WO2022024717A1 - 電池用接着剤及び電池用接着積層体 - Google Patents
電池用接着剤及び電池用接着積層体 Download PDFInfo
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- WO2022024717A1 WO2022024717A1 PCT/JP2021/025915 JP2021025915W WO2022024717A1 WO 2022024717 A1 WO2022024717 A1 WO 2022024717A1 JP 2021025915 W JP2021025915 W JP 2021025915W WO 2022024717 A1 WO2022024717 A1 WO 2022024717A1
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- adhesive
- battery
- weight
- meth
- sulfide
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- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/414—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of a copolymer
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2425/00—Presence of styrenic polymer
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
-
- 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 invention relates to a battery adhesive and a battery adhesive laminate.
- Patent Documents 1 and 2 In recent years, with the spread of electric vehicles, the use of secondary batteries is increasing. In the exterior of the secondary battery, in order to bond and fix the battery component to the exterior of the secondary battery, or to make the member compact and fit in the exterior by attaching it to the battery component. Adhesives or adhesive tapes may be used (Patent Documents 1 and 2).
- Lithium-ion secondary batteries have been put into practical use as secondary batteries, but there is a demand for secondary batteries with higher reliability and higher energy density. Under such a demand, an all-solid secondary battery in which the electrolyte is a solid electrolyte instead of the conventional solution-based electrolyte is attracting attention, and in particular, a battery using a sulfide-based solid electrolyte as the solid electrolyte is attracting attention. , Development is in progress.
- the sulfide-based solid electrolyte means a solid electrolyte containing sulfide.
- a trace amount of impurities such as water may be mixed inside the battery.
- hydrogen sulfide may be generated inside the battery due to the reaction between impurities such as water and the sulfide-based solid electrolyte.
- hydrogen sulfide may be generated when a battery containing a sulfide-based solid electrolyte is charged and discharged.
- the metal collector constituting the battery may be corroded by the hydrogen sulfide, and the resistance value of the metal collector may increase.
- a gap may be generated between the electrodes, or the exterior body may swell. Therefore, hydrogen sulfide inside the battery can be a factor that deteriorates the battery performance.
- the present inventor can absorb hydrogen sulfide and the adhesive is good by containing a metal compound in a specific range in the adhesive used for the battery.
- the present invention has been completed by discovering that it can exhibit excellent adhesive strength. That is, the present invention provides the following.
- An adhesive for batteries used for batteries containing a sulfide-based solid electrolyte Contains metal compounds and resins A battery adhesive in which the metal compound is 1% by weight or more and less than 60% by weight based on the total weight of the metal compound and the resin.
- the resin contains an acrylic polymer containing an acrylic compound unit.
- a battery adhesive capable of absorbing hydrogen sulfide generated inside a battery containing a sulfide-based solid electrolyte and having good adhesive strength; hydrogen sulfide generated inside a battery containing a sulfide-based solid electrolyte. It is possible to provide an adhesive laminate for a battery, which can be absorbed and can exhibit a good adhesive force with an adherend.
- FIG. 1 is a schematic cross-sectional view of an adhesive laminate for a battery according to an embodiment of the present invention.
- the "agent" may be composed of one kind of substance or may be composed of two or more kinds of substances.
- the "resin” may be composed of one kind of polymer or may be composed of two or more kinds of polymers.
- the "adhesive” also includes an adhesive (pressure sensitive adhesive) unless otherwise specified.
- (meth) acrylic ((meth) acrylic, (meth) acrylic) includes “acrylic” (acryl, acrylic), “methacrylic” (methacrylic, methylyl), and combinations thereof.
- the phrase “(meth) acrylic acid” includes “acrylic acid”, “methacrylic acid”, and combinations thereof
- the phrase “(meth) acrylamide” includes “acrylamide", "methacrylamide”.
- the term “(meth) acrylate” includes “acrylate”, “methacrylate”, and combinations thereof.
- (meth) acrylo includes “acrylo", "methacrylo” and combinations thereof.
- the battery adhesive according to an embodiment of the present invention contains a metal compound and a resin.
- the "adhesive for a battery” is also simply referred to as an “adhesive”.
- the battery adhesive according to the present embodiment has a hydrogen sulfide absorption capacity and a good adhesive strength.
- the resin is composed of a polymer.
- the polymer exhibits adhesiveness to the adhesive.
- any polymer that can make the adhesive exhibit adhesiveness can be used.
- a polymer capable of exhibiting adhesiveness is also called a base polymer.
- Preferred examples of the polymer constituting the resin include (1) an acrylic polymer and (2) a rubber polymer.
- the resin may be composed of a single polymer of one kind, or may be composed of a combination of arbitrary ratios of two or more kinds of polymers.
- Acrylic polymer means a polymer containing an acrylic compound unit.
- the acrylic compound unit means a structural unit having a structure obtained by polymerizing an acrylic compound as a monomer.
- the acrylic compound unit is not limited by the production method thereof, and may be a structural unit obtained by any production method.
- the acrylic compound means (meth) acrylic acid and its derivatives.
- (meth) acrylic acid derivatives include (meth) acrylic acid esters, (meth) acrylic acid anhydrides, (meth) acrylic acid amides, and (meth) acrylonitrile.
- (meth) acrylic acid esters are alkyls having 1 to 20 carbon atoms and esters of (meth) acrylic acid (eg, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate).
- aryl groups eg, phenyl (meth) acrylates, benzyl (meth) acrylates, and phenoxyethyl (meth) acrylates
- (Meta) acrylic acid ester containing eg, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4- Hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, and 4- (hydroxymethyl).
- 2-hydroxyethyl (meth) acrylate 2-hydroxypropyl (meth) acrylate
- 3-hydroxypropyl (meth) acrylate 2-hydroxybutyl (meth) acrylate
- 4- Hydroxybutyl (meth) acrylate 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acryl
- Cyclohexyl (meth) acrylate and (meth) acrylic acid ester containing an alkyloxy group (meth) Examples thereof include methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate).
- (meth) acrylic acid amides are (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N- Butyl (meth) acrylamide, N-methylol (meth) acrylamide, N- (2-hydroxypropyl) (meth) acrylamide, N- (methoxymethyl) (meth) acrylamide, N- (butoxymethyl) (meth) acrylamide, and Diacetone (meth) acrylamide may be mentioned.
- the acrylic compound unit contained in the acrylic polymer may be one kind or a combination of two or more kinds in any ratio.
- the acrylic polymer is preferably a polymer containing a (meth) acrylic acid alkyl ester unit.
- the number of carbon atoms of the alkyl group in the (meth) acrylic acid alkyl ester unit is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5.
- the weight ratio of the (meth) acrylic acid alkyl ester unit to the total weight of the acrylic compound unit in the acrylic polymer is preferably 80% by weight or more, more preferably 90% by weight or more, still more preferably 95% by weight or more. Yes, it is usually 100% by weight or less, and may be 100% by weight.
- the acrylic polymer may contain any monomer unit in addition to the acrylic compound unit.
- the weight ratio of the acrylic compound unit to all the constituent units of the acrylic polymer is preferably 50% by weight or more, more preferably 60% by weight or more, still more preferably 80% by weight or more, and particularly preferably 90% by weight or more. Yes, it is usually 100% by weight or less, and may be 100% by weight.
- acrylic polymers examples include vinyl ester units; vinyl ether units; olefin units; substituted olefin units; ethylenically unsaturated monocarboxylic acid units other than (meth) acrylic acid. Included are ethylenically unsaturated dicarboxylic acid units (eg, maleic acid, fumaric acid, itaconic acid, and citraconic acid) and their anhydride units.
- Rubber-based polymer As the rubber-based polymer, a polymer having rubber elasticity can be used. Examples of the rubber-based polymer include natural rubber; polybutadiene; polyisoprene; polychloroprene; ethylene-propylene copolymer; acrylonitrile-butadiene copolymer; and aromatic vinyl compound-diene-based copolymer.
- the aromatic vinyl compound-diene-based copolymer means a copolymer containing an aromatic vinyl compound unit and a diene unit.
- the aromatic vinyl compound unit means a structural unit having a structure obtained by polymerizing an aromatic vinyl compound.
- the diene unit means a structural unit having a structure obtained by polymerizing a diene.
- the aromatic vinyl compound unit and the diene unit are not limited by the production method thereof, and may be a structural unit obtained by any production method.
- aromatic vinyl compounds for forming aromatic vinyl compound units include styrene, styrene derivatives (eg, ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4- (Dimethylstyrene) and vinylnaphthalene (eg, 1-vinylnaphthalene, 2-vinylnaphthalene) may be mentioned, and these may be used alone or in any combination of two or more kinds.
- styrene styrene derivatives (eg, ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4- (Dimethylstyrene) and vinylnaphthalene (eg, 1-vinylnaphthalene, 2-vinylnaphthalene) may be mentioned, and these may be used alone or in any combination of two or more kinds.
- aromatic vinyl compound-diene copolymer a copolymer in which the aromatic vinyl compound unit is at least one selected from the group consisting of styrene units and styrene derivative units is preferable, and the aromatic vinyl compound unit is styrene.
- a copolymer, which is a unit, is more preferable.
- diene for forming a diene unit examples include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene, which can be used alone. Often, it may be used in any combination of two or more kinds of ratios.
- aromatic vinyl compound-diene-based copolymer a copolymer having a diene unit of 1,3-butadiene unit is preferable.
- the amount of the acrylic polymer in the resin is preferably 50% by weight or more, more preferably 70% by weight or more, still more preferably 90% by weight or more, and usually 100% by weight, based on the amount of the resin. It is less than% by weight.
- the amount of the aromatic vinyl compound-diene copolymer in the resin is preferably 50% by weight or more, more preferably 70% by weight or more, still more preferably 90% by weight, based on the amount of the resin. % Or more, usually 100% by weight or less.
- the weight average molecular weight (Mw) of the polymer contained in the resin is preferably 10,000 or more, more preferably 50,000 or more, still more preferably 80,000 or more, and preferably 1,000,000 or less. It is preferably 800,000 or less, more preferably 700,000 or less.
- the weight average molecular weight can be determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a mobile phase as a polystyrene standard.
- the polymer constituting the resin can be produced by any method.
- Examples of the production method are not particularly limited, and examples thereof include a solution polymerization method, a suspension polymerization method, a bulk polymerization method, and an emulsion polymerization method.
- the metal compound examples include a monovalent metal salt and a divalent or higher polyvalent metal salt, and the polyvalent metal salt is preferable.
- the salt means a compound that can be produced by a reaction between an acid and a base.
- metal atoms constituting the metal compound include atoms belonging to transition metal elements such as copper atom, zinc atom, and iron atom.
- metal compounds which are polyvalent metal salts and include transition metal atoms having a valence (II) or higher and organic compounds include copper compounds which are organic substances (eg, copper (II) dimethyldithiocarbamate, copper (II). ) Ethoxide, copper ethylacetate acetate (II), copper 2-ethylhexanoate (II), copper gluconate (II), copper isobutyrate (II), copper (II) isopropoxide, copper methacrylate (II), phthal.
- organic tin compounds eg, tin acetate, acetylacetonatostin, tin ethoxydo, tin 2-ethylhexanoate, tin stearate
- Organic iron compounds eg iron acetate, iron acetylacetonate, iron acrylate, iron
- metal compounds which are polyvalent metal salts and contain transition metal atoms having a valence (II) or higher and inorganic ions include copper compounds which are inorganic substances (eg, copper chromate, copper nitrate (II), Copper sulfate (II), copper thiosianate (II)); inorganic tin compounds (eg tin sulfate); inorganic iron compounds (eg iron diphosphate, iron nitrate, iron sulfate); inorganic zinc Examples include compounds (eg, zinc carbonate, zinc sulfate, zinc thiosianate).
- copper compounds which are inorganic substances eg, copper chromate, copper nitrate (II), Copper sulfate (II), copper thiosianate (II)
- inorganic tin compounds eg tin sulfate
- inorganic iron compounds eg iron diphosphate, iron nitrate, iron sulfate
- the metal compound may be contained in the adhesive by itself, or may be contained in the adhesive as a combination of two or more kinds in any ratio.
- the metal compound is preferably one or more selected from the group consisting of a copper compound, a zinc compound, and an iron compound, and is one or more selected from the group consisting of a copper compound and a zinc compound, and more preferably copper. It is a compound, and particularly preferably copper sulfate (II) or copper stearate (II). In yet another embodiment, the metal compound is preferably a zinc compound, more preferably zinc stearate (II).
- the metal compound is preferably a compound that does not contain any of hydroxy groups, hydroxy ions, and water. As a result, the generation of water due to the reaction between hydrogen sulfide and the metal compound can be suppressed.
- the metal compound preferably does not contain chloride ions. As a result, it is possible to suppress the reaction between the chloride ion and the lithium ion to form a stable compound.
- the weight ratio of the metal compound is usually 1% by weight or more, preferably 10% by weight or more, more preferably 20% by weight or more, and usually 60% by weight, based on the total weight of the metal compound and the resin contained in the adhesive. Less than, preferably 50% by weight or less, more preferably 45% by weight or less.
- the adhesive can effectively exert the ability to absorb hydrogen sulfide.
- the weight ratio of the metal compound is not more than the upper limit value, the adhesive strength of the adhesive can be improved.
- the adhesive of the present embodiment may contain any component in addition to the metal compound and the resin.
- the optional component include various additives such as gas adsorbents (eg, activated carbon) other than the metal compound, tackifiers, and softeners.
- the ratio of these additives in the adhesive may be 0 to 10 parts by weight with respect to 100 parts by weight of the resin.
- the method for producing the adhesive is not particularly limited, and the adhesive can be produced by a conventionally known method.
- an adhesive can be produced by dissolving a resin containing a polymer and other optional components in a solvent, adding a metal compound to the obtained solution, and stirring to disperse the metal compound.
- the adhesive of the present embodiment is usually used for a battery containing a sulfide-based solid electrolyte.
- the sulfide-based solid electrolyte means a solid electrolyte containing sulfide.
- Solid electrolytes containing sulfides include sulfide materials produced using a raw material composition containing Li 2S and sulfides of elements of Groups 13 to 15 of the Periodic Table.
- the raw material composition include a composition containing Li 2 S and P 2 S 5 , a composition containing Li 2 S and Si S 2 , a composition containing Li 2 S and Ge S 2 , and Li 2 S and Al.
- examples thereof include compositions containing 2 S 3 .
- a composition containing Li 2 S and P 2 S 5 is preferable because it has excellent lithium ion conductivity.
- the raw material composition of the sulfide-based solid electrolyte is selected from the group consisting of Al 2 S 3 , B 2 S 3 and Si S 2 in addition to the above Li 2 S and P 2 S 5 to the extent that the ionic conductivity is not deteriorated. It may contain one or more sulfides to be treated. This makes it possible to stabilize the glass component in the sulfide-based solid electrolyte.
- the raw material composition for the sulfide-based solid electrolyte is from the group consisting of Li 2 S and P 2 S 5 , as well as Li 3 PO 4 , Li 4 SiO 4 , Li 4 GeO 4 , Li 3 BO 3 and Li 3 AlO 3 . It may contain one or more lithium orthooxoates of choice. This makes it possible to stabilize the glass component in the sulfide-based solid electrolyte.
- compositions containing Li 2 S and P 2 S 5 compositions containing Li 2 S and Si S 2 , compositions containing Li 2 S and Ge S 2 , and compositions containing Li 2 S and Al 2 S 3 .
- the molar fraction of Li 2S in the raw material composition of the sulfide-based solid electrolyte is preferably 50% or more, more preferably, from the viewpoint of more reliably obtaining the sulfide-based solid electrolyte having crosslinked sulfur. Is 60% or more, preferably 74% or less.
- Examples of the method for producing a sulfide-based solid electrolyte from the above-mentioned raw material composition include an amorphization method such as a mechanical milling method and a melt quenching method.
- the sulfide-based solid electrolyte may be sulfide glass or crystallized sulfide glass.
- the sulfide glass can be obtained, for example, by the above-mentioned amorphization method. Crystallized sulfide glass can be obtained, for example, by heat-treating the sulfide glass.
- the sulfide - based solid electrolyte is preferably a crystallized sulfide glass represented by Li 7P 3S 11 from the viewpoint of exhibiting excellent Li ion conductivity.
- a crystallized sulfide glass represented by Li 7P 3S 11 Li 2 S and P 2 S 5 are mixed at a molar ratio of 70:30 and amorphized with a ball mill. Examples thereof include a method of obtaining sulfide glass and heat-treating the obtained sulfide glass at 150 ° C to 360 ° C to produce the glass.
- the adhesive of the present embodiment is used, for example, in a battery containing the above-mentioned sulfide-based solid electrolyte.
- a battery containing a sulfide-based solid electrolyte usually includes a positive electrode and a negative electrode, and a layer of the sulfide-based solid electrolyte is arranged as an electrolyte layer between the positive electrode and the negative electrode.
- the positive electrode usually includes a layer containing a positive electrode active material and a positive electrode current collector.
- the negative electrode usually includes a layer containing a negative electrode active material and a negative electrode current collector.
- the battery may be a winding type battery having a structure in which a positive electrode, a solid electrolyte layer, a negative electrode, and a separator are laminated and then wound around the positive electrode, a solid electrolyte layer, a negative electrode, and a separator. It may be a laminated battery having a structure in which a plurality of laminated bodies are further laminated. Further, the outer body of the battery may be any of a cylindrical type, a square type, and a laminated type.
- the battery containing the sulfide-based solid electrolyte is a lithium ion all-solid secondary battery in which the electrolyte is a sulfide-based solid electrolyte.
- the adhesive of the present embodiment is used for adhering the constituent members of the battery containing the sulfide-based solid electrolyte, and for example, instead of the conventional adhesive used for the battery, the adhesive of the present embodiment is used.
- the adhesive of the present embodiment is composed of an adhesive between the outer body of the battery and an electrode winding body or a laminated body containing an electrode and a sulfide-based solid electrolyte, and a current collector constituting the outer body of the battery and the electrode.
- the adhesive is used as a form of the adhesive laminate for a battery [2. It can also be used for the purposes described in the item [Adhesive laminate for batteries].
- the adhesive of the present embodiment instead of the conventional adhesive used for the battery, the following advantages are obtained.
- the battery component may become brittle.
- the adhesive since the content ratio of the metal compound can be increased, a more hydrogen sulfide absorption effect can be expected.
- the adhesive of the present embodiment is used instead of the conventional adhesive, it can be expected that the output efficiency of the battery is maintained without changing the thickness of the battery.
- the adhesive is preferably used for adhering the exterior body to the electrode and the electrode laminate containing the sulfide-based solid electrolyte. From the viewpoint of suppressing the deterioration of the tab and suppressing the change in the resistance value of the tab, it is preferable to use it for adhering the tab and other constituent members.
- the battery adhesive laminate according to an embodiment of the present invention includes a base material and a layer of the battery adhesive provided on the base material. Since the battery adhesive laminate according to the present embodiment contains the layer of the battery adhesive, it has the same effect as the battery adhesive. That is, the adhesive laminate for a battery has a hydrogen sulfide absorption capacity and a good adhesive force with an adherend.
- FIG. 1 is a schematic cross-sectional view of an adhesive laminate for a battery according to an embodiment of the present invention.
- the battery adhesive laminate 100 includes a base material 10 and a layer 20 of a battery adhesive provided on the base material 10 so as to be in contact with one surface 10U of the base material 10.
- the battery adhesive laminate 100 of the present embodiment has only one layer of the battery adhesive, but in another embodiment, the battery adhesive laminate is bonded to the base material and two batteries.
- a layer of battery adhesive, including a layer of agent, may be provided on each of both sides of the substrate.
- a base material formed from any material can be used.
- a base material made of a resin containing a polymer can be used.
- resins for forming the substrate are polyesters (eg polyethylene terephthalate (PET), polyethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate); polyolefins (eg polyethylene, polypropylene, ethylene-propylene co-weight).
- polyvinyl alcohol polyvinylidene chloride; polyvinyl chloride; vinyl chloride-vinyl acetate copolymer; polyvinyl acetate; polyamide; polyimide; cellulose-based resin; fluororesin; polyether; polyetheramide; polyphenylene sulfide; polystyrene Examples thereof include based resins (eg, polystyrene); polycarbonate; and polyether sulfone. Two or more of these may be used in combination.
- the base material may have a single-layer structure or may have a multi-layer structure.
- the base material may be surface-treated, such as chromic acid treatment, ozone treatment, and corona treatment.
- the thickness of the base material can be any thickness, and may be, for example, 1 ⁇ m to 200 ⁇ m, preferably 5 ⁇ m to 50 ⁇ m.
- the base material may be in the form of a tape, and the adhesive laminate for a battery may be in the form of an adhesive tape.
- the base material can be manufactured by any method, and a commercially available product may be used.
- the layer of the battery adhesive is a layer formed from the battery adhesive and usually contains the battery adhesive.
- the layer of the battery adhesive contains a metal compound and a resin, and the metal compound is 1% by weight or more and less than 60% by weight with respect to the total weight of the metal compound and the resin.
- the layer of battery adhesive can be formed by any method.
- the layer of the battery adhesive is formed by applying the battery adhesive as it is or diluting it with a solvent to form a coating film, and drying the coating film as necessary.
- Can be formed Further, for example, it can be formed by applying a battery adhesive or a diluted solution thereof on a release film to form a layer of the battery adhesive, and transferring this layer onto a substrate.
- any method can be adopted as the coating method, for example, a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, a comma coater, a direct coater, and the like.
- the coating may be performed by a coating method using an arbitrary coater such as a die coater.
- the layer of the adhesive for batteries may be formed by melt-coextruding the base material and the adhesive to form a film.
- the thickness of the layer of the adhesive for the battery can be any thickness, and may be, for example, 2 ⁇ m to 100 ⁇ m, preferably 5 ⁇ m to 20 ⁇ m.
- the adhesive laminate for a battery has a hydrogen sulfide absorbing ability and also has a good adhesive force with an adherend.
- the peel strength when the adherend is a copper plate measured in accordance with JIS Z0237, is preferably 40 N / m or more, more preferably 50 N / m or more, and is large. It is more preferable, but it may be 500 N / m or less, for example.
- the adhesive laminate for a battery is usually used for a battery containing a sulfide-based solid electrolyte.
- a specific application in addition to the application of the adhesive for a battery, it can be used for attaching to a component member of a battery.
- an adhesive laminate for a battery it is attached to the periphery of an electrode laminate containing an electrode and a solid electrolyte, and is extended from an application for collecting the components of the electrode laminate and a current collector. The use of pasting around the tab is mentioned.
- the binder solution was produced by the following procedure. In a glass container with a stirrer, 50 parts of n-butyl acrylate, 50 parts of ethyl acrylate, 1 part of sodium dodecylbenzene sulfonate as an emulsifier, 150 parts of ion-exchanged water, and 0.5 part of potassium persulfate as a polymerization initiator. was added, the mixture was sufficiently stirred, and then the mixture was heated to 70 ° C. to initiate polymerization.
- 2 S / P 2 S 5 70 mol% / 30 mol%, number average particle diameter: 1.2 ⁇ m, cumulative 90% particle diameter: 2.1 ⁇ m) 100 parts and a binder solution (as a solid content) produced by the above procedure. 2 parts) and mixed.
- Xylene as an organic solvent was added to the mixture in an amount having a solid content concentration of 65% by weight, and then the mixture was mixed with a planetary mixer to prepare a slurry composition for a solid electrolyte layer having a solid content concentration of 65% by weight. ..
- the obtained slurry composition was applied to a copper foil having a thickness of 12 ⁇ m with a doctor blade having a gap of 100 ⁇ m. Then, it was dried on a hot plate at 50 ° C. for 20 minutes to form a coating film composed of a solid electrolyte on the copper foil. The formed coating film was scraped from the copper foil except for the portion other than the 40 mm square, and a square-shaped coating film having a side of 40 mm was left on the copper foil. A copper foil was layered on the coating film and pressed so as to sandwich the remaining square-shaped coating film. The press pressure was 20 MPa. After pressing, it was processed into a shape having a square-shaped portion having a side of 40 mm and two tape-shaped tabs.
- Each of the two tabs is provided so as to extend from the center of each of the two opposite sides of the square portion.
- the circumference of the square-shaped part excluding the tab of the cell was wrapped with an adhesive laminate.
- the square-shaped portion was sealed with an aluminum laminate film from above the adhesive laminate to obtain a test cell.
- the rate of increase from the initial resistance value is an index that hydrogen sulfide is absorbed by the adhesive laminate in the battery containing the sulfide-based solid electrolyte and the deterioration of the battery is suppressed.
- Examples 1 to 4, Comparative Examples 3 to 4 The copolymer shown in Table 1 (copolymer produced in Production Example 1 or Production Example 2) was dissolved in xylene so that the concentration of the copolymer was 10% by weight, and the metal shown in Table 1 was dissolved therein. A compound (zinc stearate or copper sulfate) was blended and dispersed. The blending amount of the metal compound was set so that the weight of the metal compound became the weight percentage in Table 1 with respect to the total weight of the polymer and the metal compound in the dispersion liquid. As a result, a dispersion liquid as an adhesive was obtained.
- the obtained dispersion was applied to a polyethylene terephthalate (PET) film as a base material having a thickness of 50 ⁇ m to obtain a coating film.
- PET polyethylene terephthalate
- the coating film was dried by heating on a hot plate at 60 ° C. for 20 minutes to obtain an adhesive laminate having a layer structure of (PET film) / (adhesive layer).
- the thickness of the adhesive layer was 20 ⁇ m.
- the obtained adhesive laminate was evaluated by the above method. The results are shown in Table 1.
- the description in the table below has the following meanings.
- the "adhesive composition” is shown as the weight percentage of each component with respect to the total weight of the metal compound and the resin.
- "Styrene-butadiene copolymer” The copolymer obtained in Production Example 2.
- Acrylic polymer The copolymer obtained in Production Example 1.
- Zinc stearate Zinc stearate (II) manufactured by Kanto Chemical Co., Inc.
- Copper sulfate Copper sulfate (II) manufactured by Kanto Chemical Co., Inc.
- the adhesive laminate according to Comparative Example 3 and Comparative Example 4 in which the amount of the metal compound is 60% by weight or more with respect to the total weight of the polymer and the resin has a significantly low peel strength value.
- the adhesive laminates according to Examples 1 to 4 wherein the amount of the metal compound is 1% by weight or more and less than 60% by weight with respect to the total weight of the polymer and the resin have an ability to absorb hydrogen sulfide.
- the value of the peel strength is good, and the rate of increase in the resistance value is low.
- Zinc stearate (II) which is a polyvalent metal salt and contains a transition metal atom and an organic compound
- copper (II) sulfate which is a polyvalent metal salt and contains a transition metal atom and an inorganic ion.
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Abstract
Description
そのような要求の下、電解質を、従来の溶液系の電解質に代えて固体電解質とした全固体二次電池が注目されており、特に、固体電解質として、硫化物系固体電解質を用いた電池は、開発が進んでいる。ここで、硫化物系固体電解質とは、硫化物を含む固体電解質を意味する。
また、硫化物系固体電解質を含む電池を充放電する際にも、硫化水素が発生する場合がある。
電池内部で硫化水素が発生すると、硫化水素により電池を構成する金属集電体が腐食されて、金属集電体の抵抗値が上昇する場合がある。また、電極間に隙間が発生したり、外装体が膨れたりするなどする場合もある。したがって、電池内部の硫化水素は、電池性能を低下させる要因となりうる。
すなわち、本発明は、以下を提供する。
金属化合物及び樹脂を含み、
前記金属化合物が、前記金属化合物及び前記樹脂の合計重量に対して、1重量%以上60重量%未満である、電池用接着剤。
[2] 前記金属化合物が、多価金属塩である、[1]に記載の電池用接着剤。
[3] 前記金属化合物が、銅化合物である、[1]又は[2]に記載の電池用接着剤。
[4] 前記樹脂が、アクリル化合物単位を含むアクリル系重合体を含む、[1]~[3]のいずれか一項に記載の電池用接着剤。
[5] 前記アクリル系重合体の量が、前記樹脂の量に対して、50重量%以上100重量%以下である、[4]に記載の電池用接着剤。
[6] 前記樹脂が、芳香族ビニル化合物単位及びジエン単位を含む芳香族ビニル化合物-ジエン系共重合体を含む、[1]~[3]のいずれか一項に記載の電池用接着剤。
[7] 前記芳香族ビニル化合物-ジエン系共重合体の量が、前記樹脂の量に対して、50重量%以上100重量%以下である、[6]に記載の電池用接着剤。
[8] 硫化物系固体電解質を含む電池に用いられる、電池用接着積層体であって、
基材と、前記基材上に設けられた[1]~[7]のいずれか一項に記載の電池用接着剤の層とを含む、電池用接着積層体。
以下の説明において、「(メタ)アクリレート」の文言は、「アクリレート」、「メタクリレート」、及びこれらの組み合わせを包含する。
以下の説明において、「(メタ)アクリロ」の文言は、「アクリロ」、「メタクリロ」及びこれらの組み合わせを包含する。
本発明の一実施形態に係る電池用接着剤は、金属化合物及び樹脂を含む。以下、「電池用接着剤」を、単に「接着剤」ともいう。本実施形態に係る電池用接着剤は、硫化水素吸収能力を有すると共に、良好な接着力を有する。
樹脂は、重合体から構成される。重合体により、接着剤に接着性が発揮される。重合体として、接着剤に接着性を発揮させうる任意の重合体を用いうる。接着剤において、接着性を発揮させうる重合体は、ベースポリマーとも呼ばれる。
樹脂を構成する重合体の好ましい例としては、(1)アクリル系重合体及び(2)ゴム系重合体が挙げられる。樹脂は、一種単独の重合体から構成されていてもよく、二種以上の重合体の任意の比率の組み合わせから構成されていてもよい。
アクリル系重合体とは、アクリル化合物単位を含む重合体を意味する。アクリル化合物単位とは、アクリル化合物を単量体として重合させて得られる構造を有する構成単位を意味する。アクリル化合物単位は、その製造方法によって限定されず、任意の製造方法によって得られる構成単位であってよい。
アクリル系重合体中のアクリル化合物単位の全重量に対する、(メタ)アクリル酸アルキルエステル単位の重量比率は、好ましくは80重量%以上、より好ましくは90重量%以上、更に好ましくは95重量%以上であり、通常100重量%以下であり、100重量%であってもよい。
ゴム系重合体として、ゴム弾性を有する重合体を用いうる。
ゴム系重合体の例としては、天然ゴム;ポリブタジエン;ポリイソプレン;ポリクロロプレン;エチレン-プロピレン共重合体;アクリロニトリル-ブタジエン共重合体;及び、芳香族ビニル化合物-ジエン系共重合体が挙げられる。
金属化合物の例としては、一価金属塩及び二価以上の多価金属塩が挙げられ、多価金属塩が好ましい。ここで塩とは、酸と塩基との反応により生成されうる化合物を意味する。
金属化合物を構成する金属原子の例としては、銅原子、亜鉛原子、鉄原子などの、遷移金属元素に属する原子が挙げられる。
多価金属塩であって、価数(II)以上の遷移金属原子及び無機イオンを含む、金属化合物の例としては、無機物である銅化合物(例、亜クロム酸銅、硝酸銅(II)、硫酸銅(II)、チオシアン酸銅(II));無機物であるスズ化合物(例、硫酸スズ);無機物である鉄化合物(例、二リン酸鉄、硝酸鉄、硫酸鉄);無機物である亜鉛化合物(例、炭酸亜鉛、硫酸亜鉛、チオシアン酸亜鉛)が挙げられる。
また別の実施形態において、金属化合物は、好ましくは亜鉛化合物であり、より好ましくは、ステアリン酸亜鉛(II)である。
本実施形態の接着剤は、前記金属化合物及び樹脂の他に、任意の成分を含みうる。
任意の成分の例としては、前記金属化合物以外のガス吸着剤(例、活性炭)、粘着付与剤、軟化剤などの各種添加剤が挙げられる。接着剤におけるこれらの添加剤の割合は、樹脂100重量部に対して0~10重量部としうる。
接着剤の製造方法は、特に限定されず、従来公知の方法により製造できる。
例えば、重合体を含む樹脂及び他の任意成分を、溶媒に溶解し、得られた溶解液に金属化合物を添加し、撹拌して金属化合物を分散させることにより、接着剤を製造しうる。
本実施形態の接着剤は、通常、硫化物系固体電解質を含む電池に用いられる。ここで、硫化物系固体電解質とは、硫化物を含む固体電解質を意味する。
硫化物を含む固体電解質の例としては、Li2Sと、周期表第13族~第15族の元素の硫化物とを含有する原料組成物を用いて製造された硫化物材料が挙げられる。原料組成物の具体例としては、Li2S及びP2S5を含む組成物、Li2S及びSiS2を含む組成物、Li2S及びGeS2を含む組成物、及びLi2S及びAl2S3を含む組成物が挙げられる。これらの中でも、リチウムイオン伝導性が優れている点で、Li2S及びP2S5を含む組成物が好ましい。
電池は、正極、固体電解質の層、負極、及びセパレータを積層したのち、これを巻き回した構造を有する、巻き回し式電池であってもよく、正極、固体電解質の層、負極、及びセパレータを積層した積層体の複数を、更に積層した構造を有する、積層式電池であってもよい。また、電池の外装体は、円筒型、角型、及びラミネート型のいずれであってもよい。
・例えば、セパレータなどのフィルム状の電池構成部材に金属化合物を含有させると、電池構成部材が脆くなる場合がある。一方、接着剤では、金属化合物の含有割合をより多くしうるので、より硫化水素の吸収効果が期待できる。
・金属化合物を含有させたフィルム部材を電池内に新たに配置すると、電池全体の厚みが大きくなる、電池の出力効率が低下するなどの可能性がある。一方、従来の接着剤に代えて、本実施形態の接着剤を使用すれば、電池の厚みを変化させることなく、電池の出力効率も維持されることが期待できる。
タブの劣化を抑制し、タブの抵抗値変化を抑制する観点から、タブと他の構成部材とを接着するために用いることが好ましい。
本発明の一実施形態に係る電池用接着積層体は、基材と、前記基材上に設けられた前記電池用接着剤の層とを含む。本実施形態に係る電池用接着積層体は、前記電池用接着剤の層を含んでいるので、前記電池用接着剤と同様の効果を有する。すなわち、電池用接着積層体は、硫化水素吸収能力を有するとともに、被着体との接着力が良好である。
図1に示すように、電池用接着積層体100は、基材10と、基材10の一方の面10Uに接するように、基材10の上に設けられた電池用接着剤の層20とを備える。
本実施形態の電池用接着積層体100は、電池用接着剤の層を1つのみ有しているが、別の実施形態では、電池用接着積層体は、基材と、2つの電池用接着剤の層とを含み、電池用接着剤の層が、基材の両方の面のそれぞれの上に設けられていてもよい。
基材としては、任意の材料から形成された基材を用いうる。例えば、基材として、重合体を含む樹脂からなる基材を用いうる。
基材を形成するための樹脂の例としては、ポリエステル(例、ポリエチレンテレフタレート(PET)、ポリエチレンナフタレート、ポリブチレンテレフタレート、ポリブチレンナフタレート);ポリオレフィン(例、ポリエチレン、ポリプロピレン、エチレン-プロピレン共重合体);ポリビニルアルコール;ポリ塩化ビニリデン;ポリ塩化ビニル;塩化ビニル-酢酸ビニル共重合体;ポリ酢酸ビニル;ポリアミド;ポリイミド;セルロース系樹脂;フッ素系樹脂;ポリエーテル;ポリエーテルアミド;ポリフェニレンサルファイド;ポリスチレン系樹脂(例、ポリスチレン);ポリカーボネート;及び、ポリエーテルスルホンが挙げられる。これらの二種以上を組み合わせて使用してもよい。
基材には、クロム酸処理、オゾン処理、コロナ処理などの、表面処理がされていてもよい。
基材をテープ状として、電池用接着積層体を接着テープの形態としてもよい。
電池用接着剤の層は、前記電池用接着剤から形成された層であり、通常、前記電池用接着剤を含む。通常、電池用接着剤の層は、金属化合物及び樹脂を含み、前記金属化合物が、前記金属化合物及び前記樹脂の合計重量に対して、1重量%以上60重量%未満である。
電池用接着剤の層は、任意の方法で形成することができる。例えば電池用接着剤の層は、前記電池用接着剤をそのまま、又は溶媒で希釈して、基材の上に塗工して塗膜を形成し、必要に応じて塗膜を乾燥することにより、形成できる。また例えば、電池用接着剤又はその希釈液を剥離フィルムの上に塗工して、電池用接着剤の層を形成し、この層を、基材上に転写することにより、形成できる。
電池用接着積層体は、硫化水素吸収能力を有すると共に、被着体との良好な接着力を有する。
例えば、電池用接着積層体は、JIS Z0237に準拠して測定された、被着体が銅板である場合の剥離強度が、好ましくは40N/m以上、より好ましくは50N/m以上であり、大きいほど好ましいが、例えば500N/m以下であってもよい。
電池用接着積層体は、通常、硫化物系固体電解質を含む電池に用いられる。具体的な用途の例としては、前記電池用接着剤の用途に加えて、電池の構成部材に貼り付けるために用いられうる。このような電池用接着積層体の使用方法の具体例としては、電極及び固体電解質を含む電極積層体の周囲に貼り付けて、電極積層体の構成要素をまとめる用途、集電体から延長されるタブの周囲に貼り付ける用途が挙げられる。
(重量平均分子量)
重合体の重量平均分子量を、THFを移動相としたGPCにより測定した。基準物質は、ポリスチレンとした。
実施例及び比較例で得られた接着積層体を、10ppm(重量基準)の硫化水素を含むアルゴンガスに、10分間接触させた。次いで、接着積層体が備える接着剤の層が変色しているか否かを、目視で確認した。
接着剤の層が変色している場合は、接着積層体が、硫化水素の吸収能力を有すると判断した。
接着剤の層が変色していない場合は、接着積層体が、硫化水素の吸収能力を有さないと判断した。
JIS Z0237「粘着テープ・粘着シート試験方法」に準拠して、90°引きはがし法による剥離強度を測定した。
接着積層体の接着剤層側の面を、銅板に貼り付け、手動圧着装置(2.0kgローラー)を2往復させて、評価用サンプルとした。
試験装置(引っ張り試験機)として、協和界面科学社製「角度自在タイプ粘着・皮膜剥離解析装置(VPA-2S)」を用いた。
剥離強度が大きいほど、接着剤及び接着積層体の接着力が強い。
バインダー溶液を、下記の手順で製造した。
撹拌機付きガラス容器に、n-ブチルアクリレート50部、エチルアクリレート50部、乳化剤としてのドデシルベンゼンスルホン酸ナトリウム1部、イオン交換水150部、及び、重合開始剤としての過硫酸カリウム0.5部を添加し、十分に撹拌し、次いで、70℃に加温して重合を開始した。重合転化率が96%になった時点でメタノール10部を添加して反応を停止したのち冷却して、バインダーポリマーの水分散液を得た。
次いで、得られた水分散液を10重量%のNaOH水溶液を用いてpHを7に調整した。また、未反応単量体を除去するため加熱減圧処理を行った。
固形分濃度を43重量%に調整したバインダーポリマーの水分散液100gに、キシレンを500g添加し、減圧下で水を蒸発させた。これにより、バインダーポリマーの溶媒が水から有機溶媒に置換されて、水分量28ppm(重量基準)のバインダー溶液を得た。
残された正方形状の塗膜を挟むように、塗膜上に銅箔を重ね、プレスを行った。プレスの圧力は20MPaとした。プレスしたのち、一辺が40mmの正方形状部と、テープ状の二本のタブとを有する形状に加工した。二本のタブのそれぞれは、正方形状部の対向する二辺のそれぞれの中央から延びるように設けた。これにより、一辺が40mmの正方形状である、固体電解質の塗膜が、一辺が40mmの二枚の銅箔により挟まれた構造を有するセルを得た。
抵抗値増加率(%)=(R1-R0)/R0×100
初期抵抗値からの増加率が小さいほど、接着積層体により試験用セルが保護されていることを示す。初期抵抗値からの増加率は、硫化物系固体電解質を含む電池において、硫化水素が接着積層体により吸収されて、電池の劣化が抑制されることの指標となる。
撹拌機及び冷却器付きの2Lのガラス容器に、トルエン400g、アクリル酸2-エチルヘキシル85g、及びアクリル酸ブチル15gを投入し、混合して加温して還流させた。これに、ジクミルパーオキサイド0.1gをトルエン5gに溶解させた開始剤溶液を投入して重合を開始させた。モノマー転化率が98%になった時点で反応液を冷却し、メタノール中に投入してポリマーをろ別により回収した。これによりアクリル系重合体としての、アクリル酸エステル系共重合体(重量平均分子量(Mw)15万)を得た。
撹拌機及び温度調節用ジャケットを備えた容量2Lのステンレス鋼製加圧容器に、n-ヘキサン500g、1,3-ブタジエン90g、及びスチレン10gを入れて撹拌しながら50℃に加温した。次いで、開始剤としてのn-ブチルリチウムの5%ヘキサン溶液を0.2ml添加して溶液重合を行い、反応を終了させ、ポリマーを回収し、ゴム系重合体としての及び芳香族ビニル化合物-ジエン系共重合体としての、スチレン-ブタジエン系共重合体(重量平均分子量(Mw)18万)を得た。
表1に示す共重合体(製造例1又は製造例2で製造された共重合体)を、キシレンに共重合体の濃度が10重量%になるように溶解し、これに表1記載の金属化合物(ステアリン酸亜鉛、又は硫酸銅)を配合し、分散させた。金属化合物の配合量は、分散液における重合体及び金属化合物の合計重量に対して、金属化合物の重量が、表1の重量百分率となるような量とした。これにより、接着剤としての分散液を得た。得られた分散液を、厚み50μmである、基材としてのポリエチレンテレフタレート(PET)フィルムに塗工し、塗膜を得た。塗膜を60℃のホットプレート上で20分間加熱することにより乾燥させて、(PETフィルム)/(接着剤の層)の層構成を有する、接着積層体を得た。接着剤の層の厚みは、20μmであった。
得られた接着積層体を、前記の方法により評価した。結果を表1に示す。
表1に示す共重合体を、キシレンに共重合体の濃度が10重量%になるように溶解して、接着剤を得た。得られた接着剤を、厚み50μmのPETフィルムに塗工し、塗膜を得た。塗膜を60℃のホットプレート上で20分間加熱することにより乾燥させて、(PETフィルム)/(接着剤の層)の層構成を有する、接着積層体を得た。接着剤の層の厚みは、20μmであった。
得られた接着積層体を、前記の方法により評価した。結果を表1に示す。
下表における記載は、以下の意味を表す。
「接着剤組成」は、金属化合物及び樹脂の合計重量に対する、各成分の重量百分率として示されている。
「スチレン-ブタジエン系共重合体」:製造例2で得られた共重合体。
「アクリル系重合体」:製造例1で得られた共重合体。
「ステアリン酸亜鉛」:関東化学社製 ステアリン酸亜鉛(II)
「硫酸銅」:関東化学社製 硫酸銅(II)
硫化水素吸収能力の項目において、「あり」は、変色があったことを示し、「無し」は、変色がなかったことを示す。
「剥離強度」:(接着積層体の接着力評価)における、剥離強度の値を示す。
「抵抗値増加率」:(試験用セルの抵抗値変化)評価における、初期抵抗値からの増加率を示す。
金属化合物の量が、重合体及び樹脂の合計重量に対して60重量%以上である、比較例3及び比較例4に係る接着積層体は、剥離強度の値が顕著に低い。
金属化合物の量が、重合体及び樹脂の合計重量に対して0重量%である、比較例1及び比較例2に係る接着積層体は、硫化水素の吸収能力を有さず、抵抗値増加率が高い。
一方、金属化合物の量が、重合体及び樹脂の合計重量に対して1重量%以上60重量%未満である、実施例1~4に係る接着積層体は、硫化水素の吸収能力を有し、かつ剥離強度の値が良好であり、さらに抵抗値増加率が低い。
また、多価金属塩であって、遷移金属原子及び有機化合物を含む、ステアリン酸亜鉛(II)、及び、多価金属塩であって、遷移金属原子及び無機イオンを含む、硫酸銅(II)のいずれを用いても、接着積層体が硫化水素の吸収能力を有し、かつ剥離強度の値が良好であり、さらに抵抗値増加率が低い結果が得られた。
10U 面
20 電池用接着剤の層
100 電池用接着積層体
Claims (8)
- 硫化物系固体電解質を含む電池に用いられる、電池用接着剤であって、
金属化合物及び樹脂を含み、
前記金属化合物が、前記金属化合物及び前記樹脂の合計重量に対して、1重量%以上60重量%未満である、電池用接着剤。 - 前記金属化合物が、多価金属塩である、請求項1に記載の電池用接着剤。
- 前記金属化合物が、銅化合物である、請求項1又は2に記載の電池用接着剤。
- 前記樹脂が、アクリル化合物単位を含むアクリル系重合体を含む、請求項1~3のいずれか一項に記載の電池用接着剤。
- 前記アクリル系重合体の量が、前記樹脂の量に対して、50重量%以上100重量%以下である、請求項4に記載の電池用接着剤。
- 前記樹脂が、芳香族ビニル化合物単位及びジエン単位を含む芳香族ビニル化合物-ジエン系共重合体を含む、請求項1~3のいずれか一項に記載の電池用接着剤。
- 前記芳香族ビニル化合物-ジエン系共重合体の量が、前記樹脂の量に対して、50重量%以上100重量%以下である、請求項6に記載の電池用接着剤。
- 硫化物系固体電解質を含む電池に用いられる、電池用接着積層体であって、
基材と、前記基材上に設けられた請求項1~7のいずれか一項に記載の電池用接着剤の層とを含む、電池用接着積層体。
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EP21849441.7A EP4191762A1 (en) | 2020-07-28 | 2021-07-09 | Adhesive for battery, and adhesive layered body for battery |
JP2022540130A JPWO2022024717A1 (ja) | 2020-07-28 | 2021-07-09 | |
KR1020237000938A KR20230047077A (ko) | 2020-07-28 | 2021-07-09 | 전지용 접착제 및 전지용 접착 적층체 |
US18/005,850 US20230272248A1 (en) | 2020-07-28 | 2021-07-09 | Adhesive for battery, and adhesive layered body for battery |
CN202180049022.5A CN115803943A (zh) | 2020-07-28 | 2021-07-09 | 电池用黏合剂和电池用黏合层叠体 |
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US20130157086A1 (en) | 2011-12-20 | 2013-06-20 | Nitto Denko Corporation | Pressure-sensitive adhesive tape for battery, battery using the pressure-sensitive adhesive tape and process for manufacturing a battery |
JP2014200751A (ja) * | 2013-04-05 | 2014-10-27 | 共同印刷株式会社 | 硫黄系ガス吸着用樹脂組成物 |
WO2018180405A1 (ja) | 2017-03-27 | 2018-10-04 | 日本ゼオン株式会社 | 電極構成体固定用接着剤及び電気化学素子 |
JP2020082624A (ja) * | 2018-11-29 | 2020-06-04 | 共同印刷株式会社 | ガス吸収フィルム |
JP2020110756A (ja) * | 2019-01-09 | 2020-07-27 | イビデン株式会社 | 硫黄系ガス吸着構造体及び組電池 |
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US20130157086A1 (en) | 2011-12-20 | 2013-06-20 | Nitto Denko Corporation | Pressure-sensitive adhesive tape for battery, battery using the pressure-sensitive adhesive tape and process for manufacturing a battery |
JP2013149603A (ja) | 2011-12-20 | 2013-08-01 | Nitto Denko Corp | 電池用粘着テープ、及び該粘着テープを使用した電池 |
JP2014200751A (ja) * | 2013-04-05 | 2014-10-27 | 共同印刷株式会社 | 硫黄系ガス吸着用樹脂組成物 |
WO2018180405A1 (ja) | 2017-03-27 | 2018-10-04 | 日本ゼオン株式会社 | 電極構成体固定用接着剤及び電気化学素子 |
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WO2024080339A1 (ja) * | 2022-10-12 | 2024-04-18 | 大日本印刷株式会社 | 全固体電池 |
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JPWO2022024717A1 (ja) | 2022-02-03 |
KR20230047077A (ko) | 2023-04-06 |
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