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WO2018101294A1 - Dispersion de matériau carboné conducteur - Google Patents

Dispersion de matériau carboné conducteur Download PDF

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Publication number
WO2018101294A1
WO2018101294A1 PCT/JP2017/042729 JP2017042729W WO2018101294A1 WO 2018101294 A1 WO2018101294 A1 WO 2018101294A1 JP 2017042729 W JP2017042729 W JP 2017042729W WO 2018101294 A1 WO2018101294 A1 WO 2018101294A1
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Prior art keywords
carbon material
conductive carbon
oxazoline
material dispersion
conductive
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PCT/JP2017/042729
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English (en)
Japanese (ja)
Inventor
辰也 畑中
佑紀 柴野
卓司 吉本
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Nissan Chemical Corp
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Nissan Chemical Corp
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Priority to JP2018554177A priority Critical patent/JP7081493B2/ja
Publication of WO2018101294A1 publication Critical patent/WO2018101294A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C08L57/06—Homopolymers or copolymers containing elements other than carbon and hydrogen
    • C08L57/12—Homopolymers or copolymers containing elements other than carbon and hydrogen containing nitrogen atoms
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/66—Current collectors
    • H01G11/68—Current collectors characterised by their material
    • 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

Definitions

  • the present invention relates to a conductive carbon material dispersion, and more specifically, relates to a conductive carbon material dispersion containing a conductive carbon material and an antifoaming agent and suitable as a composition for a conductive thin film.
  • a lithium ion secondary battery is a secondary battery that has been developed most vigorously at present because it has a high energy density and a high voltage and has no memory effect during charging and discharging.
  • the development of electric vehicles has been actively promoted due to recent efforts to deal with environmental problems, and higher performance has been demanded for secondary batteries as a power source.
  • a lithium ion secondary battery contains a positive electrode and a negative electrode capable of occluding and releasing lithium, and a separator interposed therebetween in a container, and an electrolyte solution (liquid in the case of a lithium ion polymer secondary battery) therein. It has a structure filled with a gel-like or all solid electrolyte instead of the electrolyte.
  • an active material capable of occluding and releasing lithium, a conductive material mainly composed of a carbon material, and a composition containing a polymer binder are generally applied on a current collector such as a copper foil or an aluminum foil. It is manufactured by doing.
  • This binder is used to bond an active material and a conductive material, and further to the metal foil, and is a fluorine-based resin soluble in N-methylpyrrolidone (NMP) such as polyvinylidene fluoride (PVdF) or an olefin-based heavy polymer.
  • NMP N-methylpyrrolidone
  • PVdF polyvinylidene fluoride
  • olefin-based heavy polymer Combined aqueous dispersions are commercially available.
  • the lithium ion secondary battery is also expected to be applied as a power source for electric vehicles and the like, and a longer life and safety than ever before are required.
  • the adhesive strength of the binder to the current collector cannot be said to be sufficient, and part of the active material or conductive material is peeled off from the current collector during the manufacturing process such as the cutting process or winding process of the electrode plate.
  • this may cause a minute short circuit and a variation in battery capacity.
  • the contact resistance between the electrode mixture and the current collector increases due to the volume change of the electrode mixture due to the swelling of the binder due to the electrolytic solution and the volume change due to the lithium occlusion and release of the active material after long-term use.
  • a method of inserting a conductive binder layer between a current collector and an electrode mixture has been developed.
  • a conductive carbon material is dispersed by using a surfactant-containing polymer having an oxazoline group as a dispersant, and a conductive thin film (hereinafter, referred to as a conductive thin film) obtained from this conductive carbon material dispersion.
  • Current collector (hereinafter also referred to as a composite current collector) can reduce the contact resistance between the current collector and the electrode mixture, and reduce the capacity during high-speed discharge. It has been shown that the degradation of the battery can also be suppressed.
  • An object of the present invention is to provide a conductive carbon material dispersion that can produce a uniform conductive thin film.
  • an acetylene-based surfactant As a result of intensive studies to achieve the above object, the present inventors have determined that an acetylene-based surfactant, a silicone-based surfactant, a metal soap-based surfactant, and an acrylic interface with respect to a conductive carbon material.
  • at least one antifoaming agent selected from activators it is possible to suppress the generation of bubbles, and in particular, by adding an acetylene-based surfactant, specifically a uniformly dispersed state of the conductive carbon material
  • the present inventors have found that a conductive carbon material dispersion liquid that can suppress the generation of bubbles while maintaining the viscosity and can be applied uniformly is obtained.
  • the present invention includes a conductive carbon material and one or more antifoaming agents selected from acetylene surfactants, silicone surfactants, metal soap surfactants, and acrylic surfactants.
  • Conductive carbon material dispersion 2. 1 conductive carbon material dispersion liquid in which the antifoaming agent contains an acetylene-based surfactant; 3. Furthermore, 1 or 2 conductive carbon material dispersion liquid containing the conductive carbon material dispersing agent which has surface active action, and a dispersion medium, 4).
  • the conductive carbon material dispersion liquid according to any one of 1 to 3, wherein the conductive carbon material includes one or more selected from graphite, carbon black, and carbon nanotubes, 5).
  • the conductive carbon material is a conductive carbon material dispersion liquid of any one of 1 to 4, wherein the conductive carbon material contains carbon nanotubes, 6).
  • the dispersion medium is any one of 3 to 5 conductive carbon material dispersion liquid containing water, 7).
  • a conductive carbon material dispersion of 8 wherein the chain hydrocarbon group containing a polymerizable carbon-carbon double bond is an alkenyl group having 2 to 8 carbon atoms; 10.
  • the oxazoline monomer is 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-4-ethyl-2-oxazoline, 2-vinyl-4-propyl-2-oxazoline, 2 -Vinyl-4-butyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-vinyl-5-ethyl-2-oxazoline, 2-vinyl-5-propyl-2-oxazoline, 2-vinyl -5-butyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-4-ethyl-2-oxazoline, 2-isopropenyl-4 -Propyl-2-oxazoline, 2-isopropenyl-4-butyl-2-oxazoline, 2-isopropenyl-5-methyl 1 selected from
  • conductive carbon material dispersions wherein the oxazoline monomer is 2-isopropenyl-2-oxazoline; 12 Any one of the conductive carbon material dispersions 1 to 11 containing a crosslinking agent; 13. 12 conductive carbon material dispersions, wherein the crosslinking agent comprises a compound that causes a crosslinking reaction with an oxazoline group, 14 A compound that undergoes a crosslinking reaction with the oxazoline group exhibits a crosslinking reactivity in the presence of an acid catalyst, a synthetic polymer metal salt and a natural polymer metal salt, and exhibits a crosslinking reactivity when heated.
  • conductive carbon material dispersions containing a compound selected from ammonium salts of molecules and ammonium salts of natural polymers 15. 14 conductive substances, wherein the compound causing a crosslinking reaction with the oxazoline group includes a compound selected from lithium polyacrylate, sodium polyacrylate, ammonium polyacrylate, lithium carboxymethylcellulose, sodium carboxymethylcellulose, ammonium carboxymethylcellulose, and ammonium alginate.
  • a conductive binder layer obtained from the conductive carbon material dispersion liquid of any one of 1 to 16, 18. 17 conductive binder layers having a thickness of 5 ⁇ m or less, 19.
  • a composite current collector for an electrode of an energy storage device comprising: a current collecting substrate; and any one of conductive bonding layers 17 to 20 formed on the substrate, 22.
  • An electrode for an energy storage device comprising a composite current collector for an electrode of 21 energy storage devices, 23. 22 energy storage device electrodes comprising 21 energy storage device electrode composite current collectors and an active material layer formed on the conductive binder layer of the composite current collectors, 24.
  • An energy storage device comprising 22 or 23 electrodes for energy storage devices, 25. 24 energy storage devices which are lithium ion secondary batteries, 26.
  • a method for producing a conductive carbon material dispersion liquid with suppressed foaming comprising mixing a conductive carbon material, a conductive carbon material dispersant having a surface-active action, a dispersion medium, and an acetylene-based surfactant; 27.
  • a method for defoaming a conductive carbon material dispersion comprising mixing a conductive carbon material, a conductive carbon material dispersant having a surface active action, a dispersion medium, and an acetylene surfactant.
  • the conductive carbon material dispersion of the present invention is difficult to foam, its preparation and uniform coating are easy, and a uniform thin film can be easily obtained by coating the dispersion on a substrate. Since the obtained thin film exhibits high conductivity, it is suitable for the production of a conductive thin film and not only provides a thin film with excellent adhesion to a substrate, but also efficiently by a wet method with good reproducibility. Since a thin film having a large area can be formed, it can be suitably used not only for energy storage devices but also for various applications such as various semiconductor materials and conductor materials.
  • the conductive thin film for forming a conductive binder layer for joining the current collector substrate constituting the energy storage device electrode and the active material is suitable as a composition for use.
  • this conductive binder layer the electrical resistance of the energy storage device can be lowered, so that current can be taken out without causing a voltage drop, especially in applications that require a large current instantaneously, such as in electric vehicles. At the same time, the service life can be extended.
  • the conductive carbon material dispersion according to the present invention is one or two selected from conductive carbon materials, acetylene surfactants, silicone surfactants, metal soap surfactants, and acrylic surfactants.
  • the above-mentioned antifoaming agent is included.
  • an antifoaming agent containing an acetylene surfactant is preferable, and an antifoaming agent containing 50% by mass or more of an acetylene surfactant is preferable.
  • an antifoaming agent containing 80% by mass or more of an acetylenic surfactant is more preferable, and an antifoaming agent consisting of only an acetylenic surfactant (100% by mass) is optimal.
  • the amount of the antifoaming agent is not particularly limited, but while sufficiently exerting the foaming suppression effect, the aggregation of the conductive carbon material is suppressed.
  • the content is preferably 0.001 to 1.0 mass%, more preferably 0.01 to 0.5 mass%, based on the entire dispersion.
  • acetylene-based surfactant used as an antifoaming agent in the present invention are not particularly limited, but a surfactant containing an ethoxylated acetylene glycol represented by the following formula (A) is used. It is preferable to use it.
  • Specific examples of the alkyl group having 1 to 10 carbon atoms may be linear, branched, or cyclic.
  • acetylene glycol represented by the above formula (A) include 2,5,8,11-tetramethyl-6-dodecin-5,8-diol, 5,8-dimethyl-6-dodecin-5, 8-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 4,7-dimethyl-5-decyne-4,7-diol, 2,3,6,7-tetra Methyl-4-octyne-3,6-diol, 3,6-dimethyl-4-octyne-3,6-diol, 2,5-dimethyl-3-hexyne-2,5-diol, 2,4,7, Ethoxylate of 9-tetramethyl-5-decyne-4,7-diol (number of moles of ethylene oxide added: 1.3), 2,4,7,9-tetramethyl-5-decyne-4,7-diol (
  • the acetylene-based surfactant that can be used in the present invention can also be obtained as a commercial product.
  • a commercial product examples include Olphine D-10PG (manufactured by Nissin Chemical Industry Co., Ltd., active ingredient 50 mass).
  • Olphine E-1004 manufactured by Nissin Chemical Industry Co., Ltd., active ingredient 100% by mass, pale yellow liquid
  • Olphine E-1010 manufactured by Nissin Chemical Industry Co., Ltd., active ingredient 100% by mass
  • Olphine E-1020 manufactured by Nissin Chemical Industry Co., Ltd., active ingredient 100% by mass, pale yellow liquid
  • Olphine E-1030W manufactured by Nissin Chemical Industry Co., Ltd., active ingredient 75 masses) %, Light yellow liquid
  • Surfynol 420 manufactured by Nissin Chemical Industry Co., Ltd., active ingredient 100 mass%, pale yellow viscous substance
  • Surfynol 440 manufactured by Nissin Chemical Industry Co., Ltd., active ingredient 100 mass
  • SURFYNOL 104E Nisshin Chemical Industry Co., Ltd.
  • the silicone surfactant used as an antifoaming agent in the present invention is not particularly limited, and may be linear, branched, or cyclic as long as it contains at least a silicone chain. Either a hydrophobic group or a hydrophilic group may be contained.
  • hydrophobic group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n- Examples thereof include alkyl groups such as heptyl group, n-octyl group, n-nonyl group and n-decyl group; cyclic alkyl groups such as cyclohexyl group; aromatic hydrocarbon groups such as phenyl group.
  • hydrophilic groups include amino groups, thiol groups, hydroxyl groups, alkoxy groups, carboxylic acids, sulfonic acids, phosphoric acids, nitric acids and their organic and inorganic salts, ester groups, aldehyde groups, glycerol groups, heterocyclic rings. Groups and the like.
  • silicone surfactants include dimethyl silicone, methylphenyl silicone, chlorophenyl silicone, alkyl modified silicone, fluorine modified silicone, amino modified silicone, alcohol modified silicone, phenol modified silicone, carboxy modified silicone, epoxy modified silicone, fatty acid. Examples thereof include ester-modified silicone and polyether-modified silicone.
  • Silicone-based surfactants that can be used in the present invention can also be obtained as commercial products, such as BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK-313, BYK-320BYK-333, BYK-341, BYK-345, BYK-346, BYK-347, BYK-348, BYK-349 (above trade names, manufactured by BYK Japan KK) , KM-80, KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-6020, X -22-4515, KF-6011, KF-6012, KF-6015, KF-6017 (Manufactured by Gaku Kogyo Co., Ltd.), SH-28PA, SH8400, SH-190, SF
  • the metal soap surfactant used as an antifoaming agent in the present invention is not particularly limited, and includes any of linear, branched, and cyclic containing at least a polyvalent metal ion such as calcium and magnesium. It may be a structured metal soap. More specifically, fatty acids having 12 to 22 carbon atoms such as aluminum stearate, manganese stearate, cobalt stearate, copper stearate, iron stearate, nickel stearate, calcium stearate, zinc laurate, magnesium behenate and the like And salts with metals (alkaline earth metals, aluminum, manganese, cobalt, copper, iron, zinc, nickel, etc.).
  • the metal soap-based surfactant that can be used in the present invention can also be obtained as a commercial product. Examples of such a commercial product include Nopco NXZ (trade name, manufactured by San Nopco Co., Ltd.).
  • the acrylic surfactant used as an antifoaming agent in the present invention is not particularly limited as long as it is a polymer obtained by polymerizing at least an acrylic monomer, but is obtained by polymerizing at least an alkyl acrylate.
  • the polymer obtained is preferably a polymer obtained by polymerizing an alkyl acrylate having at least 2 to 9 carbon atoms in the alkyl group.
  • acrylic acid alkyl ester having 2 to 9 carbon atoms in the alkyl group examples include acrylic acid ethyl ester, acrylic acid n-propyl ester, acrylic acid isopropyl ester, acrylic acid n-butyl ester, acrylic acid isobutyl ester, Examples thereof include t-butyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, isononyl acrylate and the like.
  • the acrylic surfactant that can be used in the present invention can also be obtained as a commercially available product.
  • commercially available products include 1970, 230, LF-1980, LF-1982 (-50), LF- 1983 (-50), LF-1984 (-50), LHP-95, LHP-96, UVX-35, UVX-36, UVX-270, UVX-271, UVX-272, AQ-7120, AQ-7130 ( As mentioned above, trade names manufactured by Enomoto Kasei Co., Ltd.), BYK-350, BYK-352, BYK-354, BYK-355, BYK-358, BYK-380, BYK-381, BYK-392 (above, Big Chemie Japan ( Product name), Polyflow No.
  • the conductive carbon material is not particularly limited, but when used for forming a binding layer of a secondary battery, a fibrous conductive carbon material, a layered conductive carbon material, a particulate conductive carbon material. Is preferred. These conductive carbon materials can be used alone or in combination of two or more.
  • the fibrous conductive carbon material include carbon nanotubes (CNT) and carbon nanofibers (CNF).
  • CNT is preferable from the viewpoint of conductivity, dispersibility, availability, and the like.
  • CNTs are generally produced by arc discharge, chemical vapor deposition (CVD), laser ablation, etc., but the CNTs used in the present invention may be obtained by any method.
  • single-walled CNT hereinafter referred to as SWCNT in which one carbon film (graphene sheet) is wound in a cylindrical shape and two-layered CNT in which two graphene sheets are wound in a concentric shape.
  • DWCNT multi-layer CNT
  • MWCNT multi-layer CNT
  • SWCNT, DWCNT, and MWCNT are each a single unit, Or a combination of several can be used.
  • catalyst metals such as nickel, iron, cobalt, yttrium may remain, so that removal or purification of this impurity may be required. is there.
  • acid treatment with nitric acid, sulfuric acid or the like destroys the ⁇ -conjugated system constituting CNT and may impair the original characteristics of CNT. Therefore, it is desirable to purify and use under appropriate conditions.
  • the layered conductive carbon material include graphite and graphene.
  • the graphite is not particularly limited, and various commercially available graphites can be used.
  • Graphene is a sheet of sp2 bonded carbon atoms with a thickness of 1 atom, and has a hexagonal lattice structure like a honeycomb made of carbon atoms and their bonds, and its thickness is about 0.38 nm. It is said.
  • graphene oxide obtained by processing graphite by the Hummers method may be used.
  • the particulate conductive carbon material include carbon black such as furnace black, channel black, acetylene black, and thermal black. These carbon blacks are not particularly limited, and various commercially available carbon blacks can be used, and the particle diameter is preferably 5 to 500 nm.
  • Solvents include pure water; ethers such as tetrahydrofuran (THF), diethyl ether, 1,2-dimethoxyethane (DME); halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane; N, N Amides such as dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP); ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; methanol, ethanol, Alcohols such as isopropanol and n-propanol; aliphatic hydrocarbons such as n-heptane, n-hexane and cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; ethylene glycol monoethyl
  • the conductive carbon material dispersant used in the present invention is not particularly limited as long as the conductive carbon material can be dispersed in a solvent. However, the conductive thin film obtained by drying can have strength. A polymer dispersant having a surface active action is preferred.
  • polymeric dispersant having a surface active action examples include oxazoline polymers; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; polyacrylamide; polystyrene sulfonic acid; poly (meth) acrylic acid, poly (meth) acrylic Poly (meth) acrylic acid derivatives such as sodium acid and ammonium poly (meth) acrylate; polyvinyl alcohol derivatives such as polyvinyl alcohol and polyvinyl acetal; cellulose derivatives such as methylcellulose, carboxycellulose and hydroxymethylcellulose; starch, lignin sulfonate, Natural polymers such as sodium alginate and derivatives thereof, copolymers of polymerizable monomers that are constituent units of these polymers, or copolymers with other monomers Examples include phase transfer catalysts such as crown ethers, etc., but when used for forming a binding layer of a secondary battery, viewpoints such as dispersibility, solubility, and adhesion to a current collector substrate
  • the oxazoline polymer is not particularly limited as long as it is a polymer in which an oxazoline group is bonded directly to a repeating unit constituting the main chain or via a spacer group such as an alkylene group.
  • a vinyl polymer having an oxazoline group in the side chain is preferred.
  • X represents a polymerizable carbon-carbon double bond-containing group
  • R 1 to R 4 are independently of each other a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a 6 to 20 carbon atoms.
  • An aryl group or an aralkyl group having 7 to 20 carbon atoms is represented.
  • the polymerizable carbon-carbon double bond-containing group of the oxazoline monomer is not particularly limited as long as it contains a polymerizable carbon-carbon double bond, but a chain containing a polymerizable carbon-carbon double bond.
  • a hydrocarbon group having 2 to 8 carbon atoms such as vinyl group, allyl group and isopropenyl group is preferable.
  • examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the alkyl group having 1 to 5 carbon atoms may be linear, branched or cyclic, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group. Tert-butyl group, n-pentyl group, cyclohexyl group and the like.
  • Specific examples of the aryl group having 6 to 20 carbon atoms include phenyl group, xylyl group, tolyl group, biphenyl group, naphthyl group and the like.
  • Specific examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group, phenylethyl group, phenylcyclohexyl group and the like.
  • oxazoline monomer having a polymerizable carbon-carbon double bond-containing group at the 2-position represented by the formula (1) include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-4-ethyl-2-oxazoline, 2-vinyl-4-propyl-2-oxazoline, 2-vinyl-4-butyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2- Vinyl-5-ethyl-2-oxazoline, 2-vinyl-5-propyl-2-oxazoline, 2-vinyl-5-butyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4- Methyl-2-oxazoline, 2-isopropenyl-4-ethyl-2-oxazoline, 2-isopropenyl-4-propyl-2-oxazoline, 2- Sopropenyl-4-butyl
  • the oxazoline polymer is also preferably water-soluble.
  • a water-soluble oxazoline polymer may be a homopolymer of the oxazoline monomer represented by the above formula (1), but has a oxazoline monomer and a hydrophilic functional group in order to further enhance the solubility in water (meta ) It is preferable to be obtained by radical polymerization of at least two monomers with an acrylate monomer.
  • (meth) acrylic monomer having a hydrophilic functional group examples include (meth) acrylic acid, 2-hydroxyethyl acrylate, methoxypolyethylene glycol acrylate, monoesterified product of acrylic acid and polyethylene glycol, acrylic acid 2-aminoethyl and its salt, 2-hydroxyethyl methacrylate, methoxypolyethylene glycol methacrylate, monoesterified product of methacrylic acid and polyethylene glycol, 2-aminoethyl methacrylate and its salt, sodium (meth) acrylate, ( Ammonium methacrylate, (meth) acrylonitrile, (meth) acrylamide, N-methylol (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, sodium styrenesulfonate, etc. The like, which may be used singly or may be used in combination of two or more. Among these, (meth) acrylic acid methoxypolyethylene glycol and mono
  • the oxazoline monomer and other monomers other than the (meth) acrylic monomer having a hydrophilic functional group are used in combination as long as the conductive carbon material dispersibility of the obtained oxazoline polymer is not adversely affected.
  • Specific examples of other monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylic.
  • (Meth) acrylic acid ester monomers such as perfluoroethyl acid and phenyl (meth) acrylate; ⁇ -olefin monomers such as ethylene, propylene, butene and pentene; haloolefins such as vinyl chloride, vinylidene chloride and vinyl fluoride Monomers: Styrene monomers such as styrene and ⁇ -methyl styrene; Vinyl ester monomers such as vinyl acetate and vinyl propionate; Vinyl ether monomers such as methyl vinyl ether and ethyl vinyl ether, and the like. But two or more A combination of the above may also be used.
  • the content of the oxazoline monomer is preferably 10% by mass or more, more preferably 20% by mass or more from the viewpoint of further increasing the CNT dispersibility of the obtained oxazoline polymer. Preferably, 30% by mass or more is even more preferable.
  • the upper limit of the content rate of the oxazoline monomer in a monomer component is 100 mass%, and the homopolymer of an oxazoline monomer is obtained in this case.
  • the content of the (meth) acrylic monomer having a hydrophilic functional group in the monomer component is preferably 10% by mass or more, more preferably 20% by mass or more from the viewpoint of further increasing the water solubility of the obtained oxazoline polymer. 30% by mass or more is even more preferable.
  • the content of other monomers in the monomer component is a range that does not affect the CNT dispersibility of the obtained oxazoline polymer, and since it varies depending on the type, it cannot be determined unconditionally. What is necessary is just to set suitably in the range of 5-95 mass%, Preferably it is 10-90 mass%.
  • the average molecular weight of the oxazoline polymer is not particularly limited, but the weight average molecular weight is preferably 1,000 to 2,000,000. When the weight average molecular weight of the polymer is less than 1,000, there is a possibility that the dispersibility of the conductive carbon material is remarkably lowered or the dispersibility is not exhibited. On the other hand, if the weight average molecular weight exceeds 2,000,000, handling in the dispersion treatment may become extremely difficult. An oxazoline polymer having a weight average molecular weight of 2,000 to 1,000,000 is more preferable.
  • the weight average molecular weight in this invention is a measured value (polystyrene conversion) by gel permeation chromatography.
  • the oxazoline polymer that can be used in the present invention can be synthesized by a conventional radical polymerization of the above-mentioned monomers, but can also be obtained as a commercial product, and as such a commercial product, for example, Epocross WS-300 (Manufactured by Nippon Shokubai Co., Ltd., solid content concentration 10% by mass, aqueous solution), Epocross WS-700 (manufactured by Nippon Shokubai Co., Ltd., solid content concentration 25% by mass, aqueous solution), Epocross WS-500 (manufactured by Nippon Shokubai Co., Ltd.) Manufactured, solid content concentration 39% by mass, water / 1-methoxy-2-propanol solution), Poly (2-ethyl-2-oxazoline) (Aldrich), Poly (2-ethyl-2-oxazoline) (AlfaAesar), Poly (2-ethyl-2-oxazole) (
  • the mixing ratio of the conductive carbon material dispersant to the conductive carbon material can be about 100: 1 to 1: 100 by mass ratio.
  • the concentration of the surfactant in the dispersion is not particularly limited as long as the conductive carbon material can be dispersed in a solvent.
  • the concentration of the surfactant is 0.001 to 50. It is preferably about mass%, more preferably about 0.01 to 40 mass%.
  • the concentration of the conductive carbon material in the dispersion changes in the mechanical, electrical, and thermal characteristics required for the thin film, and at least a part of the conductive carbon material is isolated and dispersed. In the present invention, it is preferably about 0.001 to 50% by mass, more preferably about 0.01 to 40% by mass, and more preferably 0.02 to More preferably, it is about 30% by mass.
  • the conductive carbon material dispersion of the present invention may contain a crosslinking agent that is soluble in the above-described solvent.
  • the crosslinking agent may be either a compound that causes a crosslinking reaction with the dispersant to be used or a compound that self-crosslinks, but reacts with the dispersant to form a crosslinked structure from the viewpoint of further improving the solvent resistance of the resulting thin film.
  • a crosslinking agent is preferred.
  • the dispersant is an oxazoline polymer
  • a functional group having reactivity with an oxazoline group such as a carboxyl group, a hydroxyl group, a thiol group, an amino group, a sulfinic acid group, and an epoxy group.
  • an oxazoline group such as a carboxyl group, a hydroxyl group, a thiol group, an amino group, a sulfinic acid group, and an epoxy group.
  • it will not specifically limit if it is a compound which has two or more groups, The compound which has two or more carboxyl groups is preferable.
  • a compound having a functional group that causes a crosslinking reaction by heating during thin film formation or in the presence of an acid catalyst such as a sodium salt, potassium salt, lithium salt, or ammonium salt of a carboxylic acid is also crosslinked. It can be used as an agent.
  • an acid catalyst such as a sodium salt, potassium salt, lithium salt, or ammonium salt of a carboxylic acid
  • these compounds include metal salts of synthetic polymers such as polyacrylic acid and copolymers thereof and natural polymers such as carboxymethylcellulose and alginic acid that exhibit crosslinking reactivity in the presence of an acid catalyst, and crosslinking reaction by heating.
  • ammonium salts of the above-described synthetic polymers and natural polymers that exhibit the properties in particular, sodium polyacrylate, lithium polyacrylate, which exhibit crosslinking reactivity in the presence of an acid catalyst or under heating conditions, Ammonium polyacrylate, sodium carboxymethyl cellulose, lithium carboxymethyl cellulose, carboxymethyl cellulose ammonium and the like are preferable.
  • the compound that causes a crosslinking reaction with the oxazoline group can also be obtained as a commercial product.
  • a commercial product examples include sodium polyacrylate (manufactured by Wako Pure Chemical Industries, Ltd., degree of polymerization 2,700).
  • Examples of the self-crosslinking compound include an aldehyde group, an epoxy group, a vinyl group, an isocyanate group, an alkoxy group, and a carboxyl group with respect to a hydroxyl group, an aldehyde group, an amino group, an isocyanate group, an epoxy group, and an amino group.
  • crosslinkable functional groups that react with each other in the same molecule, such as isocyanate groups and aldehyde groups, hydroxyl groups that react with the same crosslinkable functional groups (dehydration condensation), mercapto groups (disulfide bonds), esters And compounds having a group (Claisen condensation), a silanol group (dehydration condensation), a vinyl group, an acrylic group, and the like.
  • Specific examples of the self-crosslinking compound include polyfunctional acrylate that exhibits crosslinking reactivity in the presence of an acid catalyst, tetraalkoxysilane, a monomer having a blocked isocyanate group, and at least one of a hydroxyl group, a carboxylic acid, and an amino group. Examples include monomer block copolymers.
  • Such a self-crosslinking crosslinking agent can also be obtained as a commercial product.
  • a commercial product examples include A-9300 (ethoxylated isocyanuric acid triacrylate, Shin-Nakamura Chemical ( ), A-GLY-9E (Ethoxylatedinglycerine triacrylate (EO9 mol), Shin-Nakamura Chemical Co., Ltd.), A-TMMT (pentaerythritol tetraacrylate, Shin-Nakamura Chemical Co., Ltd.), tetraalkoxysilane In the case of tetramethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), tetraethoxysilane (manufactured by Toyoko Chemical Co., Ltd.), and polymers having a blocked isocyanate group, Elastron series E-37, H-3, H38, BAP, NEW BAP-15, C-52, F-2 9, W-11P, MF-9, MF-25K (D
  • crosslinking agents may be used alone or in combination of two or more.
  • the addition amount of the crosslinking agent varies depending on the solvent used, the substrate used, the required viscosity, the required film shape, etc., but is preferably 0.001 to 80% by mass with respect to the dispersant, Is more preferably from 50 to 50% by mass, and even more preferably from 0.05 to 40% by mass.
  • a catalyst for accelerating the crosslinking reaction p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthalenecarboxylic acid And / or a thermal acid generator such as 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and organic sulfonic acid alkyl ester can be added.
  • the addition amount of the catalyst is 0.0001 to 20% by mass, preferably 0.0005 to 10% by mass, and more preferably 0.001 to 3% by mass with respect to the dispersant.
  • a polymer serving as a matrix may be added to the conductive carbon material dispersion of the present invention.
  • the matrix polymer include polyvinylidene fluoride (PVdF), polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, vinylidene fluoride-hexafluoropropylene copolymer [P (VDF-HFP)], Fluorine resin such as vinylidene fluoride-trichloroethylene copolymer [P (VDF-CTFE)], polyvinyl pyrrolidone, ethylene-propylene-diene terpolymer, PE (polyethylene), PP (polypropylene), Polyolefin resins such as EVA (ethylene-vinyl acetate copolymer), EEA (ethylene-ethyl acrylate copolymer); PS (polystyrene), HIPS (high impact polystyrene), AS (acryl
  • Examples thereof include sodium boxymethylcellulose, water-soluble cellulose ether, sodium alginate, polyvinyl alcohol, polystyrene sulfonic acid, polyethylene glycol and the like, and particularly, sodium polyacrylate and sodium carboxymethylcellulose are preferable.
  • the matrix polymer can also be obtained as a commercial product.
  • a commercial product examples include sodium polyacrylate (manufactured by Wako Pure Chemical Industries, Ltd., degree of polymerization 2,700 to 7,500), carboxy Sodium methylcellulose (manufactured by Wako Pure Chemical Industries, Ltd.), sodium alginate (manufactured by Kanto Chemical Co., Ltd., deer grade 1), Metrol's SH series (hydroxypropylmethylcellulose, Shin-Etsu Chemical Co., Ltd.), Metrolose SE series (hydroxyl) Ethyl methyl cellulose, manufactured by Shin-Etsu Chemical Co., Ltd.), JC-25 (completely saponified polyvinyl alcohol, manufactured by Nippon Vineyard Poval Co., Ltd.), JM-17 (intermediate saponified polyvinyl alcohol, Nippon Vinegared / Poval) Manufactured by Co., Ltd.), JP-03 (partially saponified polyvinyl alcohol, Nippon Vinegar Po
  • the method for preparing the conductive carbon material dispersion of the present invention is arbitrary, and the surfactant, the conductive carbon material, the solvent and the antifoaming agent, and the cross-linking agent and matrix polymer used as necessary are in any order.
  • a dispersion may be prepared by mixing. At this time, it is preferable to disperse a mixture of a surfactant, a conductive carbon material and a solvent, and this treatment can further improve the dispersion ratio of the conductive carbon material.
  • the dispersion treatment include mechanical treatment, wet treatment using a ball mill, bead mill, jet mill, etc., and ultrasonic treatment using a bath-type or probe-type sonicator. In particular, wet treatment using a jet mill.
  • An antifoaming agent is preferable because it can suppress foaming during the dispersion treatment by adding it before the dispersion treatment, but it may inhibit the dispersion of the conductive carbon material by the surfactant. It may be added after processing. Moreover, you may add a crosslinking agent and a matrix polymer, after preparing the dispersion liquid containing components other than these. In the conductive carbon material dispersion prepared as described above, it is presumed that the dispersant is physically adsorbed on the surface of the conductive carbon material to form a composite.
  • the conductive carbon material dispersion liquid (composition for conductive thin film) described above is applied onto a substrate or a product on which a thin film is to be formed. This can be produced by natural or heat drying to form a conductive binder layer.
  • the substrate and the formed product are not particularly limited.
  • metals such as copper, aluminum, nickel, gold, silver, and alloys thereof; carbon materials; metal oxides; conductive polymers; Synthetic polymers such as tarate, polypropylene and polyimide; natural polymers such as cellulose and chitosan can be used.
  • the thickness is not particularly limited, but is preferably 1 to 100 ⁇ m in the present invention.
  • the conductive thin film obtained from the conductive carbon material dispersion of the present invention is interposed between the current collecting substrate constituting the electrode of the energy storage device and the active material layer, and is formed into a conductive binding layer that binds both. Especially suitable.
  • various energy storage devices such as an electric double layer capacitor, a lithium secondary battery, a lithium ion secondary battery, a proton polymer battery, a nickel metal hydride battery, an aluminum solid capacitor, an electrolytic capacitor, and a lead storage battery.
  • the electroconductive thin film obtained from the electroconductive carbon material dispersion liquid of this invention can be applied suitably for the electrode of an electrical double layer capacitor and a lithium ion secondary battery especially.
  • a composite current collector comprising a current collector substrate and a conductive binder layer.
  • the conductive carbon material dispersion liquid (composition for conductive thin film) described above is applied onto a current collector substrate, and this is naturally or heat-dried to form a conductive binder layer.
  • the current collecting substrate may be appropriately selected from those conventionally used as a current collecting substrate for electrodes for energy storage devices. For example, copper, aluminum, nickel, gold, silver, alloys thereof, carbon materials, metals
  • a thin film such as an oxide or a conductive polymer can be used.
  • the thickness is not particularly limited, but is preferably 1 to 100 ⁇ m in the present invention.
  • the thickness of the conductive binder layer in the present invention is preferably 5 ⁇ m or less, more preferably 1 ⁇ m or less, in consideration of improving the energy density of the battery and reducing the bulk resistance of the conductive binder layer. 5 ⁇ m or less is even more preferable.
  • the thickness of the conductive binder layer can be calculated by observing the cross section of the conductive binder layer with a scanning microscope (hereinafter referred to as SEM) or by dividing the basis weight by the specific gravity of the conductive binder layer. it can.
  • SEM scanning microscope
  • the cross section of the conductive binder layer can be obtained, for example, by tearing the composite current collector or processing with an ion beam.
  • the basis weight is the ratio of the mass (g) of the conductive binder layer to the area (m 2 ) of the conductive binder layer, and when the conductive binder layer is formed in a pattern, the area is conductive It is the area of only the conductive binding layer, and does not include the area of the current collector substrate exposed between the conductive binding layers formed in a pattern.
  • a test piece of an appropriate size is cut out from the composite current collector, its mass W0 is measured, and then the conductive binder layer is peeled off from the composite current collector.
  • the mass W3 of the composite current collector measured can be measured and calculated from the difference (W3-W2).
  • a method of peeling the conductive binder layer for example, a method of immersing the conductive binder layer in a solvent in which the conductive binder layer is dissolved or swells and wiping the conductive binder layer with a cloth or the like is available. Can be mentioned.
  • the specific gravity of the conductive binder layer can be calculated, for example, by dividing the basis weight by the film thickness. Further, it can be measured by a bead replacement method, a tap density measurement or the like.
  • the film thickness can be adjusted by a known method.
  • the solid content concentration of the coating liquid (CNT-containing composition) for forming the conductive binder layer, the number of coating times, and the coating liquid inlet of the coating machine It can be adjusted by changing the clearance.
  • increase the weight per unit area increase the solid content concentration, increase the number of coatings, or increase the clearance.
  • the solid content concentration is decreased, the number of coatings is decreased, or the clearance is decreased.
  • coating methods include spin coating, dip coating, flow coating, ink jet, spray coating, bar coating, gravure coating, slit coating, roll coating, flexographic printing, transfer printing, Brush coating, blade coating method, air knife coating method, etc. are mentioned, but from the viewpoint of work efficiency etc., inkjet method, casting method, dip coating method, bar coating method, blade coating method, roll coating method, gravure coating method, A flexographic printing method and a spray coating method are suitable.
  • the temperature for drying by heating is also arbitrary, but is preferably about 50 to 200 ° C, more preferably about 80 to 150 ° C.
  • the energy storage device electrode can be produced by forming an active material layer on the conductive binding layer of the composite current collector.
  • an active material the various active materials conventionally used for the electrode for energy storage devices can be used.
  • a chalcogen compound capable of adsorbing / leaving lithium ions or a lithium ion-containing chalcogen compound, a polyanion compound, a simple substance of sulfur and a compound thereof may be used as a positive electrode active material. it can.
  • the chalcogen compound that can adsorb and desorb lithium ions include FeS 2 , TiS 2 , MoS 2 , V 2 O 6 , V 6 O 13 , and MnO 2 .
  • the lithium ion-containing chalcogen compound include LiCoO 2 , LiMnO 2 , LiMn 2 O 4 , LiMo 2 O 4 , LiV 3 O 8 , LiNiO 2 , Li x Ni y M 1-y O 2 (where M is Represents at least one metal element selected from Co, Mn, Ti, Cr, V, Al, Sn, Pb, and Zn, and 0.05 ⁇ x ⁇ 1.10, 0.5 ⁇ y ⁇ 1. 0) and the like.
  • Specific examples of the polyanionic compound include LiFePO 4 .
  • Specific examples of the sulfur compound include Li 2 S and rubeanic acid.
  • the negative electrode active material constituting the negative electrode at least one element selected from alkali metals, alkali alloys, and elements of Groups 4 to 15 of the periodic table that occlude / release lithium ions, oxides, sulfides, nitrides Or a carbon material capable of reversibly occluding and releasing lithium ions can be used.
  • the alkali metal include Li, Na, and K.
  • Specific examples of the alkali metal alloy include metals Li, Li—Al, Li—Mg, Li—Al—Ni, Na, Na—Hg, and Na—Zn. Etc.
  • At least one element selected from Group 4 to 15 elements of the periodic table that store and release lithium ions include silicon, tin, aluminum, zinc, and arsenic.
  • specific examples of the oxide include tin silicon oxide (SnSiO 3 ), lithium bismuth oxide (Li 3 BiO 4 ), lithium zinc oxide (Li 2 ZnO 2 ), lithium titanium oxide (Li 4 Ti 5 O 12 ), and the like. Is mentioned.
  • specific examples of sulfides include lithium iron sulfide (Li x FeS 2 (0 ⁇ x ⁇ 3)), lithium copper sulfide (Li x CuS (0 ⁇ x ⁇ 3)), and the like.
  • Li x M y N Co, Ni, Cu, 0 ⁇ x ⁇ 3,0 ⁇ y ⁇ 0.5
  • lithium iron nitride Li 3 FeN 4
  • Specific examples of the carbon material capable of reversibly occluding and releasing lithium ions include graphite, carbon black, coke, glassy carbon, carbon fiber, carbon nanotube, or a sintered body thereof.
  • a carbonaceous material can be used as an active material.
  • the carbonaceous material include activated carbon and the like, for example, activated carbon obtained by carbonizing a phenol resin and then activating treatment.
  • a conductive additive can also be added to the electrode of the present invention.
  • the conductive aid include carbon black, ketjen black, acetylene black, carbon whisker, carbon fiber, natural graphite, artificial graphite, titanium oxide, ruthenium oxide, aluminum, nickel and the like.
  • the active material layer can be formed by applying the electrode slurry containing the active material, the binder polymer, and, if necessary, the solvent described above onto the conductive binder layer and naturally or by heating and drying.
  • the binder polymer can be appropriately selected from known materials and used, for example, polyvinylidene fluoride (PVdF), polyvinylpyrrolidone, polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, vinylidene fluoride- Hexafluoropropylene copolymer [P (VDF-HFP)], vinylidene fluoride-trichloroethylene copolymer [P (VDF-CTFE)], polyvinyl alcohol, polyimide, ethylene-propylene-diene ternary copolymer Examples thereof include conductive polymers such as coalescence, styrene-butadiene rubber, carboxymethyl cellulose (CMC), polyacrylic acid (PAA),
  • the added amount of the binder polymer is preferably 0.1 to 20 parts by mass, particularly 1 to 10 parts by mass with respect to 100 parts by mass of the active material.
  • the solvent include those exemplified for the above oxazoline polymer, and may be appropriately selected according to the type of the binder, but in the case of a water-insoluble binder such as PVdF, NMP is preferable, and PAA In the case of a water-soluble binder such as water, water is preferred.
  • Examples of the method for applying the electrode slurry include the same method as that for the conductive binder layer forming composition described above.
  • the temperature for drying by heating is also arbitrary, but is preferably about 50 to 200 ° C, more preferably about 80 to 150 ° C.
  • An energy storage device includes the above-described electrodes, and more specifically, includes at least a pair of positive and negative electrodes, a separator interposed between these electrodes, and an electrolyte. At least one of the positive and negative electrodes is composed of the above-described electrode for energy storage device. Since this energy storage device is characterized by the use of the above-mentioned electrode for energy storage device as an electrode, other device constituent members such as separators and electrolytes may be appropriately selected from known materials and used. it can. Specific examples of the separator include a cellulose separator and a polyolefin separator.
  • the electrolyte may be either liquid or solid, and may be either aqueous or non-aqueous.
  • the electrode for an energy storage device of the present invention is practically sufficient even when applied to a device using a non-aqueous electrolyte. Performance can be demonstrated.
  • non-aqueous electrolyte examples include a non-aqueous electrolyte obtained by dissolving an electrolyte salt in a non-aqueous organic solvent.
  • electrolyte salts include lithium salts such as lithium tetrafluoroborate, lithium hexafluorophosphate, lithium perchlorate, and lithium trifluoromethanesulfonate; tetramethylammonium hexafluorophosphate, tetraethylammonium hexafluorophosphate, tetrapropylammonium hexa
  • examples thereof include quaternary ammonium salts such as fluorophosphate, methyltriethylammonium hexafluorophosphate, tetraethylammonium tetrafluoroborate, and tetraethylammonium perchlorate.
  • non-aqueous organic solvent examples include alkylene carbonates such as propylene carbonate, ethylene carbonate, and butylene carbonate; dialkyl carbonates such as dimethyl carbonate, methyl ethyl carbonate, and diethyl carbonate; nitriles such as acetonitrile; and amides such as dimethylformamide. .
  • a precursor dispersion C was prepared in the same manner as in Production Example 1-1 except that the conductive carbon material was changed to 0.5 g of acetylene black (“DENKA BLACK” manufactured by Denki Kagaku Kogyo Co., Ltd.).
  • acetylene black (“DENKA BLACK” manufactured by Denki Kagaku Kogyo Co., Ltd.).
  • a conductive precursor dispersion D was prepared in the same manner as in Production Example 1-2 except that the precursor dispersion A was changed to the precursor dispersion C.
  • Example 1-1 Example 1-1, except that acetylene surfactant Olfine E-1004 was changed to 25 mg of acetylene surfactant Surfynol 420 (manufactured by Nissin Chemical Industry Co., Ltd., solid concentration 100 mass%).
  • a conductive carbon material dispersion was prepared by the method described above.
  • Example 1-3 50 g of the precursor dispersion D prepared in Production Example 1-4 and 25 mg of acetylene surfactant Olfine E-1004 (manufactured by Nissin Chemical Industry Co., Ltd., solid content concentration: 100% by mass) are mixed to form conductive carbon. A material dispersion was prepared.
  • Example 1-4 Except for changing the acetylene surfactant Olphine E-1004 to 25 mg of acetylene surfactant Surfynol 420 (manufactured by Nissin Chemical Industry Co., Ltd., solid content concentration: 100% by mass), the same as in Example 1-3 A conductive carbon material dispersion was prepared by the method described above.
  • Example 1-5 Except for changing the acetylene surfactant Olphine E-1004 to 25 mg of a silicone antifoaming agent Polyflow KL100 (manufactured by Kyoeisha Chemical Co., Ltd., solid content concentration: 100% by mass), the same method as in Example 1-1. A conductive carbon material dispersion was prepared.
  • Example 1-6 The same method as in Example 1-1, except that the acetylene-based surfactant Olphine E-1004 was changed to 25 mg of a metal soap-based antifoaming agent Nopco NXZ (manufactured by San Nopco, solid content concentration 100% by mass). A conductive carbon material dispersion was prepared.
  • Example 1-7 Except for changing the acetylene surfactant Olphine E-1004 to 26.9 mg of acrylic antifoaming agent Polyflow KL800 (manufactured by Kyoeisha Chemical Co., Ltd., solid content concentration: 93 mass%) 26.9 mg, the same as Example 1-1 A conductive carbon material dispersion was prepared by the method.
  • Example 1-1 The same method as in Example 2-1, except that the acetylene surfactant Olfine E-1004 was changed to 25 mg of the polyether antifoam SN deformer 170 (manufactured by San Nopco, solid content concentration 100% by mass). A conductive carbon material dispersion was prepared.
  • Example 1-2 The same method as in Example 1-1, except that the acetylene surfactant Olphine E-1004 was changed to 25 mg of the polyether antifoam SN deformer 260 (manufactured by San Nopco, solid concentration 100% by mass). A conductive carbon material dispersion was prepared.
  • Example 1-1 and Example 1-1 were used except that the acetylene surfactant Olfine E-1004 was changed to 25 mg of the polyether antifoam Disperse CC-438 (manufactured by NOF Corporation, solid content concentration: 100% by mass).
  • a conductive carbon material dispersion was prepared in the same manner.
  • Example 1-1 is the same as Example 1-1 except that the acetylene surfactant Olfine E-1004 was changed to 25 mg of a polyether antifoaming agent Distro CD-432 (manufactured by NOF Corporation, solid content concentration: 100% by mass).
  • Distro CD-432 manufactured by NOF Corporation, solid content concentration: 100% by mass.
  • a conductive carbon material dispersion was prepared in the same manner.
  • Example 1-1 and Example 1-1 except that the acetylene surfactant Olphine E-1004 was changed to 25 mg of a polyether antifoaming agent Disform CE-457 (manufactured by NOF Corporation, solid content concentration: 100% by mass).
  • a conductive carbon material dispersion was prepared in the same manner.
  • Example 1 except that the acetylene surfactant Olphine E-1004 was changed to 25 mg of a polyether antifoaming agent, an antifoaming agent PF-H (manufactured by Wako Pure Chemical Industries, Ltd., solid content concentration: 100% by mass).
  • a conductive carbon material dispersion was prepared in the same manner as in -1.
  • Example 1 except that the acetylene surfactant Olfine E-1004 was changed to 25 mg of a polyether antifoaming agent, an antifoaming agent PF-M (manufactured by Wako Pure Chemical Industries, Ltd., solid content concentration: 100% by mass).
  • a conductive carbon material dispersion was prepared in the same manner as in -1.
  • Example 2 except that the acetylene surfactant Orphine E-1004 was changed to 25 mg of a polyether antifoaming agent, an antifoaming agent PF-L (manufactured by Wako Pure Chemical Industries, Ltd., solid content concentration: 100% by mass).
  • PF-L an antifoaming agent manufactured by Wako Pure Chemical Industries, Ltd., solid content concentration: 100% by mass.
  • a conductive carbon material dispersion was prepared in the same manner as in -1.
  • Example 1-9 Example 1-1, except that the acetylene surfactant Olfine E-1004 was changed to 25 mg of the fluorine-based antifoaming agent Floren AO-82 (manufactured by San Nopco, solid concentration 1.8% by mass).
  • a conductive carbon material dispersion was prepared by the method described above.
  • Example 1-10 Except that the acetylene surfactant Olphine E-1004 was changed to 25 mg of a polyether antifoam Disperse CD-432 (manufactured by NOF Corporation, solid content concentration 100% by mass), Example 1-3 and A conductive carbon material dispersion was prepared in the same manner.
  • Example 2-1 Evaluation of conductive carbon material dispersion
  • the conductive carbon material dispersion prepared in Example 1-1 was added to a screw tube (manufactured by Maruemu Co., Ltd., No. 8), and shaken vigorously for 30 seconds to generate bubbles. After standing for 300 seconds, the liquid state of the conductive carbon material dispersion and the amount of bubbles on the liquid surface were visually confirmed. As a result, the liquid state of the conductive carbon material dispersion was maintained, the bubbles disappeared, and the liquid surface was exposed.
  • Example 2-2 Evaluation was made in the same manner as in Example 2-1, except that the conductive carbon material dispersion was changed to the conductive carbon material dispersion prepared in Example 1-2. As a result, the liquid state of the conductive carbon material dispersion was maintained, the bubbles disappeared, and the liquid surface was exposed.
  • Example 2-3 Evaluation was made in the same manner as in Example 2-1, except that the conductive carbon material dispersion was changed to the conductive carbon material dispersion prepared in Example 1-3. As a result, the liquid state of the conductive carbon material dispersion was maintained, the bubbles disappeared, and the liquid surface was exposed.
  • Example 2-4 Evaluation was made in the same manner as in Example 2-1, except that the conductive carbon material dispersion was changed to the conductive carbon material dispersion prepared in Example 1-4. As a result, the liquid state of the conductive carbon material dispersion was maintained, the bubbles disappeared, and the liquid surface was exposed.
  • Example 2-5 Evaluation was made in the same manner as in Example 2-1, except that the conductive carbon material dispersion was changed to the conductive carbon material dispersion prepared in Example 1-5. As a result, although the liquid state of the conductive carbon material dispersion changed and the CNTs aggregated, the bubbles disappeared and the liquid surface was exposed.
  • Example 2-6 Evaluation was made in the same manner as in Example 2-1, except that the conductive carbon material dispersion was changed to the conductive carbon material dispersion prepared in Example 1-6. As a result, although the liquid state of the conductive carbon material dispersion changed and aggregated, the bubbles disappeared and the liquid surface was exposed.
  • Example 2-7 Evaluation was made in the same manner as in Example 2-1, except that the conductive carbon material dispersion was changed to the conductive carbon material dispersion prepared in Example 1-7. As a result, although the liquid state of the conductive carbon material dispersion changed and the CNTs aggregated, the bubbles disappeared and the liquid surface was exposed.
  • Example 2-1 Evaluation was made in the same manner as in Example 2-1, except that the conductive carbon material dispersion was changed to the conductive carbon material dispersion prepared in Comparative Example 1-1. As a result, the liquid state of the conductive carbon material dispersion changed, the CNTs aggregated, and the liquid surface was covered with bubbles.
  • Example 2-2 Evaluation was made in the same manner as in Example 2-1, except that the conductive carbon material dispersion was changed to the conductive carbon material dispersion prepared in Comparative Example 1-2. As a result, the liquid state of the conductive carbon material dispersion changed, the CNTs aggregated, and the liquid surface was covered with bubbles.
  • Example 2-3 Evaluation was made in the same manner as in Example 2-1, except that the conductive carbon material dispersion was changed to the conductive carbon material dispersion prepared in Comparative Example 1-3. As a result, the liquid state of the conductive carbon material dispersion changed, the CNTs aggregated, and the liquid surface was covered with bubbles.
  • Example 2-4 Evaluation was made in the same manner as in Example 2-1, except that the conductive carbon material dispersion was changed to the conductive carbon material dispersion prepared in Comparative Example 1-4. As a result, the liquid state of the conductive carbon material dispersion changed, the CNTs aggregated, and the liquid surface was covered with bubbles.
  • Example 2-5 Evaluation was made in the same manner as in Example 2-1, except that the conductive carbon material dispersion was changed to the conductive carbon material dispersion prepared in Comparative Example 1-5. As a result, the liquid state of the conductive carbon material dispersion changed, the CNTs aggregated, and the liquid surface was covered with bubbles.
  • Example 2-6 Evaluation was made in the same manner as in Example 2-1, except that the conductive carbon material dispersion was changed to the conductive carbon material dispersion prepared in Comparative Example 1-6. As a result, the liquid state of the conductive carbon material dispersion liquid was maintained, but the liquid surface was covered with bubbles.
  • Example 2-7 Evaluation was made in the same manner as in Example 2-1, except that the conductive carbon material dispersion was changed to the conductive carbon material dispersion prepared in Comparative Example 1-7. As a result, the liquid state of the conductive carbon material dispersion liquid was maintained, but the liquid surface was covered with bubbles.
  • Example 2-8 Evaluation was made in the same manner as in Example 2-1, except that the conductive carbon material dispersion was changed to the conductive carbon material dispersion prepared in Comparative Example 1-8. As a result, the liquid state of the conductive carbon material dispersion liquid was maintained, but the liquid surface was covered with bubbles.
  • Example 2-9 Evaluation was made in the same manner as in Example 2-1, except that the conductive carbon material dispersion was changed to the conductive carbon material dispersion prepared in Comparative Example 1-9. As a result, the liquid state of the conductive carbon material dispersion changed, the CNTs aggregated, and the liquid surface was covered with bubbles.
  • Example 2-10 Evaluation was made in the same manner as in Example 2-1, except that the conductive carbon material dispersion was changed to the conductive carbon material dispersion prepared in Comparative Example 1-10. As a result, the liquid state of the conductive carbon material dispersion changed, acetylene black aggregated, and the liquid surface was covered with bubbles.
  • Example 2-11 Evaluation was made in the same manner as in Example 2-1, except that the conductive carbon material dispersion was changed to the precursor dispersion B prepared in Production Example 1-2. As a result, the liquid state of the conductive carbon material dispersion liquid was maintained, but the liquid surface was covered with bubbles.
  • Example 2-12 Evaluation was made in the same manner as in Example 2-1, except that the conductive carbon material dispersion was changed to the precursor dispersion D prepared in Production Example 1-4. As a result, the liquid state of the conductive carbon material dispersion liquid was maintained, but the liquid surface was covered with bubbles.
  • Table 1 A summary of Examples 2-1 to 2-7 and Comparative Examples 2-1 to 2-12 is shown in Table 1.
  • conductive carbon material dispersions prepared in Comparative Examples 2-1 to 2-8, 2-10 containing a polyether surfactant and Comparative Example 2-9 containing a fluorosurfactant In the conductive carbon material dispersion liquids prepared in Comparative Examples 2-11 and 12 to which no surfactant as a liquid or an antifoaming agent was added, when bubbles are generated, the bubbles do not disappear immediately.
  • Examples 2-1 to 2-4 containing an acetylene-based antifoaming agent examples 2-5 containing a silicone-based surfactant, Example 2-6 containing a metal soap-based antifoaming agent, acrylic-based antifoaming
  • the bubbles disappear immediately.
  • the conductive carbon material dispersion prepared in Example 2-5 containing a silicone surfactant, Example 2-6 containing a metal soap antifoaming agent, and Example 2-7 containing an acrylic antifoaming agent Then, the bubbles disappear immediately, but the liquid state of the conductive carbon material dispersion changes and aggregates.
  • the conductive carbon material dispersion liquid prepared in Examples 2-1 to 2-4 containing an acetylene-based antifoaming agent the bubbles disappeared immediately and a uniform dispersion state can be maintained.
  • Example 3-1 Coating of conductive carbon material dispersion
  • the conductive carbon material dispersion prepared in Example 1-1 was uniformly spread on an aluminum foil (thickness 15 ⁇ m) with a wire bar coater (select roller: OSP-30), and then dried at 150 ° C. for 20 minutes.
  • An aluminum foil hereinafter referred to as a composite current collector
  • the obtained composite current collector was cut into an area of 120 cm 2 and weighed, and then washed with a 0.1 mol / L dilute hydrochloric acid aqueous solution to remove the conductive binder layer.
  • the basis weight of the conductive binder layer was determined and found to be 268 mg / m 2 .
  • the film thickness was 0.199 micrometer.
  • the specific gravity of the conductive binder obtained from these values was 1.35 g / cm 3 .
  • Example 3-2 A composite current collector was obtained in the same manner as in Example 3-1, except that the selection roller: OSP-30 was changed to the selection roller: OSP-13. As a result of obtaining the basis weight of the obtained conductive binder layer, it was 147 mg / m 2 . The film thickness calculated from the basis weight and the specific gravity obtained in Example 3-1 was 0.109 ⁇ m.
  • Example 3-3 A composite current collector was obtained in the same manner as in Example 3-1, except that the selection roller: OSP-30 was changed to the selection roller: OSP-8. As a result of obtaining the basis weight of the obtained conductive binder layer, it was 93 mg / m 2 . The film thickness calculated from the basis weight and the specific gravity obtained in Example 3-1 was 0.069 ⁇ m.
  • Example 3-4 A composite current collector was obtained in the same manner as in Example 3-1, except that 10 g of the conductive carbon material dispersion prepared in Example 1-1 was diluted by adding 50 g of pure water. As a result of obtaining the basis weight of the obtained conductive binder layer, it was 19 mg / m 2 . The film thickness calculated from the basis weight and the specific gravity obtained in Example 3-1 was 0.014 ⁇ m.

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Abstract

La présente invention concerne une dispersion de matériau carboné conducteur comprenant un matériau carboné conducteur et au moins un agent antimousse choisi parmi des tensioactifs à base d'acétylène, des tensioactifs à base de silicone, des tensioactifs à base de savon métallique et des tensioactifs acryliques. La dispersion de matériau carboné conducteur peut supprimer la génération de bulles dans la dispersion de matériau carboné conducteur, peut être appliquée uniformément, et peut produire un film mince conducteur uniforme, même lorsqu'un dispersant ayant une activité tensioactive est utilisé.
PCT/JP2017/042729 2016-12-02 2017-11-29 Dispersion de matériau carboné conducteur Ceased WO2018101294A1 (fr)

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
JP2020029471A (ja) * 2018-08-20 2020-02-27 東洋インキＳｃホールディングス株式会社 カーボンナノチューブ分散液およびその利用
WO2022124160A1 (fr) * 2020-12-11 2022-06-16 株式会社豊田自動織機 Électrode destinée à un dispositif d'accumulation d'énergie et son procédé de fabrication
US11658302B2 (en) 2019-11-15 2023-05-23 Arakawa Chemical Industries, Ltd. Conductive carbon material dispersing agent for lithium ion battery, slurry for lithium ion battery electrode, electrode for lithium ion battery, and lithium ion battery
JP2023121647A (ja) * 2022-02-21 2023-08-31 住友ゴム工業株式会社 高帯電防止塗り床材および塗り床

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JP2003142105A (ja) * 2001-06-22 2003-05-16 Natl Starch & Chem Investment Holding Corp カソード塗料分散液
WO2005121263A1 (fr) * 2004-06-09 2005-12-22 Nippon Kayaku Kabushiki Kaisha Dispersion aqueuse, composition d’encre et méthode d’écriture à jet d’encre utilisant ladite méthode
JP2008056914A (ja) * 2006-07-31 2008-03-13 Honda Motor Co Ltd 水性プライマー塗料組成物及び塗膜形成方法
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020029471A (ja) * 2018-08-20 2020-02-27 東洋インキＳｃホールディングス株式会社 カーボンナノチューブ分散液およびその利用
US11658302B2 (en) 2019-11-15 2023-05-23 Arakawa Chemical Industries, Ltd. Conductive carbon material dispersing agent for lithium ion battery, slurry for lithium ion battery electrode, electrode for lithium ion battery, and lithium ion battery
WO2022124160A1 (fr) * 2020-12-11 2022-06-16 株式会社豊田自動織機 Électrode destinée à un dispositif d'accumulation d'énergie et son procédé de fabrication
JP2023121647A (ja) * 2022-02-21 2023-08-31 住友ゴム工業株式会社 高帯電防止塗り床材および塗り床

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