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WO2011074269A1 - Liquide de revêtement - Google Patents

Liquide de revêtement Download PDF

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Publication number
WO2011074269A1
WO2011074269A1 PCT/JP2010/007317 JP2010007317W WO2011074269A1 WO 2011074269 A1 WO2011074269 A1 WO 2011074269A1 JP 2010007317 W JP2010007317 W JP 2010007317W WO 2011074269 A1 WO2011074269 A1 WO 2011074269A1
Authority
WO
WIPO (PCT)
Prior art keywords
coating liquid
active material
electrode active
polymer
layer
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/JP2010/007317
Other languages
English (en)
Japanese (ja)
Inventor
忠利 黒住
仁 横内
石井　伸晃
陽太郎 服部
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.)
Resonac Holdings Corp
Original Assignee
Showa Denko KK
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 Showa Denko KK filed Critical Showa Denko KK
Publication of WO2011074269A1 publication Critical patent/WO2011074269A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • 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
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
    • 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
    • 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
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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

Definitions

  • the present invention relates to a coating liquid.
  • this invention relates to the coating liquid for manufacturing the electrode used for electrochemical elements, such as a secondary battery and an electrical double layer capacitor.
  • Electrode of an electrochemical element generally comprises a current collector and an electrode active material layer.
  • the electrode is usually produced by applying a coating liquid containing an electrode active material, a binder, and a solvent to a current collector and drying it. Further, in order to reduce the internal resistance or impedance of the secondary battery or electric double layer capacitor, it has been proposed to interpose an undercoat layer between the electrode active material layer and the current collector.
  • Patent Document 1 discloses that an electrode active material layer or an undercoat layer is produced by applying a coating liquid containing a hydroxyalkyl chitosan and an organic acid and / or a derivative thereof onto a current collector and drying it. Proposed. Organic acids and their derivatives have the role of crosslinking hydroxyalkylchitosan.
  • Patent Document 2 discloses that an undercoat layer is coated with an electrode active material layer and a current collector by applying a coating solution containing a crosslinked polysaccharide and a carbon particle on the current collector and drying it. Between the two.
  • Organic compounds such as maleic anhydride are exemplified as compounds used for crosslinking polysaccharides.
  • Patent Document 3 contains a carbonaceous material, a hydroxyalkyl polysaccharide derivative, a compound having an isocyanate group in the molecule, and a compound having two or more active hydrogen groups capable of reacting with the isocyanate group.
  • a coating liquid is disclosed.
  • a three-dimensional network structure can be formed by a compound having an isocyanate group in the molecule and a compound having two or more active hydrogen groups capable of reacting with the isocyanate group.
  • an acid component may remain in the electrode active material layer or the undercoat layer obtained with the coating solution containing an organic acid described in Patent Document 1 or 2.
  • This acid component may erode a current collector made of aluminum or copper. When the current collector is eroded, there is a concern that resistance or impedance increases.
  • the compound which has an isocyanate group used with the coating liquid of patent document 3 has very high reactivity. Therefore, it is necessary to lower the crosslinking temperature to about 80 ° C.
  • the solvent may be sealed inside the film. The encapsulated solvent is difficult to evaporate and may cause blistering.
  • an object of the present invention is to provide an electrochemical device having excellent storage stability and low internal resistance or impedance, and a coating solution used for the production thereof.
  • the present inventors have collected a coating solution containing a polysaccharide, a polymer having a blocked isocyanate structure, a solvent, a conductivity-imparting material and / or an electrode active material. It was found that an electrochemical element having excellent storage stability and low internal resistance or impedance can be obtained by applying to a body and drying. The present invention has been completed by further studies based on this finding.
  • the present invention includes the following.
  • the polymer having a blocked isocyanate structure is a polymer including a repeating unit derived from a monomer having a blocked isocyanate structure and at least one polymerizable unsaturated group.
  • liquid. ⁇ 3> The coating liquid according to ⁇ 2>, wherein the monomer having a blocked isocyanate structure and at least one polymerizable unsaturated group is a compound represented by formula (1) or formula (2). .
  • R 1 represents a hydrogen atom or a methyl group.
  • R 2 represents a hydrogen atom or a methyl group.
  • ⁇ 4> Any of the above ⁇ 1> to ⁇ 3>, wherein the polysaccharide is at least one selected from the group consisting of chitosan, hydroxyalkylchitosan, carboxyalkylchitosan, caprolactone-modified chitosan, hydroxyalkylcellulose and carboxyalkylcellulose
  • ⁇ 5> The coating solution according to any one of ⁇ 1> to ⁇ 4>, wherein the amount of the polymer having a blocked isocyanate structure is 20 to 300 parts by mass with respect to 100 parts by mass of the polysaccharide.
  • ⁇ 6> A film formed using the coating liquid according to any one of ⁇ 1> to ⁇ 5>.
  • a laminate for an electrode comprising a current collector and a layer a formed using a coating liquid containing a polysaccharide, a polymer having a blocked isocyanate structure, a solvent, and a conductivity-imparting material.
  • ⁇ 10> An electrochemical device having the electrode according to ⁇ 8> or ⁇ 9>.
  • ⁇ 11> A power supply system having the electrochemical element according to ⁇ 10>.
  • ⁇ 12> An automobile having the electrochemical element according to ⁇ 10>.
  • ⁇ 13> A transport device having the electrochemical element according to ⁇ 10>.
  • ⁇ 14> A portable device having the electrochemical element according to ⁇ 10>.
  • ⁇ 15> A power generation system having the electrochemical element according to ⁇ 10>.
  • the electrode active material layer or the undercoat layer having excellent storage stability can be formed on the current collector by applying the coating liquid of the present invention to the current collector and drying it.
  • an electrode having the electrode active material layer or the undercoat layer is used, an electrochemical element having excellent storage stability and low internal resistance or impedance can be obtained.
  • the coating liquid according to the present invention contains a polysaccharide, a polymer having a blocked isocyanate structure, a solvent, a conductivity imparting material and / or an electrode active material.
  • the polysaccharide used in the coating solution according to the present invention is a polymer compound in which a large number of monosaccharides (including monosaccharide substitutes and derivatives) are polymerized by glycosidic bonds.
  • the polymer compound generates a large number of monosaccharides by hydrolysis. Usually, 10 or more monosaccharides are polymerized.
  • the polysaccharide may have a substituent, for example, a polysaccharide in which an alcoholic hydroxyl group is substituted with an amino group (amino sugar), a one in which a carboxyl group or an alkyl group is substituted, or a deacetylated polysaccharide Etc. are included.
  • the polysaccharide may be either a homopolysaccharide or a heteropolysaccharide. Since the solubility in a polar solvent can be increased and the mobility of ions can be increased by crosslinking with a polymer having a blocked isocyanate structure, hydroxyalkyl polysaccharides or derivatives thereof, carboxyalkyl polysaccharides are preferred, and hydroxyalkyl polysaccharides are preferred. preferable. Hydroxyalkyl polysaccharides or derivatives thereof and carboxyalkyl polysaccharides can be produced by known methods.
  • polysaccharides include agarose, amylose, amylopectin, arabinan, arabinogalactan, alginic acid, inulin, carrageenan, galactan, glucan, xylan, xyloglucan, carboxyalkylchitin, chitin, glycogen, glucomannan, keratan sulfate, colomine Acid, chondroitin sulfate A, chondroitin sulfate B, chondroitin sulfate C, cellulose, dextran, starch, hyaluronic acid, fructan, pectic acid, pectin, heparic acid, heparin, hemicellulose, pentozan, ⁇ -1,4'-mannan, ⁇ -1,6'-mannan, lichenan, levan, lentinan, chitosan, pullulan, curdlan and the like.
  • agarose, amylose, amylopectin, arabinan, arabinogalactan, inulin, carrageenan, galactan, glucan, xylan, xyloglucan, chitin, glycogen, glucomannan, cellulose, dextran, starch, fructan, pectic substance, hemicellulose, pentozan , ⁇ -1,4′-mannan, ⁇ -1,6′-mannan, lichenan, levan, lentinan, chitosan, pullulan, and curdlan are layers a or layers described below obtained by using the coating solution of the present invention. Since b is difficult to become acidic, it is preferable.
  • Chitin, chitosan, hydroxyalkyl chitosan, carboxyalkyl chitosan, caprolactone-modified chitosan, hydroxyalkyl cellulose or carboxyalkyl cellulose are preferable because of high ion permeability.
  • at least one selected from the group consisting of chitosan, hydroxyalkyl chitosan, carboxyalkyl chitosan, caprolactone-modified chitosan, hydroxyalkyl cellulose and carboxyalkyl cellulose is most preferable.
  • These polysaccharides can be used individually by 1 type or in combination of 2 or more types.
  • hydroxyalkyl chitosan examples include hydroxyethyl chitosan, hydroxypropyl chitosan, glycerylated chitosan and the like.
  • hydroxyalkyl cellulose examples include hydroxyethyl cellulose and hydroxypropyl cellulose.
  • carboxyalkyl chitosan examples include carboxymethyl chitosan and carboxyethyl chitosan.
  • carboxyalkyl cellulose include carboxymethyl cellulose and carboxyethyl cellulose.
  • the polymer having a blocked isocyanate structure used in the coating liquid according to the present invention is not particularly limited.
  • the blocked isocyanate structure is obtained by reacting an isocyanate group with an active hydrogen compound to make it inactive at room temperature. When this blocked isocyanate structure is heated, the active hydrogen compound is separated and an isocyanate group is generated. The generated isocyanate group can react with the hydroxyl group of the aforementioned polysaccharide to form a crosslinked structure.
  • Examples of the polymer having a blocked isocyanate structure include a polymer containing a repeating unit derived from a monomer (A) having a blocked isocyanate structure and at least one polymerizable unsaturated group in the molecule, the monomer (A) For example, a polymer containing a repeating unit other than the repeating unit derived from. Among these, a polymer containing a repeating unit derived from the monomer (A) having a blocked isocyanate structure and at least one polymerizable unsaturated group in the molecule is preferable.
  • the urethane polymer containing a carbamoyl sulfonate group can be mentioned.
  • examples of commercially available products include Elastron MF-9 (Daiichi Kogyo Seiyaku Co., Ltd.).
  • a compound represented by the formula (1) or the formula (2) is preferable.
  • R 1 represents a hydrogen atom or a methyl group.
  • R 2 represents a hydrogen atom or a methyl group.
  • monomers (A) are commercially available.
  • 2- (O- [1′methylpropylideneamino] carboxyamino) ethyl methacrylate (“Karenz MOI-BM” (registered trademark); manufactured by Showa Denko KK ), 2-[(3,5-dimethylpyrazolyl) carboxyamino] ethyl methacrylate (“Karenz MOI-BP” (registered trademark); manufactured by Showa Denko KK) and the like.
  • the polymer having a blocked isocyanate structure used in the present invention may contain a repeating unit derived from another monomer (B) in addition to the repeating unit derived from the monomer (A).
  • the monomer (B) is not particularly limited as long as it has at least one polymerizable unsaturated group in the molecule.
  • ethylenically unsaturated aromatic compounds such as styrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene; acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid
  • Carboxyl group-containing compounds such as 2- (meth) acryloyloxyethyl succinic acid and 2- (meth) acryloyloxyethyl hexahydrophthalic acid; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (Meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, amyl (meth) acryl
  • Isocyanic acid (meth) acrylates such as 2- (meth) acryloyloxyethyl isocyanate, 1,3-bis (meth) acryloyloxy-2-methylpropane-2-isocyanate, 3- (meth) acryloyloxyphenyl isocyanate, methyl -Benzyl (meth) acrylate, hydroxy (meth) acrylates, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, cap Hydroxyl-containing (meth) acrylates such as lactone-modified alcohol mono (meth) acrylate, phenyl (meth) acrylate
  • Aromatic (meth) acrylates cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) ) (Meth) acrylates having an alicyclic skeleton such as acrylate, norbornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) Acrylate, caprolactone-modified one-terminal (meth) acrylate, and one end (meth) acrylate having a siloxane skeleton.
  • (meth) acrylate represents either a methacrylate or an acrylate.
  • (Meth) acryloyl represents either methacryloyl or acryloyl.
  • monomers (B) (meth) acrylates having an alicyclic skeleton are preferable, and dicyclopentanyl methacrylate is particularly preferable.
  • the repeating unit derived from the monomer (A) is preferably 5 to 100 mol%, more preferably 20 to 85 mol%, still more preferably 25 to
  • the repeating unit derived from the monomer (B) is preferably 0 to 95 mol%, more preferably 15 to 80 mol%, and still more preferably 20 to 75 mol%.
  • the monomer (B) acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthal
  • the repeating unit derived from the carboxyl group-containing compound is preferably 60 mol% or less in the polymer containing the repeating unit derived from the monomer (A). Preferably it is 50 mol% or less, Most preferably, it is 40 mol% or less.
  • the polymer having a blocked isocyanate structure suitably used in the present invention has a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC) of preferably 1000 to 10,000, more preferably 2000 to 8000.
  • the amount of the polymer having a blocked isocyanate structure in the coating solution is preferably 20 to 300 parts by mass with respect to 100 parts by mass of the polysaccharide.
  • Examples of the solvent used in the coating liquid according to the present invention include an aprotic polar solvent and a protic polar solvent.
  • Examples of the aprotic polar solvent include ethers, carbonates, amides and the like.
  • the aprotic polar solvent is preferably one that evaporates at a temperature not higher than the temperature at which the crosslinking reaction between the generated isocyanate group and the polysaccharide starts.
  • the boiling point at normal pressure is preferably 50 to 300 ° C., more preferably 100 to 220 ° C.
  • a solvent containing an aprotic polar solvent is preferable.
  • the protic polar solvent examples include alcohols and polyhydric alcohols.
  • the protic polar solvent preferably has a boiling point at normal pressure lower than the isocyanate generation temperature of the polymer having a blocked isocyanate structure. Specifically, the boiling point at normal pressure is preferably 100 ° C. or lower.
  • the boiling point of the protic polar solvent is higher than the isocyanate generation temperature of the polymer having a blocked isocyanate structure, the protic polar solvent may remain in the coating film. It becomes easy to react, and it may become difficult to fully produce bridge
  • Preferable protic polar solvents include ethanol, isopropyl alcohol, and n-propyl alcohol.
  • the amount of the protic polar solvent is not particularly limited, but is preferably 1 to 20% by mass with respect to the total amount of the solvent in the coating solution. If it is less, the effect of improving wettability will be reduced. If the amount is large, transpiration tends to be insufficient during drying, and crosslinking between the polysaccharide and the isocyanate group may be difficult to occur.
  • the amount of the solvent used in the coating liquid according to the present invention is not particularly limited as long as it can be adjusted to a viscosity suitable for the coating work.
  • the amount of the solvent used is such that the viscosity of the coating solution at the temperature at which the coating operation is performed is preferably 100 to 100,000 mPa ⁇ s, more preferably 1,000 to 50,000 mPa ⁇ s, and still more preferably 5, The amount is 000 to 20,000 mPa ⁇ s.
  • the amount of solvent used is preferably 50 to 99 parts by weight, more preferably 70 to 95 parts by weight, and still more preferably 80 to 95 parts in 100 parts by weight of the coating solution. Part by mass.
  • the conductivity imparting material used in the coating liquid according to the present invention is preferably a conductive carbon material containing carbon as a main component.
  • a conductive carbon material carbon black such as acetylene black and ketjen black; vapor grown carbon fiber; graphite and the like are suitable. These conductive carbon materials can be used singly or in combination of two or more.
  • the conductivity imparting material preferably has a powder electrical resistance of 1 ⁇ 10 ⁇ 1 ⁇ ⁇ cm or less in 100% green compact.
  • the conductivity-imparting material may be particles such as a spherical shape, or may have an anisotropic shape such as a fiber shape, a needle shape, or a rod shape.
  • the particulate conductivity imparting material is not particularly limited by the particle size, but preferably has a volume-based average particle size of 10 nm to 50 ⁇ m, more preferably 10 nm to 100 nm.
  • An anisotropic conductivity imparting material has a large surface area per weight and a large contact area with the current collector, electrode active material, etc., so even if it is added in a small amount, it is between the current collector and the electrode active material or the electrode active material. The conductivity between substances can be increased.
  • anisotropic conductive carbon material examples include carbon nanotubes and carbon nanofibers.
  • Carbon nanotubes and carbon nanofibers have a fiber diameter of usually 0.001 to 0.5 ⁇ m, preferably 0.003 to 0.2 ⁇ m, and a fiber length of usually 1 to 100 ⁇ m, preferably 1 to 30 ⁇ m. It is suitable for improvement.
  • the total amount of the polysaccharide and the polymer having a blocked isocyanate structure in the coating liquid for forming the layer a described later is preferably 20 to 300 parts by mass with respect to 100 parts by mass of the conductivity-imparting material.
  • the solid content of the coating solution for forming the layer a is preferably 1 to 50% by mass.
  • the electrode active material used in the coating liquid according to the present invention is not particularly limited as long as it is used in an electrochemical element such as a lithium ion battery or an electric double layer capacitor.
  • the electrode active material used for lithium ion batteries is different for positive and negative electrodes.
  • the positive electrode active material used for the lithium ion battery is not particularly limited as long as it is a substance capable of inserting and extracting lithium ions.
  • lithium cobalt oxide (LiCoO 2); lithium manganate (LiMn 2 O 4); lithium nickel oxide (LiNiO 2); Co, 3 ternary lithium compounds of Mn and Ni (Li (Co x Mn y Ni z ) O 2 ), sulfur-based compounds (TiS 2 ), olivine-based compounds (LiFePO 4 ) and the like can be mentioned as suitable ones.
  • the total amount of the polysaccharide and the polymer having a blocked isocyanate structure in the coating liquid for forming the positive electrode layer b of the lithium ion battery is preferably 0.1 to 100 parts by mass of the positive electrode active material. 30 parts by mass.
  • the negative electrode active material used for the lithium ion battery is not particularly limited. Specific examples include graphite carbon such as graphite, amorphous graphite carbon, and oxide.
  • the total amount of the polysaccharide and the polymer having a blocked isocyanate structure in the coating solution for forming the negative electrode layer b of the lithium ion battery is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of the negative electrode active material. 30 parts by mass.
  • the coating liquid for forming the layer b of the lithium ion battery electrode it is preferable to use the aforementioned conductivity imparting material and the electrode active material in combination in order to increase the conductivity of the layer b obtained.
  • the amount of the conductivity imparting material is preferably 1 to 15 parts by mass with respect to 100 parts by mass of the electrode active material.
  • the solid content of the coating liquid for forming the layer b is preferably 50 to 99% by mass.
  • the electrode active material used for the electric double layer capacitor can be the same for the positive electrode and the negative electrode.
  • the electrode active material used for the electric double layer capacitor is preferably activated carbon.
  • the activated carbon preferably has a large specific surface area from the viewpoint of increasing the electric capacity.
  • the activated carbon preferably has a BET specific surface area of 800 to 2500 m 2 / g.
  • the activated carbon preferably has an average particle size (D50) of 1 ⁇ m to 50 ⁇ m.
  • the average particle diameter (D50) of the activated carbon is a volume-based 50% cumulative particle diameter ( ⁇ m) measured with a Microtrac particle size distribution meter.
  • the activated carbon examples include coconut shell activated carbon and fibrous activated carbon.
  • the activated carbon is not particularly limited by its activation method, and those obtained by a steam activation method, a chemical activation method, or the like can be employed.
  • what performed the alkali activation process, ie, alkali activated carbon is suitable.
  • the alkali activated carbon is obtained, for example, by heat-treating coconut shell, coke, polymer carbide, non-graphitizable carbide or graphitizable carbide in the presence of an alkali metal compound.
  • Examples of graphitizable carbides include those obtained by heat-treating pitches such as petroleum pitch, coal pitch, and their organic solvent soluble components, and carbides of polyvinyl chloride compounds.
  • Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, and potassium carbonate.
  • the activated carbon preferably has a hardened bulk density (tap density) in the range of 0.3 g / cm 3 to 0.9 g / cm 3 . If the compacted bulk density is too small, the packing density is decreased, and the electric capacity per volume of the electric double layer capacitor and per cell tends to decrease. If the hardened bulk density is too large, the electric capacity per weight decreases, and the amount of electrolyte that can be retained tends to decrease, so the capacity retention rate may decrease.
  • the total amount of the polysaccharide and the polymer having a blocked isocyanate structure in the coating liquid for forming the layer b of the electrode for an electric double layer capacitor is preferably 0.1 to 20 with respect to 100 parts by mass of the electrode active material. Part by mass.
  • the coating liquid for forming the layer b of the electrode for an electric double layer capacitor it is preferable to use the aforementioned conductivity imparting material and the electrode active material in combination in order to increase the conductivity of the layer b obtained.
  • the amount of the conductivity imparting material is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the electrode active material.
  • the solid content of the coating liquid for forming the layer b is preferably 50 to 99% by mass.
  • additives may be added to the coating liquid of the present invention as necessary.
  • other crosslinking agents dispersants, wetting agents, thickeners, coupling agents, anti-settling agents, anti-skinning agents, polymerization inhibitors, antifoaming agents, electrostatic coating property improving agents, anti-sagging agents, colors
  • examples include a minute inhibitor, a leveling agent, an effect accelerator, and a repellency inhibitor.
  • the method for preparing the coating liquid according to the present invention is not particularly limited.
  • a method in which a polysaccharide and a polymer having a blocked isocyanate structure are dissolved in a solvent, and a conductivity imparting material and / or an electrode active material is added and dispersed in the solution can be mentioned as a preferable example.
  • a well-known kneader and a stirrer can be selected suitably, and it can be used for preparation of a coating liquid.
  • the electrode laminate according to the present invention includes a current collector and a layer a formed using a coating liquid containing a polysaccharide, a polymer having a blocked isocyanate structure, a solvent, and a conductivity-imparting material. is there.
  • the laminate for an electrode according to the present invention can be used in place of a conventionally known current collector in the production of an electrode.
  • An electrode according to the present invention includes a current collector, a layer a formed using a coating liquid containing a polysaccharide, a polymer having a blocked isocyanate structure, a solvent, and a conductivity-imparting material, and an electrode active material layer. And a current collector, and a layer b formed using a coating liquid containing a polysaccharide, a polymer having a blocked isocyanate structure, a solvent, and an electrode active material.
  • the layer a corresponds to an undercoat layer in the background art
  • the layer b corresponds to an electrode active material layer in the background art.
  • the layer a or the layer b can be formed by a method including applying the coating liquid according to the present invention to a current collector and drying it.
  • the coating method and the drying method of the coating liquid are not particularly limited, and there are known coating methods and drying methods used in the production of an undercoat layer or an electrode active material layer used for a lithium ion battery or an electric double layer capacitor. Can be used as is.
  • Examples of the coating method include a casting method, a bar coater method, a dip method, and a printing method. Among these, from the point that it is easy to control the thickness of the coating film, bar coater, gravure coat, gravure reverse coat, roll coat, Meyer bar coat, blade coat, knife coat, air knife coat, comma coat, slot diamond coat, A slide die coat and a dip coat are preferred. Further, in order to adjust the coating amount, the concentration of the coating solution can be adjusted with the above solvent.
  • the application may be performed on a part of the current collector, on the entire surface, or on one surface or both surfaces. In the case of applying to both sides, the application operation may be performed on each side, or the application operation may be performed on both sides simultaneously.
  • Drying can be performed under air, inert gas, or vacuum. Of these, it is preferable to perform in the atmosphere because of low cost.
  • the drying temperature varies depending on the coating speed, heating method, etc., but is preferably 100 to 400 ° C. If the drying temperature is too low, curing of the coating liquid tends to be insufficient, and if the drying temperature is too high, the current collector tends to be annealed.
  • the drying time is preferably 10 seconds to 10 minutes. If the drying time is too short, the coating solution is likely to be insufficiently cured. If the drying time is too long, productivity is lowered and cost is likely to increase.
  • the current collector is not particularly limited as long as it is used in a lithium ion battery, an electric double layer capacitor, or the like.
  • the current collector includes not only a non-perforated foil but also a punched metal foil or a perforated foil such as a net.
  • the current collector is not particularly limited as long as it is composed of a conductive material, and examples thereof include those made of a conductive metal and those made of a conductive resin. Particularly preferred are aluminum and copper.
  • As the aluminum foil pure aluminum-based A1085 material, A3003 material, or the like is usually used.
  • As the copper foil rolled copper foil or electrolytic copper foil is usually used.
  • the current collector may have a smooth surface, but a surface roughened by an electrical or chemical etching process, that is, an etching foil is also suitable.
  • the current collector is not particularly limited by the thickness, but it is usually preferable to have a thickness of 5 ⁇ m to 100 ⁇ m. If the thickness is 5 ⁇ m or less, the strength may be insufficient and the foil may be broken in the coating process. On the other hand, when the thickness exceeds 100 ⁇ m, the ratio of the current collector in the predetermined volume increases, which may lead to a decrease in capacity.
  • aluminum is often used for the positive electrode and copper is often used for the negative electrode. In an electric double layer capacitor, aluminum is often used for both the positive electrode and the negative electrode.
  • the aluminum current collector is preferably an aluminum foil, an aluminum etching foil or an aluminum punching foil.
  • the copper current collector is preferably a copper foil, a copper etching foil or a copper punching foil.
  • the layer a is formed using a coating liquid containing a polysaccharide, a polymer having a blocked isocyanate structure, a solvent, and a conductivity-imparting material.
  • the layer b is formed using a coating liquid containing a polysaccharide, a polymer having a blocked isocyanate structure, a solvent, and an electrode active material.
  • An electrode active material layer is usually formed on the layer a.
  • the electrode active material layer formed on the layer a is a layer b formed using a coating liquid containing a polysaccharide, a polymer having a blocked isocyanate structure, a solvent, and an electrode active material. It may be a well-known electrode active material layer other than this.
  • the thickness of the layer a is preferably 0.01 ⁇ m or more and 50 ⁇ m or less, more preferably 0.1 ⁇ m or more and 10 ⁇ m or less. If the thickness is too thin, desired effects such as a decrease in internal resistance or impedance tend not to be obtained. On the other hand, the resistance or impedance does not become smaller than a certain value even if the thickness is increased too much.
  • the thickness of the electrode active material layer or layer b in the electric double layer capacitor is preferably 10 ⁇ m or more and 500 ⁇ m or less.
  • the thickness of the electrode active material layer or layer b in the lithium ion battery is preferably 0.1 ⁇ m or more and 500 ⁇ m or less. When the thickness is 0.1 ⁇ m or less, the desired effect tends not to be obtained. When the thickness is 500 ⁇ m or more, it is easy for the current collector to fall off.
  • the layer a or the layer b formed with the coating liquid according to the present invention can be peeled off from the current collector and used as a film.
  • the membrane has high ion permeability or ion mobility.
  • the electrochemical device according to the present invention has the electrode according to the present invention described above, and further usually has a separator and an electrolytic solution.
  • the electrodes in the electrochemical device according to the present invention may both be the electrodes according to the present invention, or one of them may be the electrode according to the present invention and the other may be a known electrode.
  • a separator and electrolyte solution will not be restrict
  • the electrochemical element according to the present invention can be applied to a power supply system.
  • this power supply system includes automobiles; transport equipment such as railways, ships and airplanes; portable equipment such as mobile phones, personal digital assistants and portable electronic computers; office equipment; solar power generation systems, wind power generation systems, fuel cell systems, etc. It can be applied to the power generation system.
  • Production Example 1 Synthesis of polymer having blocked isocyanate structure (P-1) A four-necked flask equipped with a dropping funnel, a thermometer, a condenser tube and a stirrer was charged with 185.61 g of N-methylpyrrolidone. The flask was purged with nitrogen. It heated to 100 degreeC with the oil bath.
  • Production Example 2 Synthesis of polymer having blocked isocyanate structure (P-2) A four-necked flask equipped with a dropping funnel, a thermometer, a condenser tube and a stirrer was charged with 189.23 g of N-methylpyrrolidone. The flask was purged with nitrogen. It heated to 100 degreeC with the oil bath.
  • Production Example 3 Preparation of solutions 1 to 7 According to the formulation shown in Table 1, polysaccharides and polymers or cross-linking agents were added to a solvent and dissolved to obtain solutions 1 to 7.
  • Example 1> Manufacture of coating liquid for undercoat layer manufacturing 10 parts by mass of acetylene black (average particle diameter: 40 nm) as a conductivity imparting material and 90 parts by mass of the solution were stirred and mixed at a rotation speed of 60 rpm for 120 minutes with a planetary mixer. The mixed solution was diluted with N-methyl-2-pyrrolidone and isopropyl alcohol so that the thickness of the resulting undercoat layer was 5 ⁇ m to obtain a slurry-like coating solution for producing an undercoat layer.
  • N-methyl- 2-Pyrrolidone was added to produce a negative electrode paste. N-methyl-2-pyrrolidone was added so that the thickness of the obtained electrode active material layer was 250 ⁇ m.
  • the negative electrode paste was applied to an electrolytic copper foil having a thickness of 9 ⁇ m and dried to form an electrode active material layer having a thickness of 250 ⁇ m, thereby obtaining a negative electrode for a lithium ion secondary battery.
  • a lithium polyethylene separator was assembled by incorporating a porous polyethylene separator between the positive electrode and the negative electrode obtained above and impregnating the separator with an organic electrolyte.
  • the organic electrolyte is a mixed solution of ethylene carbonate and diethyl carbonate in a volume ratio of 1/1, the electrolyte is LiPF 6 , and the concentration is 1 mol / liter, trade name LIPASTER-EDMC / PF1 manufactured by Toyama Pharmaceutical Co., Ltd. used.
  • the initial capacity retention ratio and internal resistance of the lithium ion battery were measured. The results are shown in Table 2.
  • the initial capacity retention rate was determined by measuring the capacity after 100 cycles at a current rate of 20 C using a battery charging / discharging device HJ-2010 model manufactured by Hokuto Denko Co., Ltd. as the measuring instrument. The percentage relative to is expressed as a percentage.
  • the internal resistance was measured at a measurement frequency of 1 kHz by an AC impedance method using a HIOKI3551 battery tester.
  • the aluminum foil provided with the undercoat layer obtained above was stored for 100 hours in an environment of a temperature of 60 ° C. and a relative humidity of 90%. Using the aluminum foil stored in the environment, a lithium ion battery was manufactured in the same manner as described above. The internal resistance of this lithium ion battery was measured. The results are shown in Table 2.
  • the electrode paste is applied to the aluminum foil having the undercoat layer obtained above and dried to form an electrode active material layer having a thickness of 200 ⁇ m on the undercoat layer. Obtained.
  • two electric double layer capacitor electrodes were punched out with a diameter of 20 mm ⁇ in accordance with the size of the capacitor container for evaluation.
  • Two electrodes are stacked with a glass nonwoven fabric separator in between, placed in an evaluation capacitor container, poured into the container with an organic electrolyte, immersed in the electrode, and finally covered with a container, An electric double layer capacitor for evaluation was produced.
  • organic electrolytic solution trade name LIPASTE-P / EAFIN manufactured by Toyama Pharmaceutical Co., Ltd., having a solvent of propylene carbonate, an electrolyte of (C 2 H 5 ) 4 NBF 4 and a concentration of 1 mol / liter was used.
  • the impedance and electric capacity of the electric double layer capacitor were measured. The results are shown in Table 3.
  • the impedance was measured under the condition of 1 kHz using an impedance measuring instrument (PAN110-5AM) manufactured by KIKUSUI.
  • the electric capacity was measured using a charge / discharge test apparatus (HJ-101SM6) manufactured by Hokuto Denko Corporation at a current density of 1.59 mA / cm 2 at a voltage of 0 to 2.5 V, during the second constant current discharge.
  • the electric capacity (F / cell) per cell of the electric double layer capacitor was calculated from the measured discharge curve.
  • the capacity retention rate (%) was calculated by a formula of (electric capacity at the 50th cycle) / (electric capacity at the second cycle) ⁇ 100.
  • the aluminum foil provided with the undercoat layer obtained above was stored for 100 hours in an environment of a temperature of 60 ° C. and a relative humidity of 90%. Using the aluminum foil stored in the environment, an electric double layer capacitor was manufactured in the same manner as described above. The impedance of this electric double layer capacitor was measured. The results are shown in Table 3.
  • Examples 2 to 4 A coating liquid for producing an undercoat layer was prepared in the same manner as in Example 1 except that Solution 2, Solution 3 and Solution 4 were used in place of Solution 1, and an aluminum foil provided with an undercoat layer was prepared. Obtained. Then, the pH of the undercoat layer, the characteristics of the lithium ion battery, and the electric double layer capacitor were measured in the same manner as in Example 1. The results are shown in Table 2 and Table 3.
  • Example 1 A coating solution for producing an undercoat layer was produced in the same manner as in Example 1 except that the solution 5 was used instead of the solution 1, and an aluminum foil provided with the undercoat layer was obtained. Then, the pH of the undercoat layer, the characteristics of the lithium ion battery, and the electric double layer capacitor were measured in the same manner as in Example 1. The results are shown in Table 2 and Table 3.
  • Example 5 Manufacture of copper foil with an undercoat layer
  • a copper foil provided with an undercoat layer was obtained in the same manner as in Example 1 except that an electrolytic copper foil having a thickness of 9 ⁇ m was used instead of the aluminum foil.
  • N— Methyl-2-pyrrolidone was added to produce a positive electrode paste. N-methyl-2-pyrrolidone was added so that the thickness of the obtained electrode active material layer was 200 ⁇ m.
  • the positive electrode paste was applied to a 30 ⁇ m thick aluminum foil made of alkali-cleaned A1085 material and dried to form a positive electrode active material layer having a thickness of 200 ⁇ m to obtain a positive electrode for a lithium ion secondary battery.
  • a lithium polyethylene separator was assembled by incorporating a porous polyethylene separator between the positive electrode and the negative electrode obtained above and impregnating the separator with an organic electrolyte.
  • the organic electrolyte solution is a mixture of ethylene carbonate and diethyl carbonate having a volume ratio of 1/1, the electrolyte is LiPF 6 , and the concentration is 1 mol / liter, trade name LIPASTER-EDMC / PF1 manufactured by Toyama Pharmaceutical Co., Ltd. used.
  • Example 4 shows the measurement results.
  • the copper foil provided with the undercoat layer obtained above was stored for 100 hours in an environment of a temperature of 60 ° C. and a relative humidity of 90%.
  • a lithium ion battery was manufactured in the same manner as described above.
  • the internal resistance of this lithium ion battery was measured. Table 4 shows the measurement results.
  • Examples 6 to 8> A copper foil provided with an undercoat layer was obtained in the same manner as in Example 5 except that Solution 2, Solution 3, and Solution 4 were used instead of Solution 1, respectively. Then, the pH of the undercoat layer and the characteristics of the lithium ion battery were measured by the same method as in Example 5. The results are shown in Table 4.
  • Example 9> Manufacture of coating liquid for manufacturing electrode active material layer of electric double layer capacitor 85 parts by mass of activated carbon (alkaline activated charcoal having a specific surface area of 1500 m 2 / g) as an electrode active material, 5 parts by mass of acetylene black (average particle diameter 40 nm) as a conductivity imparting material, and 150 parts by mass of a solution, The mixture was stirred and mixed at a rotation speed of 60 rpm for 120 minutes with a planetary mixer. The mixed solution is diluted with N-methyl-2-pyrrolidone and isopropyl alcohol so that the resulting electrode active material layer has a thickness of 200 ⁇ m to obtain a slurry-like electrode active material layer production coating solution. It was.
  • activated carbon alkaline activated charcoal having a specific surface area of 1500 m 2 / g
  • acetylene black average particle diameter 40 nm
  • Example 5 In the same manner as in Example 1, the impedance and capacitance of the electric double layer capacitor obtained above were measured. The results are shown in Table 5.
  • the electrode obtained above was stored for 100 hours in an environment of a temperature of 60 ° C. and a relative humidity of 90%. Using the electrode stored in the environment, an electric double layer capacitor was manufactured in the same manner as described above. The impedance of this electric double layer capacitor was measured. The results are shown in Table 5.
  • Example 10 to 12 An electrode was obtained in the same manner as in Example 9, except that Solution 2, Solution 3, and Solution 4 were used instead of Solution 1, respectively.
  • the pH of the electrode active material layer and the characteristics of the electric double layer capacitor were measured. The results are shown in Table 5.
  • Example 13> Manufacture of coating solution for manufacturing positive electrode of lithium ion battery 95 parts by mass of lithium cobaltate as a positive electrode active material, 5 parts by mass of acetylene black (average particle diameter 40 nm) as a conductivity-imparting material, and 40 parts by mass of a solution 120 at a rotational speed of 60 rpm for 120 minutes using a planetary mixer Stir and mix.
  • the mixed solution is diluted with N-methyl-2-pyrrolidone and isopropyl alcohol so that the thickness of the obtained positive electrode active material layer becomes 200 ⁇ m, and a slurry-like coating solution for producing a lithium ion battery positive electrode is obtained.
  • a lithium polyethylene separator was assembled by incorporating a porous polyethylene separator between the positive electrode and the negative electrode obtained above and impregnating the separator with an organic electrolyte.
  • the initial capacity retention rate and internal resistance of the lithium ion battery were measured.
  • Table 6 shows the measurement results.
  • the positive electrode and the negative electrode obtained above were stored for 100 hours in an environment of a temperature of 60 ° C. and a relative humidity of 90%.
  • a lithium ion battery was manufactured in the same manner as described above. The internal resistance of this lithium ion battery was measured. Table 6 shows the measurement results.
  • Example 14 to 16> A positive electrode and a negative electrode were obtained in the same manner as in Example 13 except that Solution 2, Solution 3, and Solution 4 were used instead of Solution 1, respectively.
  • the pH of the positive electrode active material layer and the negative electrode active material layer and the characteristics of the lithium ion battery were measured. The results are shown in Table 6.
  • Example 10 A positive electrode and a negative electrode were obtained in the same manner as in Example 13 except that the solution 5 was used instead of the solution 1. In the same manner as in Example 13, the pH of the positive electrode active material layer and the negative electrode active material layer and the characteristics of the lithium ion battery were measured. The results are shown in Table 6.
  • an undercoat layer or an electrode produced in accordance with the present invention is a coating liquid containing a polysaccharide, a polymer having a blocked isocyanate structure, a solvent, a conductivity-imparting material and / or an electrode active material.
  • the active material layer is formed, the undercoat layer or the electrode active material layer has a pH of around 7, and the lithium ion battery and the electric double layer capacitor manufactured according to the present invention have the characteristics of the comparative examples. It turns out that it is favorable compared.

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

Abstract

L'invention porte sur un liquide de revêtement qui contient : un polysaccharide ; un polymère ayant une structure d'isocyanate séquencé tel qu'un polymère qui contient un motif répété issu d'un monomère qui a une structure d'isocyanate séquencé et au moins un groupe insaturé polymérisable ; un solvant ; et un agent conférant de la conductivité et/ou une matière active d'électrode. Une sous-couche ou une couche de matière active d'électrode est formée par l'application du liquide de revêtement sur un collecteur et par le séchage du liquide de revêtement appliqué sur celui-ci. Une batterie secondaire telle qu'une batterie au lithium-ion ou un condensateur à double couche électrique est fabriqué à l'aide d'une électrode qui comporte la sous-couche ou la couche de matière active d'électrode.
PCT/JP2010/007317 2009-12-18 2010-12-17 Liquide de revêtement Ceased WO2011074269A1 (fr)

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WO2013154165A1 (fr) * 2012-04-12 2013-10-17 三菱レイヨン株式会社 Résine liante d'électrode de batterie secondaire, composition d'électrode de batterie secondaire, électrode de batterie secondaire, et batterie secondaire
WO2015037558A1 (fr) * 2013-09-13 2015-03-19 日立マクセル株式会社 Matériau de revêtement de mélange d'électrode, électrode pour cellule secondaire à électrolyte non aqueux, procédé de production d'électrode pour cellule secondaire à électrolyte non aqueux, et cellule secondaire à électrolyte non aqueux
JP2016192409A (ja) * 2012-04-09 2016-11-10 昭和電工株式会社 電気化学素子用集電体の製造方法、電気化学素子用電極の製造方法、及び、電気化学素子用集電体を作製するための塗工液
US9659716B2 (en) 2011-07-29 2017-05-23 Uacj Corporation Collector and electrode structure, non-aqueous electrolyte cell, electrical double layer capacitor, lithium ion capacitor, or electrical storage device using same

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JP2002289174A (ja) * 2001-01-17 2002-10-04 Nisshinbo Ind Inc 電池用活物質混合粉体、電極組成物、二次電池用電極及び二次電池並びに電気二重層キャパシタ用炭素材料混合粉体、分極性電極組成物、分極性電極及び電気二重層キャパシタ
JP2007265890A (ja) * 2006-03-29 2007-10-11 Dainippon Printing Co Ltd 非水電解液二次電池用電極板及びその製造方法並びに非水電解液二次電池
WO2008015828A1 (fr) * 2006-08-04 2008-02-07 Kyoritsu Chemical & Co., Ltd. Liquide de revêtement pour la fabrication d'une plaque d'électrode, agent de sous-couche, et utilisation de ceux-ci

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JP2002289174A (ja) * 2001-01-17 2002-10-04 Nisshinbo Ind Inc 電池用活物質混合粉体、電極組成物、二次電池用電極及び二次電池並びに電気二重層キャパシタ用炭素材料混合粉体、分極性電極組成物、分極性電極及び電気二重層キャパシタ
JP2007265890A (ja) * 2006-03-29 2007-10-11 Dainippon Printing Co Ltd 非水電解液二次電池用電極板及びその製造方法並びに非水電解液二次電池
WO2008015828A1 (fr) * 2006-08-04 2008-02-07 Kyoritsu Chemical & Co., Ltd. Liquide de revêtement pour la fabrication d'une plaque d'électrode, agent de sous-couche, et utilisation de ceux-ci

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Publication number Priority date Publication date Assignee Title
US9659716B2 (en) 2011-07-29 2017-05-23 Uacj Corporation Collector and electrode structure, non-aqueous electrolyte cell, electrical double layer capacitor, lithium ion capacitor, or electrical storage device using same
JP2016192409A (ja) * 2012-04-09 2016-11-10 昭和電工株式会社 電気化学素子用集電体の製造方法、電気化学素子用電極の製造方法、及び、電気化学素子用集電体を作製するための塗工液
WO2013154165A1 (fr) * 2012-04-12 2013-10-17 三菱レイヨン株式会社 Résine liante d'électrode de batterie secondaire, composition d'électrode de batterie secondaire, électrode de batterie secondaire, et batterie secondaire
WO2015037558A1 (fr) * 2013-09-13 2015-03-19 日立マクセル株式会社 Matériau de revêtement de mélange d'électrode, électrode pour cellule secondaire à électrolyte non aqueux, procédé de production d'électrode pour cellule secondaire à électrolyte non aqueux, et cellule secondaire à électrolyte non aqueux
JPWO2015037558A1 (ja) * 2013-09-13 2017-03-02 日立マクセル株式会社 電極合剤塗料、非水電解質二次電池用電極、非水電解質二次電池用電極の製造方法、及び非水電解質二次電池

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