WO2010024327A1 - リチウムイオンキャパシタ用電極およびリチウムイオンキャパシタ - Google Patents
リチウムイオンキャパシタ用電極およびリチウムイオンキャパシタ Download PDFInfo
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- WO2010024327A1 WO2010024327A1 PCT/JP2009/064954 JP2009064954W WO2010024327A1 WO 2010024327 A1 WO2010024327 A1 WO 2010024327A1 JP 2009064954 W JP2009064954 W JP 2009064954W WO 2010024327 A1 WO2010024327 A1 WO 2010024327A1
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- WIPO (PCT)
- Prior art keywords
- electrode
- lithium ion
- ion capacitor
- carbon particles
- current collector
- Prior art date
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Classifications
-
- 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
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to an electrode for a lithium ion capacitor and a lithium ion capacitor. More specifically, the present invention relates to an electrode for a lithium ion capacitor and a lithium ion capacitor that are excellent in electrode strength, reduce internal resistance, and increase output density.
- lithium-ion capacitors which are small and light, have high energy density, and can be repeatedly charged and discharged, is rapidly expanding due to their characteristics.
- the lithium ion capacitor since the lithium ion capacitor has a high energy density and output density, it is expected to be used in small applications such as mobile phones and notebook personal computers, and in large applications such as in-vehicle use. For this reason, lithium ion capacitors are required to be further improved in accordance with expansion and development of applications, such as lowering resistance, increasing capacity, increasing withstand voltage, and improving mechanical characteristics.
- the lithium ion capacitor has a polarizable electrode on the positive electrode and a non-polarizable electrode on the negative electrode, and can increase the operating voltage and energy density by using an organic electrolyte, but has a hole penetrating the front and back. There is a problem that the contact resistance between the current collector and the electrode composition layer is large and the internal resistance is large.
- Patent Document 1 a conductive paint for the purpose of reducing internal resistance
- the electrode for a lithium ion capacitor in Patent Document 1 is coated with a conductive paint on a current collector having a through-hole, and a slurry for an electrode composition layer comprising an electrode active material, a conductive material and a binder is coated thereon. It is obtained by coating.
- Such electrodes have been insufficient in reducing internal resistance.
- An object of the present invention is to provide a lithium ion capacitor electrode having excellent electrode strength and a lithium ion capacitor capable of reducing internal resistance and increasing output density.
- the present inventor is an electrode for a lithium ion capacitor comprising an electrode composition layer containing an electrode active material, a conductive material, and a binder, and a current collector.
- an electrode composition layer containing an electrode active material, a conductive material, and a binder, and a current collector.
- the inventors have completed the present invention based on these findings.
- an electrode for a lithium ion capacitor comprising an electrode composition layer containing an electrode active material, a conductive material and a binder and a current collector, wherein the electrode composition layer and the current collector.
- an electrode for a lithium ion capacitor having a conductive adhesive layer containing carbon particles.
- a lithium ion capacitor having a positive electrode, a negative electrode, an electrolytic solution, and a separator, wherein the positive electrode and the negative electrode are the electrodes.
- the lithium ion capacitor electrode of the present invention can easily produce a lithium ion capacitor having high electrode strength, low internal resistance, and high output density.
- the lithium ion capacitor of the present invention includes a memory backup power source for a personal computer or a portable terminal, a power source for instantaneous power failure such as a personal computer, application to an electric vehicle or a hybrid vehicle, a solar power generation energy storage system used in combination with a solar cell, a battery, It can be suitably used for various applications such as a combined load leveling power source.
- An electrode for a lithium ion capacitor according to the present invention comprises an electrode composition layer containing an electrode active material, a conductive material and a binder, and a current collector, and carbon particles are interposed between the electrode composition layer and the current collector. It has the electroconductive adhesive layer formed, It is characterized by the above-mentioned.
- the binder used for the electrode composition layer may be described as “binder for electrode composition”, and the binder used for the conductive adhesive layer described later is described as “binder for conductive adhesive”. There are things to do.
- the material of the current collector used for the electrode for the lithium ion capacitor of the present invention for example, metal, carbon, conductive polymer, and the like can be used, and metal is preferably used.
- metal aluminum, platinum, nickel, tantalum, titanium, stainless steel, copper, other alloys and the like are usually used. Among these, it is preferable to use copper, aluminum, or an aluminum alloy in terms of conductivity and voltage resistance.
- Examples of the shape of the current collector used for the electrode for the lithium ion capacitor of the present invention include current collectors such as metal foils and metal edged foils; current collectors having through-holes such as expanded metal, punching metal, and mesh.
- a collector having a through-hole is preferable in that the diffusion resistance of electrolyte ions can be reduced and the output density of the lithium ion capacitor can be improved.
- expanded metal and punching metal are particularly preferable in terms of excellent electrode strength. preferable.
- the current collector having a through hole refers to a current collector having a hole penetrating the front and back surfaces.
- the ratio of the through-holes of the current collector having through-holes suitably used for the lithium ion capacitor electrode of the present invention is 10 to 80 area%, preferably 20 to 60 area%, more preferably 30 to 50 area%. It is. When the ratio of the penetrating holes is within this range, the diffusion resistance of the electrolytic solution is reduced, and the internal resistance of the lithium ion capacitor is reduced.
- the average diameter of the through-holes is usually 0.1 to 5,000 ⁇ m, preferably 0.5 to 3,000 ⁇ m, more preferably 1 to 1,000 ⁇ m.
- the average diameter of the holes is a value obtained by the formula (X + Y) / 2 from the length X in the major axis direction and the length Y in the minor axis direction.
- the thickness of the current collector used for the electrode for the lithium ion capacitor of the present invention is 5 to 100 ⁇ m, preferably 10 to 70 ⁇ m, particularly preferably 20 to 50 ⁇ m.
- a conductive adhesive layer containing carbon particles is formed between the current collector and the electrode composition layer.
- the carbon particles used for the conductive adhesive layer of the electrode for a lithium ion capacitor of the present invention are particles composed of only carbon or substantially only carbon. Specific examples include graphite with high conductivity due to the presence of delocalized ⁇ -electrons (specifically, natural graphite, artificial graphite, etc.); Carbon black (specifically, acetylene black, ketjen black, other furnace blacks, channel blacks, thermal lamp blacks, etc.), which are spherical aggregates formed; include carbon fibers and carbon whiskers.
- Graphite or carbon black is particularly preferable in that the carbon particles of the conductive adhesive layer can be packed at a high density, the electron transfer resistance can be reduced, and the internal resistance of the lithium ion capacitor can be further reduced.
- the carbon particles used for the electrode for the lithium ion capacitor of the present invention may be those listed above, but it is particularly preferable to use two types in combination. Specific examples include graphite and carbon black, graphite and carbon fiber, graphite and carbon whisker, carbon black and carbon fiber, and a combination of carbon black and carbon whisker. Graphite and carbon black, graphite and carbon fiber, carbon black A combination of graphite and carbon fiber is preferable, and a combination of graphite and carbon black and graphite and carbon fiber is particularly preferable.
- the carbon particles are in this combination, the carbon particles of the conductive adhesive layer are filled with high density, so that the electron transfer resistance is further reduced and the internal resistance of the lithium ion capacitor is further reduced.
- the electrical resistivity of the carbon particles used for the lithium ion capacitor electrode of the present invention is preferably 0.0001 to 1 ⁇ ⁇ cm, more preferably 0.0005 to 0.5 ⁇ ⁇ cm, and particularly preferably 0.001 to 0.1 ⁇ ⁇ cm.
- the electrical resistivity of the carbon particles is within this range, the electron transfer resistance of the conductive adhesive layer can be further reduced, and the internal resistance of the lithium ion capacitor can be further reduced.
- the electrical resistivity is measured by using a powder resistance measurement system (MCP-PD51 type; manufactured by Dia Instruments Co., Ltd.) while measuring the resistance value while applying pressure to the carbon particles, and the resistance value converged with respect to the pressure.
- the volume average particle diameter of the carbon particles used in the electrode for the lithium ion capacitor of the present invention is preferably 0.01 to 20 ⁇ m, more preferably 0.05 to 15 ⁇ m, and particularly preferably 0.1 to 10 ⁇ m.
- the volume average particle diameter of the carbon particles is within this range, the carbon particles of the conductive adhesive layer are filled with high density, so that the electron transfer resistance is further reduced and the internal resistance of the lithium ion capacitor is further reduced.
- the volume average particle diameter is a volume average particle diameter calculated by measuring with a laser diffraction particle size distribution measuring device (SALD-3100; manufactured by Shimadzu Corporation).
- the volume average particle size distribution of the carbon particles used for the conductive adhesive layer is preferably bimodal.
- the volume average particle size distribution of the carbon particles is bimodal, the carbon particles of the conductive adhesive layer are filled with high density, so that the electron transfer resistance is reduced and the internal resistance of the lithium ion capacitor is reduced.
- the volume average particle size distribution is a volume average particle size distribution calculated by measuring with a laser diffraction particle size distribution analyzer (SALD-3100; manufactured by Shimadzu Corporation).
- That the volume average particle size distribution of carbon particles is bimodal means that at least two peaks are observed in the volume average particle size distribution in which the horizontal axis indicates the particle size and the vertical axis indicates the frequency of appearance of the particle.
- the particle diameter is preferably 0.01 ⁇ m or more and less than 1 ⁇ m, and the particle diameter is 1 ⁇ m or more and 10 ⁇ m or less, more preferably the particle diameter is 0.1 ⁇ m or more and 0.5 ⁇ m or less, and the particle diameter is 1 ⁇ m or more and 5 ⁇ m. Peaks are observed in each of the following areas.
- the weight ratio of the two types of carbon particles (A) and carbon particles (B) used suitably for the lithium ion capacitor electrode of the present invention is preferably a ratio of (A) / (B) of 0.05 to 1. 0.1 to 0.8 is more preferable, and 0.2 to 0.5 is particularly preferable.
- the weight ratio of the two types of carbon particles is within this range, the carbon particles of the conductive adhesive layer are filled with high density, so that the electron transfer resistance is further reduced and the internal resistance of the lithium ion capacitor is further reduced.
- the weight ratio of the carbon particles (A ′) having a particle diameter of 0.01 ⁇ m or more and less than 1 ⁇ m to the carbon particles (B ′) having a particle diameter of 1 ⁇ m or more and 10 ⁇ m or less is (A ′) /
- the ratio of (B ′) is preferably 0.05 to 1, more preferably 0.1 to 0.8, and particularly preferably 0.2 to 0.5.
- the conductive adhesive layer used for the lithium ion capacitor electrode of the present invention contains carbon particles as an essential component.
- the conductive adhesive layer used in the present invention preferably contains a binder in addition to the carbon particles.
- the binder for conductive adhesives suitably used for the conductive adhesive layer of the lithium ion capacitor electrode of the present invention is not particularly limited as long as it is a compound capable of binding carbon particles to each other.
- a suitable binder is a dispersion-type binder having a property of being dispersed in a solvent.
- the dispersion-type binder include polymer compounds such as a fluoropolymer, a diene polymer, an acrylate polymer, a polyimide, a polyamide, and a polyurethane polymer, and a fluoropolymer, a diene polymer, or an acrylate polymer is preferable.
- a polymer or an acrylate polymer is more preferable in that the withstand voltage can be increased and the energy density of the lithium ion capacitor can be increased.
- the diene polymer is a homopolymer of a conjugated diene or a copolymer obtained by polymerizing a monomer mixture containing a conjugated diene, or a hydrogenated product thereof.
- the proportion of the conjugated diene in the monomer mixture is usually 40% by weight or more, preferably 50% by weight or more, more preferably 60% by weight or more.
- the diene polymer include conjugated diene homopolymers such as polybutadiene and polyisoprene; aromatic vinyl / conjugated diene copolymers such as carboxy-modified styrene / butadiene copolymer (SBR); acrylonitrile -Vinyl cyanide * conjugated diene copolymers, such as a butadiene copolymer (NBR); Hydrogenated SBR, hydrogenated NBR, etc. are mentioned.
- conjugated diene homopolymers such as polybutadiene and polyisoprene
- aromatic vinyl / conjugated diene copolymers such as carboxy-modified styrene / butadiene copolymer (SBR); acrylonitrile -Vinyl cyanide * conjugated diene copolymers, such as a butadiene copolymer (NBR); Hydrogenated SBR, hydrogenated NBR, etc.
- the acrylate polymer is represented by the general formula (1): CH 2 ⁇ CR 1 —COOR 2 (wherein R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkyl group or a cycloalkyl group). It is a polymer obtained by polymerizing a monomer mixture containing a compound.
- Specific examples of the compound represented by the general formula (1) include ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, n-amyl acrylate, Acrylates such as isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, hexyl acrylate, nonyl acrylate, lauryl acrylate, stearyl acrylate; ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n methacrylate -Butyl, isobutyl methacrylate, t-butyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate,
- acrylate is preferable, and n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferable in that the strength of the obtained electrode can be improved.
- the proportion of monomer units derived from acrylic acid ester and / or methacrylic acid ester in the acrylate polymer is usually 50% by weight or more, preferably 70% by weight or more.
- a copolymerizable carboxylic acid group-containing monomer can be used in addition to the compound represented by the general formula (1). Specific examples thereof include acrylic acid and methacrylic acid.
- Basic acid-containing monomers dibasic acid-containing monomers such as maleic acid, fumaric acid, and itaconic acid.
- a dibasic acid-containing monomer is preferable, and itaconic acid is particularly preferable in terms of enhancing the binding property with the current collector and improving the electrode strength.
- These monobasic acid-containing monomers and dibasic acid-containing monomers can be used alone or in combination of two or more.
- the amount of the carboxylic acid group-containing monomer in the monomer mixture is usually 0.1 to 50 parts by weight with respect to 100 parts by weight of the compound represented by the general formula (1).
- the range is preferably 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight.
- a copolymerizable nitrile group-containing monomer can be used for the acrylate polymer.
- the nitrile group-containing monomer include acrylonitrile, methacrylonitrile, and the like.
- acrylonitrile is preferable in that the binding strength with the current collector is increased and the electrode strength can be improved.
- the amount of acrylonitrile in the monomer mixture at the time of copolymerization is usually 0.1 to 40 parts by weight, preferably 0.5 to 4 parts by weight with respect to 100 parts by weight of the compound represented by the general formula (1). It is 30 parts by weight, more preferably in the range of 1 to 20 parts by weight. When the amount of acrylonitrile is within this range, the binding property with the current collector is excellent, and the obtained electrode strength is increased.
- the shape of the binder used for the conductive adhesive layer of the electrode for the lithium ion capacitor of the present invention is not particularly limited, but it has good binding properties with the current collector, and the capacity and charge / discharge of the prepared electrode are reduced. Since it is possible to suppress deterioration due to repetition of the above, it is preferably in the form of particles.
- the particulate binder include those in which binder particles such as latex are dispersed in water, and powders obtained by drying such a dispersion.
- the glass transition temperature (Tg) of the binder used for the conductive adhesive layer of the lithium ion capacitor electrode of the present invention is preferably 50 ° C. or lower, more preferably ⁇ 40 to 0 ° C.
- Tg glass transition temperature
- the number average particle diameter is not particularly limited, but is usually 0.0001 to 100 ⁇ m, preferably 0.00. Those having a number average particle diameter of 001 to 10 ⁇ m, more preferably 0.01 to 1 ⁇ m. When the number average particle size of the binder is within this range, an excellent binding force can be imparted to the electrode even when used in a small amount.
- the number average particle diameter is a number average particle diameter calculated as an arithmetic average value obtained by measuring the diameter of 100 binder particles randomly selected in a transmission electron micrograph. The shape of the particles can be either spherical or irregular. These binders can be used alone or in combination of two or more.
- the content of the binder for the conductive adhesive in the conductive adhesive layer is preferably 0.5 to 20 parts by weight, more preferably 1 to 15 parts by weight, with respect to 100 parts by weight of the carbon particles. Particularly preferred is 2 to 10 parts by weight.
- the conductive adhesive layer used for the electrode for a lithium ion capacitor of the present invention comprises carbon particles, a binder for a conductive adhesive that is suitably used, and a dispersant added as necessary in water or an organic solvent.
- a conductive adhesive slurry composition obtained by kneading can be applied to a current collector and dried.
- the dispersant include cellulosic polymers such as carboxymethylcellulose, methylcellulose, ethylcellulose and hydroxypropylcellulose, and ammonium salts or alkali metal salts thereof; poly (meth) acrylates such as sodium poly (meth) acrylate Polyvinyl alcohol, modified polyvinyl alcohol, polyethylene oxide; polyvinyl pyrrolidone, polycarboxylic acid, oxidized starch, phosphate starch, casein, various modified starches, chitin, chitosan derivatives and the like. These dispersants can be used alone or in combination of two or more. Among these, a cellulose polymer is preferable, and carboxymethyl cellulose or an ammonium salt or an alkali metal salt thereof is particularly preferable.
- the amount of these dispersants can be used within a range not impairing the effects of the present invention, and is not particularly limited, but is usually 0.1 to 15 parts by weight, preferably 100 parts by weight of carbon particles. Is in the range of 0.5 to 10 parts by weight, more preferably 0.8 to 5 parts by weight.
- the conductive adhesive layer may be formed by applying and drying the obtained conductive adhesive slurry composition on a current collector, or obtained on the electrode composition layer.
- the conductive adhesive slurry composition may be applied and dried.
- the solid content concentration of the conductive adhesive slurry composition used in the present invention is usually 10 to 60%, preferably 15 to 50%, particularly preferably 20 to 40%, although it depends on the coating method. When the solid content concentration is in this range, the conductive adhesive layer is highly filled, and the energy density and output density of the lithium ion capacitor are increased.
- the viscosity of the conductive adhesive slurry composition used in the present invention is usually 50 to 10,000 mPa ⁇ s, preferably 100 to 5,000 mPa ⁇ s, particularly preferably 200 to 2,000 mPa ⁇ s, although it depends on the coating method. s. When the viscosity of the conductive adhesive slurry composition is within this range, a uniform conductive adhesive layer can be formed on the current collector.
- the method for forming the conductive adhesive layer used for the lithium ion capacitor electrode of the present invention is not particularly limited. For example, it is formed on the current collector or the electrode composition layer by a doctor blade method, a dip method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, a brush coating, or the like.
- Examples of the method for drying the conductive adhesive layer include drying by hot air, hot air, low-humidity air, vacuum drying, and drying by irradiation with (far) infrared rays or electron beams. Of these, a drying method using hot air and a drying method using irradiation with far infrared rays are preferable.
- the drying temperature and the drying time are preferably a temperature and a time at which the solvent in the slurry coated on the current collector or the electrode composition layer can be completely removed.
- the drying temperature is usually 50 to 300 ° C., preferably 80 to 250 ° C. It is.
- the drying time is usually 2 hours or less, preferably 5 seconds to 30 minutes.
- the thickness of the conductive adhesive layer is usually 0.01 to 20 ⁇ m, preferably 0.1 to 10 ⁇ m, particularly preferably 1 to 5 ⁇ m. When the thickness of the conductive adhesive layer is within the above range, good adhesiveness can be obtained and the electron transfer resistance can be reduced.
- the type and particle size of the carbon particles in the conductive adhesive layer can be identified by performing image analysis on the electrode cross section using FE-SEM or FE-TEM.
- the electrode composition layer used in the present invention contains an electrode active material, a conductive material and a binder.
- the electrode active material used for the lithium ion capacitor electrode of the present invention is a substance that transfers electrons in the lithium ion capacitor electrode.
- the electrode active material used for the positive electrode of the lithium ion capacitor electrode may be any material that can reversibly carry lithium ions and anions such as tetrafluoroborate.
- an allotrope of carbon is usually used, and electrode active materials used in electric double layer capacitors can be widely used.
- Specific examples of the allotrope of carbon include activated carbon, polyacene (PAS), carbon whisker, and graphite, and these powders or fibers can be used. Among these, activated carbon is preferable.
- Specific examples of the activated carbon include activated carbon made from phenol resin, rayon, acrylonitrile resin, pitch, coconut shell, and the like.
- carbon allotropes When carbon allotropes are used in combination, two or more types of carbon allotropes having different average particle diameters or particle size distributions may be used in combination.
- an electrode active material used for the positive electrode in addition to the above materials, a heat-treated product of an aromatic condensation polymer having a hydrogen atom / carbon atom atomic ratio of 0.50 to 0.05, a polyacene skeleton structure
- a polyacene-based organic semiconductor (PAS) having the following can also be suitably used.
- the electrode active material used for the negative electrode of the lithium ion capacitor electrode may be any material that can reversibly carry lithium ions.
- electrode active materials used in the negative electrode of lithium ion secondary batteries can be widely used.
- crystalline carbon materials such as graphite and non-graphitizable carbon, carbon materials such as hard carbon and coke, and polyacene-based materials (PAS) described as the electrode active material of the positive electrode are preferable.
- These carbon materials and PAS are obtained by carbonizing a phenol resin or the like, activated as necessary, and then pulverized.
- the shape of the electrode active material used for the electrode for the lithium ion capacitor is preferably a granulated particle. Furthermore, when the shape of the particles is spherical, a higher density electrode can be formed during electrode molding.
- the volume average particle diameter of the electrode active material used for the electrode for the lithium ion capacitor is usually 0.1 to 100 ⁇ m, preferably 0.5 to 50 ⁇ m, more preferably 1 to 20 ⁇ m for both the positive electrode and the negative electrode.
- These electrode active materials can be used alone or in combination of two or more.
- the conductive material used for the lithium ion capacitor electrode of the present invention is made of an allotrope of particulate carbon having conductivity and no pores capable of forming an electric double layer.
- furnace black Conductive carbon black such as acetylene black, and ketjen black (registered trademark of Akzo Nobel Chemicals Bethloten Fennaut Shap).
- acetylene black and furnace black are preferable.
- the volume average particle diameter of the conductive material used for the electrode for the lithium ion capacitor of the present invention is preferably smaller than the volume average particle diameter of the electrode active material, and the range is usually 0.001 to 10 ⁇ m, preferably 0.05 to The thickness is 5 ⁇ m, more preferably 0.01 to 1 ⁇ m. When the volume average particle diameter of the conductive material is within this range, high conductivity can be obtained with a smaller amount of use. These conductive materials can be used alone or in combination of two or more.
- the amount of the conductive material in the electrode composition layer is usually in the range of 0.1 to 50 parts by weight, preferably 0.5 to 15 parts by weight, more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the electrode active material. is there. When the amount of the conductive material is within this range, the capacity of the lithium ion capacitor using the obtained lithium ion capacitor electrode can be increased and the internal resistance can be decreased.
- the binder used for the electrode composition layer of the electrode for a lithium ion capacitor of the present invention is not particularly limited as long as it is a compound that can bind the electrode active material and the conductive material to each other.
- a suitable binder is a dispersion-type binder having a property of being dispersed in a solvent.
- the dispersion-type binder include high molecular compounds such as fluoropolymers, diene polymers, acrylate polymers, polyimides, polyamides, polyurethane polymers, and preferred are fluoropolymers, diene polymers, and acrylate polymers.
- a polymer or an acrylate polymer is more preferable in that the withstand voltage can be increased and the energy density of the lithium ion capacitor can be increased.
- the diene polymer is a homopolymer of a conjugated diene or a copolymer obtained by polymerizing a monomer mixture containing a conjugated diene, or a hydrogenated product thereof.
- the proportion of the conjugated diene in the monomer mixture is usually 40% by weight or more, preferably 50% by weight or more, more preferably 60% by weight or more.
- the diene polymer include conjugated diene homopolymers such as polybutadiene and polyisoprene; aromatic vinyl / conjugated diene copolymers such as carboxy-modified styrene / butadiene copolymer (SBR); acrylonitrile -Vinyl cyanide * conjugated diene copolymers, such as a butadiene copolymer (NBR); Hydrogenated SBR, hydrogenated NBR, etc. are mentioned.
- conjugated diene homopolymers such as polybutadiene and polyisoprene
- aromatic vinyl / conjugated diene copolymers such as carboxy-modified styrene / butadiene copolymer (SBR); acrylonitrile -Vinyl cyanide * conjugated diene copolymers, such as a butadiene copolymer (NBR); Hydrogenated SBR, hydrogenated NBR, etc.
- Specific examples of the compound represented by the general formula (2) include ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, n-amyl acrylate, Acrylates such as isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, hexyl acrylate, nonyl acrylate, lauryl acrylate, stearyl acrylate; ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n methacrylate -Butyl, isobutyl methacrylate, t-butyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate,
- acrylate is preferable, and n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferable in that the strength of the obtained electrode can be improved.
- the proportion of monomer units derived from acrylic acid ester and / or methacrylic acid ester in the acrylate polymer is usually 50% by weight or more, preferably 70% by weight or more.
- a copolymerizable carboxylic acid group-containing monomer can be used in addition to the compound represented by the general formula (2).
- Specific examples include acrylic acid and methacrylic acid.
- Basic acid-containing monomers dibasic acid-containing monomers such as maleic acid, fumaric acid, and itaconic acid.
- a dibasic acid-containing monomer is preferable, and itaconic acid is particularly preferable in terms of improving the binding property with the conductive adhesive layer and improving the electrode strength.
- These monobasic acid-containing monomers and dibasic acid-containing monomers can be used alone or in combination of two or more.
- the amount of the carboxylic acid group-containing monomer in the monomer mixture is usually 0.1 to 50 parts by weight with respect to 100 parts by weight of the compound represented by the general formula (2).
- the range is preferably 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight.
- a copolymerizable nitrile group-containing monomer can be used for the acrylate polymer.
- the nitrile group-containing monomer include acrylonitrile, methacrylonitrile, and the like.
- acrylonitrile is preferable in that the binding strength with the conductive adhesive layer is increased and the electrode strength can be improved.
- the amount of acrylonitrile in the monomer mixture at the time of copolymerization is usually 0.1 to 40 parts by weight, preferably 0.5 to 4 parts by weight with respect to 100 parts by weight of the compound represented by the general formula (2). It is 30 parts by weight, more preferably in the range of 1 to 20 parts by weight. When the amount of acrylonitrile is within this range, the binding strength with the conductive adhesive layer is excellent, and the obtained electrode strength is increased.
- the shape of the binder used in the electrode composition layer of the lithium ion capacitor electrode of the present invention is not particularly limited, but it has good binding properties with the conductive adhesive layer, and the capacity and reduction of the capacity of the prepared electrode are reduced. Since deterioration due to repeated discharge can be suppressed, it is preferably in the form of particles.
- the particulate binder include those in which binder particles such as latex are dispersed in water, and powders obtained by drying such a dispersion.
- the glass transition temperature (Tg) of the binder used for the electrode composition layer of the lithium ion capacitor electrode of the present invention is preferably 50 ° C. or less, more preferably ⁇ 40 to 0 ° C.
- Tg glass transition temperature
- the number average particle diameter is not particularly limited, but is usually 0.0001 to 100 ⁇ m, preferably 0.001 to The number average particle size is 10 ⁇ m, more preferably 0.01 to 1 ⁇ m.
- the number average particle diameter is a number average particle diameter calculated as an arithmetic average value obtained by measuring the diameter of 100 binder particles randomly selected in a transmission electron micrograph.
- the shape of the particles can be either spherical or irregular.
- the amount of the electrode composition binder in the electrode composition layer is usually 0.1 to 50 parts by weight, preferably 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight based on 100 parts by weight of the electrode active material.
- the range is parts by weight.
- the electrode composition layer of the lithium ion capacitor electrode of the present invention is provided on the conductive adhesive layer, but the formation method is not limited. Specifically, 1) A sheet-shaped electrode forming composition obtained by kneading an electrode active material, a conductive material and a binder is formed into a sheet, and the resulting sheet-shaped electrode forming composition is formed into a conductive adhesive layer. A method of laminating on the current collector (kneading sheet molding method), 2) A paste-like electrode forming composition comprising an electrode active material, a conductive material and a binder was prepared, and a conductive adhesive layer was formed.
- a method of applying and drying on a current collector (wet molding method), 3) On a current collector on which a composite particle comprising an electrode active material, a conductive material and a binder is prepared and a conductive adhesive layer is formed
- the method include sheet molding and roll pressing (dry molding method).
- dry molding method 2) a wet molding method, 3) a dry molding method are preferable, and 3) a lithium ion capacitor from which the dry molding method can be obtained is more preferable in that the capacity can be increased and the internal resistance can be reduced.
- an electrode active material, a conductive material and a binder are essential components, and other dispersants and additives may be blended as necessary.
- other dispersants include cellulosic polymers such as carboxymethylcellulose, methylcellulose, ethylcellulose and hydroxypropylcellulose, and ammonium or alkali metal salts thereof; poly (meth) acrylic such as sodium poly (meth) acrylate.
- Acid salts polyvinyl alcohol, modified polyvinyl alcohol, polyethylene oxide; polyvinyl pyrrolidone, polycarboxylic acid, oxidized starch, phosphate starch, casein, various modified starches, chitin, chitosan derivatives and the like.
- These dispersants can be used alone or in combination of two or more.
- a cellulose polymer is preferable, and carboxymethyl cellulose or an ammonium salt or an alkali metal salt thereof is particularly preferable.
- the amount of these dispersants can be used within a range that does not impair the effects of the present invention, and is not particularly limited. Is in the range of 0.5 to 5 parts by weight, more preferably 0.8 to 2 parts by weight.
- the paste-like electrode forming composition (hereinafter sometimes referred to as “electrode composition layer slurry”) may be used.
- the electrode active material, the conductive material, the essential components of the binder, and other dispersants and additives can be produced by kneading in water or an organic solvent such as N-methyl-2-pyrrolidone or tetrahydrofuran.
- the slurry for an electrode composition layer is preferably an aqueous slurry using water as a dispersion medium from the viewpoint of easy drying of the electrode composition layer and excellent environmental load.
- water and each of the above components can be mixed and produced using a mixer.
- a mixer a ball mill, a sand mill, a pigment disperser, a pulverizer, an ultrasonic disperser, a homogenizer, a planetary mixer, a Hobart mixer, and the like can be used.
- the electrode active material and the conductive material are first mixed using a mixer such as a crusher, a planetary mixer, a Henschel mixer, and an omni mixer, and then a binder, other dispersing agents and additives are added and the mixture is uniform. It is also preferable to mix them. By adopting this method, a uniform slurry can be easily obtained.
- the viscosity of the slurry for the electrode composition layer used in the present invention varies depending on the type of coating machine and the shape of the coating line, but is usually 100 to 100,000 mPa ⁇ s, preferably 1,000 to 50, 000 mPa ⁇ s, more preferably 5,000 to 20,000 mPa ⁇ s.
- the method for applying the slurry onto the current collector is not particularly limited. Examples thereof include a doctor blade method, a dip method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, and a brush coating method.
- the coating thickness of the slurry is appropriately set according to the thickness of the target electrode composition layer.
- drying method examples include drying with warm air, hot air, low-humidity air, vacuum drying, and drying by irradiation with (far) infrared rays or electron beams. Among these, a drying method by irradiation with far infrared rays is preferable.
- the drying temperature and the drying time in the present invention are preferably a temperature and a time at which the solvent in the slurry applied to the current collector can be completely removed, and the drying temperature is 100 to 300 ° C., preferably 120 to 250 ° C.
- the drying time is usually 10 minutes to 100 hours, preferably 20 minutes to 20 hours.
- the composite particles used are particles in which an electrode active material, a conductive material, a binder, and other dispersants and additives are integrated. .
- the production method of the composite particles is not particularly limited, and is a spray drying granulation method, a rolling bed granulation method, a compression granulation method, a stirring granulation method, an extrusion granulation method, a crushing granulation method, a fluidized bed granulation method. It can be produced by a known granulation method such as a granulation method, a fluidized bed multifunctional granulation method, a pulse combustion type drying method, or a melt granulation method. Among these, the spray-drying granulation method is preferable because composite particles in which a binder and a conductive material are unevenly distributed near the surface can be easily obtained. When composite particles obtained by the spray drying granulation method are used, the electrode for an electrochemical element of the present invention can be obtained with high productivity. In addition, the internal resistance of the electrode can be further reduced.
- the electrode active material, conductive material, binder and other components described above are first dispersed or dissolved in a solvent, and the electrode active material, conductive material, binder, other dispersant and additive are dispersed. Alternatively, a dissolved slurry is obtained.
- the solvent used for obtaining the slurry is not particularly limited, but when the above dispersant is used, a solvent capable of dissolving the dispersant is preferably used. Specifically, water is usually used, but an organic solvent may be used, or a mixed solvent of water and an organic solvent may be used.
- the organic solvent examples 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; diethylformamide, dimethylacetamide and N-methyl- Amides such as 2-pyrrolidone and dimethylimidazolidinone; sulfur solvents such as dimethyl sulfoxide and sulfolane; and the like.
- alcohols are preferable as the organic solvent.
- water and an organic solvent having a lower boiling point than water are used in combination, the drying rate can be increased during spray drying.
- the dispersibility of the binder or the solubility of the dispersant varies depending on the amount or type of the organic solvent used in combination with water. Thereby, the viscosity and fluidity
- the amount of the solvent used when preparing the slurry is such that the solid content concentration of the slurry is usually in the range of 1 to 50% by mass, preferably 5 to 50% by mass, more preferably 10 to 30% by mass. .
- the binder is preferably dispersed uniformly.
- the method or procedure for dispersing or dissolving the electrode active material, conductive material, binder, and other dispersants and additives in the solvent is not particularly limited.
- the electrode active material, conductive material, binder, and other dispersants in the solvent Method of adding and mixing the additive; Dissolving the dispersant in the solvent, adding and mixing the binder dispersed in the solvent, and finally adding and mixing the electrode active material and the conductive material; Dispersing in the solvent Examples thereof include a method in which an electrode active material and a conductive material are added to and mixed with the binder, and a dispersant dissolved in a solvent is added to and mixed with the mixture.
- mixing means examples include mixing equipment such as a ball mill, a sand mill, a bead mill, a pigment disperser, a crusher, an ultrasonic disperser, a homogenizer, a homomixer, and a planetary mixer. Mixing is usually carried out in the range of room temperature to 80 ° C. for 10 minutes to several hours.
- the viscosity of the slurry is usually in the range of 10 to 3,000 mPa ⁇ s, preferably 30 to 1,500 mPa ⁇ s, more preferably 50 to 1,000 mPa ⁇ s at room temperature.
- the viscosity of the slurry is within this range, the productivity of the composite particles can be increased. Further, the higher the viscosity of the slurry, the larger the spray droplets and the larger the weight average particle diameter of the resulting composite particles.
- the rotating disk system is a system in which slurry is introduced almost at the center of a disk that rotates at a high speed, and the slurry is released out of the disk by the centrifugal force of the disk, and the slurry is atomized at that time.
- the rotational speed of the disk depends on the size of the disk, but is usually 5,000 to 30,000 rpm, preferably 15,000 to 30,000 rpm.
- a pin-type atomizer is a type of centrifugal spraying device that uses a spraying plate, and the spraying plate has a plurality of spraying rollers removably mounted on a concentric circle along its periphery between upper and lower mounting disks. It consists of The slurry is introduced from the center of the spray platen, adheres to the spraying roller by centrifugal force, moves outside the roller surface, and finally sprays away from the roller surface.
- the pressurization method is a method in which the slurry is pressurized and sprayed from a nozzle to be dried.
- the temperature of the slurry to be sprayed is usually room temperature, but it may be heated to room temperature or higher.
- the hot air temperature at the time of spray drying is usually 80 to 250 ° C., preferably 100 to 200 ° C.
- the method of blowing hot air is not particularly limited, for example, a method in which the hot air and the spray direction flow in the horizontal direction, a method in which the hot air is sprayed at the top of the drying tower and descends with the hot air, and the sprayed droplets and hot air are in countercurrent contact. And a system in which sprayed droplets first flow in parallel with hot air and then drop by gravity to make countercurrent contact.
- the composite particles are preferably spherical.
- the minor axis diameter Ls and the major axis diameter Ll are average values for 100 arbitrary composite particles measured from a photographic image obtained by observing the composite particles using a reflection electron microscope. A smaller sphericity value or a larger sphericity value indicates that the composite particle is closer to a true sphere.
- the particle observed as a square in the photographic image has a sphericity of 34.4%, so the composite particle showing a sphericity exceeding 34.4% is not at least spherical.
- the sphericity of the composite particles is preferably 20% or less, and more preferably 15% or less.
- the sphericity of the composite particles is preferably 80% or more, more preferably 90% or more.
- the composite particles obtained by the above production method can be subjected to post-treatment after production of the particles, if necessary.
- the particle surface is modified to improve or decrease the fluidity of the composite particles. Improving the continuous pressure moldability and improving the electrical conductivity of the composite particles.
- the weight average particle size of the composite particles suitably used in the present invention is usually in the range of 0.1 to 1,000 ⁇ m, preferably 5 to 500 ⁇ m, more preferably 10 to 100 ⁇ m. When the weight average particle diameter of the composite particles is within this range, the composite particles are less likely to aggregate and electrostatic force is increased against gravity, which is preferable.
- the weight average particle diameter can be measured using a laser diffraction particle size distribution measuring apparatus.
- the feeder used in the step of supplying composite particles is not particularly limited, but is preferably a quantitative feeder capable of supplying composite particles quantitatively.
- the quantitative feeder preferably used in the present invention has a CV value of preferably 2 or less.
- Specific examples of the quantitative feeder include a gravity feeder such as a table feeder and a rotary feeder, and a mechanical force feeder such as a screw feeder and a belt feeder. Of these, the rotary feeder is preferred.
- the current collector on which the conductive adhesive layer is formed and the supplied composite particles are pressed with a pair of rolls to form an electrode composition layer on the conductive adhesive layer.
- the composite particles heated as necessary are formed into a sheet-like electrode composition layer by a pair of rolls.
- the temperature of the supplied composite particles is preferably 40 to 160 ° C., more preferably 70 to 140 ° C. When composite particles in this temperature range are used, there is no slip of the composite particles on the surface of the press roll, and the composite particles are continuously and uniformly supplied to the press roll. An electrode composition layer with small variations can be obtained.
- the molding temperature is usually 0 to 200 ° C., preferably higher than the melting point or glass transition temperature of the electrode composition binder, and more preferably 20 ° C. or more higher than the melting point or glass transition temperature.
- the forming speed is usually larger than 0.1 m / min, preferably 35 to 70 m / min.
- the press linear pressure between the press rolls is usually 0.2 to 30 kN / cm, preferably 0.5 to 10 kN / cm.
- the arrangement of the pair of rolls is not particularly limited, but is preferably arranged substantially horizontally or substantially vertically.
- the current collector is continuously supplied between a pair of rolls, and a composite particle is supplied to at least one of the rolls, whereby a current collector having a conductive adhesive layer formed thereon.
- Composite particles are supplied to the gap between the roll and the roll, and the electrode composition layer can be formed by pressurization.
- the current collector on which the conductive adhesive layer is formed is transported in the horizontal direction, and composite particles are supplied onto the current collector, and the supplied composite particles are bladed as necessary. After leveling, etc., the current collector on which the conductive adhesive layer is formed can be supplied between a pair of rolls, and an electrode composition layer can be formed by pressurization.
- the post-pressing method is generally a press process using a roll.
- the roll press process two cylindrical rolls are arranged in parallel at a narrow interval in the vertical direction, and each is rotated in the opposite direction.
- the roll may be temperature controlled, such as heated or cooled.
- the density of the electrode composition layer of the lithium ion capacitor electrode of the present invention is not particularly limited, but is usually 0.30 to 10 g / cm 3 , preferably 0.35 to 5.0 g / cm 3 , more preferably 0. 40-3.0 g / cm 3 .
- the thickness of the electrode composition layer is not particularly limited, but is usually 5 to 1000 ⁇ m, preferably 20 to 500 ⁇ m, more preferably 30 to 300 ⁇ m.
- the lithium ion capacitor of this invention has a positive electrode, a negative electrode, electrolyte solution, and a separator,
- the said positive electrode or negative electrode is the said electrode, It is characterized by the above-mentioned.
- a positive electrode and a negative electrode are the said electrodes for lithium ion capacitors.
- the durability of the lithium ion capacitors can be further improved.
- the separator is not particularly limited as long as it can insulate between the electrodes for the lithium ion capacitor and can pass cations and anions. Specifically, polyolefins such as polyethylene and polypropylene, microporous membranes or nonwoven fabrics made of rayon or glass fiber, and porous membranes mainly made of pulp called electrolytic capacitor paper can be used.
- the separator is arranged between the lithium ion capacitor electrodes so that the pair of electrode layers face each other, and an element is obtained.
- the thickness of the separator is appropriately selected depending on the purpose of use, but is usually 1 to 100 ⁇ m, preferably 10 to 80 ⁇ m, more preferably 20 to 60 ⁇ m.
- the electrolytic solution is usually composed of an electrolyte and a solvent.
- the electrolyte can use lithium ions as cations.
- As anions PF 6 ⁇ , BF 4 ⁇ , AsF 6 ⁇ , SbF 6 ⁇ , N (RfSO 3 ) 2 ⁇ , C (RfSO 3 ) 3 ⁇ , RfSO 3 ⁇ (Rf is a fluoro having 1 to 12 carbon atoms, respectively) Represents an alkyl group), F ⁇ , ClO 4 ⁇ , AlCl 4 ⁇ , AlF 4 ⁇ and the like.
- These electrolytes can be used alone or in combination of two or more.
- the solvent of the electrolytic solution is not particularly limited as long as it is generally used as a solvent for the electrolytic solution.
- Specific examples include carbonates such as propylene carboat, ethylene carbonate, and butylene carbonate; lactones such as ⁇ -butyrolactone; sulfolanes; nitriles such as acetonitrile. These solvents can be used alone or as a mixed solvent of two or more. Of these, carbonates are preferred.
- a lithium ion capacitor is obtained by impregnating the above element with an electrolytic solution.
- the device can be manufactured by winding, laminating, or folding the device in a container as necessary, and pouring the electrolyte into the container and sealing it.
- a device in which an element is previously impregnated with an electrolytic solution may be stored in a container. Any known container such as a coin shape, a cylindrical shape, or a square shape can be used as the container.
- a lithium-ion capacitor of a laminated laminate cell is produced using the electrodes for lithium-ion capacitors produced in Examples and Comparative Examples.
- the capacity and internal resistance are measured by charging / discharging after standing for 24 hours.
- charging starts with a constant current of 2 A, and when the voltage reaches 3.6 V, the voltage is maintained for 1 hour to be constant voltage charging.
- Discharging is performed immediately after the end of charging until it reaches 1.9 V at a constant current of 0.9 A.
- the soot capacity is calculated as the capacity per unit weight of the electrode active material from the amount of energy during discharge.
- the internal resistance is calculated from the voltage drop immediately after discharge. The lower the internal resistance, the higher the power density. Further, the durability is evaluated based on the following criteria by calculating a capacity maintenance ratio with respect to an initial capacity after continuous application of a lithium ion capacitor in a constant temperature bath at 70 ° C. for 3.6 V for 1000 hours. The greater the capacity retention rate, the better the durability.
- Capacity maintenance rate is 90% or more
- Capacity maintenance rate is 80% or more and less than 90%
- Capacity maintenance rate is less than 80%
- the electrode for the lithium ion capacitor is cut into a rectangular shape having a length of 100 mm and a width of 10 mm so that the coating direction of the electrode composition layer becomes a long side to obtain a test piece, and the cell composition is formed on the surface of the electrode composition layer with the electrode composition layer side down.
- Attach a tape (specified in JIS Z1522) and measure the stress when one end of the current collector is pulled vertically and pulled at a pulling speed of 50 mm / min. (The cellophane tape is fixed to the test stand. ing.). This measurement is performed 3 times, the average value is calculated
- Example 1 As carbon particles, 100 parts of graphite having a volume average particle diameter of 3.7 ⁇ m and an electrical resistivity of 0.004 ⁇ ⁇ cm (KS-6; manufactured by Timcal Corporation, hereinafter may be referred to as “carbon particles B1”), dispersant. As a 4.0% aqueous solution of carboxymethyl cellulose (DN-10L; manufactured by Daicel Chemical Industries, Ltd.) in an amount equivalent to 4 parts, a glass transition temperature of ⁇ 48 ° C.
- a slurry composition for forming a conductive adhesive layer was prepared by mixing 8 parts of a 40% aqueous dispersion of a 25 ⁇ m diene polymer corresponding to a solid content and ion-exchanged water so that the total solid concentration was 30%. Prepared.
- a pair of dies are collected so as to sandwich an expanded aluminum current collector (percentage of holes penetrating the front and back surfaces: 40 area%) with a thickness of 30 ⁇ m that travels vertically (the current collector travels from the bottom upward).
- the slurry composition for forming the conductive adhesive layer is discharged from a pair of dies, and applied to both the front and back surfaces of the current collector at a molding speed of 30 m / min. And dried at 120 ° C. for 5 minutes to form a conductive adhesive layer.
- an electrode active material for the positive electrode 100 parts of an activated carbon powder (MSP-20; manufactured by Kansai Thermochemical Co., Ltd.) having a volume average particle size of 8 ⁇ m, which is an alkali activated carbon made from phenol resin, and carboxymethyl cellulose ammonium as a dispersant.
- MSP-20 manufactured by Kansai Thermochemical Co., Ltd.
- aqueous solution (DN-800H; manufactured by Daicel Chemical Industries, Ltd.) corresponding to a solid content of 2.0 parts, and 5 parts of acetylene black (denka black powder; manufactured by Denki Kagaku Kogyo Co., Ltd.) as a conductive material, electrode composition
- a 40% aqueous dispersion of a diene polymer having a glass transition temperature of ⁇ 48 ° C. and a number average particle size of 0.25 ⁇ m is equivalent to a solid content of 3.0 parts
- ion-exchanged water is a total solid content concentration Was mixed by a planetary mixer so as to be 35% to prepare a positive electrode composition.
- Running in the vertical direction (the running direction of the current collector is from the bottom to the top) so as to sandwich the expanded aluminum current collector (percentage of holes penetrating the front and back surfaces: 40 area%) with the conductive adhesive layer formed thereon.
- a pair of dies are arranged downstream with respect to the traveling direction of the current collector, the positive electrode composition is discharged from the pair of dies, and applied to both the front and back surfaces of the current collector at an electrode forming speed of 20 m / min. Then, after drying at 120 ° C. for 5 minutes, it was punched out in a square of 5 cm to obtain a positive electrode for a lithium ion capacitor having an electrode composition layer with a thickness of 100 ⁇ m on one side.
- a pair of dies are collected so as to sandwich an expanded copper current collector (percentage of holes penetrating the front and back surfaces: 40 area%) having a thickness of 20 ⁇ m that travels in the vertical direction (the travel direction of the current collector is from the bottom to the top).
- the slurry composition for forming the conductive adhesive layer is discharged from a pair of dies, and applied to both the front and back surfaces of the current collector at a molding speed of 30 m / min. And dried at 120 ° C. for 5 minutes to form a conductive adhesive layer.
- a 40% aqueous dispersion of a diene polymer having a number average particle size of 0.25 ⁇ m is mixed to a solid content equivalent to 3.0 parts, and ion-exchanged water is mixed to a total solid content concentration of 35% to obtain a negative electrode A composition was prepared.
- Running in the vertical direction (the running direction of the current collector is from the bottom to the top) so as to sandwich the expanded copper current collector with the conductive adhesive layer formed thereon (ratio of holes penetrating the front and back surfaces: 40 area%)
- a pair of dies are arranged downstream with respect to the running direction of the current collector, the negative electrode composition is discharged from the pair of dies, and applied to both the front and back surfaces of the current collector at an electrode forming speed of 20 m / min. Then, after drying at 120 ° C. for 5 minutes, it was punched out in a square of 5 cm to obtain a negative electrode for a lithium ion capacitor having an electrode composition layer having a thickness of 100 ⁇ m on one side.
- the electrolyte solution was impregnated with a cellulose / rayon nonwoven fabric as the positive electrode, the negative electrode for lithium ion capacitor and the separator at room temperature for 1 hour.
- the positive electrode lithium ion capacitor electrode and the negative electrode lithium ion capacitor electrode are opposed to each other via a separator, and the respective lithium ion capacitor electrodes are not electrically contacted with each other.
- 10 pairs of negative electrodes were arranged to produce a laminated laminate cell shaped lithium ion capacitor.
- the electrolytic solution a solution obtained by dissolving LiPF 6 at a concentration of 1.0 mol / liter in a mixed solvent of ethylene carbonate, diethyl carbonate and propylene carbonate in a weight ratio of 3: 4: 1 was used.
- a lithium electrode of the laminated laminate cell As a lithium electrode of the laminated laminate cell, a lithium metal foil (82 ⁇ m thick, 5 cm long ⁇ 5 cm wide) bonded to an 80 ⁇ m thick stainless steel mesh is used, and the lithium electrode is completely opposed to the outermost negative electrode. One electrode was placed on each of the upper and lower portions of the stacked electrodes. In addition, the terminal welding part (two sheets) of the lithium electrode current collector was resistance welded to the negative electrode terminal welding part. Table 1 shows the measurement results for each characteristic of the lithium ion capacitor.
- Example 2 In Example 1, instead of carbon particles B1, carbon black having a volume average particle size of 0.3 ⁇ m and an electric resistivity of 0.07 ⁇ ⁇ cm (acetylene black; manufactured by Denki Kagaku Kogyo Co., Ltd., hereinafter “carbon particles” is used as carbon particles.
- An electrode for a lithium ion capacitor and a lithium ion capacitor were produced in the same manner as in Example 1 except that “A1” may be used. Table 1 shows the measurement results for each characteristic of the lithium ion capacitor.
- Example 3 In Example 1, instead of the carbon particles B1, carbon black (Super-P; manufactured by Timcal Corporation, hereinafter referred to as “carbon particles A2” having a volume average particle diameter of 0.3 ⁇ m and an electric resistivity of 0.06 ⁇ ⁇ cm was used as the carbon particles.
- the electrode for lithium ion capacitors and the lithium ion capacitor were produced in the same manner as in Example 1 except that the above was used. Table 1 shows the measurement results for each characteristic of the lithium ion capacitor.
- Example 4 In Example 1, instead of carbon particles B1, carbon black having a volume average particle size of 0.3 ⁇ m and an electric resistivity of 0.02 ⁇ ⁇ cm (BMAB; manufactured by Denki Kagaku Kogyo Co., Ltd., hereinafter “carbon particles A3” is used as carbon particles.
- BMAB manufactured by Denki Kagaku Kogyo Co., Ltd.
- carbon particles A3 The electrode for lithium ion capacitors and the lithium ion capacitor were produced in the same manner as in Example 1 except that the above was used. Table 1 shows the measurement results for each characteristic of the lithium ion capacitor.
- Example 8 In Example 6, an acrylate polymer having a glass transition temperature of ⁇ 20 ° C. and a number average particle diameter of 0.25 ⁇ m was used instead of a diene polymer as a binder for a conductive adhesive used in the conductive adhesive slurry composition.
- Example 6 is the same as Example 6 except that 76 parts by weight of 2-ethylhexyl acrylate, 20% by weight of acrylonitrile, and 4% by weight of itaconic acid are copolymerized by emulsion polymerization) Similarly, an electrode for a lithium ion capacitor and a lithium ion capacitor were produced. Table 1 shows the measurement results for each characteristic of the lithium ion capacitor.
- a copolymer obtained by emulsion polymerization of 76% by weight of 2-ethylhexyl, 20% by weight of acrylonitrile, and 4% by weight of itaconic acid) is equivalent to a solid content of 8 parts, and ion exchange water has a total solid content concentration of 8 parts.
- a slurry composition for forming a conductive adhesive layer was prepared by mixing at 30%.
- a pair of dies are collected so as to sandwich an expanded aluminum current collector (percentage of holes penetrating the front and back surfaces: 40 area%) with a thickness of 30 ⁇ m that travels vertically (the current collector travels from the bottom upward).
- the slurry composition for forming the conductive adhesive layer is discharged from a pair of dies, and applied to both the front and back surfaces of the current collector at a molding speed of 30 m / min. And dried at 120 ° C. for 5 minutes to form a conductive adhesive layer.
- an electrode active material for the positive electrode 100 parts of activated carbon powder (MSP-20; manufactured by Kansai Thermal Chemical Co., Ltd.) having a volume average particle diameter of 8 ⁇ m, which is an alkali activated carbon made from phenol resin, and 1.5 parts of carboxymethyl cellulose as a dispersant.
- % Aqueous solution (DN-800H; manufactured by Daicel Chemical Industries, Ltd.) in terms of solid content, 2.0 parts, 5 parts of acetylene black (Denka black powder; manufactured by Denki Kagaku Kogyo Co., Ltd.) as a conductive material, and glass as a binder for an electrode composition 40 of an acrylate polymer having a transition temperature of ⁇ 12 ° C.
- % Aqueous dispersion was mixed to a solid content of 3.0 parts, and ion-exchanged water was mixed so that the total solid content concentration was 35%.
- a slurry for the composition layer was prepared.
- electrode composition layer (electrode composition) of a spherical positive electrode having a volume average particle diameter of 56 ⁇ m and a sphericity of 93%.
- the composite particle for an electrode composition layer of the positive electrode and the expanded aluminum current collector on which the conductive adhesive layer is formed are supplied to a roll press machine (pressed rough surface heat roll; manufactured by Hirano Giken Co., Ltd.), and the molding speed Roll press molding is performed under the conditions of 20 m / min, roll temperature of 100 ° C., press linear pressure of 3.9 kN / cm, and this is sequentially molded on both sides of the current collector to have an electrode composition layer with a thickness of 200 ⁇ m on one side.
- a positive electrode for a lithium ion capacitor was obtained.
- a pair of dies are collected so as to sandwich an expanded copper current collector (percentage of holes penetrating the front and back surfaces: 40 area%) having a thickness of 20 ⁇ m that travels in the vertical direction (the travel direction of the current collector is from the bottom to the top).
- the slurry composition for forming the conductive adhesive layer is discharged from a pair of dies, and applied to both the front and back surfaces of the current collector at a molding speed of 30 m / min. And dried at 120 ° C. for 5 minutes to form a conductive adhesive layer.
- a 40% aqueous dispersion of a 0.25 ⁇ m acrylate polymer (a copolymer obtained by emulsion polymerization of 70 parts of 2-ethylhexyl acrylate, 15 parts of acrylonitrile, and 15 parts of itaconic acid) is 3.0 parts in terms of solid content.
- ion-exchanged water are mixed so that the total solid concentration is 35% to prepare a slurry for the electrode composition layer of the negative electrode.
- this slurry was sprayed using a spray dryer (OC-16; manufactured by Okawara Chemical Co., Ltd.).
- the rotating disk type atomizer (diameter 65 mm) had a rotational speed of 25,000 rpm, a hot air temperature of 150 ° C., and a particle recovery outlet temperature.
- Spray drying granulation was performed under the condition of 90 ° C. to obtain composite particles (electrode composition) for the electrode composition layer of a spherical negative electrode having a volume average particle diameter of 28 ⁇ m and a sphericity of 93%.
- the composite particles for the electrode composition layer of the negative electrode and the expanded aluminum current collector on which the conductive adhesive layer is formed are supplied to a roll press machine (pressed rough surface heat roll; manufactured by Hirano Giken Co., Ltd.), and the forming speed is increased.
- Roll press molding is performed under the conditions of 20 m / min, roll temperature of 100 ° C., and press linear pressure of 3.9 kN / cm, and this is sequentially molded on both sides of the current collector to have an electrode composition layer with a thickness of 100 ⁇ m on one side.
- a negative electrode for a lithium ion capacitor was obtained.
- Example 1 A lithium ion capacitor was produced in the same manner as in Example 1 except that the electrode obtained above was used as the positive electrode for the lithium ion capacitor and the negative electrode for the lithium ion capacitor. Table 1 shows the measurement results for each characteristic of the lithium ion capacitor electrode and the lithium ion capacitor.
- Example 1 (Comparative Example 1) In Example 1, a 30 ⁇ m thick expanded aluminum current collector without forming a conductive adhesive layer as a positive electrode current collector, and a 20 ⁇ m thick expanded material without forming a conductive adhesive layer as a negative electrode current collector An electrode for a lithium ion capacitor and a lithium ion capacitor were produced in the same manner as in Example 1 except that a copper current collector was used. Table 1 shows the measurement results for each characteristic of the lithium ion capacitor.
- the electrode strength is excellent, the internal resistance is low, that is, the output density is high, and the durability can be increased. Become.
- Comparative Example 1 having no conductive adhesive layer has high internal resistance, and is inferior in durability and peel strength of the electrode.
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Abstract
Description
本発明のリチウムイオンキャパシタ用電極に用いる集電体の材料は、例えば、金属、炭素、導電性高分子などを用いることができ、好適には金属が用いられる。集電体用金属としては、通常、アルミニウム、白金、ニッケル、タンタル、チタン、ステンレス鋼、銅、その他の合金等が使用される。これらの中で導電性、耐電圧性の面から銅、アルミニウムまたはアルミニウム合金を使用するのが好ましい。
本発明のリチウムイオンキャパシタ用電極の導電性接着剤層に用いる炭素粒子とは、炭素のみ、又は実質的に炭素のみからなる粒子である。その具体例としては、非局在化したπ電子の存在によって高い導電性を有する黒鉛(具体的には天然黒鉛、人造黒鉛など);黒鉛質の炭素微結晶が数層集まって乱層構造を形成した球状集合体であるカーボンブラック(具体的にはアセチレンブラック、ケッチェンブラック、その他のファーネスブラック、チャンネルブラック、サーマルランプブラックなど);炭素繊維やカーボンウィスカーなどが挙げられ、これらの中でも、導電性接着剤層の炭素粒子が高密度に充填し、電子移動抵抗を低減でき、さらにリチウムイオンキャパシタの内部抵抗をより低減できる点で、黒鉛又はカーボンブラックが、特に好ましい。
本発明のリチウムイオンキャパシタ用電極の導電性接着剤層に好適に用いる導電性接着剤用バインダーは、炭素粒子を相互に結着させることができる化合物であれば特に制限はない。好適なバインダーは、溶媒に分散する性質のある分散型バインダーである。分散型バインダーとして、例えば、フッ素重合体、ジエン重合体、アクリレート重合体、ポリイミド、ポリアミド、ポリウレタン重合体等の高分子化合物が挙げられ、フッ素重合体、ジエン重合体又はアクリレート重合体が好ましく、ジエン重合体又はアクリレート重合体が、耐電圧を高くでき、かつリチウムイオンキャパシタのエネルギー密度を高くすることができる点でより好ましい。
本発明のリチウムイオンキャパシタ用電極に用いる電極活物質は、リチウムイオンキャパシタ用電極内で電子の受け渡しをする物質である。
本発明のリチウムイオンキャパシタ用電極に用いる導電材は、導電性を有し、電気二重層を形成し得る細孔を有さない、粒子状の炭素の同素体からなり、具体的には、ファーネスブラック、アセチレンブラック、及びケッチェンブラック(アクゾノーベル ケミカルズ ベスローテン フェンノートシャップ社の登録商標)などの導電性カーボンブラックが挙げられる。これらの中でも、アセチレンブラックおよびファーネスブラックが好ましい。
本発明のリチウムイオンキャパシタ用電極の電極組成物層に用いるバインダーは、電極活物質、導電材を相互に結着させることができる化合物であれば特に制限はない。好適なバインダーは、溶媒に分散する性質のある分散型バインダーである。分散型バインダーとして、例えば、フッ素重合体、ジエン重合体、アクリレート重合体、ポリイミド、ポリアミド、ポリウレタン重合体等の高分子化合物が挙げられ、フッ素重合体、ジエン重合体又はアクリレート重合体が好ましく、ジエン重合体又はアクリレート重合体が、耐電圧を高くでき、かつリチウムイオンキャパシタのエネルギー密度を高くすることができる点でより好ましい。
本発明のリチウムイオンキャパシタ用電極の電極組成物層は、導電性接着剤層上に設けられるが、その形成方法は制限されない。具体的には、1)電極活物質、導電材およびバインダーを混練してなる電極形成用組成物を、シート成形し、得られたシート状電極形成用組成物を、導電性接着剤層を形成した集電体上に積層する方法(混練シート成形法)、2)電極活物質、導電材およびバインダーを含んでなるペースト状の電極形成用組成物を調製し、導電性接着剤層を形成した集電体上に塗布し、乾燥する方法(湿式成形法)、3)電極活物質、導電材およびバインダーを含んでなる複合粒子を調製し、導電性接着剤層を形成した集電体上にシート成形、ロールプレスし得る方法(乾式成形法)などが挙げられる。中でも、2)湿式成形法、3)乾式成形法が好ましく、3)乾式成形法が得られるリチウムイオンキャパシタの容量を高く、且つ内部抵抗を低減できる点でより好ましい。
本発明のリチウムイオンキャパシタは、正極、負極、電解液及びセパレータを有し、前記正極又は負極が、前記電極であることを特徴とする。本発明のリチウムイオンキャパシタにおいては、正極及び負極が、前記リチウムイオンキャパシタ用電極であることが好ましい。正極及び負極が、前記リチウムイオンキャパシタ用電極であることにより、リチウムイオンキャパシタの耐久性をより向上させることができる。
実施例および比較例で製造するリチウムイオンキャパシタ用電極を用いて積層型ラミネートセルのリチウムイオンキャパシタを作製する。このリチウムイオンキャパシタの電池特性として、容量と内部抵抗について、24時間静置させた後に充放電の操作を行い測定する。ここで、充電は2Aの定電流で開始し、電圧が3.6Vに達したらその電圧を1時間保って定電圧充電とする。また、放電は充電終了直後に定電流0.9Aで1.9Vに達するまで行う。
また、耐久性は、リチウムイオンキャパシタを、70℃の恒温槽内で3.6V、1000時間連続印加後の初期容量に対する容量維持率を算出し、以下の基準で評価を行う。容量維持率が大きいほど耐久性に優れる。
B:容量維持率が80%以上90%未満
C:容量維持率が80%未満
電極組成物層の塗布方向が長辺となるようにリチウムイオンキャパシタ用電極を長さ100mm、幅10mmの長方形に切り出して試験片とし、電極組成物層面を下にして電極組成物層表面にセロハンテープ(JIS Z1522に規定されるもの)を貼り付け、集電体の一端を垂直方向に引張り速度50mm/分で引張って剥がしたときの応力を測定する(なお、セロハンテープは試験台に固定されている。)。この測定を3回行い、その平均値を求めてこれをピール強度とし、以下の基準で評価する。ピール強度が大きいほど電極組成物層の集電体への結着力が大きい、すなわち電極強度が大きいことを示す。
B:ピール強度が10N/m以上20N/m未満
C:ピール強度が10N/m未満
炭素粒子として体積平均粒子径が3.7μm、電気抵抗率0.004Ω・cmの黒鉛(KS-6;ティムカル社製、以下「炭素粒子B1」と記すことがある。)を100部、分散剤としてカルボキシメチルセルロースの4.0%水溶液(DN-10L;ダイセル化学工業社製)を固形分相当で4部、導電性接着剤用バインダーとしてガラス転移温度が-48℃で、数平均粒子径が0.25μmのジエン重合体の40%水分散体を固形分相当で8部及びイオン交換水を全固形分濃度が30%となるように混合し、導電性接着剤層形成用のスラリー組成物を調製した。
実施例1において、炭素粒子として、炭素粒子B1のかわりに、体積平均粒子径が0.3μm、電気抵抗率0.07Ω・cmのカーボンブラック(アセチレンブラック;電気化学工業社製、以下「炭素粒子A1」と記すことがある。)を用いる他は、実施例1と同様にしてリチウムイオンキャパシタ用電極、リチウムイオンキャパシタを作製した。このリチウムイオンキャパシタの各特性について測定結果を表1に示す。
実施例1において、炭素粒子として、炭素粒子B1のかわりに、体積平均粒子径が0.3μm、電気抵抗率0.06Ω・cmのカーボンブラック(Super-P;ティムカル社製、以下「炭素粒子A2」と記すことがある。)を用いる他は、実施例1と同様にしてリチウムイオンキャパシタ用電極、リチウムイオンキャパシタを作製した。このリチウムイオンキャパシタの各特性について測定結果を表1に示す。
実施例1において、炭素粒子として、炭素粒子B1のかわりに、体積平均粒子径が0.3μm、電気抵抗率0.02Ω・cmのカーボンブラック(BMAB;電気化学工業社製、以下「炭素粒子A3」と記すことがある。)を用いる他は、実施例1と同様にしてリチウムイオンキャパシタ用電極、リチウムイオンキャパシタを作製した。このリチウムイオンキャパシタの各特性について測定結果を表1に示す。
実施例1において、炭素粒子として、炭素粒子(A)として炭素粒子A3を10部、炭素粒子(B)として炭素粒子B1を90部(炭素粒子(A)/炭素粒子(B)の重量比=0.11)を用いる他は、実施例1と同様にしてリチウムイオンキャパシタ用電極、リチウムイオンキャパシタを作製した。このリチウムイオンキャパシタの各特性について測定結果を表1に示す。
実施例1において、炭素粒子として、炭素粒子(A)として炭素粒子A3を20部、炭素粒子(B)として炭素粒子B1を80部(炭素粒子(A)/炭素粒子(B)の重量比=0.25)を用いる他は、実施例1と同様にしてリチウムイオンキャパシタ用電極、リチウムイオンキャパシタを作製した。このリチウムイオンキャパシタの各特性について測定結果を表1に示す。
実施例1において、炭素粒子として、炭素粒子(A)として炭素粒子A3を50部、炭素粒子(B)として炭素粒子B1を50部(炭素粒子(A)/炭素粒子(B)の重量比=1)を用いる他は、実施例1と同様にしてリチウムイオンキャパシタ用電極、リチウムイオンキャパシタを作製した。このリチウムイオンキャパシタの各特性について測定結果を表1に示す。
実施例6において、導電性接着剤スラリー組成物に用いる導電接着剤用バインダーとして、ジエン重合体のかわりに、ガラス転移温度が-20℃で、数平均粒子径が0.25μmのアクリレート重合体(アクリル酸2-エチルヘキシル76重量%、アクリロニトリル20重量%、イタコン酸4重量%を乳化重合により得られる共重合体)の40%水分散体を固形分相当で8部用いる他は、実施例6と同様にしてリチウムイオンキャパシタ用電極、リチウムイオンキャパシタを作製した。このリチウムイオンキャパシタの各特性について測定結果を表1に示す。
炭素粒子として、前記炭素粒子A3を20部、炭素粒子B1を80部(炭素粒子(A)/炭素粒子(B)の重量比=0.25)、分散剤としてカルボキシメチルセルロースの4.0%水溶液(DN-10L;ダイセル化学工業社製)を固形分相当で4部、導電性接着剤用バインダーとしてガラス転移温度が-20℃で、数平均粒子径が0.25μmのアクリレート重合体(アクリル酸2-エチルヘキシル76重量%、アクリロニトリル20重量%、イタコン酸4重量%を乳化重合により得られる共重合体)の40%水分散体を固形分相当で8部及びイオン交換水を全固形分濃度が30%となるように混合し、導電性接着剤層形成用のスラリー組成物を調製した。
実施例1において、正極用集電体として導電性接着剤層を形成していない厚み30μmのエキスパンドアルミニウム集電体、負極用集電体として導電性接着剤層を形成していない厚み20μmのエキスパンド銅集電体を用いる他は、実施例1と同様にしてリチウムイオンキャパシタ用電極、リチウムイオンキャパシタを作製した。このリチウムイオンキャパシタの各特性について測定結果を表1に示す。
Claims (9)
- 電極活物質、導電材およびバインダーを含有してなる電極組成物層と集電体とを有するリチウムイオンキャパシタ用電極であって、前記電極組成物層と集電体との間に、炭素粒子を含有してなる導電性接着剤層を有することを特徴とするリチウムイオンキャパシタ用電極。
- 前記集電体が、貫通する孔を有する集電体である請求項1に記載のリチウムイオンキャパシタ用電極。
- 前記炭素粒子が、黒鉛又はカーボンブラックである請求項1または2に記載のリチウムイオンキャパシタ用電極。
- 前記炭素粒子の電気抵抗率が、0.0001~1Ω・cmである請求項1~3のいずれかに記載のリチウムイオンキャパシタ用電極。
- 前記炭素粒子の体積平均粒子径分布が、バイモーダルである請求項1~4のいずれかに記載のリチウムイオンキャパシタ用電極。
- 前記炭素粒子が、体積平均粒子径が0.01μm以上1μm未満である炭素粒子(A)と体積平均粒子径が1μm以上10μm以下である炭素粒子(B)とを含むものである請求項1~5のいずれかに記載のリチウムイオンキャパシタ用電極。
- 前記炭素粒子(A)と炭素粒子(B)との重量比が、(A)/(B)の比で0.05~1の範囲である請求項6に記載のリチウムイオンキャパシタ用電極。
- 前記導電性接着剤層が、さらに導電性接着剤用バインダーとして、(メタ)アクリレート重合体又はジエン重合体を含んでなるものである請求項1~7記載のリチウムイオンキャパシタ用電極。
- 正極、負極、電解液及びセパレータを有し、前記正極又は負極が、請求項1~8のいずれかに記載の電極であるリチウムイオンキャパシタ。
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CN2009801426013A CN102203891A (zh) | 2008-08-28 | 2009-08-27 | 锂离子电容器用电极以及锂离子电容器 |
KR1020117004590A KR101455445B1 (ko) | 2008-08-28 | 2009-08-27 | 리튬 이온 커패시터용 전극 및 리튬 이온 커패시터 |
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Cited By (9)
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CN102618097A (zh) * | 2011-01-28 | 2012-08-01 | 日立化成工业株式会社 | 锂离子电池用导电基底涂料、锂离子电池用电极以及锂离子电池 |
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CN102618097A (zh) * | 2011-01-28 | 2012-08-01 | 日立化成工业株式会社 | 锂离子电池用导电基底涂料、锂离子电池用电极以及锂离子电池 |
CN102618097B (zh) * | 2011-01-28 | 2016-09-28 | 日立化成工业株式会社 | 锂离子电池用导电基底涂料、锂离子电池用电极以及锂离子电池 |
CN102746805A (zh) * | 2011-04-18 | 2012-10-24 | 日立化成工业株式会社 | 电容器用导电基底涂料、电容器用电极以及双电层电容器和锂离子电容器 |
CN102746805B (zh) * | 2011-04-18 | 2017-04-12 | 日立化成工业株式会社 | 电容器用导电基底涂料、电容器用电极以及双电层电容器和锂离子电容器 |
KR20140051893A (ko) | 2011-08-03 | 2014-05-02 | 제온 코포레이션 | 전기 화학 소자 전극용 도전성 접착제 조성물, 접착제층이 부착된 집전체 및 전기 화학 소자 전극 |
JP2013077734A (ja) * | 2011-09-30 | 2013-04-25 | Asahi Kasei Corp | 電極およびその製造方法 |
WO2013146548A1 (ja) | 2012-03-26 | 2013-10-03 | 日本ゼオン株式会社 | 二次電池負極用複合粒子、その用途及び製造方法、並びにバインダー組成物 |
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JP2014120757A (ja) * | 2012-12-14 | 2014-06-30 | Samsung Electro-Mechanics Co Ltd | 電極構造物およびそれを備えるエネルギー貯蔵装置 |
US9773620B2 (en) | 2013-04-24 | 2017-09-26 | Commissariat à l'énergie atomique et aux énergies alternatives | Electrochemical supercapacitor device made from an electrolyte comprising, as a conductive salt, at least one salt made from an alkali element other than lithium |
JP2016029629A (ja) * | 2014-07-22 | 2016-03-03 | 日本ゼオン株式会社 | 電気化学素子電極用複合粒子、電気化学素子電極、電気化学素子、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の製造方法 |
WO2024053362A1 (ja) * | 2022-09-06 | 2024-03-14 | 日産化学株式会社 | 蓄電デバイス用導電性結着層形成用組成物 |
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JPWO2010024327A1 (ja) | 2012-01-26 |
JP2014075597A (ja) | 2014-04-24 |
KR20110045024A (ko) | 2011-05-03 |
US20110157773A1 (en) | 2011-06-30 |
KR101455445B1 (ko) | 2014-10-27 |
JP5423991B2 (ja) | 2014-02-19 |
US8564933B2 (en) | 2013-10-22 |
CN102203891A (zh) | 2011-09-28 |
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