Exterior material for energy storage devices, method for manufacturing the same, and energy storage device

Abstract

It is composed of a laminate comprising, at least from the outside, a base layer, a barrier layer, and a heat-fusible resin layer in that order. The aforementioned substrate layer includes a polyester film. The thickness of the polyester film is 10 μm or less. An exterior material for an energy storage device, wherein the ratio of the thickness (μm) of the substrate layer to the thickness (μm) of the barrier layer is 40% or less.

Description

Technical Field

[0001] The present disclosure relates to an exterior material for a power storage device, a method for manufacturing the same, and a power storage device.

Background Art

[0002] Conventionally, various types of power storage devices have been developed. In all power storage devices, an exterior material is an essential member for sealing power storage device elements such as electrodes and electrolytes. Conventionally, a metal exterior material has been frequently used as the exterior material for power storage devices.

[0003] On the other hand, in recent years, with the improvement in performance of electric vehicles, hybrid electric vehicles, personal computers, cameras, mobile phones, etc., various shapes are required for power storage devices, and thinning and weight reduction are also demanded. However, the conventionally frequently used metal exterior material for power storage devices has drawbacks that it is difficult to follow the diversification of shapes and there is also a limit to weight reduction.

[0004] Therefore, in recent years, as an exterior material for a power storage device that can be easily processed into various shapes and can achieve thinning and weight reduction, a film-like laminate in which a base material layer / barrier layer / heat-sealable resin layer are sequentially laminated has been proposed (for example, see Patent Document 1).

[0005] In such an exterior material for a power storage device, generally, a concave portion is formed by cold forming, power storage device elements such as electrodes and electrolytic solution are arranged in the space formed by the concave portion, and by heat-sealing the heat-sealable resin layer, a power storage device in which the power storage device elements are housed inside the exterior material for a power storage device is obtained.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Summary of the Invention

[0007] For example, large energy storage devices used in automotive batteries and stationary batteries require even higher capacity. Therefore, the aforementioned film-like outer casing materials for energy storage devices require greater moldability to expand the space for housing the energy storage device elements.

[0008] Conventionally, in order to meet the demand for high moldability of exterior materials for energy storage devices, measures have been taken to increase the thickness of the layers constituting the exterior material for energy storage devices (specifically, the aforementioned base material layer, barrier layer, heat-fusible resin layer, etc.).

[0009] However, the inventors of this disclosure have found that when such a thick exterior material is subjected to cold forming to form a recess, the area around the recessed part of the exterior material curls significantly (large forming curl).

[0010] The primary objective of this disclosure is to provide an exterior material for an energy storage device, comprising a laminate comprising, at least, a base material layer, a barrier layer, and a heat-fusible resin layer in that order from the outside, wherein molding curl is suppressed when the exterior material is subjected to cold forming to form a recess. The primary objective of this disclosure is to provide a method for manufacturing the exterior material for an energy storage device and an energy storage device using the exterior material for an energy storage device. [Means for solving the problem]

[0011] The inventors of this disclosure have diligently studied to solve the above-mentioned problems. As a result, they have found that in an exterior material for an energy storage device, which is composed of a laminate comprising, from the outside, a base layer, a barrier layer, and a heat-fusible resin layer in that order, if the base layer includes a polyester film of a predetermined thickness or less, and the ratio of the thickness of the base layer to the thickness of the barrier layer is limited to a predetermined value or less, then molding curl when the exterior material for an energy storage device is subjected to cold forming to form a recess is suppressed.

[0012] This disclosure is the result of further consideration based on these novel findings. Specifically, this disclosure provides the inventions listed below.

[0013] It is composed of a laminate comprising, at least from the outside, a base layer, a barrier layer, and a heat-fusible resin layer in that order. The aforementioned substrate layer includes a polyester film. The thickness of the polyester film is 10 μm or less. An exterior material for an energy storage device, wherein the ratio of the thickness (μm) of the substrate layer to the thickness (μm) of the barrier layer is 40% or less. [Effects of the Invention]

[0014] According to this disclosure, it is possible to provide an exterior material for an energy storage device, which is composed of a laminate comprising, at least, a base material layer, a barrier layer, and a heat-fusible resin layer in that order from the outside, wherein molding curl is suppressed when the exterior material is subjected to cold forming to form a recess. Furthermore, according to this disclosure, it is possible to provide a method for manufacturing the exterior material for an energy storage device and an energy storage device using the exterior material for an energy storage device.

[0015] Furthermore, the exterior material for energy storage devices disclosed herein, as described later, can also exhibit even greater advantages, such as high mechanical strength in high-temperature environments and high dead-hold properties. [Brief explanation of the drawing]

[0016] [Figure 1] This is a schematic diagram showing an example of the cross-sectional structure of the exterior material for the energy storage device of this disclosure. [Figure 2] This is a schematic diagram showing an example of the cross-sectional structure of the exterior material for the energy storage device of this disclosure. [Figure 3] This is a schematic diagram showing an example of the cross-sectional structure of the exterior material for the energy storage device of this disclosure. [Figure 4] This is a schematic diagram showing an example of the cross-sectional structure of the exterior material for the energy storage device of this disclosure. [Figure 5] This is a schematic diagram illustrating a method for housing energy storage device elements in a package formed from the exterior material for energy storage devices of the present disclosure. [Figure 6] This is a schematic diagram of the deadhold evaluation method disclosed herein. [Modes for carrying out the invention]

[0017] The exterior material for energy storage devices of this disclosure is composed of a laminate comprising, from the outside in, a base layer, a barrier layer, and a heat-sealable resin layer, wherein the base layer includes a polyester film. The polyester film is characterized by having a thickness of 10 μm or less, and the ratio of the thickness of the base material layer (μm) to the thickness of the barrier layer (μm) is 40% or less. The exterior material for energy storage devices of this disclosure, having this configuration, suppresses molding curl when the exterior material for energy storage devices is subjected to cold forming to form a recess.

[0018] The exterior materials for energy storage devices described herein will be described in detail below. In this disclosure, numerical ranges indicated by "~" mean "greater than or equal to" and "less than or equal to". For example, the notation 2~15mm means 2mm or more and 15mm or less. In numerical ranges described in stages in this disclosure, the upper or lower limit stated in one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Alternatively, upper and lower limits, upper and lower limits, or lower limits described separately may be combined to form numerical ranges. Furthermore, in numerical ranges described in this disclosure, the upper or lower limit stated in one numerical range may be replaced with the values ​​shown in the examples.

[0019] Furthermore, in the case of exterior materials for energy storage devices, the Machine Direction (MD) and Transverse Direction (TD) of the barrier layer 3 described later can usually be determined during the manufacturing process. For example, when the barrier layer 3 includes metal foil such as aluminum alloy foil or stainless steel foil, linear lines called rolling marks are formed on the surface of the metal foil in the rolling direction (RD) of the metal foil. Since the rolling marks extend along the rolling direction, the rolling direction of the metal foil can be determined by observing the surface of the metal foil. Also, in the manufacturing process of a laminate, the MD of the laminate and the RD of the metal foil usually coincide, so the MD of the laminate can be determined by observing the surface of the metal foil in the laminate and identifying the rolling direction (RD) of the metal foil. In addition, since the TD of the laminate is perpendicular to the MD of the laminate, the TD of the laminate can also be determined. Similarly, since the MD of the heat-fusible resin layer and the RD of the metal foil coincide, the MD of the heat-fusible resin layer can be determined by observing the surface of the metal foil in the laminate and identifying the rolling direction (RD) of the metal foil. Furthermore, since the TD of the heat-fusible resin layer is perpendicular to the MD of the heat-fusible resin layer, the TD of the heat-fusible resin layer can also be identified.

[0020] Furthermore, if the MD of the exterior material for energy storage devices cannot be identified by the rolling marks of metal foils such as aluminum alloy foil and stainless steel foil, it can be identified by the following method. One method for confirming the MD of the exterior material for energy storage devices is to observe the cross-section of the heat-fusible resin layer of the exterior material of the energy storage device with an electron microscope and confirm the sea-island structure. In this method, the direction parallel to the cross-section where the average diameter of the island shapes perpendicular to the thickness direction of the heat-fusible resin layer is maximum can be determined as the MD. Specifically, the sea-island structure is confirmed by observing each of the cross-sections in the longitudinal direction of the heat-fusible resin layer and the direction perpendicular to the longitudinal cross-section (a total of 10 cross-sections) by changing the angle by 10 degrees from the direction parallel to the longitudinal cross-section. Next, the shape of each individual island is observed in each cross-section. For the shape of each island, the straight-line distance connecting the leftmost point perpendicular to the thickness direction of the heat-fusible resin layer and the rightmost point perpendicular to that point is defined as the diameter y. For each cross-section, the average of the top 20 diameters y of the island shape, ordered from largest to smallest, is calculated. The direction parallel to the cross-section with the largest average diameter y of the island shape is determined to be the MD (Movement Direction).

[0021] [Laminated structure and physical properties of exterior materials for energy storage devices] The exterior material 10 for energy storage devices of this disclosure is composed of a laminate comprising a base layer 1, a barrier layer 3, and a heat-fusible resin layer 4 in that order, as shown in Figure 1, for example. In the exterior material 10 for energy storage devices, the base layer 1 is the outermost layer, and the heat-fusible resin layer 4 is the innermost layer. When assembling an energy storage device using the exterior material 10 and an energy storage device element, the energy storage device element is housed in a space formed by heat-fussing the peripheral edges of the heat-fusible resin layers 4 of the exterior material 10 facing each other. In the laminate constituting the exterior material 10 for energy storage devices of this disclosure, with respect to the barrier layer 3, the heat-fusible resin layer 4 side is inward of the barrier layer 3, and the base layer 1 side is outward of the barrier layer 3.

[0022] The exterior material 10 for the energy storage device may, for example, have an adhesive layer 2 between the base layer 1 and the barrier layer 3, as needed, for the purpose of improving the adhesion between these layers, as shown in Figures 2 to 4. Also, as shown in Figures 3 and 4, an adhesive layer 5 may, as needed, have an adhesive layer 5 between the barrier layer 3 and the heat-fusible resin layer 4, for the purpose of improving the adhesion between these layers. Furthermore, as shown in Figure 4, a surface coating layer 6 or the like may be provided on the outside of the base layer 1 (opposite the heat-fusible resin layer 4 side), as needed.

[0023] The thickness of the laminate constituting the exterior material 10 for energy storage devices is not particularly limited, but from the viewpoint of cost reduction and improvement of energy density, for example, it can be about 300 μm or less, preferably about 250 μm or less, about 210 μm or less, about 190 μm or less, about 180 μm or less, about 155 μm or less, or about 120 μm or less. Furthermore, from the viewpoint of maintaining the function of the exterior material for energy storage devices, which is to protect the energy storage device elements, the thickness of the laminate constituting the exterior material 10 for energy storage devices can be preferably about 35 μm or more, about 45 μm or more, about 60 μm or more, about 155 μm or more, or about 190 μm or more. Furthermore, the preferred range for the laminate constituting the outer casing material 10 for the energy storage device is, for example, approximately 35-300 μm, approximately 35-250 μm, approximately 35-210 μm, approximately 35-190 μm, approximately 35-180 μm, approximately 35-155 μm, approximately 35-120 μm, approximately 45-300 μm, approximately 45-250 μm, approximately 45-210 μm, approximately 45-190 μm, approximately 45-180 μm, approximately 45-155 μm, approximately 45-120 μm, approximately 60-300 μm, approximately 60-250 μm, and 60- Examples of thicknesses include approximately 210 μm, 60-190 μm, 60-180 μm, 60-155 μm, 60-120 μm, 155-300 μm, 155-250 μm, 155-210 μm, 155-190 μm, 155-180 μm, 190-300 μm, 190-250 μm, and 190-210 μm. In particular, when creating lightweight thin films for energy storage devices, approximately 60-155 μm is preferred, and when improving moldability, approximately 155-190 μm is preferred.

[0024] In the exterior material 10 for energy storage devices, the ratio of the total thickness of the base layer 1, the adhesive layer 2 (optionally provided), the barrier layer 3, the adhesive layer 5 (optionally provided), the heat-fusible resin layer 4, and the surface coating layer 6 (optionally provided) to the thickness (total thickness) of the laminate constituting the exterior material 10 for energy storage devices is preferably 90% or more, more preferably 95% or more, and even more preferably 98% or more. For example, if the exterior material 10 for energy storage devices of this disclosure includes a base layer 1, an adhesive layer 2, a barrier layer 3, an adhesive layer 5, and a heat-fusible resin layer 4, the ratio of the total thickness of each of these layers to the thickness (total thickness) of the laminate constituting the exterior material 10 for energy storage devices is preferably 90% or more, more preferably 95% or more, and even more preferably 98% or more. Furthermore, even if the exterior material 10 for energy storage devices of this disclosure is a laminate comprising a base layer 1, an adhesive layer 2, a barrier layer 3, and a 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 energy storage devices can be, for example, 80% or more, preferably 90% or more, more preferably 95% or more, and even more preferably 98% or more.

[0025] In the exterior material for energy storage devices of this disclosure, the base layer 1 includes a polyester film with a thickness of 10 μm or less. Furthermore, the ratio A of the thickness of the base layer (μm) to the thickness of the barrier layer 3 (μm) is 40% or less. From the viewpoint of more favorably exhibiting the effects of the invention of this disclosure, the ratio A (%) is preferably about 38% or less, more preferably about 37% or less, even more preferably about 36% or less, and also preferably about 5% or more, more preferably about 6% or more, even more preferably about 7% or more. Preferred ranges include about 5-38%, about 5-37%, about 5-36%, about 6-38%, about 6-37%, about 6-36%, about 7-38%, about 7-37%, and about 7-36%.

[0026] Furthermore, from the viewpoint of more favorably exhibiting the effects of the present invention, the ratio B (%) of the thickness of the base layer 1 to the total thickness of the layers located inside the barrier layer 3 (for example, an adhesive layer 5, a heat-fusible resin layer 4, etc., provided as needed) is preferably about 50% or less, more preferably about 40% or less, even more preferably about 35% or less, even more preferably 28% or less, also preferably about 20% or more, more preferably about 23% or more, even more preferably about 25% or more, and preferred ranges include about 20-50%, about 20-40%, about 20-35%, about 20-28%, about 23-50%, about 23-40%, about 23-35%, about 23-28%, about 25-50%, about 25-40%, about 25-35%, and about 25-28%.

[0027] Furthermore, from the viewpoint of more favorably exhibiting the effects of the present invention, the sum of ratio A (%) and ratio B (%) (thickness ratio C (%)) is preferably about 80% or less, more preferably about 75% or less, even more preferably about 70% or less, even more preferably about 50% or less, also preferably about 30% or more, more preferably about 32% or more, even more preferably about 33% or more, and preferred ranges include about 30-80%, about 30-75%, about 30-70%, about 30-50%, about 32-80%, about 32-75%, about 32-70%, about 32-50%, about 33-80%, about 33-75%, about 33-70%, and about 33-50%.

[0028] Furthermore, from the viewpoint of more favorably exhibiting the effects of the present invention, the ratio D (%) of the thickness of the polyester film contained in the base layer 1 to the thickness of the barrier layer 3 is preferably about 20% or less, more preferably about 15% or less, even more preferably about 12% or less, even more preferably about 9% or less, also preferably about 5% or more, more preferably about 6% or more, even more preferably about 7% or more, and preferred ranges include about 5-20%, about 5-15%, about 5-12%, about 5-9%, about 6-20%, about 6-15%, about 6-12%, about 6-9%, about 7-20%, about 7-15%, about 7-12%, and about 7-9%.

[0029] Furthermore, from the viewpoint of more favorably exhibiting the effects of the present invention, the ratio E (%) of the thickness of the polyester film contained in the base layer 1 to the total thickness of the layers located inside the barrier layer 3 (for example, the adhesive layer 5 and the heat-fusible resin layer 4, which may be provided as needed) is preferably about 30% or less, more preferably about 25% or less, even more preferably about 10% or less, and also preferably about 6% or more, more preferably about 7% or more, even more preferably about 8% or more. Preferred ranges include about 6-30%, about 6-25%, about 6-10%, about 7-30%, about 7-25%, about 7-10%, about 8-30%, about 8-25%, and about 8-10%.

[0030] Furthermore, from the viewpoint of more favorably exhibiting the effects of the present invention, the sum of ratio D (%) and ratio E (%) (thickness ratio F (%)) is preferably about 50% or less, more preferably about 35% or less, even more preferably about 20% or less, and also preferably about 10% or more, more preferably about 12% or more, even more preferably about 15% or more. Preferred ranges include about 10-50%, about 10-35%, about 10-20%, about 12-50%, about 12-35%, about 12-20%, about 15-50%, about 15-35%, and about 15-20%.

[0031] From the viewpoint of more favorably exhibiting the effects of the present invention (particularly improved processability during molding), the exterior material for energy storage devices of the present disclosure preferably has a molded curl of about 5 mm or less, more preferably about 4 mm or less, and even more preferably about 2 mm or less, as measured by the following measurement method.

[0032] (Measurement of shaped curl) A rectangular exterior material for an energy storage device, with dimensions of TD150mm x MD90mm in plan view, is used as the measurement sample. A straight mold consisting of a rectangular male mold measuring 31.6mm vertically x 54.5mm horizontally and a female mold with a clearance of 0.53mm from the male mold is used. The measurement sample is placed on the female mold so that the heat-fusible resin layer is positioned on the male mold side. The measurement sample is then pressed with a pressing pressure (surface pressure) of 0.1MPa to form a sample with dimensions of 31.6mm (MD direction) x 54.5mm (TD direction) and a molding depth of 5mm, and cold forming (single-stage pull-in forming) is performed. The forming is carried out so that the center of the energy storage device exterior material, the MD direction, and the TD direction coincide with the center of the male mold, the vertical direction, and the horizontal direction, respectively. After molding, the measurement sample is stored for one day in an environment of 25°C and 60% relative humidity. Then, with the heat-fusible resin layer facing downwards, it is placed on a horizontal surface, and the distance between the horizontal surface and the point on one of the four sides of the molded measurement sample furthest from the horizontal surface is measured. This distance is defined as the molding curl. The surface of the ridge of the male mold has a maximum height roughness (nominal value of Rz) of 1.6 μm, as specified in Table 2 of the comparative surface roughness standard specimens in Annex 1 (Reference) of JIS B 0659-1:2002. The surface other than the ridge has a maximum height roughness (nominal value of Rz) of 3.2 μm, as specified in Table 2 of the comparative surface roughness standard specimens in Annex 1 (Reference) of JIS B 0659-1:2002. The corner radius of the male mold is 2.0 mm, and the ridge radius is 1.0 mm. The surface of the female mold has a maximum height roughness (nominal value of Rz) of 3.2 μm, as specified in Table 2 of the comparative surface roughness standard specimens in Annex 1 (Reference) of JIS B 0659-1:2002. The corner radius of the female mold is 2.0 mm, and the edge radius is 1.0 mm.

[0033] Furthermore, from the viewpoint of more favorably exhibiting the further excellent effects of the invention disclosed here (especially high mechanical strength in high-temperature environments), the exterior material for energy storage devices of the disclosure has a strength of 20% elongation in the MD direction in the following tensile test at a 120°C environment, preferably about 60.0 N / 15 mm or more, more preferably about 65.0 N / 15 mm or more, and even more preferably about 70.0 N / 15 mm or more, with an upper limit of, for example, about 150.0 N / 15 mm or less, and preferred ranges include about 60.0 to 150.0 N / 15 mm, about 65.0 to 150.0 N / 15 mm, and about 70.0 to 150.0 N / 15 mm.

[0034] <Tensile Test> The tensile strength is measured using a tensile testing machine in accordance with the provisions of JIS K7127:1999. The measurement conditions are as follows: a rectangular sample with a width of 15 mm, a gauge length of 50 mm, a tensile speed of 5 mm / min, and a test environment of 120°C. The average value of three measurements is used. In the tensile test described in this disclosure, the initial distance between the chucks is 50 mm, and this initial distance between the chucks is used as the gauge length.

[0035] Furthermore, from the viewpoint of more favorably exhibiting the effects of the present invention (especially high deadhold performance), the exterior material for the energy storage device of the present disclosure preferably has a length α value measured by the following deadhold performance evaluation method that is about 10 mm or less, more preferably about 5 mm or less, and even more preferably about 3 mm or less.

[0036] (Method for evaluating deadhold performance) A rectangular exterior material for an energy storage device, with dimensions of TD100mm x MD200mm in plan view, is used as the measurement sample. The measurement sample is folded in half so that the base material layers face each other in the MD direction and the heat-sealable resin layer is on the outside. A 2kg roller is placed on the folded portion and the roller is moved back and forth 5 times in the TD direction. The folded measurement sample is placed on a glass plate and left to stand for 1 minute. At this time, as shown in Figure 6, the surface of one side of the heat-sealable resin layer of the folded measurement sample is placed in contact with the surface of the glass plate. The length α (mm) of the closest parts at both ends of the folded measurement sample is measured. The measurement environment is set to a temperature of 25°C and a relative humidity of 60%.

[0037] [Each layer forming the exterior material for energy storage devices] [Base material layer 1] In this disclosure, the base material layer 1 is a layer provided for purposes such as enabling it to function as a base material for the exterior material of an energy storage device. The base material layer 1 is located on the outer layer side of the exterior material for the energy storage device.

[0038] In this disclosure, the base layer 1 includes a polyester film with a thickness of 10 μm or less. That is, the polyester film included in the base layer 1 has a thickness of 10 μm or less.

[0039] Examples of polyesters include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, and copolymerized polyesters. Examples of copolymerized polyesters include copolymerized polyesters with ethylene terephthalate as the main repeating unit. Specifically, examples include copolymerized polyesters polymerized with ethylene isophthalate using ethylene terephthalate as the main repeating unit (hereinafter abbreviated as polyethylene(terephthalate / isophthalate)), polyethylene(terephthalate / adipate), polyethylene(terephthalate / sodium sulfoisophthalate), polyethylene(terephthalate / sodium isophthalate), polyethylene(terephthalate / phenyl dicarboxylate), and polyethylene(terephthalate / decanedicarboxylate). Furthermore, the polyester may be a copolymer of two or more polyesters selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and polyethylene isophthalate. These polyesters may be used individually or as mixtures of two or more. The polyester film may contain the additives described below.

[0040] A polyester film is a resin film that contains polyester as its main component. Here, "main component" means that among the resin components contained in the polyester film, the content is, for example, 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, even more preferably 98% by mass or more, and even more preferably 99% by mass or more. In other words, when a polyester film contains polyester as its main component, it means that among the resin components contained in the polyester film, the polyester content is, for example, 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, even more preferably 98% by mass or more, and even more preferably 99% by mass or more.

[0041] In this disclosure, the thickness of the polyester film contained in the base layer 1 may be 10 μm or less, but from the viewpoint of more favorably exhibiting the effects of the invention of this disclosure, it is preferably about 8 μm or less, more preferably about 7 μm or less, and also preferably about 4 μm or more, more preferably about 5 μm or more. Preferred ranges include about 4 to 10 μm, about 4 to 8 μm, about 4 to 7 μm, about 5 to 10 μm, about 5 to 8 μm, and about 5 to 7 μm.

[0042] The base layer 1 may further contain a resin film different from the polyester film (another resin film) in addition to the polyester film.

[0043] The other materials used to form the resin film are not particularly limited, as long as they possess the function of a substrate, that is, at least insulating properties. The substrate layer 1 can be formed using, for example, a resin, and the resin may contain additives described later.

[0044] Other resins that form the resin film include, for example, polyamides, polyolefins, epoxy resins, acrylic resins, fluororesins, polyurethanes, silicon resins, phenolic resins, and modified versions of these resins. These resins may also be copolymers of these resins, or modified versions of copolymers. Furthermore, mixtures of these resins may also be used.

[0045] Other resin films preferably contain these resins as their main component, and more preferably contain polyamide or polyolefin as their main component. Here, "main component" means a resin component that, among the resin components contained in the other resin film, has a content of, for example, 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, even more preferably 98% by mass or more, and even more preferably 99% by mass or more. For example, if the other resin film contains polyamide as its main component, it means that among the resin components contained in the other resin film, the polyamide content is, for example, 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, even more preferably 98% by mass or more, and even more preferably 99% by mass or more.

[0046] Among these resins, polyamide is a preferred choice for forming other resin films.

[0047] Furthermore, specific examples of polyamides include aliphatic polyamides such as nylon 6, nylon 66, nylon 610, nylon 12, nylon 46, and copolymers of nylon 6 and nylon 66; hexamethylenediamine-isophthalic acid-terephthalic acid copolymer polyamides such as nylon 6I, nylon 6T, nylon 6IT, and nylon 6I6T (where I represents isophthalic acid and T represents terephthalic acid), which contain constituent units derived from terephthalic acid and / or isophthalic acid; aromatic polyamides such as polyamide MXD6 (polymetaxylylene adipamide); alicyclic polyamides such as polyamide PACM6 (polybis(4-aminocyclohexyl)methaneadipamide); polyamides copolymerized with lactam components or isocyanate components such as 4,4'-diphenylmethane-diisocyanate; polyesteramide copolymers and polyether esteramide copolymers, which are copolymers of copolymerized polyamides with polyester or polyalkylene ether glycol; and other polymers of these polyamides. These polyamides may be used individually or in combination of two or more types.

[0048] The base layer 1 preferably contains at least one of a polyamide film and a polyolefin film in addition to a polyester film, preferably at least one of a stretched polyamide film and a stretched polyolefin film in addition to a stretched polyester film, more preferably at least one of a stretched nylon film and a stretched polypropylene film in addition to a stretched polyethylene terephthalate film, and even more preferably at least one of a biaxially oriented nylon film and a biaxially oriented polypropylene film in addition to a biaxially oriented polyethylene terephthalate film.

[0049] The base layer 1 may be a single layer or may consist of two or more layers. If the base layer 1 consists of two or more layers, the base layer 1 may be a laminate formed by laminating resin films with an adhesive, or it may be a laminate of two or more resin films formed by co-extruding resin. Furthermore, the laminate of two or more resin films formed by co-extruding resin may be used as the base layer 1 in its unstretched state, or it may be used as the base layer 1 after uniaxial stretching or biaxial stretching.

[0050] Specific examples of a laminate of two or more resin films in the base layer 1 include a laminate of polyester film and nylon film, a laminate of two or more nylon films, and a laminate of two or more polyester films. Preferably, a laminate of stretched nylon film and stretched polyester film, a laminate of two or more stretched nylon films, and a laminate of two or more stretched polyester films are preferred. For example, when the base layer 1 is a laminate of two resin films, a laminate of polyester resin film and polyester resin film, a laminate of polyamide resin film and polyamide resin film, or a laminate of polyester resin film and polyamide resin film is preferred, and a laminate of polyethylene terephthalate film and polyethylene terephthalate film, a laminate of nylon film and nylon film, or a laminate of polyethylene terephthalate film and nylon film is more preferred. Furthermore, since polyester resin is less likely to discolor when an electrolyte adheres to its surface, for example, when the base layer 1 is a laminate of two or more resin films, it is preferable that the polyester resin film be located in the outermost layer of the base layer 1.

[0051] From the viewpoint of more favorably exhibiting the effects of the present invention, the thickness of other resin films that may be included in the base layer 1 is preferably about 25 μm or less, more preferably about 20 μm or less, even more preferably about 15 μm or less, and also preferably about 8 μm or more, more preferably about 10 μm or more, even more preferably about 12 μm or more. Preferred ranges include about 8 to 25 μm, about 8 to 20 μm, about 8 to 15 μm, about 10 to 25 μm, about 10 to 20 μm, about 10 to 15 μm, about 12 to 25 μm, about 12 to 20 μm, and about 12 to 15 μm.

[0052] If the base layer 1 is a laminate of two or more resin films, the two or more resin films may be laminated with an adhesive in between. Preferred adhesives include those similar to those exemplified in adhesive layer 2 described later. The method for laminating the two or more resin films is not particularly limited, and known methods can be used, such as dry lamination, sandwich lamination, extrusion lamination, and thermal lamination, with dry lamination being preferred. When laminating by dry lamination, it is preferable to use a polyurethane adhesive. In this case, the thickness of the adhesive is, for example, about 2 to 5 μm. Alternatively, an anchor coat layer may be formed on the resin film and laminated. The anchor coat layer is similar to the adhesive exemplified in adhesive layer 2 described later. In this case, the thickness of the anchor coat layer is, for example, about 0.01 to 1.0 μm.

[0053] In this disclosure, the thickness of the base layer 1 does not include the thickness of the adhesive layer (such as the anchor coat layer) that bonds the resin films together. This is because the adhesive layer has very little effect on the molding curl. Therefore, for example, if the base layer 1 is composed of a laminate of a polyester film with a thickness of 10 μm or less and a nylon film, the thickness of the adhesive layer (such as the anchor coat layer) that bonds the polyester film and the nylon film together is not included in the thickness of the base layer 1.

[0054] Furthermore, when manufacturing the exterior material 10 for the energy storage device of this disclosure by laminating the base layer 1 with a barrier layer 3 or the like, a pre-formed resin film may be used as the base layer 1. Alternatively, the resin forming the base layer 1 may be formed into a film on the surface of the barrier layer 3 or the like by extrusion molding or coating, and the base layer 1 may be formed from a resin film. The resin film may be an unstretched film or a stretched film. Examples of stretched films include uniaxially stretched films and biaxially stretched films, with biaxially stretched films being preferred. Examples of stretching methods for forming a biaxially stretched film include sequential biaxial stretching, inflation method, and simultaneous biaxial stretching. Examples of methods for coating the resin include roll coating, gravure coating, and extrusion coating.

[0055] Furthermore, at least one of the surface and interior of the base layer 1 may contain additives such as lubricants, flame retardants, antiblocking agents, antioxidants, light stabilizers, tackifiers, antistatic agents, and colorants. Only one type of additive may be used, or two or more types may be mixed and used.

[0056] In this disclosure, from the viewpoint of improving the moldability of the exterior material for energy storage devices, it is preferable that a lubricant be present on at least one of the surface and interior of the base layer 1. The lubricant is not particularly limited, but amide lubricants are preferred. Specific examples of amide lubricants include saturated fatty acid amides, unsaturated fatty acid amides, substituted amides, methylolamides, saturated fatty acid bisamides, unsaturated fatty acid bisamides, fatty acid ester amides, and aromatic bisamides. Specific examples of saturated fatty acid amides include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, and hydroxystearic acid amide. Specific examples of unsaturated fatty acid amides include oleic acid amide and erucic acid amide. Specific examples of substituted amides include N-oleyl palmitic acid amide, N-stearyl stearate amide, N-stearyl oleic acid amide, N-oleyl stearate amide, and N-stearyl erucic acid amide. Specific examples of methylolamides include methylol stearate amide. Specific examples of saturated fatty acid bisamides include methylenebisstearate, ethylenebiscaprate, ethylenebislaurate, ethylenebisstearate, ethylenebishydroxystearate, ethylenebisbehenamide, hexamethylenebisstearate, hexamethylenebisbehenamide, hexamethylenehydroxystearate, N,N'-distearyladipamide, and N,N'-distearylsebacinamide. Specific examples of unsaturated fatty acid bisamides include ethylenebisoleamide, ethylenebiserucamide, hexamethylenebisoleamide, N,N'-dioleyladipamide, and N,N'-dioleylsebacinamide. Specific examples of fatty acid ester amides include stearamidoethylstearate. Specific examples of aromatic bisamides include m-xylylenebisstearamide, m-xylylenebishydroxystearamide, and N,N'-distearyl isophthalamide.The lubricant may be used alone or in combination of two or more kinds, and it is preferable to use two or more kinds in combination.

[0057] When the lubricant is present on the surface of the base material layer 1, its amount of presence is not particularly limited. For example, it is about 3 mg / m 2 or more, preferably about 4 mg / m 2 or more, about 5 mg / m 2 or more. Also, as the amount of the lubricant present on the surface of the base material layer 1, for example, it is about 15 mg / m 2 or less, preferably about 14 mg / m 2 or less, about 10 mg / m 2 or less. Also, the preferable range of the amount of the lubricant present on the surface of the base material layer 1 is about 3 - 15 mg / m 2 level, about 3 - 14 mg / m 2 level, about 3 - 10 mg / m 2 level, about 4 - 15 mg / m 2 level, about 4 - 14 mg / m 2 level, about 4 - 10 mg / m 2 level, about 5 - 15 mg / m 2 level, about 5 - 14 mg / m 2 level, about 5 - 10 mg / m 2 level.

[0058] The lubricant present on the surface of the base material layer 1 may be one obtained by exuding the lubricant contained in the resin constituting the base material layer 1, or may be one obtained by coating the lubricant on the surface of the base material layer 1.

[0059] The thickness of the base layer 1 is not particularly limited as long as it performs its function as a base material, but for example, it can be about 3 μm or more, preferably about 10 μm or more. Also, examples of thicknesses for the base layer 1 include about 100 μm or less, about 90 μm or less, about 70 μm or less, about 50 μm or less, preferably about 35 μm or less, 25 μm or less, 11 μm or less, and 8 μm or less. Furthermore, preferred thickness ranges for the substrate layer 1 include approximately 3-100 μm, 3-90 μm, 3-70 μm, 3-50 μm, 3-35 μm, 3-25 μm, 3-11 μm, 3-8 μm, 10-100 μm, 10-90 μm, 10-70 μm, 10-50 μm, 10-35 μm, and 10-11 μm. In particular, from the viewpoint of making the energy storage device lightweight and thin and suppressing molding curl, approximately 3-35 μm, 3-25 μm, 3-11 μm, and 3-8 μm are preferred, and approximately 35-50 μm is preferred when improving moldability. When the base layer 1 is a laminate of two or more resin films, the thickness of the resin film constituting each layer is not particularly limited, but examples include about 2 μm or more, preferably about 10 μm or more and about 18 μm or more, respectively. Also, examples of the thickness of the resin film constituting each layer include about 33 μm or less, preferably about 28 μm or less, about 23 μm or less, about 18 μm or less, 11 μm or less, and 8 μm or less. Furthermore, preferred ranges for the thickness of the resin film constituting each layer include about 2 to 33 μm, about 2 to 28 μm, about 2 to 23 μm, about 2 to 18 μm, about 2 to 11 μm, about 2 to 8 μm, about 10 to 33 μm, about 10 to 28 μm, about 10 to 23 μm, about 10 to 18 μm, about 10 to 11 μm, about 18 to 33 μm, about 18 to 28 μm, and about 18 to 23 μm.

[0060] The base layer 1 contains a coloring agent, which allows the exterior material for the energy storage device to be colored. Known coloring agents such as pigments and dyes can be used. Furthermore, only one type of coloring agent may be used, or two or more types may be mixed and used.

[0061] The type of pigment is not particularly limited, as long as it does not impair the function of the substrate layer 1 as a substrate. Examples of organic pigments include azo, phthalocyanine, quinacridone, anthraquinone, dioxazine, indigothioindigo, perinone-perylene, isoindorenine, and benzimidazolon pigments. Examples of inorganic pigments include carbon black, titanium dioxide, cadmium, lead, chromium oxide, and iron pigments. Other examples include fine mica powder and fish scale foil.

[0062] Among colorants, carbon black is preferred for, for example, to give the exterior material of an energy storage device a black appearance. Furthermore, from the viewpoint of dissipating heat generated from the energy storage device, mica is preferred.

[0063] The average particle size of the pigment is not particularly limited, but for example, it can be about 0.03 to 5 μm, preferably about 0.05 to 2 μm. The average particle size of the pigment is the median diameter measured by a laser diffraction / scattering particle size distribution analyzer.

[0064] The amount of coloring agent in the base layer 1 is not particularly limited as long as the exterior material for the energy storage device is colored, and for example, it can be about 5 to 60% by mass, preferably about 10 to 40% by mass.

[0065] [Adhesive layer 2] In the exterior material for energy storage devices of this disclosure, the adhesive layer 2 is a layer provided between the substrate layer 1 and the barrier layer 3 as needed, for the purpose of improving the adhesion between them.

[0066] The adhesive layer 2 is formed by an adhesive capable of bonding the substrate layer 1 and the barrier layer 3. The adhesive used to form the adhesive layer 2 is not limited, but may be a chemical reaction type, solvent evaporation type, heat melt type, hot pressure type, etc. It may also be a two-component curing adhesive (two-part adhesive), a one-component curing adhesive (one-part adhesive), or a resin that does not undergo a curing reaction. Furthermore, the adhesive layer 2 may be a single layer or a multi-layer layer.

[0067] Specifically, adhesive components included in adhesives include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, copolymerized polyester; polyethers; polyurethanes; epoxy resins; phenolic resins; polyamides such as nylon 6, nylon 66, nylon 12, copolymerized polyamides; polyolefin resins such as polyolefins, cyclic polyolefins, acid-modified polyolefins, and acid-modified cyclic polyolefins; polyvinyl acetate; cellulose; (meth)acrylic resins; polyimides; polycarbonates; amino resins such as urea resins and melamine resins; rubbers such as chloroprene rubber, nitrile rubber, and styrene-butadiene rubber; and silicone resins. These adhesive components may be used individually or in combination of two or more. Among these adhesive components, polyurethane adhesives are particularly preferred. Furthermore, the adhesive strength of these adhesive resins can be increased by using an appropriate curing agent. The curing agent is selected appropriately from polyisocyanates, polyfunctional epoxy resins, oxazoline group-containing polymers, polyamine resins, acid anhydrides, etc., depending on the functional groups of the adhesive components.

[0068] Examples of polyurethane adhesives include polyurethane adhesives comprising a first agent containing a polyol compound and a second agent containing an isocyanate compound. Preferably, a two-component curing type polyurethane adhesive is used, in which a polyol such as polyester polyol, polyether polyol, and acrylic polyol is used as the first agent and an aromatic or aliphatic polyisocyanate is used as the second agent. Another example of a polyurethane adhesive is a polyurethane adhesive comprising a polyurethane compound obtained by pre-reacting a polyol compound with an isocyanate compound and an isocyanate compound. Another example of a polyurethane adhesive is a polyurethane adhesive comprising a polyurethane compound obtained by pre-reacting a polyol compound with an isocyanate compound and an isocyanate compound and an isocyanate compound. Another example of a polyurethane adhesive is a polyurethane adhesive obtained by curing a polyurethane compound obtained by pre-reacting a polyol compound with an isocyanate compound by reacting it with moisture such as air. As the polyol compound, it is preferable to use a polyester polyol having hydroxyl groups on the side chains in addition to the hydroxyl groups at the ends of the repeating units. Examples of the second agent are aliphatic, alicyclic, aromatic, and aromaticaliphatic isocyanate compounds. Examples of isocyanate compounds include hexamethylene diisocyanate (HDI), xylylene diisocyanate (XDI), isophorone diisocyanate (IPDI), hydrogenated XDI (H6XDI), hydrogenated MDI (H12MDI), tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and naphthalene diisocyanate (NDI). Also, polyfunctional isocyanate modified compounds derived from one or more of these diisocyanates are used. Furthermore, polymers (e.g., trimers) can be used as polyisocyanate compounds. Examples of such polymers include adducts, biuretes, and nurates. The adhesive layer 2 is formed from a polyurethane adhesive, which provides excellent electrolyte resistance to the exterior material for energy storage devices, preventing peeling of the substrate layer 1 even if electrolyte adheres to the sides.

[0069] Furthermore, the adhesive layer 2 may contain other components as long as they do not impair adhesion, and may include colorants, thermoplastic elastomers, tackifiers, fillers, etc. The inclusion of a colorant in the adhesive layer 2 allows for the coloring of the exterior material for energy storage devices. Known colorants such as pigments and dyes can be used. Additionally, only one type of colorant may be used, or two or more types may be mixed.

[0070] The type of pigment is not particularly limited, as long as it does not impair the adhesion of adhesive layer 2. Examples of organic pigments include azo, phthalocyanine, quinacridone, anthraquinone, dioxazine, indigothioindigo, perinone-perylene, isoindorenine, and benzimidazolon pigments. Examples of inorganic pigments include carbon black, titanium dioxide, cadmium, lead, chromium oxide, and iron pigments. Other examples include fine mica powder and fish scale foil.

[0071] Among colorants, carbon black is preferred for, for example, to give the exterior material of an energy storage device a black appearance. Furthermore, from the viewpoint of dissipating heat generated from the energy storage device, mica is preferred.

[0072] The average particle size of the pigment is not particularly limited, but for example, it can be about 0.03 to 5 μm, preferably about 0.05 to 2 μm. The average particle size of the pigment is the median diameter measured by a laser diffraction / scattering particle size distribution analyzer.

[0073] The content of the coloring agent in the adhesive layer 2 is not particularly limited as long as the exterior material for the energy storage device is colored, and for example, it is about 5 to 60% by mass, preferably 10 to 40% by mass.

[0074] The thickness of the adhesive layer 2 is not particularly limited as long as it can bond the substrate layer 1 and the barrier layer 3, but for example, it is about 1 μm or more and about 2 μm or more. Also, the thickness of the adhesive layer 2 is, for example, about 10 μm or less and about 5 μm or less. Furthermore, preferred ranges for the thickness of the adhesive layer 2 include about 1 to 10 μm, about 1 to 5 μm, about 2 to 10 μm, and about 2 to 5 μm.

[0075] [Colored layer] The colored layer is a layer provided between the base layer 1 and the barrier layer 3 as needed (not shown in the figure). If an adhesive layer 2 is present, the colored layer may be provided between the base layer 1 and the adhesive layer 2, and between the adhesive layer 2 and the barrier layer 3. Alternatively, the colored layer may be provided on the outside of the base layer 1. By providing a colored layer, the exterior material for the energy storage device can be colored.

[0076] The colored layer can be formed, for example, by applying an ink containing a coloring agent to the surface of the substrate layer 1 or the surface of the barrier layer 3. Known coloring agents such as pigments and dyes can be used. In addition, only one type of coloring agent may be used, or two or more types may be mixed and used.

[0077] Specific examples of colorants included in the colored layer are the same as those exemplified in the [Adhesive Layer 2] section.

[0078] [Barrier layer 3] In the exterior material for energy storage devices, the barrier layer 3 is a layer that at least prevents the intrusion of moisture.

[0079] Examples of barrier layer 3 include metal foil, vapor-deposited film, and resin layer with barrier properties. Examples of vapor-deposited films include metal vapor-deposited films, inorganic oxide vapor-deposited films, and carbon-containing inorganic oxide vapor-deposited films. Examples of resin layers include fluorine-containing resins such as polymers mainly composed of polyvinylidene chloride, chlorotrifluoroethylene (CTFE), polymers mainly composed of tetrafluoroethylene (TFE), polymers having fluoroalkyl groups, and polymers mainly composed of fluoroalkyl units, as well as ethylene vinyl alcohol copolymers. In addition, a resin film having at least one of these vapor-deposited films and resin layers can also be provided as barrier layer 3. Multiple layers of barrier layer 3 may be provided. It is preferable that barrier layer 3 includes a layer composed of a metal material. Specific examples of metal materials constituting barrier layer 3 include aluminum alloy, stainless steel, titanium steel, and steel plates. When used as a metal foil, it is preferable that it includes at least one of aluminum alloy foil and stainless steel foil.

[0080] In barrier layer 3, the layer composed of the aforementioned metal material may include recycled metal material. Examples of recycled metal material include recycled aluminum alloy, stainless steel, titanium steel, or steel sheet. These recycled materials can each be obtained by known methods. Recycled aluminum alloy can be obtained, for example, by the manufacturing method described in International Publication No. 2022 / 092231. Barrier layer 3 may be composed solely of recycled material, or it may be composed of a mixture of recycled material and virgin material. Recycled metal material refers to metal material that has been recovered, isolated, and purified from various products used in the market or waste generated from manufacturing processes to make it reusable. Virgin metal material refers to new metal material refined from natural metal resources (raw materials) and is not recycled material.

[0081] From the viewpoint of improving the formability of the exterior material for energy storage devices, the aluminum alloy foil is more preferably a soft aluminum alloy foil composed of, for example, an annealed aluminum alloy, and from the viewpoint of further improving formability, it is more preferably an aluminum alloy foil containing iron. In an iron-containing aluminum alloy foil (100% by mass), the iron content is preferably 0.1 to 9.0% by mass, and more preferably 0.5 to 2.0% by mass. By having an iron content of 0.1% by mass or more, an exterior material for energy storage devices with better formability can be obtained. By having an iron content of 9.0% by mass or less, an exterior material for energy storage devices with better flexibility can be obtained. Examples of soft aluminum alloy foils include aluminum alloy foils having compositions specified in JIS H4160:1994 A8021H-O, JIS H4160:1994 A8079H-O, JIS H4000:2014 A8021P-O, or JIS H4000:2014 A8079P-O. Silicon, magnesium, copper, manganese, etc., may also be added as needed. Softening can be achieved through annealing or other treatments.

[0082] Furthermore, examples of stainless steel foils include austenitic, ferritic, austenitic-ferritic, martensitic, and precipitation-hardening stainless steel foils. Moreover, from the viewpoint of providing an exterior material for energy storage devices with excellent formability, it is preferable that the stainless steel foil be made of austenitic stainless steel.

[0083] Specific examples of austenitic stainless steels that make up stainless steel foil include SUS304, SUS301, and SUS316L, with SUS304 being particularly preferred among these.

[0084] In this disclosure, the thickness of the barrier layer 3 is not particularly limited, as long as the ratio (μm) of the thickness of the substrate layer 1 to the thickness (μm) of the barrier layer 3 satisfies the relationship of 40% or less.

[0085] In the case of metal foil, the thickness of the barrier layer 3 should at least function as a barrier layer that prevents moisture from penetrating, and can be, for example, about 9 to 200 μm. The thickness of the barrier layer 3 is preferably about 85 μm or less, more preferably about 50 μm or less, even more preferably about 40 μm or less, and particularly preferably about 35 μm or less. Alternatively, the thickness of the barrier layer 3 is preferably about 10 μm or more, even more preferably about 20 μm or more, more preferably about 25 μm or more, and particularly preferably about 58 μm or more. Furthermore, preferred thickness ranges for the barrier layer 3 include approximately 10-85 μm, 10-50 μm, 10-40 μm, 10-35 μm, 20-85 μm, 20-50 μm, 20-40 μm, 20-35 μm, 25-85 μm, 25-50 μm, 25-40 μm, 25-35 μm, and 58-85 μm. When the barrier layer 3 is made of aluminum alloy foil, the above ranges are particularly preferred. Furthermore, from the viewpoint of providing high moldability and high rigidity to the exterior material 10 for the energy storage device, the thickness of the barrier layer 3 is preferably about 35 μm or more, more preferably about 45 μm or more, even more preferably about 50 μm or more, even more preferably about 55 μm or more, and also preferably about 200 μm or less, more preferably about 85 μm or less, even more preferably about 75 μm or less, even more preferably about 70 μm or less, and The suitable ranges are approximately 35-200 μm, 35-85 μm, 35-75 μm, 35-70 μm, 45-200 μm, 45-85 μm, 45-75 μm, 45-70 μm, 50-200 μm, 50-85 μm, 50-75 μm, 50-70 μm, 55-200 μm, 55-85 μm, 55-75 μm, and 55-70 μm. The high moldability of the exterior material 10 for energy storage devices facilitates deep drawing, which can contribute to increasing the capacity of energy storage devices. Furthermore, while increasing the capacity of an energy storage device increases its weight, the increased rigidity of the exterior material 10 for energy storage devices contributes to the high sealing performance of the energy storage device.Furthermore, in particular when the barrier layer 3 is composed of stainless steel foil, the thickness of the stainless steel foil is preferably about 60 μm or less, more preferably about 50 μm or less, even more preferably about 40 μm or less, even more preferably about 30 μm or less, and especially preferably about 25 μm or less. Also, the thickness of the stainless steel foil is preferably about 10 μm or more, more preferably about 15 μm or more. Furthermore, preferred ranges for the thickness of the stainless steel foil include 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, and about 15 to 25 μm.

[0086] Furthermore, if the barrier layer 3 is a metal foil, it is preferable to provide a corrosion-resistant coating on at least the side opposite to the substrate layer to prevent dissolution and corrosion. The barrier layer 3 may also have a corrosion-resistant coating on both sides. Here, a corrosion-resistant coating refers to a thin film that provides corrosion resistance (e.g., acid resistance, alkali resistance, etc.) to the barrier layer by performing treatments such as hot water modification treatment such as boehmite treatment, chemical conversion treatment, anodizing treatment, plating treatment with nickel or chromium, or corrosion prevention treatment by applying a coating agent to the surface of the barrier layer. Specifically, a corrosion-resistant coating means a coating that improves the acid resistance of the barrier layer (acid-resistant coating), a coating that improves the alkali resistance of the barrier layer (alkali-resistant coating), etc. One type of treatment may be performed to form the corrosion-resistant coating, or two or more types may be combined. In addition, it is possible to have multiple layers instead of just one. Furthermore, among these treatments, hot water modification treatment and anodizing treatment are treatments that dissolve the surface of the metal foil with a treatment agent and form a metal compound with excellent corrosion resistance. These processes may also be included in the definition of chemical conversion treatment. Furthermore, if barrier layer 3 has a corrosion-resistant coating, the barrier layer 3 includes the corrosion-resistant coating.

[0087] The corrosion-resistant coating prevents delamination between the barrier layer (e.g., aluminum alloy foil) and the base layer during the molding of exterior materials for energy storage devices. It also prevents dissolution and corrosion of the barrier layer surface due to hydrogen fluoride generated by the reaction of electrolyte and water, particularly the dissolution and corrosion of aluminum oxide present on the barrier layer surface when the barrier layer is aluminum alloy foil. Furthermore, it improves the adhesion (wettability) of the barrier layer surface, preventing delamination between the base layer and the barrier layer during heat sealing and molding.

[0088] Various corrosion-resistant coatings are known to be formed by chemical conversion treatments, mainly including corrosion-resistant coatings containing at least one of the following: phosphates, chromates, fluorides, triazinethiol compounds, and rare earth oxides. Examples of chemical conversion treatments using phosphates and chromates include chromate treatment, phosphate chromate treatment, phosphate-chromate treatment, and chromate treatment. Examples of chromium compounds used in these treatments include chromium nitrate, chromium fluoride, chromium sulfate, chromium acetate, chromium oxalate, chromium biphosphate, acetyl acetate chromate, chromium chloride, and potassium chromium sulfate. Examples of phosphorus compounds used in these treatments include sodium phosphate, potassium phosphate, ammonium phosphate, and polyphosphate. Examples of chromate treatments include etching chromate treatment, electrolytic chromate treatment, and coating-type chromate treatment, with coating-type chromate treatment being preferred. This coating-type chromate treatment involves first degreasing at least the inner surface of a barrier layer (e.g., aluminum alloy foil) using a well-known treatment method such as alkaline immersion, electrolytic cleaning, acid cleaning, electrolytic acid cleaning, or acid activation. Then, a treatment solution mainly composed of metal phosphate salts such as chromium phosphate, titanium phosphate, zirconium phosphate, and zinc phosphate, or mixtures thereof, or a treatment solution mainly composed of nonmetallic phosphates and mixtures thereof, or a treatment solution consisting of a mixture of these with synthetic resins, etc., is applied to the degreased surface using a well-known coating method such as roll coating, gravure printing, or immersion, and then dried. Various solvents can be used as the treatment solution, such as water, alcohol-based solvents, hydrocarbon-based solvents, ketone-based solvents, ester-based solvents, and ether-based solvents, with water being preferred. Furthermore, examples of resin components used in this process include polymers such as phenolic resins and acrylic resins, and examples of chromate treatment using an amination phenol polymer having repeating units represented by the following general formulas (1) to (4). In this amination phenol polymer, the repeating units represented by the following general formulas (1) to (4) may be included individually or in any combination of two or more types.The acrylic resin is preferably polyacrylic acid, acrylate methacrylate copolymer, acrylate maleic acid copolymer, acrylate styrene copolymer, or derivatives thereof such as sodium salts, ammonium salts, or amine salts. Derivatives of polyacrylic acid, such as ammonium salts, sodium salts, or amine salts of polyacrylic acid, are particularly preferred. In this disclosure, polyacrylic acid means a polymer of acrylic acid. Furthermore, the acrylic resin is also preferably a copolymer of acrylic acid and a dicarboxylic acid or dicarboxylic acid anhydride, and also preferably an ammonium salt, sodium salt, or amine salt of a copolymer of acrylic acid and a dicarboxylic acid or dicarboxylic acid anhydride. Only one type of acrylic resin may be used, or two or more types may be mixed and used.

[0089] [ka]

[0090] [ka]

[0091] [ka]

[0092] [ka]

[0093] In general formulas (1) to (4), X represents a hydrogen atom, a hydroxyl group, an alkyl group, a hydroxyalkyl group, an allyl group, or a benzyl group. Also, R 1 and R 2 Each of these represents a hydroxyl group, an alkyl group, or a hydroxyalkyl group, either identical or different. In general formulas (1) to (4), X and R 1 and R 2Examples of alkyl groups represented by include linear or branched alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl groups. Also, X, R 1 and R 2 Examples of hydroxyalkyl groups represented by include linear or branched alkyl groups having 1 to 4 carbon atoms with one hydroxyl group 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 general formulas (1) to (4), X and R 1 and R 2 The alkyl group and hydroxyalkyl group shown may be the same or different. In general formulas (1) to (4), X is preferably a hydrogen atom, a hydroxyl group, or a hydroxyalkyl group. The number-average molecular weight of the amination phenol polymer having repeating units represented by general formulas (1) to (4) is preferably about 500 to 1,000,000, and more preferably about 1,000 to 20,000. The amination phenol polymer is produced, for example, by polycondensing a phenol compound or naphthol compound with formaldehyde to produce a polymer consisting of repeating units represented by the above general formula (1) or general formula (3), and then adding formaldehyde and amine (R 1 R 2 Using NH) to form the functional group (-CH2NR 1 R 2 It is produced by introducing ) into the polymer obtained above. The amination phenol polymer can be used alone or in a mixture of two or more types.

[0094] Another example of a corrosion-resistant coating is a thin film formed by a coating-type corrosion prevention treatment, which involves applying a coating agent containing at least one selected from the group consisting of rare earth element oxide sols, anionic polymers, and cationic polymers. The coating agent may further contain phosphoric acid or phosphate, and a crosslinking agent for crosslinking the polymer. In the rare earth element oxide sol, fine particles of rare earth element oxides (for example, particles with an average particle size of 100 nm or less) are dispersed in a liquid dispersion medium. Examples of rare earth element oxides include cerium oxide, yttrium oxide, neodymium oxide, and lanthanum oxide, with cerium oxide being preferred from the viewpoint of further improving adhesion. The rare earth element oxides contained in the corrosion-resistant coating can be used individually or in combination of two or more. Various solvents can be used as the liquid dispersion medium for the rare earth element oxide sol, such as water, alcohol-based solvents, hydrocarbon-based solvents, ketone-based solvents, ester-based solvents, and ether-based solvents, with water being preferred. Preferred cationic polymers include, for example, polyethyleneimine, ionic polymer complexes comprising polyethyleneimine and a polymer having a carboxylic acid, primary amine-grafted acrylic resins obtained by graft polymerization of a primary amine onto an acrylic main skeleton, polyallylamine or its derivatives, and amination phenols. Preferred anionic polymers are poly(meth)acrylic acid or its salts, or copolymers mainly composed of (meth)acrylic acid or its salts. Furthermore, the crosslinking agent is preferably at least one selected from the group consisting of a compound having one of the functional groups of isocyanate, glycidyl, carboxyl, or oxazoline, and a silane coupling agent. Additionally, the phosphoric acid or phosphate is preferably condensed phosphoric acid or condensed phosphate.

[0095] An example of a corrosion-resistant coating is one formed by dispersing metal oxides such as aluminum oxide, titanium oxide, cerium oxide, and tin oxide, or fine particles of barium sulfate, in phosphoric acid, applying this mixture to the surface of a barrier layer, and then baking it at a temperature of 150°C or higher.

[0096] The corrosion-resistant coating may, if necessary, be a laminated structure in which at least one of a cationic polymer and an anionic polymer is further laminated. Examples of cationic and anionic polymers include those mentioned above.

[0097] Furthermore, the composition of the corrosion-resistant coating can be analyzed, for example, using time-of-flight secondary ion mass spectrometry.

[0098] The amount of corrosion-resistant film to be formed on the surface of the barrier layer 3 in the chemical conversion treatment is not particularly limited, but for example, in the case of coating-type chromate treatment, the surface of the barrier layer 3 is 1 m 2 It is desirable that the product contains, for example, about 0.5 to 50 mg of chromium-based chromium, preferably about 1.0 to 40 mg of phosphorus-based chromium

[0099] The thickness of the corrosion-resistant coating is not particularly limited, but from the viewpoint of the cohesive force of the coating and the adhesion force with the barrier layer and the heat-fusible resin layer, it is preferably about 1 nm to 20 μm, more preferably about 1 nm to 100 nm, and even more preferably about 1 nm 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 energy-dispersive X-ray spectroscopy or electron beam energy loss spectroscopy. By analyzing the composition of the corrosion-resistant coating using time-of-flight secondary ion mass spectrometry, for example, secondary ions consisting of Ce, P, and O (e.g., Ce2PO4) can be identified. + CePO4 - (at least one of the above), or, for example, a secondary ion consisting of Cr, P, and O (e.g., CrPO2) + , CrPO4 - Peaks originating from at least one of the following are detected.

[0100] The chemical conversion treatment is carried out by applying a solution containing compounds used to form a corrosion-resistant film to the surface of the barrier layer using methods such as bar coating, roll coating, gravure coating, or immersion, and then heating the barrier layer to a temperature of approximately 70-200°C. Alternatively, before applying the chemical conversion treatment to the barrier layer, it may be subjected to a degreasing treatment using methods such as alkaline immersion, electrolytic cleaning, acid cleaning, or electrolytic acid cleaning. This degreasing treatment makes it possible to perform the chemical conversion treatment on the surface of the barrier layer more efficiently. Furthermore, by using an acid degreasing agent, which is a fluorine-containing compound dissolved in an inorganic acid, it is possible to not only degrease the metal foil but also form a fluoride of the passive metal; in such cases, only the degreasing treatment may be performed.

[0101] [Thermal adhesive resin layer 4] In the exterior material for energy storage devices of this disclosure, the heat-sealable resin layer 4 is the innermost layer and is a layer (sealant layer) that performs the function of sealing the energy storage device elements by heat-sealing the heat-sealable resin layers together during the assembly of the energy storage device.

[0102] The resin constituting the heat-fusible resin layer 4 is not particularly limited as long as it is heat-fusible, but resins containing a polyolefin backbone, such as polyolefins and acid-modified polyolefins, are preferred. The presence of a polyolefin backbone in the resin constituting the heat-fusible resin layer 4 can be analyzed, for example, by infrared spectroscopy or gas chromatography-mass spectrometry. Furthermore, when the resin constituting the heat-fusible resin layer 4 is analyzed by infrared spectroscopy, it is preferable to detect a peak originating from maleic anhydride. For example, when maleic anhydride-modified polyolefin is measured by infrared spectroscopy, a peak originating from maleic anhydride is detected at wavenumber 1760 cm⁻¹. -1 Nearby wave frequency 1780cm -1 A peak derived from maleic anhydride is detected in the vicinity. If the heat-fusible resin layer 4 is composed of maleic anhydride-modified polyolefin, a peak derived from maleic anhydride will be detected when measured by infrared spectroscopy. However, if the degree of acid modification is low, the peak may become small and not be detected. In that case, analysis is possible by nuclear magnetic resonance spectroscopy.

[0103] The heat-fusible resin layer 4 preferably contains a resin containing a polyolefin skeleton as its main component, more preferably contains polyolefin as its main component, and even more preferably contains polypropylene as its main component. Here, "main component" means a resin component in which the content of the resin components contained in the heat-fusible resin layer 4 is, for example, 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, even more preferably 98% by mass or more, and even more preferably 99% by mass or more. For example, if the heat-fusible resin layer 4 contains polypropylene as its main component, it means that the content of polypropylene in the resin components contained in the heat-fusible resin layer 4 is, for example, 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, even more preferably 98% by mass or more, and even more preferably 99% by mass or more.

[0104] Examples of polyolefins include polyethylene such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, and linear low-density polyethylene; ethylene-α-olefin copolymers; polypropylene such as homopolypropylene, block copolymers of polypropylene (e.g., block copolymer of propylene and ethylene), and random copolymers of polypropylene (e.g., random copolymer of propylene and ethylene); propylene-α-olefin copolymers; and ethylene-butene-propylene terpolymers. Among these, polypropylene is preferred. When polyolefin resins are copolymers, they may be block copolymers or random copolymers. These polyolefin resins may be used individually or in combination of two or more.

[0105] Furthermore, the polyolefin may be a cyclic polyolefin. A cyclic polyolefin is a copolymer of an olefin and a cyclic monomer. Examples of olefins that are constituent monomers of the cyclic polyolefin include ethylene, propylene, 4-methyl-1-pentene, styrene, butadiene, isoprene, and the like. Examples of cyclic monomers that are constituent monomers of the cyclic polyolefin include cyclic alkenes such as norbornene; and cyclic dienes such as cyclopentadiene, dicyclopentadiene, cyclohexadiene, norbornadiene, and the like. Among these, cyclic alkenes are preferred, and norbornene is more preferred.

[0106] Furthermore, the polyolefin may be an acid-modified polyolefin. An acid-modified polyolefin is a polymer modified by block polymerization or graft polymerization of a polyolefin with an acid component. As the polyolefin to be acid-modified, the above-mentioned polyolefin, copolymers obtained by copolymerizing the above-mentioned polyolefin with polar molecules such as acrylic acid or methacrylic acid, or polymers such as cross-linked polyolefins can also be used. Examples of acid components used for acid modification include carboxylic acids or their anhydrides such as maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, and itaconic anhydride.

[0107] Acid-modified polyolefins may also be acid-modified cyclic polyolefins. Acid-modified cyclic polyolefins are polymers obtained by copolymerizing a portion of the monomers constituting a cyclic polyolefin with an acid component, or by block polymerization or graft polymerization of an acid component to a cyclic polyolefin. The cyclic polyolefin to be acid-modified is the same as described above. Furthermore, the acid component used for acid modification is the same as the acid component used for modifying the polyolefin described above.

[0108] Preferred acid-modified polyolefins include polyolefins modified with carboxylic acids or their anhydrides, polypropylenes modified with carboxylic acids or their anhydrides, maleic anhydride-modified polyolefins, and maleic anhydride-modified polypropylenes.

[0109] The heat-sealable resin layer 4 may be formed by a single resin or by a blended polymer of two or more resins. Furthermore, the heat-sealable resin layer 4 may be formed as a single layer or as two or more layers made of the same or different resins.

[0110] When manufacturing the exterior material 10 for the energy storage device of this disclosure by laminating the heat-fusible resin layer 4 with a barrier layer 3, an adhesive layer 5, etc., a pre-formed resin film may be used as the heat-fusible resin layer 4. Alternatively, the heat-fusible resin that forms the heat-fusible resin layer 4 may be formed into a film on the surface of the barrier layer 3, adhesive layer 5, etc. by extrusion molding or coating, and the heat-fusible resin layer 4 may be formed from a resin film.

[0111] Furthermore, the heat-fusible resin layer 4 may contain a lubricant or the like as needed. When the heat-fusible resin layer 4 contains a lubricant, the moldability of the exterior material for the energy storage device can be improved. The lubricant is not particularly limited, and known lubricants can be used.

[0112] The lubricant is not particularly limited, but amide-based lubricants are preferred. Specific examples of lubricants include those exemplified in base layer 1. The lubricant may be used alone or in combination of two or more types, with a combination of two or more being preferable.

[0113] In this disclosure, from the viewpoint of improving the moldability of the exterior material for energy storage devices, it is preferable that a lubricant be present on at least one of the surface and interior of the heat-fusible resin layer 4. The lubricant is not particularly limited, but amide lubricants are preferred. Specific examples of amide lubricants include saturated fatty acid amides, unsaturated fatty acid amides, substituted amides, methylolamides, saturated fatty acid bisamides, unsaturated fatty acid bisamides, fatty acid ester amides, and aromatic bisamides. Specific examples of saturated fatty acid amides include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, and hydroxystearic acid amide. Specific examples of unsaturated fatty acid amides include oleic acid amide and erucic acid amide. Specific examples of substituted amides include N-oleyl palmitic acid amide, N-stearyl stearate amide, N-stearyl oleic acid amide, N-oleyl stearate amide, and N-stearyl erucic acid amide. Specific examples of methylolamides include methylol stearate amide. Specific examples of saturated fatty acid bisamides include methylenebisstearate, ethylenebiscaprate, ethylenebislaurate, ethylenebisstearate, ethylenebishydroxystearate, ethylenebisbehenamide, hexamethylenebisstearate, hexamethylenebisbehenamide, hexamethylenehydroxystearate, N,N'-distearyladipamide, and N,N'-distearylsebacinamide. Specific examples of unsaturated fatty acid bisamides include ethylenebisoleamide, ethylenebiserucamide, hexamethylenebisoleamide, N,N'-dioleyladipamide, and N,N'-dioleylsebacinamide. Specific examples of fatty acid ester amides include stearamidoethylstearate. Specific examples of aromatic bisamides include m-xylylenebisstearamide, m-xylylenebishydroxystearamide, and N,N'-distearyl isophthalamide.The lubricant may be used alone or in combination of two or more types, and it is preferable to use a combination of two or more types.

[0114] When a lubricant is present on the surface of the heat-fusible resin layer 4, there are no particular restrictions on its amount, but from the viewpoint of improving the moldability of the exterior material for energy storage devices, it is preferably about 1 mg / m². 2 More preferably, approximately 3 mg / m² 2 More preferably, about 5 mg / m² 2 More preferably, about 10 mg / m² 2 More preferably, about 15 mg / m² 2 The above is true, and preferably about 50 mg / m² 2 More preferably, about 40 mg / m² 2 The following are preferred ranges, with a preferred range being 1 to 50 mg / m². 2 degree, 1~40mg / m 2 degree, 3~50mg / m 2 degree, 3~40mg / m 2 degree, 5~50mg / m 2 degree, 5~40mg / m 2 degree, 10~50mg / m 2 degree, 10~40mg / m 2 degree, 15~50mg / m 2 degree, 15~40mg / m 2 The degree can be described as follows.

[0115] When a lubricant is present inside the heat-fusible resin layer 4, there are no particular limitations on its amount, but from the viewpoint of improving the moldability of the exterior material for energy storage devices, it is preferably about 100 ppm or more, more preferably about 300 ppm or more, even more preferably about 500 ppm or more, and also preferably about 3000 ppm or less, more preferably about 2000 ppm or less. Preferred ranges include about 100 to 3000 ppm, about 100 to 2000 ppm, about 300 to 3000 ppm, about 300 to 2000 ppm, about 500 to 3000 ppm, and about 500 to 2000 ppm. When two or more types of lubricants are present inside the heat-fusible resin layer 4, the above amount of lubricant is the total amount of lubricant. Furthermore, when two or more types of lubricants are present inside the heat-fusible resin layer 4, the amount of the first type of lubricant is not particularly limited, but from the viewpoint of improving the moldability of the exterior material for energy storage devices, it is preferably about 100 ppm or more, more preferably about 300 ppm or more, even more preferably about 500 ppm or more, and also preferably about 3000 ppm or less, more preferably about 2000 ppm or less. Preferred ranges include about 100 to 3000 ppm, about 100 to 2000 ppm, about 300 to 3000 ppm, about 300 to 2000 ppm, about 500 to 3000 ppm, and about 500 to 2000 ppm. The amount of the second lubricant is not particularly limited, but from the viewpoint of improving the moldability of the exterior material for energy storage devices, it is preferably about 50 ppm or more, more preferably about 100 ppm or more, even more preferably about 200 ppm or more, and also preferably about 1500 ppm or less, more preferably about 1000 ppm or less. Preferred ranges include about 50 to 1500 ppm, about 50 to 1000 ppm, about 100 to 1500 ppm, about 100 to 1000 ppm, about 200 to 1500 ppm, and about 200 to 1000 ppm.

[0116] The lubricant present on the surface of the heat-fusible resin layer 4 may be a lubricant contained in the resin constituting the heat-fusible resin layer 4 that has seeped out, or a lubricant may be applied to the surface of the heat-fusible resin layer 4.

[0117] Furthermore, the thickness of the heat-fusible resin layer 4 is not particularly limited as long as the heat-fusible resin layers heat-fuse together to seal the energy storage device elements, but for example, it can be about 100 μm or less, preferably about 85 μm or less, and more preferably about 15 to 85 μm. For example, if the thickness of the adhesive layer 5 described later is 10 μm or more, the thickness of the heat-fusible resin layer 4 can be preferably about 85 μm or less, and more preferably about 15 to 45 μm. For example, if the thickness of the adhesive layer 5 described later is less than 10 μm or if the adhesive layer 5 is not provided, the thickness of the heat-fusible resin layer 4 can be preferably about 20 μm or more, and more preferably about 35 to 85 μm.

[0118] [Adhesive layer 5] In the exterior material for energy storage devices of this disclosure, the adhesive layer 5 is a layer provided as necessary between the barrier layer 3 (or corrosion-resistant coating) and the heat-fusible resin layer 4 in order to firmly bond them together.

[0119] The adhesive layer 5 is formed of a resin capable of bonding the barrier layer 3 and the heat-fusible resin layer 4. As the resin used to form the adhesive layer 5, for example, the same type of adhesive as exemplified in the adhesive layer 2 can be used.

[0120] Furthermore, from the viewpoint of firmly bonding the adhesive layer 5 and the heat-fusible resin layer 4, it is preferable that the resin used to form the adhesive layer 5 contains a polyolefin skeleton, and examples of such resins include the polyolefins, acid-modified polyolefins, cyclic polyolefins, and acid-modified cyclic polyolefins exemplified in the heat-fusible resin layer 4 mentioned above. On the other hand, from the viewpoint of firmly bonding the barrier layer 3 and the adhesive layer 5, it is preferable that the adhesive layer 5 contains an acid-modified polyolefin. Examples of acid-modified components include dicarboxylic acids such as maleic acid, itaconic acid, succinic acid, and adipic acid, as well as their anhydrides, acrylic acid, and methacrylic acid, but maleic anhydride is most preferred in terms of ease of modification and versatility. Furthermore, from the viewpoint of heat resistance of the exterior material for energy storage devices, it is preferable that the olefin component be a polypropylene-based resin, and it is most preferable that the adhesive layer 5 contains maleic anhydride-modified polypropylene.

[0121] When the resin used to form the adhesive layer 5 contains a polyolefin skeleton, the adhesive layer 5 preferably contains a resin containing a polyolefin skeleton as its main component, more preferably contains acid-modified polyolefin as its main component, and even more preferably contains acid-modified polypropylene as its main component. Here, "main component" means a resin component in which the content of the resin components contained in the adhesive layer 5 is, for example, 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, even more preferably 98% by mass or more, and even more preferably 99% by mass or more. For example, when the adhesive layer 5 contains acid-modified polypropylene as its main component, it means that the content of acid-modified polypropylene in the resin components contained in the adhesive layer 5 is, for example, 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, even more preferably 98% by mass or more, and even more preferably 99% by mass or more.

[0122] The presence of a polyolefin skeleton in the resin constituting the adhesive layer 5 can be analyzed by methods such as infrared spectroscopy and gas chromatography-mass spectrometry, and the analytical method is not particularly limited. Furthermore, the presence of an acid-modified polyolefin in the resin constituting the adhesive layer 5 can be determined, for example, by measuring maleic anhydride-modified polyolefin using infrared spectroscopy, at a wavenumber of 1760 cm⁻¹. -1 Nearby wave frequency 1780cm -1 A peak originating from maleic anhydride is detected in the vicinity. However, if the degree of acid denaturation is low, the peak may become small and not be detected. In that case, analysis is possible by nuclear magnetic resonance spectroscopy.

[0123] Furthermore, from the viewpoint of ensuring durability such as heat resistance and resistance to contents of the exterior material for energy storage devices, as well as ensuring moldability while keeping the thickness thin, it is more preferable that the adhesive layer 5 is a cured product of a resin composition containing an acid-modified polyolefin and a curing agent. The above-mentioned products are examples of the acid-modified polyolefin.

[0124] Furthermore, the adhesive layer 5 is preferably a cured product of a resin composition comprising an acid-modified polyolefin and at least one selected from the group consisting of compounds having isocyanate groups, compounds having oxazoline groups, and compounds having epoxy groups, and is particularly preferably a cured product of a resin composition comprising an acid-modified polyolefin and at least one selected from the group consisting of compounds having isocyanate groups and compounds having epoxy groups. Furthermore, the adhesive layer 5 preferably contains at least one selected from the group consisting of polyurethane, polyester, and epoxy resin, and more preferably contains polyurethane and epoxy resin. As polyester, for example, ester resins produced by the reaction of epoxy groups and maleic anhydride groups, and amide ester resins produced by the reaction of oxazoline groups and maleic anhydride groups are preferred. If unreacted curing agents such as compounds having isocyanate groups, compounds having oxazoline groups, and epoxy resins remain in the adhesive layer 5, the presence of unreacted substances can be confirmed by methods selected from, for example, infrared spectroscopy, Raman spectroscopy, and time-of-flight secondary ion mass spectrometry (TOF-SIMS).

[0125] Furthermore, from the viewpoint of further improving the adhesion between the barrier layer 3 and the adhesive layer 5, it is preferable that the adhesive layer 5 is a cured product of a resin composition containing a curing agent having at least one selected from the group consisting of oxygen atoms, heterocyclic rings, C=N bonds, and COC bonds. Examples of curing agents having heterocyclic rings include curing agents having oxazoline groups and curing agents having epoxy groups. Examples of curing agents having C=N bonds include curing agents having oxazoline groups and curing agents having isocyanate groups. Examples of curing agents having COC bonds include curing agents having oxazoline groups and curing agents having epoxy groups. The fact that the adhesive layer 5 is a cured product of a resin composition containing these curing agents 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).

[0126] While there are no particular limitations on the compound having an isocyanate group, polyfunctional isocyanate compounds are preferred 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 is a compound having two or more isocyanate groups. Specific examples of polyfunctional isocyanate curing agents include pentane diisocyanate (PDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymerized or nurated versions thereof, mixtures thereof, and copolymers with other polymers. Adducts, biuretes, and isocyanurates are also examples.

[0127] The content of the compound having an isocyanate group in the adhesive layer 5 is preferably in the range of 0.1 to 50% by mass, and more preferably in the range of 0.5 to 40% by mass, of the resin composition constituting the adhesive layer 5. This effectively enhances the adhesion between the barrier layer 3 and the adhesive layer 5.

[0128] Compounds containing an oxazoline group are not particularly limited as long as they have an oxazoline skeleton. Specific examples of compounds containing an oxazoline group include those with a polystyrene main chain and those with an acrylic main chain. Commercially available examples include the Epocross series manufactured by Nippon Shokubai Co., Ltd.

[0129] The proportion of the compound having an oxazoline group in the adhesive layer 5 is preferably in the range of 0.1 to 50% by mass, and more preferably in the range of 0.5 to 40% by mass, of the resin composition constituting the adhesive layer 5. This effectively enhances the adhesion between the barrier layer 3 and the adhesive layer 5.

[0130] Examples of compounds having epoxy groups include epoxy resins. The epoxy resin is not particularly limited as long as it is capable of forming a crosslinked structure by the epoxy groups present in the molecule; known epoxy resins can be used. The weight-average molecular weight of the epoxy resin is preferably around 50 to 2000, more preferably around 100 to 1000, and even more preferably around 200 to 800. In this disclosure, the weight-average molecular weight of the epoxy resin is the value measured by gel permeation chromatography (GPC) under conditions using polystyrene as a standard sample.

[0131] Specific examples of epoxy resins include glycidyl ether derivatives of trimethylolpropane, bisphenol A diglycidyl ether, modified bisphenol A diglycidyl ether, bisphenol F type glycidyl ether, novolac glycidyl ether, glycerin polyglycidyl ether, and polyglycerin polyglycidyl ether. Epoxy resins may be used individually or in combination of two or more types.

[0132] The proportion of epoxy resin in the adhesive layer 5 is preferably in the range of 0.1 to 50% by mass, and more preferably in the range of 0.5 to 40% by mass, of the resin composition constituting the adhesive layer 5. This effectively enhances the adhesion between the barrier layer 3 and the adhesive layer 5.

[0133] The polyurethane is not particularly limited, and any known polyurethane can be used. The adhesive layer 5 may be, for example, a cured product of a two-component polyurethane.

[0134] The proportion of polyurethane in the adhesive layer 5 is preferably in the range of 0.1 to 50% by mass, and more preferably in the range of 0.5 to 40% by mass, of the resin composition constituting the adhesive layer 5. This effectively enhances the adhesion between the barrier layer 3 and the adhesive layer 5 in an atmosphere where components that induce corrosion of the barrier layer, such as electrolytes, are present.

[0135] Furthermore, if the adhesive layer 5 is a cured product of a resin composition containing at least one compound selected from the group consisting of compounds having isocyanate groups, compounds having oxazoline groups, and epoxy resins, and the acid-modified polyolefin, the acid-modified polyolefin functions as the main agent, and the compounds having isocyanate groups, compounds having oxazoline groups, and compounds having epoxy groups each function as curing agents.

[0136] The adhesive layer 5 may contain a modifier having a carbodiimide group.

[0137] When manufacturing the exterior material 10 for the energy storage device of this disclosure by laminating the adhesive layer 5 with a barrier layer 3, a heat-fusible resin layer 4, etc., a pre-formed resin film may be used as the adhesive layer 5. Alternatively, the heat-fusible resin that forms the adhesive layer 5 may be formed into a film on the surface of the barrier layer 3, the heat-fusible resin layer 4, etc. by extrusion molding or coating, and the adhesive layer 5 may be formed from a resin film.

[0138] 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, or about 5 μm or less. Alternatively, the thickness of the adhesive layer 5 is preferably about 0.1 μm or more, or about 0.5 μm or more. The range of the thickness of the adhesive layer 5 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 adhesive exemplified in adhesive layer 2, or the cured product of acid-modified polyolefin and a curing agent, the thickness is preferably about 1 to 10 μm, more preferably about 1 to 5 μm. Furthermore, when using the resin exemplified in the heat-fusible resin layer 4, the thickness is preferably about 2 to 50 μm, more preferably about 10 to 40 μm. When the adhesive layer 5 is the adhesive exemplified in the adhesive layer 2, or a cured product of a resin composition containing an acid-modified polyolefin and a curing agent, the adhesive layer 5 can be formed, for example, by applying the resin composition and curing it by heating. Also, when using the resin exemplified in the heat-fusible resin layer 4, it can be formed, for example, by extrusion molding of the heat-fusible resin layer 4 and the adhesive layer 5.

[0139] [Surface coating layer 6] The exterior material for energy storage devices of this disclosure may optionally include a surface coating layer 6 on the base layer 1 (on the side opposite to the barrier layer 3 of the base layer 1) for the purpose of improving at least one of the following: design, electrolyte resistance, scratch resistance, and moldability. The surface coating layer 6 is the outermost layer of the exterior material for energy storage devices when the energy storage device is assembled using the exterior material for energy storage devices.

[0140] The surface coating layer 6 may be made of resins such as polyvinylidene chloride, polyester, polyamide, epoxy resin, acrylic resin, fluororesin, polyurethane, silicon resin, or phenolic resin, or modified versions of these resins. It may also be a copolymer of these resins, or a modified version of a copolymer. Furthermore, it may be a mixture of these resins. The resin is preferably a curable resin. That is, the surface coating layer 6 is preferably composed of a cured product of a resin composition containing a curable resin.

[0141] If the resin forming the surface coating layer 6 is a curable resin, it may be either a one-component curable resin or a two-component curable resin, but is preferably a two-component curable resin. Examples of two-component curable resins include two-component curable polyurethane, two-component curable polyester, and two-component curable epoxy resin. Among these, two-component curable polyurethane is preferred.

[0142] Examples of two-component curable polyurethanes include polyurethanes comprising a first agent containing a polyol compound and a second agent containing an isocyanate compound. Preferably, two-component curable polyurethanes include those comprising a polyol such as polyester polyol, polyether polyol, and acrylic polyol as the first agent and an aromatic or aliphatic polyisocyanate as the second agent. Examples of polyurethanes include polyurethanes comprising a polyurethane compound obtained by reacting a polyol compound and an isocyanate compound in advance, and an isocyanate compound. Examples of polyurethanes include polyurethanes comprising a polyurethane compound obtained by reacting a polyol compound and an isocyanate compound in advance, and a polyol compound. Examples of polyurethanes include polyurethanes cured by reacting a polyurethane compound obtained by reacting a polyol compound and an isocyanate compound in advance with moisture such as air. As the polyol compound, it is preferable to use a polyester polyol having hydroxyl groups on the side chains in addition to the hydroxyl groups at the ends of the repeating units. Examples of the second agent include aliphatic, alicyclic, aromatic, and aromaticaliphatic isocyanate compounds. Examples of isocyanate compounds include hexamethylene diisocyanate (HDI), xylylene diisocyanate (XDI), isophorone diisocyanate (IPDI), hydrogenated XDI (H6XDI), hydrogenated MDI (H12MDI), tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and naphthalene diisocyanate (NDI). Polyfunctional isocyanate modified compounds derived from one or more of these diisocyanates are also possible. Furthermore, polymers (e.g., trimers) can be used as polyisocyanate compounds. Examples of such polymers include adducts, biuretes, and nurates. Furthermore, aliphatic isocyanate compounds refer to isocyanates that have an aliphatic group and no aromatic ring, alicyclic isocyanate compounds refer to isocyanates that have an alicyclic hydrocarbon group, and aromatic isocyanate compounds refer to isocyanates that have an aromatic ring.The surface coating layer 6 is formed of polyurethane, which provides the exterior material for energy storage devices with excellent electrolyte resistance.

[0143] The surface coating layer 6 may contain additives such as lubricants, flame retardants, antiblocking agents, antioxidants, light stabilizers, tackifiers, antistatic agents, and pigments in at least one of its surface and interior, depending on the functionality to be provided to the surface coating layer 6 and its surface. Examples of additives include fine particles with an average particle size of about 0.5 nm to 5 μm. The average particle size of the additive is the median diameter measured by a laser diffraction / scattering particle size distribution analyzer.

[0144] The additive may be either inorganic or organic. Furthermore, there are no particular restrictions on the shape of the additive; examples include spherical, fibrous, plate-like, amorphous, or flaky forms.

[0145] Specific examples of 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, alumina, carbon black, carbon nanotubes, high-melting-point nylon, acrylate resin, cross-linked acrylic, cross-linked styrene, cross-linked polyethylene, benzoguanamine, gold, aluminum, copper, and nickel. Additives may be used individually or in combination of two or more. Among these additives, silica, barium sulfate, and titanium oxide are preferred from the viewpoint of dispersion stability and cost. Mica is also preferred from the viewpoint of heat dissipation from the energy storage device. In addition, various surface treatments such as insulation treatment and high-dispersibility treatment may be applied to the surface of the additives.

[0146] The method for forming the surface coating layer 6 is not particularly limited, and for example, a method of applying a resin to form the surface coating layer 6 can be used. If an additive is to be incorporated into the surface coating layer 6, the resin mixed with the additive can be applied.

[0147] In this disclosure, from the viewpoint of improving the moldability of the exterior material for energy storage devices, it is preferable that a lubricant be present on at least one of the surface and interior of the surface coating layer 6. The lubricant is not particularly limited, but amide lubricants are preferred. Specific examples of amide lubricants include saturated fatty acid amides, unsaturated fatty acid amides, substituted amides, methylolamides, saturated fatty acid bisamides, unsaturated fatty acid bisamides, fatty acid ester amides, and aromatic bisamides. Specific examples of saturated fatty acid amides include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, and hydroxystearic acid amide. Specific examples of unsaturated fatty acid amides include oleic acid amide and erucic acid amide. Specific examples of substituted amides include N-oleyl palmitic acid amide, N-stearyl stearate amide, N-stearyl oleic acid amide, N-oleyl stearate amide, and N-stearyl erucic acid amide. Specific examples of methylolamides include methylol stearate amide. Specific examples of saturated fatty acid bisamides include methylenebisstearate, ethylenebiscaprate, ethylenebislaurate, ethylenebisstearate, ethylenebishydroxystearate, ethylenebisbehenamide, hexamethylenebisstearate, hexamethylenebisbehenamide, hexamethylenehydroxystearate, N,N'-distearyladipamide, and N,N'-distearylsebacinamide. Specific examples of unsaturated fatty acid bisamides include ethylenebisoleamide, ethylenebiserucamide, hexamethylenebisoleamide, N,N'-dioleyladipamide, and N,N'-dioleylsebacinamide. Specific examples of fatty acid ester amides include stearamidoethylstearate. Specific examples of aromatic bisamides include m-xylylenebisstearamide, m-xylylenebishydroxystearamide, and N,N'-distearyl isophthalamide.The lubricant may be used alone or in combination of two or more types, and it is preferable to use a combination of two or more types.

[0148] If a lubricant is present on the surface of the surface coating layer 6, there are no particular restrictions on its amount, but for example, it may be about 3 mg / m². 2 Preferably about 4 mg / m² 2 More than about 5mg / m 2 The above points are given. In addition, the amount of lubricant present on the surface of the surface coating layer 6 is, for example, about 15 mg / m². 2 Preferably about 14 mg / m² 2 Below, about 10mg / m 2 The following are examples. Furthermore, a preferred range for the amount of lubricant present on the surface of the surface coating layer 6 is 3 to 15 mg / m². 2 degree, 3~14mg / m 2 degree, 3~10mg / m 2 degree, 4~15mg / m 2 degree, 4~14mg / m 2 degree, 4~10mg / m 2 degree, 5~15mg / m 2 degree, 5~14mg / m 2 degree, 5~10mg / m 2 The degree can be described as follows.

[0149] The lubricant present on the surface of the surface coating layer 6 may be a lubricant contained in the resin constituting the surface coating layer 6 that has seeped out, or a lubricant may be applied to the surface of the surface coating layer 6.

[0150] The surface coating layer 6 contains a coloring agent, which allows the exterior material for the energy storage device to be colored. Known coloring agents such as pigments and dyes can be used. In addition, only one type of coloring agent may be used, or two or more types may be mixed and used.

[0151] The types of pigments are not particularly limited. Examples of organic pigments include azo, phthalocyanine, quinacridone, anthraquinone, dioxazine, indigothioindigo, perinone-perylene, isoindorenine, and benzimidazolon pigments. Examples of inorganic pigments include carbon black, titanium dioxide, cadmium, lead, chromium oxide, and iron pigments. Other examples include fine mica powder and fish scale foil.

[0152] Among colorants, carbon black is preferred for, for example, to give the exterior material of an energy storage device a black appearance. Furthermore, from the viewpoint of dissipating heat generated from the energy storage device, mica is preferred.

[0153] The average particle size of the pigment is not particularly limited, but for example, it can be about 0.03 to 5 μm, preferably about 0.05 to 2 μm. The average particle size of the pigment is the median diameter measured by a laser diffraction / scattering particle size distribution analyzer.

[0154] The content of the coloring agent in the surface coating layer 6 is not particularly limited as long as the exterior material for the energy storage device is colored, and for example, it can be about 5 to 60% by mass, preferably about 10 to 40% by mass.

[0155] The thickness of the surface coating layer 6 is not particularly limited as long as it performs the above-mentioned functions as a surface coating layer 6, and for example, it can be about 0.5 to 10 μm, preferably about 1 to 5 μm. In this disclosure, the thickness of the substrate layer 1 does not include the thickness of the surface coating layer 6.

[0156] [Manufacturing method for exterior materials for energy storage devices] The method for manufacturing an exterior material for energy storage devices is not particularly limited, as long as a laminate is obtained by stacking the layers of the exterior material for energy storage devices of this disclosure. One example is a method that includes the step of stacking the layers in the following order from the outside: at least the base layer 1, the barrier layer 3, and the heat-fusible resin layer 4.

[0157] An example of a method for manufacturing the exterior material for energy storage devices of this disclosure is as follows. First, a laminate (hereinafter sometimes referred to as "laminated laminate A") is formed by sequentially laminating a base layer 1, an adhesive layer 2, and a barrier layer 3. Specifically, laminate A can be formed by a dry lamination method in which the adhesive used to form the adhesive layer 2 is applied to the base layer 1 or, if necessary, to the barrier layer 3 whose surface has been chemically treated, using a coating method such as gravure coating or roll coating, and after drying, the barrier layer 3 or base layer 1 is laminated and the adhesive layer 2 is cured.

[0158] Next, a heat-fusible resin layer 4 is laminated onto the barrier layer 3 of laminate A. When the heat-fusible resin layer 4 is directly laminated onto the barrier layer 3, the heat-fusible resin layer 4 can be laminated onto the barrier layer 3 of laminate A by methods such as thermal lamination or extrusion lamination. Also, when an adhesive layer 5 is provided between the barrier layer 3 and the heat-fusible resin layer 4, the adhesive layer 5 and the heat-fusible resin layer 4 can be laminated by methods such as (1) extrusion lamination, (2) thermal lamination, (3) sandwich lamination, or (4) dry lamination. (1) An example of the extrusion lamination method is a method in which the adhesive layer 5 and the heat-fusible resin layer 4 are laminated by extruding them onto the barrier layer 3 of laminate A (co-extrusion lamination method, tandem lamination method). Furthermore, (2) as a thermal lamination method, for example, a laminate is formed by separately laminating an adhesive layer 5 and a heat-fusible resin layer 4, and this is laminated onto the barrier layer 3 of laminate A, or a laminate is formed by laminating an adhesive layer 5 on the barrier layer 3 of laminate A, and this is laminated with the heat-fusible resin layer 4. Furthermore, (3) as a sandwich lamination method, for example, a molten adhesive layer 5 is poured between the barrier layer 3 of laminate A and a heat-fusible resin layer 4 that has been previously made into a sheet, thereby bonding laminate A and heat-fusible resin layer 4 via the adhesive layer 5. Furthermore, (4) as a dry lamination method, for example, an adhesive for forming the adhesive layer 5 is solution-coated onto the barrier layer 3 of laminate A and dried, or further laminated by baking, and a heat-fusible resin layer 4 that has been previously made into a sheet is laminated onto this adhesive layer 5.

[0159] When a surface coating layer 6 is provided, the surface coating layer 6 is laminated on the surface of the base layer 1 opposite to the barrier layer 3. The surface coating layer 6 can be formed, for example, by applying the resin used to form the surface coating layer 6 to the surface of the base layer 1. The order of the steps of laminating the barrier layer 3 to the surface of the base layer 1 and laminating the surface coating layer 6 to the surface of the base layer 1 is not particularly limited. For example, the surface coating layer 6 may be formed on the surface of the base layer 1, and then the barrier layer 3 may be formed on the surface of the base layer 1 opposite to the surface coating layer 6.

[0160] As described above, a laminate is formed comprising, as necessary, a surface coating layer 6, a base material layer 1, an adhesive layer 2 as necessary, a barrier layer 3, an adhesive layer 5 as necessary, and a heat-fusible resin layer 4 in this order. In order to strengthen the adhesion of the adhesive layer 2 and adhesive layer 5 as necessary, the laminate may be subjected to further heat treatment.

[0161] In exterior materials for energy storage devices, the processability of each layer constituting the laminate may be improved by subjecting it to surface activation treatments such as corona treatment, blast treatment, oxidation treatment, or ozone treatment, as needed. For example, by applying corona treatment to the surface of the substrate layer 1 opposite to the barrier layer 3, the printability of ink on the surface of the substrate layer 1 can be improved.

[0162] [Applications of exterior materials for energy storage devices] The exterior material for energy storage devices of this disclosure is used in packaging for sealing and housing energy storage device elements such as a positive electrode, a negative electrode, and an electrolyte. In other words, an energy storage device can be formed by housing an energy storage device element comprising at least a positive electrode, a negative electrode, and an electrolyte in packaging formed from the exterior material for energy storage devices of this disclosure. In other words, an energy storage device can be formed by wrapping an energy storage device element with the exterior material for energy storage devices of this disclosure.

[0163] Specifically, an energy storage device is provided by covering an energy storage device element, which comprises at least a positive electrode, a negative electrode, and an electrolyte, with the energy storage device exterior material of this disclosure, such that a flange portion (an area where heat-sealable resin layers come into contact) is formed around the periphery of the energy storage device element, with the metal terminals connected to the positive electrode and negative electrode respectively protruding outward, and then heat-sealing the heat-sealable resin layers of the flange portion to seal it. When housing the energy storage device element in a package formed from the energy storage device exterior material of this disclosure, the package is formed such that the heat-sealable resin portion of the energy storage device exterior material of this disclosure faces inward (the surface in contact with the energy storage device element). The packaging can be formed by overlapping the heat-sealable resin layers of two energy storage device casing materials facing each other and heat-sealing the periphery of the overlapped casing materials. Alternatively, as shown in the example in Figure 5, one energy storage device casing material can be folded and overlapped, and the periphery can be heat-sealed to form the packaging. When folding and overlapping, as shown in the example in Figure 5, the edges other than the folded edge can be heat-sealed to form a three-sided seal, or the edges can be folded to form a flange and then sealed on all four sides. Furthermore, if the innermost and outermost layers of the energy storage device casing material are heat-sealable resin layers, the packaging can be formed by heat-sealing the innermost heat-sealable resin layer and the outermost heat-sealable resin layer.

[0164] The energy storage device element may be sealed by a cover in addition to the energy storage device exterior material. That is, the energy storage device exterior material and the cover constitute an exterior that seals the energy storage device element (an exterior for the energy storage device). For example, the energy storage device element may be housed inside a cylindrical energy storage device exterior material, and the opening may be closed with a cover. In another example, the energy storage device element, connected to a cover, may be housed inside a cylindrical energy storage device exterior material such that an opening is formed, and the opening may be closed with a cover. It is preferable that the cover and the energy storage device exterior material are joined by any means. From the viewpoint of reducing dead space between the energy storage device element and the energy storage device exterior material in order to improve the volumetric energy density of the energy storage device, it is preferable that the energy storage device exterior material is wrapped around the energy storage device element and the cover.

[0165] The cover can be formed, for example, from a resin molded product, a metal molded product, an exterior material for an energy storage device, or a combination thereof. In this disclosure, when the cover is described as a resin molded product, the cover does not include embodiments in which the cover is composed solely of a film as defined by JIS K6900-1994 [Plastics - Terminology]. When the cover is a metal molded product, the metal terminals can be omitted as the cover also functions as a metal terminal. The cover may be composed of a resin material and a conductive material.

[0166] Furthermore, recesses for housing energy storage device elements may be formed in the exterior material for the energy storage device by deep drawing or stretch molding. As shown in the example in Figure 5, recesses may be provided in one exterior material for the energy storage device while not being provided in the other, or recesses may be provided in the other exterior material for the energy storage device as well.

[0167] The casing material for energy storage devices disclosed herein can be suitably used in energy storage devices such as batteries (including capacitors, capacitors, etc.). Furthermore, the casing material for energy storage devices disclosed herein can be used in either primary batteries or secondary batteries, but is preferably used in secondary batteries. The types of secondary batteries to which the casing material for energy storage devices disclosed herein can be applied are not particularly limited, and examples include lithium-ion batteries, lithium-ion polymer batteries, all-solid-state batteries, semi-solid-state batteries, pseudo-solid-state batteries, polymer batteries, all-resin batteries, lead-acid batteries, nickel-metal hydride batteries, nickel-cadmium batteries, nickel-iron batteries, nickel-zinc batteries, silver oxide-zinc batteries, metal-air batteries, polyvalent cation batteries, capacitors, capacitors, etc. Among these secondary batteries, lithium-ion batteries and lithium-ion polymer batteries are particularly suitable applications for the casing material for energy storage devices disclosed herein. [Examples]

[0168] The present disclosure will be described in detail below with reference to examples and comparative examples. However, the present disclosure is not limited to the examples.

[0169] <Manufacturing of exterior materials for energy storage devices> (Example 1) As base layers, polyethylene terephthalate film (6 μm thick) and nylon film (15 μm thick) were prepared. These were bonded together with a two-component curing urethane adhesive (polyester polyol and aromatic isocyanate compound, curing thickness 3 μm), creating a laminated film with an adhesive layer between the polyethylene terephthalate film and the nylon film. In addition, aluminum alloy foil (JIS H4160:1994 A8079H-O, 60 μm thick) was prepared as a barrier layer. Both sides of the aluminum alloy foil were treated with a chemical conversion treatment. The chemical conversion treatment of the aluminum alloy foil consisted of a treatment solution made of phenolic resin, chromium fluoride compound, and phosphoric acid, with a chromium coating amount of 10 mg / m². 2 The process was carried out by applying the coating to both sides of the aluminum alloy foil using the roll coating method and then baking it to achieve the desired (dry mass).

[0170] Next, using a two-component curing urethane adhesive (polyester polyol and aromatic isocyanate compound), the nylon film side of the laminated film and the barrier layer were bonded by a dry lamination method to create a laminate in which the base layer (polyethylene terephthalate film) / adhesive layer / base layer (nylon film) / adhesive layer / barrier layer were laminated in that order.

[0171] Next, maleic anhydride-modified polypropylene as the adhesive layer and polypropylene as the heat-fusible resin layer were co-extruded and laminated on the barrier layer with an adhesive layer (33 μm thick) and a heat-fusible resin layer (33 μm thick). Then, the resulting laminate was aged and heated to obtain an exterior material for an energy storage device consisting of a laminate in which a base layer (PET) / adhesive layer (DL) / base layer (ONY) / adhesive layer (DL) / barrier layer (ALM) / adhesive layer (PPa) / heat-fusible resin layer (PP) were laminated in this order.

[0172] (Example 2) As the base layer, a polyethylene terephthalate film (6 μm thick) was prepared with corona treatment applied to the laminated side. As the barrier layer, an aluminum alloy foil (JIS H4160:1994 A8079H-O, 80 μm thick) was prepared. Both sides of the aluminum alloy foil were treated with a chemical conversion treatment. The chemical conversion treatment of the aluminum alloy foil involved a treatment solution consisting of phenolic resin, chromium fluoride compound, and phosphoric acid, with a chromium coating amount of 10 mg / m². 2 The process was carried out by applying the coating to both sides of the aluminum alloy foil using the roll coating method and then baking it to achieve the desired (dry mass).

[0173] Next, a laminate was fabricated using a two-component curing urethane adhesive (polyester polyol and aromatic isocyanate compound) by dry lamination, in which a substrate layer (PET), adhesive layer (DL), and barrier layer (ALM) were sequentially laminated.

[0174] Next, maleic anhydride-modified polypropylene as the adhesive layer and polypropylene as the heat-fusible resin layer were co-extruded and laminated on the barrier layer with an adhesive layer (13 μm thick) and a heat-fusible resin layer (10 μm thick). Then, the resulting laminate was aged and heated to obtain an exterior material for an energy storage device consisting of a laminate in which the base layer (PET) / adhesive layer (DL) / barrier layer (ALM) / adhesive layer (PPa) / heat-fusible resin layer (PP) were laminated in this order.

[0175] (Example 3) As base layers, polyethylene terephthalate film (6 μm thick) and nylon film (12 μm thick) were prepared. These were bonded together with a two-component curing urethane adhesive (polyester polyol and aromatic isocyanate compound, curing thickness 3 μm), creating a laminated film with an adhesive layer between the polyethylene terephthalate film and the nylon film. In addition, aluminum alloy foil (JIS H4160:1994 A8079H-O, 50 μm thick) was prepared as a barrier layer. Both sides of the aluminum alloy foil were treated with a chemical conversion treatment. The chemical conversion treatment of the aluminum alloy foil consisted of a treatment solution made of phenolic resin, chromium fluoride compound, and phosphoric acid, with a chromium coating amount of 10 mg / m². 2 The process was carried out by applying the coating to both sides of the aluminum alloy foil using the roll coating method and then baking it to achieve the desired (dry mass).

[0176] Next, using a two-component curing urethane adhesive (polyester polyol and aromatic isocyanate compound), the nylon film side of the laminated film and the barrier layer were bonded by a dry lamination method to create a laminate in which the base layer (PET) / adhesive layer (DL) / base layer (Ny) / adhesive layer (DL) / barrier layer (ALM) were laminated in that order.

[0177] Next, maleic anhydride-modified polypropylene as the adhesive layer and polypropylene as the heat-fusible resin layer were co-extruded and laminated on the barrier layer (adhesive layer (35 μm) / heat-fusible resin layer (35 μm)). Then, the resulting laminate was aged and heated to obtain an exterior material for an energy storage device consisting of a laminate in which the following layers were laminated in this order: base layer (PET) / adhesive layer (DL) / base layer (ONY) / adhesive layer (DL) / barrier layer (ALM) / adhesive layer (PPa) / heat-fusible resin layer (PP).

[0178] (Example 4) As the base layer, a polyethylene terephthalate film (6 μm thick) was prepared with corona treatment applied to the laminated side. As the barrier layer, an aluminum alloy foil (JIS H4160:1994 A8079H-O, 40 μm thick) was prepared. Both sides of the aluminum alloy foil were treated with a chemical conversion solution. The chemical conversion treatment of the aluminum alloy foil involved a treatment solution consisting of phenolic resin, chromium fluoride compound, and phosphoric acid, with a chromium coating amount of 10 mg / m². 2 The process was carried out by applying the coating to both sides of the aluminum alloy foil using the roll coating method and then baking it to achieve the desired (dry mass).

[0179] Next, a laminate was fabricated using a two-component curing urethane adhesive (polyester polyol and aromatic isocyanate compound) by dry lamination, in which a substrate layer (PET), adhesive layer (DL), and barrier layer (ALM) were sequentially laminated.

[0180] Next, maleic anhydride-modified polypropylene as the adhesive layer and polypropylene as the heat-fusible resin layer were co-extruded and laminated on the barrier layer with an adhesive layer (thickness 22.5 μm) and a heat-fusible resin layer (thickness 22.5 μm). Then, the resulting laminate was aged and heated to obtain an exterior material for an energy storage device consisting of a laminate in which the following layers were laminated in this order: base layer (PET) / adhesive layer (DL) / base layer (ONY) / adhesive layer (DL) / barrier layer (ALM) / adhesive layer (PPa) / heat-fusible resin layer (PP).

[0181] (Example 5) As the base layer, a polyethylene terephthalate film (6 μm thick) was prepared with corona treatment applied to the laminated side. As the barrier layer, an aluminum alloy foil (JIS H4160:1994 A8021H-O, 25 μm thick) was prepared. Both sides of the aluminum alloy foil were treated with a chemical conversion treatment. The chemical conversion treatment of the aluminum alloy foil involved a treatment solution consisting of phenolic resin, chromium fluoride compound, and phosphoric acid, with a chromium coating amount of 10 mg / m². 2 The process was carried out by applying the coating to both sides of the aluminum alloy foil using the roll coating method and then baking it to achieve the desired (dry mass).

[0182] Next, a laminate was fabricated using a two-component curing urethane adhesive (polyester polyol and aromatic isocyanate compound) by dry lamination, in which a substrate layer (PET), adhesive layer (DL), and barrier layer (ALM) were sequentially laminated.

[0183] Next, maleic anhydride-modified polypropylene as the adhesive layer and polypropylene as the heat-fusible resin layer were co-extruded and laminated on the barrier layer with an adhesive layer (14 μm thick) and a heat-fusible resin layer (10 μm thick). Then, the resulting laminate was aged and heated to obtain an exterior material for an energy storage device consisting of a laminate in which the following layers were laminated in this order: base layer (PET) / adhesive layer (DL) / base layer (ONY) / adhesive layer (DL) / barrier layer (ALM) / adhesive layer (PPa) / heat-fusible resin layer (PP).

[0184] (Example 6) As base layers, polyethylene terephthalate film (thickness 4.5 μm) and nylon film (thickness 15 μm) were prepared. These were bonded together with a two-component curing urethane adhesive (polyester polyol and aromatic isocyanate compound, thickness after curing 3 μm), resulting in a laminated film with an adhesive layer between the polyethylene terephthalate film and the nylon film. In addition, aluminum alloy foil (JIS H4160:1994 A8079H-O, thickness 60 μm) was prepared as a barrier layer. Both sides of the aluminum alloy foil were treated with a chemical conversion treatment. The chemical conversion treatment of the aluminum alloy foil consisted of a treatment solution made of phenolic resin, chromium fluoride compound, and phosphoric acid, with a chromium coating amount of 10 mg / m². 2 The process was carried out by applying the coating to both sides of the aluminum alloy foil using the roll coating method and then baking it to achieve the desired (dry mass).

[0185] Next, using a two-component curing urethane adhesive (polyester polyol and aromatic isocyanate compound), the nylon film side of the laminated film and the barrier layer were bonded by a dry lamination method to create a laminate in which the base layer (PET) / adhesive layer (DL) / base layer (Ny) / adhesive layer (DL) / barrier layer (ALM) were laminated in that order.

[0186] Next, maleic anhydride-modified polypropylene as the adhesive layer and polypropylene as the heat-fusible resin layer were co-extruded and laminated on the barrier layer with an adhesive layer (33 μm thick) and a heat-fusible resin layer (33 μm thick). Then, the resulting laminate was aged and heated to obtain an exterior material for an energy storage device consisting of a laminate in which a base layer (PET) / adhesive layer (DL) / base layer (ONY) / adhesive layer (DL) / barrier layer (ALM) / adhesive layer (PPa) / heat-fusible resin layer (PP) were laminated in this order.

[0187] (Comparative Example 1) As base layers, polyethylene terephthalate film (12 μm thick) and nylon film (15 μm thick) were prepared. These were bonded together with a two-component curing urethane adhesive (polyester polyol and aromatic isocyanate compound, curing thickness 3 μm), creating a laminated film with an adhesive layer between the polyethylene terephthalate film and the nylon film. In addition, aluminum alloy foil (JIS H4160:1994 A8021H-O, 40 μm thick) was prepared as a barrier layer. Both sides of the aluminum alloy foil were treated with a chemical conversion treatment. The chemical conversion treatment of the aluminum alloy foil consisted of a treatment solution made of phenolic resin, chromium fluoride compound, and phosphoric acid, with a chromium coating amount of 10 mg / m². 2 The process was carried out by applying the coating to both sides of the aluminum alloy foil using the roll coating method and then baking it to achieve the desired (dry mass).

[0188] Next, using a two-component curing urethane adhesive (polyester polyol and aromatic isocyanate compound), the nylon film side of the laminated film and the barrier layer were bonded by a dry lamination method to create a laminate in which the base layer (PET) / adhesive layer (DL) / base layer (Ny) / adhesive layer (DL) / barrier layer (ALM) were laminated in that order.

[0189] Next, maleic anhydride-modified polypropylene as the adhesive layer and polypropylene as the heat-fusible resin layer were co-extruded and laminated on the barrier layer with an adhesive layer (40 μm thick) and a heat-fusible resin layer (40 μm thick). Then, the resulting laminate was aged and heated to obtain an exterior material for an energy storage device consisting of a laminate in which a base layer (PET) / adhesive layer (DL) / base layer (ONY) / adhesive layer (DL) / barrier layer (ALM) / adhesive layer (PPa) / heat-fusible resin layer (PP) were laminated in this order.

[0190] (Comparative Example 2) As base layers, polyethylene terephthalate film (12 μm thick) and nylon film (25 μm thick) were prepared. These were bonded together with a two-component curing urethane adhesive (polyester polyol and aromatic isocyanate compound, curing thickness 3 μm), creating a laminated film with an adhesive layer between the polyethylene terephthalate film and the nylon film. In addition, aluminum alloy foil (JIS H4160:1994 A8079H-O, 80 μm thick) was prepared as a barrier layer. Both sides of the aluminum alloy foil were treated with a chemical conversion treatment. The chemical conversion treatment of the aluminum alloy foil consisted of a treatment solution made of phenolic resin, chromium fluoride compound, and phosphoric acid, with a chromium coating amount of 10 mg / m². 2 The process was carried out by applying the coating to both sides of the aluminum alloy foil using the roll coating method and then baking it to achieve the desired (dry mass).

[0191] Next, using a two-component curing urethane adhesive (polyester polyol and aromatic isocyanate compound), the nylon film side of the laminated film and the barrier layer were bonded by a dry lamination method to create a laminate in which the base layer (PET) / adhesive layer (DL) / base layer (ONY) / adhesive layer (DL) / barrier layer (ALM) were laminated in that order.

[0192] Next, maleic anhydride-modified polypropylene as the adhesive layer and polypropylene as the heat-fusible resin layer were co-extruded and laminated on the barrier layer with an adhesive layer (30 μm thick) and a heat-fusible resin layer (30 μm thick). Then, the resulting laminate was aged and heated to obtain an exterior material for an energy storage device consisting of a laminate in which a base layer (PET) / adhesive layer (DL) / base layer (ONY) / adhesive layer (DL) / barrier layer (ALM) / adhesive layer (PPa) / heat-fusible resin layer (PP) were laminated in this order.

[0193] (Comparative Example 3) As base layers, polyethylene terephthalate film (12 μm thick) and nylon film (25 μm thick) were prepared. These were bonded together with a two-component curing urethane adhesive (polyester polyol and aromatic isocyanate compound, curing thickness 3 μm), creating a laminated film with an adhesive layer between the polyethylene terephthalate film and the nylon film. In addition, aluminum alloy foil (JIS H4160:1994 A8079H-O, 60 μm thick) was prepared as a barrier layer. Both sides of the aluminum alloy foil were treated with a chemical conversion treatment. The chemical conversion treatment of the aluminum alloy foil consisted of a treatment solution made of phenolic resin, chromium fluoride compound, and phosphoric acid, with a chromium coating amount of 10 mg / m². 2 The process was carried out by applying the coating to both sides of the aluminum alloy foil using the roll coating method and then baking it to achieve the desired (dry mass).

[0194] Next, using a two-component curing urethane adhesive (polyester polyol and aromatic isocyanate compound), the nylon film side of the laminated film and the barrier layer were bonded by a dry lamination method to create a laminate in which the base layer (PET) / adhesive layer (DL) / base layer (ONY) / adhesive layer (DL) / barrier layer (ALM) were laminated in that order.

[0195] Next, maleic anhydride-modified polypropylene as the adhesive layer and polypropylene as the heat-fusible resin layer were co-extruded and laminated on the barrier layer with an adhesive layer (40 μm thick) and a heat-fusible resin layer (40 μm thick). Then, the resulting laminate was aged and heated to obtain an exterior material for an energy storage device consisting of a laminate in which a base layer (PET) / adhesive layer (DL) / base layer (ONY) / adhesive layer (DL) / barrier layer (ALM) / adhesive layer (PPa) / heat-fusible resin layer (PP) were laminated in this order.

[0196] (Comparative Example 4) As base layers, polyethylene terephthalate film (12 μm thick) and nylon film (15 μm thick) were prepared. These were bonded together with a two-component curing urethane adhesive (polyester polyol and aromatic isocyanate compound, curing thickness 3 μm), creating a laminated film with an adhesive layer between the polyethylene terephthalate film and the nylon film. In addition, aluminum alloy foil (JIS H4160:1994 A8079H-O, 40 μm thick) was prepared as a barrier layer. Both sides of the aluminum alloy foil were treated with a chemical conversion treatment. The chemical conversion treatment of the aluminum alloy foil consisted of a treatment solution made of phenolic resin, chromium fluoride compound, and phosphoric acid, with a chromium coating amount of 10 mg / m². 2 The process was carried out by applying the coating to both sides of the aluminum alloy foil using the roll coating method and then baking it to achieve the desired (dry mass).

[0197] Next, using a two-component curing urethane adhesive (polyester polyol and aromatic isocyanate compound), the nylon film side of the laminated film and the barrier layer were bonded by a dry lamination method to create a laminate in which the base layer (PET) / adhesive layer (DL) / base layer (ONY) / adhesive layer (DL) / barrier layer (ALM) were laminated in that order.

[0198] Next, maleic anhydride-modified polypropylene as the adhesive layer and polypropylene as the heat-fusible resin layer were co-extruded and laminated on the barrier layer with an adhesive layer (20 μm thick) and a heat-fusible resin layer (20 μm thick). Then, the resulting laminate was aged and heated to obtain an exterior material for an energy storage device consisting of a laminate in which a base layer (PET) / adhesive layer (DL) / base layer (ONY) / adhesive layer (DL) / barrier layer (ALM) / adhesive layer (PPa) / heat-fusible resin layer (PP) were laminated in this order.

[0199] (Comparative Example 5) As base layers, polyethylene terephthalate film (6 μm thick) and nylon film (15 μm thick) were prepared. These were bonded together with a two-component curing urethane adhesive (polyester polyol and aromatic isocyanate compound, curing thickness 3 μm), creating a laminated film with an adhesive layer between the polyethylene terephthalate film and the nylon film. In addition, aluminum alloy foil (JIS H4160:1994 A8079H-O, 40 μm thick) was prepared as a barrier layer. Both sides of the aluminum alloy foil were treated with a chemical conversion treatment. The chemical conversion treatment of the aluminum alloy foil consisted of a treatment solution made of phenolic resin, chromium fluoride compound, and phosphoric acid, with a chromium coating amount of 10 mg / m². 2 The process was carried out by applying the coating to both sides of the aluminum alloy foil using the roll coating method and then baking it to achieve the desired (dry mass).

[0200] Next, using a two-component curing urethane adhesive (polyester polyol and aromatic isocyanate compound), the nylon film side of the laminated film and the barrier layer were bonded by a dry lamination method to create a laminate in which the base layer (PET) / adhesive layer (DL) / base layer (ONY) / adhesive layer (DL) / barrier layer (ALM) were laminated in that order.

[0201] Next, maleic anhydride-modified polypropylene as the adhesive layer and polypropylene as the heat-fusible resin layer were co-extruded and laminated on the barrier layer with an adhesive layer (thickness 22.5 μm) and a heat-fusible resin layer (thickness 22.5 μm). Then, the resulting laminate was aged and heated to obtain an exterior material for an energy storage device consisting of a laminate in which the following layers were laminated in this order: base layer (PET) / adhesive layer (DL) / base layer (ONY) / adhesive layer (DL) / barrier layer (ALM) / adhesive layer (PPa) / heat-fusible resin layer (PP).

[0202] (Comparative Example 6) As the base layer, a polyethylene terephthalate film (12 μm thick) was prepared with corona treatment applied to the laminated side. As the barrier layer, an aluminum alloy foil (JIS H4160:1994 A8079H-O, 40 μm thick) was prepared. Both sides of the aluminum alloy foil were treated with a chemical conversion treatment. The chemical conversion treatment of the aluminum alloy foil involved a treatment solution consisting of phenolic resin, chromium fluoride compound, and phosphoric acid, with a chromium coating amount of 10 mg / m². 2 The process was carried out by applying the coating to both sides of the aluminum alloy foil using the roll coating method and then baking it to achieve the desired (dry mass).

[0203] Next, a laminate was fabricated using a two-component curing urethane adhesive (polyester polyol and aromatic isocyanate compound) by dry lamination, in which a substrate layer (PET), adhesive layer (DL), and barrier layer (ALM) were sequentially laminated.

[0204] Next, maleic anhydride-modified polypropylene as the adhesive layer and polypropylene as the heat-fusible resin layer were co-extruded and laminated on the barrier layer with the adhesive layer (thickness 22.5 μm) and the heat-fusible resin layer (thickness 22.5 μm). Then, the resulting laminate was aged and heated to obtain an exterior material for an energy storage device consisting of a laminate in which the base layer (PET) / adhesive layer (DL) / barrier layer (ALM) / adhesive layer (PPa) / heat-fusible resin layer (PP) were laminated in this order.

[0205] Table 1 shows the relationship between the thicknesses of each layer of the exterior material for energy storage devices obtained in each example and comparative example.

[0206] <Tensile test in a 120°C environment> Tensile tests were conducted on the exterior material for energy storage devices in a 120°C environment, and the strength (N / 15mm) when stretched 20% in the MD direction was measured. The measurement was performed using a tensile testing machine in accordance with the provisions of JIS K7127:1999. The measurement conditions were a sample width of 15mm, a length of 100mm, a gauge length of 50mm, a tensile speed of 5mm / min, and a test environment of 120°C. The average value of three measurements was used. The three measured values ​​were rounded to one decimal place by rounding to two decimal places. The measurement was performed 2 minutes after the temperature in the constant temperature chamber reached 120°C. In the tensile test in this disclosure, the initial distance between the chucks was 50mm, and this initial distance between the chucks was used as the gauge length. If the strength (N / 15mm) is 60.0N / 15mm or higher, the mechanical strength of the exterior material for energy storage devices in a high-temperature environment is considered to be particularly high. The results are shown in Table 1.

[0207] (Measurement of shaped curl) The molding curl of the exterior material for energy storage devices was measured using the following procedure. The results are shown in Table 1. If the molding curl is 5 mm or less, the molding curl of the exterior material for energy storage devices is evaluated as being suitably suppressed. (procedure) A rectangular exterior material for an energy storage device, with dimensions of TD150mm x MD90mm in plan view, is used as the measurement sample. A straight mold consisting of a rectangular male mold measuring 31.6mm vertically x 54.5mm horizontally and a female mold with a clearance of 0.53mm from the male mold is used. The measurement sample is placed on the female mold so that the heat-fusible resin layer is positioned on the male mold side. The measurement sample is then pressed with a pressing pressure (surface pressure) of 0.1MPa to form a sample with dimensions of 31.6mm (MD direction) x 54.5mm (TD direction) and a molding depth of 5mm, and cold forming (single-stage pull-in forming) is performed. The forming is carried out so that the center of the energy storage device exterior material, the MD direction, and the TD direction coincide with the center of the male mold, the vertical direction, and the horizontal direction, respectively. After molding, the measurement sample is stored for one day in an environment of 25°C and 60% relative humidity. Then, with the heat-fusible resin layer facing downwards, it is placed on a horizontal surface, and the distance between the horizontal surface and the point on one of the four sides of the molded measurement sample furthest from the horizontal surface is measured. This distance is defined as the molding curl. The surface of the ridge of the male mold has a maximum height roughness (nominal value of Rz) of 1.6 μm, as specified in Table 2 of the comparative surface roughness standard specimens in Annex 1 (Reference) of JIS B 0659-1:2002. The surface other than the ridge has a maximum height roughness (nominal value of Rz) of 3.2 μm, as specified in Table 2 of the comparative surface roughness standard specimens in Annex 1 (Reference) of JIS B 0659-1:2002. The corner radius of the male mold is 2.0 mm, and the ridge radius is 1.0 mm. The surface of the female mold has a maximum height roughness (nominal value of Rz) of 3.2 μm, as specified in Table 2 of the comparative surface roughness standard specimens in Annex 1 (Reference) of JIS B 0659-1:2002. The corner radius of the female mold is 2.0 mm, and the edge radius is 1.0 mm.

[0208] (Method for evaluating deadhold performance) The deadhold properties of the exterior material for energy storage devices were evaluated using the following procedure. The results are shown in Table 1. If the value of length α (mm) measured by the deadhold properties evaluation method is 5 or less, the exterior material for energy storage devices is evaluated as having high deadhold properties. (procedure) A rectangular exterior material for an energy storage device, with dimensions of TD100mm x MD200mm in plan view, is used as the measurement sample. The measurement sample is folded in half so that the base material layers face each other in the MD direction and the heat-sealable resin layer is on the outside. A 2kg roller is placed on the folded portion and the roller is moved back and forth 5 times in the TD direction. The folded measurement sample is placed on a glass plate and left to stand for 1 minute. At this time, as shown in Figure 6, the surface of one side of the heat-sealable resin layer of the folded measurement sample is placed in contact with the surface of the glass plate. The length of the closest parts of the folded ends of the measurement sample is denoted as α (mm). The measurement environment is 25°C and 60% relative humidity.

[0209] [Table 1]

[0210] The exterior materials for energy storage devices of Examples 1 to 6 are composed of a laminate comprising, at least from the outside, a base layer, a barrier layer, and a heat-fusible resin layer in that order. The base layer includes a polyester film, the thickness of which is 10 μm or less, and the ratio of the thickness of the base layer (μm) to the thickness of the barrier layer (μm) is 40% or less. The exterior materials for energy storage devices of Examples 1 to 6 exhibit suppressed molding curl when subjected to cold forming to create recesses. Furthermore, the exterior materials for energy storage devices of Examples 1 to 3 and 6 have high strength at 20% stretch in a 120°C environment and also exhibit high mechanical strength in high-temperature environments. In addition, the exterior materials for energy storage devices of Examples 1 to 6 have high dead-hold properties.

[0211] In the laminated structure of exterior materials for energy storage devices, PET refers to polyethylene terephthalate, ONY to stretched nylon, PPa to maleic anhydride-modified polypropylene, PP to polypropylene, DL to a layer formed by an adhesive using the dry lamination method (adhesive layer or bonding layer), and ALM to aluminum alloy foil.

[0212] As described above, this disclosure provides inventions in the following embodiments. Item 1. The laminate comprises, at least, a base layer, a barrier layer, and a heat-sealable resin layer in that order from the outside. The aforementioned substrate layer includes a polyester film. The thickness of the polyester film is 10 μm or less. An exterior material for an energy storage device, wherein the ratio of the thickness (μm) of the substrate layer to the thickness (μm) of the barrier layer is 40% or less. Item 2. The exterior material for an energy storage device according to Item 1, wherein the sum of the ratio (%) of the thickness of the base material layer to the thickness of the barrier layer and the ratio (%) of the thickness of the base material layer to the total thickness of the layers located inside the barrier layer is 80% or less. Item 3. An exterior material for energy storage devices as described in Item 1 or 2, wherein the strength when stretched by 20% in the MD direction in the following tensile test in a 120°C environment is 60.0 N / 15 mm or more. <Tensile Test> The measurement shall be performed using a tensile testing machine in accordance with the provisions of JIS K7127:1999. The measurement conditions shall be a rectangular sample with a width of 15 mm, a gauge length of 50 mm, a tensile speed of 5 mm / min, and a test environment of 120°C, and the average value of three measurements shall be used. Item 4. An exterior material for an energy storage device as described in any one of items 1 to 3, wherein the molded curl measured by the following measurement method is 5 mm or less. (Measurement of shaped curl) A rectangular exterior material for an energy storage device, with dimensions of TD150mm x MD90mm in plan view, is used as the measurement sample. A straight mold consisting of a rectangular male mold measuring 31.6mm vertically x 54.5mm horizontally and a female mold with a clearance of 0.53mm from the male mold is used. The measurement sample is placed on the female mold so that the heat-fusible resin layer is positioned on the male mold side. The measurement sample is then pressed with a pressing pressure (surface pressure) of 0.1MPa to form a sample with dimensions of 31.6mm (MD direction) x 54.5mm (TD direction) and a molding depth of 5mm, and cold forming (single-stage pull-in forming) is performed. The forming is carried out so that the center of the energy storage device exterior material, the MD direction, and the TD direction coincide with the center of the male mold, the vertical direction, and the horizontal direction, respectively. After molding, the measurement sample is stored for one day in an environment of 25°C and 60% relative humidity. Then, with the heat-fusible resin layer facing downwards, it is placed on a horizontal surface, and the distance between the horizontal surface and the point on one of the four sides of the molded measurement sample furthest from the horizontal surface is measured. This distance is defined as the molding curl. The surface of the ridge of the male mold has a maximum height roughness (nominal value of Rz) of 1.6 μm, as specified in Table 2 of the comparative surface roughness standard specimens in Annex 1 (Reference) of JIS B 0659-1:2002. The surface other than the ridge has a maximum height roughness (nominal value of Rz) of 3.2 μm, as specified in Table 2 of the comparative surface roughness standard specimens in Annex 1 (Reference) of JIS B 0659-1:2002. The corner radius of the male mold is 2.0 mm, and the ridge radius is 1.0 mm. The surface of the female mold has a maximum height roughness (nominal value of Rz) of 3.2 μm, as specified in Table 2 of the comparative surface roughness standard specimens in Annex 1 (Reference) of JIS B 0659-1:2002. The corner radius of the female mold is 2.0 mm, and the edge radius is 1.0 mm. Item 5. An exterior material for an energy storage device as described in any one of Items 1 to 3, wherein the length α measured by the following deadhold performance evaluation method is 5 mm or less. (Method for evaluating deadhold performance) A rectangular exterior material for an energy storage device, with dimensions of TD100mm x MD200mm in plan view, is used as the measurement sample. The measurement sample is folded in half so that the base material layers face each other in the MD direction and the heat-sealable resin layer is on the outside. A 2kg roller is placed on the folded portion and the roller is moved back and forth 5 times in the TD direction. The folded measurement sample is placed on a glass plate and left to stand for 1 minute. At this time, the surface of one side of the heat-sealable resin layer of the folded measurement sample is in contact with the surface of the glass plate. The length of the closest parts of the folded ends of the measurement sample is defined as α (mm). The measurement environment is 25°C and 60% relative humidity. Item 6. An exterior material for an energy storage device according to any one of items 1 to 5, further comprising an adhesive layer between the base material layer and the barrier layer. Item 7. The exterior material for an energy storage device according to any one of items 1 to 6, wherein the base layer further comprises a polyamide film. Item 8. An exterior material for an energy storage device according to any one of items 1 to 7, further comprising an adhesive layer between the barrier layer and the heat-fusible resin layer. Item 9. The process includes obtaining a laminate in which, from the outside inward, at least a base layer, a barrier layer, and a heat-fusible resin layer are laminated in this order. The aforementioned substrate layer includes a polyester film. The thickness of the polyester film is 10 μm or less. A method for manufacturing an exterior material for an energy storage device, wherein the ratio (μm) of the thickness of the base material layer to the thickness (μm) of the barrier layer is 40% or less. Item 10. An energy storage device in which an energy storage device element comprising at least a positive electrode, a negative electrode, and an electrolyte is housed in a package formed from an outer casing material for an energy storage device as described in any one of items 1 to 8. [Explanation of Symbols]

[0213] 1 Base material layer 2 Adhesive layer 3. Barrier layer 4 Heat-fusible resin layer 5 Adhesive layer 6 Surface coating layer 10. Exterior materials for energy storage devices

Claims

1. At a minimum, the exterior material for an energy storage device is composed of a laminate comprising a base material layer, a barrier layer, and a heat-sealable resin layer in that order from the outside. The substrate layer includes a laminate of a polyester film and a stretched nylon film. The thickness of the polyester film is 4 μm or more and 8 μm or less. The thickness of the stretched nylon film is 10 μm or more and 25 μm or less. The ratio of the thickness of the substrate layer (μm) to the thickness of the barrier layer (μm) is 40% or less. The aforementioned exterior material for the energy storage device exhibits a strength of 60.0 N / 15 mm or more when stretched by 20% in the MD direction in the following tensile test conducted in a 120°C environment: An exterior material for energy storage devices, wherein the molded curl, measured by the following measurement method, is 5 mm or less. <Tensile Test> The measurement shall be performed using a tensile testing machine in accordance with the provisions of JIS K7127:1999. The measurement conditions shall be a rectangular sample with a width of 15 mm, a gauge length of 50 mm, a tensile speed of 5 mm / min, and a test environment of 120°C, and the average value of three measurements shall be used. (Measurement of shaped curl) A rectangular exterior material for an energy storage device, with dimensions of TD 150 mm x MD 90 mm in plan view, is used as the measurement sample. A straight mold consisting of a rectangular male mold measuring 31.6 mm vertically x 54.5 mm horizontally and a female mold with a clearance of 0.53 mm from the male mold is used. The measurement sample is placed on the female mold so that the heat-fusible resin layer is positioned on the male mold side, and the measurement sample is pressed with a pressing pressure (surface pressure) of 0.1 MPa to form a sample of 31.6 mm (MD direction) x 54.5 mm (TD direction) with a molding depth of 5 mm, and cold forming (single-stage pull-in forming) is performed. The molding is performed such that the central part of the outer casing material for the energy storage device, the MD direction, and the TD direction coincide with the central part of the male mold, the vertical direction, and the horizontal direction, respectively. After molding, the measurement sample is stored for one day in an environment of 25°C and 60% relative humidity. Then, with the heat-fusible resin layer facing downwards, it is placed on a horizontal surface, and the distance between the horizontal surface and the point on one of the four sides of the molded measurement sample furthest from the horizontal surface is measured. This distance is defined as the molding curl. The surface of the ridge of the male mold has a maximum height roughness (nominal value of Rz) of 1.6 μm, as specified in Table 2 of the comparative surface roughness standard specimens in Annex 1 (Reference) of JIS B 0659-1:2002. The surface other than the ridge has a maximum height roughness (nominal value of Rz) of 3.2 μm, as specified in Table 2 of the comparative surface roughness standard specimens in Annex 1 (Reference) of JIS B 0659-1:2002. The corner radius of the male mold is 2.0 mm, and the ridge radius is 1.0 mm. The surface of the female mold has a maximum height roughness (nominal value of Rz) of 3.2 μm, as specified in Table 2 of the comparative surface roughness standard specimens in JIS B 0659-1:2002 Annex 1 (informative). The corner radius of the female mold is 2.0 mm, and the edge radius is 1.0 mm.

2. The exterior material for an energy storage device according to claim 1, wherein the sum of the ratio (%) of the thickness of the base material layer to the thickness of the barrier layer and the ratio (%) of the thickness of the base material layer to the total thickness of the layers located inside the barrier layer is 80% or less.

3. An exterior material for an energy storage device according to claim 1 or 2, wherein the strength when stretched by 20% in the MD direction in the following tensile test in a 120°C environment is 65.0 N / 15 mm or more. <Tensile Test> The measurement shall be performed using a tensile testing machine in accordance with the provisions of JIS K7127:1999. The measurement conditions shall be a rectangular sample with a width of 15 mm, a gauge length of 50 mm, a tensile speed of 5 mm / min, and a test environment of 120°C, and the average value of three measurements shall be used.

4. The exterior material for an energy storage device according to claim 1 or 2, wherein the molded curl measured by the following measurement method is 4 mm or less. (Measurement of shaped curl) A rectangular exterior material for an energy storage device, with dimensions of TD 150 mm x MD 90 mm in plan view, is used as the measurement sample. A straight mold consisting of a rectangular male mold measuring 31.6 mm vertically x 54.5 mm horizontally and a female mold with a clearance of 0.53 mm from the male mold is used. The measurement sample is placed on the female mold so that the heat-fusible resin layer is positioned on the male mold side, and the measurement sample is pressed with a pressing pressure (surface pressure) of 0.1 MPa to form a sample of 31.6 mm (MD direction) x 54.5 mm (TD direction) with a molding depth of 5 mm, and cold forming (single-stage pull-in forming) is performed. The molding is performed such that the central part of the outer casing material for the energy storage device, the MD direction, and the TD direction coincide with the central part of the male mold, the vertical direction, and the horizontal direction, respectively. After molding, the measurement sample is stored for one day in an environment of 25°C and 60% relative humidity. Then, with the heat-fusible resin layer facing downwards, it is placed on a horizontal surface, and the distance between the horizontal surface and the point on one of the four sides of the molded measurement sample furthest from the horizontal surface is measured. This distance is defined as the molding curl. The surface of the ridge of the male mold has a maximum height roughness (nominal value of Rz) of 1.6 μm, as specified in Table 2 of the comparative surface roughness standard specimens in Annex 1 (Reference) of JIS B 0659-1:2002. The surface other than the ridge has a maximum height roughness (nominal value of Rz) of 3.2 μm, as specified in Table 2 of the comparative surface roughness standard specimens in Annex 1 (Reference) of JIS B 0659-1:2002. The corner radius of the male mold is 2.0 mm, and the ridge radius is 1.0 mm. The surface of the female mold has a maximum height roughness (nominal value of Rz) of 3.2 μm, as specified in Table 2 of the comparative surface roughness standard specimens in JIS B 0659-1:2002 Annex 1 (informative). The corner radius of the female mold is 2.0 mm, and the edge radius is 1.0 mm.

5. The exterior material for an energy storage device according to claim 1 or 2, wherein the length α measured by the following deadhold performance evaluation method is 5 mm or less. (Method for evaluating deadhold performance) A rectangular exterior material for an energy storage device, with dimensions of TD 100 mm x MD 200 mm in plan view, is used as the measurement sample. The measurement sample is folded in half so that the base material layers face each other in the MD direction and the heat-sealable resin layer is on the outside. A roller with a mass of 2 kg is placed on the bending section, and the roller is moved back and forth five times in the TD direction. Place the bent measurement sample on a glass plate and leave it undisturbed for one minute. At this time, the sample should be placed so that one side of the heat-sealable resin layer on the bent measurement sample is in contact with the surface of the glass plate. Let α (mm) be the length of the closest point between the two folded ends of the measurement sample. The measurement environment is 25°C and 60% relative humidity.

6. The exterior material for an energy storage device according to claim 1 or 2, further comprising an adhesive layer between the base material layer and the barrier layer.

7. The exterior material for an energy storage device according to claim 1 or 2, further comprising an adhesive layer between the barrier layer and the heat-fusible resin layer.

8. The process includes obtaining an exterior material for an energy storage device, which is composed of a laminate in which at least a base layer, a barrier layer, and a heat-sealable resin layer are laminated in that order from the outside, The substrate layer includes a laminate of a polyester film and a stretched nylon film. The thickness of the polyester film is 4 μm or more and 8 μm or less. The thickness of the stretched nylon film is 10 μm or more and 25 μm or less. The ratio of the thickness of the substrate layer (μm) to the thickness of the barrier layer (μm) is 40% or less. The aforementioned exterior material for the energy storage device exhibits a strength of 60.0 N / 15 mm or more when stretched by 20% in the MD direction in the following tensile test conducted in a 120°C environment: A method for manufacturing an exterior material for an energy storage device, wherein the molded curl measured by the following measurement method is 5 mm or less. <Tensile Test> The measurement shall be performed using a tensile testing machine in accordance with the provisions of JIS K7127:1999. The measurement conditions shall be a rectangular sample with a width of 15 mm, a gauge length of 50 mm, a tensile speed of 5 mm / min, and a test environment of 120°C, and the average value of three measurements shall be used. (Measurement of shaped curl) A rectangular exterior material for an energy storage device, with dimensions of TD 150 mm x MD 90 mm in plan view, is used as the measurement sample. A straight mold consisting of a rectangular male mold measuring 31.6 mm vertically x 54.5 mm horizontally and a female mold with a clearance of 0.53 mm from the male mold is used. The measurement sample is placed on the female mold so that the heat-fusible resin layer is positioned on the male mold side, and the measurement sample is pressed with a pressing pressure (surface pressure) of 0.1 MPa to form a sample of 31.6 mm (MD direction) x 54.5 mm (TD direction) with a molding depth of 5 mm, and cold forming (single-stage pull-in forming) is performed. The molding is performed such that the central part of the outer casing material for the energy storage device, the MD direction, and the TD direction coincide with the central part of the male mold, the vertical direction, and the horizontal direction, respectively. After molding, the measurement sample is stored for one day in an environment of 25°C and 60% relative humidity. Then, with the heat-fusible resin layer facing downwards, it is placed on a horizontal surface, and the distance between the horizontal surface and the point on one of the four sides of the molded measurement sample furthest from the horizontal surface is measured. This distance is defined as the molding curl. The surface of the ridge of the male mold has a maximum height roughness (nominal value of Rz) of 1.6 μm, as specified in Table 2 of the comparative surface roughness standard specimens in Annex 1 (Reference) of JIS B 0659-1:2002. The surface other than the ridge has a maximum height roughness (nominal value of Rz) of 3.2 μm, as specified in Table 2 of the comparative surface roughness standard specimens in Annex 1 (Reference) of JIS B 0659-1:2002. The corner radius of the male mold is 2.0 mm, and the ridge radius is 1.0 mm. The surface of the female mold has a maximum height roughness (nominal value of Rz) of 3.2 μm, as specified in Table 2 of the comparative surface roughness standard specimens in JIS B 0659-1:2002 Annex 1 (informative). The corner radius of the female mold is 2.0 mm, and the edge radius is 1.0 mm.

9. An energy storage device in which an energy storage device element comprising at least a positive electrode, a negative electrode, and an electrolyte is housed in a package formed from the outer material for energy storage devices described in claim 1 or 2.

Images