CN111492499B - Battery packaging material, method for producing same, and battery - Google Patents

Battery packaging material, method for producing same, and battery Download PDF

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Publication number
CN111492499B
CN111492499B CN201880081147.4A CN201880081147A CN111492499B CN 111492499 B CN111492499 B CN 111492499B CN 201880081147 A CN201880081147 A CN 201880081147A CN 111492499 B CN111492499 B CN 111492499B
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layer
heat
packaging material
resin layer
battery
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CN111492499A (en
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安田大佑
山下孝典
山下力也
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Dai Nippon Printing Co Ltd
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Dai Nippon 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
    • H01M50/102—Primary casings, jackets or wrappings of a single cell or a single battery characterised by their shape or physical structure
    • H01M50/105—Pouches or flexible bags
    • 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

A packaging material for a battery, comprising a laminate having at least a base material layer, a barrier layer and a heat-sealable resin layer in this order, wherein the thickness of the laminate is not more than 195 μm, and the thickness is determined by a method according to JIS Z1707:1997, the puncture strength of the laminate when punctured from the base layer side is 30N or more, and the thickness of the barrier layer is in the range of 75 to 85 μm.

Description

Battery packaging material, method for producing same, and battery
Technical Field
The invention relates to a battery packaging material, a method for producing the same, and a battery.
Background
Various types of batteries have been developed, and in all batteries, a packaging material becomes an indispensable component for sealing battery elements such as electrodes and electrolytes. Conventionally, a metal packaging material has been used as a battery package in many cases.
On the other hand, in recent years, along with the increase in performance of electric vehicles, hybrid electric vehicles, personal computers, cameras, mobile phones, and the like, batteries having various shapes have been required, and thinning and weight reduction have been also required. However, the metal-made battery packaging materials that are currently used in large quantities have disadvantages that it is difficult to cope with diversification of shapes and that weight reduction is limited.
In recent years, as a battery packaging material that can be easily processed into various shapes and can be made thinner and lighter, a film-shaped laminate in which a base material layer, a barrier layer, and a heat-sealable resin layer are sequentially laminated has been proposed (for example, see patent document 1).
In such a battery packaging material, a battery in which a battery element is housed inside the battery packaging material is generally obtained by forming a concave portion by cold forming, disposing a battery element such as an electrode and an electrolyte solution in a space formed by the concave portion, and thermally welding heat-weldable resin layers to each other. However, such a film-shaped packaging material is thinner than a metal packaging material, and has a disadvantage that pinholes and cracks are likely to occur during molding. When the battery packaging material has pinholes or cracks, the electrolyte permeates into the barrier layer to form metal precipitates, which may result in short circuits, and therefore, it is essential for the film-shaped battery packaging material to have a characteristic of being less likely to cause pinholes during molding, that is, excellent moldability.
Documents of the prior art
Patent literature
Patent document 1: japanese patent laid-open No. 2008-287971
Patent document 2: japanese patent laid-open publication No. 2013-201027
Disclosure of Invention
Technical problems to be solved by the invention
In recent years, the use of a battery packaging material comprising the above film-shaped laminate has been studied for large batteries such as electric vehicles and hybrid electric vehicles. In addition, in order to increase the capacity and the volumetric energy density of the battery, attempts have been made to increase the capacity of the battery element housed in the battery by increasing the depth of the molded portion of the battery and reducing the thickness of the battery packaging material. However, when the depth of the molded portion is increased, there is a problem that a battery packaging material is likely to have pinholes or cracks during molding.
Further, the peripheral edge portion of the recess portion formed by molding the battery packaging material may be curled (bent) by the molding, which may prevent storage of the battery element or heat welding of the heat-weldable resin layer, thereby reducing the production efficiency of the battery. In particular, a battery packaging material used for a large battery such as a vehicle battery has a problem that the battery packaging material has a large size and a large area of a peripheral edge portion of a concave portion, and therefore curling greatly affects productivity of the battery.
Under such circumstances, a main object of the present invention is to provide a battery packaging material having excellent moldability, capable of effectively suppressing curling after molding, and capable of improving the volume energy density.
Means for solving the problems
The present inventors have conducted intensive studies in order to solve the above-mentioned technical problems. As a result, it has been found that a battery packaging material having excellent moldability and capable of effectively suppressing curling after molding. The packaging material for a battery is composed of a laminate having at least a base material layer, a barrier layer and a heat-fusible resin layer in this order, wherein the thickness of the laminate is not more than 195 [ mu ] m, and the thickness is determined by the following formula according to JIS Z1707:1997, the puncture strength of the laminate when punctured from the substrate layer side is 30N or more, and the thickness of the barrier layer is 75 to 85 μm. The present invention has been completed based on these findings and further research and study has been conducted.
That is, the present invention provides the following embodiments.
The packaging material for a battery according to item 1, which comprises a laminate comprising at least a substrate layer, a barrier layer and a heat-sealable resin layer in this order,
the thickness of the laminate is not more than 195 μm,
by adjusting the molar ratio in accordance with JIS Z1707:1997 the puncture resistance strength of the laminate when punctured from the base layer side of the laminate is 30N or more,
the thickness of the barrier layer is in the range of 75 to 85 μm.
The battery packaging material according to item 1, wherein the thickness of the base material layer is in the range of 30 to 45 μm.
The battery packaging material according to item 1 or 2, wherein the thickness of the heat-fusible resin layer is in the range of 55 to 65 μm.
The battery packaging material according to any one of claims 1 to 3, wherein the base layer is a laminate of a polyester film and a polyamide film.
The battery packaging material according to any one of claims 1 to 4, wherein the ultimate molding depth measured under the following measurement conditions is 10mm or more.
(measurement conditions for ultimate Molding depth)
The battery packaging material was a rectangular shape having a length of 150mm and a width of 100mm, and used as a test sample. The samples were cold-formed into 10 pieces by changing the molding depth from the molding depth of 0.5mm to the molding depth of 0.5mm with a pressing surface pressure of 0.23MPa using a female die having a rectangular caliber of 55mm in length and 32mm in width and a male die corresponding thereto. At this time, the test sample was placed on a female mold so that the side of the heat-fusible resin layer was on the male mold side, and was molded. The distance between the male and female dies was set to 0.3mm. For the samples after cold forming, the deepest forming depth at which no pin hole or crack occurred in the aluminum alloy foil layer was a (mm), the number of samples at which pin holes or cracks occurred at the shallowest forming depth of pin holes or cracks in the aluminum alloy foil layer was B (mm), and the value calculated from the following equation was used as the limit forming depth of the battery packaging material.
Ultimate forming depth = Amm + (0.5 mm/10) × (10-B)
The battery packaging material according to any one of claims 1 to 5, wherein a formed curl measured under the following measurement conditions is 0mm to 10 mm.
(measurement conditions for curl formation)
The battery packaging material was a rectangular shape having a length of 200mm and a width of 100mm, and used as a test sample. The sample was cold-formed by using a female die having a rectangular diameter of 55mm in length and 32mm in width and a male die corresponding thereto at a pressing surface pressure of 0.23MPa and a forming depth of 6mm. At this time, the test sample was placed on a female mold so that the side of the heat-fusible resin layer was positioned on the side of the male mold, and was molded. The distance between the male and female dies was set to 0.3mm. The position of the molding portion M is located such that the shortest distance d between the molding portion M, which is rectangular in a plan view and is formed by a die in the longitudinal direction of the battery packaging material, and the end P of the battery packaging material is 122mm, and the shortest distance between the molding portion M and both ends of the battery packaging material in the width direction of the battery packaging material is 34 mm. The molded battery packaging material has a concave portion of a molded portion with its opening facing downward, and the maximum value t of the distance in the vertical direction y from the position Q to the end P is defined as the curl (mm) with reference to the position Q of the molded portion where no concave portion is formed.
The battery packaging material according to any one of claims 1 to 6, wherein the temperature difference T is measured by the following method 1 And temperature difference T 2 Above temperature difference T 2 Except for the above temperature difference T 1 The obtained value is 0.55 or more.
(temperature difference T) 1 Measurement of (2)
Measuring the temperature difference T between the extrapolated melting start temperature and the extrapolated melting end temperature of the melting peak temperature of the heat-sealable resin layer by differential scanning calorimetry 1 。
(temperature difference T) 2 Measurement of (2)
Allowing the heat-fusible resin layer to stand in an electrolyte for 72 hours in an environment of 85 ℃ and drying the same, measuring the difference T between the extrapolated melting start temperature and the extrapolated melting end temperature of the melting peak temperature of the heat-fusible resin layer after drying by differential scanning calorimetry 2 . The electrolyte was a solution in which the concentration of lithium hexafluorophosphate was 1mol/l and the volume ratio of ethylene carbonate, diethyl carbonate and dimethyl carbonate was 1: 1.
The battery packaging material according to any one of claims 1 to 7, wherein a logarithmic decrement Δ E of the surface of the heat-sealable resin layer on the side of the barrier layer at 120 ℃ in rigid body pendulum measurement is 0.50 or less.
The battery according to item 9, wherein a battery element having at least a positive electrode, a negative electrode, and an electrolyte is contained in a package formed of the battery packaging material according to any one of items 1 to 8.
The method of producing a packaging material for a battery according to item 10, which comprises a step of sequentially laminating at least a substrate layer, a barrier layer and a heat-fusible resin layer to obtain a laminate,
the thickness of the laminate is not more than 195 μm,
by adjusting the molar ratio in accordance with JIS Z1707:1997 the puncture resistance strength of the laminate when punctured from the base layer side is 30N or more,
the thickness of the barrier layer is in the range of 75 to 85 μm.
Effects of the invention
According to the present invention, a battery packaging material comprising a laminate comprising at least a base material layer, a barrier layer and a heat-sealable resin layer in this order, which has excellent moldability and can effectively suppress curling after molding, can be provided. Further, the present invention can provide a battery using the battery packaging material.
Drawings
Fig. 1 is a view showing an example of a cross-sectional structure of a battery packaging material of the present invention.
Fig. 2 is a view showing an example of a cross-sectional structure of the battery packaging material of the present invention.
Fig. 3 is a view showing an example of a cross-sectional structure of the battery packaging material of the present invention.
Fig. 4 is a view showing an example of a cross-sectional structure of the battery packaging material of the present invention.
Fig. 5 is a schematic diagram for explaining the method of evaluating the formed curl.
Fig. 6 is a schematic diagram for explaining the method of evaluating the formed curl.
Fig. 7 is a schematic diagram for explaining the method of evaluating the formed curl.
Fig. 8 is a schematic diagram for explaining a method of measuring the seal strength.
Fig. 9 is a schematic diagram for explaining a method of measuring the logarithmic decrement Δ E by rigid body pendulum measurement.
Fig. 10 is a schematic diagram for explaining a method of measuring the seal strength.
FIG. 11 is a schematic view showing a temperature difference T in the differential scanning calorimetry 1 And temperature difference T 2 Is shown in (a).
Detailed Description
The battery packaging material of the present invention is characterized by comprising a laminate having at least a base material layer, a barrier layer and a heat-sealable resin layer in this order, wherein the thickness of the laminate is 195 μm or less, and the thickness is determined by the following formula according to JIS Z1707:1997, the puncture strength of the laminate when punctured from the substrate layer side is 30N or more, and the thickness of the barrier layer is 75 to 85 μm. The battery packaging material of the present invention has such a structure, and thus has excellent moldability, and the curl after molding can be effectively suppressed. Therefore, the battery packaging material of the present invention is particularly suitable for use as a packaging material for large batteries such as vehicle batteries. The battery packaging material of the present invention will be described in detail below.
In the present specification, the numerical ranges indicated by "to" mean "above" and "below" with respect to the numerical ranges. For example, the expression 2 to 15mm means 2mm or more and 15mm or less.
1. Lamination and physical properties of battery packaging material
For example, as shown in fig. 1, a battery packaging material 10 of the present invention is composed of a laminate having a base material layer 1, a barrier layer 3, and a heat-sealable resin layer 4 in this order. In the battery packaging material of the present invention, the base material layer 1 is the outermost layer side, and the heat-sealable resin layer 4 is the innermost layer side. That is, when the battery is assembled, the battery elements are sealed by thermally welding the thermally-adhesive resin layers 4 located at the peripheral edges of the battery elements to each other, thereby sealing the battery elements.
The battery packaging material of the present invention may have an adhesive layer 2 between the base layer 1 and the barrier layer 3, as shown in fig. 2, for example. As shown in fig. 3, an adhesive layer 5 may be provided between the barrier layer 3 and the heat-fusible resin layer 4. As shown in fig. 4, the surface coating layer 6 may be provided on the outer side of the base material layer 1 (the side opposite to the heat-fusible resin layer 4) as necessary.
The battery packaging material of the present invention is produced by a method according to JIS Z1707:1997, the puncture strength of the laminate constituting the battery packaging material when punctured from the substrate layer 1 side was 30N or more. From the viewpoint of exhibiting excellent moldability and effectively suppressing curling caused by molding, the puncture strength is preferably about 30 to 45N, about 30 to 40N, about 35 to 45N, and about 35 to 40N. The puncture strength of the laminate was measured as follows.
< puncture resistance of laminate >
The puncture resistance strength of the laminate constituting the battery packaging material from the base material layer side was determined in accordance with JIS Z1707: 1997. Specifically, the test piece was fixed by a table having an opening with a diameter of 15mm at the center and a pressing plate and having a diameter of 115mm and a tip having a diameter of 15mm, and the test piece was pierced by a semicircular needle having a diameter of 1.0mm and a tip shape with a radius of 0.5mm at a speed of 50. + -. 5mm per minute in a measuring environment of 23. + -. 2 ℃ and a relative humidity (50. + -.5)% to measure the maximum stress until the needle piercing. The number of test pieces was 5, and the average value was obtained. When the number of test pieces is less than 5 and cannot be measured, the measurable number is measured and the average value is taken.
The thickness of the laminate constituting the battery packaging material of the present invention may be not more than 195 μm, and is not particularly limited, and when used in a large-sized battery, from the viewpoint of reducing the thickness of the laminate as much as possible, exerting excellent moldability, and effectively suppressing curling due to molding, it is preferably 170 to 195 μm, 170 to 190 μm, 180 to 195 μm, 180 to 190 μm, and 170 to 180 μm.
The battery packaging material of the present invention has a limit molding depth of preferably 10mm or more, more preferably 10.5mm or more, still more preferably 11mm or more, and particularly preferably 12mm or more, when molded under the following conditions. The upper limit of the limit molding depth is usually about 13 mm.
< measuring Condition of Limit Molding depth >
The battery packaging material was a rectangular shape having a length of 150mm and a width of 100mm, and used as a test sample. The samples were cold-formed into 10 samples by changing the molding depth in units of 0.5mm from the molding depth of 0.5mm with a pressing surface pressure of 0.23MPa using a female die having a rectangular diameter of 55mm in length and 32mm in width and a male die corresponding thereto. At this time, the test sample was placed on a female mold so that the side of the heat-fusible resin layer was positioned on the side of the male mold, and was molded. The distance between the male and female dies was set at 0.3mm. For the samples after cold forming, the deepest forming depth at which no pin hole or crack occurred in the aluminum alloy foil layer was a (mm), the number of samples at which pin holes or cracks occurred at the shallowest forming depth of pin holes or cracks in the aluminum alloy foil layer was B (mm), and the value calculated from the following equation was used as the limit forming depth of the battery packaging material.
Ultimate forming depth = Amm + (0.5 mm/10) × (10-B)
The battery packaging material of the present invention preferably has a curl as measured under the following conditions of 0mm to 10 mm. In the later-described embodiment, when the direction of the forming curl is the same as the direction of the recess (the vertical direction y 1) (the shape of fig. 6), the forming curl t is expressed as a positive value; when the direction of the forming curl and the direction of the concave portion are opposite directions (vertical direction y 2) (the shape of fig. 7), the forming curl t is expressed as a negative value. The curl of the battery packaging material of the present invention is positive, and is preferably 0mm to 10 mm. For example, in the shape of FIG. 7, the forming curl was-5 mm, and as a result, the forming curl was out of the range of 0mm to 10 mm.
When the direction of the forming curl is the direction (vertical direction y 2) opposite to the direction of the recessed portion (the shape of fig. 7), even if the absolute value of the forming curl t is 0 to 10mm, a misalignment of the sealing position is likely to occur in the step of housing the formed battery element and heat-sealing the peripheral portion, or wrinkles are likely to occur after sealing. Therefore, in the battery packaging material of the present invention, when the forming curl is measured under the following conditions, the direction of the forming curl is preferably the same as the direction of the concave portion (vertical direction y 1).
< measurement Condition for formed curl >
The battery packaging material was a rectangular shape having a length of 200mm and a width of 100mm, and used as a test sample. The sample was cold-formed by using a female die having a rectangular diameter of 55mm in length and 32mm in width and a male die corresponding thereto at a pressing surface pressure of 0.23MPa and a forming depth of 6mm. At this time, the test sample was placed on a female mold so that the side of the heat-fusible resin layer was on the male mold side, and was molded. The distance between the male and female dies was set to 0.3mm. The position of the molding portion M is located such that the shortest distance d between the molding portion M, which is rectangular in a plan view and is formed by a die in the longitudinal direction of the battery packaging material, and the end P of the battery packaging material is 122mm, and the shortest distance between the molding portion M and both ends of the battery packaging material in the width direction of the battery packaging material is 34 mm. The molded battery packaging material has a concave portion of a molded portion with its opening facing downward, and the maximum value t of the distance in the vertical direction y from the position Q to the end P is defined as the curl (mm) with reference to the position Q of the molded portion where no concave portion is formed.
Further, in the battery packaging material 10 of the present invention, after the battery packaging material is brought into contact with an electrolyte (a solution in which the concentration of lithium hexafluorophosphate is 1mol/l and the volume ratio of ethylene carbonate, diethyl carbonate and dimethyl carbonate is 1: 1) in an environment of 85 ℃ for 72 hours, the heat-fusible resin layers are heat-fused to each other under conditions of a temperature of 190 ℃, a surface pressure of 2.0MPa and a time of 3 seconds in a state in which the electrolyte is adhered to the surfaces of the heat-fusible resin layers, and the sealing strength at the time of peeling off the interface after the heat fusion is preferably 60% or more (the retention rate of the sealing strength is 60% or more), more preferably 80% or more, and still more preferably 100% of the sealing strength without being contacted with the electrolyte.
(method of measuring the Retention ratio of seal Strength)
The retention (%) of the seal strength after contacting the electrolyte was calculated on the basis of the seal strength before contacting the electrolyte measured by the following method (100%).
< measurement of seal Strength before contact with electrolyte >
In the following measurement of the sealing strength after contact with the electrolyte solution, the tensile strength (sealing strength) was measured in the same manner except that the electrolyte solution was not injected into the test sample. The maximum tensile strength until the thermally welded portion was completely peeled off was taken as the seal strength before contacting the electrolyte.
< measurement of seal Strength after contact with electrolyte >
As shown in the schematic view of FIG. 10, the battery packaging material was cut into a rectangular shape having a width (x direction) of 100mm × a length (z direction) of 200mm, and used as a test sample (FIG. 10 a). The test sample was folded back at the center in the z direction so that the heat-fusible resin layer sides were overlapped (fig. 10 b). Subsequently, both ends of the folded test sample in the x direction were sealed by heat sealing (temperature 190 ℃, surface pressure 2.0MPa, time 3 seconds) to form a bag shape having 1 opening E (fig. 10 c). Then, 6g of an electrolyte (a solution in which the concentration of lithium hexafluorophosphate was 1mol/l and the volume ratio of ethylene carbonate, diethyl carbonate and dimethyl carbonate was 1: 1) was injected from the opening E of the test sample formed in a bag shape (FIG. 10 d), and the end of the opening E was sealed by heat sealing (temperature 190 ℃, surface pressure 2.0MPa, time 3 seconds) (FIG. 10E). Then, the bag-shaped test specimen was left to stand at a temperature of 85 ℃ for a predetermined storage time (time of contacting the electrolyte, 72 hours, etc.) with the folded portion facing downward. Next, the end of the test sample was cut (fig. 10 e), and the electrolyte was completely discharged. Next, the upper and lower surfaces of the test sample were sandwiched between metal plates (7 mm in width) with the electrolyte solution adhering to the surfaces of the heat-fusible resin layers, and the heat-fusible resin layers were heat-fused together at a temperature of 190 ℃ and a surface pressure of 1.0MPa for a time of 3 seconds (fig. 10 f). Next, in order to measure the sealing strength at a position of 15mm in width (x direction), the test sample was cut into a width of 15mm using a double-edged sample cutter (fig. 10f, g). Next, T-peeling was performed, and the interface where thermal welding occurred was peeled off under conditions of a tensile speed of 300 mm/min, a peeling angle of 180 °, and an inter-jig distance of 50mm in an environment at a temperature of 25 ℃ using a tensile tester, and the tensile strength (seal strength) was measured (fig. 8). The maximum tensile strength until the thermal welding portion was completely peeled off was used as the sealing strength after the electrolyte was contacted.
2. Each layer forming the packaging material for batteries
[ base Material layer 1]
In the battery packaging material of the present invention, the base material layer 1 is a layer located on the outermost layer side. The material forming the base layer 1 is not particularly limited as long as it can have insulating properties. Examples of the material forming the base layer 1 include resin films such as polyester resins, polyamide resins, epoxy resins, acrylic resins, fluorine-containing resins, polyurethane resins, silicon-containing resins, phenol resins, polycarbonates, and mixtures or copolymers thereof. Among these, polyester resins and polyamide resins are preferred, and biaxially stretched polyester resins and biaxially stretched polyamide resins are more preferred. Specific examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and a copolyester. Specific examples of the polyamide resin include nylon 6, nylon 66, a copolymer of nylon 6 and nylon 66, nylon 6,10, and polyamide MXD6 (polycaprometaxylylenediamine).
The base material layer 1 may be formed of 1 resin film, but may be formed of 2 or more resin films for the purpose of improving pinhole resistance and insulation. Specific examples thereof include a multilayer structure in which a polyester film and a nylon film are laminated, a multilayer structure in which a multilayer nylon film is laminated, and a multilayer structure in which a multilayer polyester film is laminated. When the base layer 1 has a multilayer structure, a laminate of a biaxially stretched nylon film and a biaxially stretched polyester film, a laminate of a plurality of biaxially stretched nylon films, and a laminate of a plurality of biaxially stretched polyester films are preferable. For example, when the base layer 1 is formed of 2 resin films, it is preferable to form a structure in which a polyester resin and a polyester resin are laminated, a structure in which a polyamide resin and a polyamide resin are laminated, or a structure in which a polyester resin and a polyamide resin are laminated, and more preferably, a structure in which polyethylene terephthalate and polyethylene terephthalate are laminated, a structure in which nylon and nylon are laminated, or a structure in which polyethylene terephthalate and nylon are laminated. Further, since the polyester resin is less likely to be discolored even when an electrolytic solution is adhered to the surface thereof, for example, in the laminated structure, it is preferable to laminate the base layer 1 so that the polyester resin is positioned as the outermost layer. When the substrate layer 1 has a multilayer structure, the thickness of each layer is preferably about 2 to 25 μm.
When the base layer 1 is formed of a multilayer resin film, 2 or more layers of resin films may be laminated with an adhesive component such as an adhesive or an adhesive resin, and the type, amount, and the like of the adhesive component used are the same as those of the adhesive layer 2 described later. Among them, the method for laminating 2 or more resin films is not particularly limited, and known methods can be used, and examples thereof include a dry lamination method, an interlayer lamination method, and the like, and a dry lamination method is preferable. When the layers are laminated by a dry lamination method, a urethane adhesive is preferably used as the adhesive layer. In this case, the thickness of the adhesive layer is, for example, about 2 to 5 μm.
When the base material layer 1 is formed of a plurality of layers and the layers constituting the base material layer are bonded with an adhesive or the like (usually, the thickness is 3 μm or less), the base material layer 1 does not include a portion of the adhesive.
In the present invention, from the viewpoint of improving the moldability of the battery packaging material, it is preferable that a lubricant is adhered to the surface of the base material layer 1. The lubricant is not particularly limited, but preferably includes an amide-based lubricant. Specific examples of the amide-based lubricant include the same ones as exemplified in the heat-fusible resin layer 4 described later.
When the lubricant is present on the surface of the base layer 1, the amount of the lubricant present is not particularly limited, but is preferably about 3mg/m in an environment of 24 ℃ and 60% relative humidity 2 Above, more preferably 4 to 15mg/m 2 About 5 to 14mg/m, more preferably 2 Left and right.
The base material layer 1 may contain a lubricant. The lubricant present on the surface of the base material layer 1 may be a lubricant exuded from the resin constituting the base material layer 1, or may be a lubricant applied to the surface of the base material layer 1.
The thickness of the substrate layer 1 is not particularly limited as long as it can function as a substrate layer, but in the battery packaging material having the above-described configuration of the present invention, from the viewpoint of more effectively exhibiting excellent moldability and suppressing curling after molding, it is preferably about 30 to 45 μm, about 30 to 41 μm, about 34 to 45 μm, or about 34 to 41 μm.
[ adhesive layer 2]
In the battery packaging material 10 of the present invention, the adhesive layer 2 is provided between the base layer 1 and the barrier layer 3 as necessary for firmly bonding them.
The adhesive layer 2 is formed of an adhesive capable of bonding the base layer 1 and the barrier layer 3. The adhesive used to form the adhesive layer 2 may be a two-component curing adhesive or a one-component curing adhesive. The bonding mechanism of the adhesive used for forming the adhesive layer 2 is not particularly limited, and may be any of chemical reaction type, solvent volatilization type, hot melt type, hot press type, and the like.
As the adhesive components that can be used for forming the adhesive layer 2, specifically, there can be mentioned: polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, and copolyester; a polyether adhesive; a polyurethane adhesive; an epoxy resin; a phenolic resin; polyamide resins such as nylon 6, nylon 66, nylon 12, and copolyamide; polyolefin resins such as polyolefin, carboxylic acid-modified polyolefin, and metal-modified polyolefin, and polyvinyl acetate resins; a cellulose-based binder; (meth) acrylic resins; a polyimide-based resin; a polycarbonate; amino resins such as urea resins and melamine resins; rubbers such as chloroprene rubber, nitrile rubber, and styrene-butadiene rubber; silicone resins, and the like. These adhesive components can be used alone in 1 kind, also can be combined with 2 or more. Among these adhesive components, a polyurethane adhesive is preferably used.
The thickness of the adhesive layer 2 is not particularly limited as long as it can function as a layer for adhesion, and in the battery packaging material having the above-described configuration of the present invention, from the viewpoint of more effectively exhibiting excellent moldability and suppressing curling after molding, for example, it is about 1 to 10 μm, preferably about 2 to 5 μm.
[ Barrier layer 3]
In the battery packaging material, the barrier layer 3 is a layer having a function of improving the strength of the battery packaging material and preventing water vapor, oxygen, light, and the like from entering the inside of the battery. The barrier layer 3 may be formed of a metal foil, a metal vapor-deposited film, an inorganic oxide vapor-deposited film, a carbon-containing inorganic oxide vapor-deposited film, a film provided with these vapor-deposited layers, or the like, and is preferably formed of a metal foil. Specific examples of the metal constituting the barrier layer include aluminum, stainless steel, and titanium, and aluminum is preferably used. From the viewpoint of preventing generation of wrinkles or pinholes in the barrier layer 3 at the time of producing the packaging material for a battery, it is more preferable that the barrier layer is formed of, for example, a soft aluminum alloy foil such as annealed aluminum (JIS H4160:1994A8021H-O, JIS H4160:1994A8079H-O, JIS H4000:2014A8021P-O, JIS H4000:2014A 8079P-O).
In the battery packaging material of the present invention, the thickness of the barrier layer 3 is in a specific range of 75 to 85 μm. In the battery packaging material of the present invention, as described above, the thickness of the laminate constituting the battery packaging material is 195 μm or less, the puncture strength at the time of puncturing from the base material layer side is 30N or more, and the thickness of the barrier layer 3 is within such a specific range, so that excellent moldability can be effectively exhibited and curling after molding can be suppressed.
The thickness of the barrier layer 3 may be in the range of 75 to 85 μm, and from the viewpoint of more effectively exhibiting the effects of improving moldability and suppressing molding curl, it is preferably about 75 to 82 μm, about 77 to 85 μm, about 77 to 82 μm, about 80 to 85 μm, or about 80 to 82 μm.
In addition, at least one surface, preferably both surfaces, of the barrier layer 3 are preferably subjected to a chemical surface treatment for stabilization of adhesion, prevention of dissolution, corrosion, or the like. The chemical surface treatment is a treatment for forming an acid-resistant coating on the surface of the barrier layer. Examples of the chemical surface treatment include: chromate treatment with chromium compounds such as chromium nitrate, chromium fluoride, chromium sulfate, chromium acetate, chromium oxalate, chromium dihydrogen phosphate, chromic acid acetoacetate, chromium chloride, and chromium potassium sulfate; phosphoric acid treatment using phosphoric acid compounds such as sodium phosphate, potassium phosphate, ammonium phosphate, polyphosphoric acid, and the like; chromate treatment with an aminated phenol polymer having repeating units represented by the following general formulae (1) to (4). In the aminated phenol polymer, the repeating units represented by the following general formulae (1) to (4) may be contained in 1 kind alone, or may be contained in any combination of 2 or more kinds.
Figure BDA0002540973500000131
In the general formulae (1) to (4), X represents a hydrogen atom, a hydroxyl group, an alkyl group, a hydroxyalkyl group, an allyl group or a benzyl group. In addition, R 1 And R 2 Identical to or different from each other, represents a hydroxyl group, an alkyl group or a hydroxyalkyl group. In the general formulae (1) to (4), X and R are 1 And R 2 Examples of the alkyl group include linear or branched alkyl groups having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. In addition, as X and R 1 And R 2 Examples of the hydroxyalkyl group include a linear or branched alkyl group having 1 to 4 carbon atoms, which is substituted with 1 hydroxyl group, such as a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, or 4-hydroxybutyl group. In the general formulae (1) to (4), X and R 1 And R 2 The alkyl and hydroxyalkyl groups shown may be the same or different from each other. In the general formulae (1) to (4), X is preferably a hydrogen atom, a hydroxyl group or a hydroxyalkyl group. Examples of the number average molecular weight of aminated phenol polymers having repeating units represented by the general formulae (1) to (4)For example, about 500 to 100 ten thousand is preferable, and about 1000 to 2 ten thousand is more preferable.
As a chemical surface treatment method for imparting corrosion resistance to the barrier layer 3, there is a method in which a substance obtained by dispersing fine particles of barium sulfate or a metal oxide such as aluminum oxide, titanium oxide, cerium oxide, or tin oxide in phosphoric acid is applied, and baking treatment is performed at 150 ℃. Further, a resin layer obtained by crosslinking a cationic polymer with a crosslinking agent may be formed on the acid-resistant coating film. Among them, examples of the cationic polymer include polyethyleneimine, an ionic polymer complex comprising polyethyleneimine and a polymer having a carboxylic acid, a primary amine-grafted acrylic resin obtained by graft-polymerizing a primary amine onto an acrylic backbone, polyallylamine or a derivative thereof, and aminophenol. These cationic polymers may be used alone in 1 kind, or in combination with 2 or more kinds. Examples of the crosslinking agent include compounds having at least 1 functional group selected from the group consisting of an isocyanate group, a glycidyl group, a carboxyl group and an oxazoline group, and silane coupling agents. These crosslinking agents may be used alone in 1 kind, or may be used in combination with 2 or more kinds.
As a specific method for providing the acid-resistant coating, for example, a method in which at least the surface of the aluminum alloy foil on the inner layer side is degreased by a known treatment method such as an alkali immersion method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method, or an acid activation method, and then a treatment liquid (aqueous solution) containing a metal phosphate such as a chromium phosphate, a titanium phosphate, a zirconium phosphate, or a zinc phosphate and a metal salt thereof as a main component, or a treatment liquid (aqueous solution) containing a nonmetal phosphate and a mixture thereof as a main component, or a treatment liquid (aqueous solution) containing a mixture thereof with an aqueous synthetic resin such as an acrylic resin, a phenol resin, or a urethane resin is applied to the degreased surface by a known application method such as a roll coating method, a gravure printing method, or an immersion method, to form the acid-resistant coating is described. For example, in the case of treatment with a chromium phosphate treatment liquid, an acid-resistant coating film composed of chromium phosphate, aluminum oxide, aluminum hydroxide, aluminum fluoride, or the like is formed; when the treatment is performed with a zinc phosphate-based treatment liquid, an acid-resistant coating film composed of zinc phosphate hydrate, aluminum phosphate, alumina, aluminum hydroxide, aluminum fluoride, or the like is formed.
As another specific example of the method for forming the acid-resistant coating, for example, a known treatment method such as an alkali immersion method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method, or an acid activation method is used to degrease at least the surface of the aluminum alloy foil on the inner layer side, and then a known anodic oxidation treatment is performed on the degreased surface to form the acid-resistant coating.
As another example of the acid-resistant coating, a phosphate-based coating or a chromic acid-based coating may be mentioned. Examples of the phosphate system include zinc phosphate, iron phosphate, manganese phosphate, calcium phosphate, and chromium phosphate; examples of the chromic acid series include chromic chromate.
As another example of the acid-resistant coating, by forming an acid-resistant coating of phosphate, chromate, fluoride, triazine thiol compound, or the like, the following effects can be obtained: the method prevents delamination between aluminum and a base material layer during embossing, prevents dissolution and corrosion of the aluminum surface, particularly dissolution and corrosion of aluminum oxide present on the aluminum surface, due to hydrogen fluoride generated by reaction of an electrolyte with moisture, improves adhesion (wettability) of the aluminum surface, prevents delamination between the base material layer and aluminum during heat sealing, and prevents delamination between the base material layer and aluminum during press molding in the embossing type. Among the substances for forming the acid-resistant coating, it is preferable to apply an aqueous solution composed of three components, that is, a phenol resin, a chromium (III) fluoride compound, and phosphoric acid, to the aluminum surface, and then dry and bake the aluminum surface.
The acid-resistant coating film may include a layer containing cerium oxide, phosphoric acid or a phosphate, an anionic polymer, and a crosslinking agent for crosslinking the anionic polymer, and the phosphoric acid or the phosphate may be added in an amount of about 1 to 100 parts by mass based on 100 parts by mass of the cerium oxide. The acid-resistant coating film preferably has a multilayer structure further including a layer containing a cationic polymer and a crosslinking agent for crosslinking the cationic polymer.
The anionic polymer is preferably poly (meth) acrylic acid or a salt thereof, or a copolymer mainly composed of (meth) acrylic acid or a salt thereof. The crosslinking agent is preferably at least 1 selected from compounds having at least 1 functional group selected from an isocyanate group, a glycidyl group, a carboxyl group and an oxazoline group, and silane coupling agents.
The phosphoric acid or phosphate is preferably a condensed phosphoric acid or a condensed phosphate.
The chemical surface treatment may be performed by only 1 kind of chemical surface treatment, or may be performed by combining 2 or more kinds of chemical surface treatments. These chemical surface treatments may be carried out using 1 compound alone or 2 or more compounds in combination. Among the chemical surface treatments, chromate treatment, or chemical surface treatment combining a chromium compound, a phosphoric acid compound, and an aminated phenol polymer, and the like are preferable. Among the chromium compounds, a chromic acid compound is preferable.
Specific examples of the acid-resistant coating film include a coating film containing at least 1 of phosphate, chromate, fluoride, and triazine thiol. Further, an acid-resistant coating film containing a cerium compound is also preferable. As the cerium compound, cerium oxide is preferable.
Specific examples of the acid-resistant coating include a phosphate coating, a chromate coating, a fluoride coating, and a triazine thiol compound coating. The acid-resistant coating may be 1 of these or a combination of two or more. Further, as the acid-resistant film, a film formed by degreasing the chemical surface-treated surface of the aluminum alloy foil and then using a treatment liquid composed of a mixture of a metal phosphate and an aqueous synthetic resin or a treatment liquid composed of a mixture of a nonmetal salt of phosphoric acid and an aqueous synthetic resin may be used.
The composition analysis of the acid-resistant coating film can be performed, for example, by time-of-flight secondary ion mass spectrometry. By using time-of-flight type secondary ion mass spectrometryThe composition analysis of the acid-resistant coating film by the method can be detected from, for example, ce + And Cr + At least one peak of (1).
Preferably, the surface of the aluminum alloy foil is provided with an acid-resistant coating film containing at least 1 element selected from phosphorus, chromium and cerium. Among them, the acid-resistant coating film on the surface of the aluminum alloy foil of the battery packaging material contains at least 1 element selected from phosphorus, chromium and cerium, and can be confirmed by X-ray photoelectron spectroscopy. Specifically, first, in the battery packaging material, the heat-fusible resin layer, the adhesive layer, and the like laminated on the aluminum alloy foil are physically peeled off. Next, the aluminum alloy foil was placed in an electric furnace, and organic components present on the surface of the aluminum alloy foil were removed at about 300 ℃ for about 30 minutes. Then, it was confirmed that these elements were contained by using X-ray photoelectron spectroscopy on the surface of the aluminum alloy foil.
The amount of the acid-resistant coating film formed on the surface of the barrier layer 3 in the chemical surface treatment is not particularly limited, and for example, in the case of performing the chromate treatment described above, it is preferable that the amount of the acid-resistant coating film is 1m per one barrier layer 3 2 In the surface, the content of the chromium compound is about 0.5 to 50mg, preferably about 1.0 to 40mg, in terms of chromium, the content of the phosphorus compound is about 0.5 to 50mg, preferably about 1.0 to 40mg, in terms of phosphorus, and the content of the aminated phenol polymer is about 1 to 200mg, preferably about 5.0 to 150 mg.
The thickness of the acid-resistant coating is not particularly limited, but is preferably about 1nm to 10 μm, more preferably about 1 to 100nm, and still more preferably about 1 to 50nm, from the viewpoint of the aggregating power of the coating and the adhesion to the barrier layer 3 or the heat-sealing resin layer 4. The thickness of the acid-resistant coating film can be measured by a combination of observation with a transmission electron microscope or observation with a transmission electron microscope and energy-dispersive X-ray spectrometry or an electron energy loss spectrum.
The chemical surface treatment can be performed by applying a solution containing a compound for forming an acid-resistant coating film on the surface of the barrier layer by a bar coating method, a roll coating method, a gravure coating method, a dipping method, or the like, and then heating the barrier layer so that the temperature of the barrier layer becomes about 70 to 200 ℃. Before the barrier layer is subjected to the chemical surface treatment, the barrier layer may be subjected to degreasing treatment by an alkali immersion method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method, or the like. By performing the degreasing treatment in this manner, the chemical surface treatment of the surface of the barrier layer can be performed more efficiently.
[ Heat-fusible resin layer 4]
In the battery packaging material of the present invention, the heat-fusible resin layer 4 corresponds to the innermost layer, and is a layer in which the heat-fusible resin layers are heat-fused to each other at the time of assembling the battery to seal the battery element.
The resin component used for the heat-fusible resin layer 4 is not particularly limited as long as it can be heat-fused, and examples thereof include polyolefins, cyclic polyolefins, acid-modified polyolefins, and acid-modified cyclic polyolefins. That is, the resin constituting the heat-fusible resin layer 4 may or may not contain a polyolefin skeleton, and preferably contains a polyolefin skeleton. The resin containing the polyolefin skeleton constituting the heat-sealable resin layer 4 can be analyzed by, for example, infrared spectroscopy, gas chromatography mass spectrometry, or the like, and the analysis method is not particularly limited. For example, when the maleic anhydride-modified polyolefin is measured by infrared spectroscopy, the wavenumber is 1760cm -1 Neighborhood and wavenumber 1780cm -1 A peak derived from maleic anhydride was detected nearby. However, when the acid modification degree is low, the peak becomes small and may not be detected. In this case, the analysis can be performed by nuclear magnetic resonance spectroscopy.
Specific examples of the polyolefin include: polyethylene such as low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene; polypropylene such as homopolypropylene, a block copolymer of polypropylene (for example, a block copolymer of propylene and ethylene), a random copolymer of polypropylene (for example, a random copolymer of propylene and ethylene), and the like; ethylene-butene-propylene terpolymers, and the like. Among these polyolefins, polyethylene and polypropylene are preferably cited.
The cyclic polyolefin is a copolymer of an olefin and a cyclic monomer, and examples of the olefin which becomes a constituent monomer of the cyclic polyolefin include ethylene, propylene, 4-methyl-1-pentene, butadiene, isoprene, and the like. Examples of the cyclic monomer which constitutes the constituent monomer of the cyclic polyolefin include cyclic olefins such as norbornene; specific examples thereof include cyclic dienes such as cyclopentadiene, dicyclopentadiene, cyclohexadiene and norbornadiene. Among these polyolefins, cyclic olefins are preferred, and norbornene is more preferred.
The acid-modified polyolefin is a polymer obtained by modifying the polyolefin by block polymerization or graft polymerization using an acid component such as a carboxylic acid. Examples of the acid component used for modification include carboxylic acids such as maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, and itaconic anhydride, and anhydrides thereof.
The acid-modified cyclic polyolefin is a polymer obtained by copolymerizing an α, β -unsaturated carboxylic acid or an anhydride thereof instead of a part of monomers constituting the cyclic polyolefin, or by block polymerization or graft polymerization of an α, β -unsaturated carboxylic acid or an anhydride thereof and a cyclic polyolefin. The cyclic polyolefin modified with carboxylic acid is the same as described above. The carboxylic acid used for the modification is the same as the acid component used for the modification of the polyolefin.
Among these resin components, polyolefins such as polypropylene and carboxylic acid-modified polyolefins are preferred, and polypropylene and acid-modified polypropylene are more preferred.
The heat-fusible resin layer 4 may be formed of 1 resin component alone or a polymer blend in which 2 or more resin components are combined. The heat-fusible resin layer 4 may be formed of only 1 layer, or may be formed of 2 or more layers using the same or different resin components.
In the present invention, from the viewpoint of improving the moldability of the battery packaging material, it is preferable that a lubricant is adhered to the surface of the heat-sealable resin layer. The lubricant is not particularly limited, but preferably includes an amide-based lubricant. Specific examples of the amide-based lubricant include saturated fatty acid amides, unsaturated fatty acid amides, substituted amides, methylol amides, saturated fatty acid bisamides, and unsaturated fatty acid bisamides. Specific examples of the saturated fatty acid amide include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, and hydroxystearic acid amide. Specific examples of the unsaturated fatty acid amide include oleamide and erucamide. Specific examples of the substituted amide include N-oleyl palmitamide, N-stearyl stearamide, N-stearyl oleamide, N-oleyl stearamide, and N-stearyl erucamide. Specific examples of the methylolamide include methylolstearic acid amide. Specific examples of the saturated fatty acid bisamide include methylene bisstearamide, ethylene bisdecanoic acid amide, ethylene bislauric acid amide, ethylene bisstearamide, ethylene bishydroxystearic acid amide, ethylene bisbehenic acid amide, hexamethylene bisstearamide, hexamethylene bisbehenic acid amide, hexamethylene hydroxystearic acid amide, N '-distearyldiadipamide, N' -distearyldisebacamide, and the like. Specific examples of the unsaturated fatty acid bisamide include ethylene bisoleamide, ethylene biserucamide, hexamethylene bisoleamide, N '-dioleyl adipamide, N' -dioleyl sebacamide, and the like. Specific examples of the fatty acid ester amide include stearic acid amide ethyl stearate. Specific examples of the aromatic bisamide include m-xylylene bisstearamide, m-xylylene bishydroxystearamide, and N, N' -distearyl isophthalamide. The lubricant may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
When the lubricant is present on the surface of the heat-sealable resin layer 4, the amount of the lubricant is not particularly limited, but is preferably about 3mg/m in an environment of 24 ℃ and 60% relative humidity 2 More preferably 4 to 15mg/m 2 About, more preferably 5 to 14mg/m 2 Left and right.
The heat-fusible resin layer 4 may contain a lubricant. The lubricant present on the surface of the heat-fusible resin layer 4 may be one which is a lubricant contained in the resin constituting the heat-fusible resin layer 4 and which is exuded, or may be one which is applied to the surface of the heat-fusible resin layer 4.
The thickness of the heat-fusible resin layer 4 is not particularly limited as long as the function as a heat-fusible resin layer can be exhibited, but in the battery packaging material having the above-described configuration of the present invention, from the viewpoint of more effectively exhibiting excellent moldability and the effect of suppressing curling after molding, it is preferably 50 to 70 μm, 50 to 65 μm, 55 to 70 μm, 55 to 65 μm, 60 to 70 μm, or 60 to 65 μm.
From the viewpoint that even when the heat-fusible resin layers are heat-fused to each other in a state where the electrolyte solution contacts the heat-fusible resin layer and the electrolyte solution adheres to the heat-fusible resin layer in a high-temperature environment, a higher sealing strength can be exhibited by the heat fusion, the temperature difference T is measured by the following method 1 And temperature difference T 2 Time, temperature difference T 2 Divided by the temperature difference T 1 The obtained value (ratio T) 2 /T 1 ) For example, it is preferably 0.55 or more, more preferably 0.60 or more. According to the following temperature difference T 1 、T 2 As can be understood from the measurement contents of (A), the ratio T 2 /T 1 As the upper limit value is closer to 1.0, it is shown that the width change between the start point (extrapolated melting start temperature) and the end point (extrapolated melting end temperature) of the melting peak before and after the heat-fusible resin layer contacts the electrolyte is smaller (see the schematic diagram of fig. 11). I.e. T 2 Is usually at T 1 The value of (a) is as follows. As a factor that the change in the width of the extrapolated melting start temperature and extrapolated melting end temperature of the melting peak is increased, there is a case where a low-molecular-weight resin contained in the resin constituting the heat-sealable resin layer is eluted into the electrolyte by contacting the electrolyte, and the width of the extrapolated melting start temperature and extrapolated melting end temperature of the melting peak of the heat-sealable resin layer after contacting the electrolyte is smaller than that before contacting the electrolyte. As one of methods for reducing the width variation of the extrapolated melting start temperature and the extrapolated melting end temperature of the melting peak, a method of adjusting the ratio of a low-molecular-weight resin contained in a resin constituting the heat-sealable resin layer is cited.
(temperature difference T) 1 Measurement of (2)
According to JIS K7121:2012, a Differential Scanning Calorimetry (DSC) curve was obtained for the resin used for the heat-fusible resin layer of each of the above-mentioned battery packaging materials. From the obtained DSC curve, the temperature difference T between the extrapolated melting start temperature and the extrapolated melting end temperature of the melting peak temperature of the heat-sealable resin layer was measured 1 。
(temperature difference T) 2 Measurement of (2)
The resin used for the heat-fusible resin layer was allowed to stand for 72 hours in an electrolyte solution having a lithium hexafluorophosphate concentration of 1mol/l and a volume ratio of ethylene carbonate, diethyl carbonate and dimethyl carbonate of 1: 1 at a temperature of 85 ℃ and then sufficiently dried. Next, according to JIS K7121:2012, differential Scanning Calorimetry (DSC) was used to obtain a DSC curve for the polypropylene after drying. Then, the temperature difference T between the extrapolated melting start temperature and the extrapolated melting end temperature of the melting peak temperature of the heat-fusible resin layer after drying was measured from the obtained DSC curve 2 。
In the measurement of the extrapolated melting start temperature and the extrapolated melting end temperature of the melting peak temperature, a commercially available product was used as a differential scanning calorimeter. In addition, as a DSC curve, a DSC curve obtained by holding a test sample at-50 ℃ for 10 minutes, raising the temperature to 200 ℃ at a rate of 10 ℃/minute (1 st), holding the temperature at 200 ℃ for 10 minutes, lowering the temperature to-50 ℃ at a rate of-10 ℃/minute, holding the temperature at-50 ℃ for 10 minutes, raising the temperature to 200 ℃ at a rate of 10 ℃/minute (2 nd), holding the temperature at 200 ℃ for 10 minutes, and raising the temperature to 200 ℃ at 2 nd was used. In addition, the temperature difference T is measured 1 And temperature difference T 2 In each DSC curve, the melting peak having the largest difference in input of thermal energy among melting peaks appearing in the range of 120 to 160 ℃ is analyzed. When there are 2 or more peaks overlapping, only the melting peak having the largest difference in thermal energy input is analyzed.
The extrapolated melting start temperature represents the starting point of the melting peak temperature, and is the temperature of the intersection point between a straight line extending from the base line on the low temperature side (65 to 75 ℃) to the high temperature side and a tangent line drawn at the point where the gradient is the largest on the curve on the low temperature side of the melting peak where the difference in thermal energy input is the largest. The extrapolated melting end temperature represents the end point of the melting peak temperature, and is the temperature of the intersection point of a straight line extending from the base line on the high temperature side (170 ℃) to the low temperature side and a tangent line drawn at the point where the slope is the largest on the curve on the high temperature side of the melting peak where the difference in thermal energy input is the largest.
In the battery packaging material of the present invention, the temperature difference T is set so that even when the heat-fusible resin layers are heat-fused to each other in a state where the electrolyte solution contacts the heat-fusible resin layer and the electrolyte solution adheres to the heat-fusible resin layer in a high-temperature environment, a higher sealing strength can be exhibited by the heat fusion 2 Divided by the temperature difference T 1 And the obtained value (ratio T) 2 /T 1 ) Examples thereof include 0.55 or more, preferably 0.60 or more, more preferably 0.70 or more, and further preferably 0.75 or more, and preferable ranges include about 0.55 to 1.0, about 0.60 to 1.0, about 0.70 to 1.0, and about 0.75 to 1.0. The upper limit is, for example, 1.0. In addition, in order to set the ratio T 2 /T 1 For example, the kind, composition, molecular weight, and the like of the resin constituting the heat-fusible resin layer 4 are adjusted.
In addition, the temperature difference T is a temperature difference that can be used to develop a higher sealing strength by heat welding even when the heat-fusible resin layers are heat-welded to each other in a state where the electrolyte solution is in contact with the heat-fusible resin layer or the electrolyte solution adheres to the heat-fusible resin layer in a high-temperature environment 2 Difference T from temperature 1 Absolute value of the difference | T 2 －T 1 Examples of the preferable ranges include about 0 to about 15 ℃, about 0 to about 10 ℃, about 0 to about 8 ℃, about 0 to about 7.5 ℃, about 1 to about 15 ℃, about 1 to about 10 ℃, about 1 to about 8 ℃, about 2 to about 7.5 ℃, about 5 to about 15 ℃, about 5 to about 10 ℃, about 5 to about 8 ℃ and about 5 to about 7.5 ℃. Wherein, the differenceAbsolute value | T 2 －T 1 The lower limit of |, for example, is 0 ℃,1 ℃,2 ℃, 5 ℃ or the like. In order to set the absolute value | T of the difference 2 －T 1 For example, the kind, composition, molecular weight, and the like of the resin constituting the heat-fusible resin layer 4 are adjusted.
In addition, as the temperature difference T 1 Preferably about 29 to 38 ℃ and more preferably about 32 to 36 ℃. As a temperature difference T 2 Preferably about 17 to 30 ℃ and more preferably about 26 to 29 ℃. In addition, to set such T 1 、T 2 For example, the kind, composition, molecular weight, and the like of the resin constituting the heat-fusible resin layer 4 are adjusted.
In the battery packaging material of the present invention, the logarithmic decrement Δ E at 120 ℃ in rigid body pendulum measurement of the surface on the barrier layer 3 side of the heat-fusible resin layer 4 (the layer present on the side closest to the barrier layer 3 when the heat-fusible resin layer 4 is composed of a plurality of layers) is preferably 0.50 or less, 0.40 or less, 0.30 or less, 0.22 or less, and more preferably 0.20 or less. In the present invention, the logarithmic decrement Δ E at 120 ℃ is, for example, 0.50 or less, 0.40 or less, 0.30 or less, 0.22 or less, and further 0.20 or less, whereby curling after molding of the battery packaging material can be effectively suppressed. When the logarithmic decrement at 120 ℃ is low, it can be said that the rigidity of the resin constituting the heat-fusible resin layer 4 is improved. That is, when the logarithmic decrement Δ E at 120 ℃ of the surface of the heat-sealable resin layer 4 on the side of the barrier layer 3 is as low as, for example, 0.50 or less, 0.40 or less, 0.30 or less, 0.22 or less, and further 0.20 or less, when the base material layer shrinks during molding of the battery packaging material, the heat-sealable resin layer 4 can increase the resistance to shrinkage of the entire laminate, and as a result, it is considered that the post-molding curl of the battery packaging material can be effectively suppressed.
The logarithmic decrement at 120 ℃ in the rigid pendulum measurement is an index indicating the hardness of the resin in a high-temperature environment of 120 ℃, and a smaller logarithmic decrement indicates a higher hardness of the resin. In the rigid pendulum measurement, the rate of attenuation of the pendulum when the temperature of the resin rises from low temperature to high temperature is measured. In rigid body pendulum measurement, a surface of a measurement object is usually brought into contact with a ridge portion, and a pendulum bob is swung in the left-right direction to apply vibration to the measurement object. In the battery packaging material of the present invention, the hard heat-fusible resin layer 4 having a logarithmic decrement of, for example, 0.50 or less, 0.40 or less, 0.30 or less, 0.22 or less, and further 0.20 or less in a high-temperature environment of 120 ℃ is disposed on the barrier layer 3 side, whereby curling after molding of the battery packaging material can be effectively suppressed.
The logarithmic decrement Δ E is calculated by the following equation.
ΔE＝[ln(A1/A2)+ln(A2/A3)+···ln(An/An+1)]/n
A: amplitude of vibration
n: wave number
In the battery packaging material of the present invention, from the viewpoint of more effectively suppressing curling after molding, the logarithmic decrement Δ E at 120 ℃ may be, for example, about 0.10 to 0.50, about 0.10 to 0.40, about 0.10 to 0.30, about 0.10 to 0.22, about 0.10 to 0.20, or about 0.10 to 0.16. In order to set the logarithmic decrement Δ E, for example, the kind, composition, molecular weight, and the like of the resin constituting the heat-fusible resin layer 4 (the layer located closest to the barrier layer 3 when the heat-fusible resin layer 4 is formed of a plurality of layers) are adjusted.
In the measurement of the logarithmic decrement Δ E, a rigid body pendulum physical property test was performed on the heat-fusible resin layer 4 at a temperature range of 30 ℃ to 200 ℃ at a temperature rise rate of 3 ℃/min using a commercially available rigid body pendulum physical property tester, using a cylindrical rib as a rib portion to be brought into contact with the heat-fusible resin layer 4, with an initial amplitude of 0.3 ℃. In addition, the heat-fusible resin layer 4 for measuring the logarithmic decrement Δ E was subjected to measurement by immersing the battery packaging material in 15% hydrochloric acid to dissolve the base layer and the barrier layer, and sufficiently drying only the sample of the heat-fusible resin layer.
Further, the battery packaging material may be obtained from a battery, and the logarithmic decrement Δ E of the heat-fusible resin layer 4 may be measured. When the logarithmic decrement Δ E of the heat-fusible resin layer 4 is measured from the battery-packaging material obtained from the battery, a sample is cut from the top surface portion of the battery-packaging material which is not stretched by molding, and the sample is set as a measurement target.
The logarithmic decrement Δ E of the heat-fusible resin layer 4 can be adjusted by adjusting, for example, the Melt Flow Rate (MFR), the molecular weight, the melting point, the softening point, the molecular weight distribution, the crystallinity, and the like of the resin constituting the heat-fusible resin layer 4.
[ adhesive layer 5]
In the battery packaging material of the present invention, the adhesive layer 5 is a layer provided between the barrier layer 3 and the heat-fusible resin layer 4 as needed to firmly adhere them.
The adhesive layer 5 is formed of a resin capable of bonding the barrier layer 3 and the heat-fusible resin layer 4. As the resin used for forming the adhesive layer 5, the same adhesive as exemplified in the adhesive layer 2 can be used, such as the adhesion mechanism and the type of the adhesive component. As the resin used for forming the adhesive layer 5, polyolefin-based resins such as polyolefin, cyclic polyolefin, carboxylic acid-modified polyolefin, and carboxylic acid-modified cyclic polyolefin exemplified in the above-described heat-sealable resin layer 4 can be used. The polyolefin is preferably a carboxylic acid-modified polyolefin, and particularly preferably a carboxylic acid-modified polypropylene, from the viewpoint of excellent adhesion between the barrier layer 3 and the heat-fusible resin layer 4. That is, the resin constituting the adhesive layer 5 may or may not contain a polyolefin skeleton, and preferably contains a polyolefin skeleton. The resin constituting the adhesive layer 5 containing a polyolefin skeleton can be analyzed by, for example, infrared spectroscopy, gas chromatography mass spectrometry, or the like, and the analyzing method is not particularly limited. For example, when the maleic anhydride-modified polyolefin is measured by infrared spectroscopy, the wavenumber is 1760cm -1 Neighborhood and wavenumber 1780cm -1 A peak derived from maleic anhydride was detected nearby. However, when the acid modification degree is low, the peak becomes small and may not be detected. In this case, the analysis can be performed by nuclear magnetic resonance spectroscopy.
In addition, the adhesive layer 5 may be a cured product of a resin composition containing an acid-modified polyolefin and a curing agent, from the viewpoint of reducing the thickness of the battery packaging material and producing a battery packaging material having excellent shape stability after molding. The acid-modified polyolefin is preferably the same as the carboxylic acid-modified polyolefin and the carboxylic acid-modified cyclic polyolefin exemplified in the heat-sealable resin layer 4.
The curing agent is not particularly limited as long as it can cure the acid-modified polyolefin. Examples of the curing agent include epoxy curing agents, polyfunctional isocyanate curing agents, carbodiimide curing agents, and oxazoline curing agents.
The epoxy curing agent is not particularly limited as long as it is a compound having at least 1 epoxy group. Examples of the epoxy curing agent include epoxy resins such as bisphenol a diglycidyl ether, modified bisphenol a diglycidyl ether, novolac glycidyl ether, glycerol polyglycidyl ether, and polyglycerol polyglycidyl ether.
The polyfunctional isocyanate curing agent is not particularly limited as long as it is a compound having 2 or more isocyanate groups. Specific examples of the polyfunctional isocyanate-based curing agent include isophorone diisocyanate (IPDI), hexamethylene Diisocyanate (HDI), toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), a product obtained by polymerizing or urethanizing these, a mixture of these, and a copolymer with another polymer.
The carbodiimide-based curing agent is not particularly limited as long as it is a compound having at least 1 carbodiimide group (-N = C = N-). The carbodiimide-based curing agent is preferably a polycarbodiimide compound having at least 2 or more carbodiimide groups.
The oxazoline curing agent is not particularly limited as long as it is a compound having an oxazoline skeleton. Specific examples of the oxazoline-based curing agent include EPOCROS series produced by Nippon catalyst Co.
The curing agent may be composed of 2 or more compounds from the viewpoint of improving the adhesion between the barrier layer 3 and the heat-fusible resin layer 4 by the adhesive layer 5.
The content of the curing agent in the resin composition for forming the adhesive layer 5 is preferably about 0.1 to 50 mass%, more preferably about 0.1 to 30 mass%, and still more preferably about 0.1 to 10 mass%.
The thickness of the adhesive layer 5 is not particularly limited as long as it can function as an adhesive layer, but when the adhesive exemplified in the adhesive layer 2 is used, it is preferably about 1 to 10 μm, more preferably about 1 to 5 μm. When the resin exemplified in the heat-fusible resin layer 4 is used, it is preferably about 2 to 50 μm, more preferably about 10 to 40 μm. In the case of a cured product of an acid-modified polyolefin and a curing agent, the thickness is preferably about 30 μm or less, more preferably about 0.1 to 20 μm, and still more preferably about 0.5 to 5 μm. When the adhesive layer 5 is a cured product of a resin composition containing an acid-modified polyolefin and a curing agent, the adhesive layer 5 can be formed by applying the resin composition and curing the resin composition by heating or the like.
[ surface coating layer 6]
In the battery packaging material of the present invention, the surface coating layer 6 may be provided on the substrate layer 1 (on the side of the substrate layer 1 opposite to the barrier layer 3) as necessary in order to improve design properties, electrolyte resistance, scratch resistance, moldability, and the like. The surface coating layer 6 is a layer located at the outermost layer when the battery is assembled.
The surface coating layer 6 may be formed of, for example, polyvinylidene chloride, polyester resin, polyurethane resin, acrylic resin, epoxy resin, or the like. Of these, the surface coating layer 6 is preferably formed of a two-liquid curable resin. Examples of the two-component curable resin for forming the surface coating layer 6 include two-component curable polyurethane resins, two-component curable polyester resins, and two-component curable epoxy resins. The surface coating layer 6 may contain an additive.
Examples of the additive include fine particles having a particle diameter of about 0.5nm to 5 μm. The material of the additive is not particularly limited, and examples thereof include metals, metal oxides, inorganic substances, and organic substances. The shape of the additive is not particularly limited, and examples thereof include spherical, fibrous, plate-like, amorphous, and hollow spherical shapes. Specific examples of the additive include talc, silica, graphite, kaolin, montmorillonite, synthetic mica, hydrotalcite, silica gel, zeolite, aluminum hydroxide, magnesium hydroxide, zinc oxide, magnesium oxide, aluminum oxide, neodymium oxide, antimony oxide, titanium oxide, cerium oxide, calcium sulfate, barium sulfate, calcium carbonate, calcium silicate, lithium carbonate, calcium benzoate, calcium oxalate, magnesium stearate, aluminum oxide, carbon black, carbon nanotubes, high-melting nylon, crosslinked acrylic acid, crosslinked styrene, crosslinked polyethylene, benzoguanamine, gold, aluminum, copper, nickel, and the like. These additives may be used alone in 1 kind, or may be used in combination of 2 or more kinds. Among these additives, silica, barium sulfate, and titanium oxide are preferable from the viewpoints of dispersion stability, cost, and the like. The additive may be subjected to various surface treatments such as an insulating treatment and a high-dispersibility treatment on the surface.
The content of the additive in the surface coating layer is not particularly limited, but is preferably about 0.05 to 1.0 mass%, more preferably about 0.1 to 0.5 mass%.
The method for forming the surface coating layer 6 is not particularly limited, and for example, a method of applying a two-liquid curable resin for forming the surface coating layer 6 to one surface of the base material layer 1 may be mentioned. When the additive is blended, the additive may be added to the two-liquid curable resin and mixed and then applied.
The thickness of the surface coating layer 6 is not particularly limited as long as the above function as the surface coating layer 6 can be exerted, and may be, for example, about 0.5 to 10 μm, preferably about 1 to 5 μm.
3. Method for producing battery packaging material
The method for producing the battery packaging material of the present invention is not particularly limited as long as a laminate in which layers having a predetermined composition are laminated can be obtained. That is, the method for producing a battery packaging material of the present invention includes a step of laminating at least a substrate layer 1, a barrier layer 3, and a heat-sealable resin layer 4 in this order to obtain a laminate.
An example of the method for producing the battery packaging material of the present invention is as follows. First, a laminate (hereinafter, sometimes referred to as "laminate a") in which a base material layer 1, an adhesive layer 2, and a barrier layer 3 are laminated in this order is formed. The formation of the laminate a can be specifically performed by a dry lamination method as follows: an adhesive for forming the adhesive layer 2 is applied and dried on the substrate layer 1 or the barrier layer 3 whose surface is chemically treated as necessary by a coating method such as a gravure coating method or a roll coating method, and then the barrier layer 3 or the substrate layer 1 is laminated and the adhesive layer 2 is cured.
Next, the adhesive layer 5 and the heat-fusible resin layer 4 are sequentially laminated on the barrier layer 3 of the laminate a. Examples of the lamination method include: (1) A method of laminating the adhesive layer 5 and the heat-fusible resin layer 4 by co-extrusion on the barrier layer 3 of the laminate a (co-extrusion lamination method); (2) A method of separately forming a laminate in which the adhesive layer 5 and the heat-fusible resin layer 4 are laminated, and laminating the laminate on the barrier layer 3 of the laminate A by a heat lamination method; (3) A method of laminating the barrier layer 3 of the laminate a by extrusion or solution coating of an adhesive agent for forming the adhesive layer 5, drying and baking at a high temperature, and laminating the heat-fusible resin layer 4 previously formed into a sheet shape on the adhesive layer 5 by a heat lamination method; (4) A method (interlayer lamination method) in which the laminate a and the heat-fusible resin layer 4 are bonded to each other by the adhesive layer 5 while the molten adhesive layer 5 is poured between the barrier layer 3 of the laminate a and the heat-fusible resin layer 4 formed in a sheet shape in advance.
When the surface coating layer 6 is provided, the surface coating layer 6 is laminated on the surface of the substrate layer 1 opposite to the barrier layer 3. The surface coating layer 6 can be formed by, for example, applying the resin forming the surface coating layer 6 to the surface of the base material layer 1. The order of the step of laminating the barrier layer 3 on the surface of the base material layer 1 and the step of laminating the surface coating layer 6 on the surface of the base material layer 1 is not particularly limited. For example, after the surface coating layer 6 is formed on the surface of the base material layer 1, the barrier layer 3 may be formed on the surface of the base material layer 1 opposite to the surface coating layer 6.
As described above, the laminate comprising the surface coating layer 6 provided as needed, the base material layer 1, the adhesive layer 2 provided as needed, the barrier layer 3 whose surface is subjected to a chemical surface treatment as needed, the adhesive layer 5 provided as needed, and the heat-fusible resin layer 4 may be further subjected to a heat treatment such as a heat roller contact type, a hot air type, a near infrared type, or a far infrared type in order to enhance the adhesiveness of the adhesive layer 2 or the adhesive layer 5. Examples of the conditions for such heat treatment include heat treatment at 150 to 250 ℃ for 1 to 5 minutes.
In the battery packaging material of the present invention, each layer constituting the laminate may be subjected to surface activation treatment such as corona discharge treatment, sand blast treatment, oxidation treatment, ozone treatment, and the like, as necessary, for the purpose of improving or stabilizing the suitability for film formation, lamination, 2-pass processing (bagging, embossing) of the final product, and the like.
4. Use of a packaging material for batteries
The battery packaging material of the present invention can be used in a package for sealing and housing battery elements such as a positive electrode, a negative electrode, and an electrolyte. That is, a battery can be produced by housing a battery element including at least a positive electrode, a negative electrode, and an electrolyte in a package formed of the battery packaging material of the present invention.
Specifically, the battery packaging material of the present invention is capable of providing a battery using the battery packaging material by covering a battery element including at least a positive electrode, a negative electrode, and an electrolyte so that flange portions (regions where heat-fusible resin layers are in contact with each other) can be formed at the peripheral edge of the battery element in a state where metal terminals connected to the positive electrode and the negative electrode, respectively, protrude outward, and sealing the heat-fusible resin layers of the flange portions by heat-sealing the heat-fusible resin layers to each other. When a battery element is housed in a package formed of the battery packaging material of the present invention, the package is formed such that the heat-fusible resin portion of the battery packaging material of the present invention is on the inside (the surface in contact with the battery element).
The battery packaging material of the present invention can be used for either a primary battery or a secondary battery, and is preferably a secondary battery. The type of secondary battery to which the battery packaging material of the present invention is applied is not particularly limited, and examples thereof include lithium ion batteries, lithium ion polymer batteries, lead storage batteries, nickel-hydrogen storage batteries, nickel-cadmium storage batteries, nickel-iron storage batteries, nickel-zinc storage batteries, silver oxide-zinc storage batteries, metal air batteries, polyvalent cation batteries, capacitors (condensers), and the like. Among these secondary batteries, lithium ion batteries and lithium ion polymer batteries are suitable as an application target of the battery packaging material of the present invention.
The battery packaging material of the present invention has excellent moldability, and can effectively suppress curling after molding, and is therefore suitable for use in large batteries such as vehicle batteries. The battery to which the battery packaging material of the present invention is particularly suitably applied includes a large battery having a battery capacity of 30Ah or more.
Examples
The present invention will be described in detail below by way of examples and comparative examples. However, the present invention is not limited to the examples.
< production of packaging Material for Battery >
Examples 1 to 28 and comparative examples 1 to 150
As the substrate layer, a polyethylene terephthalate (PET) film, a stretched nylon (ONy) film, and a laminate film in which polyethylene terephthalate (PET) and stretched nylon (ONy) were bonded with a two-pack type polyurethane adhesive (a polyol compound and an aromatic isocyanate compound) having a thickness of 3 μm were prepared. The thicknesses of PET and ONy are shown in tables 1 to 7, respectively. In tables 2 to 7, the thickness is represented as "0" when PET or ONy is not provided. When a laminated film of PET and ONy is used as the base layer, ONy is disposed on the barrier layer side.
Further, as barrier layers, aluminum foils (JIS H4160:1994A 8021H-O) having the thicknesses shown in tables 1 to 7 were prepared, respectively. Then, a two-pack type polyurethane adhesive (a polyol compound and an aromatic isocyanate compound) was applied to one surface of the aluminum foil,an adhesive layer (thickness: 3 μm) was formed on the barrier layer. Next, the adhesive layer on the barrier layer and the base layer are laminated by a dry lamination method, and then subjected to a curing treatment to produce a laminate of base layer/adhesive layer/barrier layer. The aluminum foil is subjected to chemical surface treatment on both sides. Chemical surface treatment of aluminum foil by coating a treatment liquid composed of a phenol resin, a chromium fluoride compound and phosphoric acid on both side surfaces of the aluminum foil by a roll coating method so that the amount of chromium coating reaches 10mg/m 2 (drying quality) and baking.
Next, on each of the laminated layers obtained above, as a heat-fusible resin layer, maleic anhydride-modified polypropylene and polypropylene were melt-coextruded at the same thickness to have the thickness described in tables 1 to 7, and the heat-fusible resin layer was laminated on the barrier layer to obtain a battery packaging material in which a base layer/an adhesive layer/a barrier layer/a heat-fusible resin layer were laminated in this order. Wherein erucamide as a lubricant was applied to the surface of each laminate on the base layer side in an atmosphere of 24 ℃ and 60% relative humidity so that the amount of erucamide present was 7.0mg/m 2 。
< measurement of puncture resistance of laminate >
Each of the battery packaging materials obtained above was measured by a method according to JIS Z1707:1997, the puncture resistance was measured. The piercing is performed from the substrate layer side. Specifically, in a measuring environment of 23. + -. 2 ℃ and relative humidity (50. + -.5)%, a test piece was fixed by a table having an opening of 15mm in diameter at the center and a pressing plate and having a diameter of 115mm, and a semicircular needle having a diameter of 1.0mm and a tip with a radius of 0.5mm was pierced at a rate of 50. + -.5 mm per minute to measure the maximum stress until the needle was pierced. The number of test pieces was 5, and the average value was obtained. As the measurement device for puncture resistance, ZP-50N (force sensor) and MX2-500N (measurement holder) manufactured by IMADA co. The results are shown in tables 1 to 7.
< measurement of ultimate Forming depth >
Each of the battery packaging materials obtained above was cut into a rectangular shape having a length (z direction) of 150mm × a width (x direction) of 100mm, and used as a test sample. The test samples were cold-formed (drawn into 1 stage) by changing the forming depth in units of 0.5mm from the forming depth of 0.5mm at a pressing pressure (surface pressure) of 0.23MPa (surface pressure) using a forming die (female die, JIS B0659-1 (reference) of the surface) having a rectangular caliber of 31.6mm (x direction) × 54.5mm (z direction) and a surface roughness standard sheet specified in table 2, the maximum height roughness (nominal value of Rz) being 3.2 μm, the corner R being 2.3, and the ridge line R being 1), and a forming die (male die, JIS B0659-1 (reference) of the surface. At this time, the test sample was placed on a female mold so that the side of the heat-fusible resin layer was positioned on the side of the male mold, and was molded. Further, the distance between the male die and the female die was set to 0.3mm. For the cold-formed sample, a small flashlight was used to irradiate light in a dark room, and the presence of pinholes or cracks in the barrier layer was confirmed by light projection. The deepest molding depth at which no pin hole or crack occurred in the barrier layer was defined as am for all 10 samples, the number of samples in which pin holes or the like occurred at the shallowest molding depth of pin holes or the like in the barrier layer was defined as B, and the value calculated from the following equation was defined as the limit molding depth of the battery packaging material. The results are shown in tables 1 to 7.
Ultimate forming depth = Amm + (0.5 mm/10) × (10-B)
< measurement of Forming crimp >
Each of the battery packaging materials obtained above was cut into a rectangular shape having a length (z direction) of 200mm × a width (x direction) of 100mm, and used as a test sample. Next, using a molding die used for moldability evaluation, a test sample was placed on a female die so that the side of the heat-fusible resin layer was positioned on the side of the male die, and cold molding was performed (pull-in 1-stage molding) by pressing the test sample at a pressing pressure (surface pressure) of 0.23MPa so that the molding depth of the test sample became 6mm. At this time, the molding was stopped in a state where pinholes or cracks were formed in the barrier layer for the sample having a molding depth of less than 6.0 mm. The details of the position where the molding is performed are shown in fig. 5. As shown in fig. 5, the molding is performed at a position where the shortest distance d =122mm from the end P of the battery packaging material 10 and the shortest distance from both ends of the battery packaging material reaches 34mm in a rectangular molding portion M in a plan view. The maximum height (formed curl (mm)) of the curled portion is determined by taking the position Q of the portion of the battery packaging material where no recess is formed as a reference and the maximum value t of the distance from the position Q to the end P in the vertical direction y. In tables 1 to 7, when the direction of the forming curl is the same as the direction of the concave portion (vertical direction y 1) (the shape of fig. 6), the forming curl t is expressed as a positive value; when the direction of the forming curl and the direction of the concave portion are opposite directions (vertical direction y 2) (the shape of fig. 7), the forming curl t is written as a negative value. For example, in example 1 of table 1, as shown in fig. 6, the direction of the forming curl is the same as the direction of the concave portion (vertical direction y 1), and the forming curl t is 6mm. In contrast, in comparative example 1, as shown in FIG. 7, the direction of the forming curl and the direction of the concave portion were opposite to each other (vertical direction y 2), and the forming curl t was-115 mm. When the direction of the forming curl and the direction of the concave portion are opposite directions (vertical direction y 2) (the shape of fig. 7), even if the absolute value of the forming curl t is 0 to 10mm, the sealing position is likely to be displaced or wrinkles are likely to occur after sealing in the step of housing the formed battery element and heat-sealing the peripheral portion. The results are shown in tables 1 to 7.
[ Table 1]
Figure BDA0002540973500000301
[ Table 2]
Figure BDA0002540973500000311
[ Table 3]
Figure BDA0002540973500000321
[ Table 4]
Figure BDA0002540973500000331
[ Table 5]
Figure BDA0002540973500000341
[ Table 6]
Figure BDA0002540973500000351
[ Table 7]
Figure BDA0002540973500000361
From the results shown in tables 1 to 7, it is understood that the battery packaging materials of examples 1 to 28, in which the total thickness of the laminate constituting the battery packaging material was 195 μm or less, the puncture strength was 30N or more, and the thickness of the barrier layer was in the specific range of 75 to 85 μm, had the limit molding depth as deep as 10mm or more, and the molding curl was also 10mm or less, and it was found that the moldability was excellent and the molding curl could be effectively suppressed. On the other hand, in comparative examples 1 to 150 which do not satisfy these conditions, it is found that excellent moldability, effective suppression of molding curl, and improvement in the volumetric energy density of the battery are not achieved in any of the cases where the ultimate molding depth is less than 10mm, the molding curl exceeds 10mm, and the thickness of the battery packaging material exceeds 195 μm.
< measurement of logarithmic decrement Δ E of surface on barrier layer side of Heat-sealable resin layer >
The battery packaging materials of examples 14 and 28 obtained as described above were cut into a rectangular shape having a width (TD: transverse Direction) of 15mm and a length (MD: machine Direction) of 150mm, and the rectangular shape was used as a test sample (battery packaging material 10). The MD of the battery packaging material corresponds to the Rolling Direction (RD) of the aluminum alloy foil, the TD of the battery packaging material corresponds to the TD of the aluminum alloy foil, and the Rolling Direction (RD) of the aluminum alloy foil can be distinguished by rolling marks. When the MD of the battery packaging material cannot be determined by the rolling mark of the aluminum alloy foil, it can be determined by the following method. As a method for confirming MD of the battery packaging material, a cross section of the heat-fusible resin layer of the battery packaging material was observed with an electron microscope to confirm the sea-island structure, and a direction parallel to the cross section in which the average value of the diameters of the island shapes in a direction perpendicular to the thickness direction of the heat-fusible resin layer was the largest was determined as MD. Specifically, the sea-island structure was confirmed by observing each of a cross section in the longitudinal direction of the heat-fusible resin layer and cross sections (10 cross sections in total) from the direction parallel to the cross section in the longitudinal direction to the direction perpendicular to the cross section in the longitudinal direction at an angle of 10 degrees. Next, the shape of each island was observed for each cross section. The diameter y is a straight line distance connecting the leftmost end in the direction perpendicular to the thickness direction of the heat-fusible resin layer and the rightmost end in the perpendicular direction, for each island shape. On each cross section, the average value of the first 20 diameters y when the diameters y of the island shapes are arranged in descending order is calculated. The direction parallel to the cross section where the average value of the diameter y of the island shape is the largest is determined as MD. Fig. 9 is a schematic diagram for explaining a method of measuring the logarithmic decrement Δ E by rigid body pendulum measurement. A rigid pendulum type physical testing machine (model: manufactured by RPT-3000W, inc.; A & D) was used, FRB-100 was used as a holder for the pendulum 30, RBP-060 was used as a cylindrical column edge 30a of a supporting edge portion, CHB-100 was used as a cooling/heating block 31, and a vibration displacement detector 32 and a hammer 33 were used to set an initial amplitude of 0.3 degrees. The test sample was placed on the cold/hot block 31 with its measurement surface (heat-fusible resin layer (acid-modified polypropylene)) facing upward, and the axial direction of the cylindrical ridge 30a with the pendulum 30 was set so as to be orthogonal to the MD direction of the test sample on the measurement surface. In order to prevent the test sample from floating or warping during measurement, an adhesive tape is attached to a portion of the test sample that does not affect the measurement result and is fixed to the cold/hot block 31. The cylindrical ribs are brought into contact with the surface of the heat-fusible resin layer. Next, the logarithmic decrement Δ E of the heat-fusible resin layer was measured at a temperature range of 30 ℃ to 200 ℃ at a temperature rise rate of 3 ℃/min using the cooling/heating module 31. The logarithmic decrement Δ E of the state in which the surface temperature of the heat-fusible resin layer of the test sample (the battery packaging material 10) reached 120 ℃. (the test samples that have been measured once are not used again, and newly cut samples are used, and 3 times (N = 3) are measured using the average value) for the heat-sealable resin layer, the battery packaging materials of examples 14 and 28 obtained above are immersed in 15% hydrochloric acid to dissolve the base layer and the aluminum foil, and the test samples having only the heat-sealable resin layer are sufficiently dried to measure the logarithmic decrement Δ E. The logarithmic decrement Δ E at 120 ℃ is shown in Table 8. (wherein, the logarithmic decrement Δ E is calculated by the following equation.
ΔE＝[ln(A1/A2)+ln(A2/A3)+...+ln(An/An+1)]/n
A: amplitude of vibration
n: wave number
[ Table 8]
Figure BDA0002540973500000381
From the results shown in tables 1 and 8, it was found that the logarithmic decrement Δ E at 120 ℃ in the rigid body pendulum measurement of the surfaces of the aluminum alloy foil layer and the heat-fusible resin layer on the barrier layer side in the battery packaging materials of examples 14 and 28 was 0.50 or less, and the mold curl was effectively suppressed. It is understood that the logarithmic decrement Δ E of the battery packaging material of example 28 is further 0.20 or less, and the curl after molding is particularly effectively suppressed.
< measurement of extrapolated melting Start temperature and extrapolated melting end temperature of melting Peak temperature >
With respect to the polypropylene used for the heat-sealable resin layers of the battery packaging materials of examples 14 and 28, the extrapolated melting start temperature and extrapolated melting end temperature of the melting peak temperature were measured, and the temperature difference T between the extrapolated melting start temperature and the extrapolated melting end temperature was measured by the following method 1 、T 2 According to the resulting temperature difference T 1 、T 2 To calculate the values of (a) and (b)Ratio of (T) 2 /T 1 ) And absolute value of the difference | T 2 －T 1 L. The results are shown in Table 9.
(temperature difference T) 1 Measurement of (2)
According to JIS K7121:2012, a Differential Scanning Calorimetry (DSC) curve was obtained for the polypropylene used for the heat-sealable resin layers of the battery packaging materials of examples 14 and 28. From the obtained DSC curve, the temperature difference T between the extrapolated melting start temperature and the extrapolated melting end temperature of the melting peak temperature of the heat-sealable resin layer was measured 1 。
(temperature difference T) 2 Measurement of (2)
The polypropylene used for the heat-fusible resin layer was allowed to stand for 72 hours in an electrolyte solution having a lithium hexafluorophosphate concentration of 1mol/l and a volume ratio of ethylene carbonate, diethyl carbonate and dimethyl carbonate of 1: 1 at a temperature of 85 ℃ and then sufficiently dried. Next, according to JIS K7121:2012, differential Scanning Calorimetry (DSC) was used to obtain a DSC curve for the polypropylene after drying. Then, the temperature difference T between the extrapolated melting start temperature and the extrapolated melting end temperature of the melting peak temperature of the heat-fusible resin layer after drying was measured from the obtained DSC curve 2 。
In the measurement of the extrapolated melting start temperature and extrapolated melting end temperature of the melting peak temperature, Q200 manufactured by TA Instruments was used as a differential scanning calorimetry analyzer. As the DSC curve, the DSC curve was used in which the test sample was kept at-50 ℃ for 10 minutes, then heated at a heating rate of 10 ℃/min to 200 ℃ (1 st time), kept at 200 ℃ for 10 minutes, then cooled at a cooling rate of-10 ℃/min to-50 ℃, kept at-50 ℃ for 10 minutes, then heated at a heating rate of 10 ℃/min to 200 ℃ (2 nd time), kept at 200 ℃ for 10 minutes, and then heated at 2 nd to 200 ℃. In addition, the temperature difference T is measured 1 And temperature difference T 2 In each DSC curve, the melting peak having the largest difference in input of thermal energy among melting peaks appearing in the range of 120 to 160 ℃ is analyzed. Even when there are 2 or more peaks overlapping, only the pairsThe melting peak having the largest difference in heat energy input was analyzed.
The extrapolated melting start temperature represents the starting point of the melting peak temperature, and is the temperature of the intersection point between a straight line extending from the base line on the low temperature side (65 to 75 ℃) to the high temperature side and a tangent line drawn at the point where the gradient is the largest on the curve on the low temperature side of the melting peak where the difference in thermal energy input is the largest. The extrapolated melting end temperature represents the end point of the melting peak temperature, and is the temperature of the intersection point of a straight line extending from the base line on the high temperature side (170 ℃) to the low temperature side and a tangent line drawn at the point where the slope is the largest on the curve on the high temperature side of the melting peak where the difference in thermal energy input is the largest.
< measurement of seal Strength before contact with electrolyte >
In the following measurement of the sealing strength after contact with the electrolyte solution, the tensile strength (sealing strength) was measured in the same manner except that the electrolyte solution was not injected into the test sample. The maximum tensile strength until the thermal welding portion was completely peeled off was defined as the sealing strength before the electrolyte solution was applied. In table 9, the sealing strength before contact with the electrolyte was defined as the sealing strength at 85 ℃ at 0h of the contact time of the electrolyte.
< measurement of seal Strength after contact with electrolyte >
The battery packaging materials of examples 14 and 28 obtained as described above were cut into a rectangular shape having a width (x direction) of 100mm × a length (z direction) of 200mm as shown in the schematic diagram of fig. 10, and used as a test sample (battery packaging material 10) (fig. 10 a). The test sample (the battery packaging material 10) was folded back at the center in the z direction so that the heat-fusible resin layer sides were overlapped (fig. 10 b). Then, both ends of the folded test sample in the x direction were sealed by heat sealing (temperature 190 ℃, surface pressure 2.0MPa, time 3 seconds), and a bag shape having 1-point opening E was formed (fig. 10 c). Then, 6g of an electrolyte (a solution in which the concentration of lithium hexafluorophosphate was 1mol/l and the volume ratio of ethylene carbonate, diethyl carbonate and dimethyl carbonate was 1: 1) was injected from the opening E of the test sample formed in a bag shape (FIG. 10 d), and the end of the opening E was sealed by heat sealing (temperature 190 ℃, surface pressure 2.0MPa, time 3 seconds) (FIG. 10E). Then, the pouch-shaped test specimen was left to stand with its folded portion facing downward at a temperature of 85 ℃ for a predetermined storage time (time of contact with the electrolyte, 0 hour, 24 hours, 72 hours). Next, the end of the test sample was cut (fig. 10 e), and the electrolyte was completely discharged. Next, the upper and lower surfaces of the test sample were sandwiched by metal plates 20 (7 mm in width) with the electrolyte solution adhering to the surfaces of the heat-fusible resin layers, and the heat-fusible resin layers were heat-fused together at a temperature of 190 ℃ and a surface pressure of 1.0MPa for a period of 3 seconds (fig. 10 f). Next, in order to measure the sealing strength at a position of 15mm in width (x direction), the test sample was cut into a width of 15mm using a double-edged sample cutter (fig. 10f, g). Subsequently, T-peeling was performed, and the interface where thermal fusion occurred was peeled off under the conditions of a tensile speed of 300 mm/min, a peeling angle of 180 degrees and an inter-jig distance of 50mm in an environment at a temperature of 25 ℃ by using a tensile tester (AGS-xplus (trade name) manufactured by Shimadzu corporation), and the tensile strength (seal strength) was measured (FIG. 8). The maximum tensile strength until the portion where thermal welding occurred was completely peeled (until the peeled distance was 7mm in width of the metal plate) was taken as the sealing strength after contacting the electrolyte.
The sealing strength before the contact with the electrolyte was taken as (100%), and the retention (%) of the sealing strength after the contact with the electrolyte was shown in table 9.
[ Table 9]
Figure BDA0002540973500000401
[ Table 10]
Figure BDA0002540973500000402
From the results shown in Table 9, the temperature difference T was observed among the battery packaging materials of examples 14 and 28 2 Divided by the temperature difference T 1 The obtained value was 0.55 or more, and it was found that even when the electrolyte solution was brought into contact with the heat-fusible resin layer in a high-temperature environment, the heat-fusible resin layers were thermally fused to each other in a state where the electrolyte solution was adhered to the heat-fusible resin layerIn this case, high sealing strength can be exhibited by thermal welding. Temperature difference T of Battery packaging Material of example 28 2 Divided by the temperature difference T 1 The obtained value is further 0.60 or more, and it is found that even when the heat-fusible resin layers are heat-fused in a state in which the electrolyte solution adheres to the heat-fusible resin layers in a state in which the electrolyte solution is in contact with the heat-fusible resin layers under a high-temperature environment, high sealing strength can be exhibited by the heat fusion.
Description of the symbols
1 \ 8230and base material layer
2 8230and adhesive layer
3' \ 8230and barrier layer
4-8230and heat-fusible resin layer
5-8230and adhesive layer
6' \ 8230and surface coating layer
10-8230and packaging material for battery

Claims (9)

1. A packaging material for a battery, characterized in that,
comprising a laminate having at least a base material layer, a barrier layer and a heat-sealable resin layer in this order,
the thickness of the laminate is not more than 195 μm,
by the method according to JIS Z1707:1997 in the laminate from the base layer side when the puncture resistance strength of the puncture is more than 30N,
the substrate layer is a laminate of a polyester film and a polyamide film, a polyester film or a polyamide film,
the barrier layer is composed of aluminum or stainless steel,
the resin constituting the heat-sealable resin layer contains a polyolefin skeleton,
the thickness of the barrier layer is in the range of 75 to 85 μm,
the thickness of the substrate layer is within the range of 34-45 μm,
the thickness of the heat-fusible resin layer is in the range of 55-65 μm,
the battery packaging material has an ultimate molding depth of 10mm or more as measured under the following measurement conditions,
conditions for measuring the ultimate molding depth:
the test sample was cold-formed by using a female mold having a rectangular bore with a length of 150mm and a width of 100mm as a test sample and changing the forming depth of the sample by 0.5mm from the forming depth of 0.5mm with a pressing surface pressure of 0.23MPa using a female mold having a rectangular bore with a length of 55mm and a width of 32mm and a male mold corresponding thereto, wherein the test sample was placed on the female mold so that the side of the heat-fusible resin layer was positioned on the side of the male mold and formed, the distance between the male mold and the female mold was 0.3mm, the deepest forming depth at which no pinholes or cracks were formed in the aluminum alloy foil layer among the 10 samples after cold forming was A in mm, the number of pinholes or cracks that occurred at the shallowest forming depth of pinholes or cracks in the aluminum alloy foil layer was B in units, and the number of pinholes or cracks that occurred in units was one, and the value calculated by the following equation was used as the limit forming depth of the battery packaging material,
ultimate molding depth = am + (0.5 mm/10) × (10-B).
2. The packaging material for batteries according to claim 1,
the heat-fusible resin layer includes an acid-modified polyolefin.
3. The packaging material for batteries according to claim 1 or 2,
the heat-fusible resin layer contains polypropylene.
4. The packaging material for batteries according to claim 1 or 2,
the heat-fusible resin layer is formed of maleic anhydride-modified polypropylene and polypropylene.
5. The packaging material for batteries according to claim 1 or 2,
the molded curl measured under the following measurement conditions is 0mm to 10mm,
measurement conditions for formation curl:
the test sample was cold-formed using a female mold having a rectangular bore with a length of 200mm and a width of 100mm and a male mold corresponding thereto at a pressing surface pressure of 0.23MPa and a forming depth of 6mm, the test sample was placed on the female mold so that the side of the heat-fusible resin layer was on the male mold side, and was formed, the distance between the male mold and the female mold was 0.3mm, the position of the forming section M was located at a position where the shortest distance d between the forming section M of the rectangular shape in a plan view formed by the mold in the length direction of the battery packaging material and the end P of the battery packaging material was 122mm, the shortest distance between the forming section M and both ends of the battery packaging material was 34mm in the width direction of the battery packaging material, the opening of the forming section was directed downward, the position Q of the forming section where no recess was formed was used as the test sample, the maximum value of the curl distance in the y direction from the vertical position Q to the end P was used as the reference distance.
6. The packaging material for batteries according to claim 1 or 2,
the temperature difference T was measured according to the following method 1 And temperature difference T 2 Said temperature difference T 2 Divided by said temperature difference T 1 And the value obtained is above 0.55,
temperature difference T 1 The determination of (1):
measuring a temperature difference T between an extrapolated melting start temperature and an extrapolated melting end temperature of a melting peak temperature of the heat-sealable resin layer by differential scanning calorimetry 1 ；
Temperature difference T 2 The determination of (1):
allowing the heat-fusible resin layer to stand in an electrolyte for 72 hours in an environment of 85 ℃ and drying the same, measuring the difference T between the extrapolated melting start temperature and the extrapolated melting end temperature of the melting peak temperature of the heat-fusible resin layer after drying by differential scanning calorimetry 2 What is meant byThe electrolyte is a solution in which the concentration of lithium hexafluorophosphate is 1mol/l and the volume ratio of ethylene carbonate, diethyl carbonate and dimethyl carbonate is 1: 1.
7. The packaging material for batteries according to claim 1 or 2,
in the rigid body pendulum weight measurement, the logarithmic decrement Delta E of the surface of the heat-fusible resin layer on the side of the barrier layer at 120 ℃ is 0.50 or less.
8. A battery, characterized in that it comprises a battery body,
a battery element having at least a positive electrode, a negative electrode and an electrolyte is housed in a package formed of the battery packaging material according to any one of claims 1 to 7.
9. A method for producing the battery packaging material according to any one of claims 1 to 7, characterized in that,
comprises a step of laminating at least a base material layer, a barrier layer and a heat-fusible resin layer in this order to obtain a laminate,
the thickness of the laminate is not more than 195 μm,
by the method according to JIS Z1707:1997 in the laminate from the base layer side when the puncture resistance strength of the puncture is more than 30N,
the thickness of the barrier layer is in the range of 75 to 85 μm,
the thickness of the substrate layer is within the range of 34-45 μm,
the thickness of the heat-fusible resin layer is in the range of 55 to 65 μm.
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