WO2015008615A1 - Matériau d'électrode à alignement hydroxyde métallique, électrode contenant un hydroxyde métallique, procédé de fabrication de ces électrodes, et condensateur contenant un hydroxyde métallique - Google Patents

Matériau d'électrode à alignement hydroxyde métallique, électrode contenant un hydroxyde métallique, procédé de fabrication de ces électrodes, et condensateur contenant un hydroxyde métallique Download PDF

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WO2015008615A1
WO2015008615A1 PCT/JP2014/067514 JP2014067514W WO2015008615A1 WO 2015008615 A1 WO2015008615 A1 WO 2015008615A1 JP 2014067514 W JP2014067514 W JP 2014067514W WO 2015008615 A1 WO2015008615 A1 WO 2015008615A1
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electrode
metal hydroxide
graphene
plate
sheet
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PCT/JP2014/067514
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English (en)
Japanese (ja)
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捷 唐
騫 程
禄昌 秦
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独立行政法人物質・材料研究機構
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Priority claimed from JP2013148218A external-priority patent/JP6057293B2/ja
Priority claimed from JP2013155384A external-priority patent/JP6161158B2/ja
Application filed by 独立行政法人物質・材料研究機構 filed Critical 独立行政法人物質・材料研究機構
Publication of WO2015008615A1 publication Critical patent/WO2015008615A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/04—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/02—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 using combined reduction-oxidation reactions, e.g. redox arrangement or solion
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present invention relates to a metal hydroxide oriented electrode material, a metal hydroxide-containing electrode, a method for producing them, and a metal hydroxide-containing capacitor.
  • the present invention relates to a Co (OH) 2 vertically aligned graphene / carbon nanotube composite (hereinafter sometimes referred to as Co (OH) 2 vertically aligned graphene / CNT composite), a method for producing the same, Co (OH) 2 vertically aligned graphene / carbon nanotube composite electrode (hereinafter sometimes referred to as Co (OH) 2 vertically aligned graphene / CNT composite electrode) and Co (OH) 2 vertically aligned graphene / carbon nanotube composite electrode
  • the present invention relates to a body capacitor (hereinafter sometimes referred to as a Co (OH) 2 vertically aligned graphene / CNT composite capacitor).
  • the present invention also relates to a sheet metal hydroxide-containing sheet electrode, a method for producing the same, and a plate metal hydroxide-containing capacitor.
  • the capacitor is a device with a simple operation mechanism and high charge generation efficiency, and has a cycle life of 100,000 cycles or more.
  • the following three electrode materials are mainly used for capacitors.
  • the electrode material is composed of an active substance capable of electrode reaction on the surface and / or inside thereof.
  • the first electrode material is a carbon-based material, for example, activated carbon, carbon nanotube, graphene, or a composite material thereof. With these materials, electrolyte ions can be efficiently absorbed on a wide access surface of the active material, and electrostatically charged to form a double-layer capacitance, thereby forming an electrochemically stable capacitor. Can be formed.
  • the second electrode material is a metal oxide material, for example, a transition metal oxide material such as MnO 2 or RuO 2 .
  • a metal oxide material for example, a transition metal oxide material such as MnO 2 or RuO 2 .
  • the third electrode material is a conductive polymer material, such as ponianiline (PANI) or polypyrrole.
  • PANI ponianiline
  • polypyrrole polypyrrole
  • PANI has advantages that it can be easily synthesized at low cost, has high stability in air, and has high conductivity. Further, when used for a supercapacitor, the specific capacity is as high as 233-1220 F / g (Non-patent Document 1). However, there is a problem that the polymer skeleton is easily decomposed and the cycle stability is poor.
  • graphene which is one of carbon materials and has a wide active surface area per unit amount
  • graphene has a problem in that active surfaces easily overlap each other and become agglomerated by van der Waals force, reducing the active surface area per unit amount.
  • the capacitor performance was greatly reduced.
  • FIG. 8A is a diagram for explaining how ions come into contact with graphene
  • FIG. 8B is a diagram for explaining how ions are brought into contact with restacked graphene.
  • FIG. 8A when the graphene is in a separated state, ions can easily come into contact with the active surface and a reaction can be performed on the active surface.
  • FIG. 7B when graphene easily overlaps with each other on the active surfaces to form a lump, ions cannot easily come into contact with the overlapping active surfaces. Reduced the reaction efficiency.
  • Non-Patent Documents 2 to 8 there is an electrode in which a metal hydroxide or a metal oxide is coated on a carbon material.
  • Cobalt hydroxide such as Co (OH) 2 has been studied as a metal hydroxide to be coated.
  • Cobalt hydroxide is a particularly excellent material as an electrode material because it has a layer structure with a wide interlayer distance, so that ions can be taken in and out quickly between layers, and ions can be efficiently supplied to the surface of the active material. Because.
  • Non-Patent Document 2 relates to “potentiostatically deposited nanostructured a-Co (OH) 2 : A high performance elec trode material for redox-capacitors”.
  • Non-Patent Document 3 relates to “Synthesis of Co (OH) 2 USY composite and its application for electrical supercapacitors”.
  • Non-Patent Document 3 discloses a high theoretical value of a specific capacity of 3458 F / g.
  • Non-Patent Document 4 relates to “Surfactant-associated electrochemical deposition of ⁇ -covalent hydride for supercapacitors”.
  • Non-Patent Document 5 relates to “Selective and Controlled Synthesis of ⁇ -and ⁇ -cobalt Hydroxides in Highly Developed Hexagonal Platelets”.
  • Non-Patent Document 6 relates to “Nanoflake-like cobalt hydroxide / ordered mesoporous carbon composite for electrical capacitors”.
  • Non-Patent Document 7 relates to “High capacity and excellent cycling stability of branched cobalt oxides as Li-insertion materials”.
  • Non-Patent Document 8 relates to “Facile preparation and electrochemical char- acterization of cobalt oxide / multi-walled carbon nanocomposites for supercapacitors”.
  • Non-patent Document 1 There is also a report of a capacitor using an electrode made of a composite of graphene and carbon nanotubes that prevents the formation of such a mass by interposing carbon nanotubes between active surfaces.
  • Non-patent Document 1 Even these capacitor electrode materials have a short cycle life, and sufficient characteristics have not been obtained.
  • the capacitor electrode requires a metallic current collector that conducts electrons, so the total specific capacity of the capacitor electrode as a whole is reduced, and industrial application In addition, sufficient capacitor performance was not obtained. Therefore, a capacitor electrode having a higher specific capacity is desired.
  • An object of the present invention is to provide a metal hydroxide-oriented electrode material, a metal hydroxide-containing electrode, a production method thereof, and a metal hydroxide-containing capacitor having a high specific capacity and a long cycle life.
  • the present invention also provides a Co (OH) 2 vertically aligned graphene / CNT composite having a high specific capacity and a long cycle life, a manufacturing method thereof, a Co (OH) 2 vertically aligned graphene / CNT composite electrode, and Co (OH). ) It is an object to provide a two vertically aligned graphene / CNT composite capacitor.
  • an object of the present invention is to provide a plate-like metal hydroxide-containing sheet-like electrode having a high specific capacity and a long cycle life, a method for producing the same, and a capacitor.
  • the metal hydroxide-containing capacitor of the present invention has a configuration shown in the following (1).
  • Two metal hydroxide-containing electrodes containing a metal hydroxide-oriented electrode material are sandwiched between the electrolyte-impregnated layers, and one or both of the electrodes are Co (OH) 2 vertically aligned graphene / CNT composite is formed on one surface of a plate-like electrode and Co (OH) 2 vertically aligned graphene / CNT composite electrode or groove-formed conductive fibers are knitted in a mesh shape
  • Metallic water characterized in that it is a sheet-like metal hydroxide-containing sheet-like electrode comprising a rare sheet and a plurality of plate-like metal hydroxides accumulated on the surface of the groove-formed conductive fiber Oxide-containing capacitor.
  • the present inventor accumulated Co (OH) 2 by growing a crystal of Co (OH) 2 in the direction perpendicular to the surface of the graphene / CNT composite, and coating the graphene / CNT composite with Co (OH) 2.
  • Co (OH) 2 it is possible to create a porous structure made of Co (OH) 2, to secure an electron transfer path and an ion diffusion path to the surface of the graphene / CNT composite, and to efficiently move these electrons and ions on the active material. It has been found that it can be involved in the redox reaction and can improve the capacitor performance. That is, the present invention has configurations shown in the following (2) to (9).
  • a Co (OH) 2 vertically aligned graphene / CNT composite comprising a composite of graphene and a carbon nanotube having a plate crystal of Co (OH) 2 grown on the surface.
  • Co (OH) 2 is grown on the surface of the graphene so that the main surface of the plate-like Co (OH) 2 is not in contact with the surface of the graphene and only the side surface is in contact with the surface of the graphene.
  • the electrodeposition treatment is a treatment of applying a voltage using the counter electrode and the reference electrode in the electrolytic solution of cobalt chloride or cobalt salt, using the graphene / CNT composite as a work electrode.
  • the method for producing a Co (OH) 2 vertically aligned graphene / CNT composite according to (5) which is characterized in that
  • the inventor of the present invention electrodeposited newly produced Co (OH) 2 flakes on a sheet made of electroetched carbon fiber to create a plate-like metal hydroxide-containing sheet-like electrode.
  • the surface of the sheet-like metal hydroxide-containing sheet-like electrode formed a nanostructure in which Co (OH) 2 flakes were integrated so as to be aligned perpendicular to the surface of the carbon fiber.
  • this plate-like metal hydroxide-containing sheet electrode had a mass standard specific capacity of 3404.8 F / g and an area standard specific capacity of 3.3 F / cm 2 which was very high. It became.
  • (10) It is characterized by comprising a sheet in which the groove-formed conductive fibers are knitted in a mesh shape and a plurality of plate-like metal hydroxides accumulated on the surface of the groove-formed conductive fibers.
  • a plate-like metal hydroxide-containing sheet electrode (11) A plurality of groove portions extending in a direction substantially parallel to the axial direction and a wall portion partitioning each groove portion are provided on the surface of the conductive fiber that has been subjected to the groove formation treatment.
  • the plate-like metal hydroxide is made of any material selected from the group consisting of Co (OH) 2 , Ni (OH) 2 , and Mn (OH) 2. Plate-like metal hydroxide-containing sheet-like electrode.
  • the plate-like metal hydroxide-containing sheet-like electrode according to (14), wherein the groove-formed conductive fiber is made of any material selected from the group consisting of carbon, nickel, and titanium. .
  • a sheet in which conductive fibers are woven into a mesh shape is electroetched to form a plurality of grooves on the surface of the conductive fibers, and the groove-formed conductive fibers are knitted into a mesh shape.
  • a step of producing a rare sheet, and a sheet obtained by braiding the groove-formed conductive fibers into a network, and electrodepositing in a solution containing a plate-like metal hydroxide, to form the groove Forming a plate-like metal hydroxide-containing sheet-like electrode in which a plurality of plate-like metal hydroxides are accumulated on the surface of the formed conductive fiber.
  • a method for producing a material-containing sheet-like electrode is produced.
  • Electrodes are disposed opposite each other with an electrolyte-impregnated layer interposed therebetween, and one or both of the electrodes is a sheet metal hydroxide-containing sheet according to any one of (10) to (15) A plate-like metal hydroxide-containing capacitor, wherein the capacitor is a plate-like electrode.
  • a metal hydroxide oriented electrode material a metal hydroxide-containing electrode, a method for producing them, and a metal hydroxide-containing capacitor having a high specific capacity and a long cycle life are provided.
  • the Co (OH) 2 vertically aligned graphene / CNT composite of the present invention is composed of a composite of graphene having a plate crystal of Co (OH) 2 grown on the surface and a carbon nanotube, the surface of the graphene Even when plate crystals are grown at a high density and accumulated, the surface activity of graphene can be prevented from being lowered, and it can be used as an electrode material capable of constituting a capacitor having a high specific capacity and a long cycle life.
  • the method for producing a Co (OH) 2 vertically aligned graphene / CNT composite according to the present invention includes a step of preparing a graphene / CNT composite, and the graphene / CNT composite is electrolyzed in an electrolytic solution of cobalt chloride or a cobalt salt. And forming a Co (OH) 2 vertically aligned graphene / CNT composite in which Co (OH) 2 is crystal-grown on the surface of the graphene, so that the graphene can be easily and in a short time.
  • Co which can be used as an electrode material that can grow a plate crystal at a high density on the surface of the metal and can prevent the surface activity of graphene from being lowered even if it is accumulated, can be used to construct a capacitor with a high specific capacity and a long cycle life.
  • (OH) 2 vertically aligned graphene / CNT composites can be made.
  • Co (OH) 2 vertically aligned graphene / CNT composite electrode of the present invention has a constitution in which Co described previously (OH) 2 vertically aligned graphene / CNT composite is formed on one surface of the plate-shaped electrode, the specific capacity Therefore, an electrode capable of forming a capacitor having a high cycle life is provided.
  • the Co (OH) 2 vertically aligned graphene / CNT composite capacitor according to the present invention has two Co (OH) 2 vertically aligned graphene / CNT composite electrodes, which are described above, sandwiched between the electrolyte-impregnated layers. Therefore, a capacitor having a high specific capacity and a long cycle life can be obtained.
  • the plate-like metal hydroxide-containing sheet-like electrode of the present invention includes a sheet in which groove-formed conductive fibers are knitted in a mesh shape, and a plurality of grooves integrated on the surface of the groove-formed conductive fibers. Since it is composed of a plate-like metal hydroxide, it is possible to provide an electrode that can constitute a capacitor having a high specific capacity and a long cycle life.
  • the method for producing a plate-like metal hydroxide-containing sheet-like electrode according to the present invention is such that a sheet in which conductive fibers are knitted in a mesh shape is electroetched to provide a plurality of grooves on the surface of the conductive fibers. And forming a sheet in which the groove-formed conductive fibers are woven into a mesh shape, and forming a sheet in which the groove-formed conductive fibers are knitted into a mesh shape.
  • a plate-like metal hydroxide-containing sheet-like electrode in which a plurality of plate-like metal hydroxides are accumulated on the surface of the groove-formed conductive fiber is prepared by electrodeposition in a solution containing a product. Therefore, an electrode capable of forming a capacitor having a high specific capacity and a long cycle life can be easily produced.
  • the plate-like metal hydroxide-containing capacitor of the present invention two electrodes are disposed opposite to each other with an electrolyte-impregnated layer interposed therebetween, and one or both of the electrodes are any one of (10) to (15). Since it is a structure which is a plate-shaped metal hydroxide containing sheet-like electrode of description, it can be set as a capacitor with a high specific capacity and a long cycle life.
  • They are the TEM image (a) of Example 1, an enlarged TEM image (b), an SEM image (c), and an enlarged SEM image (d).
  • They are the TEM image (a), STEM image (b), C component mapping image (c), O component mapping image (d), and Co component mapping image (e) of Example 1.
  • FIG. 10B is an enlarged view (B) of FIG. 10C, a cross-sectional view taken along line CC ′ of FIG.
  • Example 4 is a CV curve of a plate-like metal hydroxide-containing sheet-like electrode of Example 2-1 (working electrode: coating density 1 mg / cm 2 ), and is a graph showing scan speed dependency.
  • 6 is a charge / discharge curve of a plate-like metal hydroxide-containing sheet-like electrode of Example 2-1 (working electrode: coating density 1 mg / cm 2 ), and is a graph showing the charge current value dependency.
  • It is an EIS curve of the sheet metal hydroxide-containing sheet electrode (work electrode: coating density 1 mg / cm 2 ) of Example 2-1.
  • the inset is a graph with Z1 in the range of 1.5 to 2.0 (high frequency region).
  • FIG. 1 is a schematic view showing an example of a Co (OH) 2 vertically aligned graphene / CNT composite capacitor according to the first embodiment of the present invention, and is a plan view (a) and a side view (b). .
  • the Co (OH) 2 vertically aligned graphene / CNT composite capacitor 1 according to the first embodiment of the present invention has a substantially circular shape in plan view.
  • the shape is not limited to this planar view shape, and may be a rectangular shape or a polygonal shape.
  • FIG. 1 is a schematic view showing an example of a Co (OH) 2 vertically aligned graphene / CNT composite capacitor according to the first embodiment of the present invention, and is a plan view (a) and a side view (b).
  • the Co (OH) 2 vertically aligned graphene / CNT composite capacitor 1 according to the first embodiment of the present invention has a substantially circular shape in plan view.
  • the shape is not limited to this planar view shape, and may be
  • the Co (OH) 2 vertically aligned graphene / CNT composite capacitor 1 according to the first embodiment of the present invention is composed of two sheets of Co according to the first embodiment of the present invention.
  • the (OH) 2 vertically aligned graphene / CNT composite electrode 21 is roughly configured with the electrolyte solution impregnated layer 13 sandwiched therebetween.
  • the electrolyte solution impregnated layer 13 also serves as a separator.
  • the configuration of the symmetric electrode is used, for example, a configuration of an asymmetric electrode in which the positive electrode is Graphene / CNT coated with Co (OH) 2 and the negative electrode is Graphene / CNT may be used.
  • a capacitor In the case of a coin cell, a capacitor is configured by bringing a coin cell cap into contact with each of the two Co (OH) 2 vertically aligned graphene / CNT composite electrodes 21. In this case, a gasket, a spring, a steel spacer, etc. are interposed in the coin cell.
  • the Co (OH) 2 vertically aligned graphene / CNT composite capacitor is an electric double layer capacitor and one of supercapacitors.
  • the Co (OH) 2 vertically aligned graphene / CNT composite electrode 21 according to the first embodiment of the present invention is the Co (OH) according to the first embodiment of the present invention.
  • Two vertically aligned graphene / CNT composites 12 are formed on one surface of the plate electrode 11.
  • the plate-like electrode 11 uses, for example, a metal such as stainless steel, titanium (Titanium), nickel (Nickel) or the like.
  • the plate electrode 11 is used as a current collector.
  • the film thickness of the Co (OH) 2 vertically aligned graphene / CNT composite 12 is 100 nm or more and 10 ⁇ m or less. Thereby, an electric double layer capacitor having a high specific capacity can be formed.
  • FIG. 2 is a schematic view showing an example of the Co (OH) 2 vertically aligned graphene / CNT composite according to the first embodiment of the present invention, and is a plan view (a), a side view (b), (a (B) is an enlarged view (d) of a portion B in (b).
  • the Co (OH) 2 vertically aligned graphene / CNT composite 12 according to the first embodiment of the present invention has a substantially circular shape in plan view.
  • the shape is not limited to this planar view shape, and may be a rectangular shape or a polygonal shape.
  • the Co (OH) 2 vertically aligned graphene / CNT composite 12 includes a graphene 31 having a plate crystal 33 of Co (OH) 2 grown on the surface, and It consists of a composite with carbon nanotubes 32.
  • the carbon nanotube 32 is interposed between the two graphenes 31.
  • Co (OH) 2 is crystal-grown by aligning perpendicularly to the surface of graphene so that the main surface of Co (OH) 2 that is a plate-like crystal does not contact the surface of graphene, but only its side surface contacts the surface of graphene It is preferable that Thereby, a porous structure composed of a large number of pores 33c communicating with the surface from the outside is formed. This can be utilized as a supply path of electrons and / or ions to the active surface, and the high active surface performance of graphene can be maintained.
  • the diameter of Co (OH) 2 is 50 nm or more and 400 nm or less and the thickness is less than 20 nm. Thereby, a porous structure composed of pores having a diameter of 400 nm or less can be formed.
  • FIG. 3 is a process diagram illustrating a graphene oxide creation process and a graphene creation process.
  • graphene creation process First, graphene oxide is dispersed in distilled water and irradiated with ultrasonic waves for a predetermined time (for example, 30 minutes). The suspension is then heated to 100 ° C. Next, hydrazine hydrate is added. Next, the suspension is heated at 98 ° C. for a predetermined time (for example, 24 hours) to reduce the graphene oxide to graphene. Next, the reduced graphene is collected by filtration. The collection is then washed with distilled water to remove excess hydrazine. Next, redispersion in water, application of ultrasonic waves, and centrifugation. The final product is then collected by vacuum filtration. Graphene is created through the above steps.
  • FIG. 4 is a process diagram showing an example of a method for producing a Co (OH) 2 vertically aligned graphene / CNT composite according to the first embodiment of the present invention.
  • the Co (OH) 2 vertically aligned graphene / CNT composite manufacturing method according to the embodiment of the present invention includes a graphene / CNT composite creating step S1 and a Co (OH) 2 vertically aligned graphene / CNT composite production process S2.
  • Graphene / CNT composite production process S1 First, the graphene prepared in the above process is mixed in an alcohol (for example, ethanol) together with carbon nanotubes (CNT). Next, vacuum filtration is performed. Through the above steps, a film-like graphene / CNT composite is prepared.
  • an alcohol for example, ethanol
  • CNT carbon nanotubes
  • cobalt salt include cobalt (II) acetate (Co (II) acetate: Co (C 2 H 3 O 2 ) 2 ⁇ 4H 2 O), sulfuric acid that is a divalent cobalt sulfate.
  • cobalt (II) Cobalt (II) sulfate: CoSO 4 ).
  • An example of cobalt chloride is cobalt (II) chloride represented by CoCl 2 .
  • the electrolytic solution of cobalt chloride or cobalt salt is an alcohol solution. A 10% ethanol solution is preferred. The concentration of cobalt chloride or cobalt salt is, for example, 1M. Moreover, it is preferable to disperse potassium hydroxide (Potassium hydroxide).
  • each electrode is connected to a power source, and a voltage is applied between the electrodes to perform electrodeposition (cathode deposition) treatment for crystal growth of Co (OH) 2 on the graphene surface of the graphene / CNT composite.
  • the electrodeposition process is preferably performed in two stages, a nucleation process and a crystal growth process.
  • the nucleation step is a step of passing a current of 1 mA or less at room temperature. In this step, nuclei for crystal growth can be formed on the graphene surface.
  • the current density is set to 5 mA / cm 2 or more.
  • crystals can be grown so as to extend from the nucleus in a direction perpendicular to the surface.
  • the Co (OH) 2 vertically aligned graphene / CNT composite 12 includes a graphene 31 having a plate crystal 33 of Co (OH) 2 grown on the surface, a carbon nanotube 32, Because it is composed of a composite of the above, a plate-like crystal can be grown at a high density on the surface of graphene, and even if accumulated, the surface activity of graphene is not lowered, and a capacitor with a high specific capacity and a long cycle life can be configured Can be used for various electrode materials.
  • the Co (OH) 2 vertically aligned graphene / CNT composite 12 has a main surface of Co (OH) 2 that is the plate crystal 33 without contacting the surface of the graphene 31. Since Co (OH) 2 is grown on the surface of the graphene 31 so that only the side surface is in contact with the surface of the graphene 31, the plate crystal is vertically oriented at a high density on the surface of the graphene. Even when grown, formed into a porous structure, and integrated, it can be used as an electrode material that can secure a ion path without degrading the surface activity of graphene, and can constitute a capacitor with a high specific capacity and a long cycle life.
  • the Co (OH) 2 vertically aligned graphene / CNT composite 12 according to the first embodiment of the present invention has a configuration in which the diameter of Co (OH) 2 is 50 nm or more and 400 nm or less and the thickness is less than 20 nm.
  • a porous structure composed of dense pores can be formed, and can be used as an electrode material capable of constituting a capacitor having a high specific capacity and a long cycle life.
  • the method for producing the Co (OH) 2 vertically aligned graphene / CNT composite 12 according to the first embodiment of the present invention includes a step of producing a graphene / CNT composite, and the graphene / CNT composite is made of cobalt chloride or And a step of producing a Co (OH) 2 vertically aligned graphene / CNT composite in which Co (OH) 2 is crystal-grown on the surface of graphene by electrodeposition in an electrolytic solution of a cobalt salt, Easily grow plate crystals at a high density on the surface of graphene in a short time, so that the surface activity of graphene is not lowered even if it is accumulated, and it is possible to construct a capacitor with a high specific capacity and a long cycle life A Co (OH) 2 vertically aligned graphene / CNT composite that can be used as an electrode material can be produced.
  • the method for producing a Co (OH) 2 vertically aligned graphene / CNT composite 12 according to the first embodiment of the present invention is such that the electrodeposition treatment is carried out in an electrolytic solution of cobalt chloride or a cobalt salt. Since the body is a work electrode and a voltage is applied using a counter electrode and a reference electrode, a Co (OH) 2 vertically aligned graphene / CNT composite can be easily produced in a short time. Since the cobalt chloride is CoCl 2 and the cobalt salt is cobalt acetate or cobalt sulfate, the Co (OH) 2 vertically aligned graphene / CNT composite 12 manufacturing method according to the first embodiment of the present invention is configured. A Co (OH) 2 vertically aligned graphene / CNT composite can be easily produced in a short time.
  • the Co (OH) 2 vertically aligned graphene / CNT composite electrode 21 according to the first embodiment of the present invention has a Co (OH) 2 vertically aligned graphene / CNT composite electrode 12 formed on one surface of the plate electrode 11. Therefore, an electrode having a high specific capacity and a long cycle life can be formed.
  • the Co (OH) 2 vertically aligned graphene / CNT composite capacitor 1 includes two Co (OH) 2 vertically aligned graphene / CNT composite electrodes 21 and an electrolyte-impregnated layer 13. Since the structure is sandwiched and opposed, a capacitor having a high specific capacity and a long cycle life can be obtained.
  • Co (OH) 2 vertically aligned graphene / CNT composite manufacturing method thereof, Co (OH) 2 vertically aligned graphene / CNT composite electrode and Co (OH) 2 vertically aligned graphene /
  • the CNT composite capacitor is not limited to the above embodiment, and can be implemented with various modifications within the scope of the technical idea of the present invention. A specific example of this embodiment is shown in Example 1 below. However, the present invention is not limited to these examples.
  • FIG. 9 is a schematic view showing an example of a plate-like metal hydroxide-containing capacitor according to the second embodiment of the present invention, and is a plan view (a) and a side view (b).
  • the plate-shaped metal hydroxide containing capacitor 101 which is 2nd embodiment of this invention is a substantially circular shape in planar view.
  • the present invention is not limited to this, and may be a substantially rectangular shape or a polygonal shape in plan view. As shown in FIG.
  • both of the electrodes are plate-like metal hydroxide-containing sheet-like electrodes 111 which are the second embodiment of the present invention. However, at least one may be configured as a plate-like metal hydroxide-containing sheet electrode 111.
  • a capacitor is configured by bringing a coin cell cap into contact with each of the two plate-like metal hydroxide-containing sheet-like electrodes 111.
  • a gasket, a spring, a steel spacer, etc. are interposed in the coin cell.
  • the plate-like metal hydroxide-containing capacitor is an electric double layer capacitor and is a supercapacitor.
  • FIG. 10 is a schematic view showing an example of a plate-like metal hydroxide-containing sheet electrode according to the second embodiment of the present invention, and is a plan view (a), a side view (b), and (a). It is an A section enlarged view (c).
  • the plate-shaped metal hydroxide containing sheet-like electrode 111 which is 2nd embodiment of this invention is substantially circular shape in planar view.
  • FIG. 10 is a schematic view showing an example of a plate-like metal hydroxide-containing sheet electrode according to the second embodiment of the present invention, and is a plan view (a), a side view (b), and (a). It is an A section enlarged view (c).
  • the plate-shaped metal hydroxide containing sheet-like electrode 111 which is 2nd embodiment of this invention is substantially circular shape in planar view.
  • FIG. 10 is a schematic view showing an example of a plate-like metal hydroxide-containing sheet electrode according to the second embodiment of the present invention, and is a plan view (a), a side view
  • the sheet-like metal hydroxide-containing sheet-like electrode 111 is formed by braiding a surface-coated conductive fiber 121 into a mesh shape. A large number of holes 111c are provided and have a porous structure.
  • FIG. 11 is an enlarged view (b) of the B part in FIG. 10 (c), a sectional view (b) taken along the line CC ′ of (a), and an enlarged view (c) of the D part in (b).
  • the surface-coated conductive fiber 121 includes a groove-formed conductive fiber 43 and a plurality of plate-like metal hydroxides 131 integrated and arranged on the surface 43z.
  • the groove-formed conductive fiber 43 has a plurality of groove portions 43k, 43g, 43e, and 43b extending on the surface 43z thereof in a direction substantially parallel to the axial direction. And it is preferable that the wall part 43m, 43i, 43f, 43d, 43a which divides each groove part is provided, and is comprised roughly.
  • the plate-like metal hydroxide 131 is crystal-grown so as to extend from the surface 43 z of the groove-formed conductive fiber 43.
  • the plate-like metal hydroxide 131 is preferably formed such that its side surface is in contact with the surface.
  • the direction perpendicular to the plane of the plate-like metal hydroxide 131 is preferably a random direction.
  • packing can be arranged on the surface 43z of the groove-formed conductive fiber 43 so that the direction perpendicular to the plane of the plate-like metal hydroxide 131 is aligned.
  • the plate-like metal hydroxide 131 preferably has a diameter d 131a of less than 1 ⁇ m and a thickness t 131b of less than 100 nm. Thereby, packing density can be improved.
  • the plate-like metal hydroxide 131 is preferably any one selected from the group consisting of Co (OH) 2 , Ni (OH) 2 , and Mn (OH) 2 .
  • Cobalt hydroxide has a layer structure with a wide interlayer distance, ions can be taken in and out quickly between the layers, and ions can be efficiently supplied to the layer surface serving as the surface of the active substance.
  • the groove-formed conductive fiber 43 is preferably made of any material selected from the group consisting of carbon, nickel, and titanium. By using these materials, it is possible to efficiently absorb the electrolyte ions on the wide access surface of the active substance, and by electrostatic charging, a double layer capacitance is formed, which is electrochemically stable. Capacitors can be formed.
  • the diameter of the groove-formed conductive fiber 43 is preferably 8 ⁇ m or less. Thereby, the sheet
  • FIG. 12 is a flowchart figure which shows an example of the manufacturing method of the plate-shaped metal hydroxide containing sheet-like electrode which is 2nd embodiment of this invention.
  • FIG. 13 is a process diagram showing an example of a method for producing a plate-like metal hydroxide-containing sheet electrode according to the second embodiment of the present invention.
  • the method for producing a plate-like metal hydroxide-containing sheet-like electrode according to the second embodiment of the present invention includes a groove-formed conductive fiber sheet production step S1 and a plate-like metal hydroxide.
  • FIG. 14 is a figure which shows an example of the electroconductive fiber sheet which is 2nd embodiment of this invention, Comprising: The A section enlarged view (c) of a top view (a), a side view (b), (a) FIG. 4B is an enlarged view (d) of a portion B in FIG.
  • the conductive fiber sheet include a carbon fiber sheet.
  • the carbon fiber has a diameter of 1 ⁇ m to 100 ⁇ m, a thickness of 0.1 mm to 1 cm, and a density of 0.1 g / cm 3 to 10 g / cm 3 .
  • the area and shape are not particularly limited.
  • the carbon fiber sheet is formed by weaving carbon fibers, provided with a large number of holes, and has a porous structure. There may be anisotropy in the direction of the surface resistance of the carbon fiber sheet.
  • the lateral surface resistance may be 5.8 m ⁇ ⁇ cm
  • the vertical resistance may be 80 m ⁇ ⁇ cm.
  • the conductive fiber sheet is electrically etched.
  • the conditions are such that 2 V is applied for 10 minutes in a 1 M H2SO4 electrolyte.
  • the carbon fiber can be changed to an electrically etched carbon fiber.
  • a plurality of groove portions extending in a direction substantially parallel to the axial direction and a wall portion defining each groove portion can be provided on the surface of the conductive fiber.
  • FIG. 15 is a figure which shows an example of the conductive fiber sheet by which the groove formation process which is 2nd embodiment of this invention was carried out, Comprising: The A section expansion of a top view (a), a side view (b), (a) It is a figure (c).
  • FIG. 16 is a view showing an example of the groove-formed conductive fiber, and is an enlarged view of a portion B in FIG. 15C (a), a cross-sectional view taken along the line CC ′ in FIG. ). As shown in FIGS.
  • 43a, 43d, 43f, 43i, and 43m can be provided.
  • the groove portion is made hydrophobic, and can easily form a plate-like metal hydroxide nucleus. Further, by providing the groove portion, the surface area per unit mass of the conductive fiber 43 can be increased.
  • Platinum-like metal hydroxide-containing sheet-like electrode production step S2 Next, using a conductive fiber sheet after groove formation as a working electrode, using a platinum plate as a counter electrode, and using a saturated Ag / AgCl reference electrode, one end side of each electrode Is immersed in an ethanol solution in which raw materials of plate-like metal hydroxide and potassium hydroxide are dispersed.
  • the distance between the work function and the counter electrode is fixed at, for example, 1.5 cm.
  • Examples of the raw material for the plate-like metal hydroxide include cobalt acetate.
  • the cobalt acetate concentration is, for example, 1M.
  • each electrode is connected to a power source, and a voltage is applied between the electrodes.
  • a constant current having a current density of 5 mA / cm 2 is passed.
  • the film thickness and density are controlled by controlling the voltage application time, that is, the time during which the current is applied.
  • FIGS. 17A and 17B are diagrams showing an example of the surface of the groove-formed conductive fiber in the initial stage of the electrodeposition process, where FIG. 17A corresponds to FIG. 16A and FIG. 16B corresponds to FIG. FIG.
  • a small amount of the plate-like metal hydroxide 131 is electrodeposited on the surface 43z of the groove-formed conductive fiber 43 to nucleate.
  • more of the plate-like metal hydroxide 131 is electrodeposited on the surface 43z of the groove-formed conductive fiber 43 and more nucleates. Further, crystals grow from the formed nuclei so as to extend from the surface 43z of the groove-formed conductive fiber 43.
  • a plate-like metal hydroxide-containing sheet-like electrode 111 in which a plurality of plate-like metal hydroxides 131 are accumulated on the surface 43z of the groove-formed conductive fiber 43 is created.
  • the surface 43z can be completely covered with the plate-like metal hydroxide 131 according to the processing time.
  • a second layer can be formed on the formed layer of the plate-like metal hydroxide 131.
  • a multilayer structure of the plate-like metal hydroxide 131 can be formed.
  • the plate-like metal hydroxide-containing sheet-like electrode 111 according to the second embodiment of the present invention includes a sheet in which the groove-formed conductive fibers 43 are knitted in a mesh shape, and the groove-formed conductive material. Since it is composed of a plurality of plate-like metal hydroxides 131 integrated on the surface 43z of the fiber 41, an electrode capable of constituting a capacitor having a high specific capacity and a long cycle life can be obtained.
  • the plate-like metal hydroxide-containing sheet-like electrode 111 according to the second embodiment of the present invention has a plurality of groove portions 43b extending in a direction substantially parallel to the axial direction on the surface 43z of the groove-formed conductive fiber 43.
  • the plate-like metal hydroxide-containing sheet-like electrode 111 has a plate-like metal hydroxide 131 having a diameter d 131a of less than 1 ⁇ m and a thickness t 131b of less than 100 nm. Since it is a structure, it can be set as the electrode which can comprise a capacitor with a high specific capacity and a long cycle life.
  • the plate-like metal hydroxide 131 is a group of Co (OH) 2 , Ni (OH) 2 , and Mn (OH) 2 . Therefore, an electrode having a high specific capacity and a long cycle life can be formed.
  • the plate-like metal hydroxide-containing sheet-like electrode 111 according to the second embodiment of the present invention has a configuration in which the diameter of the groove-formed conductive fiber 43 is 8 ⁇ m or less, so that the specific capacity is high and the cycle life is long. It can be set as the electrode which can comprise a capacitor.
  • the plate-like metal hydroxide-containing sheet-like electrode 111 according to the second embodiment of the present invention has a configuration in which the groove-formed conductive fiber 43 is made of any material selected from the group of carbon, nickel, and titanium. Therefore, an electrode capable of forming a capacitor having a high specific capacity and a long cycle life can be obtained.
  • the sheet 52 formed by braiding the conductive fibers 42 in a mesh shape is subjected to an electrical etching treatment, thereby providing a conductive property.
  • the sheet 53 in which the conductive fiber 43 is woven into a mesh is electrodeposited in a solution containing the plate-like metal hydroxide 131, and a plurality of plates are formed on the surface 43z of the groove-formed conductive fiber 43.
  • the manufacturing method of the plate-like metal hydroxide-containing sheet-like electrode 111 according to the second embodiment of the present invention is a step of creating a sheet 53 in which the groove-formed conductive fibers 43 are woven into a mesh shape.
  • the surface 43z of the conductive fiber 42 is provided with a plurality of groove portions 43b, 43e, 43g, 43k extending in a direction substantially parallel to the axial direction, and wall portions 43a, 43d, 43f, 43i, 43m partitioning each groove portion.
  • An electrode capable of constituting a capacitor having a high specific capacity and a long cycle life can be easily produced.
  • the method for producing the plate-like metal hydroxide-containing sheet electrode 111 according to the second embodiment of the present invention has a high specific capacity because the electric etching process is a process of applying a voltage with a potentiostat. Thus, an electrode capable of constituting a capacitor having a long cycle life can be easily produced.
  • the electrodeposition treatment is performed in the solution containing the plate-like metal hydroxide.
  • a structure in which a sheet of conductive fibers woven in a mesh is used as a work electrode, and a voltage is applied using a counter electrode and a reference electrode, so a capacitor with a high specific capacity and a long cycle life can be configured.
  • a simple electrode can be easily produced.
  • the plate-like metal hydroxide-containing capacitor 101 In the plate-like metal hydroxide-containing capacitor 101 according to the second embodiment of the present invention, two electrodes are arranged opposite to each other with the electrolyte solution impregnated layer 113 interposed therebetween, and both of the electrodes are plate-like metal water. Since it is the structure which is the oxide containing sheet-like electrode 111, it can be set as a capacitor with a high specific capacity and a long cycle life.
  • the sheet-like metal hydroxide-containing sheet-like electrode, the method for producing the same, and the plate-like metal hydroxide-containing capacitor according to the second embodiment of the present invention are not limited to the above-described embodiment, but the technology of the present invention. Various modifications can be made within the scope of the technical idea. A specific example of this embodiment is shown in Example 2 below. However, the present invention is not limited to these examples.
  • Example 1 ⁇ Creation of graphene oxide> Graphene oxide was synthesized from graphite by the modified Hummers-Offman method as follows. First, graphite and NaNO 3 were mixed in a flask. Next, H 2 SO 4 (95%) was added into the flask. Next, it was stirred in an ice bath. Next, potassium permanganate was added to the suspension. The suspension was then stirred at room temperature for 2 hours. The suspension became a light brown color. The suspension was then diluted and stirred at 98 ° C. for 12 hours. Then H 2 O 2 was added. The product was then washed with 5% HCl and deionized water. Next, it was centrifuged, filtered, and dried in vacuo. Through the above process, black powder graphene oxide was prepared.
  • (Ii) Crystal growth step The current density was controlled at 5 mA / cm 2 for 30 minutes. The thickness of the Co (OH) 2 layer was controlled by the coating time. Through the above steps, a Co (OH) 2 vertically aligned graphene / CNT composite (Example 1) was prepared.
  • FIG. 5 shows a TEM image (a), an enlarged TEM image (b), an SEM image (c), and an enlarged SEM image (d) of Example 1. Both are graphene images immediately after synthesis. As shown in FIGS. 5A and 5B, a sheet made of several thin and flat graphene layers was observed. As shown in FIGS.
  • Co (OH) 2 arranged in a direction perpendicular to the graphene sheet surface, the main surface facing a random direction, and forming a porous structure could be observed.
  • the thickness of Co (OH) 2 was about 10 nm.
  • FIG. 6 shows TEM images (a), STEM images (b), and (b) of C component mapping images (c) and (b) of Co (OH) 2 vertically aligned graphene / CNT composites (Example 1). It is explanatory drawing (f) of Co component mapping image (e), (a) of O component mapping image (d), (b). Since an amorphous carbon grid was used, no clear image was seen in the C component mapping image. However, from the results shown in FIGS. 6B, 6D, and 6E, as shown in FIG. 6F, FIG. 6A shows that Co (OH) 2 is bonded to the surface of graphene. It was judged that it was a sample. The TEM sample was prepared by irradiating with strong ultrasonic waves. However, since Co (OH) 2 bond to the surface of graphene was observed, this bond was estimated to be very strong.
  • FIG. 7A is a CV curve for each scan speed of 10, 20, 50, and 100 mV / s in EMI-TFSI. As shown in FIG. 7A, a symmetrical and substantially rectangular CV curve was obtained. It is known that the ideal capacitor CV curve has a rectangular shape when the contact resistance is small, and is deformed so that the shape is slanted and the ring is small when the contact resistance is large. It has been. Since the shape of FIG. 7A was symmetrical and was almost rectangular, it was found that charge propagation at the electrode was excellent.
  • FIG. 7B is a galvanostatic charge / discharge curve at 1 mA and 2 mA.
  • the galvanostatic charge discharge curve was relatively flat above 3.5V.
  • the energy density was 172 Wh / kg.
  • the specific capacity of 1 mA was 310 F / g.
  • FIG. 7C is a Nyquist plot of EIS. As shown in FIG. 7C, the imaginary part is rapidly increased so as to be almost vertical in the low-frequency region, and a Warburg curve that is hemispherical in the high-frequency region is shown.
  • R F which is a faradic leak resistance, due to a redox reaction or overcharge due to a functional group or an impurity was estimated, and the dynamic reversibility of the faradic reaction increased as R F decreased.
  • Equivalent series resistance (ESR) was 8.2 ⁇ from the Z1 intercept. The maximum power density p max was obtained by the following formula (1).
  • R ESR is the equivalent series resistance
  • (Cycle characteristics) 7 (d) is a graph showing the cycle characteristics results in a current density of 1 mg / cm 2 coated samples 2A / g. It decreased by 30% at 1500 cycles.
  • Example 2 ⁇ Sheet electrode manufacturing> First, the lateral surface resistance is 5.8 m ⁇ ⁇ cm, the vertical resistance is 80 m ⁇ ⁇ cm, and the density is 0.44 g / cm 3 .
  • a carbon fiber cloth Carbon fiber cloth, Toray, Inc., Japan having an average diameter of 8 ⁇ m and a thickness of 0.19 mm was prepared.
  • the carbon fiber cloth was electrically etched using a potentiostat.
  • the conditions were such that 2 V was applied for 10 minutes in 1 MH 2 SO 4 electrolyte.
  • the electrically etched carbon fiber cloth was cut, and a work electrode was created with a plan view area of 1 ⁇ 2 cm 2 .
  • cobalt acetate (Potassium hydroxide) and ethanol are prepared as Sigma-Aldrich analytical reagent grades, and these are mixed and mixed with 0.1 M acetic acid. A cobalt solution was prepared.
  • FIG. 18 is an SEM image of the carbon fiber sheet.
  • FIG. 19 is an SEM image of carbon fiber. A smooth carbon fiber having an average diameter of 8 ⁇ m was observed.
  • FIG. 20 is an SEM image of the groove-formed carbon fiber sheet. A carbon fiber was observed on the surface, which was elongated in the axial direction and formed with a groove having a groove width of 0.1 to 0.5 ⁇ m.
  • FIG. 21 is an SEM image of a sheet-like metal hydroxide-containing sheet electrode having a coating density of 1 mg / cm 2
  • FIG. 22 is an enlarged SEM image thereof.
  • the plurality of plate-like metal hydroxides were arranged so as to stand perpendicular to the surface of the groove-formed conductive fiber. It was integrated so as to completely cover the surface and to form a uniform layer. The direction perpendicular to the main surface of the plate-like metal hydroxide standing vertically was disordered as a whole.
  • FIG. 23 is an electron diffraction pattern of Co (OH) 2 .
  • the pattern of Bragg reflection arranged in a hexagonal shape is shown, and the crystal orientation of [001] is shown.
  • FIG. 24 is a TEM image of Co (OH) 2 .
  • the crystal contained a hexagonal crystal in plan view.
  • FIG. 25 is a high-resolution TEM (High-Resolution TEM) image. 4.46 angstrom lattice fringes corresponding to the (001) plane of the ⁇ phase of Co (OH) 2 , 2.76 angstrom lattice fringes corresponding to the (100) plane, and 2.37 angstroms corresponding to the (101) plane was observed.
  • FIG. 26 is an SEM image with a coating density of 3 mg / cm 2 .
  • the average diameter was 40 ⁇ m.
  • a substantially bell-shaped lump having an average diameter of about 10 ⁇ m was formed on the surface. Therefore, the surface uniformity was inferior to the plate-like metal hydroxide-containing sheet-like electrode having a coating density of 1 mg / cm 2 .
  • Electrochemical properties and capacitance were measured with a three-electrode system by cyclic voltammetry (CV), constant current charge / discharge test, and electrochemical impedance spectroscopy (EIS). CV was measured at a scan rate of 20 to 500 mV / s.
  • FIG. 27 is a CV curve of the plate-like metal hydroxide-containing sheet-like electrode (work electrode: coating density 1 mg / cm 2 ) of Example 2-1, and is a graph showing the scan speed dependency.
  • the scan speeds were 20, 50, 100, 200, and 500 mV / s.
  • the potential range was -0.3V to 0.5V. Strong redox peaks and non-rectangular CV curves were observed, indicating CV characteristics dominated by the response of the induced current, rather than pure electric double layer capacitance.
  • the scanning speed was fast, 500 mV / s, the current value changed the most.
  • the electrochemical reaction corresponding to this redox reaction is represented by the following chemical reaction formula (1).
  • the reaction at high potential is expressed by the following chemical reaction formula (2).
  • FIG. 28 is a charge / discharge curve of the plate-like metal hydroxide-containing sheet-like electrode (work electrode: coating density 1 mg / cm 2 ) of Example 2-1, and is a graph showing the dependency of the charge current value. .
  • the charge current values were 1, 2, 3, 4 mA. When the charge current value was 1 mA, the potential changed most over time.
  • the specific capacity is expressed by the following equation (3).
  • Cm is a specific capacity (F / g)
  • I is a constant charge / discharge current
  • ⁇ t is a discharge time
  • ⁇ V is a charge potential
  • m is an active electrode.
  • FIG. 29 is an EIS curve of the sheet metal hydroxide-containing sheet electrode (work electrode: coating density 1 mg / cm 2 ) of Example 2-1.
  • the inset is a graph with Z1 in the range of 1.5 to 2.0 (high frequency region).
  • the EIS curve is a Nyquist plot of impedance.
  • Z2 vertical axis
  • Z1 horizontal axis
  • the EIS curve could be divided into three regions depending on the frequency.
  • the EIS curve became a small semicircular shape and behaved like a pure resistor.
  • This semi-circular characteristic also indicates the correlation between the active substance and the collector, and the semi-circular diameter depends on the resistance R F of the induced current corresponding to the reciprocal of the potential depending on the charge transfer rate. Involved.
  • a Warburg curve is observed in which the electrolyte penetrates deeper into the pores of the electrode and the surface of the electrode that can be used for ion adsorption increases.
  • the effect of the porosity of the electrode on the EIS curve Observed.
  • the imaginary component increased rapidly and became almost linear, behaving like a capacitor.
  • ESR is an important factor that determines the power density of a supercapacitor and determines the rate at which the supercapacitor can be charged and discharged.
  • FIG. 30 is a graph showing the relationship between the mass standard specific capacity of the plate-like metal hydroxide-containing sheet electrode (work electrode) and the charge current value, and shows the coating density dependency.
  • the coating density was 1.0 mg / cm 2 (Example 2-1), 2.0 mg / cm 2 (Example 2-2), and 3.0 mg / cm 2 (Example 2-3).
  • the coating density was proportional to the thickness.
  • the coating density of 1.0 mg / cm 2 (Example 2-1) was 3404.8 F / g when the charge current value was 1 mA. This was very close to the theoretical value 3458. When the charge current value was 10 mA, it was 1327.3 F / g.
  • the coating density of 2.0 mg / cm 2 (Example 2-2) was 1396.1 F / g when the charge current value was 1 mA.
  • the coating density of 3.0 mg / cm 2 (Example 2-3) was 876.1 F / g when the charge current value was 1 mA.
  • FIG. 31 is a graph showing the relationship between the area-specific specific capacity and the charge current value of the plate-like metal hydroxide-containing sheet electrode (work electrode: coating density 1 mg / cm 2 ) of Example 2-1.
  • the charge current value was 1 mA
  • the area standard specific capacity was 3.3 F / cm 2 .
  • FIG. 32 is a graph showing the relationship between the retention force of the plate-like metal hydroxide-containing sheet electrode (work electrode: coating density 1 mg / cm 2 ) of Example 2-1 and the number of cycles. Even after 2000 times, the holding power of 80% was maintained. The charge current value was 10 mA. Although it was reduced by about 10% by 500 cycles, it was relatively stable up to 1500 cycles thereafter and was only reduced by about 10%. In Examples 2-2 and 2-3, almost the same results were obtained.
  • FIG. 33 is a graph showing the relationship between the total specific capacity of the plate-like metal hydroxide-containing sheet electrode (work electrode: coating density 1 mg / cm 2 ) and the charge current value of Example 2-1.
  • the total specific capacity composed of the carbon fiber and the active substance Co (OH) 2 was 614.0 F / g when the charge current value was 1 mA.
  • the mass-specific specific capacity of Co (OH) 2 that is an active substance is 3404.8 F / g.
  • Co (OH) 2 vertically aligned graphene / CNT composite of the present invention its production method, Co (OH) 2 vertically aligned graphene / CNT composite electrode and Co (OH) 2 vertically aligned graphene / CNT composite capacitor are High capacity and long cycle life can be used in the battery industry, energy industry and the like.
  • the plate-like metal hydroxide-containing sheet-like electrode of the present invention has a high specific capacity and a long cycle life.
  • the manufacturing method and the plate-like metal hydroxide-containing capacitor can be provided, and can be used in the battery industry, the energy industry, and the like.
  • DESCRIPTION OF SYMBOLS 101 ... Plate-shaped metal hydroxide containing capacitor, 111 ... Plate-shaped metal hydroxide containing sheet-like electrode, 111c ... Hole, 113 ... Electrolyte impregnation layer (separator), 121 ... Surface coating conductive fiber, 131 ... Plate Metal hydroxide, 131a ... diameter, 131b ... thickness, 42 ... conductive fiber, 43 ... groove-formed conductive fiber, 43a, 43d, 43f, 43i, 43m ... wall, 43b, 43e, 43g, 43k ... groove part, 43z ... surface, 52 ... conductive fiber sheet, 53 ... groove-formed conductive fiber sheet.

Abstract

Condensateur contenant un hydroxyde métallique, caractérisé en ce qu'il comprend deux électrodes contenant un hydroxyde métallique qui contiennent un matériau d'électrode à alignement hydroxyde métallique et qui sont agencées de façon opposée en prenant en sandwich une couche imprégnée d'un électrolyte. Une électrode ou les deux électrodes sont soit une électrode composite de graphène à alignement vertical Co (OH)2 /CNT formée d'un composite de graphène à alignement vertical Co (OH)2 /CNT sur une surface d'une électrode en forme de plaque, soit une électrode en forme de feuille contenant un hydroxyde métallique en forme de plaque, laquelle électrode comprend une feuille formée de fibres conductrices traitées à formation de gorge et tissées en forme de mailles, et plusieurs hydroxydes métalliques en forme de plaques accumulés sur la surface des fibres conductrices traitées à formation de gorge.
PCT/JP2014/067514 2013-07-17 2014-07-01 Matériau d'électrode à alignement hydroxyde métallique, électrode contenant un hydroxyde métallique, procédé de fabrication de ces électrodes, et condensateur contenant un hydroxyde métallique WO2015008615A1 (fr)

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JP2013148218A JP6057293B2 (ja) 2013-07-17 2013-07-17 Ｃｏ（ＯＨ）２垂直配向グラフェン／ＣＮＴ複合体、その製造方法、Ｃｏ（ＯＨ）２垂直配向グラフェン／ＣＮＴ複合体電極及びＣｏ（ＯＨ）２垂直配向グラフェン／ＣＮＴ複合体キャパシター
JP2013-148218 2013-07-17
JP2013-155384 2013-07-26
JP2013155384A JP6161158B2 (ja) 2013-07-26 2013-07-26 板状金属水酸化物含有シート状電極、その製造方法及び板状金属水酸化物含有キャパシター

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CN106920932A (zh) * 2017-03-10 2017-07-04 上海应用技术大学 一种竹叶状Co(OH)2/石墨烯复合电极材料及其制备方法
CN107644743A (zh) * 2017-08-25 2018-01-30 天津大学 一种自支撑三维多孔氮掺杂石墨烯－氢氧化镍超电容电极材料的制备方法
CN109903998A (zh) * 2019-02-26 2019-06-18 内蒙古科技大学 一种复合电极及其制备方法和应用
CN112002564A (zh) * 2020-08-26 2020-11-27 郑州航空工业管理学院 一种超级电容器的电极材料、制备方法及应用
CN114429868A (zh) * 2021-12-17 2022-05-03 西安理工大学 三明治结构石墨烯/四硫化二钴合镍电极材料的制备方法
CN114768810A (zh) * 2022-05-13 2022-07-22 重庆科技学院 一种石墨烯载氢氧化钴光催化剂及其制备方法
JP7399958B2 (ja) 2018-10-19 2023-12-18 オシア インク． 無線電力対応の電子棚札

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CN105036107A (zh) * 2015-06-05 2015-11-11 郑州大学 超级电容器用Ni1-x-yCoxMny(OH)2@C材料及其制备方法
CN106920932A (zh) * 2017-03-10 2017-07-04 上海应用技术大学 一种竹叶状Co(OH)2/石墨烯复合电极材料及其制备方法
CN106920932B (zh) * 2017-03-10 2019-12-03 上海应用技术大学 一种竹叶状Co(OH)2/石墨烯复合电极材料及其制备方法
CN107644743A (zh) * 2017-08-25 2018-01-30 天津大学 一种自支撑三维多孔氮掺杂石墨烯－氢氧化镍超电容电极材料的制备方法
JP7399958B2 (ja) 2018-10-19 2023-12-18 オシア インク． 無線電力対応の電子棚札
CN109903998A (zh) * 2019-02-26 2019-06-18 内蒙古科技大学 一种复合电极及其制备方法和应用
CN112002564A (zh) * 2020-08-26 2020-11-27 郑州航空工业管理学院 一种超级电容器的电极材料、制备方法及应用
CN112002564B (zh) * 2020-08-26 2021-09-07 郑州航空工业管理学院 一种超级电容器的电极材料、制备方法及应用
CN114429868A (zh) * 2021-12-17 2022-05-03 西安理工大学 三明治结构石墨烯/四硫化二钴合镍电极材料的制备方法
CN114429868B (zh) * 2021-12-17 2023-11-28 西安理工大学 三明治结构石墨烯/四硫化二钴合镍电极材料的制备方法
CN114768810A (zh) * 2022-05-13 2022-07-22 重庆科技学院 一种石墨烯载氢氧化钴光催化剂及其制备方法

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