CN112117395A - Packaging material for lithium ion battery - Google Patents

Packaging material for lithium ion battery Download PDF

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Publication number
CN112117395A
CN112117395A CN202010975943.1A CN202010975943A CN112117395A CN 112117395 A CN112117395 A CN 112117395A CN 202010975943 A CN202010975943 A CN 202010975943A CN 112117395 A CN112117395 A CN 112117395A
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China
Prior art keywords
layer
base material
lithium ion
adhesive
sealing
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CN202010975943.1A
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Chinese (zh)
Inventor
谷口智昭
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Toppan Inc
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Toppan Printing Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
    • H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
    • H01M50/124—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
    • H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
    • H01M50/121—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
    • H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
    • H01M50/117—Inorganic material
    • H01M50/119—Metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
    • H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
    • H01M50/124—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure
    • H01M50/126—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure comprising three or more layers
    • H01M50/129—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure comprising three or more layers with two or more layers of only organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
    • H01M50/131—Primary casings, jackets or wrappings of a single cell or a single battery characterised by physical properties, e.g. gas-permeability or size
    • H01M50/133—Thickness
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/543—Terminals
    • H01M50/545—Terminals formed by the casing of the cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The lithium ion battery packaging material (1) of the present invention comprises: a base material layer (11) having a 1 st base material layer (11a) formed of a polyester resin or a polyamide resin, and a 2 nd base material layer (11b) containing a polyester elastomer and formed on the 1 st base material layer (11 a); a 1 st adhesive layer (12) laminated on the 1 st base material layer (11 a); a metal foil layer (13) laminated on the 1 st adhesive layer (12); an anticorrosion treated layer (14) laminated on the metal foil layer (13); a 2 nd adhesion layer (15) formed on the corrosion prevention treated layer (14); and a sealing layer (16) formed on the 2 nd adhesive layer (15).

Description

Packaging material for lithium ion battery
The present application is a divisional application of the application having an application number of 201480061523.5, an application date of 2014, 11/11, and an invention name of "encapsulant for lithium ion battery".
Technical Field
The present invention relates to a sealing material for lithium ion batteries.
The present application claims priority based on Japanese application No. 2013-234082 filed 11/12/2013, the contents of which are incorporated herein by reference.
Background
Conventionally, nickel-metal hydride batteries and lead storage batteries are known as secondary batteries. On the other hand, lithium ion batteries having high energy density have been attracting attention because secondary batteries must be miniaturized due to miniaturization of portable devices, restriction of installation space, and the like. As a sealing material for a lithium ion battery (hereinafter, sometimes simply referred to as "sealing material"), a metal can is used, but a multilayer film which is lightweight, has high heat dissipation properties, and can be produced at low cost is often used.
The electrolyte of the lithium ion battery is composed of an aprotic solvent such as propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, or the like, and an electrolyte. As the electrolyte, LiPF can be used6、LiBF4And the like lithium salts. However, these lithium salts generate hydrofluoric acid due to hydrolysis reaction by water. Hydrofluoric acid may cause corrosion of the metal surface of the battery member and a decrease in the lamination strength between layers of the sealing material formed of a multilayer film.
Therefore, in the sealing material formed of the multilayer film, the aluminum foil layer is provided inside to suppress the entry of moisture from the surface of the multilayer film. For example, the following encapsulating materials are known: a base material layer/1 st adhesive layer/aluminum foil layer/corrosion prevention treated layer/2 nd adhesive layer/sealant layer having heat resistance and preventing corrosion by hydrofluoric acid are laminated in this order. A lithium ion battery using such a packaging material is also referred to as an aluminum laminate type lithium ion battery.
As one of the aluminum laminate type lithium ion batteries, the following structure is known: a concave portion is formed in a part of the sealing material by cold molding, and the battery contents such as a positive electrode, a separator, a negative electrode, and an electrolyte are accommodated in the concave portion, and the remaining part of the sealing material is folded back, and the edge portion is sealed by heat sealing. Such cells are also known as embossed lithium ion cells. In recent years, in order to improve energy density, the following embossed lithium ion batteries have been manufactured: recesses are formed on both sides of the sealing material that is attached together so that more of the battery contents can be accommodated.
The energy density of the lithium ion battery becomes higher as the recess formed by cold forming becomes deeper. However, as the formed recess is deeper, a pin hole or a crack is likely to be generated when the sealing material is molded. Therefore, a biaxially stretched polyamide film is used as a base layer of the sealing material to protect the metal foil.
As a conventional technique for improving moldability of an encapsulating material, it has been proposed to use, as a base layer, a film having a tensile strength of 150MPa until breaking in a tensile test in 4 directions of 0 °, 45 °, 90 ° and 135 ° with respect to the tensile direction and an elongation of 80% or more in the 4 directions (for example, see patent document 1).
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 3567230
Disclosure of Invention
Problems to be solved by the invention
However, in the technique of patent document 1, no consideration is given to warpage after molding. Therefore, there are the following problems: when the molding process is performed while the sealing material is stretched, the stretched base material layer tends to return to its original state, and therefore the warpage that occurs cannot be improved.
In view of the above problems, an object of the present invention is to provide a sealing material for a lithium ion battery, which can reduce the amount of warpage after molding while maintaining excellent moldability.
Means for solving the problems
An encapsulating material for a lithium ion battery according to an embodiment of the present invention includes: a base material layer having a 1 st base material layer formed of a polyester resin or a polyamide resin, and a 2 nd base material layer containing a polyester elastomer and formed on the 1 st base material layer; a 1 st adhesive layer laminated on the 1 st base material layer; a metal foil layer laminated on the 1 st adhesive layer; an anticorrosion treated layer laminated on the metal foil layer; a 2 nd adhesion layer formed on the corrosion prevention treated layer; and a sealing layer formed on the 2 nd adhesive layer.
In the above aspect, the thickness of the 1 st base material layer may be 4 μm to 20 μm, the thickness of the 2 nd base material layer may be 2 μm to 15 μm, and the thickness of the base material layer may be 6 μm to 25 μm.
In the above aspect, the base material layer may be formed by a co-extrusion method.
Effects of the invention
According to the aspect of the present invention, the lithium ion battery sealing material can reduce the amount of warpage after molding while maintaining excellent moldability.
Drawings
FIG. 1 is a sectional view showing a lithium ion battery sealing material according to an embodiment of the present invention.
FIG. 2 is a plan view of a lithium ion battery sealing material according to an embodiment of the present invention.
FIG. 3 is a cross-sectional view taken along line I-I of FIG. 2.
Detailed Description
One embodiment of the present invention is explained with reference to fig. 1 to 3. Fig. 1 is a sectional view showing a lithium ion battery sealing material (hereinafter, simply referred to as "sealing material") 1 according to the present embodiment.
As shown in fig. 1, the sealing material 1 is a laminate in which a 1 st adhesive layer 12, a metal foil layer 13, an anticorrosion treatment layer 14, a 2 nd adhesive layer 15, and a sealant layer 16, which are also sheet-like, are laminated in this order on one surface (1 st surface) of a sheet-like base material layer 11. When the lithium ion battery is formed using the sealing material 1, the base layer 11 is the outermost layer, and the sealing layer 16 is the innermost layer. The base material layer 11 is a multilayer film, the outer side of the battery is a 2 nd base material layer 11b, and the layer in contact with the 1 st adhesive layer 12 is a 1 st base material layer 11 a.
[ base Material layer 11]
The base material layer 11 functions to: the heat resistance is provided in a sealing step in the production of a lithium ion battery, and the generation of pinholes which may occur during processing or flow-through is suppressed.
The base material layer 11 has a multilayer structure including a 1 st base material layer 11a and a 2 nd base material layer 11 b. The 1 st base material layer 11a in contact with the 1 st adhesive layer 12 is made of a polyester resin or a polyamide resin. The 2 nd substrate layer 11b laminated on the surface (2 nd surface) 19 opposite to the surface (1 st surface) 18 of the 1 st substrate layer 11a in contact with the 1 st adhesive layer 12 side contains a polyester elastomer.
For the purpose of forming a thin and sharp shape, a film of polyamide (nylon) or polyester having high strength, high elongation, and softness is preferably used for the 1 st base material layer 11 a. Further, from the viewpoint of excellent puncture strength and impact strength, a biaxially stretched nylon (ONy) film or a biaxially stretched polyethylene terephthalate (PET) film is more preferable. Among them, a biaxially stretched PET film whose physical properties are less likely to change due to the moisture absorption state and whose moldability is stable is more preferable.
The 2 nd base material layer 11b is a layer for alleviating the shrinkage rate of the base material layer 11 stretched by molding, and has a structure containing a polyester elastomer so as to reduce the elastic limit (yield point). This structure also has an advantage that the physical properties can be easily adjusted by the amount of the polyester elastomer added.
The polyester elastomer contained in the 2 nd base material layer 11b has a hard segment and a soft segment. Examples of the hard segment include crystalline polyesters such as polybutylene terephthalate, polybutylene naphthalate and polyethylene terephthalate, and polybutylene terephthalate is particularly preferable. Examples of the soft segment include polyoxyalkylene glycols such as polytetramethylene glycol, polyesters such as polycaprolactone and polybutylene adipate, and polytetramethylene glycol is particularly preferable.
The thickness of the first substrate layer 11a of 1 is preferably 4 to 20 μm, more preferably 6 to 15 μm.
The thickness of the 2 nd base material layer 11b is preferably 2 to 15 μm, and more preferably 3 to 10 μm.
The thickness of the base layer 11 is preferably 6 to 25 μm, and more preferably 10 to 20 μm.
The 1 st base material layer 11a has a thickness of 4 μm or more and the 2 nd base material layer 11b has a thickness of 15 μm or less, and thus has excellent moldability. If the thickness of the 1 st base material layer 11a is 20 μm or less and the thickness of the 2 nd base material layer 11b is 2 μm or more, the shrinkage rate of the base material layer 11 at the portion stretched by the molding process is not so large, and the shape after the molding process can be appropriately maintained.
The substrate layer 11 is preferably formed by a coextrusion method in which a plurality of layers can be formed at a time and each layer can be made thin.
[ 1 st adhesive layer 12]
The 1 st adhesive layer 12 is a layer that adheres the base material layer 11 and the metal foil layer 13.
The adhesive material constituting the 1 st adhesive layer 12 is preferably a two-pack curable polyurethane adhesive obtained by reacting a difunctional or higher aromatic or aliphatic isocyanate compound as a curing agent with a base material such as polyester polyol, polyether polyol or acryl polyol. After the application, the urethane adhesive is cured at 40 ℃ for four days or more, for example, whereby the reaction between the hydroxyl group of the main agent and the isocyanate group of the curing agent proceeds, whereby a strong bond can be formed.
The thickness of the 1 st adhesive layer 12 is preferably 1 to 10 μm, more preferably 3 to 7 μm, from the viewpoint of adhesive strength, conformability, processability, 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 in view of processability such as moisture resistance and ductility and cost. As the aluminum foil, a general soft aluminum foil can be used. Among them, aluminum foil containing iron is preferable in terms of excellent pinhole resistance and ductility during molding.
The iron content in the iron-containing aluminum foil (100 mass%) is preferably 0.1 to 9.0 mass%, more preferably 0.5 to 2.0 mass%. When the content of iron is 0.1 mass% or more, the potting material 1 is excellent in pinhole resistance and ductility. When the content of iron is 9.0 mass% or less, the flexibility of the sealing material 1 is excellent.
The thickness of the metal foil layer 13 is preferably 9 to 200 μm, and more preferably 15 to 100 μm in view of barrier performance, pinhole resistance, and processability.
[ Corrosion prevention treated layer 14]
The corrosion prevention treated layer 14 functions to suppress corrosion of the metal foil layer 13 caused by the electrolyte solution or hydrofluoric acid generated by a reaction between the electrolyte solution and moisture. In addition, it acts to improve the adhesion between the metal foil layer 13 and the 2 nd adhesive layer 15.
The corrosion-prevention treated layer 14 is preferably a coating film formed of a coating-type or immersion-type acid-resistant corrosion-prevention treating agent. Such a coating film makes the metal foil layer 13 excellent in the corrosion prevention effect against acid. In addition, such a coating film can obtain excellent resistance to contents such as an electrolyte because the adhesion force between the metal foil layer 13 and the 2 nd adhesive layer 15 is stronger due to the anchor effect.
Examples of the coating film constituting the corrosion-prevention treated layer 14 include: a coating film formed by ceria sol treatment with an anti-corrosion treatment agent containing cerium oxide, phosphate and various thermosetting resins, a coating film formed by chromate treatment with an anti-corrosion treatment agent containing chromate, phosphate, fluoride and various thermosetting resins, and the like.
The corrosion-resistant treatment layer 14 is not limited to the above coating film as long as it can provide a coating film that can sufficiently provide the corrosion resistance of the metal foil layer 13. For example, a coating film formed by phosphate treatment, boehmite treatment, or the like may be used.
The corrosion prevention treated layer 14 may be a single layer or a plurality of layers. Further, an additive such as a silane coupling agent may be added to the anticorrosion treated layer 14.
The thickness of the corrosion prevention treated layer 14 is preferably 10nm to 5 μm, and more preferably 20nm to 500nm, from the viewpoint of the corrosion prevention function and the anchoring function.
The corrosion prevention treated layer 14 may be provided between the 1 st adhesive layer 12 and the metal foil layer 13 according to a desired function.
[ 2 nd adhesive layer 15]
The 2 nd adhesive layer 15 is a layer in which the metal foil layer 13 having the corrosion prevention treated layer 14 formed thereon and the sealant layer 16 are bonded to each other. The sealing material 1 is roughly classified into a hot lamination structure and a dry lamination structure according to the adhesive composition forming the 2 nd adhesive layer 15.
As the bonding component for forming the 2 nd bonding layer 15 in the heat laminated structure, an acid-modified polyolefin resin obtained by graft-modifying a polyolefin resin with an acid such as maleic anhydride is preferable. The acid-modified polyolefin resin has a polar group introduced into a part of the nonpolar polyolefin resin. Therefore, the acid-modified polyolefin resin can strongly adhere to both the nonpolar sealing layer 16 and the polar corrosion prevention treated layer 14 formed of a polyolefin resin film or the like. Further, by using the acid-modified polyolefin resin, the resistance to the contents such as an electrolytic solution is improved, and even if hydrofluoric acid is generated inside the battery, the decrease in the adhesion force due to the deterioration of the 2 nd adhesive layer 15 is easily prevented.
The acid-modified polyolefin-based resin used in the 2 nd adhesive layer 15 may be one kind, or two or more kinds.
Examples of the polyolefin resin used for the acid-modified polyolefin resin include low-density, medium-density, and high-density polyethylene; ethylene-alpha olefin copolymers; homo-polypropylene, block polypropylene or random polypropylene; propylene-alpha olefin copolymers, and the like. Further, a copolymer obtained by copolymerizing a polar molecule such as acrylic acid or methacrylic acid with the above-mentioned compound, a polymer such as a crosslinked polyolefin, or the like can also be used.
Examples of the acid for modifying the polyolefin resin include carboxylic acids, epoxy compounds, and acid anhydrides, and maleic anhydride is preferable.
As the adhesive component of the 2 nd adhesive layer 15 in the heat laminated structure, a maleic anhydride-modified polyolefin resin in which a polyolefin resin is graft-modified with maleic anhydride is preferable, and maleic anhydride-modified polypropylene is particularly preferable, from the viewpoint that the adhesive force between the sealant layer 16 and the metal foil layer 13 is easily maintained even when the electrolyte penetrates.
The modification rate by maleic anhydride (mass of a portion derived from maleic anhydride based on the total mass of the maleic anhydride-modified polypropylene) in the maleic anhydride-modified polypropylene is preferably 0.1 to 20 mass%, more preferably 0.3 to 5 mass%.
Preferably, the 2 nd adhesive layer 15 in the heat laminated structure contains a styrene-based elastomer or an olefin-based elastomer. This can be expected to easily suppress occurrence of cracks and whitening in the 2 nd adhesive layer 15 during cold forming, improve adhesion force by improving wettability, and improve film formation property by reducing anisotropy. These elastomers are preferably dispersed and compatible in the acid-modified polyolefin resin on a nano-scale.
The 2 nd adhesive layer 15 in the heat laminated structure may be formed by extruding the above adhesive composition by an extrusion device. The Melt Flow Rate (MFR) of the adhesive component is 4-30 g/10 min at 230 ℃ and 2.16 kgf.
The thickness of the No. 2 adhesive layer 15 in the heat laminated structure is preferably 2 to 50 μm.
The adhesive component of the 2 nd adhesive layer 15 in the dry lamination structure includes, for example, a two-pack type curable polyurethane adhesive similar to the component of the 1 st adhesive layer 12.
The 2 nd adhesive layer 15 in the dry lamination structure has a bonding portion having high hydrolyzability such as an ester group or a urethane group. Therefore, in applications requiring higher reliability, the 2 nd adhesive layer 15 of the heat laminated structure is preferable.
[ sealing layer ]
The sealing layer 16 is a layer to which sealability is imparted by heat sealing in the sealing material 1. The sealing layer 16 may be a resin film made of a polyolefin resin or an acid-modified polyolefin resin obtained by graft-modifying a polyolefin resin with an acid such as maleic anhydride.
Examples of the polyolefin resin include low-density, medium-density, and high-density polyethylene; ethylene-alpha olefin copolymers; homo-polypropylene, block polypropylene or random polypropylene; propylene-alpha olefin copolymers, and the like. These polyolefin resins may be used alone or in combination of two or more.
Examples of the acid-modified polyolefin resin include the same resins as those of the 2 nd adhesive layer 15.
The sealing layer 16 may be a single layer film or a multilayer film, as long as it is selected according to the required function. For example, a multilayer film in which a resin such as an ethylene-cyclic olefin copolymer or polymethylpentene is incorporated can be used for imparting moisture resistance.
In addition, various additives such as a flame retardant, a slip agent, an antiblocking agent, an antioxidant, a light stabilizer, and a tackifier may be blended in the sealing layer 16.
The thickness of the sealing layer 16 is preferably 10 to 100 μm, and more preferably 20 to 60 μm.
The sealing material 1 may be a structure in which the sealing layer 16 is laminated by dry lamination. However, from the viewpoint of improving the adhesiveness, it is preferable that the 2 nd adhesive layer 15 is made of an acid-modified polyolefin resin, and the sealing layer 16 is laminated by sandwich lamination.
[ production method ]
The following describes a method for manufacturing the sealing material 1. However, the following is an example, and the method for manufacturing the sealing material 1 is not limited to the following.
Examples of the method for producing the sealing material 1 include a method including the following steps (1) to (3).
Step (1): and a step of forming an anti-corrosion treatment layer 14 on the metal foil layer 13.
Step (2): and a step of bonding the base material layer 11 to the surface of the metal foil layer 13 opposite to the surface thereof on which the corrosion prevention treated layer 14 is formed, with the 1 st adhesive layer 12 interposed therebetween.
Step (3): and a step of bonding a sealing layer 16 to the corrosion prevention treated layer 14 formed on the metal foil layer 13 via a 2 nd adhesive layer 15.
(step (1))
The corrosion-preventing treatment agent is applied to one surface (1 st surface) of the metal foil layer 13, and dried to form the corrosion-preventing treatment layer 14. Examples of the anticorrosive treatment agent include the above-mentioned anticorrosive treatment agent for ceria sol treatment, anticorrosive treatment agent for chromate treatment, and the like.
The method of applying the corrosion-preventing treatment agent is not particularly limited, and various methods such as gravure coating, reverse coating, roll coating, and bar coating can be employed.
(step (2))
The base material layer 11 is bonded to the surface (2 nd surface) of the metal foil layer 13 opposite to the surface on which the corrosion prevention treated layer 14 is formed, by a method such as dry lamination, using an adhesive for forming the 1 st adhesive layer 12.
When the base material layer 11 is bonded, the 1 st base material layer 11a is bonded to the 1 st adhesive layer 12.
In the step (2), curing treatment may be performed at room temperature to 100 ℃ in order to promote adhesiveness.
(step (3))
The 2 nd adhesive layer 15 is formed by an extrusion lamination method on the corrosion prevention treated layer 14 of the laminate in which the base material layer 11, the 1 st adhesive layer 12, the metal foil layer 13, and the corrosion prevention treated layer 14 are laminated in this order, and a resin film forming the sealant layer 16 is bonded thereto. The lamination of the sealing layer 16 is preferably performed by a sandwich lamination method.
The sealing material 1 is obtained through the steps (1) to (3) described above.
The order of steps in the method for producing the sealing material 1 is not limited to the sequential implementation of the above-described methods (1) to (3). For example, the step (1) may be performed after the step (2).
Two pieces of the completed sealing material 1 are prepared and the sealing layers 16 are opposed to each other, or 1 piece of the sealing material 1 is folded so that the sealing layers 16 are opposed, a power generating element, a joint member serving as a terminal, and the like are arranged inside, and the periphery is joined by heat sealing, thereby completing a lithium ion battery cell using the sealing material 1.
An example of a method of molding the sealing material 1 in the method of manufacturing a lithium ion battery using the sealing material 1 according to the present embodiment will be described below with reference to fig. 2 and 3. Fig. 2 is a plan view of the potting material 1, and fig. 3 is a cross-sectional view taken along line I-I of fig. 2.
Here, a molding method for forming the molding region 17 shown in fig. 2 and 3 as a rectangular recess in a plan view on the sealing material 1 in the process of manufacturing the lithium ion battery will be described.
The molding region 17 is formed by, for example, pressing a pressing member having a rectangular pressure surface against a part of the potting material 1 in the thickness direction thereof. It is preferable that the pressing position, i.e., the molding region 17, is formed at a position offset from the center of the rectangular sealing material 1 as shown in fig. 2 and 3. In this way, the sealing material 1 can be formed so that the cap is formed in the molding region 17 by folding the portion where the molding region 17 is not formed after the molding process.
After such molding, the following steps are performed on the sealing material 1 to manufacture a lithium ion battery.
That is, after the molding region 17 is formed as the recess as in the above-described step, the positive electrode, the separator, and the negative electrode are placed in the recess. Thereafter, the sealing material 1 is folded so that the sealing layers are superposed so as to face each other, and both sides thereof are heat-sealed. Thereafter, an electrolyte solution is injected from the remaining one side in a vacuum state, and the remaining one side is heat-sealed to form a lithium ion battery.
The lithium ion battery using the sealing material for a lithium ion battery of the present invention is not limited to the structure manufactured by the above-described method. For example, two sheets of the sealing material 1 may be prepared, and the sealing layers 16 may be bonded to each other so as to face each other, thereby forming a lithium ion battery.
As described above, according to the sealing material 1 of the present embodiment, the first base material layer 11a is formed of a polyester resin or a polyamide resin, whereby the metal foil layer 13 can be protected and the moldability can be improved.
In addition, since the 2 nd base material layer 11b contains the polyester elastomer, the amount of warp of the encapsulating material after molding can be reduced.
Further, by setting the thickness of the 1 st base material layer 11a to 4 μm to 20 μm and the thickness of the 2 nd base material layer 11b to 2 μm to 15 μm, the amount of warpage of the encapsulating material after molding can be reduced with the moldability improved.
Further, by forming the base layer 11 by a coextrusion method, the 1 st base layer 11a and the 2 nd base layer 11b can be made thin.
The sealing material and the secondary battery of the present invention will be further described with reference to examples and comparative examples, but the present invention is not limited to the specific contents of the examples.
[ materials used ]
First, materials of respective layers used in examples and comparative examples are shown below.
(substrate layer)
Table 1 shows the structures of the base material layers used in examples 1 to 7 and comparative examples 1 to 5.
Figure BDA0002685784680000111
(1 st adhesive layer)
Adhesive B-1: polyester urethane adhesive
(Metal foil layer)
Metal foil C-1: soft aluminum foil 8079 material (made by Toyo aluminum Co., Ltd., thickness 40 μm)
(anticorrosion-treated layer)
Process D-1: treating agent for treating ceria sol coated mainly with cerium oxide, phosphoric acid and acrylic resin
(No. 2 adhesive layer 15)
Adhesive resin E-1: polypropylene resin graft-modified with maleic anhydride (trade name: アドマー, manufactured by Mitsui chemical Co., Ltd.)
(sealing layer 16)
Film F-1: a film having a surface to be an inner surface of a non-stretched polypropylene film (thickness: 40 μm) subjected to corona treatment
[ production of packaging Material ]
A treatment agent D-1 is applied to one surface of a metal foil C-1 formed into a metal foil layer and dried to form an anticorrosive treatment layer. Then, any one of the substrates A-1 to A-12 is bonded to the surface of the metal foil layer opposite to the surface thereof on which the corrosion-resistant treated layer is formed, by a dry lamination method using an adhesive B-1. Thereafter, aging was carried out at 60 ℃ for 6 days. Then, on the corrosion-resistant treated layer of the obtained laminate, extrusion was usedThe apparatus extrudes the adhesive resin E-1 to form a 2 nd adhesive layer, and forms a sealant layer by adhering the film F-1 and performing sandwich lamination. Then, at 190 ℃, 4kg/cm2And the obtained laminate was subjected to thermocompression bonding under the condition of 2 m/min to prepare an encapsulating material.
[ evaluation of moldability ]
The sealing materials obtained in the respective examples were cut into a 150mm × 190mm blank shape, subjected to cold forming while changing the forming depth under a forming environment of 23 ℃ and 40% RH (relative humidity), and evaluated for formability.
As the punches, punches having a shape of 100mm X150 mm, a punch angle R (RCP) of 1.5mm, a punch shoulder R (RP) of 0.75mm and a die shoulder R (RD) of 0.75mm were used. The evaluation criteria were as follows.
E (good): the deep press forming can be carried out without breaking and cracking and with a forming depth of more than 6 mm.
F (good): the deep drawing can be carried out without breaking and cracking and with a forming depth of 4mm or more and less than 6 mm.
I (poor): when deep drawing is performed to a forming depth of less than 4mm, cracks and fractures occur.
[ evaluation of warpage amount after Molding ]
The sealing materials obtained in the respective examples were cut into a blank shape of 120mm × 260mm with the direction of large tensile elongation obtained by tensile evaluation as the long side, and cold-formed with a forming depth of 3mm in a forming environment of 23 ℃ and 40% RH.
The molding was performed in a state where the molding region was set to a position 25mm from the end of the blank shape and close to the side of the blank shape.
As the punch, a punch having a shape of 70mm X80 mm, RCP of 1.5mm, RP of 0.75mm and RD of 0.75mm was used.
The molded sealing material was fixed to a flat reference surface so that the base layer side of the molded region was positioned at the upper portion, and the amount of warpage (distance from the reference surface) at the end edge of the unmolded region 60 minutes after the molding was measured. The evaluation criteria were as follows.
E (good): the warping amount is less than 50 mm.
F (good): the warping amount is more than 50mm and less than 100 mm.
I (poor): the warping amount is more than 100 mm.
Table 2 shows the results of the moldability and the warpage after molding evaluation of examples 1 to 7 and comparative examples 1 to 5.
[ Table 2]
Substrate layer Formability Deflection after forming
Example 1 A-1 E E
Example 2 A-2 E E
Example 3 A-3 F F
Example 4 A-4 F E
Example 5 A-5 E F
Example 6 A-6 E F
Example 7 A-7 E F
Comparative example 1 A-8 I E
Comparative example 2 A-9 E I
Comparative example 3 A-10 E I
Comparative example 4 A-11 I E
Comparative example 5 A-12 E I
In examples 1 to 7 having the structure according to one embodiment of the present invention, it is possible to provide a sealing material for a lithium ion battery, which can obtain sufficient moldability and can reduce the amount of warpage after molding.
While the embodiments and examples of the present invention have been described above, the technical scope of the present invention is not limited to the above-described embodiments, and various modifications may be made by changing the combination of the components or by adding or deleting various components without departing from the scope of the present invention.
Description of the symbols
1 sealing Material for lithium ion Battery
11 base material layer
11a No. 1 base material layer
11b 2 nd base material layer
12 st adhesive layer
13 metal foil layer
14 anticorrosive treatment layer
15 No. 2 adhesive layer
16 sealing layer

Claims (3)

1. A packaging material for a lithium ion battery, which is composed of:
a 1 st base material layer formed of only a polyester resin;
a 2 nd substrate layer having a single-layer structure and containing a polyester elastomer and formed directly on the 1 st substrate layer;
a 1 st adhesive layer laminated on the 1 st base material layer;
a metal foil layer laminated on the 1 st adhesive layer;
an anticorrosion treated layer laminated on the metal foil layer;
a 2 nd adhesion layer formed on the corrosion prevention treated layer; and
and a sealing layer formed on the 2 nd adhesive layer.
2. The packaging material for lithium ion batteries according to claim 1,
the thickness of the 1 st base material layer is more than 4 mu m and less than 20 mu m,
the thickness of the 2 nd base material layer is more than 2 μm and less than 15 μm
The thickness of the substrate layer is 6-25 μm.
3. The encapsulating material for a lithium ion battery according to claim 1 or 2, wherein,
the substrate layer is formed by a coextrusion method.
CN202010975943.1A 2013-11-12 2014-11-11 Packaging material for lithium ion battery Pending CN112117395A (en)

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JP2017059388A (en) * 2015-09-16 2017-03-23 凸版印刷株式会社 Jacket material for power storage device and power storage device using the same
EP3605642B1 (en) * 2017-03-21 2023-05-03 Dai Nippon Printing Co., Ltd. Packaging material for batteries, method for producing same, polybutylene terephthalate film for packaging material for batteries, and battery
CN108530882A (en) * 2018-04-16 2018-09-14 合肥羿振电力设备有限公司 A kind of high-performance package material of cell phone lithium-ion batteries and preparation method thereof
KR20210076022A (en) * 2018-10-24 2021-06-23 다이니폰 인사츠 가부시키가이샤 Packaging material for electrical storage device, manufacturing method thereof, and electrical storage device
CN109728207B (en) * 2018-12-27 2022-04-05 东莞澳中新材料科技股份有限公司 Environment-friendly lithium cell plastic-aluminum protection film
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CN114714726B (en) * 2022-02-21 2024-04-05 浙江华正能源材料有限公司 Aluminum plastic film and preparation method and application thereof
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