WO2005124801A1 - 電気二重層キャパシタ用電極材料およびその製造方法 - Google Patents
電気二重層キャパシタ用電極材料およびその製造方法 Download PDFInfo
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- WO2005124801A1 WO2005124801A1 PCT/JP2005/011274 JP2005011274W WO2005124801A1 WO 2005124801 A1 WO2005124801 A1 WO 2005124801A1 JP 2005011274 W JP2005011274 W JP 2005011274W WO 2005124801 A1 WO2005124801 A1 WO 2005124801A1
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- Prior art keywords
- electrode
- electric double
- double layer
- layer capacitor
- particles
- Prior art date
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Classifications
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- 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
- H01G11/42—Powders or particles, e.g. composition thereof
-
- 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
-
- 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
- Electrode material for electric double layer capacitor and method of manufacturing the same are Electrode material for electric double layer capacitor and method of manufacturing the same
- the present invention relates to an electrode material for an electric double layer capacitor and a method for producing the same, an electrode for an electric double layer capacitor obtained from the electrode material, and an electric double layer capacitor provided with the electrode.
- An electric double layer capacitor provided with an electrode obtained from the electrode material of the present invention has characteristics of high capacitance and low internal resistance.
- Electric double layer capacitors that are small, light in weight, have a high energy density and can be repeatedly charged and discharged are rapidly increasing in demand by virtue of their characteristics. Electric double-layer capacitors can be rapidly charged and discharged, and are therefore used as small memory backup power sources such as non-sound computers. In recent years, it is expected to be used as a large power source for electric vehicles due to environmental problems and resource problems.With the expansion and development of applications, low internal resistance, high capacitance, mechanical properties, etc. There is a need for further performance improvements.
- the electrode material for an electric double layer capacitor mainly contains an electrode active material such as activated carbon, and, if necessary, a conductive material and a binder for imparting functions such as conductivity, adhesion and flexibility to the electrode. Etc.
- components other than these electrode active materials may cause a decrease in electrode performance, such as increasing the resistance of the electrode or decreasing the capacitance of the capacitor.
- Patent Document 1 discloses that powder obtained by pulverizing activated carbon fibers is dispersed in water as an electrode active material, mixed with a latex of chlorosulfonated polyethylene as a thermoplastic binder, and then water is removed. There is disclosed a method in which a solid obtained by removal is pulverized and granulated to obtain an electrode material for an electric double layer capacitor, and the electrode material is pressure-formed to form an electrode for an electric double layer capacitor.
- Patent Document 2 discloses a method of dissolving and dispersing an activated carbon as an electrode active material and a thermosetting binder in a ketone such as acetone, and then performing spray-drying granulation to form a particulate electric double layer capacitor.
- a method for producing an electrode for an electric double layer capacitor has been proposed in which an electrode material for an electric double layer capacitor is manufactured after the granulated material is formed into an electrode layer shape, and a thermosetting binder is sintered at a high temperature of 900 ° C. ! Puru.
- the electrode for an electric double layer capacitor obtained by this method is hard, and depending on the application, the flexibility may be insufficient or the strength of the electrode may be insufficient.
- Patent Document 1 JP-A-62-179711
- Patent Document 2 JP-A-9-289142
- An object of the present invention is to provide an electric double layer capacitor having a small internal resistance S and a high capacitance, having flexibility, high strength, and a uniform electric double layer capacitor. It is an object of the present invention to provide an electrode for an electric double layer capacitor, and to provide an electrode material for an electric double layer capacitor suitable for producing such an electrode for an electric double layer capacitor and a method for producing the same.
- the present inventors have conducted intensive studies to achieve the above object, and as a result, using a thermoplastic binder as a binder, an electrode active material and a mixture containing such a thermoplastic binder. It has been found that an electrode material for an electric double layer capacitor, which is obtained as spherical particles, has excellent moldability. Further, they have found that when an electrode for an electric double layer capacitor is manufactured using the electrode material for an electric double layer capacitor, the electrode active material and the thermoplastic binder are uniformly dispersed in the electrode layer. Further, they have found that this electrode for an electric double layer capacitor has a uniform electrode density, excellent flexibility, high strength, and high internal resistance and high capacitance. The present inventors have completed the present invention based on these findings.o
- Electrode material for electric double layer capacitors containing spherical particles (A) having a sphericity of 20% or less Fees are provided.
- a step of mixing and dispersing the electrode active material and the thermoplastic binder in a solvent, and spray-drying the obtained dispersion to form the particles (A)
- a method for producing an electrode material for an electric double layer capacitor comprising the steps of:
- a method for manufacturing an electrode for an electric double layer capacitor comprising a step of forming an electrode layer made of the electrode material for an electric double layer capacitor on a current collector.
- an electrode for an electric double layer capacitor obtained by the above manufacturing method.
- an electric double layer capacitor having the electric double layer capacitor electrode.
- an electrode for an electric double layer capacitor in which an electrode active material and a thermoplastic binder are uniformly dispersed in an electrode layer can be manufactured. Further, the electrode for an electric double layer capacitor obtained from the electrode material of the present invention has a uniform electrode density, excellent flexibility, and high strength, and therefore has an internal resistance and a very high capacitance.
- the electrode material for an electric double layer capacitor of the present invention contains spherical particles (A) containing an electrode active material and a thermoplastic binder.
- the electrode active material used in the present invention is not limited as long as it can accumulate charges in the electric double layer formed at the interface between the electrode and the electrolytic solution, but the specific surface area is preferably 30 m 2 / g or more. ⁇ Is 500 to 5,000 m 2 Zg, more preferred ⁇ is 1,000 to 3, OOO mg of allotrope of carbon is preferably used.
- Specific examples of allotropes of carbon include activated carbon, polyacene, carbon whiskers, graphite, and the like. Among them, activated carbon is preferable. Activated carbons include phenolic resin, rayon, acrylic resin, pitch, and charcoal. Activated carbon such as cigarettes can be used.
- the allotrope of carbon is preferably in the form of powder or fiber. Furthermore, a nanocomposite of these allotropes of carbon and an organic material can also be used.
- Non-porous carbon having microcrystalline carbon similar to graphite and having an increased interlayer distance between the microcrystalline carbons can be used as the electrode active material.
- Such non-porous carbon is obtained by dry-distilling easily-graphitized carbonized coal having multi-layered graphite structure microcrystals at 700 to 850 ° C, and then heat-treating with caustic at 800 to 900 ° C. Further, it can be obtained by removing residual alkali components by heating steam as needed.
- the electrode active material is a powder, it is preferable that the weight average particle diameter is 0.1 to: LOO / zm, because the thin film of the electrode for an electric double layer capacitor can be easily formed and the capacitance can be increased.
- the weight average particle diameter of the electrode active material is more preferably 1 to 50 ⁇ m, and further preferably 5 to 20 ⁇ m.
- Electrode active materials are used alone or in combination of two or more.
- two or more types of electrode active materials having different particle size distributions may be used in combination.
- the thermoplastic binder used in the present invention is a thermoplastic polymer having a binding force and a material having a transition temperature.
- the transition temperature of a thermoplastic polymer is usually represented by a glass transition temperature (Tg), but a thermoplastic polymer having a high crystallinity may be represented by a melting point (Tm).
- Tg glass transition temperature
- Tm melting point
- the transition temperature of the thermoplastic binder used in the present invention is usually in the range of 80 ° C to 180 ° C.
- the transition temperature of the thermoplastic binder is preferably ⁇ 80 ° C. to 20 ° C., and more preferably ⁇ 60 ° C. to 0 ° C. When the transition temperature is in this range, The thermoplastic binder exhibits a higher binding force, and can form an electrode for an electric double layer capacitor at a relatively low temperature. The binder binds the electrode active material and, if necessary, the conductive material to the current collector. The use of a thermoplastic binder increases the strength and flexibility of the electric double layer capacitor electrode. Can be given.
- thermoplastic binder used in the present invention examples include a gen-based polymer and a (meth) acrylate polymer.
- the gen-based polymer is a homopolymer of conjugated gen, a copolymer obtained by polymerizing a monomer mixture containing conjugated gen, or a hydrogenated product thereof.
- the proportion of the conjugated gen in the monomer mixture is usually at least 40% by weight, preferably at least 50% by weight, more preferably at least 60% by weight.
- the gen-based polymer include conjugated gen homopolymers such as polybutadiene and polyisoprene; aromatic butyls which may be carboxy-modified such as styrene / butadiene copolymer (SBR); And cyanide butyl 'conjugated copolymer such as acrylo-tolyl.
- conjugated gen homopolymers such as polybutadiene and polyisoprene
- aromatic butyls which may be carboxy-modified such as styrene / butadiene copolymer (SBR); And cyanide butyl 'conjugated copolymer such as acrylo-tolyl.
- SBR styrene / butadiene copolymer
- NBR Butadiene copolymer
- the (meth) acrylate polymer is a homopolymer of an acrylate ester and Z or a methacrylate ester, or a copolymer obtained by polymerizing a monomer mixture containing these.
- the proportion of the acrylate and Z or methacrylate in the monomer mixture is usually at least 40% by weight, preferably at least 50% by weight, more preferably at least 60% by weight.
- Specific examples of the (meth) acrylate polymer include 2-ethylhexyl acrylate, methacrylic acid, acrylonitrile, ethylene glycol dimethacrylate copolymer, 2-ethylhexyl acrylate, and methacrylic acid. -Tolyl.
- the (meth) acrylate copolymer ethylene'methyl acrylate copolymer, ethylene'methyl methacrylate copolymer, ethylene'ethyl acrylate copolymer, and ethylene'ethyl methacrylate copolymer
- a copolymer of ethylene and a (meth) acrylate such as a polymer; a graft polymer obtained by grafting a radical polymerizable monomer to the above-mentioned copolymer of ethylene and a (meth) acrylate; Plastic elastomers can also be used.
- the radical polymerizable monomer used in the graft polymer include methyl methacrylate, acrylonitrile, methacrylic acid, and the like.
- thermoplastic binder ethylene 'acrylic acid copolymer; ethylene' methacrylic acid copolymer; Fluorinated resins such as bi-lidene fluoride (hereinafter sometimes referred to as PVDF); can also be used as the thermoplastic binder.
- PVDF bi-lidene fluoride
- gen-based polymers and crosslinked (meth) acrylate polymers are preferred, and crosslinked (meth) acrylate polymers are particularly preferred.
- thermoplastic binder an electrode layer having excellent binding properties to the current collector and excellent surface smoothness can be obtained, and an electric double layer capacitor having a high capacitance and a low internal resistance can be obtained. Electrodes can be manufactured.
- the binder has good binding properties and minimizes the decrease in the capacitance of the produced electrode and the deterioration during use. It is preferable that the particles are in a particulate form.
- the particulate thermoplastic binder include, for example, latex produced by a known method such as emulsion polymerization, in which particles of the thermoplastic binder are dispersed in water or an organic solvent, and such a thermoplastic binder. Powders obtained by drying the dispersion are mentioned.
- the average particle size of the particulate thermoplastic binder used in the present invention is not particularly limited, and the power is usually 0.0001 to 100 / ⁇ , preferably 0.001 to 10 ⁇ m, more preferably Is 0.01-1 ⁇ m.
- the average particle diameter of the particulate thermoplastic binder is within this range, a high binder can be provided to the electrode layer.
- the average particle diameter is a number average particle diameter calculated by measuring the diameter of 100 polymer particles randomly selected in a transmission electron micrograph and calculating the arithmetic average value.
- the shape of the particles may be a true sphere or an irregular shape.
- the thermoplastic binder used in the present invention may have a core-shell structure obtained by stepwise polymerizing a mixture of two or more monomers.
- the thermoplastic binder having a core-shell structure is obtained by first polymerizing a monomer that gives a first-stage polymer, and using this polymer as seed particles in the same vessel or in a predetermined amount in another polymer. After the addition to the container, it is preferable to produce it by a method of polymerizing a monomer that gives the second-stage polymer.
- the ratio of the core to the shell of the thermoplastic binder having the core-shell structure is not particularly limited, but the core part: shell part is usually 20:80 to 99: 1, preferably 30:70 to 100 by mass ratio. 9 7: 3, preferably 40:60 to 95: 5.
- the polymer constituting the core portion and the shell portion any of the above thermoplastic polymers can be used. Its glass transition temperature is 2 points When observed, the Tg on the low temperature side is preferably in the above range, and the Tg force on the low temperature side is less than SO ° C, and the Tg on the high temperature side is more preferably o ° c or more.
- the difference in glass transition temperature between the core and the shell is usually 20 ° C. or higher, preferably 50 ° C. or higher.
- thermoplastic binders can be used alone or in combination of two or more.
- the amount used is usually in the range of 0.001 to 50 parts by weight, preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the electrode active material. If the amount of the thermoplastic binder used is too small, it becomes difficult to form the electrode material for an electric double layer capacitor into a sheet. Conversely, if the amount of the binder is too large, the internal resistance of the obtained electrode for an electric double layer capacitor may increase.
- the particles (A) may contain a conductive material, a dispersant described below, and other additives as necessary.
- the conductive material that can be used in the present invention can impart conductivity to the electrode composition for an electric double layer capacitor. It is preferable that the particles (A) include a conductive material, since the conductive material can be uniformly dispersed during electrode formation.
- the conductive material includes a carbon-based material and a metal-based material, and a carbon-based conductive material is preferably used.
- the carbon-based conductive material is a carbon allotrope that has conductivity and does not have pores that can form an electric double layer.
- carbon blacks such as furnace black, acetylene black, and Ketjen black (registered trademark of Axon Nobel Chemicals Vesroten Fennoutshap); carbon fibers such as vapor-grown carbon fibers; natural graphite; ; And the like.
- the metal-based conductive material is a metal compound having conductivity, for example, particles of titanium oxide, ruthenium oxide, aluminum, nickel, and the like; metal fibers, and the like. Of these, acetylene black and furnace black are more preferred, where carbon black is preferred.
- the weight average particle diameter of the conductive material used in the present invention is usually in the range of 0.1 to 100 / ⁇ .
- These conductive materials can be used alone or in combination of two or more.
- the amount used is generally in the range of 0 to 50 parts by weight, preferably 0.5 to 15 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the electrode active material. When the amount of conductive material used is within this range, the resulting electrode must have a high balance between capacitance and internal resistance. Can do.
- the particles (A) may contain other additives such as a surfactant!
- a surfactant examples include nonionic surfactants, and among them, nonionic surfactants which are easily thermally decomposed are preferable among them, including a-one, cation, non-one, and nonionic-one.
- These additives can be used alone or in combination of two or more.
- the amount of each additive is not particularly limited, but is 0 to 50 parts by weight, preferably 0.1 to: LO parts by weight, more preferably 0.5 to 100 parts by weight based on 100 parts by weight of the electrode active material. It is in the range of 5 parts by weight.
- the short axis diameter 1 and the long axis diameter 1 Preferably 10% or less.
- the short axis diameter 1 and the long axis diameter 1 Preferably 10% or less.
- the particle diameter of the particles (A) is usually from 0.1 to 1,000 ⁇ m, preferably from 5 to 500 ⁇ m, more preferably from 10 to 100 m, as measured by the weight classification method. .
- the angle of repose of the particles (A) is 50 ° or less, preferably 40 ° or less, and more preferably 30 ° or less.
- the electrode material for an electric double layer capacitor of the present invention may contain non-spherical particles other than the particles (A) as long as the effect of the present invention is not impaired, but the average value of the sphericity of the electrode material is used. Is preferably 20% or less, more preferably 10% or less.
- the proportion of the particles (A) in the electrode material is usually at least 50% by weight, preferably at least 70% by weight, more preferably at least 90% by weight.
- the particles (A) are obtained by mixing an electrode active material, a thermoplastic binder, and other components as necessary, and molding the mixture into a spherical shape.
- the method for producing particles (A) depends on the method used to obtain spherical particles. The method is not particularly limited as long as it is a method.Examples include spray drying granulation, rolling bed granulation, compression granulation, stirring granulation, extrusion granulation, and melt granulation. No. Among them, spray drying granulation, rolling bed granulation and agitation type granulation can be used to achieve high uniformity.
- V ⁇ is preferable because spherical particles can be obtained, and spray drying granulation is particularly preferable.
- the spray-drying granulation method comprises a step of mixing an electrode active material, a thermoplastic binder, and other components as necessary in a solvent to form a dispersion, and spraying the dispersion. Drying to form the particles (A). Specifically, in the step of forming the particles (A), the above dispersion is sprayed with an atomizer using a spray drier, and the sprayed dispersion is dried inside a drying tower, so that the dispersion is dispersed in the dispersion. A spherical particle (A) composed of an electrode active material, a binder and other components contained in (A) is formed.
- the solvent that can be used for preparing the dispersion is appropriately selected according to the type of the thermoplastic binder.
- an organic solvent that uses water can be used.
- the organic solvent include alkyl 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; and getyl formamide; Amides such as dimethylacetamide, N-methyl 2-pyrrolidone (hereinafter referred to as NMP), dimethylimidazolidinone, etc .; and azo-based solvents such as dimethylsulfoxide and sulfolane; .
- alkyl alcohols are preferred.
- the drying speed can be increased during fluidized granulation.
- the dispersibility of the thermoplastic binder or the solubility of the dispersant changes, the viscosity and fluidity of the slurry can be adjusted depending on the amount or type of the solvent, and handling suitability and production efficiency can be improved.
- These solvents can be used alone or in combination of two or more.
- the amount used is adjusted so that the solid content concentration is usually in the range of 1 to 50% by weight, preferably 5 to 40% by weight, and more preferably 10 to 30% by weight. When the solid content is in this range, the dispersibility of the thermoplastic binder is highly enhanced, which is preferable.
- a dispersant may be used together with these solvents.
- the dispersant that can be used in the present invention has an effect of improving the uniform dispersibility of the electrode active material, the thermoplastic binder, and the like. Dispersant May or may not be present. Further, as long as it is soluble in the solvent to be used, the above-mentioned binder may be used as a dispersant.
- water-soluble dispersant used when the solvent is water examples include cellulosic polymers such as carboxymethylcellulose, methylcellulose and hydroxypropylcellulose, and their ammonium salts and alkali metal salts; acrylic acid, methacrylic acid, Homopolymers of unsaturated carboxylic acids such as fumaric acid, maleic acid and maleic anhydride, or copolymers containing unsaturated carboxylic acid units and vinyl alcohol units, or salts thereof; polybutyl alcohol and modified polybutyl alcohol; Examples include oxide, polyvinylpyrrolidone, polyethylene glycol, oxidized starch, starch phosphate, casein, various modified starches, chitin, and chitosan derivatives.
- cellulosic polymers such as carboxymethylcellulose, methylcellulose and hydroxypropylcellulose, and their ammonium salts and alkali metal salts
- acrylic acid, methacrylic acid Homopolymers of unsaturated carboxylic acids such as fuma
- fluorinated polymers such as PVDF
- diene polymers such as acrylonitrile'butadiene copolymer and its hydride.
- solvents are appropriately selected according to the type of the solvent, but are preferably water-soluble dispersants, and more preferably cellulosic polymers and their ammonium salts and alkali metal salts.
- the amount of the dispersant is not particularly limited, but is 0 to 50 parts by weight, preferably 0.1 to: LO parts by weight, and more preferably 0.5 to 5 parts by weight based on 100 parts by weight of the electrode active material. Range.
- the mixing method for preparing the dispersion is not particularly limited, and examples thereof include mixing using a ball mill, a sand mill, a pigment disperser, a crusher, an ultrasonic disperser, a homogenizer, a planetary mixer, or the like. Equipment can be used.
- the mixing conditions are appropriately selected depending on the type of the mixture, but the mixing temperature is usually from room temperature to 80 ° C, and the mixing time is from 10 minutes to several hours.
- the method of spraying the obtained dispersion is not particularly limited, and for example, a commonly used spray dryer (also referred to as a spray dryer) can be used.
- the spray dryer also has a pulverizing section, a drying section, and a powder collecting section.
- the fine powder shaving unit is provided with a device (atomizer) for finely shaping the dispersion liquid into fine droplets and spraying the dispersion inside the drying unit.
- atomizer atomizer
- the type of the dither is roughly classified into a rotating disk type and a spraying type, and a force rotating disk type that can use both types is preferable.
- the undiluted solution is introduced almost at the center of the high-speed rotating disk, and when the undiluted solution leaves the disk, the dispersion becomes small droplets.
- the rotation speed of the disk depends on the size of the disk, and is usually 5,000-30, OOOrpm, preferably 15,000-30, OOOrpm.
- the spray method the dispersion is sprayed into small droplets with a small nozzle force by pressurization.
- the temperature of the dispersion to be sprayed is usually about 20 to 250 ° C.
- hot air circulates inside, and the hot air evaporates and removes the solvent in the droplets of the dispersion micronized by the atomizer, and the solid content contained in the dispersion is dried to form spherical particles. Become a child.
- the temperature of the hot air is usually 80 to 300 ° C, preferably 100 to 200 ° C.
- the obtained spherical particles are collected in the powder collecting section.
- the particles (A) obtained by this method are particles having a substantially uniform spherical shape and particle diameter, which balance the electrode active material and the thermoplastic binder.
- the dispersion liquid is aggregated by drying, and the force density of the electrode material is improved.
- the rolling bed granulation method and the stirring granulation method are methods in which a binder is sprayed on a forcibly fluidized electrode active material to perform granulation.
- the method of flowing the electrode active material is different in each method.
- the electrode active material and other components are rolled inside a rotating container such as a rotating drum or a rotating dish. Let it.
- the stirring type granulation method a raw material powder is forcibly given a fluid motion by a stirring blade or the like provided in a container.
- the components can be flowed together with the electrode active material or can be added to the electrode active material together with the binder. May be sprayed.
- other components such as a conductive material are attached to the surface of the electrode active material in advance because materials having different specific gravities can be uniformly dispersed.
- a mechanochemical treatment of mixing the electrode active material and a conductive agent while applying a mechanical external force such as a compressive force or a shear force is used.
- Apparatuses for performing mechanochemical treatment include kneading machines such as pressurized-single-roll and two-roll mills; and high-speed impact-type dry powders such as a rotary ball mill and a no-bridization system (Nara Machinery Co., Ltd.). Compression-shear type such as body complexing device; Mechanofusion system (manufactured by Hosokawa Micron Corp.) Dry powder compounding device; and the like can be used.
- a thermoplastic binder, a conductive material, and a dispersant are uniformly mixed in a solvent, and the obtained dispersion is mixed with the fluid of the electrode active material.
- the layer can be sprayed and granulated.
- the dispersibility of the electrode active material and the thermoplastic binder is improved.
- the amount of the thermoplastic binder contained in the electrode for an electric double layer capacitor can be reduced, so that an electrode for an electric double layer capacitor having a low internal resistance and a high capacitance can be manufactured.
- the method for producing an electrode for an electric double layer capacitor of the present invention includes a step of forming an electrode layer made of the electrode material for an electric double layer capacitor of the present invention on a current collector.
- the current collector used in the present invention for example, metal, carbon, a conductive polymer, or the like can be used, and a metal is preferably used.
- a metal is preferably used.
- the metal for the current collector aluminum, platinum, nickel, tantalum, titanium, stainless steel, other alloys, and the like are usually used. Among them, it is preferable to use aluminum or an aluminum alloy which is conductive and has high withstand voltage. When high voltage resistance is required, high-purity aluminum disclosed in Japanese Patent Application Laid-Open No. 2001-176757 can be suitably used.
- the current collector is in the form of a film or a sheet.
- the thickness is a force appropriately selected according to the purpose of use, usually 1 to 200 ⁇ m, preferably 5 to: LOO ⁇ m, more preferably 10 to 50 ⁇ m.
- the electrode layer may be formed by forming an electrode material for an electric double layer capacitor into a sheet and then laminating the sheet on a current collector, but the electrode layer may be formed directly on the current collector. It may be formed.
- the electrode layer is directly formed on the current collector, it is preferable to supply the electrode material onto the current collector and then level the thickness of the electrode material with a blade or the like because the electrode density can be easily made uniform during molding.
- the method of forming the electrode layer of the electrode material for an electric double layer capacitor of the present invention is not particularly limited, for example, a dry molding method such as a pressure molding method, and a wet molding method such as a coating method.
- a dry molding method such as a pressure molding method
- a wet molding method such as a coating method.
- the dry molding method is preferable because the drying step is unnecessary and the production cost is low.
- the dry molding method is not particularly limited.Specific examples include filling the electrode material for an electric double layer capacitor in a mold, applying pressure, and rearranging and deforming the electrode material to densify the electrode layer.
- the pressure molding method is preferable because it can be performed with simple equipment.
- the particles (A) can be sprayed on a current collector using a screw feeder, and pressure molding can be performed using a pressure device.
- the electrode material quantitatively using a feeder onto the protective film or the current collector, and to continuously form the electrode layer by pressing with a roller or the like.
- the electrode layer can be formed by supplying the particles (A) to a roll-type pressure forming apparatus having two parallel rolls by a supply device such as a screw feeder.
- a small amount of a molding aid such as water or alcohol may be added.
- the temperature during molding is usually in the range of 0 ° C to 200 ° C, which is 20 ° C or more higher than the transition temperature of the thermoplastic binder!
- an additional post-pressing may be performed as necessary.
- the method of post-pressing is generally a pressing step using a roll.
- two cylindrical rolls are arranged up and down in parallel at a narrow interval, and each is rotated in the opposite direction.
- the temperature of the roll may be adjusted by heating or cooling.
- the electric double layer capacitor of the present invention has an electric double layer capacitor electrode obtained by the above-described manufacturing method.
- the electric double layer capacitor can be manufactured according to a conventional method using the above-described electrodes, components such as an electrolytic solution and a separator.
- components such as an electrolytic solution and a separator.
- the electrode for an electric double layer capacitor is cut into an appropriate size, then the electrodes are overlapped with one another through a separator, and this is wound into a capacitor shape and placed in a container. It can be manufactured by injecting an electrolytic solution into a container and sealing the container.
- the electrolytic solution is not particularly limited, but a non-aqueous electrolytic solution in which an electrolyte is dissolved in an organic solvent is preferable.
- the electrolyte any of conventionally known electrolytes can be used, such as tetraethylammonium tetrafluoroborate, triethylmonomethylammonium-tetrafluoroborate, and tetraethylammonium-dimethylhexafluorophosphate. Fate and the like.
- the solvent for dissolving these electrolytes is not particularly limited as long as it is generally used as an electrolyte solvent.
- Specific examples include carbonates such as propylene carbonate, ethylene carbonate and butylene carbonate; ratatanes such as y butyrolataton; sulfolanes; and -tolyls such as acetonitrile. These can be used alone or as a mixture of two or more solvents. Among them, carbonates are preferable.
- the concentration of the electrolytic solution is generally 0.5 mol ZL or more, preferably 0.8 mol ZL or more.
- separator for example, a microporous membrane or nonwoven fabric made of polyolefin such as polyethylene or polypropylene, a porous membrane mainly made of pulp generally called electrolytic capacitor paper, or the like can be used. Further, a solid electrolyte or a gel electrolyte may be used instead of the separator.
- acetylene black denka black powder; manufactured by Denki Kagaku Kogyo Co., Ltd.
- an aqueous solution containing 5% carboxymethylcellulose as a dispersant (Cellogen 7A; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 200 parts and 50 parts of water were mixed and dispersed using a planetary mixer to obtain a conductive material dispersion having a solid concentration of 20%.
- slurry composition (I) 30 parts of the conductive material dispersion liquid, 8 parts of an aqueous solution containing 5% carboxymethylcellulose (cellogen 7A), 100 parts of high-purity activated carbon powder having a specific surface area of 2, OOO mg and an average particle diameter of 5 / zm as an electrode active material, Thermoplastic Dispersion of carboxy-modified styrene'butadiene copolymer (average particle size 0.12 m, glass transition temperature 5 ° C) dispersed in water as a binder (BM400B; manufactured by Nippon Zeon, 40% concentration) 7.5 Parts and water were mixed together and mixed with a planetary mixer to obtain a slurry composition (I).
- BM400B manufactured by Nippon Zeon, 40% concentration
- composition (I) is further diluted with water so that the solid content concentration becomes 21%, and a spray disk dryer (OC-16; manufactured by Okawara Kakoki Co., Ltd.) is used. Spray drying and granulation were performed at a rotational speed of 20, OOOrpm with a diameter of 65 mm, hot air temperature of 150 ° C, and a particle recovery outlet temperature of 90 ° C to obtain particles (A-1).
- a spray disk dryer OC-16; manufactured by Okawara Kakoki Co., Ltd.
- the weight average particle size was 70 ⁇ m.
- short axis diameter 1 and long axis diameter s were determined for 20 randomly selected particles in electron micrographs.
- the sphericity expressed as 1 as 1 Isa was 5% or less for all the particles, and the particles were spherical.
- the particles (A-1) were filled in a funnel used for measuring bulk specific gravity according to JIS K6720-2, and the damper was immediately pulled out. 1) The funnel mouth fell smoothly.
- Table 1 shows the results of measuring the angle of repose of the particles (A-1) with a repose angle measuring device (Powder Tester PT-R) and evaluating the fluidity by a four-step method based on the following criteria.
- the obtained particles (A-1) were sprayed on a 40 ⁇ m-thick aluminum current collector with a screw feeder, and the thickness of the particles on the current collector was made uniform using a blade.
- An electrode for electric double layer capacitor with an electrode layer thickness of 200 m was obtained by pressure molding at room temperature (25 ° C) using a pressure device. Using the obtained electrode for an electric double layer capacitor, electrode flexibility, electrode strength, electrode density, and uniformity of the electrode density were measured by the following methods. The results are shown in Table 1.
- the obtained electrode for an electric double layer capacitor was cut into two rectangular pieces each having a length of 100 mm and a width of 50 mm to obtain test pieces, which were measured according to the method described in JIS K5600-5-1.
- the test device used was a type 1 device, and the diameter of the cylindrical mandrel at the bent part was 25 mm and 32 mm.
- Electrode strength Cut the electrode obtained by the above method into a rectangle of 2.5 cm width x 10 cm length, and fix it with the electrode layer surface up. A cellophane tape was adhered to the surface of the electrode layer, and the stress (NZcm) when the tape was peeled in the 180 ° direction at a speed of 50 mmZ was measured 10 times, and the average value was obtained. The evaluation was based on the four-step method based on the criteria of
- the cut-out electrode was further divided into a uniform size of 10 mm ⁇ 10 mm, and the weight of each was measured to calculate the electrode density excluding the current collector portion.
- the maximum value of the difference between the obtained electrode density after division and the electrode density before division was defined as the electrode density variation, and the uniformity of the electrode density was evaluated by a four-step method based on the following criteria.
- Two electrodes having a size of 4 cm ⁇ 6 cm were cut out while leaving the lead terminals, the two electrodes were opposed to each other, and a polyethylene separator having a thickness of 25 ⁇ m was sandwiched. This was sandwiched between two polypropylene plates having a thickness of 2 mm, a width of 5 cm, and a height of 7 cm. The thickness between the two propylene plates is 0 It was 68 mm. This was impregnated under reduced pressure with an electrolytic solution in which propylene carbonate was dissolved at a concentration of 1.5 mol ZL of triethylene monomethylammonium ammonium tetrafluoroborate and stored in a polypropylene container to prepare an electric double layer capacitor.
- the electric double layer capacitor was charged from OV to 2.7 V at a constant current of 10 mA at 25 ° C. for 10 minutes, and thereafter, constant at 1 mA until OV. Discharge was performed with current.
- the capacitance was obtained from the obtained charge / discharge curve, and the capacitance per unit mass of the electrode layer was obtained by dividing the mass of the current collector by the mass of the electrode layer obtained by subtracting the mass of the current collector from the mass of the electrode.
- the internal resistance was calculated from the charge / discharge curve in accordance with the calculation method of the standard RC-2377 specified by the Japan Electronics and Information Technology Industries Association. The internal resistance and capacitance were evaluated by a four-step method based on the following criteria.
- Electrode materials for electric double layer capacitors are Electrode materials for electric double layer capacitors
- Particles (A-2) were obtained in the same manner as in Example 1.
- Example 2 When the shape of the obtained particles (A-2) was measured in the same manner as in Example 1, the average particle size was m Met. The sphericity was 5% or less for all the particles, and the particles were spherical. In addition, when the fluidity of the particles (A-2) was confirmed using the funnel used in Example 1, the particles (A-2) also fell smoothly on the funnel rocker. Table 1 shows the results of measuring the angle of repose in the same manner as in Example 1.
- An electrode for an electric double layer capacitor was prepared at room temperature in the same manner as in Example 1 except that the particles (A-2) were used instead of the particles (A-1).
- the electrode strength, electrode density, and electrode density uniformity were measured. The results are shown in Table 1.
- Example 1 an electric double layer capacitor was prepared in the same manner as in Example 1, and the characteristics of the obtained electric double layer capacitor for the same items as in Example 1 were measured. Table 1 shows the results.
- Electrode materials for electric double layer capacitors are Electrode materials for electric double layer capacitors
- the slurry-like composition (I) obtained in Example 1 was poured into a vat and dried to obtain an agglomerated mixture, which was pulverized to obtain particles (B-1). Since the size of the obtained particles (B-1) was dissimilar, after passing through a 40-mesh sieve, the particles (B-1) ′ remaining in the 80-mesh sieve were used to obtain Example 1. When the sphericity was evaluated in the same manner as in the above, the sphericity exceeded 40% for all the particles, and the particles were amorphous. When the fluidity of the particles (B-1) ′ was confirmed using the funnel used in Example 1, the particles did not fall smoothly from the funnel opening. Table 1 shows the results of measuring the angle of repose and determining the fluidity in the same manner as in Example 1.
- the particles (B-1) ' were sprayed on the current collector using a screw feeder, and the thickness of the particles was made uniform using a blade. As a result, traces were formed on the surface.
- the electrode flexibility, the electrode strength, the electrode density, and the uniformity of the electrode density were determined in the same manner as in Example 1 by using a portion of the obtained electric double layer capacitor electrode with no trace. The results are shown in Table 1. [0078] Electric Double Layer Capacitor
- An electric double layer capacitor was prepared in the same manner as in Example 1 by using a portion of the obtained electric double layer capacitor electrode without traces. The characteristics of the electric double layer capacitor obtained for the same items as in Example 1 were determined. The results are shown in Table 1.
- Electrode materials for electric double layer capacitors are Electrode materials for electric double layer capacitors
- a slurry was prepared by mixing 70 parts of high-purity activated carbon powder with a specific surface area of 2000 m 2 Zg and an average particle size of 5 m as the electrode active material, 30 parts of phenol resin as a thermosetting binder, and 200 parts of acetone with a planetary mixer.
- a composition ( ⁇ ) was obtained.
- spray granulation was performed under the same conditions as in Example 1 to obtain particles (B-2).
- the average particle size was 70 m.
- the sphericity of all particles was 5% or less, and the particles were spherical.
- Table 1 shows the results of measuring the angle of repose and determining the fluidity in the same manner as in Example 1.
- the obtained particles were subjected to pressure molding, and the obtained molded body was subjected to a heat treatment in an electric furnace at 900 ° C. for 2 hours in a nitrogen gas atmosphere to obtain an electrode layer.
- a conductive adhesive is applied on the current collector to a thickness of 5 m after drying, dried, and the electrode layer obtained above is laminated.
- An electrode for an electric double layer capacitor with a thickness of 200 m was obtained.
- the conductive adhesive is 100 parts by weight of acetylene black, 20 parts by weight of a 10% carboxymethyl cellulose aqueous solution (Cellogen 7H; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and a latex of carboxy-modified styrene Z-butadiene copolymer (BM-400B; Japan 31.3 parts by weight and 10.2 parts by weight of soft water were kneaded with a kneader and further diluted with soft water to produce.
- the obtained conductive adhesive had an average particle size of acetylene black of 0.5 m measured by a light scattering method and a solid content of 30%.
- the electrode flexibility, electrode strength, electrode density, and uniformity of the electrode density were determined in the same manner as in Example 1. Table 1 shows the results. [0081] Electric double layer capacitor
- Example 1 Using the obtained electrode for an electric double layer capacitor, an electric double layer capacitor was prepared in the same manner as in Example 1. The characteristics of the electric double layer capacitors obtained for the same items as in Example 1 were determined. The results are shown in Table 1.
- Electrode materials for electric double layer capacitors are Electrode materials for electric double layer capacitors
- Particles (B-3) having an average particle diameter of 48 m were obtained.
- the same kind of acetylene black, a 5% aqueous solution of carboxymethylcellulose, a 40% aqueous dispersion of an acrylate polymer and activated carbon powder were used as in Example 2.
- the shape of the particles (B-3) was measured in the same manner as in Example 1, the sphericity of all the particles exceeded 40%, and the particles were irregular.
- Table 1 shows the results of measuring the angle of repose and determining the fluidity in the same manner as in Example 1.
- An electrode for an electric double layer capacitor was prepared at room temperature in the same manner as in Example 1 except that the particles (B-3) were used instead of the particles (A-1).
- the electrode strength, electrode density, and uniformity of the electrode density were measured. The results are shown in Table 1.
- Example 1 Using the obtained electrode for an electric double layer capacitor, an electric double layer capacitor was prepared in the same manner as in Example 1. The characteristics of the electric double layer capacitors obtained for the same items as in Example 1 were determined. The results are shown in Table 1.
- a long aluminum current collector with a thickness of 40 ⁇ m is placed on a belt, and the particles (A-1) are sprayed with a screw feeder to make the thickness of the particles on the current collector uniform. Use role Then, pressure molding was continuously performed at room temperature (25 ° C.) to obtain a long electrode for an electric double layer capacitor having a thickness of 200 m (Example 3). Similarly, the use of the particles (A-2) instead of the particles (A-1) stably formed a long electrode for an electric double layer capacitor (Example 4).
- the properties of the electrodes obtained in Example 3 and Example 4 were evaluated in the same manner as in Example 1, and are shown in Table 1. Using these electrodes, an electric double layer capacitor was prepared in the same manner as in Example 1, and the characteristics of the electric double layer capacitor obtained for the same items as in Example 1 were determined. Table 1 shows the results.
- the examples using the electrode material of the present invention are excellent in the strength and flexibility of the electrode for an electric double layer capacitor, and the uniformity of the electrode density where the electrode density is high. Further, the electric double layer capacitor of the embodiment has a low internal resistance and a large capacitance. On the other hand, in Comparative Example 1 in which the electrode material particles are irregular and have low fluidity, the electric double layer capacitor using the electrode with low electrode strength, density, and uniformity of density is inferior in internal resistance and capacitance. . In Comparative Example 2 using a thermosetting binder instead of a thermoplastic binder, the electric double layer capacitor using this electrode, which has low strength, flexibility, and low density, has an internal resistance and electrostatic resistance. The result was inferior capacity.
- the electrode for an electric double layer capacitor obtained from the electrode material of the present invention has characteristics of low internal resistance and high capacitance. Taking advantage of this characteristic, electric double-layer capacitors using the electrodes for electric double-layer capacitors can be used as knock-up power supplies for memories such as personal computers and mobile terminals, power supplies for instantaneous power failure measures such as personal computers, electric vehicles or hybrid vehicles. It is suitable for various applications such as application to paddy cars, solar power generation energy storage system combined with solar cells, and load leveling power supply combined with batteries.
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Abstract
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JP2006514820A JP5069464B2 (ja) | 2004-06-22 | 2005-06-20 | 電気二重層キャパシタ用電極材料およびその製造方法 |
US11/630,203 US7567429B2 (en) | 2004-06-22 | 2005-06-20 | Electrode material for electric double layer capacitor and process for producing the same |
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JP2008140809A (ja) * | 2006-11-30 | 2008-06-19 | Nippon Zeon Co Ltd | 電気化学素子電極用複合粒子の製造方法 |
US20090301764A1 (en) * | 2008-03-14 | 2009-12-10 | Murata Manufacturing Co., Ltd. | Method for smoothing electrode, method for manufacturing ceramic substrate, and ceramic substrate |
JP2010171212A (ja) * | 2009-01-23 | 2010-08-05 | Nippon Zeon Co Ltd | 電気二重層キャパシタ用電極およびその製造方法 |
CN101410915B (zh) * | 2006-03-30 | 2011-04-13 | 日本瑞翁株式会社 | 电化学元件电极用复合粒子、电化学元件电极用复合粒子的制造方法及电化学元件电极 |
WO2015019947A1 (ja) * | 2013-08-06 | 2015-02-12 | 日本バルカー工業株式会社 | 電気二重層キャパシタ用電極膜の製造方法 |
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WO2007116718A1 (ja) * | 2006-03-30 | 2007-10-18 | Zeon Corporation | 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及び電気化学素子電極 |
CN101410915B (zh) * | 2006-03-30 | 2011-04-13 | 日本瑞翁株式会社 | 电化学元件电极用复合粒子、电化学元件电极用复合粒子的制造方法及电化学元件电极 |
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US20090301764A1 (en) * | 2008-03-14 | 2009-12-10 | Murata Manufacturing Co., Ltd. | Method for smoothing electrode, method for manufacturing ceramic substrate, and ceramic substrate |
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JP2010171212A (ja) * | 2009-01-23 | 2010-08-05 | Nippon Zeon Co Ltd | 電気二重層キャパシタ用電極およびその製造方法 |
WO2015019947A1 (ja) * | 2013-08-06 | 2015-02-12 | 日本バルカー工業株式会社 | 電気二重層キャパシタ用電極膜の製造方法 |
JP2015032769A (ja) * | 2013-08-06 | 2015-02-16 | 日本バルカー工業株式会社 | 電気二重層キャパシタ用電極膜の製造方法 |
US10373768B2 (en) | 2013-08-06 | 2019-08-06 | Valqua, Ltd. | Method for producing electrode film for electric double layer capacitors |
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US20080030924A1 (en) | 2008-02-07 |
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JPWO2005124801A1 (ja) | 2008-04-17 |
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