KR20130081545A - Method of fabricaing graphene - Google Patents

Method of fabricaing graphene Download PDF

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KR20130081545A
KR20130081545A KR1020120002580A KR20120002580A KR20130081545A KR 20130081545 A KR20130081545 A KR 20130081545A KR 1020120002580 A KR1020120002580 A KR 1020120002580A KR 20120002580 A KR20120002580 A KR 20120002580A KR 20130081545 A KR20130081545 A KR 20130081545A
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South Korea
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graphite
graphene
mixture
generating material
interlayer compound
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KR1020120002580A
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Korean (ko)
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공영민
전상기
유인규
구재본
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한국전자통신연구원
울산대학교 산학협력단
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Priority to KR1020120002580A priority Critical patent/KR20130081545A/en
Publication of KR20130081545A publication Critical patent/KR20130081545A/en

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    • 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
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/19—Preparation by exfoliation

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
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  • Carbon And Carbon Compounds (AREA)

Abstract

PURPOSE: A method for fabricating graphene is provided to cost-effectively fabricate a high quality of graphene by simply fabricating a graphite interlayer compound. CONSTITUTION: A method for fabricating graphene comprises the steps of: preparing an inserting material containing at least one alkaline metal or alkaline earth metal; preparing a graphite generating material; forming a mixture by mixing the inserting material and the graphite generating material (S110); forming a graphite interlayer compound by thermally treating the mixture (S120); and exfoliating graphene from the graphite interlayer compound (S130). The graphite generating material further contains a sacrificial graphite generating material. [Reference numerals] (S110) Form a mixture by mixing an inserting material containing at least one alkaline metal or alkaline earth metal and a graphite generating material; (S120) Form a graphite interlayer compound by thermally treating the mixture; (S130) Exfoliate graphene from the graphite interlayer compound; (S140) Centrifuge and filter the exfoliated graphene

Description

Graphene manufacturing method {Method of Fabricaing Graphene}

The present invention relates to a method for producing graphene, and more particularly to a method for producing a graphene interlayer compound and a graphene using the same.

Indium Tin Oxide (ITO) electrodes, which are used as electrodes for plastic substrates, exhibit more than 1,000 times more sheet resistance when they are bent, and the brittle nature of indium tin oxide itself Due to the difference in the coefficient of thermal expansion (CTE) with and has shown a number of problems when applied to the actual flexible electronic devices. Currently, conductive polymers, carbon nanotubes (CNTs), and carbon nanofibers are being considered as conductive materials that can replace indium tin oxide, but among them, conductivity and substrate Carbon nanotubes, which have excellent adhesion and are mechanically and thermally stable, have been spotlighted as next generation electrode materials.

However, carbon nanotubes are a single functional element, and when applied to electronic devices, have low input / output current, a small contact area, and a problem of synthesizing linear carbon nanotubes at desired positions. Graphene is the perfect two-dimensional carbon nanoelectronic material that can solve this problem.

Graphene refers to a planar two-dimensional carbon structure that forms sp2 bonds, and is a physically and chemically stable material. At room temperature, electrons can be moved 100 times faster than silicon and 100 times more current per unit area than copper. In addition, graphene is more than twice the thermal conductivity of diamond (diamond), 200 times more mechanical strength than steel, and has transparency. In addition, graphene is stretched due to the spatial clearance of hexagonal honeycomb structure in which carbon is connected like a net, and does not lose electrical conductivity even when stretched or folded. The unique structure and physical properties of graphene can replace indium tin oxide, which is the main material of current transparent electrodes, and silicon, which is the main material of semiconductors.

In order to apply graphene having excellent characteristics to flexible electronic devices, a large-area graphene having a high quality of a single layer must be able to be mass produced, and graphene should be manufactured at low temperature. In addition, to be commercialized, the price must be competitive and the safety of the process must be secured.

Current methods for producing graphene include mechanical methods, epitaxial growth methods, thermal expansion methods, vapor growth methods, chemical vapor deposition (CVD), graphene oxidation-reduction Method, graphite intercalation compound (GIC) method and the like.

Among these, the graphite interlayer compound method is a method of preparing graphene by inserting a metal between graphite layers to form a graphite interlayer compound. The interlayer spacing of the original graphite is 3.35 Å, but when the alkali metal or alkaline earth metal ions are intercalated between the graphite layers, the interlayer spacing is widened. At this time, the interlayer spacing becomes larger as ions located below the periodic table, that is, having a larger atomic radius are inserted.

However, conventionally, graphite intercalation compounds have been prepared by directly using metals to insert alkali metal ions or alkaline earth metal ions between graphite layers, melting the metals themselves or metals in an appropriate organic solvent, and then reacting with graphite. . Alkali metals and alkaline earth metals are elements of Groups 1 and 2 of the periodic table, which are very reactive, and therefore cannot be processed in an oxygen atmosphere, and are extremely explosive and difficult to handle. In addition, the price of the metal itself is very expensive, there is a disadvantage that the unit price of graphene is very high.

The problem to be solved by the present invention is to provide a method for producing high quality graphene does not contain oxygen (O).

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

In order to achieve the above object, the present invention is to prepare an insertion material comprising at least one alkali metal or alkaline earth metal, to prepare a graphite generating material, to form a mixture by mixing the insertion material and the graphite generating material And heat treating the mixture to form a graphite intercalation compound and exfoliating graphene from the graphite interlayer compound.

Peeling graphene from the graphite interlayer compound may be by using ultrasonic waves.

After centrifuging the exfoliated graphene may further comprise filtering.

Mixing the insert material and the graphite generating material may be to have a range of molar ratios or weight ratios. The graphite generating material may further comprise a sacrificial graphite generating material. The sacrificial graphite generating material may serve to remove oxygen during the heat treatment of the mixture.

Prior to the heat treatment of the mixture, the mixture may further comprise containing the container and sealing the container. After sealing the container, the method may further include removing air in the container.

The heat treatment of the mixture may be carried out in an atmospheric pressure atmosphere.

Heat treatment of the mixture may be carried out in the temperature range 700 ~ 1,000 ℃.

The insert material may be in the form of a carbonate.

Graphite generating materials may include charcoal, carbon black, graphite or combinations thereof.

As described above, according to the problem solving means of the present invention, by simply mixing the insertion material containing a metal and the graphite generating material, and then producing a graphite interlayer compound through heat treatment, the graphite interlayer compound can be prepared in a simple process. . Accordingly, a method for producing high quality graphene at a low cost may be provided.

In addition, since the graphite generating material further includes a sacrificial graphite generating material, oxygen may be removed in a heat treatment process for producing the graphite interlayer compound. Accordingly, a method capable of producing high quality graphene free of oxygen at low cost may be provided.

1 is a block flow diagram illustrating a graphene manufacturing method according to an embodiment of the present invention;
2A and 2B are cross-sectional views illustrating a heat treatment process of the graphene manufacturing method according to the embodiments of the present invention, respectively;
3A and 3B are graphs showing weight change and temperature change characteristics of each of the materials by the graphene manufacturing method according to the embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention and the manner of achieving them will become apparent with reference to the embodiments described in detail below with reference to the accompanying drawings. However, the present invention is not limited to the embodiments described herein but may be embodied in different forms. Rather, the embodiments disclosed herein are provided so that the disclosure can be thorough and complete, and will fully convey the concept of the invention to those skilled in the art, and the invention is only defined by the scope of the claims. Like reference numerals refer to like elements throughout the specification.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In the present specification, the singular form includes plural forms unless otherwise specified in the specification. As used herein, the terms 'comprises' and / or 'comprising' mean that the stated element, step, operation and / or element does not imply the presence of one or more other elements, steps, operations and / Or additions. In addition, since they are in accordance with the preferred embodiment, the reference numerals presented in the order of description are not necessarily limited to the order. In addition, in this specification, when it is mentioned that a film is on another film or substrate, it means that it may be formed directly on another film or substrate, or a third film may be interposed therebetween.

In addition, the embodiments described herein will be described with reference to cross-sectional views and / or plan views, which are ideal illustrations of the present invention. In the drawings, the thicknesses of films and regions are exaggerated for effective explanation of technical content. Thus, the shape of the illustrations may be modified by manufacturing techniques and / or tolerances. Accordingly, the embodiments of the present invention are not limited to the specific forms shown, but also include variations in forms generated by the manufacturing process. For example, the etched area shown at right angles may be rounded or may have a shape with a certain curvature. Thus, the regions illustrated in the figures have schematic attributes, and the shapes of the regions illustrated in the figures are intended to illustrate specific types of regions of the elements and are not intended to limit the scope of the invention.

Graphene refers to graphene composed of monolayer or graphene composed of multiple layers. Hereinafter, although used in plural terms graphene, the present invention is not limited thereto and may include graphene formed of a single layer.

1 is a block diagram illustrating a graphene manufacturing method according to an embodiment of the present invention.

Referring to FIG. 1, an insertion material including at least one alkali metal or alkaline earth metal is prepared, and a graphite generating material is prepared. The insert material may be a material in the form of a carbonate comprising various kinds of alkali metals and / or alkaline earth metals. Preferably, the insert material according to the embodiment of the present invention is potassium carbonate (K 2 CO 3 ), sodium carbonate (Na 2 CO 3 ), lithium carbonate (Li 2 CO 3 ), calcium carbonate (CaCO 3 ), magnesium carbonate Alkali metal carbonates such as (MgCO 3 ), alkaline earth metal carbonates, or a combination thereof. Graphite generating materials may include charcoal, carbon black, graphite or combinations thereof. Preferably, the graphite generating material according to the embodiment of the present invention may be graphite.

The insertion material and the graphite generating material are mixed to form a mixture (S110). Mixing the insert material and the graphite generating material may be to have a range of molar ratios or weight ratios.

The mixture is heat treated to form a graphite interlayer compound (S120). The heat treatment of the mixture may be carried out in an atmospheric pressure atmosphere. Heat treatment of the mixture may be carried out in the temperature range 700 ~ 1,000 ℃. The graphite generating material of the mixture may further comprise a sacrificial graphite generating material. The sacrificial graphite generating material may serve to remove oxygen during the heat treatment of the mixture. Accordingly, a graphite interlayer compound that does not contain oxygen may be formed.

Prior to the heat treatment of the mixture, it may comprise placing the mixture in a container. The container may be a crucible. This is because the heat treatment of the mixture is carried out in the temperature range of 700 to 1,000 ° C. Dry ice, water, ethanol or a combination thereof may be further contained in the vessel to remove oxygen in the vessel containing the mixture.

In addition, the method may further include sealing a container containing the mixture. In addition, after sealing the container, the method may further include removing air in the container. Removing the air in the vessel may be using a vacuum device. This may be to form a graphite intercalation compound that does not contain oxygen by minimizing or removing oxygen in the vessel. When the air in the vessel is removed, the graphite generating material of the mixture does not contain additional sacrificial graphite generating material.

Graphene is peeled off (S130) from the graphite interlayer compound. Peeling the graphenes (S130) from the graphite interlayer compound may be using ultrasonic waves. The graphite interlayer compound formed by the heat treatment may be immersed in distilled water or a mixed solution of distilled water and alcohol (alcohol) to exfoliate graphene from the graphite interlayer compound using ultrasonic waves (S130).

After peeling off the separated graphene is filtered (S140). After centrifuging the exfoliated graphene, the filtration (S140) is for removing the graphite interlayer compound including the graphene that did not exfoliate in the process of exfoliating the graphene (S130) from the graphite interlayer compound using the preceding ultrasonic waves It may be. Since the graphite interlayer compound containing the unpeeled graphene is heavier than the graphene, it is settled by centrifugation, and since the graphite interlayer compound containing the non-peeled graphene is larger than the graphene, it can be filtered out. Can be. Accordingly, graphene consisting of only pure graphenes may be manufactured.

2A and 2B are cross-sectional views illustrating a heat treatment process of the graphene manufacturing method according to the exemplary embodiments of the present invention, respectively.

Referring to FIG. 2A, in the foregoing description of FIG. 1, the heat treatment is performed on a mixture of the insertion material and the graphite generating material g ′ contained in the open container. The graphite generating material g 'further comprises a sacrificial graphite generating material. When the heat treatment is performed, oxygen (O 2 ) around the vessel containing the mixture reacts with the graphite generating material (g ') to generate carbon monoxide (CO) or / and carbon dioxide (CO 2 ), and the oxygen around the vessel containing the mixture is generated. (O 2 ) can be removed. This may reduce the amount of mixture contained in the container as shown.

Continuous heat treatment may result in the formation of graphite intercalation compounds in the mixture in the vessel. At this time, when oxygen (O 2 ) around the vessel containing the mixture remains, the graphite and oxygen (O 2 ) of the graphite interlayer compound reacts to generate a graphite oxide (red color), the mixture in the vessel Graphite intercalation compounds that do not contain oxygen can be formed.

Referring to FIG. 2B, in the foregoing description of FIG. 1, the heat treatment is performed on a mixture of the insertion material pc and the graphite generating material g ′ contained in the sealed container. Since the container containing the mixture is sealed, the graphite generating material g 'of the mixture contained in the container does not include the sacrificial graphite generating material. However, sacrificial graphite generating material s.g 'may be provided around the outside of the container in order to remove oxygen O 2 outside the container during the heat treatment process. When the heat treatment is performed, a graphite interlayer compound containing no oxygen is formed in the mixture contained in the container, and oxygen (O 2 ) and the sacrificial graphite generating material (s.g ') outside the container react to form carbon monoxide or / and carbon dioxide. As it occurs, oxygen (O 2 ) outside the vessel containing the mixture may be removed. When the heat treatment is continuously performed, the graphite oxide may be generated by the reaction between the graphite generated from the sacrificial graphite oxide outside the vessel and the oxygen O 2 remaining outside the vessel.

3A and 3B are graphs showing weight change and temperature change characteristics of each of the materials by the graphene manufacturing method according to an embodiment of the present invention.

Referring to Figure 3a, the thermogravimetric analyzer (ThermoGravimetry Analyzer: TGA) is a result of analyzing the weight change for each of the materials used in the graphene production. 1 is a weight change of the graphite generating material (g '), 2 is a weight change of the inserting material (pc), 3 is a mixture of the graphite generating material (g') and the inserting material (pc) according to an embodiment of the present invention (U1) ), And No. 4 shows the weight change of the mixture (K) of the graphite generating material (g ') and the inserting material (pc) suggested by another graphene manufacturing method. As shown, it can be seen that mixture 3 (U1) has different characteristics from mixture 4 (K).

Referring to FIG. 3B, a differential thermal analyzer (DTA) analyzes the temperature change of each of the materials used for preparing graphene. 1 is heat absorption / release of graphite generating material (g '), 2 is heat absorption / emitting of inserting material (pc), 3 is graphite generating material (g') and inserting material (pc) according to an embodiment of the present invention. The heat absorption / emission of the mixture (U1) of, and No. 4 shows the heat absorption / emission results of the mixture (K) of the graphite generating material (g ') and the insertion material (pc) presented in another graphene manufacturing method. As shown, it can be seen that mixture 3 (U1) has different characteristics from mixture 4 (K).

In the graphene manufacturing method according to the embodiments of the present invention described above, the graphite interlayer compound may be prepared by a simple process by simply mixing the insertion material including the metal and the graphite generating material and then preparing the graphite interlayer compound through heat treatment. Can be. Accordingly, a method for producing high quality graphene at a low cost may be provided.

In addition, since the graphite generating material further includes a sacrificial graphite generating material, oxygen may be removed in a heat treatment process for producing the graphite interlayer compound. Accordingly, a method capable of producing high quality graphene free of oxygen at low cost may be provided.

In conclusion, the graphene manufacturing method according to the embodiments of the present invention can lower the cost of graphene, mass production of graphene due to a simple process, and high-quality graphene containing no oxygen It can manufacture. Accordingly, the possibility of applying graphene to flexible electronic devices including various electrodes, displays, and the like can be presented.

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. It is therefore to be understood that the above-described embodiments are illustrative and non-restrictive in every respect.

Claims (12)

Preparing an intercalation material comprising at least one alkali metal or alkaline earth metal;
Preparing a graphite generating material;
Mixing the insert material and the graphite generating material to form a mixture;
Heat treating the mixture to form a graphite intercalation compound; And
Graphene manufacturing method comprising peeling the graphene from the graphite interlayer compound. The method of claim 1,
Peeling the graphene from the graphite interlayer compound is a graphene manufacturing method using ultrasonic waves. The method of claim 1,
Centrifuging the exfoliated graphene, and further comprising filtering the graphene. The method of claim 1,
Mixing the insert material and the graphite generating material is graphene manufacturing method to have a range of molar ratio or weight ratio. 5. The method of claim 4,
The graphite generating material further comprises a sacrificial graphite generating material. 6. The method of claim 5,
The sacrificial graphite generating material is graphene manufacturing method that serves to remove oxygen during the heat treatment of the mixture. The method of claim 1,
Before heat treating the mixture,
Placing the mixture in a container; And
Graphene manufacturing method further comprises sealing the container. 8. The method of claim 7,
Sealing the container, and then removing the air in the container. The method of claim 1,
Heat-treating the mixture is a graphene manufacturing method performed in an atmospheric pressure atmosphere. The method of claim 1,
Heat treatment of the mixture is a graphene manufacturing method performed in the temperature range 700 ~ 1,000 ℃. The method of claim 1,
The insert material is a graphene manufacturing method in the form of a carbonate. The method of claim 1,
The graphite generating material is a graphene manufacturing method comprising charcoal, carbon black, graphite or a combination thereof.
KR1020120002580A 2012-01-09 2012-01-09 Method of fabricaing graphene KR20130081545A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101478627B1 (en) * 2013-09-02 2015-01-02 한국과학기술원 method of controlling photoluminescence properties of 2-dimensional structured transition metal chacogenide
US9644275B2 (en) 2014-03-31 2017-05-09 Korea Institute Of Science And Technology Method for preparation of graphene using spontaneous process
KR20180129221A (en) * 2017-05-25 2018-12-05 한국과학기술원 Method of manufacturing graphene from ternary graphite intercalation compound
KR20190117923A (en) * 2018-04-09 2019-10-17 한국화학연구원 Manufacturing method of graphene oxides

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101478627B1 (en) * 2013-09-02 2015-01-02 한국과학기술원 method of controlling photoluminescence properties of 2-dimensional structured transition metal chacogenide
US9644275B2 (en) 2014-03-31 2017-05-09 Korea Institute Of Science And Technology Method for preparation of graphene using spontaneous process
KR20180129221A (en) * 2017-05-25 2018-12-05 한국과학기술원 Method of manufacturing graphene from ternary graphite intercalation compound
KR20190117923A (en) * 2018-04-09 2019-10-17 한국화학연구원 Manufacturing method of graphene oxides

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