WO2013100382A1 - Procédé de préparation d'un composite graphène-nanotubes de carbone à l'aide de pyrolyse par pulvérisation et composite graphène-nanotubes de carbone préparé par ce procédé - Google Patents

Procédé de préparation d'un composite graphène-nanotubes de carbone à l'aide de pyrolyse par pulvérisation et composite graphène-nanotubes de carbone préparé par ce procédé Download PDF

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Publication number
WO2013100382A1
WO2013100382A1 PCT/KR2012/010027 KR2012010027W WO2013100382A1 WO 2013100382 A1 WO2013100382 A1 WO 2013100382A1 KR 2012010027 W KR2012010027 W KR 2012010027W WO 2013100382 A1 WO2013100382 A1 WO 2013100382A1
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graphene
carbon nanotube
nanotube composite
precursor solution
catalyst precursor
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PCT/KR2012/010027
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English (en)
Korean (ko)
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송이화
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제일모직주식회사
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Priority claimed from KR1020120130391A external-priority patent/KR20130079144A/ko
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Publication of WO2013100382A1 publication Critical patent/WO2013100382A1/fr

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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
    • B01J2/02—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops
    • B01J2/04—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops in a gaseous medium
    • 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
    • C01B32/16—Preparation
    • C01B32/162—Preparation characterised by catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area

Definitions

  • the present invention relates to a graphene-carbon nanotube composite. More specifically, it relates to a new method for producing a graphene-carbon nanotube composite of the present invention and a graphene-carbon nanotube composite prepared by the method.
  • a carbon allotrope refers to a substance composed of carbon but different in physical or chemical properties because of its different structure.
  • graphite is a carbon layer bonded by van der Waals attraction to form a three-dimensional structure by stacking layers
  • carbon nanotubes (CNT) is a carbon layer is dried one-dimensional structure
  • fullerene (fullerene) It has a shape of 0-dimensional structure
  • graphene has a structure in which carbon atoms have a thickness of a layer of atoms in a two-dimensional honeycomb shape.
  • Graphene is a conductor having a theoretical surface area of about 2000 m 2 / g or more and an electron mobility of about 200,000 cm 2 / Vs, having an electron mobility of about 100 times that of silicon.
  • the electrical resistance value of graphene is very small, about 2/3 of the electrical resistance value of copper, the breaking strength is 42 N / m, and the Young's modulus value is similar to diamond, and the mechanical strength is excellent. Due to such excellent characteristics of graphene, attempts to actively apply graphene to electrodes and composites have been actively made.
  • Graphene synthesis methods known to date include chemical vapor deposition (CVD) and chemical methods.
  • CVD chemical vapor deposition
  • high quality graphene may be synthesized, and the graphene may be used in a transparent electrode or a flexible display.
  • the graphene prepared by the chemical method is prepared from natural graphite, oxidized the natural graphite to graphene oxide (graphene oxide) using an acid, and then ultrasonically dispersed in water, separated by one layer, and then reducing agent or Prepared by reducing with heat.
  • graphene produced by this method essentially has many defects.
  • the chemical method including the wet process has a relatively low specific surface area by the lamination of the graphene during the drying process, there is a problem that the graphene fragments are finely divided in the ultrasonic dispersion step.
  • the present inventors have developed a graphene-carbon nanotube composite having a high specific surface area and excellent electrical conductivity by forming a three-dimensional network of graphene and carbon nanotubes by using a spray pyrolysis process.
  • An object of the present invention is to provide a graphene-carbon nanotube composite having a wide specific surface area and excellent electrical conductivity by forming a three-dimensional network of graphene and carbon nanotubes.
  • Another object of the present invention is to provide a new method for producing a graphene-carbon nanotube composite having a wide specific surface area and excellent electrical conductivity by forming a three-dimensional network of graphene and carbon nanotubes.
  • Still another object of the present invention is to provide a method for preparing a new graphene-carbon nanotube composite having excellent process efficiency and economy.
  • Still another object of the present invention is to provide a new, friendly method for preparing graphene-carbon nanotube composites.
  • Graphene-carbon nanotube composite production method comprises the steps of preparing a catalyst precursor solution containing a graphene, a solvent, and a metal catalyst, spraying the catalyst precursor solution, and sprayed droplets in the reactor ( It is characterized by consisting of a step of synthesizing the graphene-carbon nanotube composite via a reaction furnace.
  • the solvent is an organic solvent having 5 or less carbon atoms in the main chain, preferably ethanol, methanol, or propanol.
  • the metal catalyst peroxine, iron chloride, cobalt nitrite or a mixture thereof may be preferably used, and the amount of the metal catalyst is preferably used in a range of 0.01 to 0.5 mol / l relative to the solvent.
  • graphene is preferably included in an amount of 0.5 to 2 mg / ml relative to the solvent.
  • Spraying the catalyst precursor solution sprays the catalyst precursor solution into the reactor using a droplet generator, and uses an ultrasonic nozzle for the droplet generator. It is preferable that the droplets of the catalyst precursor solution sprayed using the ultrasonic nozzle have a size of 5 to 50 ⁇ m.
  • the carrier gas is supplied to the reactor through which the graphene-carbon nanotube composite is synthesized via the liquid crystal generator.
  • the carrier gas is preferably an inert gas such as argon or nitrogen, methane or propane.
  • As for the temperature of a reactor 600-1500 degreeC is preferable.
  • the graphene-carbon nanotube composite of the present invention sprays the catalyst precursor solution into the reactor using a droplet generator, and pyrolysis the sprayed droplets through the reactor. Since it is manufactured by the spray pyrolysis process (Spray Pyrolysis Process) can be said.
  • graphene and carbon nanotubes form a three-dimensional network.
  • the graphene-carbon nanotube composite has a specific surface area in the range of 300 to 2000 m 2 / g, a weight ratio of graphene and carbon nanotubes in the range of 2: 1 to 1: 5, and excellent electrical conductivity.
  • Such graphene-carbon nanotube composite can produce a supercapacitor.
  • the present invention provides a graphene-carbon nanotube composite having a high specific surface area and excellent electrical conductivity by forming a three-dimensional network of graphene and carbon nanotubes, and provides a new process with excellent process efficiency and economical efficiency and an eco-friendly method. It has the effect of the invention.
  • Figure 1 is a schematic diagram showing a manufacturing process of the graphene-carbon nanotube composite by the spray pyrolysis process of the present invention.
  • Figure 2 (a) is a SEM picture of the graphene-carbon nanotube composite prepared in Example 1
  • Figure 2 (b) is a graph showing the results of EDS analysis.
  • the present invention relates to a graphene-carbon nanotube composite, a novel method for producing a graphene-carbon nanotube composite, and a graphene-carbon nanotube composite prepared by the method.
  • Method for producing a graphene-carbon nanotube composite comprises the steps of preparing a catalyst precursor solution containing a graphene, a solvent, and a metal catalyst, spraying the catalyst precursor solution, sprayed droplets reaction (reaction through a furnace) and the graphene-carbon nanotube composite is synthesized.
  • the method for producing a graphene-carbon nanotube composite is prepared by adding a graphene and a metal catalyst to a solvent to prepare a catalyst precursor solution, using a droplet generator to convert the catalyst precursor solution into a reactor Spraying, and sprayed droplets are synthesized through pyrolysis via a reaction furnace to synthesize graphene-carbon nanotube composites.
  • the present invention may further comprise the step of synthesizing the graphene before preparing the catalyst precursor solution.
  • Graphite used in the synthesis of graphene may be used as natural graphite without limitation, preferably expanded natural graphite (expanded graphite or exfoliated graphite) can be used.
  • an acid generally used such as sulfuric acid or nitric acid
  • the temperature at the time of acid treatment is 50-200 degreeC, Preferably it is 50-100 degreeC, More preferably, it is good to process below the breaking point of the acidic solution to be used.
  • the acid treatment time may vary from 1 to 24 hours depending on the acid treatment temperature, and preferably, treatment is performed within 1 to 5 hours.
  • the acid treated graphite solution is filtered to remove the solution, and further washed with water or diluted hydrochloric acid solution before filtration to increase the filtration efficiency.
  • the diluted hydrochloric acid solution is used instead of water, there is an advantage that the exothermic phenomenon occurs when using water.
  • graphene is synthesized as ions trapped in the graphite are released as a gas.
  • the heat treatment temperature can be made at 200 to 2000 °C, for effective gas release is preferably made at 500 to 1200 °C, more preferably at 700 to 1200 °C.
  • Inert gas such as nitrogen, argon, helium may be used as the gas used for the heat treatment, and a mixture of hydrogen gas may be used to remove defects of graphene that may be generated due to high temperature acid treatment.
  • the catalyst precursor solution for synthesizing the graphene-carbon nanotube composite of the present invention is prepared by dissolving a graphene and a metal catalyst in a solvent. After graphene is uniformly dispersed in a solvent, a metal catalyst is further dissolved to prepare a catalyst precursor solution.
  • the solvent can be used without limitation as long as it is a carbon-containing organic solvent that can be a carbon source.
  • an organic solvent having 5 or less carbon atoms in the main chain such as ethanol, methanol, propanol, and the like.
  • Graphene is preferably mixed in a concentration that can be uniformly dispersed in a solvent, it may be included in 0.1 to 5 mg / ml, preferably 0.5 to 2 mg / ml compared to the solvent.
  • metal ions such as iron (Fe), cobalt (Co), and nickel (Ni), which can grow and synthesize carbon nanotubes, can be used.
  • a metal catalyst that can be dissolved and ionized in an organic solvent such as ethanol may be used, and more preferably, Ferrocene, iron chloride, and cobalt nitrate may be used alone or in combination thereof. It can be used as a mixture of.
  • the metal catalyst is preferably included in an amount of 0.01 to 0.5 mol / l relative to the solvent.
  • the amount of carbon nanotubes synthesized between the graphenes may be reduced, causing aggregation between graphenes.
  • the metal catalyst particles The reactivity of these compounds increases the synthesis yield of carbon nanotubes.
  • FIG. 1 is a schematic diagram showing a manufacturing process of the graphene-carbon nanotube composite by the spray pyrolysis process of the present invention.
  • the graphene-carbon nanotube composite manufacturing apparatus of the present invention is a droplet generator (2) for spraying the catalyst precursor solution, the sprayed droplet is synthesized into the graphene-carbon nanotube composite It consists of a high temperature reactor 3 and a collector 4 for collecting the synthesized graphene-carbon nanotube composite.
  • An ultrasonic nozzle is used for the droplet generator 2. It is preferable that the droplets of the catalyst precursor solution sprayed using the ultrasonic nozzle have a size of 5 to 50 ⁇ m.
  • the carrier gas is supplied to the reactor 3 through which the graphene-carbon nanotube composite is synthesized via the liquid crystal generator 2. In order to measure the amount of carrier gas supplied, a gas flow meter 1 is installed before the liquid crystal generator 2.
  • the carrier gas is preferably an inert gas such as argon or nitrogen, methane, or propane. As for the temperature of a reactor, 600-1500 degreeC is preferable.
  • various spraying methods such as an ultrasonic nozzle method and a general nozzle method may be used.
  • an ultrasonic nozzle method capable of giving sufficient residence time for synthesizing carbon nanotubes is preferable.
  • the droplet size of the catalyst precursor produced is 100 ⁇ m or more.
  • the size of the droplet is 100 ⁇ m or more, it is difficult to synthesize graphene-carbon nanotubes because the drying step, the reaction / synthesis step, and the firing step in the reactor are difficult to occur in a single step.
  • the droplet size is sprayed into the reactor is 5 to 50 ⁇ m, it can be synthesized in a single process.
  • the size of the sprayed spray can be changed according to the concentration of the precursor and the intensity of the ultrasonic wave.
  • the sprayed droplets can be moved into the high temperature reactor 3 by the carrier gas, and the speed, the reactor temperature and the length of the carrier gas determine the time the droplets stay in the reactor.
  • the residence time is short, the catalytic ion becomes a catalyst particle, and it is difficult to complex the graphene with the growth of carbon nanotubes from the catalyst particle.
  • the supply rate of the carrier gas may be determined in consideration of the residence time of the droplets.
  • the carrier gas may be supplied at a feed rate of 0.2 to 3 LPM (l / min).
  • the droplets of the sprayed catalyst precursor solution are passed through the high temperature reactor 3 through the carrier gas supplied to the reactor, and thermally decomposes carbon nanotubes on the metal catalyst, thereby gradually increasing the graphene-carbon nanotubes. Is synthesized.
  • argon, nitrogen, or the like which is an inert gas
  • methane, propane, or the like may be mixed and used together with argon, nitrogen, hydrogen, and the like to auxiliaryly supply a carbon source.
  • graphene-carbon nanotube composites can be synthesized using argon and nitrogen gas, which are inert gases, without supplying a separate carbon source. Therefore, the post-treatment process of the expensive carbon source gas discharged unreacted is not necessary, and there is no fear that a problem such as an explosion may occur because the carbon source gas does not pass the high temperature gas furnace. Therefore, it is more preferable to use inert gases argon and nitrogen as carrier gases.
  • the reactor is a long, high-temperature device that can secure a sufficient residence time while giving a high temperature.
  • the temperature of the reaction furnace is 600-1500 degreeC, Preferably it is 700-1100 degreeC.
  • the reactor has a length of 1 to 3 m, it is preferably designed to ensure a residence time of at least 5 seconds.
  • the metal catalyst contained in the catalyst precursor solution supplied to the reactor is thermally decomposed together with the carbon source of the solution or gaseous carbon sources such as methane and propane, whereby Nanotubes are synthesized.
  • the diameter and the length of the carbon nanotubes may be changed according to the reaction conditions such as the type of metal ions dissolved in the precursor and the reaction temperature.
  • the synthesized carbon nanotube length is proportional to the time that the droplets stay in the reactor.
  • the synthesized graphene-carbon nanotube composite is collected in the collector 4, the synthesis of the graphene-carbon nanotube composite is completed.
  • the graphene-carbon nanotube composite synthesized by the spray pyrolysis process of the present invention has excellent electrical conductivity by efficiently forming a three-dimensional network of graphene and linear carbon nanotubes.
  • Carbon nanotubes grown from metal catalysts serve to prevent graphene from being stacked again by forming a three-dimensional structure as well as an electrical bridge connecting graphene and graphene in terms of conductivity.
  • Figure 2 (a) is a SEM picture of the graphene-carbon nanotube composite prepared in Example 1
  • Figure 2 (b) is a graph showing the results of EDS analysis.
  • the graphene-carbon nanotube composite of the present invention is the catalyst particles are placed between the graphene layer in the ion state in the synthesis step of graphene, carbon nanotubes while solving the lamination problem of graphene As it grows, graphene is dispersed.
  • graphene and carbon nanotubes form a dense network, and the network improves electrical conductivity.
  • the graphene-carbon nanotube composite When synthesizing the graphene-carbon nanotube composite using the spray pyrolysis apparatus of the present invention, it is possible to continuously synthesize the graphene-carbon nanotube composite, shorten the synthesis time, and the post-synthesis cleaning process and Since a post-treatment process such as a heat treatment process is not required, the graphene-carbon nanotube composite may be synthesized by an environmentally friendly method.
  • graphene and carbon nanotubes form a three-dimensional network.
  • the graphene-carbon nanotube composite has a specific surface area in the range of 300 to 2000 m 2 / g, a weight ratio of graphene and carbon nanotubes in the range of 2: 1 to 1: 5, and excellent electrical conductivity.
  • Such graphene-carbon nanotube composite can produce a supercapacitor.
  • Graphene prepared by ultrasonic separation method was dispersed in ethanol at a concentration of 1 mg / ml, and then ferrocene (ferrocene) was dissolved in a concentration of 0.1 M / L to prepare a precursor solution.
  • the precursor solution was sprayed onto the spray pyrolysis apparatus in the form of droplets using argon gas as a carrier gas by ultrasonic spraying.
  • Precursor droplets were synthesized into a graphene-carbon nanotube composite while passing through a high temperature reactor at 900 ° C. having a length of 1 m. After collecting the synthesized complex collected in a filter, the specific surface area was measured according to the following physical property measurement method is shown in Table 1 below.
  • Example 2 The same procedure as in Example 1 was conducted except that a precursor solution containing no catalyst was prepared.
  • the specific surface area was measured using the Brunauer-Emmett-Teller (BET) method. After determining the adsorption-desorption amount of nitrogen using a Model NOVA 4200 instrument, it was measured using the BET method. Degassing at 200 ° C. for 2 hours prior to measurement removed impurities physically adsorbed to the measurement sample.
  • BET Brunauer-Emmett-Teller
  • FIG. 1 is a SEM picture of the graphene-carbon nanotube composite prepared in Example 1
  • Figure 2 (b) is a graph showing the results of EDS analysis.
  • the SEM photograph shows that the plate-like material and the linear carbon nanotubes form a dense network
  • the EDS analysis shows that the plate-like material is composed of carbon (C) rather than iron (Fe). It can be seen that.
  • the graphene-carbon nanotube composite of the present invention can be seen that graphene and carbon nanotubes form a three-dimensional network to prevent re-lamination of graphene and have an excellent specific surface area.
  • the graphene-carbon nanotube composite of the present invention can be suitably used as an electrode material of various batteries such as secondary batteries and supercapacitors having excellent electrical conductivity.

Abstract

Conformément à la présente invention, un composite graphène-nanotubes de carbone est préparé par les étapes suivantes : ajouter du graphène à un catalyseur métallique à un solvant pour préparer une solution de précurseur de catalyseur ; pulvériser la solution de précurseur de catalyseur à un four de réaction à l'aide d'un générateur d'aérosol ; et synthétiser un composite graphène-nanotubes de carbone par pyrolyse alors que l'aérosol pulvérisé traverse le four de réaction. Le rapport de graphène et de nanotubes de carbone dans le composite graphène-nanotubes de carbone de la présente est de 2:1 à 1:5 en poids. Conformément à la présente invention, le composite graphène-nanotubes de carbone forme un réseau tridimensionnel de graphène et de nanotubes de carbone, a une surface spécifique de 300-2 000 m2/g et a une excellente conductivité électrique.
PCT/KR2012/010027 2011-12-31 2012-11-26 Procédé de préparation d'un composite graphène-nanotubes de carbone à l'aide de pyrolyse par pulvérisation et composite graphène-nanotubes de carbone préparé par ce procédé WO2013100382A1 (fr)

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KR20110147998 2011-12-31
KR10-2011-0147998 2011-12-31
KR10-2012-0130391 2012-11-16
KR1020120130391A KR20130079144A (ko) 2011-12-31 2012-11-16 분무열분해 공정을 이용한 그래핀-탄소나노튜브 복합체의 제조방법 및 그 제조방법으로 제조된 그래핀-탄소나노튜브 복합체

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Cited By (4)

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EP2769960A1 (fr) * 2013-02-22 2014-08-27 Samsung Electronics Co., Ltd Composite de graphène-nanomatériau, électrode et dispositif électrique le comprenant et procédé de fabrication du composite de graphène-nanomatériau
US20180025853A1 (en) * 2015-02-06 2018-01-25 Thales Method of depositing oxidized carbon-based microparticles and nanoparticles
CN111170310A (zh) * 2020-01-15 2020-05-19 北京科技大学 一种三维石墨烯/碳纳米管复合材料及其制备方法
CN114068927A (zh) * 2020-08-04 2022-02-18 北京大学 石墨烯碳纳米管复合材料及其制备方法

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2769960A1 (fr) * 2013-02-22 2014-08-27 Samsung Electronics Co., Ltd Composite de graphène-nanomatériau, électrode et dispositif électrique le comprenant et procédé de fabrication du composite de graphène-nanomatériau
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US20180025853A1 (en) * 2015-02-06 2018-01-25 Thales Method of depositing oxidized carbon-based microparticles and nanoparticles
CN111170310A (zh) * 2020-01-15 2020-05-19 北京科技大学 一种三维石墨烯/碳纳米管复合材料及其制备方法
CN111170310B (zh) * 2020-01-15 2022-02-25 北京科技大学 一种三维石墨烯/碳纳米管复合材料及其制备方法
CN114068927A (zh) * 2020-08-04 2022-02-18 北京大学 石墨烯碳纳米管复合材料及其制备方法
CN114068927B (zh) * 2020-08-04 2023-10-13 北京大学 石墨烯碳纳米管复合材料及其制备方法

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