WO2013062088A1 - 導電性接着剤組成物、接着剤層付集電体および電気化学素子電極 - Google Patents
導電性接着剤組成物、接着剤層付集電体および電気化学素子電極 Download PDFInfo
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- WO2013062088A1 WO2013062088A1 PCT/JP2012/077729 JP2012077729W WO2013062088A1 WO 2013062088 A1 WO2013062088 A1 WO 2013062088A1 JP 2012077729 W JP2012077729 W JP 2012077729W WO 2013062088 A1 WO2013062088 A1 WO 2013062088A1
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- water
- soluble polymer
- conductive adhesive
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/668—Composites of electroconductive material and synthetic resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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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
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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- 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 conductive adhesive composition, and in particular, a conductive adhesive layer having a uniform and good adhesion on a current collector surface constituting an electrode of an electrochemical element such as a lithium ion secondary battery or a lithium ion capacitor. It relates to an adhesive composition suitable for forming.
- the present invention also provides a current collector with an adhesive layer having a conductive adhesive layer formed from such an adhesive composition, and an electrode active material layer containing an electrode active material on the conductive adhesive layer of the current collector
- the present invention relates to an electrochemical element electrode in which is formed.
- Lithium-ion secondary batteries have a relatively high energy density, so they are used in the fields of mobile phones and notebook personal computers, and electric double layer capacitors can be charged and discharged rapidly. It is used as a small power source. Furthermore, the electric double layer capacitor is expected to be applied as a large power source for electric vehicles.
- lithium ion capacitors that take advantage of lithium ion secondary batteries and electric double layer capacitors are attracting attention because of their high energy density and power density. With the expansion and development of applications, these electrochemical devices are required to be further improved such as lowering resistance, increasing capacity, and improving mechanical properties.
- These electrochemical elements are provided with a positive electrode and a negative electrode, and by using an organic electrolyte, the operating voltage can be increased and the energy density can be increased.
- an organic electrolyte there is a problem that the contact resistance between the current collector and the electrode active material layer is large, the electrode strength is small, and the internal resistance is large.
- these electrochemical elements can increase the operating voltage and energy density by using an organic electrolytic solution, but on the other hand, since the viscosity of the electrolytic solution is high, there is a problem that the internal resistance is large. there were. Therefore, various studies have been made to solve these problems.
- Patent Document 1 (WO2011 / 13756) includes a conductive material such as carbon black, an acrylic binder, and a conductive material including carboxymethylcellulose (hereinafter, sometimes referred to as “CMC”) as a dispersant.
- CMC carboxymethylcellulose
- the binder for the conductive adhesive as described above, various binder polymers such as diene polymers are used in addition to acrylic polymers, but generally water-insoluble polymers are used as binders. in use.
- the conductive adhesive layer includes CMC used for improving the dispersibility of the conductive material and the binder.
- CMC is contained in the aqueous coating liquid for forming the conductive adhesive layer, it is difficult for water to evaporate from the coating film (adhesive layer) even if the coating liquid is applied and then dried. Takes time. Furthermore, since moisture hardly evaporates, moisture may remain in the adhesive layer. If moisture remains in the adhesive layer, the electrolytic element is decomposed during repeated operation of the electrochemical element, and the lifetime of the electrochemical element is impaired. In addition, since CMC also has an action as a thickener, it is easy to adjust the viscosity of the coating solution, but when the amount is increased to improve dispersibility, the coating solution thickens and the coating thickness increases. It becomes difficult to make the adhesive layer thin.
- an object of the present invention is to provide a conductive adhesive composition used for forming a conductive adhesive layer capable of sufficiently adhering a current collector and an electrode active material layer even if it is thinned.
- the present inventor has continually studied to solve the above problems, and as a dispersant for the conductive adhesive layer provided between the current collector and the electrode active material layer, a water-soluble polymer having a specific composition is used. By using it, the conductive material and the binder are uniformly dispersed, there is little residual moisture after coating and drying, and even if the adhesive layer is thinned, the current collector and the electrode active material layer are sufficiently adhered As a result, the present invention has been completed.
- a conductive adhesive composition comprising a conductive carbon material, a water-soluble polymer and a binder, Conductive adhesion wherein the water-soluble polymer is a copolymer comprising an ethylenically unsaturated carboxylic acid monomer unit, a (meth) acrylic acid ester monomer unit, and a fluorine-containing (meth) acrylic acid ester monomer unit Agent composition.
- a current collector with a conductive adhesive layer comprising a conductive adhesive layer comprising a water-soluble polymer containing a body unit.
- An electrode for an electrochemical element having an electrode active material layer comprising an electrode active material and a binder.
- An electrochemical element comprising a positive electrode, a negative electrode, an electrolytic solution, and a separator, wherein at least one of the positive electrode and the negative electrode is an electrode for an electrochemical element according to (9).
- the composition is obtained.
- the water-soluble polymer has affinity for both the conductive material and the binder constituting the adhesive layer, and can uniformly disperse the conductive material and the binder.
- the coating film can be dried in a short time, and no moisture remains in the resulting coating film (adhesive layer). For this reason, even if the electrochemical device is operated repeatedly, the electrolyte does not decompose and the function of the device is maintained for a long time.
- the adhesive layer can be thinned. Even if the layer is thinned, a conductive adhesive layer that can sufficiently adhere the current collector and the electrode active material layer can be formed. .
- the water-soluble polymer contains an ethylenically unsaturated carboxylic acid monomer unit, a (meth) acrylic acid ester monomer unit, and a fluorine-containing (meth) acrylic acid ester monomer unit.
- the ethylenically unsaturated carboxylic acid monomer unit is considered to improve the adhesion to the current collector and electrode active material layer.
- the (meth) acrylic acid ester monomer unit mainly contributes to the improvement of the flexibility of the conductive adhesive layer.
- alkali resistance is provided to the conductive adhesive layer by including a fluorine-containing (meth) acrylic acid ester monomer unit.
- the slurry for electrode formation may contain an alkaline substance, and the alkaline substance may be generated by oxidation-reduction due to the operation of the electrochemical element.
- Such an alkaline substance corrodes the current collector and impairs the performance and life of the electrochemical device.
- the conductive adhesive layer has alkali resistance, corrosion of the current collector due to the alkaline substance is suppressed. . And by these effects, the high-temperature storage characteristic and high-temperature cycling characteristic, and low-temperature output characteristic of the electrochemical element obtained can be improved with good balance.
- the conductive adhesive composition according to the present invention contains a conductive carbon material, a water-soluble polymer and a binder, and may contain other components as necessary. Hereinafter, each component will be described.
- the form of the conductive carbon material used in the conductive adhesive composition according to the present invention is not particularly limited, but is generally a carbon particle. It is.
- a carbon particle is a particle which consists only of carbon, or consists only of carbon substantially. Specific examples include graphite with high conductivity due to the presence of delocalized ⁇ -electrons (specifically, natural graphite, artificial graphite, etc.), and several layers of graphitic carbon microcrystals gathered together to form a turbulent structure.
- Carbon black specifically, acetylene black, ketjen black, other furnace blacks, channel blacks, thermal lamp blacks, etc.
- carbon fibers carbon whiskers, etc.
- Graphite or carbon black is particularly preferable in that the particles can be packed at high density, the electron transfer resistance of the conductive adhesive layer can be reduced, and the internal resistance of the device can be further reduced.
- These conductive carbon materials may be used alone or in combination of two kinds.
- the electrical resistivity of the conductive carbon material is preferably 0.0001 to 1 ⁇ ⁇ cm, more preferably 0.0005 to 0.5 ⁇ ⁇ cm, and particularly preferably 0.001 to 0.1 ⁇ ⁇ cm.
- the electrical resistivity is a resistance value converged with respect to the pressure measured by continuously applying pressure to the carbon particles using a powder resistance measurement system (MCP-PD51 type: manufactured by Dia Instruments).
- the electrical resistivity ⁇ ( ⁇ ⁇ cm) R ⁇ (S / d) is calculated from R ( ⁇ ), the area S (cm 2 ) and the thickness d (cm) of the compressed carbon particle layer.
- the volume average particle diameter of the conductive carbon material is preferably 0.01 to 20 ⁇ m, more preferably 0.05 to 15 ⁇ m, and particularly preferably 0.1 to 10 ⁇ m.
- the volume average particle diameter of the conductive carbon material is within this range, the conductive carbon material of the conductive adhesive layer is filled with high density, so that the electron transfer resistance is further reduced and the internal resistance of the electrochemical device is further increased. Reduce.
- the volume average particle diameter is a volume average particle diameter calculated by measuring with a laser diffraction particle size distribution analyzer (SALD-3100, manufactured by Shimadzu Corporation).
- the water-soluble polymer is a copolymer containing an ethylenically unsaturated carboxylic acid monomer unit, a (meth) acrylic acid ester monomer unit, and a fluorine-containing (meth) acrylic acid ester monomer unit.
- This copolymer may further contain a crosslinkable monomer unit, a structural unit derived from a functional monomer such as a reactive surfactant monomer, and other copolymer units.
- a structural unit derived from a polymerizable monomer may be contained.
- the ethylenically unsaturated carboxylic acid monomer unit is a structural unit obtained by polymerizing an ethylenically unsaturated carboxylic acid monomer.
- the ethylenically unsaturated carboxylic acid monomer include ethylenically unsaturated monocarboxylic acid and derivatives thereof, ethylenically unsaturated dicarboxylic acid and acid anhydrides thereof, and derivatives thereof.
- Examples of ethylenically unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, and crotonic acid.
- Examples of derivatives of ethylenically unsaturated monocarboxylic acids include 2-ethylacrylic acid, isocrotonic acid, ⁇ -acetoxyacrylic acid, ⁇ -trans-aryloxyacrylic acid, ⁇ -chloro- ⁇ -E-methoxyacrylic acid, And ⁇ -diaminoacrylic acid.
- Examples of ethylenically unsaturated dicarboxylic acids include maleic acid, fumaric acid, and itaconic acid.
- Examples of acid anhydrides of ethylenically unsaturated dicarboxylic acids include maleic anhydride, acrylic anhydride, methyl maleic anhydride, and dimethyl maleic anhydride.
- Examples of derivatives of ethylenically unsaturated dicarboxylic acids include methylmaleic acid, dimethylmaleic acid, phenylmaleic acid, chloromaleic acid, dichloromaleic acid, fluoromaleic acid and the like methylallyl maleate; and diphenyl maleate, nonyl maleate And maleate esters such as decyl maleate, dodecyl maleate, octadecyl maleate and fluoroalkyl maleate.
- ethylenically unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid are preferable. It is because the dispersibility with respect to water of the obtained water-soluble polymer can be improved more.
- the ratio of the ethylenically unsaturated carboxylic acid monomer unit in the water-soluble polymer is preferably 20% by mass or more, more preferably 25% by mass or more, particularly preferably 30% by mass or more, and preferably 60% by mass or less. More preferably, it is 55 mass% or less, Most preferably, it is 50 mass% or less.
- the water-soluble polymer contains the ethylenically unsaturated carboxylic acid monomer unit in such a range, the water-soluble polymer comes to exhibit adhesion to the current collector and the electrode active material layer, and constitutes an electrode. It is considered that the adhesion of each layer is improved.
- the ratio of ethylenically unsaturated carboxylic acid monomer units in the water-soluble polymer is adjusted by the ratio (preparation ratio) of ethylenically unsaturated carboxylic acid monomers in all monomers used for the polymerization of the water-soluble polymer.
- the ratio of the monomer units corresponds to the ratio of monomer (charge ratio).
- the (meth) acrylic acid ester monomer unit is a structural unit obtained by polymerizing a (meth) acrylic acid ester monomer.
- those containing fluorine are distinguished from (meth) acrylate monomers as fluorine-containing (meth) acrylate monomers described later.
- (meth) acryl includes both acrylic and methacryl.
- Examples of (meth) acrylic acid ester monomers include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, Acrylic acid alkyl esters such as 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, lauryl acrylate, n-tetradecyl acrylate, stearyl acrylate; and methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n- Butyl methacrylate, t-butyl methacrylate, pentyl methacrylate, hexyl methacrylate Rate, heptyl
- (Meth) acrylic acid ester monomer may be used alone or in combination of two or more at any ratio. Therefore, the water-soluble polymer may contain only one type of (meth) acrylic acid ester monomer unit, or may contain two or more types in combination at any ratio.
- the ratio of the (meth) acrylic acid ester monomer unit is preferably 30% by mass or more, more preferably 35% by mass or more, particularly preferably 40% by mass or more, and preferably 70%. It is at most mass%, more preferably at most 65 mass%, particularly preferably at most 60 mass%.
- the ratio of (meth) acrylic acid ester monomer units in the water-soluble polymer is adjusted by the ratio (preparation ratio) of (meth) acrylic acid ester monomers in all monomers used for the polymerization of the water-soluble polymer.
- the ratio of the monomer units corresponds to the ratio of monomer (charge ratio).
- Fluorine-containing (meth) acrylic acid ester monomer examples include monomers represented by the following formula (I).
- R 1 represents a hydrogen atom or a methyl group.
- R 2 represents a hydrocarbon group containing a fluorine atom.
- the carbon number of the hydrocarbon group is usually 1 or more and usually 18 or less.
- the number of fluorine atoms contained in R 2 may be one or two or more.
- fluorine-containing (meth) acrylic acid ester monomers represented by formula (I) include (meth) acrylic acid alkyl fluoride, (meth) acrylic acid fluoride aryl, and (meth) acrylic acid fluoride.
- Aralkyl is mentioned.
- alkyl fluoride (meth) acrylate is preferable.
- Specific examples of such a monomer include (meth) acrylic acid-2,2,2-trifluoroethyl, (meth) acrylic acid- ⁇ - (perfluorooctyl) ethyl, (meth) acrylic acid-2.
- One type of fluorine-containing (meth) acrylic acid ester monomer may be used alone, or two or more types may be used in combination at any ratio. Therefore, the water-soluble polymer may contain only one type of fluorine-containing (meth) acrylic acid ester monomer unit, or may contain two or more types in combination at any ratio.
- the ratio of fluorine-containing (meth) acrylate monomer units in the water-soluble polymer is preferably 0.5% by mass or more, more preferably 1% by mass or more, particularly preferably 2% by mass or more, preferably It is 20 mass% or less, More preferably, it is 15 mass% or less, Most preferably, it is 10 mass% or less.
- the ratio of the fluorine-containing (meth) acrylic acid ester monomer unit in the water-soluble polymer is the ratio of the fluorine-containing (meth) acrylate monomer monomer in all the monomers used for the polymerization of the water-soluble polymer (preparation)
- the ratio of the monomer units usually matches the ratio of the monomers (feeding ratio).
- the water-soluble polymer contains a fluorine-containing (meth) acrylic acid ester monomer unit
- alkali resistance is imparted to the conductive adhesive layer.
- the slurry for electrode formation may contain an alkaline substance, and the alkaline substance may be generated by oxidation-reduction due to the operation of the electrochemical element. Such an alkaline substance corrodes the current collector and impairs the life of the electrochemical device.
- the conductive adhesive layer has alkali resistance, corrosion of the current collector due to the alkaline substance is suppressed.
- the crosslinkable monomer water-soluble polymer may further contain a crosslinkable monomer unit in addition to the above structural units.
- the crosslinkable monomer unit is a structural unit capable of forming a crosslinked structure during or after polymerization by heating or energy irradiation of the crosslinkable monomer.
- a monomer having thermal crosslinkability can be usually mentioned. More specifically, a monofunctional monomer having a heat-crosslinkable crosslinkable group and one olefinic double bond per molecule, and a polyfunctional having two or more olefinic double bonds per molecule. Ionic monomers.
- thermally crosslinkable groups contained in the monofunctional monomer include epoxy groups, N-methylolamide groups, oxetanyl groups, oxazoline groups, and combinations thereof.
- an epoxy group is more preferable in terms of easy adjustment of crosslinking and crosslinking density.
- crosslinkable monomer having an epoxy group as a thermally crosslinkable group and having an olefinic double bond examples include vinyl glycidyl ether, allyl glycidyl ether, butenyl glycidyl ether, o-allylphenyl glycidyl.
- Unsaturated glycidyl ethers such as ether; 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; and glycidyl acrylate, glycidyl methacrylate Glycidyl crotonate Unsaturated carboxylic acids such as glycidyl-4-heptenoate, glycidyl sorbate, glycidyl linoleate, glycidyl-4-methyl-3-pentenoate, glycidyl ester of
- crosslinkable monomer having an N-methylolamide group as a thermally crosslinkable group and having an olefinic double bond have a methylol group such as N-methylol (meth) acrylamide (meta ) Acrylamides.
- crosslinkable monomer having an oxetanyl group as a thermally crosslinkable group and having an olefinic double bond examples include 3-((meth) acryloyloxymethyl) oxetane, 3-((meth) Acryloyloxymethyl) -2-trifluoromethyloxetane, 3-((meth) acryloyloxymethyl) -2-phenyloxetane, 2-((meth) acryloyloxymethyl) oxetane, and 2-((meth) acryloyloxymethyl) ) -4-Trifluoromethyloxetane.
- crosslinkable monomer having an oxazoline group as a heat crosslinkable group and having an olefinic double bond examples include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2- Oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, and 2-isopropenyl-5-ethyl-2-oxazoline.
- multifunctional monomers having two or more olefinic double bonds include allyl (meth) acrylate, ethylene di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Tetraethylene glycol di (meth) acrylate, trimethylolpropane-tri (meth) acrylate, dipropylene glycol diallyl ether, polyglycol diallyl ether, triethylene glycol divinyl ether, hydroquinone diallyl ether, tetraallyloxyethane, trimethylolpropane-diallyl Ethers, allyl or vinyl ethers of polyfunctional alcohols other than those mentioned above, triallylamine, methylene bisacrylamide, and divinylbenzene.
- crosslinkable monomer ethylene dimethacrylate, allyl glycidyl ether, and glycidyl methacrylate can be preferably used.
- the ratio is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and particularly preferably 0.5% by mass or more. , Preferably 5% by mass or less, more preferably 4% by mass or less, and particularly preferably 2% by mass or less.
- the ratio of the crosslinkable monomer unit in the water-soluble polymer can be adjusted to or less than the upper limit of the above range, the water-soluble polymer can be improved in water solubility and the dispersibility can be improved. Therefore, by setting the ratio of the crosslinkable monomer unit in the water-soluble polymer within the above range, both the swelling degree and dispersibility of the water-soluble polymer can be improved.
- the ratio of the crosslinkable monomer unit in the water-soluble polymer can be adjusted by the ratio (charge ratio) of the crosslinkable monomer in all monomers used for the polymerization of the water-soluble polymer.
- the ratio of the monomer units corresponds to the ratio of the monomers (feeding ratio).
- monomer unit water-soluble polymers include structural units derived from functional monomers such as reactive surfactant monomers, and other copolymers. Constituent units derived from possible monomers may be included.
- the reactive surfactant monomer is a monomer having a polymerizable group that can be copolymerized with other monomers and having a surfactant group (hydrophilic group and hydrophobic group).
- the reactive surfactant unit obtained by polymerizing the reactive surfactant monomer constitutes a part of the molecule of the water-soluble polymer and is a structural unit that can function as a surfactant.
- the reactive surfactant monomer has a polymerizable unsaturated group, and this group also acts as a hydrophobic group after polymerization.
- the polymerizable unsaturated group that the reactive surfactant monomer has include a vinyl group, an allyl group, a vinylidene group, a propenyl group, an isopropenyl group, and an isobutylidene group.
- the type of the polymerizable unsaturated group may be one type or two or more types.
- the reactive surfactant monomer usually has a hydrophilic group as a portion that exhibits hydrophilicity.
- Reactive surfactant monomers are classified into anionic, cationic and nonionic surfactants depending on the type of hydrophilic group.
- anionic hydrophilic group examples include —SO 3 M, —COOM, and —PO (OH) 2 .
- M represents a hydrogen atom or a cation.
- cations include alkali metal ions such as lithium, sodium and potassium; alkaline earth metal ions such as calcium and magnesium; ammonium ions; ammonium ions of alkylamines such as monomethylamine, dimethylamine, monoethylamine and triethylamine; and Examples include ammonium ions of alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine.
- Examples of the cationic hydrophilic group include —Cl, —Br, —I, and —SO 3 ORX.
- RX represents an alkyl group.
- Examples of RX include methyl group, ethyl group, propyl group, and isopropyl group.
- nonionic hydrophilic group is —OH.
- Suitable reactive surfactant monomers include compounds represented by the following formula (II).
- R represents a divalent linking group. Examples of R include —Si—O— group, methylene group and phenylene group.
- R 3 represents a hydrophilic group. An example of R 3 includes —SO 3 NH 4 .
- n is an integer of 1 or more and 100 or less.
- Another example of a suitable reactive surfactant has a polymerized unit based on ethylene oxide and a polymerized unit based on butylene oxide, and further has an alkenyl group having a terminal double bond and —SO 3 NH 4 at the terminal.
- a compound for example, trade name “Latemul PD-104”, manufactured by Kao Corporation).
- a reactive surfactant monomer may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
- the ratio is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and particularly preferably 0.5% by mass or more. Preferably it is 15 mass% or less, More preferably, it is 10 mass% or less, Most preferably, it is 5 mass% or less.
- the dispersibility of the conductive adhesive composition can be improved by setting the ratio of the reactive surfactant unit in the water-soluble polymer to the lower limit value or more of the above range.
- the durability of the conductive adhesive layer can be improved by setting the ratio of the reactive surfactant unit in the water-soluble polymer to be not more than the upper limit of the above range.
- the water-soluble polymer may have include units obtained by polymerizing the following monomers. That is, styrene monomers such as styrene, chlorostyrene, vinyl toluene, t-butyl styrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl naphthalene, chloromethyl styrene, hydroxymethyl styrene, ⁇ -methyl styrene and divinyl benzene; Amide monomers such as acrylamide and acrylamide-2-methylpropanesulfonic acid; ⁇ , ⁇ -unsaturated nitrile compound monomers such as acrylonitrile and methacrylonitrile; Olefin monomers such as ethylene and propylene; Vinyl chloride , Halogen atom-containing monomers such as vinylidene chloride; vinyl ester monomers such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; vinyl styrene mono
- the water-soluble polymer may have, a monomer containing a sulfonic acid group (—SO 3 H), a monomer containing a phosphoric acid group (—PO 3 H 2 ) Units obtained by polymerizing the like and the like are also included.
- the sulfonic acid group-containing monomer examples include a sulfonic acid group-containing monomer having no functional group other than the sulfonic acid group or a salt thereof, a monomer containing an amide group and a sulfonic acid group, or a salt thereof And monomers containing a hydroxyl group and a sulfonic acid group, or salts thereof.
- these may be used individually by 1 type and may be used combining two or more types by arbitrary ratios. Therefore, the water-soluble polymer may contain only one type of sulfonic acid group-containing monomer unit, or may contain two or more types in combination at any ratio.
- the sulfonic acid group-containing monomer having no functional group other than the sulfonic acid group examples include a monomer sulfonated one of conjugated double bonds of a diene compound such as isoprene and butadiene, vinyl sulfonic acid, Examples thereof include styrene sulfonic acid, allyl sulfonic acid, sulfoethyl methacrylate, sulfopropyl methacrylate, and sulfobutyl methacrylate.
- the salt lithium salt, sodium salt, potassium salt etc. are mentioned, for example. In addition, these may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.
- Examples of the monomer containing an amide group and a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid (AMPS).
- AMPS 2-acrylamido-2-methylpropanesulfonic acid
- salt lithium salt, sodium salt, potassium salt etc. are mentioned, for example. In addition, these may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.
- Examples of the monomer containing a hydroxyl group and a sulfonic acid group include 3-allyloxy-2-hydroxypropanesulfonic acid (HAPS).
- HAPS 3-allyloxy-2-hydroxypropanesulfonic acid
- salt lithium salt, sodium salt, potassium salt etc. are mentioned, for example. In addition, these may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.
- sulfonic acid group-containing monomers include styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid (AMPS), monomers containing amide groups and sulfonic acid groups, or salts thereof. Is preferred.
- the ratio of the sulfonic acid group-containing monomer unit in the water-soluble polymer is preferably 0.1% by weight or more, more preferably 0.2% by weight or more, while preferably 5% by weight or less, more preferably 3% by weight or less.
- the sulfonic acid group-containing monomer unit is contained within the range of the water-soluble polymer, the dispersibility of the slurry for electrode formation may be improved.
- a cross-linked structure may be formed by the sulfonic acid group in the electrode active material layer, which increases the strength of the electrode active material layer, and also provides high temperature storage characteristics and low temperature output of the secondary battery. In some cases, the characteristics can be improved.
- the phosphoric acid group that the phosphoric acid group-containing monomer may have includes a monomer having a group —OP ( ⁇ O) (— OR 4 ) —OR 5 group (R 4 and R 5 are independently , Hydrogen atom, or any organic group), or a salt thereof.
- R 4 and R 5 are independently , Hydrogen atom, or any organic group
- Specific examples of the organic group as R 4 and R 5 include an aliphatic group such as an octyl group, an aromatic group such as a phenyl group, and the like.
- a phosphate group containing monomer the compound containing a phosphate group and an allyloxy group, and a phosphate group containing (meth) acrylic acid ester can be mentioned, for example.
- Examples of the compound containing a phosphate group and an allyloxy group include 3-allyloxy-2-hydroxypropane phosphate.
- Examples of phosphoric acid group-containing (meth) acrylic acid esters include dioctyl-2-methacryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, monomethyl-2-methacryloyloxyethyl phosphate, dimethyl-2-methacryloyloxy Ethyl phosphate, monoethyl-2-methacryloyloxyethyl phosphate, diethyl-2-methacryloyloxyethyl phosphate, monoisopropyl-2-methacryloyloxyethyl phosphate, diisopropyl-2-methacryloyloxyethyl phosphate, mono n-butyl-2 -Methacryloyloxyethyl phosphate, di-n-
- a phosphate group containing monomer may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios. Therefore, the water-soluble polymer may contain only one type of phosphate group-containing monomer unit, or may contain two or more types in combination at any ratio.
- the ratio of the phosphate group-containing monomer unit in the water-soluble polymer is preferably 0.1% by weight or more, more preferably 0.2% by weight or more, while preferably 10% by weight or less, more preferably. Is 5% by weight or less.
- Based on phosphoric acid group-containing monomer units such as improved adhesion between the current collector and the electrode active material layer by including the phosphoric acid-containing monomer units within the range of the water-soluble polymer. When the effect can be obtained, an appropriate degree of polymerization can be obtained in the polymerization of the water-soluble polymer, and an undesirable effect such as a decrease in durability can be prevented in some cases.
- water-soluble polymer in the present specification refers to a polymer having a 1% aqueous solution viscosity of 0.1 to 100,000 mPa ⁇ s at pH 12.
- the solution viscosity of a water-soluble polymer at a pH of 12 when a 1% aqueous solution is prepared is preferably 0.1 to 20000 mPa ⁇ s, more preferably 1 to 10000 mPa ⁇ s, and particularly preferably 10 to 5000 mPa ⁇ s. It is in the range.
- the pH value for adjusting the 1% aqueous solution of the water-soluble polymer is not particularly limited as long as the pH is 7.0 or higher, and the 1% aqueous solution at any pH value of pH 7.0 or higher is used. You may adjust and measure solution viscosity (1% aqueous solution viscosity).
- the measured 1% aqueous solution viscosity of the water-soluble polymer does not change greatly at any pH value as long as the pH is 7.0 or higher. Therefore, the preferable viscosity range of the 1% aqueous solution viscosity at any pH value of pH 7.0 or more of the water-soluble polymer is the same as the above range. If the solution viscosity is too high, the adhesiveness of the conductive adhesive layer to the current collector may be reduced, and if it is too low, the flexibility of the conductive adhesive layer may be reduced.
- the weight average molecular weight of the water-soluble polymer is usually smaller than that of the polymer to be a binder, preferably 100 or more, more preferably 500 or more, particularly preferably 1000 or more, preferably 500000 or less, more preferably 250,000 or less. Particularly preferably, it is 100,000 or less.
- the weight average molecular weight of the water-soluble polymer can be determined by GPC as a value in terms of polystyrene using a solution obtained by dissolving 0.85 g / ml sodium nitrate in a 10% by volume aqueous solution of dimethylformamide.
- the glass transition temperature of the water-soluble polymer is usually 0 ° C. or higher, preferably 5 ° C. or higher, and is usually 100 ° C. or lower, preferably 50 ° C. or lower.
- the glass transition temperature of the water-soluble polymer can be adjusted by combining various monomers.
- the binder used in the present invention is not particularly limited as long as it is a compound capable of binding conductive carbon materials to each other.
- a suitable binder is a dispersion-type binder having a property of being dispersed in a solvent.
- the dispersion-type binder include polymer compounds such as a fluoropolymer, a diene polymer, an acrylate polymer, a polyimide, a polyamide, and a polyurethane polymer, and a fluoropolymer, a diene polymer, or an acrylate polymer is preferable.
- a polymer or an acrylate polymer is more preferable in that the withstand voltage can be increased and the energy density of the electrochemical element can be increased.
- the diene polymer is a homopolymer of a conjugated diene; a copolymer of different types of conjugated dienes; a copolymer obtained by polymerizing a monomer mixture containing a conjugated diene, or a hydrogenated product thereof.
- the ratio of the conjugated diene in the monomer mixture is usually 20% by mass or more, preferably 25% by mass or more, more preferably 30% by mass or more.
- the diene polymer include conjugated diene homopolymers such as polybutadiene and polyisoprene; aromatic vinyl / conjugated diene copolymers such as carboxy-modified styrene / butadiene copolymer (SBR); Copolymers of styrene / butadiene / methacrylic acid copolymer and aromatic vinyl / conjugated diene / carboxylic acid group-containing monomers such as styrene / butadiene / itaconic acid copolymer; acrylonitrile / butadiene copolymer (NBR) And vinyl cyanide / conjugated diene copolymers such as hydrogenated SBR and hydrogenated NBR.
- conjugated diene homopolymers such as polybutadiene and polyisoprene
- aromatic vinyl / conjugated diene copolymers such as carboxy-modified styrene / butadiene copo
- the acrylate polymer is represented by the general formula (1): CH 2 ⁇ CR 1 —COOR 2 (wherein R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkyl group or a cycloalkyl group). It is a polymer containing a monomer unit derived from a compound.
- Specific examples of the compound represented by the general formula (1) include ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, n-amyl acrylate, Acrylates such as isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, nonyl acrylate, lauryl acrylate, stearyl acrylate; ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n methacrylate -Butyl, isobutyl methacrylate, t-butyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate,
- acrylate is preferable, and n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferable in that the strength of the obtained electrode can be improved.
- the ratio of the monomer unit derived from the compound represented by the general formula (1) in the acrylate polymer is usually 50% by mass or more, preferably 70% by mass or more.
- the binder used in the present invention preferably has a polar group.
- the polar group means a functional group capable of dissociating in water or a functional group having polarization.
- an acid group, a nitrile group, an amide group, an amino group, a hydroxyl group, an epoxy group, etc. Is mentioned.
- an acid group, a nitrile group, and an epoxy group are preferable, and an acid group or a nitrile group is more preferable in that the withstand voltage can be increased.
- the binder to be used may have at least one kind of the polar group, but preferably has two or more kinds.
- the binder has two or more types of polar groups, the binding property between the current collector and the electrode active material layer can be further improved.
- Specific combinations in the case of having two types of polar groups include an acid group and a nitrile group, an acid group and an amide group, and an acid group and an amino group.
- the combination in the case of having three or more types of polar groups may be a combination of three types from the exemplified polar groups.
- the polar group in the binder is introduced into the polymer by, for example, using a monomer having a polar group or a polymerization initiator having a polar group when polymerizing the polymer constituting the binder. can do.
- the content ratio of the polar group in the binder is the content ratio of the monomer having a polar group, preferably 0.1 to 40% by mass, more preferably 0.5 to 30% by mass, and particularly preferably 1 to 20% by mass. %.
- Examples of the monomer containing a nitrile group as a polar group include acrylonitrile and methacrylonitrile, and acrylonitrile is preferable in that the withstand voltage can be increased.
- Monomers containing acid groups as polar groups include monobasic acid-containing monomers such as acrylic acid and methacrylic acid, and carboxylic acids such as dibasic acid-containing monomers such as maleic acid, fumaric acid, and itaconic acid.
- Monomer having a group a monomer having a sulfonic acid group such as styrene sulfonic acid and methallyl sulfonic acid, and the like.
- a monomer having a carboxylic acid group is preferable, and the withstand voltage can be increased.
- Dibasic acid-containing monomers are particularly preferred.
- the shape of the binder is not particularly limited, but it has good binding properties with the current collector, and can be prevented from being deteriorated due to a decrease in the capacity of the created electrode or repeated charge / discharge, so it is particulate. Is preferred.
- the particulate binder is not particularly limited as long as it is present in a state where the particle shape is maintained in the conductive adhesive composition, but is preferably one that can be present in a state where the particle shape is also retained in the conductive adhesive layer.
- the “state in which the particle state is maintained” does not have to be a state in which the particle shape is completely maintained, and may be in a state in which the particle shape is maintained to some extent.
- the particulate binder examples include those in which binder particles such as latex are dispersed in water, and powders obtained by drying such a dispersion.
- the particulate binder here is preferably water-insoluble, that is, dispersed in a particulate form without being dissolved in an aqueous solvent.
- the term “insoluble in water” means that at 25 ° C., when 0.5 g of the binder is added to 100 g of water and sufficiently stirred, the insoluble content becomes 90% by weight or more.
- the glass transition temperature (Tg) of the binder is preferably 50 ° C. or lower, more preferably ⁇ 40 to 0 ° C.
- Tg glass transition temperature
- the glass transition temperature (Tg) of the binder is within this range, the binding property is excellent with a small amount of use, the binding property between the current collector and the electrode active material layer is excellent, the electrode strength is strong, and the flexibility is achieved. It is rich, and the electrode density can be easily increased by a pressing process during electrode formation.
- the number average particle diameter is not particularly limited, but is usually 0.0001 to 100 ⁇ m, preferably 0.001 to 10 ⁇ m, more preferably 0.01 to 1 ⁇ m. It is. When the binder is a particulate binder and the number average particle diameter is in this range, an excellent binding force can be imparted to the conductive adhesive layer even with a small amount of use.
- the number average particle diameter is a number average particle diameter calculated as an arithmetic average value obtained by measuring the diameter of 100 binder particles randomly selected in a transmission electron micrograph. The shape of the particles can be either spherical or irregular. These binders can be used alone or in combination of two or more.
- the production method of the binder is not particularly limited.
- the binder can be obtained by emulsion polymerization of a monomer mixture containing monomers constituting each copolymer.
- the method for emulsion polymerization is not particularly limited, and a conventionally known emulsion polymerization method may be employed.
- water, an additive such as a dispersant, an emulsifier, a crosslinking agent, a polymerization initiator, and a monomer are added to a sealed container equipped with a stirrer and a heating device so as to have a predetermined composition, and the composition in the container
- a product is stirred to emulsify monomers and the like in water, and the temperature is increased while stirring to initiate polymerization.
- it is the method of putting into a sealed container and starting reaction similarly.
- Examples of the polymerization initiator used for emulsion polymerization include inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, and hydrogen peroxide; t-butyl peroxide, cumene hydroperoxide, p-menthane hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide Organic peroxides such as oxide and t-butylperoxyisobutyrate; azo compounds such as azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, methyl azobisisobutyrate, etc. Et That.
- inorganic peroxides can be preferably used.
- These polymerization initiators can be used alone or in combination of two or more.
- the peroxide initiator can also be used as a redox polymerization initiator in combination with a reducing agent such as sodium bisulfite.
- the amount of the polymerization initiator used is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the total amount of the monomer mixture used for the polymerization.
- the amount of the polymerization initiator used is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the total amount of the monomer mixture used for the polymerization.
- a chain transfer agent during emulsion polymerization in order to adjust the tetrahydrofuran-insoluble content of the copolymer obtained.
- the chain transfer agent include alkyl mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-stearyl mercaptan; dimethylxanthogen disulfide, diisopropylxanthogendi Xanthogen compounds such as sulfides; thiuram compounds such as terpinolene, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetramethylthiuram monosulfide; phenols such as 2,6-di-t-butyl-4-methyl
- alkyl mercaptans are preferable, and t-dodecyl mercaptan can be more preferably used.
- chain transfer agents can be used alone or in combination of two or more.
- the amount of the chain transfer agent used is preferably 0.05 to 2 parts by mass, more preferably 0.1 to 1 part by mass with respect to 100 parts by mass of the monomer mixture.
- a surfactant may be used during emulsion polymerization. Unlike the reactive surfactant described above, the surfactant is non-reactive and may be any of an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant. Good.
- anionic surfactant examples include sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecyl sulfate, ammonium dodecyl sulfate, sodium octyl sulfate, sodium decyl sulfate, sodium tetradecyl sulfate, sodium hexadecyl sulfate, sodium octadecyl sulfate and the like.
- alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, sodium lauryl benzene sulfonate, sodium hexadecyl benzene sulfonate
- fats such as sodium lauryl sulfonate, sodium dodecyl sulfonate, sodium tetradecyl sulfonate Group sulfonates; and the like.
- the reactive surfactant described above also has a similar emulsifying action, only the reactive surfactant may be used, or a reactive surfactant and a non-reactive surfactant may be used in combination. Furthermore, when a reactive surfactant is not used, emulsion polymerization is stabilized by using the non-reactive surfactant.
- the amount of the surfactant used is preferably 0.5 to 10 parts by mass, more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the monomer mixture.
- seed latex refers to a dispersion of fine particles that becomes the nucleus of the reaction during emulsion polymerization.
- the fine particles often have a particle size of 100 nm or less.
- the fine particles are not particularly limited, and general-purpose polymers such as acrylic polymers are used. According to the seed polymerization method, copolymer particles having a relatively uniform particle diameter can be obtained.
- the polymerization temperature for carrying out the polymerization reaction is not particularly limited, but is usually 0 to 100 ° C., preferably 40 to 80 ° C. Emulsion polymerization is performed in such a temperature range, and the polymerization reaction is stopped at a predetermined polymerization conversion rate by adding a polymerization terminator or cooling the polymerization system.
- the polymerization conversion rate for stopping the polymerization reaction is preferably 93% by mass or more, more preferably 95% by mass or more.
- the unreacted monomer is removed, the pH and solid content concentration are adjusted, and the binder is obtained in a form (latex) in which the particulate copolymer is dispersed in the dispersion medium. . Thereafter, if necessary, the dispersion medium may be replaced, or the dispersion medium may be evaporated to obtain a particulate copolymer in powder form.
- a monomer mixture containing monomers constituting the water-soluble polymer is polymerized in an aqueous solvent to obtain a water-dispersed polymer and alkalized to pH 7-13.
- a method is mentioned.
- an aqueous solvent and a polymerization method it is the same as that of the above-mentioned binder.
- the method for alkalinizing to pH 7 to 13 is not particularly limited, but alkaline earth solutions such as an aqueous alkali metal solution such as an aqueous lithium hydroxide solution, an aqueous sodium hydroxide solution, and an aqueous potassium hydroxide solution, an aqueous calcium hydroxide solution, and an aqueous magnesium hydroxide solution.
- alkaline earth solutions such as an aqueous alkali metal solution such as an aqueous lithium hydroxide solution, an aqueous sodium hydroxide solution, and an aqueous potassium hydroxide solution, an aqueous calcium hydroxide solution, and an aqueous magnesium hydroxide solution.
- alkaline earth solutions such as an aqueous alkali metal solution such as an aqueous lithium hydroxide solution, an aqueous sodium hydroxide solution, and an aqueous potassium hydroxide solution, an aqueous calcium hydroxide solution, and an aqueous magnesium hydroxide solution.
- examples include
- the conductive adhesive composition according to the present invention includes the above-described conductive carbon material, a water-soluble polymer, and a binder. Furthermore, the coating liquid for forming the conductive adhesive layer is a slurry-like composition in which the conductive adhesive composition is dispersed in a dispersion medium.
- the dispersion medium water and various organic solvents can be used without particular limitation as long as the above-described components can be uniformly dispersed and the dispersion state can be stably maintained.
- an adhesive composition without performing operations such as solvent replacement after the emulsion polymerization, and the reaction solvent used during the emulsion polymerization is used as the dispersion medium.
- the reaction solvent used during the emulsion polymerization is used as the dispersion medium.
- water is often used as a reaction solvent, and it is particularly preferable to use water as a dispersion medium from the viewpoint of working environment.
- the coating liquid for the conductive adhesive composition of the present invention may contain a dispersant for dispersing the above-described components.
- the dispersant include cellulosic polymers such as carboxymethylcellulose, methylcellulose, ethylcellulose, and hydroxypropylcellulose, and ammonium salts or alkali metal salts thereof, and poly (meth) acrylates such as sodium poly (meth) acrylate.
- cellulosic polymers such as carboxymethylcellulose, methylcellulose, ethylcellulose, and hydroxypropylcellulose, and ammonium salts or alkali metal salts thereof
- poly (meth) acrylates such as sodium poly (meth) acrylate.
- These dispersants can be used alone or in combination of two or more.
- the use of a water-soluble polymer is proposed as an alternative to the above-mentioned dispersant, but general-purpose dispersions such as carboxymethyl cellulose such as DN-10L (manufactured by Daicel Finechem) are used within the range not impairing the effects of the present invention.
- An agent may be included. If the amount of carboxymethyl cellulose is excessive, it takes time to dry the adhesive layer, and the risk of moisture remaining in the adhesive layer increases. Therefore, the amount of the dispersant as described above is preferably 5 parts by mass or less, more preferably in the range of 0.5 to 3 parts by mass with respect to 100 parts by mass of the conductive carbon material. .
- the content ratio of each component in the conductive adhesive composition according to the present invention is not particularly limited, but from the viewpoint of dispersibility and coating properties of each component, the blending amount of the water-soluble polymer is 100% of the conductive carbon material 100.
- the content is preferably 1 to 30 parts by mass, more preferably 1.5 to 25 parts by mass, and particularly preferably 2 to 20 parts by mass with respect to parts by mass. If the amount of the water-soluble polymer is too large, the relative amount of the conductive carbon material decreases, the internal resistance increases, and the output characteristics may deteriorate. On the other hand, if the blending amount of the water-soluble polymer is too small, the alkali resistance of the adhesive layer is lowered and the current collector may be corroded.
- the blending amount of the binder in the conductive adhesive composition is preferably 0.5 to 20 parts by weight, more preferably 1 to 15 parts by weight, and particularly preferably 2 to 10 parts by weight with respect to 100 parts by weight of the conductive carbon material. Part. When the blending amount of the binder is within such a range, an adhesive layer having good conductivity can be obtained.
- binders, thickeners, anti-aging agents, antifoaming agents, antiseptics, antibacterial agents, anti-blistering agents, pH adjusting agents and the like other than the above may be added to the conductive adhesive composition as necessary. Can do.
- the content ratio of the dispersion medium is preferably 60 to 90% by mass, more preferably 65 to 85% by mass, and particularly preferably 68 to 85% by mass.
- the solid content concentration of the conductive adhesive composition in the coating solution is usually 10 to 60% by mass, preferably 15 to 50% by mass, and particularly preferably 20 to 40% by mass, depending on the coating method. When the solid content concentration is in this range, the conductive adhesive layer is highly filled, and the energy density and output density of the resulting electrochemical device are increased.
- the coating solution of the conductive adhesive composition is in the form of a slurry, and the viscosity thereof is usually 10 to 10,000 mPa ⁇ s, preferably 50 to 5,000 mPa ⁇ s, particularly preferably 100 to 100 ⁇ m depending on the coating method. 2,000 mPa ⁇ s.
- the viscosity of the adhesive composition slurry is within this range, a uniform conductive adhesive layer can be formed on the current collector.
- the method for producing the conductive adhesive composition is not particularly limited, and any means may be used as long as the above solid components can be uniformly dispersed.
- any means may be used as long as the above solid components can be uniformly dispersed.
- water-soluble polymer, binder dispersion, conductive carbon material, and optional components added as needed are mixed together, and then a dispersion medium is added as needed to adjust the solid content concentration of the dispersion. May be.
- the conductive carbon material may be added in a state dispersed in any dispersion medium.
- the water-soluble polymer contains an ethylenically unsaturated carboxylic acid monomer unit, it has high affinity with the conductive carbon material contained in the conductive adhesive composition, and the conductive carbon in the conductive adhesive composition.
- the dispersibility of the material can be improved.
- the current collector with an adhesive layer of the present invention can be obtained by applying and drying the coating liquid (composition slurry) of the above-mentioned conductive adhesive composition on a current collector for an electrochemical element.
- the material of the current collector used in the present invention is not particularly limited as long as it is an electrically conductive and electrochemically durable material.
- a metal, carbon, a conductive polymer, or the like is used.
- a metal is used.
- the current collector metal aluminum, platinum, nickel, tantalum, titanium, stainless steel, copper, other alloys and the like are usually used. Among these, it is preferable to use copper, aluminum, or an aluminum alloy in terms of conductivity and voltage resistance.
- the shape of the current collector used in the present invention is a current collector such as a metal foil or a metal edge foil; a current collector having through-holes such as an expanded metal, a punching metal, or a net (hereinafter referred to as “perforated current collector”) May be described.).
- the ratio of through holes is preferably 10 to 80 area%, more preferably 20 to 60 area%, and particularly preferably 30 to 50 area%. .
- the ratio of the through-hole is in this range, the diffusion resistance of the electrolytic solution is reduced, and the internal resistance of the electrochemical element is reduced.
- the thickness of the current collector used in the present invention is preferably 5 to 100 ⁇ m, more preferably 10 to 70 ⁇ m, and particularly preferably 20 to 50 ⁇ m.
- the method for forming the conductive adhesive layer is not particularly limited. For example, it is formed on the current collector by a doctor blade method, a dip method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, a brush coating, or the like. Moreover, after forming a conductive adhesive layer on release paper, it may be transferred to a current collector.
- Examples of the method for drying the conductive adhesive layer include drying by hot air, hot air, low-humidity air, vacuum drying, and drying by irradiation with (far) infrared rays or electron beams. Of these, a drying method using hot air and a drying method using irradiation with far infrared rays are preferable.
- the drying temperature and the drying time are preferably a temperature and a time at which the solvent in the slurry coated on the current collector can be completely removed, and the drying temperature is usually 50 to 300 ° C., preferably 80 to 250 ° C.
- the drying time is usually 2 hours or less, preferably 5 seconds to 30 minutes.
- the thickness of the conductive adhesive layer is preferably 0.5 to 15 ⁇ m, more preferably 0.8 to ⁇ 10 m, and particularly preferably 1.0 to 5.0 ⁇ m.
- the electrode active material layer and the current collector can be favorably bonded via the adhesive layer, and the electron transfer resistance can be reduced.
- the conductive adhesive layer has a composition corresponding to the solid composition of the conductive adhesive composition, and includes a conductive carbon material, a water-soluble polymer and a binder, and other components added as desired.
- the electrode for an electrochemical element of the present invention has an electrode active material layer on the conductive adhesive layer of the current collector with the adhesive layer.
- the electrode active material layer includes an electrode active material and an electrode binder, and is prepared from an electrode active material layer slurry containing these components.
- the electrode for an electrochemical element of the present invention may be used for either the positive electrode or the negative electrode, or may be used for both.
- the electrode active material used in the present invention is a substance that transfers electrons in an electrode for an electrochemical element.
- the electrode active material mainly includes an active material for a lithium ion secondary battery, an active material for an electric double layer capacitor, and an active material for a lithium ion capacitor.
- Examples of the active material for a lithium ion secondary battery include a positive electrode and a negative electrode.
- the electrode active material used for the positive electrode of the electrode for a lithium ion secondary battery is an active material capable of inserting and removing lithium ions.
- LiCoO 2 , LiNiO 2 , LiMnO 2 , LiMn 2 O 4 , LiFePO 4 4 lithium-containing composite metal oxides such as LiFeVO 4 ; transition metal sulfides such as TiS 2 , TiS 3 , and amorphous MoS 3 ; Cu 2 V 2 O 3 , amorphous V 2 O ⁇ P 2 O 5 , Transition metal oxides such as MoO 3 , V 2 O 5 , V 6 O 13 are exemplified.
- Further examples include conductive polymers such as polyacetylene and poly-p-phenylene. Preferred is a lithium-containing composite metal oxide.
- the electrode active material used for the negative electrode of a lithium ion secondary battery electrode is a material that can reversibly carry electrons (lithium ions) in the negative electrode.
- amorphous carbon, graphite, natural graphite, mesocarbon micro Examples thereof include carbonaceous materials such as beads (MCMB) and pitch-based carbon fibers; and conductive polymers such as polyacene.
- Crystalline carbonaceous materials such as graphite, natural graphite, and mesocarbon microbeads (MCMB) are preferable.
- the shape of the electrode active material used for the electrode for a lithium ion secondary battery is preferably a granulated particle.
- a higher density electrode can be formed during electrode molding.
- the volume average particle diameter of the electrode active material used for the electrode for a lithium ion secondary battery is usually 0.1 to 100 ⁇ m, preferably 1 to 50 ⁇ m, more preferably 5 to 20 ⁇ m for both the positive electrode and the negative electrode.
- the tap density of the electrode active material used for the electrode for the lithium ion secondary battery is not particularly limited, but preferably 2 g / cm 3 or more for the positive electrode and 0.6 g / cm 3 or more for the negative electrode.
- carbon allotrope is usually used as the electrode active material used for the electric double layer capacitor electrode.
- the allotrope of carbon include activated carbon, polyacene, carbon whisker, and graphite, and these powders or fibers can be used.
- a preferred electrode active material is activated carbon, and specific examples include activated carbon made from phenol resin, rayon, acrylonitrile resin, pitch, coconut shell, and the like.
- the volume average particle diameter of the electrode active material used for the electrode for the electric double layer capacitor is usually 0.1 to 100 ⁇ m, preferably 1 to 50 ⁇ m, more preferably 5 to 20 ⁇ m.
- the specific surface area of the electrode active material used for the electrode for the electric double layer capacitor is 30 m 2 / g or more, preferably 500 to 5,000 m 2 / g, more preferably 1,000 to 3,000 m 2 / g. preferable. Since the density of the obtained electrode active material layer tends to decrease as the specific surface area of the electrode active material increases, an electrode active material layer having a desired density can be obtained by appropriately selecting the electrode active material.
- Electrode active materials used for electrodes for lithium ion capacitors include positive and negative electrodes.
- the electrode active material used for the positive electrode of the lithium ion capacitor electrode is not particularly limited as long as it can reversibly carry lithium ions and anions such as tetrafluoroborate.
- an allotrope of carbon is usually used, and electrode active materials used in electric double layer capacitors can be widely used.
- carbon allotropes are used in combination, two or more types of carbon allotropes having different average particle diameters or particle size distributions may be used in combination.
- a polyacene organic semiconductor (PAS) having a polyacene skeleton structure which is a heat-treated product of an aromatic condensation polymer and has an atomic ratio of hydrogen atom / carbon atom of 0.50 to 0.05, can be suitably used.
- PAS polyacene organic semiconductor
- it is an electrode active material used for the electrode for electric double layer capacitors.
- the electrode active material used for the negative electrode of the lithium ion capacitor electrode is a substance that can reversibly carry lithium ions.
- electrode active materials used in the negative electrode of lithium ion secondary batteries can be widely used.
- Preferred examples include crystalline carbon materials such as graphite and non-graphitizable carbon, and polyacene-based materials (PAS) described as the positive electrode active material. These carbon materials and PAS are obtained by carbonizing a phenol resin or the like, activated as necessary, and then pulverized.
- the shape of the electrode active material used for the electrode for the lithium ion capacitor is preferably a granulated particle.
- a higher density electrode can be formed during electrode molding.
- the volume average particle diameter of the electrode active material used for the electrode for a lithium ion capacitor is usually 0.1 to 100 ⁇ m, preferably 1 to 50 ⁇ m, more preferably 5 to 20 ⁇ m for both the positive electrode and the negative electrode.
- These electrode active materials can be used alone or in combination of two or more.
- the electrode binder is not particularly limited as long as it is a compound that can bind the electrode active material and the electrode conductive material described later.
- a suitable binder is a dispersion-type binder having a property of being dispersed in a solvent.
- the dispersion-type binder include polymer compounds such as a fluoropolymer, a diene polymer, an acrylate polymer, a polyimide, a polyamide, and a polyurethane polymer, and a fluoropolymer, a diene polymer, or an acrylate polymer is preferable.
- a polymer or an acrylate polymer is more preferable in that the withstand voltage can be increased and the energy density of the electrochemical element can be increased.
- the diene polymer is a homopolymer of a conjugated diene or a copolymer obtained by polymerizing a monomer mixture containing a conjugated diene, or a hydrogenated product thereof.
- the ratio of the conjugated diene in the monomer mixture is usually 20% by mass or more, preferably 25% by mass or more, more preferably 30% by mass or more.
- the diene polymer include conjugated diene homopolymers such as polybutadiene and polyisoprene; aromatic vinyl / conjugated diene copolymers such as carboxy-modified styrene / butadiene copolymer (SBR); acrylonitrile -Vinyl cyanide * conjugated diene copolymers, such as a butadiene copolymer (NBR); Hydrogenated SBR, hydrogenated NBR, etc. are mentioned.
- conjugated diene homopolymers such as polybutadiene and polyisoprene
- aromatic vinyl / conjugated diene copolymers such as carboxy-modified styrene / butadiene copolymer (SBR); acrylonitrile -Vinyl cyanide * conjugated die
- the acrylate polymer is represented by the general formula (1): CH 2 ⁇ CR 1 —COOR 2 (wherein R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkyl group or a cycloalkyl group). It is a polymer obtained by polymerizing a monomer mixture containing a compound. Specific examples of the compound represented by the general formula include ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, n-amyl acrylate, and isoamyl acrylate.
- Acrylates such as n-hexyl acrylate, 2-ethylhexyl acrylate, hexyl acrylate, nonyl acrylate, lauryl acrylate, stearyl acrylate; ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, Isobutyl methacrylate, t-butyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, isodecyl methacrylate, methacryl Lauryl, tridecyl methacrylate include methacrylates such as such as stearyl methacrylate.
- acrylate is preferable, and n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferable in that the strength of the obtained electrode can be improved.
- the proportion of the monomer units derived from the acrylic ester and / or methacrylic ester in the acrylate polymer is usually 50% by mass or more, preferably 70% by mass or more.
- a copolymerizable carboxylic acid group-containing monomer can be used in addition to the compound represented by the general formula (1).
- Specific examples thereof include acrylic acid and methacrylic acid.
- Examples include basic acid-containing monomers, and dibasic acid-containing monomers such as maleic acid, fumaric acid, and itaconic acid.
- a dibasic acid-containing monomer is preferable, and itaconic acid is particularly preferable in terms of improving the binding property with the conductive adhesive layer and improving the electrode strength.
- These monobasic acid-containing monomers and dibasic acid-containing monomers can be used alone or in combination of two or more.
- the amount of the carboxylic acid group-containing monomer in the monomer mixture is usually 0.1 to 50 parts by mass with respect to 100 parts by mass of the compound represented by the general formula (1).
- the range is preferably 0.5 to 20 parts by mass, more preferably 1 to 10 parts by mass.
- a copolymerizable nitrile group-containing monomer can be used for the acrylate polymer.
- the nitrile group-containing monomer include acrylonitrile, methacrylonitrile, and the like.
- acrylonitrile is preferable in that the binding strength with the conductive adhesive layer is increased and the electrode strength can be improved.
- the amount of acrylonitrile in the monomer mixture at the time of copolymerization is usually 0.1 to 40 parts by mass, preferably 0.5 to 100 parts by mass with respect to 100 parts by mass of the compound represented by the general formula (1). It is in the range of 30 parts by weight, more preferably 1-20 parts by weight. When the amount of acrylonitrile is within this range, the binding strength with the conductive adhesive layer is excellent, and the obtained electrode strength is increased.
- the shape of the binder for the electrode is not particularly limited, but it has good binding properties with the conductive adhesive layer, and can suppress deterioration of the capacity of the prepared electrode and deterioration due to repeated charge and discharge. It is preferable that it is a shape.
- the glass transition temperature (Tg) of the electrode binder is preferably 50 ° C. or lower, more preferably ⁇ 40 to 0 ° C. When the glass transition temperature (Tg) of the electrode binder is within this range, it is excellent in binding property with a small amount of use, strong in electrode strength, rich in flexibility, and easy to increase the electrode density by the press process at the time of electrode formation. Can be increased.
- the number average particle diameter is not particularly limited, but is usually 0.0001 to 100 ⁇ m, preferably 0.001 to 10 ⁇ m, more preferably 0.01 to 1 ⁇ m. .
- the number average particle diameter of the binder for an electrode is within this range, an excellent binding force can be imparted to the electrode even with a small amount of use.
- the number average particle diameter is a number average particle diameter calculated as an arithmetic average value obtained by measuring the diameter of 100 binder particles randomly selected in a transmission electron micrograph.
- the shape of the particles can be either spherical or irregular.
- the amount of the electrode binder is usually in the range of 0.1 to 50 parts by weight, preferably 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the electrode active material. When the amount of the electrode binder is within this range, sufficient adhesion between the obtained electrode active material layer and the conductive adhesive layer can be secured, the capacity of the electrochemical device can be increased, and the internal resistance can be decreased. .
- the electrode active material layer is provided on the conductive adhesive layer, but the formation method is not limited.
- the electrode-forming composition can include an electrode active material and an electrode binder as essential components, and optionally an electrode conductive material, a dispersant, and an additive as optional components.
- the dispersant include cellulosic polymers such as carboxymethylcellulose, methylcellulose, ethylcellulose and hydroxypropylcellulose, and ammonium salts or alkali metal salts thereof; poly (meth) acrylates such as sodium poly (meth) acrylate Polyvinyl alcohol, modified polyvinyl alcohol, polyethylene oxide, polyvinyl pyrrolidone, polycarboxylic acid, oxidized starch, phosphate starch, casein, and various modified starches. These dispersants can be used alone or in combination of two or more. Among these, a cellulose polymer is preferable, and carboxymethyl cellulose or an ammonium salt or an alkali metal salt thereof is particularly preferable.
- the amount of these dispersants is not particularly limited, but is usually 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, more preferably 0.8 parts per 100 parts by weight of the electrode active material. It is in the range of 8 to 2 parts by mass.
- the conductive material for electrodes is made of an allotrope of particulate carbon that has conductivity and does not have pores that can form an electric double layer.
- furnace black, acetylene black, and ketjen black examples thereof include conductive carbon material black such as (Registered trademark of Akzo Nobel Chemicals Beslo Tenfen Note Shap).
- acetylene black and furnace black are preferable.
- the volume average particle diameter of the electrode conductive material is preferably smaller than the volume average particle diameter of the electrode active material, and the range is usually 0.001 to 10 ⁇ m, preferably 0.05 to 5 ⁇ m, more preferably 0.01. ⁇ 1 ⁇ m.
- the amount of the electrode conductive material in the electrode active material layer is usually 0.1 to 50 parts by mass, preferably 0.5 to 15 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the electrode active material. Range. When the amount of the electrode conductive material in the electrode active material layer is within this range, the capacity of the electrochemical element using the obtained electrode for electrochemical element can be increased and the internal resistance can be decreased.
- the paste-like composition for electrode formation (hereinafter sometimes referred to as “slurry for electrode active material layer”) includes an essential component of the electrode active material and the electrode binder, Further, it can be produced by kneading optional components such as a conductive material for electrodes, a dispersant and an additive in water or an organic solvent such as N-methyl-2-pyrrolidone or tetrahydrofuran.
- the solvent used for obtaining the slurry is not particularly limited, but when the above dispersant is used, a solvent capable of dissolving the dispersant is preferably used. Specifically, water is usually used, but an organic solvent may be used, or a mixed solvent of water and an organic solvent may be used.
- organic solvent examples include alkyl alcohols such as methyl alcohol, ethyl alcohol and propyl alcohol; alkyl ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran, dioxane and diglyme; diethylformamide, dimethylacetamide and N-methyl- Amides such as 2-pyrrolidone and dimethylimidazolidinone; sulfur solvents such as dimethyl sulfoxide and sulfolane; and the like.
- alkyl alcohols such as methyl alcohol, ethyl alcohol and propyl alcohol
- alkyl ketones such as acetone and methyl ethyl ketone
- ethers such as tetrahydrofuran, dioxane and diglyme
- diethylformamide dimethylacetamide and N-methyl- Amides
- sulfur solvents such as dimethyl sulfoxide and sulfolane; and the like.
- the slurry for the electrode active material layer is preferably an aqueous slurry using water as a dispersion medium from the viewpoint of easy drying of the electrode active material layer and excellent environmental load.
- water and an organic solvent having a lower boiling point than water are used in combination, the drying rate can be increased during spray drying.
- the dispersibility of the binder or the solubility of the dispersant varies depending on the amount or type of the organic solvent used in combination with water. Thereby, the viscosity and fluidity
- the amount of the solvent used when preparing the slurry is such that the solid content concentration of the slurry is usually in the range of 1 to 90% by mass, preferably 5 to 85% by mass, more preferably 10 to 80% by mass. . When the solid content concentration of the slurry is within this range, it is preferable because each component is uniformly dispersed.
- the method or procedure for dispersing or dissolving the electrode active material, the electrode binder, the electrode conductive material, the dispersant or the additive in the solvent is not particularly limited.
- the electrode active material, the conductive material, the binder, and other dispersions in the solvent Method of adding and mixing agents and additives; Method of dissolving the dispersant in the solvent, adding and mixing the binder dispersed in the solvent, and finally adding and mixing the electrode active material and the conductive material;
- Solvent For example, there may be mentioned a method in which an electrode active material and a conductive material are added to a binder dispersed in the mixture and mixed, and a dispersant dissolved in a solvent is added to the mixture and mixed.
- mixing means examples include mixing equipment such as a ball mill, a sand mill, a bead mill, a pigment disperser, a crusher, an ultrasonic disperser, a homogenizer, a homomixer, and a planetary mixer. Mixing is usually carried out in the range of room temperature to 80 ° C. for 10 minutes to several hours.
- the viscosity of the slurry is usually in the range of 10 to 100,000 mPa ⁇ s, preferably 30 to 50,000 mPa ⁇ s, more preferably 50 to 20,000 mPa ⁇ s at room temperature. When the viscosity of the slurry is within this range, productivity can be increased.
- the method for applying the slurry onto the conductive adhesive layer is not particularly limited. Examples thereof include a doctor blade method, a dip method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, and a brush coating method.
- the coating thickness of the slurry is appropriately set according to the thickness of the target electrode active material layer.
- drying method examples include drying with warm air, hot air, low-humidity air, vacuum drying, and drying by irradiation with (far) infrared rays or electron beams. Among these, a drying method by irradiation with far infrared rays is preferable.
- the drying temperature and the drying time are preferably a temperature and a time at which the solvent in the slurry applied to the current collector can be completely removed.
- the drying temperature is 100 to 300 ° C., preferably 120 to 250 ° C.
- the drying time is usually 10 minutes to 100 hours, preferably 20 minutes to 20 hours.
- the density of the electrode active material layer is not particularly limited, but is preferably 0.30 to 10 g / cm 3 , more preferably 0.35 to 8.0 g / cm 3 , and particularly preferably 0.40 to 6.0 g / cm 3 . 3 .
- the thickness of the electrode active material layer is not particularly limited, but is preferably 5 to 1000 ⁇ m, more preferably 20 to 500 ⁇ m, and particularly preferably 30 to 300 ⁇ m.
- Electrochemical element Examples of usage of the electrode for an electrochemical element include a lithium ion secondary battery, an electric double layer capacitor, a lithium ion capacitor, a sodium battery, and a magnesium battery using the electrode, and a lithium ion secondary battery is preferable. is there.
- a lithium ion secondary battery is composed of the electrochemical element electrode, a separator, and an electrolytic solution.
- the electrochemical element electrode of the present invention may be used for either the positive electrode or the negative electrode, or may be used for both the positive and negative electrodes.
- a separator will not be specifically limited if it can insulate between the electrodes for electrochemical elements, and can pass a cation and an anion.
- a porous separator having pores (a) a porous separator having pores, (b) a porous separator having a polymer coat layer formed on one or both sides, or (c) a porous resin coat layer containing inorganic ceramic powder A porous separator in which is formed.
- Non-limiting examples of these include solids such as polypropylene, polyethylene, polyolefin, or aramid porous separators, polyvinylidene fluoride, polyethylene oxide, polyacrylonitrile, or polyvinylidene fluoride hexafluoropropylene copolymers.
- a polymer film for a polymer electrolyte or a gel polymer electrolyte, a separator coated with a gelled polymer coating layer, or a separator coated with a porous membrane layer made of an inorganic filler or a dispersant for inorganic filler is used. be able to.
- a separator is arrange
- the thickness of the separator is appropriately selected depending on the purpose of use, but is usually 1 to 100 ⁇ m, preferably 10 to 80 ⁇ m, more preferably 20 to 60 ⁇ m.
- the electrolytic solution is not particularly limited.
- a solution obtained by dissolving a lithium salt as a supporting electrolyte in a non-aqueous solvent can be used.
- the lithium salt 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 other lithium salts.
- LiPF 6 , LiClO 4 , and CF 3 SO 3 Li that are easily soluble in a solvent and exhibit a high degree of dissociation are preferably used. These can be used alone or in admixture of two or more.
- the amount of the supporting electrolyte is usually 1% by mass or more, preferably 5% by mass or more, and usually 30% by mass or less, preferably 20% by mass or less, with respect to the electrolytic solution. If the amount of the supporting electrolyte is too small or too large, the ionic conductivity is lowered and the battery charging and discharging characteristics are lowered.
- the solvent used in the electrolytic solution is not particularly limited as long as it can dissolve the supporting electrolyte.
- Alkyl carbonates such as carbonate (BC) and methyl ethyl carbonate (MEC); esters such as ⁇ -butyrolactone and methyl formate; ethers such as 1,2-dimethoxyethane; tetrahydrofuran; sulfolane and dimethyl sulfoxide Sulfur-containing compounds are used.
- dimethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, and methyl ethyl carbonate are preferable because high ion conductivity is easily obtained and the use temperature range is wide. These can be used alone or in admixture of two or more. Moreover, it is also possible to use an electrolyte containing an additive.
- the additive is preferably a carbonate compound such as vinylene carbonate (VC).
- Examples of the electrolytic solution other than the above include a gel polymer electrolyte obtained by impregnating a polymer electrolyte such as polyethylene oxide and polyacrylonitrile with an electrolytic solution, and an inorganic solid electrolyte such as lithium sulfide, LiI, and Li 3 N.
- various general-purpose electrolytes and electrolytes can be used as the electrolyte and electrolyte of the electric double layer capacitor and the lithium ion capacitor without any particular limitation.
- a secondary battery is obtained by stacking a negative electrode and a positive electrode through a separator, and winding and folding the negative electrode and the positive electrode in a battery container according to the shape of the battery, and then injecting an electrolyte into the battery container and sealing it. Further, if necessary, an expanded metal, an overcurrent prevention element such as a fuse or a PTC element, a lead plate and the like can be inserted to prevent an increase in pressure inside the battery and overcharge / discharge.
- the shape of the battery may be any of a laminated cell type, a coin type, a button type, a sheet type, a cylindrical type, a square type, a flat type, and the like.
- the positive electrode for lithium ion secondary batteries produced in Examples and Comparative Examples was cut into a rectangle having a length of 100 mm and a width of 10 mm to obtain a test piece, and cellophane tape was attached to the surface of the electrode active material layer with the electrode active material layer side down. It was. At this time, a cellophane tape defined in JIS Z1522 was used. Moreover, the cellophane tape was fixed to the test bench. Thereafter, the stress was measured when one end of the current collector was pulled off in the vertical direction at a pulling speed of 50 mm / min. This measurement was performed 3 times, the average value was calculated
- the positive electrode active material layer slurry for the secondary battery is dried to a thickness of about 150 ⁇ m on the aluminum current collector formed with the conductive adhesive layer having a thickness of 4 ⁇ m manufactured in Examples and Comparative Examples. And then dried. Such drying was performed by conveying the aluminum current collector in an oven at 60 ° C. at a speed of 0.5 m / min for 2 minutes. Thereafter, heat treatment was performed at 120 ° C. for 2 minutes to obtain a positive electrode for a secondary battery.
- the obtained positive electrode for a secondary battery was cut into 10 cm ⁇ 10 cm, and the number of pinholes having a diameter of 0.1 mm or more was visually measured. It shows that it is excellent in alkali resistance, so that the number of pinholes is small.
- a lithium ion secondary battery of a laminate type cell was prepared and allowed to stand in a 25 ° C. environment for 24 hours.
- the initial capacity C0 was measured by charging to 4.2V and discharging to 3.0V at a discharge rate of 0.1C. Further, the battery was charged to 4.2 V at a charging rate of 0.1 C in a 25 ° C. environment, and then stored for 7 days in a 60 ° C. environment. Next, the capacity C1 after high-temperature storage was measured by discharging to 3.0 V at a discharge rate of 0.1 C in a 25 ° C. environment.
- Example 1 (Production of water-soluble polymer) In a 5 MPa pressure vessel with a stirrer, 59 parts of ethyl acrylate, 32.5 parts of methacrylic acid, 7.5 parts of 2,2,2-trifluoroethyl methacrylate, 1 part of ethylene dimethacrylate (crosslinkable monomer), emulsifier After adding 1.5 parts of polyoxyalkylene alkenyl ether ammonium sulfate (Latemul PD-104, manufactured by Kao Corporation), 150 parts of ion exchange water and 0.5 part of potassium persulfate as a polymerization initiator, To initiate polymerization. When the polymerization conversion rate reached 96%, the reaction was stopped by cooling to obtain an aqueous dispersion containing a water-soluble polymer.
- polyoxyalkylene alkenyl ether ammonium sulfate Lithylene alkenyl ether ammonium sulfate
- the aqueous dispersion containing the water-soluble polymer was adjusted to pH 8 by adding 10% aqueous ammonia to obtain a desired water-soluble polymer aqueous solution.
- the 1% aqueous solution viscosity at pH 12 of the water-soluble polymer was 50 mPa ⁇ s.
- spherical graphite 80 parts of spherical graphite (manufactured by Nippon Carbon Co., Ltd.) having an aspect ratio of 7 and a volume average particle diameter of 1.0 ⁇ m, and furnace black (Super-P) having a volume average particle diameter of 0.4 ⁇ m as carbon black. ; Manufactured by Timcal Co., Ltd.) as a dispersant, 10 parts of a 5.0% aqueous solution of the water-soluble polymer corresponding to the solid content, a glass transition temperature of ⁇ 40 ° C. as a binder, and a number average particle size of 0.
- Solid 40% aqueous dispersion of 25 ⁇ m acrylate polymer (copolymer obtained by emulsion polymerization of monomer mixture containing 2-ethylhexyl acrylate 76% by mass, acrylonitrile 20% by mass, itaconic acid 4% by mass) Eight parts and ion-exchanged water were mixed so that the total solid concentration was 30%, thereby preparing a coating solution (slurry) for the conductive adhesive composition.
- the conductive adhesive composition slurry is discharged from a die onto an aluminum current collector having a thickness of 30 ⁇ m, applied to one side of the current collector at a molding speed of 30 m / min, and dried at 120 ° C. for 5 minutes.
- a conductive adhesive layer having a thickness of 4 ⁇ m was formed.
- An acrylate polymer having a glass transition temperature of ⁇ 40 ° C. and a number average particle size of 0.25 ⁇ m (76% by mass of 2-ethylhexyl acrylate, 20% by mass of acrylonitrile, 4% by mass of itaconic acid) is used as a binder in the above mixture.
- the secondary battery positive electrode active material layer slurry is applied at a speed of 3 m / min on the aluminum current collector on which the conductive adhesive layer is formed, dried at 80 ° C. for 5 minutes, and then heated at 120 ° C. for 5 minutes.
- the positive electrode for secondary batteries of thickness 100micrometer was obtained by processing.
- KS-6 graphite having a volume average particle diameter of 3.7 ⁇ m and a 1.5% aqueous solution of carboxymethyl cellulose ammonium (DN-800H; Daicel Chemical) as a dispersant are used.
- the negative electrode active material layer slurry was applied on one side of a 20 ⁇ m thick copper foil with a comma coater and dried at 110 ° C. for 20 minutes to form a 90 ⁇ m thick negative electrode active material layer. This was rolled with a roll press to obtain a negative electrode for a secondary battery having a negative electrode active material layer thickness of 60 ⁇ m.
- the obtained positive electrode for a secondary battery was cut into a 4 cm ⁇ 4 cm square and arranged so that the current collector-side surface was in contact with the aluminum packaging exterior.
- a 5 cm ⁇ 5 cm square separator was disposed on the surface of the positive electrode active material layer.
- As the separator a single-layer polypropylene separator (thickness 25 ⁇ m, manufactured by a dry method, porosity 55%) was used.
- the negative electrode for secondary batteries was cut into a square of 4.2 cm ⁇ 4.2 cm, and this was arranged on the separator so that the surface on the negative electrode active material layer side faces the separator.
- Example 2 Example 1 (Production of conductive adhesive composition) was the same as Example 1 except that only 100 parts of spherical graphite was used as the conductive carbon material. The results are shown in Table 1.
- Example 3 Example 1 (Production of conductive adhesive composition) was the same as Example 1 except that only 100 parts of carbon black was used as the conductive carbon material. The results are shown in Table 1.
- Example 4 In Example 1 (Production of conductive adhesive composition), instead of an acrylate polymer as a binder, a diene polymer having a glass transition temperature of ⁇ 15 ° C. and a number average particle size of 0.15 ⁇ m (styrene 58. Example 1 except that a copolymer obtained by emulsion polymerization of a monomer mixture containing 5% by mass, 1,3-butadiene 58.5% by mass, and itaconic acid 3% by mass was used. . The results are shown in Table 1.
- Example 5 In Example 1 (Production of conductive adhesive composition), a diene polymer (acrylonitrile 18.5) having a glass transition temperature of ⁇ 36 ° C. and a number average particle size of 0.15 ⁇ m was used instead of an acrylate polymer as a binder. Example 1 except that a copolymer obtained by emulsion polymerization of a monomer mixture containing 5% by mass, 1,3-butadiene 78.5% by mass, and itaconic acid 3% by mass was used. . The results are shown in Table 1.
- Example 6 An aqueous dispersion containing a water-soluble polymer was obtained in the same manner as in Example 1 (Production of water-soluble polymer) except that acrylic acid was used instead of methacrylic acid.
- the 1% aqueous solution viscosity at pH 12 of the water-soluble polymer was 76 mPa ⁇ s.
- the procedure was the same as in Example 1 except that this water-soluble polymer was used. The results are shown in Table 1.
- Example 7 In Example 1 (Production of water-soluble polymer), the amount of ethyl acrylate used was changed to 69.5 parts, and the amount of methacrylic acid used was changed to 22 parts. An aqueous dispersion was obtained. The 1% aqueous solution viscosity at pH 12 of the water-soluble polymer was 24 mPa ⁇ s. The procedure was the same as in Example 1 except that this water-soluble polymer was used. The results are shown in Table 1.
- Example 8 In Example 1 (Production of water-soluble polymer), the amount of ethyl acrylate used was changed to 35.5 parts, and the amount of methacrylic acid used was changed to 56 parts. An aqueous dispersion was obtained. The 1% aqueous solution viscosity at pH 12 of the water-soluble polymer was 1200 mPa ⁇ s. The procedure was the same as in Example 1 except that this water-soluble polymer was used. The results are shown in Table 1.
- Example 9 An aqueous dispersion containing a water-soluble polymer was prepared in the same manner as in Example 1 (Production of water-soluble polymer) except that trifluoromethyl acrylate was used instead of 2,2,2-trifluoroethyl methacrylate. Obtained. The 1% aqueous solution viscosity at pH 12 of the water-soluble polymer was 55 mPa ⁇ s. The procedure was the same as in Example 1 except that this water-soluble polymer was used. The results are shown in Table 1.
- Example 10 An aqueous dispersion containing a water-soluble polymer was prepared in the same manner as in Example 1 (Production of water-soluble polymer) except that perfluorooctyl methacrylate was used instead of 2,2,2-trifluoroethyl methacrylate. Obtained.
- the 1% aqueous solution viscosity at pH 12 of the water-soluble polymer was 70 mPa ⁇ s.
- the procedure was the same as in Example 1 except that this water-soluble polymer was used. The results are shown in Table 1.
- Example 11 In Example 1 (Production of water-soluble polymer), except that the amount of ethyl acrylate used was changed to 55.7 parts and the amount of 2,2,2-trifluoroethyl methacrylate used was changed to 0.8 parts, Similarly, an aqueous dispersion containing a water-soluble polymer was obtained. The 1% aqueous solution viscosity at pH 12 of the water-soluble polymer was 44 mPa ⁇ s. The procedure was the same as in Example 1 except that this water-soluble polymer was used. The results are shown in Table 1.
- Example 12 In the same manner as in Example 1 (Production of water-soluble polymer), except that the amount of ethyl acrylate used was changed to 48.5 parts and the amount of 2,2,2-trifluoroethyl methacrylate used was changed to 18 parts. Thus, an aqueous dispersion containing a water-soluble polymer was obtained. The 1% aqueous solution viscosity at pH 12 of the water-soluble polymer was 78 mPa ⁇ s. The procedure was the same as in Example 1 except that this water-soluble polymer was used. The results are shown in Table 1.
- Example 13 In Example 1 (Production of water-soluble polymer), an aqueous dispersion containing a water-soluble polymer was obtained in the same manner except that allyl glycidyl ether was used instead of ethylene dimethacrylate. The 1% aqueous solution viscosity of the water-soluble polymer at pH 12 was 66 mPa ⁇ s. The procedure was the same as in Example 1 except that this water-soluble polymer was used. The results are shown in Table 1.
- Example 14 An aqueous dispersion containing a water-soluble polymer was obtained in the same manner as in Example 1 (Production of water-soluble polymer) except that glycidyl methacrylate was used instead of ethylene dimethacrylate.
- the 1% aqueous solution viscosity at pH 12 of the water-soluble polymer was 78 mPa ⁇ s.
- the procedure was the same as in Example 1 except that this water-soluble polymer was used. The results are shown in Table 1.
- Example 15 An aqueous dispersion containing a water-soluble polymer was obtained in the same manner as in Example 1 (Production of water-soluble polymer) except that ethylene dimethacrylate was not used.
- the 1% aqueous solution viscosity at pH 12 of the water-soluble polymer was 30 mPa ⁇ s.
- the procedure was the same as in Example 1 except that this water-soluble polymer was used. The results are shown in Table 1.
- Example 16 A water-soluble polymer was prepared in the same manner as in Example 1 (Production of water-soluble polymer) except that the amount of ethyl acrylate used was changed to 59.8 parts and the amount of ethylene dimethacrylate was changed to 0.2 parts. An aqueous dispersion containing was obtained. The 1% aqueous solution viscosity at pH 12 of the water-soluble polymer was 32 mPa ⁇ s. The procedure was the same as in Example 1 except that this water-soluble polymer was used. The results are shown in Table 1.
- Example 17 A water-soluble polymer was prepared in the same manner as in Example 1 (Production of water-soluble polymer) except that the amount of ethyl acrylate used was changed to 58.2 parts and the amount of ethylene dimethacrylate was changed to 1.8 parts. An aqueous dispersion containing was obtained. The viscosity of the 1% aqueous solution at pH 12 of the water-soluble polymer was 880 mPa ⁇ s. The procedure was the same as in Example 1 except that this water-soluble polymer was used. The results are shown in Table 1.
- Example 18 Example 1 (Production of conductive adhesive composition) was the same as Example 1 except that 2 parts of the 5.0% aqueous solution of the water-soluble polymer was used corresponding to the solid content. The results are shown in Table 1.
- Example 19 In Example 1 (Production of conductive adhesive composition), the procedure was the same as Example 1, except that 28 parts of a 5.0% aqueous solution of the water-soluble polymer was used corresponding to the solid content. The results are shown in Table 1.
- Example 1 (Production of conductive adhesive composition) was the same as Example 1 except that 1 part of carboxymethyl cellulose (DN-10L; manufactured by Daicel Finechem) was used corresponding to the solid content. The results are shown in Table 1.
- Example 21 Example 1 (Production of conductive adhesive composition) was the same as Example 1 except that carboxymethylcellulose (DN-10L; manufactured by Daicel Finechem) was used in an amount of 3 parts corresponding to the solid content. The results are shown in Table 1.
- Example 1 (Production of conductive adhesive composition) was the same as Example 1 except that carboxymethylcellulose (CMC) was used instead of the water-soluble polymer as a dispersant. The results are shown in Table 1. The 1% aqueous solution viscosity of CMC was 3500 mPa ⁇ s.
- Example 1 (Production of conductive adhesive composition) was the same as Example 1 except that sodium polyacrylate was used in place of the water-soluble polymer as a dispersant. The results are shown in Table 1. The 1% aqueous solution viscosity of sodium polyacrylate was 150 mPa ⁇ s.
- Example 1 (Production of conductive adhesive composition) was the same as Example 1 except that 35 parts of a 5.0% aqueous solution of the water-soluble polymer was used in an amount corresponding to the solid content. The results are shown in Table 1.
- Example 1 (Production of conductive adhesive composition) was the same as Example 1 except that 35 parts of a 5.0% aqueous solution of the water-soluble polymer was used in an amount corresponding to the solid content. The results are shown in Table 1.
- the reaction was stopped by cooling to obtain an aqueous dispersion containing a water-soluble polymer.
- the 1% aqueous solution viscosity at pH 12 of the water-soluble polymer was 65 mPa ⁇ s.
- Example 1 (Production of conductive adhesive composition) was the same as Example 1 except that the above water-soluble polymer was used. The results are shown in Table 1.
- Example 6 (Comparative Example 6)
- PVDF polyvinylidene fluoride
- Example 1 production of conductive adhesive composition
- PVDF polyvinylidene fluoride
- Example 1 was repeated except that N-methylpyrrolidone was used in place of water as a solvent for the conductive adhesive composition. The results are shown in Table 1.
- Example 22 and Comparative Example 7 evaluated the electric double layer capacitor.
- the evaluation method is as follows.
- a laminate type electric double layer capacitor was produced using the electric double layer capacitor electrode produced in the examples and comparative examples, and allowed to stand in a 25 ° C. environment for 24 hours, and then at a charge rate of 1C.
- the initial capacity C0 was measured by charging to 7V and then discharging to 0V at a discharge rate of 1C. Furthermore, by charging to 2.7 V at a charge rate of 1 C in a 25 ° C. environment, storing for 7 days in a 60 ° C. environment, and then discharging to 0 V at a charge / discharge rate of 1 C in a 25 ° C. environment.
- the capacity C1 after high temperature storage was measured.
- a laminate-type electric double layer capacitor was prepared using the electric double layer capacitor electrode produced in the examples and comparative examples, and allowed to stand at 25 ° C. for 24 hours, and then 2.7 V at a charge rate of 1C. Then, the initial capacity C0 was measured by discharging to 0V at a discharge rate of 1C. Furthermore, after charging to 2.7 V at a charge rate of 1 C in a 60 ° C. environment, a charge / discharge cycle of discharging to 0 V at a discharge rate of 1 C was performed 100 times (100 cycles), and the capacity C2 after 100 cycles was measured.
- a laminate-type electric double layer capacitor was prepared using the electric double layer capacitor electrode produced in the examples and comparative examples, and was allowed to stand for 24 hours. Then, the battery was charged to 7 V, and then discharged at a discharge rate of 1 C in an environment of ⁇ 10 ° C., and the voltage V 10 seconds after the start of discharge was measured.
- Example 22 In the same manner as in Example 1, an aluminum current collector on which a conductive adhesive was formed was obtained.
- aqueous solution (DN-800H; manufactured by Daicel Chemical Industries, Ltd.) corresponding to a solid content of 2.0 parts, acetylene black (denka black powder; manufactured by Denki Kagaku Kogyo Co., Ltd.) as a conductive material, and 5 parts as a binder Diene polymer having a glass transition temperature of ⁇ 40 ° C.
- a number average particle size of 0.25 ⁇ m obtained by emulsion polymerization of a monomer mixture containing 60% by mass of styrene, 35% by mass of butadiene and 5% by mass of itaconic acid
- a planetary mixer so that a 40% aqueous dispersion of the copolymer) is 5 parts in terms of solid content, and ion-exchanged water is 20% in total solid content.
- the slurry for positive and negative electrode active material layers was prepared.
- Electrode for electric double layer capacitor On the aluminum current collector on which the conductive adhesive layer is formed, the electrode active material layer slurry is applied at a speed of 3 m / min, dried at 60 ° C. for 5 minutes, and then dried at 120 ° C. for 5 minutes. A positive electrode and a negative electrode for an electric double layer capacitor having a thickness of 100 ⁇ m were obtained.
- the obtained positive electrode for an electric double layer capacitor was cut into a 4 cm ⁇ 4 cm square and arranged so that the surface on the current collector side was in contact with the aluminum packaging exterior.
- a 5 cm ⁇ 5 cm square separator was disposed on the surface of the positive electrode active material layer.
- the obtained negative electrode for an electric double layer capacitor was cut into a 4.2 cm ⁇ 4.2 cm square, and this was arranged on the separator so that the surface on the negative electrode active material layer side faces the separator.
- the separator cellulose (manufactured by Nippon Kogyo Paper Industries, TF-40) was used.
- Example 7 (Comparative Example 7) In Example 1 (manufacture of a conductive adhesive composition) referred to in Example 22, the same procedure was followed except that carboxymethyl cellulose (CMC) was used as a dispersant instead of the water-soluble polymer. The results are shown in Table 2.
- CMC carboxymethyl cellulose
- Example 23 and Comparative Example 8 evaluated lithium ion capacitors.
- the evaluation method is as follows.
- a laminate type electric double layer capacitor was produced using the lithium ion capacitor electrode produced in the examples and comparative examples, and allowed to stand for 24 hours in an environment of 25 ° C., and then up to 3.8 V at a charge rate of 1 C.
- the initial capacity C0 was measured by charging and discharging to 3.0V at a discharge rate of 1C.
- the capacity C1 after high temperature storage was measured.
- a laminate-type lithium ion capacitor was prepared using the lithium ion capacitor electrodes produced in the examples and comparative examples, and allowed to stand for 24 hours, and then charged to 3.8 V at a charge rate of 1 C in a 25 ° C. environment. did. Thereafter, a discharge operation was performed at a discharge rate of 1 C under a -10 ° C environment, and the voltage V 10 seconds after the start of discharge was measured.
- Example 23 In the same manner as in Example 1, an aluminum current collector on which a conductive adhesive was formed was obtained.
- an electrode active material of the positive electrode 100 parts of an activated carbon powder (CEP-21; manufactured by Nippon Oil Corporation), which is an alkali-activated activated carbon made from petroleum pitch as a raw material, and 1 of carboxymethylcellulose ammonium as a dispersant. 2.0% of 5% aqueous solution (DN-800H; manufactured by Daicel Chemical Industries) corresponding to the solid content, 5 parts of acetylene black (denka black powder; manufactured by Denki Kagaku Kogyo) as the conductive agent, and glass transition as the binder Copolymer obtained by emulsion polymerization of a diene polymer having a temperature of ⁇ 40 ° C.
- CEP-21 activated carbon powder
- DN-800H manufactured by Daicel Chemical Industries
- acetylene black denka black powder
- Denki Kagaku Kogyo glass transition as the binder Copolymer obtained by emulsion polymerization of a diene polymer having a temperature of ⁇ 40
- KS-6 graphite
- DN-800H carboxymethyl cellulose ammonium
- the lithium-ion capacitor negative electrode active material layer slurry is applied at a speed of 3 m / min, dried at 80 ° C. for 5 minutes, and then at 110 ° C. for 5 minutes. This was dried to obtain a lithium ion capacitor negative electrode having a thickness of 100 ⁇ m.
- the obtained positive electrode for a lithium ion capacitor was cut into a 4 cm ⁇ 4 cm square and arranged so that the surface on the current collector side was in contact with the aluminum packaging exterior.
- a 5 cm ⁇ 5 cm square separator was disposed on the surface of the positive electrode active material layer.
- the negative electrode for lithium ion capacitors was cut into a square of 4.2 cm ⁇ 4.2 cm, and this was placed on the separator so that the surface on the negative electrode active material layer side faces the separator.
- the separator cellulose (manufactured by Nippon Kogyo Paper Industries, TF-40) was used.
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Abstract
Description
(1)導電性炭素材料、水溶性重合体およびバインダーを含む導電性接着剤組成物であって、
前記水溶性重合体がエチレン性不飽和カルボン酸単量体単位、(メタ)アクリル酸エステル単量体単位およびフッ素含有(メタ)アクリル酸エステル単量体単位を含む共重合体である導電性接着剤組成物。
電極活物質およびバインダーを含んでなる電極活物質層を有する電気化学素子用電極。
そして、これらの効果により、得られる電気化学素子の高温保存特性や高温サイクル特性と、低温出力特性とを、バランスよく向上させることができる。
本発明に係る導電性接着剤組成物は、導電性炭素材料、水溶性重合体およびバインダーを含み、必要に応じその他の成分を含んでいてもよい。以下、各成分について説明する。
本発明に係る導電性接着剤組成物(以下、単に「接着剤組成物」と記載することがある)に用いる導電性炭素材料は、その形態は特に限定はされないが、一般的には炭素粒子である。炭素粒子とは、炭素のみからなるか、又は実質的に炭素のみからなる粒子である。その具体例としては、非局在化したπ電子の存在によって高い導電性を有する黒鉛(具体的には天然黒鉛、人造黒鉛など)、黒鉛質の炭素微結晶が数層集まって乱層構造を形成した球状集合体であるカーボンブラック(具体的にはアセチレンブラック、ケッチェンブラック、その他のファーネスブラック、チャンネルブラック、サーマルランプブラックなど)、炭素繊維やカーボンウィスカなどが挙げられ、これらの中でも、炭素粒子が高密度に充填し、導電性接着剤層の電子移動抵抗を低減でき、さらに素子の内部抵抗をより低減できる点で、黒鉛又はカーボンブラックが、特に好ましい。これらの導電性炭素材料は、単独で用いてもよいが、二種類を組み合わせて用いてもよい。
水溶性重合体は、エチレン性不飽和カルボン酸単量体単位、(メタ)アクリル酸エステル単量体単位およびフッ素含有(メタ)アクリル酸エステル単量体単位を含む共重合体である。この共重合体には、さらに架橋性単量体単位が含まれていてもよく、また反応性界面活性剤単量体などの機能性を有する単量体から導かれる構成単位や、その他の共重合可能な単量体から導かれる構成単位が含まれていてもよい。
エチレン性不飽和カルボン酸単量体単位は、エチレン性不飽和カルボン酸単量体を重合して得られる構成単位である。エチレン性不飽和カルボン酸単量体の例としては、エチレン性不飽和モノカルボン酸及びその誘導体、エチレン性不飽和ジカルボン酸及びその酸無水物並びにそれらの誘導体が挙げられる。エチレン性不飽和モノカルボン酸の例としては、アクリル酸、メタクリル酸、及びクロトン酸が挙げられる。エチレン性不飽和モノカルボン酸の誘導体の例としては、2-エチルアクリル酸、イソクロトン酸、α-アセトキシアクリル酸、β-trans-アリールオキシアクリル酸、α-クロロ-β-E-メトキシアクリル酸、及びβ-ジアミノアクリル酸が挙げられる。エチレン性不飽和ジカルボン酸の例としては、マレイン酸、フマル酸、及びイタコン酸が挙げられる。エチレン性不飽和ジカルボン酸の酸無水物の例としては、無水マレイン酸、アクリル酸無水物、メチル無水マレイン酸、及びジメチル無水マレイン酸が挙げられる。エチレン性不飽和ジカルボン酸の誘導体の例としては、メチルマレイン酸、ジメチルマレイン酸、フェニルマレイン酸、クロロマレイン酸、ジクロロマレイン酸、フルオロマレイン酸等のマレイン酸メチルアリル;並びにマレイン酸ジフェニル、マレイン酸ノニル、マレイン酸デシル、マレイン酸ドデシル、マレイン酸オクタデシル、マレイン酸フルオロアルキル等のマレイン酸エステルが挙げられる。これらの中でも、アクリル酸、メタクリル酸等のエチレン性不飽和モノカルボン酸が好ましい。得られる水溶性重合体の水に対する分散性がより高めることができるからである。
(メタ)アクリル酸エステル単量体単位は、(メタ)アクリル酸エステル単量体を重合して得られる構成単位である。ただし、(メタ)アクリル酸エステル単量体の中でもフッ素を含有するものは、後述するフッ素含有(メタ)アクリル酸エステル単量体として(メタ)アクリル酸エステル単量体とは区別する。なお、本明細書では、(メタ)アクリルはアクリルおよびメタアクリルの両者を包含する。
フッ素含有(メタ)アクリル酸エステル単量体としては、例えば、下記の式(I)で表される単量体が挙げられる。
水溶性重合体は、上記各構成単位に加え、さらに架橋性単量体単位を含んでいてもよい。架橋性単量体単位は、架橋性単量体を加熱又はエネルギー照射により、重合中又は重合後に架橋構造を形成しうる構造単位である。架橋性単量体の例としては、通常は、熱架橋性を有する単量体を挙げることができる。より具体的には、熱架橋性の架橋性基及び1分子あたり1つのオレフィン性二重結合を有する単官能性単量体、及び1分子あたり2つ以上のオレフィン性二重結合を有する多官能性単量体が挙げられる。
水溶性重合体には、上記各単量体単位に加え、反応性界面活性剤単量体などの機能性を有する単量体から導かれる構成単位や、その他の共重合可能な単量体から導かれる構成単位が含まれていてもよい。
好適な反応性界面活性剤の別の例としては、エチレンオキシドに基づく重合単位及びブチレンオキシドに基づく重合単位を有し、さらに末端に、末端二重結合を有するアルケニル基及び-SO3NH4を有する化合物(例えば、商品名「ラテムルPD-104」、花王株式会社製)を挙げることができる。
反応性界面活性剤単量体は、1種類を単独で用いてもよく、2種類以上を任意の比率で組み合わせて用いてもよい。
リン酸基含有単量体としては、例えば、リン酸基及びアリロキシ基を含む化合物、及びリン酸基含有(メタ)アクリル酸エステルを挙げることができる。リン酸基及びアリロキシ基を含む化合物としては、3-アリロキシ-2-ヒドロキシプロパンリン酸を挙げることができる。リン酸基含有(メタ)アクリル酸エステルとしては、ジオクチル-2-メタクリロイロキシエチルホスフェート、ジフェニル-2-メタクリロイロキシエチルホスフェート、モノメチル-2-メタクリロイロキシエチルホスフェート、ジメチル-2-メタクリロイロキシエチルホスフェート、モノエチル-2-メタクリロイロキシエチルホスフェート、ジエチル-2-メタクリロイロキシエチルホスフェート、モノイソプロピル-2-メタクリロイロキシエチルホスフェート、ジイソプロピル-2-メタクリロイロキシエチルホスフェート、モノn-ブチル-2-メタクリロイロキシエチルホスフェート、ジn-ブチル-2-メタクリロイロキシエチルホスフェート、モノブトキシエチル-2-メタクリロイロキシエチルホスフェート、ジブトキシエチル-2-メタクリロイロキシエチルホスフェート、モノ(2-エチルヘキシル)-2-メタクリロイロキシエチルホスフェート、ジ(2-エチルヘキシル)-2-メタクリロイロキシエチルホスフェートなどが挙げられる。
本発明に用いるバインダーは、導電性炭素材料を相互に結着させることができる化合物であれば特に制限はない。好適なバインダーは、溶媒に分散する性質のある分散型バインダーである。分散型バインダーとして、例えば、フッ素重合体、ジエン重合体、アクリレート重合体、ポリイミド、ポリアミド、ポリウレタン重合体等の高分子化合物が挙げられ、フッ素重合体、ジエン重合体又はアクリレート重合体が好ましく、ジエン重合体又はアクリレート重合体が、耐電圧を高くでき、かつ電気化学素子のエネルギー密度を高くすることができる点でより好ましい。
バインダーは、その製法は特に限定はされないが、上述したように、各共重合体を構成する単量体を含む単量体混合物を、それぞれ乳化重合して得ることができる。乳化重合の方法としては、特に限定されず、従来公知の乳化重合法を採用すればよい。すなわち、攪拌機および加熱装置付きの密閉容器に水と、分散剤、乳化剤、架橋剤などの添加剤と、重合開始剤と、単量体とを所定の組成になるように加え、容器中の組成物を攪拌して単量体等を水に乳化させ、攪拌しながら温度を上昇させて重合を開始する方法である。あるいは、上記組成物を乳化させた後に密閉容器に入れ、同様に反応を開始させる方法である。
本発明に係る導電性接着剤組成物は、上記した導電性炭素材料、水溶性重合体およびバインダーを含む。さらに、導電接着剤層を形成するための塗布液は、上記導電性接着剤組成物が、分散媒に分散されたスラリー状の組成物である。ここで分散媒は、上記各成分を均一に分散でき、安定的に分散状態を保ちうる限り、水、各種有機溶媒が特に制限されることなく使用できる。製造工程の簡素化の観点から、上記の乳化重合後に溶媒置換などの操作を行うことなく、直接接着剤組成物を製造することが好ましく、分散媒としては乳化重合時の反応溶媒を使用することが望ましい。乳化重合時には、水が反応溶媒として用いられることが多く、また作業環境の観点からも水を分散媒とすることが特に好ましい。
本発明に係る導電性接着剤組成物における各成分の含有割合は特に限定はされないが、各成分の分散性や塗工性の観点から、水溶性重合体の配合量は、導電性炭素材料100質量部に対して、好ましくは1~30質量部、さらに好ましくは1.5~25質量部、特に好ましくは2~20質量部の割合で含まれる。水溶性重合体の配合量が多すぎると、導電性炭素材料の相対量が減少し、内部抵抗が増大し、出力特性が低下することがある。一方、水溶性重合体の配合量が少なすぎると、接着剤層の耐アルカリ性が低下し、集電体が腐食されるおそれがある。
本発明の接着剤層付集電体は、上記の導電性接着剤組成物の塗布液(組成物スラリー)を電気化学素子用集電体に塗布乾燥して得られる。
本発明の電気化学素子用電極は、上記接着剤層付集電体の導電性接着剤層上に電極活物質層を有する。電極活物質層は、電極活物質および電極用バインダーを含んでなり、これら成分を含む電極活物質層用スラリーから調整される。本発明の電気化学素子用電極は、正極あるいは負極の何れに用いてもよく、また両方に用いてもよい。
本発明に用いる電極活物質は、電気化学素子用電極内で電子の受け渡しをする物質である。電極活物質には主としてリチウムイオン二次電池用活物質、電気二重層キャパシタ用活物質やリチウムイオンキャパシタ用活物質がある。
電極用バインダーは、電極活物質、後述する電極用導電材を相互に結着させることができる化合物であれば特に制限はない。好適なバインダーは、溶媒に分散する性質のある分散型バインダーである。分散型バインダーとして、例えば、フッ素重合体、ジエン重合体、アクリレート重合体、ポリイミド、ポリアミド、ポリウレタン重合体等の高分子化合物が挙げられ、フッ素重合体、ジエン重合体又はアクリレート重合体が好ましく、ジエン重合体又はアクリレート重合体が、耐電圧を高くでき、かつ電気化学素子のエネルギー密度を高くすることができる点でより好ましい。
電極活物質層は、導電性接着剤層上に設けられるが、その形成方法は制限されない。電極形成用組成物は、電極活物質及び電極用バインダーを必須成分として、必要に応じて、任意成分として、電極用導電材、分散剤および添加剤を配合することができる。分散剤の具体例としては、カルボキシメチルセルロース、メチルセルロース、エチルセルロースおよびヒドロキシプロピルセルロースなどのセルロース系ポリマー、ならびにこれらのアンモニウム塩またはアルカリ金属塩;ポリ(メタ)アクリル酸ナトリウムなどのポリ(メタ)アクリル酸塩;ポリビニルアルコール、変性ポリビニルアルコール、ポリエチレンオキシド、ポリビニルピロリドン、ポリカルボン酸、酸化スターチ、リン酸スターチ、カゼイン、各種変性デンプンなどが挙げられる。これらの分散剤は、それぞれ単独でまたは2種以上を組み合わせて使用できる。中でも、セルロース系ポリマーが好ましく、カルボキシメチルセルロースまたはそのアンモニウム塩もしくはアルカリ金属塩が特に好ましい。これらの分散剤の量は、格別な限定はないが、電極活物質100質量部に対して、通常は0.1~10質量部、好ましくは0.5~5質量部、より好ましくは0.8~2質量部の範囲である。
前記電気化学素子用電極の使用態様としては、かかる電極を用いたリチウムイオン二次電池、電気二重層キャパシタ、リチウムイオンキャパシタ、ナトリウム電池、マグネシウム電池などが挙げられ、リチウムイオン二次電池が好適である。たとえばリチウムイオン二次電池は、上記電気化学素子用電極、セパレータおよび電解液で構成される。これらの電気化学素子において、本発明の電気化学素子用電極は、正極あるいは負極の何れに用いられてもよく、また正負極の両方に用いられてもよい。
セパレータは、電気化学素子用電極の間を絶縁でき、陽イオンおよび陰イオンを通過させることができるものであれば特に限定されない。具体的には、(a)気孔部を有する多孔性セパレータ、(b)片面または両面に高分子コート層が形成された多孔性セパレータ、または(c)無機セラミック粉末を含む多孔質の樹脂コート層が形成された多孔性セパレータが挙げられる。これらの非制限的な例としては、ポリプロピレン系、ポリエチレン系、ポリオレフィン系、またはアラミド系多孔性セパレータ、ポリビニリデンフルオリド、ポリエチレンオキシド、ポリアクリロニトリルまたはポリビニリデンフルオリドヘキサフルオロプロピレン共重合体などの固体高分子電解質用またはゲル状高分子電解質用の高分子フィルム、ゲル化高分子コート層がコートされたセパレータ、または無機フィラー、無機フィラー用分散剤からなる多孔膜層がコートされたセパレータなどを用いることができる。セパレータは、上記一対の電極活物質層が対向するように、電気化学素子用電極の間に配置され、電気化学素子が得られる。セパレータの厚みは、使用目的に応じて適宜選択されるが、通常は1~100μm、好ましくは10~80μm、より好ましくは20~60μmである。
電解液は、特に限定されないが、例えば、非水系の溶媒に支持電解質としてリチウム塩を溶解したものが使用できる。リチウム塩としては、例えば、LiPF6、LiAsF6、LiBF4、LiSbF6、LiAlCl4、LiClO4、CF3SO3Li、C4F9SO3Li、CF3COOLi、(CF3CO)2NLi、(CF3SO2)2NLi、(C2F5SO2)NLiなどのリチウム塩が挙げられる。特に溶媒に溶けやすく高い解離度を示すLiPF6、LiClO4、CF3SO3Liは好適に用いられる。これらは、単独、または2種以上を混合して用いることができる。支持電解質の量は、電解液に対して、通常1質量%以上、好ましくは5質量%以上、また通常は30質量%以下、好ましくは20質量%以下である。支持電解質の量が少なすぎても多すぎてもイオン導電度は低下し電池の充電特性、放電特性が低下する。
実施例および比較例で製造したリチウムイオン二次電池用正極を長さ100mm、幅10mmの長方形に切り出して試験片とし、電極活物質層面を下にして電極活物質層表面にセロハンテープを貼り付けた。この際、セロハンテープとしては、JIS Z1522に規定されるものを用いた。また、セロハンテープは試験台に固定しておいた。その後、集電体の一端を垂直方向に引張り速度50mm/分で引っ張って剥がしたときの応力を測定した。この測定を3回行い、その平均値を求めて、当該平均値をピール強度とした。ピール強度が大きいほど導電性接着剤層と電極活物質層との結着力が大きいこと、すなわち密着強度が大きいことを示す。
実施例および比較例で製造したリチウムイオン二次電池用正極を長さ100mm、幅10mmの長方形に切り出して試験片とし、所定の曲げ径に巻きつけ、目視でひび割れが入らない最小径を最小曲げ径とした。最小曲げ径が小さいほど、柔軟性に優れていることを示す。
実施例および比較例で製造した厚さ4μmの導電性接着剤層を形成したアルミ集電体の上に、二次電池用正極活物質層用スラリーを、乾燥後の膜厚が150μm程度になるように塗布し、乾燥させた。かかる乾燥は、アルミ集電体を0.5m/分の速度で60℃のオーブン内を2分間かけて搬送することにより行った。その後、120℃にて2分間加熱処理して二次電池用正極を得た。得られた二次電池用正極を10cm×10cmに切り出し、目視にて直径0.1mm以上のピンホールの個数を測定した。ピンホールの個数が小さいほど、耐アルカリ性に優れることを示す。
(高温保存特性)
実施例および比較例で製造したリチウムイオン二次電池用正極を用いて、ラミネート型セルのリチウムイオン二次電池を作製し、25℃環境下、24時間静置させた後に、充電レート0.1Cにて、4.2Vまで充電し、放電レート0.1Cにて、3.0Vまで放電することにより、初期容量C0を測定した。さらに、25℃環境下、充電レート0.1Cにて、4.2Vまで充電し、その後、60℃環境下で7日間保存した。次いで、25℃環境下、放電レート0.1Cにて、3.0Vまで放電することにより、高温保存後の容量C1を測定した。高温保存特性は、ΔCs=C1/C0×100(%)で示す容量変化率ΔCsにて評価した。この容量変化率ΔCsが高いほど、高温保存特性に優れることを示す。
実施例および比較例で製造するリチウムイオン二次電池用正極を用いて、ラミネート型セルのリチウムイオン二次電池を作製し、25℃環境下、24時間静置させた後に、充電レート0.1Cにて、4.2Vまで充電し、放電レート0.1Cにて、3.0Vまで放電することにより、初期容量C0を測定した。さらに、60℃環境下で、充電レート0.1Cにて、4.2Vまで充電し、放電レート0.1Cにて、3.0Vまで放電する充放電サイクルを100回(100サイクル)行い、100サイクル後の容量C2を測定した。高温サイクル特性は、ΔCc=C2/C0×100(%)で示す容量変化率ΔCcにて評価した。この容量変化率ΔCcが高いほど高温サイクル特性に優れることを示す。
実施例および比較例で製造するリチウムイオン二次電池用正極を用いて、ラミネート型セルのリチウムイオン二次電池を作製し、25℃環境下、24時間静置させた後に、充電レート0.1Cにて、4.2Vまで充電し、放電レート0.1Cにて、3.0Vまで放電した。その後、25℃環境下、0.1C、5時間の充電操作を行い、このときの電圧V0を測定した。その後、-25℃環境下、放電レート0.1Cにて放電の操作を行い、放電開始10秒後の電圧V1を測定した。低温出力特性は、ΔV=V0-V1で示す電圧変化ΔVにて評価した。この電圧変化ΔVが小さいほど低温出力特性に優れることを示す。
実施例および比較例で製造する導電性接着剤層付集電体を、カールフィッシャー法(使用装置名:カールフィッシャー水分計(京都電子工業社製))により、導電性接着剤層の水分量を測定した。導電性接着剤層の水分量が小さいほど耐久性に優れることを示す。
(水溶性重合体の製造)
攪拌機付き5MPa耐圧容器に、アクリル酸エチル59部、メタアクリル酸32.5部、2,2,2-トリフルオロエチルメタクリレート7.5部、エチレンジメタクリレート(架橋性単量体)1部、乳化剤としてポリオキシアルキレンアルケニルエーテル硫酸アンモニウム(ラテムルPD-104、花王社製)1.5部、イオン交換水150部及び重合開始剤として過硫酸カリウム0.5部を入れ、十分に攪拌した後、60℃に加温して重合を開始した。重合転化率が96%になった時点で冷却し反応を停止して、水溶性重合体を含む水分散液を得た。
球状黒鉛として、アスペクト比が7で、体積平均粒子径が1.0μmの球状黒鉛(日本カーボン社製)を80部、カーボンブラックとして、体積平均粒子径が0.4μmのファーネスブラック(Super-P;ティムカル社製)を20部、分散剤として前記水溶性重合体の5.0%水溶液を固形分相当で10部、バインダーとして、ガラス転移温度が-40℃で、数平均粒子径が0.25μmのアクリレート重合体(アクリル酸2-エチルヘキシル76質量%、アクリロニトリル20質量%、イタコン酸4質量%を含む単量体混合物を乳化重合して得られる共重合体)の40%水分散体を固形分相当で8部及びイオン交換水を全固形分濃度が30%となるように混合し、導電性接着剤組成物の塗布液(スラリー)を調製した。
ディスパー付きのプラネタリーミキサーに、正極活物質としてNi-Mn-Coのリチウム複合酸化物(Ni:Mn:Co=8:1:1、平均粒子径:11.3μm)を100部、分散剤としてCMC(MAC350HC、日本製紙ケミカル社製)の2%水溶液を固形分相当で1部をそれぞれ加え、イオン交換水で固形分濃度60%に調整した後、25℃で60分混合した。次に、イオン交換水で固形分濃度57%に調整した後、さらに25℃で15分混合し混合液を得た。
前記導電性接着剤層を形成したアルミ集電体上に、前記二次電池正極活物質層用スラリーを速度3m/分で塗工し、80℃で5分乾燥後、120℃で5分間加熱処理して、厚さ100μmの二次電池用正極を得た。
負極の電極活物質として、体積平均粒子径が3.7μmである黒鉛(KS-6;ティムカル社製)を100部、分散剤としてカルボキシメチルセルロースアンモニウムの1.5%水溶液(DN-800H;ダイセル化学工業社製)を固形分相当で2.0部、導電剤としてアセチレンブラック(デンカブラック粉状;電気化学工業社製)を5部、バインダーとして、ガラス転移温度が-40℃、数平均粒子径が0.25μmのジエン重合体(スチレン60質量%、ブタジエン35質量%、イタコン酸5質量%を含む単量体混合物を乳化重合して得られる共重合体)の40%水分散体を固形分相当で5部、並びにイオン交換水を全固形分濃度が20%となるようにプラネタリーミキサーにより混合し、負極活物質層用スラリーを調製した。
厚さ20μmの銅箔の片面上に、前記負極活物質層用スラリーを、コンマコーターで塗布し、110℃で20分間乾燥して、厚さ90μmの負極活物質層を形成した。これをロールプレスで圧延して、負極活物質層の厚さが60μmの二次電池用負極を得た。
上記得られた二次電池用正極を、4cm×4cmの正方形に切り出し、集電体側の表面がアルミ包材外装に接するように配置した。正極活物質層の面上に、5cm×5cmの正方形のセパレータを配置した。セパレータは、単層のポリプロピレン製セパレータ(厚さ25μm、乾式法により製造、気孔率55%)を用いた。さらに、二次電池用負極を、4.2cm×4.2cmの正方形に切り出し、これをセパレータ上に、負極活物質層側の表面がセパレータに向かい合うよう配置した。さらに、電解液として1.0MLiPF6(溶媒EC/EMC=3/7体積比)を用い、アルミ包材の開口を密封するために、150℃のヒートシールをしてアルミ外装を閉口し、リチウムイオン二次電池を製造した。
実施例1の(導電性接着剤組成物の製造)において、導電性炭素材料として、球状黒鉛100部のみを用いた他は、実施例1と同様とした。結果を表1に示す。
実施例1の(導電性接着剤組成物の製造)において、導電性炭素材料として、カーボンブラック100部のみを用いた他は、実施例1と同様とした。結果を表1に示す。
実施例1の(導電性接着剤組成物の製造)において、バインダーとして、アクリレート重合体に代えて、ガラス転移温度が-15℃、数平均粒子径が0.15μmのジエン重合体(スチレン58.5質量%、1,3-ブタジエン58.5質量%、イタコン酸3質量%を含む単量体混合物を乳化重合して得られる共重合体)を用いた他は、実施例1と同様とした。結果を表1に示す。
実施例1の(導電性接着剤組成物の製造)において、バインダーとして、アクリレート重合体に代えて、ガラス転移温度が-36℃、数平均粒子径が0.15μmのジエン重合体(アクリロニトリル18.5質量%、1,3-ブタジエン78.5質量%、イタコン酸3質量%を含む単量体混合物を乳化重合して得られる共重合体)を用いた他は、実施例1と同様とした。結果を表1に示す。
実施例1の(水溶性重合体の製造)において、メタアクリル酸に代えてアクリル酸を用いた他は、同様にして水溶性重合体を含む水分散液を得た。該水溶性重合体の、pH12における、1%水溶液粘度は、76mPa・sであった。この水溶性重合体を用いた他は、実施例1と同様とした。結果を表1に示す。
実施例1の(水溶性重合体の製造)において、アクリル酸エチルの使用量を69.5部、メタアクリル酸の使用量を22部に変更した他は、同様にして水溶性重合体を含む水分散液を得た。該水溶性重合体の、pH12における、1%水溶液粘度は、24mPa・sであった。この水溶性重合体を用いた他は、実施例1と同様とした。結果を表1に示す。
実施例1の(水溶性重合体の製造)において、アクリル酸エチルの使用量を35.5部、メタアクリル酸の使用量を56部に変更した他は、同様にして水溶性重合体を含む水分散液を得た。該水溶性重合体の、pH12における、1%水溶液粘度は、1200mPa・sであった。この水溶性重合体を用いた他は、実施例1と同様とした。結果を表1に示す。
実施例1の(水溶性重合体の製造)において、2,2,2-トリフルオロエチルメタクリレートに代えてトリフルオロメチルアクリレートを用いた他は、同様にして水溶性重合体を含む水分散液を得た。該水溶性重合体の、pH12における、1%水溶液粘度は、55mPa・sであった。この水溶性重合体を用いた他は、実施例1と同様とした。結果を表1に示す。
実施例1の(水溶性重合体の製造)において、2,2,2-トリフルオロエチルメタクリレートに代えてパーフルオロオクチルメタクリレートを用いた他は、同様にして水溶性重合体を含む水分散液を得た。該水溶性重合体の、pH12における、1%水溶液粘度は、70mPa・sであった。この水溶性重合体を用いた他は、実施例1と同様とした。結果を表1に示す。
実施例1の(水溶性重合体の製造)において、アクリル酸エチルの使用量を55.7部、2,2,2-トリフルオロエチルメタクリレートの使用量を0.8部に変更した他は、同様にして水溶性重合体を含む水分散液を得た。該水溶性重合体の、pH12における、1%水溶液粘度は、44mPa・sであった。この水溶性重合体を用いた他は、実施例1と同様とした。結果を表1に示す。
実施例1の(水溶性重合体の製造)において、アクリル酸エチルの使用量を48.5部、2,2,2-トリフルオロエチルメタクリレートの使用量を18部に変更した他は、同様にして水溶性重合体を含む水分散液を得た。該水溶性重合体の、pH12における、1%水溶液粘度は、78mPa・sであった。この水溶性重合体を用いた他は、実施例1と同様とした。結果を表1に示す。
実施例1の(水溶性重合体の製造)において、エチレンジメタクリレートに代えて、アリルグリシジルエーテルを用いた他は、同様にして水溶性重合体を含む水分散液を得た。該水溶性重合体の、pH12における、1%水溶液粘度は、66mPa・sであった。この水溶性重合体を用いた他は、実施例1と同様とした。結果を表1に示す。
実施例1の(水溶性重合体の製造)において、エチレンジメタクリレートに代えて、グリシジルメタアクリレートを用いた他は、同様にして水溶性重合体を含む水分散液を得た。該水溶性重合体の、pH12における、1%水溶液粘度は、78mPa・sであった。この水溶性重合体を用いた他は、実施例1と同様とした。結果を表1に示す。
実施例1の(水溶性重合体の製造)において、エチレンジメタクリレートを使用しなかった他は、同様にして水溶性重合体を含む水分散液を得た。該水溶性重合体の、pH12における、1%水溶液粘度は、30mPa・sであった。この水溶性重合体を用いた他は、実施例1と同様とした。結果を表1に示す。
実施例1の(水溶性重合体の製造)において、アクリル酸エチルの使用量を59.8部、エチレンジメタクリレートの使用量を0.2部に変更した他は、同様にして水溶性重合体を含む水分散液を得た。該水溶性重合体の、pH12における、1%水溶液粘度は、32mPa・sであった。この水溶性重合体を用いた他は、実施例1と同様とした。結果を表1に示す。
実施例1の(水溶性重合体の製造)において、アクリル酸エチルの使用量を58.2部、エチレンジメタクリレートの使用量を1.8部に変更した他は、同様にして水溶性重合体を含む水分散液を得た。該水溶性重合体の、pH12における、1%水溶液粘度は、880mPa・sであった。この水溶性重合体を用いた他は、実施例1と同様とした。結果を表1に示す。
実施例1の(導電性接着剤組成物の製造)において、前記水溶性重合体の5.0%水溶液を固形分相当で2部用いた他は、実施例1と同様とした。結果を表1に示す。
実施例1の(導電性接着剤組成物の製造)において、前記水溶性重合体の5.0%水溶液を固形分相当で28部用いた他は、実施例1と同様とした。結果を表1に示す。
実施例1の(導電性接着剤組成物の製造)において、さらにカルボキシメチルセルロース(DN-10L;ダイセルファインケム社製)を固形分相当で1部用いた他は、実施例1と同様とした。結果を表1に示す。
実施例1の(導電性接着剤組成物の製造)において、さらにカルボキシメチルセルロース(DN-10L;ダイセルファインケム社製)を固形分相当で3部用いた他は、実施例1と同様とした。結果を表1に示す。
実施例1の(導電性接着剤組成物の製造)において、分散剤として前記水溶性重合体に代えて、カルボキシメチルセルロース(CMC)を用いた他は、実施例1と同様とした。結果を表1に示す。なお、CMCの1%水溶液粘度は、3500mPa・sであった。
実施例1の(導電性接着剤組成物の製造)において、分散剤として前記水溶性重合体に代えて、ポリアクリル酸ナトリウムを用いた他は、実施例1と同様とした。結果を表1に示す。なお、ポリアクリル酸ナトリウムの1%水溶液粘度は、150mPa・sであった。
(水溶性重合体の製造)
攪拌機付き5MPa耐圧容器に、スチレン82部、メタアクリル酸18部、乳化剤としてポリオキシアルキレンアルケニルエーテル硫酸アンモニウム(ラテムルPD-104、花王社製)1.5部、イオン交換水150部及び重合開始剤として過硫酸カリウム0.5部を入れ、十分に攪拌した後、60℃に加温して重合を開始した。重合転化率が96%になった時点で冷却し反応を停止して、水溶性重合体を含む水分散液を得た。該水溶性重合体の、pH12における、1%水溶液粘度は、0.5mPa・sであった。
(水溶性重合体の製造)
攪拌機付き5MPa耐圧容器に、アクリル酸エチル35部、メタアクリル酸65部、乳化剤としてポリオキシアルキレンアルケニルエーテル硫酸アンモニウム(ラテムルPD-104、花王社製)1.5部、イオン交換水150部及び重合開始剤として過硫酸カリウム0.5部を入れ、十分に攪拌した後、60℃に加温して重合を開始した。重合転化率が96%になった時点で冷却し反応を停止して、水溶性重合体を含む水分散液を得た。該水溶性重合体の、pH12における、1%水溶液粘度は、120mPa・sであった。
(水溶性重合体の製造)
攪拌機付き5MPa耐圧容器に、アクリル酸エチル66.5部、メタアクリル酸32.5部、エチレンジメタクリレート(架橋性単量体)1部、乳化剤としてポリオキシアルキレンアルケニルエーテル硫酸アンモニウム(ラテムルPD-104、花王社製)1.5部、イオン交換水150部及び重合開始剤として過硫酸カリウム0.5部を入れ、十分に攪拌した後、60℃に加温して重合を開始した。重合転化率が96%になった時点で冷却し反応を停止して、水溶性重合体を含む水分散液を得た。該水溶性重合体の、pH12における、1%水溶液粘度は、65mPa・sであった。
実施例1の(導電性接着剤組成物の製造)において、水溶性重合体およびアクリレート重合体を用いずに、ポリフッ化ビニリデン(PVDF、クレハ社製#7208)を用いたこと、および溶媒置換により導電性接着剤組成物の溶媒として水の代わりにN-メチルピロリドンを用いたこと以外は、実施例1と同様とした。結果を表1に示す。
(高温保存特性)
実施例および比較例で製造する電気二重層キャパシタ用電極を用いて、ラミネート型の電気二重層キャパシタを作製し、25℃環境下、24時間静置させた後に、1Cの充電レートにて2.7Vまで充電し、次いで、1Cの放電レートにて0Vまで放電することにより、初期容量C0を測定した。さらに、25℃環境下、1Cの充電レートにて2.7Vに充電し、60℃の環境下で7日間保存した後、25℃環境下、充放電レート1Cにて、0Vまで放電することにより、高温保存後の容量C1を測定した。高温保存特性は、ΔCs=C1/C0×100(%)で示す容量変化率ΔCsにて評価し、この容量変化率ΔCsが高いほど高温保存特性に優れることを示す。
実施例および比較例で製造する電気二重層キャパシタ用電極を用いて、ラミネート型の電気二重層キャパシタを作製し、25℃環境下、24時間静置させた後に、充電レート1Cにて2.7Vまで充電し、次いで、放電レート1Cにて0Vまで放電することにより、初期容量C0を測定した。さらに、60℃環境下、充電レート1Cで2.7Vまで充電した後、放電レート1Cで0Vまで放電する充放電サイクルを100回(100サイクル)行い、100サイクル後の容量C2を測定した。高温サイクル特性は、ΔCc=C2/C0×100(%)で示す容量変化率ΔCcにて評価し、この容量変化率ΔCcが高いほど高温サイクル特性に優れることを示す。
実施例および比較例で製造する電気二重層キャパシタ用電極を用いて、ラミネート型の電気二重層キャパシタを作製し、24時間静置させた後に、25℃環境下、1Cの充電レートにて、2.7Vまで充電し、その後、-10℃環境下、1Cの放電レートにて放電の操作を行い、放電開始10秒後の電圧Vを測定した。低温出力特性は、ΔV=2.7V-Vで示す電圧変化ΔVにて評価し、この電圧変化ΔVが小さいほど低温出力特性に優れることを示す。
実施例1と同様にして、導電性接着剤を形成したアルミ集電体を得た。
正極・負極の電極活物質として、石油ピッチを原料とするアルカリ賦活活性炭である体積平均粒子径が11μmの活性炭粉末(CEP-21;新日本石油社製)を100部、分散剤としてカルボキシメチルセルロースアンモニウムの1.5%水溶液(DN-800H;ダイセル化学工業社製)を固形分相当で2.0部、導電材としてアセチレンブラック(デンカブラック粉状;電気化学工業社製)を5部、バインダーとしてガラス転移温度が-40℃で、数平均粒子径が0.25μmのジエン重合体(スチレン60質量%、ブタジエン35質量%、イタコン酸5質量%を含む単量体混合物を乳化重合して得られる共重合体)の40%水分散体を固形分相当で5部、およびイオン交換水を全固形分濃度が20%となるようにプラネタリーミキサーにより混合し、正負極の電極活物質層用スラリーを調製した。
前記導電性接着剤層を形成したアルミ集電体上に、前記電極活物質層用スラリーを速度3m/分で塗工し、60℃で5分間乾燥し、次いで120℃で5分間乾燥し、厚み100μmの電気二重層キャパシタ用正極および負極を得た。
上記得られた電気二重層キャパシタ用正極を、4cm×4cmの正方形に切り出し、集電体側の表面がアルミ包材外装に接するように配置した。正極活物質層の面上に、5cm×5cmの正方形のセパレータを配置した。さらに、上記得られた電気二重層キャパシタ用負極を、4.2cm×4.2cmの正方形に切り出し、これをセパレータ上に、負極活物質層側の表面がセパレータに向かい合うよう配置した。なお、セパレータは、セルロース(日本高度紙工業製、TF-40)を用いた。さらに、電解液として1.0Mテトラエチルアンモニウムフルオロボレート(溶媒PC)を用い、アルミ包材の開口を密封するために、150℃のヒートシールをしてアルミ外装を閉口し、電気二重層キャパシタを製造した。
実施例22で参照する実施例1(導電性接着剤組成物の製造)において、分散剤として前記水溶性重合体に代えて、カルボキシメチルセルロース(CMC)を用いた他は、同様とした。結果を表2に示す。
(高温保存特性)
実施例および比較例で製造するリチウムイオンキャパシタ用電極を用いて、ラミネート型の電気二重層キャパシタを作製し、25℃環境下、24時間静置させた後に、充電レート1Cにて3.8Vまで充電し、放電レート1Cにて3.0Vまで放電することにより、初期容量C0を測定した。さらに、25℃環境下、充電レート1Cにて3.8Vに充電し、60℃環境下で7日間保存した後、25℃環境下、放電レート1Cにて3.0Vまで放電を行うことにより、高温保存後の容量C1を測定した。高温保存特性は、ΔCs=C1/C0×100(%)で示す容量変化率ΔCsにて評価し、この容量変化率ΔCsが高いほど高温保存特性に優れることを示す。
実施例および比較例で製造するリチウムイオンキャパシタ用電極を用いて、ラミネート型の電気二重層キャパシタを作製し、25℃環境下、24時間静置させた後に、充電レート1Cにて3.8Vまで充電し、放電レート1Cにて3.0Vまで放電することにより、初期容量C0を測定した。さらに、60℃環境下、充電レート1Cにて3.8Vまで充電し、放電レート1Cにて3.0Vまで放電する充放電サイクルを100回(100サイクル)行い、100サイクル後の容量C2を測定した。高温サイクル特性は、ΔCc=C2/C0×100(%)で示す容量変化率ΔCcにて評価し、この容量変化率ΔCcが高いほど高温サイクル特性に優れることを示す。
実施例および比較例で製造するリチウムイオンキャパシタ用電極を用いて、ラミネート型のリチウムイオンキャパシタを作製し、24時間静置させた後に、25℃環境下、充電レート1Cにて3.8Vまで充電した。その後、-10℃環境下、放電レート1Cにて放電の操作を行い、放電開始10秒後の電圧Vを測定した。低温出力特性は、ΔV=3.8V-Vで示す電圧変化ΔVにて評価し、この電圧変化ΔVが小さいほど低温出力特性に優れることを示す。
実施例1と同様にして、導電性接着剤を形成したアルミ集電体を得た。
正極の電極活物質として、石油ピッチを原料とするアルカリ賦活活性炭である体積平均粒子径が11μmの活性炭粉末(CEP-21;新日本石油社製)を100部、分散剤としてカルボキシメチルセルロースアンモニウムの1.5%水溶液(DN-800H;ダイセル化学工業社製)を固形分相当で2.0部、導電剤としてアセチレンブラック(デンカブラック粉状;電気化学工業社製)を5部、バインダーとしてガラス転移温度が-40℃で、数平均粒子径が0.25μmのジエン重合体(スチレン60質量%、ブタジエン35質量%、イタコン酸5質量%を含む単量体混合物を乳化重合して得られる共重合体)の40%水分散体を固形分相当で5部、およびイオン交換水を全固形分濃度が20%となるようにプラネタリーミキサーにより混合し、リチウムイオンキャパシタ正極活物質層用スラリーを調製した。
前記導電性接着剤層を形成したアルミ集電体上に、前記リチウムイオンキャパシタ正極活物質層用スラリーを速度3m/分で塗工し、60℃で5分間乾燥し、次いで120℃で5分間乾燥し、厚み100μmのリチウムイオンキャパシタ用正極を得た。
負極の電極活物質として、体積平均粒子径が3.7μmである黒鉛(KS-6;ティムカル社製)を100部、分散剤としてカルボキシメチルセルロースアンモニウムの1.5%水溶液(DN-800H;ダイセル化学工業社製)を固形分相当で2.0部、導電剤としてアセチレンブラック(デンカブラック粉状;電気化学工業社製)を5部、バインダーとして、ガラス転移温度が-40℃、数平均粒子径が0.25μmのジエン重合体(スチレン60質量%、ブタジエン35質量%、イタコン酸5質量%を含む単量体混合物を乳化重合して得られる共重合体)の40%水分散体を固形分相当で5部、並びにイオン交換水を全固形分濃度が40%となるようにプラネタリーミキサーにより混合し、リチウムイオンキャパシタ負極活物質層用スラリーを調製した。
前記導電性接着剤層を形成したアルミ集電体上に、前記リチウムイオンキャパシタ負極活物質層用スラリーを速度3m/分で塗工し、80℃で5分間乾燥し、次いで110℃で5分間乾燥し、厚み100μmのリチウムイオンキャパシタ負極を得た。
上記得られたリチウムイオンキャパシタ用正極を、4cm×4cmの正方形に切り出し、集電体側の表面がアルミ包材外装に接するように配置した。正極活物質層の面上に、5cm×5cmの正方形のセパレータを配置した。さらに、リチウムイオンキャパシタ用負極を、4.2cm×4.2cmの正方形に切り出し、これをセパレータ上に、負極活物質層側の表面がセパレータに向かい合うよう配置した。なお、セパレータは、セルロース(日本高度紙工業製、TF-40)を用いた。さらに、電解液として1.0MLiPF6(溶媒EC/EMC=3/7体積比)を用い、アルミ包材の開口を密封するために、150℃のヒートシールをしてアルミ外装を閉口し、リチウムイオンキャパシタを製造した。
Claims (10)
- 導電性炭素材料、水溶性重合体およびバインダーを含む導電性接着剤組成物であって、
前記水溶性重合体がエチレン性不飽和カルボン酸単量体単位、(メタ)アクリル酸エステル単量体単位およびフッ素含有(メタ)アクリル酸エステル単量体単位を含む共重合体である導電性接着剤組成物。 - 前記導電性炭素材料が、黒鉛またはカーボンブラックである請求項1記載の導電性接着剤組成物。
- 前記水溶性重合体のエチレン性不飽和カルボン酸単量体単位が、エチレン性不飽和モノカルボン酸単量体単位である請求項1または2に記載の導電性接着剤組成物。
- 前記水溶性重合体が、さらに架橋性単量体単位を含む請求項1~3の何れかに記載の導電性接着剤組成物。
- 前記水溶性重合体の1%水溶液粘度が、0.1~20000mPa・sである請求項1~4の何れかに記載の導電性接着剤組成物。
- 前記水溶性重合体の含有割合が、導電性炭素材料100質量部に対して、1~30質量部である請求項1~5の何れかに記載の導電性接着剤組成物。
- 集電体上に、
導電性炭素材料、バインダー、並びに、エチレン性不飽和カルボン酸単量体単位、(メタ)アクリル酸エステル単量体単位およびフッ素含有(メタ)アクリル酸エステル単量体単位を含む水溶性重合体を含んでなる導電性接着剤層を有する、導電性接着剤層付集電体。 - 前記集電体が、金属である請求項7に記載の導電性接着剤層付集電体。
- 請求項7または8に記載の導電性接着剤層付集電体上に、
電極活物質およびバインダーを含んでなる電極活物質層を有する電気化学素子用電極。 - 正極、負極電極、電解液、並びにセパレータを備える電気化学素子であって、前記正極又は負極の少なくとも一方電極が請求項9に記載の電気化学素子用電極である電気化学素子。
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Also Published As
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JPWO2013062088A1 (ja) | 2015-04-02 |
JP5967098B2 (ja) | 2016-08-10 |
CN103890124A (zh) | 2014-06-25 |
CN103890124B (zh) | 2016-01-20 |
KR101988452B1 (ko) | 2019-06-12 |
KR20140095475A (ko) | 2014-08-01 |
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