KR101114948B1 - Method of fabrication of purified graphene sheets using PVA-coagulation technique - Google Patents
Method of fabrication of purified graphene sheets using PVA-coagulation technique Download PDFInfo
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- KR101114948B1 KR101114948B1 KR1020100003087A KR20100003087A KR101114948B1 KR 101114948 B1 KR101114948 B1 KR 101114948B1 KR 1020100003087 A KR1020100003087 A KR 1020100003087A KR 20100003087 A KR20100003087 A KR 20100003087A KR 101114948 B1 KR101114948 B1 KR 101114948B1
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
- C01B32/192—Preparation by exfoliation starting from graphitic oxides
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- C—CHEMISTRY; METALLURGY
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- 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
- C01B32/194—After-treatment
- C01B32/196—Purification
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- 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
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/23—Oxidation
Abstract
The present invention relates to a method for producing a graphene sheet, and more particularly to a method for producing a graphene sheet to separate the pure graphene sheet using a PVA-coagulation method from partially or incompletely reduced graphene oxide.
Description
The present invention relates to a method for producing a graphene sheet, and more particularly to a method for producing a graphene sheet to separate the pure graphene sheet using a PVA-coagulation method from partially or incompletely reduced graphene oxide.
Graphene is a monolayer of carbon atoms densely compacted in the benzene ring structure and forms blocks of various structures such as carbon black, carbon fiber, nanotubes and fullerene.
As such, graphene is an interesting 2D flat material composed of single-walled carbon atoms, with individual graphene sheets freed and immobilized with unique properties and promising for the production of nanoscale engineering and nanoscale devices.
In other words, graphene's unique properties are reinforced with fillers in high-performance polymer nanocomposites, such as field effect transistors, lithium ion batteries, nanochemical sensors, hydrogen storage, ultra-sensitive biosensors, molecular sensors, artificial muscle actuators, and high-performance polymer nanocomposites. This is because it has very promising applicability in fillers for reinforcing materials.
Many techniques have been developed since the first report of the production of graphene by mechanical peeling (pilling method), which repeatedly strips the carbon layer from the multilayered graphite using adhesive tape. Bottom up method for growing graphene through chemical reaction at large atomic or molecular size, and top down method for separating graphene layer by mechanical and chemical energy gradually from large volume materials Has been developed. In particular, the top-down method is a direct and simple method, and it is easy to additionally process the blending, blending, casting, reduction-penetration, spin coating, and functionalization of the graphene sheet prepared in the form of a colloidal solution.
With a variety of reducing agents such as gras by reduction of the separated oxidizing graphite (exfoliated graphite oxide (GO)) the conventional method to obtain a pin, but known to be easy to mass production, with hydrazine (hydrazine), sodium borohydride (NaBH 4) excess Since it should be used, there is a problem that it is not environmentally friendly, and in particular, pure graphene is not always produced, and there is a problem that a large amount of incompletely reduced graphene oxide sheet is present.
The present inventors have completed the present invention by developing a graphene sheet manufacturing method for separating the pure graphene sheet from graphite oxide or graphene oxide in an eco-friendly environment suitable for large-scale synthesis as a result of research efforts to solve the above problems.
Therefore, an object of the present invention is to provide a graphene sheet manufacturing method for separating the pure graphene sheet while reducing the amount of reducing agents such as hydrazine, sodium borohydride used to reduce the graphite oxide.
The objects of the present invention are not limited to the above-mentioned objects, and other objects that are not mentioned will be clearly understood by those skilled in the art from the following description.
In order to achieve the above object, the present invention provides an oxidation step of oxidizing graphite to obtain graphite oxide composed of a plurality of graphene layers; A reduction step of reducing the graphite oxide using a reducing agent; And a separation step of separating the pure graphene sheet by reacting the graphene sheet obtained after the reduction step with a polyvinyl alcohol (PVA) solution.
In order to achieve the above object, the present invention also provides an oxidation step of oxidizing graphite to obtain graphite oxide composed of a plurality of graphene layers; An ultrasonic treatment step of separating the graphite oxide into a graphene oxide sheet by sonicating the graphite oxide; A reduction step of reducing the graphene oxide sheet using a reducing agent; And a separation step of separating the pure graphene sheet by reacting the graphene sheet obtained after the reduction step with a polyvinyl alcohol (PVA) solution.
In a preferred embodiment, the oxidation step is characterized in that the graphite is dispersed by dispersing the graphite in sulfuric acid and stirring with potassium permanganate.
In a preferred embodiment, the graphite oxide is composed of an oxidized graphene sheet surrounded by a -OH group, a carbonyl and a carboxyl group on the base surface.
In a preferred embodiment, the reducing agent may use sodium borohydride or hydrazine.
In a preferred embodiment, the reducing agent may be used as the secondary reducing agent, while using sodium borohydride as the primary reducing agent.
In a preferred embodiment, the separating step is the step of storing the graphene sheet obtained after the reduction step in distilled water and sonicating; Mixing the PVA solution with the distilled water; A collection step of collecting the pure graphene sheet which floated without reacting in the PVA solution; And drying the collected pure graphene sheet. It is preferable to maintain the temperature of the distilled water mixed with the PVA solution at 45 to 50 ℃.
In a preferred embodiment, the separating step is the step of storing the graphene sheet obtained after the reduction step in distilled water and sonicating; Mixing the PVA solution with the distilled water; And separating the pure graphene sheet using a centrifuge. It is preferable to maintain the temperature of the distilled water mixed with the PVA solution at 45 to 50 ℃.
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The present invention has the following excellent effects.
First, according to the graphene sheet manufacturing method of the present invention, in order to obtain a pure graphene sheet from partially reduced graphene oxide by using a PVA solution without the addition of a reducing agent such as sodium borohydride and hydrazine, it is an environmentally friendly pure graphene sheet There is an advantage that can be separated.
According to the graphene sheet manufacturing method of the present invention is suitable for the synthesis of large-scale graphene sheet through low cost and short manufacturing time.
In addition, the graphene sheet manufacturing method of the present invention can additionally obtain a graphene-enhanced PVA hydrogel.
1 is an SEM image showing graphite (a) and graphite oxide layers (b) expanded interlayer by modified Hummers method,
Figure 2 is a photograph showing the pure graphene emerged by the PVA coagulation method of Example 1,
FIG. 3 is a SEM photograph (b) of graphene oxide enhanced with graphene oxide (a) and graphene oxide in PVA hydrogel formed according to Example 1;
4 is a conceptual diagram of hydrogen bonding between graphene oxide surrounded by OH and COOH groups of Example 1 and OH groups of PVA,
5 is a graph of the FTIR measurement of PVA / graphene oxide collected according to Example 1,
6 is a SEM (a) and TEM (b) of the collected graphene sheet according to Example 1,
7 is a nanopropyllomitri image of the graphene sheet collected according to Example 1,
8 is a Raman spectra of graphene sheets collected according to Example 1. FIG.
The terms used in the present invention were selected as general terms as widely used as possible, but in some cases, the terms arbitrarily selected by the applicant are included. In this case, the meanings described or used in the detailed description of the present invention are considered, rather than simply the names of the terms. The meaning should be grasped.
Hereinafter, the technical structure of the present invention will be described in detail with reference to the accompanying drawings and preferred embodiments.
However, the present invention is not limited to the embodiments described herein but may be embodied in other forms. Like reference numerals designate like elements throughout the specification.
First, the present invention provides an oxidation step of oxidizing graphite to obtain graphite oxide composed of a plurality of graphene layers; A reduction step of reducing the graphite oxide using a reducing agent; And a separation step of separating the pure graphene sheet by reacting the graphene sheet obtained after the reduction step with a PVA (Polyvinyl Alcohol) solution. The graphene sheet manufacturing method includes oxidizing graphite and oxidizing the graphite to form a plurality of graphene layers. An oxidation step of obtaining; An ultrasonic treatment step of separating the graphite oxide into a graphene oxide sheet by sonicating the graphite oxide; A reduction step of reducing the graphene oxide sheet using a reducing agent; And a separation step of separating the pure graphene sheet by reacting the graphene sheet obtained after the reduction step with a PVA solution. The technical features of the graphene sheet include: In addition, the partially reduced graphene oxide sheet can be easily separated from the pure graphene sheet using an environmentally friendly and biocompatible PVA solution.
Here, the oxidation step may be performed by dispersing graphite in sulfuric acid and then stirring with potassium permanganate. In the reducing step, the reducing agent may use various reducing agents, bar sodium hydride or hydrazine, and may also use sodium borohydride as the primary reducing agent, hydrazine may be used as a secondary reducing agent. In the separation step, the graphene sheet obtained after the reduction step is stored in distilled water (DI water), the PVA solution is mixed with distilled water, and the graphene oxide partially or incompletely reduced in the PVA solution is reacted with PVA to precipitate. It may be performed, including a collection step of collecting the pure graphene sheet floated without reaction and drying the collected pure graphene sheet. At this time, the temperature of the distilled water mixed with the PVA solution is preferably maintained at 45 to 50 ℃.
By introducing a pure graphene sheet separation step using a very simple yet simple PVA solution, it was possible to obtain a pure graphene sheet without the use of additional sodium borohydride and hydrazine in the reduction step. In addition, low cost and short manufacturing time make it possible to synthesize high quality graphene sheets on a large scale.
On the other hand, the separation step may be separated bar pure graphene sheet using a centrifuge, the step of storing the graphene sheet obtained after the reduction step in distilled water and sonicating; Mixing the PVA solution with the distilled water; And separating the pure graphene sheet using a centrifuge. At this time, it is preferable to maintain the temperature of the distilled water mixed with the PVA solution at 45 to 50 ℃. By introducing a pure graphene sheet separation step using a PVA solution and a centrifugal separator as described above, the pure graphene sheet can be easily separated without the use of additional sodium borohydride and hydrazine in the reduction step. Hydrogels can also be obtained.
Example 1
Pure graphene sheets were obtained from graphite in the following manner.
1. Oxidation stage
The modified Hummers method, ie, graphite flakes is made of graphite oxide using sulfuric acid (H 2 SO 4 ) and potassium permanganate (KMnO 4 ). In detail, 5 g of graphite flakes are dispersed in sulfuric acid (100 ml) bathed in ice water, and then 15 g of potassium permanganate is gradually added during stirring. At this time, the reaction temperature is not to exceed 20 ℃. The graphite oxidized through this process is functionalized with -COOH and carbonyl groups around the base surface, with functional groups of -OH and> O decay on the interlayer hexagonal carbon base.
FIG. 1 is an SEM photograph showing graphite oxide layers (b) expanded by graphite (a) and modified Hummers method.
Referring to FIG. 1, it can be seen that the interlayer distance of graphite oxide is increased from about 0.34 nm to 8.18 nm, which means a decrease in inner layer van der Waals binding force.
2. Ultrasonication step
After the graphite oxide is stored in distilled water, sonication is performed 5 to 6 times for 30 seconds to separate the graphene oxide sheets constituting the graphite oxide from each other.
3. First and Second Reduction Stage
The oxidized graphene sheet was first reduced using sodium borohydride as a reducing agent, and sodium borohydride (35 wt%) was dissolved in distilled water (DI water), followed by oxidized graphene sheet (0.5 wt%). Partial reduction of the graphene oxide sheet was performed by performing a primary reduction at 80 ° C. for 1 hour. Then, the secondary reduction using hydrazine bar, put the primary reduced graphene oxide sheet (0.5wt%) in the hydrazine (10wt%) solution to perform secondary reduction at 100 ℃ for about 24 hours graphene oxide The sheet is further reduced.
On the other hand, the graphene oxide obtained through the primary and secondary reduction is not a fully reduced state, which was confirmed by the XPS test results that the graphene oxide residues including nitrogen impurities. At this time, in the conventional method, sodium borohydride and hydrazine were additionally used to further reduce partially reduced graphite oxide, but in the present invention, the process time is shortened and a large amount of reducing agent is used by using the following process without using additional sodium borohydride and hydrazine. The environmental problems caused by the use could be improved.
4. Separation step
First, the partially reduced graphene oxide sheet containing nitrogen impurities is dispersed in distilled water, sonicated for 10 minutes, and then stored in distilled water again. Then, heat the mixed solution while mixing the PVA solution. At this time, when the mixed solution reaches about 45 ~ 50 ℃ pure graphene sheet floats on the surface of the mixed solution as shown in Figure 2, the graphene oxide reacted with PVA is precipitated down. The pure graphene sheet floated on the surface of the mixed solution is not formed of a film such as graphene bucky paper, but is present in the downy thin pieces. The pure graphene sheet is collected on a substrate and dried to obtain a fluffy pure graphene sheet.
The graphene oxide precipitate reacted with PVA is a sticky mass of gel type and becomes a precursor of graphene oxide enhanced PVA hydrogel. Graphene oxide PVA gel (5-10wt%) precipitated through the above process was reacted with dimethyl sulfoxide (DMSO) in a solvent having a distilled water ratio of 50:50 while microwave was irradiated with a cross-linking reaction. As shown in 3 (a), it is possible to obtain a PVA hydrogel enhanced with a solid graphene oxide. In addition, SEM images of graphene oxide in the graphene oxide-enhanced PVA hydrogel, as shown in FIG. 3 (b), show that the layered graphene oxide having no additional aggregation phenomenon is reinforced in the hydrogel. have.
In addition, the separation of pure graphene from partially reduced graphene oxide in the PVA coagulation reaction can be obtained stably and easily using a centrifuge. In other words, using a centrifuge, it is possible to quickly and easily obtain a graphene oxide precipitate precipitated with PVA functionally together with pure graphene sheets.
Experimental Example 1
Graphite oxide is composed of oxidized graphene sheet surrounded by -OH group, carbonyl, and carboxyl group on the base surface. Especially, oxygen functional group gives hydrophilicity to graphite oxide, which is easily interconnected with water molecules to form mutual passage layer. . The PVA aqueous solution is colloidal, and the -OH group easily accepts hydrogen bonds, thereby increasing interaction with water molecules. This hydrogen bond also causes the PVA molecules to interact with each other, increasing the viscosity of the PVA solution, especially at slightly higher reaction temperatures. Through this reaction, as shown in FIG. 4, the OH group of the PVA forms a strong hydrogen bond with the OH group and the carboxyl group present in the graphene oxide, and as a result, a hydrogen bond crosslinked between the PVA molecules.
These hydrogen bonds become relatively strong when reacted with DMSO and distilled water solvents and irradiated with microwaves, and these hydrogen bonds become considerably dynamic with the crosslinkers that move randomly between the PVA molecules, resulting in continuous binding and separation together. do. The critical temperature at which this crosslinking reaction occurs is about 50 ° C, and the crosslinking reaction during the relatively short reaction time causes the hydrogel to be elastic, and the longer crosslinking reaction time causes the PVA molecules to be relatively Make each other sticky mucus.
5 is a FTIR measurement graph of PVA / graphene oxide collected according to Example 1, confirming the crosslinking reaction between the OH group of PVA and the COOH group of graphene oxide. The resulting spectra show a decrease in peak around 3200 cm −1 , which represents the peak of the hydroxyl group, indicating that there is a crosslinking reaction.
Experimental Example 2
6 is a SEM (a) and TEM (b) photograph of a graphene sheet separated from a graphene oxide partially reduced by a PVA solidification method according to Example 1 collected on a porous AAO substrate. Looking at Figure 6 (a) it can be seen that the graphene sheet collected on the porous AAO substrate, it was observed that it is partially curled or folded, which is similar to the previously reported previous results, the TEM of Figure 6 (b) In the picture, the folded shape is visible, but no drying phenomenon is found.
FIG. 7 is a non-contact nanoprofile image using monochromatic optical light to measure the thickness of the graphene sheet collected according to Example 1, wherein the graphene sheet has a transverse size of several micrometers. The thickness was 0.9nm, which is comparable to the thickness of graphene layer (0.4 ~ 2.4nm) measured by AFM.
FIG. 8 is a Raman spectra of the graphene sheets collected according to Example 1, showing a very small bump shape in the D band region (˜1350 cm −1 ), which means that the graphene sheet has almost no defects. In the 2D (~ 2700 cm -1 ) band, a single peak is sharp, indicating that a high-purity graphene sheet is produced by the method proposed in the present invention. Also shown is a single G peak that may not be intertwined with the four peaks (inserted in FIG. 8) suggesting that high purity graphene can be obtained.
As described above, the present invention has been illustrated and described with reference to preferred embodiments, but is not limited to the above-described embodiments, and is provided to those skilled in the art without departing from the spirit of the present invention. Various changes and modifications will be possible.
Claims (11)
A reduction step of reducing the graphite oxide using a reducing agent; And
And a separation step of separating the pure graphene sheet by reacting the graphene sheet obtained after the reduction step with a polyvinyl alcohol (PVA) solution.
An ultrasonic treatment step of separating the graphite oxide into a graphene oxide sheet by sonicating the graphite oxide;
A reduction step of reducing the graphene oxide sheet using a reducing agent; And
And a separation step of separating the pure graphene sheet by reacting the graphene sheet obtained after the reduction step with a polyvinyl alcohol (PVA) solution.
The oxidation step is a graphene sheet manufacturing method characterized in that to disperse the graphite in sulfuric acid and then stirred with potassium permanganate to make the graphite oxide.
The graphite oxide is a graphene sheet manufacturing method characterized in that consisting of an oxidized graphene sheet surrounded by -OH group, carbonyl, carboxyl group on the base surface.
The reducing agent is a graphene sheet manufacturing method, characterized in that sodium borohydride or hydrazine.
The reducing agent is a graphene sheet production method characterized in that using sodium borohydride as a primary reducing agent, hydrazine as a secondary reducing agent.
The separation step
Storing the graphene sheet obtained after the reducing step in distilled water and sonicating;
Mixing the PVA solution with the distilled water;
Partially reduced graphite oxide in the PVA solution is precipitated by reacting with the PVA, the collection step of collecting the pure graphene sheet floated without reacting with the PVA; And
Drying the collected pure graphene sheet; Graphene sheet manufacturing method comprising a.
Graphene sheet manufacturing method characterized in that the temperature of the distilled water mixed with the PVA solution is maintained at 45 to 50 ℃.
The separation step
Storing the graphene sheet obtained after the reducing step in distilled water and sonicating;
Mixing the PVA solution with the distilled water; And
Separating the pure graphene sheet using a centrifuge; Graphene sheet manufacturing method comprising a.
Graphene sheet manufacturing method characterized in that the temperature of the distilled water mixed with the PVA solution is maintained at 45 to 50 ℃.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
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| KR1020100003087A KR101114948B1 (en) | 2010-01-13 | 2010-01-13 | Method of fabrication of purified graphene sheets using PVA-coagulation technique |
| PCT/KR2011/000265 WO2011087305A2 (en) | 2010-01-13 | 2011-01-13 | Method for producing pure graphene sheets using pva coagulation, and graphene sheets produced by the method |
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| Application Number | Priority Date | Filing Date | Title |
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| KR1020100003087A KR101114948B1 (en) | 2010-01-13 | 2010-01-13 | Method of fabrication of purified graphene sheets using PVA-coagulation technique |
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| KR20110083068A KR20110083068A (en) | 2011-07-20 |
| KR101114948B1 true KR101114948B1 (en) | 2012-03-06 |
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| KR101472915B1 (en) * | 2012-10-09 | 2014-12-16 | 주식회사 그래핀올 | Method of producing graphene oxide |
| CN113831894A (en) * | 2021-08-13 | 2021-12-24 | 中国航天空气动力技术研究院 | Ferrite graphene composite material and preparation method thereof |
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| US7892514B2 (en) * | 2007-02-22 | 2011-02-22 | Nanotek Instruments, Inc. | Method of producing nano-scaled graphene and inorganic platelets and their nanocomposites |
| JP2009062241A (en) * | 2007-09-07 | 2009-03-26 | Hokkaido Univ | Method for producing graphene sheet |
| KR20090026568A (en) * | 2007-09-10 | 2009-03-13 | 삼성전자주식회사 | Graphene sheet and process for preparing the same |
| JP5470610B2 (en) * | 2007-10-04 | 2014-04-16 | 国立大学法人福井大学 | Graphene sheet manufacturing method |
| KR100923304B1 (en) * | 2007-10-29 | 2009-10-23 | 삼성전자주식회사 | Graphene sheet and process for preparing the same |
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Non-Patent Citations (1)
| Title |
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| Nature Chemistry, Vol 1, 2009, pages 403-408 |
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| WO2011087305A3 (en) | 2011-12-22 |
| KR20110083068A (en) | 2011-07-20 |
| WO2011087305A2 (en) | 2011-07-21 |
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