WO2012088697A1 - 石墨烯衍生物-碳纳米管复合材料及其制备方法 - Google Patents

石墨烯衍生物-碳纳米管复合材料及其制备方法 Download PDF

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Publication number
WO2012088697A1
WO2012088697A1 PCT/CN2010/080531 CN2010080531W WO2012088697A1 WO 2012088697 A1 WO2012088697 A1 WO 2012088697A1 CN 2010080531 W CN2010080531 W CN 2010080531W WO 2012088697 A1 WO2012088697 A1 WO 2012088697A1
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graphene
carbon nanotube
graphene oxide
nanotube composite
derivative
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English (en)
French (fr)
Chinese (zh)
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周明杰
吴凤
王要兵
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Oceans King Lighting Science and Technology Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
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Priority to US13/990,113 priority Critical patent/US20130252499A1/en
Priority to PCT/CN2010/080531 priority patent/WO2012088697A1/zh
Priority to EP10861263.1A priority patent/EP2660192B1/en
Priority to JP2013546556A priority patent/JP5775603B2/ja
Priority to CN201080069677.0A priority patent/CN103153843B/zh
Publication of WO2012088697A1 publication Critical patent/WO2012088697A1/zh
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/168—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]

Definitions

  • the invention relates to a nano carbon composite material, in particular to a graphene derivative-carbon nanotube composite material and a preparation method thereof.
  • Single-layer graphite is considered to be an ideal material due to its large specific surface area, excellent electrical conductivity, thermal conductivity, and low coefficient of thermal expansion.
  • its high conductivity properties, large specific surface properties and its two-dimensional nanoscale structural properties of monolayers can be used as electrode materials in supercapacitors and lithium ion batteries.
  • Carbon nanotubes were discovered in carbon fibers produced by the arc method in 1991 (S. Iijima, Nature 354, 56 (1991)). It is a tubular carbon molecule, and each carbon atom on the tube adopts Sp 2 hybridization, and is combined with carbon-carbon bonds to form a honeycomb structure composed of hexagons as a skeleton of carbon nanotubes; carbon nano
  • the length-to-diameter ratio of the tube is generally above 1000:1, the strength is 100 times higher than that of the same volume of steel, and the weight is only 1/6 to 1/7 of the latter; the hardness is comparable to that of diamond, but it has good flexibility.
  • the ideal high-strength fiber material is thus called 'super fiber'.
  • Fujitsu Research Institute uses chemical vapor deposition growth method at 510 °C At the temperature of the multi-walled carbon nanotubes which are formed in a vertical direction with respect to the bottom plate, a composite structure formed of several layers to several tens of layers of graphite self-organization is formed. This is the first non-atomic structure bonded structure in which a one-dimensional carbon nanotube is vertically joined to a two-dimensional graphene.
  • a graphene derivative - a carbon nanotube composite material comprising a mass ratio of 1 to 5:1 Graphene derivative and carbon nanotube, the graphene derivative - the graphene derivative and the carbon nanotube in the carbon nanotube composite material interpenetrate and entangle each other to form a connected network structure.
  • the graphene derivative is a fluorinated graphene oxide or a nitrogen-doped graphene oxide.
  • the carbon nanotubes have a diameter of 5 to 200 nanometers and a length of 0.1 to 100. Micron hollow tubular carbon material.
  • a graphene derivative-carbon nanotube composite material preparation method comprising the following steps:
  • Step 1 adding the graphene derivative and the carbon nanotube to the alcohol dispersant, and ultrasonically dispersing for 120 to 150 minutes to form a stable suspension;
  • Step 2 The suspension is filtered, and the solid is dried and cooled to room temperature to obtain a graphene derivative-carbon nanotube composite.
  • the mass ratio of the graphene derivative to the carbon nanotube in the first step is 1 to 5:1.
  • the alcohol dispersant in step one is one of ethanol, ethylene glycol, and isopropanol.
  • the drying temperature in the second step is 50 to 80 ° C and the drying time is 48 to 56 hours.
  • the graphene derivative in step one is a fluorinated graphene oxide or a nitrogen-doped graphene oxide.
  • the fluorinated graphene oxide is prepared by the following method:
  • the graphene oxide and the mixed gas composed of N 2 and F 2 are reacted at a temperature of 20 to 200 ° C for 0.5 to 24 hours to obtain the fluorinated graphene oxide.
  • the nitrogen-doped graphene oxide is prepared by the following method:
  • the graphene oxide is heated to a temperature of 500 to 800 ° C at a rate of 10 ° C / min in an ammonia atmosphere, and the heat preservation 2 After cooling to room temperature, nitrogen-doped graphene oxide was obtained.
  • the graphene derivative and the carbon nanotube composite form a hybrid interpenetrating structure, avoiding agglomeration and lamination of the graphene derivative, and better making the graphene derivative and the carbon nanotube structurally and functionally.
  • the complementary design enhances the electrical conductivity of the composite.
  • FIG. 1 is a flow chart showing a method for preparing a graphene derivative-carbon nanotube composite material according to an embodiment
  • FIG. 2 is a scanning electron micrograph of a carbon nanotube according to an embodiment
  • Figure 3 is a scanning electron micrograph of a fluorinated graphene oxide of an embodiment
  • Figure 5 is a scanning electron micrograph of nitrogen-doped graphene oxide of an embodiment
  • FIG. 6 is a scanning electron micrograph of a nitrogen-doped graphene oxide-carbon nanotube composite of an embodiment.
  • the graphene derivative-carbon nanotube composite of one embodiment comprises a graphene derivative and a carbon nanotube having a mass ratio of 1 to 5:1.
  • the two-dimensional structure of the monolayer of the graphene derivative is prone to agglomeration and lamination, curling or high wrinkling during drying of the water that loses the interlayer, and eventually the utilization of the specific surface area is greatly reduced.
  • carbon nanotubes and graphene derivatives have many similarities in structure and properties, they can be inserted into layers of graphene derivatives through carbon nanotubes, or functional groups on carbon nanotubes and functional groups on graphene derivatives. Reacting with each other to graft carbon nanotubes on the surface of the graphene derivative, so that the graphene layer and the layer are separated from each other, so as to increase the specific surface area of the graphene derivative after drying, and avoid agglomeration and stacking of the graphene derivative.
  • the layer which in turn increases the specific capacitance of the supercapacitor.
  • the graphene derivative may be a fluorinated graphene oxide or a nitrogen-doped graphene.
  • the carbon nanotubes can be hollow tubular carbon materials having a diameter of 5 to 200 nm and a length of 0.1 to 100 ⁇ m.
  • the discharge capacity of fluorinated graphite oxide is much higher than that of graphite oxide, and the discharge capacity and energy density at a discharge current density of 0.5 mA/cm 2 (1M LiClO 4 -PC ) are 675 mA h/g, respectively. 1420W h/Kg.
  • the graphene oxide is doped with a nitrogen atom, the N-doped graphene oxide can not only improve its stability, but also enhance the electrical conductivity, and also exhibit a significant biological n-type effect.
  • a method for preparing a graphene derivative-carbon nanotube composite material includes the following steps:
  • Step S110 providing or preparing a graphene derivative and a carbon nanotube.
  • the graphene derivative may be a fluorinated graphene oxide or a nitrogen-doped graphene oxide.
  • Fluorinated graphite oxide can be prepared by a conventional method. Preferably, it can be prepared by the following method:
  • step S111 graphite oxide is prepared using graphite.
  • step S112 the graphene oxide and the mixed gas composed of N 2 and F 2 are reacted at a temperature of 20 to 200 ° C for 0.5 to 24 hours to obtain the fluorinated graphene oxide.
  • the graphene oxide obtained in S111 is placed in a reactor, and a mixed gas of N 2 and F 2 is introduced (the volume fraction of F 2 is 5% to 30%), and the heating is maintained at a temperature of 20 to 200 ° C, and the reaction is 0.5. ⁇ 24 h, the graphene oxide is reacted with F 2 , and the F portion is substituted with O to obtain a fluorinated graphene oxide.
  • the volume fraction of F 2 in the mixed gas is 10%
  • the reaction temperature is 100 ° C
  • the reaction time is 1 h.
  • Nitrogen-doped graphene oxide can be prepared by a conventional method. Preferably, it can be prepared by the following method:
  • Step S111' using graphite to prepare graphene oxide.
  • the process of this step is substantially the same as step S111.
  • Step S112' the graphene oxide obtained in step S111' is heated to a temperature of 10 ° C / min in an ammonia atmosphere to The mixture was kept at 500 to 800 ° C for 2 hours, and cooled to room temperature to obtain nitrogen-doped graphene oxide.
  • the graphene oxide sample is placed in a heating furnace and is passed with high-purity ammonia gas, and the flow rate of the ammonia gas is controlled at 80 ml/min, and ammonia gas is introduced. 5 ⁇ 10 minutes, the air in the tube furnace is discharged, then the furnace is heated and heated at a heating rate of 10 °C /min to a reaction temperature of 500 °C ⁇ 800 °C, keeping 2 Hours. After completion of the reaction, it was cooled to room temperature in an ammonia atmosphere to obtain nitrogen-doped graphene oxide.
  • Carbon nanotubes can be prepared by conventional methods.
  • a hollow tubular carbon material having a diameter of 5 to 200 nm and a length of 0.1 to 100 ⁇ m is preferred.
  • Step S120, step S110 The obtained graphene derivative and carbon nanotubes are added to an alcohol dispersant and ultrasonically dispersed to form a stable suspension.
  • the graphene derivative and the carbon nanotube are added to the alcohol dispersant in a ratio of 1 to 5:1, and the ultrasonic dispersion is 120 to 150 minutes. , so that the two are evenly dispersed to form a stable suspension.
  • the alcohol dispersant is preferably one of ethanol, ethylene glycol and isopropyl alcohol.
  • Step S130 filtering the suspension, drying the solid matter, and cooling to room temperature to obtain a graphene derivative - Carbon nanotube composites.
  • the solid matter is placed in a vacuum drying oven and dried at 50 to 80 ° C for 48 to 56 hours, and cooled to room temperature to form a graphene derivative-carbon nanotube composite material.
  • Fluorine or nitrogen-doped graphene oxide can be conveniently prepared by graphene oxide to improve the stability of graphene oxide.
  • the oxygen atom is replaced, and the doping of fluorine or nitrogen can significantly increase the capacity of the electrode material.
  • the graphene derivative - The supercapacitor prepared by carbon nanotube composite has a charging specific capacity of 99 F /g ⁇ 112 F/g and a specific discharge capacity of 96 F /g ⁇ 110 F/g. The charge-discharge efficiency is 97% ⁇ 99.5%.
  • the graphene derivative is combined with the carbon nanotube to form a hybrid interpenetrating structure, avoiding agglomeration and lamination of the graphene derivative, and better achieving the structural and functional design of the graphene derivative and the carbon nanotube. Complementary.
  • the dried graphene oxide is charged into the reactor and passed through a dry nitrogen gas for 4 hours, and then fluorine gas and graphene oxide are introduced into the reactor.
  • the fluorinated graphene oxide can be obtained by reacting at ° C for 1 h.
  • the fluorine gas accounts for 10% of the volume of the mixed gas.
  • FIG. 2 a scanning electron microscope (SEM) photograph of the carbon nanotube of Example 1 is shown.
  • SEM scanning electron microscope
  • FIG. 4 SEM photograph of the fluorinated graphene oxide of Example 1 is shown.
  • FIG. 4 an SEM photograph of the fluorinated graphene oxide-carbon nanotube composite of Example 1 is shown.
  • Figure 2 ⁇ 4 It can be seen that a single carbon nanotube or a fluorinated graphene oxide has agglomeration phenomenon, but fluorinated graphene oxide - The fluorinated graphene oxide in the carbon nanotube composite material is uniformly separated by the carbon nanotubes, and no lamination or agglomeration occurs.
  • the graphene oxide is placed in the middle of the heating furnace tube and is supplied with high-purity ammonia gas.
  • the flow rate of the ammonia gas is controlled by the gas flow rate, and the flow rate of the ammonia gas is controlled at 80 ml/min, and the ammonia gas is introduced. Minute, the air in the tube furnace is discharged, and then the furnace is heated and heated at a heating rate of 10 °C /min to a reaction temperature of 800 °C, keeping 2 Hours. After completion of the reaction, the mixture was cooled to room temperature in an ammonia atmosphere, and then the nitrogen-doped graphene oxide after the reaction was taken out from the heating furnace.
  • FIG. 5 an SEM photograph of the nitrogen-doped graphene oxide of Example 2 is shown. As can be seen from Fig. 5, the nitrogen-doped graphene oxide was agglomerated and wrinkled.
  • FIG. 6 a SEM photograph of the nitrogen-doped graphene oxide-carbon nanotube composite of Example 2 is shown. As can be seen from FIG. 6, the nitrogen-doped graphene oxide in the nitrogen-doped graphene oxide-carbon nanotube composite material is uniformly separated by the carbon nanotubes without lamination or agglomeration.
  • the carbon nanotubes have a diameter of 100 nm and a length of 50 ⁇ m, and the ultrasonic dispersion is 150 min to uniformly disperse the two to form a stable suspension. Filtered and dried under vacuum at 60 °C for 50 h After that, a nitrogen-doped graphene oxide-carbon nanotube composite material is obtained.
  • the graphene derivative-carbon nanotube composite material obtained in each of Examples 1 to 4 was used as an electrode material of a supercapacitor, and the charge/discharge specific capacity and charge and discharge efficiency of the obtained supercapacitor are shown in Table 1.

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PCT/CN2010/080531 2010-12-30 2010-12-30 石墨烯衍生物-碳纳米管复合材料及其制备方法 Ceased WO2012088697A1 (zh)

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US13/990,113 US20130252499A1 (en) 2010-12-30 2010-12-30 Graphene derivative-carbon nanotube composite material and preparation methods thereof
PCT/CN2010/080531 WO2012088697A1 (zh) 2010-12-30 2010-12-30 石墨烯衍生物-碳纳米管复合材料及其制备方法
EP10861263.1A EP2660192B1 (en) 2010-12-30 2010-12-30 Graphene derivative-carbon nanotube composite material and preparation method thereof
JP2013546556A JP5775603B2 (ja) 2010-12-30 2010-12-30 グラフェン誘導体−カーボンナノチューブ複合材料と、その作製方法
CN201080069677.0A CN103153843B (zh) 2010-12-30 2010-12-30 石墨烯衍生物-碳纳米管复合材料及其制备方法

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