WO2023149485A1 - 全固体電池用外装材及び全固体電池 - Google Patents

全固体電池用外装材及び全固体電池 Download PDF

Info

Publication number
WO2023149485A1
WO2023149485A1 PCT/JP2023/003263 JP2023003263W WO2023149485A1 WO 2023149485 A1 WO2023149485 A1 WO 2023149485A1 JP 2023003263 W JP2023003263 W JP 2023003263W WO 2023149485 A1 WO2023149485 A1 WO 2023149485A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
solid
exterior material
state battery
sealant layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2023/003263
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
拓也 村木
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toppan Inc
Original Assignee
Toppan Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toppan Inc filed Critical Toppan Inc
Priority to CN202380017806.9A priority Critical patent/CN118575334A/zh
Priority to KR1020247025610A priority patent/KR20240140086A/ko
Priority to EP23749801.9A priority patent/EP4475291A4/en
Publication of WO2023149485A1 publication Critical patent/WO2023149485A1/ja
Priority to US18/788,000 priority patent/US20240387911A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/105—Pouches or flexible bags
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • H01M50/126—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers
    • H01M50/129—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers with two or more layers of only organic material
    • 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
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/117—Inorganic material
    • H01M50/119—Metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/121—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/14—Primary casings; Jackets or wrappings for protecting against damage caused by external factors
    • H01M50/141—Primary casings; Jackets or wrappings for protecting against damage caused by external factors for protecting against humidity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H01M50/186—Sealing members characterised by the disposition of the sealing members
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H01M50/19—Sealing members characterised by the material
    • H01M50/193—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • 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

Definitions

  • the present disclosure relates to an all-solid-state battery exterior material and an all-solid-state battery.
  • all-solid-state batteries capable of increasing capacity has progressed rapidly. Unlike the current lithium-ion batteries, all-solid-state batteries can be used at high temperatures that were previously unattainable because the electrolyte is solid, and there is no need for equipment to cool the battery, so the space associated with that is reduced. It is expected to improve efficiency, reduce costs, and reduce power consumption.
  • Such an all-solid-state battery includes a battery body containing a solid electrolyte and electrodes, and an exterior bag that houses the battery body.
  • the exterior bag is obtained by heat-sealing the exterior material.
  • the exterior material of such an all-solid-state battery includes a substrate layer, a barrier layer, and a sealant layer in this order, and the sealant layer is made of a polyester film or the like to impart heat resistance (for example, See Patent Document 1).
  • Japanese Patent No. 6747636 (for example, claim 5)
  • the exterior material for the all-solid-state battery described in Patent Literature 1 described above has the following problems. That is, in the exterior material of the all-solid-state battery described in Patent Literature 1 described above, air bubbles may be found all over the sealant layer at the time of heat sealing.
  • the present disclosure has been made in view of the above problems, and aims to provide an all-solid-state battery exterior material that can suppress the generation of air bubbles in the sealant layer during heat sealing, and an all-solid-state battery using the same. .
  • the inventors of the present invention investigated the cause of the phenomenon in which the generation of air bubbles was observed over the entire surface of the sealant layer as described above. As a result, it was thought that the reason why bubbles were generated all over the sealant layer was that the exterior material was heat-sealed at a high temperature. That is, when the exterior material is heat-sealed at a high temperature, the moisture in the sealant layer of the exterior material evaporates, and the generated air bubbles expand at once and easily combine with other air bubbles to grow and remain after cooling. The inventors of the present invention thought that Moreover, the inventors of the present invention have considered that the above phenomenon may be greatly dependent on the moisture content in the sealant layer of the exterior material. Therefore, the inventors of the present invention have further conducted extensive research, and as a result, have found that the above-described problems can be solved by the following disclosure.
  • the present disclosure is an all-solid battery exterior material comprising at least a substrate layer, a barrier layer, and a sealant layer in this order, wherein the sealant layer has a water content of 2700 ppm by mass or less. It is an exterior material for
  • the exterior material of the present disclosure it is possible to suppress the generation of air bubbles in the sealant layer during heat sealing. Therefore, it is possible to prevent the sealant layer from having a rough portion (a portion with many bubbles) and a dense portion (a portion with few bubbles), and a decrease in the sealing strength at the rough portion. Therefore, even if the battery main body containing the solid electrolyte expands due to the use of the all-solid-state battery in a high-temperature environment, and a force that tries to open the exterior bag acts, the exterior bag obtained by heat-sealing the exterior material is used. can be kept sealed.
  • the all-solid-state battery contains a sulfide-based solid electrolyte as a solid electrolyte in the exterior bag
  • gas such as hydrogen sulfide is generated due to the reaction between the moisture and the sulfide-based solid electrolyte in the exterior bag of the all-solid-state battery. Even if it occurs, such gas leakage can be suppressed.
  • the sealant layer since the generation of air bubbles, which tend to become passages for moisture, is suppressed, the intrusion of moisture from the outside of the exterior material is suppressed.
  • the all-solid-state battery contains a sulfide-based solid electrolyte as a solid electrolyte in the exterior bag
  • the reaction between the moisture and the sulfide-based solid electrolyte in the exterior bag of the all-solid-state battery causes the generation of gas such as hydrogen sulfide. It can also be suppressed.
  • the water content of the sealant layer may be 2000 mass ppm or less. In this case, it is possible to further suppress the generation of air bubbles in the sealant layer during heat sealing.
  • the water content of the sealant layer may be 200 ppm by mass or more.
  • the sealant layer is preferably a polyolefin film containing a polyolefin resin or a polyester film containing a polyester resin.
  • the sealing performance will be better.
  • the exterior material can further improve the heat resistance of the all-solid-state battery.
  • the sealant layer is the polyolefin film
  • the polyolefin film includes an acid-modified polyolefin resin layer
  • the acid-modified polyolefin resin layer is directly laminated to the barrier layer. is preferred.
  • the acid-modified polyolefin resin layer of the polyolefin film is directly laminated to the barrier layer, and the acid-modified polyolefin resin layer of the polyolefin film and the barrier layer are bonded with a polyurethane adhesive that is used as a high-temperature-resistant adhesive. Moisture is less likely to be trapped in the sealant layer than when the Therefore, even if the exterior material is repeatedly exposed to high temperatures, it is difficult for the sealant layer to release moisture each time.
  • the all-solid-state battery accommodates a sulfide-based solid electrolyte as a solid electrolyte in the exterior bag, it is possible to suppress the generation of hydrogen sulfide due to the reaction between released moisture and sulfide.
  • the sealant layer preferably has a melting point of 250°C or less.
  • the sealant layer has a melting point of 250°C or less, the heat sealing temperature can be lowered. Therefore, it is possible to further suppress the generation of air bubbles in the sealant layer during heat sealing. Therefore, deterioration of the sealing strength and barrier properties of the exterior material is further suppressed. Therefore, the exterior material can more sufficiently maintain the sealing performance of the exterior bag of the all-solid-state battery.
  • the sealant layer preferably has a melting point of 150°C or higher.
  • the sealant layer has a melting point of 150°C or higher, it is possible to suppress deterioration of the sealing strength of the exterior material even when the exterior material is used in a high-temperature environment. Therefore, when the all-solid-state battery contains a sulfide-based solid electrolyte as a solid electrolyte in the exterior bag, gas such as hydrogen sulfide is generated due to the reaction between the moisture and the sulfide-based solid electrolyte in the exterior bag of the all-solid-state battery. Even if it occurs, such gas leakage can be further suppressed.
  • the present disclosure includes a battery body having a solid electrolyte and an exterior bag that houses the battery body, and the exterior bag is an exterior bag obtained by heat-sealing the exterior material for the all-solid-state battery described above. , an all-solid-state battery.
  • the exterior bag is obtained by heat-sealing the all-solid-state battery exterior material described above.
  • the exterior material described above it is possible to suppress the generation of air bubbles in the sealant layer during heat sealing.
  • the all-solid-state battery of the present disclosure it is possible to prevent the sealant layer of the exterior material from having a rough portion and a dense portion, resulting in a decrease in sealing strength at the rough portion. Therefore, even if the battery main body expands due to use of the all-solid-state battery in a high-temperature environment and a force acts on the exterior bag to open it, the all-solid-state battery can keep the exterior bag sealed by the exterior material.
  • the sealant layer since the generation of air bubbles, which tend to become passages for moisture, is suppressed, the intrusion of moisture from the outside of the exterior material is suppressed. Therefore, when a sulfide-based solid electrolyte is used as the solid electrolyte, it is possible to suppress the generation of gas such as hydrogen sulfide due to the reaction between moisture and the sulfide-based solid electrolyte in the exterior bag of the all-solid-state battery.
  • the solid electrolyte may be a sulfide-based solid electrolyte.
  • melting point means “melting peak temperature” determined according to the method described in JIS K7121-1987, and when two or more melting peaks appear independently, the lowest melting point Peak temperature is taken.
  • the melting point refers to the melting point of the layer having the lowest melting point among the layers constituting the multilayer film.
  • an exterior material for an all-solid-state battery that can suppress the generation of air bubbles in the sealant layer during heat sealing and an all-solid-state battery using the same are provided.
  • FIG. 1 is a cross-sectional view schematically showing an exterior material for an all-solid-state battery according to an embodiment of the present disclosure
  • FIG. 3 is a cross-sectional view schematically showing an all-solid-state battery exterior material according to another embodiment of the present disclosure
  • FIG. 4 is a cross-sectional view schematically showing an all-solid-state battery exterior material according to still another embodiment of the present disclosure.
  • 1 is a perspective view showing an all-solid-state battery according to an embodiment of the present disclosure
  • FIG. FIG. 2 is a plan view showing a structure for obtaining evaluation samples in Examples and Comparative Examples;
  • FIG. 1 is a cross-sectional view schematically showing an exterior material for an all-solid-state battery according to an embodiment of the present disclosure.
  • an all-solid-state battery exterior material (hereinafter also simply referred to as “exterior material”) 10 of the present embodiment includes a base material layer 11, a first adhesive layer 12a, and a barrier layer 13. , a second adhesive layer 12b and a sealant layer 16 in this order.
  • the moisture content of the sealant layer 16 is 2700 mass ppm or less.
  • the exterior material 10 can further suppress the generation of bubbles in the sealant layer 16 of the exterior material 10 when the exterior material 10 is heat-sealed, compared to when the moisture content of the sealant layer 16 exceeds 2700 ppm by mass.
  • the barrier layer 13 may have the first corrosion prevention treatment layer 14a on the base layer 11 side. Also, the barrier layer 13 may have a second corrosion prevention treatment layer 14b on the sealant layer 16 side.
  • the base material layer 11 is the outermost layer
  • the sealant layer 16 is the innermost layer. That is, the exterior material 10 is used with the base material layer 11 facing the outside of the all-solid-state battery and the sealant layer 16 facing the inside of the all-solid-state battery.
  • the base material layer 11 provides heat resistance in the sealing process when manufacturing an all-solid-state battery, and plays a role in suppressing the generation of pinholes that may occur during molding and distribution. Especially in the case of exterior materials for all-solid-state batteries for large applications, scratch resistance, chemical resistance, insulating properties, etc. can be imparted.
  • the base material layer 11 is preferably a layer made of an insulating resin.
  • Resins include polyester resin, polyamide resin, polyimide resin, polyamideimide resin, polyetherketone resin, polyphenylene sulfide resin, polyetherimide resin, polysulfone resin, fluorine resin, phenolic resin, melamine resin, urethane resin, allyl resin, Silicone resins, epoxy resins, furan resins, acetylcellulose resins, and the like can be used.
  • these resins When these resins are applied to the substrate layer 11, they may be in the form of a stretched or unstretched film, or in the form of a coating film. Further, the substrate layer 11 may be a single layer or multiple layers, and in the case of multiple layers, different resins can be used in combination. If it is a film, it can be co-extruded or laminated via an adhesive. In the case of a coating film, one coated by the number of times of lamination can be used, and a film and a coating film can be combined to form multiple layers.
  • polyester resins and polyamide resins are preferable as the base material layer 11 because of their excellent moldability.
  • polyester resins include polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate.
  • Polyamide resins include, for example, nylon 6, nylon 6,6, copolymers of nylon 6 and nylon 6,6, nylon 6, nylon 9T, nylon 10, polymetaxylylene adipamide (MXD6), nylon 11, Nylon 12 and the like can be mentioned.
  • biaxially stretched film When using these resins in the form of a film, it is preferably a biaxially stretched film.
  • the stretching method for the biaxially stretched film include successive biaxial stretching, tubular biaxial stretching, and simultaneous biaxial stretching.
  • the biaxially stretched film is preferably stretched by a tubular biaxial stretching method from the viewpoint of obtaining better deep drawability.
  • the thickness of the base material layer 11 is preferably 6-50 ⁇ m, more preferably 10-30 ⁇ m. When the thickness of the base material layer 11 is 6 ⁇ m or more, there is a tendency that the pinhole resistance and insulating properties of the exterior material 10 can be improved. By setting the thickness of the base material layer 11 to 50 ⁇ m or less, the total thickness of the exterior material 10 can be reduced.
  • the melting point of the base material layer 11 is preferably higher than the melting point of the sealant layer 16, and preferably higher than the melting point of the sealant layer 16 by 30°C or more, in order to suppress deformation of the base material layer 11 during sealing.
  • the first adhesive layer 12a is a layer that bonds the base material layer 11 and the barrier layer 13 together.
  • the material constituting the first adhesive layer 12a includes, for example, a main agent such as polyester polyol, polyether polyol, acrylic polyol, and carbonate polyol, and a bifunctional or higher isocyanate compound (polyfunctional isocyanate compound ) is applied to polyurethane resins and the like.
  • a main agent such as polyester polyol, polyether polyol, acrylic polyol, and carbonate polyol
  • a bifunctional or higher isocyanate compound polyfunctional isocyanate compound
  • the various polyols described above can be used alone or in combination of two or more according to the functions and performances required for the exterior material 10 .
  • an epoxy resin as a main ingredient and a curing agent, but the present invention is not limited to this.
  • various other additives and stabilizers may be added to the above-described adhesive.
  • the thickness of the first adhesive layer 12a is not particularly limited, but is preferably 1 to 10 ⁇ m, and preferably 2 to 7 ⁇ m, from the viewpoint of obtaining desired adhesive strength, followability, workability, and the like. more preferred.
  • the barrier layer 13 has water vapor barrier properties that prevent moisture from entering the interior of the all-solid-state battery. Also, the barrier layer 13 may have extensibility for deep drawing.
  • various metal foils such as aluminum, stainless steel, copper, etc., metal vapor deposition films, inorganic oxide vapor deposition films, carbon-containing inorganic oxide vapor deposition films, films provided with these vapor deposition films, and the like are used. can be used.
  • As the film provided with a vapor deposition film for example, an aluminum vapor deposition film or an inorganic oxide vapor deposition film can be used. These can be used individually by 1 type or in combination of 2 or more types.
  • metal foil is preferable, and aluminum foil is more preferable, in terms of mass (specific gravity), moisture resistance, workability and cost.
  • the aluminum foil a soft aluminum foil that has been subjected to an annealing treatment can be preferably used because it can impart the desired ductility during molding.
  • the content of iron in the aluminum foil is preferably 0.1 to 9.0% by mass, more preferably 0.5 to 2.0% by mass, based on 100% by mass of the aluminum foil.
  • the iron content is 0.1% by mass or more, it is possible to obtain the exterior material 10 having more excellent pinhole resistance and extensibility.
  • the iron content is 9.0% by mass or less, it is possible to obtain the exterior material 10 with more excellent flexibility.
  • an untreated aluminum foil may be used, but it is preferable to use a degreased aluminum foil in terms of imparting corrosion resistance.
  • a degreased aluminum foil in terms of imparting corrosion resistance.
  • only one side of the aluminum foil may be degreased, or both sides may be degreased.
  • the thickness of the barrier layer 13 is not particularly limited, it is preferably 9 to 200 ⁇ m, more preferably 15 to 100 ⁇ m, in consideration of barrier properties, pinhole resistance, and workability.
  • the first and second corrosion prevention treatment layers 14a and 14b are layers provided to prevent corrosion of the metal foil (metal foil layer) and the like that constitute the barrier layer 13 .
  • the first anti-corrosion treatment layer 14a plays a role of enhancing adhesion between the barrier layer 13 and the first adhesive layer 12a.
  • the second anti-corrosion treatment layer 14b plays a role of enhancing adhesion between the barrier layer 13 and the second adhesive layer 12b.
  • the first corrosion prevention treatment layer 14a and the second corrosion prevention treatment layer 14b may be layers with the same composition or layers with different compositions.
  • the first and second corrosion prevention treatment layers 14a and 14b are, for example, degreasing treatment, hydrothermal transformation treatment, anodizing treatment, chemical conversion treatment, or It is formed by a combination of these processes.
  • Examples of degreasing include acid degreasing and alkaline degreasing.
  • Examples of acid degreasing include a method using an inorganic acid such as sulfuric acid, nitric acid, hydrochloric acid, and hydrofluoric acid alone, or a mixed solution thereof.
  • an acid degreasing agent obtained by dissolving a fluorine-containing compound such as monosodium ammonium difluoride in the above-mentioned inorganic acid is used. can be obtained, and passive aluminum fluoride can be formed, which is effective in terms of corrosion resistance.
  • Alkaline degreasing includes a method using sodium hydroxide or the like.
  • hydrothermal transformation treatment is boehmite treatment, in which aluminum foil is immersed in boiling water to which triethanolamine has been added.
  • anodizing treatment include alumite treatment.
  • the chemical conversion treatment includes immersion type and coating type.
  • Immersion-type chemical conversion treatments include, for example, chromate treatment, zirconium treatment, titanium treatment, vanadium treatment, molybdenum treatment, calcium phosphate treatment, strontium hydroxide treatment, cerium treatment, ruthenium treatment, and various chemical conversion treatments consisting of mixed phases thereof. be done.
  • coating-type chemical conversion treatment includes a method of applying a coating agent having corrosion prevention performance onto the barrier layer 13 .
  • the anti-corrosion treatment layer is formed by any one of hydrothermal transformation treatment, anodizing treatment, and chemical conversion treatment, it is preferable to perform the above-described degreasing treatment in advance.
  • a degreased metal foil such as a metal foil that has undergone an annealing process, is used as the barrier layer 13, it is not necessary to perform another degreasing treatment in forming the corrosion prevention treatment layers 14a and 14b.
  • the coating agent used for coating-type chemical conversion treatment preferably contains trivalent chromium.
  • the coating agent may contain at least one polymer selected from the group consisting of cationic polymers and anionic polymers, which will be described later.
  • the surface of the aluminum foil is dissolved by a treatment agent to form an aluminum compound (boehmite, alumite) with excellent corrosion resistance. Therefore, since a co-continuous structure is formed from the barrier layer 13 using aluminum foil to the corrosion prevention treatment layers 14a and 14b, the above treatment is included in the definition of chemical conversion treatment. On the other hand, as will be described later, it is also possible to form the corrosion prevention treatment layers 14a and 14b only by a pure coating method, which is not included in the definition of chemical conversion treatment.
  • a rare earth element oxide sol such as cerium oxide having an average particle size of 100 nm or less is used as a material that has an aluminum corrosion prevention effect (inhibitor effect) and is also suitable from an environmental point of view. method to be used. By using this method, it is possible to impart a corrosion-preventing effect to a metal foil such as an aluminum foil even by a general coating method.
  • sol of the rare earth element oxide examples include sol using various solvents such as water-based, alcohol-based, hydrocarbon-based, ketone-based, ester-based, and ether-based solvents. Among them, a water-based sol is preferable.
  • inorganic acids such as nitric acid, hydrochloric acid and phosphoric acid or salts thereof, and organic acids such as acetic acid, malic acid, ascorbic acid and lactic acid are added to stabilize the dispersion. used as a modifier.
  • phosphoric acid in particular is used in the exterior material 10 to (1) stabilize the dispersion of the sol, (2) improve adhesion with the barrier layer 13 using the aluminum chelating ability of phosphoric acid (3) Provision of corrosion resistance by trapping aluminum ions (formation of passivation); (4) Cohesive force of corrosion prevention treatment layers (oxide layers) 14a and 14b due to easy dehydration condensation of phosphoric acid even at low temperatures. is expected to improve.
  • the corrosion prevention treatment layers 14a and 14b formed from the rare earth element oxide sol are aggregates of inorganic particles, there is a risk that the cohesion of the layers themselves will be low even after the drying and curing process. Therefore, the corrosion prevention treatment layers 14a and 14b in this case are preferably compounded with an anionic polymer or a cationic polymer in order to supplement the cohesive force.
  • the corrosion prevention treatment layers 14a and 14b are not limited to the layers described above.
  • coating-type chromate which is a known technique, it may be formed using a treatment agent in which phosphoric acid and a chromium compound are blended in a resin binder (such as aminophenol).
  • a resin binder such as aminophenol
  • this treatment agent it is possible to form a layer having both corrosion prevention function and adhesion.
  • a coating agent in which the rare earth element oxide sol and polycationic polymer or polyanionic polymer are made into a single component in advance. It can be a layer that also has
  • the mass per unit area of the corrosion prevention treatment layers 14a and 14b is preferably 0.005 to 0.200 g/m 2 , and more preferably 0.010 to 0.100 g/m 2 , regardless of whether it has a multilayer structure or a single layer structure. is more preferred. If the mass per unit area is 0.005 g/m 2 or more, the barrier layer 13 is likely to have a corrosion prevention function. Moreover, even if the mass per unit area exceeds 0.200 g/m 2 , the corrosion prevention function does not change much. On the other hand, when a rare earth element oxide sol is used, if the coating film is thick, curing by heat during drying may be insufficient, which may lead to a decrease in cohesive strength. The thickness of the corrosion prevention treatment layers 14a and 14b can be converted from their specific gravity.
  • the corrosion prevention treatment layers 14a and 14b are composed of, for example, cerium oxide and 1 to 100 parts by weight of phosphorus per 100 parts by weight of the cerium oxide. It may be a mode containing an acid or a phosphate and a cationic polymer, or a mode formed by subjecting the barrier layer 13 to chemical conversion treatment. It may be formed and may include a cationic polymer.
  • the second adhesive layer 12b is a layer that bonds the barrier layer 13 and the sealant layer 16 together.
  • a general adhesive for bonding the barrier layer 13 and the sealant layer 16 can be used for the second adhesive layer 12b.
  • a second corrosion prevention treatment layer 14b is provided on the barrier layer 13, and the second corrosion prevention treatment layer 14b is made of at least one selected from the group consisting of the above-described cationic polymers and anionic polymers.
  • the second adhesive layer 12b is a layer containing a compound (hereinafter also referred to as a "reactive compound") reactive with the polymer contained in the second corrosion prevention treatment layer 14b. is preferably
  • the second adhesive layer 12b when the second corrosion prevention treatment layer 14b contains a cationic polymer, the second adhesive layer 12b contains a compound reactive with the cationic polymer.
  • the second adhesive layer 12b when the second corrosion prevention treatment layer 14b contains an anionic polymer, the second adhesive layer 12b contains a compound reactive with the anionic polymer.
  • the second adhesive layer 12b when the second corrosion prevention treatment layer 14b contains a cationic polymer and an anionic polymer, the second adhesive layer 12b contains a compound reactive with the cationic polymer and a compound reactive with the anionic polymer. including.
  • the second adhesive layer 12b does not necessarily contain the above two types of compounds, and may contain a compound reactive with both the cationic polymer and the anionic polymer.
  • “having reactivity” means forming a covalent bond with a cationic polymer or an anionic polymer.
  • the second adhesive layer 12b may further contain an acid-modified polyolefin resin.
  • Examples of compounds reactive with cationic polymers include at least one compound selected from the group consisting of polyfunctional isocyanate compounds, glycidyl compounds, compounds having a carboxy group, and compounds having an oxazoline group.
  • polyfunctional isocyanate compounds examples include the polyfunctional isocyanate compounds, glycidyl compounds, and carboxy groups previously exemplified as cross-linking agents for forming the cationic polymer into a cross-linked structure. and a compound having an oxazoline group.
  • polyfunctional isocyanate compounds are preferred because they are highly reactive with cationic polymers and tend to form a crosslinked structure.
  • the compound reactive with the anionic polymer includes at least one compound selected from the group consisting of glycidyl compounds and compounds having an oxazoline group.
  • the glycidyl compound and the compound having an oxazoline group include the glycidyl compound and the compound having an oxazoline group which are exemplified above as a cross-linking agent for forming the cationic polymer into a cross-linked structure.
  • glycidyl compounds are preferred because of their high reactivity with the anionic polymer.
  • the reactive compound preferably has reactivity with the acid groups in the acid-modified polyolefin resin (that is, forms covalent bonds with the acid groups). This further enhances the adhesion with the second corrosion prevention treatment layer 14b.
  • the acid-modified polyolefin resin becomes a crosslinked structure, and the solvent resistance of the exterior material 10 is further improved.
  • the content of the reactive compound is preferably equivalent to 10 times the amount of the acidic groups in the acid-modified polyolefin resin. If the content of the reactive compound is equal to or more than the equivalent amount, the reactive compound sufficiently reacts with the acidic groups in the acid-modified polyolefin resin. On the other hand, if the content of the reactive compound exceeds 10 times the equivalent amount, the cross-linking reaction with the acid-modified polyolefin resin is sufficiently saturated, so unreacted substances are present, and various performances may be lowered. . Therefore, for example, the content of the reactive compound is preferably 5 to 20 parts by mass (solid content ratio) with respect to 100 parts by mass of the acid-modified polyolefin resin.
  • Acid-modified polyolefin resin is obtained by introducing acidic groups into polyolefin resin.
  • the acidic group include a carboxy group, a sulfonic acid group, an acid anhydride group and the like, and particularly preferred are a maleic anhydride group and a (meth)acrylic acid group.
  • the acid-modified polyolefin resin for example, the same modified polyolefin resin as used for the sealant layer 16 can be used.
  • additives such as flame retardants, slip agents, anti-blocking agents, antioxidants, light stabilizers, and tackifiers may be added to the second adhesive layer 12b.
  • the second adhesive layer 12b is, for example, an acid-modified polyolefin from the viewpoint of suppressing a decrease in lamination strength when a corrosive gas such as hydrogen sulfide or an electrolytic solution is involved, and from the viewpoint of further suppressing a decrease in insulation.
  • a polyfunctional isocyanate compound a glycidyl compound, a compound having a carboxy group, a compound having an oxazoline group, and at least one curing agent selected from the group consisting of a carbodiimide compound.
  • carbodiimide compounds include N,N'-di-o-toluylcarbodiimide, N,N'-diphenylcarbodiimide, N,N'-di-2,6-dimethylphenylcarbodiimide, N,N'-bis (2,6-diisopropylphenyl)carbodiimide, N,N'-dioctyldecylcarbodiimide, N-triyl-N'-cyclohexylcarbodiimide, N,N'-di-2,2-di-t-butylphenylcarbodiimide, N- triyl-N'-phenylcarbodiimide, N,N'-di-p-nitrophenylcarbodiimide, N,N'-di-p-aminophenylcarbodiimide, N,N'-di-p-hydroxyphenylcarbodiimide, N,N '-di-cyclo
  • the adhesive for forming the second adhesive layer 12b for example, a polyurethane adhesive obtained by blending a polyester polyol composed of a hydrogenated dimer fatty acid and a diol and a polyisocyanate can be used.
  • polyurethane resins are made by reacting difunctional or higher isocyanate compounds to main agents such as polyester polyols, polyether polyols, acrylic polyols, and carbonate polyols
  • epoxy resins are made by reacting amine compounds to main agents having epoxy groups. and the like, and are preferable from the viewpoint of heat resistance.
  • the thickness of the second adhesive layer 12b is not particularly limited, it is preferably 1 to 10 ⁇ m, more preferably 2 to 7 ⁇ m, from the viewpoint of obtaining desired adhesive strength, workability, and the like.
  • the sealant layer 16 is a layer that imparts sealing properties to the exterior material 10 by heat sealing, and is a layer that is arranged inside and heat-sealed (heat-sealed) when the all-solid-state battery is assembled.
  • the moisture content of the sealant layer 16 is 2700 ppm by mass or less. In this case, the generation of air bubbles in the sealant layer during heat sealing can be more suppressed than when the moisture content of the sealant layer 16 exceeds 2700 ppm by mass.
  • the moisture content of the sealant layer 16 may be 2600 mass ppm or less, 2500 mass ppm or less, or 2200 mass ppm or less.
  • the moisture content of the sealant layer 16 is preferably 2000 ppm by mass or less, more preferably 1500 ppm by mass or less, from the viewpoint of further suppressing the generation of air bubbles in the sealant layer 16 during heat sealing.
  • the moisture content of the sealant layer 16 may be 0 mass ppm.
  • the moisture content of the sealant layer 16 may be 200 mass ppm or more, 300 mass ppm or more, 400 mass ppm or more, or 500 mass ppm or more.
  • the sealant layer 16 may have a water content of 2700 ppm by mass or less as a whole. Therefore, when the sealant layer 16 is composed of a multilayer film, each layer may have a water content of 2700 mass ppm or less, but some layers have a water content of 2700 mass ppm or less and the remaining layers have a water content of 2700 mass ppm or less. is greater than 2700 ppm by mass, the water content as a whole should be 2700 ppm by mass or less.
  • thermoplastic resins such as polyolefin resins, polyester resins, polycarbonate resins, polyphenylene ether resins, polyacetal resins, polystyrene resins, polyvinyl chloride resins, and polyvinyl acetate resins
  • Sealing suitability and heat resistance can be controlled by blending the various resins listed above to form a polymer alloy.
  • the exterior material 10 can further improve the heat resistance of the all-solid-state battery.
  • the thermoplastic resin does not contain a hydrophilic group component or contains a small proportion of the hydrophilic group component. In this case, the moisture content of the sealant layer 16 is easily reduced to 2700 ppm by mass or less because moisture is less likely to be adsorbed to the thermoplastic resin.
  • Polyolefin resins include, for example, low-density, medium-density or high-density polyethylene; ethylene- ⁇ -olefin copolymers; polypropylene; block or random copolymers containing propylene as a copolymerization component; Examples include polyolefin resins such as polymers.
  • the polyolefin resin may be an acid-modified polyolefin resin obtained by modifying a polyolefin resin with acid or glycidyl.
  • the polyolefin film When the polyolefin film is directly laminated to the barrier layer 13 without interposing the corrosion prevention treatment layer 14b and the second adhesive layer 12b, the polyolefin film contains an acid-modified polyolefin resin layer containing an acid-modified polyolefin resin, It is preferable that this acid-modified polyolefin resin layer is directly laminated on the barrier layer 13 .
  • the acid-denatured polyolefin resin layer of the polyolefin film is directly laminated to the barrier layer 13, and the acid-denatured polyolefin resin layer of the polyolefin film and the barrier layer 13 are made of a polyurethane adhesive used as an adhesive having high temperature resistance.
  • polyester resins examples include polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, polyethylene naphthalate (PEN) resin, polybutylene naphthalate (PBN) resin, and copolymers thereof. be done.
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PEN polyethylene naphthalate
  • PBN polybutylene naphthalate
  • copolymers thereof be done.
  • One of these polyester-based resins may be used alone, or two or more thereof may be used in combination. Copolymerization of any acid and glycol may also be used.
  • the sealant layer 16 contains, for example, an antioxidant, a slip agent, a flame retardant, an anti-blocking agent, a light stabilizer, a dehydrating agent, a tackifier, and a crystal nucleus in order to impart sealability, heat resistance and other functionality. Additives such as agents and plasticizers may be further included.
  • the melting point of the sealant layer 16 is not particularly limited, it is preferably 150°C or higher, more preferably 155°C or higher, and even more preferably 160°C or higher. Since the melting point of the sealant layer 16 is 150° C. or higher, it is possible to suppress a decrease in the sealing strength of the exterior material 10 even when the exterior material 10 is used in a high-temperature environment. Therefore, when the all-solid-state battery contains a sulfide-based solid electrolyte as a solid electrolyte in the exterior bag, gas such as hydrogen sulfide is generated due to the reaction between the moisture and the sulfide-based solid electrolyte in the exterior bag of the all-solid-state battery. Even if it occurs, such gas leakage can be further suppressed.
  • the melting point of the sealant layer 16 is preferably 250°C or lower, more preferably 240°C or lower, and even more preferably 230°C or lower.
  • the heat sealing temperature can be lowered by setting the melting point of the sealant layer 16 to 250° C. or less. Therefore, it is possible to further suppress the generation of air bubbles in the sealant layer 16 during heat sealing. Therefore, deterioration of the sealing strength and barrier properties of the exterior material 10 is further suppressed. Therefore, the exterior material 10 can more sufficiently maintain the sealing performance of the exterior bag of the all-solid-state battery. In addition, the exterior material 10 can also suppress intrusion of moisture through the exterior material 10 .
  • the sealant layer 16 may be either a single layer film or a multilayer film, and may be selected according to the required functions.
  • the sealant layer 16 is a multilayer film, the layers may be laminated by coextrusion or by dry lamination.
  • the sealant layer 16 is a multilayer film, it is preferable to use the same kind of resin from the viewpoint of interlayer adhesion.
  • a layer containing a modified polyolefin resin is placed in the layer in contact with the barrier layer 13, and a non-modified polyolefin resin layer is extruded or multiple polyolefin resin layers are co-extruded and laminated on the layer. may be
  • the thickness of the sealant layer 16 is not particularly limited, it is preferably 10-100 ⁇ m, more preferably 20-60 ⁇ m. Sufficient sealing strength can be obtained by setting the thickness of the sealant layer 16 to 10 ⁇ m or more. By setting the thickness of the sealant layer 16 to 100 ⁇ m or less, it is possible to reduce the amount of water vapor that enters from the peripheral portion of the exterior material 10 .
  • At least one layer of the layers constituting the exterior material 10 of the present embodiment contains a hydrogen sulfide decomposition and adsorption material that decomposes or adsorbs hydrogen sulfide. may contain. In this case, even if water and the sulfide-based solid electrolyte react to generate hydrogen sulfide in the all-solid-state battery, hydrogen sulfide is suppressed from permeating the exterior material 10 .
  • the hydrogen sulfide decomposition and adsorption material is contained in, for example, the first adhesive layer 12a, the second adhesive layer 12b, the sealant layer 16, or at least one of these.
  • the hydrogen sulfide decomposition and adsorption material is preferably contained in the sealant layer 16 . In this case, permeation of hydrogen sulfide through the exterior material 10 is effectively suppressed.
  • Hydrogen sulfide decomposition and adsorption materials include zinc oxide, amorphous metal silicates (mainly containing copper and zinc as metals), hydrates of zirconium and tantanoid elements, and tetravalent metal phosphates (especially those containing metals).
  • copper amorphous metal silicates (mainly containing copper and zinc as metals), hydrates of zirconium and tantanoid elements, and tetravalent metal phosphates (especially those containing metals).
  • copper mixtures of zeolite and zinc ions, mixtures of zeolite, zinc oxide and copper(II) oxide, potassium permanganate, sodium permanganate, silver sulfate, silver acetate, aluminum oxide, iron hydroxide, Isocyanate compounds, aluminum silicate, potassium aluminum sulfate, zeolite, activated carbon, amine compounds, ionomers and the like.
  • the hydrogen sulfide decomposition and adsorption material preferably contains zinc oxide (ZnO) and/or zinc ions from the viewpoints of making hydrogen sulfide more harmless and from the viewpoint of cost and handling.
  • the hydrogen sulfide decomposition and adsorption material can be used alone or in combination of two or more.
  • the hydrogen sulfide decomposition and adsorption material As the hydrogen sulfide decomposition and adsorption material, the following deodorant that has a deodorant effect on hydrogen sulfide may be used. Specifically, for example, Dainichi Seika Kogyo Co., Ltd.'s "Daime Shoe PE-M 3000-Z” (polyethylene masterbatch product), Toagosei Co., Ltd.'s “Kesmon”, Rasa Kogyo Co., Ltd.'s “Shokulens , and "Dashlight ZU” and "Dashlight CZU” manufactured by Sinanen Zeomic Co., Ltd.
  • a metallic soap such as zinc stearate may be added to the layer containing the hydrogen sulfide decomposition and adsorption material from the viewpoint of improving the dispersibility of the hydrogen sulfide decomposition and adsorption material.
  • the dispersibility of the hydrogen sulfide decomposition and adsorption material in the layer can be improved, and the effect of detoxifying hydrogen sulfide is less likely to occur. It is easy to suppress deterioration of the function (for example, adhesion strength, seal strength, etc.) of the layer containing the adsorbent material.
  • the hydrogen sulfide decomposition/adsorption material may be used as a masterbatch in advance.
  • a high-concentration blended product is prepared in advance as a masterbatch, and then the masterbatch is blended with the resin of the sealant layer 16 so that the resin of the sealant layer 16 has an appropriate concentration.
  • the hydrogen sulfide decomposition and adsorption material may be blended in the first adhesive layer 12a or the second adhesive layer 12b, when the first adhesive layer 12a or the second adhesive layer 12b is applied, the second It may be directly blended into one adhesive layer 12a or the second adhesive layer 12b, or when the first adhesive layer 12a or the second adhesive layer 12b is formed by extrusion or the like, the above sealant layer 16, a masterbatch may be prepared and mixed with the first adhesive layer 12a or the second adhesive layer 12b.
  • thermoplastic resins such as polyolefin resins, polyamide resins, polyester resins, polycarbonate resins, polyphenylene ether resins, polyacetal resins, polystyrene resins, polyvinyl chloride resins, and polyvinyl acetate resins can be used.
  • Resin can be used.
  • the content of the hydrogen sulfide decomposition and adsorption material in the layer containing the hydrogen sulfide decomposition and adsorption material may be 0.01% by mass or more and 30% by mass or less based on the total amount of the layer, and may be 0.05% by mass or more and 20% by mass. It may be less than or equal to 0.1% by mass or more and 15% by mass or less.
  • the content of the hydrogen sulfide decomposition and adsorption material is at least the above lower limit value, the effect of detoxifying hydrogen sulfide can be sufficiently obtained, and when it is at most the above upper limit value, the layer containing the hydrogen sulfide decomposition and adsorption material is reduced. A decrease in functions (for example, adhesion strength, seal strength, etc.) can be suppressed.
  • FIG. 1 shows the case where the corrosion prevention treatment layers 14a and 14b are provided on both sides of the barrier layer 13, but only one of the corrosion prevention treatment layers 14a and 14b may be provided.
  • the corrosion prevention treatment layer may not be provided.
  • FIG. 1 shows the case where the barrier layer 13 and the sealant layer 16 are laminated using the second adhesive layer 12b.
  • a layer 15 may be used to laminate the barrier layer 13 and the sealant layer 16 .
  • a second adhesive layer 12 b may be provided between the barrier layer 13 and the adhesive resin layer 15 .
  • the adhesive resin layer 15 is roughly configured to contain an adhesive resin composition as a main component and, if necessary, additive components.
  • the adhesive resin composition is not particularly limited, it preferably contains a modified polyolefin resin.
  • the modified polyolefin resin is preferably a polyolefin resin graft-modified with an unsaturated carboxylic acid and an unsaturated carboxylic acid derivative derived from either an acid anhydride or an ester thereof.
  • polyolefin resins examples include low-density polyethylene, medium-density polyethylene, high-density polyethylene, ethylene- ⁇ -olefin copolymer, homopolypropylene, block polypropylene, random polypropylene, and propylene- ⁇ -olefin copolymer.
  • the modified polyolefin resin is preferably a polyolefin resin modified with maleic anhydride.
  • the modified polyolefin resin for example, "ADMER” manufactured by Mitsui Chemicals, Inc. and "MODIC” manufactured by Mitsubishi Chemical Corporation are suitable. Since such a modified polyolefin resin is excellent in reactivity with various metals and polymers having various functional groups, the reactivity can be used to impart adhesion to the adhesive resin layer 15 .
  • the adhesive resin layer 15 may optionally include various compatible and incompatible elastomers, flame retardants, slip agents, anti-blocking agents, antioxidants, light stabilizers, tackifiers, and the like. may contain various additives.
  • the thickness of the adhesive resin layer 15 is not particularly limited, it is preferably equal to or less than that of the sealant layer 16 from the viewpoint of stress relaxation and moisture permeation.
  • the total thickness of the adhesive resin layer 15 and the sealant layer 16 is 5 to 5 from the viewpoint of achieving both thinning and improvement in heat seal strength in a high temperature environment. It is preferably in the range of 100 ⁇ m, more preferably in the range of 20-80 ⁇ m.
  • the hydrogen sulfide decomposition and adsorption material may be contained in the adhesive resin layer 15 .
  • the hydrogen sulfide decomposition and adsorption material may be contained in at least one layer selected from the group consisting of the first adhesive layer 12 a , the adhesive resin layer 15 and the sealant layer 16 .
  • the exterior material of the present disclosure further includes a protective layer 17 disposed on the surface of the substrate layer 11 opposite to the barrier layer 13 side, like the all-solid-state battery exterior material 30 shown in FIG. may be
  • the adhesive resin layer 15 may be the second adhesive layer 12b.
  • the protective layer 17 is a layer that protects the base material layer 11 .
  • a material for forming the protective layer 17 the same material as for the first adhesive layer 12a can be used.
  • the protective layer 17 can be formed on the base material layer 11 by coating or the like.
  • the hydrogen sulfide decomposition and adsorption material may be contained in the protective layer 17 .
  • the hydrogen sulfide decomposition and adsorption material may be contained in at least one layer selected from the group consisting of the protective layer 17, the first adhesive layer 12a, the adhesive resin layer 15 and the sealant layer 16.
  • the method for manufacturing the exterior material 10 of the present embodiment comprises a step of providing the barrier layer 13 with the corrosion prevention treatment layers 14a and 14b, and bonding the base material layer 11 and the barrier layer 13 together using the first adhesive layer 12a. a step of further laminating the sealant layer 16 via the second adhesive layer 12b to produce a laminate; and, if necessary, a step of aging the obtained laminate. It is
  • This step is a step of forming corrosion prevention treatment layers 14 a and 14 b on the barrier layer 13 .
  • the barrier layer 13 may be subjected to degreasing treatment, hydrothermal transformation treatment, anodizing treatment, or chemical conversion treatment, or a coating agent having corrosion prevention performance may be applied.
  • a coating liquid (coating agent) that constitutes the corrosion prevention treatment layer on the lower layer side (barrier layer 13 side) is applied to the barrier layer 13 and baked to form the second layer.
  • a coating liquid (coating agent) that constitutes the upper corrosion prevention treatment layer may be applied to the first layer and baked to form the second layer.
  • the degreasing treatment may be performed by a spray method or an immersion method.
  • the hydrothermal transformation treatment and the anodizing treatment may be performed by an immersion method.
  • an immersion method, a spray method, a coating method, or the like may be appropriately selected according to the type of chemical conversion treatment.
  • the various treatments may be performed on either one side or both sides of the metal foil, but in the case of single-sided treatment, the treated side is preferably the side on which the sealant layer 16 is laminated. Note that the surface of the base layer 11 may also be subjected to the above-described treatment as required.
  • the coating amount of the coating agent for forming the first layer and the second layer is preferably 0.005 to 0.200 g/m 2 , more preferably 0.010 to 0.100 g/m 2 .
  • dry curing when dry curing is required, it can be carried out at a base material temperature of 60 to 300° C. depending on the drying conditions of the corrosion prevention treatment layers 14a and 14b used.
  • Step of bonding substrate layer and barrier layer This step is a step of bonding together the barrier layer 13 provided with the corrosion prevention treatment layers 14a and 14b and the base layer 11 via the first adhesive layer 12a.
  • a bonding method dry lamination, non-solvent lamination, wet lamination, or the like is used, and both are bonded together with the material constituting the first adhesive layer 12a described above.
  • the first adhesive layer 12a is provided in a dry coating amount of 1 to 10 g/m 2 , more preferably 2 to 7 g/m 2 .
  • This step is a step of bonding the sealant layer 16 to the second corrosion prevention treatment layer 14b side of the barrier layer 13 via the second adhesive layer 12b.
  • a wet process, a dry lamination, etc. are mentioned as the method of bonding.
  • the solution or dispersion of the adhesive that constitutes the second adhesive layer 12b is applied onto the second corrosion prevention treatment layer 14b, and the solvent is removed at a predetermined temperature to form a dry film. Then, if necessary, the baking process is further performed. After that, the sealant layer 16 is laminated to manufacture the exterior material 10 .
  • the coating method include the various coating methods exemplified above.
  • the preferred dry coating amount for the second adhesive layer 12b is the same as for the first adhesive layer 12a.
  • the sealant layer 16 can be produced, for example, by a melt extruder using a sealant layer-forming resin composition containing the constituent components of the sealant layer 16 described above.
  • the processing speed can be 80 m/min or more from the viewpoint of productivity.
  • This step is a step of aging (curing) the laminate.
  • the adhesion between the barrier layer 13/second anti-corrosion treatment layer 14b/second adhesive layer 12b/sealant layer 16 can be promoted.
  • Aging treatment can be performed at room temperature to 100°C. Aging time is, for example, 1 to 10 days.
  • the exterior material 10 of this embodiment as shown in FIG. 1 can be manufactured.
  • the method for manufacturing the exterior material 20 of the present embodiment includes a step of providing the barrier layer 13 with the corrosion prevention treatment layers 14a and 14b, and bonding the base layer 11 and the barrier layer 13 together using the first adhesive layer 12a. , a step of further laminating the adhesive resin layer 15 and the sealant layer 16 to form a laminate, and, if necessary, a step of heat-treating the obtained laminate.
  • the steps up to the step of bonding the base material layer 11 and the barrier layer 13 together can be performed in the same manner as in the method of manufacturing the exterior material 10 described above.
  • This step is a step of forming an adhesive resin layer 15 and a sealant layer 16 on the second corrosion prevention treatment layer 14b formed in the previous step.
  • a method thereof there is a method of sand laminating the adhesive resin layer 15 together with the sealant layer 16 using an extrusion lamination machine.
  • lamination is also possible by a tandem lamination method or a co-extrusion method in which the adhesive resin layer 15 and the sealant layer 16 are extruded.
  • each component is blended so as to satisfy the configuration of the adhesive resin layer 15 and the sealant layer 16 described above.
  • the sealant layer-forming resin composition described above is used to form the sealant layer 16 .
  • substrate layer 11/first adhesive layer 12a/first corrosion prevention treatment layer 14a/barrier layer 13/second corrosion prevention treatment layer 14b/adhesive resin layer A laminate is obtained in which each layer is laminated in the order of 15/sealant layer 16 .
  • the adhesive resin layer 15 may be laminated by directly extruding dry-blended materials with an extrusion laminator so as to have the above-described material composition.
  • the adhesive resin layer 15 is prepared by melt-blending in advance using a melt-kneading device such as a single-screw extruder, a twin-screw extruder, or a Brabender mixer. It may be laminated by extrusion using.
  • the sealant layer 16 may be laminated by directly extruding with an extrusion laminator the materials dry-blended so as to have the material formulation composition described above as the constituent components of the resin composition for forming the sealant layer.
  • the adhesive resin layer 15 and the sealant layer 16 may be obtained by using a granulated product that has been melt-blended in advance using a melt-kneading device such as a single-screw extruder, a twin-screw extruder, or a Brabender mixer.
  • the layers may be laminated by a tandem lamination method in which the adhesive resin layer 15 and the sealant layer 16 are extruded by an extrusion laminator, or by a co-extrusion method.
  • a sealant single film may be formed in advance as a cast film using the resin composition for forming a sealant layer, and this film may be laminated together with an adhesive resin by a method of sand lamination.
  • the formation speed (processing speed) of the adhesive resin layer 15 and the sealant layer 16 can be, for example, 80 m/min or more from the viewpoint of productivity.
  • This step is a step of heat-treating the laminate.
  • the adhesion between the barrier layer 13/second corrosion prevention treatment layer 14b/adhesive resin layer 15/sealant layer 16 can be improved.
  • the exterior material 20 of this embodiment as shown in FIG. 2 can be manufactured.
  • FIG. 4 is a perspective view showing an embodiment of an all-solid-state battery produced using the exterior material 10 described above.
  • the all-solid-state battery 50 includes a battery body 52 having a sulfide-based electrolyte as a solid electrolyte, and two metal terminals (current extraction terminals) 53 for extracting current from the battery body 52 to the outside. and an exterior bag 54 that encloses the battery body 52 in an airtight state.
  • the exterior bag 54 is obtained by heat-sealing the exterior material 10 according to the present embodiment described above, and is used as a container for housing the battery body 52 .
  • the base material layer 11 is the outermost layer
  • the sealant layer 16 is the innermost layer.
  • the exterior material 10 is made by folding one laminate film in two so that the base material layer 11 is on the outside of the all-solid-state battery 50 and the sealant layer 16 is on the inside of the all-solid-state battery 50, and the peripheral edge is heat-fused.
  • the battery main body 52 is included in the interior of the two laminate films, or by stacking the two laminate films and heat-sealing the peripheral edge portions.
  • the metal terminal 53 is sandwiched by an exterior bag 54 with the sealant layer 16 inside.
  • the metal terminal 53 may be sandwiched by the exterior bag 54 via a tab sealant.
  • the battery body 52 has at least one power generation element consisting of a positive electrode, a solid electrolyte and a negative electrode.
  • the metal terminal 53 is formed by extracting a part of the current collector to the outside of the exterior material 10, and is made of metal foil such as copper foil or aluminum foil.
  • the exterior bag 54 is obtained by heat-sealing the exterior material 10 .
  • the exterior material 10 it is possible to suppress the generation of air bubbles in the sealant layer 16 during heat sealing. Therefore, according to the all-solid-state battery 50, the sealant layer 16 of the exterior material 10 is prevented from having a rough portion and a dense portion and a decrease in sealing strength at the rough portion. Therefore, even if the battery main body 52 expands due to the use of the all-solid-state battery 50 in a high-temperature environment, and a force that attempts to open the exterior bag 54 acts, the all-solid-state battery 50 keeps the exterior bag 54 sealed by the exterior material 10. status can be maintained.
  • the exterior bag 54 may be obtained by heat-sealing the exterior material 20 or the exterior material 30 instead of the exterior material 10.
  • the solid electrolyte is not limited to a sulfide-based solid electrolyte, and may be an oxide-based solid electrolyte or the like.
  • the following films were used as the substrate layer.
  • Semi-aromatic polyamide (nylon 9T) film manufactured by Unitika Ltd., melting point: 305 ° C.
  • First adhesive layer As the first adhesive layer, a polyurethane-based adhesive (manufactured by Toyo Ink Co., Ltd.) in which a tolylene diisocyanate adduct-based curing agent is blended with a polyester polyol-based main agent was used.
  • the first corrosion prevention treatment layer (base material layer side) and the second corrosion prevention treatment layer (sealant layer side) were formed using the following (CL-1) and (CL-2).
  • CL-1 A sodium polyphosphate-stabilized cerium oxide sol prepared by using distilled water as a solvent and adjusting the solid content concentration to 10% by mass. In the sodium polyphosphate-stabilized cerium oxide sol, 10 parts by mass of Na salt of phosphoric acid was blended with 100 parts by mass of cerium oxide.
  • polyallylamine manufactured by Nittobo Co., Ltd.
  • polyglycerol polyglycidyl ether manufactured by Nagase ChemteX Corporation
  • barrier layer Annealed and degreased soft aluminum foil (manufactured by Toyo Aluminum Co., Ltd., product name: 8079 material, thickness: 40 ⁇ m) was used as the barrier layer.
  • the same polyurethane-based adhesive manufactured by Toyo Ink Co., Ltd., trade name: TM-K55 was used as in the first adhesive layer.
  • a barrier layer was provided with a first corrosion prevention treatment layer and a second corrosion prevention treatment layer in the following procedure. Specifically, (CL-1) was first applied to both surfaces of the barrier layer by micro gravure coating so that the dry coating amount was 70 mg/m 2 , and baked at 200° C. in a drying unit. Then, (CL-2) was applied on the obtained layer by microgravure coating so that the dry coating amount was 20 mg/m 2 . Thus, composite layers composed of (CL-1) and (CL-2) were formed on both sides of the barrier layer as first and second corrosion prevention treatment layers, respectively, to obtain a first laminate. These composite layers exhibit anti-corrosion performance by combining two types (CL-1) and (CL-2).
  • the first corrosion prevention treatment layer side of the barrier layer (first laminate) provided with the first corrosion prevention treatment layer and the second corrosion prevention treatment layer is dry-laminated with a polyurethane adhesive (second 1 adhesive layer) to obtain a laminate (second laminate) of the first laminate and the substrate layer.
  • a polyurethane-based adhesive was applied to the surface of the barrier layer on the side of the first corrosion prevention treatment layer so that the thickness after curing was 5 ⁇ m, dried at 80° C. for 1 minute, and then the substrate was applied.
  • a second laminate was obtained by laminating with a material layer and aging at 60° C. for 120 hours.
  • the laminate (second laminate) including the barrier layer and the base layer is set in the unwinding section of an extrusion laminator, and a polyurethane adhesive ( A second adhesive layer) was used to adhere to a sealant layer of the type shown in Table 1 to give a structure.
  • a polyurethane-based adhesive was applied to the surface of the barrier layer on the side of the second corrosion prevention treatment layer so that the thickness after curing was 5 ⁇ m, dried at 80° C. for 1 minute, and then applied to the surface.
  • the structure was obtained by laminating with a sealant layer of the type indicated in No. 1 and aging at 60° C. for 120 hours.
  • an exterior material (laminated body of base layer/first adhesive layer/first anti-corrosion treatment layer/barrier layer/second anti-corrosion treatment layer/second adhesive layer/sealant layer) is obtained. rice field.
  • Example 5 The laminate of the barrier layer and the base layer is set in the unwinding section of an extrusion laminating machine, and a sealant layer of the type shown in Table 1 is attached on the second corrosion prevention treatment layer by a thermal lamination method to form a structure. Exterior material (base material layer / first adhesive layer / first corrosion prevention treatment layer / barrier layer / second corrosion prevention treatment layer / sealant layer lamination in the same manner as in Example 1 except that body) was produced. At this time, the heat lamination of the second laminate including the barrier layer and the base layer and the sealant layer was performed by heating to a temperature of 190° C. under a pressure of 0.5 MPa.
  • Exterior material base material layer/first adhesive layer/first corrosion prevention treatment layer/barrier layer/second 2 anti-corrosion treatment layer/second adhesive layer/sealant layer laminates) were prepared.
  • ⁇ Evaluation of Exterior Material> Cut the exterior material into a size of 120 mm ⁇ 60 mm, fold it in half so that the sealant layer is on the inside, overlap both ends of the exterior material in the longitudinal direction, and pressurize both ends with a pressure of 0.5 MPa. , and the melting point of the sealant layer +20° C. for 3 seconds to form a heat-sealed portion (shaded area in FIG. 5) having a width of 10 mm, thereby producing a structure.
  • the construction was then stored at room temperature for 12 hours. Thereafter, a central portion of the heat-sealed portion in the longitudinal direction was cut out from the structure with a width of 15 mm ⁇ 30 mm (see FIG. 5) to prepare an evaluation sample.
  • this evaluation sample was separated into two separate pieces at the heat-sealed portion. Then, the sealant layer of the separated piece was visually observed, and the state of bubble generation in the sealant layer was evaluated based on the following criteria. Table 1 shows the results.
  • the "melting point of the sealant layer" is the melting point of the layer having the lowest melting point among the layers constituting the multilayer film. (Evaluation criteria) ⁇ : no bubbles are observed ⁇ : bubbles are observed locally ⁇ : bubbles are observed on the entire surface
  • the all-solid-state battery exterior material of the present disclosure can suppress the generation of air bubbles during heat sealing.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
  • Secondary Cells (AREA)
  • Laminated Bodies (AREA)
PCT/JP2023/003263 2022-02-02 2023-02-01 全固体電池用外装材及び全固体電池 Ceased WO2023149485A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN202380017806.9A CN118575334A (zh) 2022-02-02 2023-02-01 全固态电池用封装材料以及全固态电池
KR1020247025610A KR20240140086A (ko) 2022-02-02 2023-02-01 전고체 전지용 외장재 및 전고체 전지
EP23749801.9A EP4475291A4 (en) 2022-02-02 2023-02-01 SHEATHING MATERIAL FOR ALL-SOLID-STATE BATTERY AND ALL-SOLID-STATE BATTERY
US18/788,000 US20240387911A1 (en) 2022-02-02 2024-07-29 Fully-solid-state battery packaging material and fully-solid-state battery

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022015074A JP7556367B2 (ja) 2022-02-02 2022-02-02 全固体電池用外装材及び全固体電池
JP2022-015074 2022-02-02

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US18/788,000 Continuation US20240387911A1 (en) 2022-02-02 2024-07-29 Fully-solid-state battery packaging material and fully-solid-state battery

Publications (1)

Publication Number Publication Date
WO2023149485A1 true WO2023149485A1 (ja) 2023-08-10

Family

ID=87552439

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/003263 Ceased WO2023149485A1 (ja) 2022-02-02 2023-02-01 全固体電池用外装材及び全固体電池

Country Status (6)

Country Link
US (1) US20240387911A1 (enExample)
EP (1) EP4475291A4 (enExample)
JP (2) JP7556367B2 (enExample)
KR (1) KR20240140086A (enExample)
CN (1) CN118575334A (enExample)
WO (1) WO2023149485A1 (enExample)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025205669A1 (ja) * 2024-03-28 2025-10-02 株式会社レゾナック 蓄電デバイス用外装材、蓄電デバイス、及び蓄電デバイスの製造方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009032539A (ja) * 2007-07-27 2009-02-12 Toyota Motor Corp 固体型電池
JP2012178256A (ja) * 2011-02-25 2012-09-13 Toyota Motor Corp イオン伝導体材料、固体電解質層、電極活物質層および全固体電池
JP2016062712A (ja) * 2014-09-17 2016-04-25 トヨタ自動車株式会社 全固体リチウム二次電池の製造方法
JP2021152993A (ja) * 2020-03-24 2021-09-30 凸版印刷株式会社 蓄電装置用外装材及びこれを用いた蓄電装置

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0798109B1 (en) * 1996-03-25 2002-10-16 Toyo Boseki Kabushiki Kaisha Laminating film for metal, laminated metal sheet and metal container
JP2001062974A (ja) 1999-08-26 2001-03-13 Mitsubishi Polyester Film Copp 熱ラミネート用多層ポリエステルフィルム
JP4993051B2 (ja) 2001-02-19 2012-08-08 大日本印刷株式会社 リチウムイオン電池用包装材料およびその製造方法
JP2015179618A (ja) * 2014-03-19 2015-10-08 凸版印刷株式会社 外装ケース、外装ケース用ラミネートフィルム、及び、電池モジュール
JP2018170071A (ja) 2017-03-29 2018-11-01 マクセルホールディングス株式会社 電気化学素子
EP3916874A4 (en) 2019-01-23 2024-08-21 Dai Nippon Printing Co., Ltd. Exterior material for all-solid-state battery, method for manufacturing same, and all-solid-state battery
WO2021033473A1 (ja) 2019-08-21 2021-02-25 株式会社マキタ 電動作業機
JP7423964B2 (ja) 2019-09-30 2024-01-30 大日本印刷株式会社 全固体リチウムイオンバッテリー用包装材料、及び包装体

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009032539A (ja) * 2007-07-27 2009-02-12 Toyota Motor Corp 固体型電池
JP2012178256A (ja) * 2011-02-25 2012-09-13 Toyota Motor Corp イオン伝導体材料、固体電解質層、電極活物質層および全固体電池
JP2016062712A (ja) * 2014-09-17 2016-04-25 トヨタ自動車株式会社 全固体リチウム二次電池の製造方法
JP2021152993A (ja) * 2020-03-24 2021-09-30 凸版印刷株式会社 蓄電装置用外装材及びこれを用いた蓄電装置

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4475291A4 *

Also Published As

Publication number Publication date
CN118575334A (zh) 2024-08-30
US20240387911A1 (en) 2024-11-21
JP2023113000A (ja) 2023-08-15
EP4475291A4 (en) 2025-07-09
KR20240140086A (ko) 2024-09-24
JP7556367B2 (ja) 2024-09-26
EP4475291A1 (en) 2024-12-11
JP7761099B2 (ja) 2025-10-28
JP2024167918A (ja) 2024-12-04

Similar Documents

Publication Publication Date Title
WO2021131865A1 (ja) 蓄電装置用外装材及びこれを用いた蓄電装置、蓄電装置用外装材の製造方法、並びに蓄電装置用外装材におけるシーラント層として使用されるシーラントフィルムの選定方法
US12489141B2 (en) Packaging material for solid-state batteries and solid-state battery including the packaging material
JP2025138882A (ja) 蓄電装置用外装材
JP2024147799A (ja) 蓄電装置用外装材及びこれを用いた蓄電装置
JP7761099B2 (ja) 全固体電池用外装材及び全固体電池
JP7567214B2 (ja) 蓄電装置用外装材及びこれを用いた蓄電装置
JP7596636B2 (ja) 蓄電装置用外装材及びこれを用いた蓄電装置
JP7508783B2 (ja) 蓄電装置用外装材及びこれを用いた蓄電装置
WO2023189932A1 (ja) 全固体電池用外装材及び全固体電池
WO2023048067A1 (ja) 蓄電装置用外装材及びこれを用いた蓄電装置
WO2023157726A1 (ja) 全固体電池用外装材及びこれを用いた全固体電池
US20240396108A1 (en) Packaging material for fully-solid-state batteries and fully-solid-state battery including the packaging material
WO2024122592A1 (ja) 蓄電デバイス用外装材及び蓄電デバイス
JP2022041469A (ja) 蓄電装置用外装材及びこれを用いた蓄電装置
US20250309417A1 (en) Exterior material for power storage device and power storage device
JP2025035351A (ja) 蓄電装置用外装材及び蓄電装置
WO2024242142A1 (ja) 蓄電装置用外装材及び蓄電装置
WO2024009869A1 (ja) 蓄電装置用外装材及びこれを用いた蓄電装置
WO2021157489A1 (ja) 蓄電装置用外装材及びこれを用いた蓄電装置

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23749801

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 202380017806.9

Country of ref document: CN

ENP Entry into the national phase

Ref document number: 20247025610

Country of ref document: KR

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2023749801

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2023749801

Country of ref document: EP

Effective date: 20240902