CN118124220A - Outer packaging material for power storage device, method for producing same, power storage device, and polyamide film - Google Patents

Outer packaging material for power storage device, method for producing same, power storage device, and polyamide film Download PDF

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Publication number
CN118124220A
CN118124220A CN202410265750.5A CN202410265750A CN118124220A CN 118124220 A CN118124220 A CN 118124220A CN 202410265750 A CN202410265750 A CN 202410265750A CN 118124220 A CN118124220 A CN 118124220A
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China
Prior art keywords
peak intensity
layer
storage device
absorption
polyamide film
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CN202410265750.5A
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Chinese (zh)
Inventor
上所宽典
天野真
立泽雅博
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Dai Nippon Printing Co Ltd
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Dai Nippon Printing Co Ltd
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Publication of CN118124220A publication Critical patent/CN118124220A/en
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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
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/103—Primary casings; Jackets or wrappings characterised by their shape or physical structure prismatic or rectangular
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/78—Cases; Housings; Encapsulations; Mountings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • 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

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention provides an outer packaging material for an electric storage device, which can inhibit the outer packaging material for the electric storage device from being damaged when the electric storage device fixed on a shell by double-sided tape or the like is peeled off from the shell. The exterior material for a power storage device is composed of a laminate having, in order from the outside, at least a base layer, a barrier layer, and a heat-fusible resin layer, wherein the base layer comprises a polyamide film, and the polyamide film has a crystallization index of 1.50 or more as measured from the outside of the base layer by the ATR method of the Fourier transform infrared spectroscopy method.

Description

Outer packaging material for power storage device, method for producing same, power storage device, and polyamide film
The application is carried out on the application date of 2020, 05, 18 and 202080036390.1,
The invention provides an external packaging material for an electric storage device, a method for producing the same, an electric storage device, and a polyamide film
Technical Field
The present invention relates to an exterior material for an electric storage device, a method for producing the same, an electric storage device, and a polyamide film.
Background
Various types of power storage devices have been developed, and in all of the power storage devices, an exterior material has become an indispensable component for packaging power storage device elements such as electrodes and electrolytes. Conventionally, as an exterior material for an electric storage device, a metal exterior material is generally used.
On the other hand, in recent years, with the increase in performance of electric vehicles, hybrid electric vehicles, computers, cameras, cellular phones, and the like, various shapes and thickness reduction and weight reduction have been demanded for power storage devices. However, conventionally, there are drawbacks in that it is difficult to adapt to the variety of shapes and that it is limited to weight reduction by using a metal outer package for an electric storage device.
In recent years, therefore, as an exterior material for a power storage device that can be easily processed into various shapes and can be thinned and lightened, a film-like laminate in which a base layer, a barrier layer, and a heat-fusible resin layer are laminated in this order has been proposed (for example, see patent document 1).
In such an exterior material for power storage devices, a recess is generally formed by cold rolling, power storage device elements such as electrodes and electrolyte are disposed in a space formed by the recess, and a heat-fusible resin layer is heat-fused to obtain a power storage device in which the power storage device elements are housed inside the exterior material for power storage devices.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2008-287971
Disclosure of Invention
Technical problem to be solved by the invention
Components such as rare metals are used for the power storage device element, and the demand for these components is rapidly increasing. Therefore, in various products such as electrical equipment, it is required to take out the power storage device from the product, collect and reuse various components contained in the power storage device element, for example, when replacing the power storage device.
In various products such as electric devices, the power storage device is firmly fixed to a case of the product by a double-sided tape, an adhesive, or the like. Therefore, when the power storage device is removed from the case of the product, a large external force is applied to the power storage device. Specifically, a metal blade or the like is generally used to remove the power storage device from the case, and a large external force is applied to the power storage device. When the power storage device is removed, if a large external force is applied to the power storage device outer package made of the film-shaped laminate, the power storage device outer package may be damaged.
Under such circumstances, the main object of the present invention is to: provided is an exterior material for an electric storage device, which can prevent the exterior material for the electric storage device from being damaged when the electric storage device fixed to a case by a double-sided tape or the like is peeled from the case.
Technical scheme for solving technical problems
The inventors of the present invention have made intensive studies in order to solve the above-mentioned technical problems. As a result, it has been found that when an outer package for an electric storage device is formed of a laminate having, in order from the outside, at least a base material layer, a barrier layer, and a heat-fusible resin layer, the base material layer includes a polyamide film, and the crystallization index of the polyamide film measured from the outside of the base material layer by the ATR method of the fourier transform infrared spectroscopy is equal to or greater than a predetermined value, and an electric storage device fixed to a case by a double-sided tape or the like is peeled from the case, breakage of the outer package for an electric storage device can be suppressed.
The present invention has been completed based on further repeated studies based on these knowledge. That is, the present invention provides the following aspects of the invention.
An exterior material for an electric storage device, comprising a laminate having, in order from the outside, at least a base layer, a barrier layer, and a heat-fusible resin layer, wherein the base layer comprises a polyamide film, and the polyamide film has a crystallization index of 1.50 or more as measured from the outside of the base layer by the ATR method of the Fourier transform infrared spectroscopy method.
Effects of the invention
The present invention can provide an exterior material for an electric storage device, which can suppress breakage of the exterior material for an electric storage device when the electric storage device fixed to the case by a double-sided tape or the like is peeled from the case using a metal blade or the like. The present invention also provides a method for producing the exterior material for an electric storage device, an electric storage device using the exterior material for an electric storage device, and a polyamide film suitable for use as a base layer of the exterior material for an electric storage device.
Drawings
Fig. 1 is a schematic view showing an example of a cross-sectional structure of an exterior material for a power storage device according to the present invention.
Fig. 2 is a schematic diagram showing an example of a cross-sectional structure of an outer casing for a power storage device according to the present invention.
Fig. 3 is a schematic view showing an example of a cross-sectional structure of the outer casing for a power storage device according to the present invention.
Fig. 4 is a schematic view showing an example of a cross-sectional structure of the outer casing for a power storage device according to the present invention.
Fig. 5 is a schematic diagram for explaining a method of producing a sample used for the peeling test of the power storage device of the example.
Fig. 6 is a side view (a) and a top view (b) of a sample used for a peeling test of the power storage device of the example.
Fig. 7 is a side view (a) and a plan view (b) of a case where a double-sided tape is attached to a sample used in a peeling test of the power storage device of the example.
Fig. 8 is a schematic view showing a case where the power storage device is peeled from the stainless steel plate using a metal blade in the peeling test of the power storage device of the example.
Detailed Description
The outer packaging material for the power storage device of the present invention is characterized in that: the laminate is composed of a laminate comprising, in order from the outside, at least a base material layer, a barrier layer, and a heat-fusible resin layer, wherein the base material layer comprises a polyamide film, and the polyamide film has a crystallization index of 1.50 or more as measured from the outside of the base material layer by the ATR method of the Fourier transform infrared spectroscopy method. The outer packaging material for the power storage device of the present invention suppresses breakage of the outer packaging material for the power storage device when the power storage device fixed to the case by a double-sided tape or the like is peeled off from the case.
Hereinafter, the outer packaging material for a power storage device according to the present invention will be described in detail. In the present specification, the numerical range indicated by "to" means "above" and "below". For example, the expression of 2 to 15mm means 2mm to 15 mm.
1. Laminate structure and physical properties of outer packaging material for power storage device
As shown in fig. 1, for example, the exterior material 10 for a power storage device of the present invention is composed of a laminate having a base layer 1, a barrier layer 3, and a heat-fusible resin layer 4 in this order from the outside. In the outer packaging material 10 for the power storage device, the base material layer 1 is the outermost layer side, and the heat-fusible resin layer 4 is the innermost layer. When the power storage device is assembled using the power storage device outer package 10 and the power storage device element, the peripheral edge portion is thermally welded with the thermally-fusible resin layers 4 of the power storage device outer package 10 facing each other, and the power storage device element is accommodated in the space thus formed. In the laminate constituting the exterior material 10 for a power storage device of the present invention, the heat-fusible resin layer 4 side is the inner side than the barrier layer 3 and the base material layer 1 side is the outer side than the barrier layer 3 with respect to the barrier layer 3.
As shown in fig. 2 to 4, for example, the outer packaging material 10 for the power storage device may have an adhesive layer 2 between the base layer 1 and the barrier layer 3, for the purpose of improving adhesion between these layers, or the like, as required. As shown in fig. 3 and 4, for example, an adhesive layer 5 may be provided between the barrier layer 3 and the heat-fusible resin layer 4, as needed, for the purpose of improving adhesion between these layers. As shown in fig. 5, a surface coating layer 6 or the like may be provided on the outer side of the base material layer 1 (on the side opposite to the heat-fusible resin layer 4) as needed.
The thickness of the laminate constituting the exterior material 10 for a power storage device is not particularly limited, but from the standpoint of cost reduction, energy density improvement, and the like, it is preferable that the thickness is about 180 μm or less, about 155 μm or less, about 120 μm or less, from the standpoint of maintaining the function of the exterior material for a power storage device, such as protecting the power storage device element, the thickness is preferably about 35 μm or more, about 45 μm or more, about 60 μm or more, from the standpoint of maintaining the function of the exterior material for a power storage device, and from the standpoint of maintaining the function of the exterior material for a power storage device, the thickness is preferably about 35 μm or more, about 45 μm or more, about 60 μm or more, from the standpoint of the lower limit, and from the standpoint of the preferable range, it is, for example, about 35 to 180 μm, about 35 to 155 μm, about 35 to 120 μm, about 45 to 180 μm, about 45 to 155 μm, about 45 to 120 μm, about 60 to 180 μm, about 60 to 120 μm, and, particularly preferably about 60 to 120 μm.
In the exterior material 10 for an electric storage device, the ratio of the total thickness of the base material layer 1, the adhesive layer 2, the barrier layer 3, the adhesive layer 5, the heat-fusible resin layer 4, and the surface coating layer 6, which are provided as needed, to the thickness (total thickness) of the laminate constituting the exterior material 10 for an electric storage device is preferably 90% or more, more preferably 95% or more, and still more preferably 98% or more. Specifically, when the exterior material 10 for an electric storage device of the present invention includes the base material layer 1, the adhesive layer 2, the barrier layer 3, the adhesive layer 5, and the heat-fusible resin layer 4, the ratio of the total thickness of these layers to the thickness (total thickness) of the laminate constituting the exterior material 10 for an electric storage device is preferably 90% or more, more preferably 95% or more, and even more preferably 98% or more.
The base material layer 1 of the outer package 10 for a power storage device of the present invention includes a polyamide film, and the polyamide film has a crystallization index of 1.50 or more, measured from the outside of the base material layer 1, by the ATR method of the fourier transform infrared spectroscopy. The method for measuring the crystallization index of the base material layer 1 of the exterior material 10 for a power storage device according to the present invention is as follows.
< Measurement of crystallization index of base layer of exterior Material for electric storage device >
The exterior material for the power storage device was cut into a square shape of 100mm×100mm, and samples were produced. The surface of the polyamide film located outside the obtained sample was subjected to infrared absorption spectrometry in an environment having a temperature of 25℃and a relative humidity of 50% by using the ATR measurement mode of FT-IR. As the device, for example, manufactured by sameidie science and technology, inc: nicolet iS10. From the obtained absorption spectrum, the peak intensity P around 1200cm -1 of absorption from the α -crystal of nylon and the peak intensity Q around 1370cm -1 of absorption from the non-crystal were measured, and the intensity ratio x=p/Q of the peak intensity P to the peak intensity Q was calculated as the crystallization index. In the case of obtaining an exterior material for an electric storage device from the electric storage device and measuring the crystallization index of the base material layer, a sample is prepared by obtaining the exterior material for an electric storage device from the top surface or the bottom surface, not from the heat-welded portion or the side surface of the electric storage device.
(Measurement conditions)
The method comprises the following steps: macroATR process;
Wave number resolution: 8cm -1;
Cumulative number of times: 32 times;
A detector: a DTGS detector;
ATR prism: ge;
Incidence angle: 45 °;
Baseline: the wave numbers between 1100cm -1 and 1400cm -1 were determined in a straight-line approximation.
Absorption peak intensity Y 1200: a value obtained by subtracting the value of the baseline from the maximum value of the peak intensities in the range of the wave number 1195cm -1 to 1205cm -1;
Absorption peak intensity Y 1370: a value obtained by subtracting the value of the base line from the maximum value of the peak intensity in the range of the wave numbers 1365cm -1 to 1375cm -1.
In addition, when the outer surface of the outer cover 10 for the power storage device is made of the polyamide film of the base material layer 1, the outer cover 10 for the power storage device can be directly used as a measurement target of the crystallization index. As described later, when the base material layer 1 has a multilayer structure, a resin film (for example, a polyester film) different from a polyamide film is located further outside than the polyamide film, or when the surface covering layer 6 described later is laminated on the outside of the base material layer 1, or the outside surface of the outer packaging material 10 for the power storage device is not composed of the polyamide film of the base material layer 1, the layer located further outside than the polyamide film may be removed from the outer packaging material 10 for the power storage device, and the crystallization index may be measured in a state where the surface of the polyamide film is exposed.
In the outer package 10 for the power storage device, the crystallization index is 1.50 or more, and is preferably 1.55 or more, more preferably 1.60 or more, and particularly preferably 1.65 or more, from the viewpoint of more effectively suppressing breakage of the outer package for the power storage device at the time of the peeling. The upper limit of the crystallization index is not particularly limited, and examples thereof include 2.50 or less and 1.80 or less. Preferable ranges of the crystallization index include, for example, 1.50 to 2.50, 1.60 to 2.50, 1.65 to 2.50, 1.50 to 1.80, 1.60 to 1.80, and 1.65 to 1.80.
As a method for increasing the crystallization index of the polyamide film contained in the base material layer 1 of the outer packaging material 10 for an electric storage device to 1.50 or more, there is a method for promoting crystallization (promoting the formation of α -crystals) by using the stretching ratio, the heat fixing temperature, the post-heating temperature, the time, and the like of the production process of the polyamide film.
2. Layers forming an exterior material for an electric storage device
[ Substrate layer 1]
In the present invention, the base material layer 1 is a layer provided for the purpose of functioning as a base material of an outer package material for an electric storage device, and the like. The base material layer 1 is located on the outer layer side of the outer package material for the power storage device.
The substrate layer 1 comprises a polyamide film. As described above, the crystallization index of the polyamide film measured from the outside of the base material layer 1 by ATR method using fourier transform infrared spectroscopy is 1.50 or more.
The polyamide forming the polyamide film may be any polyamide having an alpha-crystal, and specifically includes aliphatic polyamides such as nylon 6, nylon 66, nylon 46, and copolymers of nylon 6 and nylon 66. These polyamides may be used alone in an amount of 1, or may be used in an amount of 2 or more. The polyamide membrane is preferably a nylon membrane.
The polyamide film may be an unstretched film or a stretched film. When the base material layer 1 includes an unstretched film, each layer of the outer packaging material 10 for the power storage device may be laminated by extrusion molding to form an unstretched film, a previously prepared unstretched film may be bonded, or a resin (polyamide) may be applied to form an unstretched film. Examples of the method for coating the resin include a roll coating method, a gravure coating method, and an extrusion coating method. When the base material layer 1 is a stretched film, a previously prepared stretched film may be bonded when the layers of the outer package material 10 for the power storage device are laminated. The stretched film may be a uniaxially stretched film or a biaxially stretched film, and is preferably a biaxially stretched film. Examples of the stretching method for forming the biaxially stretched film include a sequential biaxial stretching method, a inflation method, and a simultaneous biaxial stretching method.
The polyamide film is particularly preferably a biaxially stretched nylon film.
In the outer package 10 for an electric storage device of the present invention, a polyamide film having a crystallization index of 1.50 or more as measured by the ATR method using the fourier transform infrared spectroscopy can be produced for the base material layer 1, and the crystallization index can be increased to 1.50 or more by applying heat to the polyamide film during the production of the outer package 10 for an electric storage device. As described in the item "5. Polyamide film" described later, in the outer package 10 for a power storage device according to the present invention, a polyamide film having a crystallization index of 1.50 or more as measured by the ATR method using the fourier transform infrared spectroscopy is preferably produced for the base material layer 1. That is, it is preferable to use a polyamide film having the crystallization index adjusted to 1.50 or more in advance for the base layer 1, and laminate each layer such as the barrier layer 3 and the heat-fusible resin layer 4, to thereby produce the exterior material 10 for an electric storage device according to the present invention. As shown in examples described later, the polyamide film contained in the base material layer 1 can have an improved crystallization index after being laminated on the exterior material 10 for the power storage device, compared with the polyamide film before being applied to the exterior material 10 for the power storage device.
The thickness of the polyamide film is preferably about 3 μm or more, more preferably about 10 μm or more, and preferably about 50 μm or less, more preferably about 35 μm or less, from the viewpoint of more effectively suppressing breakage of the exterior material for the power storage device at the time of the foregoing peeling, and the preferable range is about 3 to 50 μm, about 3 to 35 μm, about 10 to 50 μm, about 10 to 35 μm, and about 10 to 35 μm is particularly preferable.
The base material layer 1 may also have a resin film different from the polyamide film. Examples of the resin forming the resin film different from the polyamide film include resins such as polyesters, polyolefins, epoxy resins, acrylic resins, fluorine resins, polyurethanes, silicone resins, and phenolic resins, and modified products of these resins. The resin may be a copolymer of these resins or a modified product of the copolymer. Mixtures of these resins are also possible. Among these, polyesters are preferably exemplified.
Specific examples of the polyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, and a copolyester. Further, as the copolyester, a copolyester having ethylene terephthalate as a main unit of a repeating unit, and the like can be exemplified. Specifically, there may be mentioned a copolymer polyester (hereinafter, abbreviated as poly (terephthalic acid/isophthalic acid) ethylene glycol), poly (terephthalic acid/adipic acid) ethylene glycol, poly (terephthalic acid/sodium sulfoisophthalic acid) ethylene glycol, poly (terephthalic acid/sodium isophthalic acid) ethylene glycol, poly (terephthalic acid/phenyl-dicarboxylic acid) ethylene glycol, poly (terephthalic acid/decanedicarboxylic acid) ethylene glycol, and the like, which are mainly composed of a terephthalic acid ethylene glycol and polymerized with an isophthalic acid ethylene glycol. These polyesters may be used alone in an amount of 1 kind, or may be used in an amount of 2 or more kinds in combination. Among these, polyethylene terephthalate and polybutylene terephthalate are preferable.
The polyester film is preferably a stretched polyester film, more preferably a biaxially stretched polyester film.
The polyester film is particularly preferably a biaxially stretched polyethylene terephthalate film or a biaxially stretched polybutylene terephthalate film.
In the case where the base material layer 1 further has a resin film different from the polyamide film, the thickness of the other resin film is not particularly limited as long as the effect of the present invention is not impaired, but is preferably about 3 μm or more, more preferably about 10 μm or more, and preferably about 50 μm or less, more preferably about 35 μm or less, and the preferable range is about 3 to 50 μm, about 3 to 35 μm, about 10 to 50 μm, or about 10 to 35 μm, and particularly about 10 to 35 μm.
When the base layer 1 includes a polyamide film, it may be a single layer or may be composed of 2 or more layers, and is preferably a single layer of the polyamide film from the viewpoint of reducing the thickness of the outer packaging material 10 for the power storage device.
When the base material layer 1 is composed of 2 or more layers, the base material layer 1 may be a laminate obtained by laminating resin films with an adhesive or the like, or may be a laminate obtained by coextruding resins into 2 or more layers of resin films. In addition, the base material layer 1 may be directly formed without stretching a laminate of 2 or more resin films obtained by coextrusion of the resins, or the base material layer 1 may be formed after uniaxial stretching or biaxial stretching.
Specific examples of the laminate of 2 or more resin films in the base layer 1 include a laminate of a polyester film and a nylon film, a laminate of 2 or more nylon films, and the like, and a laminate of a stretched nylon film and a stretched polyester film, and a laminate of 2 or more stretched nylon films are preferable. For example, in the case where the base material layer 1 is a laminate of 2 resin films, a laminate of a polyamide resin film and a polyamide resin film, or a laminate of a polyester resin film and a polyamide resin film is preferable, and a laminate of a nylon film and a nylon film, or a laminate of a polyethylene terephthalate film and a nylon film is more preferable. In addition, in the case where the base layer 1 is a laminate of 2 or more resin films, it is preferable that the polyester resin film is located at the outermost layer of the base layer 1, for example, because the polyester resin is less likely to be discolored when the electrolyte is adhered to the surface.
When the base material layer 1 is a laminate of 2 or more resin films, the 2 or more resin films may be laminated with an adhesive. The preferred adhesive is the same as the adhesive exemplified in the adhesive layer 2 described later. Among them, the method of laminating 2 or more resin films is not particularly limited, and known methods may be used, and examples thereof include a dry lamination method, a sandwich lamination method, an extrusion lamination method, and a thermal lamination method, and a dry lamination method is preferable. When the lamination is performed by a dry lamination method, a polyurethane adhesive is preferably used as the adhesive. In this case, the thickness of the adhesive may be, for example, about 2 to 5. Mu.m. In addition, an anchor coat layer may be formed and laminated on the resin film. The anchor coat layer may be the same as the adhesive exemplified in the adhesive layer 2 described later. In this case, the thickness of the anchor coat layer may be, for example, about 0.01 to 1.0. Mu.m.
In addition, additives such as lubricants, flame retardants, antiblocking agents, antioxidants, light stabilizers, tackifiers, antistatic agents, and the like may be present on at least one of the surface and the inside of the base material layer 1. The additive may be used in an amount of 1 or 2 or more.
In the present invention, it is preferable that a lubricant is present on the surface of the base material layer 1 from the viewpoint of improving the moldability of the outer packaging material for the power storage device. The lubricant is not particularly limited, and an amide-based lubricant is preferable. Specific examples of the amide-based lubricant include saturated fatty acid amide, unsaturated fatty acid amide, substituted amide, methylol amide, saturated fatty bisamide, unsaturated fatty bisamide, fatty acid ester amide, and aromatic bisamide. Specific examples of the saturated fatty amide include lauramide, palmitoamide, stearamide, behenamide, and hydroxystearamide. Specific examples of the unsaturated fatty amide include oleamide and erucamide. Specific examples of the substituted amide include N-oleyl palmitoamide, N-stearyl stearamide, N-stearyl oleamide, N-oleyl stearamide, and N-stearyl erucamide. Specific examples of the methylol amide include methylol stearamide and the like. Specific examples of the saturated fatty bisamide include methylene bis-stearamide, ethylene bis-decanoamide, ethylene bis-lauramide, ethylene bis-stearamide, ethylene bis-hydroxystearamide, ethylene bis-behenamide, hexamethylenebis-stearamide, hexamethylenebis-behenamide, hexamethylenehydroxystearamide, N '-distearyladipamide, and N, N' -distearylsebacamide. Specific examples of the unsaturated fatty bisamide include ethylene bis-oleamide, ethylene bis-erucamide, hexamethylene bis-oleamide, N '-dioleyladipamide, and N, N' -dioleylsebacamide. Specific examples of the fatty acid ester amide include ethyl stearamide stearate. Specific examples of the aromatic bisamide include m-xylylene bisstearamide, m-xylylene bishydroxystearamide, and N, N' -distearyl m-xylylene bisformamide. The lubricant may be used alone or in combination of 2 or more.
When a lubricant is present on the surface of the base material layer 1, the amount thereof is not particularly limited, and examples thereof include preferably about 3mg/m 2 or more, more preferably about 4 to 15mg/m 2, and still more preferably about 5 to 14mg/m 2.
The lubricant present on the surface of the base material layer 1 may be a lubricant oozing out from the lubricant contained in the resin constituting the base material layer 1, or may be a lubricant applied to the surface of the base material layer 1.
The total thickness of the base material layer 1 is not particularly limited as long as the function as a base material can be exhibited, and examples thereof include about 3 to 50 μm, preferably about 10 to 35 μm.
[ Coating ]
The exterior material for an electric storage device according to the present invention may have a coating layer (not shown) on the base layer 1 (on the side opposite to the barrier layer 3 side of the base layer 1) for the purpose of improving printability, moldability, and the like, if necessary. The coating is arranged in contact with the substrate layer 1. The thickness of the coating layer is not particularly limited as long as the above-mentioned function as the coating layer can be exhibited, and examples thereof include about 0.01 to 0.40 μm, preferably about 0.01 to 0.30 μm, and more preferably about 0.1 to 0.30 μm. By having a thickness of 0.01 μm or more, a layer having a uniform film thickness can be formed on the base layer 1. As a result, the outer packaging material for a power storage device of the present invention can be printed uniformly without unevenness in printability, and can obtain uniform moldability.
Examples of the resin forming the coating layer include various synthetic resins such as polyvinylidene chloride, vinylidene chloride-vinyl chloride copolymer, polyolefin, acid-modified polyolefin, polyester, epoxy resin, phenolic resin, fluororesin, cellulose ester, polyurethane, acrylic resin, and polyamide. Among these, polyurethane, polyester, and acrylic are preferable.
To improve the smoothness, the coating may contain lubricants, additives, as required. As the lubricant, the same lubricants as those described above can be exemplified. The additives may be the same additives as those exemplified for the surface coating layer 6 described later. The content and particle diameter of these lubricants or additives can be appropriately adjusted according to the thickness of the coating layer.
In order to improve the adhesiveness of the layer adjacent to the base material layer, the outer packaging material for an electric storage device of the present invention may have a coating layer (not shown) on one surface (the barrier layer 3 side of the base material layer 1, the side opposite to the barrier layer 3 side of the base material layer 1) or on both surfaces of the base material layer 1, if necessary. That is, the coating layer provided on the base material layer may be a layer provided for the purpose of improving printability, moldability, or the like, or may be a layer provided for the purpose of improving the adhesiveness of the base material layer. When the coating layer is intended to improve the adhesiveness of the base material layer, the resin and the thickness of the coating layer may be the same as those of the coating layer. The lubricant and the additive may be contained, and in the case where a layer adjacent to the base material layer is present on the side of the coating layer opposite to the base material layer, the lubricant and the additive are preferably not contained.
[ Adhesive layer 2]
In the outer packaging material for a power storage device of the present invention, the adhesive layer 2 is a layer that is provided between the base layer 1 and the barrier layer 3 as needed in order to improve the adhesion therebetween.
The adhesive layer 2 is formed of an adhesive capable of bonding the base material layer 1 and the barrier layer 3. The adhesive used for forming the adhesive layer 2 is not limited, and may be of a chemical reaction type, solvent evaporation type, hot melt type, hot press type, or the like. The resin may be a two-part curable adhesive (two-part adhesive), a one-part curable adhesive (one-part adhesive), or a resin which does not undergo a curing reaction. The adhesive layer 2 may be a single layer or a plurality of layers.
Specifically, the adhesive component contained in the adhesive includes: polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, and copolyesters; polyether; polyurethane; an epoxy resin; a phenolic resin; polyamides such as nylon 6, nylon 66, nylon 12, and copolyamide; polyolefin resins such as polyolefin, cyclic polyolefin, acid-modified polyolefin and acid-modified cyclic polyolefin; polyvinyl acetate; cellulose; (meth) acrylic resin; polyimide; a polycarbonate; amino resins such as urea resin and melamine resin; chloroprene rubber, nitrile rubber, styrene-butadiene rubber, and other rubbers; silicone resins, and the like. These adhesive components may be used alone in an amount of 1 kind, or may be used in an amount of 2 or more kinds. Among these adhesive components, polyurethane adhesives are preferable. In addition, the bonding strength can be improved by using a suitable curing agent in combination with the resin as the bonding component. The curing agent is appropriately selected from polyisocyanates, multifunctional epoxy resins, oxazoline group-containing polymers, polyamine resins, acid anhydrides, and the like, depending on the functional groups possessed by the adhesive component.
Examples of the urethane adhesive include urethane adhesives containing a main agent containing a polyol compound and a curing agent containing an isocyanate compound. A two-part curable polyurethane adhesive containing a polyol such as a polyester polyol, a polyether polyol, and an acrylic polyol as a main component and an aromatic or aliphatic polyisocyanate as a curing agent is preferable. Further, as the polyol compound, a polyester polyol having a hydroxyl group in the outer chain in addition to the hydroxyl group at the terminal of the repeating unit is preferably used. Since the adhesive layer 2 is formed of the urethane adhesive, excellent electrolyte resistance can be imparted to the exterior material for the power storage device, and even if the electrolyte adheres to the side surface, peeling of the base material layer 1 can be suppressed.
The adhesive layer 2 may contain a colorant, a thermoplastic elastomer, an adhesion promoter, a filler, and the like, as long as the adhesion is not impaired. The outer packaging material for the power storage device can be colored by the adhesive layer 2 containing a colorant. As the colorant, known colorants such as pigments and dyes can be used. In addition, 1 kind of colorant may be used alone, or 2 or more kinds may be mixed and used.
The type of pigment is not particularly limited as long as the adhesiveness of the adhesive layer 2 is not impaired. Examples of the organic pigment include pigments such as azo pigments, phthalocyanine pigments, quinacridone pigments, anthraquinone pigments, dioxazine pigments, indigo-thioindigo pigments, perinone-perylene pigments, isoindolenine pigments, and benzimidazolone pigments; examples of the inorganic pigment include carbon black-based, titanium oxide-based, cadmium-based, lead-based, chromium oxide-based, iron-based, copper-based and other pigments, and further include fine mica (mica) powder, fish scale foil and the like. The pigment may be used alone or in combination of 2 or more kinds, for example, a mixture of an organic pigment and an inorganic pigment.
Among the colorants, carbon black is preferable, for example, in order to make the appearance of the exterior material for the power storage device black.
The average particle diameter of the pigment is not particularly limited, and examples thereof include about 0.05 to 5. Mu.m, preferably about 0.08 to 2. Mu.m. The average particle diameter of the pigment is a median particle diameter measured by a laser diffraction/scattering type particle diameter distribution measuring device.
The content of the pigment in the adhesive layer 2 is not particularly limited as long as the exterior material for the power storage device can be colored, and examples thereof include about 5 to 60% by mass, preferably 8 to 40% by mass.
The thickness of the adhesive layer 2 is not particularly limited as long as the base layer 1 and the barrier layer 3 can be bonded, and examples of the lower limit include about 1 μm or more and about 2 μm or more, and examples of the upper limit include about 10 μm or less and about 5 μm or less, and examples of the preferred range include about 1 to 10 μm, about 1 to 5 μm, about 2 to 10 μm, and about 2 to 5 μm.
[ Coloring layer ]
The colored layer is a layer (not shown) provided between the base layer 1 and the barrier layer 3 as needed. In the case of having the adhesive layer 2, a coloring layer may be provided between the base material layer 1 and the adhesive layer 2 and between the adhesive layer 2 and the barrier layer 3. Further, a coloring layer may be provided on the outer side of the base material layer 1. By providing the coloring layer, the exterior material for the power storage device can be colored.
The colored layer can be formed by, for example, applying an ink containing a colorant to the surface of the base material layer 1, the surface of the adhesive layer 2, or the surface of the barrier layer 3. As the colorant, known colorants such as pigments and dyes can be used. In addition, 1 kind of colorant may be used alone, or 2 or more kinds may be mixed and used.
Specific examples of the colorant contained in the coloring layer include the same colorants as those exemplified in the column of [ adhesive layer 2 ].
[ Barrier layer 3]
In the exterior material for the power storage device, the barrier layer 3 is a layer that at least suppresses the penetration of moisture.
Examples of the barrier layer 3 include a metal foil, a vapor deposited film, and a resin layer having barrier properties. Examples of the vapor-deposited film include a metal vapor-deposited film, an inorganic oxide vapor-deposited film, and a carbon-containing inorganic oxide vapor-deposited film; examples of the resin layer include a fluororesin such as polyvinylidene chloride, a polymer mainly composed of Chlorotrifluoroethylene (CTFE), a polymer mainly composed of Tetrafluoroethylene (TFE), a polymer having a fluoroalkyl group, and a polymer mainly composed of a fluoroalkyl unit, and an ethylene vinyl alcohol copolymer. The barrier layer 3 may be a resin film provided with at least 1 layer of these vapor deposited films and resin layers. The barrier layer 3 may be provided in multiple layers. The barrier layer 3 preferably comprises a layer composed of a metallic material. The metal material constituting the barrier layer 3 may be specifically an aluminum alloy, stainless steel, titanium steel, or steel sheet, and when used as a metal foil, it is preferable to include at least one of an aluminum alloy foil and a stainless steel foil.
The aluminum alloy foil is preferably a soft aluminum alloy foil composed of an annealed aluminum alloy or the like, for example, from the viewpoint of improving the moldability of the outer packaging material for the power storage device; from the viewpoint of further improving the formability, an aluminum alloy foil containing iron is preferable. In the aluminum alloy foil (100 mass%) containing iron, the content of iron is preferably 0.1 to 9.0 mass%, more preferably 0.5 to 2.0 mass%. When the iron content is 0.1 mass% or more, an outer package for an electric storage device having more excellent moldability can be obtained. When the iron content is 9.0 mass% or less, an outer package for a power storage device having more excellent flexibility can be obtained. Examples of the soft aluminum alloy foil include aluminum alloy foils having a composition defined in JIS H4160:1994A 8021H-O, JIS H4160:1994A 8079H-O, JIS H4000:2014A 8021P-O, or JIS H4000:2014A 8079P-O. Silicon, magnesium, copper, manganese, and the like may also be added as needed. The softening may be performed by annealing or the like.
Examples of the stainless steel foil include austenitic stainless steel foils, ferritic stainless steel foils, austenitic stainless steel foils, martensitic stainless steel foils, and precipitation hardening stainless steel foils. Further, from the viewpoint of providing an exterior material for a power storage device excellent in formability, the stainless steel foil is preferably composed of austenitic stainless steel.
Specific examples of austenitic stainless steel constituting the stainless steel foil include SUS304, SUS301, and SUS316L, and among these, SUS304 is particularly preferred.
In the case of a metal foil, the thickness of the barrier layer 3 may be about 9 to 200 μm, for example, as long as it can function as a barrier layer that at least suppresses the penetration of moisture. The thickness of the barrier layer 3 may be, for example, about 85 μm or less, more preferably about 50 μm or less, still more preferably about 40 μm or less, particularly preferably about 35 μm or less, and about 10 μm or more, still more preferably about 20 μm or more, more preferably about 25 μm or more, and the preferred range of the thickness may be about 10 to 85 μm, about 10 to 50 μm, about 10 to 40 μm, about 10 to 35 μm, about 20 to 85 μm, about 20 to 50 μm, about 20 to 40 μm, about 20 to 35 μm, about 25 to 85 μm, about 25 to 50 μm, about 25 to 40 μm, about 25 to 35 μm, particularly preferably about 25 to 40 μm. In the case where the barrier layer 3 is made of an aluminum alloy foil, the above range is particularly preferable. In particular, when the barrier layer 3 is made of a stainless steel foil, the upper limit of the thickness of the stainless steel foil is preferably about 60 μm or less, more preferably about 50 μm or less, still more preferably about 40 μm or less, still more preferably about 30 μm or less, particularly preferably about 25 μm or less, and the lower limit of the thickness thereof is preferably about 10 μm or more, more preferably about 15 μm or more, and the range of the thickness thereof is preferably about 10 to 60 μm, about 10 to 50 μm, about 10 to 40 μm, about 10 to 30 μm, about 10 to 25 μm, about 15 to 60 μm, about 15 to 50 μm, about 15 to 40 μm, about 15 to 30 μm, or about 15 to 25 μm.
In the case where the barrier layer 3 is a metal foil, it is preferable that at least the surface opposite to the base layer has a corrosion-resistant coating film for preventing dissolution, corrosion, and the like. The barrier layer 3 may have corrosion-resistant coating films on both surfaces. The corrosion-resistant coating is a film in which a surface of a barrier layer is subjected to a hot water modification treatment such as boehmite treatment, a chemical surface treatment, an anodic oxidation treatment, a plating treatment such as nickel or chromium, and a corrosion-resistant treatment by which a coating agent is applied to impart corrosion resistance to the barrier layer. The treatment for forming the corrosion-resistant coating may be performed in 1 type, or may be performed in combination of 2 or more types. In addition, not only 1 layer but also a plurality of layers may be provided. Further, among these treatments, the hot water modification treatment and the anodic oxidation treatment are treatments in which the surface of the metal foil is dissolved by a treating agent to form a metal compound excellent in corrosion resistance. These treatments are sometimes included in the definition of chemical surface treatments. In addition, when the barrier layer 3 has a corrosion-resistant coating, the barrier layer 3 is formed by including the corrosion-resistant coating.
The corrosion-resistant coating film exhibits the following effects when the exterior material for an electrical storage device is molded: preventing delamination between the barrier layer (e.g., aluminum alloy foil) and the substrate layer; the dissolution and corrosion of the surface of the barrier layer due to hydrogen fluoride generated by the reaction of the electrolyte and the moisture are prevented, and particularly when the barrier layer is an aluminum alloy foil, the dissolution and corrosion of aluminum oxide existing on the surface of the barrier layer are prevented; improving the adhesion (wettability) of the barrier layer surface; preventing delamination of the substrate layer from the barrier layer during heat sealing; preventing delamination of the substrate layer and the barrier layer during molding.
As the corrosion-resistant coating formed by the chemical surface treatment, various coatings are known, and examples thereof include corrosion-resistant coatings containing at least 1 of phosphate, chromate, fluoride, triazinethiol compound, and rare earth oxide. Examples of the chemical surface treatment using phosphate and chromate include chromate treatment, phosphate-chromate treatment, and examples of the chromium compound used for these treatments include chromium nitrate, chromium fluoride, chromium sulfate, chromium acetate, chromium oxalate, chromium dihydrogen phosphate, chromic acid acetoacetate, chromium chloride, and potassium chromium sulfate. The phosphorus compounds used in these treatments include sodium phosphate, potassium phosphate, ammonium phosphate, and polyphosphoric acid. Examples of the chromate treatment include etching chromate treatment, electrolytic chromate treatment, and coating chromate treatment, and preferably coating chromate treatment. The coating type chromate treatment is as follows: first, a surface of at least the inner layer side of the barrier layer (for example, aluminum alloy foil) is subjected to degreasing treatment by a known treatment method such as an alkali dipping method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method, or an acid activation method, and then a treatment liquid containing a metal phosphate such as Cr (chromium) phosphate, ti (titanium) phosphate, zr (zirconium) phosphate, zn (zinc) phosphate, or a mixture of a non-metal phosphate and a non-metal salt, or a treatment liquid composed of a mixture of these and a synthetic resin is applied to the degreased surface by a known application method such as a roll coating method, a gravure printing method, or a dipping method, and then the treated surface is dried. The treatment liquid may be, for example, water, an alcohol-based solvent, a hydrocarbon-based solvent, a ketone-based solvent, an ester-based solvent, or an ether-based solvent, and water is preferable. The resin component used in this case may be a polymer such as a phenol resin or an acrylic resin, and examples thereof include chromate treatment using an aminated phenol polymer having a repeating unit represented by the following general formulae (1) to (4). In the aminated phenol polymer, 1 or 2 or more repeating units represented by the following general formulae (1) to (4) may be contained alone or in any combination. The acrylic resin is preferably polyacrylic acid, acrylic methacrylate copolymer, acrylic maleic acid copolymer, acrylic styrene copolymer, or derivatives thereof such as sodium salt, ammonium salt, amine salt, or the like. Particularly preferred are derivatives of polyacrylic acid such as ammonium salts, sodium salts, or amine salts of polyacrylic acid. In the present invention, polyacrylic acid refers to a polymer of acrylic acid. The acrylic resin is also preferably a copolymer of acrylic acid and a dicarboxylic acid or dicarboxylic anhydride, and is also preferably an ammonium salt, sodium salt or amine salt of a copolymer of acrylic acid and a dicarboxylic acid or dicarboxylic anhydride.
The acrylic resin may be used in an amount of 1 or 2 or more kinds.
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. R 1 and R 2 are the same or different and each represents a hydroxyl group, an alkyl group or a hydroxyalkyl group. Examples of the alkyl group represented by the general formulae (1) to (4) include straight-chain or branched alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups, as the alkyl group represented by X, R 1 and R 2. Examples of the hydroxyalkyl group represented by X, R 1 and R 2 include straight-chain or branched alkyl groups having 1 to 4 carbon atoms, in which 1 hydroxyl group is substituted, such as 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, and 4-hydroxybutyl group. In the general formulae (1) to (4), the alkyl group and the hydroxyalkyl group shown by X, R 1 and R 2 may be the same or different. In the general formulae (1) to (4), X is preferably a hydrogen atom, a hydroxyl group or a hydroxyalkyl group. The number average molecular weight of the aminated phenol polymer having the repeating units represented by the general formulae (1) to (4) is, for example, preferably about 500 to 100 ten thousand, more preferably about 1000 to 2 ten thousand. The aminated phenolic polymer can be manufactured, for example, as follows: a phenol compound or a naphthol compound is polycondensed with formaldehyde to produce a polymer comprising a repeating unit represented by the above general formula (1) or (3), and then a functional group (-CH 2NR1R2) is introduced into the obtained polymer by using formaldehyde and an amine (R 1R2 NH), thereby producing an aminated phenol polymer. The aminated phenolic polymer may be used alone in 1 kind or in a mixture of 2 or more kinds.
As another example of the corrosion-resistant coating film, a film formed by a coating corrosion-resistant treatment by coating a coating agent containing at least 1 kind selected from rare earth element oxide sol, anionic polymer, and cationic polymer is cited. The coating agent may further contain a crosslinking agent that crosslinks the polymer with phosphoric acid or a phosphate. The rare earth oxide sol is obtained by dispersing fine particles (for example, particles having an average particle diameter of 100nm or less) of a rare earth oxide in a liquid dispersion medium. Examples of the rare earth element oxide include cerium oxide, yttrium oxide, neodymium oxide, and lanthanum oxide, and cerium oxide is preferable from the viewpoint of further improving adhesion. The rare earth element oxide contained in the corrosion-resistant coating may be used alone in 1 kind or in combination of 2 or more kinds. As the liquid dispersion medium of the rare earth element oxide sol, various solvents such as water, alcohol solvents, hydrocarbon solvents, ketone solvents, ester solvents, and ether solvents can be used, and water is preferable. 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 with an acrylic main skeleton, polyallylamine or a derivative thereof, and aminated phenol. The anionic polymer is preferably poly (meth) acrylic acid or a salt thereof, or a copolymer containing (meth) acrylic acid or a salt thereof as a main component. The crosslinking agent is preferably at least 1 kind selected from the group consisting of a compound having any of an isocyanate group, a glycidyl group, a carboxyl group, and an oxazoline group, and a silane coupling agent. The phosphoric acid or phosphate is preferably a condensed phosphoric acid or a condensed phosphate.
As an example of the corrosion-resistant coating film, there is listed: a coating film formed by dispersing fine particles of a metal oxide such as aluminum oxide, titanium oxide, cerium oxide, or tin oxide, or barium sulfate in phosphoric acid, applying the dispersion to the surface of the barrier layer, and performing a firing treatment at 150 ℃.
The corrosion-resistant coating film may have a laminated structure in which at least one of a cationic polymer and an anionic polymer is laminated, as required. Examples of the cationic polymer and the anionic polymer include the above-mentioned polymers.
Among them, the composition analysis of the corrosion-resistant coating can be performed by, for example, time-of-flight secondary ion mass spectrometry.
The amount of the corrosion-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 coating type chromate treatment, it is desirable that the content ratio of the chromic acid compound is, for example, about 0.5 to 50mg, preferably about 1.0 to 40mg in terms of chromium per 1m 2 of the surface of the barrier layer 3; the content ratio of the phosphorus compound is, for example, about 0.5 to 50mg, preferably about 1.0 to 40mg in terms of phosphorus; the content ratio of the aminated phenolic polymer is, for example, about 1.0 to 200mg, preferably about 5.0 to 150 mg.
The thickness of the corrosion-resistant coating film is not particularly limited, and from the viewpoints of the cohesive force of the coating film and the adhesion force to the barrier layer or the heat-fusible resin layer, it is preferably about 1nm to 20. Mu.m, more preferably about 1nm to 100nm, and still more preferably about 1nm to 50 nm. The thickness of the corrosion-resistant coating can be measured by observation with a transmission electron microscope or by a combination of observation with a transmission electron microscope and an energy-dispersive X-ray spectrometry or an electron-ray energy loss spectrometry. By composition analysis of the corrosion-resistant coating film by time-of-flight secondary ion mass spectrometry, peaks from secondary ions composed of, for example, ce, P, and O (for example, at least 1 of Ce 2PO4 +、CePO4 - and the like), and secondary ions composed of, for example, cr, P, and O (for example, at least 1 of CrPO 2 +、CrPO4 - and the like) can be detected.
The chemical surface treatment is performed as follows: the chemical surface treatment is performed by applying a solution containing a compound for forming a corrosion-resistant coating film to 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 to a temperature of about 70 to 200 ℃. The barrier layer may be subjected to degreasing treatment by an alkali dipping method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method, or the like, before the barrier layer is subjected to chemical surface treatment. By performing degreasing in this manner, the surface of the barrier layer can be more effectively subjected to chemical surface treatment. In addition, in the degreasing treatment, an acid degreasing agent obtained by dissolving a fluorine-containing compound in an inorganic acid is used, and not only the degreasing effect of the metal foil but also a passive metal fluoride can be formed, and in this case, only the degreasing treatment may be performed.
[ Heat-fusible resin layer 4]
In the exterior material for an electric storage device according to the present invention, the heat-fusible resin layer 4 corresponds to the innermost layer, and is a layer (sealing layer) that functions to seal the electric storage device element by heat-fusing the heat-fusible resin layers to each other when the electric storage device is assembled.
The resin constituting the heat-fusible resin layer 4 is not particularly limited as long as it can be heat-fused, and a resin containing a polyolefin skeleton such as polyolefin or acid-modified polyolefin is preferable. The resin constituting the heat-fusible resin layer 4 contains a polyolefin skeleton, and can be analyzed by infrared spectroscopy, gas chromatography mass spectrometry, or the like, for example. In addition, when the resin constituting the heat-fusible resin layer 4 is analyzed by infrared spectroscopy, a peak derived from maleic anhydride is preferably detected. For example, when the maleic anhydride-modified polyolefin is measured by infrared spectroscopy, a peak derived from maleic anhydride is detected in the vicinity of wave number 1760cm -1 and in the vicinity of wave number 1780cm -1. When the heat-fusible resin layer 4 is a layer made of a maleic anhydride-modified polyolefin, a peak derived from maleic anhydride is detected when measured by infrared spectroscopy. However, if the acid modification degree is low, the peak may be small and undetectable. In this case, the analysis can be performed by nuclear magnetic resonance spectroscopy.
As the polyolefin, specifically, there can be mentioned: polyethylene such as low density polyethylene, medium density polyethylene, high density polyethylene and linear low density polyethylene; ethylene-alpha olefin copolymers; polypropylene such as homopolypropylene, a block copolymer of polypropylene (e.g., a block copolymer of propylene and ethylene), and a random copolymer of polypropylene (e.g., a random copolymer of propylene and ethylene); propylene-alpha olefin copolymers; ethylene-butene-propylene terpolymers, and the like. Among these, polypropylene is preferable. When the copolymer is used, the polyolefin resin may be a block copolymer or a random copolymer. These polyolefin resins may be used singly or in combination of 1 or 2 or more.
In addition, the polyolefin may be a cyclic polyolefin. The cyclic polyolefin is a copolymer of an olefin and a cyclic monomer, and examples of the olefin which is a constituent monomer of the cyclic polyolefin include ethylene, propylene, 4-methyl-1-pentene, styrene, butadiene, isoprene, and the like. Examples of the cyclic monomer that is a constituent monomer of the cyclic polyolefin include cyclic olefins such as norbornene; cyclic dienes such as cyclopentadiene, dicyclopentadiene, cyclohexadiene, norbornadiene, and the like. Among these, cyclic olefins are preferable, and norbornene is further preferable.
The acid-modified polyolefin is a polymer obtained by modifying a polyolefin by block polymerization or graft polymerization with an acid component. As the polyolefin modified with an acid, the above-mentioned polyolefin, a copolymer obtained by copolymerizing a polar molecule such as acrylic acid or methacrylic acid with the above-mentioned polyolefin, a polymer such as a crosslinked polyolefin, or the like can also be used. Examples of the acid component used for acid 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 polyolefin may be an acid-modified cyclic polyolefin. The acid-modified cyclic polyolefin is a polymer obtained by replacing a part of monomers constituting the cyclic polyolefin with an acid component and copolymerizing the same, or by block polymerizing or graft polymerizing the acid component and the cyclic polyolefin. The cyclic polyolefin modified with an acid is the same as described above. The acid component used for the acid modification is the same as that used for the modification of the polyolefin described above.
Preferred examples of the acid-modified polyolefin include polyolefin modified with carboxylic acid or its anhydride, polypropylene modified with carboxylic acid or its anhydride, maleic anhydride-modified polyolefin, and maleic anhydride-modified polypropylene.
The heat-fusible resin layer 4 may be formed of 1 resin alone or a polymer blend in which 2 or more resins are combined. The heat-fusible resin layer 4 may be formed of only 1 layer, or may be formed of 2 or more layers of the same or different resins.
The heat-fusible resin layer 4 may contain a lubricant or the like as necessary. When the heat-fusible resin layer 4 contains a lubricant, the moldability of the exterior material for the power storage device can be improved. The lubricant is not particularly limited, and a known lubricant may be used. The lubricant may be used alone in an amount of 1 kind, or may be used in an amount of 2 or more kinds in combination.
The lubricant is not particularly limited, and an amide-based lubricant is preferable. Specific examples of the lubricant include the lubricants exemplified in the base material layer 1. The lubricant may be used alone or in combination of 2 or more.
In the case where a lubricant is present on the surface of the heat-fusible resin layer 4, the amount of the lubricant present is not particularly limited, and from the viewpoint of improving the moldability of the exterior material for the power storage device, it is preferably about 10 to 50mg/m 2, more preferably about 15 to 40mg/m 2.
The lubricant present on the surface of the heat-fusible resin layer 4 may be a lubricant that oozes out from the lubricant contained in the resin constituting the heat-fusible resin layer 4, or may be a lubricant that 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 it can exert a function of sealing the power storage device element by heat-fusing the heat-fusible resin layers to each other, and examples thereof include about 100 μm or less, preferably about 85 μm or less, and more preferably about 15 to 85 μm. In addition, for example, when the thickness of the adhesive layer 5 to be described later is 10 μm or more, the thickness of the heat-fusible resin layer 4 is preferably about 85 μm or less, more preferably about 15 to 45 μm, and when the thickness of the adhesive layer 5 to be described later is less than 10 μm or no adhesive layer 5 is provided, the thickness of the heat-fusible resin layer 4 is preferably about 20 μm or more, more preferably about 35 to 85 μm.
[ Adhesive layer 5]
In the outer packaging material for a power storage device of the present invention, the adhesive layer 5 is a layer provided between the barrier layer 3 (or the corrosion-resistant coating film) and the heat-fusible resin layer 4 as needed to firmly adhere them.
The adhesive layer 5 is formed of a resin capable of adhering the barrier layer 3 to the heat-fusible resin layer 4. As the resin for forming the adhesive layer 5, for example, the same adhesive as the adhesive exemplified in the adhesive layer 2 can be used. The resin used to form the adhesive layer 5 preferably includes a polyolefin skeleton, and examples thereof include the polyolefin and the acid-modified polyolefin exemplified in the heat-fusible resin layer 4. The resin constituting the adhesive layer 5 includes a polyolefin skeleton, and can be analyzed by, for example, infrared spectroscopy, gas chromatography-mass spectrometry, or the like, and the analysis method is not particularly limited. In addition, when the resin constituting the adhesive layer 5 is analyzed by infrared spectroscopy, a peak derived from maleic anhydride is preferably detected. For example, when the maleic anhydride-modified polyolefin is measured by infrared spectroscopy, a peak derived from maleic anhydride is detected in the vicinity of wave number 1760cm -1 and in the vicinity of wave number 1780cm -1. However, if the acid modification degree is low, the peak may be small and undetectable. In this case, the analysis can be performed by nuclear magnetic resonance spectroscopy.
The adhesive layer 5 preferably contains an acid-modified polyolefin from the viewpoint of firmly adhering the barrier layer 3 to the heat-fusible resin layer 4. The acid-modified polyolefin is particularly preferably a polyolefin modified with a carboxylic acid or an anhydride thereof, a polypropylene modified with a carboxylic acid or an anhydride thereof, a maleic anhydride-modified polyolefin, or a maleic anhydride-modified polypropylene.
Further, from the viewpoint of reducing the thickness of the exterior material for an electric storage device and making the exterior material for an electric storage device excellent in shape stability after molding, the adhesive layer 5 is more preferably a cured product of a resin composition containing an acid-modified polyolefin and a curing agent. The acid-modified polyolefin is preferably exemplified by the above-mentioned compounds.
The adhesive layer 5 is preferably a cured product of a resin composition containing an acid-modified polyolefin and at least 1 selected from the group consisting of a compound having an isocyanate group, a compound having an oxazoline group and a compound having an epoxy group, and particularly preferably a cured product of a resin composition containing an acid-modified polyolefin and at least 1 selected from the group consisting of a compound having an isocyanate group and a compound having an epoxy group. The adhesive layer 5 preferably contains at least 1 selected from polyurethane, polyester, and epoxy resin, and more preferably contains polyurethane and epoxy resin. As the polyester, for example, an amide ester resin is preferable. Amide ester resins are typically formed by the reaction of carboxyl groups with oxazoline groups. The adhesive layer 5 is more preferably a cured product of a resin composition containing at least 1 of these resins and the acid-modified polyolefin described above. When unreacted materials such as isocyanate group-containing compounds, oxazoline group-containing compounds, and curing agents such as epoxy resins remain in the adhesive layer 5, the presence of the unreacted materials can be confirmed by a method selected from infrared spectroscopy, raman spectroscopy, time-of-flight secondary ion mass spectrometry (TOF-SIMS), and the like.
In addition, from the viewpoint of further improving the adhesion between the barrier layer 3 and the adhesive layer 5, the adhesive layer 5 is preferably a cured product of a resin composition containing a curing agent having at least 1 selected from the group consisting of an oxygen atom, a heterocycle, a c=n bond, and a c—o—c bond. Examples of the curing agent having a heterocyclic ring include a curing agent having an oxazoline group and a curing agent having an epoxy group. Examples of the curing agent having a c=n bond include a curing agent having an oxazoline group, a curing agent having an isocyanate group, and the like. Examples of the curing agent having a C-O-C bond include a curing agent having an oxazoline group, a curing agent having an epoxy group, and polyurethane. The adhesive layer 5 is a cured product of a resin composition containing these curing agents, and can be confirmed by methods such as Gas Chromatography Mass Spectrometry (GCMS), infrared spectroscopy (IR), time-of-flight secondary ion mass spectrometry (TOF-SIMS), and X-ray photoelectron spectroscopy (XPS).
The compound having an isocyanate group is not particularly limited, and a polyfunctional isocyanate compound is preferable from the viewpoint of effectively improving the adhesion between the barrier layer 3 and the adhesive layer 5. The polyfunctional isocyanate compound is not particularly limited as long as it has 2 or more isocyanate groups. Specific examples of the polyfunctional isocyanate curing agent include Pentane Diisocyanate (PDI), isophorone diisocyanate (IPDI), hexamethylene Diisocyanate (HDI), toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), a compound obtained by polymerizing or urethanizing them, a mixture thereof, and a copolymer with other polymers. Further, adducts, biurets, isocyanurates, and the like can be cited.
The content of the compound having an isocyanate group in the adhesive layer 5 is preferably in the range of 0.1 to 50 mass%, more preferably in the range of 0.5 to 40 mass% in the resin composition constituting the adhesive layer 5. This effectively improves the adhesion between the barrier layer 3 and the adhesive layer 5.
The compound having an oxazoline group is not particularly limited as long as it has an oxazoline skeleton. Specific examples of the compound having an oxazoline group include a compound having a polystyrene main chain, a compound having an acrylic main chain, and the like. Further, commercially available products include Epocros series manufactured by japan catalyst corporation.
The proportion of the oxazoline group-containing compound in the adhesive layer 5 is preferably in the range of 0.1 to 50 mass%, more preferably in the range of 0.5 to 40 mass% in the resin composition constituting the adhesive layer 5. This effectively improves the adhesion between the barrier layer 3 and the adhesive layer 5.
Examples of the compound having an epoxy group include epoxy resins. The epoxy resin is not particularly limited as long as it can form a crosslinked structure using an epoxy group existing in a molecule, and a known epoxy resin can be used. The weight average molecular weight of the epoxy resin is preferably about 50 to 2000, more preferably about 100 to 1000, and further preferably about 200 to 800. Wherein, in the first invention, the weight average molecular weight of the epoxy resin is a value measured by Gel Permeation Chromatography (GPC) under the condition of using polystyrene as a standard sample.
Specific examples of the epoxy resin include glycidyl ether derivatives of trimethylolpropane, bisphenol a diglycidyl ether, modified bisphenol a diglycidyl ether, novolac glycidyl ether, glycerol polyglycidyl ether, and polyglycerol polyglycidyl ether. The epoxy resin may be used alone or in combination of 1 kind or 2 or more kinds.
The proportion of the epoxy resin in the adhesive layer 5 is preferably in the range of 0.1 to 50 mass%, more preferably in the range of 0.5 to 40 mass%, in the resin composition constituting the adhesive layer 5. This effectively improves the adhesion between the barrier layer 3 and the adhesive layer 5.
The polyurethane is not particularly limited, and known polyurethane can be used. The adhesive layer 5 may be, for example, a cured product of a two-part curable polyurethane.
The proportion of polyurethane in the adhesive layer 5 is preferably in the range of 0.1 to 50 mass%, more preferably in the range of 0.5 to 40 mass%, in the resin composition constituting the adhesive layer 5. This effectively improves the adhesion between the barrier layer 3 and the adhesive layer 5 in an atmosphere in which a component such as an electrolyte solution that induces corrosion of the barrier layer is present.
In addition, in the case where the adhesive layer 5 is a cured product of a resin composition containing at least 1 selected from the group consisting of a compound having an isocyanate group, a compound having an oxazoline group, and an epoxy resin, and the acid-modified polyolefin, the acid-modified polyolefin functions as a main agent, and the compound having an isocyanate group, the compound having an oxazoline group, and the compound having an epoxy group function as curing agents, respectively.
The thickness of the adhesive layer 5 is preferably about 50 μm or less, about 40 μm or less, about 30 μm or less, about 20 μm or less, about 5 μm or less, and the lower limit is preferably about 0.1 μm or more, about 0.5 μm or more, and the thickness is preferably about 0.1 to 50 μm, about 0.1 to 40 μm, about 0.1 to 30 μm, about 0.1 to 20 μm, about 0.1 to 5 μm, about 0.5 to 50 μm, about 0.5 to 40 μm, about 0.5 to 30 μm, about 0.5 to 20 μm, or about 0.5 to 5 μm. More specifically, in the case of the cured product of the adhesive, the acid-modified polyolefin, and the curing agent exemplified in the adhesive layer 2, it is preferably about 1 to 10 μm, and more preferably about 1 to 5 μm. In the case of using the resin exemplified for the heat-fusible resin layer 4, it is preferable to use a resin having a particle size of about 2 to 50. Mu.m, more preferably about 10 to 40. Mu.m. In the case where the adhesive layer 5 is a cured product of the adhesive agent exemplified in the adhesive layer 2 and a resin composition containing an acid-modified polyolefin and a curing agent, the adhesive layer 5 can be formed by, for example, applying the resin composition and curing the composition by heating or the like. In the case of using the resin exemplified for the heat-fusible resin layer 4, it can be formed by, for example, extrusion molding of the heat-fusible resin layer 4 and the adhesive layer 5.
[ Surface coating 6]
The exterior material for an electric storage device of the present invention may have a surface coating layer 6 on the base material layer 1 (on the side of the base material layer 1 opposite to the barrier layer 3) for the purpose of improving at least one of design properties, electrolyte resistance, scratch resistance, moldability, and the like, as required. The surface coating layer 6 is a layer located on the outermost layer side of the exterior material for the power storage device when the power storage device is assembled using the exterior material for the power storage device.
The surface coating layer 6 is formed of, for example, a resin such as polyvinylidene chloride, polyester, polyurethane, acrylic resin, or epoxy resin.
In the case where the resin forming the surface coating layer 6 is a curable resin, the resin may be any of a one-fluid curable type and a two-fluid curable type, and is preferably a two-fluid curable type. Examples of the two-part curable resin include two-part curable polyurethane, two-part curable polyester, and two-part curable epoxy resin. Of these, two-liquid curable polyurethane is preferable.
Examples of the two-part curable polyurethane include a polyurethane containing a main agent containing a polyol compound and a curing agent containing an isocyanate compound. Preferably, a two-part curable polyurethane is exemplified which comprises a polyol such as a polyester polyol, a polyether polyol and an acrylic polyol as a main component and an aromatic or aliphatic polyisocyanate as a curing agent. Further, as the polyol compound, a polyester polyol having a hydroxyl group in the outer chain in addition to the hydroxyl group at the terminal of the repeating unit is preferably used. The surface coating layer 6 is made of polyurethane, so that excellent electrolyte resistance can be imparted to the outer packaging material for the power storage device.
The surface coating layer 6 may contain additives such as the aforementioned lubricants, antiblocking agents, matting agents, flame retardants, antioxidants, tackifiers, antistatic agents, and the like, as required, on at least one of the surface and the inside of the surface coating layer 6, depending on the surface coating layer 6 or the functions to be provided on the surface thereof, and the like. Examples of the additive include fine particles having an average particle diameter of about 0.5nm to 5. Mu.m. The average particle diameter of the additive is the median particle diameter measured by a laser diffraction/scattering type particle diameter distribution measuring apparatus.
The additive may be any of inorganic and organic substances. The shape of the additive is not particularly limited, and examples thereof include spherical, fibrous, plate-like, amorphous, and scaly.
Specific examples of the additives include talc, silica, graphite, kaolin, montmorillonite, 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, acrylate resin, crosslinked acrylic acid, crosslinked styrene, crosslinked polyethylene, benzoguanamine, gold, aluminum, copper, nickel, and the like. The additive may be used alone in an amount of 1 kind, or may be used in an amount 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 surface of the additive may be subjected to various surface treatments such as an insulating treatment and a high dispersibility treatment.
The method for forming the surface coating layer 6 is not particularly limited, and examples thereof include a method of coating a resin for forming the surface coating layer 6. When the additive is blended in the surface coating layer 6, the resin mixed with the additive may be applied.
The thickness of the surface coating layer 6 is not particularly limited as long as the above-described function as the surface coating layer 6 can be exhibited, and examples thereof include about 0.5 to 10 μm, preferably about 1 to 5 μm.
3. Method for producing exterior material for power storage device
The method for producing the exterior material for an electric storage device is not particularly limited as long as a laminate in which the layers of the exterior material for an electric storage device of the present invention are laminated can be obtained, and a method including a step of laminating at least the base layer 1, the barrier layer 3, and the heat-fusible resin layer 4 in this order from the outside may be used. Specifically, the method for producing an exterior material for a power storage device according to the present invention comprises a step of obtaining a laminate in which at least a base material layer, a barrier layer, and a heat-fusible resin layer are laminated in this order from the outside, wherein the base material layer comprises a polyamide film, and the polyamide film has a crystallization index of 1.50 or more as measured from the outside of the base material layer by the ATR method of fourier transform infrared spectroscopy.
As an example of the method for producing the exterior material for a power storage device of the present invention, the following is given. First, a laminate (hereinafter, also referred to as "laminate a") in which the base material layer 1, the adhesive layer 2, and the barrier layer 3 are laminated in this order is formed. The laminate a can be formed specifically by the following dry lamination method: the adhesive for forming the adhesive layer 2 is applied to the base layer 1 or the barrier layer 3, the surface of which is chemically surface-treated as needed, by a coating method such as gravure coating or roll coating, and then dried, and then the barrier layer 3 or the base layer 1 is laminated, and then the adhesive layer 2 is cured.
Next, a heat-fusible resin layer 4 is laminated on the barrier layer 3 of the laminate a. In the case of directly laminating the heat-fusible resin layer 4 on the barrier layer 3, the heat-fusible resin layer 4 may be laminated on the barrier layer 3 of the laminate a by a method such as a heat lamination method or an extrusion lamination method. In addition, when the adhesive layer 5 is provided between the barrier layer 3 and the heat-fusible resin layer 4, the following method can be used, for example: (1) A method of laminating by extruding the adhesive layer 5 and the heat-fusible resin layer 4 onto the barrier layer 3 of the laminate a (coextrusion lamination method, tandem lamination method); (2) A method of forming a laminate comprising an adhesive layer 5 and a heat-fusible resin layer 4 laminated on the barrier layer 3 of the laminate a by a heat lamination method, or a method of forming a laminate comprising an adhesive layer 5 laminated on the barrier layer 3 of the laminate a and a heat-fusible resin layer 4 laminated by a heat lamination method; (3) A method (sandwich lamination method) in which a molten adhesive layer 5 is flowed between a barrier layer 3 of a laminate A and a heat-fusible resin layer 4 formed into a sheet in advance, and the laminate A and the heat-fusible resin layer 4 are bonded by the adhesive layer 5; (4) A method of laminating an adhesive for forming the adhesive layer 5 on the barrier layer 3 of the laminate a by a solution coating and drying method, a method of further baking, a method of laminating a heat-fusible resin layer 4 prepared in advance in a sheet form on the adhesive layer 5, and the like.
In the case where the surface coating layer 6 is provided, the surface coating layer 6 is laminated on the surface of the base material layer 1 on the opposite side of 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, a laminate having the surface coating layer 6, the base material layer 1, the adhesive layer 2, the barrier layer 3, and the adhesive layer 5, and the heat-fusible resin layer 4, which are provided as needed, in this order from the outside can be formed, and the laminate can be subjected to a heat treatment in order to secure adhesion between the adhesive layer 2 and the adhesive layer 5, which are provided as needed.
In the outer packaging material for the power storage device, the surface activation treatment such as corona treatment, sandblasting treatment, oxidation treatment, ozone treatment, etc. is applied to each layer constituting the laminate as needed, whereby the processing suitability can be improved. For example, by corona treatment of the surface of the base material layer 1 opposite to the barrier layer 3, the printing suitability of the ink to the surface of the base material layer 1 can be improved.
4. Use of outer packaging material for power storage device
The outer packaging material for a power storage device of the present invention is used in a package for sealing and housing power storage device elements such as a positive electrode, a negative electrode, and an electrolyte. That is, the power storage device can be formed by housing a power storage device element having at least a positive electrode, a negative electrode, and an electrolyte in a package formed of the outer package material for a power storage device of the present invention.
Specifically, with the exterior material for an electric storage device according to the present invention, an electric storage device element having at least a positive electrode, a negative electrode, and an electrolyte is covered so that a flange portion (a region where heat-fusible resin layers contact each other) can be formed at the peripheral edge of the electric storage device element in a state in which metal terminals respectively connecting the positive electrode and the negative electrode described below protrude outward, and the heat-fusible resin layers of the flange portion are heat-sealed with each other to seal the heat-fusible resin layers, thereby providing an electric storage device using the exterior material for an electric storage device. When the power storage device element is stored in the package formed of the power storage device outer package of the present invention, the heat-fusible resin portion of the power storage device outer package of the present invention is located inside (at the surface in contact with the power storage device element), and the package is formed.
The exterior material for a power storage device of the present invention can be applied to a power storage device such as a battery (including a capacitor), a capacitor (capacitor), and the like). The exterior material for a power storage device of the present invention can be used for both primary batteries and secondary batteries, and is preferably a secondary battery. The type of secondary battery to which the outer packaging material for a power storage device of the present invention is applied is not particularly limited, and examples thereof include lithium ion batteries, lithium ion polymer batteries, all-solid 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), capacitors (capacitors), and the like. Among these secondary batteries, preferred examples of the outer packaging material for a power storage device of the present invention include lithium ion batteries and lithium ion polymer batteries.
The power storage device is generally fixed to the case of various products using a double-sided tape or an adhesive. That is, the exterior material 10 for a power storage device of the present invention is fixed to the cases of various products by double-sided tape or adhesive. The material of the case is various depending on the kind of the product, and for example, various kinds of metals such as stainless steel, aluminum alloy and nickel alloy, plastics such as polyolefin, polyamide, polyester, polyimide and polystyrene, glass and the like are involved.
The adhesive strength between the power storage device and the case is adjusted, for example, to a level at which the power storage device can be peeled off from the case. The peel strength between the power storage device and the case is preferably fixed using, for example, a double-sided tape having a peel strength of about 5 to 15N/7.5mm with respect to the stainless steel plate, which is measured in the later-described (measurement of the peel strength of the double-sided tape). The outer packaging material 10 for the power storage device can be suitably used for the power storage device fixed to the case by a double-sided tape having a peel strength of about 5 to 15N/7.5mm with respect to the case.
5. Polyamide film
The polyamide film of the present invention is a polyamide film for a base material layer of an outer package for a power storage device, which is composed of a laminate comprising at least a base material layer, a barrier layer and a heat-fusible resin layer, and has a crystallization index of 1.50 or more as measured by the ATR method of the fourier transform infrared spectroscopy method. The details of the outer package material 10 for the power storage device are as described above.
By using the polyamide film of the present invention for the base material layer 1 of the outer package material for an electric storage device, the crystallinity index of the polyamide film of the base material layer 1 of the outer package material 10 for an electric storage device can be appropriately set to 1.50 or more, and breakage of the outer package material for an electric storage device can be effectively suppressed at the time of the foregoing peeling. That is, the polyamide film of the present invention having the crystallization index adjusted to 1.50 or more is preferably used for the base layer 1 and laminated with each layer such as the barrier layer 3 and the heat-fusible resin layer 4, thereby producing the outer package 10 for an electric storage device of the present invention. As described above, the crystallinity index of the polyamide film contained in the base material layer 1 can be improved after being laminated on the exterior material 10 for the power storage device, compared with the polyamide film before being applied to the exterior material 10 for the power storage device. Specifically, the crystallization index can be improved by applying heat to the polyamide film during the production of the outer packaging material 10 for the power storage device.
The method for measuring the crystallization index of the polyamide film of the present invention is as follows.
< Determination of crystallization index of Polyamide film >
The polyamide film was cut into square shapes of 100mm×100mm, and samples were produced. The surface of the obtained sample was subjected to infrared absorption spectrometry using an ATR measurement mode of FT-IR at a temperature of 25 ℃ and a relative humidity of 50%. As the device, for example, nicolet iS10 manufactured by sameimers technology corporation (Thermo FISHER SCIENTIFIC) can be used. From the obtained absorption spectrum, the peak intensity P near 1200cm -1 of absorption from the α -crystal of nylon and the peak intensity Q near 1370cm -1 of absorption not related to crystallization were measured, and the intensity ratio x=p/Q of the peak intensity P to the peak intensity Q was calculated as the crystallization index.
(Measurement conditions)
The method comprises the following steps: macroATR process;
Wave number resolution: 8cm -1;
Cumulative number of times: 32 times;
A detector: a DTGS detector;
ATR prism: ge;
Incidence angle: 45 °;
Baseline: the wave numbers between 1100cm -1 and 1400cm -1 were determined in a straight-line approximation.
Absorption peak intensity Y 1200: a value obtained by subtracting the value of the base line from the maximum value of the peak intensity in the range of the wave number 1195cm -1 to 1205cm -1;
Absorption peak intensity Y 1370: a value obtained by subtracting the value of the base line from the maximum value of the peak intensity in the range of the wave numbers 1365cm -1 to 1375cm -1.
In the polyamide film of the present invention, the crystallization index is 1.50 or more, and is preferably 1.55 or more, more preferably 1.60 or more, and particularly preferably 1.65 or more, from the viewpoint of more effectively suppressing breakage of the outer packaging material for the power storage device at the time of the peeling. The upper limit of the crystallization index is not particularly limited, and examples thereof include 2.50 or less and 1.80 or less. Preferable ranges of the crystallization index include, for example, 1.50 to 2.50, 1.60 to 2.50, 1.65 to 2.50, 1.50 to 1.80, 1.60 to 1.80, and 1.65 to 1.80.
Specific examples of the polyamide forming the polyamide film are described in the item of the base material layer 1 of the outer packaging material 10 for an electric storage device. The polyamide film may be an unstretched film or a stretched film. The stretched film may be a uniaxially stretched film or a biaxially stretched film, and is preferably a biaxially stretched film. Examples of the stretching method for forming the biaxially stretched film include a sequential biaxial stretching method, a inflation method, and a simultaneous biaxial stretching method. Examples of the method for coating the resin include a roll coating method, a gravure coating method, and an extrusion coating method.
The polyamide film is particularly preferably a biaxially stretched nylon film.
The thickness of the polyamide film is preferably about 3 μm or more, more preferably about 10 μm or more, and preferably about 50 μm or less, more preferably about 35 μm or less, from the viewpoint of more effectively suppressing breakage of the exterior material for the power storage device at the time of the foregoing peeling, and the preferable range is about 3 to 50 μm, about 3 to 35 μm, about 10 to 50 μm, about 10 to 35 μm, and about 10 to 35 μm is particularly preferable.
Additives such as lubricants, flame retardants, antiblocking agents, antioxidants, light stabilizers, tackifiers, antistatic agents, and the like may be present on at least one of the surface and the interior of the polyamide film. The additive may be used in an amount of 1 or 2 or more. The details of the additives are as described in the item of the base material layer 1 of the outer packaging material 10 for an electric storage device.
Examples
Hereinafter, the present invention will be described in detail with reference to examples and comparative examples. However, the present invention is not limited to the examples.
Production of outer packaging Material for electric storage device
Examples 1-3 and comparative examples 1-2
As a base material layer, stretched nylon (ONy) films (thickness 25 μm) were prepared, respectively. As described later, the stretched nylon films used in examples 1 to 3 and comparative examples 1 to 2 were each changed in stretching ratio and heat-set temperature, and the crystallization index was adjusted to the values shown in table 1. Erucamide is coated on the stretched nylon film as a lubricant. As a barrier layer, an aluminum alloy foil (JIS H4160:1994A 8021H-O (thickness 40 μm)) was prepared. Next, an adhesive (two-part polyurethane adhesive) was applied to one surface of the aluminum alloy foil, and dried. Next, the adhesive on the barrier layer and the base material layer were laminated by a dry lamination method, and then cured, whereby a laminate of base material layer (thickness 25 μm)/adhesive layer (thickness 3 μm after curing)/barrier layer (thickness 40 μm) was produced. Both surfaces of the aluminum alloy foil were subjected to chemical surface treatment. The chemical surface treatment of the aluminum alloy foil is performed as follows: the aluminum alloy foil was subjected to chemical surface treatment by applying a treatment liquid containing a phenolic resin, a chromium fluoride compound and phosphoric acid to both surfaces of the aluminum alloy foil by roll coating so that the coating amount of chromium was 10mg/m 2 (dry mass), and then firing the resultant foil.
Next, maleic anhydride-modified polypropylene as an adhesive layer (thickness 23 μm) and random polypropylene as a heat-fusible resin layer (thickness 23 μm) were coextruded onto the barrier layer of each laminate obtained as described above, whereby the adhesive layer/heat-fusible resin layer was laminated on the barrier layer, and then cured to obtain a laminate (total thickness 114 μm) in which a base layer (thickness 25 μm)/adhesive layer (3 μm)/barrier layer (40 μm)/adhesive layer (23 μm)/heat-fusible resin layer (23 μm) were laminated in this order from the outside.
Example 4
As a base material layer, a stretched nylon (ONy) film (thickness: 20 μm) was prepared. As described later, the stretched nylon film used in example 4 was changed in stretching ratio and heat-set temperature, and the crystallization index was adjusted to the values shown in table 1. The stretched nylon film has a coating layer (a coating layer obtained by coating a polyester polyurethane containing a lubricant at a thickness of 300nm or less) on the surface opposite to the barrier layer, and has a coating layer (a coating layer obtained by coating a polyester polyurethane at a thickness of 300nm or less) on the surface on the barrier layer side. As a barrier layer, an aluminum alloy foil (JIS H4160:1994A 8021H-O (thickness 35 μm)) was prepared. Next, an adhesive (two-part polyurethane adhesive) was applied to one surface of the aluminum alloy foil and dried. Next, the adhesive on the barrier layer and the base material layer were laminated by a dry lamination method, and then cured, whereby a laminate of base material layer (thickness 20 μm)/adhesive layer (thickness 3 μm after curing)/barrier layer (thickness 35 μm) was produced. Both surfaces of the aluminum alloy foil were subjected to chemical surface treatment. The chemical surface treatment of the aluminum alloy foil is performed as follows: the aluminum alloy foil was subjected to chemical surface treatment by applying a treatment liquid containing a phenolic resin, a chromium fluoride compound and phosphoric acid to both surfaces of the aluminum alloy foil by roll coating so that the coating amount of chromium was 10mg/m 2 (dry mass), and then firing the resultant foil.
Next, maleic anhydride-modified polypropylene as an adhesive layer (thickness 15 μm) and random polypropylene as a heat-fusible resin layer (thickness 15 μm) were coextruded onto the barrier layer of each laminate obtained as described above, whereby the adhesive layer/heat-fusible resin layer was laminated on the barrier layer, and then cured to obtain a laminate (total thickness 88 μm) in which a base layer (thickness 20 μm)/adhesive layer (3 μm)/barrier layer (35 μm)/adhesive layer (15 μm)/heat-fusible resin layer (15 μm) were laminated in this order from the outside.
Example 5
As a base material layer, a stretched nylon (ONy) film (thickness: 20 μm) was prepared. The stretched nylon film used in example 5 was the same as that used in example 4. The stretched nylon film has a coating layer (a coating layer obtained by coating a polyester polyurethane containing a lubricant at a thickness of 300nm or less) on the surface opposite to the barrier layer, and has a coating layer (a coating layer obtained by coating a polyester polyurethane at a thickness of 300nm or less) on the surface on the barrier layer side. As a barrier layer, an aluminum alloy foil (JIS H4160:1994A 8021H-O (thickness 30 μm)) was prepared. Next, an adhesive (two-part polyurethane adhesive) was applied to one surface of the aluminum alloy foil and dried. Next, the adhesive on the barrier layer and the base material layer were laminated by a dry lamination method, and then cured, whereby a laminate of base material layer (thickness 20 μm)/adhesive layer (thickness 3 μm after curing)/barrier layer (thickness 30 μm) was produced. Both surfaces of the aluminum alloy foil were subjected to chemical surface treatment. The chemical surface treatment of the aluminum alloy foil is performed as follows: the aluminum alloy foil was subjected to chemical surface treatment by applying a treatment liquid containing a phenolic resin, a chromium fluoride compound and phosphoric acid to both surfaces of the aluminum alloy foil by roll coating so that the coating amount of chromium was 10mg/m 2 (dry mass), and then firing the resultant foil.
Next, maleic anhydride-modified polypropylene as an adhesive layer (thickness 14 μm) and random polypropylene as a heat-fusible resin layer (thickness 10 μm) were coextruded onto the barrier layer of each laminate obtained as described above, whereby the adhesive layer/heat-fusible resin layer was laminated on the barrier layer, and then cured to obtain a laminate (total thickness 77 μm) in which a base layer (thickness 20 μm)/adhesive layer (3 μm)/barrier layer (30 μm)/adhesive layer (14 μm)/heat-fusible resin layer (10 μm) were laminated in this order from the outside.
Example 6
A laminate (total thickness 114 μm) was obtained by laminating a base layer (thickness 25 μm)/an adhesive layer (3 μm)/a barrier layer (40 μm)/an adhesive layer (23 μm)/a heat-fusible resin layer (23 μm) in this order from the outside in the same manner as in example 1, except that a stretched nylon (ONy) film having a coating layer (coating layer obtained by coating polyester polyurethane at a thickness of 300nm or less) on the surface on the barrier layer side was used as the base layer.
Example 7
As a base material layer, a stretched nylon (ONy) film (thickness: 20 μm) was prepared. The stretched nylon film used in example 7 was the same as the stretched nylon film used in example 4. As a barrier layer, an aluminum alloy foil (JIS H4160:1994A 8021H-O (thickness 35 μm)) was prepared. Next, a barrier layer and a base material layer were laminated by a dry lamination method using an adhesive (a two-component polyurethane adhesive containing carbon black), and then cured to produce a laminate of a base material layer (thickness 20 μm)/an adhesive layer (thickness 3 μm after curing)/a barrier layer (thickness 35 μm). Both surfaces of the aluminum alloy foil were subjected to chemical surface treatment. The chemical surface treatment of the aluminum alloy foil is performed by the following method: the aluminum alloy foil was subjected to chemical surface treatment by applying a treatment liquid containing a phenolic resin, a chromium fluoride compound and phosphoric acid to both surfaces of the aluminum alloy foil by roll coating so that the coating amount of chromium was 10mg/m 2 (dry mass), and then firing the resultant foil.
Next, maleic anhydride-modified polypropylene as an adhesive layer (thickness 15 μm) and random polypropylene as a heat-fusible resin layer (thickness 15 μm) were coextruded onto the barrier layer of each laminate obtained as described above, whereby an adhesive layer/heat-fusible resin layer was laminated on the barrier layer, and a laminate was obtained in which a base layer (thickness 20 μm)/adhesive layer (3 μm)/barrier layer (35 μm)/adhesive layer (15 μm)/heat-fusible resin layer (15 μm) was laminated in this order. Next, a resin (two-liquid polyurethane resin containing silica particles and resin beads) for forming a rough layer as a surface coating layer was applied to the surface of the stretched nylon film of the obtained laminate so as to have a thickness of 3 μm, and then cured, whereby a laminate (total thickness 91 μm) was obtained in which a surface coating layer (thickness 3 μm)/a base material layer (thickness 20 μm)/an adhesive layer (3 μm)/a barrier layer (35 μm)/an adhesive layer (15 μm)/a heat-fusible resin layer (15 μm) were laminated in this order from the outside.
Example 8
As a base material layer, a stretched nylon (ONy) film (thickness: 20 μm) was prepared. The stretched nylon film used in example 8 was the same as the stretched nylon film used in example 4. As a barrier layer, an aluminum alloy foil (JIS H4160:1994A 8021H-O (thickness 40 μm)) was prepared. Next, an adhesive (two-part polyurethane adhesive) was applied to one surface of the aluminum alloy foil and dried. Next, the adhesive on the barrier layer and the base material layer were laminated by a dry lamination method, and then cured to prepare a laminate of base material layer (thickness 20 μm)/adhesive layer (thickness 3 μm after curing)/barrier layer (thickness 40 μm). Both surfaces of the aluminum alloy foil were subjected to chemical surface treatment. The chemical surface treatment of the aluminum alloy foil is performed as follows: the aluminum alloy foil was subjected to chemical surface treatment by applying a treatment liquid containing a phenolic resin, a chromium fluoride compound and phosphoric acid to both surfaces of the aluminum alloy foil by roll coating so that the coating amount of chromium was 10mg/m 2 (dry mass), and then firing the resultant foil.
Next, maleic anhydride-modified polypropylene as an adhesive layer (thickness 14 μm) and random polypropylene as a heat-fusible resin layer (thickness 10 μm) were coextruded onto the barrier layer of each laminate obtained as described above, whereby the adhesive layer/heat-fusible resin layer was laminated on the barrier layer, and then cured to obtain a laminate (total thickness 87 μm) in which a base layer (thickness 20 μm)/adhesive layer (3 μm)/barrier layer (40 μm)/adhesive layer (14 μm)/heat-fusible resin layer (10 μm) were laminated in this order from the outside.
Example 9
As a base material layer, a stretched nylon (ONy) film (thickness: 20 μm) was prepared. The stretched nylon film used in example 9 was the same as the stretched nylon film used in example 4. As a barrier layer, an aluminum alloy foil (JIS H4160:1994A 8021H-O (thickness 40 μm)) was prepared. Next, a barrier layer and a base material layer were laminated by a dry lamination method using an adhesive (a two-component polyurethane adhesive containing carbon black), and then cured to produce a laminate of a base material layer (thickness 20 μm)/an adhesive layer (thickness 3 μm after curing)/a barrier layer (thickness 40 μm). Both surfaces of the aluminum alloy foil were subjected to chemical surface treatment. The chemical surface treatment of the aluminum alloy foil is performed as follows: the aluminum alloy foil was subjected to chemical surface treatment by applying a treatment liquid containing a phenolic resin, a chromium fluoride compound and phosphoric acid to both surfaces of the aluminum alloy foil by roll coating so that the coating amount of chromium was 10mg/m 2 (dry mass), and then firing the resultant foil.
Next, maleic anhydride-modified polypropylene as an adhesive layer (thickness 14 μm) and random polypropylene as a heat-fusible resin layer (thickness 10 μm) were coextruded onto the barrier layer of each laminate obtained as described above, whereby an adhesive layer/heat-fusible resin layer was laminated on the barrier layer, and a laminate was obtained in which a base layer (thickness 20 μm)/adhesive layer (3 μm)/barrier layer (40 μm)/adhesive layer (14 μm)/heat-fusible resin layer (10 μm) was laminated in this order. Next, a resin (two-liquid polyurethane resin containing silica particles and resin beads) for forming a rough layer as a surface coating layer was applied to the surface of the stretched nylon film of the obtained laminate so as to have a thickness of 3 μm, and then cured, whereby a laminate (total thickness of 90 μm) was obtained in which a surface coating layer (thickness 3 μm)/a base material layer (thickness of 20 μm)/an adhesive layer (3 μm)/a barrier layer (40 μm)/an adhesive layer (14 μm)/a heat-fusible resin layer (10 μm) were laminated in this order from the outside.
Example 10
As a base material layer, a stretched nylon (ONy) film (thickness: 20 μm) was prepared. The stretched nylon film used in example 10 was the same as the stretched nylon film used in example 4. As a barrier layer, an aluminum alloy foil (JIS H4160:1994A 8021H-O (thickness 40 μm)) was prepared. Next, an adhesive (two-part polyurethane adhesive) was applied to one surface of the aluminum alloy foil and dried. Next, the adhesive on the barrier layer and the base material layer were laminated by a dry lamination method, and then cured to prepare a laminate of base material layer (thickness 20 μm)/adhesive layer (thickness 3 μm after curing)/barrier layer (thickness 40 μm). Both surfaces of the aluminum alloy foil were subjected to chemical surface treatment. The chemical surface treatment of the aluminum alloy foil is performed as follows: the aluminum alloy foil was subjected to chemical surface treatment by applying a treatment liquid containing a phenolic resin, a chromium fluoride compound and phosphoric acid to both surfaces of the aluminum alloy foil by roll coating so that the coating amount of chromium was 10mg/m 2 (dry mass), and then firing the resultant foil.
Next, maleic anhydride-modified polypropylene as an adhesive layer (thickness 15 μm) and random polypropylene as a heat-fusible resin layer (thickness 15 μm) were coextruded onto the barrier layer of each laminate obtained as described above, whereby the adhesive layer/heat-fusible resin layer was laminated on the barrier layer, and then cured to obtain a laminate (total thickness 93 μm) in which a base layer (thickness 20 μm)/adhesive layer (3 μm)/barrier layer (40 μm)/adhesive layer (15 μm)/heat-fusible resin layer (15 μm) were laminated in this order from the outside.
Example 11
As a base material layer, a stretched nylon (ONy) film (thickness: 20 μm) was prepared. The stretched nylon film used in example 11 was the same as the stretched nylon film used in example 4. As a barrier layer, an aluminum alloy foil (JIS H4160:1994A 8021H-O (thickness 40 μm)) was prepared. Next, a barrier layer and a base material layer were laminated by a dry lamination method using an adhesive (a two-component polyurethane adhesive containing carbon black), and then cured to produce a laminate of a base material layer (thickness 20 μm)/an adhesive layer (thickness 3 μm after curing)/a barrier layer (thickness 40 μm). Both surfaces of the aluminum alloy foil were subjected to chemical surface treatment. The chemical surface treatment of the aluminum alloy foil is performed as follows: the aluminum alloy foil was subjected to chemical surface treatment by applying a treatment liquid containing a phenolic resin, a chromium fluoride compound and phosphoric acid to both surfaces of the aluminum alloy foil by roll coating so that the coating amount of chromium was 10mg/m 2 (dry mass), and then firing the resultant foil.
Next, maleic anhydride-modified polypropylene as an adhesive layer (thickness 14 μm) and random polypropylene as a heat-fusible resin layer (thickness 10 μm) were coextruded onto the barrier layer of each laminate obtained as described above, whereby an adhesive layer/heat-fusible resin layer was laminated on the barrier layer, and a laminate was obtained in which a base layer (thickness 20 μm)/adhesive layer (3 μm)/barrier layer (40 μm)/adhesive layer (15 μm)/heat-fusible resin layer (15 μm) was laminated in this order. Next, a resin (two-liquid polyurethane resin containing silica particles and resin beads) for forming a rough layer as a surface coating layer was applied to the surface of the stretched nylon film of the obtained laminate so as to have a thickness of 3 μm, and then cured, whereby a laminate (total thickness 96 μm) was obtained in which a surface coating layer (thickness 3 μm)/a base material layer (thickness 20 μm)/an adhesive layer (3 μm)/a barrier layer (40 μm)/an adhesive layer (15 μm)/a heat-fusible resin layer (15 μm) were laminated in this order from the outside.
< Measurement of crystallization index of base layer of exterior Material for electric storage device >
The exterior material for the power storage device was cut into a square of 100mm×100mm, and a sample was produced. The surface of the stretched nylon film located on the outer side of the obtained sample was subjected to infrared absorption spectrometry at a temperature of 25℃and a relative humidity of 50% using the ATR measurement mode of Nicolet iS10 FT-IR manufactured by Semer Feier technology Co. From the obtained absorption spectrum, the peak intensity P near 1200cm -1 of absorption from the α -crystal of nylon and the peak intensity Q near 1370cm -1 of absorption not related to crystallization were measured, and the intensity ratio x=p/Q of the peak intensity P to the peak intensity Q was calculated as the crystallization index. For examples 7, 9, 11, the measurements were performed prior to application of the surface coating. The results are shown in Table 1.
(Measurement conditions)
The method comprises the following steps: macroATR process;
Wave number resolution: 8cm -1;
Cumulative number of times: 32 times;
A detector: a DTGS detector;
ATR prism: ge;
Incidence angle: 45 °;
Baseline: the wave numbers between 1100cm -1 and 1400cm -1 were determined in a straight-line approximation.
Absorption peak intensity Y 1200: a value obtained by subtracting the value of the baseline from the maximum value of the peak intensities in the range of the wave number 1195cm -1 to 1205cm -1;
Absorption peak intensity Y 1370: a value obtained by subtracting the value of the base line from the maximum value of the peak intensity in the range of the wave numbers 1365cm -1 to 1375cm -1.
< Determination of crystallization index of stretched Nylon film >
The stretched nylon film used for the base material layer of the outer packaging material for the power storage device was cut into a square of 100mm×100mm, and a sample was produced. The surface of the obtained sample was subjected to infrared absorption spectrometry at a temperature of 25℃and a relative humidity of 50% using the ATR measurement mode of Nicolet iS10 FT-IR manufactured by Semer Feishan technologies. From the obtained absorption spectrum, the peak intensity P near 1200cm -1 of absorption from the α -crystal of nylon and the peak intensity Q near 1370cm -1 of absorption not related to crystallization were measured, and the intensity ratio x=p/Q of the peak intensity P to the peak intensity Q was calculated as the crystallization index. The results are shown in Table 1.
(Measurement conditions)
The method comprises the following steps: macroATR process;
Wave number resolution: 8cm -1;
Cumulative number of times: 32 times;
A detector: a DTGS detector;
ATR prism: ge;
Incidence angle: 45 °;
Baseline: the wave numbers between 1100cm -1 and 1400cm -1 were determined in a straight-line approximation.
Absorption peak intensity Y 1200: a value obtained by subtracting the value of the baseline from the maximum value of the peak intensities in the range of the wave number 1195cm -1 to 1205cm -1;
Absorption peak intensity Y 1370: a value obtained by subtracting the value of the base line from the maximum value of the peak intensity in the range of the wave numbers 1365cm -1 to 1375cm -1.
< Peeling test of Electrical storage device >)
The peeling test of the power storage device was performed by the following method. The description is made with reference to fig. 5 to 8. First, a method of producing a sample for use in a peeling test of an electric storage device will be described with reference to fig. 5. As shown in fig. 5a, the exterior material for the power storage device was cut into a rectangular shape having a longitudinal direction (MD) of 200mm and a Transverse Direction (TD) of 90 mm. Next, using a molding die (female die) having a diameter of 55Mm (MD) ×32mm (TD) and a corresponding molding die (male die), cold rolling was performed from the heat-fusible resin layer side at a depth of 5.0mm at a position 15mm away from the short side of the exterior material for the power storage device, to form a concave portion M (a region surrounded by a broken line in fig. 5 a). Then, an acrylic plate having a length of 55mm, a width of 32mm, and a thickness of 5mm was inserted into the recess M (FIGS. 5b and c). Next, the molded outer package for the power storage device is folded in half in the TD direction at the position of the fold P (at the position along the short side of the recess M) so that the recess M is inward (fig. 5 d). Next, 3 parts (190 ℃ for 3 seconds and 1MPa in surface pressure) of the portion where the heat-fusible resin layers overlap each other along the peripheral edge of the recess M were heat-sealed along MD and TD, and the recess M was sealed (fig. 5 e). In fig. 5e, the colored region S is a heat-sealed portion. Next, as shown in fig. 5f, sample 12 for a peeling test of the power storage device was prepared by trimming the concave portion M to a dimension of 60mm in the Machine Direction (MD) and 37mm in the Transverse Direction (TD). Fig. 6 shows a side view (fig. 6 a) and a top view (fig. 6 b) of the sample 12.
Next, as shown in the schematic diagram of fig. 7, 3 double-sided tapes (width 7.5mm, length 55 mm) were attached to the top surface (surface opposite to the surface on which the concave portion M was formed) of the sample 12 at both ends and the center along the Machine Direction (MD). The peel strength of the double-sided tape with respect to the object is measured by a method described later.
Then, the sample 12 with the double-sided tape attached thereto was attached to a stainless steel plate, and cured at 60℃for 24 hours. Among them, stainless steel plates are regarded as cases for fixing the power storage device with double-sided adhesive tape. Next, as shown in the schematic diagram of fig. 8, the sample 12 was carefully peeled from the stainless steel plate using a metal blade, and the presence of the hole in the peeled sample 12 was visually confirmed, and the peeling test of the power storage device was evaluated for each of the 3 samples according to the following criteria. As shown in fig. 8, the power storage device is peeled off by applying a force from the Transverse Direction (TD) of the sample 12. The results are shown in Table 1.
A: none of the 3 samples had an opening.
B:1 or 2 samples were perforated.
C: all 3 samples were perforated.
TABLE 1
The exterior materials for power storage devices of examples 1 to 11 were composed of a laminate having at least a base layer, a barrier layer, and a heat-fusible resin layer in this order from the outside, wherein the base layer included a polyamide film, and the polyamide film had a crystallization index of 1.50 or more as measured from the outside of the base layer by the ATR method of fourier transform infrared spectroscopy. The polyamide films used in the base material layers of the outer packaging materials for power storage devices of examples 1 to 11 had crystallization indexes of 1.50 or more as measured by the ATR method of fourier transform infrared spectroscopy. It is understood that the outer packaging materials for power storage devices of examples 1 to 11 can effectively suppress breakage of the outer packaging materials for power storage devices when the power storage devices fixed by the double-sided tape or the like are peeled from the case.
It is considered that the difference between the crystallization index measured on the base material layer of the exterior material for the power storage device and the value of the crystallization index measured on the stretched nylon film is affected by the aging of the exterior material for the power storage device. The values of the crystallization indexes of the stretched nylon films used in comparative examples 1 and 2 were significantly smaller than those of examples 1 to 11, and the values measured after the base material layer of the outer package material for an electric storage device was produced were significantly larger than those measured in the state of the stretched nylon film. However, in comparative examples 1 and 2, the crystallization index of the polyamide film measured from the outside of the base material layer was not as high as 1.50 or more due to aging of the outer packaging material for the power storage device, and the peel test evaluation of the power storage device was inferior to examples 1 to 11.
(Measurement of peel Strength of double-sided adhesive tape)
The outer packaging materials for power storage devices (vertical 15mm. Times. Horizontal 70 mm) and the double-sided adhesive tapes (vertical 7.5 mm. Times. Horizontal 60 mm), aluminum foils (thickness 35 μm. Times. Vertical 15mm. Times. Horizontal 150 mm), double-sided adhesive tapes for fixing (vertical 5mm. Times. Horizontal 60 mm) and acrylic plates (thickness 3 mm. Times. Vertical 50 mm. Times. Horizontal 70 mm) used in the peeling test > of the power storage devices of examples 1 to 11 were prepared. First, a surface of an exterior material for an electric storage device on the side of a stretched nylon film (a surface of a coating layer on the stretched nylon film in examples 4 and 5, and a surface of a surface covering layer on the stretched nylon film in examples 7, 9 and 11) was bonded to one surface of a double-sided tape, and then an aluminum foil was bonded to the other surface of the double-sided tape, and a 2kg roller was reciprocated once from above the aluminum foil, to obtain a laminate P. Further, an acrylic plate and one surface of a double-sided adhesive tape for fixing were bonded to each other to obtain a laminate Q. Then, the surface of the heat-fusible resin layer of the exterior material for the power storage device of the laminate P was bonded to the other surface of the double-sided adhesive tape for fixing the laminate Q, and the laminate R in which an acrylic plate, the double-sided adhesive tape for fixing, the exterior material for the power storage device, the double-sided adhesive tape, and an aluminum foil were laminated in this order was obtained by pressing with a hand, and this was used as a test sample M. Test sample M was stored in an environment at 60℃for 24 hours. Then, the surface of the stretched nylon film of the outer packaging material for the power storage device and the end of the double-sided tape were peeled by about 1mm, and an initial portion for measuring the peel strength was set. Next, the acrylic plate of the test sample M was fixed, and the aluminum foil was pulled at a tensile angle of 180 ° at a peeling speed of 300mm/min and a peeling distance of 50mm or more using a tensile tester (AG-Xplus (trade name) manufactured by shimadzu corporation) to peel off the aluminum foil from the surface of the stretched nylon film of the exterior material for the power storage device at the interface of the double-sided tape (from the above-mentioned starting portion), and the average of the total 5 peeling strengths of the peeling strengths at peeling distances of 10mm, 20mm, 30mm, 40mm and the maximum peeling strength between 10 and 40mm was calculated as the peeling strength (peeling strength of the double-sided tape to the stretched nylon film (N/7.5 mm)). The results are shown in Table 2.
Next, a stainless steel plate (thickness 3 mm. Times.50 mm. Times.70 mm. Longitudinal) and a double-sided tape (7.5 mm. Times.60 mm. Longitudinal) used for the peeling test of the power storage device and the aluminum foil (thickness 35 μm. Times.15 mm. Times.150 mm) were prepared. The surface of the stainless steel plate was bonded to one surface of the double-sided tape, and then an aluminum foil was bonded to the other surface of the double-sided tape, and a 2kg roller was reciprocated once from above the aluminum foil, to obtain a laminate, which was used as a test sample N. Test sample N was stored in an environment at 60℃for 24 hours. Then, the surface of the stainless steel plate and the end of the double-sided tape were peeled by about 1mm, and an initial portion for measuring the peel strength was set. Next, the stainless steel sheet of the test sample N was fixed, and the aluminum foil was pulled at a tensile angle of 180 °, a peeling speed of 300mm/min, and a peeling distance of 50mm or more using a tensile tester (AG-Xplus (trade name) manufactured by shimadzu corporation) to peel off the surface of the stainless steel sheet at the interface of the double-sided tape (from the above-mentioned starting portion), and the average of the total 5 peeling strengths of the peeling strengths at peeling distances of 10mm, 20mm, 30mm, and 40mm and the maximum peeling strength between 10 and 40mm was calculated as the peeling strength (peeling strength of the double-sided tape to the stainless steel sheet (N/7.5 mm)). The results are shown in Table 2.
TABLE 2
As is clear from the results shown in table 2, the peel strength of the double-sided tape used in the peel test > of the power storage device was equivalent to that of the stretched nylon film and the stainless steel sheet.
As described above, the present invention provides the following embodiments.
An exterior material for an electrical storage device comprising a laminate having, in order from the outside, at least a base layer, a barrier layer, and a heat-fusible resin layer,
The substrate layer comprises a polyamide film,
The polyamide film has a crystallization index of 1.50 or more, as measured from the outside of the base layer, by an ATR method using a fourier transform infrared spectroscopy.
The outer packaging material for a power storage device according to item 1, wherein an adhesive layer is provided between the base layer and the barrier layer.
The exterior material for a power storage device according to item 1 or 2, wherein an adhesive layer is provided between the barrier layer and the heat-fusible resin layer.
A method for producing an exterior material for an electrical storage device, comprising the step of obtaining a laminate comprising, in order from the outside, at least a base layer, a barrier layer and a heat-fusible resin layer,
The substrate layer comprises a polyamide film,
The polyamide film has a crystallization index of 1.50 or more, as measured from the outside of the base layer, by an ATR method using a fourier transform infrared spectroscopy.
An electricity storage device according to item 5, wherein an electricity storage device element having at least a positive electrode, a negative electrode, and an electrolyte is housed in a package formed of the outer packaging material for an electricity storage device according to any one of items 1 to 3.
In the case of using a polyamide film for an outer package for an electric storage device comprising a laminate of at least a base layer, a barrier layer and a heat-fusible resin layer, the polyamide film has a crystallization index of 1.50 or more as measured by the ATR method of fourier transform infrared spectroscopy.
Symbol description
1A base material layer, 2 an adhesive layer, 3a barrier layer, 4a heat-fusible resin layer, 5 an adhesive layer, 6a surface coating layer, and 10 an outer packaging material for an electric storage device.

Claims (40)

1. An exterior material for an electrical storage device, characterized in that:
Comprises a laminate comprising, in order from the outside, at least a base layer, a barrier layer and a heat-fusible resin layer,
The substrate layer comprises a polyamide film,
The polyamide film has a thickness of 20 μm,
An ATR method using a Fourier transform infrared spectroscopy, wherein the polyamide film has a crystallization index of 1.50 or more as measured from the outside of the base material layer in a state where the surface of the polyamide film is exposed,
The method for determining the crystallization index comprises the following steps:
Cutting an outer packaging material for an electric storage device into square shapes of 100mm×100mm, and preparing a sample; an infrared absorption spectrum measurement was performed on the surface of the polyamide film located outside the obtained sample in an environment having a temperature of 25℃and a relative humidity of 50% using the ATR measurement mode of FT-IR; as the device, nicoletiS manufactured by sameimers technologies corporation (Thermo FISHER SCIENTIFIC) was used; based on the obtained absorption spectrum, the peak intensity P around 1200cm -1 of absorption from the α -crystal of nylon and the peak intensity Q around 1370cm -1 of absorption not related to crystallization were measured, and the intensity ratio x=p/Q of the peak intensity P to the peak intensity Q was calculated as the crystallization index,
The measurement conditions were:
the method comprises the following steps: macroATR process;
Wave number resolution: 8cm -1;
Cumulative number of times: 32 times;
A detector: a DTGS detector;
ATR prism: ge;
Incidence angle: 45 °;
Baseline: obtaining the wave number between 1100cm -1 and 1400cm -1 in a straight line approximation mode;
Absorption peak intensity Y 1200: a value obtained by subtracting the value of the baseline from the maximum value of the peak intensities in the range of the wave number 1195cm -1 to 1205cm -1;
Absorption peak intensity Y 1370: a value obtained by subtracting the value of the base line from the maximum value of the peak intensity in the range of the wave numbers 1365cm -1 to 1375cm -1.
2. An exterior material for an electrical storage device, characterized in that:
Comprises a laminate comprising, in order from the outside, at least a base layer, a barrier layer and a heat-fusible resin layer,
The substrate layer comprises a polyamide film,
The polyamide film has a thickness of 20 μm,
The thickness of the barrier layer is 40 μm,
An ATR method using a Fourier transform infrared spectroscopy, wherein the polyamide film has a crystallization index of 1.50 or more as measured from the outside of the base material layer in a state where the surface of the polyamide film is exposed,
The method for determining the crystallization index comprises the following steps:
Cutting an outer packaging material for an electric storage device into square shapes of 100mm×100mm, and preparing a sample; an infrared absorption spectrum measurement was performed on the surface of the polyamide film located outside the obtained sample in an environment having a temperature of 25℃and a relative humidity of 50% using the ATR measurement mode of FT-IR; as the device, nicoletiS manufactured by sameimers technologies corporation (Thermo FISHER SCIENTIFIC) was used; based on the obtained absorption spectrum, the peak intensity P around 1200cm -1 of absorption from the α -crystal of nylon and the peak intensity Q around 1370cm -1 of absorption not related to crystallization were measured, and the intensity ratio x=p/Q of the peak intensity P to the peak intensity Q was calculated as the crystallization index,
The measurement conditions were:
the method comprises the following steps: macroATR process;
Wave number resolution: 8cm -1;
Cumulative number of times: 32 times;
A detector: a DTGS detector;
ATR prism: ge;
Incidence angle: 45 °;
Baseline: obtaining the wave number between 1100cm -1 and 1400cm -1 in a straight line approximation mode;
Absorption peak intensity Y 1200: a value obtained by subtracting the value of the baseline from the maximum value of the peak intensities in the range of the wave number 1195cm -1 to 1205cm -1;
Absorption peak intensity Y 1370: a value obtained by subtracting the value of the base line from the maximum value of the peak intensity in the range of the wave numbers 1365cm -1 to 1375cm -1.
3. An exterior material for an electrical storage device, characterized in that:
comprises a laminate comprising, in order from the outside, at least a surface coating layer, a base material layer, a barrier layer and a heat-fusible resin layer,
At least one of the surface and the interior of the surface covering layer contains titanium oxide,
The substrate layer comprises a polyamide film,
An ATR method using a Fourier transform infrared spectroscopy, wherein the polyamide film has a crystallization index of 1.50 or more as measured from the outside of the base material layer in a state where the surface of the polyamide film is exposed,
The method for determining the crystallization index comprises the following steps:
Cutting an outer packaging material for an electric storage device into square shapes of 100mm×100mm, and preparing a sample; an infrared absorption spectrum measurement was performed on the surface of the polyamide film located outside the obtained sample in an environment having a temperature of 25℃and a relative humidity of 50% using the ATR measurement mode of FT-IR; as the device, nicoletiS manufactured by sameimers technologies corporation (Thermo FISHER SCIENTIFIC) was used; based on the obtained absorption spectrum, the peak intensity P around 1200cm -1 of absorption from the α -crystal of nylon and the peak intensity Q around 1370cm -1 of absorption not related to crystallization were measured, and the intensity ratio x=p/Q of the peak intensity P to the peak intensity Q was calculated as the crystallization index,
The measurement conditions were:
the method comprises the following steps: macroATR process;
Wave number resolution: 8cm -1;
Cumulative number of times: 32 times;
A detector: a DTGS detector;
ATR prism: ge;
Incidence angle: 45 °;
Baseline: obtaining the wave number between 1100cm -1 and 1400cm -1 in a straight line approximation mode;
Absorption peak intensity Y 1200: a value obtained by subtracting the value of the baseline from the maximum value of the peak intensities in the range of the wave number 1195cm -1 to 1205cm -1;
Absorption peak intensity Y 1370: a value obtained by subtracting the value of the base line from the maximum value of the peak intensity in the range of the wave numbers 1365cm -1 to 1375cm -1.
4. An exterior material for an electrical storage device, characterized in that:
comprises a laminate comprising, in order from the outside, at least a surface coating layer, a base material layer, a barrier layer and a heat-fusible resin layer,
At least one of the surface and the interior of the surface covering layer contains silicon dioxide,
The substrate layer comprises a polyamide film,
An ATR method using a Fourier transform infrared spectroscopy, wherein the polyamide film has a crystallization index of 1.50 or more as measured from the outside of the base material layer in a state where the surface of the polyamide film is exposed,
The method for determining the crystallization index comprises the following steps:
Cutting an outer packaging material for an electric storage device into square shapes of 100mm×100mm, and preparing a sample; an infrared absorption spectrum measurement was performed on the surface of the polyamide film located outside the obtained sample in an environment having a temperature of 25℃and a relative humidity of 50% using the ATR measurement mode of FT-IR; as the device, nicoletiS manufactured by sameimers technologies corporation (Thermo FISHER SCIENTIFIC) was used; based on the obtained absorption spectrum, the peak intensity P around 1200cm -1 of absorption from the α -crystal of nylon and the peak intensity Q around 1370cm -1 of absorption not related to crystallization were measured, and the intensity ratio x=p/Q of the peak intensity P to the peak intensity Q was calculated as the crystallization index,
The measurement conditions were:
the method comprises the following steps: macroATR process;
Wave number resolution: 8cm -1;
Cumulative number of times: 32 times;
A detector: a DTGS detector;
ATR prism: ge;
Incidence angle: 45 °;
Baseline: obtaining the wave number between 1100cm -1 and 1400cm -1 in a straight line approximation mode;
Absorption peak intensity Y 1200: a value obtained by subtracting the value of the baseline from the maximum value of the peak intensities in the range of the wave number 1195cm -1 to 1205cm -1;
Absorption peak intensity Y 1370: a value obtained by subtracting the value of the base line from the maximum value of the peak intensity in the range of the wave numbers 1365cm -1 to 1375cm -1.
5. An exterior material for an electrical storage device, characterized in that:
comprises a laminate comprising, in order from the outside, at least a surface coating layer, a base material layer, a barrier layer and a heat-fusible resin layer,
At least one of the surface and the interior of the surface covering layer contains kaolin,
The substrate layer comprises a polyamide film,
An ATR method using a Fourier transform infrared spectroscopy, wherein the polyamide film has a crystallization index of 1.50 or more as measured from the outside of the base material layer in a state where the surface of the polyamide film is exposed,
The method for determining the crystallization index comprises the following steps:
Cutting an outer packaging material for an electric storage device into square shapes of 100mm×100mm, and preparing a sample; an infrared absorption spectrum measurement was performed on the surface of the polyamide film located outside the obtained sample in an environment having a temperature of 25℃and a relative humidity of 50% using the ATR measurement mode of FT-IR; as the device, nicoletiS manufactured by sameimers technologies corporation (Thermo FISHER SCIENTIFIC) was used; based on the obtained absorption spectrum, the peak intensity P around 1200cm -1 of absorption from the α -crystal of nylon and the peak intensity Q around 1370cm -1 of absorption not related to crystallization were measured, and the intensity ratio x=p/Q of the peak intensity P to the peak intensity Q was calculated as the crystallization index,
The measurement conditions were:
the method comprises the following steps: macroATR process;
Wave number resolution: 8cm -1;
Cumulative number of times: 32 times;
A detector: a DTGS detector;
ATR prism: ge;
Incidence angle: 45 °;
Baseline: obtaining the wave number between 1100cm -1 and 1400cm -1 in a straight line approximation mode;
Absorption peak intensity Y 1200: a value obtained by subtracting the value of the baseline from the maximum value of the peak intensities in the range of the wave number 1195cm -1 to 1205cm -1;
Absorption peak intensity Y 1370: a value obtained by subtracting the value of the base line from the maximum value of the peak intensity in the range of the wave numbers 1365cm -1 to 1375cm -1.
6. An exterior material for an electrical storage device, characterized in that:
comprises a laminate comprising, in order from the outside, at least a surface coating layer, a base material layer, a barrier layer and a heat-fusible resin layer,
At least one of the surface and the inside of the surface coating layer contains at least 2 selected from talc, silica, graphite, kaolin, montmorillonite, 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, acrylate resin, crosslinked acrylic acid, crosslinked styrene, crosslinked polyethylene, benzoguanamine, gold, aluminum, copper and nickel,
The substrate layer comprises a polyamide film,
An ATR method using a Fourier transform infrared spectroscopy, wherein the polyamide film has a crystallization index of 1.50 or more as measured from the outside of the base material layer in a state where the surface of the polyamide film is exposed,
The method for determining the crystallization index comprises the following steps:
Cutting an outer packaging material for an electric storage device into square shapes of 100mm×100mm, and preparing a sample; an infrared absorption spectrum measurement was performed on the surface of the polyamide film located outside the obtained sample in an environment having a temperature of 25℃and a relative humidity of 50% using the ATR measurement mode of FT-IR; as the device, nicoletiS manufactured by sameimers technologies corporation (Thermo FISHER SCIENTIFIC) was used; based on the obtained absorption spectrum, the peak intensity P around 1200cm -1 of absorption from the α -crystal of nylon and the peak intensity Q around 1370cm -1 of absorption not related to crystallization were measured, and the intensity ratio x=p/Q of the peak intensity P to the peak intensity Q was calculated as the crystallization index,
The measurement conditions were:
the method comprises the following steps: macroATR process;
Wave number resolution: 8cm -1;
Cumulative number of times: 32 times;
A detector: a DTGS detector;
ATR prism: ge;
Incidence angle: 45 °;
Baseline: obtaining the wave number between 1100cm -1 and 1400cm -1 in a straight line approximation mode;
Absorption peak intensity Y 1200: a value obtained by subtracting the value of the baseline from the maximum value of the peak intensities in the range of the wave number 1195cm -1 to 1205cm -1;
Absorption peak intensity Y 1370: a value obtained by subtracting the value of the base line from the maximum value of the peak intensity in the range of the wave numbers 1365cm -1 to 1375cm -1.
7. An exterior material for an electrical storage device, characterized in that:
comprises a laminate comprising, in order from the outside, at least a surface coating layer, a base material layer, a barrier layer and a heat-fusible resin layer,
The substrate layer comprises a polyamide film,
An ATR method using a Fourier transform infrared spectroscopy, wherein the polyamide film has a crystallization index of 1.50 or more as measured from the outside of the base material layer in a state where the surface of the polyamide film is exposed,
The method for determining the crystallization index comprises the following steps:
Cutting an outer packaging material for an electric storage device into square shapes of 100mm×100mm, and preparing a sample; an infrared absorption spectrum measurement was performed on the surface of the polyamide film located outside the obtained sample in an environment having a temperature of 25℃and a relative humidity of 50% using the ATR measurement mode of FT-IR; as the device, nicoletiS manufactured by sameimers technologies corporation (Thermo FISHER SCIENTIFIC) was used; based on the obtained absorption spectrum, the peak intensity P around 1200cm -1 of absorption from the α -crystal of nylon and the peak intensity Q around 1370cm -1 of absorption not related to crystallization were measured, and the intensity ratio x=p/Q of the peak intensity P to the peak intensity Q was calculated as the crystallization index,
The measurement conditions were:
the method comprises the following steps: macroATR process;
Wave number resolution: 8cm -1;
Cumulative number of times: 32 times;
A detector: a DTGS detector;
ATR prism: ge;
Incidence angle: 45 °;
Baseline: obtaining the wave number between 1100cm -1 and 1400cm -1 in a straight line approximation mode;
Absorption peak intensity Y 1200: a value obtained by subtracting the value of the baseline from the maximum value of the peak intensities in the range of the wave number 1195cm -1 to 1205cm -1;
Absorption peak intensity Y 1370: a value obtained by subtracting the value of the base line from the maximum value of the peak intensity in the range of the wave numbers 1365cm -1 to 1375cm -1.
8. The exterior material for an electrical storage device according to any one of claims 1 to 7, wherein:
an adhesive layer is provided between the substrate layer and the barrier layer.
9. The exterior material for an electrical storage device according to any one of claims 1 to 7, wherein:
An adhesive layer is provided between the barrier layer and the heat-fusible resin layer.
10. The exterior material for an electrical storage device according to any one of claims 1 to 7, wherein: a lubricant is present on at least one of the surface and the interior of the substrate layer.
11. The exterior material for an electrical storage device according to any one of claims 1 to 7, wherein: there are more than 2 lubricants on at least one of the surface and the interior of the substrate layer.
12. The exterior material for an electrical storage device according to any one of claims 1 to 7, wherein: a lubricant is present on at least one of the surface and the interior of the heat-fusible resin layer.
13. The exterior material for an electrical storage device according to any one of claims 1 to 7, wherein: at least 2 kinds of lubricants are present on at least one of the surface and the inside of the heat-fusible resin layer.
14. The exterior material for an electrical storage device according to any one of claims 1 to 7, wherein: the heat-fusible resin layer is formed of the same or different resins in at least 2 layers.
15. The exterior material for an electrical storage device according to any one of claims 1 to 7, wherein: the polyamide film has a crystallization index of 1.65 or more as measured from the outside of the base layer by an ATR method using a fourier transform infrared spectroscopy.
16. The exterior material for an electrical storage device according to any one of claims 1 to 7, wherein: there are more than 2 lubricants on at least one of the surface and the interior of the substrate layer.
17. The exterior material for an electrical storage device according to any one of claims 1 to 7, wherein: at least 2 or more kinds selected from the group consisting of saturated fatty acid amide, unsaturated fatty acid amide, substituted amide, methylol amide, saturated fatty bisamide, unsaturated fatty bisamide, fatty acid ester amide, and aromatic bisamide are present on at least one of the surface and the inside of the base material layer.
18. The exterior material for an electrical storage device according to any one of claims 1 to 7, wherein:
a lubricant is present on the surface of the substrate layer,
The lubricant is present in an amount of 3mg/m 2 or more.
19. The exterior material for an electrical storage device according to any one of claims 1 to 7, wherein: the heat-fusible resin layer is formed of the same or different resins in at least 2 layers.
20. The exterior material for an electrical storage device according to any one of claims 1 to 7, wherein: at least 2 kinds of lubricants are present on at least one of the surface and the inside of the heat-fusible resin layer.
21. The exterior material for an electrical storage device according to claim 1, wherein: at least 2 or more kinds selected from the group consisting of saturated fatty acid amide, unsaturated fatty acid amide, substituted amide, methylol amide, saturated fatty bisamide, unsaturated fatty bisamide, fatty acid ester amide and aromatic bisamide are present on at least one of the surface and the inside of the heat-fusible resin layer.
22. The exterior material for an electrical storage device according to any one of claims 1 to 7, wherein:
A lubricant is present on the surface of the heat-fusible resin layer,
The lubricant is present in an amount of 10mg/m 2 or more.
23. The exterior material for an electrical storage device according to any one of claims 1 to 7, wherein:
a surface coating layer is provided on the opposite side of the substrate layer from the barrier layer side.
24. A method for producing an exterior material for an electrical storage device, characterized by comprising:
comprises a step of obtaining a laminate comprising a base layer, a barrier layer and a heat-fusible resin layer laminated in this order from the outside,
The substrate layer comprises a polyamide film,
The polyamide film has a thickness of 20 μm,
An ATR method using a Fourier transform infrared spectroscopy, wherein the polyamide film has a crystallization index of 1.50 or more as measured from the outside of the base material layer in a state where the surface of the polyamide film is exposed,
The method for determining the crystallization index comprises the following steps:
Cutting an outer packaging material for an electric storage device into square shapes of 100mm×100mm, and preparing a sample; an infrared absorption spectrum measurement was performed on the surface of the polyamide film located outside the obtained sample in an environment having a temperature of 25℃and a relative humidity of 50% using the ATR measurement mode of FT-IR; as the device, nicoletiS manufactured by sameimers technologies corporation (Thermo FISHER SCIENTIFIC) was used; based on the obtained absorption spectrum, the peak intensity P around 1200cm -1 of absorption from the α -crystal of nylon and the peak intensity Q around 1370cm -1 of absorption not related to crystallization were measured, and the intensity ratio x=p/Q of the peak intensity P to the peak intensity Q was calculated as the crystallization index,
The measurement conditions were:
the method comprises the following steps: macroATR process;
Wave number resolution: 8cm -1;
Cumulative number of times: 32 times;
A detector: a DTGS detector;
ATR prism: ge;
Incidence angle: 45 °;
Baseline: obtaining the wave number between 1100cm -1 and 1400cm -1 in a straight line approximation mode;
Absorption peak intensity Y 1200: a value obtained by subtracting the value of the baseline from the maximum value of the peak intensities in the range of the wave number 1195cm -1 to 1205cm -1;
Absorption peak intensity Y 1370: a value obtained by subtracting the value of the base line from the maximum value of the peak intensity in the range of the wave numbers 1365cm -1 to 1375cm -1.
25. A method for producing an exterior material for an electrical storage device, characterized by comprising:
comprises a step of obtaining a laminate comprising a base layer, a barrier layer and a heat-fusible resin layer laminated in this order from the outside,
The substrate layer comprises a polyamide film,
The polyamide film has a thickness of 20 μm,
The thickness of the barrier layer is 40 μm,
An ATR method using a Fourier transform infrared spectroscopy, wherein the polyamide film has a crystallization index of 1.50 or more as measured from the outside of the base material layer in a state where the surface of the polyamide film is exposed,
The method for determining the crystallization index comprises the following steps:
Cutting an outer packaging material for an electric storage device into square shapes of 100mm×100mm, and preparing a sample; an infrared absorption spectrum measurement was performed on the surface of the polyamide film located outside the obtained sample in an environment having a temperature of 25℃and a relative humidity of 50% using the ATR measurement mode of FT-IR; as the device, nicoletiS manufactured by sameimers technologies corporation (Thermo FISHER SCIENTIFIC) was used; based on the obtained absorption spectrum, the peak intensity P around 1200cm -1 of absorption from the α -crystal of nylon and the peak intensity Q around 1370cm -1 of absorption not related to crystallization were measured, and the intensity ratio x=p/Q of the peak intensity P to the peak intensity Q was calculated as the crystallization index,
The measurement conditions were:
the method comprises the following steps: macroATR process;
Wave number resolution: 8cm -1;
Cumulative number of times: 32 times;
A detector: a DTGS detector;
ATR prism: ge;
Incidence angle: 45 °;
Baseline: obtaining the wave number between 1100cm -1 and 1400cm -1 in a straight line approximation mode;
Absorption peak intensity Y 1200: a value obtained by subtracting the value of the baseline from the maximum value of the peak intensities in the range of the wave number 1195cm -1 to 1205cm -1;
Absorption peak intensity Y 1370: a value obtained by subtracting the value of the base line from the maximum value of the peak intensity in the range of the wave numbers 1365cm -1 to 1375cm -1.
26. A method for producing an exterior material for an electrical storage device, characterized by comprising:
comprises a step of obtaining a laminate comprising a surface coating layer, a base material layer, a barrier layer and a heat-fusible resin layer laminated in this order from the outside,
At least one of the surface and the interior of the surface covering layer contains titanium oxide,
The substrate layer comprises a polyamide film,
An ATR method using a Fourier transform infrared spectroscopy, wherein the polyamide film has a crystallization index of 1.50 or more as measured from the outside of the base material layer in a state where the surface of the polyamide film is exposed,
The method for determining the crystallization index comprises the following steps:
Cutting an outer packaging material for an electric storage device into square shapes of 100mm×100mm, and preparing a sample; an infrared absorption spectrum measurement was performed on the surface of the polyamide film located outside the obtained sample in an environment having a temperature of 25℃and a relative humidity of 50% using the ATR measurement mode of FT-IR; as the device, nicoletiS manufactured by sameimers technologies corporation (Thermo FISHER SCIENTIFIC) was used; based on the obtained absorption spectrum, the peak intensity P around 1200cm -1 of absorption from the α -crystal of nylon and the peak intensity Q around 1370cm -1 of absorption not related to crystallization were measured, and the intensity ratio x=p/Q of the peak intensity P to the peak intensity Q was calculated as the crystallization index,
The measurement conditions were:
the method comprises the following steps: macroATR process;
Wave number resolution: 8cm -1;
Cumulative number of times: 32 times;
A detector: a DTGS detector;
ATR prism: ge;
Incidence angle: 45 °;
Baseline: obtaining the wave number between 1100cm -1 and 1400cm -1 in a straight line approximation mode;
Absorption peak intensity Y 1200: a value obtained by subtracting the value of the baseline from the maximum value of the peak intensities in the range of the wave number 1195cm -1 to 1205cm -1;
Absorption peak intensity Y 1370: a value obtained by subtracting the value of the base line from the maximum value of the peak intensity in the range of the wave numbers 1365cm -1 to 1375cm -1.
27. A method for producing an exterior material for an electrical storage device, characterized by comprising:
comprises a step of obtaining a laminate comprising a surface coating layer, a base material layer, a barrier layer and a heat-fusible resin layer laminated in this order from the outside,
At least one of the surface and the interior of the surface covering layer contains silicon dioxide,
The substrate layer comprises a polyamide film,
An ATR method using a Fourier transform infrared spectroscopy, wherein the polyamide film has a crystallization index of 1.50 or more as measured from the outside of the base material layer in a state where the surface of the polyamide film is exposed,
The method for determining the crystallization index comprises the following steps:
Cutting an outer packaging material for an electric storage device into square shapes of 100mm×100mm, and preparing a sample; an infrared absorption spectrum measurement was performed on the surface of the polyamide film located outside the obtained sample in an environment having a temperature of 25℃and a relative humidity of 50% using the ATR measurement mode of FT-IR; as the device, nicoletiS manufactured by sameimers technologies corporation (Thermo FISHER SCIENTIFIC) was used; based on the obtained absorption spectrum, the peak intensity P around 1200cm -1 of absorption from the α -crystal of nylon and the peak intensity Q around 1370cm -1 of absorption not related to crystallization were measured, and the intensity ratio x=p/Q of the peak intensity P to the peak intensity Q was calculated as the crystallization index,
The measurement conditions were:
the method comprises the following steps: macroATR process;
Wave number resolution: 8cm -1;
Cumulative number of times: 32 times;
A detector: a DTGS detector;
ATR prism: ge;
Incidence angle: 45 °;
Baseline: obtaining the wave number between 1100cm -1 and 1400cm -1 in a straight line approximation mode;
Absorption peak intensity Y 1200: a value obtained by subtracting the value of the baseline from the maximum value of the peak intensities in the range of the wave number 1195cm -1 to 1205cm -1;
Absorption peak intensity Y 1370: a value obtained by subtracting the value of the base line from the maximum value of the peak intensity in the range of the wave numbers 1365cm -1 to 1375cm -1.
28. A method for producing an exterior material for an electrical storage device, characterized by comprising:
comprises a step of obtaining a laminate comprising a surface coating layer, a base material layer, a barrier layer and a heat-fusible resin layer laminated in this order from the outside,
At least one of the surface and the interior of the surface covering layer contains kaolin,
The substrate layer comprises a polyamide film,
An ATR method using a Fourier transform infrared spectroscopy, wherein the polyamide film has a crystallization index of 1.50 or more as measured from the outside of the base material layer in a state where the surface of the polyamide film is exposed,
The method for determining the crystallization index comprises the following steps:
Cutting an outer packaging material for an electric storage device into square shapes of 100mm×100mm, and preparing a sample; an infrared absorption spectrum measurement was performed on the surface of the polyamide film located outside the obtained sample in an environment having a temperature of 25℃and a relative humidity of 50% using the ATR measurement mode of FT-IR; as the device, nicoletiS manufactured by sameimers technologies corporation (Thermo FISHER SCIENTIFIC) was used; based on the obtained absorption spectrum, the peak intensity P around 1200cm -1 of absorption from the α -crystal of nylon and the peak intensity Q around 1370cm -1 of absorption not related to crystallization were measured, and the intensity ratio x=p/Q of the peak intensity P to the peak intensity Q was calculated as the crystallization index,
The measurement conditions were:
the method comprises the following steps: macroATR process;
Wave number resolution: 8cm -1;
Cumulative number of times: 32 times;
A detector: a DTGS detector;
ATR prism: ge;
Incidence angle: 45 °;
Baseline: obtaining the wave number between 1100cm -1 and 1400cm -1 in a straight line approximation mode;
Absorption peak intensity Y 1200: a value obtained by subtracting the value of the baseline from the maximum value of the peak intensities in the range of the wave number 1195cm -1 to 1205cm -1;
Absorption peak intensity Y 1370: a value obtained by subtracting the value of the base line from the maximum value of the peak intensity in the range of the wave numbers 1365cm -1 to 1375cm -1.
29. A method for producing an exterior material for an electrical storage device, characterized by comprising:
comprises a step of obtaining a laminate comprising a surface coating layer, a base material layer, a barrier layer and a heat-fusible resin layer laminated in this order from the outside,
At least one of the surface and the inside of the surface coating layer contains at least 2 selected from talc, silica, graphite, kaolin, montmorillonite, 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, acrylate resin, crosslinked acrylic acid, crosslinked styrene, crosslinked polyethylene, benzoguanamine, gold, aluminum, copper and nickel,
The substrate layer comprises a polyamide film,
An ATR method using a Fourier transform infrared spectroscopy, wherein the polyamide film has a crystallization index of 1.50 or more as measured from the outside of the base material layer in a state where the surface of the polyamide film is exposed,
The method for determining the crystallization index comprises the following steps:
Cutting an outer packaging material for an electric storage device into square shapes of 100mm×100mm, and preparing a sample; an infrared absorption spectrum measurement was performed on the surface of the polyamide film located outside the obtained sample in an environment having a temperature of 25℃and a relative humidity of 50% using the ATR measurement mode of FT-IR; as the device, nicoletiS manufactured by sameimers technologies corporation (Thermo FISHER SCIENTIFIC) was used; based on the obtained absorption spectrum, the peak intensity P around 1200cm -1 of absorption from the α -crystal of nylon and the peak intensity Q around 1370cm -1 of absorption not related to crystallization were measured, and the intensity ratio x=p/Q of the peak intensity P to the peak intensity Q was calculated as the crystallization index,
The measurement conditions were:
the method comprises the following steps: macroATR process;
Wave number resolution: 8cm -1;
Cumulative number of times: 32 times;
A detector: a DTGS detector;
ATR prism: ge;
Incidence angle: 45 °;
Baseline: obtaining the wave number between 1100cm -1 and 1400cm -1 in a straight line approximation mode;
Absorption peak intensity Y 1200: a value obtained by subtracting the value of the baseline from the maximum value of the peak intensities in the range of the wave number 1195cm -1 to 1205cm -1;
Absorption peak intensity Y 1370: a value obtained by subtracting the value of the base line from the maximum value of the peak intensity in the range of the wave numbers 1365cm -1 to 1375cm -1.
30. A method for producing an exterior material for an electrical storage device, characterized by comprising:
comprises a step of obtaining a laminate comprising a surface coating layer, a base material layer, a barrier layer and a heat-fusible resin layer laminated in this order from the outside,
The substrate layer comprises a polyamide film,
An ATR method using a Fourier transform infrared spectroscopy, wherein the polyamide film has a crystallization index of 1.50 or more as measured from the outside of the base material layer in a state where the surface of the polyamide film is exposed,
The method for determining the crystallization index comprises the following steps:
Cutting an outer packaging material for an electric storage device into square shapes of 100mm×100mm, and preparing a sample; an infrared absorption spectrum measurement was performed on the surface of the polyamide film located outside the obtained sample in an environment having a temperature of 25℃and a relative humidity of 50% using the ATR measurement mode of FT-IR; as the device, nicoletiS manufactured by sameimers technologies corporation (Thermo FISHER SCIENTIFIC) was used; based on the obtained absorption spectrum, the peak intensity P around 1200cm -1 of absorption from the α -crystal of nylon and the peak intensity Q around 1370cm -1 of absorption not related to crystallization were measured, and the intensity ratio x=p/Q of the peak intensity P to the peak intensity Q was calculated as the crystallization index,
The measurement conditions were:
the method comprises the following steps: macroATR process;
Wave number resolution: 8cm -1;
Cumulative number of times: 32 times;
A detector: a DTGS detector;
ATR prism: ge;
Incidence angle: 45 °;
Baseline: obtaining the wave number between 1100cm -1 and 1400cm -1 in a straight line approximation mode;
Absorption peak intensity Y 1200: a value obtained by subtracting the value of the baseline from the maximum value of the peak intensities in the range of the wave number 1195cm -1 to 1205cm -1;
Absorption peak intensity Y 1370: a value obtained by subtracting the value of the base line from the maximum value of the peak intensity in the range of the wave numbers 1365cm -1 to 1375cm -1.
31. The method for producing an exterior material for an electrical storage device according to claim 30, wherein:
An adhesive layer is provided between the barrier layer and the heat-fusible resin layer,
The adhesive layer and the heat-fusible resin layer are formed by a coextrusion lamination method, a tandem lamination method, a heat lamination method, a sandwich lamination method, or a method in which an adhesive for forming the adhesive layer is applied to the barrier layer by solution application and the heat-fusible resin layer previously formed into a sheet is laminated on the adhesive layer,
The coextrusion lamination process and the tandem lamination process are: a method of forming a laminate comprising a base layer, an adhesive layer and a barrier layer laminated in this order, and then extruding the adhesive layer and the heat-fusible resin layer onto the barrier layer of the laminate,
The sandwich lamination method is as follows: after forming a laminate in which a base layer, an adhesive layer and a barrier layer are laminated in this order, a method is proposed in which the laminate and a heat-fusible resin layer are bonded by the adhesive layer while flowing a molten adhesive layer between the barrier layer of the laminate and the heat-fusible resin layer which has been previously sheeted.
32. An electrical storage device characterized in that:
a package formed of the exterior material for an electric storage device according to any one of claims 1 to 23, wherein an electric storage device element having at least a positive electrode, a negative electrode, and an electrolyte is housed.
33. A polyamide membrane characterized in that:
For use in a base layer of an outer packaging material for an electric storage device, the base layer comprising a laminate comprising at least a base layer, a barrier layer and a heat-fusible resin layer,
The polyamide film has a thickness of 20 μm,
The polyamide film has a crystallization index of 1.50 or more as measured by an ATR method using a Fourier transform infrared spectroscopy,
The method for determining the crystallization index comprises the following steps:
Cutting an outer packaging material for an electric storage device into square shapes of 100mm×100mm, and preparing a sample; an infrared absorption spectrum measurement was performed on the surface of the polyamide film located outside the obtained sample in an environment having a temperature of 25℃and a relative humidity of 50% using the ATR measurement mode of FT-IR; as the device, nicoletiS manufactured by sameimers technologies corporation (Thermo FISHER SCIENTIFIC) was used; based on the obtained absorption spectrum, the peak intensity P around 1200cm -1 of absorption from the α -crystal of nylon and the peak intensity Q around 1370cm -1 of absorption not related to crystallization were measured, and the intensity ratio x=p/Q of the peak intensity P to the peak intensity Q was calculated as the crystallization index,
The measurement conditions were:
the method comprises the following steps: macroATR process;
Wave number resolution: 8cm -1;
Cumulative number of times: 32 times;
A detector: a DTGS detector;
ATR prism: ge;
Incidence angle: 45 °;
Baseline: obtaining the wave number between 1100cm -1 and 1400cm -1 in a straight line approximation mode;
Absorption peak intensity Y 1200: a value obtained by subtracting the value of the baseline from the maximum value of the peak intensities in the range of the wave number 1195cm -1 to 1205cm -1;
Absorption peak intensity Y 1370: a value obtained by subtracting the value of the base line from the maximum value of the peak intensity in the range of the wave numbers 1365cm -1 to 1375cm -1.
34. A polyamide membrane characterized in that:
For use in a base layer of an outer packaging material for an electric storage device, the base layer comprising a laminate comprising at least a base layer, a barrier layer and a heat-fusible resin layer,
The polyamide film has a thickness of 20 μm,
The thickness of the barrier layer is 40 μm,
The polyamide film has a crystallization index of 1.50 or more as measured by an ATR method using a Fourier transform infrared spectroscopy,
The method for determining the crystallization index comprises the following steps:
Cutting an outer packaging material for an electric storage device into square shapes of 100mm×100mm, and preparing a sample; an infrared absorption spectrum measurement was performed on the surface of the polyamide film located outside the obtained sample in an environment having a temperature of 25℃and a relative humidity of 50% using the ATR measurement mode of FT-IR; as the device, nicoletiS manufactured by sameimers technologies corporation (Thermo FISHER SCIENTIFIC) was used; based on the obtained absorption spectrum, the peak intensity P around 1200cm -1 of absorption from the α -crystal of nylon and the peak intensity Q around 1370cm -1 of absorption not related to crystallization were measured, and the intensity ratio x=p/Q of the peak intensity P to the peak intensity Q was calculated as the crystallization index,
The measurement conditions were:
the method comprises the following steps: macroATR process;
Wave number resolution: 8cm -1;
Cumulative number of times: 32 times;
A detector: a DTGS detector;
ATR prism: ge;
Incidence angle: 45 °;
Baseline: obtaining the wave number between 1100cm -1 and 1400cm -1 in a straight line approximation mode;
Absorption peak intensity Y 1200: a value obtained by subtracting the value of the baseline from the maximum value of the peak intensities in the range of the wave number 1195cm -1 to 1205cm -1;
Absorption peak intensity Y 1370: a value obtained by subtracting the value of the base line from the maximum value of the peak intensity in the range of the wave numbers 1365cm -1 to 1375cm -1.
35. A polyamide membrane characterized in that:
For use in a base layer of an outer packaging material for an electric storage device, the base layer comprising a laminate comprising at least a surface coating layer, a base layer, a barrier layer and a heat-fusible resin layer,
At least one of the surface and the interior of the surface covering layer contains titanium oxide,
The polyamide film has a crystallization index of 1.50 or more as measured by an ATR method using a Fourier transform infrared spectroscopy,
The method for determining the crystallization index comprises the following steps:
Cutting an outer packaging material for an electric storage device into square shapes of 100mm×100mm, and preparing a sample; an infrared absorption spectrum measurement was performed on the surface of the polyamide film located outside the obtained sample in an environment having a temperature of 25℃and a relative humidity of 50% using the ATR measurement mode of FT-IR; as the device, nicoletiS manufactured by sameimers technologies corporation (Thermo FISHER SCIENTIFIC) was used; based on the obtained absorption spectrum, the peak intensity P around 1200cm -1 of absorption from the α -crystal of nylon and the peak intensity Q around 1370cm -1 of absorption not related to crystallization were measured, and the intensity ratio x=p/Q of the peak intensity P to the peak intensity Q was calculated as the crystallization index,
The measurement conditions were:
the method comprises the following steps: macroATR process;
Wave number resolution: 8cm -1;
Cumulative number of times: 32 times;
A detector: a DTGS detector;
ATR prism: ge;
Incidence angle: 45 °;
Baseline: obtaining the wave number between 1100cm -1 and 1400cm -1 in a straight line approximation mode;
Absorption peak intensity Y 1200: a value obtained by subtracting the value of the baseline from the maximum value of the peak intensities in the range of the wave number 1195cm -1 to 1205cm -1;
Absorption peak intensity Y 1370: a value obtained by subtracting the value of the base line from the maximum value of the peak intensity in the range of the wave numbers 1365cm -1 to 1375cm -1.
36. A polyamide membrane characterized in that:
For use in a base layer of an outer packaging material for an electric storage device, the base layer comprising a laminate comprising at least a surface coating layer, a base layer, a barrier layer and a heat-fusible resin layer,
At least one of the surface and the interior of the surface covering layer contains silicon dioxide,
The polyamide film has a crystallization index of 1.50 or more as measured by an ATR method using a Fourier transform infrared spectroscopy,
The method for determining the crystallization index comprises the following steps:
Cutting an outer packaging material for an electric storage device into square shapes of 100mm×100mm, and preparing a sample; an infrared absorption spectrum measurement was performed on the surface of the polyamide film located outside the obtained sample in an environment having a temperature of 25℃and a relative humidity of 50% using the ATR measurement mode of FT-IR; as the device, nicoletiS manufactured by sameimers technologies corporation (Thermo FISHER SCIENTIFIC) was used; based on the obtained absorption spectrum, the peak intensity P around 1200cm -1 of absorption from the α -crystal of nylon and the peak intensity Q around 1370cm -1 of absorption not related to crystallization were measured, and the intensity ratio x=p/Q of the peak intensity P to the peak intensity Q was calculated as the crystallization index,
The measurement conditions were:
the method comprises the following steps: macroATR process;
Wave number resolution: 8cm -1;
Cumulative number of times: 32 times;
A detector: a DTGS detector;
ATR prism: ge;
Incidence angle: 45 °;
Baseline: obtaining the wave number between 1100cm -1 and 1400cm -1 in a straight line approximation mode;
Absorption peak intensity Y 1200: a value obtained by subtracting the value of the baseline from the maximum value of the peak intensities in the range of the wave number 1195cm -1 to 1205cm -1;
Absorption peak intensity Y 1370: a value obtained by subtracting the value of the base line from the maximum value of the peak intensity in the range of the wave numbers 1365cm -1 to 1375cm -1.
37. A polyamide membrane characterized in that:
For use in a base layer of an outer packaging material for an electric storage device, the base layer comprising a laminate comprising at least a surface coating layer, a base layer, a barrier layer and a heat-fusible resin layer,
At least one of the surface and the interior of the surface covering layer contains kaolin,
The polyamide film has a crystallization index of 1.50 or more as measured by an ATR method using a Fourier transform infrared spectroscopy,
The method for determining the crystallization index comprises the following steps:
Cutting an outer packaging material for an electric storage device into square shapes of 100mm×100mm, and preparing a sample; an infrared absorption spectrum measurement was performed on the surface of the polyamide film located outside the obtained sample in an environment having a temperature of 25℃and a relative humidity of 50% using the ATR measurement mode of FT-IR; as the device, nicoletiS manufactured by sameimers technologies corporation (Thermo FISHER SCIENTIFIC) was used; based on the obtained absorption spectrum, the peak intensity P around 1200cm -1 of absorption from the α -crystal of nylon and the peak intensity Q around 1370cm -1 of absorption not related to crystallization were measured, and the intensity ratio x=p/Q of the peak intensity P to the peak intensity Q was calculated as the crystallization index,
The measurement conditions were:
the method comprises the following steps: macroATR process;
Wave number resolution: 8cm -1;
Cumulative number of times: 32 times;
A detector: a DTGS detector;
ATR prism: ge;
Incidence angle: 45 °;
Baseline: obtaining the wave number between 1100cm -1 and 1400cm -1 in a straight line approximation mode;
Absorption peak intensity Y 1200: a value obtained by subtracting the value of the baseline from the maximum value of the peak intensities in the range of the wave number 1195cm -1 to 1205cm -1;
Absorption peak intensity Y 1370: a value obtained by subtracting the value of the base line from the maximum value of the peak intensity in the range of the wave numbers 1365cm -1 to 1375cm -1.
38. A polyamide membrane characterized in that:
For use in a base layer of an outer packaging material for an electric storage device, the base layer comprising a laminate comprising at least a surface coating layer, a base layer, a barrier layer and a heat-fusible resin layer,
At least one of the surface and the inside of the surface coating layer contains at least 2 selected from talc, silica, graphite, kaolin, montmorillonite, 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, acrylate resin, crosslinked acrylic acid, crosslinked styrene, crosslinked polyethylene, benzoguanamine, gold, aluminum, copper and nickel,
The polyamide film has a crystallization index of 1.50 or more as measured by an ATR method using a Fourier transform infrared spectroscopy,
The method for determining the crystallization index comprises the following steps:
Cutting an outer packaging material for an electric storage device into square shapes of 100mm×100mm, and preparing a sample; an infrared absorption spectrum measurement was performed on the surface of the polyamide film located outside the obtained sample in an environment having a temperature of 25℃and a relative humidity of 50% using the ATR measurement mode of FT-IR; as the device, nicoletiS manufactured by sameimers technologies corporation (Thermo FISHER SCIENTIFIC) was used; based on the obtained absorption spectrum, the peak intensity P around 1200cm -1 of absorption from the α -crystal of nylon and the peak intensity Q around 1370cm -1 of absorption not related to crystallization were measured, and the intensity ratio x=p/Q of the peak intensity P to the peak intensity Q was calculated as the crystallization index,
The measurement conditions were:
the method comprises the following steps: macroATR process;
Wave number resolution: 8cm -1;
Cumulative number of times: 32 times;
A detector: a DTGS detector;
ATR prism: ge;
Incidence angle: 45 °;
Baseline: obtaining the wave number between 1100cm -1 and 1400cm -1 in a straight line approximation mode;
Absorption peak intensity Y 1200: a value obtained by subtracting the value of the baseline from the maximum value of the peak intensities in the range of the wave number 1195cm -1 to 1205cm -1;
Absorption peak intensity Y 1370: a value obtained by subtracting the value of the base line from the maximum value of the peak intensity in the range of the wave numbers 1365cm -1 to 1375cm -1.
39. A polyamide membrane characterized in that:
For the base layer of an outer packaging material for an electric storage device, which is composed of a laminate comprising at least a surface covering layer, a coating layer, a base layer, a barrier layer and a heat-fusible resin layer,
The polyamide film has a crystallization index of 1.50 or more as measured by an ATR method using a Fourier transform infrared spectroscopy,
The method for determining the crystallization index comprises the following steps:
Cutting an outer packaging material for an electric storage device into square shapes of 100mm×100mm, and preparing a sample; an infrared absorption spectrum measurement was performed on the surface of the polyamide film located outside the obtained sample in an environment having a temperature of 25℃and a relative humidity of 50% using the ATR measurement mode of FT-IR; as the device, nicoletiS manufactured by sameimers technologies corporation (Thermo FISHER SCIENTIFIC) was used; based on the obtained absorption spectrum, the peak intensity P around 1200cm -1 of absorption from the α -crystal of nylon and the peak intensity Q around 1370cm -1 of absorption not related to crystallization were measured, and the intensity ratio x=p/Q of the peak intensity P to the peak intensity Q was calculated as the crystallization index,
The measurement conditions were:
the method comprises the following steps: macroATR process;
Wave number resolution: 8cm -1;
Cumulative number of times: 32 times;
A detector: a DTGS detector;
ATR prism: ge;
Incidence angle: 45 °;
Baseline: obtaining the wave number between 1100cm -1 and 1400cm -1 in a straight line approximation mode;
Absorption peak intensity Y 1200: a value obtained by subtracting the value of the baseline from the maximum value of the peak intensities in the range of the wave number 1195cm -1 to 1205cm -1;
Absorption peak intensity Y 1370: a value obtained by subtracting the value of the base line from the maximum value of the peak intensity in the range of the wave numbers 1365cm -1 to 1375cm -1.
40. The polyamide membrane of any one of claims 33-39 wherein:
the polyamide film has a crystallization index of 1.65 or more as measured by an ATR method using a Fourier transform infrared spectroscopy.
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