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WO2021215578A1 - Appareil pour la synthèse rouleau à rouleau de graphène de grande surface, méthode de fabrication de graphène de grande surface, et méthode de réduction de tissu d'oxyde de graphène - Google Patents

Appareil pour la synthèse rouleau à rouleau de graphène de grande surface, méthode de fabrication de graphène de grande surface, et méthode de réduction de tissu d'oxyde de graphène Download PDF

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WO2021215578A1
WO2021215578A1 PCT/KR2020/007373 KR2020007373W WO2021215578A1 WO 2021215578 A1 WO2021215578 A1 WO 2021215578A1 KR 2020007373 W KR2020007373 W KR 2020007373W WO 2021215578 A1 WO2021215578 A1 WO 2021215578A1
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graphene
roll
fabric
reaction chamber
area
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Korean (ko)
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진영호
장성온
정희수
정현숙
가동원
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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
    • C01B32/184—Preparation
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0006—Controlling or regulating processes
    • B01J19/0013—Controlling the temperature of the process
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/087—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • B01J19/088—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
    • 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
    • C01B32/198—Graphene oxide
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
    • D06M10/025—Corona discharge or low temperature plasma
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock

Definitions

  • the present invention relates to a roll-to-roll large-area graphene synthesis apparatus, a method for producing large-area graphene, and a method for reducing graphene oxide fabric.
  • Graphene having a two-dimensional planar structure in which carbon atoms are arranged in a single layer has very high physicochemical stability.
  • Graphene is a material that is 200 times stronger than iron and conducts electricity up to 100 times better than copper.
  • it is recognized as an innovative material that will lead the 4th industrial revolution due to its excellent thermal conductivity and excellent transparency and airtightness, which is more than twice that of single-crystal silicon, which boasts the best thermal conductivity.
  • Graphene can be used in various fields such as displays, electronic papers, wearable smart devices, high-speed transistors, and energy electrodes. Such graphene can be synthesized by various methods such as mechanical exfoliation, chemical exfoliation, and chemical vapor deposition (CVD). In addition, the metal catalyst on which the graphene thin film is uniformly grown is etched with a solution to be transferred to a desired substrate in a wet manner, or transferred in a dry manner using a thermal film.
  • CVD chemical vapor deposition
  • the plasma pretreatment chamber was used for pretreatment purposes such as removing impurities on the metal catalyst or making the structure of the metal member dense. have.
  • graphene has a problem in that it has to undergo a complicated transfer process, which further limits its commercialization.
  • graphene synthesis by chemical exfoliation is a graphene synthesis method that can mass-produce reduced graphene with excellent mechanical and electrical properties of graphene by exfoliating graphite and chemically reducing graphene oxide.
  • graphene can be easily coated on flexible substrates such as fabrics
  • the process of reducing graphene oxide again has a low yield, is difficult to maintain high quality, uses a chemical reducing agent with high toxicity, or through heat treatment. It is insufficient to achieve commercialization because the process has to be carried out.
  • the present invention is to solve the above problems, and an object of the present invention is to provide a roll-to-roll large-area graphene synthesizing apparatus capable of continuous mass synthesis of large-area graphene.
  • Another object of the present invention is to directly grow graphene on a metal-catalyzed substrate or a non-catalyst substrate at a synthesis temperature lower than that of the prior art, and to provide a method for manufacturing large-area graphene capable of continuous mass synthesis.
  • Another object of the present invention is to provide a method for reducing graphene oxide fabric that can achieve high reduction efficiency and low process cost.
  • a roll-to-roll large-area graphene synthesizing apparatus includes: a reaction chamber formed to be sealed with the outside; a supply roll device provided inside the reaction chamber and for unwinding the reaction substrate; a gas supply unit for supplying a gas necessary for graphene synthesis into the reaction chamber; a plasma supply unit supplying plasma to the inside of the reaction chamber; a heating unit for synthesizing graphene in the reaction chamber; and a recovery roll device for recovering the synthesized large-area graphene from the heating unit.
  • the reaction chamber may be integrally connected from the supply roll device to the recovery roll device and replaceable, and the plasma supply unit and the heating unit may surround the outside of the reaction chamber.
  • the supply roll device and the recovery roll device may be movable in both directions, and the supply of the reaction substrate and the recovery of the large-area graphene may be possible in both directions.
  • the plasma supply unit may include an ICP plasma supply unit, and the plasma supply unit may be selected from the group consisting of a circle, a helical type, a flat plate type, and an annular shape in a quartz tube inside, outside, or both.
  • the large-area graphene may include at least one selected from the group consisting of graphene, pure graphene fabric, and graphene fabric.
  • the axial length of the supply roll device and the recovery roll device may be 1.0 m to 3.0 m.
  • a method for manufacturing large-area graphene includes: a reactive substrate mounting step of mounting a reactive substrate to a supply roll device; sealing the reaction chamber and forming a vacuum to separate the internal environment from the external environment; a reaction substrate supply step of continuously supplying the reaction substrate into the reaction chamber by using a supply roll device; a graphene synthesis step of synthesizing graphene by supplying a gaseous precursor into the reaction chamber through a gas supply unit, and supplying plasma and thermal energy to deposit graphene on the reaction substrate; and a large-area graphene recovery step of recovering the large-area graphene prepared from the reaction chamber through a continuous process using a recovery roll device.
  • a gas supply step of supplying a gaseous precursor, a carrier gas, a reaction gas, or a mixture thereof to the reaction chamber by controlling the ratio and flow rate; may further include have.
  • the gaseous precursor is methane (CH 4 ), acetylene (C 2 H 2 ), ethylene (C 2 H 4 ), ethane (C 2 H 6 ), propene (C 3 H 6 ) and At least one selected from the group consisting of propane (C 3 H 8 ), wherein the carrier gas is helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), At least one inert gas selected from the group consisting of radon (Rn) and nitrogen (N) may be included, and the reaction gas may include hydrogen.
  • the carrier gas is helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe)
  • At least one inert gas selected from the group consisting of radon (Rn) and nitrogen (N) may be included, and the reaction gas may include hydrogen.
  • the reaction substrate may include a metal catalyst substrate, a non-catalyst fabric substrate, or both.
  • the metal catalyst substrate, Ni, Co, Fe, Pt, Au, Al, Cu, Mg, Mn, Mo, Rh, Si, Ta, Ti, W, U, V and Zr group consisting of Including at least one selected from, the non-catalytic fabric substrate may include at least one selected from the group consisting of carbon fibers, activated carbon fibers, glass fibers, Kevola and inorganic fibers.
  • the graphene synthesis step may be performed in a temperature range of 300 °C to 1000 °C.
  • a direction parallel to the surface of the reaction substrate may be synthesized, and single-layer graphene or multi-layer graphene may be synthesized.
  • the plasma in the graphene synthesis step, may be discharged by applying an AC power of 10 MHz to 30 MHz.
  • reaction substrate supply step and the large-area graphene recovery step are controlled at a speed of 1 mm/min to 600 mm/min, and the substrate supply and the large-area graphene by automatic tension control This may be recoverable.
  • the graphene oxide fabric mounting step of mounting the graphene oxide fabric to the supply roll device; sealing the reaction chamber and forming a vacuum, sealing the reaction chamber and forming a vacuum; a graphene oxide fabric supply step of continuously supplying the graphene oxide fabric into the reaction chamber using a supply roll device; a graphene oxide fabric reduction step of reducing the graphene oxide fabric by supplying plasma, thermal energy, or both to the reaction chamber; and a reduced graphene fabric recovery step of recovering the reduced graphene fabric from the reaction chamber through a continuous process using a recovery roll device.
  • the graphene oxide fabric reduction step is performed under atmospheric pressure conditions, vacuum conditions, or both, and CCP and ICP with temperature control can be obtained by using a quartz tube of PECVD and a high-temperature furnace together. It may be to discharge the existing plasma.
  • the graphene oxide fabric reduction step may be to discharge the plasma by applying 1.0 kHz to 9.0 GHz AC power under a pressure condition of 0.1 mTorr to 760 Torr.
  • the roll-to-roll large-area graphene synthesizing apparatus enables a low synthesis temperature and a manufacturing process capable of continuous production to shorten the manufacturing time and reduce the production cost.
  • Large-area graphene and graphene fabrics manufactured using a roll-to-roll large-area graphene synthesis device enable various commercialization in the field of electronic materials based on high electrical conductivity and provide protection against toxic chemicals and flames It can be expected to be used in the field of smart protective clothing.
  • all processes can be automatically performed by the internal control program according to the set conditions, and all operations can be performed easily and quickly.
  • the method of manufacturing large-area graphene according to an embodiment of the present invention enables shortening of manufacturing time and reduction of production cost by using a low synthesis temperature and a manufacturing process capable of continuous production, and is environmentally friendly.
  • the reduction method of graphene oxide suggests reduction functionalization of graphene oxide fabric that can achieve high reduction efficiency and low process cost.
  • the reduction of graphene oxide fabric is linked to the trend of technology development such as multifunctional, integrated, integrated, e-textile, EMI shielding, signal transmission, energy harvesting, smart wearable, sensor, etc.
  • graphene-based electronic fiber e-textile
  • the reduction fabric of the graphene oxide fabric can provide a graphene-based toxic chemical protection fabric or a flame retardant fabric and a manufacturing method thereof to which a new material that can simultaneously impart various functions is applied.
  • FIG. 1 is a schematic diagram of a roll-to-roll large-area graphene synthesizing apparatus according to an embodiment of the present invention.
  • FIG. 2 is an internal perspective view of a roll-to-roll large-area graphene synthesizing apparatus according to an embodiment of the present invention.
  • FIG. 3 is a flowchart illustrating a method of manufacturing large-area graphene according to an embodiment of the present invention.
  • FIG. 4 is a flowchart illustrating a method for reducing graphene oxide fabric according to an embodiment of the present invention.
  • Example 5 is a graph showing the impedance characteristics of the single-layer graphene of the large-area single-layer graphene prepared according to Example 1 of the present invention.
  • Example 6 is a graph of Raman spectroscopy measurement results of large-area monolayer graphene prepared according to Example 1 of the present invention.
  • Example 7 is a graph of the impedance measurement result of the reduced graphene fabric prepared according to Example 2 of the present invention.
  • FIG. 8A is a diagram illustrating graphene synthesis in a plasma generating unit of a roll-to-roll large-area graphene synthesis apparatus (PECVD) according to an embodiment of the present invention.
  • PECVD roll-to-roll large-area graphene synthesis apparatus
  • Fig. 8b is a view of the coil shown in Fig. 8a with a high-temperature furnace
  • FIG. 9a shows two annular coils of a roll-to-roll large-area graphene synthesis apparatus (PECVD) according to an embodiment of the present invention at both ends outside a quartz tube containing a high-temperature furnace and applying an electric field to the inside of the quartz tube. It is a diagram showing the process of synthesizing graphene through discharge.
  • PECVD roll-to-roll large-area graphene synthesis apparatus
  • FIG. 9B is a view showing a process of discharging high-temperature CCP plasma inside the quartz tube by placing the annular coil shown in FIG. 9A inside the high-temperature furnace and applying an electric field from the outside of the quartz tube.
  • 10A is a view showing a process of synthesizing graphene through CCP plasma discharge by placing the annular coil of FIG. 9A at both ends inside a quartz tube containing a high-temperature furnace.
  • FIG. 10b is a view showing a process of discharging high-temperature CCP plasma inside a quartz tube and synthesizing graphene by placing the annular coil shown in FIG.
  • 11A is a view showing a process of obtaining plasma by wrapping an annular electrode of a certain size on the outer surface and the lower surface of the quartz tube of the roll-to-roll large-area graphene synthesis apparatus (PECVD) according to an embodiment of the present invention and applying an electric field. .
  • PECVD roll-to-roll large-area graphene synthesis apparatus
  • 11B is a diagram illustrating a process of obtaining plasma by wrapping an annular electrode having a predetermined size on the upper and lower surfaces of the quartz tube and applying an electric field as in FIG. 11A .
  • PECVD roll-to-roll large-area graphene synthesis apparatus
  • a roll-to-roll large-area graphene synthesizing apparatus includes: a reaction chamber formed to be sealed with the outside; a supply roll device provided inside the reaction chamber and for unwinding the reaction substrate; a gas supply unit for supplying a gas necessary for graphene synthesis into the reaction chamber; a plasma supply unit supplying plasma to the inside of the reaction chamber; a heating unit for synthesizing graphene in the reaction chamber; and a recovery roll device for recovering the synthesized large-area graphene from the heating unit.
  • FIG. 1 is a schematic diagram of a roll-to-roll large-area graphene synthesizing apparatus according to an embodiment of the present invention
  • FIG. 2 is an internal perspective view of a roll-to-roll large-area graphene synthesizing apparatus according to an embodiment of the present invention.
  • the roll-to-roll large-area graphene synthesis apparatus 100 includes a reaction chamber 110, a supply roll apparatus 120, a gas supply unit 130, and a plasma. It includes a supply unit 140 , a heating unit 150 , a recovery roll device 160 , and a control system 170 .
  • the roll-to-roll large-area graphene synthesis apparatus 100 is a plasma enhanced chemical vapor deposition (PECVD)-based apparatus.
  • PECVD plasma enhanced chemical vapor deposition
  • the reaction chamber 110 may separate an internal environment and an external environment through sealing. 1 and 2, it is shown that the supply roll device 120, the plasma supply part 140, the heating part 150, and the recovery roll device 160 are in each chamber.
  • reaction chamber 110 may be an integral reaction chamber configured in a cylindrical shape, and may be replaceable.
  • the supply roll device 120 may be provided in the reaction chamber 110 and may be to unwind a reaction substrate (not shown).
  • heat and plasma energy are supplied to the inside of the reaction chamber, so that it is possible to synthesize graphene on a non-catalytic substrate including a fabric as well as a metal-catalyzed substrate.
  • the reaction substrate may include a metal catalyst substrate, a non-catalyst fabric substrate, or both.
  • the metal catalyst substrate Ni, Co, Fe, Pt, Au, Al, Cu, Mg, Mn, Mo, Rh, Si, Ta, Ti, W, U, V and Zr group consisting of It may be to include at least any one selected from.
  • the non-catalytic fabric substrate may include at least one selected from the group consisting of carbon fibers, activated carbon fibers, glass fibers, Kevola and inorganic fibers.
  • the supply roll device 120 and the recovery roll device 160 to be described later may be movable in both directions, and the supply of the reaction substrate and the recovery of the large-area graphene may be possible in both directions. .
  • the gas supply unit 130 may supply a gas required for graphene synthesis into the reaction chamber.
  • the gas supply unit 130 may further include a flow controller and a valve.
  • the gas required for graphene synthesis may include a gaseous precursor including carbon, a carrier gas, and a reaction gas.
  • the gaseous precursor is methane (CH 4 ), acetylene (C 2 H 2 ), ethylene (C 2 H 4 ), ethane (C 2 H 6 ), propene (C 3 H 6 ) and Propane (C 3 H 8 ) It may include at least one selected from the group consisting of.
  • the carrier gas is selected from the group consisting of helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), radon (Rn) and nitrogen (N). It may be to include at least one inert gas.
  • the reaction gas may include hydrogen
  • the plasma supply unit 140 may supply plasma to the inside of the reaction chamber.
  • the synthesis temperature of graphene may be lowered to a level of 300° C. under the influence of various radicals generated by plasma in the plasma supply unit 140 .
  • the heating unit 150 may be a graphene synthesis in the reaction chamber.
  • plasma energy from the plasma supply unit 140 and thermal energy from the heating unit 150 are supplied to the inside of the reaction chamber 110 so that the gaseous precursor is decomposed, diffused, adsorbed, desorbed, etc. It may be synthesized on the surface of the reaction substrate. These synthesis conditions allow not only the synthesis of graphene on the metal catalyst substrate, but also the synthesis of graphene on the non-catalytic substrate including fabrics such as carbon fibers and activated carbon fibers.
  • the plasma supply unit 140 and the heating unit 150 may surround the outside of the reaction chamber 110 .
  • the plasma supply unit 140 may include an ICP plasma supply unit (not shown).
  • the plasma supply unit 140, the quartz tube (chamber, 132) inside, outside, or both may be selected from the group consisting of a circular shape, a helical type, a flat plate type, and an annular shape.
  • the recovery roll device 160 may be to recover the synthesized large-area graphene from the heating unit 150 .
  • the large-area graphene may include at least one selected from the group consisting of graphene, pure graphene fabric, and graphene fabric.
  • the pure graphene fabric a metal catalyst substrate; and a pure graphene layer deposited on the substrate, wherein the pure graphene may be directly deposited on the substrate in a large area at a lower temperature than in the prior art by a roll-to-roll plasma chemical vapor deposition method.
  • the graphene fabric may be directly deposited on the fabric by the roll-to-roll plasma chemical vapor deposition method.
  • the axial length of the supply roll device and the recovery roll device may be 1.0 m to 3.0 m. Preferably, it may be 1.0 m to 2.4 m.
  • the recovery roll device 160 may include a pumping chamber (not shown) for controlling the pressure inside the graphene synthesis chamber.
  • control system 170 controls and controls the entire process of graphene synthesis and functionalization, and includes a control panel 172 , embedded control software 174 and an emergency switch 176 . it could be
  • all processes using the roll-to-roll large-area graphene synthesizing apparatus may be automatically performed by the internal control program of the control system 170 according to set conditions, and all operations may be performed easily and quickly.
  • the reaction chamber in order to keep the tension of the rolls of the supply roll device 110 and the recovery roll device 160 constant by a control program and prevent the flexible reaction substrate from sagging due to gravity, the reaction chamber
  • the ceramic guide roll 162 may be disposed therein.
  • the guide roll 162 is of a variable type to facilitate movement and recovery of the position.
  • the roll-to-roll large-area graphene synthesizing apparatus enables a low synthesis temperature and a manufacturing process capable of continuous production to shorten the manufacturing time and reduce the production cost.
  • Large-area graphene and graphene fabrics manufactured using a roll-to-roll large-area graphene synthesis device enable various commercialization in the field of electronic materials based on high electrical conductivity and provide protection against toxic chemicals and flames It can be expected to be used in the field of smart protective clothing.
  • all processes can be automatically performed by the internal control program according to the set conditions, and all operations can be performed easily and quickly.
  • a method for manufacturing large-area graphene includes: a reactive substrate mounting step of mounting a reactive substrate to a supply roll device; sealing the reaction chamber and forming a vacuum to separate the internal environment from the external environment; a reaction substrate supply step of continuously supplying the reaction substrate into the reaction chamber by using a supply roll device; a graphene synthesis step of synthesizing graphene by supplying a gaseous precursor into the reaction chamber through a gas supply unit, and supplying plasma and thermal energy to deposit graphene on the reaction substrate; and a large-area graphene recovery step of recovering the large-area graphene prepared from the reaction chamber through a continuous process using a recovery roll device.
  • FIG. 3 is a flowchart illustrating a method of manufacturing large-area graphene according to an embodiment of the present invention.
  • the method for manufacturing large-area graphene includes a reaction substrate mounting step 210 , a reaction chamber sealing and vacuum forming step 220 , a reaction substrate supply step 230 , yes It includes a fin synthesis step 240 and a large-area graphene recovery step 250 .
  • the method of manufacturing large-area graphene according to an embodiment of the present invention may be manufacturing using a roll-to-roll large-area graphene synthesizing apparatus.
  • the reaction substrate mounting step 210 is a step of mounting the reaction substrate on a supply roll device.
  • the reaction substrate may include a metal catalyst substrate, a non-catalyst fabric substrate, or both.
  • the metal catalyst substrate Ni, Co, Fe, Pt, Au, Al, Cu, Mg, Mn, Mo, Rh, Si, Ta, Ti, W, U, V and Zr group consisting of It may be to include at least any one selected from.
  • the non-catalytic fabric substrate may include at least one selected from the group consisting of carbon fibers, activated carbon fibers, glass fibers, Kevola and inorganic fibers.
  • the step of sealing the reaction chamber and forming a vacuum 220 is a step of sealing the reaction chamber and forming a vacuum to separate the internal environment and the external environment. At this time, it may be to form a vacuum using the pumping chamber in the recovery roll device.
  • the low vacuum forming step and the high vacuum forming step may be separately performed.
  • the reaction may be performed while maintaining a degree of vacuum of several mTorr to several tens of mTorr.
  • the reaction may be carried out by forming a vacuum level of up to 10 -6 Torr.
  • the condition check of the tubular synthesis chamber and the roll-to-roll chamber, which are integrally configured, must be manufactured to a thickness sufficient to apply a high vacuum.
  • the step of supplying the reaction substrate 230 is a step of continuously supplying the reaction substrate into the reaction chamber using a supply roll device.
  • a supply roll device When supplying the reaction substrate, it is possible to control various speeds, and it is possible to supply a stable reaction substrate by automatic tension control. Since the reaction substrate is supplied on a roll-to-roll basis, it is economical because high-quality graphene can be continuously synthesized on the reaction substrate.
  • a gas supply step of supplying a gaseous precursor, a carrier gas, a reaction gas, or a mixture thereof to the reaction chamber by controlling the ratio and flow rate (not shown) ); may further include.
  • a gaseous precursor is supplied into the reaction chamber through a gas supply unit, and plasma and thermal energy are supplied so that graphene is deposited on the reaction substrate to produce graphene. This is the synthesis step.
  • the gaseous precursor is methane (CH 4 ), acetylene (C 2 H 2 ), ethylene (C 2 H 4 ), ethane (C 2 H 6 ), propene (C 3 H 6 ) and Propane (C 3 H 8 ) It may include at least one selected from the group consisting of.
  • the carrier gas is selected from the group consisting of helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), radon (Rn) and nitrogen (N). It may be to include at least one inert gas.
  • the reaction gas may include hydrogen
  • the concentration distribution of the gas including the carbon precursor in order to grow graphene on the non-catalytic fabric substrate, the concentration distribution of the gas including the carbon precursor must be uniform, and the graphene growth point is random. If the gas concentration is non-uniform, graphene grows from a high concentration to a low concentration of gaseous precursor containing carbon.
  • a gas manifold may be configured.
  • the growth of graphene may be achieved by adsorption of C x H x , CH x , C 2 radicals and hydrogen.
  • Synthesis of graphene can be made at a temperature lower than the graphene synthesis temperature of general TCVD under the influence of C x H x , CH x , C 2 radicals, and the temperature is determined by the amount of plasma power applied, the concentration and flow rate of the gaseous precursor containing carbon, It is possible in the range of 300 °C to 1000 °C depending on the moving speed of the roll, the type of the reaction substrate, and the like.
  • the graphene synthesis step may be performed in a temperature range of 300 °C to 1000 °C.
  • the roll-to-roll large-area graphene synthesis apparatus according to an embodiment of the present invention applies a roll-to-roll technique to plasma chemical vapor deposition (PECVD), and radicals generated by plasma are decomposition, diffusion, It can be used to lower the temperature at which the adsorption and desorption processes are performed. Therefore, it can be performed at a temperature lower than the conventional graphene synthesis temperature.
  • PECVD plasma chemical vapor deposition
  • a direction parallel to the surface of the reaction substrate may be synthesized, and single-layer graphene or multi-layer graphene may be synthesized.
  • 10 MHz to 30 MHz AC power may be applied to discharge the plasma.
  • 13.56 MHz to 27.12 MHz AC power may be applied.
  • 10 MHz is generally used, but when 30 MHz is used, the deposition rate can be increased.
  • plasma is formed in the chamber by applying plasma power of several tens to several hundreds of W when forming process conditions by plasma, and adsorption of hydrocarbon radicals on a metal catalyst substrate or a non-catalyst fabric substrate in the chamber , it may be that the graphene synthesis proceeds due to diffusion and the occurrence of graphene growth nuclei on the surface.
  • the large-area graphene recovery step 250 is a step of recovering the large-area graphene prepared from the reaction chamber through a continuous process using a recovery roll device.
  • reaction substrate supply step and the large-area graphene recovery step are controlled at a speed of 1 mm/min to 600 mm/min, and the substrate supply and the large-area graphene by automatic tension control This may be recoverable.
  • all steps after the step of mounting the reaction substrate may be automatically performed according to steps and values set by a built-in control program.
  • the large-area graphene may include at least one selected from the group consisting of graphene, pure graphene fabric, and graphene fabric.
  • a graphene fabric when graphene is directly grown using a non-catalytic fabric substrate such as carbon fiber or activated carbon fiber as the reaction substrate, a graphene fabric may be formed.
  • Graphene fabric can increase the potential of graphene in the field of electronic textiles (e-textile), and it can be expected to be used as a fabric that provides protection against toxic substances and flames based on the high airtightness and flame retardancy of graphene. .
  • the method of manufacturing large-area graphene according to an embodiment of the present invention enables shortening of manufacturing time and reduction of production cost by using a low synthesis temperature and a manufacturing process capable of continuous production, and is environmentally friendly.
  • the manufactured large-area graphene and graphene fabrics will enable various commercialization in the field of electronic materials based on their high electrical conductivity, and are also expected to be used in the field of smart protective clothing that provides protection against toxic chemicals and flames. can
  • the graphene oxide fabric mounting step of mounting the graphene oxide fabric to the supply roll device; sealing the reaction chamber and forming a vacuum, sealing the reaction chamber and forming a vacuum; a graphene oxide fabric supply step of continuously supplying the graphene oxide fabric into the reaction chamber using a supply roll device; a graphene oxide fabric reduction step of reducing the graphene oxide fabric by supplying plasma, thermal energy, or both to the reaction chamber; and a reduced graphene fabric recovery step of recovering the reduced graphene fabric from the reaction chamber through a continuous process using a recovery roll device.
  • FIG. 4 is a flowchart illustrating a method for reducing graphene oxide fabric according to an embodiment of the present invention.
  • the reduction method of the graphene oxide fabric according to an embodiment of the present invention, the graphene oxide fabric mounting step 310, the reaction chamber sealing and vacuum forming step 320, the graphene oxide fabric supply step (330), the graphene oxide fabric reduction step (340) and the reduced graphene recovery step (350).
  • the reduction method of the graphene oxide fabric according to an embodiment of the present invention may be manufactured using a roll-to-roll large-area graphene synthesis apparatus.
  • the graphene oxide fabric mounting step 310 is a step of mounting the graphene oxide fabric to the supply roll device.
  • the graphene oxide fabric mounting step 310 may be to mount the graphene oxide fabric in the reaction chamber using a supply roll device.
  • the step of sealing the reaction chamber and forming a vacuum ( 320 ) is sealing the reaction chamber and forming a vacuum.
  • the internal environment and the external environment of the reaction chamber may be separated and sealed, and a vacuum may be formed if necessary.
  • the graphene oxide fabric reduction step may be performed under atmospheric pressure conditions, vacuum conditions, or both.
  • the reaction when performing the reduction of the graphene oxide fabric in the vacuum forming step, it may be to proceed by separating the low vacuum forming step and the high vacuum forming step during vacuum forming.
  • the reaction may be carried out while maintaining a degree of vacuum of several mTorr to several tens of mTorr.
  • the reaction When forming a high vacuum, the reaction may proceed by forming a vacuum level of up to 10 -6 Torr.
  • the condition check of the tubular synthesis chamber and the roll-to-roll chamber, which are integrally configured, must be manufactured to a thickness sufficient to apply a high vacuum.
  • the graphene oxide fabric supply step 330 is a step of continuously supplying the graphene oxide fabric into the reaction chamber using a supply roll device.
  • the supplied graphene oxide fabric uses a fabric manufactured by a roll-to-roll dip coating and padding method in 1% to 2% aqueous solution of graphene oxide, and, if necessary, a roll-to-roll dip coating equipment and drying equipment It may be connected in series to the roll-to-roll PECVD equipment to perform graphene oxide coating and reduction functionalization in a single process.
  • the reaction chamber may be an integral reaction chamber configured in a cylindrical shape, and the plasma generator and the heat source may be of a type surrounding the outside of the chamber.
  • various speed control is possible when supplying the graphene oxide fabric, and it may be possible to supply stable graphene oxide fabric by automatic tension control.
  • various speed control is possible when supplying the graphene oxide fabric, and stable supply of the graphene oxide fabric is possible by automatic tension control. Since graphene oxide fabric is supplied on a roll-to-roll basis, it is economical because high-quality graphene can be continuously synthesized on a reactive substrate.
  • the supply roll device for supplying the graphene oxide fabric and the recovery roll device for recovering the reduced graphene fabric are movable in both directions, and the supply of the graphene oxide fabric and the reduced graphene fabric are movable. Recovery may be possible in both directions.
  • the graphene oxide fabric reduction step 340 is a step of reducing the graphene oxide fabric by supplying plasma, thermal energy, or both to the reaction chamber.
  • the graphene oxide fabric reduction step may be to discharge the plasma by applying 1.0 kHz to 9.0 GHz AC power under a pressure condition of 0.1 mTorr to 760 Torr in the graphene oxide fabric reduction step.
  • a quartz tube of PECVD and a high-temperature furnace may be to discharge a plasma capable of obtaining a CCP and an ICP capable of temperature control.
  • the reduction method of the graphene oxide fabric of the present invention is simpler than the reduction method of graphene oxide through the conventional wet process or the reduction method of graphene oxide by a simple thermal process, the manufacturing time can be shortened, and masks of various shapes Precise patterning of the reduced area is possible by applying
  • the reaction gas may be a mixed gas of hydrogen and an inert carrier gas.
  • the carrier gas includes at least one selected from the group consisting of helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), radon (Rn), and nitrogen (N). may be doing
  • the reduced graphene recovery step 350 is a step of recovering the reduced graphene fabric from the reaction chamber through a continuous process using a recovery roll device.
  • the reduction method of graphene oxide according to an embodiment of the present invention provides graphene, graphene fabric, and reduction fabric of graphene oxide fabric through a continuous process capable of large-area production.
  • the large-area graphene may include at least one selected from the group consisting of graphene, pure graphene fabric, and graphene fabric.
  • the pure graphene fabric a metal catalyst substrate; and a pure graphene layer deposited on the substrate, wherein the pure graphene may be directly deposited on the substrate in a large area at a lower temperature than in the prior art by a roll-to-roll plasma chemical vapor deposition method.
  • the graphene fabric may be directly deposited on the fabric by the roll-to-roll plasma chemical vapor deposition method.
  • the reduced graphene fabric may be a reduced graphene oxide fabric through a continuous process, and the reduction process may be continuously made at room temperature.
  • the reduction method of graphene oxide suggests reduction functionalization of graphene oxide fabric that can achieve high reduction efficiency and low process cost.
  • the reduction of graphene oxide fabric is linked to the trend of technology development such as multifunctional, integrated, integrated, e-textile, EMI shielding, signal transmission, energy harvesting, smart wearable, sensor, etc.
  • graphene-based electronic fiber e-textile
  • the reduction fabric of the graphene oxide fabric can provide a graphene-based toxic chemical protection fabric or a flame retardant fabric and a manufacturing method thereof to which a new material that can simultaneously impart various functions is applied.
  • a roll-to-roll large-area graphene synthesizing apparatus includes: an unwinder for unwinding a fabric; a plasma reactor for depositing graphene on the surface of the fabric; a gas supply device for supplying the reaction raw material of the plasma reactor; a draw roll for drawing the graphene-coated fabric into a reactor; and a winding machine for winding the coated fabric; including, a vacuum pump for forming pressure conditions of the plasma reactor, and an embedded control system for controlling the equipment.
  • a method for manufacturing a conductive graphene-based composite protective fabric comprises the steps of: (a) unwinding the fabric by an unwinder; (b) depositing pure graphene on the surface of the fabric; (c) draw roll withdrawing the fabric on which graphene is deposited from the reactor; and (d) winding the graphene deposition fabric by a winding machine.
  • the conductive graphene-based composite protective fabric manufactured by the method for manufacturing the conductive graphene-based composite protective fabric may provide high electrical conductivity, signal transmission capability, and toxic chemical protection capability.
  • An embedded control system for controlling equipment for controlling equipment according to another embodiment of the present invention, the unwinder for unwinding the fabric; a plasma reactor for reducing the graphene oxide layer coated on the fabric surface; a gas supply device for supplying a reaction gas of the plasma reactor; a draw roll for withdrawing the reduced graphene-coated fabric into a reactor; and a winding machine for winding the coated fabric.
  • a method for manufacturing a reduced graphene-based composite protective fabric comprises the steps of: (a) unwinding the fabric by an unwinder; (b) reducing the graphene oxide coated on the surface of the fabric; (c) withdrawing the graphene-coated fabric with the draw roll reduced from the reactor; and (d) winding the fabric by a winding machine.
  • the reduced graphene-based composite protective fabric produced by the method for manufacturing the reduced graphene-based composite protective fabric provides high electrical conductivity, signal transmission capability, and toxic substance detection sensor capability.
  • High-quality single-layer graphene was prepared using the roll-to-roll large-area graphene synthesis apparatus capable of large-area continuous production of the present invention.
  • the reaction chamber is an integrated reaction chamber configured in a cylindrical shape, and a device surrounding the outside of the chamber is used for the heat source and plasma generator.
  • the reaction substrate was supplied to the reaction chamber using a supply roll device.
  • a metal catalyst roll of copper (Cu) and nickel (Ni) as a reaction substrate was mounted in a roll-to-roll supply device.
  • the metal catalyst roll sealed the reaction chamber by separating the internal and external environments of the reaction chamber, and formed a vacuum using the pumping chamber. During vacuum formation, the low vacuum formation and high vacuum formation steps were separated.
  • the reaction was carried out while maintaining the vacuum level of several to 1 to 10 mTorr, and when the high vacuum was formed, the reaction was carried out by forming a vacuum level of 10 -6 Torr at the maximum.
  • the tubular synthesis chamber and roll-to-roll chamber, which are integrally configured, were manufactured to a thickness sufficient to apply a high vacuum to the transparent window.
  • reaction substrate was continuously supplied into the reaction chamber by using a supply roll device.
  • the reaction substrate was supplied at a speed of 0.06 rpm to 0.6 rpm, and a stable reaction substrate was supplied by automatic tension control.
  • Graphene is produced by supplying plasma and thermal energy so that graphene can be deposited on the reactor substrate, and methane as a gaseous precursor containing carbon in the reaction chamber after supply of the reactor substrate, and hydrogen as a reaction gas 1:10 It was supplied to the reaction chamber by controlling the flow rate at a rate.
  • plasma is formed inside the chamber by applying plasma power of 100 W to 600 W, and adsorption and diffusion of hydrocarbon radicals on the metal catalyst in the chamber and graphene growth nuclei on the surface are generated.
  • Graphene synthesis was carried out.
  • the synthesis temperature was carried out in the range of 300 °C to 500 °C.
  • the graphene prepared from the reaction chamber was recovered by winding through a continuous process using a recovery roll device at the same speed as the supply roll device.
  • Example 5 is a graph showing the impedance characteristics of the single-layer graphene of the large-area single-layer graphene prepared according to Example 1 of the present invention.
  • the impedance was measured in the range of 1 to 1 MHz, and was measured using a probe with an interval of 1 mm as an electrode.
  • the resistance was very low at the level of 1 Ohm, and it can be seen that the electrical conductivity was very high.
  • capacitive characteristics which increased as the frequency increased, and showed resistive characteristics that did not change with frequency in the section below 10 kHz.
  • Example 6 is a graph of Raman spectroscopy measurement results of large-area monolayer graphene prepared according to Example 1 of the present invention.
  • a reduced graphene fabric was prepared by performing a reduction process on the graphene oxide fabric.
  • the graphene oxide fabric used a fabric manufactured by a roll-to-roll dip coating and padding method in 1% to 2% aqueous solution of graphene oxide.
  • Graphene oxide coating and reduction functionalization can be performed in a single process.
  • the internal and external environments of the reaction chamber were separated and sealed, and atmospheric pressure or vacuum conditions were formed.
  • the reduction process of the graphene oxide fabric was carried out under both atmospheric pressure and vacuum conditions.
  • vacuum formation the low vacuum formation and high vacuum formation steps were separated.
  • the reaction proceeded while maintaining a vacuum level of several to tens of mTorr during the process using only a low vacuum, and a vacuum level of up to 10 -6 Torr was formed when forming a high vacuum to proceed with the reaction.
  • the tubular synthesis chamber and roll-to-roll chamber which are integrally configured, were manufactured to a thickness sufficient to apply a high vacuum to the transparent window.
  • the graphene oxide fabric was supplied to the reactor substrate continuously supplied into the reaction chamber at a rate of 1 mm/min to 600 mm/min using a feed roll device.
  • a plasma of 1.0 kHz to 9.0 GHz, 100 W to 600 W was supplied to reduce the graphene oxide fabric in the reaction chamber to reduce the graphene oxide.
  • a mixed gas of hydrogen and helium as an inert carrier gas was used as the reaction gas.
  • the graphene fabric reduced from the reaction chamber was recovered by winding through a continuous process using a recovery roll device.
  • Example 7 is a graph of the impedance measurement result of the reduced graphene fabric prepared according to Example 2 of the present invention. As the reduction process progressed, it was confirmed that the electrical conductivity increased by more than 10 5 times. Further improvement of electrical conductivity is expected through optimization of the process and the number of reduction cycles.
  • FIG. 8A is a diagram illustrating graphene synthesis in a plasma generating unit of a roll-to-roll large-area graphene synthesis apparatus (PECVD) according to an embodiment of the present invention.
  • the fabric or metal film supplied to the unwinder and the winder is passed through a quartz tube (chamber) wrapped with a temperature-controlled coil electrode and fed to a high-temperature furnace. At this time, a current of 1.0 kHz to 9.0 GHz may flow through the coil, and ICP plasma discharge is possible inside the quartz.
  • Fig. 8b is a view of the coil shown in Fig. 8a with a high-temperature furnace; In this case, graphene can be synthesized at a high temperature by using a high-temperature ICP plasma.
  • FIG. 9a shows two annular coils of a roll-to-roll large-area graphene synthesis apparatus (PECVD) according to an embodiment of the present invention at both ends outside a quartz tube containing a high-temperature furnace and applying an electric field to the inside of the quartz tube. It is a diagram showing the process of synthesizing graphene through discharge.
  • PECVD roll-to-roll large-area graphene synthesis apparatus
  • FIG. 9B is a view showing a process of discharging high-temperature CCP plasma inside the quartz tube by placing the annular coil shown in FIG. 9A inside the high-temperature furnace and applying an electric field from the outside of the quartz tube.
  • 10A is a view showing a process of synthesizing graphene through CCP plasma discharge by placing the annular coil of FIG. 9A at both ends inside a quartz tube containing a high-temperature furnace.
  • FIG. 10b is a view showing a process of discharging high-temperature CCP plasma inside a quartz tube and synthesizing graphene by placing the annular coil shown in FIG.
  • 11A is a view showing a process of obtaining plasma by wrapping an annular electrode of a certain size on the outer top and bottom surfaces of a quartz butte of a roll-to-roll large-area graphene synthesis apparatus (PECVD) according to an embodiment of the present invention and applying an electric field. .
  • PECVD roll-to-roll large-area graphene synthesis apparatus
  • FIG. 11B is a diagram illustrating a process of obtaining plasma by enclosing an annular electrode of a certain size on the upper and lower surfaces of the quartz butte and applying an electric field as in FIG. 11A . At this time, if the furnace is placed in the region where the discharge occurs, high-temperature CCP plasma can be obtained.
  • FIG. 12 is a structure for obtaining plasma by placing a flat electrode in parallel with a tube inside a quartz butte of a roll-to-roll large-area graphene synthesis apparatus (PECVD) according to an embodiment of the present invention. At this time, if the furnace is placed in the region where the discharge occurs, high-temperature CCP plasma can be obtained.
  • PECVD roll-to-roll large-area graphene synthesis apparatus

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Abstract

La présente invention concerne un appareil pour la synthèse rouleau à rouleau de graphène de grande surface, une méthode de fabrication de graphène de grande surface, et une méthode de réduction de tissu d'oxyde de graphène. Un appareil pour la synthèse rouleau à rouleau de graphène de grande surface selon un mode de réalisation de la présente invention comprend : une chambre de réaction formée pour être scellée de l'extérieur ; une unité de rouleau d'alimentation disposée à l'intérieur de la chambre de réaction et pour dérouler un substrat de réaction ; une unité d'alimentation en gaz pour fournir du gaz nécessaire à la synthèse de graphène dans la chambre de réaction ; une unité d'alimentation en plasma pour fournir du plasma dans la chambre de réaction ; une unité de chauffage pour effectuer la synthèse du graphène dans la chambre de réaction ; et une unité de rouleau de récupération pour récupérer le graphène de grande surface synthétisé de l'unité de chauffage.
PCT/KR2020/007373 2020-04-20 2020-06-08 Appareil pour la synthèse rouleau à rouleau de graphène de grande surface, méthode de fabrication de graphène de grande surface, et méthode de réduction de tissu d'oxyde de graphène Ceased WO2021215578A1 (fr)

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