US20160006036A1 - Carbon material and electrode material using same - Google Patents

Carbon material and electrode material using same Download PDF

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Publication number
US20160006036A1
US20160006036A1 US14/768,932 US201414768932A US2016006036A1 US 20160006036 A1 US20160006036 A1 US 20160006036A1 US 201414768932 A US201414768932 A US 201414768932A US 2016006036 A1 US2016006036 A1 US 2016006036A1
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carbon material
conductive polymer
dispersion
polyaniline
carbon
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Tsukasa Maruyama
Tomoyuki Sakai
Yoshimasa Imazaki
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Yokohama Rubber Co Ltd
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Yokohama Rubber Co Ltd
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Assigned to THE YOKOHAMA RUBBER CO., LTD. reassignment THE YOKOHAMA RUBBER CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: IMAZAKI, YOSHIMASA, MARUYAMA, TSUKASA, SAKAI, TOMOYUKI
Publication of US20160006036A1 publication Critical patent/US20160006036A1/en
Priority to US15/819,102 priority Critical patent/US10128505B2/en
Abandoned legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • 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
    • H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/38—Carbon pastes or blends; Binders or additives therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/48—Conductive polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the present invention relates to a carbon material, an electrode material using same, and an electrochemical element.
  • Lithium ion secondary batteries and electric double-layer capacitors are known as electrochemical elements.
  • the lithium ion secondary battery has higher energy density and is capable of operation over a longer time interval.
  • the electric double-layer capacitor is capable of rapid electrical charging and discharging, and working life over repeated uses is longer.
  • lithium ion capacitor that combines the advantages of both the lithium ion secondary battery and the electric double-layer capacitor has been developed as an electrochemical element, and in addition, from the perspective of cost, a sodium ion capacitor (sodium ion electrical storage device) has been developed.
  • Patent Document 1 the present applicants have provided “an electrode material for an electric double-layer capacitor using a polyaniline/carbon composite that is a composite of polyaniline or a derivative thereof with a carbonaceous material selected from activated carbon, ketjen black, acetylene black, and furnace black, wherein the polyaniline or derivative thereof is conductive polyaniline dispersed in a nonpolar organic solvent that is undoped by a base treatment” as an electric double-layer capacitor.
  • Patent Document 2 provides “a composite of a conductive polymer that includes a nitrogen atom and a porous carbon material, obtained by bonding the conductive polymer to the surface of the porous carbon material, and after mixing the conductive polymer and the porous carbon material, undoping by heat treatment at a temperature at least 20° C.
  • the total pore volume of all pores having a diameter of 0.5 to 100.0 nm measured by the BJH method is 0.3 to 3.0 cm 3 /g, and the pore volume of pores having a diameter of 2.0 nm or more and less than 20.0 nm measured by the BJH method as a percentage of the total pore volume is 10% or more”.
  • an electrode material for a lithium ion capacitor that includes a composite of a conductive polymer having a nitrogen atom and a porous carbon material as active material, obtained by bonding the conductive polymer to the surface of the porous carbon material, and after mixing the conductive polymer and the porous carbon material, undoping by heat treatment at a temperature at least 20° C.
  • the total pore volume of all pores having a diameter of 0.5 to 100.0 nm measured by the BJH method is 0.3 to 3.0 cm 3 /g, and the pore volume of pores having a diameter of 2.0 nm or more and less than 20.0 nm measured by the BJH method as a percentage of the total pore volume is 10% or more”.
  • Patent Document 1 Japanese Patent No. 4294067
  • Patent Document 2 Japanese Patent No. 5110147
  • Patent Document 3 Japanese Patent No. 5041058
  • an electrochemical element with high electrostatic capacitance could be obtained by using as the electrode material a carbon material having specific surface area and methylene blue adsorption performance within predetermined ranges, and, having a specific number of peaks in a predetermined Raman spectrum.
  • the present invention provides the following (1) to (9).
  • the conductive polymer is a conductive polymer that includes a nitrogen atom and/or a conductive polymer that includes a sulfur atom.
  • the carbon material according to No. 4 above, wherein the conductive polymer that includes a nitrogen atom is at least one selected from the group consisting of polyaniline, polypyrrole, polypyridine, polyquinoline, polythiazole, polyquinoxaline, and derivatives thereof.
  • an electrode material and a carbon material used in the electrode material that enable an electrochemical element with high electrostatic capacitance to be obtained.
  • FIG. 1 is a chart showing the Raman spectrum of a carbon material prepared in Working Example 1 and a Standard Example.
  • the carbon material according to the present invention is a carbon material that has a specific surface area of 750 to 3000 m 2 /g, has a methylene blue adsorption performance of 150 mL/g or more, and has at least three peaks in the range 1250 to 1700 cm ⁇ 1 in a spectrum obtained by laser Raman spectroscopy with an excitation wavelength of 532 nm (hereafter simply referred to as “Raman spectrum”).
  • specific surface area refers to the value obtained from a measurement taken using the nitrogen adsorption BET method in accordance with the method stipulated in JIS K 1477: 2007.
  • methylene blue adsorption performance refers to the value calculated from the amount of methylene blue solution adsorbed, in accordance with the activated carbon test method prescribed in JIS K 1474: 2007.
  • the “Raman spectrum” refers to a spectrum for light scattered as per the Raman effect that indicates how strongly a particular wavelength of light is scattered, and in the present invention it refers to the spectrum measured with an excitation wavelength of 532 nm using a micro laser Raman spectrograph HoloLab 5000R (Kaiser Optical Systems Inc.).
  • the range of the specific surface area of the carbon material according to the present invention (750 to 3000 m 2 /g) is prescribed to be about the same as the specific surface area of porous carbon materials such as activated carbon and the like, and as indicated by the Working Examples and Comparative Examples described below, is prescribed to be different than the specific surface area of the electrode material disclosed in Patent Document 1.
  • the value of the methylene blue adsorption performance of the carbon material according to the present invention is prescribed to have a similar value to that of porous carbon material, the same as for the specific surface area, and as indicated by the Working Examples and Comparative Examples described below, is prescribed to have a different methylene blue adsorption performance to that of the electrode material disclosed in Patent Document 1.
  • the prescription of the Raman spectrum of the carbon material according to the present invention (at least three peaks within the range 1250 to 1700 cm ⁇ 1 ) means that there is at least one peak apart from the peaks originating from the SP 2 carbon bond in commonly known carbon materials (for example, activated carbon, carbon black, and the like) at about 1350 cm ⁇ 1 and about 1600 cm ⁇ 1 , which prescribes that the carbon material according to the present invention is not made from porous carbon material only.
  • commonly known carbon materials for example, activated carbon, carbon black, and the like
  • the carbon material according to the present invention has surface properties that are similar to those of porous carbon materials, it is considered that organic material (for example, conductive polymers as described below) exists selectively in the interior thereof (for example, within the pores of the porous carbon material), so there is no contact resistance, there is no hindrance to the adsorption (intercalation) of supporting electrolyte that exists within the electrolyte, so it is possible to increase the electrostatic capacitance.
  • organic material for example, conductive polymers as described below
  • the specific surface area of the carbon material according to the present invention is 750 to 2800 m 2 /g, and more preferably is 800 to 2600 m 2 /g.
  • the isoelectric point of the carbon material according to the present invention is within the range pH 3.5 to pH 5.0.
  • the carbon material according to the present invention has a methylene blue adsorption performance of 150 to 300 mL/g, and more preferably 160 to 300 mL/g.
  • the carbon material according to the present invention has a zeta potential isoelectric point within the range pH 3.0 to pH 5.5.
  • zeta potential isoelectric point refers to the pH at zero zeta potential measured by laser Doppler electrophoresis, in accordance with the method of measurement of the isoelectric point prescribed by JIS R 1638:1999.
  • the range of the zeta potential isoelectric point (pH 3.0 to pH 5.5) is prescribed to be similar to that of the isoelectric point of porous carbon materials, the same as for the specific surface area, and as indicated by the Working Examples and Comparative Examples described below, is prescribed to have a different isoelectric point to that of the electrode material disclosed in Patent Document 1.
  • the carbon material according to the present invention can maintain semi-permanent charging and discharging properties and high-speed charging and discharging properties, and to provide an electrode material that enables an electrochemical element with even higher electrostatic capacitance to be obtained, preferably it is made from a composite of a porous carbon material and a conductive polymer as described below.
  • composite generally means a material resulting from compositing and integrating (combining two or more materials), however in the present invention it refers to the state in which at least a portion of the conductive polymer is adsorbed inside the pores of the porous carbon material.
  • the polymer may be doped by a dopant or may be a polymer obtained by undoping a polymer, for example it may be a conductive polymer that contains a nitrogen atom (hereafter referred to as a “nitrogen-containing conductive polymer”), a conductive polymer containing a sulfur atom (hereafter referred to as a “sulfur-containing conductive polymer”), or a polyfluorene derivative, and the like.
  • a nitrogen-containing conductive polymer or a sulfur-containing conductive polymer described below is preferable for reasons of electrochemical stability and ease of procurement.
  • nitrogen-containing conductive polymer examples include polyaniline, polypyrrole, polypyridine, polyquinoline, polythiazole, polyquinoxaline, and derivatives and the like thereof. One of these may be used alone, or two or more may be used in combination.
  • sulfur-containing conductive polymer examples include polythiophene, polycyclopentadithiophene, and derivatives and the like thereof. One of these may be used alone, or two or more may be used in combination.
  • nitrogen-containing conductive polymer are preferred, and polyaniline, polypyridine, and derivatives thereof are more preferred due to low cost of the raw materials and ease of synthesis.
  • the average molecular weight of the a conductive polymer is 1000 to 2,000,000, more preferably is 3000 to 1,500,000, and still more preferably is 5000 to 1,000,000.
  • the average molecular weight is measured using gel permeation chromatography (GPC), and refers to the value converted with polystyrene of known molecular weight, or, the value measured by a light scattering method (static light scattering method).
  • GPC gel permeation chromatography
  • the method of preparing the conductive polymer it can be manufactured as a dispersion of the conductive polymer, by chemical polymerization (for example, oxidative polymerization, dehalogenation polymerization, and the like) of the corresponding monomer (for example aniline, pyridine, and the like) in a non-polar solvent or an aprotic solvent.
  • chemical polymerization for example, oxidative polymerization, dehalogenation polymerization, and the like
  • the corresponding monomer for example aniline, pyridine, and the like
  • the aforementioned dopants or additives for chemical polymerization can be any of those disclosed in Patent Document 1.
  • a commercially available product can be used as the conductive polymer.
  • Specific commercially available products include, for example, polyaniline organic solvent dispersion manufactured by Nissan Chemical Industries, Ltd. (trade name: Ormecon), polyaniline aqueous dispersion manufactured by Nissan Chemical Industries, Ltd., polyaniline dispersion manufactured by Kaken Sangyo K.K (toluene dispersion, aqueous dispersion), polyaniline xylene dispersion manufactured by Sigma-Aldrich Co. Llc., polythiophene dispersion manufactured by Shin-Etsu Polymer Co., Ltd. (trade name: SEPLEGYDA), polythiophene dispersion manufactured by Sigma-Aldrich Co. Llc. (product numbers: 483095, 739324, 739332, and the like), polypyrrole dispersion manufactured by Japan Carlit Co., Ltd., and the like.
  • the porous carbon material which constitutes the composite is a carbon material having a specific surface area of 750 to 3000 m 2 /g.
  • porous carbon material examples include activated carbon, carbon black, carbon nanotubes, porous carbon material containing boron, porous carbon material containing nitrogen. One of these may be used alone, or two or more may be used in combination.
  • the porous carbon material is preferably at least one selected from the group consisting of activated carbon, carbon black, and carbon nanotubes.
  • activated carbon there is no particular limitation on the activated carbon, and known activated carbon particles that are used in carbon electrodes and the like can be used. Specific examples include activated carbon particles or fibers obtained by activating coconut shell, wood dust, petroleum pitch, phenolic resins, and the like using water vapor, various chemicals, alkali, and the like. One of these may be used alone, or two or more may be used in combination.
  • carbon black there is no particular limitation on the carbon black, and fine carbon particulates used in the electrode material of known electric double-layer capacitors can be used. Specific examples include furnace black, channel black, lamp black, thermal black, and the like.
  • the carbon nanotubes and carbon in fiber form used in the electrode material of known electric double-layer capacitors can be used, and it may be single-layer carbon nanotubes with one graphene sheet layer, or it may be multilayer carbon nanotubes with two or more graphene sheets.
  • each of the following methods are methods of preparing a composite made from the conductive polymer and the porous carbon material as described above.
  • the composite of the conductive polymer and the porous carbon material can be produced by preparing a dispersion solution of the porous carbon material in a solvent (for example, a non-polar solvent such as toluene or the like) (hereafter referred to as “porous carbon material dispersion”), heating to about 90 to 130° C. to reduce the viscosity of the solvent, then adding a dispersion in which the conductive polymer is dispersed in advance in a solvent (for example, a non-polar solvent such as toluene or the like) (hereafter referred to as “conductive polymer dispersion”), and after mixing these, dopant is removed by undoping as necessary.
  • a solvent for example, a non-polar solvent such as toluene or the like
  • Examples of methods of undoping include a method of base treatment that can neutralize the dopant and thereby undope the doped conductive polymer, a method of heat treatment of the dopant at a temperature that does not damage the conductive polymer, and the like. Specifically, the methods disclosed in Patent Documents 2 and 3 can be adopted.
  • the composite of the conductive polymer and the porous carbon material can be produced by preparing the porous carbon material dispersion and the conductive polymer dispersion as described in the Method of Preparing (No. 1), and after mixing the conductive polymer dispersion that has been processed in advance in a high-pressure homogenizer, and the porous carbon material dispersion in a high-pressure homogenizer, dopant is removed by undoping as necessary.
  • the composite of the conductive polymer and the porous carbon material can be produced by mixing a dispersion solution of the porous carbon material dispersed in a solvent (for example, a non-polar solvent such as toluene or the like) and a dispersion of the conductive polymer in a solvent (for example, a non-polar solvent such as toluene or the like), then dopant is removed by undoping as necessary.
  • a solvent for example, a non-polar solvent such as toluene or the like
  • a solvent for example, a non-polar solvent such as toluene or the like
  • the electrode material according to the present invention is an electrode material that uses the carbon material according to the present invention as described above as the active material, and it can be advantageously used as the electrode material of, for example, electrochemical elements (for example, electric double-layer capacitors, lithium ion secondary batteries, lithium ion capacitors, sodium ion capacitors, and the like).
  • electrochemical elements for example, electric double-layer capacitors, lithium ion secondary batteries, lithium ion capacitors, sodium ion capacitors, and the like.
  • the electrode material according to the present invention can be advantageously used in the electrode material of the polarizable electrode of an electric double-layer capacitor, the negative electrode of the lithium ion secondary battery, the negative electrode of the lithium ion capacitor, and the like.
  • the electrochemical element according to the present invention uses the electrode material according to the present invention as described above, and can otherwise adopt a conventionally known configuration, and can be manufactured by conventional commonly known manufacturing methods.
  • reaction solution was separated into the toluene layer and the aqueous layer, and only the aqueous layer was removed so as to obtain a polyaniline toluene dispersion.
  • reaction solution was poured into 200 mL of 0.5 mol/L hydrochloric acid aqueous solution. After stirring for 2 h at room temperature, the precipitate was filtered out and recovered.
  • the recovered precipitate was stirred in 200 mL of 0.1 mol/L ammonium aqueous solution for 3 h at room temperature to isolate and purify the polypyridine.
  • the particle size of the polypyridine particles in the dispersion was analyzed by an ultrasonic particle size distribution measurement apparatus (manufactured by Matec Applied Sciences, APS-100). As a result, it was learned that the particle size distribution was uniform (peak value of 0.25 ⁇ m, half width of 0.12 ⁇ m).
  • reaction solution was separated into the toluene layer and the aqueous layer, and only the aqueous layer was removed so as to obtain a polypyrrole toluene dispersion.
  • Poly(3-dodecylthiophene-2,5-diyl) (manufactured by Sigma-Aldrich Co. Llc., average molecular weight 60,000) dispersed in toluene was used (solid content 1.2 mass %).
  • an activated carbon toluene dispersion was prepared by dispersing 300 g of activated carbon (NY1151, specific surface area 1325 m 2 /g, primary average particle size: 5 ⁇ m, specific resistance: 1.5 ⁇ 10 ⁇ 1 ⁇ cm, manufactured by Kurarey Chemical) in 1000 g of toluene.
  • the carbon material made from the polyaniline/activated carbon composite was prepared by vacuum drying the washed and purified precipitate.
  • the carbon material made from polypyridine/activated carbon composite was prepared by the same method as that of Working Example 1, except that polypyridine aqueous dispersion prepared in advance was used instead of the polyaniline toluene dispersion. Note that, as described below, in the case of the carbon material prepared in Working Example 8, an electric double-layer capacitor with an electrode for evaluation disposed in the negative electrode was prepared.
  • the carbon material made from polypyrrole/activated carbon composite was prepared by the same method as that of Working Example 1, except that polypyrrole toluene dispersion prepared in advance was used instead of the polyaniline toluene dispersion.
  • the carbon material made from polythiophene/activated carbon composite was prepared by the same method as that of Working Example 1, except that polythiophene toluene dispersion prepared in advance was used instead of the polyaniline toluene dispersion, and the undoping process using triethylamine was not carried out.
  • the carbon material made from polyfluorene/activated carbon composite was prepared by the same method as that of Working Example 1, except that polyfluorene toluene dispersion prepared in advance was used instead of the polyaniline toluene dispersion.
  • an activated carbon methanol dispersion was prepared by dispersing 300 g of activated carbon (NY1151, specific surface area 1325 m 2 /g, primary average particle size: 5 ⁇ m, specific resistance: 1.5 ⁇ 10 ⁇ 1 ⁇ cm, manufactured by Kurarey Chemical) in 1000 g of methanol.
  • the carbon material made from the polyaniline/activated carbon composite was prepared by vacuum drying the washed and purified precipitate.
  • an activated carbon toluene dispersion was prepared by dispersing 300 g of activated carbon (NY1151, specific surface area 1325 m 2 /g, primary average particle size: 5 ⁇ m, specific resistance: 1.5 ⁇ 10 ⁇ 1 ⁇ cm, manufactured by Kurarey Chemical) in 1000 g of toluene.
  • a polyaniline toluene dispersion (polyaniline content: 4.3 mass %) that was processed in advance in a high-pressure homogenizer (Star Burst Labo manufactured by Sugino Machine Ltd., pressure: 150 MPa, chamber nozzle diameter: ⁇ 0.75 mm) was added to the activated carbon toluene dispersion so that the blending quantity of polyaniline was the value (number within brackets) in the following Table 1, and the mixed dispersion in which these were mixed was prepared by further processing thereof in a high pressure homogenizer (Star Burst Labo manufactured by Sugino Machine Ltd., pressure: 150 MPa, chamber nozzle diameter ⁇ 0.75 mm).
  • the carbon material made from the polyaniline/activated carbon composite was prepared by vacuum drying the washed and purified precipitate.
  • the carbon material made from polyaniline/activated carbon composite was prepared by the same method (method of preparing A) as that of Working Example 1, except that activated carbon and polyaniline was added so that the blending quantities were the values (polyaniline value within brackets) indicated in the following Table 1.
  • the carbon material made from polyaniline/activated carbon composite was prepared by the same method (method of preparing B) as that of Working Example 12, except that activated carbon and polyaniline was added so that the blending quantities were the values (polyaniline value within brackets) indicated in the following Table 1.
  • the carbon material made from polyaniline/activated carbon composite was prepared by the same method (method of preparing C) as that of Working Example 15, except that activated carbon and polyaniline was added so that the blending quantities were the values (polyaniline value within brackets) indicated in the following Table 1.
  • a mixed dispersion was obtained by adding the quantity indicated in the following Table 1 of activated carbon (NY1151, specific surface area: 1325 m 2 /g, primary average particle size: 5 ⁇ m, specific resistance: 1.5 ⁇ 10 ⁇ 1 ⁇ cm, manufactured by Kurarey Chemical) to the quantity indicated in the following Table 1 of polyaniline toluene dispersion.
  • activated carbon NY1151, specific surface area: 1325 m 2 /g, primary average particle size: 5 ⁇ m, specific resistance: 1.5 ⁇ 10 ⁇ 1 ⁇ cm, manufactured by Kurarey Chemical
  • the carbon material made from the polyaniline/activated carbon composite was prepared by vacuum drying the washed and purified precipitate.
  • Activated carbon (NY1151, specific surface area: 1325 m 2 /g, primary average particle size: 5 ⁇ m, specific resistance: 1.5 ⁇ 10 ⁇ 1 ⁇ cm, manufactured by Kurarey Chemical) was used as the Standard Example of the carbon material.
  • the pH at zero zeta potential was measured by measuring the zeta potential by laser doppler electrophoresis using a zeta potential measurement system (ELSZ-1000ZS, manufactured by Otsuka Electronics Co., Ltd.), in accordance with the method of isoelectric point measurement prescribed by JIS R 1638:1999.
  • ELSZ-1000ZS manufactured by Otsuka Electronics Co., Ltd.
  • the Raman spectrum was measured with an excitation wavelength of 532 nm using a micro laser Raman spectrograph HoloLab 5000R (manufactured by Kaiser Optical Systems Inc.). Note that the charts of the Raman spectrum of the carbon material produced for Working Example 1 and the Standard Example are shown in FIG. 1 .
  • the quantity of methylene blue solution adsorbed was calculated using a spectrophotometer (UH5300, manufactured by Hitachi Ltd.), in accordance with the method of testing activated carbon prescribed by JIS K 1474:2007.
  • conduction aid acetylene black
  • binding agent polyfluorethylene resin
  • the electrostatic capacitance was measured using a three-electrode model test cell manufactured by Toyo System Co., Ltd. A solution of tetraethylammonium tetrafluoroborate in propylene carbonate with a concentration of 1.0 mol/L was used as the electrolyte solution. Note that for the reference electrode, silver wire (vs. Ag/Ag + ) was used.
  • the activated carbon, the conduction aid (acetylene black), and the binding agent (polyfluorethylene resin) were mixed and dispersed in the mass ratio 85:10:5, and then formed into sheet form using a pressure roll, and discs (diameter 1.6 cm) were cut from the sheets obtained to produce the electrodes (30 mg).
  • a separator glass fiber paper manufactured by Nippon Sheet Glass Co., Ltd. was interposed between the positive electrodes and the negative electrodes.
  • the electrostatic capacitance evaluated by the three electrode method was 15 to 30% higher compared with that of the Standard Example and the Comparative Examples (Working Examples 1 to 20).

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20190173087A1 (en) * 2016-08-31 2019-06-06 Sekisui Chemical Co., Ltd. Electrode material for electricity storage devices, electrode for electricity storage devices, and electricity storage device
US20190382582A1 (en) * 2016-12-02 2019-12-19 The Willamette Valley Company Llc Wax-Organic Extender Emulsion and Method for Manufacture Thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020187881A (ja) * 2019-05-13 2020-11-19 株式会社リコー 活物質、電極、及び蓄電素子

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012023196A (ja) * 2010-07-14 2012-02-02 Yokohama Rubber Co Ltd:The 導電性高分子／多孔質炭素材料複合体
US20120171575A1 (en) * 2009-06-26 2012-07-05 Nanyang Technological University Energy charge storage device using a printable polyelectrolyte as electrolyte material

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5011561B2 (ja) * 2006-02-28 2012-08-29 日本ケミコン株式会社 電極材料
JP2008072079A (ja) * 2006-08-18 2008-03-27 Yokohama Rubber Co Ltd:The ポリアニリン／多孔性炭素複合体及びそれを用いた電気二重層キャパシタ
CN102315461A (zh) * 2006-09-13 2012-01-11 日立麦克赛尔能源株式会社 膜电极接合体及固体高分子型燃料电池
JP4294067B2 (ja) 2006-11-28 2009-07-08 横浜ゴム株式会社 ポリアニリン／炭素複合体を用いた電気二重層キャパシタ
JP2011121785A (ja) * 2009-12-08 2011-06-23 Habikkusu Kk 活性炭化物
JP5041058B2 (ja) * 2010-12-27 2012-10-03 横浜ゴム株式会社 リチウムイオンキャパシタ用電極材料およびリチウムイオンキャパシタ
JP5110147B2 (ja) * 2010-10-15 2012-12-26 横浜ゴム株式会社 導電性高分子／多孔質炭素材料複合体
DE112011103474T5 (de) * 2010-10-15 2013-08-01 The Yokohama Rubber Co., Ltd. Leitfähiger Verbundwerkstoff aus Polymer/porösem Kohlenstoffmaterial und Elektrodenmaterial, das diesen verwendet
DE112012001940B4 (de) * 2011-04-11 2018-02-08 The Yokohama Rubber Co., Ltd. Elektrodenmaterial, umfassend einen verbundwerkstoff aus leitfähigem polymer und porösem kohlenstoffmaterial, und elektrischer doppelschichtkondensator, li-ionen-sekundärbatterie und li-ionen-kondesator, welche dieses elektrodenmaterial verwenden

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120171575A1 (en) * 2009-06-26 2012-07-05 Nanyang Technological University Energy charge storage device using a printable polyelectrolyte as electrolyte material
JP2012023196A (ja) * 2010-07-14 2012-02-02 Yokohama Rubber Co Ltd:The 導電性高分子／多孔質炭素材料複合体

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Translation JP2012023196 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20190173087A1 (en) * 2016-08-31 2019-06-06 Sekisui Chemical Co., Ltd. Electrode material for electricity storage devices, electrode for electricity storage devices, and electricity storage device
US10998551B2 (en) * 2016-08-31 2021-05-04 Sekisui Chemical Co., Ltd. Electrode material for electricity storage devices, electrode for electricity storage devices, and electricity storage device
US20190382582A1 (en) * 2016-12-02 2019-12-19 The Willamette Valley Company Llc Wax-Organic Extender Emulsion and Method for Manufacture Thereof
US11566134B2 (en) 2016-12-02 2023-01-31 The Williamette Valley Company Llc Organic slurry and method for manufacture thereof
US11591472B2 (en) * 2016-12-02 2023-02-28 The Williamette Valley Company Llc Wax-organic extender emulsion and method for manufacture thereof
US11866587B2 (en) 2016-12-02 2024-01-09 The Williamette Valley Company Llc Organic slurry and method for manufacture thereof
US12054615B2 (en) 2016-12-02 2024-08-06 The Williamette Valley Company Llc Organic slurry and method for manufacture thereof

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