KR20170075126A - Method for separating graphene oxide and method for manufacturing graphene coated steel sheet - Google Patents

Method for separating graphene oxide and method for manufacturing graphene coated steel sheet Download PDF

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KR20170075126A
KR20170075126A KR1020150184123A KR20150184123A KR20170075126A KR 20170075126 A KR20170075126 A KR 20170075126A KR 1020150184123 A KR1020150184123 A KR 1020150184123A KR 20150184123 A KR20150184123 A KR 20150184123A KR 20170075126 A KR20170075126 A KR 20170075126A
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graphene oxide
solution
acid
group
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KR101819302B1 (en
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유혜진
정용균
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주식회사 포스코
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    • C01B31/043—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/10—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing sonic or ultrasonic vibrations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • C23C26/02—Coating not provided for in groups C23C2/00 - C23C24/00 applying molten material to the substrate
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases

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Abstract

Preparing an aqueous graphene oxide solution, adjusting the acidity by adding an acid or a base to the graphene oxide aqueous solution, and separating the aqueous solution of the graphene oxide solution with the upper layer and the lower layer A method for separating graphene oxide and a method for producing a graphene coated steel sheet using the same are disclosed.

Description

TECHNICAL FIELD [0001] The present invention relates to a method of separating graphene oxide and a method of manufacturing a graphene coated steel sheet,

The present invention relates to a method for separating graphene oxide and a method for producing a graphene coated steel sheet.

Graphene has a planar monolayer structure in which carbon atoms are packed into a two-dimensional lattice, and is applied to various applications of next generation electronic devices due to various inherent characteristics such as excellent charge mobility, low surface resistance, mechanical properties and thermal / chemical stability can do. Controlling the size and structure of the graphene sheet is a very important factor in improving the usability of the graphene.

Among the various methods for obtaining graphene (mechanical exfoliation, chemical exfoliation, SiC crystal pyrolysis, chemical vapor deposition and epitaxy synthesis), chemical exfoliation is a method of mass-producing graphene of uniform size It is advantageous for the application of industrial electric devices. In other words, chemical peeling method in which graphite is oxidized and separated in a solution phase and then reduced is subjected to a great deal of research due to the possibility of mass production and easy chemical modification and hybridization with other materials. However, when it is used in a state of being dispersed in a solvent, it is known that the graphene produced by the chemical stripping method is dispersed in a small amount in an organic solvent of N-methyl-2-pyrrolidone (NMP) or dimethylformamide But they are not easily dispersed in most organic solvents and have a problem of being aggregated or superimposed.

Accordingly, there is a desperate need for a method for producing graphene which is excellent in dispersibility in an organic solvent and can be easily produced by mass production. Above all, there is a strong demand for a method for preparing graphene having excellent dispersibility in various organic solvents by simply controlling the size of graphene without any additives such as additional surfactants or stabilizers. Patent Documents 1 and 2 are related prior art documents.

Korean Patent Registration No. 10-1488619 Korean Patent Publication No. 10-2015-0075743

One of the objects of the present invention is to provide a method of separating graphene oxide by size and a method of manufacturing a graphene coated steel sheet using the same.

According to an aspect of the present invention, there is provided a method for preparing a graphene oxide aqueous solution, comprising the steps of preparing a graphene oxide aqueous solution, adjusting the acidity by adding an acid or a base to the graphene oxide aqueous solution, And separating the graphene oxide from the graphene oxide.

According to another aspect of the present invention, there is provided a method for producing a graphene oxide, which comprises preparing an upper layer or a lower layer separated by the above method, separating the graphene oxide contained in the upper layer or lower layer separately, A step of forming a graphene oxide coating layer by coating the graphene oxide coating solution on a base steel sheet, and a step of heat treating the base steel sheet on which the graphene oxide coating layer is formed to form graphene oxide coating solution, And a step of reducing the oxide coating layer.

As one of the effects of the present invention, it is advantageous to obtain monodisperse graphene oxide with a high yield through a simple process.

As one of the various effects of the present invention, there is an advantage that it can be applied to a large-area coating such as a steel plate because it is easy to mass-produce.

The various and advantageous advantages and effects of the present invention are not limited to the above description, and can be more easily understood in the course of describing a specific embodiment of the present invention.

1 (a) is an SEM (Scanning Electron Microscopy) image of an aqueous graphene oxide solution before acidity control, and FIG. 1 (b) is an SEM (Scanning Electron Microscopy) image of an upper layer after controlling acidity at a specific pH, 1 (c) is an SEM (Scanning Electron Microscopy) image of the lower layer after adjusting the acidity to a specific pH.
FIG. 2 (a) is a histogram of the size distribution of graphene oxide contained in the graphene oxide aqueous solution of FIG. 1 (a), and FIG. 2 (b) is a histogram of the size distribution of graphene oxide contained in the graphene oxide aqueous solution of FIG. FIG. 3 (c) is a histogram of the size distribution of graphene oxide contained in the graphene oxide aqueous solution of FIG. 1 (c). FIG.
FIG. 3 (a) is a graph for explaining the affinity of the graphene oxide, and FIG. 3 (b) is a graph showing the zeta potential versus the pH of the graphene oxide.

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

All terms (including technical and scientific terms) used herein can be used in a sense commonly understood by one of ordinary skill in the art to which the present invention belongs, unless otherwise defined. Whenever a component is referred to as "including" an element throughout the specification, it is to be understood that the element may include other elements, not the exclusion of any other element, unless the context clearly dictates otherwise.

Hereinafter, a method for separating graphene oxide, which is one aspect of the present invention, will be described in detail.

Grapina  Preparation of oxide aqueous solution

A graphene oxide aqueous solution is prepared. In the present invention, the step of preparing the graphene oxide aqueous solution is not particularly limited, but it can be prepared by the following method as an example.

First, graphite is prepared and then subjected to acid treatment to obtain a mixed solution of graphene oxide and impurities. Here, the impurity may mean metal ions remaining after the acid treatment. On the other hand, the acid treatment can be performed by the Hummers method, which is one of the well-known methods, but is not limited thereto.

Next, impurities are removed from the mixed solution of the graphene oxide and the impurity to obtain an aqueous solution of graphene oxide. At this time, to remove impurities, an acid solution in which water and strong acid were mixed at a weight ratio of about 1:10 was added to the mixed solution, stirred for about 24 hours, and then filtered using a glass filter But the present invention is not limited thereto.

Next, if necessary, the obtained graphene oxide aqueous solution can be subjected to ultrasonic treatment. In this case, graphene oxide can be easily dispersed, but the present invention is not limited thereto.

On the other hand, at the time of ultrasonic treatment, the temperature of the graphene oxide aqueous solution may be 50 ° C or lower, but it is not limited thereto. However, when the temperature of the aqueous solution of the graphene oxide solution exceeds 50 ° C during the ultrasonic treatment, as the moisture generated by the heat generated by the ultrasonic treatment evaporates, the dispersibility of the graphene oxide decreases or the viscosity of the aqueous solution increases, The aggregation of the oxide may occur.

Grapina  The acidity of the aqueous oxide solution and The supernatant Sublayer  detach

An acid or base is added to the graphene oxide aqueous solution to adjust the acidity. This step is carried out to separate graphene oxide by size.

1 (a) and 2 (a) are Scanning Electron Microscopy (SEM) images and size distribution histograms of the aqueous graphene oxide solution before acidity control, and FIGS. 1 (b) and 2 1 (c) and 2 (c) show the SEM (Scanning Electron Microscopy) images and size distribution histograms of the supernatant after adjusting the acidity to a specific pH, Microscopy) Image and size distribution histogram.

1 and 2, graphene oxides having various sizes before mixing with each other are mixed, and graphene oxide having a very narrow size distribution and a small size is present in the upper layer after controlling the acidity. In the lower layer, It can be seen that the distribution is somewhat large and separated into large graphene oxide.

The theoretical reason why the graphene oxide is separated by size by controlling the acidity of the graphene oxide aqueous solution is as follows.

FIG. 3 (a) is a graph for explaining the affinity of the graphene oxide, and FIG. 3 (b) is a graph showing the zeta potential versus the pH of the graphene oxide.

Referring to FIG. 3 (a), graphene oxide has an amphiphilic nature such as a conventional surfactant, the planar portion having hydrophobicity and the edge portion having hydrophilicity. The reason why graphene oxide retains its dispersibility in water is due to the functional group located at the edge portion. As the size of graphene oxide is changed, the number of functional groups is different from that of graphene oxide, so that the dispersibility is different .

Furthermore, when the graphene oxide aqueous solution has an acidity or basicity that is not neutral, the above-mentioned functional groups have a negative charge or a positive charge, and this difference in dispersibility becomes larger. 3 (b), when the acidity of the graphene oxide aqueous solution reaches a specific pH window, the relatively large graphene oxide having a small number of functional groups relative to the graphene oxide size is precipitated, Relatively small graphene oxide having a large number of functional groups relative to the size of graphene oxide has a stable state in the aqueous solution, and graphene oxide is separated by size.

For reference, the functional group of the graphene oxide may be at least one selected from the group consisting of a hydroxyl group, a carbonyl group, a carboxyl group and an amine group, but is not limited thereto.

On the other hand, the acid used for controlling the acidity is hydrochloric acid (HCl), perchloric acid (HClO 4 ), nitric acid (HNO 3 ), sulfuric acid (H 2 SO 4 ), phosphoric acid (H 3 PO 4 ), acetic acid (CH 3 COOH) 2 CO 3 ), but the present invention is not limited thereto.

In addition, the pH the base to be used for the control, but be at least one selected from the group consisting of potassium hydroxide (KOH), sodium (NaOH), calcium hydroxide (Ca (OH) 2) and ammonium hydroxide (NH 4 OH) hydroxide, be But is not limited thereto.

Thereafter, the graphene oxide can be separated by size by separating the upper layer and the lower layer of the aqueous solution of the graphene oxide whose acidity has been adjusted, and if necessary, the acidity control process described above is repeatedly carried out at different pH values, It is possible to secure a graphene oxide having a narrower width.

According to the present invention, it is possible to obtain monodisperse graphene oxide with a high yield through a simple process, which is advantageous in mass production.

Hereinafter, a method for manufacturing a graphene-coated steel sheet, which is another aspect of the present invention, will be described in detail.

Grapina  Preparation of oxides

First, an upper layer or a lower layer separated by the above-described method is prepared and then dried to separate the graphene oxide contained in the upper layer or lower layer separately.

Grapina  Preparation of oxide coating solution

Next, the graphene oxide is mixed with an organic resin to obtain a graphene oxide coating solution.

According to one example, the graphene oxide may be included in an amount of 5 to 80 parts by weight, preferably 25 to 75 parts by weight, based on 100 parts by weight of the graphene oxide coating solution. If the content of graphene oxide is less than 5 parts by weight, the content of graphene in the final product may be too small to exhibit excellent physical properties of graphene. On the other hand, if the content of graphene oxide exceeds 80 parts by weight, The adhesion of the pin coating layer may be deteriorated or it may be difficult to secure a uniform graphene coating layer.

The organic resin uniformly disperses the graphene oxide and serves as a binder in coating. Examples of the organic resin may be a mixture of one or more kinds selected from the group consisting of water-dispersible urethane resin, water-dispersible acrylic resin, water-soluble epoxy resin, water-soluble polyester resin and water-soluble amino resin, no. The water-dispersible urethane resin is preferably used. More preferably, it may be selected from the group consisting of an aqueous dispersion urethane resin having a carboxyl group or a hydroxy group, an aqueous dispersion urethane resin modified with an acrylic monomer, an aqueous dispersion urethane resin modified with a vinyl monomer, , And most preferably an aqueous dispersion urethane resin using a polycarbonate polyol.

According to one example, the organic resin may be contained in an amount of 25 to 70 parts by weight, preferably 40 to 55 parts by weight, based on 100 parts by weight of the graphene coating solution. If the content of the organic resin is less than 25 parts by weight, the adhesion to the surface of the base steel sheet may be deteriorated and it may be difficult to form a uniform graphene coating layer. If the content exceeds 70 parts by weight, the viscosity of the graphene oxide coating solution The workability may be deteriorated.

According to one example, the graphene oxide coating solution may further include at least one corrosion resistance improving agent selected from the group consisting of an inorganic metal sol, a rust inhibitor, an organic metal complex, and a crosslinking agent. To 5 parts by weight, preferably 0.5 to 4 parts by weight, more preferably 1 to 4 parts by weight.

The inorganic metal sol serves to improve the corrosion resistance. Specific examples thereof include, but are not limited to, silica sol, alumina sol, titania sol, and zirconia sol, or a mixture of two or more thereof.

Rust inhibitors also serve to improve corrosion resistance, including metal compounds such as aluminum or aluminum aluminum; An aqueous solution of phosphoric acid of hexaammonium heptamolybdate tetrahydrate; zinc; molybdenum; Fluorine; Boric acid; A mixture thereof or a phosphate solution thereof, but is not limited thereto.

The organometallic complex improves the adhesion property by the condensation reaction with the base steel sheet, particularly the zinc-plated steel sheet and the hydrogen bond formation, and thereby improves the corrosion resistance of the base steel sheet, and the silane coupling agent, Zirconium-based coupling agents, and mixtures of two or more thereof. However, the present invention is not limited thereto.

The crosslinking agent serves to crosslink the organic resin through cross-linking with a carboxyl group or a hydroxy group contained in the organic resin, thereby enhancing the adhesion and corrosion resistance of the coating layer. The crosslinking agent has a carbodiimide group But are not limited to, a compound selected from the group consisting of a melamine crosslinking agent, an isocyanate crosslinking agent, an aziridine crosslinking agent, and a mixture thereof.

According to one example, the graphene oxide coating solution may further comprise at least one of an antifoaming agent, a smoothing agent, a wax, and a solvent, and the additive may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the graphene oxide coating solution .

The solvent may be water, ethanol or a mixture thereof. In order to improve wettability and dispersibility of the graphene coating solution, it is preferable that 0.1 to 10% by weight of ethanol is contained as a mixture of water and ethanol. However, the content of the solvent in the graphene oxide coating solution is not particularly limited and may be appropriately selected depending on the content of the above-mentioned components.

Grapina  Formation of oxide coating layer

Next, a graphene oxide coating solution is applied on the base steel sheet to form a graphene oxide coating layer.

In the present invention, the kind of the base steel sheet is not particularly limited, and for example, a cold-rolled steel sheet; Hot - rolled steel; galvanized steel; Aluminum-plated steel sheet; Copper, magnesium, iron, manganese, titanium, zinc, or a mixture thereof, or a mixture of two or more of these metals, But it is not necessarily limited to these.

Also, in the present invention, a method of applying the graphene oxide coating solution on the base steel sheet is not particularly limited, and any one of spray coating, bar coating, roll coating, gravure coating, dip coating and solution cast coating , But the present invention is not limited thereto.

Grapina  Oxide coating layer reduction

The base steel sheet on which the graphene oxide coating layer is formed is heat-treated to reduce the graphene oxide coating layer. This step is carried out in order to reduce the graphene oxide contained in the graphene oxide coating layer, in addition to strengthening the adhesion between the substrate steel and the coating layer.

According to one example, during the heat treatment, the heat treatment temperature may be 800 to 900 占 폚. The stable phase of the steel sheet at this temperature range is austenite, and the solubility of carbon is high. Therefore, when the heat treatment is performed in the above temperature range, a part of the graphene oxide coated on the surface thereof is solidified in the steel. When the heat treatment is finished, the solubility of carbon becomes lower due to the decrease of solubility and the bonding force between the steel sheet and the coating layer .

According to an example, the heat treatment may be performed in an atmosphere of nitrogen (80 to 100 vol%) + hydrogen (0 to 20 vol%), but it is preferably performed in an atmosphere of nitrogen of 100 vol%. Generally, an annealing furnace maintains a reducing atmosphere to suppress the formation of oxides that may be formed on the surface of the steel sheet during heat treatment, and usually contains about 5 to 15 vol% of hydrogen. However, in the process for coating graphene in the present invention, since there is a possibility of reaction between hydrogen and graphene when heat treatment is performed in a hydrogen atmosphere, it is advantageous to exclude hydrogen as much as possible and heat treatment in a nitrogen atmosphere.

Hereinafter, the present invention will be described in more detail by way of examples. It should be noted, however, that the embodiments described below are intended to illustrate the present invention and to make it more specific and not to limit the scope of the present invention. And the scope of the present invention is defined by the matters described in the claims and the matters reasonably inferred therefrom.

( Example )

The graphite was acid-treated by the Hummers method to obtain a slurry, and impurities in the slurry were removed to obtain an aqueous solution of graphene oxide. More specifically, 0.75 g of NaNO 3 and 34 ml of H 2 SO 4 were placed in a 500 ml three-necked glass reactor and stirred. The temperature was adjusted to 0 ° C by using an ice bath, and 1 g of graphite was added thereto and dispersed. Thereafter, the temperature of the reactor was adjusted to 20 캜, and 5 g of potassium permanganate was slowly added. Thereafter, the temperature of the reactor was gradually raised to 35 DEG C, and the reaction was allowed to proceed for 2 hours. Thereafter, 50 ml of distilled water was added and stirred. Then, 4 ml of hydrogen peroxide was added and stirred until no more gas was generated. Thereafter, after 15 minutes, 140 ml of distilled water was added to obtain an aqueous graphene oxide solution. In the graphene oxide aqueous solution thus obtained, the average size of the graphene oxide was 2 to 3 占 퐉, and the size distribution was 0 to 11 占 퐉.

Next, after adjusting the acidity of the graphene oxide aqueous solution obtained by using HCl or KOH, the upper layer and lower layer in each acidity were separated, and their average particle size and particle size distribution were analyzed. The results are shown in Table 1 below.

Solution pH division Average size Size distribution One Supernatant 400 nm 0 to 1 탆 Sublayer 1 탆 0 to 11 μm 3 Supernatant 1 탆 0 to 2 μm Sublayer 8.5 탆 5 to 11 μm 5 Supernatant 2 탆 0 to 4 μm Sublayer 8 탆 6 to 10 μm 6 Supernatant 3 탆 1 ~ 5㎛ Sublayer 7.7 탆 5 to 11 μm 8 Supernatant 6.8 탆 0 to 8 μm Sublayer 7.1 탆 4 ~ 10㎛ 10 Supernatant 2.6 탆 0 to 5 μm Sublayer 3.2 3 to 11 μm 12 Supernatant 4.7 0 to 6 μm Sublayer 5.2 4 to 11 μm 14 Supernatant 2.2 탆 0 to 5 μm Sublayer 2.5 탆 1 to 10 μm

Referring to Table 1, it can be seen that the graphene oxide aqueous solution according to the present embodiment is easily separated by size in the pH range of 3 to 6. However, the range of the pH that can be easily separated by size means that the graphene oxide has a different functional group, which means that the pH of the graphene oxide aqueous solution can be easily separated from 3 to 6 by size no.

Claims (15)

Preparing a graphene oxide aqueous solution;
Adjusting an acidity by adding an acid or a base to the graphene oxide aqueous solution; And
Separating the upper layer solution and the lower layer solution of the aqueous acid solution-adjusted graphene oxide solution;
≪ / RTI >
The method according to claim 1,
Wherein the step of preparing the graphene oxide aqueous solution comprises:
Treating the graphite with an acid to obtain a mixed solution of the graphene oxide and the impurity; And
Removing impurities from the mixed solution to obtain an aqueous graphene oxide solution;
≪ / RTI >
3. The method of claim 2,
And ultrasonically treating the graphene oxide aqueous solution.
The method of claim 3,
Wherein the temperature of the graphene oxide aqueous solution during the ultrasonic treatment is 50 DEG C or lower.
The method according to claim 1,
Wherein the graphene oxide has at least one functional group selected from the group consisting of a hydroxyl group, a carbonyl group, a carboxyl group and an amine group.
The method according to claim 1,
The acid group consisting of hydrochloric acid (HCl), perchloric acid (HClO 4), nitric acid (HNO 3), sulfuric acid (H 2 SO 4), phosphoric acid (H 3 PO 4), acetic acid (CH3COOH) and carbon dioxide (H 2 CO 3) ≪ / RTI >
The method according to claim 1,
The base separation method of the graphene oxide at least one member selected from the group consisting of potassium hydroxide (KOH), sodium (NaOH), calcium hydroxide (Ca (OH) 2) and ammonium hydroxide (NH 4 OH) hydroxide.
Preparing a supernatant or subcolumn separated by the method of any one of claims 1 to 7;
Separately separating the graphene oxide contained in the upper layer solution or the lower layer solution, and then mixing the separated graphene oxide with an organic resin to obtain a graphene oxide coating solution;
Coating the graphene oxide coating solution on a base steel sheet to form a graphene oxide coating layer;
Treating the base steel sheet on which the graphene oxide coating layer is formed to heat the graphene oxide coating layer;
Coated steel sheet.
9. The method of claim 8,
Wherein the graphene oxide is contained in an amount of 5 to 80 parts by weight based on 100 parts by weight of the graphene oxide coating solution.
9. The method of claim 8,
Wherein the organic resin is contained in an amount of 25 to 70 parts by weight based on 100 parts by weight of the graphene oxide coating solution.
9. The method of claim 8,
Wherein the organic resin is one or a mixture of two or more kinds selected from the group consisting of a water-dispersible urethane resin, a water-dispersible acrylic resin, a water-soluble epoxy resin, a water-soluble polyester resin and a water-soluble amino resin.
9. The method of claim 8,
Wherein the graphene oxide coating solution further comprises at least one corrosion inhibitor selected from among inorganic metal sols, rust inhibitors, organometallic complexes and crosslinking agents, and the corrosion resistance improver is 0.1 to 5 parts by weight per 100 parts by weight of the graphene oxide coating solution Coated steel sheet.
13. The method of claim 12,
Wherein the graphene oxide coating solution further comprises at least one additive selected from the group consisting of a defoaming agent, a smoothing agent, a wax, and a solvent, wherein the additive is present in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the graphene oxide coating solution Gt;
9. The method of claim 8,
Wherein the heat treatment temperature during the heat treatment is 800 to 900 占 폚.
9. The method of claim 8,
Wherein the heat treatment is performed in an atmosphere of nitrogen (80 to 100 vol%) + hydrogen (0 to 20 vol%).
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