WO2020230632A1 - Sulfide-based fully solid battery laminated sheet and laminated pack using same - Google Patents

Sulfide-based fully solid battery laminated sheet and laminated pack using same Download PDF

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Publication number
WO2020230632A1
WO2020230632A1 PCT/JP2020/018182 JP2020018182W WO2020230632A1 WO 2020230632 A1 WO2020230632 A1 WO 2020230632A1 JP 2020018182 W JP2020018182 W JP 2020018182W WO 2020230632 A1 WO2020230632 A1 WO 2020230632A1
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WIPO (PCT)
Prior art keywords
layer
sulfide
laminated
laminate
absorption layer
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PCT/JP2020/018182
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French (fr)
Japanese (ja)
Inventor
篤史 安田
直美 関谷
周 加藤
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共同印刷株式会社
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Application filed by 共同印刷株式会社 filed Critical 共同印刷株式会社
Priority to CN202080032993.4A priority Critical patent/CN113784835A/en
Publication of WO2020230632A1 publication Critical patent/WO2020230632A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
    • H01M50/102—Primary casings, jackets or wrappings of a single cell or a single battery characterised by their shape or physical structure
    • H01M50/105—Pouches or flexible bags
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a sulfide-based all-solid-state battery laminate sheet and a laminate pack using the same.
  • an all-solid-state battery in which the electrolyte is changed to a solid electrolyte layer and the battery is completely solidified does not use a flammable organic solvent in the battery, so that the safety device can be simplified and the manufacturing cost and productivity can be improved. It is considered excellent.
  • a sulfide-based all-solid-state battery using a sulfide-based solid electrolyte as a solid electrolyte is attracting attention, particularly from the viewpoint of improving the output current.
  • Patent Document 1 in an all-solid lithium secondary battery using a sulfide-based solid electrolyte material, at least the electrolyte-containing layer containing the sulfide-based solid electrolyte material and the outside air
  • An all-solid-state lithium secondary characterized by having an oxide layer-containing power generating element in which an oxide layer formed by oxidizing the sulfide-based solid electrolyte material, which is substantially free of water, is formed at a site where the sulfide-based solid electrolyte material comes into contact with the material. Batteries are disclosed.
  • the sealing port on the side surface of the laminate pack containing the sulfide-based all-solid-state battery For example, when water or the like has entered the laminate pack when the sulfide-based all-solid-state battery is stored in the laminate pack, or the sealing port on the side surface of the laminate pack containing the sulfide-based all-solid-state battery. If external moisture etc. invades from the pinhole, or a pinhole is generated in the laminate pack containing the sulfide-based all-solid-state battery, moisture etc. invades into the laminate pack from the pinhole. In some cases, such as when water has penetrated into the laminate pack, the water may react with the sulfide-based solid electrolyte.
  • the present inventors adsorb and retain the water content of the sulfide-based gas absorber itself, thereby releasing the water content retained by the sulfide-based gas absorber, and in some situations. , It has been found that water is given to the sulfide-based solid electrolyte, and as a result, further sulfide-based gas may be generated.
  • an object of the present invention is to provide a sulfide-based all-solid-state battery laminate sheet capable of suppressing the generation of sulfide-based gas and a laminate pack using the same. ..
  • ⁇ Aspect 8> The laminate sheet according to any one of aspects 1 to 7, wherein the hygroscopic agent contains at least one selected from the group consisting of zeolite, calcium oxide, magnesium sulfate, silica gel, calcium chloride, quicklime, and aluminum oxide. .. ⁇ Aspect 9>
  • the sulfide-based gas absorber comprises at least one selected from the group consisting of copper, cobalt, manganese, iron, nickel, zinc, silver, calcium, and titanium, according to any one of aspects 2 to 8. Described laminated sheet.
  • ⁇ Aspect 10> The laminated sheet according to any one of aspects 1 to 9 is provided, and the laminated sheet is bent with the inner side surface facing inward so that the peripheral edges of the inner side surface are brought together.
  • Laminate pack for sulfide-based all-solid-state batteries It is made into a bag by heat sealing, Laminate pack for sulfide-based all-solid-state batteries.
  • Aspect 11> The laminated sheet according to any one of aspects 1 to 9 as the A-side laminated sheet, and the B-side barrier layer and B, which are laminated in this order from the outer side surface to the inner side surface.
  • a B-side laminated sheet having a surface sealant layer is provided, and the internal side surface of the A-side laminated sheet and the B-side sealant layer face each other to face the internal side.
  • the peripheral edges of the surface and the B-side sealant layer are heat-sealed to form a bag.
  • Laminate pack for sulfide-based all-solid-state batteries are heat sealing, Laminate pack for sulfide-based all-solid-state batteries.
  • ⁇ Aspect 12> Two or more of the laminated sheets according to any one of aspects 1 to 9 are provided, and the inner side surfaces face each other, and the peripheral edges of the inner side surfaces are heat-sealed.
  • Laminate pack for sulfide-based all-solid-state batteries By being made into a bag, Laminate pack for sulfide-based all-solid-state batteries.
  • Laminate pack for sulfide-based all-solid-state batteries By being made into a bag, Laminate pack for sulfide-based all-solid-state batteries.
  • ⁇ Aspect 13> A laminated battery comprising the sulfide-based all-solid-state battery laminate pack according to any one of aspects 10 to 12 and a sulfide-based all-solid-state battery.
  • a sulfide-based all-solid-state battery laminate sheet capable of suppressing the generation of sulfide-based gas and a laminate pack using the same.
  • FIG. 1 is a schematic view showing one form of a layer structure of the laminated sheet for a sulfide-based all-solid-state battery of the present invention.
  • FIG. 2 is a schematic view showing the morphology of the absorption layer when the absorption layer has a multi-layer structure.
  • FIG. 3 is a schematic view showing the morphology of the A side and the B side of the laminate pack of the present invention.
  • the sulfide-based all-solid-state battery laminate sheet of the present invention has a barrier layer and an absorption layer containing a hygroscopic agent, which are laminated in this order from the outer side surface to the inner side surface.
  • laminated sheet for sulfide-based all-solid-state battery of the present invention is also simply referred to as “laminated sheet of the present invention” or “laminated sheet”.
  • the "outside surface” is a surface that is used facing the outside of the laminate pack when the sulfide-based all-solid-state battery is housed in the laminate pack formed from the laminate sheet.
  • the “internal side surface” is a surface that is used toward the sulfide-based all-solid-state battery inside the laminate pack when the sulfide-based all-solid-state battery is housed in the laminate pack formed from the laminate sheet. is there.
  • FIG. 1 is a schematic view showing one form of a layer structure of the laminated sheet for a sulfide-based all-solid-state battery of the present invention.
  • the laminate sheet 100 of the present invention has a barrier layer 10 and an absorption layer 11 containing a hygroscopic agent, which are laminated in this order from the outer side surface to the inner side surface.
  • a barrier layer 10 and an absorption layer 11 containing a hygroscopic agent which are laminated in this order from the outer side surface to the inner side surface.
  • the present invention focuses on moisture, which is the root cause of sulfide-based gas generation, and includes an absorption layer containing a hygroscopic agent, so that the inside of a laminate pack containing a sulfide-based all-solid-state battery is contained. It absorbs and removes water. That is, according to the laminate sheet of the present invention, it is possible not only to prevent the intrusion of moisture from the outside to the inside of the laminate pack, but also to remove the moisture that has invaded the inside of the laminate pack.
  • the barrier layer is a layer for preventing the permeation of gas such as water and water vapor, particularly the invasion of water vapor from the outside to the inside of the laminate pack.
  • the barrier layer is not particularly limited and may include, for example, at least one selected from the group consisting of a metal foil and a vapor-deposited film of a metal or a metal oxide. More specifically, the barrier layer is made of an organic coating film such as an aluminum foil, an alloy aluminum foil, an aluminum vapor deposition film, a silica vapor deposition film, an alumina vapor deposition film, a silica-alumina dual vapor deposition film, and a polyvinylidene fluoride coating film. It may contain at least one selected from the group. Further, from the viewpoint of facilitating both barrier property and handleability, the barrier layer preferably contains at least one selected from the group consisting of an aluminum foil, an alloy aluminum foil, and an aluminum vapor-deposited film, and includes an aluminum foil. Is more preferable.
  • the barrier layer may be transparent, translucent, or opaque.
  • the thickness of the barrier layer is not particularly limited, and is preferably 7 ⁇ m or more, 8 ⁇ m or more, 9 ⁇ m or more, 10 ⁇ m or more, or 15 ⁇ m or more from the viewpoint of ensuring strength and barrier properties, and improves handleability. From the viewpoint, it is preferably 45 ⁇ m or less, 40 ⁇ m or less, or 35 ⁇ m or less.
  • the absorption layer is a layer that essentially contains a hygroscopic agent and a binder.
  • the absorption layer can further contain an arbitrary component, for example, a sulfide-based gas absorber.
  • a sulfide-based gas absorber By including the sulfide-based gas absorber, for example, when the sulfide-based gas is generated inside the laminate pack containing the sulfide-based all-solid-state battery, the generated sulfide-based gas is used. Can be absorbed.
  • the sulfide-based gas absorber may be contained in the same layer as the hygroscopic agent, or may be contained in a different layer.
  • the absorption layer may have a single layer structure or a multi-layer structure.
  • the absorbing layer can include a moisture absorbing agent and a binder, or an absorbing agent, a sulfide-based absorbing agent, and a binder.
  • the hygroscopic agent is not particularly limited as long as it can chemically and / or physically adsorb water.
  • the hygroscopic agent may contain, for example, at least one selected from the group consisting of zeolite, calcium oxide, magnesium sulfate, silica gel, calcium chloride, quicklime, and aluminum oxide.
  • the zeolite may be a natural zeolite or a synthetic zeolite.
  • the synthetic zeolite may be a hydrophilic zeolite.
  • Specific examples of the synthetic zeolite include, but are not limited to, molecular sieves (trade names) 3A, 4A, 5A, and 13X manufactured by Union Showa Co., Ltd.
  • the content (parts by mass) of the hygroscopic agent is 1 part by mass or more, 5 parts by mass or more, 10 parts by mass or more, 15 parts by mass in consideration of kneading property and moisture absorption performance with respect to 100 parts by mass of the binder.
  • Parts or more 20 parts by mass or more, 25 parts by mass or more, 30 parts by mass or more, 35 parts by mass or more, 40 parts by mass or more, 45 parts by mass or more, 50 parts by mass or more, 60 parts by mass or more, 70 parts by mass or more, 80 parts by mass It may be 5 parts or more, 90 parts by mass or more, 100 parts by mass or more or 110 parts by mass or more, and may be 500 parts by mass or less, 300 parts by mass or less, 200 parts by mass or less, or 150 parts by mass or less.
  • Sulfide-based gas absorber The sulfide-based gas absorber is not particularly limited as long as it can chemically and / or physically adsorb the sulfide-based gas.
  • the sulfide-based gas is not particularly limited, and may be, for example, a sulfide-based gas that can be generated from the sulfide-based electrolyte of the sulfide-based all-solid-state battery. More specifically, for example, hydrogen sulfide gas, mercaptan-based gas, or the like may be used.
  • Examples of the sulfide-based gas absorber capable of physically adsorbing the sulfide-based gas include, but are not limited to, activated carbon.
  • the sulfide gas absorber capable of chemically adsorbing the sulfide gas may contain at least one selected from the group consisting of copper, cobalt, manganese, iron, nickel, zinc, silver, calcium, and titanium. It can also contain compounds containing these metal simple substances, such as metal salts thereof, or metal silicates thereof.
  • the element composition (molar) ratio of metal to silicon is metal / Silicon may be in the range of 0.60 to 0.80.
  • the above-mentioned metal silicate can be produced by reacting a metal salt with an alkali silicate.
  • a metal salt an inorganic salt such as sulfuric acid, hydrochloric acid, nitric acid, and / or formic acid of at least one metal selected from the group consisting of copper, cobalt, manganese, iron, nickel, zinc, silver, calcium, and titanium. , Acetic acid, formic acid and other organic salts can be used.
  • the metal is preferably copper (I), copper (II), or zinc (I).
  • silicate M 2 O, nSiO 2 , xH 2 O (here, M represents a monovalent alkali metal, n is 1 or more, and x is 0 or more). It may be an alkali silicate.
  • sulfide-based gas absorber a commercially available product may be used.
  • Commercially available products include, for example, Kesmon (registered trademark) manufactured by Toagosei Co., Ltd .: NS-10C, NS-10Z, NS-10J, NS-20, NS-40M, NS-20C, TNS-100, TNS-110, And TNS-200 and the like.
  • the content (parts by mass) of the sulfide-based gas absorber is set to 0, in consideration of kneading property and gas adsorption performance with respect to 100 parts by mass of the binder. It is preferably 1 part by mass or more, 1 part by mass or more, 2 parts by mass or more, 3 parts by mass or more, 5 parts by mass or more or 10 parts by mass or more, and 500 parts by mass or less, 300 parts by mass or less, 100 parts by mass or less. , 50 parts by mass or less, 40 parts by mass or less, or 30 parts by mass or less. 3. 3. Binder The binder is not particularly limited, and may be, for example, a thermoplastic resin, a thermosetting resin, or a mixture thereof.
  • thermoplastic resin examples include ethylene- (meth) acrylic monomer copolymer, ethylene-vinyl acetate copolymer, polyolefin resin, saturated or unsaturated polyester, polyvinyl chloride, polystyrene, and derivatives thereof. However, it is not limited to these.
  • the ethylene- (meth) acrylic monomer copolymer is a resin obtained by copolymerizing a monomer composition containing at least ethylene and a (meth) acrylic monomer.
  • the content of the (meth) acrylic monomer in the monomer composition is 2% by weight or more, 3% by weight or more, 5% by weight or more, or 10% by weight or more, and 50% by weight or less and 40% by weight or less. , Or 30% by weight or less.
  • the content of the (meth) acrylic monomer is high, the softening temperature of the obtained resin is low, and when the content of the (meth) acrylic monomer is low, the density of the obtained resin is low.
  • a resin having an appropriate (meth) acrylic monomer content can be selected.
  • suitable (meth) acrylic monomers include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl acrylate, and pentyl (meth). ) Acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and the like can be mentioned.
  • ethylene- (meth) acrylic monomer copolymers include ethylene-acrylic acid copolymers (EAA), ethylene-methacrylic acid copolymers (EMAA), and ethylene-ethyl acrylate copolymers (EEA). ), Ethylene-methylacrylate copolymer (EMA), ethylene-methacrylate copolymer (EMMA) and the like, but are not limited thereto.
  • Ethylene-vinyl acetate copolymer is a resin obtained by copolymerizing a monomer composition containing at least ethylene and vinyl acetate.
  • the vinyl acetate content in the monomer composition is 2% by weight or more, 3% by weight or more, 5% by weight or more, or 10% by weight or more, and 50% by weight or less, 40% by weight or less, or 30% by weight. It can be as follows. In general, when the vinyl acetate content is high, the crystallinity of the obtained resin is low, and when the vinyl acetate content is low, the density of the obtained resin is low. Depending on the final application, a resin having an appropriate vinyl acetate content can be selected.
  • polyolefin resin examples include polyethylene resin, polypropylene resin, polybutene and the like.
  • a polyethylene-based resin is a resin containing a repeating unit of an ethylene group in the main chain of a polymer in an amount of more than 50 mol%, 60 mol% or more, 70 mol% or more, or 80 mol% or more.
  • polyethylene such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), medium-density polyethylene (MDPE), and high-density polyethylene (HDPE) may be used, and polyethylene and carboxyl are used.
  • LDPE low-density polyethylene
  • LLDPE linear low-density polyethylene
  • MDPE medium-density polyethylene
  • HDPE high-density polyethylene
  • a copolymer with an ethylene-based monomer having a group or an ester group may be used.
  • the polypropylene-based resin is a resin containing a repeating unit of a propylene group in the main chain of a polymer in an amount of more than 50 mol%, 60 mol% or more, 70 mol% or more, or 80 mol% or more.
  • polypropylene-based resins include polypropylene (PP) homopolymers, random polypropylene (random PP), block polypropylene (block PP), chlorinated polypropylene, carboxylic acid-modified polypropylene, derivatives thereof, and mixtures thereof.
  • thermoplastic resin an aromatic vinyl-diene-based copolymer and an olefin-based thermoplastic elastomer may be used as the thermoplastic resin.
  • the aromatic vinyl-diene-based copolymer means a copolymer having a repeating unit derived from an aromatic vinyl monomer and a repeating unit derived from a diene monomer.
  • an aromatic vinyl-diene-based copolymer for example, those listed in JP-A-2014-200751 can be used.
  • Olefin-based thermoplastic elastomer is a material that can be fluidized and molded at high temperatures and exhibits rubber elasticity at room temperature.
  • thermosetting resin any resin can be used, and examples thereof include, but are not limited to, phenol resin, melamine resin, and epoxy resin.
  • the thickness of the absorption layer is not particularly limited, and from the viewpoint of water adsorption performance, moldability, and elasticity, 10 ⁇ m or more, 20 ⁇ m or more, 30 ⁇ m or more, 40 ⁇ m or more, 50 ⁇ m or more, 60 ⁇ m or more, 70 ⁇ m or more, 80 ⁇ m or more, 90 ⁇ m. It is preferably 300 ⁇ m or more, or more than 100 ⁇ m, and more preferably 300 ⁇ m or less, 200 ⁇ m or less, 100 ⁇ m or less, 80 ⁇ m or less, or 50 ⁇ m or less.
  • the absorption layer can take, for example, the forms shown in (1) to (5) below, but is not limited thereto.
  • the absorption layer may have a moisture absorption layer and a sulfide gas absorption layer, which are laminated in this order from the outer side surface to the inner side surface.
  • the "hygroscopic layer” is at least a layer containing a hygroscopic agent, particularly a layer having the highest hygroscopic agent content.
  • the "sulfide-based gas absorbing layer” is a layer containing at least a sulfide-based gas absorbing agent, particularly a layer having the highest content of the sulfide-based gas absorbing agent.
  • the absorption layer 21 is a moisture absorption layer 21a and a sulfide gas absorption layer, which are laminated in this order from the outer side surface to the inner side surface. It has 21b.
  • the absorption layer may have a sulfide-based gas absorption layer and a moisture absorption layer, which are laminated in this order from the outer side surface to the inner side surface.
  • the absorption layer 31 is a sulfide-based gas absorption layer 31b and a moisture absorption layer, which are laminated in this order from the outer side surface to the inner side surface. It has 31a.
  • the absorption layer may have skin layers on both sides thereof.
  • the skin layer can prevent the hygroscopic agent or any sulfide-based gas absorbent contained in the hygroscopic layer from falling off, or can improve the strength of the laminate pack. Therefore, from this point of view, it is preferable that the absorption layer further has skin layers on both sides thereof.
  • the absorbing layer has a first skin layer, a moisture absorbing layer, and a second skin layer, which are laminated in this order from the outer side surface to the inner side surface. You can.
  • the absorption layer 41 is laminated in this order from the outer side surface to the inner side surface, the first skin layer 41c and the moisture absorption layer 41a. , And a second skin layer 41d.
  • an absorption layer having such a form it is possible to prevent moisture from entering from the outside to the inside of the laminate pack containing the sulfide-based all-solid-state battery. In addition, it is possible to prevent the hygroscopic agent contained in the hygroscopic layer from falling off.
  • the absorption layers are laminated in this order from the outer side surface to the inner side surface. It may have a skin layer, a moisture absorbing layer, a sulfide gas absorbing layer, and a second skin layer.
  • the absorption layer 51 is laminated in this order from the outer side surface to the inner side surface, the first skin layer 51c and the moisture absorption layer 51a. , A sulfide-based gas absorbing layer 51b, and a second skin layer 51d.
  • an absorption layer having such a form it is possible to prevent moisture from entering from the outside to the inside of the laminate pack containing the sulfide-based all-solid-state battery. Further, it is possible to prevent the hygroscopic agent contained in the moisture absorbing layer and the sulfide gas absorbing agent contained in the sulfide gas absorbing layer from falling off.
  • the absorption layers are laminated in this order from the outer side surface to the inner side surface. It may have a skin layer, a sulfide gas absorbing layer, a moisture absorbing layer, and a second skin layer.
  • the absorption layer 61 is a first skin layer 61c, sulfide-based, which is laminated in this order from the outer side surface to the inner side surface. It has a gas absorbing layer 61b, a moisture absorbing layer 61a, and a second skin layer 61d.
  • an absorption layer having such a form it is possible to prevent moisture from entering the inside from the sealing port on the side surface of the laminate pack containing the sulfide-based all-solid-state battery. Further, it is possible to prevent the hygroscopic agent contained in the moisture absorbing layer and the sulfide gas absorbing agent contained in the sulfide gas absorbing layer from falling off.
  • the moisture absorbing layer and the sulfide gas absorbing layer may have skin layers on both sides thereof. That is, the absorption layer is laminated in this order from the outer side surface to the inner side surface, the first skin layer, the moisture absorbing layer, the second skin layer, the third skin layer, and the sulfide system. It may have a gas absorbing layer and a fourth skin layer, or a first skin layer, a sulfide gas absorbing layer, a second skin layer, a third skin layer, a moisture absorbing layer, and a fourth. It may have a skin layer (not shown).
  • the hygroscopic layer contains at least a hygroscopic agent and a binder. Therefore, as the moisture absorbing layer, the case where the above-mentioned absorbing layer has a single layer structure can be appropriately referred to.
  • the sulfide-based gas absorption layer contains at least a sulfide-based gas absorber and a binder.
  • the sulfide-based gas absorber is not particularly limited as long as it can chemically and / or physically adsorb the above-mentioned sulfide-based gas.
  • the binder the binder used for the absorption layer described above can be appropriately used.
  • the content (parts by mass) of the sulfide-based gas absorber is 0.1 part by mass or more and 1 part by mass or more in consideration of kneading property and gas adsorption performance with respect to 100 parts by mass of the binder. It is preferably 3 parts by mass or more, 5 parts by mass or more, 10 parts by mass or more, 20 parts by mass or more, 30 parts by mass or more, 40 parts by mass or more or 50 parts by mass or more, and 500 parts by mass or less. It is preferably 300 parts by mass or less, 100 parts by mass or less, 50 parts by mass or less, 40 parts by mass or less, or 30 parts by mass or less.
  • the thickness of the sulfide gas absorbing layer is not particularly limited, and from the viewpoint of gas adsorption performance, moldability, and elasticity, 10 ⁇ m or more, 20 ⁇ m or more, 30 ⁇ m or more, 40 ⁇ m or more, 50 ⁇ m or more, 60 ⁇ m or more, 70 ⁇ m or more, It is preferably 80 ⁇ m or more, 90 ⁇ m or more, or 100 ⁇ m or more, and preferably 300 ⁇ m or less, 200 ⁇ m or less, 100 ⁇ m or less, 80 ⁇ m or less, or 50 ⁇ m or less.
  • the skin layer may be fused to a layer adjacent thereto (for example, an absorption layer, a moisture absorption layer and / or a sulfide gas absorption layer).
  • a layer adjacent thereto for example, an absorption layer, a moisture absorption layer and / or a sulfide gas absorption layer.
  • the binder used for the absorption layer described above can be appropriately adopted.
  • the thickness of the skin layer can be 1 ⁇ m or more, 3 ⁇ m or more, 5 ⁇ m or more, or 7 ⁇ m or more, and can be 50 ⁇ m or less, 40 ⁇ m or less, 30 ⁇ m or less, 20 ⁇ m or less, or 15 ⁇ m or less.
  • the laminated sheet of the present invention may further contain other layers in addition to the above-mentioned layers.
  • it may further have a base material layer, a sealant layer, or the like.
  • the laminated sheet of the present invention may further have a base material layer on the surface of the barrier layer opposite to the absorption layer.
  • the base material layer can protect the barrier layer described above.
  • a thermoplastic resin having excellent impact resistance, abrasion resistance, etc. for example, polyolefin, vinyl polymer, polyester, polyamide, etc. can be used alone or in combination of two or more types in a plurality of layers. it can.
  • This base material layer may be a stretched film or a non-stretched film.
  • polystyrene-based resin examples include polyethylene-based resin and polypropylene-based resin.
  • polyethylene-based resin the polyethylene-based resin mentioned for the absorption layer can be used
  • polypropylene-based resin the polypropylene-based resin mentioned for the first heat-resistant layer can be used.
  • vinyl polymer examples include polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polychlorotrifluoroethylene, polytetrafluoroethylene, polyacrylonitrile (PAN) and the like.
  • polyester examples include polyethylene terephthalate (PET) and polybutylene terephthalate.
  • polyamide examples include nylon such as nylon (registered trademark) 6 and nylon MXD6.
  • the thickness of the base material layer is preferably 7 ⁇ m or more, 10 ⁇ m or more, or 15 ⁇ m or more from the viewpoint of good protection of the barrier layer, and 55 ⁇ m or less, 50 ⁇ m or less, or 45 ⁇ m or less for handleability. It is preferable from the viewpoint of improving.
  • the laminated sheet of the present invention may further have a sealant layer on the surface of the absorption layer opposite to the barrier layer.
  • the sealant layer is a layer used for heat sealing. Therefore, when the laminate sheet of the present invention is used in a laminate pack, the sealant layer is placed in the innermost layer of the laminate pack closest to the sulfide-based all-solid-state battery and heat-sealed to obtain the laminate pack. It may be something that can be done. In the present invention, when a separate sealant layer is not provided, a layer arranged as the innermost layer of the laminate pack, for example, an absorption layer, a skin layer, or the like can be used as the sealant layer.
  • the material constituting the sealant layer may be the thermoplastic material described with respect to the binder used for the absorption layer described above, and in particular, for example, polypropylene (PP), low density polyethylene (LDPE), medium density polyethylene (MDPE), etc. High-density polyethylene (HDPE), polyethylene catalyzed by metallocene, a copolymer resin having a repeating unit of ethylene and a repeating unit of acrylic, or a copolymer resin having a repeating unit of ethylene and a repeating unit other than acrylic, or a combination thereof. However, it is not limited to these. These resins may be in the form of, for example, a stretched or unstretched film, a molten resin for extrusion lamination, a paint for hot melting, and the like.
  • sealant layer a commercially available easy peel resin or an easy peel sealant film may be used.
  • the thickness of the sealant layer is not particularly limited, and is preferably 10 ⁇ m or more, 20 ⁇ m or more, 30 ⁇ m or more, 40 ⁇ m or more, or 50 ⁇ m or more from the viewpoint of forming a strong seal by melting, and the handleability is improved. From the viewpoint of improvement, it is preferably 100 ⁇ m or less, 80 ⁇ m or less, or 50 ⁇ m or less.
  • each layer of the laminated sheet of the present invention is fixed with an appropriate adhesive.
  • the adhesive in this case can be appropriately selected by a person skilled in the art according to the method for producing the laminated film.
  • it may be a urethane-based adhesive for dry laminating.
  • the adhesive for example, a combination of Takelac (registered trademark) A-525S manufactured by Mitsui Kagaku Co., Ltd. and Takenate (registered trademark) A-52, Takelac (registered trademark) A-520 and Takenate (registered trademark). ) Combination with A-50, combination of Takelac (registered trademark) A-525 and Takenate (registered trademark) A-52, and combination of Takelac (registered trademark) A-525S and Takelac (registered trademark) A-50. Etc., but are not limited to these.
  • the amount of the adhesive can be, for example, 0.5 g / m 2 or more, preferably 1 g / m 2 or more, or 3 g / m 2 or more for each layer as the adhesive material per unit area of the laminated sheet. ..
  • the amount of this adhesive can be, for example, 10 g / m 2 or less, preferably 5 g / m 2 or less.
  • the method for producing the laminated sheet of the present invention is not particularly limited, and for example, the material constituting each layer of the above-mentioned laminated sheet is melt-kneaded, formed into a film, and laminated with each other, if necessary. be able to.
  • melt kneading can be performed using a batch type kneader, a continuous kneader, or the like. More specifically, melt kneading can be performed using, for example, a Banbury mixer, a kneader, a Henschel mixer, a mixing roll, or the like.
  • the temperature of melt kneading is not particularly limited and can be appropriately set according to the material constituting each layer, and is, for example, 50 ° C. or higher, 80 ° C. or higher, 100 ° C. or higher, 150 ° C. or higher, or 200 ° C. or higher. It may be 350 ° C. or lower, 300 ° C. or lower, or 200 ° C.
  • melt-kneading time is not particularly limited, and may be, for example, 1 minute or more, 5 minutes or more, 10 minutes or more, 20 minutes or more, 30 minutes or more, or 60 minutes or more, and 48 hours or less, 24 hours or less. , 12 hours or less, or 2 hours or less.
  • Film formation can be performed by, for example, an inflation method, a T-die method, a calendar method, a casting method, hot press molding, extrusion molding, injection molding, or the like.
  • Lamination can be performed by extrusion laminating method such as sand laminating method, heat sealing method, heat press molding, dry laminating or the like.
  • film formation and lamination may be performed at the same time by a coextrusion method such as a coextrusion inflation method and a coextrusion T-die method.
  • a coextrusion method such as a coextrusion inflation method and a coextrusion T-die method.
  • Laminate pack for sulfide-based all-solid-state batteries The present invention also provides a laminate pack for a sulfide-based all-solid-state battery.
  • the laminate pack of the present invention may be formed in a bag shape by using one of the above-mentioned laminate sheets. That is, the laminate pack of the present invention includes one laminate sheet, and the laminate sheet is bent with the inner side surface facing inward, and the peripheral edge portion of the inner side surface is heat-sealed to form a bag. It may be a laminated pack for a sulfide-based all-solid-state battery, which is shaped like this.
  • the laminate pack of the present invention may be formed in a bag shape by using the above-mentioned laminate sheet and another laminate sheet in combination.
  • the laminate pack of the present invention is the above-mentioned laminate sheet as A-side laminate sheet.
  • a B-side laminate sheet having a B-side barrier layer and a B-side sealant layer, which are laminated in this order from the outer side surface to the inner side surface, and the A surface.
  • the inner side surface of the laminate sheet and the B surface sealant layer face each other, and the peripheral edges of the inner side surface and the B surface sealant layer are heat-sealed to form a bag shape.
  • It may be a laminate pack for a sulfide-based all-solid-state battery.
  • the B-side barrier layer and the B-side sealant layer As the B-side barrier layer and the B-side sealant layer, the above-mentioned "barrier layer” and “sealant layer” used for the A-side may be appropriately referred to. Further, the B-side laminated sheet may further have other layers such as the above-mentioned base material layer.
  • the B-side laminated sheet has a B-side base material layer, a B-side barrier layer, and a B-side sealant layer, which are laminated in this order from the outer side surface to the inner side surface. You can do it.
  • the laminate pack of the present invention may also be formed in a bag shape by using two or more of the above-mentioned laminate sheets. That is, the laminate pack of the present invention is provided with two or more laminate sheets, and the inner side surfaces face each other, and the peripheral edges of the inner side surfaces are heat-sealed to form a bag. It may be a sulfide-based all-solid-state battery laminate pack.
  • the configurations of the two or more laminated sheets may be the same or different.
  • a laminate pack can be formed by using two different laminates as the A side and the B side of the laminate pack.
  • a laminated sheet having a barrier layer 70a and an absorption layer 71 which are laminated in this order from the outer side surface to the inner side surface.
  • the absorption layer 71 has a moisture absorption layer 71a and a sulfide-based gas absorption layer 71b, which are laminated in this order from the outer side surface to the inner side surface.
  • a laminated sheet having a barrier layer 70b and a sealant layer 72 which are laminated in this order from the outer side surface to the inner side surface, is used.
  • the internal side surfaces that is, the internal side surfaces of the sulfide gas absorption layer 71b and the sealant layer 72 face each other, and the sulfide gas absorption layer 71b and It may be a laminated pack in which the peripheral edges of the inner surfaces of the sealant layer 72 are heat-sealed to form a bag.
  • a laminated sheet having a barrier layer 80a and an absorption layer 81, which are laminated in this order from the outer side surface to the inner side surface, is used as the A surface.
  • the absorption layer 81 has a moisture absorption layer 81a and a sulfide gas absorption layer 81b that are laminated in this order from the outer side surface to the inner side surface.
  • a laminated sheet having a barrier layer 80b and a sulfide gas absorption layer 81b, which are laminated in this order from the outer side surface to the inner side surface is used as the B surface.
  • the inner side surfaces that is, the inner side surfaces of the two sulfide gas absorption layers 81b face each other, and each of the two sulfide gas absorption layers 81b.
  • It may be a laminated pack in which the peripheral edges of the inner surfaces are heat-sealed to form a bag.
  • the size of the peripheral edge of the inner surface may be set to a size that allows heat sealing by heating and / or pressurizing.
  • it may be either a three-way seal type, a four-way seal type, or a pillow pouch type that seals a sulfide-based all-solid-state battery by heat-sealing the inner surface of the laminate pack of the present invention.
  • the present invention provides a laminated battery comprising the above-mentioned laminate pack and a sulfide-based all-solid-state battery.
  • the laminated battery of the present invention can adopt a known form including a sulfide-based all-solid-state battery, except that the laminated pack of the present invention is used.
  • a masterbatch was prepared by an extruder by a melt kneading method using the following hygroscopic agent and binder.
  • Moisture absorber 53 parts by mass: Hydrophilic zeolite (Molecular sieve 3A; manufactured by Union Showa Co., Ltd.)
  • Binder 47 parts by mass: Ethylene-methacrylic acid copolymer (thermoplastic resin).
  • the master batch obtained above is used as a moisture absorbing layer, and linear low-density polyethylene is used as a first skin layer and a second skin layer, and is laminated in the following order by coextrusion molding by air-cooled inflation.
  • Two types and three layers of moisture absorbing layers were prepared: First skin layer (10 ⁇ m) / moisture absorbing layer (30 ⁇ m) / second skin layer (10 ⁇ m).
  • ⁇ Preparation of sulfide gas absorption layer 50 parts by mass of polyethylene as a binder and 50 parts by mass of Kessmon NS-20C (manufactured by Toagosei Co., Ltd.) as a gas absorber were mixed, and a kneaded product was prepared by a Banbury mixer.
  • the kneading temperature was 150 ° C. and the kneading time was 10 minutes.
  • a sulfide-based gas absorption layer of 2 types and 3 layers laminated in the following order was prepared: First skin layer (10 ⁇ m) / sulfide gas absorption layer (50 ⁇ m) / second skin layer (10 ⁇ m).
  • a masterbatch was prepared by an extruder by a melt-kneading method using the following hygroscopic agent, sulfide-based gas absorber and binder.
  • Moisture absorber 53 parts by mass: Hydrophilic zeolite (Molecular sieve 3A; manufactured by Union Showa Co., Ltd.)
  • Sulfide-based gas absorber (1 part by mass): Kesmon NS-20C (manufactured by Toagosei Co., Ltd.)
  • Binder 46 parts by mass: Ethylene-methacrylic acid copolymer (thermoplastic resin).
  • the masterbatch obtained above is used as an absorption layer containing a hygroscopic agent and a sulfide-based gas absorber, and linear low-density polyethylene is used as a first skin layer and a second skin layer, and coextruded by air-cooled inflation.
  • Example 1 As the A side of the laminate pack, a laminate sheet having a base material layer, a barrier layer, and a moisture absorbing layer, which are laminated in this order from the outer side surface to the inner side surface, is used, and the laminate pack is also provided.
  • the laminate pack of Example 1 was prepared using a laminate sheet having a base material layer, a barrier layer, and a sealant layer, which are laminated in this order from the outer side surface to the inner side surface as the B surface. did.
  • an aluminum foil was used as the barrier layer; polyethylene terephthalate (PET) was used as the base material layer; polyethylene (PE) was used as the sealant layer.
  • PET polyethylene terephthalate
  • PE polyethylene
  • each layer was laminated by dry lamination.
  • a dry laminate adhesive a combination of Takelac (registered trademark) A-525S manufactured by Mitsui Chemicals, Inc. and Takenate (registered trademark) A-50 was used, and this adhesive and ethyl acetate were mixed in a predetermined compounding ratio. The mixture was mixed, applied between the layers with a hand coater so that the coating amount was 3 g / m 2, and then pressure-bonded.
  • Example 2 As the A side of the laminate pack, a laminate sheet having a base material layer, a barrier layer, a sulfide gas absorption layer, and a moisture absorption layer, which are laminated in this order from the outer side surface to the inner side surface, is used. A laminate pack of Example 2 was prepared in the same manner as in Example 1 except for the above.
  • the barrier layer and the sulfide-based gas absorption layer were laminated in the same manner as in Example 1.
  • Example 3 As the A side of the laminate pack, a laminate sheet having a base material layer, a barrier layer, a moisture absorbing layer, and a sulfide gas absorbing layer, which are laminated in this order from the outer side surface to the inner side surface, is used. A laminate pack of Example 3 was prepared in the same manner as in Example 1 except for the above.
  • the moisture absorbing layer and the sulfide gas absorbing layer were laminated in the same manner as in Example 1.
  • Example 4 A laminate pack of Example 4 was prepared in the same manner as in Example 1 except that only the above-mentioned 2 types and 3 layers of sulfide-based gas absorption layer of 10 cm ⁇ 10 cm were included.
  • Example 5 Except for using a laminate sheet having a base material layer, a barrier layer, and a sulfide-based gas absorption layer, which are laminated in this order from the outer side surface to the inner side surface as the B surface of the laminate pack. Made a laminate pack of Example 5 in the same manner as in Example 1.
  • the barrier layer and the sulfide-based gas absorption layer were laminated in the same manner as in Example 1.
  • Example 6 As the A side of the laminate pack, a laminate having an absorption layer containing a base material layer, a barrier layer, a hygroscopic agent and a sulfide-based gas absorber, which are laminated in this order from the outer side surface to the inner side surface.
  • a laminate pack of Example 6 was prepared in the same manner as in Example 1 except that a sheet was used.
  • the barrier layer and the sulfide-based gas absorption layer were laminated in the same manner as in Example 1.
  • Comparative Example 1 Examples except that a laminate sheet having a base material layer, a barrier layer, and a sealant layer, which are laminated in this order from the outer side surface to the inner side surface, was used as the A surface of the laminate pack.
  • a laminate pack of Comparative Example was prepared in the same manner as in 1.
  • Comparative Example 2 Except for using a laminate sheet having a base material layer, a barrier layer, and a sulfide-based gas absorption layer, which are laminated in this order from the outer side surface to the inner side surface as the A surface of the laminate pack. Made a laminate pack of Comparative Example in the same manner as in Example 1.
  • the barrier layer and the sulfide-based gas absorption layer were laminated in the same manner as in Example 1.
  • the laminate packs of Comparative Examples 1 and 2 had an internal humidity of 40% after 2 weeks. As described above, it was found that the generation of sulfide-based gas cannot be suppressed due to the presence of water, which is the root cause of sulfide-based gas generation, in the laminate pack.
  • Kesmon NS-20C manufactured by Toagosei Co., Ltd. was weighed (this weight is a), placed in a disposable cup and weighed again (this weight is b).
  • Kesmon NS-20C and a cup were placed in a high-temperature and high-humidity tank in an environment of 40 ° C. and 90% (relative humidity) and weighed at predetermined time intervals (this weight is defined as c).
  • Weight increase rate (cc + a) / a
  • Kesmon NS-20C As shown in Table 2, it was found that when Kesmon NS-20C was used, a maximum of 30% of water was adsorbed after about 6 hours on average for the three samples.

Abstract

Provided is a sulfide-based fully solid battery laminated sheet 100 comprising a barrier layer 10 and an absorption layer 11 containing a moisture absorption agent, which are layered in said order from the surface for the outer side toward the surface for the inner side.

Description

硫化物系全固体電池用ラミネートシート及びそれを用いたラミネートパックLaminate sheet for sulfide-based all-solid-state battery and laminate pack using it
　本発明は、硫化物系全固体電池用ラミネートシート及びそれを用いたラミネートパックに関する。 The present invention relates to a sulfide-based all-solid-state battery laminate sheet and a laminate pack using the same.
　近年、エネルギー密度が高い二次電池が注目されている。特に、電解液を固体電解質層に変えて、電池を全固体化した全固体電池は、電池内に可燃性の有機溶媒を用いないため、安全装置の簡素化が図れ、製造コストや生産性に優れると考えられている。 In recent years, secondary batteries with high energy density have been attracting attention. In particular, an all-solid-state battery in which the electrolyte is changed to a solid electrolyte layer and the battery is completely solidified does not use a flammable organic solvent in the battery, so that the safety device can be simplified and the manufacturing cost and productivity can be improved. It is considered excellent.
　このような全固体電池として、特に、出力電流を向上できる観点から、固体電解質として硫化物系固体電解質を用いた硫化物系全固体電池が注目されている。 As such an all-solid-state battery, a sulfide-based all-solid-state battery using a sulfide-based solid electrolyte as a solid electrolyte is attracting attention, particularly from the viewpoint of improving the output current.
　しかしながら、硫化物系全固体電池では、硫化物系固体電解質は、硫化物系固体電解質が水分と接触すると、硫化水素等の硫化物系のガスが発生してしまい、硫化物系全固体電池が劣化してしまう問題がある。 However, in the sulfide-based all-solid-state battery, in the sulfide-based solid-state battery, when the sulfide-based solid electrolyte comes into contact with water, sulfide-based gas such as hydrogen sulfide is generated, and the sulfide-based all-solid-state battery becomes There is a problem of deterioration.
　この問題の対策として、例えば特許文献１では、硫化物系固体電解質材料を用いた全固体リチウム二次電池であって、少なくとも前記硫化物系固体電解質材料が含まれている電解質含有層と外気とが接触する部位に、実質的に水分を含まない前記硫化物系固体電解質材料が酸化されてなる酸化物層が形成された酸化物層含有発電素子を有することを特徴とする全固体リチウム二次電池が開示されている。 As a countermeasure for this problem, for example, in Patent Document 1, in an all-solid lithium secondary battery using a sulfide-based solid electrolyte material, at least the electrolyte-containing layer containing the sulfide-based solid electrolyte material and the outside air An all-solid-state lithium secondary characterized by having an oxide layer-containing power generating element in which an oxide layer formed by oxidizing the sulfide-based solid electrolyte material, which is substantially free of water, is formed at a site where the sulfide-based solid electrolyte material comes into contact with the material. Batteries are disclosed.
特開２００９－１９３７２７号公報JP-A-2009-193727
　例えば、硫化物系全固体電池をラミネートパックで収容する際に水分等がラミネートパック内に侵入してしまった場合や、硫化物系全固体電池を収容しているラミネートパックの側面の封止口から外部の水分等が侵入してしまった場合、又は硫化物系全固体電池を収容しているラミネートパックにピンホールが発生して、ピンホールから水分等がラミネートパック内に侵入してしまった場合等、ラミネートパックの内部に水が浸入してしまった場合、水分が硫化物系固体電解質と反応する可能性がある。 For example, when water or the like has entered the laminate pack when the sulfide-based all-solid-state battery is stored in the laminate pack, or the sealing port on the side surface of the laminate pack containing the sulfide-based all-solid-state battery. If external moisture etc. invades from the pinhole, or a pinhole is generated in the laminate pack containing the sulfide-based all-solid-state battery, moisture etc. invades into the laminate pack from the pinhole. In some cases, such as when water has penetrated into the laminate pack, the water may react with the sulfide-based solid electrolyte.
　なお、硫化物系ガスの発生に対する対策として、ラミネートパックの内部に硫化物系ガス吸収層を設けることが考えられる。 As a countermeasure against the generation of sulfide-based gas, it is conceivable to provide a sulfide-based gas absorption layer inside the laminate pack.
　しかしながら、本発明者らは、硫化物系ガス吸収剤自体が水分を吸着して、保持しており、それによって、硫化物系ガス吸収剤が保持していた水分を放出して、状況によっては、硫化物系固体電解質に水分を与えてしまい、その結果、更に硫化物系ガスが発生する可能性があることを見出した。 However, the present inventors adsorb and retain the water content of the sulfide-based gas absorber itself, thereby releasing the water content retained by the sulfide-based gas absorber, and in some situations. , It has been found that water is given to the sulfide-based solid electrolyte, and as a result, further sulfide-based gas may be generated.
　そこで、本発明は、上記事情を鑑みてなされたものであり、硫化物系ガスの発生を抑制できる硫化物系全固体電池用ラミネートシート及びそれを用いたラミネートパックを提供することを目的とする。 Therefore, the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a sulfide-based all-solid-state battery laminate sheet capable of suppressing the generation of sulfide-based gas and a laminate pack using the same. ..
　本発明者らは、以下の手段により、上記課題を解決できることを見出した。 The present inventors have found that the above problems can be solved by the following means.
　〈態様１〉
　外部側用面から内部側用面に向かって、この順に積層されている、バリア層、及び吸湿剤を含む吸収層を有する、硫化物系全固体電池用ラミネートシート。
　〈態様２〉
　前記吸収層は、硫化物系ガス吸収剤を更に含む、態様１に記載のラミネートシート。
　〈態様３〉
　前記吸収層は、前記外部側用面から前記内部側用面に向かって、この順に積層されている、吸湿層及び硫化物系ガス吸収層を有する、態様１に記載のラミネートシート。
　〈態様４〉
　前記吸収層は、前記外部側用面から前記内部側用面に向かって、この順に積層されている、硫化物系ガス吸収層及び吸湿層を有する、態様１に記載のラミネートシート。
　〈態様５〉
　前記吸収層は、その両面にスキン層を有する、態様１～４のいずれか一項に記載のラミネートシート。
　〈態様６〉
　前記バリア層の、前記吸収層とは反対側の面に、基材層を更に有する、態様１～５のいずれか一項に記載のラミネートシート。
　〈態様７〉
　前記吸収層の、前記バリア層とは反対側の面に、シーラント層を更に有する、態様１～６のいずれか一項に記載のラミネートシート。
　〈態様８〉
　前記吸湿剤は、ゼオライト、酸化カルシウム、硫酸マグネシウム、シリカゲル、塩化カルシウム、生石灰、及び酸化アルミニウムからなる群より選択される少なくとも１つを含む、態様１～７のいずれか一項に記載のラミネートシート。
　〈態様９〉
　前記硫化物系ガス吸収剤は、銅、コバルト、マンガン、鉄、ニッケル、亜鉛、銀、カルシウム、及びチタンからなる群より選択される少なくとも１つを含む、態様２～８のいずれか一項に記載のラミネートシート。
　〈態様１０〉
　態様１～９のいずれか一項に記載のラミネートシートを１つ具備しており、かつ
　前記ラミネートシートが前記内部側用面を内側にして折り曲げられて、前記内部側用面の周縁部同士がヒートシールされることによって袋状にされている、
硫化物系全固体電池用ラミネートパック。
　〈態様１１〉
　Ａ面用ラミネートシートとしての態様１～９のいずれか一項に記載のラミネートシートと、外部側用面から内部側用面に向かって、この順に積層されている、Ｂ面用バリア層及びＢ面用シーラント層を有するＢ面用ラミネートシートとを具備しており、かつ
　前記Ａ面用ラミネートシートの前記内部側用面と、前記Ｂ面用シーラント層とが互いに対向して、前記内部側用面と前記Ｂ面用シーラント層との周縁部同士がヒートシールされることによって袋状にされている、
硫化物系全固体電池用ラミネートパック。
　〈態様１２〉
　態様１～９のいずれか一項に記載のラミネートシートを２つ以上具備しており、かつ
　前記内部側用面同士が互いに対向して、前記内部側用面の周縁部同士がヒートシールされることによって袋状にされている、
硫化物系全固体電池用ラミネートパック。
　〈態様１３〉
　態様１０～１２のいずれか一項に記載の硫化物系全固体電池用ラミネートパック、及び
　硫化物系全固体電池
を具備している、ラミネート電池。 <Aspect 1>
A sulfide-based all-solid-state battery laminate sheet having a barrier layer and an absorption layer containing a hygroscopic agent, which are laminated in this order from the outer side surface to the inner side surface.
<Aspect 2>
The laminated sheet according to aspect 1, wherein the absorption layer further contains a sulfide-based gas absorber.
<Aspect 3>
The laminate sheet according to aspect 1, wherein the absorption layer has a moisture absorption layer and a sulfide-based gas absorption layer, which are laminated in this order from the outer side surface to the inner side surface.
<Aspect 4>
The laminate sheet according to aspect 1, wherein the absorption layer has a sulfide-based gas absorption layer and a moisture absorption layer, which are laminated in this order from the outer side surface to the inner side surface.
<Aspect 5>
The laminated sheet according to any one of aspects 1 to 4, wherein the absorbent layer has skin layers on both sides thereof.
<Aspect 6>
The laminate sheet according to any one of aspects 1 to 5, further comprising a base material layer on the surface of the barrier layer opposite to the absorption layer.
<Aspect 7>
The laminate sheet according to any one of aspects 1 to 6, further comprising a sealant layer on the surface of the absorption layer opposite to the barrier layer.
<Aspect 8>
The laminate sheet according to any one of aspects 1 to 7, wherein the hygroscopic agent contains at least one selected from the group consisting of zeolite, calcium oxide, magnesium sulfate, silica gel, calcium chloride, quicklime, and aluminum oxide. ..
<Aspect 9>
The sulfide-based gas absorber comprises at least one selected from the group consisting of copper, cobalt, manganese, iron, nickel, zinc, silver, calcium, and titanium, according to any one of aspects 2 to 8. Described laminated sheet.
<Aspect 10>
The laminated sheet according to any one of aspects 1 to 9 is provided, and the laminated sheet is bent with the inner side surface facing inward so that the peripheral edges of the inner side surface are brought together. It is made into a bag by heat sealing,
Laminate pack for sulfide-based all-solid-state batteries.
<Aspect 11>
The laminated sheet according to any one of aspects 1 to 9 as the A-side laminated sheet, and the B-side barrier layer and B, which are laminated in this order from the outer side surface to the inner side surface. A B-side laminated sheet having a surface sealant layer is provided, and the internal side surface of the A-side laminated sheet and the B-side sealant layer face each other to face the internal side. The peripheral edges of the surface and the B-side sealant layer are heat-sealed to form a bag.
Laminate pack for sulfide-based all-solid-state batteries.
<Aspect 12>
Two or more of the laminated sheets according to any one of aspects 1 to 9 are provided, and the inner side surfaces face each other, and the peripheral edges of the inner side surfaces are heat-sealed. By being made into a bag,
Laminate pack for sulfide-based all-solid-state batteries.
<Aspect 13>
A laminated battery comprising the sulfide-based all-solid-state battery laminate pack according to any one of aspects 10 to 12 and a sulfide-based all-solid-state battery.
　本発明によれば、硫化物系ガスの発生を抑制できる硫化物系全固体電池用ラミネートシート及びそれを用いたラミネートパックを提供することができる。 According to the present invention, it is possible to provide a sulfide-based all-solid-state battery laminate sheet capable of suppressing the generation of sulfide-based gas and a laminate pack using the same.
図１は、本発明の硫化物系全固体電池用ラミネートシートの層構成の一形態を示す概略図である。FIG. 1 is a schematic view showing one form of a layer structure of the laminated sheet for a sulfide-based all-solid-state battery of the present invention. 図２は、吸収層が多層の構造である場合の、吸収層の形態を示す概略図である。FIG. 2 is a schematic view showing the morphology of the absorption layer when the absorption layer has a multi-layer structure. 図３は、本発明のラミネートパックのＡ面及びＢ面の形態を示す概略図である。FIG. 3 is a schematic view showing the morphology of the A side and the B side of the laminate pack of the present invention.
　以下、図面を参照しながら、本発明を実施するための形態について、詳細に説明する。なお、説明の便宜上、各図において、同一又は相当する部分には同一の参照符号を付し、重複説明は省略する。実施の形態の各構成要素は、全てが必須のものであるとは限らず、一部の構成要素を省略可能な場合もある。ただし、以下の図に示される形態は本発明の例示であり、本発明を限定するものではない。 Hereinafter, a mode for carrying out the present invention will be described in detail with reference to the drawings. For convenience of explanation, the same or corresponding parts are designated by the same reference numerals in each figure, and duplicate description will be omitted. Not all of the components of the embodiment are essential, and some components may be omitted. However, the form shown in the following figure is an example of the present invention, and does not limit the present invention.
　《硫化物系全固体電池用ラミネートシート》
　本発明の硫化物系全固体電池用ラミネートシートは、外部側用面から内部側用面に向かって、この順に積層されている、バリア層、及び吸湿剤を含む吸収層を有する。 << Laminated sheet for sulfide-based all-solid-state batteries >>
The sulfide-based all-solid-state battery laminate sheet of the present invention has a barrier layer and an absorption layer containing a hygroscopic agent, which are laminated in this order from the outer side surface to the inner side surface.
　以下、「本発明の硫化物系全固体電池用ラミネートシート」を単に「本発明のラミネートシート」又は「ラミネートシート」とも称する。 Hereinafter, the "laminated sheet for sulfide-based all-solid-state battery of the present invention" is also simply referred to as "laminated sheet of the present invention" or "laminated sheet".
　ここで、「外部側用面」とは、ラミネートシートから形成されたラミネートパックに硫化物系全固体電池を収容する場合に、ラミネートパックの外側に向いて使用する面である。また、「内部側用面」とは、ラミネートシートから形成されたラミネートパックに硫化物系全固体電池を収容する場合に、ラミネートパックの内部の硫化物系全固体電池に向いて使用する面である。 Here, the "outside surface" is a surface that is used facing the outside of the laminate pack when the sulfide-based all-solid-state battery is housed in the laminate pack formed from the laminate sheet. The "internal side surface" is a surface that is used toward the sulfide-based all-solid-state battery inside the laminate pack when the sulfide-based all-solid-state battery is housed in the laminate pack formed from the laminate sheet. is there.
　例えば、図１は、本発明の硫化物系全固体電池用ラミネートシートの層構成の一形態を示す概略図である。図１に示されているように、本発明のラミネートシート１００は、外部側用面から内部側用面に向かって、この順に積層されている、バリア層１０、及び吸湿剤を含む吸収層１１を有する。 For example, FIG. 1 is a schematic view showing one form of a layer structure of the laminated sheet for a sulfide-based all-solid-state battery of the present invention. As shown in FIG. 1, the laminate sheet 100 of the present invention has a barrier layer 10 and an absorption layer 11 containing a hygroscopic agent, which are laminated in this order from the outer side surface to the inner side surface. Has.
　本発明は、硫化物系ガスが発生する根本的な原因である水分に着目して、吸湿剤を含む吸収層を含むことによって、硫化物系全固体電池を収容しているラミネートパックの内部の水分を吸収して除去するものである。すなわち、本発明のラミネートシートによれば、ラミネートパックの外部から内部への水分の侵入を防止するだけではなく、ラミネートパックの内部に侵入してしまった水分を除去することもできる。 The present invention focuses on moisture, which is the root cause of sulfide-based gas generation, and includes an absorption layer containing a hygroscopic agent, so that the inside of a laminate pack containing a sulfide-based all-solid-state battery is contained. It absorbs and removes water. That is, according to the laminate sheet of the present invention, it is possible not only to prevent the intrusion of moisture from the outside to the inside of the laminate pack, but also to remove the moisture that has invaded the inside of the laminate pack.
　以下では、本発明のラミネートシートを構成する各層について、詳細に説明する。 In the following, each layer constituting the laminated sheet of the present invention will be described in detail.
　〈バリア層〉
　バリア層は、水分や水蒸気等のガスの透過、特にラミネートパックの外部から内部への水蒸気の侵入を防止するための層である。 <Barrier layer>
The barrier layer is a layer for preventing the permeation of gas such as water and water vapor, particularly the invasion of water vapor from the outside to the inside of the laminate pack.
　バリア層は、特に限定されず、例えば金属箔、及び金属又は金属酸化物の蒸着膜からなる群より選択される少なくとも１つを含んでよい。より具体的には、バリア層は、例えばアルミニウム箔、合金アルミニウム箔、アルミニウム蒸着フィルム、シリカ蒸着フィルム、アルミナ蒸着フィルム、シリカ・アルミナ二元蒸着フィルム、及びポリフッ化ビニリデンコーティング膜等の有機物コーティング膜からなる群より選択される少なくとも１つを含んでよい。また、バリア性及び取り扱い性を両立させやすくする観点から、バリア層は、アルミニウム箔、合金アルミニウム箔、及びアルミニウム蒸着フィルムからなる群より選択される少なくとも１つを含むことが好ましく、アルミニウム箔を含むことがより好ましい。 The barrier layer is not particularly limited and may include, for example, at least one selected from the group consisting of a metal foil and a vapor-deposited film of a metal or a metal oxide. More specifically, the barrier layer is made of an organic coating film such as an aluminum foil, an alloy aluminum foil, an aluminum vapor deposition film, a silica vapor deposition film, an alumina vapor deposition film, a silica-alumina dual vapor deposition film, and a polyvinylidene fluoride coating film. It may contain at least one selected from the group. Further, from the viewpoint of facilitating both barrier property and handleability, the barrier layer preferably contains at least one selected from the group consisting of an aluminum foil, an alloy aluminum foil, and an aluminum vapor-deposited film, and includes an aluminum foil. Is more preferable.
　バリア層は、透明、半透明、又は不透明のいずれであってもよい。 The barrier layer may be transparent, translucent, or opaque.
　バリア層の厚さは、特に限定されず、強度及びバリア性を確保する観点から、７μｍ以上、８μｍ以上、９μｍ以上、１０μｍ以上、又は１５μｍ以上であることが好ましく、また、取り扱い性を向上させる観点から、４５μｍ以下、４０μｍ以下、又は３５μｍ以下であることが好ましい。 The thickness of the barrier layer is not particularly limited, and is preferably 7 μm or more, 8 μm or more, 9 μm or more, 10 μm or more, or 15 μm or more from the viewpoint of ensuring strength and barrier properties, and improves handleability. From the viewpoint, it is preferably 45 μm or less, 40 μm or less, or 35 μm or less.
　〈吸収層〉
　吸収層は、吸湿剤及びバインダーを必須的に含む層である。また、吸収層は、随意の成分、例えば硫化物系ガス吸収剤を更に含むことができる。硫化物系ガス吸収剤を含むことによって、例えば硫化物系全固体電池を収容しているラミネートパックの内部に硫化物系ガスが発生してしまった場合には、発生された硫化物系ガスを吸収することができる。なお、硫化物系ガス吸収剤は、吸湿剤と同じ層に含まれてもよく、異なる層に含まれてもよい。 <Absorption layer>
The absorption layer is a layer that essentially contains a hygroscopic agent and a binder. In addition, the absorption layer can further contain an arbitrary component, for example, a sulfide-based gas absorber. By including the sulfide-based gas absorber, for example, when the sulfide-based gas is generated inside the laminate pack containing the sulfide-based all-solid-state battery, the generated sulfide-based gas is used. Can be absorbed. The sulfide-based gas absorber may be contained in the same layer as the hygroscopic agent, or may be contained in a different layer.
　吸収層は、単層の構造であってもよく、多層の構造であってもよい。 The absorption layer may have a single layer structure or a multi-layer structure.
　（単層の構造）
　吸収層が単層の構造である場合、上述したように、吸収層は、吸湿剤及びバインダー、又は吸収剤、硫化物系吸収剤、及びバインダーを含むことができる。 (Single layer structure)
When the absorbing layer has a single-layer structure, as described above, the absorbing layer can include a moisture absorbing agent and a binder, or an absorbing agent, a sulfide-based absorbing agent, and a binder.
　１．吸湿剤
　吸湿剤としては、水分を化学的にかつ／又は物理的に吸着できるものであれば、特に限定されない。 1. 1. Moisture absorbent The hygroscopic agent is not particularly limited as long as it can chemically and / or physically adsorb water.
　吸湿剤は、例えば、ゼオライト、酸化カルシウム、硫酸マグネシウム、シリカゲル、塩化カルシウム、生石灰、及び酸化アルミニウムからなる群より選択される少なくとも１つを含んでよい。 The hygroscopic agent may contain, for example, at least one selected from the group consisting of zeolite, calcium oxide, magnesium sulfate, silica gel, calcium chloride, quicklime, and aluminum oxide.
　また、ゼオライトとしては、天然ゼオライトであってもよく、合成ゼオライトであってもよい。また、合成ゼオライトとしては、親水性ゼオライトであってよい。合成ゼオライトの具体例としては、例えばユニオン昭和株式会社製のモレキュラーシーブ（商品名）３Ａ、４Ａ、５Ａ、及び１３Ｘ等が挙げられるがこれらに限定されない。 Further, the zeolite may be a natural zeolite or a synthetic zeolite. The synthetic zeolite may be a hydrophilic zeolite. Specific examples of the synthetic zeolite include, but are not limited to, molecular sieves (trade names) 3A, 4A, 5A, and 13X manufactured by Union Showa Co., Ltd.
　吸収層において、吸湿剤の含有量（質量部）は、バインダー１００質量部に対して、混練性及び吸湿性能を考慮して、１質量部以上、５質量部以上、１０質量部以上、１５質量部以上、２０質量部以上、２５質量部以上、３０質量部以上、３５質量部以上、４０質量部以上、４５質量部以上、５０質量部以上、６０質量部以上、７０質量部以上、８０質量部以上、９０質量部以上、１００質量部以上又は１１０質量部以上であってよく、また、５００質量部以下、３００質量部以下、２００質量部以下、又は１５０質量部以下であってよい。 In the absorption layer, the content (parts by mass) of the hygroscopic agent is 1 part by mass or more, 5 parts by mass or more, 10 parts by mass or more, 15 parts by mass in consideration of kneading property and moisture absorption performance with respect to 100 parts by mass of the binder. Parts or more, 20 parts by mass or more, 25 parts by mass or more, 30 parts by mass or more, 35 parts by mass or more, 40 parts by mass or more, 45 parts by mass or more, 50 parts by mass or more, 60 parts by mass or more, 70 parts by mass or more, 80 parts by mass It may be 5 parts or more, 90 parts by mass or more, 100 parts by mass or more or 110 parts by mass or more, and may be 500 parts by mass or less, 300 parts by mass or less, 200 parts by mass or less, or 150 parts by mass or less.
　２．硫化物系ガス吸収剤
　硫化物系ガス吸収剤としては、硫化物系ガスを化学的にかつ／又は物理的に吸着できるものであれば、特に限定されない。 2. Sulfide-based gas absorber The sulfide-based gas absorber is not particularly limited as long as it can chemically and / or physically adsorb the sulfide-based gas.
　ここで、硫化物系ガスとしては、特に限定されず、例えば硫化物系全固体電池の硫化物系電解質から生じうる硫化物系ガスであってよい。より具体的には、例えば硫化水素ガス、又はメルカプタン系ガス等であってよい。 Here, the sulfide-based gas is not particularly limited, and may be, for example, a sulfide-based gas that can be generated from the sulfide-based electrolyte of the sulfide-based all-solid-state battery. More specifically, for example, hydrogen sulfide gas, mercaptan-based gas, or the like may be used.
　硫化物系ガスを物理的に吸着できる硫化物系ガス吸収剤は、例えば活性炭が挙げられるが、これに限定されない。 Examples of the sulfide-based gas absorber capable of physically adsorbing the sulfide-based gas include, but are not limited to, activated carbon.
　硫化物系ガスを化学的に吸着できる硫化物系ガス吸収剤は、銅、コバルト、マンガン、鉄、ニッケル、亜鉛、銀、カルシウム、及びチタンからなる群より選択される少なくとも１つを含むことができ、またこれらの金属単体を含む化合物、例えばこれらの金属塩、又はこれらの金属ケイ酸塩を含むことができる。 The sulfide gas absorber capable of chemically adsorbing the sulfide gas may contain at least one selected from the group consisting of copper, cobalt, manganese, iron, nickel, zinc, silver, calcium, and titanium. It can also contain compounds containing these metal simple substances, such as metal salts thereof, or metal silicates thereof.
　銅、コバルト、マンガン、鉄、ニッケル、亜鉛、銀、カルシウム、及びチタンからなる群より選択される少なくとも１つの金属ケイ酸塩を用いる場合、金属とケイ素の元素組成（モル）比が、金属／ケイ素＝０．６０～０．８０の範囲であってよい。 When at least one metal silicate selected from the group consisting of copper, cobalt, manganese, iron, nickel, zinc, silver, calcium, and titanium is used, the element composition (molar) ratio of metal to silicon is metal / Silicon may be in the range of 0.60 to 0.80.
　また、上記のような金属ケイ酸塩は、金属塩とケイ酸アルカリ塩とを反応させて製造することができる。金属塩としては、銅、コバルト、マンガン、鉄、ニッケル、亜鉛、銀、カルシウム、及びチタンからなる群より選択される少なくとも１つの金属の、硫酸、塩酸、硝酸等の無機塩、及び／又はギ酸、酢酸、シュウ酸等の有機塩を用いることができる。これらのうち、金属としては銅（Ｉ）、銅（ＩＩ）、亜鉛（Ｉ）であることが好ましい。また、ケイ酸塩としては、Ｍ２Ｏ・ｎＳｉＯ２・ｘＨ２Ｏ（ここで、式中Ｍは１価アルカリ金属を表し、ｎは１以上、かつｘは０以上である。）の式のケイ酸アルカリ塩であってよい。 Further, the above-mentioned metal silicate can be produced by reacting a metal salt with an alkali silicate. As the metal salt, an inorganic salt such as sulfuric acid, hydrochloric acid, nitric acid, and / or formic acid of at least one metal selected from the group consisting of copper, cobalt, manganese, iron, nickel, zinc, silver, calcium, and titanium. , Acetic acid, formic acid and other organic salts can be used. Of these, the metal is preferably copper (I), copper (II), or zinc (I). Further, as the silicate, M 2 O, nSiO 2 , xH 2 O (here, M represents a monovalent alkali metal, n is 1 or more, and x is 0 or more). It may be an alkali silicate.
　また、硫化物系ガス吸収剤としては、市販品を用いてもよい。市販品としては、例えば東亞合成株式会社製のケスモン（登録商標）：ＮＳ－１０Ｃ、ＮＳ－１０Ｚ、ＮＳ－１０Ｊ、ＮＳ－２０、ＮＳ－４０Ｍ、ＮＳ－２０Ｃ、ＴＮＳ－１００、ＴＮＳ－１１０、及びＴＮＳ－２００等が挙げられる。 Further, as the sulfide-based gas absorber, a commercially available product may be used. Commercially available products include, for example, Kesmon (registered trademark) manufactured by Toagosei Co., Ltd .: NS-10C, NS-10Z, NS-10J, NS-20, NS-40M, NS-20C, TNS-100, TNS-110, And TNS-200 and the like.
　吸収層において、硫化物系ガス吸収剤を含む場合の硫化物系ガス吸収剤の含有量（質量部）は、バインダー１００質量部に対して、混練性及びガス吸着性能を考慮して、０．１質量部以上、１質量部以上、２質量部以上、３質量部以上、５質量部以上又は１０質量部以上であることが好ましく、また５００質量部以下、３００質量部以下、１００質量部以下、５０質量部以下、４０質量部以下、又は３０質量部以下であることが好ましい。
　３．バインダー
　バインダーとしては、特に限定されず、例えば熱可塑性樹脂、熱硬化性樹脂、又はこれらの混合物であってよい。 In the absorption layer, when the sulfide-based gas absorber is contained, the content (parts by mass) of the sulfide-based gas absorber is set to 0, in consideration of kneading property and gas adsorption performance with respect to 100 parts by mass of the binder. It is preferably 1 part by mass or more, 1 part by mass or more, 2 parts by mass or more, 3 parts by mass or more, 5 parts by mass or more or 10 parts by mass or more, and 500 parts by mass or less, 300 parts by mass or less, 100 parts by mass or less. , 50 parts by mass or less, 40 parts by mass or less, or 30 parts by mass or less.
3. 3. Binder The binder is not particularly limited, and may be, for example, a thermoplastic resin, a thermosetting resin, or a mixture thereof.
　熱可塑性樹脂としては、例えばエチレン―（メタ）アクリル系モノマー共重合体、エチレン―酢酸ビニル共重合体、ポリオレフィン系樹脂、飽和又は不飽和ポリエステル、ポリ塩化ビニル、ポリスチレン、及びこれらの誘導体が挙げられるが、これらに限定されない。 Examples of the thermoplastic resin include ethylene- (meth) acrylic monomer copolymer, ethylene-vinyl acetate copolymer, polyolefin resin, saturated or unsaturated polyester, polyvinyl chloride, polystyrene, and derivatives thereof. However, it is not limited to these.
　エチレン―（メタ）アクリル系モノマー共重合体とは、エチレンと（メタ）アクリル系モノマーとを少なくとも含む単量体組成物を共重合して得られる樹脂である。単量体組成物中の（メタ）アクリル系モノマーの含有量は、２重量％以上、３重量％以上、５重量％以上、又は１０重量％以上であり、５０重量％以下、４０重量％以下、又は３０重量％以下とすることができる。一般に、（メタ）アクリル系モノマーの含有量が高い場合、得られる樹脂の軟化温度が低くなり、（メタ）アクリル系モノマーの含有量が低い場合、得られる樹脂の密度が低くなる。最終の用途によって、適切な（メタ）アクリル系モノマー含有量の樹脂を選択することができる。 The ethylene- (meth) acrylic monomer copolymer is a resin obtained by copolymerizing a monomer composition containing at least ethylene and a (meth) acrylic monomer. The content of the (meth) acrylic monomer in the monomer composition is 2% by weight or more, 3% by weight or more, 5% by weight or more, or 10% by weight or more, and 50% by weight or less and 40% by weight or less. , Or 30% by weight or less. In general, when the content of the (meth) acrylic monomer is high, the softening temperature of the obtained resin is low, and when the content of the (meth) acrylic monomer is low, the density of the obtained resin is low. Depending on the final application, a resin having an appropriate (meth) acrylic monomer content can be selected.
　ここで、適切な（メタ）アクリル系モノマーとしては、（メタ）アクリル酸、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチルアクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート等を挙げることができる。 Here, examples of suitable (meth) acrylic monomers include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl acrylate, and pentyl (meth). ) Acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and the like can be mentioned.
　具体的なエチレン―（メタ）アクリル系モノマー共重合体の例としては、エチレン―アクリル酸共重合体（ＥＡＡ）、エチレン―メタクリル酸共重合体（ＥＭＡＡ）、エチレン―エチルアクリレート共重合体（ＥＥＡ）、エチレン―メチルアクリレート共重合体（ＥＭＡ）、エチレン―メタクリレート共重合体（ＥＭＭＡ）等が挙げられるが、これらに限定されない。 Specific examples of ethylene- (meth) acrylic monomer copolymers include ethylene-acrylic acid copolymers (EAA), ethylene-methacrylic acid copolymers (EMAA), and ethylene-ethyl acrylate copolymers (EEA). ), Ethylene-methylacrylate copolymer (EMA), ethylene-methacrylate copolymer (EMMA) and the like, but are not limited thereto.
　エチレン―酢酸ビニル共重合体（ＥＶＡ）とは、エチレンと酢酸ビニルとを少なくとも含む単量体組成物を共重合して得られる樹脂である。単量体組成物中の酢酸ビニル含有量は、２重量％以上、３重量％以上、５重量％以上、又は１０重量％以上であり、５０重量％以下、４０重量％以下、又は３０重量％以下とすることができる。一般に、酢酸ビニル含有量が高い場合、得られる樹脂の結晶化度が低くなり、酢酸ビニル含有量が低い場合、得られる樹脂の密度が低くなる。最終の用途によって、適切な酢酸ビニル含有量の樹脂を選択することができる。 Ethylene-vinyl acetate copolymer (EVA) is a resin obtained by copolymerizing a monomer composition containing at least ethylene and vinyl acetate. The vinyl acetate content in the monomer composition is 2% by weight or more, 3% by weight or more, 5% by weight or more, or 10% by weight or more, and 50% by weight or less, 40% by weight or less, or 30% by weight. It can be as follows. In general, when the vinyl acetate content is high, the crystallinity of the obtained resin is low, and when the vinyl acetate content is low, the density of the obtained resin is low. Depending on the final application, a resin having an appropriate vinyl acetate content can be selected.
　ポリオレフィン系樹脂としては、例えばポリエチレン系樹脂、ポリプロピレン系樹脂、又はポリブテン等が挙げられる。 Examples of the polyolefin resin include polyethylene resin, polypropylene resin, polybutene and the like.
　ポリエチレン系樹脂とは、ポリマーの主鎖にエチレン基の繰返し単位を、５０ｍｏｌ％超、６０ｍｏｌ％以上、７０ｍｏｌ％以上、又は８０ｍｏｌ％以上含む樹脂である。かかるポリエチレン系樹脂としては、低密度ポリエチレン（ＬＤＰＥ）、直鎖状低密度ポリエチレン（ＬＬＤＰＥ）、中密度ポリエチレン（ＭＤＰＥ）、高密度ポリエチレン（ＨＤＰＥ）等のポリエチレンを用いてもよく、エチレンと、カルボキシル基又はエステル基を有するエチレン系モノマーとの共重合体を用いてもよい。 A polyethylene-based resin is a resin containing a repeating unit of an ethylene group in the main chain of a polymer in an amount of more than 50 mol%, 60 mol% or more, 70 mol% or more, or 80 mol% or more. As the polyethylene-based resin, polyethylene such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), medium-density polyethylene (MDPE), and high-density polyethylene (HDPE) may be used, and polyethylene and carboxyl are used. A copolymer with an ethylene-based monomer having a group or an ester group may be used.
　また、ポリプロピレン系樹脂とは、ポリマーの主鎖にプロピレン基の繰返し単位を、５０ｍｏｌ％超、６０ｍｏｌ％以上、７０ｍｏｌ％以上、又は８０ｍｏｌ％以上含む樹脂である。かかるポリプロピレン系樹脂としては、ポリプロピレン（ＰＰ）ホモポリマー、ランダムポリプロピレン（ランダムＰＰ）、ブロックポリプロピレン（ブロックＰＰ）、塩素化ポリプロピレン、カルボン酸変性ポリプロピレン、及びこれらの誘導体、並びにこれらの混合物が挙げられる。 The polypropylene-based resin is a resin containing a repeating unit of a propylene group in the main chain of a polymer in an amount of more than 50 mol%, 60 mol% or more, 70 mol% or more, or 80 mol% or more. Examples of such polypropylene-based resins include polypropylene (PP) homopolymers, random polypropylene (random PP), block polypropylene (block PP), chlorinated polypropylene, carboxylic acid-modified polypropylene, derivatives thereof, and mixtures thereof.
　また、熱可塑性樹脂として芳香族ビニル－ジエン系共重合体、及びオレフィン系熱可塑性エラストマーを用いてもよい。 Further, an aromatic vinyl-diene-based copolymer and an olefin-based thermoplastic elastomer may be used as the thermoplastic resin.
　芳香族ビニル－ジエン系共重合体は、芳香族ビニルモノマー由来の繰返し単位及びジエンモノマー由来の繰返し単位を有する共重合体を意味する。このような芳香族ビニル－ジエン系共重合体としては、例えば特開２０１４－２００７５１号公報に挙げられているものを用いることができる。 The aromatic vinyl-diene-based copolymer means a copolymer having a repeating unit derived from an aromatic vinyl monomer and a repeating unit derived from a diene monomer. As such an aromatic vinyl-diene-based copolymer, for example, those listed in JP-A-2014-200751 can be used.
　オレフィン系熱可塑性エラストマーは、高温で流動化して成形が可能であり、常温ではゴム弾性を示す材料である。 Olefin-based thermoplastic elastomer is a material that can be fluidized and molded at high temperatures and exhibits rubber elasticity at room temperature.
　熱硬化性樹脂としては、随意の樹脂を用いることができ、例えばフェノール樹脂、メラミン樹脂、エポキシ樹脂等が挙げられるが、これらに限定されない。 As the thermosetting resin, any resin can be used, and examples thereof include, but are not limited to, phenol resin, melamine resin, and epoxy resin.
　吸収層の厚みは、特に限定されず、水分の吸着性能、成形性、及び弾性の観点から、１０μｍ以上、２０μｍ以上、３０μｍ以上、４０μｍ以上、５０μｍ以上、６０μｍ以上、７０μｍ以上、８０μｍ以上、９０μｍ以上、又は１００μｍ以上であることが好ましく、また３００μｍ以下、２００μｍ以下、１００μｍ以下、８０μｍ以下、又は５０μｍ以下であることが好ましい。 The thickness of the absorption layer is not particularly limited, and from the viewpoint of water adsorption performance, moldability, and elasticity, 10 μm or more, 20 μm or more, 30 μm or more, 40 μm or more, 50 μm or more, 60 μm or more, 70 μm or more, 80 μm or more, 90 μm. It is preferably 300 μm or more, or more than 100 μm, and more preferably 300 μm or less, 200 μm or less, 100 μm or less, 80 μm or less, or 50 μm or less.
　（多層の構造）
　吸収層が多層の構造である場合、吸収層は、例えば下記（１）～（５）に示されている形態をとることができるが、これらに限定されない。 (Multi-layer structure)
When the absorption layer has a multi-layer structure, the absorption layer can take, for example, the forms shown in (1) to (5) below, but is not limited thereto.
　（１）第１の形態
　吸収層は、外部側用面から内部側用面に向かって、この順に積層されている、吸湿層及び硫化物系ガス吸収層を有してよい。 (1) First Form The absorption layer may have a moisture absorption layer and a sulfide gas absorption layer, which are laminated in this order from the outer side surface to the inner side surface.
　なお、本発明において、「吸湿層」とは、少なくとも吸湿剤を含んでいる層、特に吸湿剤の含有率が最も高い層である。また、「硫化物系ガス吸収層」とは、少なくとも硫化物系ガス吸収剤を含んでいる層、特に硫化物系ガス吸収剤の含有率が最も高い層である。なお、任意の層の中に、吸湿剤及び硫化物系ガス吸収剤を同時に含んでいる場合には、「吸湿層」としてもよく、「硫化物系ガス吸収層」としてもよい。 In the present invention, the "hygroscopic layer" is at least a layer containing a hygroscopic agent, particularly a layer having the highest hygroscopic agent content. The "sulfide-based gas absorbing layer" is a layer containing at least a sulfide-based gas absorbing agent, particularly a layer having the highest content of the sulfide-based gas absorbing agent. When a hygroscopic agent and a sulfide-based gas absorber are simultaneously contained in any layer, it may be a "moisture-absorbing layer" or a "sulfide-based gas absorbing layer".
　例えば、図２（ａ）に示されているように、吸収層２１は、外部側用面から内部側用面に向かって、この順に積層されている、吸湿層２１ａ及び硫化物系ガス吸収層２１ｂを有する。 For example, as shown in FIG. 2A, the absorption layer 21 is a moisture absorption layer 21a and a sulfide gas absorption layer, which are laminated in this order from the outer side surface to the inner side surface. It has 21b.
　このような形態を有する吸収層を用いることによって、特に、硫化物系全固体電池を収容しているラミネートパックの外部から内部への水分の侵入を防止することができる。 By using an absorption layer having such a form, it is possible to prevent moisture from entering from the outside to the inside of the laminate pack containing the sulfide-based all-solid-state battery.
　（２）第２の形態
　吸収層は、外部側用面から内部側用面に向かって、この順に積層されている、硫化物系ガス吸収層及び吸湿層を有してよい。 (2) Second Form The absorption layer may have a sulfide-based gas absorption layer and a moisture absorption layer, which are laminated in this order from the outer side surface to the inner side surface.
　例えば、図２（ｂ）に示されているように、吸収層３１は、外部側用面から内部側用面に向かって、この順に積層されている、硫化物系ガス吸収層３１ｂ及び吸湿層３１ａを有する。 For example, as shown in FIG. 2B, the absorption layer 31 is a sulfide-based gas absorption layer 31b and a moisture absorption layer, which are laminated in this order from the outer side surface to the inner side surface. It has 31a.
　このような形態を有する吸収層を用いることによって、特に、硫化物系全固体電池を収容しているラミネートパックの側面の封止口から内部への水分の侵入を防止することができる。 By using an absorption layer having such a form, it is possible to prevent moisture from entering the inside from the sealing port on the side surface of the laminate pack containing the sulfide-based all-solid-state battery.
　（３）第３の形態
　吸収層は、その両面にスキン層を有してよい。 (3) Third Form The absorption layer may have skin layers on both sides thereof.
　スキン層は、吸湿層に含まれる吸湿剤又は任意の硫化物系ガス吸収剤等の脱落を防止すること、又はラミネートパックの強度を向上することができる。したがって、この観点から、吸収層は、その両面にスキン層を更に有することが好ましい。 The skin layer can prevent the hygroscopic agent or any sulfide-based gas absorbent contained in the hygroscopic layer from falling off, or can improve the strength of the laminate pack. Therefore, from this point of view, it is preferable that the absorption layer further has skin layers on both sides thereof.
　したがって、第３の形態として、吸収層は、外部側用面から内部側用面に向かって、この順に積層されている、第１のスキン層、吸湿層、及び第２のスキン層を有してよい。 Therefore, as a third form, the absorbing layer has a first skin layer, a moisture absorbing layer, and a second skin layer, which are laminated in this order from the outer side surface to the inner side surface. You can.
　例えば、図２（ｃ）に示されているように、吸収層４１は、外部側用面から内部側用面に向かって、この順に積層されている、第１のスキン層４１ｃ、吸湿層４１ａ、及び第２のスキン層４１ｄを有する。 For example, as shown in FIG. 2C, the absorption layer 41 is laminated in this order from the outer side surface to the inner side surface, the first skin layer 41c and the moisture absorption layer 41a. , And a second skin layer 41d.
　このような形態を有する吸収層を用いることによって、特に、硫化物系全固体電池を収容しているラミネートパックの外部から内部への水分の侵入を防止することができる。また、吸湿層に含まれる吸湿剤の脱落を防止することができる。 By using an absorption layer having such a form, it is possible to prevent moisture from entering from the outside to the inside of the laminate pack containing the sulfide-based all-solid-state battery. In addition, it is possible to prevent the hygroscopic agent contained in the hygroscopic layer from falling off.
　（４）第４の形態
　更に、上述した吸収層の両面にスキン層を有する場合には、吸収層は、外部側用面から内部側用面に向かって、この順に積層されている、第１のスキン層、吸湿層、硫化物系ガス吸収層、及び第２のスキン層を有してよい。 (4) Fourth Form Further, when the skin layers are provided on both sides of the above-mentioned absorption layer, the absorption layers are laminated in this order from the outer side surface to the inner side surface. It may have a skin layer, a moisture absorbing layer, a sulfide gas absorbing layer, and a second skin layer.
　例えば、図２（ｄ）に示されているように、吸収層５１は、外部側用面から内部側用面に向かって、この順に積層されている、第１のスキン層５１ｃ、吸湿層５１ａ、硫化物系ガス吸収層５１ｂ、及び第２のスキン層５１ｄを有する。 For example, as shown in FIG. 2D, the absorption layer 51 is laminated in this order from the outer side surface to the inner side surface, the first skin layer 51c and the moisture absorption layer 51a. , A sulfide-based gas absorbing layer 51b, and a second skin layer 51d.
　このような形態を有する吸収層を用いることによって、特に、硫化物系全固体電池を収容しているラミネートパックの外部から内部への水分の侵入を防止することができる。また、吸湿層に含まれる吸湿剤及び硫化物系ガス吸収層に含まれる硫化物系ガス吸収剤の脱落を防止することができる。 By using an absorption layer having such a form, it is possible to prevent moisture from entering from the outside to the inside of the laminate pack containing the sulfide-based all-solid-state battery. Further, it is possible to prevent the hygroscopic agent contained in the moisture absorbing layer and the sulfide gas absorbing agent contained in the sulfide gas absorbing layer from falling off.
　（５）第５の形態
　また、上述した吸収層の両面にスキン層を有する場合には、吸収層は、外部側用面から内部側用面に向かって、この順に積層されている、第１のスキン層、硫化物系ガス吸収層、吸湿層、及び第２のスキン層を有してよい。 (5) Fifth Form When the skin layers are provided on both sides of the above-mentioned absorption layer, the absorption layers are laminated in this order from the outer side surface to the inner side surface. It may have a skin layer, a sulfide gas absorbing layer, a moisture absorbing layer, and a second skin layer.
　例えば、図２（ｅ）に示されているように、吸収層６１は、外部側用面から内部側用面に向かって、この順に積層されている、第１のスキン層６１ｃ、硫化物系ガス吸収層６１ｂ、吸湿層６１ａ、及び第２のスキン層６１ｄを有する。 For example, as shown in FIG. 2E, the absorption layer 61 is a first skin layer 61c, sulfide-based, which is laminated in this order from the outer side surface to the inner side surface. It has a gas absorbing layer 61b, a moisture absorbing layer 61a, and a second skin layer 61d.
　このような形態を有する吸収層を用いることによって、特に、硫化物系全固体電池を収容しているラミネートパックの側面の封止口から内部への水分の侵入を防止することができる。また、吸湿層に含まれる吸湿剤及び硫化物系ガス吸収層に含まれる硫化物系ガス吸収剤の脱落を防止することができる。 By using an absorption layer having such a form, it is possible to prevent moisture from entering the inside from the sealing port on the side surface of the laminate pack containing the sulfide-based all-solid-state battery. Further, it is possible to prevent the hygroscopic agent contained in the moisture absorbing layer and the sulfide gas absorbing agent contained in the sulfide gas absorbing layer from falling off.
　なお、上述した第４の形態及び第５の形態において、吸湿層及び硫化物系ガス吸収層は、それぞれの両面にスキン層を有してもよい。すなわち、吸収層は、外部側用面から内部側用面に向かって、この順に積層されている、第１のスキン層、吸湿層、第２のスキン層、第３のスキン層、硫化物系ガス吸収層、及び第４のスキン層を有してもよく、又は第１のスキン層、硫化物系ガス吸収層、第２のスキン層、第３のスキン層、吸湿層、及び第４のスキン層を有してもよい（図示せず）。 In the fourth form and the fifth form described above, the moisture absorbing layer and the sulfide gas absorbing layer may have skin layers on both sides thereof. That is, the absorption layer is laminated in this order from the outer side surface to the inner side surface, the first skin layer, the moisture absorbing layer, the second skin layer, the third skin layer, and the sulfide system. It may have a gas absorbing layer and a fourth skin layer, or a first skin layer, a sulfide gas absorbing layer, a second skin layer, a third skin layer, a moisture absorbing layer, and a fourth. It may have a skin layer (not shown).
　上述した「吸湿層」、「硫化物系ガス吸収層」、「スキン層」については、以下で詳細に説明する。 The above-mentioned "moisture absorbing layer", "sulfide gas absorbing layer", and "skin layer" will be described in detail below.
　１．吸湿層
　吸湿層は、少なくとも吸湿剤及びバインダーを含む。したがって、吸湿層は、上述した吸収層が単層の構造である場合を適宜参照することができる。 1. 1. Hygroscopic layer The hygroscopic layer contains at least a hygroscopic agent and a binder. Therefore, as the moisture absorbing layer, the case where the above-mentioned absorbing layer has a single layer structure can be appropriately referred to.
　２．硫化物系ガス吸収層
　硫化物系ガス吸収層は、少なくとも硫化物系ガス吸収剤及びバインダーを含む。 2. Sulfide-based gas absorption layer The sulfide-based gas absorption layer contains at least a sulfide-based gas absorber and a binder.
　硫化物系ガス吸収剤に関しては、上述した硫化物系ガスを化学的にかつ／又は物理的に吸着できるものであれば、特に限定されない。また、バインダーに関しては、上述した吸収層に用いられるバインダーを適宜採用できる。 The sulfide-based gas absorber is not particularly limited as long as it can chemically and / or physically adsorb the above-mentioned sulfide-based gas. As for the binder, the binder used for the absorption layer described above can be appropriately used.
　硫化物系ガス吸収層において、硫化物系ガス吸収剤の含有量（質量部）は、バインダー１００質量部に対して、混練性及びガス吸着性能を考慮して、０．１質量部以上、１質量部以上、３質量部以上、５質量部以上、１０質量部以上、２０質量部以上、３０質量部以上、４０質量部以上又は５０質量部以上であることが好ましく、また５００質量部以下、３００質量部以下、１００質量部以下、５０質量部以下、４０質量部以下、又は３０質量部以下であることが好ましい。 In the sulfide-based gas absorbing layer, the content (parts by mass) of the sulfide-based gas absorber is 0.1 part by mass or more and 1 part by mass or more in consideration of kneading property and gas adsorption performance with respect to 100 parts by mass of the binder. It is preferably 3 parts by mass or more, 5 parts by mass or more, 10 parts by mass or more, 20 parts by mass or more, 30 parts by mass or more, 40 parts by mass or more or 50 parts by mass or more, and 500 parts by mass or less. It is preferably 300 parts by mass or less, 100 parts by mass or less, 50 parts by mass or less, 40 parts by mass or less, or 30 parts by mass or less.
　硫化物系ガス吸収層の厚みは、特に限定されず、ガスの吸着性能、成形性、及び弾性の観点から、１０μｍ以上、２０μｍ以上、３０μｍ以上、４０μｍ以上、５０μｍ以上、６０μｍ以上、７０μｍ以上、８０μｍ以上、９０μｍ以上、又は１００μｍ以上であることが好ましく、また３００μｍ以下、２００μｍ以下、１００μｍ以下、８０μｍ以下、又は５０μｍ以下であることが好ましい。 The thickness of the sulfide gas absorbing layer is not particularly limited, and from the viewpoint of gas adsorption performance, moldability, and elasticity, 10 μm or more, 20 μm or more, 30 μm or more, 40 μm or more, 50 μm or more, 60 μm or more, 70 μm or more, It is preferably 80 μm or more, 90 μm or more, or 100 μm or more, and preferably 300 μm or less, 200 μm or less, 100 μm or less, 80 μm or less, or 50 μm or less.
　３．スキン層
　スキン層は、それと隣接する層（例えば吸収層、吸湿層及び／又は硫化物系ガス吸収層）に融着されていてもよい。例えば、吸収層の両面にスキン層を有する場合には、それぞれの層は、吸湿層と共に押出しして製造することができる。 3. 3. Skin layer The skin layer may be fused to a layer adjacent thereto (for example, an absorption layer, a moisture absorption layer and / or a sulfide gas absorption layer). For example, when the skin layers are provided on both sides of the absorbing layer, each layer can be produced by extruding together with the moisture absorbing layer.
　スキン層を構成する材料としては、上述した吸収層に用いられるバインダーを適宜採用できる。 As the material constituting the skin layer, the binder used for the absorption layer described above can be appropriately adopted.
　スキン層の厚さは、１μｍ以上、３μｍ以上、５μｍ以上、又は７μｍ以上であることができ、また５０μｍ以下、４０μｍ以下、３０μｍ以下、２０μｍ以下、又は１５μｍ以下であることができる。 The thickness of the skin layer can be 1 μm or more, 3 μm or more, 5 μm or more, or 7 μm or more, and can be 50 μm or less, 40 μm or less, 30 μm or less, 20 μm or less, or 15 μm or less.
　〈その他の層〉
　本発明のラミネートシートは、上述した層以外に、その他の層を更に含んでよい。例えば基材層、又はシーラント層等を更に有してよい。 <Other layers>
The laminated sheet of the present invention may further contain other layers in addition to the above-mentioned layers. For example, it may further have a base material layer, a sealant layer, or the like.
　（基材層）
　本発明のラミネートシートは、バリア層の、吸収層とは反対側の面に、基材層を更に有してよい。基材層は、上述したバリア層を保護することができる。 (Base layer)
The laminated sheet of the present invention may further have a base material layer on the surface of the barrier layer opposite to the absorption layer. The base material layer can protect the barrier layer described above.
　基材層としては、耐衝撃性、耐摩耗性等に優れた熱可塑性樹脂、例えば、ポリオレフィン、ビニル系ポリマー、ポリエステル、ポリアミド等を単独で、又は２種類以上組み合わせて複層で使用することができる。この基材層は、延伸フィルムであっても、無延伸フィルムであってもよい。 As the base material layer, a thermoplastic resin having excellent impact resistance, abrasion resistance, etc., for example, polyolefin, vinyl polymer, polyester, polyamide, etc. can be used alone or in combination of two or more types in a plurality of layers. it can. This base material layer may be a stretched film or a non-stretched film.
　ポリオレフィンとしては、ポリエチレン系樹脂、ポリプロピレン系樹脂等が挙げられる。ポリエチレン系樹脂としては、吸収層に関して挙げたポリエチレン系樹脂を用いることができ、ポリプロピレン系樹脂としては、第一の耐熱層に関して挙げたポリプロピレン系樹脂を用いることができる。 Examples of the polyolefin include polyethylene-based resin and polypropylene-based resin. As the polyethylene-based resin, the polyethylene-based resin mentioned for the absorption layer can be used, and as the polypropylene-based resin, the polypropylene-based resin mentioned for the first heat-resistant layer can be used.
　ビニル系ポリマーとしては、例えばポリ塩化ビニル（ＰＶＣ）、ポリ塩化ビニリデン（ＰＶＤＣ）、ポリクロロトリフルオロエチレン、ポリテトラフルオロエチレン、ポリアクリロニトリル（ＰＡＮ）等が挙げられる。 Examples of the vinyl polymer include polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polychlorotrifluoroethylene, polytetrafluoroethylene, polyacrylonitrile (PAN) and the like.
　ポリエステルとしては、例えばポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート等が挙げられる。 Examples of polyester include polyethylene terephthalate (PET) and polybutylene terephthalate.
　ポリアミドとしては、例えばナイロン（登録商標）６、ナイロンＭＸＤ６等のナイロン等が挙げられる。 Examples of the polyamide include nylon such as nylon (registered trademark) 6 and nylon MXD6.
　基材層の厚さは、７μｍ以上、１０μｍ以上、又は１５μｍ以上であることが、バリア層を良好に保護する観点から好ましく、また５５μｍ以下、５０μｍ以下、又は４５μｍ以下であることが、取り扱い性を向上させる観点から好ましい。 The thickness of the base material layer is preferably 7 μm or more, 10 μm or more, or 15 μm or more from the viewpoint of good protection of the barrier layer, and 55 μm or less, 50 μm or less, or 45 μm or less for handleability. It is preferable from the viewpoint of improving.
　（シーラント層）
　本発明のラミネートシートは、吸収層の、バリア層とは反対側の面に、シーラント層を更に有してよい。 (Sealant layer)
The laminated sheet of the present invention may further have a sealant layer on the surface of the absorption layer opposite to the barrier layer.
　シーラント層は、ヒートシールに用いられる層である。よって、本発明のラミネートシートをラミネートパックに用いる場合に、このシーラント層を、硫化物系全固体電池に最も接近するラミネートパックの最内層に配置して、ヒートシールすることによって、ラミネートパックを得ることができるものであってよい。なお、本発明において、別個のシーラント層を有さない場合、ラミネートパックの最内層として配置される層、例えば吸収層、又はスキン層等をシーラント層として用いることができる。 The sealant layer is a layer used for heat sealing. Therefore, when the laminate sheet of the present invention is used in a laminate pack, the sealant layer is placed in the innermost layer of the laminate pack closest to the sulfide-based all-solid-state battery and heat-sealed to obtain the laminate pack. It may be something that can be done. In the present invention, when a separate sealant layer is not provided, a layer arranged as the innermost layer of the laminate pack, for example, an absorption layer, a skin layer, or the like can be used as the sealant layer.
　シーラント層を構成する材料は、上述した吸収層に用いられるバインダーに関して説明した熱可塑性材料であってよく、特に、例えば、ポリプロピレン（ＰＰ）、低密度ポリエチレン（ＬＤＰＥ）、中密度ポリエチレン（ＭＤＰＥ）、高密度ポリエチレン（ＨＤＰＥ）、メタロセン触媒によるポリエチレン、エチレンの繰返し単位とアクリルの繰返し単位とを有する共重合樹脂、若しくはエチレンの繰返し単位とアクリル以外の繰返し単位とを有する共重合樹脂、又はこれらの組合せであってよいが、これらに限定されない。これらの樹脂は、例えば、延伸又は無延伸フィルム、押出積層用の溶融樹脂、ホットメルト用の塗料等の形態であってよい。 The material constituting the sealant layer may be the thermoplastic material described with respect to the binder used for the absorption layer described above, and in particular, for example, polypropylene (PP), low density polyethylene (LDPE), medium density polyethylene (MDPE), etc. High-density polyethylene (HDPE), polyethylene catalyzed by metallocene, a copolymer resin having a repeating unit of ethylene and a repeating unit of acrylic, or a copolymer resin having a repeating unit of ethylene and a repeating unit other than acrylic, or a combination thereof. However, it is not limited to these. These resins may be in the form of, for example, a stretched or unstretched film, a molten resin for extrusion lamination, a paint for hot melting, and the like.
　また、シーラント層としては、市販のイージーピール樹脂又はイージーピールシーラントフィルムを用いてもよい。 Further, as the sealant layer, a commercially available easy peel resin or an easy peel sealant film may be used.
　シーラント層の厚さは、特に限定されず、溶融によって強固なシールを形成するとの観点から、１０μｍ以上、２０μｍ以上、３０μｍ以上、４０μｍ以上、又は５０μｍ以上であることが好ましく、また、取り扱い性を向上させる観点から、１００μｍ以下、８０μｍ以下、又は５０μｍ以下であることが好ましい。 The thickness of the sealant layer is not particularly limited, and is preferably 10 μm or more, 20 μm or more, 30 μm or more, 40 μm or more, or 50 μm or more from the viewpoint of forming a strong seal by melting, and the handleability is improved. From the viewpoint of improvement, it is preferably 100 μm or less, 80 μm or less, or 50 μm or less.
　〈接着剤〉
　本発明のラミネートシートにおける各層間は、適当な接着剤によって固定されていることが好ましい。 <adhesive>
It is preferable that each layer of the laminated sheet of the present invention is fixed with an appropriate adhesive.
　この場合の接着剤は、積層フィルムの製造方法に応じて当業者が適宜に選択することができる。例えば、ドライラミネート用のウレタン系接着剤等であってよい。 The adhesive in this case can be appropriately selected by a person skilled in the art according to the method for producing the laminated film. For example, it may be a urethane-based adhesive for dry laminating.
　より具体的は、接着剤として、例えば三井化学株式会社製のタケラック（登録商標）Ａ－５２５Ｓとタケネート（登録商標）Ａ－５２との組合せ、タケラック（登録商標）Ａ－５２０とタケネート（登録商標）Ａ－５０との組合せ、タケラック（登録商標）Ａ－５２５とタケネート（登録商標）Ａ－５２との組合せ、及びタケラック（登録商標）Ａ－５２５Ｓとタケネート（登録商標）Ａ－５０との組合せ等を用いられるが、これらに限定されない。 More specifically, as the adhesive, for example, a combination of Takelac (registered trademark) A-525S manufactured by Mitsui Kagaku Co., Ltd. and Takenate (registered trademark) A-52, Takelac (registered trademark) A-520 and Takenate (registered trademark). ) Combination with A-50, combination of Takelac (registered trademark) A-525 and Takenate (registered trademark) A-52, and combination of Takelac (registered trademark) A-525S and Takelac (registered trademark) A-50. Etc., but are not limited to these.
　接着剤の量は、ラミネートシート単位面積当たりの接着材料として、層間ごとに、例えば０．５ｇ／ｍ２以上とすることができ、好ましくは１ｇ／ｍ２以上、又は３ｇ／ｍ２以上である。一方でこの接着剤の量は、例えば１０ｇ／ｍ２以下とすることができ、好ましくは５ｇ／ｍ２以下である。 The amount of the adhesive can be, for example, 0.5 g / m 2 or more, preferably 1 g / m 2 or more, or 3 g / m 2 or more for each layer as the adhesive material per unit area of the laminated sheet. .. On the other hand, the amount of this adhesive can be, for example, 10 g / m 2 or less, preferably 5 g / m 2 or less.
　《ラミネートシートの製造方法》
　本発明のラミネートシートの製造方法は、特に限定されず、例えば上述したラミネートシートの各層を構成する材料を、必要に応じて溶融混錬し、製膜し、そして各層を積層することによって製造することができる。 << Manufacturing method of laminated sheet >>
The method for producing the laminated sheet of the present invention is not particularly limited, and for example, the material constituting each layer of the above-mentioned laminated sheet is melt-kneaded, formed into a film, and laminated with each other, if necessary. be able to.
　溶融混錬は、バッチ式混練機又は連続混練機等を用いて行うことができる。より具体的には、溶融混錬は、例えばバンバリーミキサー、ニーダー、ヘンシェルミキサー、又はミキシングロール等を用いて行うことができる。溶融混錬の温度は、特に限定されず、各層を構成する材料に応じて適宜設定することができ、例えば５０℃以上、８０℃以上、１００℃以上、１５０℃以上、又は２００℃以上であってよく、また、３５０℃以下、３００℃以下、又は２００℃以下であってよい。溶融混錬の時間は、特に限定されず、例えば１分以上、５分以上、１０分以上、２０分以上、３０分以上、又は６０分以上であってよく、また４８時間以下、２４時間以下、１２時間以下、又は２時間以下であってよい。 Melt kneading can be performed using a batch type kneader, a continuous kneader, or the like. More specifically, melt kneading can be performed using, for example, a Banbury mixer, a kneader, a Henschel mixer, a mixing roll, or the like. The temperature of melt kneading is not particularly limited and can be appropriately set according to the material constituting each layer, and is, for example, 50 ° C. or higher, 80 ° C. or higher, 100 ° C. or higher, 150 ° C. or higher, or 200 ° C. or higher. It may be 350 ° C. or lower, 300 ° C. or lower, or 200 ° C. or lower. The melt-kneading time is not particularly limited, and may be, for example, 1 minute or more, 5 minutes or more, 10 minutes or more, 20 minutes or more, 30 minutes or more, or 60 minutes or more, and 48 hours or less, 24 hours or less. , 12 hours or less, or 2 hours or less.
　製膜は、例えばインフレーション法、Ｔダイ法、カレンダー法、キャスティング法、熱プレス成形、押出成形又は射出成形等により行うことができる。 Film formation can be performed by, for example, an inflation method, a T-die method, a calendar method, a casting method, hot press molding, extrusion molding, injection molding, or the like.
　積層は、サンドラミネート法等の押出ラミネート法、ヒートシール法、熱プレス成形、又はドライラミネート等により行うことができる。 Lamination can be performed by extrusion laminating method such as sand laminating method, heat sealing method, heat press molding, dry laminating or the like.
　また、共押出インフレーション法及び共押出Ｔダイ法等の共押出法により、製膜及び積層を同時に行ってもよい。 Further, film formation and lamination may be performed at the same time by a coextrusion method such as a coextrusion inflation method and a coextrusion T-die method.
　《硫化物系全固体電池用ラミネートパック》
　本発明はまた、硫化物系全固体電池用ラミネートパックを提供する。 << Laminate pack for sulfide-based all-solid-state batteries >>
The present invention also provides a laminate pack for a sulfide-based all-solid-state battery.
　本発明のラミネートパックは、上述したラミネートシートを１つ用いて袋状に形成されていてもよい。すなわち、本発明のラミネートパックは、ラミネートシートを１つ具備しており、かつラミネートシートが内部側用面を内側にして折り曲げられて、内部側用面の周縁部がヒートシールされることによって袋状にされている、硫化物系全固体電池用ラミネートパックであってよい。 The laminate pack of the present invention may be formed in a bag shape by using one of the above-mentioned laminate sheets. That is, the laminate pack of the present invention includes one laminate sheet, and the laminate sheet is bent with the inner side surface facing inward, and the peripheral edge portion of the inner side surface is heat-sealed to form a bag. It may be a laminated pack for a sulfide-based all-solid-state battery, which is shaped like this.
　本発明のラミネートパックは、上述したラミネートシートと、他のラミネートシートとを併用して袋状に形成されていてもよい。 The laminate pack of the present invention may be formed in a bag shape by using the above-mentioned laminate sheet and another laminate sheet in combination.
　したがって、上述したラミネートシートを「Ａ面用ラミネートシート」とし、他のラミネートシートを「Ｂ面用ラミネートシート」とするとき、本発明のラミネートパックは、Ａ面用ラミネートシートとしての上述したラミネートシートと、外部側用面から内部側用面に向かって、この順に積層されている、Ｂ面用バリア層及びＢ面用シーラント層を有するＢ面用ラミネートシートとを具備しており、かつＡ面用ラミネートシートの内部側用面と、Ｂ面用シーラント層とが互いに対向して、内部側用面とＢ面用シーラント層との周縁部同士がヒートシールされることによって袋状にされている、硫化物系全固体電池用ラミネートパックであってよい。 Therefore, when the above-mentioned laminate sheet is referred to as "A-side laminate sheet" and the other laminate sheet is referred to as "B-side laminate sheet", the laminate pack of the present invention is the above-mentioned laminate sheet as A-side laminate sheet. And a B-side laminate sheet having a B-side barrier layer and a B-side sealant layer, which are laminated in this order from the outer side surface to the inner side surface, and the A surface. The inner side surface of the laminate sheet and the B surface sealant layer face each other, and the peripheral edges of the inner side surface and the B surface sealant layer are heat-sealed to form a bag shape. , It may be a laminate pack for a sulfide-based all-solid-state battery.
　なお、Ｂ面用バリア層及びＢ面用シーラント層は、上述したＡ面に用いられる「バリア層」及び「シーラント層」を適宜に参照してよい。また、Ｂ面用ラミネートシートは、例えば上述した基材層等のその他の層を更に有してもよい。例えば、Ｂ面用ラミネートシートは、外部側用面から内部側用面に向かって、この順に積層されている、Ｂ面用基材層、Ｂ面用バリア層、及びＢ面用シーラント層を有してよい。 As the B-side barrier layer and the B-side sealant layer, the above-mentioned "barrier layer" and "sealant layer" used for the A-side may be appropriately referred to. Further, the B-side laminated sheet may further have other layers such as the above-mentioned base material layer. For example, the B-side laminated sheet has a B-side base material layer, a B-side barrier layer, and a B-side sealant layer, which are laminated in this order from the outer side surface to the inner side surface. You can do it.
　本発明のラミネートパックはまた、上述したラミネートシートを２つ以上用いて袋状に形成されていてもよい。すなわち、本発明のラミネートパックは、ラミネートシートを２つ以上具備しており、かつ内部側用面同士が互いに対向して、内部側用面の周縁部同士がヒートシールされることによって袋状にされている、硫化物系全固体電池用ラミネートパックであってよい。 The laminate pack of the present invention may also be formed in a bag shape by using two or more of the above-mentioned laminate sheets. That is, the laminate pack of the present invention is provided with two or more laminate sheets, and the inner side surfaces face each other, and the peripheral edges of the inner side surfaces are heat-sealed to form a bag. It may be a sulfide-based all-solid-state battery laminate pack.
　なお、ラミネートシートを２つ以上用いて、ラミネートパックを形成する場合には、２つ以上のラミネートシートの構成は、同じであってもよく、異なっていてもよい。 When two or more laminated sheets are used to form a laminated pack, the configurations of the two or more laminated sheets may be the same or different.
　例えば、図３（ａ）及び（ｂ）に示されているように、ラミネートパックのＡ面及びＢ面として、２つの異なるラミネートを用いてラミネートパックを形成することができる。 For example, as shown in FIGS. 3A and 3B, a laminate pack can be formed by using two different laminates as the A side and the B side of the laminate pack.
　より具体的には、図３（ａ）では、Ａ面として、外部側用面から内部側用面に向かって、この順に積層されている、バリア層７０ａ、及び吸収層７１を有するラミネートシートを用いており、また、この吸収層７１は、外部側用面から内部側用面に向かって、この順に積層されている、吸湿層７１ａ及び硫化物系ガス吸収層７１ｂを有する。また、Ｂ面として、外部側用面から内部側用面に向かって、この順に積層されている、バリア層７０ｂ、及びシーラント層７２を有するラミネートシートを用いる。この場合、本発明のラミネートパックは、内部側用面同士、すなわち硫化物系ガス吸収層７１ｂ及びシーラント層７２のそれぞれの内部側用面同士が互いに対向して、硫化物系ガス吸収層７１ｂ及びシーラント層７２のそれぞれの内部側用面同士の周縁部同士がヒートシールされることによって袋状にされている、ラミネートパックであってよい。 More specifically, in FIG. 3A, as the A surface, a laminated sheet having a barrier layer 70a and an absorption layer 71, which are laminated in this order from the outer side surface to the inner side surface, is provided. The absorption layer 71 has a moisture absorption layer 71a and a sulfide-based gas absorption layer 71b, which are laminated in this order from the outer side surface to the inner side surface. Further, as the B surface, a laminated sheet having a barrier layer 70b and a sealant layer 72, which are laminated in this order from the outer side surface to the inner side surface, is used. In this case, in the laminate pack of the present invention, the internal side surfaces, that is, the internal side surfaces of the sulfide gas absorption layer 71b and the sealant layer 72 face each other, and the sulfide gas absorption layer 71b and It may be a laminated pack in which the peripheral edges of the inner surfaces of the sealant layer 72 are heat-sealed to form a bag.
　また、図３（ｂ）では、Ａ面として、外部側用面から内部側用面に向かって、この順に積層されている、バリア層８０ａ、及び吸収層８１を有するラミネートシートを用いており、また、この吸収層８１は、外部側用面から内部側用面に向かって、この順に積層されている、吸湿層８１ａ及び硫化物系ガス吸収層８１ｂを有する。また、Ｂ面として、外部側用面から内部側用面に向かって、この順に積層されている、バリア層８０ｂ、及び硫化物系ガス吸収層８１ｂを有するラミネートシートを用いる。この場合、本発明のラミネートパックは、内部側用面同士、すなわち２つの硫化物系ガス吸収層８１ｂの内部側用面同士が互いに対向して、２つの硫化物系ガス吸収層８１ｂのそれぞれの内部側用面同士の周縁部同士がヒートシールされることによって袋状にされている、ラミネートパックであってよい。 Further, in FIG. 3B, a laminated sheet having a barrier layer 80a and an absorption layer 81, which are laminated in this order from the outer side surface to the inner side surface, is used as the A surface. Further, the absorption layer 81 has a moisture absorption layer 81a and a sulfide gas absorption layer 81b that are laminated in this order from the outer side surface to the inner side surface. Further, as the B surface, a laminated sheet having a barrier layer 80b and a sulfide gas absorption layer 81b, which are laminated in this order from the outer side surface to the inner side surface, is used. In this case, in the laminate pack of the present invention, the inner side surfaces, that is, the inner side surfaces of the two sulfide gas absorption layers 81b face each other, and each of the two sulfide gas absorption layers 81b. It may be a laminated pack in which the peripheral edges of the inner surfaces are heat-sealed to form a bag.
　ここで、上述したいずれのラミネートパックの場合も、内部側用面の周縁部の大きさは、加熱及び／又は加圧してヒートシールできる程度の大きさとして設定してよい。 Here, in the case of any of the above-mentioned laminate packs, the size of the peripheral edge of the inner surface may be set to a size that allows heat sealing by heating and / or pressurizing.
　また、本発明のラミネートパックの内部側用面をヒートシールすることによって、硫化物系全固体電池を密封する三方シールタイプ、四方シールタイプ、又はピローパウチタイプのいずれであってよい。 Further, it may be either a three-way seal type, a four-way seal type, or a pillow pouch type that seals a sulfide-based all-solid-state battery by heat-sealing the inner surface of the laminate pack of the present invention.
　《ラミネート電池》
　本発明は、上述したラミネートパック及び硫化物系全固体電池を具備している、ラミネート電池を提供する。 《Laminated battery》
The present invention provides a laminated battery comprising the above-mentioned laminate pack and a sulfide-based all-solid-state battery.
　本発明のラミネート電池は、本発明のラミネートパックを使用する以外は、硫化物系全固体電池を含む公知の形態を採用することができる。 The laminated battery of the present invention can adopt a known form including a sulfide-based all-solid-state battery, except that the laminated pack of the present invention is used.
　実施例及び比較例により本発明を具体的に説明するが、本発明は、これらに限定されるものではない。 The present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
　〈吸湿層の作製〉
　下記の吸湿剤とバインダーを用いて溶融混錬法より押出機でマスターバッチを作製した。
　　吸湿剤（５３質量部）：親水性ゼオライト（モレキュラーシーブ３Ａ；ユニオン昭和株式会社製）
　　バインダー（４７質量部）：エチレン―メタクリル酸共重合体（熱可塑性樹脂）。 <Preparation of hygroscopic layer>
A masterbatch was prepared by an extruder by a melt kneading method using the following hygroscopic agent and binder.
Moisture absorber (53 parts by mass): Hydrophilic zeolite (Molecular sieve 3A; manufactured by Union Showa Co., Ltd.)
Binder (47 parts by mass): Ethylene-methacrylic acid copolymer (thermoplastic resin).
　上記得られたマスターバッチを吸湿層とし、かつ、直鎖状低密度ポリエチレンを第１のスキン層及び第２のスキン層として、空冷方式インフレーションによる共押出成形にて、以下の順に積層されている２種３層の吸湿層を作製した：
　　第１のスキン層（１０μｍ）／吸湿層（３０μｍ）／第２のスキン層（１０μｍ）。 The master batch obtained above is used as a moisture absorbing layer, and linear low-density polyethylene is used as a first skin layer and a second skin layer, and is laminated in the following order by coextrusion molding by air-cooled inflation. Two types and three layers of moisture absorbing layers were prepared:
First skin layer (10 μm) / moisture absorbing layer (30 μm) / second skin layer (10 μm).
　〈硫化物系ガス吸収層の作製〉
　バインダーとしてのポリエチレン５０質量部と、ガス吸収剤としてのケスモンＮＳ－２０Ｃ（東亞合成株式会社製）５０質量部とを配合し、バンバリーミキサーにより混錬物を作製した。なお、混錬温度は１５０℃であり、混錬時間は１０分間であった。 <Preparation of sulfide gas absorption layer>
50 parts by mass of polyethylene as a binder and 50 parts by mass of Kessmon NS-20C (manufactured by Toagosei Co., Ltd.) as a gas absorber were mixed, and a kneaded product was prepared by a Banbury mixer. The kneading temperature was 150 ° C. and the kneading time was 10 minutes.
　上記作製した混錬物２質量部とポリエチレン９８質量部を混合しガス吸収剤含有層とし、かつ直鎖状低密度ポリエチレンを第１のスキン層及び第２のスキン層として、インフレーション機にて、以下の順に積層されている２種３層の硫化物系ガス吸収層を作製した：
　　第１のスキン層（１０μｍ）／硫化物系ガス吸収層（５０μｍ）／第２のスキン層（１０μｍ）。 2 parts by mass of the above-mentioned kneaded product and 98 parts by mass of polyethylene are mixed to form a gas absorbent-containing layer, and linear low-density polyethylene is used as a first skin layer and a second skin layer by an inflation machine. A sulfide-based gas absorption layer of 2 types and 3 layers laminated in the following order was prepared:
First skin layer (10 μm) / sulfide gas absorption layer (50 μm) / second skin layer (10 μm).
　〈吸湿剤及び硫化物系ガス吸収剤を含む吸収層の作製〉
　下記の吸湿剤と硫化物系ガス吸収剤とバインダーを用いて溶融混錬法より押出機でマスターバッチを作製した。
　　吸湿剤（５３質量部）：親水性ゼオライト（モレキュラーシーブ３Ａ；ユニオン昭和株式会社製）
　　硫化物系ガス吸収剤（１質量部）：ケスモンＮＳ－２０Ｃ（東亞合成株式会社製）
　　バインダー（４６質量部）：エチレン―メタクリル酸共重合体（熱可塑性樹脂）。 <Preparation of an absorption layer containing a hygroscopic agent and a sulfide-based gas absorber>
A masterbatch was prepared by an extruder by a melt-kneading method using the following hygroscopic agent, sulfide-based gas absorber and binder.
Moisture absorber (53 parts by mass): Hydrophilic zeolite (Molecular sieve 3A; manufactured by Union Showa Co., Ltd.)
Sulfide-based gas absorber (1 part by mass): Kesmon NS-20C (manufactured by Toagosei Co., Ltd.)
Binder (46 parts by mass): Ethylene-methacrylic acid copolymer (thermoplastic resin).
　上記得られたマスターバッチを吸湿剤及び硫化物系ガス吸収剤を含む吸収層とし、かつ、直鎖状低密度ポリエチレンを第１のスキン層及び第２のスキン層として、空冷方式インフレーションによる共押出成形にて、以下の順に積層されている２種３層の吸湿剤及び硫化物系ガス吸収剤を含む吸収層を作製した：
　　第１のスキン層（１０μｍ）／吸湿剤及び硫化物系ガス吸収剤を含む吸収層（３０μｍ）／第２のスキン層（１０μｍ）。 The masterbatch obtained above is used as an absorption layer containing a hygroscopic agent and a sulfide-based gas absorber, and linear low-density polyethylene is used as a first skin layer and a second skin layer, and coextruded by air-cooled inflation. By molding, an absorption layer containing two types and three layers of a hygroscopic agent and a sulfide-based gas absorber, which are laminated in the following order, was prepared:
First skin layer (10 μm) / Absorbent layer (30 μm) containing a hygroscopic agent and a sulfide-based gas absorber / Second skin layer (10 μm).
　〈評価サンプルの作製〉
　表１に示されているラミネートシートの構成にしたがい、各実施例及び比較例のラミネートシートを作製した後、２つのラミネートシートを用いてヒートシールして、ラミネートパックとして四方袋を作製した。なお、温度２３℃湿度２０%の環境下で各実施例及び比較例のラミネートパックの中に湿度データロガーを入れ、四方のシール部分の幅を１ｍｍにカットした。 <Preparation of evaluation sample>
According to the structure of the laminated sheet shown in Table 1, the laminated sheets of each Example and Comparative Example were prepared, and then heat-sealed using the two laminated sheets to prepare a four-sided bag as a laminated pack. A humidity data logger was placed in the laminate packs of each Example and Comparative Example in an environment of a temperature of 23 ° C. and a humidity of 20%, and the width of the seal portions on all sides was cut to 1 mm.
　各実施例及び比較例のラミネートパックの構成の詳細について、以下に説明する。 Details of the configuration of the laminate packs of each example and comparative example will be described below.
　《実施例１》
　ラミネートパックのＡ面として、外部側用面から内部側用面に向かって、この順に積層されている、基材層、バリア層、及び吸湿層を有するラミネートシートを用いて、また、ラミネートパックのＢ面として、外部側用面から内部側用面に向かって、この順に積層されている、基材層、バリア層、及びシーラント層を有するラミネートシートを用いて、実施例１のラミネートパックを作製した。 << Example 1 >>
As the A side of the laminate pack, a laminate sheet having a base material layer, a barrier layer, and a moisture absorbing layer, which are laminated in this order from the outer side surface to the inner side surface, is used, and the laminate pack is also provided. The laminate pack of Example 1 was prepared using a laminate sheet having a base material layer, a barrier layer, and a sealant layer, which are laminated in this order from the outer side surface to the inner side surface as the B surface. did.
　ここで、バリア層として、アルミニウム箔を用い；基材層として、ポリエチレンテレフタレート（ＰＥＴ）を用い；シーラント層として、ポリエチレン（ＰＥ）を用いた。 Here, an aluminum foil was used as the barrier layer; polyethylene terephthalate (PET) was used as the base material layer; polyethylene (PE) was used as the sealant layer.
　また、各層の間はいずれも、ドライラミネートによって積層された。ドライラミネートの接着剤として、三井化学株式会社製のタケラック（登録商標）Ａ－５２５Ｓとタケネート（登録商標）Ａ－５０との組合せを用いて、この接着剤と酢酸エチルとを所定の配合比で混ぜ、塗布量３ｇ／ｍ２となるようにハンドコーターにて各層の間に塗布した後、圧着させた。 In addition, each layer was laminated by dry lamination. As a dry laminate adhesive, a combination of Takelac (registered trademark) A-525S manufactured by Mitsui Chemicals, Inc. and Takenate (registered trademark) A-50 was used, and this adhesive and ethyl acetate were mixed in a predetermined compounding ratio. The mixture was mixed, applied between the layers with a hand coater so that the coating amount was 3 g / m 2, and then pressure-bonded.
　《実施例２》
　ラミネートパックのＡ面として、外部側用面から内部側用面に向かって、この順に積層されている、基材層、バリア層、硫化物系ガス吸収層、及び吸湿層を有するラミネートシートを用いたこと以外は、実施例１と同様にして、実施例２のラミネートパックを作製した。 << Example 2 >>
As the A side of the laminate pack, a laminate sheet having a base material layer, a barrier layer, a sulfide gas absorption layer, and a moisture absorption layer, which are laminated in this order from the outer side surface to the inner side surface, is used. A laminate pack of Example 2 was prepared in the same manner as in Example 1 except for the above.
　なお、バリア層と硫化物系ガス吸収層との間は、実施例１と同様にラミネートした。 The barrier layer and the sulfide-based gas absorption layer were laminated in the same manner as in Example 1.
　《実施例３》
　ラミネートパックのＡ面として、外部側用面から内部側用面に向かって、この順に積層されている、基材層、バリア層、吸湿層、及び硫化物系ガス吸収層を有するラミネートシートを用いたこと以外は、実施例１と同様にして、実施例３のラミネートパックを作製した。 << Example 3 >>
As the A side of the laminate pack, a laminate sheet having a base material layer, a barrier layer, a moisture absorbing layer, and a sulfide gas absorbing layer, which are laminated in this order from the outer side surface to the inner side surface, is used. A laminate pack of Example 3 was prepared in the same manner as in Example 1 except for the above.
　なお、吸湿層と硫化物系ガス吸収層との間は、実施例１と同様にラミネートした。 The moisture absorbing layer and the sulfide gas absorbing layer were laminated in the same manner as in Example 1.
　《実施例４》
　１０ｃｍ×１０ｃｍの上記２種３層の硫化物系ガス吸収層のみを内包したこと以外は、実施例１と同様にして、実施例４のラミネートパックを作製した。 << Example 4 >>
A laminate pack of Example 4 was prepared in the same manner as in Example 1 except that only the above-mentioned 2 types and 3 layers of sulfide-based gas absorption layer of 10 cm × 10 cm were included.
　《実施例５》
　ラミネートパックのＢ面として、外部側用面から内部側用面に向かって、この順に積層されている、基材層、バリア層、及び硫化物系ガス吸収層を有するラミネートシートを用いたこと以外は、実施例１と同様にして、実施例５のラミネートパックを作製した。 << Example 5 >>
Except for using a laminate sheet having a base material layer, a barrier layer, and a sulfide-based gas absorption layer, which are laminated in this order from the outer side surface to the inner side surface as the B surface of the laminate pack. Made a laminate pack of Example 5 in the same manner as in Example 1.
　なお、バリア層と硫化物系ガス吸収層との間は、実施例１と同様にラミネートした。 The barrier layer and the sulfide-based gas absorption layer were laminated in the same manner as in Example 1.
　《実施例６》
　ラミネートパックのＡ面として、外部側用面から内部側用面に向かって、この順に積層されている、基材層、バリア層、吸湿剤及び硫化物系ガス吸収剤を含む吸収層を有するラミネートシートを用いたこと以外は、実施例１と同様にして、実施例６のラミネートパックを作製した。
　なお、バリア層と硫化物系ガス吸収層との間は、実施例１と同様にラミネートした。 << Example 6 >>
As the A side of the laminate pack, a laminate having an absorption layer containing a base material layer, a barrier layer, a hygroscopic agent and a sulfide-based gas absorber, which are laminated in this order from the outer side surface to the inner side surface. A laminate pack of Example 6 was prepared in the same manner as in Example 1 except that a sheet was used.
The barrier layer and the sulfide-based gas absorption layer were laminated in the same manner as in Example 1.
　《比較例１》
　ラミネートパックのＡ面として、外部側用面から内部側用面に向かって、この順に積層されている、基材層、バリア層、及びシーラント層を有するラミネートシートを用いたこと以外は、実施例１と同様にして、比較例のラミネートパックを作製した。 << Comparative Example 1 >>
Examples except that a laminate sheet having a base material layer, a barrier layer, and a sealant layer, which are laminated in this order from the outer side surface to the inner side surface, was used as the A surface of the laminate pack. A laminate pack of Comparative Example was prepared in the same manner as in 1.
　《比較例２》
　ラミネートパックのＡ面として、外部側用面から内部側用面に向かって、この順に積層されている、基材層、バリア層、及び硫化物系ガス吸収層を有するラミネートシートを用いたこと以外は、実施例１と同様にして、比較例のラミネートパックを作製した。 << Comparative Example 2 >>
Except for using a laminate sheet having a base material layer, a barrier layer, and a sulfide-based gas absorption layer, which are laminated in this order from the outer side surface to the inner side surface as the A surface of the laminate pack. Made a laminate pack of Comparative Example in the same manner as in Example 1.
　なお、バリア層と硫化物系ガス吸収層との間は、実施例１と同様にラミネートした。 The barrier layer and the sulfide-based gas absorption layer were laminated in the same manner as in Example 1.
　《評価》
　上記で作製した各実施例及び比較例のラミネートパックサンプルを、６０℃９０％（相対湿度）の環境に２週間置き、２週間後にラミネートパック中の湿度データロガーを取り出して、ログの値を確認した。その結果は表１に示す。 《Evaluation》
Place the laminate pack samples of the above-mentioned Examples and Comparative Examples in an environment of 60 ° C. and 90% (relative humidity) for 2 weeks, and after 2 weeks, take out the humidity data logger in the laminate pack and check the log value. did. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１から明らかであるように、実施例１～５のラミネートパックは、いずれも２週間後内部湿度０％であった。すなわち、本発明のラミネートシートを用いたラミネートパックの内部には、水分が存在しない又は存在しにくい環境である。したがって、本発明のミネートシート及びそれを用いたラミネートパックは、硫化物系ガスの発生を抑制できることが分かった。 As is clear from Table 1, all of the laminate packs of Examples 1 to 5 had an internal humidity of 0% after 2 weeks. That is, it is an environment in which moisture does not exist or hardly exists inside the laminate pack using the laminate sheet of the present invention. Therefore, it was found that the mine sheet of the present invention and the laminate pack using the same can suppress the generation of sulfide-based gas.
　これに対して、比較例１及び２のラミネートパックは、いずれも２週間後の内部湿度が４０％であった。このようにラミネートパックの中に硫化物系ガスが発生する根本的な原因である水分が存在したため、硫化物系ガスの発生を抑制できないことが分かった。 On the other hand, the laminate packs of Comparative Examples 1 and 2 had an internal humidity of 40% after 2 weeks. As described above, it was found that the generation of sulfide-based gas cannot be suppressed due to the presence of water, which is the root cause of sulfide-based gas generation, in the laminate pack.
　《参考例》
　以下の参考例によれば、硫化物系ガス吸収剤自体は、硫化物系ガスのみならず、水分を吸収する能力を有することが分かった。 << Reference example >>
According to the following reference example, it was found that the sulfide-based gas absorber itself has the ability to absorb not only sulfide-based gas but also water.
　（１）ケスモンＮＳ－２０Ｃ（東亞合成株式会社製）を秤量して（この重量をａとする）ディスポカップに入れ再び秤量した（この重量をｂとする）。 (1) Kesmon NS-20C (manufactured by Toagosei Co., Ltd.) was weighed (this weight is a), placed in a disposable cup and weighed again (this weight is b).
　（２）上記のケスモンＮＳ－２０Ｃとカップを４０℃９０％（相対湿度）環境の高温高湿槽に入れて所定時間ごとに秤量した（この重量をｃとする）。 (2) The above-mentioned Kesmon NS-20C and a cup were placed in a high-temperature and high-humidity tank in an environment of 40 ° C. and 90% (relative humidity) and weighed at predetermined time intervals (this weight is defined as c).
　（３）次の式で重量増加率を計算した。
　　　　重量増加率＝（ｃ－ｂ＋ａ）/ａ (3) The weight increase rate was calculated by the following formula.
Weight increase rate = (cc + a) / a
　その結果は、表２に示す。
Figure JPOXMLDOC01-appb-T000002
 The results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000002
　表２に示されているように、ケスモンＮＳ－２０Ｃを用いた場合、３つのサンプルの平均で約６時間後から最大で自重３０％の水分を吸着することが分かった。 As shown in Table 2, it was found that when Kesmon NS-20C was used, a maximum of 30% of water was adsorbed after about 6 hours on average for the three samples.
　１０、７０ａ、７０ｂ、８０ｂ　　バリア層
　１１、２１、３１、４１、５１、６１、７１、８１　　吸収層
　２１ａ、３１ａ、４１ａ、５１ａ、６１ａ、７１ａ、８１ａ　　吸湿層
　２１ｂ、３１ｂ、５１ｂ、６１ｂ、７１ｂ、８１ｂ　　硫化物系ガス吸収層
　４１ｃ、４１ｄ、５１ｃ、５１ｄ、６１ｃ、６１ｄ　　スキン層
　７２　　シーラント層
　１００　　ラミネートシート 10, 70a, 70b, 80b Barrier layer 11, 21, 31, 41, 51, 61, 71, 81 Absorption layer 21a, 31a, 41a, 51a, 61a, 71a, 81a Moisture absorption layer 21b, 31b, 51b, 61b, 71b , 81b Sulfide gas absorption layer 41c, 41d, 51c, 51d, 61c, 61d Skin layer 72 Sealant layer 100 Laminate sheet

Claims (13)

  1. 　外部側用面から内部側用面に向かって、この順に積層されている、バリア層、及び吸湿剤を含む吸収層を有する、硫化物系全固体電池用ラミネートシート。 A sulfide-based all-solid-state battery laminate sheet having a barrier layer and an absorption layer containing a hygroscopic agent, which are laminated in this order from the outer side surface to the inner side surface.
  2. 　前記吸収層は、硫化物系ガス吸収剤を更に含む、請求項１に記載のラミネートシート。 The laminated sheet according to claim 1, wherein the absorption layer further contains a sulfide-based gas absorber.
  3. 　前記吸収層は、前記外部側用面から前記内部側用面に向かって、この順に積層されている、吸湿層及び硫化物系ガス吸収層を有する、請求項１に記載のラミネートシート。 The laminate sheet according to claim 1, wherein the absorption layer has a moisture absorbing layer and a sulfide-based gas absorbing layer, which are laminated in this order from the outer surface to the inner surface.
  4. 　前記吸収層は、前記外部側用面から前記内部側用面に向かって、この順に積層されている、硫化物系ガス吸収層及び吸湿層を有する、請求項１に記載のラミネートシート。 The laminate sheet according to claim 1, wherein the absorption layer has a sulfide-based gas absorption layer and a moisture absorption layer, which are laminated in this order from the outer side surface to the inner side surface.
  5. 　前記吸収層は、その両面にスキン層を有する、請求項１～４のいずれか一項に記載のラミネートシート。 The laminated sheet according to any one of claims 1 to 4, wherein the absorbent layer has skin layers on both sides thereof.
  6. 　前記バリア層の、前記吸収層とは反対側の面に、基材層を更に有する、請求項１～５のいずれか一項に記載のラミネートシート。 The laminate sheet according to any one of claims 1 to 5, further comprising a base material layer on the surface of the barrier layer opposite to the absorption layer.
  7. 　前記吸収層の、前記バリア層とは反対側の面に、シーラント層を更に有する、請求項１～６のいずれか一項に記載のラミネートシート。 The laminate sheet according to any one of claims 1 to 6, further comprising a sealant layer on the surface of the absorption layer opposite to the barrier layer.
  8. 　前記吸湿剤は、ゼオライト、酸化カルシウム、硫酸マグネシウム、シリカゲル、塩化カルシウム、生石灰、及び酸化アルミニウムからなる群より選択される少なくとも１つを含む、請求項１～７のいずれか一項に記載のラミネートシート。 The laminate according to any one of claims 1 to 7, wherein the hygroscopic agent contains at least one selected from the group consisting of zeolite, calcium oxide, magnesium sulfate, silica gel, calcium chloride, quicklime, and aluminum oxide. Sheet.
  9. 　前記硫化物系ガス吸収剤は、銅、コバルト、マンガン、鉄、ニッケル、亜鉛、銀、カルシウム、及びチタンからなる群より選択される少なくとも１つを含む、請求項２～８のいずれか一項に記載のラミネートシート。 Any one of claims 2 to 8, wherein the sulfide-based gas absorber contains at least one selected from the group consisting of copper, cobalt, manganese, iron, nickel, zinc, silver, calcium, and titanium. Laminated sheet described in.
  10. 　請求項１～９のいずれか一項に記載のラミネートシートを１つ具備しており、かつ
    　前記ラミネートシートが前記内部側用面を内側にして折り曲げられて、前記内部側用面の周縁部がヒートシールされることによって袋状にされている、
    硫化物系全固体電池用ラミネートパック。     The laminated sheet according to any one of claims 1 to 9 is provided, and the laminated sheet is bent with the inner side surface facing inward so that the peripheral edge portion of the inner side surface is formed. It is made into a bag by heat-sealing,
    Laminate pack for sulfide-based all-solid-state batteries.
  11. 　Ａ面用ラミネートシートとしての請求項１～９のいずれか一項に記載のラミネートシートと、外部側用面から内部側用面に向かって、この順に積層されている、Ｂ面用バリア層及びＢ面用シーラント層を有するＢ面用ラミネートシートとを具備しており、かつ
    　前記Ａ面用ラミネートシートの前記内部側用面と、前記Ｂ面用シーラント層とが互いに対向して、前記内部側用面と前記Ｂ面用シーラント層との周縁部同士がヒートシールされることによって袋状にされている、
    硫化物系全固体電池用ラミネートパック。     The laminate sheet according to any one of claims 1 to 9 as the A-side laminate sheet, the B-side barrier layer and the B-side barrier layer laminated in this order from the outer side surface to the inner side surface. A B-side laminate sheet having a B-side sealant layer is provided, and the internal side surface of the A-side laminate sheet and the B-side sealant layer face each other, and the internal side The peripheral edges of the surface and the B-side sealant layer are heat-sealed to form a bag.
    Laminate pack for sulfide-based all-solid-state batteries.
  12. 　請求項１～９のいずれか一項に記載のラミネートシートを２つ以上具備しており、かつ
    　前記内部側用面同士が互いに対向して、前記内部側用面の周縁部同士がヒートシールされることによって袋状にされている、
    硫化物系全固体電池用ラミネートパック。     The laminated sheets according to any one of claims 1 to 9 are provided, and the inner side surfaces face each other, and the peripheral edges of the inner side surfaces are heat-sealed. It is made into a bag by
    Laminate pack for sulfide-based all-solid-state batteries.
  13. 　請求項１０～１２のいずれか一項に記載の硫化物系全固体電池用ラミネートパック、及び
    　硫化物系全固体電池
    を具備している、ラミネート電池。     A laminated battery comprising the sulfide-based all-solid-state battery laminate pack according to any one of claims 10 to 12 and a sulfide-based all-solid-state battery.
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