WO2023032718A1 - 非水系二次電池接着層用組成物、非水系二次電池用接着層及びその製造方法、非水系二次電池用積層体及びその製造方法、並びに、非水系二次電池 - Google Patents

非水系二次電池接着層用組成物、非水系二次電池用接着層及びその製造方法、非水系二次電池用積層体及びその製造方法、並びに、非水系二次電池 Download PDF

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Publication number
WO2023032718A1
WO2023032718A1 PCT/JP2022/031438 JP2022031438W WO2023032718A1 WO 2023032718 A1 WO2023032718 A1 WO 2023032718A1 JP 2022031438 W JP2022031438 W JP 2022031438W WO 2023032718 A1 WO2023032718 A1 WO 2023032718A1
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Prior art keywords
secondary battery
particulate polymer
adhesive layer
aqueous secondary
mass
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Ceased
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PCT/JP2022/031438
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English (en)
French (fr)
Japanese (ja)
Inventor
俊之 梅里
一貴 高木
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Zeon Corp
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Zeon Corp
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Publication date
Application filed by Zeon Corp filed Critical Zeon Corp
Priority to KR1020247004359A priority Critical patent/KR20240050326A/ko
Priority to US18/293,873 priority patent/US20240356160A1/en
Priority to JP2023545454A priority patent/JPWO2023032718A1/ja
Priority to EP22864302.9A priority patent/EP4398402A4/en
Priority to CN202280048979.2A priority patent/CN117642920A/zh
Publication of WO2023032718A1 publication Critical patent/WO2023032718A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • H01M50/461—Separators, membranes or diaphragms characterised by their combination with electrodes with adhesive layers between electrodes and separators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1812—C12-(meth)acrylate, e.g. lauryl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • 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
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/42—Acrylic resins
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a non-aqueous secondary battery adhesive layer composition, a non-aqueous secondary battery adhesive layer and its manufacturing method, a non-aqueous secondary battery laminate and its manufacturing method, and a non-aqueous secondary battery.
  • Non-aqueous secondary batteries such as lithium-ion secondary batteries (hereinafter also referred to as “secondary batteries”) are small, lightweight, have high energy density, and can be repeatedly charged and discharged, and are used in a wide range of applications. It is A secondary battery generally includes a positive electrode, a negative electrode, and a battery member such as a separator that separates the positive electrode from the negative electrode to prevent a short circuit between the positive electrode and the negative electrode.
  • a battery member provided with an adhesive layer for improving adhesion between battery members is used.
  • the adhesive layer is generally formed by applying a slurry-like non-aqueous secondary battery adhesive layer composition (hereinafter also referred to as "adhesive layer composition") containing a binder component to an electrode base material, a separator base material, and the like. It is formed by supplying it on a substrate of and drying it.
  • Patent Literature 1 describes an adhesive layer composition that contains organic particles having a core-shell structure, a thixotropic agent, and water and that satisfies predetermined properties. According to Patent Document 1, by discharging the adhesive layer composition as fine droplets by an inkjet method, the adhesive layer can be formed satisfactorily, and the substrate and the coating can be formed through the adhesive layer. It can be strongly adhered to the adherend.
  • the adhesive layer composition of the prior art when the laminate is produced by pressing the battery members together via the adhesive layer formed from the adhesive layer composition, the pressure bonding is performed at room temperature. Even so, it has been desired to bond the battery members together more satisfactorily. That is, the adhesive layer composition of the prior art has room for further improvement in terms of enhancing the adhesiveness of the adhesive layer formed from the adhesive layer composition under normal temperature pressure.
  • the present inventors have conducted intensive studies with the aim of solving the above problems. Then, the present inventors have found a non-aqueous secondary battery adhesive layer composition comprising a first particulate polymer and a second particulate polymer different from the first particulate polymer, The inventors have found that the above problems can be solved by a composition for a non-aqueous secondary battery adhesive layer containing a predetermined monomer unit in a desired ratio, and have completed the present invention.
  • a non-aqueous secondary battery adhesive layer composition comprising a second particulate polymer different from Both the core polymer and the second particulate polymer have a chain alkyl group having 4 or more carbon atoms (meth) acrylate monomer unit and the ratio of (meth)acrylate monomer units having a chain alkyl group having 4 or more carbon atoms in the first particulate polymer is A mass%, and the number of carbon atoms in the second particulate polymer
  • the ratio of (meth)acrylate monomer units having 4 or more chain alkyl groups is defined as B mass%
  • the first particulate polymer and the second particulate polymer account for the total mass of the first particulate polymer When the content of the polymer is X% by mass and the content of the second particulate
  • composition for a non-aqueous secondary battery adhesive layer it is possible to form an adhesive layer for a non-aqueous secondary battery that firmly adheres battery members to each other even when pressurized at room temperature.
  • second particulate polymer different from the first particulate polymer means that at least one of composition and particle structure is different, preferably at least particle structure is different.
  • the "monomer unit" of a polymer means "a repeating unit that is contained in a polymer obtained using the monomer and that can be derived from the monomer”.
  • (meth)acrylate means acrylate and/or methacrylate.
  • (meth)acrylate having a chain alkyl group having 4 or more carbon atoms means that a chain alkyl group having 4 or more carbon atoms is bonded to a non-carbonyl oxygen atom of (meth)acrylate.
  • normal temperature means a temperature in the range of 0°C or higher and 35°C or lower.
  • the glass transition temperature of the core polymer is -20°C or less, and the glass transition temperature of the second particulate polymer is -15°C.
  • the glass transition temperatures of the polymer of the core portion and the second particulate polymer are each equal to or lower than the above upper limit, an adhesive layer for a non-aqueous secondary battery that more firmly bonds the battery members to each other even under room temperature pressurization is provided. can be formed.
  • the "glass transition temperature" can be measured using the measurement method described in the Examples of the specification.
  • the glass transition temperature of the polymer of the shell portion is preferably 50° C. or higher. If the glass transition temperature of the polymer of the shell portion is at least the above lower limit, it is possible to suppress nozzle clogging when the composition for a non-aqueous secondary battery adhesive layer is ejected as fine droplets by an inkjet method. That is, the inkjet ejection characteristics can be improved.
  • the mass ratio of the shell portion in the first particulate polymer is preferably 2% by mass or more and 15% by mass or less. If the mass ratio of the shell portion is at least the above lower limit, the inkjet ejection characteristics of the composition for a non-aqueous secondary battery adhesive layer can be improved. On the other hand, if the mass ratio of the shell portion is equal to or less than the above upper limit, it is possible to form an adhesive layer for a non-aqueous secondary battery that bonds battery members more firmly to each other even when pressurized at room temperature.
  • the mass ratio of the shell portion in the first particulate polymer is obtained from the thickness ratio of the core portion to the shell portion and the specific gravity of the particulate polymer.
  • the ratio of the (meth)acrylate monomer units having a chain alkyl group having 4 or more carbon atoms in the polymer of the core part is When the total monomer unit contained in is 100% by mass, it is 90% by mass or more, and the (meth)acrylate unit having the chain alkyl group having 4 or more carbon atoms in the second particulate polymer
  • the ratio of the monomer units is preferably 75% by mass or more when the total monomer units contained in the second particulate polymer is 100% by mass.
  • the proportion of (meth)acrylate monomer units having a chain alkyl group with 4 or more carbon atoms in the polymer of the core portion and in the second particulate polymer is equal to or higher than the above lower limit, normal temperature pressurization is possible. Even with this, it is possible to form an adhesive layer for a non-aqueous secondary battery that bonds the battery members together more firmly.
  • the ratio of various monomeric units in the polymer can be measured using nuclear magnetic resonance (NMR) methods such as 1 H-NMR and 13 C-NMR.
  • the structural formula of the (meth)acrylate monomer unit having a chain alkyl group having 4 or more carbon atoms in the second particulate polymer is It is preferably the same as the structural formula of the (meth)acrylate monomer unit having a chain alkyl group having 4 or more carbon atoms in one particulate polymer.
  • the structural formula of the (meth)acrylate monomer unit having a chain alkyl group having 4 or more carbon atoms in the second particulate polymer has a chain alkyl group having 4 or more carbon atoms in the first particulate polymer ( If the structural formula is the same as that of the meth)acrylate monomer unit, it is possible to form an adhesive layer for a non-aqueous secondary battery that more strongly adheres battery members to each other even at room temperature and pressurized.
  • Both units are preferably (meth)acrylate monomer units having a chain alkyl group having 4 to 10 carbon atoms.
  • Both the (meth)acrylate monomer units having a chain alkyl group having 4 or more carbon atoms in the first particulate polymer and the second particulate polymer have a chain alkyl group having 4 or more and 10 or less carbon atoms (meth ) If it is an acrylate monomer unit, it is possible to form an adhesive layer for a non-aqueous secondary battery that more strongly adheres battery members to each other even when pressurized at room temperature.
  • the (meth)acrylate monomer having a chain alkyl group having 4 or more carbon atoms of the first particulate polymer and the second particulate polymer Both units are preferably n-butyl acrylate units. If the (meth)acrylate monomer units having a chain alkyl group having 4 or more carbon atoms in the first particulate polymer and the second particulate polymer are both n-butyl acrylate units, room temperature pressurization is possible. Even with this, it is possible to form an adhesive layer for a non-aqueous secondary battery that bonds the battery members together more firmly.
  • the non-aqueous secondary battery adhesive layer composition of the present invention it is preferable that at least one of the first particulate polymer and the second particulate polymer further contains a nitrile group-containing monomer unit. If at least one of the first particulate polymer and the second particulate polymer further contains a nitrile group-containing monomer unit, the inkjet ejection characteristics of the non-aqueous secondary battery adhesive layer composition can be improved. Moreover, if at least one of the first particulate polymer and the second particulate polymer further contains a nitrile group-containing monomer unit, a non-aqueous secondary battery with excellent cycle characteristics can be obtained.
  • Another object of the present invention is to solve the above problems, and the adhesive layer for a non-aqueous secondary battery of the present invention is formed using the composition for an adhesive layer for a non-aqueous secondary battery. be. With such an adhesive layer for a non-aqueous secondary battery, the battery members can be strongly adhered to each other even under pressure at room temperature.
  • Another object of the present invention is to solve the above problems, and a method for producing an adhesive layer for a non-aqueous secondary battery according to the present invention comprises using the composition for an adhesive layer for a non-aqueous secondary battery as a base. and a step of drying the non-aqueous secondary battery adhesive layer composition applied on the substrate.
  • a method for producing an adhesive layer for a non-aqueous secondary battery it is possible to produce an adhesive layer for a non-aqueous secondary battery that is capable of firmly adhering battery members to each other even when pressurized at room temperature.
  • the laminate for a non-aqueous secondary battery of the present invention is a laminate for a non-aqueous secondary battery comprising an electrode and a separator. Then, the electrode and the separator are adhered via the non-aqueous secondary battery adhesive layer.
  • Such a laminate for a non-aqueous secondary battery has excellent adhesiveness between battery members.
  • Another object of the present invention is to solve the above problems, and a method for producing a laminate for a non-aqueous secondary battery according to the present invention includes applying an adhesive material to the bonding surface of at least one of an electrode and a separator. and a step of pressurizing and bonding the electrode and the separator through the bonding surface to which the adhesive material is supplied, wherein the adhesive material is the non-aqueous secondary battery adhesive layer using a composition for With such a method for producing a non-aqueous secondary battery laminate, a non-aqueous secondary battery laminate having excellent adhesiveness between battery members can be produced.
  • Another object of the present invention is to solve the above problems, and a non-aqueous secondary battery of the present invention includes the non-aqueous secondary battery laminate. Such a non-aqueous secondary battery has excellent adhesion between battery members.
  • the composition for non-aqueous secondary battery adhesion layers which can form the adhesion layer for non-aqueous secondary batteries which adhere
  • FIG. 1 is a cross-sectional view schematically showing the structure of an example of a first particulate polymer;
  • FIG. It is a figure explaining an example of the manufacturing process of the laminated body for non-aqueous secondary batteries of this invention. It is a figure explaining the manufacturing process of the laminated body for non-aqueous secondary batteries in an Example and a comparative example.
  • the composition for a non-aqueous secondary battery adhesive layer of the present invention can be used when forming the adhesive layer for a non-aqueous secondary battery of the present invention.
  • the adhesive layer for non-aqueous secondary batteries of the present invention can be produced, for example, by the method for producing an adhesive layer for non-aqueous secondary batteries of the present invention.
  • the adhesive layer for non-aqueous secondary batteries of the present invention can be used when manufacturing the laminate for non-aqueous secondary batteries of the present invention and the non-aqueous secondary battery of the present invention.
  • the non-aqueous secondary battery laminate of the present invention can be used when producing the non-aqueous secondary battery of the present invention, and can be produced, for example, by the method for producing a non-aqueous secondary battery laminate of the present invention.
  • a non-aqueous secondary battery of the present invention includes the laminate for a non-aqueous secondary battery of the present invention.
  • composition for non-aqueous secondary battery adhesive layer comprises a first particulate polymer and a second particulate polymer different from the first particulate polymer.
  • the composition for a non-aqueous secondary battery adhesive layer of the present invention is usually a slurry composition in which a particulate polymer is dispersed in a solvent such as water. In addition to coalescing, other ingredients may optionally be included.
  • both the polymer of the core portion of the first particulate polymer and the second particulate polymer have a chain alkyl group having 4 or more carbon atoms.
  • the ratio of (meth)acrylate monomer units containing a (meth)acrylate monomer unit and having a chain alkyl group having 4 or more carbon atoms in the first particulate polymer is A% by mass
  • the second particulate The ratio of (meth)acrylate monomer units having a chain alkyl group having 4 or more carbon atoms in the polymer is defined as B% by mass
  • the second part of the total mass of the first particulate polymer and the second particulate polymer When the content of one particulate polymer is X mass% and the content of the second particulate polymer in the total mass of the first particulate polymer and the second particulate polymer is Y mass%, Formula (1) below: (AX+BY)/(X+Y) (1) is
  • the non-aqueous secondary battery adhesive layer composition of the present invention By using the non-aqueous secondary battery adhesive layer composition of the present invention described above, it is possible to form an adhesive layer for a non-aqueous secondary battery that firmly adheres battery members to each other even when pressurized at room temperature.
  • the reason why the adhesive layer formed from the adhesive layer composition of the present invention exhibits good adhesiveness even when pressurized at room temperature is not clear, it is presumed as follows. That is, if the first particulate polymer and the second particulate polymer contain a (meth)acrylate monomer unit having a chain alkyl group having 4 or more carbon atoms, the adhesive layer for a non-aqueous secondary battery can be satisfactorily It is possible to express strong adhesiveness and to provide strong adhesive strength.
  • the value calculated by the formula (1) is 75% by mass or more, the compatibility between the polymers in the adhesive layer for the non-aqueous secondary battery is improved, and as a result, the pressure is applied at room temperature. It is also possible to form an adhesive layer for a non-aqueous secondary battery that firmly bonds battery members together.
  • the value calculated by the formula (1) is preferably 80% by mass or more because it is possible to form an adhesive layer for non-aqueous secondary batteries that more firmly bonds battery members together even at room temperature pressurization. It is more preferably 90% by mass or more.
  • the value calculated by the formula (1) is preferably 99% by mass or less because the inkjet ejection characteristics of the non-aqueous secondary battery adhesive layer composition can be improved.
  • the first particulate polymer has a core-shell structure comprising a core and a shell covering at least a portion of the outer surface of the core.
  • the shell portion may cover the entire outer surface of the core portion, or may partially cover the outer surface of the core portion. Even if the outer surface of the core portion appears to be completely covered by the shell portion, if a hole is formed to allow communication between the inside and outside of the shell portion, the shell portion can be replaced by the core portion. is a shell part that partially covers the outer surface of the
  • first particulate polymer 300 has a core-shell structure comprising core portion 310 and shell portion 320 .
  • the core portion 310 is a portion inside the shell portion 320 in the first particulate polymer 300 .
  • the shell portion 320 is a portion that covers the outer surface 310S of the core portion 310 and is usually the outermost portion of the first particulate polymer 300 .
  • the shell portion 320 does not cover the entire outer surface 310S of the core portion 310 but partially covers the outer surface 310S of the core portion 310 .
  • the first particulate polymer may be provided with arbitrary constituent elements other than the above-described core portion and shell portion, as long as the desired effects are not significantly impaired.
  • the first particulate polymer may have a portion formed of a polymer different from the core portion inside the core portion.
  • the seed particles used in the production of the first particulate polymer by the seed polymerization method may remain inside the core portion.
  • the first particulate polymer preferably has only the core portion and the shell portion.
  • the first particulate polymer has a core portion containing a (meth)acrylate monomer unit having a chain alkyl group with 4 or more carbon atoms, so the first particulate polymer also has 4 or more carbon atoms.
  • a (meth)acrylate monomer unit having a chain alkyl group of 4 or more carbon atoms is a repeating unit that can be derived from a (meth)acrylate monomer having a chain alkyl group of 4 or more carbon atoms.
  • Examples of (meth)acrylate monomer units having a chain alkyl group having 4 or more carbon atoms include butyl acrylate units such as n-butyl acrylate units and t-butyl acrylate units; hexyl acrylate units such as n-hexyl acrylate units.
  • the first particulate polymer may contain one of these, or two or
  • the (meth)acrylate monomer unit having a chain alkyl group having 4 or more carbon atoms in the first particulate polymer is a (meth)acrylate monomer unit having a chain alkyl group having 4 or more and 10 or less carbon atoms. more preferably a (meth)acrylate monomer unit having a chain alkyl group with 4 to 8 carbon atoms.
  • the number of carbon atoms in the chain alkyl group is at least the above lower limit, it is possible to form an adhesive layer for a non-aqueous secondary battery that more strongly bonds battery members together even under pressure at room temperature.
  • the (meth)acrylate monomer unit having a chain alkyl group having 4 or more carbon atoms in the first particulate polymer is for a non-aqueous secondary battery, which further firmly bonds the battery members together even when pressurized at room temperature.
  • An n-butyl acrylate unit is particularly preferred because it can form an adhesive layer.
  • the ratio of (meth)acrylate monomer units having a chain alkyl group having 4 or more carbon atoms in the first particulate polymer is the total repeating units (total monomer units) contained in the first particulate polymer.
  • the ratio is 100% by mass, it is preferably at least 75% by mass, more preferably at least 80% by mass, even more preferably at least 85% by mass, and particularly at least 90% by mass. It is preferably 99% by mass or less, more preferably 97% by mass or less.
  • the above ratio is at least the above lower limit, it is possible to form an adhesive layer for a non-aqueous secondary battery that more firmly adheres battery members to each other even when pressurized at room temperature. Further, when the ratio is equal to or higher than the lower limit, a secondary battery with excellent cycle characteristics can be obtained. On the other hand, when the above ratio is equal to or less than the above upper limit, the inkjet ejection characteristics can be improved.
  • the first particulate polymer preferably further contains a nitrile group-containing monomer unit.
  • a nitrile group-containing monomer unit is a repeating unit that can be derived from a nitrile group-containing monomer. If the first particulate polymer further contains a nitrile group-containing monomer unit, the inkjet ejection characteristics of the composition for a non-aqueous secondary battery adhesive layer can be improved. Also, if the first particulate polymer further contains a nitrile group-containing monomer unit, a non-aqueous secondary battery with excellent cycle characteristics can be obtained.
  • Nitrile group-containing monomer units include, for example, acrylonitrile units; ⁇ -halogenoacrylonitrile units such as ⁇ -chloroacrylonitrile units and ⁇ -bromoacrylonitrile units; ⁇ -alkylacrylonitrile units such as methacrylonitrile units and ⁇ -ethylacrylonitrile units and ⁇ , ⁇ -ethylenically unsaturated nitrile monomeric units such as units.
  • the first particulate polymer may contain one of these, or two or more of them at any ratio.
  • the nitrile group-containing monomer units are preferably acrylonitrile units.
  • the proportion of nitrile group-containing monomer units in the first particulate polymer is 1% by mass when all repeating units (total monomer units) contained in the first particulate polymer are 100% by mass. It is preferably 15% by mass or less, more preferably 5% by mass or less.
  • the proportion of the nitrile group-containing monomer unit in the first particulate polymer is at least the above lower limit, the inkjet ejection characteristics of the non-aqueous secondary battery adhesive layer composition can be further improved.
  • the proportion of the nitrile group-containing monomer unit in the first particulate polymer is at least the above lower limit, it is possible to obtain a non-aqueous secondary battery with better cycle characteristics.
  • the proportion of the nitrile group-containing monomer units in the first particulate polymer is equal to or less than the above upper limit, adhesion for non-aqueous secondary batteries that more firmly bonds the battery members together even at normal temperature pressurization It can form layers.
  • the core polymer contains a (meth)acrylate monomer unit having a chain alkyl group with 4 or more carbon atoms.
  • the battery members can be firmly adhered to each other even under pressure at room temperature.
  • An adhesive layer can be formed.
  • Examples of the (meth)acrylate monomer units having a chain alkyl group having 4 or more carbon atoms include those listed above.
  • the polymer of the core portion may contain one of the above-listed polymers alone, or two or more of them in an arbitrary ratio.
  • the (meth)acrylate monomer unit having a chain alkyl group having 4 or more carbon atoms in the core polymer is a (meth)acrylate monomer unit having a chain alkyl group having 4 or more and 10 or less carbon atoms.
  • a (meth)acrylate monomer unit having a chain alkyl group having 4 or more and 8 or less carbon atoms is more preferable.
  • the number of carbon atoms in the chain alkyl group is at least the above lower limit, it is possible to form an adhesive layer for a non-aqueous secondary battery that more strongly adheres battery members to each other even when pressurized at room temperature.
  • the (meth)acrylate monomer unit having a chain alkyl group of 4 or more carbon atoms in the core polymer is an adhesive for non-aqueous secondary batteries that further strongly bonds battery members together even when pressurized at room temperature.
  • Particularly preferred are n-butyl acrylate units because they can form layers.
  • the ratio of (meth)acrylate monomer units having a chain alkyl group having 4 or more carbon atoms in the core polymer is 100% of all repeating units (total monomer units) contained in the core polymer.
  • it is preferably at least 75% by mass, more preferably at least 85% by mass, even more preferably at least 90% by mass, particularly preferably at least 95% by mass, It is preferably 99% by mass or less, more preferably 97% by mass or less.
  • the above ratio is at least the above lower limit, it is possible to form an adhesive layer for a non-aqueous secondary battery that bonds the battery members together more firmly even when pressurized at room temperature. Further, when the above ratio is at least the above lower limit, a secondary battery with excellent cycle characteristics can be obtained. On the other hand, when the above ratio is equal to or less than the above upper limit, the inkjet ejection characteristics can be improved.
  • the core polymer further contains a nitrile group-containing monomer unit. If the polymer of the core portion further contains a nitrile group-containing monomer unit, the inkjet ejection characteristics of the composition for a non-aqueous secondary battery adhesive layer can be improved. Further, if the core polymer further contains a nitrile group-containing monomer unit, a non-aqueous secondary battery with excellent cycle characteristics can be obtained. Examples of nitrile group-containing monomer units include those listed above.
  • the polymer of the core portion may contain one of the above-listed polymers alone, or two or more of them in an arbitrary ratio.
  • the nitrile group-containing monomer units are preferably acrylonitrile units.
  • the proportion of the nitrile group-containing monomer unit in the core polymer is 1% by mass or more when the total repeating units (total monomer units) contained in the core polymer is 100% by mass. preferably 15% by mass or less, more preferably 5% by mass or less. If the ratio of the nitrile group-containing monomer unit in the polymer of the core portion is at least the above lower limit, the inkjet ejection characteristics of the non-aqueous secondary battery adhesive layer composition can be further improved. Further, when the ratio of the nitrile group-containing monomer unit in the polymer of the core portion is at least the above lower limit, a non-aqueous secondary battery with better cycle characteristics can be obtained.
  • the adhesive layer for a non-aqueous secondary battery can more firmly bond the battery members together even when pressurized at room temperature. can be formed.
  • the core polymer may contain a hydrophilic group-containing monomer unit.
  • a hydrophilic group-containing monomer unit is a repeating unit that can be derived from a hydrophilic group monomer.
  • Hydrophilic group monomers include acid group-containing monomers and hydroxyl group-containing monomers. Among these, when the first particulate polymer is prepared, the dispersibility of the core polymer can be increased, and the shell can be easily formed on the outer surface of the core polymer.
  • the group monomer is an acid group-containing monomer. That is, the hydrophilic group-containing monomer unit is preferably an acid group-containing monomer unit.
  • Examples of acid group-containing monomers include monomers having an acid group, such as monomers having a carboxylic acid group, monomers having a sulfonic acid group, and monomers having a phosphoric acid group.
  • Examples of monomers having a carboxylic acid group include monocarboxylic acids and dicarboxylic acids.
  • Examples of monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid and the like.
  • Examples of dicarboxylic acids include maleic acid, fumaric acid, and itaconic acid.
  • Examples of monomers having a sulfonic acid group include vinylsulfonic acid, methylvinylsulfonic acid, (meth)allylsulfonic acid, ethyl (meth)acrylate-2-sulfonate, and 2-acrylamido-2-methylpropanesulfone. acid, 3-allyloxy-2-hydroxypropanesulfonic acid and the like.
  • Examples of the monomer having a phosphate group include 2-(meth)acryloyloxyethyl phosphate, 2-(meth)acryloyloxyethyl methyl phosphate, ethyl-(meth)acryloyloxyethyl phosphate, and the like. mentioned.
  • (meth)allyl means allyl and/or methallyl
  • (meth)acryloyl means acryloyl and/or methacryloyl
  • (meth)acryl means acrylic and/or methacrylic.
  • the acid group-containing monomer a monomer having a carboxylic acid group is preferable, monocarboxylic acid is preferable, and (meth)acrylic acid is more preferable.
  • the acid group-containing monomers may be used singly or in combination of two or more at any ratio.
  • hydroxyl group-containing monomers examples include monomers having a hydroxyl group, such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate. etc.
  • One of the hydroxyl group-containing monomers may be used alone, or two or more of them may be used in combination at any ratio.
  • the ratio of hydrophilic group-containing monomer units in the core polymer is 0.1% by mass when the total repeating units (total monomer units) contained in the core polymer are 100% by mass. It is preferably 1% by mass or more, more preferably 1% by mass or more, preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.
  • the polymer of the core portion preferably contains crosslinkable monomer units in addition to the above monomer units.
  • a crosslinkable monomer unit is a repeating unit that can be derived from a crosslinkable monomer.
  • a crosslinkable monomer is a monomer that can form a crosslinked structure during or after polymerization by heating or irradiation with energy rays.
  • crosslinkable monomers include polyfunctional monomers having two or more polymerization reactive groups in the monomer.
  • polyfunctional monomers include divinyl benzene, 1,3-butadiene, isoprene, divinyl monomers such as allyl methacrylate; ethylene dimethacrylate, diethylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, Di(meth)acrylic acid ester monomers such as 1,3-butylene glycol diacrylate; tri(meth)acrylic acid ester monomers such as trimethylolpropane trimethacrylate and trimethylolpropane triacrylate; allyl glycidyl ether, glycidyl Ethylenically unsaturated monomers containing an epoxy group such as methacrylate; ⁇ -methacryloxypropyltrimethoxysilane; and (meth)acrylamides having a methylol group such as N-methylol(me)
  • (meth)acrylamides having a methylol group have a hydroxyl group, but are classified as crosslinkable monomers.
  • di(meth)acrylate monomers are more preferred.
  • these may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios.
  • the ratio of the crosslinkable monomer units in the core polymer is 0.05% by mass or more when the total repeating units (total monomer units) contained in the core polymer are 100% by mass. preferably 0.08% by mass or more, preferably 1% by mass or less, more preferably 0.3% by mass or less, and 0.15% by mass or less is particularly preferred. If the ratio of the crosslinkable monomer units is within the above range, it is possible to form an adhesive layer for a non-aqueous secondary battery that bonds the battery members together more firmly even at room temperature and pressurized.
  • the polymer of the core portion may optionally further contain other monomer units as long as the object of the present invention is not impaired.
  • Other monomeric units are repeating units that can be derived from other monomers.
  • Other monomers include, for example, vinyl chloride-based monomers such as vinyl chloride and vinylidene chloride; vinyl acetate-based monomers such as vinyl acetate; aromatics such as styrene, ⁇ -methylstyrene, butoxystyrene, and vinylnaphthalene.
  • vinyl monomers vinylamine-based monomers such as vinylamine
  • vinylamide-based monomers such as N-vinylformamide and N-vinylacetamide
  • (meth)acrylamide monomers such as acrylamide and methacrylamide; These may be used individually by 1 type, or may be used in combination of 2 or more types by arbitrary ratios.
  • (meth)acrylamide” means acrylamide and/or methacrylamide.
  • (meth)acrylate having a chain alkyl group having 3 or less carbon atoms means that a chain alkyl group having 3 or less carbon atoms is bonded to a non-carbonyl oxygen atom of (meth)acrylate. means what is
  • the glass transition temperature of the core polymer is preferably ⁇ 50° C. or higher, more preferably ⁇ 45° C. or higher, preferably ⁇ 10° C. or lower, and preferably ⁇ 20° C. or lower. It is more preferably ⁇ 30° C. or lower. If the glass transition temperature of the polymer of the core portion is at least the above lower limit, the inkjet ejection characteristics can be improved. On the other hand, if the glass transition temperature of the core polymer is equal to or lower than the above upper limit, the core polymer can exhibit good adhesiveness, and even when pressurized at room temperature, the battery members can be more strongly bonded to each other. An adhesive layer for an aqueous secondary battery can be formed.
  • the glass transition temperature of the core polymer can be adjusted, for example, by changing the types and proportions of the monomers used in the preparation of the core polymer.
  • the shell covers at least a portion of the outer surface of the core and can preferably have different composition and/or properties than the core.
  • a different composition means that the types and/or proportions of the monomer units contained in the polymer are different.
  • Different properties mean different properties such as glass transition temperature.
  • the monomer units contained in the shell polymer include, for example, the same monomer units as those exemplified as the monomer units contained in the core polymer.
  • the polymer of the shell part may contain the above-listed monomer units singly, or may contain two or more kinds in an arbitrary ratio.
  • the polymer of the shell portion preferably contains aromatic vinyl monomer units.
  • An aromatic vinyl monomer unit is a repeating unit that can be derived from an aromatic vinyl monomer. Inkjet ejection characteristics can be improved by including aromatic vinyl monomer units in the polymer of the shell portion. It is particularly preferred that the aromatic vinyl monomer units are styrene units.
  • the ratio of the aromatic vinyl monomer units in the polymer of the shell portion is 55% by mass or more when the total repeating units (total monomer units) contained in the polymer of the shell portion is 100% by mass. preferably 70% by mass or more, still more preferably 85% by mass or more, even more preferably 90% by mass or more, and even more preferably 95% by mass or more . If the ratio of the aromatic vinyl monomer unit in the polymer of the shell portion is at least the above lower limit, the inkjet ejection characteristics can be further improved. On the other hand, the ratio of the aromatic vinyl monomer units in the polymer of the shell portion is, for example, 99.5% when the total repeating units (total monomer units) contained in the polymer of the shell portion are 100% by mass. It may be 9% by mass or less, may be 99.6% by mass or less, may be 99.3% by mass or less, may be 99% by mass or less, or may be 97% by mass or less.
  • the polymer of the shell portion may contain a hydrophilic group-containing monomer unit.
  • the hydrophilic group-containing monomer capable of forming the hydrophilic group-containing monomer units of the shell polymer the same hydrophilic group-containing monomers as those usable for forming the core may be used. mentioned.
  • the proportion of hydrophilic group-containing monomer units in the shell polymer is 0.5 mass when all repeating units (total monomer units) contained in the shell polymer are 100% by mass. % or more, more preferably 1% by mass or more, and even more preferably 3% by mass or more.
  • the ratio of the hydrophilic group-containing monomer units is at least the above lower limit, the dispersibility of the first particulate polymer is improved, and the non-aqueous two-component polymer is more strongly adhered to the battery members even when pressurized at room temperature. An adhesive layer for the next battery can be formed.
  • the ratio of the hydrophilic group-containing monomer units in the shell polymer is, for example, 15 when the total repeating units (total monomer units) contained in the shell polymer are 100% by mass. % by mass or less, may be 10% by mass or less, or may be 7% by mass or less.
  • the polymer of the shell portion optionally contains the above-mentioned (meth)acrylate monomer unit having a chain alkyl group having 4 or more carbon atoms and the above-mentioned other monomer units within the range that does not impair the object of the present invention. may further include:
  • the proportion of (meth)acrylate monomer units having a chain alkyl group having 4 or more carbon atoms in the polymer of the shell part should be the total repeating units contained in the polymer of the shell part (total When the monomer unit) is 100% by mass, it is preferably 40% by mass or less, more preferably 15% by mass or less, further preferably 1% by mass or less, and 0.1% by mass % or less, and 0% by mass (that is, the polymer of the shell portion does not contain a (meth)acrylate monomer unit having a chain alkyl group with a prime number of 4 or more). preferable.
  • the polymer of the shell part does not contain a (meth)acrylate monomer unit having a chain alkyl group with a prime number of 4 or more
  • a (meth)acrylate unit having a chain alkyl group with a carbon number of 4 or more Means not detected in the determination of the proportion of the mer units.
  • the mass ratio of the shell portion in the first particulate polymer is preferably 2% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, and 10% by mass or less. It is more preferable that the content is 5% by mass or less, and it is particularly preferable that the content is 5% by mass or less.
  • the mass ratio of the shell portion is equal to or higher than the above lower limit, the inkjet ejection characteristics can be further improved.
  • the mass ratio of the shell portion is equal to or less than the above upper limit, it is possible to form an adhesive layer for a non-aqueous secondary battery that bonds the battery members more firmly to each other even when pressurized at room temperature.
  • the mass ratio of the shell portion in the first particulate polymer is calculated from the later-described thickness ratio of the core portion to the shell portion and the specific gravity of the particulate polymer.
  • the glass transition temperature of the polymer of the shell portion of the first particulate polymer is preferably 35° C. or higher, more preferably 50° C. or higher, even more preferably 80° C. or higher, and 200° C. or lower. and more preferably 120° C. or less.
  • the glass transition temperature of the polymer of the shell portion is equal to or higher than the above lower limit, the inkjet ejection characteristics can be further improved.
  • the glass transition temperature of the polymer in the shell portion is equal to or lower than the above upper limit, the first particulate polymer becomes moderately soft, so that the non-aqueous non-aqueous polymer adheres the battery members more firmly to each other even when pressurized at room temperature.
  • An adhesive layer for a secondary battery can be formed.
  • the glass transition temperature of the shell polymer can be adjusted, for example, by changing the types and proportions of the monomers used in preparing the shell polymer.
  • the volume average particle diameter of the first particulate polymer is preferably 100 nm or more, more preferably 200 nm or more, preferably 1500 nm or less, more preferably 900 nm or less, and 800 nm or less. It is more preferably 700 nm or less. If the volume average particle diameter of the first particulate polymer is at least the above lower limit, deterioration of battery characteristics due to an increase in resistance of the secondary battery due to hindrance to the path of lithium ions in the substrate (electrode or separator) is suppressed. can.
  • the volume average particle diameter of the first particulate polymer is equal to or less than the above upper limit, clogging of nozzles when the non-aqueous secondary battery adhesive layer composition is applied by an inkjet method can be further suppressed, and inkjet ejection can be performed. Can improve characteristics.
  • the ratio of the average thickness of the shell portion to the volume average particle diameter of the first particulate polymer is preferably 0.1% or more, more preferably 0.5% or more, and 15% or less. is preferred, and 10% or less is more preferred.
  • the average thickness of the shell portion is at least the above lower limit, the inkjet ejection characteristics can be improved.
  • the average thickness of the shell portion is equal to or less than the above upper limit, it is possible to form an adhesive layer for a non-aqueous secondary battery that more strongly adheres the battery members to each other even when pressurized at room temperature.
  • the average thickness of the shell portion of the first particulate polymer is obtained by observing the cross-sectional structure of the first particulate polymer using a transmission electron microscope (TEM). Specifically, the maximum thickness of the shell portion in the cross-sectional structure of the first particulate polymer is measured using a TEM, and the maximum thickness of the shell portion of 20 or more arbitrarily selected particles of the first particulate polymer The average value of is taken as the average thickness of the shell portion.
  • the shell portion is composed of polymer particles, and the particles constituting the shell portion do not overlap in the radial direction of the particulate polymer particles, and the polymer particles are in a single layer. When the shell portion is formed, the number average particle diameter of the particles forming the shell portion is taken as the average thickness of the shell portion.
  • the first particulate polymer for example, a monomer of the core polymer and a monomer of the shell polymer are used, and the ratio of these monomers is changed over time to gradually It can be prepared by polymerization.
  • the particulate polymer can be prepared by sequential multi-step emulsion polymerization and multi-step suspension polymerization processes in which earlier stages of polymer are sequentially coated with subsequent stages of polymer.
  • emulsifiers such as anionic surfactants such as sodium dodecylbenzenesulfonate and sodium dodecylsulfate, nonionic surfactants such as polyoxyethylene nonylphenyl ether and sorbitan monolaurate, or Cationic surfactants such as octadecylamine acetate can be used.
  • peroxides such as t-butyl peroxy-2-ethylhexanoate, potassium persulfate, cumene peroxide, 2,2′-azobis(2-methyl-N-(2 -hydroxyethyl)-propionamide), 2,2'-azobis(2-amidinopropane) hydrochloride, and other azo compounds can be used.
  • the monomers forming the core portion and the emulsifier are mixed, and emulsion polymerization is performed all at once to obtain a particulate polymer forming the core portion.
  • the first particulate polymer can be obtained by polymerizing the monomer forming the shell in the presence of the particulate polymer composing the core.
  • the monomers forming the polymer of the shell portion are divided into a plurality of times or continuously. It is preferable to supply to the polymerization system at the same time. By dividing or continuously supplying the monomer forming the shell polymer to the polymerization system, the polymer forming the shell is formed into particles, and the particles are bonded to the core. Thus, a shell portion that partially covers the core portion can be formed.
  • the second particulate polymer contains a (meth)acrylate monomer unit having a chain alkyl group with 4 or more carbon atoms, and at least has a different particle structure from the first particulate polymer.
  • the second particulate polymer is not particularly limited as long as it differs from the first particulate polymer in at least one of the composition and the particle structure. It may have a structure that does not have a core-shell structure. It is preferable that the second particulate polymer is different from the first particulate polymer in composition such as the type of monomer units contained in the second particulate polymer and the ratio of the monomer units.
  • Examples of the (meth)acrylate monomer units having a chain alkyl group having 4 or more carbon atoms include those listed above.
  • the second particulate polymer may contain one of the above-listed polymers alone, or may contain two or more of them in an arbitrary ratio.
  • Structural formula of the (meth)acrylate monomer unit having a chain alkyl group having 4 or more carbon atoms of the second particulate polymer, the first particulate polymer having a chain alkyl group having 4 or more carbon atoms ( It is preferably the same as the structural formula of the meth)acrylate monomer unit.
  • the same structural formula means that the structure is different even if the number of oxygen atoms, carbon atoms, etc.
  • the (meth)acrylate monomer unit having a chain alkyl group having 4 or more carbon atoms is the same
  • the (meth)acrylate monomer unit having a chain alkyl group having 4 or more carbon atoms is an n-butyl acrylate unit
  • the t-butyl acrylate unit has the same structural formula. It means you can't say.
  • the structural formula of the (meth)acrylate monomer unit having a chain alkyl group having 4 or more carbon atoms in the second particulate polymer has a chain alkyl group having 4 or more carbon atoms in the first particulate polymer ( If the structural formula is the same as that of the meth)acrylate monomer unit, it is possible to form an adhesive layer for a non-aqueous secondary battery that more strongly adheres battery members to each other even at room temperature and pressurized.
  • the (meth)acrylate monomer unit having a chain alkyl group having 4 or more carbon atoms in the second particulate polymer is a (meth)acrylate monomer unit having a chain alkyl group having 4 or more and 10 or less carbon atoms. more preferably a (meth)acrylate monomer unit having a chain alkyl group having 4 to 8 carbon atoms.
  • the number of carbon atoms in the chain alkyl group is at least the above lower limit, it is possible to form an adhesive layer for a non-aqueous secondary battery that more strongly adheres battery members to each other even when pressurized at room temperature.
  • the (meth)acrylate monomer unit having a chain alkyl group having 4 or more carbon atoms of the second particulate polymer is a (meth)acrylate monomer having a chain alkyl group having 4 or more and 10 or less carbon atoms
  • the (meth)acrylate monomer unit having a chain alkyl group having 4 or more carbon atoms in the first particulate polymer also has a chain alkyl group having 4 or more and 10 or less carbon atoms (meth) ) It is preferably an acrylate monomer unit, and the (meth)acrylate monomer unit having a chain alkyl group having 4 or more carbon atoms in the second particulate polymer is a chain alkyl having 4 or more and 8 or less carbon
  • composition for a non-aqueous secondary battery adhesive layer is such a composition, it is possible to form an adhesive layer for a non-aqueous secondary battery that more strongly bonds battery members together even when pressurized at room temperature.
  • the (meth)acrylate monomer unit having a chain alkyl group having 4 or more carbon atoms in the second particulate polymer is for a non-aqueous secondary battery, which further strongly bonds the battery members together even when pressurized at room temperature.
  • An n-butyl acrylate unit is particularly preferred because it can form an adhesive layer.
  • carbon in the first particulate polymer is also preferably n-butyl acrylate units.
  • the (meth)acrylate monomer units having a chain alkyl group having 4 or more carbon atoms in the second particulate polymer and the first particulate polymer are both preferably n-butyl acrylate units. If both the (meth)acrylate monomer units having a chain alkyl group having 4 or more carbon atoms in the first particulate polymer and the second particulate polymer are n-butyl acrylate units, pressurization at room temperature Even if there is, it is possible to form an adhesive layer for a non-aqueous secondary battery that bonds the battery members together more firmly.
  • the ratio of (meth)acrylate monomer units having a chain alkyl group having 4 or more carbon atoms in the second particulate polymer is the total repeating units (total monomer units) contained in the second particulate polymer.
  • 100% by mass it is preferably 70% by mass or more, more preferably 75% by mass or more, still more preferably 90% by mass or more, and preferably 99% by mass or less, It is more preferably 95% by mass or less.
  • the above ratio is at least the above lower limit, it is possible to form an adhesive layer for a non-aqueous secondary battery that bonds the battery members together more firmly even when pressurized at room temperature. Further, when the above ratio is at least the above lower limit, a secondary battery with excellent cycle characteristics can be obtained. On the other hand, when the above ratio is equal to or less than the above upper limit, the inkjet ejection characteristics can be improved.
  • the second particulate polymer preferably further contains a nitrile group-containing monomer unit. If the second particulate polymer contains a nitrile group-containing monomer unit, the inkjet ejection characteristics of the composition for a non-aqueous secondary battery adhesive layer can be improved. Also, if the second particulate polymer contains a nitrile group-containing monomer unit, a non-aqueous secondary battery with excellent cycle characteristics can be obtained. Examples of nitrile group-containing monomer units include those listed above.
  • the polymer of the core portion may contain one of the above-listed polymers alone, or two or more of them in an arbitrary ratio.
  • the nitrile group-containing monomer units are preferably acrylonitrile units.
  • the proportion of nitrile group-containing monomer units in the second particulate polymer is 1% by mass when all repeating units (total monomer units) contained in the second particulate polymer are 100% by mass. It is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 5% by mass or less. If the proportion of the nitrile group-containing monomer unit in the second particulate polymer is at least the above lower limit, the inkjet ejection characteristics of the non-aqueous secondary battery adhesive layer composition can be further improved. Moreover, when the ratio of the nitrile group-containing monomer units in the second particulate polymer is at least the above lower limit, it is possible to obtain a non-aqueous secondary battery with better cycle characteristics.
  • the proportion of the nitrile group-containing monomer unit in the second particulate polymer is equal to or less than the above upper limit, adhesion for non-aqueous secondary batteries that more strongly bonds battery members together even under room temperature pressurization It can form layers.
  • the second particulate polymer includes, in addition to the (meth)acrylate monomer units having a chain alkyl group having 4 or more carbon atoms and the nitrile group-containing monomer units, the first particulate polymer. It may further contain monomer units similar to the monomer units exemplified as monomer units to be contained. Among them, the second particulate polymer has an aromatic vinyl monomer unit, a hydrophilic group-containing monomer unit, a crosslinkable monomer unit, and a chain alkyl group having 3 or less carbon atoms (meta ) preferably contains acrylate monomer units and the like.
  • the polymer of the shell portion may contain such monomer units singly or in combination of two or more in an arbitrary ratio.
  • Styrene is particularly preferred as the aromatic vinyl monomer capable of forming aromatic vinyl monomer units.
  • the hydrophilic group-containing monomer capable of forming the hydrophilic group-containing monomer unit it is preferable to use a monomer having a carboxylic acid group, more preferably to use a monocarboxylic acid, acrylic acid and methacrylic acid. It is particularly preferred to use at least one of the acids.
  • crosslinkable monomers capable of forming crosslinkable monomer units include divinyl monomers, di(meth)acrylate monomers, ethylenically unsaturated monomers containing epoxy groups, and methylol groups.
  • Ethyl acrylate can be used as the (meth)acrylate monomer having a chain alkyl group of 3 or less carbon atoms capable of forming a (meth)acrylate monomer unit having a chain alkyl group of 3 or less carbon atoms.
  • Ethyl acrylate can be used as the (meth)acrylate monomer having a chain alkyl group of 3 or less carbon atoms capable of forming a (meth)acrylate monomer unit having a chain alkyl group of 3 or less carbon atoms.
  • the ratio of the aromatic vinyl monomer units in the second particulate polymer is 10% by mass when the total repeating units (total monomer units) contained in the second particulate polymer is 100% by mass. is preferably 15% by mass or more, more preferably 20% by mass or more, preferably 40% by mass or less, more preferably 35% by mass or less, It is more preferably 30% by mass or less. If the ratio of the aromatic vinyl monomer units is within the above range, it is possible to form an adhesive layer for a non-aqueous secondary battery that more strongly adheres battery members to each other even at room temperature and pressurized.
  • the ratio of the hydrophilic group-containing monomer units in the second particulate polymer is 0.00% when the total repeating units (total monomer units) contained in the second particulate polymer is 100% by mass. It is preferably 5% by mass or more, more preferably 1% by mass or more, still more preferably 2% by mass or more, preferably 10% by mass or less, and preferably 7% by mass or less. More preferably, it is 5% by mass or less. If the ratio of the hydrophilic group-containing monomer unit is within the above range, the dispersibility of the second particulate polymer can be enhanced.
  • the ratio of the crosslinkable monomer units in the second particulate polymer is 0.2 when the total repeating units (total monomer units) contained in the second particulate polymer is 100% by mass. It is preferably at least 0.5% by mass, more preferably at least 0.5% by mass, even more preferably at least 1% by mass, preferably at most 5% by mass, and at most 4% by mass. is more preferable, and 3% by mass or less is even more preferable. If the ratio of the crosslinkable monomer units is within the above range, it is possible to form an adhesive layer for a non-aqueous secondary battery that more strongly adheres battery members to each other even at room temperature and pressurized.
  • the ratio of (meth)acrylate monomer units having a chain alkyl group having 3 or less carbon atoms in the second particulate polymer is the total repeating units (total monomer units) contained in the second particulate polymer.
  • the is 100% by mass it is preferably 1% by mass or more, more preferably 3% by mass or more, preferably 10% by mass or less, and more preferably 8% by mass or less .
  • the content of the second particulate polymer in the non-aqueous secondary battery adhesive layer composition is preferably 5 parts by mass or more, and 8 parts by mass or more per 100 parts by mass of the first particulate polymer. is more preferably 20 parts by mass or less, and more preferably 15 parts by mass or less. If the content of the second particulate polymer in the composition for a non-aqueous secondary battery adhesive layer is within the above range, the non-aqueous secondary battery can more firmly bond the battery members together even under room temperature pressurization. An adhesive layer can be formed. Moreover, if the content of the second particulate polymer in the composition for a non-aqueous secondary battery adhesive layer is within the above range, the inkjet ejection characteristics can be improved.
  • the second particulate polymer may optionally further contain the other monomer units as long as the object of the present invention is not impaired.
  • the glass transition temperature of the second particulate polymer is preferably ⁇ 50° C. or higher, more preferably ⁇ 40° C. or higher, preferably 10° C. or lower, and preferably ⁇ 15° C. or lower. It is more preferably ⁇ 25° C. or lower.
  • the glass transition temperature of the second particulate polymer is equal to or higher than the above lower limit, the inkjet ejection characteristics can be improved.
  • the glass transition temperature of the second particulate polymer is equal to or lower than the above upper limit, the second particulate polymer can exhibit good adhesiveness, and the battery members can be more strongly bonded to each other even under pressure at room temperature. It is possible to form an adhesive layer for non-aqueous secondary batteries.
  • the glass transition temperature of the second particulate polymer can be adjusted, for example, by changing the type and ratio of the monomers used in preparing the second particulate polymer.
  • the volume average particle diameter of the second particulate polymer is preferably 50 nm or more, more preferably 100 nm or more, still more preferably 200 nm or more, preferably 600 nm or less, and 500 nm or less. 400 nm or less is more preferable. If the volume-average particle size of the second particulate polymer is within the above predetermined range, it is possible to form an adhesive layer for a non-aqueous secondary battery that more firmly bonds battery members together even under pressure at room temperature.
  • the second particulate polymer is not particularly limited, and can be prepared, for example, by polymerizing a monomer composition containing the monomers described above in an aqueous solvent such as water.
  • the proportion of each monomer in the monomer composition is usually the same as the proportion of each monomer unit in the second particulate polymer.
  • the polymerization method and polymerization reaction are not particularly limited, and for example, known polymerization methods and polymerization reactions such as emulsion polymerization and suspension polymerization can be used.
  • the solvent for dispersing the first particulate polymer and the second particulate polymer is not particularly limited, and for example, water, organic solvents and mixtures thereof can be used.
  • the organic solvent is not particularly limited, and cyclic aliphatic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as toluene and xylene; ketones such as ethyl methyl ketone and cyclohexanone; ethyl acetate; , butyl acetate, ⁇ -butyrolactone, ⁇ -caprolactone and other esters; acetonitrile, propionitrile and other nitriles; tetrahydrofuran, ethylene glycol diethyl ether and other ethers; methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, ethylene alcohols such as glycol monomethyl ether;
  • One of the solvents may
  • a mixture of water and alcohols is preferably used as the solvent.
  • a mixture of water and alcohols is used, reliability such as ejection stability can be obtained when the composition is used in an inkjet recording apparatus.
  • At least part of the solvent described above may be removed by drying or the like in the manufacturing process of the non-aqueous secondary battery laminate.
  • non-aqueous secondary battery adhesive layer composition of the present invention include surface tension modifiers, dispersants, viscosity modifiers, reinforcing materials, and electrolyte Components such as additives are included. These are not particularly limited as long as they do not affect the battery reaction, and known ones such as those described in International Publication No. 2012/115096 can be used. In addition, these components may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios.
  • the method for preparing the non-aqueous secondary battery adhesive layer composition of the present invention is not particularly limited. can be prepared by stirring and mixing in the presence of a solvent.
  • the stirring and mixing method is not particularly limited, and can be carried out by a known method. Specifically, general stirring vessels, ball mills, sand mills, bead mills, pigment dispersers, ultrasonic dispersers, crushing machines, homogenizers, planetary mixers, Filmix, and the like can be used.
  • the mixing conditions are not particularly limited, but usually the mixing can be carried out at room temperature or higher and 80° C. or lower for 10 minutes or longer and several hours or shorter.
  • the adhesive layer for non-aqueous secondary batteries of the present invention is obtained using the composition for non-aqueous secondary battery adhesive layers of the present invention. Further, the adhesive layer for non-aqueous secondary batteries of the present invention functions as an adhesive material for bonding battery members used in non-aqueous secondary batteries.
  • the adhesive layer for non-aqueous secondary batteries of the present invention can be obtained, for example, by the method for producing an adhesive layer for non-aqueous secondary batteries of the present invention, which will be described later.
  • the adhesive layer for non-aqueous secondary batteries of the present invention is a dried product obtained by drying the composition for non-aqueous secondary battery adhesive layers of the present invention. Therefore, the adhesive layer for a non-aqueous secondary battery of the present invention contains at least the first particulate polymer and the second particulate polymer, and optionally other components.
  • the first particulate polymer and the second particulate polymer are present in the form of particles in the adhesive layer composition for non-aqueous secondary batteries, but may be in the form of particles in the adhesive layer for non-aqueous secondary batteries. or any other shape.
  • the shape of the adhesive layer is not particularly limited, and can be formed to have any planar shape such as stripes, dots, lattices, and the like. Above all, from the viewpoint of reducing the resistance of the secondary battery, it is preferable to form the adhesive layer in a dot shape.
  • the dot-shaped adhesive layer can be obtained, for example, by an inkjet method using a coating machine (51 to 54 in FIG. 2) described later.
  • the diameter of the dots of the adhesive layer arranged in a dot pattern is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, preferably 300 ⁇ m or less, and more preferably 200 ⁇ m or less. If the dot diameter of the adhesive layer is equal to or greater than the above lower limit, the adhesive strength between the electrode and the separator can be enhanced. On the other hand, when the dot diameter of the adhesive layer is equal to or less than the above upper limit, deterioration of the cycle characteristics of the secondary battery can be suppressed.
  • the thickness of the dots of the adhesive layer arranged in a dot pattern is preferably 5 ⁇ m or more. If the dot thickness of the adhesive layer is equal to or more than the above lower limit, the adhesive strength between the electrode and the separator can be enhanced.
  • the basis weight of the adhesive layer is preferably 0.02 g/m 2 or more, preferably 1.0 g/m 2 or less, and more preferably 0.35 g/m 2 or less. If the basis weight of the adhesive layer is at least the above lower limit, sufficient adhesive strength between the electrode and the separator can be ensured. Further, when the basis weight of the adhesive layer is equal to or less than the above upper limit, sufficiently high cycle characteristics of the secondary battery can be ensured.
  • the coverage of the adhesive layer is preferably 1% or more, more preferably 5% or more, preferably 50% or less, and more preferably 30% or less. If the coverage of the adhesive layer is equal to or higher than the above lower limit, the adhesive strength between the electrode and the separator can be ensured. Further, when the coverage of the adhesive layer is equal to or less than the above upper limit, sufficiently high cycle characteristics of the secondary battery can be ensured.
  • the "adhesive layer coverage" in a certain surface or region means the ratio of the area of the portion covered with the adhesive layer to the total area of the surface or region [(area of the part covered with the adhesive layer / area of the entire surface or region) ⁇ 100 (%)].
  • the adhesive layer composition containing the first particulate polymer and the second particulate polymer and a solvent
  • the adhesive layer composition refers to the dried product of
  • the method for producing an adhesive layer for a non-aqueous secondary battery of the present invention comprises a step of applying the adhesive layer composition for a non-aqueous secondary battery of the present invention onto a substrate (coating step); and a step of drying the non-aqueous secondary battery adhesive layer composition applied to (drying step). Further, the method for producing an adhesive layer for a non-aqueous secondary battery of the present invention includes a step of peeling off the adhesive layer for a non-aqueous secondary battery formed on the substrate (peeling step) after the drying step. good too.
  • the adhesive layer for a non-aqueous secondary battery is formed on an electrode base material or a separator base material as a base material
  • the electrode base material and the separator base material can be bonded as they are to form a laminate.
  • the adhesive layer for non-aqueous secondary batteries is formed on a release substrate as a substrate, after peeling the adhesive layer for non-aqueous secondary batteries from the release agent, the electrode substrate and the separator substrate are separated. It can be used for bonding with materials.
  • the non-aqueous secondary battery adhesive layer composition of the present invention is applied onto a base material such as an electrode base material, a separator base material, or a release base material.
  • the coating method includes, for example, an ink jet method through a nozzle of a coating machine. Since the composition for a non-aqueous secondary battery adhesive layer of the present invention is excellent in ink-jet ejection characteristics, it is preferable to apply the composition by an ink-jet method.
  • a conventionally known inkjet type coating machine can be used, and for example, coating can be performed using a coating machine (51 to 54 in FIG. 2) described later.
  • the non-aqueous secondary battery adhesive layer composition is preferably applied on an electrode substrate or a separator substrate, and from the viewpoint of facilitating the drying process, it is suitable for non-aqueous secondary battery adhesion.
  • the layer composition is preferably applied onto the electrode substrate.
  • the coating conditions by the inkjet method are not particularly limited as long as the non-aqueous secondary battery adhesive layer composition can be coated on the substrate, and the desired form of the resulting adhesive layer (plan view shape, dot diameter , dot thickness, dot pitch, coverage, basis weight, etc.).
  • the electrode base material is not particularly limited, and known electrode base materials can be used.
  • an electrode made of an electrode base material in which an electrode mixture layer is formed on one or both sides of a current collector, or a porous membrane layer is further formed on the electrode mixture layer of the electrode base material. can be used.
  • the current collector, the electrode mixture layer and the porous membrane layer are not particularly limited, and any collector that can be used in the field of secondary batteries, such as those described in JP-A-2013-145763, can be used. Electrical bodies, electrode composite layers and porous membrane layers may be used.
  • the separator base material is not particularly limited, and known separator base materials such as organic separator base materials can be used.
  • the organic separator base material is a porous member made of an organic material.
  • organic separator substrates include polyolefin resins such as polyethylene and polypropylene, and microporous membranes and nonwoven fabrics containing aromatic polyamide resins. Polyethylene microporous membranes and nonwoven fabrics are preferred because of their excellent strength.
  • a heat-resistant separator obtained by coating a ceramic on the separator is preferable.
  • the separator base material may have a porous membrane layer formed on one side or both sides thereof.
  • the porous membrane layer refers to a layer containing non-conductive particles as described in JP-A-2013-145763, for example.
  • the release base material is not particularly limited, and known ones can be used.
  • the adhesive layer composition coated on the substrate is dried to form an adhesive layer made of the dried adhesive layer composition on the substrate.
  • the drying method is not particularly limited, and known methods can be used. Examples of the drying method include a drying method using a heating device such as a heater, a dryer, and a heat roller.
  • the drying conditions are not particularly limited, the drying temperature is preferably 50° C. or higher and 90° C. or lower, and the drying time is preferably 1 second or longer and 120 seconds or shorter.
  • the non-aqueous secondary battery adhesive layer formed on the substrate is peeled off.
  • the adhesive layer for a non-aqueous secondary battery is formed on the release substrate, the adhesive layer can be peeled off from the release substrate and, for example, subjected to the production of a laminate for a non-aqueous secondary battery described later. can.
  • the non-aqueous secondary battery laminate of the present invention is a non-aqueous secondary battery laminate comprising an electrode and a separator, wherein the electrode and the separator are the above-described adhesive layer for a non-aqueous secondary battery of the present invention. It is adhered via In the non-aqueous secondary battery laminate of the present invention, the electrode and the separator are adhered via the non-aqueous secondary battery adhesive layer of the present invention, so that the adhesion between the battery members is excellent.
  • the electrode that is laminated with the separator to form the non-aqueous secondary battery laminate may be only the positive electrode, may be the negative electrode only, or may be both the positive electrode and the negative electrode. .
  • the number of the positive electrode, the negative electrode, and the separator included in the non-aqueous secondary battery laminate is one each. , or two or more. That is, the structure of the non-aqueous secondary battery laminate of the present invention may be any of the following (1) to (6).
  • a plurality of positive electrodes and negative electrodes are separators Structure alternately laminated via (for example, "separator / negative electrode / separator / positive electrode / separator / negative electrode / separator / positive electrode” etc.)
  • the electrode is not particularly limited, and known electrodes can be used.
  • the electrode described in the section "Method for producing adhesive layer for non-aqueous secondary battery” can be used.
  • the separator is not particularly limited, and known separators can be used.
  • the separator described in the section "Method for producing adhesive layer for non-aqueous secondary battery” can be used.
  • the adhesive layer that bonds the electrode and the separator is a dried product of the adhesive layer composition for a non-aqueous secondary battery of the present invention. That is, the dry matter contains at least the polymer derived from the first particulate polymer and the second particulate polymer, and optionally other components as described above.
  • the preferred form of the adhesive layer (dot diameter, dot thickness, dot pitch, coverage, basis weight, etc.) is the same as described in the section "Adhesive layer for non-aqueous secondary battery". .
  • first particulate polymer and the second particulate polymer are present in the form of particles in the non-aqueous secondary battery adhesive layer composition, but in the non-aqueous secondary battery adhesive layer in the laminate, It may be in the form of particles or in any other shape.
  • the method for producing a laminate for a non-aqueous secondary battery of the present invention includes a step of supplying an adhesive material to at least one bonding surface of an electrode and a separator (that is, a surface for forming an adhesive material (adhesive layer)) (supplying step), and a step of pressurizing and bonding the electrode and the separator via the bonding surface to which the adhesive material is supplied (bonding step).
  • the manufacturing method of the laminated body for non-aqueous secondary batteries of this invention may include the process (cutting process) which cut
  • the adhesive material is supplied to the bonding surface of at least one of the electrodes (positive electrode, negative electrode) and the separator.
  • Supply of the adhesive material is not particularly limited, but can be carried out, for example, by applying the composition for a non-aqueous secondary battery adhesive layer of the present invention by an inkjet method and drying.
  • the adhesive material may be supplied by transferring (laminating) the non-aqueous secondary battery adhesive layer obtained by peeling from the release substrate as described above onto the bonding surface.
  • the conditions of the inkjet method are not particularly limited as long as the non-aqueous secondary battery adhesive layer composition can be applied, and the desired form of the obtained adhesive material (plan view shape, dot diameter, dot thickness, It can be appropriately adjusted according to the dot pitch, coverage, basis weight, etc.).
  • the electrodes and separators are formed without contacting other members to the bonding surface to which the non-aqueous secondary battery adhesive layer composition is supplied.
  • the non-aqueous secondary battery adhesive layer composition can be dried during transportation while being transported to the bonding start position. Problems such as blocking do not occur unless other members are brought into contact with the bonding surface to which the non-aqueous secondary battery adhesive layer composition has been supplied, so that the secondary battery laminate can be produced efficiently.
  • drying does not have to be performed.
  • bonding start position refers to a position at which the bonding surface of the electrode and the bonding surface of the separator are brought into contact when bonding the electrode and the separator.
  • the transport of the electrodes and separators is not particularly limited, and can be performed using any transport mechanism such as rollers, belt conveyors, manipulators, and suction bands. Above all, from the viewpoint of further increasing the production efficiency of the secondary battery laminate, it is preferable to convey at least one of the electrode and the separator using rollers.
  • drying of the non-aqueous secondary battery adhesive layer composition is not particularly limited, and can be performed using a heating device such as a heater, a dryer, or a heat roller.
  • the temperature at which the electrode and/or the separator to which the non-aqueous secondary battery adhesive layer composition is supplied is not particularly limited, but is preferably 50° C. or higher and 90° C. or lower.
  • the drying time is not particularly limited, it is preferably 1 second or more and 120 seconds or less.
  • the electrode and the separator are bonded together via the bonding surface.
  • the lamination is performed by pressing the laminated body of the electrode and the separator which are superimposed via the lamination surface.
  • the pressing temperature of the laminate is not particularly limited as long as it is a temperature at which the electrode and the separator can be bonded together. , preferably 35° C. or lower, more preferably 30° C. or lower, and still more preferably 25° C. or lower.
  • the pressure temperature of the laminate is equal to or higher than the above lower limit, the adhesiveness between the battery members can be improved.
  • the pressing temperature of the laminate is equal to or lower than the above upper limit, the production efficiency of the laminate can be enhanced.
  • the laminate is pressurized at a pressure of preferably 0.1 MPa or higher, more preferably 0.5 MPa or higher, and preferably 5 MPa or lower. If the laminate is pressed at a pressure equal to or higher than the above lower limit, the adhesiveness between the battery members can be improved. On the other hand, if the laminate is pressurized at a pressure equal to or lower than the upper limit, deformation of the laminate (such as crushing of the electrode mixture layer and the separator) can be effectively suppressed.
  • the pressurization time of the laminate is preferably 20 seconds or less, more preferably 15 seconds or less. If the pressurization time of the laminate is equal to or less than the above upper limit, the production efficiency of the laminate can be enhanced.
  • the cutting step is a step of cutting the bonded body obtained in the bonding step into desired dimensions.
  • any cutting machine that can be used in the field of manufacturing secondary batteries such as a cutting machine that cuts the bonded body by sandwiching the bonded body with cutting blades from both sides in the thickness direction, can be used.
  • the electrodes and separators are not particularly limited, and known electrodes and separators can be used.
  • the electrodes and separators described above in the section "Method for producing adhesive layer for non-aqueous secondary battery” can be used.
  • the adhesive material for bonding the electrode and the separator is a dried product of the adhesive layer composition for non-aqueous secondary batteries of the present invention. That is, the dry matter contains at least the polymer derived from the first particulate polymer and the second particulate polymer, and optionally other components as described above.
  • the preferred form of the adhesive material (dot diameter, dot thickness, dot pitch, coverage, basis weight, etc.) is the same as described in the section "Adhesive layer for non-aqueous secondary battery". .
  • first particulate polymer and the second particulate polymer exist in the form of particles in the non-aqueous secondary battery adhesive layer composition, but the non-aqueous secondary battery adhesion in the laminated body after pressurization In the layer, it may be in the form of particles or any other shape.
  • a long first separator material roll 10A unwound from the first separator material roll is applied to one surface of the negative electrode material consisting of the long negative electrode material roll 20A unwound from the negative electrode material roll. are pasted together via an adhesive material supplied from the coating machine 51 .
  • the long second separator raw roll 30A fed out from the second separator raw roll is applied via the adhesive material supplied from the coating machine 52. to paste together.
  • bonding can be performed using pressure rollers 61 and 62, for example.
  • the positive electrode 40 is attached to the surface of the first separator material 10A on the side opposite to the negative electrode material 20A side via the adhesive material supplied from the coating machine 53 at a predetermined arrangement pitch, and the positive electrode is attached. get a combination.
  • the adhesive material is supplied from the coating machine 54 to the surface of the second separator material 30A opposite to the negative electrode material 20A side, and the bonded body is cut between the positive electrodes 40 adjacent in the longitudinal direction.
  • a cutting machine 70 is used to cut the laminated body to obtain a laminate.
  • the non-aqueous secondary battery of the present invention includes the non-aqueous secondary battery laminate of the present invention.
  • the non-aqueous secondary battery of the present invention includes, for example, electrodes (a positive electrode and a negative electrode), an electrolytic solution, and a separator. Then, at least one of the positive electrode and the negative electrode and the separator are laminated via the adhesive layer for non-aqueous secondary batteries of the present invention to form the laminate for non-aqueous secondary batteries of the present invention. Since the non-aqueous secondary battery of the present invention includes the laminate for a non-aqueous secondary battery of the present invention, the adhesion between battery members is excellent.
  • the electrode used in the secondary battery of the present invention is not limited, and known electrodes can be used. For example, those described in the section "Method for producing adhesive layer for non-aqueous secondary battery” can be used. can.
  • the separator used in the secondary battery of the present invention is not limited, and known separators can be used. For example, those described in the section "Method for producing adhesive layer for non-aqueous secondary battery” can be used. .
  • an organic electrolytic solution in which a supporting electrolyte is dissolved in an organic solvent is usually used.
  • a lithium salt is used as the supporting electrolyte.
  • lithium salts include LiPF 6 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAlCl 4 , LiClO 4 , CF 3 SO 3 Li, C 4 F 9 SO 3 Li, CF 3 COOLi, (CF 3 CO) 2 NLi. , (CF 3 SO 2 ) 2 NLi, (C 2 F 5 SO 2 ) NLi and the like.
  • LiPF 6 , LiClO 4 and CF 3 SO 3 Li are preferable, and LiPF 6 is particularly preferable, because they are easily dissolved in a solvent and exhibit a high degree of dissociation.
  • one electrolyte may be used alone, or two or more electrolytes may be used in combination at an arbitrary ratio.
  • Lithium ion conductivity usually tends to increase as a supporting electrolyte with a higher degree of dissociation is used, so lithium ion conductivity can be adjusted by the type of supporting electrolyte.
  • the organic solvent used in the electrolytic solution is not particularly limited as long as it can dissolve the supporting electrolyte.
  • Examples include dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), propylene carbonate (PC ), butylene carbonate (BC), ethyl methyl carbonate (EMC); esters such as ⁇ -butyrolactone and methyl formate; ethers such as 1,2-dimethoxyethane and tetrahydrofuran; sulfur compounds; and the like are preferably used.
  • DMC dimethyl carbonate
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • PC propylene carbonate
  • BC butylene carbonate
  • EMC ethyl methyl carbonate
  • esters such as ⁇ -butyrolactone and methyl formate
  • ethers such as 1,2-dimethoxyethane and tetrahydrofuran
  • sulfur compounds and the like
  • carbonates are preferably used because they have a high dielectric constant and a wide stable potential range, and a mixture of ethylene carbonate and ethyl methyl carbonate is more preferably used.
  • known additives such as vinylene carbonate (VC), fluoroethylene carbonate (FEC), ethyl methyl sulfone, and the like may be added to the electrolytic solution.
  • a laminated body obtained by laminating a laminated body is rolled or folded according to the shape of the battery, and placed in a device container (battery container), It can be produced by injecting an electrolytic solution into a device container and sealing the container.
  • the layered body the layered body itself may be used, or a plurality of layered bodies may be layered to be manufactured.
  • the laminated body may be produced by laminating a laminated body and additional battery members (electrodes and/or separators, etc.).
  • the secondary battery of the present invention may optionally contain a fuse, an overcurrent prevention element such as a PTC element, an expanded metal, a lead plate, or the like. may be provided.
  • the shape of the secondary battery may be, for example, coin-shaped, button-shaped, sheet-shaped, cylindrical, rectangular, or flat.
  • ⁇ Glass transition temperature> The aqueous dispersion of the first particulate polymer and the aqueous dispersion of the second particulate polymer prepared in each production example were each dried at 130° C. for 1 hour to prepare samples. Weigh 10 mg of the measurement sample in an aluminum pan, and use a differential thermal analysis measuring device ("EXSTAR DSC6220" manufactured by SII Nanotechnology Co., Ltd.) to measure the temperature range from -100 ° C. to 200 ° C., at a heating rate of 10 ° C./ Minutes, the measurement was performed under the conditions specified in JIS Z8703 to obtain a differential scanning calorimetry (DSC) curve. An empty aluminum pan was used as a reference.
  • EXSTAR DSC6220 manufactured by SII Nanotechnology Co., Ltd.
  • volume average particle size The volume average particle diameters of the first particulate polymer and the second particulate polymer prepared in each production example were measured by a laser diffraction method. Specifically, an aqueous dispersion solution (solid content concentration 0.1% by mass) containing the prepared first particulate polymer or second particulate polymer was used as a sample, and a laser diffraction particle size distribution measuring device (Beckman, In the particle size distribution (volume basis) obtained by Coulter Co., Ltd., product name "LS-13 320”), the volume average particle diameter D50 (nm) and
  • the stress was measured when one end of the separator was pulled vertically upward at a pulling rate of 50 mm/min and peeled off. This measurement was performed six times in total, and the average value of the stress was obtained as the peel strength, and the adhesiveness between the negative electrode and the separator was evaluated according to the following criteria. A higher peel strength indicates a higher adhesiveness between the electrode (negative electrode) and the separator.
  • the non-aqueous secondary battery adhesive layer composition produced in each example and comparative example was subjected to a discharge test using a high-performance head-equipped discharge test kit (IJK-200S, manufactured by Microjet). Then, the ejection characteristics were evaluated according to the following criteria.
  • the prepared cell was discharged to 3.0 V by a constant current method of 0.2 C and 1 C in an atmosphere of -10°C to determine the electric capacity.
  • (Production example 1) ⁇ Production of first particulate polymer 1> 100 parts of ion-exchanged water and 0.1 part of ammonium persulfate were supplied to a reactor equipped with a stirrer, the gas phase was replaced with nitrogen gas, and the temperature was raised to 80°C. On the other hand, in another container, 40 parts of ion-exchanged water, 0.2 parts of sodium dodecylbenzenesulfonate as an emulsifier, and 90 n-butyl acrylate as a (meth)acrylate monomer having a chain alkyl group having 4 or more carbon atoms.
  • a shell-forming monomer composition containing 4.75 parts of styrene as an aromatic monovinyl monomer and 0.25 parts of methacrylic acid as a hydrophilic group-containing monomer was added to this aqueous dispersion for 60 minutes.
  • the polymerization was continued by supplying continuously over a period of time.
  • An aqueous dispersion containing the first particulate polymer 1 was prepared by cooling to stop the reaction when the polymerization conversion reached 98%.
  • the volume average particle size and glass transition temperature of the obtained first particulate polymer 1 were measured. Table 1 shows the results.
  • the shell portion of the first particulate polymer 1 partially covered the outer surface of the core portion. It was confirmed that it has a core-shell structure.
  • Second particulate polymers 2 to 13 having a core-shell structure were prepared in the same manner as the second particulate polymer 1, except that the types of monomers and the amounts used were changed as shown in Table 2. was prepared. Various measurements and the like were performed in the same manner as in Production Example 1. Table 2 shows the results.
  • Example 1 ⁇ Preparation of non-aqueous secondary battery adhesive layer composition>
  • the aqueous dispersion of the first particulate polymer 1 obtained in Production Example 1 and the aqueous dispersion of the second particulate polymer 1 obtained in Production Example 16 were mixed so that the mass ratio of the solid content was 100:10. Further, ion-exchanged water was added to dilute the solid content concentration to 10.5%. Propylene glycol was further added to the resulting mixture to adjust the solid content concentration to 10%, thereby obtaining a non-aqueous secondary battery adhesive layer composition.
  • the adhesive strength between the electrode and the separator and the inkjet ejection characteristics were evaluated. Table 3 shows the results.
  • a 5% aqueous sodium hydroxide solution was added to the mixture containing the binder for the negative electrode mixture layer to adjust the pH to 8, and unreacted monomers were removed by heating under reduced pressure distillation. Thereafter, the mixture was cooled to a temperature of 30° C. or lower to obtain an aqueous dispersion containing the desired binder for the negative electrode mixture layer.
  • 100 parts of artificial graphite (volume average particle size: 15.6 ⁇ m) as a negative electrode active material and a 2% aqueous solution of carboxymethyl cellulose sodium salt (manufactured by Nippon Paper Industries, product name “MAC350HC”) as a viscosity modifier are solidified.
  • the mixture was further mixed at a temperature of 25° C. for 60 minutes. Furthermore, after adjusting the solid content concentration to 62% with ion-exchanged water, the mixture was further mixed at a temperature of 25° C. for 15 minutes. 1.5 parts of the aqueous dispersion containing the binder for the negative electrode mixture layer and ion-exchanged water were added to the resulting mixture so that the final solid concentration was 52%. Adjusted and mixed for an additional 10 minutes. This was defoamed under reduced pressure to obtain a highly fluid slurry composition for a non-aqueous secondary battery negative electrode.
  • the obtained slurry composition for a non-aqueous secondary battery negative electrode is coated with a comma coater on both sides of a copper foil having a thickness of 20 ⁇ m as a current collector so that the film thickness after drying is about 150 ⁇ m, dried.
  • This drying was carried out by conveying the copper foil at a speed of 0.5 m/min in an oven at a temperature of 60° C. for 2 minutes. After that, heat treatment was performed at a temperature of 120° C. for 2 minutes to obtain a negative electrode raw sheet before pressing.
  • the negative electrode raw material before pressing was rolled by a roll press to obtain a negative electrode raw material after pressing in which the thickness of the negative electrode mixture layer was 80 ⁇ m.
  • ⁇ Preparation of positive electrode original sheet 100 parts of LiCoO 2 having a volume average particle diameter of 12 ⁇ m as a positive electrode active material, 2 parts of acetylene black (manufactured by Denka Co., Ltd., product name “HS-100”) as a conductive material, and polyfluoride as a binder. 2 parts of vinylidene (manufactured by Kureha Co., Ltd., product name "#7208”) was mixed with N-methylpyrrolidone as a solvent to adjust the total solid concentration to 70%. These were mixed by a planetary mixer to obtain a slurry composition for non-aqueous secondary battery positive electrode.
  • the obtained slurry composition for a non-aqueous secondary battery positive electrode is coated on both sides of a 20 ⁇ m thick aluminum foil as a current collector with a comma coater so that the film thickness after drying is about 150 ⁇ m, dried.
  • This drying was carried out by conveying the aluminum foil at a speed of 0.5 m/min through an oven at a temperature of 60° C. for 2 minutes. After that, heat treatment was performed at a temperature of 120° C. for 2 minutes to obtain a positive electrode original fabric. Then, the obtained positive electrode raw sheet was rolled using a roll press to obtain a positive electrode raw sheet after pressing including the positive electrode mixture layer.
  • a raw separator sheet made of polyethylene (PE) (product name: “ND412” manufactured by Asahi Kasei Corporation) was prepared.
  • FIG. 3 A laminated body was produced as shown in FIG.
  • reference numeral 91 denotes a conveying roller
  • reference numeral 92 denotes a heat roller.
  • an inkjet coating machine 52 Konica, KM1024 was applied onto one surface of the negative electrode raw roll 20A. (Sheer mode type))
  • the adhesive layer composition was supplied from the inkjet head, and the second separator material 30A and the negative electrode material 20A fed out from the separator material roll were bonded together by pressure rollers 61 and 62.
  • an adhesive layer composition is supplied from an inkjet head of an inkjet coating machine 51 (Konica KM1024 (sheer mode type)), and is fed from the separator raw roll.
  • the first separator raw sheet 10A and the laminate of the negative electrode raw sheet 20A and the second separator raw sheet 30A were bonded together by pressing rollers 61 and 62 .
  • an adhesive layer composition is applied from an inkjet head of an inkjet coating machine 53 (manufactured by Konica, KM1024 (sheer mode type)).
  • the laminate of the first separator material 10A, the negative electrode material 20A, and the second separator material 30A, and the positive electrode 40 are pressed with pressure rollers 61 and 62. pasted together.
  • the adhesive layer composition onto the positive electrode 40 from the inkjet head of the inkjet coating machine 54 (manufactured by Konica, KM1024 (sheer mode type)), it is cut by the cutting machine 70 to form a second separator. , the negative electrode, the first separator, and the positive electrode were laminated in this order to obtain a laminate.
  • portions where the electrode mixture layer (the positive electrode mixture layer or the negative electrode mixture layer) is not formed are provided at the ends of the respective current collectors of the positive electrode 40 and the negative electrode raw sheet 20A.
  • the tabs were punched out to form tabs of the same size, and lamination was performed so that the positive electrode tab and the negative electrode tab were arranged on the same edge side of the bonding surfaces X and Y between the electrode and the separator.
  • the bonding using the pressing rollers 61 and 62 was performed at a temperature of 25° C. and a pressure of 1 MPa. Further, the supplied adhesive layer composition was dried by using a heat roller 92 as part of the conveying roller 91 (drying temperature: 70° C., drying time: 1 second).
  • the adhesive layer composition was supplied from the coating machines 51 to 54 so that the adhesive layer composition formed a uniform dot-like pattern.
  • the dot size was 100 ⁇ m in diameter and the interval was 400 ⁇ m pitch.
  • the basis weight of the adhesive material was 0.2 g/m 2 . Moreover, when the coverage was measured, it was 6.5%.
  • Examples 2 to 15, Comparative Examples 1 to 6 Various operations, measurements and evaluations were carried out in the same manner as in Example 1, except that the type of the first particulate polymer, the type of the second particulate polymer, and the usage ratio thereof were changed as shown in Table 3. did Table 3 shows the results.
  • Proportion X indicates the content ratio of the first particulate polymer in the total mass of the first particulate polymer and the second particulate polymer
  • Proportion Y indicates the content ratio of the second particulate polymer in the total mass of the first particulate polymer and the second particulate polymer.
  • the non-aqueous secondary battery adhesive layer composition of the present invention can form a non-aqueous secondary battery adhesive layer that firmly bonds battery members together even under room temperature and pressure. I understand. Moreover, as can be seen from the evaluation results shown in Table 3, the composition for a non-aqueous secondary battery adhesive layer of the present invention is excellent in ink-jet ejection characteristics. Moreover, as can be seen from the evaluation results shown in Table 3, the non-aqueous secondary battery obtained using the composition for a non-aqueous secondary battery adhesive layer of the present invention has excellent cycle characteristics.
  • the composition for non-aqueous secondary battery adhesion layers which can form the adhesion layer for non-aqueous secondary batteries which adhere

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PCT/JP2022/031438 2021-08-31 2022-08-19 非水系二次電池接着層用組成物、非水系二次電池用接着層及びその製造方法、非水系二次電池用積層体及びその製造方法、並びに、非水系二次電池 Ceased WO2023032718A1 (ja)

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KR1020247004359A KR20240050326A (ko) 2021-08-31 2022-08-19 비수계 이차 전지 접착층용 조성물, 비수계 이차 전지용 접착층 및 그 제조 방법, 비수계 이차 전지용 적층체 및 그 제조 방법, 그리고, 비수계 이차 전지
US18/293,873 US20240356160A1 (en) 2021-08-31 2022-08-19 Composition for non-aqueous secondary battery adhesive layer, adhesive layer for non-aqueous secondary battery and method of producing same, laminate for non-aqueous secondary battery and method of producing same, and non-aqueous secondary battery
JP2023545454A JPWO2023032718A1 (https=) 2021-08-31 2022-08-19
EP22864302.9A EP4398402A4 (en) 2021-08-31 2022-08-19 COMPOSITION FOR NONAQUEOUS SECONDARY BATTERY ADHESIVE LAYER, NONAQUEOUS SECONDARY BATTERY ADHESIVE LAYER AND METHOD FOR MANUFACTURING SAME, LAMINATE FOR NONAQUEOUS SECONDARY BATTERY AND METHOD FOR MANUFACTURING SAME, AND NONAQUEOUS SECONDARY BATTERY
CN202280048979.2A CN117642920A (zh) 2021-08-31 2022-08-19 非水系二次电池黏合层用组合物、非水系二次电池用黏合层及其制造方法、非水系二次电池用层叠体及其制造方法、以及非水系二次电池

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