KR20180013581A - Apparatus for producing graphine, method for producing graphine, and supercapacitor - Google Patents

Abstract

An apparatus for producing graphene of the present invention comprises a first roller for supplying and recovering porous metal foam in a roll-to-roll manner, a heating unit for heat-treating the porous metal foam and forming graphene on the surface of the porous metal foam, and a second roller for collecting and supplying the heat-treated metal foam in a roll-to-roll manner. The apparatus for producing graphene of the present invention has a stable three-dimensional structure, and allows continuous production of graphene.

Description

TECHNICAL FIELD [0001] The present invention relates to a graphene manufacturing apparatus, a graphene manufacturing method, and a supercapacitor,

TECHNICAL FIELD The present invention relates to a graphene manufacturing apparatus, a graphene manufacturing method, and a supercapacitor.

Graphene has a honeycomb two - dimensional crystal structure with carbon sp ² bonds. Graphene has excellent physical, chemical and electrical properties as well as excellent transparency due to the thickness of one atom. Therefore, it can be used as a touch panel, a flexible display, a solar cell, a heat radiation film, a coating material, a speaker, a desalination filter, , Chargers, and super capacitors.

Although graphene having a three-dimensional structure has superior properties than two-dimensional graphene, interest in the latter has been increasing recently. However, even if graphene having a three-dimensional structure is produced, it is difficult to return to a two- And the like.

Accordingly, there is a need for an apparatus capable of producing graphene having a stable three-dimensional structure as well as capable of continuously producing graphene with excellent productivity.

An object of the present invention is to provide a graphene manufacturing apparatus, a graphene manufacturing method, and a supercapacitor having a stable three-dimensional steric structure.

It is another object of the present invention to provide a graphene manufacturing apparatus, a graphene manufacturing method, and a supercapacitor which are capable of continuous production and are excellent in productivity.

It is still another object of the present invention to provide a graphene manufacturing apparatus, a graphene manufacturing method, and a supercapacitor having excellent processability.

The above and other objects of the present invention can be achieved by the present invention described below.

One aspect of the present invention relates to a graphene manufacturing apparatus.

In a specific example, the graphene manufacturing apparatus comprises a first roller for supplying and recovering a porous metal foam in a roll-to-roll fashion, a heating portion for heat-treating the porous metal foam, forming a graphene on the surface of the porous metal foam, And a second roller for collecting and supplying the heat-treated metal foam in a roll-to-roll manner.

The graphene formation may be performed by chemical vapor deposition.

The first roller and the second roller may include a ratchet system.

Wherein the graphene production apparatus comprises a working chamber formed between the first roller and the second roller and through which the porous metal foam passes and having the heating section, a first chamber accommodating the first roller, The first chamber and the second chamber may be integrally formed. The first chamber and the second chamber may be integrally formed.

The heating unit may include a temperature controllable heat source.

The second chamber may further include a material supply unit for supplying the material gas of the graphene.

The raw material supply part may further include a liquid raw material supplying part for supplying the raw material of the graphene by vaporizing the liquid or a dopant supplying part for supplying the raw material for doping the graphene.

The first chamber may further include a gas outlet for discharging gas.

Another aspect of the present invention relates to a method for producing graphene.

In one embodiment, the method comprises the steps of: first feeding a porous metal foam in a roll-to-roll fashion, heat treating the porous metal foam, firstly recovering the heat-treated porous metal foam in a roll-to-roll fashion, A second step of supplying the recovered porous metal foam by a roll-to-roll method, a step of forming graphene on the surface of the porous metal foam, and a step of recovering the graphene-formed porous metal foam by a roll-to-roll method can do.

The heat treatment may be performed at 800 ° C to 1100 ° C.

The graphene formation may be by chemical vapor deposition.

The chemical vapor deposition method may be performed at 800 ° C to 1100 ° C.

The graphene manufacturing method may further include removing the porous metal foam.

Another aspect of the present invention relates to a supercapacitor.

In an embodiment, the supercapacitor may comprise a porous metal foil formed of graphene or graphene, prepared in such a manner, as an electrode.

INDUSTRIAL APPLICABILITY The present invention has an effect of providing a graphene manufacturing apparatus capable of producing graphene having a stable three-dimensional steric structure and excellent in productivity and processability, a graphene manufacturing method, and a supercapacitor.

1 schematically shows a cross-sectional view of a graphene manufacturing apparatus according to an embodiment of the present invention.
2 schematically shows a cross-sectional view of a graphene manufacturing apparatus according to an embodiment of the present invention.
FIG. 3 is a photograph of graphene prepared according to an embodiment of the present invention, taken by an electron microscope.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Reference will now be made in detail to embodiments of the present application, examples of which are illustrated in the accompanying drawings. However, the techniques disclosed in this application are not limited to the embodiments described herein but may be embodied in other forms.

Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of this invention to those skilled in the art. In the drawings, the width, thickness, and the like of the components are enlarged in order to clearly illustrate the components of each device. In addition, although only a part of the components is shown for convenience of explanation, those skilled in the art can easily grasp the rest of the components.

The terms "upper" and "lower" in this specification are defined with reference to the drawings, Quot; or "on" may include not only superimposition but also interposition of another structure in the middle. On the other hand, what is referred to as "directly on" or "directly above"

Although the terms including ordinals such as first, second, etc. in this specification can be used to describe various elements, the elements are not limited by the terms. The terms are used only for the purpose of distinguishing one component from another.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the invention. In the drawings, the same reference numerals denote substantially the same elements.

It is to be understood that the singular forms "a", "an", and "the" include plural referents unless the context clearly dictates otherwise, and the terms "comprise" That does not preclude the presence or addition of one or more other features, integers, steps, operations, elements, parts, or combinations thereof, .

Further, in carrying out the method or the manufacturing method, the respective steps constituting the method may take place differently from the stated order unless the specific order is explicitly stated in the context. That is, each process may occur in the same order as described, may be performed substantially concurrently, or may be performed in reverse order.

Hereinafter, the present invention will be described in detail.

Grapina  Manufacturing apparatus

Referring to Fig. 1, a graphene manufacturing apparatus which is one aspect of the present invention will be described. 1 schematically shows a cross-sectional view of a graphene manufacturing apparatus according to an embodiment of the present invention.

The apparatus 1000 for manufacturing a graphene according to an embodiment of the present invention includes a first roller 100 for supplying and recovering a porous metal foam by a roll-to-roll method, a heat treatment device for heating the porous metal foam, A heating unit 200 for forming a fin and a second roller 300 for collecting and supplying the heat-treated metal foam in a roll-to-roll manner.

The graphene manufacturing apparatus 1000 of the present invention can form graphene on the surface of a porous metal foam to produce graphene having a stable three-dimensional structure. The porous metal foam is a sponge-like, fully-open porous metal structure to which all the pores are connected. When the graphene is formed on the surface of the porous metal foam, a stable three-dimensional structure can be maintained. Such a three-dimensional structure of graphene is excellent in physical, chemical and electrical properties, and thus can be applied to various fields. In particular, it can be used as an electrode and a supercapacitor with a large specific surface area.

The graphene preparation in the present invention includes a step of heat-treating the porous metal foams before forming the graphenes on the porous metal foam surfaces. A detailed method of producing graphene will be described later.

The graphene manufacturing apparatus 1000 according to the present invention can be continuously produced by applying a roll-to-roll method, and the heating unit 200 can be both heat-treated and graphene-formed. Specifically, the first roller 100 serves to supply and recover the porous metal foam 10 in a roll-to-roll manner, and the second roller 300 functions to roll the heat-treated metal foam 10 in a roll- Collecting and supplying them. More specifically, in the process (hereinafter referred to as a first process) in which the porous metal foam 10 wound around the first roller 100 is wound on the second roller 300 through the heating section 200, 200 heat-treat the porous metal foam 10. Thereafter, in the process (hereinafter referred to as a second process) in which the heat-treated porous metal foam 10 wrapped around the second roller 300 is wound around the first roller 100 after passing through the heating unit 200 again, (200) forms a graphene on the surface of the heat-treated porous metal foam (10). After the first step and the second step, if necessary, the third step substantially the same as the first step and / or the fourth step substantially the same as the second step may be repeated, but the present invention is not limited thereto.

The first roller 100 and the second roller 300 are connected to each other by an auto-reverse system in which the rotational direction is automatically changed when the second process is performed in the first process (additional third and fourth processes are possible) . The auto-reverse system can be applied to a commonly used auto-reverse system. Specifically, when the porous metal foams 10 are all unwound from the first roller 100, the rotational direction of the first and second rollers can be automatically changed.

The first roller 100 and the second roller 300 may include a ratchet system. In the ratchet system, only the roller that winds the porous metal foam 10 rotates by itself using a tooth which is engaged only in one rotation direction, so that a tension is generated, and the roller, on which the porous metal foam 10 is unwound, It is possible to effectively prevent the breakage of the porous metal foam 10, the generation of errors due to the change in the turning radius of the roller, and the deformation of the generated graphene.

The porous metal foam 10 may have a porosity of 80% or more, for example, 80 to 99%, specifically 85% to 99%, more specifically 90% to 99%. A stable three-dimensional structure of graphene can be formed within the above range.

In embodiments, the porous metal foam may be pressed to adjust porosity or pore size, pore size gradient, etc. of the porous metal foam. In this case, the pressing can be squeezed from 10 bar to 500 bar, specifically from 50 bar to 400 bar, more specifically from 50 to 300 bar. Within this range, graphene can be effectively grown on the porous metal foams.

The porous metal foam 10 may include at least one of nickel, cobalt, iron, platinum, gold, silver, aluminum, chromium, (Si), tantalum (Ta), titanium (Ti), tungsten (W), uranium (U), copper (Cu), magnesium (Mg), manganese (Mn), molybdenum , Vanadium (V), palladium (Pd), yttrium (Y), and zirconium (Zr), and alloys of the two or more components may be applied.

In the first step, the heating unit 200 heats the porous metal foam 10. The heating unit may include a temperature controllable heat source. The heating method of the heating unit may be resistance heating, high frequency induction heating, microwave heating, infrared heating, near infrared heating, or the like.

The heat treatment may be performed at a temperature of 600 ° C or higher, specifically 800 ° C to 1100 ° C in a reducing gas atmosphere. The reducing gas may include at least one of hydrogen, helium, argon, and ammonia. A mixed gas of hydrogen and ammonia can be applied in terms of heat treatment efficiency and cost. According to the heat treatment, the metal crystal of the porous metal foam grows to reduce the surface roughness, thereby preventing defects of the graphene during graphene growth and also removing the metal oxide.

In the second step, the heating unit 300 may form graphene on the surface of the heat-treated porous metal foam 10. The graphene formation can be performed by chemical vapor deposition (CVD), which will be described in detail in a graphene manufacturing method which is another aspect of the present invention. The graphene formation may be carried out at a temperature below the melting point of the porous metal foam 10, for example, a temperature of 800 ° C to 1100 ° C. Specifically, the difference between the heat treatment temperature and the graphening temperature may be 50 ° C or lower in terms of efficiency and operation of the graphene production apparatus.

Hereinafter, other configurations that can be included in the graphene manufacturing apparatus of the present invention will be described with reference to FIG. 2 schematically shows a cross-sectional view of a graphene manufacturing apparatus according to an embodiment of the present invention.

The apparatus 2000 for manufacturing a graphene according to the present invention is formed between the first roller 100 and the second roller 300 and passes through the porous metal foam 10, Further comprising a chamber (400), a first chamber (500) for receiving the first roller (100) and a second chamber (600) for receiving the second roller (300) The first chamber 500 and the second chamber 600 may be integrally formed.

The working chamber 400 is a space where heat treatment of the porous metal foam 10 and graphene are formed. In the working chamber, a reducing gas atmosphere, a carbon supply atmosphere and a dopant during graphene growth are formed around the porous metal foam 10 It is possible to provide a space which is shielded from the outside so as to be efficiently arranged and maintained in the space. The shape, size, length, etc. of the cross section of the working chamber 400 can be appropriately modified according to the graphene manufacturing environment.

The first chamber 500 and the second chamber 600 may serve to receive the first roller 100 and the second roller 300 and to block the first roller 100 and the second roller 300 from the outside. The working chamber 400, the first chamber 500, and the second chamber 600 are integrally formed so that the atmosphere necessary for each process can be efficiently formed. The shape, size, length, etc. of the first chamber 500 and the second chamber 600 may also be appropriately modified according to the manufacturing environment of the graphene.

The second chamber 600 may further include a material supply unit 700 for supplying a source gas of graphene. The raw material supply unit 700 may supply the carbon source to the working chamber 400 through the second chamber 600. As the carbon source is methane (CH _4), carbon monoxide (CO), ethane (C ₂ H _6), ethylene (CH _2), ethanol (C ₂ H _5), acetylene (C ₂ H _2), propane (CH ₃ CH ₂ CH _3), propylene (C ₃ H _6), butane (C ₄ H _10), pentane _{(CH 3 (CH 2) 3} CH 3), pentene (C ₅ H _10), dicyclopentadiene (C ₅ H _6), may include hexane (C ₆ H _14), cyclohexane (C ₆ H _12), one or more of the benzene (C ₆ H _6), toluene (C ₇ H _8). Alcohols can also be vaporized and applied as a carbon source. The raw material supply portion 700 may be formed of a material selected from the group consisting of pyridine (C ₅ H ₅ N), diazin (C ₄ H ₄ N ₂ ), triazine (C ₃ H ₃ N ₃ ) the triphenyl borane (C ₁₈ H ₁₅ B) nitrogen and boron atoms, such as doped So it is possible to provide a carbon source capable of forming a pin. The carbon source for forming the doped graphene may be supplied through the raw material supply unit 700 as described above, or may be provided with a separate dopant supply unit as described below, or may be supplied through the liquid raw material supply unit.

The raw material supply unit 700 may further include a liquid raw material supply unit (not shown) for vaporizing the liquid to supply the raw material to the graphene or a dopant supply unit (not shown) for supplying the raw material for doping the graphene. The liquid feed portion may vaporize a liquid such as an alcohol to provide a carbon source. The dopant feed portion may include pyridine (C ₅ H ₅ N), diazin (C ₄ H ₄ N ₂ ), triazine (C ₃ H ₃ N ₃ ), triphenylborane (C ₁₈ H ₁₅ B), or a boron atom. The raw material supply unit may further include a reducing gas supply unit (not shown) for supplying a reducing gas during the heat treatment, but the present invention is not limited thereto. For example, the reducing gas supply unit may be provided in the working chamber 400 or the first chamber 500.

The first chamber 500 may further include a gas outlet 800 for discharging gas. The gas outlet 800 serves to discharge gases in the chamber that are provided with carbon and that are not needed for the growth of graphene, and that allow new gases to be introduced and supplied. Therefore, the graphene production apparatus can maintain a desired atmosphere.

In an embodiment, the source feeder 700 may be provided in the first chamber 500, depending on the purpose or needs of the graphene production apparatus, wherein the gas outlet 800 is connected to the second chamber 600 But is not limited thereto.

Grapina  Manufacturing method

Another aspect of the present invention is a method for producing graphene, comprising the steps of: firstly supplying a porous metal foam by a roll-to-roll method; heat-treating the porous metal foam; firstly recovering the heat-treated porous metal foam by a roll- A second step of supplying the first recovered porous metal foam by a roll-to-roll method, a step of forming graphenes on the surface of the porous metal foam, and a step of recovering the grafted porous metal foam by a roll- Step < / RTI >

The first step of supplying the porous metal foam by the roll-to-roll method, the step of heat-treating the porous metal foam, and the step of recovering the heat-treated porous metal foam by the roll-to-roll method, Is substantially the same as the first step in the apparatus. The heat treatment may be performed at a temperature of 600 ° C or higher, specifically 800 ° C to 1100 ° C in a reducing gas atmosphere.

A step of supplying the first recovered porous metal foam by a roll-to-roll method, a step of forming graphene on the surface of the porous metal foam, and a step of recovering the grafted porous metal foam by a roll- Is substantially the same as the second step in the graphene manufacturing apparatus which is one aspect of the present invention. The graphene may be formed by chemical vapor deposition (CVD). Chemical vapor deposition (CVD) is a method of growing graphene by providing a carbon source and heat to the surface of the porous metal foam 10 as a graphene growth support. As the carbon source is methane (CH _4), carbon monoxide (CO), ethane (C ₂ H _6), ethylene (CH _2), ethanol (C ₂ H _5), acetylene (C ₂ H _2), propane (CH ₃ CH ₂ CH _3), propylene (C ₃ H _6), butane (C ₄ H _10), pentane _{(CH 3 (CH 2) 3} CH 3), pentene (C ₅ H _10), dicyclopentadiene (C ₅ H _6), may include hexane (C ₆ H _14), cyclohexane (C ₆ H _12), one or more of the benzene (C ₆ H _6), toluene (C ₇ H _8). Alcohols can also be vaporized and applied as a carbon source. When doped Yes synthesized pins as needed, pyridine (C ₅ H ₅ N), daah binary _{(C 4 H 4 N 2)} , tri-binary _{(C 3 H 3 N 3)} , triphenyl borane (C ₁₈ H ₁₅ B) can be used as a doping material for graphene. In this case, the raw material for forming the doped graphene may be provided through the carbon supply part, or may be supplied through the liquid raw material supply part if it is liquid, or may be injected through the separately provided dopant supply part.

The graphene formation may be carried out at a temperature below the melting point of the porous metal foam 10, for example, a temperature of 800 ° C to 1100 ° C. Specifically, the difference between the heat treatment temperature and the graphening temperature may be 50 ° C or lower in terms of efficiency and operation of the graphene production apparatus.

The graphene manufacturing method may further include removing the porous metal foam. Removal of the porous metal foam can be accomplished by removing the porous metal foil from the surface of the porous metal foil such as FeCl ₃ , Fe (NO ₃ ) ₃ H ₂ SO ₄ , HNO ₃ , HCl, H ₃ PO ₄ , CH ₃ COOH, H ₂ O ₂ NHSO ₅ , (NH ₄ ) ₂ S ₂ O ₈ , Or the like can be used to perform selective chemical wet-etching only on the metal. When the porous metal foam is removed by the above method, there is an advantage that only the porous metal foam can be effectively removed without damaging the graphene.

Supercapacitor

A supercapacitor as another aspect of the present invention may include the graphene or the porous metal foam having the graphene formed thereon as an electrode. The capacitance of the supercapacitor can be remarkably improved when the graphene on the porous metal foam is included as an electrode.

In a specific example, the supercapacitor comprising the porous metal foam-like graphene as an electrode is prepared by using a solution containing TEABF ₄ (tetraethylammonium tetrafluoroborate) at a concentration of 1 M in propylene carbonate as an electrolyte, applying a voltage of 2.5 V and a current When measuring at a density of 0.02 mAcm ^-2 , the capacitance is 30 times or more, specifically 50 times or more, more specifically 100 times or more, more than the supercapacitor including the graphene formed on the copper foil Or more.

For example, supercapacitors containing the graphene on the porous metal foams as an electrode can be formed by using a solution containing TEABF ₄ (tetraethylammonium tetrafluoroborate) at a concentration of 1 M in propylene carbonate as an electrolyte, applying a voltage of 2.5 V and a current When measured at a density of 0.02 mAcm ^-2 , the capacitance is in the range of 1 F / g to 30 F / g, specifically 5 F / g to 30 F / g, more specifically 10 F / g to 30 F / g .

Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.

The contents not described here are sufficiently technically inferior to those skilled in the art, and a description thereof will be omitted.

Example  One

A graining machine having a diameter of 10 cm inside the working chamber and a length of 45 cm was used. The porous metal foam was a porous nickel foam having a porosity of 95%, a bulk density of 0.45 gcm ^-3 , a length of 10 m, a width of 5 cm, and a thickness of 1 mm. The porous nickel foam was wound 9 m on a first roller 10 cm in diameter and the remainder was wound 20 cm on a second roller through a working chamber. The internal pressure of the working chamber was maintained at normal pressure and the temperature of the heating part was raised to 1000 DEG C while supplying argon gas at a flow rate of 150 sccm and then hydrogen as a reducing gas was further supplied at a flow rate of 65 sccm, The foam was heat treated while moving to a second roller at a speed of 0.5 m per minute. Then, the temperature of the heating section was maintained at 1000 ° C., and the heat-treated porous nickel foam was transferred from the second roller to the first roller at a speed of 0.2 m per minute, while methane (CH ₄ ) Was supplied at 50 sccm while graphene was grown for 20 minutes. The graphene thus prepared was photographed by an electron microscope (scale bar: 100 m) and is shown in Fig.

Example  2

The same graphene production apparatus and porous nickel foam as in Example 1 were used. While the internal pressure of the working chamber is kept at a vacuum state (10 mTorr or less) and argon gas, which is an inert gas, is supplied at a flow rate of 10 sccm, the temperature of the heating section is increased to 1000 ° C., and hydrogen as a reducing gas is added at a flow rate of 65 sccm The porous nickel foam was heat-treated while being transferred to the second roller at a speed of 0.5 m per minute. And, maintaining the heating temperature to 1000 ℃ portion and, while moving the thermal treatment of a porous nickel foam from the second roller to the first roller to the first roller at a speed of 0.2m per minute, pyridine as a carbon source in the material feed (C ₅ H ₅ N) was supplied at a rate of 30 μl / min while nitrogen-doped graphene was grown for 20 minutes.

Example  3

A graphene formed on the porous nickel foam prepared in Example 1 was used as an electrode of a supercapacitor and a solution containing TEABF ₄ (tetraethylammonium tetrafluoroborate) at a concentration of 1 M in propylene carbonate was used as an electrolyte, 2.5 V and a current density of 0.02 mAcm < ^-2 > are shown in Table 1 below.

Example  4

Capacitance was measured in the same manner as in Example 3 except that the graphene formed on the porous nickel foam prepared in Example 2 was used as the electrode of the supercapacitor.

Comparative Example  One

Graphene was grown in the same manner as in Example 1, except that a copper foil was used in place of the porous nickel foam.

Comparative Example  2

Graphene was grown in the same manner as in Example 2, except that a copper foil was used in place of the porous nickel foam.

Comparative Example  3

Capacitance was measured in the same manner as in Example 3 except that the graphene formed on the porous nickel foam prepared in Comparative Example 1 was used as the electrode of the supercapacitor.

Comparative Example  4

Capacitance was measured in the same manner as in Example 3 except that the graphene formed on the porous nickel foam prepared in Comparative Example 2 was used as the electrode of the supercapacitor.

Example 3 Example 4 Comparative Example 3 Comparative Example 4 Capacitance (F / g) 12.4 22.7 0.3 0.2

As shown in Table 1, the supercapacitor including the graphene formed on the porous metal foam according to the apparatus or the manufacturing method of the present invention as an electrode includes graphene formed on a copper foil as an electrode The capacitance is improved by 40 times or more, and largely by 100 times or more than that of the super capacitor.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be understood that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the embodiments described above are in all respects illustrative and not restrictive.

10: Porous metal foam 100: First roller
200: second roller 300: heating part
400: Working chamber 500: First chamber
600: second chamber 700: raw material supply part
800: gas outlet 1000, 2000: graphene manufacturing equipment

Claims (14)

A first roller for feeding and recovering the porous metal foam in a roll-to-roll manner;
A heating unit for heat-treating the porous metal foam and forming graphene on the surface of the porous metal foam; And
A second roller for collecting and supplying the heat-treated metal foam in a roll-to-roll fashion;
And the graphene producing device.
The method according to claim 1,
Wherein said graphene formation is by chemical vapor deposition.
The method according to claim 1,
Wherein the first roller and the second roller comprise a ratchet system.
2. The graphene producing apparatus according to claim 1,
A working chamber formed between the first roller and the second roller to pass the porous metal foam and having the heating unit;
A first chamber receiving the first roller; And
A second chamber receiving the second roller;
Wherein the working chamber, the first chamber, and the second chamber are integrally formed.
The method according to claim 1,
Wherein the heating unit includes a heat source capable of controlling the temperature.
5. The method of claim 4,
Wherein the second chamber further comprises a raw material supply part for supplying a raw material gas of graphene.
The method according to claim 6,
Wherein the raw material supplying portion further comprises a liquid raw material supplying portion for supplying the raw material of the graphene by vaporizing the liquid or a dopant raw material supplying portion for supplying the raw material for doping the graphene.
5. The method of claim 4,
Wherein the first chamber further comprises a gas outlet for discharging gas.
Firstly supplying the porous metal foam by a roll-to-roll method;
Heat treating the porous metal foam;
Recovering the heat-treated porous metal foam by a roll-to-roll method;
Supplying the first recovered porous metal foam by a roll-to-roll method;
Forming graphene on the porous metal foam surface; And
A second step of recovering the porous metal foam having the graphene formed thereon by a roll-to-roll method;
≪ / RTI >
10. The method of claim 9,
Wherein the heat treatment is performed at 800 to 1100 占 폚.
10. The method of claim 9, wherein the graphene formation is by chemical vapor deposition.
12. The method of claim 11, wherein the chemical vapor deposition process is performed at 800 < 0 > C to 1100 < 0 > C.
The method of claim 9, wherein the graphene manufacturing method further comprises removing the porous metal foam.
13. A supercapacitor comprising the porous metal foam formed by graphene or graphene produced according to claim 9 as an electrode.

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