WO2021215578A1 - Apparatus for roll-to-roll synthesis of large-area graphene, method for manufacturing large-area graphene, and method for reducing graphene oxide fabric - Google Patents

Abstract

The present invention relates to an apparatus for roll-to-roll synthesis of large-area graphene, a method for manufacturing large-area graphene, and a method for reducing graphene oxide fabric. An apparatus for roll-to-roll synthesis of large-area graphene according to one embodiment of the present invention comprises: a reaction chamber formed to be sealed from the outside; a supply roll unit provided inside of the reaction chamber and for unwinding a reaction substrate; a gas supply unit for supplying gas required for synthesis of graphene into the reaction chamber; a plasma supply unit for supplying plasma into the reaction chamber; a heating unit for carrying out synthesis of graphene in the reaction chamber; and a recovery roll unit for recovering the synthesized large-area graphene from the heating unit.

Description

Roll-to-roll large-area graphene synthesis apparatus, large-area graphene production method, and reduction method of graphene oxide fabric

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. In addition, 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.

Although various studies are being conducted to commercialize graphene as described above, the biggest problem is to economically expand high-quality graphene to a large area. Currently, high-quality graphene can be synthesized at an applicable level through chemical vapor deposition (CVD), but a high temperature condition of up to 1000° C. must be maintained, and accordingly, there is a problem in that the process time and cost increase. In addition, research on a device and method for continuous production of high-quality graphene using the roll-to-roll chemical vapor deposition method has been conducted, and the metal catalyst pretreatment is performed to remove impurities on the metal catalyst and dense the structure of the metal catalyst through pretreatment of the catalyst substrate using plasma and laser. and made it possible to synthesize high-quality graphene. However, in the prior research, 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. In addition, from the viewpoint of a new material to be applied to the field of wearable electronic devices or electronic textiles (e-textile), graphene has a problem in that it has to undergo a complicated transfer process, which further limits its commercialization.

On the other hand, 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. In particular, although there is an advantage in that 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.

However, the problems to be solved by the present invention are not limited to those mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

A roll-to-roll large-area graphene synthesizing apparatus according to an embodiment of the present invention 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.

In an embodiment, 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.

In one embodiment, 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.

In one embodiment, 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.

In one embodiment, the large-area graphene may include at least one selected from the group consisting of graphene, pure graphene fabric, and graphene fabric.

In one embodiment, 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 according to another embodiment of the present invention 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.

In one embodiment, after the supplying of 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; may further include have.

In one embodiment, 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.

In one embodiment, the reaction substrate may include a metal catalyst substrate, a non-catalyst fabric substrate, or both.

In one embodiment, 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.

In one embodiment, the graphene synthesis step may be performed in a temperature range of 300 °C to 1000 °C.

In one embodiment, in the step of synthesizing graphene, a direction parallel to the surface of the reaction substrate may be synthesized, and single-layer graphene or multi-layer graphene may be synthesized.

In one embodiment, in the graphene synthesis step, the plasma may be discharged by applying an AC power of 10 MHz to 30 MHz.

In one embodiment, the 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 reduction method of the graphene oxide fabric according to another embodiment of the present invention, 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.

In one embodiment, 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.

In one embodiment, 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 according to an embodiment of the present invention 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. In addition, 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 according to an embodiment of the present invention 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) can be commercialized, and various masks are applied in the reduction process to reduce graphene oxide fabric and enable patterning at the same time. In addition, 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.

1 is a schematic diagram of a roll-to-roll large-area graphene synthesizing apparatus according to an embodiment of the present invention.

2 is an internal perspective view of a roll-to-roll large-area graphene synthesizing apparatus according to an embodiment of the present invention.

3 is a flowchart illustrating a method of manufacturing large-area graphene according to an embodiment of the present invention.

4 is a flowchart illustrating a method for reducing graphene oxide fabric according to an embodiment of the present invention.

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.

6 is a graph of Raman spectroscopy measurement results of large-area monolayer graphene prepared according to Example 1 of the present invention.

7 is a graph of the impedance measurement result of the reduced graphene fabric prepared according to Example 2 of the present invention.

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.

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.

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. .

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 .

12 is a structure for obtaining plasma by placing a flat electrode in parallel with the tube inside the quartz tube of the roll-to-roll large-area graphene synthesis apparatus (PECVD) according to an embodiment of the present invention.

Hereinafter, embodiments will be described in detail with reference to the accompanying drawings. However, since various changes may be made to the embodiments, the scope of the patent application is not limited or limited by these embodiments. It should be understood that all modifications, equivalents and substitutes for the embodiments are included in the scope of the rights.

The terms used in the examples are used for description purposes only, and should not be construed as limiting. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present specification, terms such as “comprise” or “have” are intended to designate that a feature, number, step, operation, component, part, or combination thereof described in the specification exists, but one or more other features It should be understood that this does not preclude the existence or addition of numbers, steps, operations, components, parts, or combinations thereof.

Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which the embodiment belongs. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related art, and should not be interpreted in an ideal or excessively formal meaning unless explicitly defined in the present application. does not

In addition, in the description with reference to the accompanying drawings, the same components are given the same reference numerals regardless of the reference numerals, and the overlapping description thereof will be omitted. In the description of the embodiment, if it is determined that a detailed description of a related known technology may unnecessarily obscure the gist of the embodiment, the detailed description thereof will be omitted.

In addition, in describing the components of the embodiment, terms such as first, second, A, B, (a), (b), etc. may be used. These terms are only for distinguishing the components from other components, and the essence, order, or order of the components are not limited by the terms.

Components included in one embodiment and components having a common function will be described using the same names in other embodiments. Unless otherwise stated, a description described in one embodiment may be applied to another embodiment, and a detailed description in the overlapping range will be omitted.

A roll-to-roll large-area graphene synthesizing apparatus according to an embodiment of the present invention 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.

1 is a schematic diagram of a roll-to-roll large-area graphene synthesizing apparatus according to an embodiment of the present invention, and 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.

1 and 2, the roll-to-roll large-area graphene synthesis apparatus 100 according to an embodiment of the present invention 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 according to an embodiment of the present invention is a plasma enhanced chemical vapor deposition (PECVD)-based apparatus.

In an embodiment, 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.

In an embodiment, the reaction chamber 110 may be an integral reaction chamber configured in a cylindrical shape, and may be replaceable.

In an embodiment, the supply roll device 120 may be provided in the reaction chamber 110 and may be to unwind a reaction substrate (not shown).

In the roll-to-roll large-area graphene synthesizing apparatus according to an embodiment of the present invention, 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.

In one embodiment, the reaction substrate may include a metal catalyst substrate, a non-catalyst fabric substrate, or both.

In one embodiment, 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.

In one embodiment, 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.

In one embodiment, 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. .

In one embodiment, the gas supply unit 130 may supply a gas required for graphene synthesis into the reaction chamber.

In an embodiment, the gas supply unit 130 may further include a flow controller and a valve.

In one embodiment, the gas required for graphene synthesis may include a gaseous precursor including carbon, a carrier gas, and a reaction gas.

In one embodiment, 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.

In one embodiment, 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.

In one embodiment, the reaction gas may include hydrogen.

In an embodiment, 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 .

In one embodiment, the heating unit 150 may be a graphene synthesis in the reaction chamber.

In one embodiment, 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.

In an embodiment, the plasma supply unit 140 and the heating unit 150 may surround the outside of the reaction chamber 110 .

In one embodiment, the plasma supply unit 140 may include an ICP plasma supply unit (not shown).

In one embodiment, 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.

In one embodiment, the recovery roll device 160 may be to recover the synthesized large-area graphene from the heating unit 150 .

In one embodiment, the large-area graphene may include at least one selected from the group consisting of graphene, pure graphene fabric, and graphene fabric.

In one embodiment, 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.

In one embodiment, the graphene fabric may be directly deposited on the fabric by the roll-to-roll plasma chemical vapor deposition method.

In one embodiment, 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.

In one embodiment, the recovery roll device 160 may include a pumping chamber (not shown) for controlling the pressure inside the graphene synthesis chamber.

In one embodiment, the 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

In one embodiment, 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.

In one embodiment, 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 according to an embodiment of the present invention 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. In addition, 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 according to another embodiment of the present invention 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.

3 is a flowchart illustrating a method of manufacturing large-area graphene according to an embodiment of the present invention.

Referring to FIG. 3 , the method for manufacturing large-area graphene according to an embodiment of the present invention 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.

In one embodiment, the reaction substrate mounting step 210 is a step of mounting the reaction substrate on a supply roll device.

In one embodiment, the reaction substrate may include a metal catalyst substrate, a non-catalyst fabric substrate, or both.

In one embodiment, 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.

In one embodiment, 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.

In one embodiment, 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.

In one embodiment, when forming a vacuum in the vacuum forming step, the low vacuum forming step and the high vacuum forming step may be separately performed. During the low-vacuum process, the reaction may be performed while maintaining a degree of vacuum of several mTorr to several tens of mTorr. During the high vacuum process, 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.

In one embodiment, 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. 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.

In one embodiment, after the supplying step 230 of 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.

In one embodiment, in the graphene synthesis step 240, 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.

In one embodiment, 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.

In one embodiment, 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.

In one embodiment, the reaction gas may include hydrogen.

In one embodiment, 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.

In one embodiment, when the graphene is directly grown on the non-catalytic fabric substrate, 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.

In one embodiment, 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.

In one embodiment, in the step of synthesizing graphene, a direction parallel to the surface of the reaction substrate may be synthesized, and single-layer graphene or multi-layer graphene may be synthesized.

In one embodiment, in the graphene synthesis step, 10 MHz to 30 MHz AC power may be applied to discharge the plasma. Preferably, 13.56 MHz to 27.12 MHz AC power may be applied. When RF power is applied, 10 MHz is generally used, but when 30 MHz is used, the deposition rate can be increased.

In one embodiment, 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.

In one embodiment, 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.

In one embodiment, the 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.

In one embodiment, 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.

In one embodiment, the large-area graphene may include at least one selected from the group consisting of graphene, pure graphene fabric, and graphene fabric.

In one embodiment, 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 reduction method of the graphene oxide fabric according to another embodiment of the present invention, 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.

4 is a flowchart illustrating a method for reducing graphene oxide fabric according to an embodiment of the present invention.

Referring to Figure 4, 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.

In one embodiment, the graphene oxide fabric mounting step 310 is a step of mounting the graphene oxide fabric to the supply roll device. For the reduction of the graphene oxide fabric capable of a large-area continuous process, it may be to mount the graphene oxide fabric in the reaction chamber using a supply roll device.

In one embodiment, the step of sealing the reaction chamber and forming a vacuum ( 320 ) is sealing the reaction chamber and forming a vacuum.

In one embodiment, in order to form conditions for the reduction of the graphene oxide fabric, the internal environment and the external environment of the reaction chamber may be separated and sealed, and a vacuum may be formed if necessary.

In one embodiment, the graphene oxide fabric reduction step may be performed under atmospheric pressure conditions, vacuum conditions, or both.

In one embodiment, 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. When the low-vacuum process proceeds, the reaction may be carried out while maintaining a degree of vacuum of several mTorr to several tens of mTorr. 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.

In one embodiment, 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.

In one embodiment, 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.

In one embodiment, 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.

In one embodiment, 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.

In one embodiment, 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.

In one embodiment, 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.

In one embodiment, 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.

In one embodiment, 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.

In one embodiment, using a quartz tube of PECVD and a high-temperature furnace together, it 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

In one embodiment, 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

In one embodiment, 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.

In one embodiment, the large-area graphene may include at least one selected from the group consisting of graphene, pure graphene fabric, and graphene fabric.

In one embodiment, 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.

In one embodiment, the graphene fabric may be directly deposited on the fabric by the roll-to-roll plasma chemical vapor deposition method.

In one embodiment, 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 according to an embodiment of the present invention 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) can be commercialized, and various masks are applied in the reduction process to reduce graphene oxide fabric and enable patterning at the same time. In addition, 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 according to another embodiment of the present invention 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 according to another embodiment of the present invention 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 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 according to another embodiment of the present invention 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.

Hereinafter, the present invention will be described in detail with reference to the following Examples and Comparative Examples. However, the technical spirit of the present invention is not limited or limited thereto.

[Example 1]

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. First, 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. In order to form the conditions for graphene synthesis, 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. During the low vacuum process, 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.

Then, the 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.

When forming process conditions by plasma, 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.

After the synthesis of graphene was completed, 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.

All steps after the step of mounting the reactor board were automatically performed according to the steps and values set by the built-in control program.

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.

Referring to FIG. 5 , 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. In the section from 10 kHz to 1 MHz, it showed capacitive characteristics, which increased as the frequency increased, and showed resistive characteristics that did not change with frequency in the section below 10 kHz.

6 is a graph of Raman spectroscopy measurement results of large-area monolayer graphene prepared according to Example 1 of the present invention.

Referring to FIG. 6 , it was confirmed that high-quality graphene in which most of the D peak was removed was synthesized.

[Example 2]

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. When the roll-to-roll dip coating and drying equipment are connected in series to the roll-to-roll PECVD equipment, Graphene oxide coating and reduction functionalization can be performed in a single process.

In order to form the conditions for the reduction of the graphene oxide fabric, 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. During 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.

Then, 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.

All steps after the step of mounting the graphene oxide fabric were automatically performed according to the steps and values set by the built-in control program.

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.

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.

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. . At this time, if the furnace is placed in the region where the discharge occurs, high-temperature CCP plasma can be obtained.

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.

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.

As described above, although the embodiments have been described with reference to the limited drawings, those skilled in the art may apply various technical modifications and variations based on the above. For example, the described techniques are performed in a different order than the described method, and/or the described components of the system, structure, apparatus, circuit, etc. are combined or combined in a different form than the described method, or other components Or substituted or substituted by equivalents may achieve an appropriate result.

Therefore, other implementations, other embodiments, and equivalents to the claims are also within the scope of the following claims.

Claims (18)

1. The reaction chamber is 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;

   containing,

   A roll-to-roll large-area graphene synthesis device.
2. According to claim 1,

   The reaction chamber is integrally connected from the supply roll device to the recovery roll device and is replaceable,

   The plasma supply unit and the heating unit will surround the outside of the reaction chamber,

   A roll-to-roll large-area graphene synthesis device.
3. According to claim 1,

   The supply roll device and the recovery roll device are movable in both directions,

   Supply of the reaction substrate and recovery of the large-area graphene is possible in both directions,

   A roll-to-roll large-area graphene synthesis device.
4. According to claim 1,

   The plasma supply unit includes an ICP plasma supply unit,

   Wherein the plasma supply unit is selected from the group consisting of a circle, a helical type, a plate type and annular shape in the inside, outside, or both of the quartz tube,

   A roll-to-roll large-area graphene synthesis device.
5. According to claim 1,

   The large-area graphene, which includes graphene, graphene fabric, or both,

   A roll-to-roll large-area graphene synthesis device.
6. According to claim 1,

   The axial length of the supply roll device and the recovery roll device is 1.0 m to 3.0 m,

   A roll-to-roll large-area graphene synthesis device.
7. A reaction substrate mounting step of mounting the reaction substrate to the 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;

   containing,

   Method for manufacturing large-area graphene.
8. 8. The method of claim 7,

   After the step of supplying 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 a ratio and a flow rate;

   further comprising,

   Method for manufacturing large-area graphene.
9. 9. The method of claim 8,

   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 )} ) comprising at least one selected from the group consisting of,

   The carrier gas is at least one selected from the group consisting of helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), radon (Rn) and nitrogen (N). contains gas;

   The reaction gas will include hydrogen,

   Method for manufacturing large-area graphene.
10. 8. The method of claim 7,

    The reaction substrate will include a metal catalyst substrate, a non-catalyst fabric substrate, or both,

    Method for manufacturing large-area graphene.
11. 11. The method of claim 10,

    The metal catalyst substrate is at least one selected from the group consisting of Ni, Co, Fe, Pt, Au, Al, Cu, Mg, Mn, Mo, Rh, Si, Ta, Ti, W, U, V and Zr. including,

    The non-catalytic fabric substrate, which includes at least one selected from the group consisting of carbon fibers, activated carbon fibers, glass fibers, Kevola and inorganic fibers,

    Method for manufacturing large-area graphene.
12. 8. The method of claim 7,

    The graphene synthesis step is performed at a temperature range of 300 ° C to 1000 ° C.

    Method for manufacturing large-area graphene.
13. 8. The method of claim 7,

    The graphene synthesis step is synthesized in a direction parallel to the surface of the reaction substrate,

    Single-layer graphene or multi-layer graphene is synthesized,

    Method for manufacturing large-area graphene.
14. 8. The method of claim 7,

    In the graphene synthesis step,

    Discharging the plasma by applying an AC power of 10 kHz to 30 GHz,

    Method for manufacturing large-area graphene.
15. 8. The method of claim 7,

    The reaction substrate supply step and the large-area graphene recovery step are,

    Controlled at a speed of 1 mm / min to 600 mm / min, the substrate supply and the large-area graphene is recovered by automatic tension control,

    Method for manufacturing large-area graphene.
16. Graphene oxide fabric mounting step of mounting the graphene oxide fabric on 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;

    containing,

    Reduction method of graphene oxide fabric.
17. 17. The method of claim 16,

    The graphene oxide fabric reduction step is to be carried out under atmospheric pressure conditions, vacuum conditions, or both,

    It is to discharge plasma that can obtain CCP and ICP with temperature control using a quartz tube of PECVD and a high-temperature furnace together.

    Reduction method of graphene oxide fabric.
18. 17. The method of claim 16,

    The graphene oxide fabric reduction step is,

    To discharge the plasma by applying an AC power of 1.0 kHz to 9.0 GHz under a pressure condition of 0.1 mTorr to 760 Torr,

    Reduction method of graphene oxide fabric.

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