WO2019188430A1 - Liant d'électrode, mélange d'électrode, électrode pour dispositif d'énergie, dispositif d'énergie, résine pour dispositif d'énergie, dispersion de matériau carboné et procédé de production de dispersion de matériau carboné - Google Patents

Liant d'électrode, mélange d'électrode, électrode pour dispositif d'énergie, dispositif d'énergie, résine pour dispositif d'énergie, dispersion de matériau carboné et procédé de production de dispersion de matériau carboné Download PDF

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WO2019188430A1
WO2019188430A1 PCT/JP2019/010897 JP2019010897W WO2019188430A1 WO 2019188430 A1 WO2019188430 A1 WO 2019188430A1 JP 2019010897 W JP2019010897 W JP 2019010897W WO 2019188430 A1 WO2019188430 A1 WO 2019188430A1
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carbon material
polymer compound
resin
electrode
energy device
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PCT/JP2019/010897
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English (en)
Japanese (ja)
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広喜 葛岡
鈴木　健司
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日立化成株式会社
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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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/48—Conductive polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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 an electrode binder, an electrode mixture, an energy device electrode, an energy device, an energy device resin, a carbon material dispersion, and a method for producing a carbon material dispersion.
  • Lithium ion secondary batteries which are non-aqueous electrolyte energy devices having a high energy density, are widely used as power sources for portable information terminals such as notebook computers, mobile phones, and PDAs, and power sources for electric vehicles.
  • an electrode of a lithium ion secondary battery is manufactured as follows. First, a slurry-like electrode mixture is prepared by kneading an active material, a binder, a conductive additive for increasing the electronic conductivity of the active material, and a solvent. This electrode mixture is applied to one or both sides of a metal foil as a current collector with a transfer roll or the like, and the solvent is removed by drying to form a mixture layer. Then, an electrode is produced through the process of compression-molding a mixture layer with a roll press machine.
  • Patent Document 1 describes a composition for forming an electrode in which the dispersion stability of a conductive auxiliary agent is improved by using a polyvinyl alcohol-polyvinylpyrrolidone graft copolymer as a conductive auxiliary agent dispersant. .
  • the dispersion stability of the conductive auxiliary agent is enhanced by using a specific polymer in combination.
  • finding another method for improving the dispersion stability of the conductive auxiliary agent is This is beneficial from the viewpoint of improving performance.
  • Means for solving the above problems include the following embodiments.
  • An electrode binder comprising a polymer compound and an electron conductive carbon material chemically bonded to the polymer compound.
  • the polymer compound is at least one selected from the group consisting of an acrylic resin, a polydimethylsiloxane resin, a polyurethane resin, a polyamide resin, a polyimide resin, a phenol resin, and a melamine resin, ⁇ 1> or ⁇ 2>
  • ⁇ 4> The electrode binder according to any one of ⁇ 1> to ⁇ 3>, wherein the carbon material is carbon black.
  • An electrode mixture comprising the electrode binder according to any one of ⁇ 1> to ⁇ 4> and an active material.
  • the electrode for energy devices which has a ⁇ 6> collector and the electrode mixture layer provided on the at least one surface of the said collector, and containing the electrode mixture as described in ⁇ 5>.
  • An energy device comprising the energy device electrode according to ⁇ 6>.
  • the energy device resin according to ⁇ 8>, wherein the site capable of generating the radical is a peroxide structure.
  • ⁇ 10> The energy device resin according to ⁇ 8> or ⁇ 9>, wherein the polymer compound contains a nitrile group.
  • ⁇ 11> The energy device resin according to any one of ⁇ 8> to ⁇ 10>, wherein the polymer compound contains a structural unit derived from acrylonitrile.
  • ⁇ 12> A carbon material dispersion for energy devices, comprising a polymer compound, an electron conductive carbon material chemically bonded to the polymer compound, and a solvent.
  • ⁇ 13> The carbon material dispersion for energy devices according to ⁇ 12>, wherein the content of the polymer compound is 0.5% by mass or more based on the entire solid content.
  • ⁇ 14> The carbon material dispersion for energy devices according to ⁇ 12> or ⁇ 13>, wherein the solvent contains at least one selected from the group consisting of N-methyl-2-pyrrolidone and ⁇ -butyllactone.
  • ⁇ 15> The energy device according to any one of ⁇ 11> to ⁇ 14>, comprising a step of heating a polymer compound having a site capable of generating radicals, an electron conductive carbon material, and a solvent. For producing a carbon material dispersion liquid for use.
  • an electrode binder that can improve the dispersibility and dispersion stability of a conductive additive.
  • the electrode mixture using this electrode binder, the electrode for energy devices, and an energy device are provided.
  • an energy device resin, an energy device resin, a carbon material dispersion, and a method for producing the carbon material dispersion that can improve the dispersibility and dispersion stability of the conductive additive.
  • the present invention is not limited to the following embodiments.
  • the components including element steps and the like are not essential unless otherwise specified.
  • the term “process” includes a process that is independent of other processes and includes the process if the purpose of the process is achieved even if it cannot be clearly distinguished from the other processes. It is.
  • numerical values indicated by using “to” include numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range. Good. Further, in the numerical ranges described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
  • the content of each component in the composition is the sum of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. It means the content rate of.
  • the particle diameter of each component in the composition is a mixture of the plurality of types of particles present in the composition unless there is a specific indication when there are a plurality of types of particles corresponding to each component in the composition. Means the value of.
  • the term “layer” or “film” refers to a part of the region in addition to the case where the layer or the film is formed when the region where the layer or film exists is observed. It is also included when it is formed only.
  • laminate indicates that layers are stacked, and two or more layers may be combined, or two or more layers may be detachable.
  • (meth) acryl means at least one of acryl and methacryl
  • (meth) acrylate means at least one of acrylate and methacrylate
  • (meth) allyl means at least one of allyl and methallyl. Mean one.
  • the electrode binder of the present disclosure (hereinafter, also simply referred to as “binder”) is a polymer compound (sometimes referred to as an oligomer which is a polymer having a relatively low molecular weight to which a relatively small number of monomers are bonded). And an electronically conductive carbon material (hereinafter also simply referred to as a carbon material) chemically bonded to the polymer compound.
  • an electrode mixture having excellent dispersibility and dispersion stability of a carbon material used as a conductive aid can be produced. This is thought to be due to the fact that the polymer compound functions not only as a binder, but also because the polymer compound is chemically bonded to the carbon material to act to increase its dispersibility and dispersion stability. . In addition, since the polymer compound is chemically bonded to the carbon material, the effect of improving the dispersibility and dispersion stability of the carbon material by the polymer compound is greater than when both components are simply mixed. This is probably because of this.
  • the specific mode in which the polymer compound and the carbon material are “chemically bonded” is not particularly limited.
  • a covalent bond, an ionic bond, etc. are mentioned.
  • the method for producing a state in which the polymer compound and the carbon material are chemically bonded is not particularly limited.
  • the state in which the polymer compound and the carbon material are chemically bonded is It is preferable to use a polymer compound having a site capable of generating radicals. It is considered that a site capable of generating a radical of the polymer compound is cleaved by heating to generate a radical, which pulls out a hydrogen atom present on the surface of the carbon material. It is presumed that molecules of the polymer compound are bound to the carbon material by using this hydrogen atom extraction reaction as a driving force. Examples of the site capable of generating a radical include a peroxide structure (—O—O—).
  • the number of sites that can generate radicals in the polymer compound may be one or more than one per molecule.
  • the position of the site capable of generating radicals in the polymer compound is not particularly limited. For example, it may be present in the main chain of the polymer compound (for example, at least near one end) or may be present in the side chain.
  • the state in which the polymer compound and the carbon material are chemically bonded may be performed by a known grafting method other than the method described above.
  • the graft method is a polymer in which a functional group present on the surface of the carbon material is used as a polymerization reaction start point, and a monomer that is a raw material of the polymer compound is polymerized and chemically bonded to the surface of the carbon material.
  • a method for synthesizing a compound is mentioned.
  • the polymerization method is not particularly limited, and includes radical polymerization, living radical polymerization, anionic polymerization, living anion polymerization, cationic polymerization, living cationic polymerization, addition polymerization, condensation polymerization, ring-opening polymerization and the like.
  • a polymer compound is chemically bonded to the surface of the carbon material by using a polymer compound having a functional group capable of reacting with a functional group present on the surface of the carbon material.
  • a high molecular compound having a functional group at one end of the main chain (a macromonomer that is a polymer having a relatively low molecular weight, has a functional group to be polymerized, and can be regarded as a monomer, and so on. ) With a functional group present on the surface of the carbon material, a polymer compound in which one end of the main chain is chemically bonded to the carbon material can be obtained.
  • the ratio between the polymer compound and the carbon material is not particularly limited.
  • the mass of the carbon material when the mass of the polymer compound is 1 may be in the range of 0.1 to 10.0, or may be in the range of 0.5 to 5.0.
  • Polymer compound The kind of the high molecular compound which comprises the binder of this indication is not restrict
  • acrylic resin, polyester resin, polydimethylsiloxane resin, polyurethane resin, polyamide resin, polyimide resin, phenol resin, melamine resin, and the like can be given.
  • the polymer compound is preferably one having a small degree of swelling in the electrolytic solution.
  • examples of such a polymer compound include a polymer compound containing a nitrile group.
  • the polymer compound containing a nitrile group is obtained, for example, by polymerizing a monomer containing a nitrile group (hereinafter also referred to as a nitrile group-containing monomer) and other monomers as necessary. Can do.
  • the polymer compound may be a polymer of one kind of monomer or a polymer (copolymer) of two or more kinds of monomers.
  • the kind of the nitrile group-containing monomer used for the polymerization of the polymer compound is not particularly limited.
  • a compound having an ethylenically unsaturated double bond and a nitrile group which can introduce a nitrile group into the side chain of the polymer compound.
  • acrylic nitrile group-containing monomers such as acrylonitrile and methacrylonitrile
  • cyan nitrile group-containing monomers such as ⁇ -cyanoacrylate and dicyanovinylidene
  • fumaric nitrile group-containing monomers such as fumaronitrile.
  • the nitrile group containing monomer containing coupling groups such as an alkylene group, is mentioned.
  • a nitrile group containing monomer may be used individually by 1 type, and may be used in combination of 2 or more type.
  • acrylonitrile or methacrylonitrile is preferable, and acrylonitrile is more preferable in terms of ease of polymerization, cost performance, electrode flexibility and flexibility.
  • Monomers that can be used in the preparation of the polymer compound include the above-mentioned nitrile group-containing monomers, monomers containing oxyethylene chains (hereinafter also referred to as oxyethylene chain-containing monomers), acidic Examples thereof include monomers containing functional groups (hereinafter also referred to as acidic functional group-containing monomers).
  • oxyethylene chain-containing monomer By using an oxyethylene chain-containing monomer for polymerizing the polymer compound, an effect of imparting lithium ion conductivity to the polymer compound can be expected.
  • Specific examples of the oxyethylene chain-containing monomer include monomers represented by the following formula (I).
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents a hydrogen atom or a monovalent hydrocarbon group
  • n represents an integer of 1 to 50.
  • n is an integer of 1 to 50, preferably an integer of 2 to 30, and more preferably an integer of 2 to 10.
  • R 2 is a hydrogen atom or a monovalent hydrocarbon group, and is preferably a monovalent hydrocarbon group having 1 to 50 carbon atoms, for example, having 1 to 25 carbon atoms.
  • the monovalent hydrocarbon group is more preferably a monovalent hydrocarbon group having 1 to 12 carbon atoms. If R 2 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 50 carbon atoms, sufficient swelling resistance to the electrolytic solution tends to be obtained.
  • examples of the hydrocarbon group include an alkyl group and a phenyl group.
  • R 2 is particularly suitably an alkyl group having 1 to 12 carbon atoms or a phenyl group.
  • the alkyl group may be linear, branched or cyclic.
  • a part of hydrogen atoms may be substituted with a substituent.
  • substituents in the case where R 2 is an alkyl group include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, a substituent containing a nitrogen atom, a substituent containing a phosphorus atom, and an aromatic ring. .
  • Examples of the substituent when R 2 is a phenyl group include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, a substituent containing a nitrogen atom, a substituent containing a phosphorus atom, an aromatic ring, and a carbon number. Examples thereof include 3 to 10 cycloalkyl groups.
  • a monomer represented by the formula (I) a commercially available product or a synthetic product may be used. Specific examples of commercially available monomers represented by the formula (I) include 2-methoxyethyl acrylate, ethoxydiethylene glycol acrylate (trade name: Light acrylate EC-, manufactured by Kyoeisha Chemical Co., Ltd.).
  • methoxytriethylene glycol acrylate (R 1 in the general formula (I) is a hydrogen atom
  • R 2 is a methyl group, from the viewpoint of reactivity when copolymerized with a nitrile group-containing monomer, A compound in which n is 3) is more preferable.
  • These monomers represented by the general formula (I) may be used singly or in combination of two or more.
  • the acidic functional group-containing monomer used for the polymerization of the polymer compound is not particularly limited.
  • the compound which has an ethylenically unsaturated double bond and an acidic functional group Comprising: The compound which can introduce
  • the acidic functional group include a carboxy group, a sulfo group, and a phospho group, and among them, a carboxy group is preferable.
  • Monomers containing a carboxy group as an acidic functional group include acrylic carboxy group-containing monomers such as acrylic acid and methacrylic acid, croton carboxy group-containing monomers such as crotonic acid, maleic acid, and anhydrides thereof.
  • Maleic carboxy group-containing monomers such as itaconic acid and its anhydride, etc.
  • carboxy group-containing monomers such as citraconic acid and its anhydride, citraconic carboxy group-containing monomers such as vinyl benzoic acid, etc.
  • the acidic functional group containing monomer containing coupling groups such as an alkylene group, is mentioned.
  • Monomers containing a sulfo group as an acidic functional group include vinylbenzene sulfonic acid, (meth) allyl sulfonic acid, (meth) allyloxybenzene sulfonic acid, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid And salts thereof (sodium salt, lithium salt, etc.).
  • Examples of the monomer containing a phospho group as an acidic functional group include acid phosphooxyethyl methacrylate (Unichemical Co., Ltd., trade name: Phosmer M), acid phosphoxypolyoxyethylene glycol monomethacrylate (Unichemical Co., Ltd., trade name) : Phosmer PE), 3-chloro-2-acid phosphoxypropyl methacrylate (Unichemical Corporation, trade name: Phosmer CL), Acid phosphooxypolyoxypropylene glycol monomethacrylate (Unichemical Corporation, trade name: Phosmer PP) Etc.
  • acid phosphooxyethyl methacrylate Unichemical Co., Ltd., trade name: Phosmer M
  • acid phosphoxypolyoxyethylene glycol monomethacrylate Unichemical Co., Ltd., trade name) : Phosmer PE
  • 3-chloro-2-acid phosphoxypropyl methacrylate Unichemical Corporation, trade name: Phosmer CL
  • a monomer containing a carboxy group as an acidic functional group is preferable, acrylic acid or methacrylic acid is more preferable, and acrylic acid is more preferable.
  • a salt may be formed by reacting with a basic compound as necessary.
  • the polymer compound may be obtained by polymerizing monomers other than the monomers described above.
  • monomers other than the above-mentioned monomers (meth) acrylic acid esters containing alkyl groups such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, vinyl chloride, vinyl bromide And vinyl halides such as vinylidene chloride, maleic imide, phenylmaleimide, (meth) acrylamide, styrene, ⁇ -methylstyrene, and vinyl acetate.
  • the ratio of the nitrile group-containing monomer is not particularly limited, but 50 mol of all monomers. % Or more and less than 100 mol%, more preferably 80 mol% or more and less than 100 mol%, further preferably 90 mol% or more and less than 100 mol%.
  • the molecular weight of the polymer compound (the length of the graft chain from the carbon material) is not particularly limited, and is appropriately adjusted according to the selection of the constituent material.
  • the molecular weight of the polymer compound is preferably not too small in order to sufficiently obtain the effect of improving the dispersibility and dispersion stability of the carbon material.
  • the degree of polymerization does not increase due to steric hindrance due to the overlap between the graft chains, or the state where the graft chain cannot be bonded to the carbon material. Is preferably not too large.
  • the weight average molecular weight of the polymer compound is 50,000 to 200,000 from the viewpoints of the coating property and coating stability of the polymer compound fixed on the surface of the active material. And more preferably 70,000 to 150,000.
  • the weight average molecular weight of the polymer compound can be adjusted by the temperature during the polymerization reaction (the molecular weight tends to decrease as the temperature increases), the type of polymerization initiator, the addition of a chain transfer agent, and the like.
  • the weight average molecular weight of the polymer compound is a value measured as follows. A measurement object was dissolved in N-methyl-2-pyrrolidone, and a PTFE (polytetrafluoroethylene) filter [Kurashiki Boseki Co., Ltd., HPLC (high performance liquid chromatography) pretreatment, chromatodisc, model number: 13N, pore size: 0 .45 ⁇ m] to remove insoluble matter.
  • PTFE polytetrafluoroethylene
  • GPC [Pump: L6200 Pump (Hitachi, Ltd.), Detector: Differential refractive index detector L3300 RI Monitor (Hitachi, Ltd.), Column: TSKgel-G5000HXL and TSKgel-G2000HXL (both in total) (both Tosoh Corporation) ) In series, column temperature: 30 ° C., eluent: N-methyl-2-pyrrolidone, flow rate: 1.0 mL / min, standard substance: polystyrene], and the weight average molecular weight is measured.
  • the acid value of the polymer compound is preferably 0 mgKOH / g to 70 mgKOH / g, more preferably 0 mgKOH / g to 20 mgKOH / g, and still more preferably 0 mgKOH / g to 5 mgKOH / g.
  • the acid value of the polymer compound is a value measured as follows. First, after precisely weighing 1 g of a measurement object, 30 g of acetone is added to the measurement object, and the measurement object is dissolved. Next, an appropriate amount of an indicator, phenolphthalein, is added to the solution to be measured and titrated with a 0.1N aqueous KOH solution.
  • A The nonvolatile content of the solution to be measured is calculated from the weight of the residue by weighing about 1 mL of the solution to be measured in an aluminum pan, drying it on a hot plate heated to 160 ° C. for 15 minutes.
  • the method for synthesizing the polymer compound is not particularly limited. Polymerization methods such as precipitation polymerization in water, bulk polymerization, suspension polymerization, emulsion polymerization, and solution polymerization can be applied. In terms of ease of resin synthesis, ease of post-treatment such as recovery and purification, precipitation polymerization in water and emulsion polymerization are preferred, and precipitation polymerization in water is more preferred. On the other hand, the monomer used for the synthesis of the polymer compound and the solubility of the compound capable of introducing the peroxide structure used as necessary, the dissolution step in the solvent for producing the electrode for the energy device can be omitted. In view of the above, solution polymerization using an organic solvent as a solvent is preferable.
  • a polymerization initiator When synthesizing a polymer compound, a polymerization initiator may be used as necessary.
  • the polymerization initiator is preferably used in a range of 0.001 mol% to 5 mol%, for example, 0.01 mol% to 2 mol, based on the total amount of monomers used for the synthesis of the polymer compound. More preferably, it is used in the range of mol%.
  • a chain transfer agent When synthesizing a polymer compound, a chain transfer agent may be used for the purpose of adjusting the molecular weight.
  • the chain transfer agent include mercaptan compounds such as thioglycol, carbon tetrachloride, ⁇ -methylstyrene dimer, and the like. Of these, ⁇ -methylstyrene dimer is preferred from the viewpoint of low odor.
  • a solvent When synthesizing the polymer compound, a solvent may be used.
  • the solvent include water and an organic solvent.
  • water and an organic solvent When the polymer compound is synthesized by precipitation polymerization in water, water and an organic solvent may be used in combination for adjusting the particle size of the polymer compound to be precipitated.
  • solvents other than water examples include amides such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N, N-dimethylethyleneurea, N, N-dimethylpropyleneurea, tetra Ureas such as methylurea, lactones such as ⁇ -butyrolactone and ⁇ -caprolactone, carbonates such as propylene carbonate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, n-butyl acetate , Esters such as butyl cellosolve acetate, butyl carbitol acetate, ethyl cellosolve acetate and ethyl carbitol acetate, glymes such as diglyme, triglyme and tetraglyme, carbon
  • These solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the polymer compound contains a large amount of nitrile groups
  • the same solvent as that used for producing the energy device electrode may be used.
  • N-methyl-2-pyrrolidone is used. Also good.
  • the synthesis condition of the polymer compound is not particularly limited.
  • a monomer and a compound capable of introducing a peroxide compound used as necessary are introduced into a solvent, and the polymerization temperature is preferably 0 ° C. to 100 ° C., more preferably 30 ° C. to 90 ° C., preferably It is carried out by holding for 1 hour to 50 hours, more preferably 2 hours to 12 hours.
  • the method for synthesizing the polymer compound having a peroxide structure is not particularly limited. For example, it may be synthesized using a monomer that is a raw material of the polymer compound and a compound that can introduce a peroxide structure into the polymer compound.
  • the peroxide structure into the polymer compound, it is preferable to use a compound having two peroxide structures as the compound capable of introducing the peroxide structure. It is more preferable to use a compound capable of generating the radical represented.
  • R 3 in the formula is an alkyl group having 1 to 10 carbon atoms
  • R 4 is a group obtained by removing one hydrogen atom from an alkyl group having 1 to 10 carbon atoms.
  • R 3 is a t-butyl group
  • R 4 is a group obtained by removing one hydrogen atom from an alkyl group having 5 carbon atoms.
  • the radical represented by the following reaction formula (1) A radical obtained by cleaving one of the two peroxide structures of the compound by heating (eg, 70 ° C.) is ring-opened as shown in the following reaction formula (2), and polymerized with an arbitrary monomer. By doing so, a polymer compound having a peroxide structure derived from the radical represented by the general formula (II) can be obtained.
  • the presumed reaction mechanism in which the molecule of the polymer compound having a peroxide structure is chemically bonded to the carbon material is as follows.
  • a carbon material for example, 90 ° C. or more
  • the peroxide structure is cleaved to generate radical A (t-BuO.)
  • CO 2 and radical B represented by the following structural formula are generated.
  • radical A extracts hydrogen atoms bonded to carbon atoms of the carbon material and changes to t-BuOH
  • radical B combines with carbon atoms from which hydrogen atoms have been extracted by radical A, and It is estimated that a state in which the carbon material and the carbon material are chemically bonded is formed.
  • a compound capable of introducing a peroxide structure into a polymer compound there are two compounds in a molecule such as 1,1-di (t-butylperoxy) cyclohexane and 1,1-di (t-hexylperoxy) cyclohexane.
  • Examples thereof include peroxyketal compounds having a peroxide structure and alkyl-substituted or unsubstituted dicyclohexanone peroxide compounds having at least one hydroxyperoxide structure in the molecule such as 1-hydroxycyclohexyl-1-hydroxycyclohexyl peroxide.
  • these compounds are preferably used because the peroxide structure is cleaved in two stages, at the time of synthesizing the polymer compound and at the time of reacting the polymer compound with the carbon material.
  • Carbon material The carbon material in the binder of the present disclosure is not particularly limited as long as it has electronic conductivity. From the viewpoint of various properties as a conductive additive, carbon materials having electronic conductivity include carbon black, carbon nanotube, carbon nanofiber, vapor grown carbon fiber, carbon microcoil, nanodiamond, graphene nanosheet, C60 fullerene, etc. Among them, carbon black is preferable.
  • a carbon material may be used individually by 1 type, and may be used in combination of 2 or more type.
  • Carbon black includes furnace black (oil furnace black), acetylene black, ketjen black, channel black, lamp black, thermal black, and the like.
  • furnace black and acetylene black are preferable from the viewpoint of electron conductivity, and furnace black is more preferable from the viewpoint of balance between electron conductivity and the amount of functional groups described later.
  • the degree of electronic conductivity of the carbon material can be grasped with reference to a conductivity index represented by the following formula, for example.
  • Conductivity index ((specific surface area ⁇ DBP absorption)) 1/2 / (1 + volatile content)
  • the specific surface area in the above formula is a nitrogen adsorption specific surface area (m 2 / g) measured according to JIS K6217-2: 2001.
  • DBP absorption amount in the above formula, JIS K6217-2: a DBP is measured according to 2001 the amount of absorption of dibutyl phthalate () (cm 3 / 100g).
  • the volatile content in the above formula is a mass reduction rate (%) when the carbon material is heated at 950 ° C. for 7 minutes, and is an indicator of the amount of functional groups present on the surface of the carbon material. It can be said that the larger the volatile content, the more functional groups present on the surface of the carbon material.
  • the carbon material preferably has a conductivity index value of 30 or more, more preferably 40 or more, and even more preferably 50 or more.
  • the carbon material may have hydrogen atoms bonded to carbon atoms on the surface.
  • the carbon material and the polymer compound are chemically bonded using a reaction in which the generated radicals extract a hydrogen atom bonded to a carbon atom. It can be in a state of being.
  • the carbon material may have a functional group capable of reacting with a polymer compound or a monomer that is a raw material thereof on the surface. By using this functional group, the carbon material and the polymer compound can be chemically bonded.
  • the kind of functional group present on the surface of the carbon material is not particularly limited.
  • the amount of functional groups present on the surface of the carbon material is not particularly limited.
  • the amount of volatile content described above is preferably an amount that is 0.1% or more, and more preferably an amount that is 0.5% or more.
  • the upper limit of the amount of the functional group present on the surface of the carbon material is not particularly limited, but from the viewpoint of suppressing the reaction of the functional group that does not contribute to the chemical bond with the polymer compound with the electrolytic solution, for example, volatilization It is preferable that the amount is 3% or less.
  • a non-aqueous electrolyte-based energy device refers to a power storage or power generation device (apparatus) that uses an electrolyte other than water.
  • the energy device include a lithium ion secondary battery, an electric double layer capacitor, a solar cell, and a fuel cell.
  • lithium ion secondary batteries examples include all-solid batteries that use a solid electrolyte instead of the electrolyte, in addition to those that use an electrolyte. All-solid-state batteries are being actively studied for development as lithium ion secondary batteries that are superior in safety.
  • the electrode mixture of the present disclosure includes the binder described above and an active material.
  • the type of active material contained in the electrode mixture is not particularly limited, and can be selected from those generally used as an electrode material for energy devices.
  • the electrode mixture of the present disclosure may be used for producing a negative electrode (that is, including a negative electrode active material) or may be used for producing a positive electrode (that is, including a positive electrode active material).
  • the active material may be a composite of two or more materials (for example, graphite and amorphous carbon), or may be a mixture of two or more materials.
  • the electrode mixture is for a negative electrode and contains a negative electrode active material
  • a negative electrode active material specifically, as the negative electrode active material, a carbon material, silicon oxide, metal lithium, lithium alloy, intermetallic compound, metal complex, organic polymer compound, etc. Is mentioned.
  • a carbon material is preferable, and a mixture of a carbon material and a silicon oxide is preferable in terms of increasing energy density.
  • the distance (d 002 ) between the carbon hexagonal planes in the X-ray wide angle diffraction method is 3.35 mm to 3.40 mm, and the crystallite in the c-axis direction (Lc ) Is preferably a carbon material (graphite) having 100% or more.
  • a carbon material (amorphous carbon) in which the spacing (d 002 ) of the carbon hexagonal plane in the X-ray wide angle diffraction method is 3.50 to 3.95 mm Is preferred.
  • the type of the positive electrode active material is not particularly limited.
  • Specific examples include lithium-containing metal composite oxides, olivine-type lithium salts, chalcogen compounds, and manganese dioxide.
  • the lithium-containing metal composite oxide is a metal oxide containing lithium and a transition metal or a metal oxide in which a part of the transition metal in the metal oxide is substituted with a different element.
  • the different elements include Na, Mg, Sc, Y, Mn, Fe, Co, Ni, Cu, Zn, Al, Cr, Pb, Sb, V, and B.
  • Mn, Al, Co, Ni, Mg or the like is preferable.
  • Different elements may be used alone or in combination of two or more. From the viewpoint of increasing the energy density, it is preferable to use Ni at a high ratio.
  • the average particle diameter of the active material is preferably 0.1 ⁇ m to 60 ⁇ m, and more preferably 0.5 ⁇ m to 30 ⁇ m. Further, the BET specific surface area of the active material is preferably 0.1 m 2 / g to 10 m 2 / g.
  • the average particle size is a volume average particle size measured by a laser diffraction method, and is a volume-based particle size distribution measured using a laser diffraction particle size distribution measuring apparatus (for example, SALD-3000J manufactured by Shimadzu Corporation). , The value when the integration from the small diameter side becomes 50% (median diameter (D50)).
  • the BET specific surface area is, for example, a value measured from nitrogen adsorption capacity according to JIS Z 8830: 2013.
  • the electrode mixture may contain a liquid medium.
  • a liquid medium is preferably contained when the binder is used (when mixed with the active material).
  • the viscosity at the time of using the electrode mixture is, for example, preferably 500 mPa ⁇ s to 50000 mPa ⁇ s at 25 ° C., more preferably 1000 mPa ⁇ s to 20000 mPa ⁇ s, and 2000 mPa ⁇ s to 10000 mPa ⁇ s. More preferably it is.
  • the viscosity is measured at 25 ° C. and a shear rate of 1.0 s ⁇ 1 using a rotary shear viscometer.
  • the electrode mixture may contain components other than the binder, the active material, and the liquid medium as necessary.
  • a crosslinking component to supplement the swelling resistance to the electrolyte a rubber component to supplement the flexibility and flexibility of the electrode, a thickener to improve the coating property of the electrode mixture, and an anti-settling agent
  • Various additives such as an agent, an antifoaming agent, and a leveling agent may be included.
  • the conductive support agent other than the carbon material contained in the binder mentioned above may be included.
  • the state of the electrode mixture is not particularly limited and can be selected according to the storage method, the electrode formation method, and the like. For example, it may be a slurry.
  • the electrode for an energy device according to the present disclosure includes a current collector and an electrode mixture layer that is provided on at least one surface of the current collector and includes the electrode mixture described above.
  • the electrode for energy devices of this indication can be used as electrodes, such as a lithium ion secondary battery (electrolyte system and solid electrolyte system), an electric double layer capacitor, a solar cell, and a fuel cell.
  • a lithium ion secondary battery electrolyte system and solid electrolyte system
  • an electric double layer capacitor such as a solar cell, and a fuel cell.
  • the electrode for an energy device of the present disclosure is applied to an electrode of a lithium ion secondary battery (electrolytic solution system) will be described in detail.
  • the electrode for the energy device of the present disclosure is not limited to the following contents. Absent.
  • the type of current collector is not particularly limited. For example, it may be selected from those commonly used in the field of lithium ion secondary batteries.
  • Examples of the current collector (negative electrode current collector) used for the negative electrode of the lithium ion secondary battery include sheets and foils containing stainless steel, nickel, copper, and the like. Among these, a sheet or foil containing copper is preferable.
  • the thickness of the sheet and foil is not particularly limited, and is preferably 1 ⁇ m to 500 ⁇ m, more preferably 2 ⁇ m to 100 ⁇ m, and more preferably 5 ⁇ m from the viewpoint of ensuring the strength and workability required for the current collector. More preferably, it is ⁇ 50 ⁇ m.
  • Examples of the current collector (positive electrode current collector) used for the positive electrode of the lithium ion secondary battery include sheets and foils containing stainless steel, aluminum, titanium, and the like. Among these, a sheet or foil containing aluminum is preferable.
  • the thickness of the sheet and foil is not particularly limited, and is preferably 1 ⁇ m to 500 ⁇ m, more preferably 2 ⁇ m to 80 ⁇ m, and more preferably 5 ⁇ m, from the viewpoint of ensuring the strength and workability required for the current collector. More preferably, it is ⁇ 50 ⁇ m.
  • the electrode mixture layer can be formed using the electrode mixture described above. Specifically, for example, it can be formed by applying a slurry-like electrode mixture on at least one surface of the current collector, then drying and removing the solvent, and rolling as necessary.
  • the application of the slurry-like electrode mixture can be performed using, for example, a comma coater.
  • the coating is suitably performed so that the ratio between the positive electrode capacity and the negative electrode capacity (negative electrode capacity / positive electrode capacity) is 1 or more in the opposing electrode.
  • the application amount of the slurry-like electrode mixture is, for example, preferably such that the dry mass per one side of the electrode mixture layer is 5 g / m 2 to 500 g / m 2 , and is 50 g / m 2 to 300 g / m 2 . More preferably.
  • the removal of the solvent is performed, for example, by drying at 50 ° C. to 150 ° C., preferably 80 ° C. to 120 ° C., for 1 minute to 20 minutes, preferably 3 minutes to 10 minutes.
  • Rolling is performed, for example, using a roll press, and when the density of the mixture layer is a mixture layer of the negative electrode, for example, 1 g / cm 3 to 2 g / cm 3 , preferably 1.2 g / cm 3 to In the case of the positive electrode material mixture layer so as to be 1.8 g / cm 3 , for example, it is pressed so as to be 2 g / cm 3 to 5 g / cm 3 , preferably 2 g / cm 3 to 4 g / cm 3. . Furthermore, in order to remove residual solvent and adsorbed water in the electrode, for example, vacuum drying may be performed at 100 to 150 ° C. for 1 to 20 hours.
  • the energy device of this indication has the electrode for energy devices mentioned above. Since the electrode for energy devices of this indication uses the binder mentioned above, it is excellent in the dispersibility and dispersion stability of a conductive support agent. For this reason, it exists in the tendency which is excellent in characteristics, such as cycling characteristics.
  • At least the positive electrode of the energy device is the energy device electrode described above.
  • Examples of the energy device of the present disclosure include lithium ion secondary batteries (electrolyte and solid electrolyte systems), electric double layer capacitors, solar cells, fuel cells, and the like.
  • the energy device is a lithium ion secondary battery (electrolytic solution system) will be described in detail, but the energy device of the present disclosure is not limited to the following contents.
  • An electrolytic solution type lithium ion secondary battery includes, for example, a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolytic solution.
  • a positive electrode for example, a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolytic solution.
  • an electrolytic solution for details of the positive electrode and the negative electrode, reference can be made to those described in the above-mentioned energy device electrode.
  • the separator is not particularly limited as long as it has ion permeability while electronically insulating the positive electrode and the negative electrode and has resistance to oxidation on the positive electrode side and reducibility on the negative electrode side.
  • a material (material) of the separator that satisfies such characteristics a resin, an inorganic substance, or the like is used.
  • an olefin polymer As the resin, an olefin polymer, a fluorine polymer, a cellulose polymer, polyimide, nylon, or the like is used. Specifically, it is preferable to select from materials that are stable with respect to the electrolytic solution and have excellent liquid retention properties, and it is preferable to use a porous sheet made of polyolefin such as polyethylene and polypropylene, a nonwoven fabric, and the like.
  • inorganic substances include oxides such as alumina and silicon dioxide, nitrides such as aluminum nitride and silicon nitride, sulfates such as barium sulfate and calcium sulfate, and glass.
  • oxides such as alumina and silicon dioxide
  • nitrides such as aluminum nitride and silicon nitride
  • sulfates such as barium sulfate and calcium sulfate
  • glass glass
  • thin film-shaped base materials such as a nonwoven fabric, a woven fabric, and a microporous film
  • a substrate having a pore diameter of 0.01 ⁇ m to 1 ⁇ m and a thickness of 5 ⁇ m to 50 ⁇ m is preferably used.
  • a separator in which a composite porous layer is formed using the above-described inorganic material in a fiber shape or a particle shape by using a binder such as a resin can be used as a separator.
  • this composite porous layer may be formed on the surface of the positive electrode or the negative electrode to form a separator.
  • this composite porous layer may be formed on the surface of another separator to form a multilayer separator.
  • a composite porous layer in which alumina particles having a 90% particle diameter (D90) of less than 1 ⁇ m are bound using a fluororesin as a binder may be formed on the surface of the positive electrode.
  • the electrolytic solution contains a solute (supporting salt) and a nonaqueous solvent, and further contains various additives as necessary.
  • the solute is usually in a dissolved state in a non-aqueous solvent.
  • the electrolytic solution is impregnated in the separator.
  • borates include lithium bis (1,2-benzenediolate (2-)-O, O ′) borate, bis (2,3-naphthalenedioleate (2-)-O, O ′) boric acid.
  • imide salts include lithium bistrifluoromethanesulfonate imide ((CF 3 SO 2 ) 2 NLi), lithium trifluoromethanesulfonate nonafluorobutanesulfonate ((CF 3 SO 2 ) (C 4 F 9 SO 2 ) NLi ), Lithium bispentafluoroethanesulfonate imide ((C 2 F 5 SO 2 ) 2 NLi), and the like.
  • a solute may be used individually by 1 type, and may be used in combination of 2 or more type. The amount of the solute dissolved in the nonaqueous solvent is preferably 0.5 mol / L to 2 mol / L.
  • non-aqueous solvent those commonly used in this field can be used.
  • specific examples include cyclic carbonates, chain carbonates, and cyclic carboxylic acid esters.
  • the cyclic carbonate include propylene carbonate (PC) and ethylene carbonate (EC).
  • the chain carbonate include diethyl carbonate (DEC), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC) and the like.
  • the cyclic carboxylic acid ester include ⁇ -butyrolactone (GBL) and ⁇ -valerolactone (GVL).
  • a non-aqueous solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the non-aqueous solvent preferably contains vinylene carbonate (VC).
  • VC vinylene carbonate
  • the content is preferably 0.1% by mass to 2% by mass, and preferably 0.2% by mass to 1.5% by mass with respect to the total amount of the non-aqueous solvent. More preferably, it is mass%.
  • a laminate-type lithium ion secondary battery can be manufactured, for example, as follows. First, the positive electrode and the negative electrode are cut into squares, and tabs are welded to the respective electrodes to produce a positive electrode terminal and a negative electrode terminal. An electrode laminate is produced by laminating a separator between a positive electrode and a negative electrode, and accommodated in an aluminum laminate pack in that state, and the positive electrode terminal and the negative electrode terminal are taken out of the aluminum laminate pack and sealed. Next, an electrolytic solution is poured into the aluminum laminate pack, and the opening of the aluminum laminate pack is sealed. Thereby, a lithium ion secondary battery is obtained.
  • FIG. 1 is a cross-sectional view of a cylindrical lithium ion secondary battery.
  • the lithium ion secondary battery 1 has a bottomed cylindrical battery container 6 made of steel plated with nickel.
  • the battery case 6 accommodates an electrode group 5 in which a strip-like positive electrode plate 2 and a negative electrode plate 3 are wound in a spiral shape with a separator 4 interposed therebetween.
  • the separator 4 has a width of 58 mm and a thickness of 30 ⁇ m.
  • a ribbon-like positive electrode tab terminal made of aluminum and having one end fixed to the positive electrode plate 2 is led out on the upper end surface of the electrode group 5.
  • the other end of the positive electrode tab terminal is joined by ultrasonic welding to the lower surface of a disk-shaped battery lid that is disposed on the upper side of the electrode group 5 and serves as a positive electrode external terminal.
  • a ribbon-like negative electrode tab terminal made of copper with one end fixed to the negative electrode plate 3 is led out on the lower end surface of the electrode group 5.
  • the other end of the negative electrode tab terminal is joined to the inner bottom of the battery container 6 by resistance welding. Therefore, the positive electrode tab terminal and the negative electrode tab terminal are led out to the opposite sides of the both end faces of the electrode group 5, respectively.
  • FIG. 1 The battery lid is caulked and fixed to the upper part of the battery container 6 via an insulating resin gasket. For this reason, the inside of the lithium ion secondary battery 1 is sealed. In addition, an electrolyte solution (not shown) is injected into the battery container 6.
  • the resin for energy devices of this indication contains the high molecular compound which has the site
  • the portion of the polymer compound that can generate a radical is cleaved by heating to generate a radical, which pulls out a hydrogen atom bonded to a carbon atom existing on the surface of the carbon material. It is presumed that molecules of the polymer compound are bound to the carbon material by using this hydrogen atom extraction reaction as a driving force.
  • the site capable of generating a radical include a peroxide structure (—O—O—).
  • the polymer compound contained in the energy device resin examples include the polymer compound contained in the binder described above. For details and preferred embodiments thereof, refer to the details and preferred embodiments of the polymer compound contained in the binder described above. it can. From the viewpoint of swelling with respect to the electrolytic solution, the polymer compound preferably contains a nitrile group.
  • the resin for energy devices of this indication can be conveniently used as a raw material of the binder for electrodes mentioned above or the carbon material dispersion liquid for energy devices mentioned below, for example.
  • the carbon material dispersion liquid for energy devices of the present disclosure (hereinafter also referred to as carbon material dispersion liquid) includes a polymer compound, an electron conductive carbon material chemically bonded to the polymer compound, and a solvent. Including.
  • the carbon material dispersion of the present disclosure is excellent in the dispersibility and dispersion stability of the carbon material. This is because the polymer compound contained in the carbon material dispersion is chemically bonded to the carbon material, compared to the case where the resin and the carbon material that are conventionally used as a dispersant are simply mixed. This is thought to be because the effect of improving the dispersibility and dispersion stability of the carbon material is further increased.
  • the content of the polymer compound is preferably 0.5% by mass or more based on the entire solid content.
  • the solvent preferably contains at least one selected from the group consisting of N-methyl-2-pyrrolidone and ⁇ -butyllactone.
  • the manufacturing method of the carbon material dispersion liquid for energy devices of this indication includes the process of heating the high molecular compound which has the site
  • the carbon material dispersion liquid containing a high molecular compound and the electronically conductive carbon material chemically couple
  • the heating temperature is not particularly limited as long as it is carried out under conditions where radicals can be generated. For example, 80 degreeC or more may be sufficient, it is preferable that it is 85 degreeC or more, and it is more preferable that it is 90 degreeC or more.
  • the heating temperature may be, for example, 150 ° C. or less.
  • Example 1 In a 0.50 liter round bottom separable flask equipped with a stirrer, a temperature controller, a cooling tube, and a nitrogen introduction tube, 100.0 g of N-methyl-2-pyrrolidone (hereinafter sometimes abbreviated as NMP), Add 100.0 g of acrylonitrile (nitrile group-containing monomer), and while stirring, nitrogen gas is bubbled at a flow rate of 0.3 ml to remove dissolved oxygen, and the temperature inside the system is increased to 70 ° C. with an oil bath. Warm up.
  • NMP N-methyl-2-pyrrolidone
  • Example 1 (Evaluation of presence or absence of peroxide) The solutions obtained in Example 1 and Comparative Example 1 were diluted with NMP so that the nonvolatile content concentration was 10%.
  • MEK methyl ethyl ketone
  • 30 g of the diluted solution was added dropwise with stirring, and the precipitate was collected by suction filtration. The collected precipitate was dried at room temperature for 3 hours and then vacuum dried at room temperature for 12 hours to obtain a powder.
  • 0.2 g of dry powder and 10 ml of NMP were added and stirred to dissolve the dry powder.
  • Example 1 evaluated as peroxide structure "presence”, 0.1M sodium thiosulfate aqueous solution was dripped until the color of the solution became colorless, and the content rate of the peroxide structure was evaluated using following formula (1). .
  • the evaluation results are shown in Table 1.
  • the resin prepared in Example 1 is a resin containing a polymer compound having a peroxide structure (hereinafter sometimes abbreviated as “resin A”), and the resin prepared in Comparative Example 1 has a peroxide structure. It was suggested that the resin does not contain a polymer compound (hereinafter may be abbreviated as “resin B”).
  • Example 1 The solutions prepared in Example 1 and Comparative Example 1 were diluted with NMP so that the nonvolatile content concentration was 0.1%, and gel permeation chromatography (Tosoh Corporation, HLC-8320GPC, column: TSK-gel (150 mm Long x 5), eluent: NMP (containing 0.1% lithium bromide), flow rate: 0.35 ml / min, detection mode: RI, sample concentration: 0.1%, injection volume: 10 ⁇ L, measurement The weight average molecular weights of Resin A and Resin B were measured at a temperature of 40 ° C. and a calibration curve of standard polystyrene. The results are shown in Table 1.
  • Example 2 In a glass bottle with a lid of 50 ml, the white solution (NMP solution of resin A) obtained in Example 1, carbon black (Tokai Carbon Co., Ltd., Toka Black # 5500, hereinafter abbreviated as CB) and NMP as carbon materials was added so that the total amount was 25 g, and the mass ratio of resin A: CB: NMP was 5: 5: 90. Thereafter, a stirrer chip was added, the lid was capped, and the mixture was stirred at 90 ° C. for 10 hours to obtain a carbon material dispersion.
  • NMP solution of resin A obtained in Example 1
  • carbon black Tokai Carbon Co., Ltd., Toka Black # 5500, hereinafter abbreviated as CB
  • CB Toka Black # 5500
  • Examples 3 to 5 A carbon material dispersion was obtained in the same manner as in Example 2 except that the mass ratio of Resin A: CB: NMP was changed as shown in Table 2.
  • Example 6 In a 0.50 liter round bottom separable flask equipped with a stirrer, temperature controller, cooling tube and nitrogen introduction tube, 100.0 g of ethyl acetate, methoxypolyethylene glycol # 400 acrylate (Shin Nakamura Chemical Co., Ltd., product) (Name: AM-90G) was added, and while stirring, nitrogen gas was bubbled at a flow rate of 0.3 ml to remove dissolved oxygen, and heated in an oil bath so that the temperature in the system reached 70 ° C.
  • Examples 7 to 9 A carbon material dispersion was obtained in the same manner as in Example 6 except that the ratio of Resin C: CB: NMP was changed as shown in Table 2.
  • the dispersed particle diameter was used as an index.
  • the carbon material dispersions of Examples and Comparative Examples immediately after the production were diluted with NMP so that the mass ratio of CB was 1%, and stirred for 10 minutes at 50 rpm using a mix rotor.
  • the particle size (D50) at which the number ratio was 50% when the number ratio was integrated was determined from those having a small particle size.
  • This particle size (D50) corresponds to the dispersed particle size of the carbon material.
  • Dispersibility was evaluated according to the following criteria using the obtained dispersed particle diameter. The results are shown in Table 2. In addition, A shows the best dispersibility, and D shows the inferior dispersibility.
  • Particle size (D50) is less than 200 nm
  • A There is no change in appearance, and the whole dispersion is fluid when tilted.
  • B Although there is no change in appearance, there is a non-flowable mass at the bottom of the dispersion when tilted.
  • C The upper part of the dispersion is transparent, and the sedimentation of CB can be visually observed.
  • the carbon material dispersion liquid of the example in which the stirring after mixing with CB was performed at 90 ° C As shown in Table 2, using the resin A or resin C containing a polymer compound having a peroxide structure, the carbon material dispersion liquid of the example in which the stirring after mixing with CB was performed at 90 ° C. Compared with the carbon material dispersions of Comparative Examples 2 to 4 that were not carried out at 90 ° C. and Comparative Example 5 that did not use Resin A, the dispersibility and dispersion stability were excellent.

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Abstract

Ce liant d'électrode contient un composé de poids moléculaire élevé et un matériau carboné conducteur d'électrons lié chimiquement au composé de poids moléculaire élevé.
PCT/JP2019/010897 2018-03-30 2019-03-15 Liant d'électrode, mélange d'électrode, électrode pour dispositif d'énergie, dispositif d'énergie, résine pour dispositif d'énergie, dispersion de matériau carboné et procédé de production de dispersion de matériau carboné WO2019188430A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1196832A (ja) * 1997-09-19 1999-04-09 Asahi Glass Co Ltd ポリマー電解質及びリチウム電池
JP2002075375A (ja) * 2000-08-31 2002-03-15 Nippon Shokubai Co Ltd 電池用電極
JP2002141068A (ja) * 2000-10-31 2002-05-17 Nof Corp 非水系電池電極形成用バインダー、電極合剤、電極構造体及び非水系電池
JP2013143382A (ja) * 2012-01-10 2013-07-22 Samsung Sdi Co Ltd リチウム電池の電極用バインダー及びそれを採用したリチウム電池

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1196832A (ja) * 1997-09-19 1999-04-09 Asahi Glass Co Ltd ポリマー電解質及びリチウム電池
JP2002075375A (ja) * 2000-08-31 2002-03-15 Nippon Shokubai Co Ltd 電池用電極
JP2002141068A (ja) * 2000-10-31 2002-05-17 Nof Corp 非水系電池電極形成用バインダー、電極合剤、電極構造体及び非水系電池
JP2013143382A (ja) * 2012-01-10 2013-07-22 Samsung Sdi Co Ltd リチウム電池の電極用バインダー及びそれを採用したリチウム電池

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