Exterior material for energy storage devices and energy storage devices using the same

Abstract

To provide an exterior material with a superior moisture barrier property even under a high temperature environment while having a superior heat resistance property.SOLUTION: In an aspect of the present disclosure, an exterior material for a power storage device has a lamination construction comprising: a base layer; a first adhesion layer; a metal foil layer; a second adhesion layer; a sealant layer, in this order. In the exterior material, the second adhesion layer contains a product obtained by reacting at least an acid-modified polyolefin with a polyfunctional isocyanate compound, and the second adhesion layer satisfies a condition expressed by the inequality of following formula (1): 0.01≤{(C+D)-B} / A≤0.60...(1). [In the formula, A to D indicate intensities in an infrared absorption spectrum of the second adhesion layer measured by infrared spectroscopy, the A indicates the maximum intensity within the wavenumber range of 3040 to 2760 cm-1, the B indicates the maximum intensity within the wavenumber range of 1850 to 1780 cm-1, the C indicates the maximum intensity within the wavenumber range of 1760 to 1600 cm-1, and the D indicates the maximum intensity within the wavenumber range of 2150 to 2090 cm-1].SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] This disclosure relates to an exterior material for energy storage devices and an energy storage device using the same. [Background technology]

[0002] Known energy storage devices include secondary batteries such as lithium-ion batteries, nickel-metal hydride batteries, and lead-acid batteries, as well as electrochemical capacitors such as electric double-layer capacitors. Due to the miniaturization of portable devices and limitations on installation space, there is a demand for further miniaturization of energy storage devices, and lithium-ion batteries, which have high energy density, are attracting attention. Multilayer films, which are lightweight, have high heat dissipation properties, and can be manufactured at low cost, are increasingly being used as casing materials for lithium-ion batteries.

[0003] Lithium-ion batteries that use the above-mentioned multilayer film as an outer casing are called laminate-type lithium-ion batteries. The outer casing covers the battery contents (positive electrode, separator, negative electrode, electrolyte, etc.) and prevents moisture from entering the interior. Laminate-type lithium-ion batteries are manufactured, for example, by forming a recess in a part of the outer casing by cold molding, housing the battery contents in the recess, folding back the remaining part of the outer casing, and sealing the edges with heat seal (see, for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2013-101765 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] Incidentally, research and development is underway on a next-generation battery called a solid-state battery, which is considered the successor to lithium-ion batteries. Solid-state batteries are characterized by using a solid electrolyte instead of an organic electrolyte. While lithium-ion batteries cannot be used at temperatures higher than the boiling point of the electrolyte (around 80°C), solid-state batteries can be used at temperatures exceeding 100°C, and their lithium-ion conductivity can be increased by operating them at high temperatures (for example, 100-150°C).

[0006] However, when manufacturing laminate-type all-solid-state batteries using the multilayer film described above as the outer casing material, if the heat resistance of the outer casing material is insufficient, interlayer adhesion cannot be ensured in high-temperature environments, which may reduce the laminate strength and impair the airtightness of the all-solid-state battery package. The outer casing material has a structure in which a base layer, a metal foil layer, and a sealant layer are laminated with an adhesive layer or the like in between, but the adhesion between the metal foil layer and the sealant layer tends to decrease in high-temperature environments.

[0007] Furthermore, sulfide-based solid electrolytes used in all-solid-state batteries can react with moisture in the atmosphere to generate hydrogen sulfide gas, which can degrade battery performance. As adhesives used on the inner layer, urethane and epoxy adhesives are generally considered to have heat resistance. However, these adhesives do not have sufficient moisture barrier properties. On the other hand, acid-modified polyolefin adhesives offer high moisture barrier properties. However, these adhesives do not have sufficient heat resistance. Thus, there is a trade-off between the heat resistance and moisture barrier properties of adhesives. Therefore, the outer casing material used in all-solid-state batteries is required to have excellent moisture barrier properties even in high-temperature environments.

[0008] One aspect of this disclosure is to provide an exterior material that has excellent heat resistance and excellent moisture barrier properties even in high-temperature environments. [Means for solving the problem]

[0009] One aspect of the present disclosure is an exterior material for an energy storage device, having a laminated structure comprising a base layer, a first adhesive layer, a metal foil layer, a second adhesive layer, and a sealant layer in this order, wherein the second adhesive layer contains at least a reaction product of an acid-modified polyolefin and a polyfunctional isocyanate compound, and the second adhesive layer satisfies the conditions expressed by the following formula (1). 0.01≦{(C+D)-B} / A≦0.60 …(1) [In the formula, A to D are intensities in the infrared absorption spectrum of the second adhesive layer measured by infrared spectroscopy, where A is wavenumber 3040 to 2760 cm⁻¹. -1 This indicates the maximum intensity, and B corresponds to wavenumbers of 1850-1780 cm. -1 This indicates the maximum intensity, and C corresponds to wavenumbers of 1760-1600 cm. -1 This indicates the maximum intensity, where D corresponds to wavenumbers 2150-2090 cm². -1 This indicates the maximum intensity.

[0010] The above-mentioned exterior material exhibits excellent heat resistance and moisture barrier properties. The inventors believe the reason for these effects is as follows: The reaction product of the acid-modified polyolefin and the polyfunctional isocyanate compound contained in the second adhesive layer has urethane bonds. Since urethane bonds are polar groups, the adhesion between the second adhesive layer and the metal foil layer is improved. Furthermore, the reaction product of the acid-modified polyolefin and the polyfunctional isocyanate compound has a crosslinked structure formed by the reaction between the carboxylic acid in the acid-modified polyolefin and the polyfunctional isocyanate compound. Therefore, the heat resistance of the second adhesive layer itself is also improved.

[0011] Furthermore, when using general acid-modified polyolefins, the glass transition temperature is low, so the entanglement of the molecular chains of the acid-modified polyolefins is resolved in high-temperature environments. As a result, the gaps between molecules widen, and the moisture barrier properties of the exterior material decrease. On the other hand, when using a reaction product of acid-modified polyolefins and polyfunctional isocyanate compounds, a cross-linked structure is formed between multiple acid-modified polyolefin molecules by the polyfunctional isocyanate compound. As a result, the glass transition temperature increases, and the entanglement of molecular chains is less likely to be resolved.

[0012] And in the second adhesive layer, regarding the infrared absorption peak measured by infrared spectroscopy, it is defined that {(C + D) - B} / A (hereinafter also referred to as "X") is 0.01 or more and 0.60 or less. A represents the maximum intensity at a wave number of 3040 - 2760 cm -1 derived from the olefin structure of the above reactant, B represents the maximum intensity at a wave number of 1850 - 1780 cm -1 derived from the maleic anhydride structure of the above reactant, C represents the maximum intensity at a wave number of 1760 - 1600 cm -1 derived from the urethane bond of the above reactant, D represents the maximum intensity at a wave number of 2150 - 2090 cm -1 derived from the carbodiimide compound. When the above X is 0.01 or more, the second adhesive layer has sufficient urethane bonds. Thereby, the adhesion between layers and the heat resistance of the second adhesive layer itself become excellent. Also, when the above X is 0.60 or less, the affinity with water molecules of the second adhesive layer can be suppressed, and the intermolecular gaps due to the crosslinked structure can be suppressed. Thereby, the exterior material becomes excellent in heat resistance and moisture barrier properties. Also, the exterior material is excellent in hydrogen sulfide resistance

[0013] In one aspect, it may contain at least one selected from the group consisting of a multimer of an aliphatic polyfunctional isocyanate compound and a multimer of a polyfunctional isocyanate compound containing an aromatic ring. When the polyfunctional isocyanate compound is a multimer of an aliphatic polyfunctional isocyanate compound, compared with the case of a large isocyanate compound such as a multimer of isophorone diisocyanate, the intermolecular gaps constructed by the crosslinking reaction become smaller. Therefore, the exterior material is more excellent in moisture barrier properties. Also, when the polyfunctional isocyanate compound is a multimer of a polyfunctional isocyanate compound containing an aromatic ring, the intermolecular distance is narrowed due to the interaction between aromatic rings (π-π stacking). Therefore, the exterior material tends to be more excellent in moisture barrier properties.

[0014] In one aspect, the packaging material may include a corrosion prevention treatment layer on one or both of the spaces between the first adhesive layer and the metal foil layer and between the second adhesive layer and the metal foil layer. By including the corrosion prevention treatment layer, the exterior material can improve the adhesion between the adhesive layer provided with the corrosion prevention treatment layer and the metal foil layer. As a result, the exterior material tends to have even better heat resistance. In addition, the corrosion prevention treatment layer imparts hydrogen sulfide resistance to the exterior material. As a result, the exterior material tends to have excellent heat resistance even after exposure to hydrogen sulfide.

[0015] In one aspect, the sealant layer may contain at least one of a polyolefin resin and a polyester resin. These resins have a higher melting point compared to, for example, acrylic resins, and have good compatibility and excellent adhesiveness with the second adhesive layer containing a reaction product of an acid-modified polyolefin and a polyfunctional isocyanate compound. In addition, these resins are more flexible compared to, for example, acrylic resins. Also, for example, they have a lower affinity for water molecules compared to acrylic resins. Therefore, the exterior material tends to have even better heat resistance and moisture barrier properties.

[0016] In one aspect, at least one of the first adhesive layer and the second adhesive layer may contain a hydrogen sulfide adsorbing substance. As a result, the exterior material tends to have even better heat-resistant laminate strength even after exposure to hydrogen sulfide.

[0017] In one aspect, the second adhesive layer may further contain a carbodiimide compound. As a result, the exterior material tends to have even better heat resistance. Regarding the reason for such an effect, the inventors presume that it is because the highly polar carbodiimide group forms hydrogen bonds with other polar groups in the metal foil layer and the second adhesive layer.

[0018] The above exterior material may be for all-solid-state batteries.

[0019] Another aspect of this disclosure is an energy storage device comprising: an energy storage device body; current extraction terminals extending from the energy storage device body; and the exterior material that clamps the current extraction terminals and houses the energy storage device body. The energy storage device may be an all-solid-state battery. [Effects of the Invention]

[0020] According to one aspect of this disclosure, an exterior material is provided that has excellent heat resistance and excellent moisture barrier properties even in high-temperature environments. [Brief explanation of the drawing]

[0021] [Figure 1] This is a schematic cross-sectional view of an exterior material for an energy storage device according to one embodiment of the present disclosure. [Figure 2] This is a schematic diagram showing an example of the infrared absorption spectrum of the second adhesive layer measured by infrared spectroscopy. [Figure 3] This is a perspective view of an energy storage device according to one embodiment of the present disclosure. [Modes for carrying out the invention]

[0022] Preferred embodiments of this disclosure will be described in detail below, with appropriate reference to the drawings. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and redundant descriptions are omitted. Furthermore, the dimensional ratios in the drawings are not limited to those shown.

[0023] [Exterior materials for energy storage devices] Figure 1 is a schematic cross-sectional view showing one embodiment of the exterior material for energy storage devices of the present invention. As shown in Figure 1, the exterior material (exterior material for energy storage devices) 10 of this embodiment is a laminate in which a base layer 11, a first adhesive layer 12 provided on one side of the base layer 11, a metal foil layer 13 provided on the side of the first adhesive layer 12 opposite to the base layer 11 and having corrosion-preventive treatment layers 14a and 14b on both sides, a second adhesive layer 15 provided on the side of the metal foil layer 13 opposite to the first adhesive layer 12, and a sealant layer 16 provided on the side of the second adhesive layer 15 opposite to the metal foil layer 13 are laminated. Here, the corrosion-preventive treatment layer 14a is provided on the side of the metal foil layer 13 facing the first adhesive layer 12, and the corrosion-preventive treatment layer 14b is provided on the side of the metal foil layer 13 facing the second adhesive layer 15. In the exterior material 10, the base layer 11 is the outermost layer, and the sealant layer 16 is the innermost layer. In other words, the exterior material 10 is used with the base layer 11 facing the outside of the energy storage device and the sealant layer 16 facing the inside of the energy storage device. Each layer will be described below.

[0024] <Base material layer 11> The base layer 11 provides heat resistance during the sealing process when manufacturing energy storage devices and plays a role in suppressing the occurrence of pinholes that may occur during molding and distribution. In particular, for exterior materials of large-scale energy storage devices, it can also provide scratch resistance, chemical resistance, and insulation.

[0025] The base material layer 11 preferably has a melting peak temperature higher than that of the sealant layer 16. By having a melting peak temperature higher than that of the sealant layer 16 for the base material layer 11, it is possible to suppress deterioration of the appearance due to melting of the base material layer 11 (outer layer) during heat sealing. When the sealant layer 16 has a multilayer structure, the melting peak temperature of the sealant layer 16 means the melting peak temperature of the layer with the highest melting peak temperature. The melting peak temperature of the base material layer 11 is preferably 290°C or higher, more preferably 290 - 350°C. Examples of resin films that can be used as the base material layer 11 and have a melting peak temperature within the above range include nylon films, PET films, polyamide films, polyphenylene sulfide films (PPS films), polyimide films, polyester films, etc. The melting peak temperature means a value obtained in accordance with the method described in JIS K7121-1987.

[0026] As the base material layer 11, a commercially available film may be used, or the base material layer 11 may be formed by coating (application and drying of a coating liquid). Note that the base material layer 11 may have a single-layer structure or a multilayer structure, and may be formed by applying a thermosetting resin. Further, the base material layer 11 may contain various additives (for example, flame retardants, slip agents, antiblocking agents, antioxidants, light stabilizers, tackifiers, etc.).

[0027] The melting peak temperature T of the base material layer 11 11 and the melting peak temperature T of the sealant layer 16 16 The difference (T 11 -T 16 is preferably 20°C or higher. By having this temperature difference of 20°C or higher, deterioration of the appearance of the exterior material 10 due to heat sealing can be more sufficiently suppressed. The thickness of the base material layer 11 is preferably 5 - 50 μm, more preferably 12 - 30 μm.

[0028] <The first adhesive layer 12> The first adhesive layer 12 is a layer that adheres the metal foil layer 13, which is provided with a corrosion-preventive treatment layer 14a, to the base material layer 11. The first adhesive layer 12 has the adhesive strength necessary to firmly bond the base material layer 11 and the metal foil layer 13, and also has conformability to prevent the metal foil layer 13 from being broken by the base material layer 11 during molding. Conformability refers to the property that even if the member deforms due to expansion or contraction, the first adhesive layer 12 remains on the member without peeling off.

[0029] Examples of adhesive components for forming the first adhesive layer 12 include urethane compounds, urea compounds, epoxy compounds, silicon compounds, and inorganic oxides such as aluminum oxide and silica. These compounds may be used individually or in combination of two or more. Urea compounds are obtained by reacting amine compounds and amine derivatives with polyfunctional isocyanate compounds. Urethane compounds are obtained by reacting polyol resins with polyfunctional isocyanate compounds.

[0030] Amine compounds are compounds that contain an amino group in their molecule. Here, the amino group refers to -NH2, -NHR, or -NR2, where R represents an alkyl group or an aryl group. Amine derivatives are compounds derived from amine compounds that do not contain an amino group in their molecule.

[0031] Amine compounds and amine derivatives may be either visible or latent curing agents. A latent curing agent is a curing agent that is activated by external stimuli to generate a reactive group that can react with isocyanate groups. When amine compounds and amine derivatives are latent curing agents, the pot life tends to improve. Examples of external stimuli include heat and humidity. Examples of latent curing agents include imidazole curing agents, imine curing agents, amineimide curing agents, dicyandiamide curing agents, aromatic polyamine curing agents, aliphatic polyamine curing agents, polyamidoamine curing agents, tertiary amine salt curing agents, and oxazolidine curing agents. Of these, examples of latent curing agents activated by heating include imidazole curing agents, dicyandiamide curing agents, polyamine curing agents, and amineimide curing agents. Examples of latent curing agents activated by humidity include imine curing agents and oxazolidine curing agents. Since the pot life tends to improve further, it is preferable that the latent curing agent is activated by moisture.

[0032] Examples of polyol resins include polyester polyols, polyether polyols, polycarbonate diols, and polyacrylic polyols.

[0033] Examples of polyester polyols include those obtained by reacting one or more dicarboxylic acids with a diol.

[0034] Examples of polyether polyols include those produced by addition polymerization of ethylene oxide or propylene oxide to propylene glycol, glycerin, and pentaerythritol.

[0035] Examples of polycarbonate polyols include those obtained by reacting a diester of carbonate, such as diphenyl carbonate, with a diol.

[0036] Examples of polyacrylic polyols include copolymers obtained by copolymerizing at least a hydroxyl group-containing acrylic monomer with (meth)acrylic acid. In this case, it is preferable that the copolymer contains structural units derived from (meth)acrylic acid as the main component. Examples of hydroxyl group-containing acrylic monomers include 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate.

[0037] Polyfunctional isocyanate compounds contain multiple isocyanate groups and function to crosslink the amine-based resin or polyol mentioned above. Polyfunctional isocyanate compounds may be used individually or in combination of two or more. Examples of polyfunctional isocyanate compounds include aliphatic polyfunctional isocyanate compounds, alicyclic polyfunctional isocyanate compounds, and polyfunctional isocyanate compounds having aromatic rings.

[0038] Examples of aliphatic polyfunctional isocyanate compounds include hexamethylene diisocyanate (HDI) and xylylene diisocyanate (XDI). Examples of alicyclic polyfunctional isocyanate compounds include isophorone diisocyanate (IPDI). Examples of polyfunctional isocyanate compounds having an aromatic ring include tolylene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI). Polyfunctional isocyanate compounds can also be used in the form of polymers (e.g., trimers) of these compounds, specifically adducts, biuretes, isocyanurates, etc.

[0039] From the viewpoint of improving pot life, the polyfunctional isocyanate compound may have its isocyanate group bonded to a blocking agent. Examples of blocking agents include methyl ethyl ketoxime (MEKO). The temperature at which the blocking agent detaches from the isocyanate group of the polyfunctional isocyanate compound may be 50°C or higher, and is preferably 60°C or higher because it further improves pot life. The temperature at which the blocking agent detaches from the isocyanate group of the polyfunctional isocyanate compound may be 140°C or lower, and is preferably 120°C or lower because it improves the mold curl resistance of the exterior material.

[0040] To lower the dissociation temperature of the blocking agent, a catalyst that lowers the dissociation temperature may be used. Examples of such catalysts that lower the dissociation temperature include tertiary amines such as triethylenediamine and N-methylmorpholine, and metal organic salts such as dibutyltin dilaurate.

[0041] The first adhesive layer 12 may contain a hydrogen sulfide adsorbent so as to suppress corrosion of the metal foil layer 13 by hydrogen sulfide present outside the exterior material. Examples of such hydrogen sulfide adsorbents include zinc oxide and potassium permanganate. When the first adhesive layer 12 contains a hydrogen sulfide adsorbent, it can suppress corrosion of the metal foil layer 13 by hydrogen sulfide present outside the exterior material, so its content is preferably 1 to 50% by mass of the total amount of the first adhesive layer 12.

[0042] The thickness of the first adhesive layer 12 is preferably 1 to 10 μm, and more preferably 2 to 6 μm, from the viewpoint of obtaining the desired adhesive strength, conformability, and processability.

[0043] The first adhesive layer 12 is obtained, for example, by coating with a composition containing the above-mentioned components. Known methods can be used for the coating, including, for example, gravure direct, gravure reverse (direct, kiss), and microgravure.

[0044] The composition may contain a solvent. Examples of such solvents include ethyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, and alcohols. The solvent can be used alone or in combination of two or more.

[0045] <Second adhesive layer 15> The second adhesive layer 15 is a layer that adheres the metal foil layer 13, which is provided with the corrosion-preventive treatment layer 14b, to the sealant layer 16. The second adhesive layer 15 contains at least a reaction product of an acid-modified polyolefin and a polyfunctional isocyanate compound (hereinafter also referred to as "reaction product A"). The components for obtaining reaction product A may consist only of an acid-modified polyolefin and a polyfunctional isocyanate compound, or it may contain other components in addition to the acid-modified polyolefin and the polyfunctional isocyanate compound. Examples of other components include carbodiimide compounds, epoxy resins, acrylic resins, silicone resins, silane coupling agents, silica fillers, aluminum oxide, zinc oxide, latent curing agents, and antioxidants. Since reaction product A tends to have even better heat resistance and moisture barrier properties, it is preferable that it is a reaction product of at least an acid-modified polyolefin, a polyfunctional isocyanate compound, and a carbodiimide compound.

[0046] From the viewpoint of reactivity, the hydroxyl value of the acid-modified polyolefin is preferably 5 to 120 KOH mg / g, more preferably 10 to 80 KOH mg / g, and even more preferably 20 to 60 KOH mg / g.

[0047] Examples of acid-modified polyolefins include maleic anhydride-modified polyolefins obtained by reacting maleic anhydride with a polyolefin. Examples of maleic anhydride-modified polyolefins include maleic anhydride-modified polypropylene and maleic anhydride-modified polyethylene.

[0048] As the polyfunctional isocyanate compound, the same one used for the first adhesive layer may be used. Since the exterior material tends to have even better moisture barrier properties, the polyfunctional isocyanate compound is preferably a polymer of an aliphatic polyfunctional isocyanate compound or a polymer of a polyfunctional isocyanate compound containing an aromatic ring.

[0049] At least the amount of polyfunctional isocyanate compound used when reacting an acid-modified polyolefin with a polyfunctional isocyanate compound is preferably 0.5 to 40 parts by mass, more preferably 3 to 30 parts by mass, and even more preferably 5 to 20 parts by mass, per 100 parts by mass of the acid-modified polyolefin, from the viewpoint of reactivity.

[0050] At least the amount of carbodiimide compound used when reacting an acid-modified polyolefin with a polyfunctional isocyanate compound is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 7 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of acid-modified polyolefin, from the viewpoint of heat resistance and adhesion.

[0051] The amount of acid-modified polyolefin blended may be 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more, based on the total amount of components required to obtain reactant A.

[0052] Figure 2 is a schematic diagram showing an example of the infrared absorption spectrum of the second adhesive layer 15 measured by infrared spectroscopy. The second adhesive layer 15 satisfies the condition expressed by the inequality (1) below. 0.01≦{(C+D)-B} / A≦0.60 …(1) [In the formula, A to D are intensities in the infrared absorption spectrum of the second adhesive layer measured by infrared spectroscopy, where A is wavenumber 3040 to 2760 cm⁻¹. -1 This indicates the maximum intensity, and B corresponds to wavenumbers of 1850-1780 cm. -1 This indicates the maximum intensity, and C corresponds to wavenumbers of 1760-1600 cm. -1 This indicates the maximum intensity, where D corresponds to wavenumbers 2150-2090 cm². -1This indicates the maximum intensity.

[0053] Since {(C+D)-B} / A tends to have even better heat resistance, it is preferably 0.05 or higher, more preferably 0.2 or higher, and even more preferably 0.3 or higher. Since {(C+D)-B} / A tends to have even better moisture barrier properties, it is preferably 0.5 or lower, more preferably 0.45 or lower, and even more preferably 0.4 or lower.

[0054] The peak intensity of the infrared absorption spectrum can be measured by attenuated total reflection (ATR) using Fourier transform infrared (FT-IR) spectroscopy.

[0055] The second adhesive layer 15 is preferable to contain a carbodiimide compound because it tends to have even better heat resistance. The carbodiimide compound acts as a reaction accelerator and crosslinking agent for the carboxyl groups contained in the acid-modified polyolefin.

[0056] The second adhesive layer 15 may contain a hydrogen sulfide adsorbent, similar to the first adhesive layer. The type and content of the hydrogen sulfide adsorbent may be the same as those of the first adhesive layer.

[0057] The thickness of the second adhesive layer 15 is preferably 1 to 5 μm. A thickness of 1 μm or more in the second adhesive layer 15 makes it easier to obtain sufficient adhesive strength between the metal foil layer 13 and the sealant layer 16. A thickness of 5 μm or less in the second adhesive layer 15 tends to suppress the occurrence of cracks in the second adhesive layer 15.

[0058] The second adhesive layer 15 is obtained in the same manner as the first adhesive layer 12.

[0059] <Metal foil layer 13> The metal foil layer 13 has water vapor barrier properties that prevent moisture from entering the interior of the energy storage device. The metal foil layer 13 may also have ductility for deep drawing. As the metal foil layer 13, various metal foils such as aluminum, stainless steel, and copper can be used. These can be used individually or in combination of two or more. Aluminum foil is preferred as the metal foil layer 13 from the viewpoints of mass (specific gravity), moisture resistance, processability, and cost.

[0060] As for the aluminum foil, soft aluminum foil that has undergone annealing treatment is particularly preferred because it can provide the desired ductility during molding. However, it is even more preferable to use aluminum foil containing iron in order to provide further pinhole resistance and ductility during molding. The iron content in the aluminum foil is preferably 0.1 to 9.0% by mass, and more preferably 0.5 to 2.0% by mass, of 100% by mass of aluminum foil (for example, aluminum foil made of JIS standard 8021 material or 8079 material). By having an iron content of 0.1% by mass or more, an exterior material 10 with better pinhole resistance and ductility can be obtained. By having an iron content of 9.0% by mass or less, an exterior material 10 with better flexibility can be obtained.

[0061] The metal foil used in the metal foil layer 13 is preferably degreased, for example, in order to obtain the desired electrolyte resistance. Furthermore, in order to simplify the manufacturing process, it is preferable that the metal foil used is one whose surface is not etched. In particular, for the metal foil used in the metal foil layer 13, it is preferable to use aluminum foil that has been degreased in order to impart electrolyte resistance. When degreasing aluminum foil, the degreasing treatment may be applied to only one side of the aluminum foil, or to both sides. As for the degreasing treatment, for example, a wet type degreasing treatment or a dry type degreasing treatment can be used, but from the viewpoint of simplifying the manufacturing process, a dry type degreasing treatment is preferred.

[0062] One example of the dry-type degreasing treatment described above is a method in which degreasing is performed by extending the processing time during the annealing process of metal foil. Sufficient electrolyte resistance can be obtained even with a degreasing treatment performed simultaneously with the annealing process, which is carried out to soften the metal foil.

[0063] Furthermore, as the dry-type degreasing treatment described above, treatments other than the annealing treatment, such as flame treatment and corona treatment, may also be used. In addition, as the dry-type degreasing treatment described above, for example, a degreasing treatment may be used in which contaminants are oxidized, decomposed, and removed by reactive oxygen species generated when a metal foil is irradiated with ultraviolet light of a specific wavelength.

[0064] As the wet-type degreasing treatment described above, for example, treatments such as acid degreasing and alkaline degreasing can be used. As the acid used in the acid degreasing treatment, for example, inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid, and hydrofluoric acid can be used. These acids may be used individually or in combination of two or more. As the alkali used in the alkaline degreasing treatment, for example, sodium hydroxide, which has a high etching effect, can be used. Alternatively, alkaline degreasing treatment may be performed using a material containing a weakly alkaline material and a surfactant. The wet-type degreasing treatment described above can be carried out by, for example, immersion or spraying.

[0065] The thickness of the metal foil layer 13 is preferably 9 to 200 μm, more preferably 15 to 150 μm, and even more preferably 15 to 100 μm, from the viewpoint of barrier properties, pinhole resistance, and processability. A thickness of 9 μm or more in the metal foil layer 13 makes it less likely to break even when stress is applied during molding. A thickness of 200 μm or less in the metal foil layer 13 reduces the mass increase of the exterior material and suppresses the decrease in the weight energy density of the energy storage device.

[0066] <Corrosion-preventive treatment layer 14a, 14b> The corrosion-preventive treatment layers 14a and 14b are layers provided on the surface of the metal foil layer 13 to prevent corrosion of the metal foil layer 13. Furthermore, corrosion-preventive treatment layer 14a plays a role in increasing the adhesion between the metal foil layer 13 and the first adhesive layer 12. Similarly, corrosion-preventive treatment layer 14b plays a role in increasing the adhesion between the metal foil layer 13 and the second adhesive layer 15. The corrosion-preventive treatment layers 14a and 14b may be layers with the same composition or layers with different compositions.

[0067] The corrosion-preventive treatment layers 14a and 14b can be formed, for example, by performing a coating-type corrosion prevention treatment on the base material layer of the corrosion-preventive treatment layers 14a and 14b, which includes degreasing, hot water modification, anodizing, chemical conversion, and application of a coating agent having corrosion-preventive properties, or a combination of these treatments.

[0068] Of the processes described above, degreasing, hydrothermal modification, and anodizing, particularly hydrothermal modification and anodizing, are processes that dissolve the surface of the metal foil (aluminum foil) with a treatment agent to form a metal compound (aluminum compound (boehmite, anodized aluminum)) with excellent corrosion resistance. For this reason, such processes are sometimes included in the definition of chemical conversion treatment in order to obtain a structure in which a co-continuous structure is formed from the metal foil layer 13 to the corrosion prevention treatment layers 14a and 14b.

[0069] Degreasing treatments include acid degreasing and alkaline degreasing. Acid degreasing can be achieved by using an acid degreasing agent obtained by using an inorganic acid such as sulfuric acid, nitric acid, hydrochloric acid, and hydrofluoric acid, either individually or in combination thereof. Furthermore, by using an acid degreasing agent obtained by dissolving a fluorine-containing compound such as monosodium ammonium difluoride in the above inorganic acid, it is possible not only to degrease the metal foil layer 13 but also to form a fluoride of the passive metal, which is effective in terms of hydrofluoric acid resistance. Alkaline degreasing can be achieved by using sodium hydroxide, etc.

[0070] As the above-mentioned hydrothermal modification treatment, for example, a boehmite treatment obtained by immersing the metal foil layer 13 in boiling water to which triethanolamine has been added can be used. As the above-mentioned anodic oxidation treatment, for example, anodizing treatment can be used. Furthermore, as the above-mentioned chemical conversion treatment, for example, chromate treatment, zirconium treatment, titanium treatment, vanadium treatment, molybdenum treatment, calcium phosphate treatment, strontium hydroxide treatment, cerium treatment, ruthenium treatment, or a combination of two or more of these can be used. It is preferable to perform the above-mentioned degreasing treatment in advance of these hydrothermal modification treatments, anodic oxidation treatments, and chemical conversion treatments.

[0071] Furthermore, the above chemical conversion treatment is not limited to a wet method; for example, a method in which the treatment agent used in these treatments is mixed with the resin component and applied may also be used. In addition, as the above corrosion prevention treatment, a coating-type chromate treatment is preferred from the viewpoint of maximizing its effect and wastewater treatment.

[0072] Coating agents used in coating-type corrosion prevention treatments include those containing at least one selected from the group consisting of rare earth element oxide sols, anionic polymers, and cationic polymers. In particular, a method using a coating agent containing a rare earth element oxide sol is preferred.

[0073] The mass per unit area of ​​corrosion-preventive treatment layers 14a and 14b is 0.005 to 0.200 g / m². 2 Preferably within the range of 0.010 to 0.100 g / m². 2 A range within this range is more preferable. 0.005 g / m 2 If the above is true, it is easier to impart corrosion prevention functionality to the metal foil layer 13. Also, the above mass per unit area is 0.200 g / m². 2 Beyond this point, the corrosion prevention function saturates and no further effect can be expected. Note that the above description uses mass per unit area, but if the specific gravity is known, it is also possible to convert the thickness from that.

[0074] The thickness of the corrosion-preventive treatment layers 14a and 14b is preferably, for example, 10 nm to 5 μm, and more preferably 20 to 500 nm, from the viewpoint of corrosion prevention function and anchor function.

[0075] <Sealant layer 16> The sealant layer 16 is a layer that provides heat sealing properties to the exterior material 10, and is placed on the inside and heat-sealed (heat-fused) during the assembly of the energy storage device.

[0076] Examples of sealant layers 16 include films made of acrylic resin, polyolefin resin, or polyester resin. Since the sealant layer 16 has a high melting point, which further improves the heat resistance of the resulting exterior material, films made of polyolefin resin or polyester resin are preferred, and films made of polyester resin are more preferred.

[0077] Examples of acrylic resins include polymethyl methacrylate (PMMA). These acrylic resins may be used individually or in combination of two or more types.

[0078] Examples of polyolefin resins include low-density, medium-density, and high-density polyethylene; ethylene-α-olefin copolymers; polypropylene; and propylene-α-olefin copolymers. When polyolefin resins are copolymers, they may be block copolymers or random copolymers.

[0079] Examples of polyester resins include polyethylene terephthalate (PET) and polybutylene terephthalate (PBT). These polyester resins may be used individually or in combination of two or more types.

[0080] The sealant layer 16 may be a single-layer film or a multi-layer film, and can be selected according to the required function. If the sealant layer 16 has a multi-layer structure, each layer may be laminated by co-extrusion or by dry lamination.

[0081] The sealant layer 16 may contain various additives such as flame retardants, slip agents, antiblocking agents, antioxidants, light stabilizers, and tackifiers.

[0082] The thickness of the sealant layer 16 is preferably 10 to 100 μm, and more preferably 20 to 60 μm. A thickness of 10 μm or more of the sealant layer 16 provides sufficient heat seal strength, while a thickness of 100 μm or less reduces the amount of water vapor that penetrates from the edges of the exterior material.

[0083] The melting peak temperature of the sealant layer 16 is preferably 200 to 280°C, as this further improves its heat resistance.

[0084] The exterior material 10 can be suitably used as an exterior material for secondary batteries such as lithium-ion batteries, nickel-metal hydride batteries, and lead-acid batteries, as well as for energy storage devices such as electrochemical capacitors such as electric double-layer capacitors. In particular, the exterior material 10 has excellent heat resistance and excellent moisture barrier properties even in high-temperature environments, making it suitable as an exterior material for all-solid-state batteries using solid electrolytes that are expected to be used in such environments.

[0085] Although preferred embodiments of the exterior material for energy storage devices of this embodiment have been described in detail above, this disclosure is not limited to such specific embodiments, and various modifications and changes are possible within the scope of the gist of this disclosure as described in the claims.

[0086] For example, Figure 1 shows a case where corrosion-preventive treatment layers 14a and 14b are provided on both sides of the metal foil layer 13, but only one of the corrosion-preventive treatment layers 14a and 14b may be provided, or no corrosion-preventive treatment layer may be provided at all.

[0087] [Manufacturing method for exterior materials] Next, the manufacturing method of the exterior material 10 will be described. However, the manufacturing method of the exterior material 10 is not limited to the following method.

[0088] As a method for manufacturing the exterior material 10, for example, one method is to carry out the following steps S11 to S13 in this order. Step S11: A step of forming a corrosion-preventive treatment layer 14a on one surface of the metal foil layer 13 and a corrosion-preventive treatment layer 14b on the other surface of the metal foil layer 13. Step S12: A step of bonding the side of the corrosion-preventive treatment layer 14a opposite to the metal foil layer 13 and the base material layer 11 via the first adhesive layer 12. Step S13: A step of forming a sealant layer 16 on the surface of the corrosion-preventive treatment layer 14b opposite to the metal foil layer 13 via a second adhesive layer 15.

[0089] <Process S11> In step S11, a corrosion-preventive treatment layer 14a is formed on one surface of the metal foil layer 13, and a corrosion-preventive treatment layer 14b is formed on the other surface of the metal foil layer 13. The corrosion-preventive treatment layers 14a and 14b may be formed separately, or both may be formed at the same time. Specifically, for example, a corrosion-preventive treatment agent (base material for the corrosion-preventive treatment layer) is applied to both surfaces of the metal foil layer 13, and then drying, curing, and baking are performed sequentially to form the corrosion-preventive treatment layers 14a and 14b at the same time. Alternatively, a corrosion-preventive treatment agent may be applied to one surface of the metal foil layer 13, followed by drying, curing, and baking to form the corrosion-preventive treatment layer 14a, and then the corrosion-preventive treatment layer 14b may be formed on the other surface of the metal foil layer 13 in the same manner. The order in which the corrosion-preventive treatment layers 14a and 14b are formed is not particularly limited. Furthermore, different corrosion-preventive treatment agents may be used for the corrosion-preventive treatment layer 14a and the corrosion-preventive treatment layer 14b, or the same agent may be used. The method of applying the corrosion-preventive treatment agent is not particularly limited, but for example, methods such as gravure coating, gravure reverse coating, roll coating, reverse roll coating, die coating, bar coating, kiss coating, comma coating, and small-diameter gravure coating can be used.

[0090] <Process S12> In step S12, the side of the corrosion-preventive treatment layer 14a opposite to the metal foil layer 13 and the base material layer 11 are bonded together using an adhesive that forms the first adhesive layer 12, by a method such as dry lamination. In step S12, heat treatment may be performed to promote the adhesion of the first adhesive layer 12. The temperature during heat treatment is preferably 140°C or lower, as the exterior material has excellent resistance to molding curl.

[0091] <Process S13> After step S12, the side of the corrosion-preventive treatment layer 14b opposite to the metal foil layer 13 of the laminate, which is formed by laminating the base layer 11, the first adhesive layer 12, the corrosion-preventive treatment layer 14a, the metal foil layer 13, and the corrosion-preventive treatment layer 14b in this order, and the sealant layer 16 are bonded together using an adhesive that forms the second adhesive layer 15, by a method such as dry lamination. In step S13, heat treatment may be performed to promote the adhesion of the second adhesive layer 15. The temperature during heat treatment is preferably 140°C or lower, and more preferably 120°C or lower, because the exterior material has excellent resistance to molding curl.

[0092] The exterior material 10 is obtained through the processes S11 to S13 described above. However, the order of the processes for manufacturing the exterior material 10 is not limited to performing the above processes S11 to S13 in order. For example, the order of the processes may be changed as appropriate, such as performing process S12 before process S11.

[0093] [Energy storage devices] Figure 3 is a perspective view showing one embodiment of an energy storage device fabricated using the exterior material described above. As shown in Figure 3, the energy storage device 50 is composed of a battery element (energy storage device body) 52 including electrodes, two metal terminals (leads, current extraction terminals) 53 extending from the electrodes for extracting current from the battery element 52 to the outside, and an exterior material 10 that encloses the battery element 52 in an airtight state. The exterior material 10 is the exterior material 10 according to the embodiment described above and is used as a container for housing the battery element 52. In the exterior material 10, the base material layer 11 is the outermost layer and the sealant layer 16 is the innermost layer. That is, the exterior material 10 is constructed to enclose the battery element 52 inside by folding one laminate film in half and heat-sealing the periphery, or by overlapping two laminate films and heat-sealing the periphery, so that the base material layer 11 is on the outside side of the energy storage device 50 and the sealant layer 16 is on the inside side of the energy storage device 50. The metal terminal 53 is sandwiched and sealed by the outer material 10 that forms the container with the sealant layer 16 on the inside. The metal terminal 53 may also be sandwiched by the outer material 10 via a tab sealant.

[0094] The battery element 52 has an electrolyte interposed between the positive electrode and the negative electrode. The metal terminal 53 is a part of the current collector that is exposed to the outside of the outer casing material 10, and is made of metal foil such as copper foil or aluminum foil.

[0095] The energy storage device 50 of this embodiment may be an all-solid-state battery. In this case, a solid electrolyte such as a sulfide-based solid electrolyte is used as the electrolyte of the battery element 52. Because the energy storage device 50 of this embodiment uses the exterior material 10 of this embodiment, it can ensure excellent lamination strength, seal strength, and moisture barrier properties even when used in a high-temperature environment (for example, 150°C). [Examples]

[0096] The present disclosure will be described below in detail based on examples, but the present disclosure is not limited to these examples.

[0097] <Substrate layer (thickness 25 μm)> A polyethylene terephthalate film with one side treated with corona was used.

[0098] <First adhesive layer (thickness 4μm)> As the material for the first adhesive layer, a urethane resin (manufactured by Mitsui Chemicals, product name "Main component: Takelac A-515 (solid content concentration 50% by mass), curing agent: Takenate D-140 (solid content concentration 74% by mass)") was prepared. These materials were mixed in a ratio of 30 parts by mass of curing agent to 100 parts by mass of main component, and diluted with ethyl acetate to a solid content concentration of 30% by mass, and used as the adhesive.

[0099] <First corrosion-preventive treatment layer (substrate layer side) and second corrosion-preventive treatment layer (sealant layer side)> (CL-1): A "sodium polyphosphate stabilized cerium oxide sol" was used, which was prepared by adjusting the solid content to 10% by mass using distilled water as the solvent. The sodium polyphosphate stabilized cerium oxide sol was obtained by mixing 10 parts by mass of sodium phosphoric acid with 100 parts by mass of cerium oxide. (CL-2): A composition consisting of 90% by mass of "polyallylamine (manufactured by Nitto Boseki Co., Ltd.)" and 10% by mass of "polyglycerol polyglycidyl ether (manufactured by Nagase ChemteX Corporation)" was used, adjusted to a solid content concentration of 5% by mass using distilled water as a solvent.

[0100] <Second adhesive layer (thickness 3μm)> An adhesive was used, which was a mixture of the main component and polyfunctional isocyanate compound listed in Table 1 and carbodiimide in the proportions shown in Table 1. Toluene was appropriately added to the adhesive so that the non-volatile content was 15% by mass. Details of the main component and polyfunctional isocyanate compound and carbodiimide listed in Table 1 are as follows.

[0101] {Main ingredient} • Acid-modified polyolefin (percentage of non-volatile content: 30% by mass, hydroxyl value: 40KOH mg / g, manufactured by Riken Vitamin Co., Ltd., grade name: "Rikeaid MG-400EM") • Polyacrylic polyol (non-volatile content: 50% by mass, hydroxyl value: 10-20 KOH mg / g, functional group equivalent: 5610 g / mol, manufactured by Mitsubishi Rayon Co., Ltd., grade name: "LR209")

[0102] {Polyfunctional isocyanate compounds} • HDI-type (Hexamethylene diisocyanate adduct, non-volatile content: 50% by mass, NCO content: 18.7% by mass, functional group equivalent: 225 g / mol, manufactured by Asahi Kasei Corporation, grade name: "E402-80B") • TDI type (toluene diisocyanate-adduct, non-volatile content: 50% by mass, NCO content: 17.7% by mass, functional group equivalent: 237 g / mol, manufactured by Nippon Polyurethane Industry Co., Ltd., grade name: "Coronate L") • IPDI series (isophorone diisocyanate adduct, non-volatile content: 74.6% by mass, NCO content: 10.3% by mass, functional group equivalent: 408 g / mol, manufactured by Mitsui Chemicals, Inc., grade name: "D-140N")

[0103] {Carbodiimide} For the carbodiimide used, we used "V-07" (grade name, non-volatile content of 50% by mass) manufactured by Nisshinbo Chemical Co., Ltd.

[0104] <Metal foil layer (thickness 35 μm)> We prepared annealed and degreased soft aluminum foil (manufactured by Toyo Aluminum Co., Ltd., "8079 material").

[0105] <Sealant layer (thickness 40-70 μm)> The materials listed in Table 1 were used. Details of the materials listed in Table 1 are as follows: • Acrylic resin film (manufactured by Okura Industries Co., Ltd., product name "OXIS-PMMA") • Polyester film (manufactured by Toyobo Co., Ltd., product name "Oriester DE046") • PP film (polypropylene film, manufactured by Idemitsu Kosan Co., Ltd., product name "Unilux RT-680CA")

[0106] [Manufacturing of exterior materials] <Examples 1-5 and Comparative Examples 1-3> The metal foil layer was bonded to the substrate layer using an adhesive (first adhesive layer) via a dry lamination method, and aged at 80°C for 120 hours. Next, a sealant layer was bonded to the side of the metal foil layer opposite to the side to which the first adhesive layer was bonded, using an adhesive (second adhesive layer) via a dry lamination method, and aged at 60°C for 120 hours.

[0107] The laminate obtained in this way was heat-treated to produce an exterior material (base layer / first adhesive layer / metal foil layer / second adhesive layer / sealant layer).

[0108] <Examples 6-9> First, the metal foil layer was coated with a first and second corrosion-preventive treatment layer using the following procedure. Specifically, (CL-1) was applied to both surfaces of the metal foil layer at a dry coating rate of 70 mg / m². 2 The material was coated using microgravure coating and then baked in a drying unit at 200°C. Next, (CL-2) was applied to the resulting layer at a dry coating rate of 20 mg / m². 2By applying a microgravure coating in this manner, a composite layer consisting of (CL-1) and (CL-2) was formed as the first and second corrosion-preventive treatment layers. This composite layer exhibits corrosion-preventive performance by combining the two types, (CL-1) and (CL-2).

[0109] Except for using metal foil layers provided with the first and second corrosion-preventive treatment layers, the exterior material (base layer / first adhesive layer / first corrosion-preventive treatment layer / metal foil layer / second corrosion-preventive treatment layer / second adhesive layer / sealant layer) was manufactured in the same manner as in Example 1.

[0110] [Evaluation of exterior materials] <Examples 1-9 and Comparative Examples 1, 2> {Measurement of infrared absorption spectral peak} The exterior material was cut, and the sealant layer was separated from the metal foil layer, or from the sealant layer to the corrosion-preventive treatment layer. The infrared absorption spectrum peak was measured on the outermost surface of the second adhesive layer exposed by the separation using Attenuated Total Reflection (ATR) spectroscopy. X, defined by the following equation (2), was calculated from the intensity in the infrared absorption spectrum. The results are shown in Table 2. X = {(C+D)-B} / A …(2) [In the formula, A to D are intensities in the infrared absorption spectrum of the second adhesive layer measured by infrared spectroscopy, where A is wavenumber 3040 to 2760 cm⁻¹. -1 This indicates the maximum intensity, and B corresponds to wavenumbers of 1850-1780 cm. -1 This indicates the maximum intensity, and C corresponds to wavenumbers of 1760-1600 cm. -1 This indicates the maximum intensity, where D corresponds to wavenumbers 2150-2090 cm². -1 This indicates the maximum intensity.

[0111] Details of the measuring equipment and conditions are as follows: (Measurement equipment and conditions) Measurement device: Spectrum Spotlight 400 (product name, manufactured by PerkinElmer) Prism: Germanium Wavenumber resolution: 4cm -1 Total number of times: 4 Baseline: Wavelength 2400~2600cm -1 The straight section in between

[0112] [Evaluation of Lamination Strength] (Lamination strength at 80°C) Exterior material cut to a width of 15 mm was left in a high-temperature environment of 80°C for 5 minutes. Subsequently, the laminate strength between the metal foil layer and the sealant layer of the exterior material at 80°C was measured using a tensile testing machine (manufactured by Shimadzu Corporation) at a tensile speed of 50 mm / min by a 90-degree peel test. The obtained laminate strength was then evaluated according to the following criteria. The results are shown in Table 2. A: Lamination strength of 2.5N / 15mm or higher B: Lamination strength of 2.0N / 15mm or more and less than 2.5mm C: Lamination strength of 1.5N / 15mm or more and less than 2.0mm D: Lamination strength less than 1.5N / 15mm

[0113] (Lamination strength at 150°C) Except for setting the exterior material at a temperature of 150°C and performing the 90°C peel test at 150°C, the laminate strength under 150°C was measured in the same manner as under 80°C, and the obtained laminate strength was evaluated. The results are shown in Table 2.

[0114] (Laminate strength after hydrogen sulfide exposure) Exterior material cut to a width of 15 mm was left for one week in an environment with a hydrogen sulfide concentration of 20 ppm and a temperature of 100°C. Subsequently, the laminate strength between the metal foil layer and the sealant layer of the exterior material at a temperature of 150°C was measured using a tensile testing machine (manufactured by Shimadzu Corporation) at a tensile speed of 50 mm / min by a 90-degree peel test. The obtained laminate strength was evaluated using the same criteria as the laminate strength at a temperature of 80°C. The results are shown in Table 2.

[0115] [Evaluation of heat-resistant seal strength] The exterior material was cut to a size of 120 mm x 60 mm and folded in half so that the sealant layer was on the inside. Next, the end opposite the folded part was heat-sealed to a width of 10 mm at 220°C / 0.5 MPa / 3 seconds and stored at room temperature for 6 hours. After that, a sample for heat seal strength measurement was prepared by cutting out a 15 mm wide x 300 mm long section from the longitudinal center of the heat-sealed area. This sample was left in a test environment of 150°C for 5 minutes, and then a T-shaped peel test was performed on the heat-sealed part of the sample using a tensile testing machine (manufactured by Shimadzu Corporation) at a tensile speed of 50 mm / min. Based on the obtained heat seal strength, evaluation was performed according to the following criteria. The results are shown in Table 2. A: Heat seal strength of 15N / 15mm or more B: Heat seal strength of 10N / 15mm or more, and less than 15N / 15mm. C: Heat seal strength of 5N / 15mm or more, and less than 10N / 15mm. D: Heat seal strength less than 5N / 15mm

[0116] [Evaluation of moisture barrier properties] Two 120mm x 110mm outer materials were overlapped so that the sealant layers faced each other, and folded to an outer dimension of 120mm x 55mm. Next, both edges were heat-sealed to a width of 10mm at 220°C / 0.5MPa / 3 seconds to create a bag with one side open. Then, 3mL of dehydrated ethylene glycol was injected into the contents, and the remaining side was heat-sealed to a width of 3mm. The 10mm sealed portion was considered to have almost no moisture permeability, and the 3mm sealed portion was used as the measurement target. The prepared battery container was stored in an environment of 120°C and 90%RH for 4 weeks, and the amount of moisture contained in the ethylene glycol after storage was measured using a Karl Fischer meter to measure the moisture permeability. Based on the obtained moisture permeability, evaluation was performed according to the following criteria. The results are shown in Table 2. A: Water permeability is 250 ppm or less B: Water permeability is between 250 ppm and 300 ppm. C: Moisture permeability is more than 300ppm and less than 350ppm D: Water permeability exceeding 350 ppm

[0117] [comprehensive evaluation] The exterior materials were comprehensively evaluated according to the following criteria. The total value for each evaluation is the sum of the evaluation criteria "A," "B," "C," and "D" for laminate strength, heat-resistant seal strength, and moisture barrier properties, with "A," "B," "C," and "D" assigned scores of 3, 2, 1, and 0 points respectively. The results are shown in Table 2. A: If the total score of each evaluation is 13 points or more. B: If the sum of all evaluations is between 9 and 12 points. However, this excludes cases where there is at least one D rank. C: When the sum of all evaluations is between 5 and 8 points. However, this excludes cases where there is at least one D rank. D: If there is one or more D ranks in each evaluation.

[0118] [Table 1]

[0119] [Table 2]

[0120] The gist of this disclosure is found in the following [1] to [9]. [1] An exterior material for an energy storage device, A base layer and The first adhesive layer, A metal foil layer, The second adhesive layer, The sealant layer, It has a layered structure that includes these elements in this order, The second adhesive layer comprises at least a reaction product of an acid-modified polyolefin and a polyfunctional isocyanate compound. An exterior material in which the second adhesive layer satisfies the condition expressed by the inequality (1) below. 0.01≦{(C+D)-B} / A≦0.60 …(1) [In the formula, A to D are intensities in the infrared absorption spectrum of the second adhesive layer measured by infrared spectroscopy, where A is wavenumber 3040 to 2760 cm⁻¹. -1This indicates the maximum intensity, and B corresponds to wavenumbers of 1850-1780 cm. -1 This indicates the maximum intensity, and C corresponds to wavenumbers of 1760-1600 cm. -1 This indicates the maximum intensity, where D corresponds to wavenumbers 2150-2090 cm². -1 This indicates the maximum intensity. [2] The exterior material according to [1], wherein the polyfunctional isocyanate compound comprises at least one selected from the group consisting of aliphatic polyfunctional isocyanate compounds and polyfunctional isocyanate compounds containing an aromatic ring. [3] The exterior material according to [1] or [2], further comprising a corrosion-preventive treatment layer between the first adhesive layer and the metal foil layer, and between the second adhesive layer and the metal foil layer, or both. [4] The exterior material according to any one of [1] to [3], wherein the sealant layer comprises at least one of polyolefin resins and polyester resins. [5] An exterior material according to any one of [1] to [4], wherein at least one of the first adhesive layer and the second adhesive layer contains a hydrogen sulfide adsorbent. [6] The exterior material according to any one of [1] to [5], wherein the second adhesive layer further comprises a carbodiimide compound. [7] An outer covering material for all-solid-state batteries, as described in any of [1] to [6]. [8] The main body of the energy storage device, Current extraction terminals extending from the main body of the energy storage device, An exterior material, as described in any of [1] to [7], which clamps the current extraction terminals and houses the main body of the energy storage device, A power storage device equipped with the following features. [9] The energy storage device described in [8], which is an all-solid-state battery. [Explanation of Symbols]

[0121] 10...Exterior material (exterior material for energy storage device), 11...Base layer (outer layer), 12...First adhesive layer, 13...Metal foil layer, 14a,14b...Corrosion prevention treatment layer, 15...Second adhesive layer, 16...Sealant layer, 50...Energy storage device.

Claims

1. Exterior material for energy storage devices, A base layer and The first adhesive layer, A metal foil layer, The second adhesive layer, The sealant layer, It has a layered structure that includes these elements in this order, The second adhesive layer comprises at least a reaction product of an acid-modified polyolefin and a polyfunctional isocyanate compound, An exterior material wherein the second adhesive layer satisfies the conditions expressed by the following formula (1). 0.01≦{(C+D)-B} / A≦0.60…(1) [In the formula, A to D are intensities in the infrared absorption spectrum of the second adhesive layer measured by infrared spectroscopy, where A is a wavenumber of 3040 to 2760 cm² derived from the olefin structure of the reactant.] －１ The maximum intensity of the absorption peak is shown, and B is the wavenumber 1850-1780 cm, which originates from the maleic anhydride structure of the reactant. －１ The maximum intensity of the absorption peak is shown, and C is derived from the urethane bond in the reactant at wavenumbers 1760-1600 cm². －１ The maximum intensity of the absorption peak is shown, and D is derived from the carbodiimide compound at wavenumbers 2150–2090 cm⁻¹. －１ This shows the maximum intensity of the absorption peak.

2. The exterior material according to claim 1, wherein the polyfunctional isocyanate compound comprises at least one selected from the group consisting of aliphatic polyfunctional isocyanate compounds and polyfunctional isocyanate compounds containing an aromatic ring.

3. The exterior material according to claim 1 or 2, further comprising a corrosion-preventive treatment layer between the first adhesive layer and the metal foil layer, and between the second adhesive layer and the metal foil layer, or both thereof.

4. The exterior material according to claim 1 or 2, wherein the sealant layer comprises at least one of a polyolefin resin and a polyester resin.

5. The exterior material according to claim 1 or 2, wherein at least one of the first adhesive layer and the second adhesive layer contains a hydrogen sulfide adsorbent.

6. The exterior material according to claim 1 or 2, wherein the second adhesive layer further comprises a carbodiimide compound.

7. The exterior material according to claim 1 or 2, for use with all-solid-state batteries.

8. The main unit of the energy storage device, A current extraction terminal extending from the main body of the energy storage device, An exterior material according to claim 1 or 2, which clamps the current extraction terminal and houses the main body of the energy storage device, A power storage device equipped with the following features.

9. The energy storage device according to claim 8, which is an all-solid-state battery.

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