KR102416980B1 - Method for producing carbon material using subcritical or supercritical fluid - Google Patents

Abstract

Disclosed is a method for producing a carbon material using a subcritical or supercritical fluid capable of producing efficiently dispersed graphene in a short time by using a subcritical or supercritical fluid in the process of pulverizing the carbon material. The method for producing a carbon material using the subcritical or supercritical fluid includes: physically pulverizing the carbon material formed by covalent bonding of carbon atoms; By introducing a subcritical or supercritical fluid into the pulverized carbon material, the carbon gap inside the carbon material is increased, and the pulverized carbon material and the subcritical or supercritical fluid are reacted to form a functional group in the carbon material making; and dispersing the carbon material in which the functional group is formed in a solvent.

Description

Method for producing carbon material using subcritical or supercritical fluid

The present invention relates to a method for manufacturing a carbon material using a subcritical or supercritical fluid, and more particularly, graphene efficiently dispersed in a short time by using the subcritical or supercritical fluid in the process of pulverizing the carbon material. It relates to a method for producing a carbon material using a subcritical or supercritical fluid capable of producing the same.

Graphene is a carbon crystal having a two-dimensional sheet shape in which carbon atoms are connected in a hexagonal honeycomb shape, and a plurality of plate-shape graphene is stacked to form graphite. . Therefore, by exfoliating the graphite, it is possible to obtain a plate-like graphene composed of a single or a plurality of layers. Graphene is a material having both the properties of a metal and a property of a non-metal, and has higher electrical/electronic conductivity than copper and higher thermal conductivity than diamond as a property of a metal, and has high thermal stability and chemical inertness as a property of a non-metal. In addition, since graphene has higher mechanical strength and elasticity than steel, it can be applied to various uses such as special materials and electronic materials.

Graphene is usually prepared in a top-down method of exfoliating by oxidative expansion of impression graphite or natural graphite using an oxidizing agent or intercalating agent, and epoxy ( epoxy) group, hydroxyl group, carbonyl group, carboxylic acid group, ester group, formyl group, etc. , nitro, sulfur, etc. will contain a plurality of functional groups (functional groups, or functional groups), and these functional groups are well dispersed in various kinds of polar organic solvents including water. However, it takes a lot of time and cost to prepare graphene, which limits commercial use, and when manufacturing graphene physically or chemically, there is a difficulty in mass production. In addition, when the oxidizing agent and the reducing agent are used together, the manufacturing process becomes complicated. Therefore, in order to commercially apply graphene having excellent performance in various fields, a manufacturing method that is cheaper, more efficient, and capable of mass production with a simple process and shortening the manufacturing time is required.

In order to compensate for this disadvantage, various methods for producing graphene are known. Among them, graphite is put in a grinder together with dry ice, ball-milled and reacted to form a carboxyl group, and then dispersed in a solvent. A method for manufacturing a pin (paper name: Edge-carboxylated graphene nanosheets via ball milling, Jongbeom Baek (Ulsan University of Science and Technology), published: Proceedings of the National Academy of Sciences (PNAS), 2012.03.27, 109(15), 5588-5593p) is, The milling time is as long as 48 hours, and radicals remain inside the reactor, and after the reaction is completed, sparks such as sparks are generated when in contact with air, and there is a risk of explosion. In addition, a method for preparing graphene by introducing supercritical CO ₂ into the intercalated carbon with a polymer, extending the interlayer gap of carbon, and then dispersing it in a solvent (X. Zheng, RSC Advances, 2012, 2, 10632-10638p) is also known, but in the above method, supercritical CO ₂ serves only to extend the interlayer spacing of carbon, and to form a functional group such as a carboxyl group at the edge of carbon, a separate acid (acid) ) treatment process should be additionally performed.

It is an object of the present invention, by pulverizing a carbon material in an atmosphere of a subcritical or supercritical fluid, the supercritical fluid reacts with the surface of carbon and the pulverized surface generated by pulverization, and a functional group capable of extending the interlayer spacing of carbon is formed, as well as a supercritical fluid is supplied to the expanded interlayer space of the carbon to further extend the interlayer gap, so that graphene can be efficiently exfoliated or dispersed from the carbon material. A carbon material using a subcritical or supercritical fluid To provide a manufacturing method of

Another object of the present invention is to provide a method for producing a carbon material using a subcritical or supercritical fluid, which can mass-produce graphene and the like in a short time.

Another object of the present invention is to pulverize a carbon material that does not have a layered structure, such as activated carbon, carbon nanotube, and amorphous carbon, in a subcritical or supercritical fluid atmosphere, thereby forming a functional group on the pulverized surface, thereby dispersibility of the carbon material To provide a method for manufacturing a carbon material using a subcritical or supercritical fluid, which can improve the

In order to achieve the above object, the present invention comprises the steps of physically pulverizing a carbon material formed by covalent bonding of carbon atoms; By introducing a subcritical or supercritical fluid into the pulverized carbon material, the carbon gap inside the carbon material is increased, and the pulverized carbon material and the subcritical or supercritical fluid are reacted to form a functional group in the carbon material making; and dispersing the functional group-formed carbon material in a solvent.

The present invention also provides a carbon material layer comprising the carbon material manufactured by the above method, and the carbon material layer can be used as an antistatic layer, a filler for heat dissipation products, and an electrode material for a secondary battery.

In the method for manufacturing a carbon material using a subcritical or supercritical fluid according to the present invention, functional groups can be formed in the interlayer space of the carbon material in addition to the surface including the edge of the carbon material, and pulverization by high energy ball milling, etc. Since the functional group-forming reaction is performed in the process and in a fluid atmosphere in a subcritical or supercritical state, activated reaction sites such as pulverization surfaces and internal defects in the carbon material generated in the carbon material having a layered structure and a non-layer structure are increased, By reacting a fluid in a subcritical or supercritical state here, functional groups are efficiently formed in the interlayer space in the case of a layered carbon material as well as the surface including the edge of the carbon material or the pulverized surface, and the functional group is formed in the interlayer space It is possible to maximize the expansion of the interlayer gap by supplying a supercritical fluid to the In addition, the grinding process and the reaction by the supply of the subcritical or supercritical fluid can occur at the same time, and the subcritical or supercritical fluid is introduced into the layered space of carbon, so that the intercalation effect between the graphite layers is also As can be expected, it is possible to mass-produce graphene and the like by efficiently exfoliating or dispersing the carbon material in a short time.

1 is a view for explaining a method of manufacturing a carbon material using a subcritical or supercritical fluid according to an embodiment of the present invention.
2 is an X-ray photoelectron spectroscopy (XPS) analysis graph of graphene prepared according to Examples and Comparative Examples of the present invention.

Hereinafter, with reference to the accompanying drawings, the present invention will be described in detail.

1 is a view for explaining a method of manufacturing a carbon material using a subcritical or supercritical fluid according to an embodiment of the present invention. As shown in FIG. 1 , according to the present invention, in order to prepare a dispersed carbon material using a subcritical or supercritical fluid, first, a carbon material formed by covalent bonding of carbon atoms in the pulverization and reactor 10 is physically treated to form a subcritical or supercritical fluid by pressurizing and heating a fluid such as CO ₂ supplied from the fluid supply unit 30 in the pressurization and heating unit 20, and then the formed subcritical or supercritical fluid The pulverized and supplied to the reactor 10 is reacted with the pulverized carbon material. Accordingly, the method for manufacturing a carbon material according to the present invention may be specifically viewed as a processing method or a dispersion method of the carbon material.

The carbon material used as a raw material of the present invention is a layered or non-layered carbon material formed by covalent bonding of carbon atoms, for example, layered graphite (graphite), non-layered activated carbon, carbon nanotubes, amorphous carbon and mixtures thereof; and the like. The graphite may be graphene by separating several carbon layers, and the activated carbon, carbon nanotubes and amorphous carbon do not have a layered structure, and when uniformly dispersed, chemical properties such as reactivity or physical properties such as electrical conductivity properties can be improved.

Physical pulverization of the carbon material, the carbon material selected from the group consisting of graphite of the layered structure, activated carbon of the non-layered structure, carbon nanotubes and amorphous carbon, to increase the area in which the carbon material reacts with the subcritical or supercritical fluid. As a thing, as long as the carbon material can be finely pulverized, it can be used without limitation, for example, it can be carried out by methods such as a bead mill, a jet mill, an attrition mill and a stirred ball mill, and metal or ceramic It is preferable to use a bead mill made of such materials. In order to physically pulverize the carbon material, for example, a uniform carbon material solution is prepared by mixing the carbon material and a solvent and stirring for about 20 to 40 minutes, and then adding beads or The solution should be ground and dispersed by feeding a grinding medium, such as a ball, and grinding for about 70 to 90 minutes. During the dispersion, the flow rate of the carbon material solution to which the grinding medium is added should be about 10 to 30 m/sec, preferably about 15 to 25 m/sec. may not be done properly. The amount of the grinding medium may be added in a volume ratio of 2/5 to 5/1, for example, about 1/1 with respect to the carbon material solution.

Based on 100 parts by weight of the solvent, the amount of the carbon material used is preferably 0.001 to 20 parts by weight, more preferably 0.01 to 10 parts by weight. As the solvent, a solvent capable of dispersing the carbon material may be used without particular limitation, for example, methanol, ethanol, isopropyl alcohol, isobutyl alcohol, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone. , diethyl ether, petroleum ether, tetrabutylmethyl ether, ethyl acetate, tetrahydrofuran, dichloromethane, N-methylpyrrolidone, dimethylformamide, water (H ₂ O), mixtures thereof, etc. can be used, Preferably, methanol (Methanol) may be used. On the other hand, in order to improve the wettability of the carbon material and the solvent, if necessary, a surfactant or dispersant having a hydrophilic-lipophilic balance (HLB) coefficient of 10 or more may be added to the carbon material solution, The content may be 1 to 150 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the carbon material. Examples of the surfactant and dispersant include Tween 80 (sigma Aldrich), sodium dodecyl sulfate (SDS), hexadecyltrimethyl ammonium bromide (CTAB), and acetylene glycol. On the other hand, the dispersant is included within the scope of the surfactant, and a form in which a substituent capable of having pigment affinity is attached to the backbone of a polymer, such as acetylene glycol among nonionic surfactants in the industry, is called a dispersant.

Next, by introducing a subcritical or supercritical fluid into the pulverized (dispersed) carbon material (solution), the carbon gap inside the carbon material is increased, and the pulverized carbon material and the subcritical or supercritical fluid are reacted. to form a functional group on the carbon material. The subcritical or supercritical fluid can improve the dispersibility of the carbon material by forming a functional group on the pulverized surface and the internal defect portion of the carbon material generated by pulverizing the carbon material, and the functional group includes the The surface including the edge of the graphite, the pulverized surface and interlayer space defects generated by pulverization, or the pulverized face and internal defect parts generated by pulverizing the carbon material having a non-layered structure such as activated carbon, carbon nanotubes, or crystalline carbon formed on the back.

On the other hand, if the pulverized carbon material has a layered structure, the interlayer spacing is extended by the functional groups formed on the carbon material, and a subcritical or supercritical fluid is supplied to the interlayer space of the carbon material in which the interlayer spacing is extended, so that the carbon It is possible to further extend the space between the layers of the material. In the pulverized layered carbon material, layer separation is possible only with the interlayer spacing extended by the functional groups formed by the subcritical or supercritical fluid, but for easier layer separation, the interlayer spacing needs to be further extended there is In the present invention, by introducing the subcritical or supercritical fluid into the interlayer space of the carbon material whose interlayer spacing has already been extended, it is possible to further extend the interlayer spacing of the carbon material. Based on 100 parts by weight of the carbon material solution, the amount (input amount) of the subcritical or supercritical fluid is 0.1 to 1,000 parts by weight, preferably 1 to 100 parts by weight. Here, if the amount of the subcritical or supercritical fluid is too small, the number of functional groups attached to the carbon material is too small, and there is a risk that the interlayer gap expansion of the carbon material becomes insufficient, and if too large, there is no additional effect, economical is only referred to as

In this way, in order to increase the carbon gap inside the carbon material and to form functional groups on the pulverized surface generated by pulverizing the carbon material and the internal defect portions of the carbon material, a fluid in a subcritical or supercritical state must be used. As to do, examples thereof include carbon dioxide, methane, propane, ethylene, propylene, methanol, ethanol, acetone and water (H ₂ O) in a subcritical or supercritical state, and the subcritical or It is most preferred to use supercritical carbon dioxide. In order to prepare the subcritical or supercritical fluid, a material that can be a subcritical or supercritical fluid, for example, from the group consisting of carbon dioxide, methane, propane, ethylene, propylene, methanol, ethanol, acetone and water, etc. Heat and pressure should be applied to the selected material, and the heat and pressure to be applied to each of the above-exemplified materials may be different. For example, when using conventional carbon dioxide, a temperature of 25 to 300 ° C., preferably 30 to 200 ° C., more preferably 35 to 100 ° C., and 50 to 300 bar, preferably 50 to 200 bar, further Preferably, supercritical carbon dioxide can be produced using a high-pressure vessel for supercritical production capable of applying a pressure of 75 to 150 bar, and when it is outside the above range, it is difficult to apply the supercritical fluid due to the pressure problem of the reactor, However, there is a risk that the process cost will also rise sharply.

On the other hand, the critical points of several supercritical fluids, that is, the critical temperature and the critical pressure, are as shown in Table 1 below. This is because problems such as a decrease in pressure occur when moving to the reactor.

supercritical fluid Critical temperature (℃) Critical pressure (bar) carbon dioxide 31.1 73.8 water 373.1 220.5 methane -87.75 46 ethane 32.4 48.8 propane 96.8 42.5 ethylene 9.4 50.4 propylene 91.75 46 methanol 239.45 80.9 ethanol 240.9 61.4 acetone 235.1 47.0

The supercritical fluid is a material that exists at a high temperature and high pressure above the critical point of each material, and the liquid vaporization process does not occur so it is impossible to distinguish between a gas and a liquid, that is, a fluid in a critical state. . In addition, a subcritical fluid refers to a substance that exists at a temperature and pressure slightly lower than the supercritical point of each substance.

On the other hand, the subcritical or supercritical fluid is preferably supplied to the step of pulverizing the carbon material so as to be performed simultaneously with the pulverization of the carbon material (that is, the step of physically pulverizing the carbon material and the pulverized The step of introducing the subcritical or supercritical fluid into the carbon material is preferably performed simultaneously), and, if necessary, may be supplied after the carbon material is pulverized. On the other hand, regardless of whether the supply of the subcritical or supercritical fluid is made simultaneously with the pulverization of the carbon material or is made after the carbon material is pulverized, the process of finely pulverizing the carbon material (milling process) is continuous As can be carried out as, at this time, the flow rate of the solution is about 10 to 30 m / sec, preferably about 15 to 25 m / sec such that.

On the other hand, the subcritical or supercritical fluid reacts with the carbon material to form a functional group in the process of increasing the carbon gap inside the carbon material and the pulverization surface and internal defect parts of the carbon material generated by pulverizing the carbon material In the latter case, the functional group is formed after the carbon gap inside the carbon material is increased, or the functional group is formed after the carbon material The internal carbon spacing is increased. The functional group may include a surface including the edge of the layered carbon material such as graphite, a pulverized surface generated by pulverization, and a defect in the interlayer space, or pulverization of a non-lamellar structured carbon material such as activated carbon, carbon nanotubes and amorphous carbon The subcritical or supercritical fluid is formed by reacting on activated reaction sites such as the pulverized surface and internal defect parts generated by the On the other hand, the functional groups formed on the carbon material of the layered structure expand the interlayer spacing by the property of repulsing between the functional groups. The functional group may vary depending on the type of subcritical or supercritical fluid used in the reaction, for example, an epoxy group, a carboxyl group (-COOH), a formyl group (-CHO), a hydroxyl group (-OH), an ester group (-COO-), a carbonyl group (-CO-), an ether group (-O-), an amide group, an imide group, a nitro group, a nitroso group, a sulfone group and a sulfonic acid group, and the like, and the subcritical or supercritical fluid The carboxyl group formed when using carbon dioxide as the most preferred.

The reaction is to be made in a closed container so that the supplied subcritical or supercritical fluid maintains a subcritical or supercritical state, the reactor in which the reaction takes place, the carbon material and materials or tools used for pulverization Although the opening/closing port for supplying or discharging the product is formed, an enclosed environment must be created when the subcritical or supercritical fluid is supplied or the subcritical or supercritical fluid and the carbon material react. In addition, the reaction may be carried out for 0.1 to 20 hours, preferably 0.5 to 10 hours, more preferably 0.5 to 5 hours under conditions in which the subcritical or supercritical fluid is continuously supplied.

Finally, the carbon material in which the functional group is formed is dispersed and peeled off in a solvent. The solvent, in addition to the repulsive force between the functional groups formed on the carbon material, causes the dispersion and exfoliation of the carbon material more quickly and effectively to obtain graphene, which is a product of the exfoliation of the carbon material, and graphene obtained from the carbon material Solvents that do not deform and the like can be used without limitation, and examples include methanol, ethanol, isopropyl alcohol, isobutyl alcohol, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, diethyl ether, petroleum ether. , tetrabutylmethylether, ethyl acetate, tetrahydrofuran, dichloromethane, N-methylpyrrolidone, dimethylformamide, water (H ₂ O), and mixtures thereof. By such peeling and dispersing process, when the carbon material is graphite having a layered structure, planar graphene is obtained, and when the carbon material is a carbon material having a non-layered structure, a uniformly dispersed carbon material is obtained. Based on 100 parts by weight of the carbon material, the amount of the solvent used is 1 to 1,000 parts by weight, preferably 10 to 100 parts by weight. Here, if the amount of the solvent used is too small, there is a fear that the carbon material may not be uniformly dispersed, and if too large, there is no additional effect, and excessive energy is consumed in the operation, which is economically undesirable.

Since the carbon material such as graphene produced in this way has excellent electrical conductivity and heat transfer properties, the carbon material prepared according to the present invention is suitable for the formation of an antistatic layer, a filler for heat dissipation products, and an electrode material for a secondary battery. It can be usefully used. Here, the carbon material dispersion solution may further include a conventional film forming component such as a polymer binder, if necessary, and the amount of the polymer binder used is usually 1 to 400 parts by weight, based on 100 parts by weight of the carbon material, Preferably it is 10 to 200 parts by weight.

Hereinafter, the present invention will be described in more detail through specific examples. The following examples are intended to illustrate the present invention, but the present invention is not limited by the following examples.

[Example 1] Dispersion of carbon material using supercritical fluid and preparation of graphene

After adding 15 parts by weight of graphite (Timcal, Switzerland) to 500 parts by weight of methanol and supplying it to the reactor, 1.5 parts by weight of acetylene glycol as a dispersant is further added to improve wettability of methanol and graphite, and for 30 minutes A graphite solution was prepared by mixing (Step 1). Then, after adding 2/3 of beads to the prepared solution by volume, the rpm was adjusted so that the speed of the solution could maintain a flow rate of 18 m/sec and dispersed for 80 minutes to prepare a dispersion solution ( Step 2), after preparing a supercritical fluid by supplying CO ₂ gas to a high-pressure vessel for supercritical production at 35° C. and 100 bar conditions, the fluid was transferred to the reactor containing the dispersion solution (Step 3). Finally, milling is performed for 220 minutes while controlling the rpm so that the flow rate of the dispersion solution mixed with the supercritical fluid is maintained at 18 m/sec, and then centrifuged at a speed of 18,000 rpm to remove the supernatant, Then, it was dried with a freeze dryer to prepare exfoliated graphene powder (Step 4).

[Comparative Example 1] Dispersion of carbon material using supercritical fluid and preparation of graphene

Graphene powder was prepared in the same manner as in Example 1, except that physically exfoliated graphene (XG Corporation, USA) was used instead of the graphite used in Step 1.

[Comparative Example 2] Dispersion of carbon material using supercritical fluid and preparation of graphene

Graphene powder was prepared in the same manner as in Example 1, except that the bead added in Step 2 was not used and only the supercritical fluid was applied alone.

[Comparative Example 3] Dispersion of carbon material and preparation of graphene

Graphene powder was prepared in the same manner as in Example 1, except that the supercritical fluid supplied to the reactor in Step 3 was not used.

Evaluation of electrical properties of graphene

3% by weight of graphene prepared in Example 1 and Comparative Examples 1 to 3, 8% by weight of polyester resin, and 89% by weight of methanol were added and stirred for 10 minutes, then beads were added to shaker (LAU, DAS 200) was dispersed for 80 minutes to prepare an ink. Then, the prepared ink was applied to the PET film using a film applicator, put in a hot air oven and dried at 100° C. for 3 minutes, and then the surface resistance was measured using a 4-point probe. is shown in Table 2 below.

Surface resistance (Ω/sq) note Example 1 1.58×10 ⁵ Supercritical fluid + milling (18 m/sec) Comparative Example 1 3.39×10 ⁵ Using physically exfoliated graphene Comparative Example 2 1.26×10 ¹² Supercritical fluid application alone Comparative Example 3 1.20×10 ⁸ No use of supercritical fluid (milling only)

As a result of evaluating the degree of exfoliation of graphite by replacing the sheet resistance, as shown in Table 2 above, when the supercritical fluid or the milling process was applied alone (Comparative Examples 2 and 3), the exfoliation effect was small, and the supercritical fluid and milling In the case of simultaneously applying the process (the linear velocity of the solution during milling is 18 m/sec, Example 1), it has similar performance (equivalent or somewhat superior performance) to conventional graphene that is commercialized (for example, Comparative Example 1). was manufactured.

XPS Analysis and Evaluation of Graphene

In order to confirm whether the graphene prepared in Example 1 and Comparative Examples 1 to 3 was functionalized, analysis by X-ray photoelectron spectroscopy (XPS (X-ray photoelectron spectroscopy), VG Microtech, ESCA-2000) was performed. . FIG. 2 is an XPS analysis graph of a carbon material (graphene) prepared according to Examples and Comparative Examples of the present invention. FIG. 2B is an enlarged view of the red dotted line in FIG. 2-A. As a result of XPS analysis, as shown in FIG. 2, a peak is confirmed near 289 eV (widely expressed considering the shift), which is O=CO bonding, and the intensity of O=CO bonding As a result of comparison, it was confirmed that some functionalization was possible even with the graphene powder prepared in Comparative Example 1 (non-functionalized graphene), which was the lowest in graphite as a raw material. Finally, it can be seen that the graphene powder prepared in Example 1 (supercritical fluid + high-speed milling of 18 m/sec) has the highest O=CO bond strength, and thus the degree of functionalization is excellent compared to other cases. .

In the method of dispersing a carbon material using a subcritical or supercritical fluid according to the present invention, functional groups can be formed in the interlayer space of the carbon material in addition to the surface including the edge of the carbon material, and all processes are subcritical or supercritical. Since it is performed in a fluid atmosphere in a critical state, there are advantages in that the number of reaction sites in the carbon material is increased and functional groups are efficiently formed. In addition, the grinding process and the reaction by the supply of the subcritical or supercritical fluid can occur at the same time, and the subcritical or supercritical fluid is introduced into the layered space of carbon, so that the intercalation effect between the graphite layers is also As it can be expected, it is possible to mass-produce graphene and the like by efficiently exfoliating or dispersing the carbon material in a short time.

Claims (14)

mixing a carbon material formed by covalent bonding of carbon atoms with a solvent to form a carbon material solution, and physically pulverizing the carbon material solution; and
By introducing a subcritical or supercritical fluid into the pulverized carbon material solution, the carbon gap inside the carbon material is increased, and the pulverized carbon material solution and the subcritical or supercritical fluid are reacted to form a functional group on the carbon material comprising the step of forming
The step of physically pulverizing the carbon material solution and the step of introducing a subcritical or supercritical fluid into the pulverized carbon material solution are performed simultaneously,
The carbon material solution, in order to improve the wettability of the carbon material and the solvent, the hydrophilic-lipophilic balance (HLB) coefficient of 10 or more surfactant or dispersing agent for producing a carbon material further comprising. The method according to claim 1, further comprising dispersing the carbon material in which the functional group is formed in a solvent. The method according to claim 1, wherein the carbon material is selected from the group consisting of layered graphite, non-layered activated carbon, carbon nanotubes, amorphous carbon, and mixtures thereof. The method according to claim 1, wherein the carbon material is graphite having a layered structure, and the exfoliation product of the carbon material is graphene. delete The method according to claim 1, wherein the functional group, the surface including the edge of the graphite, the pulverized surface and interlayer space defects generated by pulverization, or the pulverized surface and internal defect parts generated by pulverization of activated carbon, carbon nanotubes, or crystalline carbon The method for producing a carbon material that is formed in. delete The method according to claim 1, wherein the physical pulverization of the carbon material solution is performed by a method selected from the group consisting of a bead mill, a jet mill, an attrition mill and a stirred ball mill. The method according to claim 1, wherein the subcritical or supercritical fluid is selected from the group consisting of carbon dioxide, methane, propane, ethylene, propylene, methanol, ethanol, acetone and water in a subcritical or supercritical state, the production of a carbon material Way. The method according to claim 1, wherein the reaction is carried out for 0.1 to 20 hours under a condition in which the subcritical or supercritical fluid is continuously supplied. The method according to claim 1, wherein the functional group is selected from the group consisting of an epoxy group, a carboxyl group, a formyl group, a hydroxyl group, an ester group, a carbonyl group, an ether group, an amide group, an imide group, a nitro group, a nitroso group, a sulfone group and a sulfonic acid group. , a method of manufacturing carbon materials. The method according to claim 2, In the step of dispersing the carbon material having the functional group in the solvent, the solvent is methanol, ethanol, isopropyl alcohol, isobutyl alcohol, acetone, methyl ethyl ketone, diethyl ketone, tyl isobutyl ketone, di ethyl ether, petroleum ether, tetrabutylmethyl ether, ethyl acetate, tetrahydrofuran, dichloromethane, N-methylpyrrolidone, dimethylformamide, water (H ₂ O) and mixtures thereof. , a method of manufacturing carbon materials. A carbon material layer comprising a carbon material manufactured by the method according to any one of claims 1 to 4, 6 and 8 to 12. The carbon material layer of claim 13, wherein the carbon material layer is selected from the group consisting of an antistatic layer, a filler for a heat dissipation product, and an electrode material for a secondary battery.

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