WO2014185365A1 - Particules composites pour électrode d'élément électrochimique, procédé de fabrication desdites particules composites, électrode d'élément électrochimique et élément électrochimique - Google Patents

Particules composites pour électrode d'élément électrochimique, procédé de fabrication desdites particules composites, électrode d'élément électrochimique et élément électrochimique Download PDF

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Publication number
WO2014185365A1
WO2014185365A1 PCT/JP2014/062553 JP2014062553W WO2014185365A1 WO 2014185365 A1 WO2014185365 A1 WO 2014185365A1 JP 2014062553 W JP2014062553 W JP 2014062553W WO 2014185365 A1 WO2014185365 A1 WO 2014185365A1
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electrochemical element
active material
composite particles
electrode active
water
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PCT/JP2014/062553
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English (en)
Japanese (ja)
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琢也 石井
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日本ゼオン株式会社
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Priority to KR1020157031694A priority Critical patent/KR102232543B1/ko
Priority to JP2015517064A priority patent/JP6344384B2/ja
Priority to CN201480024483.7A priority patent/CN105164837B/zh
Publication of WO2014185365A1 publication Critical patent/WO2014185365A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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 OR LIGHT-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 OR LIGHT-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
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0419—Methods of deposition of the material involving spraying
    • 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
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion 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
    • Y02E60/10—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
    • 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 a composite particle for an electrochemical element electrode, a method for producing a composite particle for an electrochemical element electrode, an electrochemical element electrode, and an electrochemical element.
  • 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, it is used as a memory backup compact power source for personal computers and the like, and is expected to be applied as an auxiliary power source for electric vehicles and 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 are usually formed by laminating an electrode active material layer formed by binding an electrode active material and a conductive aid used as necessary with a binder resin on a current collector. It will be.
  • An electrode for an electrochemical element includes a coated electrode manufactured by a method in which a slurry for a coated electrode containing an electrode active material, a binder resin, a conductive auxiliary agent, etc. is coated on a current collector and the solvent is removed by heat or the like.
  • a slurry for a coated electrode containing an electrode active material, a binder resin, a conductive auxiliary 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.
  • Such composite particles have low strength and may be broken during transfer such as pneumatic transportation.
  • the electrode active material layer is formed using the broken composite particles, the uniformity of the particle size of the composite particles is lost, so that the fluidity of the powder is deteriorated and the uniform electrode active material layer cannot be formed.
  • 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.
  • Patent Document 1 externally added particles in which the surface of the composite particle is coated with a fibrous conductive additive are used.
  • 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.
  • An object of the present invention is to provide a composite particle for an electrochemical element electrode that has sufficient strength and can provide sufficient adhesion when an electrode is formed, and a method for producing the composite particle for an electrochemical element electrode. Furthermore, it is providing the electrochemical element electrode and electrochemical element using this composite particle for electrochemical element electrodes.
  • the present inventor dispersed specific fibers made of a water-insoluble polysaccharide polymer in an electrode slurry containing a positive electrode active material, and spray-dried the slurry to obtain the above-mentioned solution.
  • the present invention has been completed by finding that the above object can be achieved by forming composite particles in which water-insoluble polysaccharide polymer fibers are dispersed to the inside and forming electrodes with the composite particles.
  • a composite particle for an electrochemical element electrode comprising a positive electrode active material, a conductive additive, a binder resin, and a water-insoluble polysaccharide polymer fiber
  • 0.2 to 4 parts by weight of the water-insoluble polysaccharide polymer fiber is contained in 100 parts by weight of the composite particles for electrochemical element electrodes.
  • Composite particles for electrochemical element electrodes (5) A method of producing composite particles for electrochemical element electrodes according to any one of (1) to (4), wherein the positive electrode active material and the conductive auxiliary agent are used. A step of dispersing the binder resin and the water-insoluble polysaccharide polymer fiber in a solvent to obtain a slurry for composite particles, and a step of spray drying and granulating the slurry for composite particles.
  • An electrochemical element electrode comprising an electrode active material layer containing the composite particles for an electrochemical element electrode according to any one of (1) to (4) on a current collector, (7) The electrochemical element according to (6), wherein the electrode active material layer is obtained by pressure-molding an electrode material containing the composite particle for an electrochemical element electrode on the current collector. electrode, (8) An electrochemical device comprising the electrochemical device electrode according to (6) or (7) is provided.
  • ADVANTAGE OF THE INVENTION According to this invention, it has sufficient intensity
  • the composite particle for an electrochemical element electrode of the present invention (hereinafter sometimes referred to as “composite particle”) includes a positive electrode active material, a conductive additive, a binder resin, and a water-insoluble polysaccharide polymer fiber. To do.
  • 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.
  • the positive electrode active material is an active material that can be doped and dedoped with lithium ions, and is broadly classified into an inorganic compound and an organic compound.
  • Examples of the positive electrode active material 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 can reduce the blending amount of the binder resin for the positive electrode when preparing the positive electrode slurry, and can suppress the decrease in battery capacity, and the positive electrode slurry.
  • the viscosity is preferably 1 to 50 ⁇ m, more preferably 2 to 30 ⁇ m.
  • the binder resin 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 suitable binder resin is a dispersion type binder resin having a property of being dispersed in a solvent.
  • the dispersion-type binder resin include high molecular compounds such as silicon polymers, fluorine-containing polymers, conjugated diene polymers, acrylate polymers, polyimides, polyamides, polyurethanes, and preferably fluorine-containing polymers. Conjugated diene polymers and acrylate polymers, more preferably conjugated diene polymers and acrylate polymers. These polymers can be used alone or in combination of two or more as a dispersion-type 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 (PVDF), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, ethylene / tetrafluoroethylene copolymer, and ethylene / chlorotrifluoroethylene copolymer. Examples thereof include a polymer and a perfluoroethylene / propene copolymer. Among these, it is preferable to include PVDF.
  • 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 ratio 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 ratio of the conjugated diene monomer unit is too large, the electrolytic solution resistance tends to be lowered when a positive electrode is produced using composite particles containing a binder resin.
  • the ratio of the conjugated diene monomer unit is too small, there is a tendency that sufficient adhesion between the composite particles and the current collector cannot 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 esters carboxylic acid-containing (meth) acrylic acid esters such as 2- (meth) acryloyloxyethylphthalic acid and 2- (meth) acryloyloxyethylphthalic acid; fluorine such as perfluorooctylethyl (meth) acrylic acid Group-containing (meth) acrylic acid ester; Phosphoric acid group-containing (meth) acrylic acid esters such as ethyl phosphate; Epoxy group-containing (meth) acrylic acid esters such as glycidyl (meth) acrylate; Amino group content such as dimethylaminoethyl (meth) acrylate ( (Meth) acrylic acid ester; and the like.
  • fluorine such as perfluorooctylethyl (meth) acrylic acid Group-containing (meth) acrylic acid ester
  • Phosphoric acid group-containing (meth) acrylic acid esters such as ethyl phosphate
  • (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 proportion of the (meth) acrylic acid ester unit in the acrylate polymer is preferably 50 to 95 from the viewpoint of improving flexibility when used as an electrode (positive electrode) and increasing resistance to cracking. % By weight, more preferably 60 to 90% by weight.
  • Examples of the ⁇ , ⁇ -unsaturated nitrile compound used in the polymer constituting the dispersion-type binder resin include acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, ⁇ -bromoacrylonitrile, and the like. 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 proportion of ⁇ , ⁇ -unsaturated nitrile compound units in the dispersion-type binder resin is preferably 0.1 to 40% by weight, more preferably 0.5 to 30% by weight, and still more preferably 1 to 20% by weight. is there.
  • an ⁇ , ⁇ -unsaturated nitrile compound unit is contained in the dispersion-type binder resin, it is difficult to be deformed when the electrode (positive electrode) is manufactured, and the strength can be increased. Further, when an ⁇ , ⁇ -unsaturated nitrile compound unit is contained in the dispersion-type binder resin, the adhesion between the positive electrode active material layer containing the composite particles and the current collector can be made sufficient.
  • 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 proportion of the vinyl compound unit having an acid component in the dispersion-type binder resin is preferably 0.5 to 10% by weight, more preferably 1 to 8% from the viewpoint of improving the stability of the composite particle slurry. % By weight, more preferably 2 to 7% by weight.
  • the shape of the dispersion-type binder resin is not particularly limited, but is preferably particulate. By being particulate, the binding property is good, and it is possible to suppress deterioration of the capacity of the manufactured electrode and deterioration due to repeated charge and discharge.
  • the particulate binder resin include those in which the binder resin particles such as latex are dispersed in water, and powders obtained by drying such a dispersion.
  • the average particle diameter of the dispersion-type binder resin is preferably 0.001 to 100 ⁇ m from the viewpoint of improving the strength and flexibility of the positive electrode obtained while maintaining good stability when the composite particle slurry is obtained. More preferably, the thickness is 10 to 1000 nm, and still more preferably 50 to 500 nm.
  • the method for producing the binder resin 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 can be employed. Among these, it is preferable to produce by an emulsion polymerization method because the particle diameter of the binder resin can be easily controlled. Further, the binder resin used in the present invention may be particles having a core-shell structure obtained by stepwise polymerization of a mixture of two or more monomers.
  • the amount of the binder resin is 100 parts by weight of the positive electrode active material from the viewpoint of ensuring sufficient adhesion between the obtained positive electrode active material layer and the current collector and reducing the internal resistance of the electrochemical element. On the other hand, it is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 20 parts by weight, and still more preferably 1 to 15 parts by weight on a dry weight basis.
  • the water-insoluble polysaccharide polymer fiber used in the present invention is a fiber (short fiber) fibrillated by a mechanical shearing force.
  • the water-insoluble polysaccharide polymer fiber used in the present invention is a polysaccharide polymer fiber whose insoluble content is 80% by weight or more when 0.5 g of polysaccharide polymer fiber is dissolved in 100 g of water at 25 ° C. Say.
  • the water-insoluble polysaccharide polymer fiber it is preferable to use polysaccharide polymer nanofibers, and among the polysaccharide polymer nanofibers, it has flexibility and high strength, and therefore has a reinforcing effect on the composite particles. From a high viewpoint, it is preferable to use single or any mixture selected from bio-derived bio-nanofibers such as cellulose nanofiber, chitin nanofiber, and chitosan nanofiber.
  • water-insoluble polysaccharide polymer fibers can be fibrillated (short fiber) by applying mechanical shearing force. After water-insoluble polysaccharide polymer fibers are dispersed in water, they are beaten. The method of making it pass is mentioned.
  • short fibers having various fiber diameters are commercially available, and these may be used by dispersing in water.
  • the average fiber diameter of the water-insoluble polysaccharide polymer fiber used in the present invention is the viewpoint that the composite particles and the electrode (positive electrode) have sufficient strength, and the electrochemical obtained because a uniform positive electrode active material layer can be formed.
  • the thickness is preferably 5 to 3000 nm, more preferably 5 to 2000 nm, still more preferably 5 to 1000 nm, and particularly preferably 5 to 100 nm. If the average fiber diameter of the water-insoluble polysaccharide polymer fiber is too large, the water-insoluble polysaccharide polymer fiber cannot be sufficiently present in the composite particle, so that the strength of the composite particle cannot be made sufficient. 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 may be composed of a single fiber that is sufficiently separated without being arranged.
  • the average fiber diameter is the average diameter of single fibers.
  • the water-insoluble polysaccharide polymer fiber 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 degree of polymerization of the water-insoluble polysaccharide polymer fiber is such that the composite particles and the electrode (positive electrode) have sufficient strength, and that a uniform positive electrode active material layer can be formed. From the viewpoint of excellent chemical properties, it is preferably 50 to 1000, more preferably 100 to 600. If the 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. If the degree of polymerization of the water-insoluble polysaccharide polymer fiber is too small, the strength of the composite particles will be insufficient.
  • the blending amount of the water-insoluble polysaccharide polymer fiber is preferably 0.2 to 4 parts by weight, more preferably 0.5 to 4 parts by weight, and further preferably 1 to 3 parts by weight with respect to 100 parts by weight of the composite particles. Particularly preferred is 1 to 2 parts 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).
  • strength of a composite particle will become inadequate.
  • the viscosity of the slurry for composite particles increases by increasing the blending amount of the water-insoluble polysaccharide polymer fiber, the viscosity can be appropriately adjusted by reducing the blending amount of the water-soluble polymer.
  • the conductive auxiliary agent used in the present invention is not particularly limited as long as it is a conductive material, but a conductive particulate material is preferable.
  • a conductive particulate material is preferable.
  • carbon black such as furnace black, acetylene black, and ketjen black Graphite such as natural graphite and artificial graphite
  • carbon fibers such as polyacrylonitrile-based carbon fiber, pitch-based carbon fiber, and vapor grown carbon fiber
  • the average particle diameter when the conductive additive is a particulate material is not particularly limited, but is preferably smaller than the average particle diameter of the positive electrode active material, from the viewpoint of expressing sufficient conductivity with a smaller amount of use.
  • the thickness 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 assistant is 100 parts 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.
  • it is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 15 parts by weight, still more preferably 1 to 10 parts by weight.
  • the composite particle for an electrochemical element electrode of the present invention may contain a water-soluble polymer, if necessary, in addition to the above components.
  • the water-soluble polymer used in the present invention refers to a polymer having an insoluble content of less than 1.0% by weight when 25 g of the polymer is dissolved in 100 g of water at 25 ° C.
  • water-soluble polymer 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 sodium alginate.
  • examples include starch, casein, various modified starches, chitin, and chitosan derivatives.
  • “(modified) poly” means “unmodified poly” or “modified poly”.
  • water-soluble polymers can be used alone or in combination of two or more.
  • a cellulose polymer is preferable, and carboxymethyl cellulose or an ammonium salt or an alkali metal salt thereof is particularly preferable.
  • the blending amount of these water-soluble polymers is not particularly limited as long as the effect of the present invention is not impaired, but is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the positive electrode active material.
  • the amount is preferably 0.1 to 5 parts by weight, more preferably 0.1 to 2 parts by weight.
  • the composite particles can be obtained by granulating using other components such as a positive electrode active material, a conductive additive, a binder resin, a water-insoluble polysaccharide polymer, and a water-soluble polymer added if necessary.
  • the composite particle includes a positive electrode active material and a binder resin, but each of the positive electrode active material and the binder resin does not exist as independent particles, but is a constituent component of the positive electrode active material and the binder resin.
  • One particle is formed by two or more components including. Specifically, 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 is preferably bonded with a binder resin 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 (hereinafter sometimes referred to as “slurry”) containing a positive electrode active material and a binder resin is prepared.
  • the composite particle slurry is prepared by dispersing or dissolving a positive electrode active material, a binder resin, a water-soluble polymer and a water-insoluble polysaccharide polymer fiber, and a conductive additive added as necessary, in a solvent. Can do.
  • the binder resin when the binder resin 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 and 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 that are easily thermally decomposed 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 50% by weight, more preferably 5 to 50% by weight, from the viewpoint of uniformly dispersing the binder resin in the slurry. More preferably, the amount is 10 to 40% by weight.
  • the method or order of dispersing or dissolving the positive electrode active material, the conductive additive, the binder resin and the water-insoluble polysaccharide polymer fiber and the water-soluble polymer added as necessary in the solvent is not particularly limited.
  • a method of adding and mixing a positive electrode active material, a binder resin, a water-soluble polymer, a water-insoluble polysaccharide polymer fiber, and a conductive additive in a solvent, and dissolving a water-soluble polymer in a solvent A method of adding and mixing a binder and a water-insoluble polysaccharide polymer fiber, and finally adding and mixing a binder resin (for example, latex) dispersed in a solvent, a binder resin dispersed in a solvent and a water-insoluble solution
  • Examples include a method in which a positive electrode active material and a conductive additive are added to and mixed with the soluble polysaccharide polymer fiber, and a water-soluble polymer dissolved in a solvent is
  • a ball mill, a sand mill, a bead mill, a pigment disperser, a crusher, an ultrasonic disperser, a homogenizer, a homomixer, a planetary mixer or the like can be used as the mixing device.
  • 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 a disk that rotates at high speed, and the slurry is removed from 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 pressurization method is a method in which the slurry for composite particles is pressurized and sprayed from a nozzle to be 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 spray direction flow in the horizontal direction the method in which the hot air is sprayed at the top of the drying tower and descends with the hot air, the sprayed droplets and the hot air are counter-current 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.
  • the electrochemical element electrode of the present invention is a positive electrode formed by laminating a positive electrode active material layer containing the above-described composite particles 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 25 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 25 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.
  • the density of the positive electrode active material layer is not particularly limited, but is usually 0.30 to 10 g / cm 3 , preferably 0.35 to 8.0 g / cm 3 , more preferably 0.40 to 6.0 g / cm 3. It is.
  • the thickness of the negative electrode active material layer is not particularly limited, but is usually 5 to 1000 ⁇ m, preferably 20 to 500 ⁇ m, more preferably 30 to 300 ⁇ m.
  • the electrochemical device of the present invention uses the electrochemical device electrode obtained as described above as a positive electrode, and further includes 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 is 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 a slurry for the negative electrode containing other components such as a conductive additive. It can be obtained by applying to the surface of the electric 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 additive 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.
  • Binder resin for negative electrode As the binder resin for the negative electrode used in the negative electrode active material layer, for example, the same binder resin as that used in the positive electrode active material layer may be used.
  • polymers such as polyethylene, tetrafluoroethylene-hexafluoropropylene copolymer (FEP), polyacrylic acid derivatives, polyacrylonitrile derivatives; acrylic soft polymers, diene soft polymers, olefin soft polymers
  • FEP tetrafluoroethylene-hexafluoropropylene copolymer
  • a soft polymer such as a vinyl-based soft polymer may be used.
  • these may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.
  • the water-soluble polymer and the conductive auxiliary used as necessary for the negative electrode slurry the water-soluble polymer and the conductive auxiliary 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; Acylonitriles 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; When using an organic solvent, N-methylpyrroli
  • 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 is preferably 5% or more, more preferably 7% or more, preferably 30% or less, more preferably 20% or less.
  • the porosity is too large, it is difficult to obtain a high volume capacity, and the negative electrode active material layer is easily peeled off from the current collector. On the other hand, if the porosity is too small, the rate characteristics are degraded.
  • 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.
  • the density of the negative electrode active material layer is not particularly limited, but is usually 0.30 to 10 g / cm 3 , preferably 0.35 to 8.0 g / cm 3 , more preferably 0.40 to 6.0 g / cm 3. It is.
  • the thickness of the negative electrode active material layer is not particularly limited, but is usually 5 to 1000 ⁇ m, preferably 20 to 500 ⁇ m, more preferably 30 to 300 ⁇ m.
  • 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, polycycloolefin, nylon, and polytetrafluoroethylene; a polyolefin fiber woven or non-woven fabric thereof; an aggregate of insulating substance particles, and the like.
  • a polyolefin resin such as polyethylene or polypropylene, or a microporous film or nonwoven fabric containing
  • 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 electrolyte solution may contain an additive.
  • 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. According to the composite particle for an electrochemical element electrode according to the present embodiment, it has sufficient strength, and sufficient adhesion can be obtained when an electrode is formed.
  • 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.
  • composite particles having a diameter of 30 to 50 ⁇ m were selected and subjected to a compression test.
  • Compressive strength is 4.50 MPa or more
  • Compressive strength is 4.10 MPa or more, less than 4.50 MPa
  • C Compressive strength is 3.70 MPa or more, less than 4.10 MPa
  • D Compressive strength is 3.30 MPa or more, 3.70 MPa Less than E: Compressive strength is less than 3.30 MPa
  • the negative 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 Table 1.
  • peel strength is 12 N / m or more
  • B Peel strength is 8 N / m or more and less than 12 N / m
  • C Peel strength is 4 N / m or more and less than 8 N / m
  • D Peel strength is less than 4 N / m
  • E Unevaluable
  • Capacity maintenance ratio is 90% or more
  • B: Capacity maintenance ratio is 80% or more and less than 90%
  • D: Capacity maintenance ratio is 70% or more and less than 75%
  • Example 1 Manufacture of binder resin for positive electrode
  • 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% ammonia water was added thereto to adjust the pH to 7.5, and an aqueous dispersion of a particulate positive electrode binder resin (acrylate system) was obtained. The polymerization conversion rate was 98%.
  • LiCoO 2 (hereinafter sometimes abbreviated as “LCO”) and 6 parts of acetylene black (hereinafter sometimes abbreviated as “AB”)
  • the above binder resin for positive electrode 1.5 parts by weight in terms of solid content
  • CMC carboxymethyl cellulose
  • BSH-12 BSH-12; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • a water-soluble polymer 2 parts of a 5% aqueous dispersion of cellulose nanofiber A (BiNFi-s (NMa-10005), fiber diameter 20 nm, polymerization degree 500; manufactured by Sugino Machine Co., Ltd.) as a water-insoluble polysaccharide polymer fiber
  • ion-exchanged water was added so as to have a solid content of 50%, and mixed with a planetary mixer to obtain a s
  • 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 (“Hirano 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, and the composite particles 1 for the secondary battery positive electrode supplied from the quantitative feeder are adhered onto the aluminum foil, and pressure-molded at a molding speed of 1.5 m / min. Thus, a positive electrode having a positive electrode active material was obtained.
  • the negative electrode slurry composition obtained above was applied onto a copper foil having a thickness of 20 ⁇ m using a comma coater so that the film thickness after drying 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 having a negative electrode active material layer.
  • 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 Preparation of water-insoluble polysaccharide polymer
  • 5% aqueous dispersion of cellulose nanofiber A as a water-insoluble polysaccharide polymer fiber with respect to 120 parts of N-methylpyrrolidone (BiNFi-s (NMa-10005), fiber diameter 20 nm, polymerization degree 500; manufactured by Sugino Machine) was mixed with 5 parts in terms of solid content, concentrated with a rotary evaporator to remove water, thereby obtaining a 5% N-methylpyrrolidone dispersion of water-insoluble polysaccharide polymer fibers.
  • LiCoO 2 was added to 90.5 parts as a positive electrode active material, and polyvinylidene fluoride (PVDF; “KF-1100” manufactured by Kureha Chemical Co., Ltd.) as a positive electrode binder resin was added to a solid content of 1.5 parts.
  • PVDF polyvinylidene fluoride
  • HS-100 acetylene black
  • N-methylpyrrolidone dispersion of the above water-insoluble polysaccharide polymer fiber solid content of water-insoluble polysaccharide polymer fiber It added so that it might become 2 parts by conversion amount. Further, N-methylpyrrolidone was added so that the solid content concentration was 50%, and mixed with a planetary mixer to obtain a slurry for composite particles.
  • the positive electrode and the lithium ion secondary battery were manufactured in the same manner as in Example 1 except that the composite particles were manufactured using the composite particle slurry.
  • Example 3 Example 1 except that chitin nanofiber 5% aqueous dispersion (BiNFi-s (SFo-10005), fiber diameter 20 nm, polymerization degree 300; manufactured by Sugino Machine Co., Ltd.) was used as the water-insoluble polysaccharide polymer fiber.
  • a slurry for composite particles, a composite particle, a positive electrode, and a lithium ion secondary battery were manufactured.
  • Example 4 Example 1 except that chitosan nanofiber 5% aqueous dispersion (BiNFi-s (EFo-10005), fiber diameter 20 nm, polymerization degree 480; manufactured by Sugino Machine Co., Ltd.) was used as the water-insoluble polysaccharide polymer fiber.
  • a slurry for composite particles, a composite particle, a positive electrode, and a lithium ion secondary battery were manufactured.
  • Example 5 Manufacture of cellulose nanofibers
  • the pulp was added to 1% by weight in ion-exchanged water and stirred with a juicer for 1 hour.
  • 1 kg of the dispersion was stirred at 15000 rpm for 3 hours with an emulsifying dispersion device (Milder MDN303V; manufactured by Taiheiyo Kiko Co., Ltd.) to prepare cellulose nanofiber B having an average fiber diameter of 100 nm and a polymerization degree of 600. It concentrated to 5% of solid content concentration with the evaporator.
  • Mill MDN303V manufactured by Taiheiyo Kiko Co., Ltd.
  • a slurry for composite particles, a composite particle, a positive electrode, and a lithium ion secondary battery were manufactured in the same manner as in Example 1 except that cellulose nanofiber B was used as the water-insoluble polysaccharide polymer fiber. .
  • Example 6 Cellulose nanofibers C were obtained by producing cellulose nanofibers in the same manner as in Example 5 except that the stirring time in the emulsifying and dispersing apparatus was 30 minutes.
  • the cellulose nanofiber C had a fiber diameter of 1000 nm and a degree of polymerization of 800.
  • cellulose nanofiber C was used as the water-insoluble polysaccharide polymer fiber, a slurry for composite particles, a composite particle, a positive electrode, and a lithium ion secondary battery were manufactured in the same manner as in Example 1. .
  • Example 7 Cellulose nanofibers D were obtained by producing cellulose nanofibers in the same manner as in Example 5 except that the stirring time in the emulsifying and dispersing apparatus was 20 minutes.
  • the cellulose nanofiber D had a fiber diameter of 2000 nm and a degree of polymerization of 1000.
  • a slurry for composite particles, a composite particle, a positive electrode, and a lithium ion secondary battery were manufactured in the same manner as in Example 1 except that cellulose nanofiber D was used as the water-insoluble polysaccharide polymer fiber. .
  • Example 8 When obtaining a composite particle slurry, 91 parts of LCO, 6 parts of acetylene black, 1.5 parts of binder resin for positive electrode, 0.5 part of CMC, and 5% water dispersion of cellulose nanofiber A as a positive electrode active material A slurry for composite particles was produced in the same manner as in Example 1 except that 1 part of each liquid was mixed in terms of solid content. Thereafter, in the same manner as in Example 1, composite particles, positive electrodes, and lithium ion secondary batteries were manufactured.
  • Example 9 When obtaining a slurry for composite particles, 89 parts of LCO as positive electrode active material, 6 parts of acetylene black, 1.5 parts of binder resin for positive electrode, 0.1 part of CMC and 5% water dispersion of cellulose nanofiber A A slurry for composite particles was produced in the same manner as in Example 1 except that 3 parts of each liquid was mixed in terms of solid content. Thereafter, in the same manner as in Example 1, composite particles, positive electrodes, and lithium ion secondary batteries were manufactured.
  • composite particles containing a positive electrode active material, a conductive additive, a binder resin, and a water-insoluble polysaccharide polymer fiber are excellent in particle strength, and the peel strength of the positive electrode obtained using this composite particle is good Met. Furthermore, the charge / discharge cycle characteristics of the lithium ion secondary battery produced using this positive electrode were also good.

Abstract

L'invention permet de former des particules composites pour électrode d'élément électrochimique, lesdites particules composites possédant une résistance adéquate et permettant d'obtenir une adhésion adéquate lors de la formation d'une électrode. L'invention concerne un procédé de fabrication des particules composites pour électrode d'élément électrochimique. L'invention se rapporte à des particules composites pour élément électrochimique qui comprennent une substance active d'électrode positive, un agent auxiliaire électroconducteur, un liant résine, et une fibre de polymère polysaccharide non soluble dans l'eau.
PCT/JP2014/062553 2013-05-13 2014-05-12 Particules composites pour électrode d'élément électrochimique, procédé de fabrication desdites particules composites, électrode d'élément électrochimique et élément électrochimique WO2014185365A1 (fr)

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JP2015517064A JP6344384B2 (ja) 2013-05-13 2014-05-12 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
CN201480024483.7A CN105164837B (zh) 2013-05-13 2014-05-12 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

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JP2021036508A (ja) * 2019-08-30 2021-03-04 株式会社豊田中央研究所 活物質複合体、電極、蓄電デバイス及び活物質複合体の製造方法
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