[go: up one dir, main page]

WO2015141464A1 - Particule composite pour une électrode d'élément électrochimique - Google Patents

Particule composite pour une électrode d'élément électrochimique Download PDF

Info

Publication number
WO2015141464A1
WO2015141464A1 PCT/JP2015/056299 JP2015056299W WO2015141464A1 WO 2015141464 A1 WO2015141464 A1 WO 2015141464A1 JP 2015056299 W JP2015056299 W JP 2015056299W WO 2015141464 A1 WO2015141464 A1 WO 2015141464A1
Authority
WO
WIPO (PCT)
Prior art keywords
water
active material
positive electrode
composite particles
electrode active
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2015/056299
Other languages
English (en)
Japanese (ja)
Inventor
梓 増田
琢也 石井
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zeon Corp
Original Assignee
Zeon Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zeon Corp filed Critical Zeon Corp
Priority to KR1020167017186A priority Critical patent/KR102311705B1/ko
Priority to CN201580009206.3A priority patent/CN106030865B/zh
Priority to JP2016508649A priority patent/JP6380526B2/ja
Publication of WO2015141464A1 publication Critical patent/WO2015141464A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/38—Carbon pastes or blends; Binders or additives therein
    • 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
    • H01G11/40—Fibres
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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
    • Y02E60/13—Energy storage using capacitors
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present invention relates to composite particles for electrochemical element electrodes.
  • Lithium ion secondary batteries have a relatively high energy density and are used in mobile fields such as mobile phones and notebook personal computers.
  • the electric double layer capacitor can be rapidly charged and discharged, the electric double layer capacitor is expected to be used as an auxiliary power source for an electric vehicle or the like in addition to being used as a memory backup small power source for a personal computer or the like.
  • the lithium ion capacitor that takes advantage of the lithium ion secondary battery and the electric double layer capacitor has higher energy density and output density than the electric double layer capacitor.
  • Application to applications that could not meet the specifications for capacitor performance is being considered.
  • lithium ion secondary batteries have been studied for application not only to in-vehicle applications such as hybrid electric vehicles and electric vehicles, but also to power storage applications.
  • Electrodes for electrochemical devices include coated electrodes manufactured by a method in which a slurry for coated electrodes containing an electrode active material, a binder resin, a conductive agent, etc. is coated on a current collector and the solvent is removed by heat or the like.
  • a slurry for coated electrodes containing an electrode active material, a binder resin, a conductive agent, etc. is coated on a current collector and the solvent is removed by heat or the like.
  • this method has a high cost and a poor working environment, and the manufacturing apparatus tends to be large.
  • Patent Document 1 discloses composite particles obtained by spraying and drying a slurry for composite particles containing an electrode active material, a binder resin, and a dispersion medium. A method of forming an electrode active material layer using composite particles is disclosed. Since such composite particles may be destroyed during transfer such as pneumatic transportation, improvement in strength is required.
  • the uniformity of the particle size of the composite particles is lost, so that the fluidity of the powder is deteriorated and a uniform electrode active material layer is formed. Can not be.
  • the adhesion between the composite particles and the adhesion between the electrode active material layer and the current collector were weakened, and the cycle characteristics of the resulting electrochemical device were not sufficient.
  • the electrode which has the electrode active material layer formed using the broken composite particle is inferior in a softness
  • Patent Document 1 externally added particles obtained by coating the surface of the composite particles with a fibrous conductive assistant are obtained, but since the fibrous conductive assistant is not present inside the composite particles, the composite particles It was not possible to improve the strength.
  • Patent Document 2 describes that carbon fiber is contained in a slurry for a coating electrode that is applied to an electrode to form an electrode layer in order to improve adhesion in the coating electrode.
  • a method for producing the coated electrode which is different from powder molding using composite particles, it has not been described to improve the strength of the composite particles.
  • Patent Document 3 describes that, in order to enhance the adhesion in the coated electrode, the coated electrode slurry for forming the electrode layer by coating the electrode contains finely divided cellulose fibers. However, since it relates to a method for producing the coated electrode, which is different from powder molding using composite particles, it has not been described to improve the strength of the composite particles.
  • An object of the present invention is an electrochemical device having sufficient strength, excellent uniformity, sufficient adhesion when forming an electrode, and an electrode having excellent flexibility. It is to provide composite particles for electrodes.
  • the present inventor has found that the above object can be achieved by obtaining composite particles by using a water-soluble polymer and a water-insoluble polysaccharide polymer fiber in combination at a predetermined ratio.
  • the present invention has been completed.
  • an electrochemical device electrode including a positive electrode active material (A), a conductive agent (B), a particulate binder resin (C), a water-soluble polymer (D), and a water-insoluble polysaccharide polymer fiber (E)
  • Composite particles for electrochemical element electrodes characterized in that (2)
  • the particulate binder resin (C) is an acrylate polymer, wherein the composite particles for electrochemical element electrodes according to (1) or (2), (4)
  • the amount of the water-soluble polymer (D) is 0.1 to 10 parts by weight in terms of solid content with respect to 100 parts by weight of the
  • Electrode composite particles can be provided.
  • positive electrode active material means an electrode active material for a positive electrode
  • negative electrode active material means an electrode active material for a negative electrode
  • the “positive electrode active material layer” means an electrode active material layer provided on the positive electrode
  • the “negative electrode active material layer” means an electrode active material layer provided on the negative electrode.
  • Positive electrode active material (A) As the positive electrode active material (A) when the electrochemical element is a lithium ion secondary battery, an active material capable of doping and dedoping lithium ions is used, and the positive electrode active material (A) is composed of an inorganic compound and an organic compound. Broadly divided.
  • Examples of the positive electrode active material (A) made of an inorganic compound include transition metal oxides, transition metal sulfides, lithium-containing composite metal oxides of lithium and transition metals, and the like.
  • Examples of the transition metal include Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Mo.
  • Transition metal oxides include MnO, MnO 2 , V 2 O 5 , V 6 O 13 , TiO 2 , Cu 2 V 2 O 3 , amorphous V 2 O—P 2 O 5 , MoO 3 , V 2 O. 5 , V 6 O 13 and the like. Among them, MnO, V 2 O 5 , V 6 O 13 and TiO 2 are preferable from the viewpoint of cycle stability and capacity.
  • the lithium-containing composite metal oxide include a lithium-containing composite metal oxide having a layered structure, a lithium-containing composite metal oxide having a spinel structure, and a lithium-containing composite metal oxide having an olivine structure.
  • lithium-containing composite metal oxide having a layered structure examples include lithium-containing cobalt oxide (LiCoO 2 ) (hereinafter sometimes referred to as “LCO”), lithium-containing nickel oxide (LiNiO 2 ), and Co—Ni—Mn.
  • LCO lithium-containing cobalt oxide
  • LiNiO 2 lithium-containing nickel oxide
  • Co—Ni—Mn examples thereof include lithium composite oxides, lithium composite oxides of Ni—Mn—Al, and lithium composite oxides of Ni—Co—Al.
  • lithium-containing composite metal oxide having a spinel structure examples include lithium manganate (LiMn 2 O 4 ) and Li [Mn 3/2 M 1/2 ] O 4 in which a part of Mn is substituted with another transition metal (here, M may be Cr, Fe, Co, Ni, Cu or the like.
  • Li x MPO 4 (wherein, M is Mn, Fe, Co, Ni, Cu, Mg, Zn, V, Ca, Sr, Ba, Ti, Al, and the like) is a lithium-containing composite metal oxide having an olivine structure.
  • An olivine type lithium phosphate compound represented by at least one selected from Si, B, and Mo, 0 ⁇ X ⁇ 2) may be mentioned.
  • a conductive polymer such as polyacetylene or poly-p-phenylene can be used.
  • An iron-based oxide having poor electrical conductivity may be used as a positive electrode active material covered with a carbon material by allowing a carbon source material to be present during reduction firing. These compounds may be partially element-substituted.
  • the positive electrode active material may be a mixture of the above inorganic compound and organic compound.
  • the positive electrode active material may be any material that can reversibly carry lithium ions and anions such as tetrafluoroborate.
  • carbon allotropes can be preferably used, and electrode active materials used in electric double layer capacitors can be widely used.
  • Specific examples of the allotrope of carbon include activated carbon, polyacene (PAS), carbon whisker, carbon nanotube, and graphite.
  • the volume average particle diameter of the positive electrode active material (A) is appropriately selected in consideration of other components of the electrode for an electrochemical element, but from the viewpoint of improving the characteristics of the electrochemical element such as load characteristics and cycle characteristics,
  • the thickness is preferably 1 to 50 ⁇ m, more preferably 2 to 30 ⁇ m.
  • the conductive agent (B) used in the present invention is not particularly limited as long as it is a conductive material, but is preferably a particulate material having conductivity, such as furnace black, acetylene black, and ketjen black. Examples thereof include conductive carbon black; graphite such as natural graphite and artificial graphite; and carbon fibers such as polyacrylonitrile-based carbon fiber, pitch-based carbon fiber, and vapor grown carbon fiber.
  • the average particle diameter when the conductive agent (B) is a particulate material is not particularly limited, but is preferably smaller than the average particle diameter of the positive electrode active material, and sufficient conductivity can be expressed with a smaller amount of use. From the viewpoint, it is preferably 0.001 to 10 ⁇ m, more preferably 0.05 to 5 ⁇ m, and still more preferably 0.1 to 1 ⁇ m.
  • the compounding amount of the conductive agent (B) in the composite particle for an electrochemical element electrode of the present invention is 100% by weight of the positive electrode active material from the viewpoint of sufficiently reducing the internal resistance while keeping the capacity of the obtained electrochemical element high.
  • the amount is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 15 parts by weight, and still more preferably 1 to 10 parts by weight with respect to parts.
  • the particulate binder resin (C) used in the present invention is not particularly limited as long as it is a substance capable of binding the above-described positive electrode active materials to each other.
  • a dispersion type particulate binder resin having a property of being dispersed in a solvent is preferable.
  • the dispersion-type particulate binder resin include high molecular compounds such as silicon polymers, fluorine-containing polymers, conjugated diene polymers, acrylate polymers, polyimides, polyamides, and polyurethanes.
  • a fluorine-containing polymer, a conjugated diene polymer, and an acrylate polymer are preferable, and a conjugated diene polymer and An acrylate polymer is more preferable.
  • These polymers can be used alone or in combination as a dispersion type particulate binder resin.
  • the fluorine-containing polymer is a polymer containing a monomer unit containing a fluorine atom.
  • Specific examples of the fluorine-containing polymer include polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, ethylene / tetrafluoroethylene copolymer, ethylene / chlorotrifluoroethylene copolymer, A perfluoroethylene propene copolymer may be mentioned.
  • the conjugated diene polymer is a homopolymer of a conjugated diene monomer, a copolymer obtained by polymerizing a monomer mixture containing a conjugated diene monomer, or a hydrogenated product thereof.
  • 1,3-butadiene is used in that the flexibility when used as an electrode can be improved and the resistance to cracking can be increased. It is more preferable.
  • the monomer mixture may contain two or more of these conjugated diene monomers.
  • conjugated diene polymer is a copolymer of the above conjugated diene monomer and a monomer copolymerizable therewith
  • examples of the copolymerizable monomer include ⁇ , Examples thereof include a ⁇ -unsaturated nitrile compound and a vinyl compound having an acid component.
  • conjugated diene polymers include conjugated diene monomer homopolymers such as polybutadiene and polyisoprene; aromatic vinyl monomers such as carboxy-modified styrene-butadiene copolymer (SBR). Monomer / conjugated diene monomer copolymer; vinyl cyanide monomer / conjugated diene monomer copolymer such as acrylonitrile / butadiene copolymer (NBR); hydrogenated SBR, hydrogenated NBR, etc. Is mentioned.
  • conjugated diene monomer homopolymers such as polybutadiene and polyisoprene
  • aromatic vinyl monomers such as carboxy-modified styrene-butadiene copolymer (SBR).
  • SBR carboxy-modified styrene-butadiene copolymer
  • Monomer / conjugated diene monomer copolymer Monomer / conjugated diene monomer copolymer
  • the amount of the conjugated diene monomer unit in the conjugated diene polymer is preferably 20 to 60% by weight, more preferably 30 to 55% by weight.
  • the compounding amount of the conjugated diene monomer unit is too large, when the positive electrode is produced using composite particles containing the particulate binder resin (C), the electrolytic solution resistance tends to decrease. If the blending amount of the conjugated diene monomer unit is too small, sufficient adhesion between the composite particles and the current collector tends not to be obtained.
  • the acrylate polymer has the general formula (1): CH 2 ⁇ CR 1 —COOR 2 (wherein R 1 represents a hydrogen atom or a methyl group, R 2 represents an alkyl group or a cycloalkyl group. R 2 further represents A monomer unit derived from a compound represented by an ether group, a hydroxyl group, a phosphate group, an amino group, a carboxyl group, a fluorine atom, or an epoxy group. Copolymer obtained by polymerizing a polymer containing, specifically, a homopolymer of a compound represented by the general formula (1) or a monomer mixture containing the compound represented by the general formula (1) It is a coalescence.
  • Specific examples of the compound represented by the general formula (1) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylate n.
  • Acid ester 2- (meth) acryloyloxyethylphthalic acid-containing (meth) acrylic acid ester; (meth) acrylic acid perfluorooctylethyl fluorine-containing (meth) acrylic acid ester; (meth) Phosphoric acid group-containing (meth) acrylates such as ethyl acrylate Acrylic acid esters; (meth) epoxy group-containing (meth) acrylic acid esters of glycidyl acrylate; (meth) containing amino group such as dimethylaminoethyl acrylate (meth) acrylic acid ester; and the like.
  • (meth) acryl means “acryl” and “methacryl”.
  • (Meth) acryloyl means “acryloyl” and “methacryloyl”.
  • (meth) acrylic acid esters can be used alone or in combination of two or more.
  • (meth) acrylic acid alkyl esters are preferable, and methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and alkyl groups have 6 to 12 carbon atoms.
  • (Meth) acrylic acid alkyl ester is more preferred. By selecting these, it becomes possible to reduce the swellability with respect to the electrolytic solution, and to improve the cycle characteristics.
  • the acrylate polymer is a copolymer of the compound represented by the general formula (1) and a monomer copolymerizable therewith
  • the copolymerizable monomer For example, carboxylic acid esters having two or more carbon-carbon double bonds, aromatic vinyl monomers, amide monomers, olefins, diene monomers, vinyl ketones, and heterocyclic rings
  • examples include ⁇ , ⁇ -unsaturated nitrile compounds and vinyl compounds having an acid component.
  • the electrode (positive electrode) can be made difficult to be deformed and strong, and sufficient adhesion between the positive electrode active material layer and the current collector can be obtained.
  • an aromatic vinyl monomer examples include styrene.
  • the blending amount of the (meth) acrylic acid ester unit in the acrylate polymer can improve flexibility when used as an electrode (positive electrode), and is preferably 50 to 50% from the viewpoint of high resistance to cracking. It is 95% by weight, more preferably 60 to 90% by weight.
  • Examples of the ⁇ , ⁇ -unsaturated nitrile compound used in the polymer constituting the particulate binder resin (C) include acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, and ⁇ -bromoacrylonitrile. These may be used alone or in combination of two or more. Among these, acrylonitrile and methacrylonitrile are preferable, and acrylonitrile is more preferable.
  • the blending amount of the ⁇ , ⁇ -unsaturated nitrile compound unit in the particulate binder resin (C) is preferably 0.1 to 40% by weight, more preferably 0.5 to 30% by weight, still more preferably 1 to 20% by weight.
  • the ⁇ , ⁇ -unsaturated nitrile compound unit is contained in the particulate binder resin (C)
  • the adhesion between the positive electrode active material layer containing the composite particles and the current collector can be made sufficient. it can.
  • vinyl compound having an acid component examples include acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid. These may be used alone or in combination of two or more. Among these, acrylic acid, methacrylic acid, and itaconic acid are preferable, methacrylic acid and itaconic acid are more preferable, and itaconic acid is particularly preferable in terms of improving adhesive strength.
  • the blending amount of the vinyl compound unit having an acid component in the dispersion type particulate binder resin is preferably 0.5 to 10% by weight, more preferably from the viewpoint of improving the stability of the composite particle slurry. Is 1 to 8% by weight, more preferably 2 to 7% by weight.
  • the particulate binder resin (C) used in the present invention is particulate, it has good binding properties and can suppress deterioration of the capacity of the produced electrode and repeated charge / discharge.
  • the particulate binder resin (C) include those in which binder resin particles such as latex are dispersed in water, and powders obtained by drying such a dispersion.
  • the average particle diameter of the particulate binder resin (C) is preferably from the viewpoint that the strength and flexibility of the positive electrode to be obtained are good while the stability when the composite particle slurry is obtained is good.
  • the thickness is from 001 to 100 ⁇ m, more preferably from 10 to 1000 nm, still more preferably from 50 to 500 nm.
  • the method for producing the particulate binder resin (C) used in the present invention is not particularly limited, and a known polymerization method such as an emulsion polymerization method, a suspension polymerization method, a dispersion polymerization method, or a solution polymerization method may be employed. it can. Among these, it is preferable to produce by an emulsion polymerization method because the particle diameter of the particulate binder resin (C) can be easily controlled.
  • the particulate binder resin (C) used in the present invention may be a particle having a core-shell structure obtained by stepwise polymerization of a mixture of two or more monomers.
  • the compounding amount of the particulate binder resin (C) in the composite particle for an electrochemical element electrode of the present invention can ensure sufficient adhesion between the obtained positive electrode active material layer and the current collector, and the electrochemical element From the viewpoint of reducing the internal resistance of the positive electrode active material (A), it is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the positive electrode active material (A). More preferably, it is 1 to 15 parts by weight.
  • the water-soluble polymer (D) used in the present invention refers to a polymer having an undissolved content of less than 10.0% by weight when 0.5 g of the polymer is dissolved in 100 g of pure water at 25 ° C.
  • water-soluble polymer (D) examples include cellulosic polymers such as carboxymethylcellulose, methylcellulose, ethylcellulose and hydroxypropylcellulose, and ammonium salts or alkali metal salts thereof, alginates such as propylene glycol alginate, and alginic acid.
  • Alginates such as sodium, polyacrylic acid, and polyacrylic acid (or methacrylic acid) salts such as sodium polyacrylic acid (or methacrylic acid), polyvinyl alcohol, modified polyvinyl alcohol, poly-N-vinylacetamide, polyethylene oxide, polyvinyl Examples include pyrrolidone, polycarboxylic acid, oxidized starch, phosphate starch, casein, various modified starches, chitin, and chitosan derivatives. It is.
  • “(modified) poly” means “unmodified poly” or “modified poly”.
  • These water-soluble polymers (D) can be used alone or in combination of two or more.
  • a cellulose-based polymer is preferable, and carboxymethyl cellulose or its ammonium salt or alkali metal salt is particularly preferable.
  • the blending amount of these water-soluble polymers (D) is not particularly limited as long as the effect of the present invention is not impaired, but is preferably 0 with respect to 100 parts by weight of the positive electrode active material in terms of solid part. 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, still more preferably 0.25 to 2 parts by weight.
  • the water-insoluble polysaccharide polymer fiber (E) used in the present invention belongs to a so-called polymer compound among polysaccharides, and there is no other limitation as long as it is a water-insoluble fiber. Usually, it is a fiber (short fiber) fibrillated by a mechanical shearing force.
  • the water-insoluble polysaccharide polymer fiber used in the present invention is a high-polysaccharide fiber having an undissolved content of 90% by weight or more when 0.5 g of polysaccharide polymer fiber is dissolved in 100 g of pure water at 25 ° C. Refers to molecular fiber.
  • the water-insoluble polysaccharide polymer fiber (E) it is preferable to use polysaccharide polymer nanofibers.
  • the polysaccharide polymer nanofibers are flexible and have a high tensile strength. From the viewpoint that the particle reinforcing effect is high, the particle strength can be improved, and the dispersibility of the conductive agent (B) is improved, it is derived from organisms such as cellulose nanofibers, chitin nanofibers, chitosan nanofibers, etc. It is more preferable to use single or any mixture selected from bionanofiber. Among these, it is more preferable to use cellulose nanofibers, and it is particularly preferable to use cellulose nanofibers made from bamboo, conifers, hardwoods, and cotton.
  • the average fiber diameter of the water-insoluble polysaccharide polymer fiber (E) used in the present invention is such that more water-insoluble polysaccharide polymer fiber (E) is present in the composite particles and the adhesion between the positive electrode active materials is strengthened. From the viewpoint of sufficient strength of the composite particles and the electrode (positive electrode), and from the viewpoint of excellent electrochemical characteristics of the obtained electrochemical device, it is preferably 5 to 3000 nm, more preferably 5 to 2000 nm, and still more preferably. It is 5 to 1000 nm, particularly preferably 5 to 100 nm.
  • the average fiber diameter of the water-insoluble polysaccharide polymer fiber (E) is too large, the water-insoluble polysaccharide polymer fiber cannot sufficiently exist in the composite particle, so that the strength of the composite particle is sufficient. I can't. Further, the fluidity of the composite particles is deteriorated, and it is difficult to form a uniform positive electrode active material layer.
  • the water-insoluble polysaccharide polymer fiber (E) may be composed of a single fiber that is sufficiently separated without being arranged. In this case, the average fiber diameter is the average diameter of single fibers. Further, the water-insoluble polysaccharide polymer fiber (E) may be one in which a plurality of single fibers are gathered in a bundle to form one yarn. In this case, the average fiber diameter is defined as the average value of the diameters of one yarn.
  • the average degree of polymerization of the water-insoluble polysaccharide polymer fiber (E) is obtained from the viewpoint of sufficient strength of the composite particles and the electrode (positive electrode), and the formation of a uniform positive electrode active material layer. From the viewpoint of excellent electrochemical characteristics of the chemical element, it is preferably 50 to 1000, more preferably 100 to 900, and still more preferably 150 to 800. If the average degree of polymerization of the water-insoluble polysaccharide polymer fiber is too large, the internal resistance of the resulting electrochemical device increases. In addition, it becomes difficult to form a uniform positive electrode active material layer. Moreover, when the average degree of polymerization of the water-insoluble polysaccharide polymer fiber is too small, the strength of the composite particles becomes insufficient.
  • the average degree of polymerization is determined by a viscosity method using the following copper ethylenediamine solution.
  • a freeze-dried water-insoluble polysaccharide polymer fiber is dissolved in a copper ethylenediamine solution 1 to prepare a solution 2, and the viscosity is measured using a viscometer.
  • the intrinsic viscosity [ ⁇ ] of the water-insoluble polysaccharide polymer fiber solution is obtained by the following calculation formula where the viscosity of the solution 2 is ⁇ and the viscosity of the solution 1 is ⁇ 0.
  • Intrinsic viscosity [ ⁇ ] ( ⁇ / ⁇ 0) / ⁇ c (1 + A ⁇ ⁇ / ⁇ 0) ⁇
  • c is the water-insoluble polysaccharide polymer fiber concentration (g / dL)
  • A is a value determined by the type of the solution 1.
  • the soot viscometer is preferably a capillary viscometer, examples of which include a Canon-Fenske viscometer.
  • the blending amount of the water-insoluble polysaccharide polymer fiber (E) is preferably 0.1 to 2 parts by weight, more preferably 0.2 to 1 part by weight in terms of solid content with respect to 100 parts by weight of the resulting composite particles. 5 parts by weight, more preferably 0.3 to 1 part by weight.
  • the blending amount of the water-insoluble polysaccharide polymer fiber is too large, the internal resistance of the obtained electrochemical element increases. In addition, it becomes difficult to form a uniform electrode layer (positive electrode active material layer).
  • the reinforcement effect by water-insoluble polysaccharide polymer fiber will be small, and the intensity
  • the viscosity of the slurry for composite particles increases by increasing the blending amount of the water-insoluble polysaccharide polymer fiber (E)
  • the viscosity is appropriately adjusted by reducing the blending amount of the water-soluble polymer. Can do.
  • the ratio between the water-soluble polymer (D) and the water-insoluble polysaccharide polymer fiber (E) used in the present invention is determined from the viewpoint of improving the dispersibility of the water-insoluble polysaccharide polymer fiber (E).
  • water-soluble polymer (D) / water-insoluble polysaccharide polymer fiber (E) 0.25 to 7.0, preferably 0.3 to 6.0, more preferably 0.4. ⁇ 5.0. If the value of the water-soluble polymer (D) / water-insoluble polysaccharide polymer fiber (E) is too large, the storage stability of the composite particle slurry will deteriorate. Moreover, when the value of water-soluble polymer (D) / water-insoluble polysaccharide polymer fiber (E) is too small, the strength of the composite particles becomes insufficient.
  • the composite particles are added to the positive electrode active material (A), the conductive agent (B), the particulate binder resin (C), the water-soluble polymer (D), the water-insoluble polysaccharide polymer fiber (E), and if necessary. It is obtained by granulating using other components.
  • the composite particle includes the positive electrode active material (A) and the particulate binder resin (C), and each of the positive electrode active material (A) and the particulate binder resin (C) exists as independent particles. Instead, one particle is formed by two or more components including the positive electrode active material (A) and the particulate binder resin (C), which are constituent components.
  • a plurality of (preferably several to several tens) secondary particles are formed by combining a plurality of the individual particles of the two or more components while maintaining the shape substantially.
  • the positive electrode active material (A) is preferably bound with the particulate binder resin (C) to form particles.
  • the minor axis diameter L s and the major axis diameter L l are values measured from a scanning electron micrograph image.
  • the average particle diameter of the composite particles is preferably from 0.1 to 200 ⁇ m, more preferably from 1 to 150 ⁇ m, and even more preferably from 10 to 10 from the viewpoint that an electrode layer (positive electrode active material layer) having a desired thickness can be easily obtained. 80 ⁇ m.
  • the average particle size is a volume average particle size calculated by measuring with a laser diffraction particle size distribution analyzer (for example, SALD-3100; manufactured by Shimadzu Corporation).
  • the production method of the composite particles is not particularly limited, but is spray drying granulation method, rolling bed granulation method, compression granulation method, stirring granulation method, extrusion granulation method, crushing granulation method, fluidized bed granulation method.
  • Composite particles can be obtained by production methods such as a granulation method, a fluidized bed multifunctional granulation method, and a melt granulation method.
  • the production method of the composite particles may be appropriately selected from the viewpoints of ease of particle size control, productivity, ease of control of particle size distribution, etc. according to the components of the composite particles, etc.
  • the spray-drying granulation method described in 1 is preferable because the composite particles can be produced relatively easily.
  • the spray drying granulation method will be described.
  • a slurry for composite particles containing a positive electrode active material (A), a conductive agent (B), a particulate binder resin (C), a water-soluble polymer (D), and a water-insoluble polysaccharide polymer fiber (E) ( Hereinafter, it may be referred to as “slurry”).
  • the composite particle slurry includes a positive electrode active material (A), a conductive agent (B), a particulate binder resin (C), a water-soluble polymer (D), a water-insoluble polysaccharide polymer fiber (E), and as necessary.
  • the other components to be added can be prepared by dispersing or dissolving in a solvent. In this case, when the particulate binder resin (C) is dispersed in water as a solvent, it can be added in a state dispersed in water.
  • water is preferably used, but a mixed solvent of water and an organic solvent may be used, or only an organic solvent may be used alone or in combination of several kinds.
  • organic solvent examples include alcohols such as methyl alcohol, ethyl alcohol, and propyl alcohol; alkyl ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran, dioxane, and diglyme; diethylformamide, dimethyl Amides such as acetamide, N-methyl-2-pyrrolidone, dimethylimidazolidinone; and the like.
  • alcohols are preferred.
  • water and an organic solvent having a lower boiling point than water the drying rate can be increased during spray drying. Thereby, the viscosity and fluidity of the slurry for composite particles can be adjusted, and the production efficiency can be improved.
  • the viscosity of the composite particle slurry is preferably 10 to 3,000 mPa ⁇ s, more preferably 30 to 1,500 mPa ⁇ s, more preferably at room temperature, from the viewpoint of improving the productivity of the spray drying granulation step. Is 50 to 1,000 mPa ⁇ s.
  • a dispersant or a surfactant when preparing the composite particle slurry, a dispersant or a surfactant may be added as necessary.
  • the surfactant include amphoteric surfactants such as anionic, cationic, nonionic, and nonionic anions, and anionic or nonionic surfactants are preferable.
  • the compounding amount of the surfactant is preferably 50 parts by weight or less, more preferably 0.1 to 10 parts by weight, and further preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the positive electrode active material. .
  • the amount of the solvent used in preparing the slurry is such that the solid content concentration of the slurry is preferably 1 to 70% by weight, more preferably 5 to 70% by weight, from the viewpoint of uniformly dispersing the binder resin in the slurry. More preferably, the amount is 10 to 65% by weight.
  • the method or order of dispersing or dissolving the components in the solvent is not particularly limited.
  • the positive electrode active material (A), the conductive agent (B), the particulate binder resin (C), and the water-soluble polymer (D) are used in the solvent.
  • the mixing device for example, a ball mill, a sand mill, a bead mill, a pigment disperser, a pulverizer, an ultrasonic disperser, a homogenizer, a homomixer, a planetary mixer, or the like can be used.
  • the mixing is preferably performed at room temperature to 80 ° C. for 10 minutes to several hours.
  • Spray drying is a method of spraying and drying a slurry in hot air.
  • An atomizer is used as an apparatus used for spraying slurry.
  • a rotating disk system slurry is introduced almost at the center of the disk that rotates at high speed, and the slurry is released outside the disk by the centrifugal force of the disk. In this case, the slurry is atomized.
  • the rotational speed of the disk depends on the size of the disk, but is preferably 5,000 to 30,000 rpm, more preferably 15,000 to 30,000 rpm.
  • a pin-type atomizer is a type of centrifugal spraying device that uses a spraying plate, and the spraying plate has a plurality of spraying rollers removably mounted on a concentric circle along its periphery between upper and lower mounting disks. It consists of The slurry for composite particles is introduced from the center of the spray disk, adheres to the spray roller by centrifugal force, moves outward on the roller surface, and finally sprays away from the roller surface.
  • the nozzle method is a method in which the slurry for composite particles is pressurized to form a mist from the nozzle and dried, or the slurry ejected from the nozzle is formed into a mist by air pressure and dried.
  • the temperature of the slurry for composite particles to be sprayed is preferably room temperature, but may be higher than room temperature by heating.
  • the hot air temperature during spray drying is preferably 25 to 250 ° C, more preferably 50 to 200 ° C, and still more preferably 80 to 150 ° C.
  • the method of blowing hot air is not particularly limited.
  • the method in which the hot air and the spraying direction flow side by side the method in which the hot air is sprayed at the top of the drying tower and descends with the hot air, and the sprayed droplets and hot air flow countercurrently. Examples include a contact method, and a method in which sprayed droplets first flow in parallel with hot air, then drop by gravity and contact countercurrent.
  • An electrochemical element electrode (positive electrode) can be obtained by laminating a positive electrode active material layer containing the composite particles for an electrochemical element electrode of the present invention on a current collector.
  • a material for the current collector for example, metal, carbon, conductive polymer, and the like can be used, and metal is preferably used.
  • metal copper, aluminum, platinum, nickel, tantalum, titanium, stainless steel, other alloys and the like are usually used. Among these, it is preferable to use copper, aluminum, or an aluminum alloy in terms of conductivity and voltage resistance. In addition, when high voltage resistance is required, high-purity aluminum disclosed in JP 2001-176757 A can be suitably used.
  • the current collector is in the form of a film or a sheet, and the thickness thereof is appropriately selected depending on the purpose of use, but is preferably 1 to 200 ⁇ m, more preferably 5 to 100 ⁇ m, and still more preferably 10 to 50 ⁇ m.
  • the composite particles When laminating the positive electrode active material layer on the current collector, the composite particles may be formed into a sheet shape and then laminated on the current collector, but the composite particles are directly pressure-molded on the current collector. Is preferred.
  • a method for pressure molding for example, a roll type pressure molding apparatus provided with a pair of rolls is used, and a roll type pressure molding apparatus is used to feed composite particles with a feeder such as a screw feeder while feeding a current collector with the roll.
  • the roll pressure molding method is preferable.
  • the composite particles of the present invention have high fluidity, they can be molded by roll press molding due to the high fluidity, thereby improving productivity.
  • the roll temperature at the time of roll press molding is preferably 25 to 200 ° C., more preferably 50 to 150 ° C., from the viewpoint of ensuring sufficient adhesion between the positive electrode active material layer and the current collector. More preferably, it is 80 to 120 ° C.
  • the press linear pressure between the rolls during roll press molding is preferably 10 to 1000 kN / m, more preferably 200 to 900 kN / m, from the viewpoint of improving the uniformity of the thickness of the positive electrode active material layer. More preferably, it is 300 to 600 kN / m.
  • the molding speed at the time of roll press molding is preferably 0.1 to 20 m / min, more preferably 4 to 10 m / min.
  • post-pressurization may be further performed as necessary in order to eliminate variations in the thickness of the formed electrochemical element electrode (positive electrode) and increase the density of the positive electrode active material layer to increase the capacity.
  • the post-pressing method is preferably a pressing process using a roll. In the roll pressing step, two cylindrical rolls are arranged vertically in parallel with a narrow interval, each is rotated in the opposite direction, and pressure is applied by interposing an electrode therebetween. In this case, the temperature of the roll may be adjusted as necessary, such as heating or cooling.
  • An electrochemical element can be obtained by using the electrochemical element electrode obtained as described above as a positive electrode and further including a negative electrode, a separator, and an electrolytic solution.
  • Examples of the electrochemical element include a lithium ion secondary battery and a lithium ion capacitor.
  • the negative electrode of an electrochemical element is formed by laminating a negative electrode active material layer on a current collector.
  • the negative electrode of the electrochemical device collects a negative electrode slurry containing a negative electrode active material, a binder resin for the negative electrode, a solvent used for preparing the negative electrode, a water-soluble polymer used as necessary, and other components such as a conductive agent. It can be obtained by applying to the surface of the body and drying. That is, the negative electrode active material layer is formed on the current collector by applying the slurry for the negative electrode to the surface of the current collector and drying it.
  • Examples of the negative electrode active material when the electrochemical device of the present invention is a lithium ion secondary battery include carbonaceous materials such as amorphous carbon, graphite, natural graphite, mesocarbon microbeads, pitch-based carbon fibers; Conductive polymers; metals such as silicon, tin, zinc, manganese, iron, nickel or alloys thereof; oxides or sulfates of the metals or alloys; metal lithium; Li—Al, Li—Bi—Cd, Li— Examples thereof include lithium alloys such as Sn—Cd; lithium transition metal nitrides; silicon and the like.
  • a material obtained by attaching a conductive agent to the surface of the negative electrode active material particles by, for example, a mechanical modification method may be used.
  • a negative electrode active material may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the particle size of the negative electrode active material particles is usually selected as appropriate in consideration of other components of the electrochemical element.
  • the 50% volume cumulative diameter of the negative electrode active material particles is preferably 1 to 50 ⁇ m, more preferably 15 to 30 ⁇ m.
  • the content of the negative electrode active material in the negative electrode active material layer can increase the capacity of the lithium ion secondary battery, and improve the flexibility of the negative electrode and the binding property between the current collector and the negative electrode active material layer. From the viewpoint of achieving the above, it is preferably 90 to 99.9% by weight, more preferably 95 to 99% by weight. Moreover, as a negative electrode active material preferably used when an electrochemical element is a lithium ion capacitor, the negative electrode active material formed with the said carbon is mentioned.
  • Binding resin for negative electrode As the negative electrode binder resin, for example, the same binder resin as that used in the positive electrode active material layer may be used.
  • resins such as polyethylene, tetrafluoroethylene-hexafluoropropylene copolymer (FEP), polyacrylic acid derivatives, polyacrylonitrile derivatives; acrylic soft polymers, diene soft polymers, olefin soft polymers, Examples thereof include soft polymers such as vinyl-based soft polymers.
  • a binder resin may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the water-soluble polymer and conductive agent used in the negative electrode slurry As the water-soluble polymer and conductive agent used in the negative electrode slurry as necessary, the water-soluble polymer and conductive agent that can be used for the composite particles described above can be used.
  • solvent used for preparation of negative electrode either water or an organic solvent may be used.
  • organic solvent include cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as toluene and xylene; ketones such as ethyl methyl ketone and cyclohexanone; ethyl acetate, butyl acetate, and ⁇ -butyrolactone Esters such as ⁇ -caprolactone; alkyl nitriles such as acetonitrile and propionitrile; ethers such as tetrahydrofuran and ethylene glycol diethyl ether: alcohols such as methanol, ethanol, isopropanol, ethylene glycol, and ethylene glycol monomethyl ether; N Amides such as -methylpyrrolidone and N, N-dimethylformamide; among them, N-methylpyrrolidon
  • the amount of the solvent may be adjusted so that the viscosity of the negative electrode slurry is suitable for coating. Specifically, it is used by adjusting so that the solid content concentration of the slurry for negative electrode is preferably 30 to 90% by weight, more preferably 40 to 80% by weight.
  • the current collector used for the negative electrode As the current collector used for the negative electrode, the same current collector as the current collector used for the electrochemical element electrode (positive electrode) can be used.
  • the method for applying the negative electrode slurry to the surface of the current collector is not particularly limited. Examples of the method include a doctor blade method, a dip method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, and a brush coating method.
  • drying method examples include drying with warm air, hot air, low-humidity air, vacuum drying, and drying by irradiation with (far) infrared rays or electron beams.
  • the drying time is preferably 5 to 30 minutes, and the drying temperature is preferably 40 to 180 ° C.
  • the negative electrode active material layer is preferably subjected to pressure treatment using, for example, a die press or a roll press as necessary.
  • the porosity of the negative electrode active material layer can be lowered.
  • the porosity is preferably 5% or more, more preferably 7% or more, preferably 30% or less, more preferably 20% or less.
  • the porosity is too small, it is difficult to obtain a high volume capacity, and the negative electrode active material layer is easily peeled off from the current collector.
  • the porosity is too large, the charging efficiency and the discharging efficiency are lowered.
  • the negative electrode active material layer contains a curable polymer, it is preferable to cure the polymer after the formation of the negative electrode active material layer.
  • separator for example, a polyolefin resin such as polyethylene or polypropylene, or a microporous film or nonwoven fabric containing an aromatic polyamide resin; a porous resin coat containing an inorganic ceramic powder; Specific examples include microporous membranes made of polyolefin resins (polyethylene, polypropylene, polybutene, polyvinyl chloride), and resins such as mixtures or copolymers thereof; polyethylene terephthalate, polycycloolefin, polyether sulfone, polyamide, Examples thereof include a microporous film made of a resin such as polyimide, polyimide amide, polyaramid, nylon, and polytetrafluoroethylene; a polyolefin fiber woven or non-woven fabric thereof; and an aggregate of insulating substance particles.
  • a polyolefin resin such as polyethylene or polypropylene, or a microporous film or nonwoven fabric containing an aromatic polyamide resin
  • the thickness of the separator is preferably 0.5 to 40 ⁇ m from the viewpoint of reducing the internal resistance due to the separator in the lithium ion secondary battery and from the viewpoint of excellent workability when manufacturing the lithium ion secondary battery. More preferably, the thickness is 1 to 30 ⁇ m, still more preferably 1 to 25 ⁇ m.
  • Electrode As an electrolytic solution for a lithium ion secondary battery, for example, a nonaqueous electrolytic solution in which a supporting electrolyte is dissolved in a nonaqueous solvent is used.
  • a lithium salt is preferably used.
  • the lithium salt include LiPF 6 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAlCl 4 , LiClO 4 , CF 3 SO 3 Li, C 4 F 9 SO 3 Li, CF 3 COOLi, (CF 3 CO) 2 NLi , (CF 3 SO 2 ) 2 NLi, (C 2 F 5 SO 2 ) NLi, and the like.
  • LiPF 6 , LiClO 4 , and CF 3 SO 3 Li that are easily soluble in a solvent and exhibit a high degree of dissociation are preferable.
  • One of these may be used alone, or two or more of these may be used in combination at any ratio. Since the lithium ion conductivity increases as the supporting electrolyte having a higher degree of dissociation is used, the lithium ion conductivity can be adjusted depending on the type of the supporting electrolyte.
  • the concentration of the supporting electrolyte in the electrolytic solution is preferably used at a concentration of 0.5 to 2.5 mol / L depending on the type of the supporting electrolyte. If the concentration of the supporting electrolyte is too low or too high, the ionic conductivity may decrease.
  • the non-aqueous solvent is not particularly limited as long as it can dissolve the supporting electrolyte.
  • non-aqueous solvents include carbonates such as dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), propylene carbonate (PC), butylene carbonate (BC), methyl ethyl carbonate (MEC);
  • DMC dimethyl carbonate
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • PC propylene carbonate
  • BC butylene carbonate
  • MEC methyl ethyl carbonate
  • esters such as ⁇ -butyrolactone and methyl formate
  • ethers such as 1,2-dimethoxyethane and tetrahydrofuran
  • sulfur-containing compounds such as sulfolane and dimethyl sulfoxide
  • ionic liquids used also as supporting electrolytes used also as supporting electrolytes.
  • a non-aqueous solvent may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios. In general, the lower the viscosity of the non-aqueous solvent, the higher the lithium ion conductivity, and the higher the dielectric constant, the higher the solubility of the supporting electrolyte, but since both are in a trade-off relationship, the lithium ion conductivity depends on the type of solvent and the mixing ratio. It is recommended to adjust the conductivity.
  • the nonaqueous solvent may be used in combination or in whole or in a form in which all or part of hydrogen is replaced with fluorine.
  • the additive include carbonates such as vinylene carbonate (VC); sulfur-containing compounds such as ethylene sulfite (ES); and fluorine-containing compounds such as fluoroethylene carbonate (FEC).
  • An additive may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.
  • an electrolyte solution for lithium ion capacitors the same electrolyte solution that can be used for the above-described lithium ion secondary battery can be used.
  • Method for producing electrochemical element As a specific method for producing an electrochemical element such as a lithium ion secondary battery or a lithium ion capacitor, for example, a positive electrode and a negative electrode are overlapped via a separator, and this is wound or folded according to the shape of the battery. Examples of the method include putting the battery in a battery container, injecting an electrolyte into the battery container, and sealing the battery. Further, if necessary, an expanded metal; an overcurrent prevention element such as a fuse or a PTC element; a lead plate or the like may be inserted to prevent an increase in pressure inside the battery or overcharge / discharge.
  • an electrochemical element such as a lithium ion secondary battery or a lithium ion capacitor
  • a positive electrode and a negative electrode are overlapped via a separator, and this is wound or folded according to the shape of the battery. Examples of the method include putting the battery in a battery container, injecting an electrolyte into the battery container, and sealing the battery. Further, if necessary, an
  • the shape of the lithium ion secondary battery may be any of a coin type, a button type, a sheet type, a cylindrical type, a square type, a flat type, and the like.
  • the material of the battery container is not particularly limited as long as it inhibits the penetration of moisture into the battery, and is not particularly limited, such as a metal or a laminate such as aluminum.
  • an electrode having sufficient strength, excellent uniformity, sufficient adhesion when forming an electrode, and excellent flexibility can be obtained.
  • the composite particle for electrochemical element electrodes of the present invention has excellent fluidity.
  • an average fiber diameter is an average value when a fiber diameter is measured about 100 water-insoluble polysaccharide polymer fibers in the visual field of an electron microscope.
  • ⁇ Particle strength of composite particles> The composite particles obtained in Examples and Comparative Examples were subjected to a compression test using a micro compression tester (“MCT-W500” manufactured by Shimadzu Corporation).
  • MCT-W500 micro compression tester
  • a compressive strength (MPa) is measured when a particle is deformed until the diameter of the composite particle is displaced by 40% by applying a load at a loading speed of 4.46 mN / sec in the center direction of the composite particle at room temperature. did.
  • a composite particle having a diameter of 40 to 60 ⁇ m was selected and a compression test was performed.
  • Compressive strength is 1.00 MPa or more
  • B Compressive strength is 0.90 MPa or more and less than 1.00 MPa
  • C Compressive strength is 0.80 MPa or more and less than 0.90 MPa
  • D Compressive strength is 0.70 MPa or more, 0.80 MPa Less than E: Compressive strength is less than 0.70 MPa
  • the positive electrodes for lithium ion secondary batteries obtained in the examples and comparative examples were cut into a rectangular shape having a width of 1 cm and a length of 10 cm. After fixing the cut positive electrode for a lithium ion secondary battery with the positive electrode active material layer face up, and applying a cellophane tape on the surface of the positive electrode active material layer, the cellophane tape is applied at a speed of 50 mm / min from one end of the test piece. The stress when peeled in the 180 ° direction was measured. This stress was measured 10 times, and the average value was defined as the peel strength. The peel strength was evaluated according to the following criteria, and the results are shown in Tables 1 and 2.
  • peel strength is 15 N / m or more
  • B Peel strength is 7 N / m or more and less than 15 N / m
  • C Peel strength is 3 N / m or more and less than 7 N / m
  • D Peel strength is less than 3 N / m
  • E Unevaluable
  • Capacity maintenance ratio is 90% or more
  • B: Capacity maintenance ratio is 80% or more and less than 90%
  • C: Capacity maintenance ratio is 75% or more and less than 80%
  • D: Capacity maintenance ratio is 70% or more and less than 75%
  • Example 1 (Production of particulate binder resin (C)) To a 1 L SUS separable flask equipped with a stirrer, a reflux condenser and a thermometer, add 130 parts of ion exchange water, and further add 0.8 parts of ammonium persulfate and 10 parts of ion exchange water as a polymerization initiator. , Heated to 80 ° C.
  • the emulsion obtained above was continuously added to the separable flask over 3 hours. After further reaction for 2 hours, the reaction was stopped by cooling. 10% aqueous ammonia was added thereto to adjust the pH to 7.5 to obtain an aqueous dispersion of the particulate binder resin (C) (acrylate polymer). The polymerization conversion rate was 98%.
  • LiCoO 2 (hereinafter sometimes abbreviated as “LCO”) having a layered structure as the positive electrode active material (A) and acetylene black (hereinafter abbreviated as “AB”) as the conductive agent (B).
  • LCO LiCoO 2
  • AB acetylene black
  • CMC carboxymethyl cellulose
  • aqueous solution BSH-12; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • 2% aqueous dispersion of cellulose nanofiber as water-insoluble polysaccharide polymer fiber E
  • 1 part of liquid BiNFi-s (NMa-120002), raw material: conifer, average degree of polymerization: 500; manufactured by Sugino Machine Co., Ltd.
  • ion-exchanged water has a solid content concentration of 50%.
  • planetary Mixture to obtain a slurry for composite particles Kisa.
  • the slurry for composite particles in a spray dryer (manufactured by Okawara Kako Co., Ltd.) was used with a rotary disk type atomizer (diameter 65 mm), rotation speed 25,000 rpm, hot air temperature 150 ° C., and particle recovery outlet temperature 90 ° C. Then, spray drying granulation was performed to obtain composite particles.
  • the composite particles had an average volume particle diameter of 40 ⁇ m.
  • the composite particles obtained above are used for a press roll (roll temperature) of a roll press machine (“Hurano Giken Kogyo Co., Ltd.“ Rough Surface Heated Roll ”) using a quantitative feeder (“ Nikka Spray KV ”manufactured by Nikka). 100 ° C., press linear pressure 500 kN / m). An aluminum foil having a thickness of 20 ⁇ m is inserted between the press rolls, the composite particles supplied from the quantitative feeder are adhered onto the aluminum foil, pressure-molded at a molding speed of 1.5 m / min, and lithium ion secondary A positive electrode for a battery was obtained.
  • the negative electrode slurry obtained above was applied onto a copper foil having a thickness of 20 ⁇ m using a comma coater so that the dried film thickness was about 150 ⁇ m and dried. This drying was performed by conveying the copper foil in an oven at 60 ° C. at a speed of 0.5 m / min for 2 minutes. Thereafter, heat treatment was performed at 120 ° C. for 2 minutes to obtain a negative electrode raw material. This negative electrode raw material was rolled with a roll press to obtain a negative electrode for a lithium ion secondary battery.
  • a single-layer polypropylene separator (width 65 mm, length 500 mm, thickness 25 ⁇ m, manufactured by dry method, porosity 55%) was cut into a square of 5 ⁇ 5 cm 2 .
  • the positive electrode for a lithium ion secondary battery obtained above was cut into a 4 ⁇ 4 cm 2 square and placed so that the current collector-side surface was in contact with the aluminum packaging exterior.
  • the square separator obtained above was disposed on the surface of the positive electrode active material layer of the positive electrode for a lithium ion secondary battery.
  • the negative electrode for a lithium ion secondary battery obtained above was cut into a square of 4.2 ⁇ 4.2 cm 2 and arranged on the separator so that the surface on the negative electrode active material layer side faced the separator. Further, containing the vinylene carbonate 2.0%, was charged with LiPF 6 solution having a concentration of 1.0 M.
  • Example 2 Production of composite particle slurry, production of composite particles, production of positive electrode for lithium ion secondary battery, lithium ion, as in Example 1, except that 90.8 parts of LiNiO 2 was used as the positive electrode active material (A) A secondary battery was manufactured.
  • Example 3 Production of slurry for composite particles and production of composite particles in the same manner as in Example 1 except that 90.8 parts of nickel manganese cobaltate (NMC (111)) having a layered structure was used as the positive electrode active material (A). Then, a positive electrode for a lithium ion secondary battery and a lithium ion secondary battery were manufactured.
  • NMC nickel manganese cobaltate
  • Example 4 Carried out except that cellulose nanofiber 1.2% aqueous dispersion (raw material: bamboo, degree of defibration: high, average degree of polymerization: 350; manufactured by Chuetsu Pulp Co., Ltd.) was used as the water-insoluble polysaccharide polymer fiber (E).
  • cellulose nanofiber 1.2% aqueous dispersion raw material: bamboo, degree of defibration: high, average degree of polymerization: 350; manufactured by Chuetsu Pulp Co., Ltd.
  • E water-insoluble polysaccharide polymer fiber
  • Example 5 Implemented except that cellulose nanofiber 1.1% aqueous dispersion (raw material: hardwood, defibration degree: low, average degree of polymerization: 600; manufactured by Chuetsu Pulp Co., Ltd.) was used as the water-insoluble polysaccharide polymer fiber (E).
  • E water-insoluble polysaccharide polymer fiber
  • Example 6 Example 1 except that a 10% aqueous dispersion of cotton cellulose nanofibers (fiber diameter 0.1 to 0.01 ⁇ m, serisch KY100G; manufactured by Daicel Finechem) was used as the water-insoluble polysaccharide polymer fiber (E). Similarly, production of a slurry for composite particles, production of composite particles, production of a positive electrode for a lithium ion secondary battery, and production of a lithium ion secondary battery were performed.
  • E water-insoluble polysaccharide polymer fiber
  • Example 7 Example 1 except that a 2% aqueous dispersion of chitin nanofibers (BiNFi-s (SFo-120002), average polymerization degree: 300; manufactured by Sugino Machine Co., Ltd.) was used as the water-insoluble polysaccharide polymer fiber (E).
  • a slurry for composite particles production of composite particles, production of composite particles, production of a positive electrode for a lithium ion secondary battery, and production of a lithium ion secondary battery were performed.
  • Example 8 Example 1 except that a 2% aqueous dispersion of chitosan nanofibers (BiNFi-s (EFo-120002), average degree of polymerization: 480; manufactured by Sugino Machine Co., Ltd.) was used as the water-insoluble polysaccharide polymer fiber (E).
  • a slurry for composite particles production of composite particles, production of composite particles, production of a positive electrode for a lithium ion secondary battery, and production of a lithium ion secondary battery were performed.
  • Example 9 As a water-soluble polymer (D), 0.5 part of a 1% aqueous solution of carboxymethyl cellulose (BSH-12; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) in terms of solid content is mixed to obtain a water-insoluble polysaccharide polymer fiber (E). 2% aqueous dispersion of cellulose nanofiber (BiNFi-s (NMa-120002), raw material: conifer, average degree of polymerization: 500; manufactured by Sugino Machine Co., Ltd.) was mixed with 1.2 parts in terms of solid content. In the same manner as in Example 1, a slurry for composite particles was produced. Thereafter, the production of composite particles, the production of a positive electrode for a lithium ion secondary battery, and the production of a lithium ion secondary battery were carried out in the same manner as in Example 1.
  • Example 10 When obtaining the composite particle slurry, 90.2 parts of LCO as the positive electrode active material (A), 6 parts of acetylene black as the conductive agent (B), 1.5 parts of the particulate binder resin (C), water-soluble
  • the polymer (D) is a 1% aqueous solution of CMC (BSH-6; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) in terms of solid content, and 2.0 parts of cellulose nanofiber as the water-insoluble polysaccharide polymer fiber (E).
  • Example 1 % Aqueous dispersion (BiNFi-s (NMa-120002), raw material: conifer, average degree of polymerization: 500; manufactured by Sugino Machine Co., Ltd.) was the same as in Example 1 except that 0.3 parts each in terms of solid content was mixed. A slurry for composite particles was produced. Thereafter, the production of composite particles, the production of a positive electrode for a lithium ion secondary battery, and the production of a lithium ion secondary battery were carried out in the same manner as in Example 1.
  • Example 11 As the water-soluble polymer (D), except that a polyacrylic resin was used, the production of the composite particle slurry, the production of the composite particle, the production of the positive electrode for the lithium ion secondary battery, the lithium ion secondary, as in Example 1. The battery was manufactured.
  • the polyacrylic resin was produced as follows.
  • the obtained emulsion aqueous solution was continuously dropped into the separable flask over 4 hours.
  • the reaction temperature was set to 80 ° C., and the reaction was further carried out for 2 hours.
  • the reaction was stopped by cooling to obtain an aqueous dispersion containing a polyacrylic resin.
  • the polymerization conversion rate was 99%. Moreover, it was 25000 when the weight average molecular weight of the obtained polyacrylic resin was measured by GPC. Moreover, the viscosity when the obtained polyacrylic resin was made into 1 weight% aqueous solution was 3000 (mPa * s).
  • Example 12 A slurry for composite particles was prepared in the same manner as in Example 1 except that poly-N-vinylacetamide (PNVA, GE191-103; Showa Denko) resin was used as the water-soluble polymer (D). Production, production of a positive electrode for a lithium ion secondary battery, and production of a lithium ion secondary battery were carried out.
  • PNVA poly-N-vinylacetamide
  • D water-soluble polymer
  • Example 13 Production of slurry for composite particles, production of composite particles, lithium as in Example 1 except that polyvinyl alcohol resin (PVA, JF-17; manufactured by Nihon Vinegar Bipoval) was used as the water-soluble polymer (D). Production of a positive electrode for an ion secondary battery and production of a lithium ion secondary battery were carried out.
  • PVA polyvinyl alcohol resin
  • JF-17 manufactured by Nihon Vinegar Bipoval
  • CMC is not added as the water-soluble polymer (D), and when obtaining a slurry for composite particles, 91.0 parts of LCO as the positive electrode active material (A), 6 parts of acetylene black as the conductive agent (B), particulate form 1.5% of binder resin (C) and 2% aqueous dispersion of cellulose nanofibers as water-insoluble polysaccharide polymer fiber (E) (BiNFi-S (NMa-120002), average polymerization degree 500; Sugino Machine Co., Ltd.)
  • the slurry for composite particles was produced in the same manner as in Example 1 except that 1.5 parts of each product was mixed in terms of solid content. Thereafter, the production of composite particles, the production of a positive electrode for a lithium ion secondary battery, and the production of a lithium ion secondary battery were carried out in the same manner as in Example 1.
  • an aqueous dispersion BaNFi-S (NMa-120002), average polymerization degree 500; manufactured by Sugino Machine Co., Ltd.
  • a water-insoluble polysaccharide polymer fiber As a water-insoluble polysaccharide polymer fiber (E), 2 parts of cellulose nanofiber A slurry for composite particles in the same manner as in Example 1, except that 0.1 part of a% aqueous dispersion (BiNFi-S (NMa-120002), average polymerization degree 500; manufactured by Sugino Machine Co., Ltd.) was mixed in an amount of 0.1 part in terms of solid content. was manufactured. Thereafter, the production of composite particles, the production of a positive electrode for a lithium ion secondary battery, and the production of a lithium ion secondary battery were carried out in the same manner as in Example 1.
  • a% aqueous dispersion BaNFi-S (NMa-120002), average polymerization degree 500; manufactured by Sugino Machine Co., Ltd.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

L'invention concerne une particule composite qui est destinée à une électrode d'élément électrochimique et contient un matériau actif de cathode (A), un agent conducteur (B), une résine adhésive particulaire (C), un polymère soluble dans l'eau (D) et une fibre polymère polysaccharidique non soluble dans l'eau (E), le polymère soluble dans l'eau (D) et la fibre polymère polysaccharidique non soluble dans l'eau (E) étant contenus selon un rapport massique de (D)/(E) = 0,25 à 7,0.
PCT/JP2015/056299 2014-03-19 2015-03-04 Particule composite pour une électrode d'élément électrochimique Ceased WO2015141464A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020167017186A KR102311705B1 (ko) 2014-03-19 2015-03-04 전기 화학 소자 전극용 복합 입자
CN201580009206.3A CN106030865B (zh) 2014-03-19 2015-03-04 电化学元件电极用复合粒子
JP2016508649A JP6380526B2 (ja) 2014-03-19 2015-03-04 電気化学素子電極用複合粒子

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014055765 2014-03-19
JP2014-055765 2014-03-19

Publications (1)

Publication Number Publication Date
WO2015141464A1 true WO2015141464A1 (fr) 2015-09-24

Family

ID=54144438

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/056299 Ceased WO2015141464A1 (fr) 2014-03-19 2015-03-04 Particule composite pour une électrode d'élément électrochimique

Country Status (4)

Country Link
JP (1) JP6380526B2 (fr)
KR (1) KR102311705B1 (fr)
CN (1) CN106030865B (fr)
WO (1) WO2015141464A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018135353A1 (fr) * 2017-01-17 2018-07-26 株式会社ダイセル Bouillie pour électrode, électrode ainsi que procédé de fabrication de celle-ci, et batterie secondaire
JP2018116819A (ja) * 2017-01-17 2018-07-26 株式会社ダイセル 電極用スラリー、電極及びその製造方法並びに二次電池
EP3358658A4 (fr) * 2015-10-01 2019-06-26 Showa Denko K.K. Composite granulaire pour la fabrication d'une électrode négative de pile rechargeable lithium-ion
WO2020090014A1 (fr) * 2018-10-30 2020-05-07 Ａｔｔａｃｃａｔｏ合同会社 Batterie secondaire à électrolyte non aqueux et procédé de fabrication de batterie secondaire à électrolyte non aqueux
JP2020094180A (ja) * 2018-09-13 2020-06-18 サイデン化学株式会社 セルロースナノファイバー含有の水系樹脂組成物、その製造方法、これを用いた超延伸性樹脂フィルム及び超延伸性樹脂製品

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7134862B2 (ja) * 2018-04-10 2022-09-12 第一工業製薬株式会社 セルロース繊維と非セルロース粉粒物を含む再分散可能な組成物
CN114464791B (zh) * 2022-01-26 2023-10-31 广东羚光新材料股份有限公司 一种水系磷酸铁锂正极浆料及其制备方法和应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02270261A (ja) * 1989-04-11 1990-11-05 Yuasa Battery Co Ltd アルカリ蓄電池用亜鉛極
JP2006179539A (ja) * 2004-12-21 2006-07-06 Tdk Corp 電極塗料、複合化粒子、電極および電気化学素子
JP2006303395A (ja) * 2005-04-25 2006-11-02 Nippon Zeon Co Ltd 電気化学素子電極用複合粒子の製造方法
WO2011024797A1 (fr) * 2009-08-27 2011-03-03 大日精化工業株式会社 Composition de bouillie aqueuse, plaque d'électrodes pour dispositif de stockage et dispositif de stockage
WO2012026009A1 (fr) * 2010-08-25 2012-03-01 トヨタ自動車株式会社 Procédé de fabrication d'électrode de batterie

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005340071A (ja) * 2004-05-28 2005-12-08 Matsushita Electric Ind Co Ltd 非水系二次電池用正極板の製造方法
JP5045761B2 (ja) 2007-10-03 2012-10-10 日本ゼオン株式会社 電気二重層キャパシタ用電極およびその製造方法
JP2009295666A (ja) 2008-06-03 2009-12-17 Nippon Zeon Co Ltd 電気化学素子用電極および電気化学素子
KR101277996B1 (ko) * 2010-06-30 2013-06-27 다이킨 고교 가부시키가이샤 전극용 바인더 조성물
EP2757620A4 (fr) * 2011-09-14 2015-07-08 Zeon Corp Électrode pour élément électrochimique
JP6017432B2 (ja) 2011-09-20 2016-11-02 日産化学工業株式会社 セルロースファイバーをバインダーとして含有するリチウム二次電池電極形成用スラリー組成物及びリチウム二次電池用電極
JP5825006B2 (ja) * 2011-09-22 2015-12-02 藤倉化成株式会社 リチウムイオン二次電池用正極材、およびリチウムイオン二次電池
CN105164837B (zh) * 2013-05-13 2017-12-26 日本瑞翁株式会社 电化学元件电极用复合粒子、电化学元件电极用复合粒子的制造方法、电化学元件电极以及电化学元件

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02270261A (ja) * 1989-04-11 1990-11-05 Yuasa Battery Co Ltd アルカリ蓄電池用亜鉛極
JP2006179539A (ja) * 2004-12-21 2006-07-06 Tdk Corp 電極塗料、複合化粒子、電極および電気化学素子
JP2006303395A (ja) * 2005-04-25 2006-11-02 Nippon Zeon Co Ltd 電気化学素子電極用複合粒子の製造方法
WO2011024797A1 (fr) * 2009-08-27 2011-03-03 大日精化工業株式会社 Composition de bouillie aqueuse, plaque d'électrodes pour dispositif de stockage et dispositif de stockage
WO2012026009A1 (fr) * 2010-08-25 2012-03-01 トヨタ自動車株式会社 Procédé de fabrication d'électrode de batterie

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3358658A4 (fr) * 2015-10-01 2019-06-26 Showa Denko K.K. Composite granulaire pour la fabrication d'une électrode négative de pile rechargeable lithium-ion
WO2018135353A1 (fr) * 2017-01-17 2018-07-26 株式会社ダイセル Bouillie pour électrode, électrode ainsi que procédé de fabrication de celle-ci, et batterie secondaire
JP2018116819A (ja) * 2017-01-17 2018-07-26 株式会社ダイセル 電極用スラリー、電極及びその製造方法並びに二次電池
US11621422B2 (en) 2017-01-17 2023-04-04 Daicel Corporation Electrode slurry, electrode and process for producing the same, and secondary battery
JP2020094180A (ja) * 2018-09-13 2020-06-18 サイデン化学株式会社 セルロースナノファイバー含有の水系樹脂組成物、その製造方法、これを用いた超延伸性樹脂フィルム及び超延伸性樹脂製品
WO2020090014A1 (fr) * 2018-10-30 2020-05-07 Ａｔｔａｃｃａｔｏ合同会社 Batterie secondaire à électrolyte non aqueux et procédé de fabrication de batterie secondaire à électrolyte non aqueux

Also Published As

Publication number Publication date
CN106030865A (zh) 2016-10-12
CN106030865B (zh) 2019-06-11
KR20160134637A (ko) 2016-11-23
KR102311705B1 (ko) 2021-10-08
JP6380526B2 (ja) 2018-08-29
JPWO2015141464A1 (ja) 2017-04-06

Similar Documents

Publication Publication Date Title
JP6954424B2 (ja) 電気化学素子電極用複合粒子、電気化学素子電極及び電気化学素子
JP6217741B2 (ja) 電気化学素子電極用複合粒子、電気化学素子電極用複合粒子の製造方法、電気化学素子電極および電気化学素子
JP6344384B2 (ja) 電気化学素子電極用複合粒子、電気化学素子電極用複合粒子の製造方法、電気化学素子電極および電気化学素子
JP6380526B2 (ja) 電気化学素子電極用複合粒子
JP6540692B2 (ja) 電気化学素子電極用複合粒子および電気化学素子電極用複合粒子の製造方法
WO2011013756A1 (fr) Electrode pour élément électrochimique, et élément électrochimique
JP6485359B2 (ja) 電気化学素子電極用複合粒子
JP2013077558A (ja) 電気化学素子用電極
JP6451934B2 (ja) 電気化学素子電極用複合粒子
JP6398461B2 (ja) 電気化学素子電極用複合粒子の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15765553

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2016508649

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20167017186

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15765553

Country of ref document: EP

Kind code of ref document: A1