinhole being generated from that portion.
The molding improvement layer 17 also functions as a buffer layer between the base material layer 11 and the metal foil layer 13. That is, the molding improving layer 17 can relieve stress applied during molding and suppress the metal foil layer 13 from being broken during molding, so that excellent moldability is obtained. In particular, when the molding improvement layer 17 is formed of the resin (A), the effect as a buffer layer at the time of molding is more satisfactorily exhibited.

The thickness of the molding improvement layer 17 is preferably 20 nm to 50 μm.
In the case of the coupling agent (B) and a relatively hard resin (polyvinyl resin, polystyrene resin, epoxy resin, etc.), it is the base material layer 11 formed by the molding improvement layer 17 that affects the improvement of the moldability. This is considered to be an improvement in adhesion between the metal foil layer 13 and the metal foil layer 13. In this case, the thickness of the molding improvement layer 17 is more preferably 20 nm to 500 nm, and more preferably 20 nm to 100 nm. If the thickness of the molding improvement layer 17 is 20 nm or more, it is easy to suppress the occurrence of film peeling, unevenness, etc., and the effects of the molding improvement layer 17 can be sufficiently exhibited. If the thickness of the molding improvement layer 17 is 500 nm or less, it is easy to suppress the molding improvement layer 17 from becoming too hard, and excellent moldability is easily obtained.
In the case where an elastic component (polyurethane resin, silicone resin, etc.) is used for the molding improvement layer 17 and a function to relieve stress is imparted, the thickness of the molding improvement layer 17 is more preferably 500 nm to 50 μm. If the thickness of the molding improvement layer 17 is 500 nm or more, the effect of the molding improvement layer 17 can be sufficiently exhibited. Further, even if the thickness of the molding improvement layer 12 exceeds 50 μm, the effect of relaxing the stress does not change so much, which is disadvantageous in terms of cost.
The exterior material 2 is preferable to the exterior material 1 in that the moldability is improved by the molding improvement layer 17.

(Production method)
Hereinafter, the manufacturing method of the exterior material 2 is demonstrated. However, the manufacturing method of the exterior material 2 is not limited to the following method.
As a manufacturing method of the exterior material 2, the method which has the following process (I-2)-(IV-2) is mentioned, for example.
(I-2) A step of forming the corrosion prevention treatment layer 14 on the metal foil layer 13.
(II-2) A step of laminating the first biaxially stretched film 11A and the second biaxially stretched film 11B to form the base material layer 11 made of a laminated film.
(III-2) The process of forming the shaping | molding improvement layer 17 on the opposite side to the side in which the corrosion prevention process layer 14 was formed in the metal foil layer 13, and bonding the base material layer 11 through the adhesive bond layer 12. FIG.
(IV-2) A step of bonding the sealant layer 16 to the corrosion prevention treatment layer 14 side of the metal foil layer 13 via the adhesive resin layer 15.

Step (I-2):
The step (I-2) can be performed in the same manner as the step (I-1) in the method for manufacturing the exterior material 1.

Step (II-2):
The step (II-2) can be performed in the same manner as the step (II-1) in the method for manufacturing the exterior material 1.

Step (III-2):
For example, the resin (A) and the coupling agent (B) are appropriately diluted with a solvent such as water or a solvent, and the diluted solution is subjected to corrosion prevention treatment in the metal foil layer 13 by a known method such as coating, dipping or spraying. The molding improving layer 17 is formed by applying to the opposite side of the layer 14 and drying appropriately.
As a coating method, the well-known coating method quoted at the said process (I-1) is employable.
When the resin (A) is used, the molding improving layer 17 may be formed by a method such as extrusion by melting at a temperature higher than the melting point of the resin (A).

  Further, using the adhesive forming the adhesive layer 12, molding of a laminate comprising the molding improving layer 17 / metal foil layer 13 / corrosion prevention treatment layer 14 by means of dry lamination, non-solvent lamination, wet lamination, or the like. The base material layer 11 is bonded onto the improvement layer 17 via the adhesive layer 12. Thereafter, an aging treatment (curing) may be performed in the range of room temperature to 100 ° C. to promote adhesion.

Step (IV-2):
The step (IV-2) can be performed in the same manner as the step (IV-1) in the method for manufacturing the exterior material 1.

The exterior material 2 is obtained by the steps (I-2) to (IV-2) described above.
In addition, the manufacturing method of the exterior material 2 is not limited to the method of implementing the said process (I-2)-(IV-2) sequentially. For example, the step (I-2) may be performed after performing the step (II-2).
Moreover, you may perform a process (II-2) and a process (III-2) simultaneously. Moreover, after performing a process (IV-2), you may perform a process (III-2). Further, the formation of the corrosion prevention treatment layer 14 may be performed in-line at the time of extrusion lamination for laminating the sealant layer 16. Moreover, you may provide a corrosion prevention process layer on both surfaces of a metal foil layer.

  Since the biaxially stretched film adjacent to the laminated film forming the base material layer is laminated so as to satisfy the above condition (1), the exterior material for a lithium ion battery of the present invention described above is biaxially stretched. Excellent moldability is obtained by reducing the anisotropy of the film and reducing the anisotropy of the base material layer.

In addition, the exterior material for lithium ion batteries of the present invention is not limited to the exterior materials 1 and 2.
For example, the laminated film forming the base material layer is not limited to a laminated film in which two biaxially stretched films are laminated, and may be a laminated film in which three or more biaxially stretched films are laminated. . In this case, the adjacent biaxially stretched films should just be laminated | stacked so that the said conditions (1) may be satisfy | filled, respectively.

In the exterior materials 1 and 2, the corrosion prevention treatment layer 14 is provided on the surface of the metal foil layer 13 on the side of the adhesive resin layer 15, that is, on the side that may come into contact with hydrofluoric acid generated by the reaction between the electrolytic solution and moisture. However, if necessary, a corrosion prevention treatment layer may also be provided on the surface of the metal foil layer 13 on the base material layer 11 side.
Further, the exterior material 2 has a form in which the molding improvement layer 17 and the adhesive layer 12 are separately provided, but the molding improvement layer 17 may also serve as the adhesive layer without providing the adhesive layer 12. . For example, by using a mixture containing at least one of the resin (A) and the coupling agent (B) forming the molding improvement layer 17 and an adhesive for dry lamination, a molding improvement layer that also serves as the adhesive layer is formed. May be. Moreover, you may use the resin which can be heat-seal | fused among resin (A), and may form the shaping | molding improvement layer which serves as an adhesive bond layer.
In the exterior material 2, the lamination structure of the molding improvement layer 17 and the adhesive layer 12 is in the order of the molding improvement layer 17 / adhesive layer 12 from the base material layer 11 side, but the adhesive layer 12 / molding improvement layer. The stacking order of 17 may be used, or the stacking order of the molding improving layer 17 / adhesive layer 12 / molding improving layer 17 may be used.

A lithium ion battery using the outer packaging material for a lithium ion battery of the present invention can be produced by a known method except that the outer packaging material for a lithium ion battery of the present invention is used. For example, it is obtained as follows. A concave portion is formed by cold molding in a part of the outer packaging material for a lithium ion battery of the present invention, and a positive electrode material, a separator, and a negative electrode material are placed inside the concave portion, and another sheet for the lithium ion battery of the present invention. The exterior materials are stacked so that the sealant layers face each other, and the three sides are heat sealed. Thereafter, in a vacuum state, an electrolyte is injected from the remaining one side, and the remaining one side is heat-sealed and sealed to obtain a lithium ion battery.
In addition, the lithium ion battery using the exterior material for lithium ion batteries of this invention is not limited to what was manufactured by the said method.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by the following description.
[Measurement of tensile strength]
The tensile strength of the film in this example was measured according to JIS K7127, using a type 5 punching die, and measured under a tensile strength of 300 mm / min.

[Materials used]
The materials used in this example are shown below.
(Base material layer 11)
Film A-1: Biaxially stretched polyamide film (thickness 25 μm).
Film A-2: Biaxially stretched PET film (thickness 12 μm).
Table 1 shows the results of measuring the tensile strength of the film A-1 and the film A-2 until they break in four directions of 0 degree, 45 degrees, 90 degrees, and 135 degrees with respect to the stretching direction.

(Adhesive layer 12)
Adhesive B-1: polyurethane adhesive.

(Metal foil layer 13)
Metal foil C-1: An annealed soft aluminum foil 8079 material (thickness 40 μm).

(Corrosion prevention treatment layer 14)
Treatment agent D-1: Treatment agent for coating chromate treatment mainly composed of trivalent chromium, phosphoric acid, and acrylic resin.

(Adhesive resin layer 15)
Adhesive resin E-1: Maleic anhydride-modified polypropylene resin.

(Sealant layer 16)
Film F-1: Polypropylene film (thickness 40 μm).

[Example 1]
The treatment agent D-1 was applied to one surface of the metal foil C-1 by microgravure coating, and baked at 150 to 250 ° C. in a drying unit to form the corrosion prevention treatment layer 14. The coating amount of the processing agent D-1 was 15 mg / m ^{2 in} terms of chromium.
Next, the film A-1 and the film A-2 were laminated using an adhesive B-1 by a dry laminating method so as to satisfy the condition (1) shown in Table 2 to obtain a laminated film. Then, the adhesive layer 12 (thickness 4 μm) is formed by laminating the laminated film on the surface of the metal foil layer 13 opposite to the corrosion prevention treatment layer 14 using the adhesive B-1 by the dry laminating method. Then, the base material layer 11 was laminated. Next, the obtained laminate is placed in the unwinding part of the extrusion laminating machine, the film F-1 is placed in the sand base part, and the adhesive resin E-1 is extruded at an extrusion temperature of 250 ° C. to a thickness of 20 μm. The sealant layer 16 was laminated | stacked through the adhesive resin layer 15 on the corrosion prevention process layer 14 of the said laminated body by sand lamination. Thereafter, thermocompression bonding (heat treatment) was performed to obtain an exterior material having a laminated structure illustrated in FIG.

[Comparative Example 1]
An exterior material was obtained in the same manner as in Example 1 except that the lamination of the film A-1 and the film A-2 was performed so as to satisfy the condition (2) shown in Table 2.

[Evaluation method]
The following evaluation was performed with respect to the obtained exterior material.
(Formability evaluation)
The obtained exterior material was subjected to cold molding at a drawing depth of 6 mm using a molding apparatus capable of cold molding with a drawn portion of 80 mm × 100 mm. Then, the fracture | rupture and pinhole of the part which performed cold forming were confirmed. The moldability was evaluated according to the following criteria.
○: There was no breakage or pinhole.
X: Breakage or pinhole occurred.
The evaluation results of each example are shown in Table 2.

As shown in Table 2, a laminated film in which the 45-degree direction of the film A-1 and the 45-degree direction of the film A-2 are aligned and laminated, that is, the direction in which the tensile strength is large among the 45-degree direction and the 135-degree direction in each film. The film of Example 1 using the laminated film laminated so that the small directions were aligned had excellent moldability. On the other hand, a laminated film in which the 45-degree direction of the film A-1 and the 135-degree direction of the film A-2 are aligned and laminated, that is, the direction in which the tensile strength is large among the 45-degree direction and the 135-degree direction in each film is aligned. The film of Comparative Example 1 using the laminated film laminated was inferior in moldability as compared with Example 1.
The above result is considered to be because the anisotropy in the laminated film forming the base material layer 11 in Example 1 was relaxed and reduced as compared with the laminated film forming the base material layer 11 in Comparative Example 1. It is done.

DESCRIPTION OF SYMBOLS 1, 2 Lithium ion battery exterior material 11 Base material layer 11A 1st biaxially stretched film 11B 2nd biaxially stretched film 12 Adhesive layer 13 Metal foil layer 14 Corrosion prevention treatment layer 15 Adhesive resin layer 16 Sealant layer 17 Molding improvement layer

Claims (9)

In the exterior material for a lithium ion battery in which at least a metal foil layer, a corrosion prevention treatment layer, an adhesive resin layer, and a sealant layer are sequentially laminated on one surface of the base material layer,
The base material layer comprises a laminated film in which a plurality of biaxially stretched films are laminated,
The biaxially stretched films adjacent to each other in the laminated film are laminated via an adhesive for dry lamination,
Adhesives for the dry lamination is a polyester polyol, a main agent selected from polyether polyols and acrylic polyols, Ri polyurethane adhesive der of two-component curable exerting aromatic or aliphatic isocyanate as a curing agent ,
The biaxially stretched film is biaxially stretched in the 0 degree direction and the 90 degree direction,
An exterior material for a lithium ion battery, wherein the adjacent biaxially stretched films in the laminated film satisfy the following condition (1) .
(1) Tensile strength out of the 45 degree direction and 135 degree direction with respect to the stretching direction of one biaxially stretched film, the direction having the largest tensile strength, and the 45 degree direction and 135 degree direction with respect to the stretching direction of the other biaxially stretched film Are stacked so that the direction in which they are small is aligned.   The exterior material for a lithium ion battery according to claim 1, wherein the base material layer is a laminated film in which a biaxially stretched polyester film and a biaxially stretched polyamide film are laminated.   The exterior material for a lithium ion battery according to claim 1 or 2, wherein the outermost layer of the base material layer is a biaxially stretched polyester film.   The thickness of the said base material layer is 6-40 micrometers, The exterior material for lithium ion batteries as described in any one of Claims 1-3.   The external packaging material for lithium ion batteries as described in any one of Claims 1-4 in which the shaping | molding improvement layer which improves a moldability is provided between the said metal foil layer and a base material layer.   The said metal foil layer is a layer which consists of a soft aluminum foil which gave the annealing process, The exterior material for lithium ion batteries as described in any one of Claims 1-5.   The lithium ion battery exterior material according to any one of claims 1 to 6, wherein the corrosion prevention treatment layer is a layer formed by a method using a sol of a rare earth element-based oxide having an average particle size of 100 nm or less.   The exterior material for a lithium ion battery according to any one of claims 1 to 6, wherein the corrosion prevention treatment layer is a layer formed by a coating type chromate treatment.   The exterior material for a lithium ion battery according to any one of claims 1 to 8, wherein the adhesive resin layer contains maleic anhydride-modified polypropylene, and the sealant layer is made of a polypropylene film.

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