Classifications

• • 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
• • 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
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
  • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F212/06—Hydrocarbons
  • C08F212/08—Styrene
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  • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
  • C08L25/02—Homopolymers or copolymers of hydrocarbons
  • C08L25/04—Homopolymers or copolymers of styrene
  • C08L25/08—Copolymers of styrene
  • C08L25/14—Copolymers of styrene with unsaturated esters
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/22—Electrodes
  • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
  • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
• • 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
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
• • 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
• • 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
• • 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
• • 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
  • H01M50/443—Particulate material
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
  • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
• • 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
  • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
  • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/22—Electrodes
  • H01G11/30—Electrodes characterised by their material
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/52—Separators
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the present invention relates to a polymer for an electrochemical element functional layer, a method for producing the same, a composition for an electrochemical element functional layer, a substrate with a functional layer for an electrochemical element, and an electrochemical element.
• Electrochemical devices such as lithium-ion secondary batteries and electric double layer capacitors are small, lightweight, have high energy density, and can be repeatedly charged and discharged, and are used in a wide range of applications.
• a lithium-ion secondary battery generally includes battery members such as a positive electrode, a negative electrode, and a separator that separates the positive electrode from the negative electrode to prevent a short circuit between the positive electrode and the negative electrode.
• constituent members provided with functional layers such as adhesive layers for the purpose of improving adhesion between constituent members have been used.
• an electrode in which a functional layer is further formed on an electrode base material in which an electrode mixture layer is provided on a current collector, and a separator in which a functional layer is formed on a separator base material are battery members.
• further improvement of the functional layer has been studied for the purpose of further improving the performance of electrochemical devices such as lithium ion secondary batteries.
• Patent Document 1 a particulate polymer having an average circularity of 0.90 or more and less than 0.99 and a volume average particle diameter of 1.0 ⁇ m or more and 10.0 ⁇ m or less is used as a functional layer. It has been proposed to form a functional layer capable of exhibiting excellent adhesiveness by blending it in a composition for use.
• the functional layer formed using the above-mentioned conventionally known particulate polymer or the like has a much higher adhesiveness after being immersed in the electrolytic solution (hereinafter also referred to as "wet adhesiveness"). There was room for improvement.
• an object of the present invention is to provide a polymer for an electrochemical element functional layer that can be suitably used to form a functional layer having excellent wet adhesion, and a method for producing the same.
• Another object of the present invention is to provide a functional layer composition capable of forming a functional layer having excellent wet adhesion.
• the present invention provides a substrate with a functional layer for an electrochemical device, which is provided with a functional layer for an electrochemical device formed using the composition for a functional layer of the present invention, and an electrochemical device comprising the same. With the goal.
• a particulate polymer containing a monomer unit containing at least one of an oxygen atom and a nitrogen atom in a predetermined proportion is an oxygen atom and a nitrogen atom contained in the particulate polymer.
• Wet adhesion of the resulting functional layer when the distribution in the vicinity of the surface of the particulate polymer is obtained for at least one atom X of The inventors have newly found that the properties can be improved, and completed the present invention.
• a polymer for an electrochemical element functional layer of the present invention is a particulate polymer for an electrochemical element functional layer At least one of epoxy group-containing unsaturated monomer units and nitrile group-containing unsaturated monomer units is contained in 5% by mass or more and 30% by mass or less, and oxygen atoms contained in the particulate polymer and nitrogen atoms, when the distribution in the vicinity of the surface of the particulate polymer is obtained, the concentration of the atom X on the outermost surface of the particulate polymer is 100%, and the particles
• the concentration of the atom X in the region of 1.0% or more and 1.5% or less in the direction from the outermost surface of the particulate polymer toward the center of the particulate polymer is 20% or more and 50% or less, and the depth
• the concentration of the atoms X in the region of 0.5% or more and less than 1.0% is 50% or more and 80% or less, and the concentration of the atom
• the expression that the polymer "contains a monomer unit” means that "the polymer obtained using the monomer contains a structural unit derived from the monomer”.
• the content of monomer units in the polymer can be measured using a nuclear magnetic resonance (NMR) method such as 1 H-NMR.
• NMR nuclear magnetic resonance
• the concentration distribution of atoms X in the polymer can be determined by energy dispersive X-ray analysis according to the method described in the Examples herein.
• the polymer for an electrochemical device functional layer described in [1] above preferably has a glass transition temperature of 40°C or higher and 150°C or lower. If the glass transition temperature of the particulate polymer is within such a range, it is possible to improve the blocking resistance of the obtained functional layer and further improve the wet adhesion. Incidentally, the glass transition temperature of the polymer can be measured according to the method described in the examples of the present specification.
• the polymer for an electrochemical element functional layer described in [1] or [2] above preferably has an average circularity of 0.90 or more and 0.99 or less. If the average circularity of the polymer is within such a range, the wet adhesion of the resulting functional layer can be further enhanced. Incidentally, the average circularity of the polymer can be measured according to the method described in the examples of the present specification.
• the polymer for an electrochemical element functional layer contains aromatic vinyl monomer units and (meth)acrylic acid ester monomer units. It is preferable to further include at least one. If the polymer has such a composition, the wet adhesion of the obtained functional layer can be further improved.
• (meth)acryl means acryl or methacryl.
• the present invention is intended to advantageously solve the above problems, and a method for producing a polymer for an electrochemical element functional layer according to any one of [1] to [4] above.
• an object of the present invention is to advantageously solve the above problems, and a composition for an electrochemical element functional layer of the present invention comprises a binder and ] and the polymer for an electrochemical element functional layer according to any one of the above.
• a functional layer composition of the present invention By using the functional layer composition of the present invention, a functional layer having excellent wet adhesion can be formed.
• an object of the present invention is to advantageously solve the above problems, and the substrate with a functional layer for an electrochemical device of the present invention comprises a substrate and a substrate formed on the substrate. and a functional layer, wherein the functional layer is formed using the composition for an electrochemical element functional layer according to [6] above.
• a substrate with a functional layer of the present invention is excellent in wet adhesiveness, and can improve the electrochemical properties of an electrochemical device provided with such a substrate.
• the base material may be a separator base material or an electrode base material.
• An object of the present invention is to advantageously solve the above problems, and an electrochemical device of the present invention comprises the substrate with a functional layer for an electrochemical device according to [7] above. It is characterized by having Such an electrochemical device of the present invention has excellent electrochemical properties.
• the polymer for functional layers which can be used suitably in order to form the functional layer which is excellent in wet adhesiveness, and its manufacturing method can be provided.
• a functional layer composition capable of forming a functional layer having excellent wet adhesion.
• a substrate with a functional layer for an electrochemical device which is provided with a functional layer for an electrochemical device formed using the composition for a functional layer of the present invention, and an electrochemical device comprising the same are provided. can do.
• the polymer for an electrochemical element functional layer of the present invention and the composition for an electrochemical element functional layer of the present invention containing the same are the electrochemical polymer of the present invention. It can be suitably used when forming a base material with a functional layer for chemical elements.
• the polymer for electrochemical device functional layer of the present invention can be efficiently produced according to the method for producing the polymer for electrochemical device functional layer of the present invention.
• the electrochemical device of the present invention is an electrochemical device comprising at least the substrate with a functional layer for an electrochemical device of the present invention.
• the polymer for an electrochemical element functional layer of the present invention is in the form of particles containing at least one of epoxy group-containing unsaturated monomer units and nitrile group-containing unsaturated monomer units in an amount of 5% by mass or more and 30% by mass or less. It is a polymer. Furthermore, the polymer for an electrochemical device functional layer of the present invention (hereinafter sometimes simply referred to as "particulate polymer”) contains at least oxygen atoms and nitrogen atoms contained in the particulate polymer.
• the concentration of atom X at the outermost surface of the particulate polymer is set to 100%, and the particulate polymer is obtained from the outermost surface of the particulate polymer.
• the concentration of atom X in the region with a depth of 1.0% or more and 1.5% or less toward the center of the The concentration is 50% or more and 80% or less, and the concentration of atoms X in a region with a depth of less than 0.5% is 80% or more and 100% or less. If the particulate polymer satisfies such compositional and structural requirements, the wet adhesion of the resulting functional layer can be enhanced.
• the distribution of at least one atom X of oxygen atoms and nitrogen atoms is as follows. A region with a depth of 1.0% or more and 1.5% or less in the direction from the outermost surface of the particulate polymer toward the center of the particulate polymer, assuming that the concentration of atoms X in the outermost surface of the particulate polymer is 100%.
• region I the concentration of atom X must be 20% or more, preferably 30% or more, 50% or less, and preferably 45% or less. Preferably, it is 40% or less; in a region with a depth of 0.5% or more and less than 1.0% (hereinafter referred to as “region II”), it must be 50% or more, and 60% or more preferably 65% or more, preferably 80% or less, preferably 75% or less; a region from the outermost surface to a depth of less than 0.5% (hereinafter referred to as " In Region III”), it is necessary to be 80% or more, preferably 90% or more, more preferably 95% or more, and may be 100%.
• the resulting functional layer can exhibit good wet adhesion. More specifically, the fact that the concentration of atoms X in regions I and II is equal to or less than the above upper limit value means that the abundance of atoms X near the outermost surface is greater than that in the inner portion. Atoms X, which are present in a relatively large number near the outermost surface of the particulate polymer, can efficiently interact with other constituent members that are adherends in the state after immersion in the electrolytic solution, and as a result, the function It is speculated that wet adhesion of the layer may be enhanced.
• the concentration of atom X in regions II and III is equal to or higher than the above lower limit value also means that the abundance of atom X near the outermost surface is greater than in the inner portion, for the same reason as above. It is believed that the wet adhesion of the resulting functional layer can be enhanced. Furthermore, when the concentration of atoms X in the region I is equal to or higher than the above lower limit, it means that a certain amount of atoms X are also present in a region slightly inside the outermost surface region. The wet adhesion of the applied functional layer can be enhanced.
• the difference D1 in concentration between the regions III and II is calculated, and the difference D2 in concentration between the regions II and I is calculated, and the value of D1-D2 is calculated.
• An absolute value can be set as the distribution parameter of oxygen atoms or nitrogen atoms in the vicinity of the surface of the particulate polymer. The smaller the value of the distribution parameter, the more uniform the gradation of the atoms X is formed in the regions I to III.
• the value of the distribution parameter is preferably 15% or less, more preferably 10% or less, even more preferably 5% or less, and may of course be 0%.
• the value of the distribution parameter is equal to or less than the above upper limit, it is possible to enhance the wet adhesion and blocking resistance of the resulting functional layer.
• the particulate polymer preferably has a glass transition temperature of 40°C or higher, more preferably 50°C or higher, even more preferably 60°C or higher, and preferably 150°C or lower, and 120°C. It is more preferably 100° C. or less, more preferably 100° C. or less. If the glass transition temperature is at least the above lower limit, the anti-blocking property of the resulting functional layer can be enhanced. Further, if the glass transition temperature is at most the above upper limit, the wet adhesion of the obtained functional layer can be further improved, thereby enhancing the electrochemical characteristics such as cycle characteristics and output characteristics of the obtained electrochemical device. be able to.
• the glass transition temperature of the particulate polymer can be controlled to a desired value by adjusting the composition of the particulate polymer.
• the particulate polymer preferably has an average circularity of 0.90 or more, more preferably 0.93 or more, still more preferably 0.95 or more, and a value as close to 1.0 as possible. may be, for example, 0.99 or less. If the average circularity of the particulate polymer is at least the above lower limit, the shape of the particulate polymer located near the surface of the functional layer or exposed from the surface of the functional layer when the functional layer is formed is a true sphere. This allows good adhesion to the adherend and effectively improves the wet adhesion of the functional layer.
• the average circularity of the particulate polymer can be controlled according to the polymerization method.
• the particulate polymer preferably has a volume average particle diameter of 0.5 ⁇ m or more, more preferably 1.0 ⁇ m or more, still more preferably 2.0 ⁇ m or more, and preferably 15 ⁇ m or less. , is more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less. If the volume-average particle size of the particulate polymer is at least the above lower limit, the wet adhesion of the resulting functional layer can be further enhanced. Further, when the volume average particle diameter of the particulate polymer is equal to or less than the above upper limit, it is possible to effectively prevent the particulate polymer from falling off from the functional layer when the functional layer is formed.
• the volume average particle diameter of the particulate polymer can be adjusted by the type and amount of the metal hydroxide used when preparing the particulate polymer. Details of the metal hydroxide will be described later.
• the volume average particle diameter of the particulate polymer the particle diameter distribution (volume basis) is obtained according to the method described in the examples of the present specification, and the particle diameter D50 at which the cumulative volume calculated from the small diameter side becomes 50% It was adopted.
• the total repeating units contained in the particulate polymer are 100% by mass, and at least one of epoxy group-containing unsaturated monomer units and nitrile group-containing unsaturated monomer units is It is necessary to contain at least 30% by mass. Furthermore, the particulate polymer contains, in addition to the epoxy group-containing unsaturated monomer unit or the nitrile group-containing unsaturated monomer unit, an aromatic vinyl monomer unit, a (meth)acrylic acid ester monomer unit, It may contain crosslinkable monomer units, N-methylolamide group-containing monomer units, and the like.
• the particulate polymer may have at least one of epoxy group-containing unsaturated monomer units and nitrile group-containing unsaturated monomer units, and may have both. When the particulate polymer has both of these, the total amount of both is preferably 5% by mass or more and 30% by mass or less, with the total repeating units contained in the particulate polymer being 100% by mass.
• At least one of the epoxy group-containing unsaturated monomer unit and the nitrile group-containing unsaturated monomer unit in the particulate polymer, or the content ratio of both is the total repeating units contained in the particulate polymer 100% by mass, it is preferably 7% by mass or more, more preferably 10% by mass or more, preferably 25% by mass or less, and more preferably 20% by mass or less. If the content of both or at least one of them is at least the above lower limit, the wet adhesion of the resulting functional layer can be further improved. Moreover, if the content ratio of both or at least one of them is equal to or less than the above upper limit, the particulate polymer can be stably produced, and the anti-blocking property of the obtained functional layer can be enhanced.
• epoxy group-containing unsaturated monomers capable of forming epoxy group-containing unsaturated monomer units include vinyl glycidyl ether, allyl glycidyl ether, butenyl glycidyl ether, o-allylphenyl glycidyl ether, and glycidyl (2-butenyl).
• Unsaturated glycidyl ethers such as ethers; butadiene monoepoxide, chloroprene monoepoxide, 4,5-epoxy-2-pentene, 3,4-epoxy-1-vinylcyclohexene, 1,2-epoxy-5,9-cyclododecadiene monoepoxides of dienes or polyenes, such as; alkenyl epoxides such as 3,4-epoxy-1-butene, 1,2-epoxy-5-hexene, 1,2-epoxy-9-decene; glycidyl crotonate, glycidyl-4-heptenoate, glycidyl sorbate, glycidyl linoleate, glycidyl-4-methyl-3-pentenoate, glycidyl ester of 3-cyclohexenecarboxylic acid, glycidyl ester of 4-methyl-3-cycl
• glycidyl esters of unsaturated carboxylic acids are preferably used, and glycidyl methacrylate is more preferably used, from the viewpoint of further enhancing the wet adhesiveness of the functional layer.
• these epoxy-group-containing unsaturated monomers may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios.
• nitrile group-containing unsaturated monomers capable of forming nitrile group-containing unsaturated monomer units include ⁇ , ⁇ -ethylenically unsaturated nitrile monomers.
• the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer is not particularly limited as long as it is an ⁇ , ⁇ -ethylenically unsaturated compound having a nitrile group.
• nitrile group-containing unsaturated monomers examples include acrylonitrile; ⁇ -chloroacrylonitrile; ⁇ -halogenoacrylonitrile such as ⁇ -bromoacrylonitrile; ⁇ -alkylacrylonitrile such as methacrylonitrile and ⁇ -ethylacrylonitrile; These nitrile group-containing unsaturated monomers may be used singly or in combination of two or more at any ratio.
• aromatic vinyl monomers capable of forming aromatic vinyl monomer units are not particularly limited, and examples include styrene, ⁇ -methylstyrene, styrenesulfonic acid, butoxystyrene, vinylnaphthalene etc., among which styrene is preferred.
• these aromatic vinyl monomers may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios.
• the content of the aromatic vinyl monomer units in the particulate polymer is preferably 30% by mass or more, more preferably 30% by mass or more, when the total monomer units in the particulate polymer is 100% by mass. It is 60% by mass or more, preferably 95% by mass or less, more preferably 90% by mass or less.
• the content of the aromatic vinyl monomer units is at least the above lower limit, the elasticity of the particulate polymer is improved, and the adhesive strength of the functional layer can be increased.
• the content of the aromatic vinyl monomer unit is equal to or less than the above upper limit, the flexibility of the particulate polymer is increased, and the film-forming properties of the functional layer composition during drying are improved. Therefore, the adhesive strength of the functional layer can be increased.
• (meth)acrylate monomers capable of forming (meth)acrylate monomer units include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate and t - alkyl acrylates such as butyl acrylate such as butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate such as 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, lauryl acrylate, n-tetradecyl acrylate, stearyl acrylate; and butyl methacrylate such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl
• n-butyl acrylate, 2-ethylhexyl acrylate and methyl methacrylate are preferred, and 2-ethylhexyl acrylate is more preferred.
• these (meth)acrylic acid ester monomers may be used singly, or two or more of them may be used in combination at an arbitrary ratio.
• the content of the (meth)acrylic acid ester monomer unit in the particulate polymer is preferably 1% by mass or more when the total repeating units of the particulate polymer is 100% by mass. It is preferably 5% by mass or more, preferably 50% by mass or less, and more preferably 40% by mass or less. If the content of the (meth)acrylic acid ester monomer units is at least the above lower limit, excessive lowering of the glass transition temperature of the particulate polymer is avoided, and the anti-blocking property of the resulting functional layer is improved. can be made On the other hand, when the content of the (meth)acrylic acid ester monomer units is equal to or less than the above upper limit, the adhesive strength of the functional layer can be increased.
• N-methylolamide group-containing monomer unit examples include (meth)acrylamides having a methylol group such as N-methylol(meth)acrylamide. One of these may be used alone, or two or more of them may be used in combination at any ratio.
• the content is preferably based on the total amount of monomer units in the particulate polymer being 100% by mass. is 0.02% by mass or more and 10% by mass or less. If the content of the N-methylolamide group-containing monomer units in the particulate polymer is within the above range, elution of the particulate polymer into the electrolytic solution can be sufficiently suppressed.
• Examples of monomers capable of forming crosslinkable monomer units include polyfunctional monomers having two or more polymerizable reactive groups in the monomer.
• Examples of such polyfunctional monomers include allyl (meth)acrylate; divinyl compounds such as divinylbenzene; diethylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, 1,3-butylene glycol diacrylate, (meth)acrylic acid ester compounds; tri(meth)acrylic acid ester compounds such as trimethylolpropane trimethacrylate and trimethylolpropane triacrylate; Among them, ethylene glycol dimethacrylate is preferred.
• crosslinkable monomers may be used singly, or two or more of them may be used in combination at an arbitrary ratio.
• the epoxy group-containing unsaturated monomer unit and the N-methylolamide group-containing monomer unit described above are also crosslinkable monomer units. Units corresponding to saturated monomeric units or N-methylolamide group-containing monomeric units are not included.
• the content of the crosslinkable monomer units in the particulate polymer is preferably 0.02% by mass or more when the amount of the total monomer units in the particulate polymer is 100% by mass. , preferably 2% by mass or less, more preferably 1.5% by mass or less, and still more preferably 1% by mass or less. If the content of the crosslinkable monomer units in the particulate polymer is within the above range, elution of the particulate polymer into the electrolytic solution can be sufficiently suppressed.
• a particulate polymer as a polymer for an electrochemical element functional layer of the present invention can be prepared by polymerizing a monomer composition containing the above monomers in an aqueous solvent such as water. .
• the proportion of each monomer in the monomer composition is generally the same as the proportion of each monomer unit in the particulate polymer.
• the polymerization mode is not particularly limited, and any method such as a suspension polymerization method, an emulsion polymerization aggregation method, and a pulverization method can be used. Among them, the suspension polymerization method and the emulsion polymerization aggregation method are preferable, and the suspension polymerization method is more preferable.
• the polymerization reaction any reaction such as radical polymerization and living radical polymerization can be used.
• the monomer composition used for preparing the particulate polymer includes a chain transfer agent, a polymerization modifier, a polymerization reaction retarder, a reactive fluidizing agent, a filler, a flame retardant, an antioxidant, a coloring agent, and a coloring agent.
• a chain transfer agent e.g., a chain transfer agent
• a polymerization modifier e.g., a polymerization modifier
• a polymerization reaction retarder e.g., a reactive fluidizing agent
• a filler e.g., a filler, a flame retardant, an antioxidant, a coloring agent, and a coloring agent.
• a coloring agent e.g., a coloring agent that can be included in any amount.
• Preparation of particulate polymer by suspension polymerization (1) Preparation of monomer composition First, monomers constituting the desired particulate polymer and other compounding agents added as necessary are mixed to prepare a monomer composition. . (2) Formation of droplets Next, the monomer composition is dispersed in water, a polymerization initiator is added, and then droplets of the monomer composition are formed.
• the method of forming droplets is not particularly limited, and for example, the droplets can be formed by shearing and stirring water containing the monomer composition using a disperser such as an emulsifying disperser.
• polymerization initiator for example, di(3,5,5-trimethylhexanoyl) peroxide, t-butylperoxy-2-ethylhexanoate, polymerization initiation such as azobisisobutyronitrile agents.
• the polymerization initiator may be added before forming droplets after the monomer composition is dispersed in water, or may be added to the monomer composition before being dispersed in water. good.
• a dispersion stabilizer to water to form the droplets of the monomer composition.
• the dispersion stabilizer for example, metal hydroxide such as magnesium hydroxide, sodium dodecylbenzenesulfonate, or the like can be used.
• the water containing the formed droplets is heated to initiate polymerization, thereby forming a particulate polymer in the water.
• the reaction temperature for the polymerization is preferably 50°C or higher and 95°C or lower.
• the polymerization reaction time is preferably 1 hour or more and 10 hours or less, preferably 8 hours or less, and more preferably 6 hours or less.
• a first monomer composition containing at least one of an epoxy group-containing unsaturated monomer unit and a nitrile group-containing unsaturated monomer unit is polymerized.
• the timing when the polymerization conversion rate in the first polymerization step is 70% or more and 95% or less in the first polymerization step at least one of the epoxy group-containing unsaturated monomer unit and the nitrile group-containing unsaturated monomer unit It is preferable to obtain a particulate polymer through a second polymerization step in which a second monomer composition containing one is added to the polymerization system for an addition time of 5 minutes to 1 hour and polymerized.
• the epoxy group-containing unsaturated monomer unit and the nitrile group-containing unsaturated monomer unit The total amount of the monomer units is preferably 5% by mass or more and 30% by mass or less.
• the mass of all monomers contained in the first monomer composition and the second monomer composition is 100% by mass
• the epoxy group-containing unsaturated monomer unit and the nitrile group-containing unsaturated monomer The total amount of body units is preferably 7% by mass or more, more preferably 10% by mass or more, preferably 25% by mass or less, and more preferably 20% by mass or less. If the total amount of the epoxy group-containing unsaturated monomer unit and the nitrile group-containing unsaturated monomer unit is at least the above lower limit, the wet adhesion of the obtained functional layer can be further improved.
• the particulate polymer can be stably produced, and the obtained function The blocking resistance of the layer can be enhanced.
• the addition time of the second monomer composition is preferably 5 minutes or longer, more preferably 10 minutes or longer, preferably 1 hour or shorter, and more preferably 30 minutes or shorter. preferable.
• the addition time is preferably 5 minutes or longer, more preferably 10 minutes or longer, preferably 1 hour or shorter, and more preferably 30 minutes or shorter. preferable.
• the particulate polymer can be obtained by washing, filtering and drying the water containing the particulate polymer in accordance with conventional methods.
• composition for an electrochemical element functional layer of the present invention contains the above particulate polymer as the polymer for an electrochemical element functional layer of the present invention and a binder, and optionally heat-resistant fine particles and the like. It may further contain other ingredients.
• a functional layer for an electrochemical device having excellent wet adhesion can be formed.
• the particulate polymer is the above-described polymer for electrochemical element functional layer of the present invention, and satisfies the various essential or preferred attributes described above.
• the particulate polymer is a polymer having a particulate shape in the functional layer composition. Note that the particulate polymer may be in a particle shape after the members are bonded through the functional layer formed using the functional layer composition, or may be in any other shape. .
• the binder contained in the functional layer composition is used to prevent components such as the particulate polymer contained in the functional layer formed using the functional layer composition of the present invention from falling off from the functional layer.
• the shape of the binder may be particulate or non-particulate. It is preferably particulate.
• the binder may be in the form of particles after bonding the members together through the functional layer formed using the composition for the functional layer, or may be in any other shape.
• the binder is not particularly limited, and may be a known polymer that is water-insoluble and dispersible in a dispersion medium such as water, for example, a binder resin such as a thermoplastic elastomer.
• a binder resin such as a thermoplastic elastomer.
• thermoplastic elastomer conjugated diene polymers and acrylic polymers are preferable, and acrylic polymers are more preferable.
• These binders may be used singly or in combination of two or more at any ratio.
• the acrylic polymer refers to a polymer containing (meth)acrylic acid ester monomer units.
• the acrylic polymer that can be preferably used as a binder is not particularly limited. At least one monomer selected from nitrile group-containing unsaturated monomer units, crosslinkable monomer units, epoxy group-containing unsaturated monomer units, and acid group-containing monomer units described below Examples include monomers containing units.
• the acid group-containing monomer capable of forming the acid group-containing monomer unit includes, for example, a monomer having a carboxylic acid group, a monomer having a sulfonic acid group, and a monomer having a phosphoric acid group. and a monomer having a hydroxyl group.
• Examples of monomers having a carboxylic acid group include monocarboxylic acids and dicarboxylic acids.
• Monocarboxylic acids include, for example, acrylic acid, methacrylic acid, and crotonic acid.
• 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-methyl propanesulfonic acid, 3-allyloxy-2-hydroxypropanesulfonic acid, and the like.
• (meth)allyl means allyl and/or methallyl
• (meth)acryl means acryl and/or methacryl
• the monomer having a phosphate group includes, for example, 2-(meth)acryloyloxyethyl phosphate, methyl 2-(meth)acryloyloxyethyl phosphate, ethyl phosphate-(meth)acryloyloxyethyl etc.
• (meth)acryloyl means acryloyl and/or methacryloyl.
• Examples of monomers having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate. These acid group-containing monomers may be used singly, or two or more of them may be used in combination at any ratio.
• the proportion of (meth)acrylate monomer units in the acrylic polymer is preferably 50% by mass or more, more preferably 55% by mass or more, still more preferably 58% by mass or more, and preferably 98% by mass. % or less, more preferably 97 mass % or less, and still more preferably 96 mass % or less.
• the proportion of the crosslinkable monomer units in the acrylic polymer is preferably 0.1% by mass or more, more preferably 1.0% by mass or more, and preferably 3.0% by mass or less, more preferably It is 2.5% by mass or less.
• the proportion of acid group-containing monomer units in the acrylic polymer is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and still more preferably 0.5% by mass or more. is 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.
• the glass transition temperature (Tg) of the binder is preferably -100°C or higher, more preferably -90°C or higher, still more preferably -80°C or higher, and preferably lower than 30°C. , more preferably 20° C. or lower, and still more preferably 15° C. or lower. If the glass transition temperature of the binder is equal to or higher than the above lower limit, the adhesiveness and strength of the binder can be enhanced. On the other hand, if the glass transition temperature of the binder is equal to or lower than the above upper limit, the flexibility of the functional layer can be enhanced.
• the volume average particle size of the binder is not particularly limited as long as it is smaller than the volume average particle size of the particulate polymer.
• the volume average particle size of the binder is preferably 0.05 ⁇ m or more, more preferably 0.10 ⁇ m or more, and preferably 0.8 ⁇ m or less. It is more preferably 5 ⁇ m or less.
• the volume average particle size of the binder is at least the above lower limit, it is possible to suppress the deterioration of the ionic conductivity of the functional layer and the deterioration of the output characteristics of the resulting electrochemical device.
• the volume average particle size of the binder is equal to or less than the above upper limit, it is possible to increase the adhesive strength between the components constituting the functional layer and between the functional layer and the adherend.
• the content of the binder in the composition is preferably 40% by mass or more, 50% by mass or more, 70% by mass or less, and 60% by mass per 100% by mass of the particulate polymer. It is below.
• the content of the binder based on 100% by mass of the particulate polymer is at least the above lower limit, the components such as the particulate polymer are prevented from falling off from the functional layer, and the resistance to falling powder is enhanced. can be done.
• the content of the binder based on 100% by mass of the particulate polymer is equal to or less than the above upper limit, the decrease in ionic conductivity of the functional layer is suppressed, and the output characteristics of the resulting electrochemical device are improved. It is possible to suppress the decrease.
• the content of the binder is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass, per 100 parts by mass of the heat-resistant fine particles described later. parts or more, more preferably 0.5 parts by mass or more, preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less.
• the content of the binder is at least the above lower limit, it is possible to suppress the components such as the particulate polymer from falling off from the functional layer, thereby enhancing the resistance to powder falling off.
• the binder content is equal to or less than the above upper limit, it is possible to suppress the deterioration of the ionic conductivity of the functional layer and the deterioration of the output characteristics of the resulting electrochemical device.
• the binder 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 generally the same as the proportion of each monomer unit in the binder.
• the polymerization method and polymerization reaction are not particularly limited, and for example, the polymerization method and polymerization reaction mentioned in the above-described polymerization method of the particulate polymer can be used.
• Heat-resistant fine particles as other components optionally contained in the functional layer composition act to increase the heat resistance of the functional layer.
• Inorganic particles can be mentioned as the heat-resistant fine particles.
• the material of the inorganic particles is stable and electrochemically stable under the operating environment of the electrochemical device.
• preferred materials for the inorganic particles include aluminum oxide (alumina), aluminum oxide hydrate (boehmite (AlOOH)), gibbsite (Al (OH 3 ), silicon oxide, magnesium oxide (magnesia), hydroxide Oxide particles such as magnesium, calcium oxide, titanium oxide (titania), barium titanate (BaTiO 3 ), ZrO, alumina-silica composite oxide; nitride particles such as aluminum nitride and boron nitride; silicon, diamond, etc. Barium sulfate, calcium fluoride, barium fluoride, etc. sparingly soluble ion crystal particles, talc, montmorillonite, etc.
• clay fine particles calcined kaolin, etc.
• aluminum oxide, boehmite, magnesium hydroxide , barium sulfate, calcined kaolin, and barium titanate are more preferable, and aluminum oxide is more preferable.
• the specific gravity of the heat-resistant fine particles is higher than that of the particulate polymer, and the functional layer obtained by coating the composition for the functional layer This is because the particulate polymer can easily come out of the head, and the wet adhesion of the resulting functional layer can be further enhanced.
• these particles may be subjected to element substitution, surface treatment, solid solution conversion, if necessary. etc.
• These heat-resistant fine particles may be used singly, or two or more of them may be used in combination at an arbitrary ratio.
• the volume average particle diameter (D50) of the heat-resistant fine particles is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, still more preferably 0.25 ⁇ m or more, and preferably 1.5 ⁇ m or less, more preferably It is 1.0 ⁇ m or less, more preferably 0.8 ⁇ m or less.
• D50 volume average particle diameter of the heat-resistant fine particles
• the volume average particle diameter of the heat-resistant fine particles is at least the above lower limit, the decrease in ion conductivity in the functional layer can be further suppressed, and the output characteristics of the electrochemical device can be improved.
• the volume average particle diameter of the heat-resistant fine particles is equal to or less than the above upper limit, the functional layer can exhibit excellent heat resistance even when the functional layer is made thin, so that the capacity of the electrochemical device can be increased. can.
• the functional layer composition may contain other optional components in addition to the components described above.
• Other components are not particularly limited as long as they do not affect the electrochemical reaction in the electrochemical element, and examples thereof include known additives such as dispersants, viscosity modifiers and wetting agents. These other components may be used singly or in combination of two or more.
• the method for preparing the composition for the functional layer is not particularly limited. It can be prepared by mixing.
• the particulate polymer and the binder are prepared by polymerizing the monomer composition in the aqueous solvent, the particulate polymer and the binder are directly mixed with other components in the form of an aqueous dispersion. may be mixed with Moreover, when the particulate polymer and the binder are mixed in the form of an aqueous dispersion, the water in the aqueous dispersion may be used as a dispersion medium.
• the method of mixing the components described above is not particularly limited, but it is preferable to mix using a disperser as a mixing device in order to efficiently disperse the components.
• the disperser is preferably a device capable of uniformly dispersing and mixing the above components. Dispersers include ball mills, sand mills, pigment dispersers, grinders, ultrasonic dispersers, homogenizers and planetary mixers.
• the functional layer for an electrochemical device can be formed, for example, on an appropriate base material using the functional layer composition described above.
• the functional layer contains at least the above-described particulate polymer, binder, and other components used as necessary.
• each component contained in the functional layer is the one contained in the composition for the functional layer, and the preferred abundance ratio of each component is the ratio of each component in the composition for the functional layer. It is the same as the preferred abundance ratio. Since the functional layer formed on the substrate has excellent wet adhesion, the electrochemical device provided with the functional layer-attached substrate can exhibit excellent electrochemical characteristics (cycle characteristics and output characteristics). .
• the base material for forming the functional layer is not particularly limited.
• a separator base material can be used as the base material.
• an electrode base material obtained by forming an electrode mixture layer on a current collector can be used as the base material.
• the substrate with a functional layer obtained by forming the functional layer on the substrate using the composition for the functional layer of the electrochemical element can be used as the base material.
• the functional layer is formed on the separator substrate or the like.
• an electrochemical element member such as a separator as it is, or a functional layer may be formed on an electrode substrate and used as an electrode as it is, or a functional layer formed on a release substrate may be used. It may be peeled off once from the base material and attached to another base material to be used as a battery member.
• a separator base material or an electrode base material it is possible to use a separator base material or an electrode base material as the base material, It is preferable to use it as it is as a chemical element member. Since the functional layer formed on the separator base material or the electrode base material contains the particulate polymer described above, it can exhibit good wet adhesiveness. Furthermore, this allows the functional layer to improve the electrochemical properties of the electrochemical device.
• the separator substrate forming the functional layer is not particularly limited, and for example, those described in JP-A-2012-204303 can be used. Among these, polyolefin-based ( A microporous membrane made of resin (polyethylene, polypropylene, polybutene, polyvinyl chloride) is preferred.
• the separator base material may partially include any layer capable of exhibiting a desired function other than the functional layer.
• the electrode base material (positive electrode base material and negative electrode base material) forming the functional layer is not particularly limited, but an electrode base material in which an electrode mixture layer is formed on a current collector is exemplified.
• the components in the current collector, the electrode mixture layer (for example, the electrode active material (positive electrode active material, negative electrode active material) and the binder for the electrode mixture layer (binder for the positive electrode mixture layer, the negative electrode mixture) Binder for material layer), etc.), and a method for forming an electrode mixture layer on a current collector can be a known method, for example, the method described in JP-A-2013-145763 is used. be able to.
• the electrode base material may partially include any layer having an intended function other than the functional layer.
• the release substrate forming the functional layer is not particularly limited, and known release substrates can be used.
• Examples of methods for forming a functional layer on a base material such as the separator base material and the electrode base material include the following methods. 1) A method of applying a functional layer composition to the surface of a separator base material or an electrode base material (in the case of an electrode base material, the surface of the electrode mixture layer side; the same shall apply hereinafter), followed by drying; 2) A method of immersing a separator base material or an electrode base material in the functional layer composition and then drying it; 3) A method of applying a composition for a functional layer onto a release substrate, drying it to produce a functional layer, and transferring the obtained functional layer to the surface of a separator substrate or an electrode substrate; Among these methods, the method 1) is particularly preferable because the film thickness of the functional layer can be easily controlled.
• the method 1) comprises, in detail, a step of applying a composition for a functional layer onto a separator substrate or an electrode substrate (application step); A step of drying the composition to form
• the method of applying the functional layer composition onto the separator base material or electrode base material is not particularly limited, and examples thereof include spray coating, doctor blade method, reverse roll method, direct roll method, gravure method, Methods such as an extrusion method and a brush coating method can be used. Among them, the spray coating method and the gravure method are preferable from the viewpoint of forming a thinner functional layer.
• the method for drying the functional layer composition on the substrate is not particularly limited, and known methods can be used. A drying method by irradiation with an electron beam or the like can be mentioned.
• the drying conditions are not particularly limited, but the drying temperature is preferably 30 to 80° C., and the drying time is preferably 30 seconds to 10 minutes.
• the thickness of the functional layer formed on the substrate is preferably 0.5 ⁇ m or more, more preferably 0.8 ⁇ m or more, still more preferably 1.0 ⁇ m or more, and preferably 15 ⁇ m or less, more preferably 10 ⁇ m or less. , and more preferably 5 ⁇ m or less.
• the thickness of the functional layer is at least the lower limit of the range, the strength of the resulting functional layer can be sufficiently ensured, and when it is at most the upper limit of the range, ions in the functional layer It is possible to ensure diffusibility and further improve the output characteristics of the electrochemical device.
• the binder, the particulate polymer, and the optional heat-resistant fine particles are usually arranged so as to be stacked in the thickness direction of the functional layer. ing. Then, depending on the combination of the specific gravity and size of these compounding components, a relatively large particulate polymer containing a binder may protrude from a filling layer that may contain optional heat-resistant fine particles.
• the thickness of the functional layer can be defined as the vertical distance from the substrate surface on which the functional layer is formed to the binder or heat-resistant fine particles forming the surface of the functional layer. can.
• the electrochemical device provided with the functional layer of the present invention may comprise at least the substrate with the functional layer for an electrochemical device of the present invention. It may have constituent elements other than the functional layer-attached base material.
• the electrochemical device of the present invention is not particularly limited, and is, for example, a lithium ion secondary battery or an electric double layer capacitor, preferably a lithium ion secondary battery.
• the electrochemical device according to the present invention comprises the above-described substrate with a functional layer for an electrochemical device of the present invention. More specifically, in the electrochemical device, at least one of the positive electrode, the negative electrode, and the separator may be made of the functional layer-attached base material for an electrochemical device of the present invention. When the functional layer is present on the separator, the functional layer may be formed on only one side of the separator substrate, or may be formed on both sides of the separator substrate. Since the functional layer of the present invention has excellent wet adhesion, an electrochemical device having such a functional layer has excellent electrochemical characteristics such as cycle characteristics and output characteristics.
• a lithium ion secondary battery as an example of the electrochemical device of the present invention will be described below.
• the positive electrode and negative electrode other than those made of the substrate with a functional layer for an electrochemical device of the present invention, and the electrolytic solution the known positive electrode, negative electrode and electrolytic solution used in lithium ion secondary batteries are used. be able to.
• an organic electrolytic solution in which a supporting electrolyte is dissolved in an organic solvent is usually used.
• a supporting electrolyte for example, a lithium salt is used in a lithium ion secondary battery.
• 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 because they are easily dissolved in a solvent and exhibit a high degree of dissociation.
• an electrolyte may be used individually by 1 type, and may be used in combination of 2 or more types.
• lithium ion conductivity tends to increase as a supporting electrolyte with a higher degree of dissociation is used, so the lithium ion conductivity can be adjusted depending on 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.
• a mixture of these solvents may also be used.
• carbonates are preferable because they have a high dielectric constant and a wide stable potential region.
• the lower the viscosity of the solvent used the higher the lithium ion conductivity tends to be, so the lithium ion conductivity can be adjusted by the type of solvent.
• concentration of the electrolyte in the electrolytic solution can be adjusted as appropriate.
• known additives may be added to the electrolytic solution.
• a lithium ion secondary battery as an electrochemical device of the present invention is, for example, superimposed with the above-described positive electrode and negative electrode via a separator with a functional layer, and if necessary, wound, folded, etc. into a battery container. It can be produced by inserting the battery into the battery container, injecting an electrolytic solution into the battery container, and sealing the battery container.
• expanded metal, fuses, overcurrent protection elements such as PTC elements, lead plates, etc. may be put in the battery container to prevent pressure rise inside the battery and overcharge/discharge.
• the shape of the battery may be, for example, coin-shaped, button-shaped, sheet-shaped, cylindrical, rectangular, or flat.
• ⁇ Glass transition temperature> The particulate polymers and binders prepared in Examples and Comparative Examples were used as measurement samples. Weigh 10 mg of the measurement sample in an aluminum pan, and use an empty aluminum pan as a reference with a differential thermal analysis measurement device (SII Nanotechnology Co., Ltd. "EXSTAR DSC6220"). Measurement was carried out under the conditions specified in JIS Z 8703 at a heating rate of 10° C./min between, and a differential scanning calorimetry (DSC) curve was obtained.
• DII Nanotechnology Co., Ltd. "EXSTAR DSC6220” differential thermal analysis measurement device
• ⁇ Volume average particle size of particulate polymer> The particulate polymers prepared in Examples and Comparative Examples were used as measurement samples. An amount equivalent to 0.1 g of a measurement sample was weighed, placed in a beaker, and 0.1 mL of an alkylbenzenesulfonic acid aqueous solution (manufactured by Fuji Film Co., Ltd., "Drywell”) was added as a dispersant. Further, 10 to 30 mL of a diluent (Beckman Coulter, "Isoton II”) was added to the beaker and dispersed for 3 minutes with a 20 W (Watt) ultrasonic disperser.
• a diluent Beckman Coulter, "Isoton II
• the volume average of the measurement sample was measured under the conditions of aperture diameter: 20 ⁇ m, medium: Isoton II, number of particles to be measured: 100,000. Particle size was measured. The particle diameter (D50) at which the cumulative volume calculated from the small diameter side becomes 50% was taken as the volume average particle diameter of the measurement sample.
• volume average particle size of binder The volume average particle size of the binders prepared in Examples and Comparative Examples was measured by a laser diffraction method. Specifically, an aqueous dispersion containing the prepared binder (adjusted to a solid content concentration of 0.1% by mass) was used as a sample. Then, in the particle size distribution (volume basis) measured using a laser diffraction particle size distribution measuring device (manufactured by Beckman Coulter, "LS-230”), the cumulative volume calculated from the small diameter side is 50%. The particle diameter D50 was taken as the volume average particle diameter.
• the particulate polymers prepared in Examples and Comparative Examples were sufficiently dispersed in a room-temperature-curing epoxy resin and then embedded to prepare a block piece containing the particulate polymer.
• the block piece was cut into a thin piece having a thickness of 80 nm to 200 nm using a microtome equipped with a diamond blade to prepare a sample for measurement. After that, if necessary, the measurement sample was dyed using, for example, ruthenium tetroxide or osmium tetroxide.
• this measurement sample was set in an atomic resolution analysis electron microscope (manufactured by JEOL Ltd., JEM-ARM200F NEOARM), and the cross-sectional structure of the particulate polymer was photographed. The image area was acquired at 125 nm square. 10 specimens were randomly selected from the image area as particles to be measured. After that, elemental analysis was performed using an energy dispersive X-ray spectrometer (EDS) (manufactured by JEOL Ltd., JED-2300). The atom X to be analyzed was an oxygen atom in Examples 1 to 5, 7 to 9, and Comparative Examples 1 to 5, and a nitrogen atom in Example 6.
• EDS energy dispersive X-ray spectrometer
• Region I A region having a depth of 1.0% or more and 1.5% or less in the direction from the outermost surface of the particulate polymer toward the center of the particulate polymer
• Region II From the outermost surface of the particulate polymer Region with a depth of 0.5% or more and less than 1.0% in the direction toward the center of the particulate polymer
• Region III Region from the outermost surface of the particulate polymer to a depth of less than 0.5%
• ⁇ Thickness of functional layer> In Examples and Comparative Examples other than Example 9, the cross section of the separator with the functional layer was observed using a field emission scanning electron microscope (FE-SEM), and the thickness of the inorganic particle layer was determined from the obtained image. Calculated. The thickness of the inorganic particle layer was the vertical distance from the surface of the separator on which the functional layer was formed to the inorganic particles forming the surface of the functional layer. In Example 9, the electrode with the functional layer was used as the observation target, and the same operation as described above was performed, and the vertical direction from the surface of the side electrode base material on which the functional layer was formed to the binder forming the surface of the functional layer. distance.
• FE-SEM field emission scanning electron microscope
• EC ethylene carbonate
• DEC diethyl carbonate
• the stress when one end of the separator was pulled vertically upward and peeled off at a pulling speed of 50 mm/min was measured. The measurement was performed three times in total. Separately, in the same manner as described above, a laminated piece of a negative electrode and a separator was obtained, and the laminated piece was pressed to obtain a test piece. Then, in the same manner as in the case of using the above positive electrode, the test piece after pressing was obtained again, and the stress measurement after immersion in the electrolytic solution was performed a total of three times.
• the second peel strength (N / m)
• the second peel strength (N / m)
• the second peel strength is 3.0 N/m or more and less than 5.0 N/m
• C The second peel strength is 1.0 N/m or more and 3.0 N/m Less than D: Second peel strength less than 1.0 N/m
• ⁇ Blocking resistance of functional layer> Two separators each having a width of 4 cm and a length of 4 cm were cut out from the functional layer-attached separators produced in Examples and Comparative Examples to obtain test pieces. The obtained two test pieces were overlapped with the functional layer sides facing each other, and then pressed for 2 minutes using a flat plate press at a temperature of 40° C. and a load of 8 kN to obtain a pressed body. One end of the obtained pressed body was fixed, and the stress when the other end of the pressed body was pulled vertically upward at a tensile speed of 50 mm/min and peeled off was measured, and the obtained stress was defined as the blocking strength. Then, the blocking strength was evaluated according to the following criteria.
• ⁇ Cycle characteristics of secondary battery> The lithium ion secondary batteries produced in Examples and Comparative Examples were allowed to stand at a temperature of 25° C. for 5 hours. Next, it was charged to a cell voltage of 3.65 V by a constant current method at a temperature of 25° C. and 0.2 C, and then subjected to aging treatment at a temperature of 60° C. for 12 hours. Then, the battery was discharged to a cell voltage of 3.00 V by a constant current method at a temperature of 25° C. and 0.2 C. After that, CC-CV charging (upper limit cell voltage 4.20 V) was performed by a 0.2C constant current method, and CC discharge was performed to 3.00V by a 0.2C constant current method.
• Capacity retention rate ⁇ C' is 90% or more
• Example 1 ⁇ Preparation of particulate polymer> [Preparation of monomer composition (A)] 65 parts of styrene as the aromatic vinyl monomer, 9.5 parts of 2-ethylhexyl acrylate as the (meth)acrylate monomer, 0.5 parts of ethylene glycol dimethacrylate as the crosslinkable monomer, and epoxy A monomer composition (A) was prepared by mixing 5 parts of glycidyl methacrylate as a group-containing unsaturated monomer.
• aqueous solution (A2) obtained by dissolving 5.6 parts of sodium hydroxide in 50 parts of ion-exchanged water is gradually added to an aqueous solution (A1) of 8 parts of magnesium chloride dissolved in 200 parts of ion-exchanged water while stirring. Then, a colloidal dispersion (A) containing magnesium hydroxide as a metal hydroxide was prepared.
• a particulate polymer was prepared by a suspension polymerization method. Specifically, the monomer composition (A) is added to the colloidal dispersion (A) containing magnesium hydroxide, and after further stirring, di(3,5,5-trimethyl) as a polymerization initiator. 2.9 parts of hexanoyl) peroxide (manufactured by NOF Corporation, "Perloyl (registered trademark) 355") was added to obtain a mixed liquid.
• the resulting mixture was stirred with high shear for 1 minute at a rotation speed of 15,000 rpm using an in-line emulsifying disperser ("Cavitron", manufactured by Taiheiyo Kiko Co., Ltd.) to obtain a colloidal dispersion containing magnesium hydroxide (A ) to form mixed droplets of the monomer composition (A).
• an in-line emulsifying disperser (“Cavitron", manufactured by Taiheiyo Kiko Co., Ltd.) to obtain a colloidal dispersion containing magnesium hydroxide (A ) to form mixed droplets of the monomer composition (A).
• the colloidal dispersion (A) containing magnesium hydroxide in which droplets of the monomer composition were formed was placed in a reactor and heated to 70°C to carry out the first polymerization step. At the timing when the polymerization conversion rate reached 90%, 10 parts of styrene as an aromatic vinyl monomer and 10 parts of glycidyl methacrylate as an epoxy group-containing unsaturated monomer were added over 10 minutes. A polymerization reaction was carried out in the double polymerization step to obtain an aqueous dispersion containing a particulate polymer.
• ⁇ Preparation of aqueous dispersion containing binder ( ⁇ )> A reactor equipped with a stirrer was charged with 70 parts of ion-exchanged water, 0.15 parts of sodium lauryl sulfate as an emulsifier (manufactured by Kao Chemical Co., Ltd., "Emal (registered trademark) 2F"), and supersulfic acid as a polymerization initiator. 0.5 part of ammonium was supplied, the gas phase was replaced with nitrogen gas, and the temperature was raised to 60°C.
• Polymerization was carried out by continuously adding the obtained monomer composition ( ⁇ ) to the above-described reactor equipped with a stirrer over 4 hours. The reaction was carried out at 60° C. during the addition. After the addition was completed, the mixture was further stirred at 70° C. for 3 hours, and the reaction was terminated to obtain an aqueous dispersion containing the binder ( ⁇ ) in the form of particles as an acrylic polymer.
• the obtained particulate binder ( ⁇ ) had a volume average particle diameter of 0.25 ⁇ m and a glass transition temperature of -40°C.
• a polyethylene microporous film (thickness: 12 ⁇ m) was prepared as a separator base material.
• the slurry composition obtained as described above was applied to one surface of this separator substrate by a bar coater method.
• the separator base material coated with the slurry composition was dried at 50° C. for 1 minute to form a functional layer.
• the same operation was performed on the other side of the separator base material to prepare a functional layer-attached separator having functional layers on both sides of the separator base material.
• the thickness of the inorganic particle layer in each functional layer was set to 2.0 ⁇ m.
• the positive electrode slurry composition was applied onto a 20 ⁇ m-thick aluminum foil as a current collector by a comma coater so that the film thickness after drying was about 150 ⁇ m, and dried. This drying was carried out by conveying the aluminum foil at a speed of 0.5 m/min in an oven at 60° C. for 2 minutes. After that, heat treatment was performed at 120° C. for 2 minutes to obtain a positive electrode material sheet before pressing. The positive electrode material before pressing was rolled by a roll press to obtain a positive electrode after pressing provided with a positive electrode mixture layer (thickness: 60 ⁇ m).
• SBR negative electrode mixture layer
• 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. After that, the mixture was cooled to 30° C. or less to obtain an aqueous dispersion containing the desired binder for the negative electrode mixture layer.
• 80 parts of artificial graphite (volume average particle size: 15.6 ⁇ m) as negative electrode active material (1) and 16 parts of silicon-based active material SiOx (volume average particle size: 4.9 ⁇ m) as negative electrode active material (2) were blended.
• 2% aqueous solution of carboxymethyl cellulose sodium salt (manufactured by Nippon Paper Industries Co., Ltd., "MAC350HC") as a viscosity modifier was mixed with 2.5 parts equivalent to solid content, and ion-exchanged water to adjust the solid content concentration to 68%. After that, it was further mixed for 60 minutes at 25°C. After adjusting the solid content concentration to 62% with ion-exchanged water, the mixture was further mixed at 25° C. for 15 minutes to obtain a mixed liquid. To this mixture, 1.5 parts of the aqueous dispersion containing the binder for the negative electrode mixture layer was added in terms of the solid content equivalent, and ion-exchanged water was added to adjust the final solid content concentration to 52%.
• carboxymethyl cellulose sodium salt manufactured by Nippon Paper Industries Co., Ltd., "MAC350HC”
• the negative electrode slurry composition was applied onto a copper foil having a thickness of 20 ⁇ m as a current collector with a comma coater so that the film thickness after drying was about 150 ⁇ m, and dried. This drying was carried out by conveying the copper foil at a speed of 0.5 m/min in an oven at 60° C. for 2 minutes. After that, heat treatment was performed at 120° C. for 2 minutes to obtain a negative electrode raw sheet before pressing.
• the unpressed negative electrode material was rolled by a roll press to obtain a pressed negative electrode provided with a negative electrode mixture layer (thickness: 80 ⁇ m).
• the positive electrode after pressing produced as described above was cut into a rectangle of 49 cm ⁇ 5 cm, placed so that the surface on the positive electrode mixture layer side faced upward, and a 120 cm ⁇ 5.5 cm square was placed on the positive electrode mixture layer.
• the cut separator with the functional layer was arranged so that the positive electrode was located on one side in the longitudinal direction of the separator with the functional layer.
• the negative electrode after pressing produced as described above was cut into a rectangle of 50 cm ⁇ 5.2 cm, and placed on the separator with the functional layer so that the surface of the negative electrode mixture layer side faces the separator with the functional layer, and the negative electrode was positioned on the other side in the longitudinal direction of the functional layer-attached separator.
• Example 2 During ⁇ preparation of particulate polymer>, the second polymerization step was started at the point of polymerization conversion rate of 95%, and the concentration distribution of oxygen atoms in regions I and II of the particulate polymer was as shown in Table 1. Various operations, measurements, and evaluations were performed in the same manner as in Example 1, except for the changes. Table 1 shows the results.
• Example 3 During ⁇ preparation of particulate polymer>, the amount of styrene blended in the monomer composition (A) was reduced to 49.5 parts and the amount of 2-ethylhexyl acrylate was increased to 25 parts to obtain particles.
• Various operations, measurements, and evaluations were carried out in the same manner as in Example 1, except that the glass transition temperature of the polymer was adjusted as shown in Table 1. Table 1 shows the results.
• Example 4 ⁇ Preparation of Particulate Polymer> Throughout the process, the amount of styrene was increased to 89 parts, the amount of 2-ethylhexyl acrylate was reduced to 0.5 parts, and the amount of glycidyl methacrylate was reduced to 10 parts. , While maintaining the concentration distribution of oxygen atoms in the regions I to III of the particulate polymer to be the same as in Example 1 by appropriately adjusting the addition timing, the glass transition temperature of the particulate polymer is shown in Table 1. Various operations, measurements, and evaluations were performed in the same manner as in Example 1, except that the results were as shown. Table 1 shows the results.
• Example 5 The same as in Example 1, except that in ⁇ Preparation of particulate polymer>, the average circularity of the particulate polymer prepared as follows using a pulverization method was as shown in Table 1. Various operations, measurements, and evaluations were performed. Table 1 shows the results.
• AIBN azobisisobutyronitrile
• the resulting polymer was then pulverized using a jet mill.
• the obtained pulverized material was classified with an airflow splitter ("100ATP” manufactured by Hosokawa Micron Corporation). After that, the classified pulverized material was subjected to thermal spheroidization treatment to obtain a particulate polymer.
• the thermal spheroidization treatment was performed in an atmosphere at a temperature of 270° C. using a thermal spheroidizer ("SFS3 type" manufactured by Nippon Pneumatic Co., Ltd.).
• Example 6 ⁇ Preparation of particulate polymer>
• glycidyl methacrylate 5 parts of acrylonitrile as a nitrile group-containing unsaturated monomer unit are blended, and In suspension polymerization, various operations, measurements and evaluations were carried out in the same manner as in Example 1, except that 10 parts of acrylonitrile as a nitrile group-containing unsaturated monomer unit was blended in place of glycidyl methacrylate. Table 1 shows the results.
• Example 7 ⁇ Preparation of particulate polymer>, in preparing the monomer composition (A), 9.5 parts of butyl acrylate as a (meth)acrylic acid ester monomer instead of 2-ethylhexyl acrylate Various operations, measurements, and evaluations were carried out in the same manner as in Example 1, except that they were blended. Table 1 shows the results.
• Example 8 In ⁇ Preparation of aqueous dispersion containing binder ( ⁇ )>, except that the composition of the monomer composition ( ⁇ ) was changed as follows to make the monomer composition ( ⁇ ), Various operations, measurements, and evaluations similar to 1 were performed. Table 1 shows the results. 94 parts of 2-ethylhexyl acrylate as a (meth)acrylic acid ester monomer, 2 parts of styrene as an aromatic vinyl monomer, 2 parts of acrylic acid as an acid group-containing monomer, and a crosslinkable monomer 1 part of allyl methacrylate and 1 part of allyl glycidyl ether were mixed to prepare a monomer composition ( ⁇ ).
• Example 9 A functional layer composition was obtained in the same manner as in Example 8 except that the heat-resistant fine particles were not blended, and the resulting functional layer composition was applied to the positive electrode substrate and the negative electrode substrate. Thus, a positive electrode and a negative electrode with a functional layer for an electrochemical device were obtained.
• As the separator a separator with a functional layer coated with the slurry before mixing in ⁇ preparation of composition for functional layer> was used.
• Various operations, measurements, and evaluations were performed in the same manner as in Example 1 except for these points. Table 1 shows the results.
• the positive electrode obtained in the same manner as in Example 1 was used as the positive electrode substrate, and the negative electrode obtained in the same manner as in Example 1 was used as the negative electrode substrate.
• ST indicates styrene
• 2EHA denotes 2-ethylhexyl acrylate
• EDMA indicates ethylene glycol dimethacrylate
• BA indicates n-butyl acrylate
• AN indicates acrylonitrile
• MAA indicates methacrylic acid
• AGE indicates allyl glycidyl ether
• AMA indicates allyl methacrylate
• GMA indicates glycidyl methacrylate.
• the functional layer having excellent wet adhesiveness could be formed by using the functional layer compositions of Examples 1 to 9, which were blended with the particulate polymer satisfying the predetermined atom X distribution structure. I understand. Further, when the functional layer compositions of Comparative Examples 1 to 5, which contain particulate polymers that do not satisfy the predetermined atom X distribution structure, were used, functional layers having excellent wet adhesion could not be formed. I understand that.
• the polymer for functional layers which can be used suitably in order to form the functional layer which is excellent in wet adhesiveness, and its manufacturing method can be provided.
• a functional layer composition capable of forming a functional layer having excellent wet adhesion.
• a substrate with a functional layer for an electrochemical device which is provided with a functional layer for an electrochemical device formed using the composition for a functional layer of the present invention, and an electrochemical device comprising the same are provided. can do.

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