KR101545637B1 - Method for preparing carbon nanostructure with 3d structure - Google Patents
Method for preparing carbon nanostructure with 3d structure Download PDFInfo
- Publication number
- KR101545637B1 KR101545637B1 KR1020130157208A KR20130157208A KR101545637B1 KR 101545637 B1 KR101545637 B1 KR 101545637B1 KR 1020130157208 A KR1020130157208 A KR 1020130157208A KR 20130157208 A KR20130157208 A KR 20130157208A KR 101545637 B1 KR101545637 B1 KR 101545637B1
- Authority
- KR
- South Korea
- Prior art keywords
- carbon
- metal catalyst
- support
- nanostructure
- carbon support
- Prior art date
Links
Images
Classifications
-
- 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
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
Abstract
A method for producing a carbon nanostructure having a three-dimensional structure in which a carbon support and a carbon nanotube are directly connected to each other is disclosed. A method for fabricating a carbon nanostructure according to an embodiment of the present invention includes: a first step of supporting a metal catalyst for synthesizing carbon nanotubes on a surface of a carbon support using electroless plating; And growing the carbon nanotubes from the metal catalyst so that the metal catalyst is positioned at the upper tip region of the carbon nanotubes.
Description
The present invention relates to a method for producing a carbon nanostructure, and more particularly, to a method for manufacturing a carbon nanostructure having a three-dimensional structure in which a carbon support and a carbon nanotube are directly connected.
Carbon materials such as graphene, fullerene, and carbon nanotube have excellent physical properties and can be applied to a wide range of fields such as photovoltaic cells, field emission devices (FED), capacitors, and batteries. .
Particularly, in recent years, researches on hybrid composites utilizing characteristics of different types of carbon materials (for example, graphene and carbon nanotubes) have been conducted. Among them, a method of producing a hybrid carbon material in which carbon nanotubes (CNTs) are grown on a carbon material such as graphene, graphite, and carbon fiber is largely classified into a method in which a functional group is introduced into the carbon material, A physical / chemical method of producing a hybrid carbon material by adsorbing and substituting carbon nanotubes in the reaction site, and a direct synthesis method of coating a carbon material with a metal catalyst and growing carbon nanotubes on the surface thereof.
In the case of hybrid carbon materials, it is important to minimize the contact resistance between different materials. In this respect, the direct synthesis method of directly growing carbon nanotubes on the carbon material is more advantageous than the physical / chemical method described above. In general, the direct synthesis may be performed by coating a metal oxide (a buffer layer) capable of providing nano pores on the surface of a carbon material, and growing a carbon nanotube by supporting a catalyst on the metal oxide Have been used.
However, in such a conventional method, there is a thermal and electrical resistance between the interface between the carbon material and the metal oxide and the dissimilar material occurring at the interface between the metal oxide and the carbon nanotube. Thus, the prepared hybrid carbon material has a characteristic .
Embodiments of the present invention provide a method for fabricating a three-dimensional carbon nanostructure having a shape in which carbon nanotubes are directly connected without a separate buffer layer on a carbon support.
According to an aspect of the present invention, there is provided a method of manufacturing a carbon nanotube, comprising: a first step of supporting a metal catalyst for synthesizing carbon nanotubes on a surface of a carbon support using electroless plating; And growing the carbon nanotubes from the metal catalyst so that the metal catalyst is positioned at an upper tip portion of the carbon nanotubes.
In this case, the first step may include a step 1-1 in which Sn 2 + is adsorbed on the surface of the carbon support; 1-2 steps of reacting Sn 2 + with a palladium salt to form Sn 4 + / Pd on the surface of the carbon support; And 1-3 steps of immersing the carbon support in a plating bath containing an Fe salt and a Co salt to carry out electroless plating to support the Fe / Co metal catalyst on the surface of the carbon support.
In the
On the other hand, the carbon support may be graphene, oxidized graphene, graphene nanoplate, graphite, expanded graphite or carbon fiber.
According to another aspect of the present invention, there is further provided a carbon nanostructure produced by the method for manufacturing a carbon nanostructure according to an aspect of the present invention.
In embodiments of the present invention, a metal catalyst is supported on the surface of a carbon support using electroless plating, and the metal catalyst is positioned at the upper tip portion of the carbon nanotube in growing the carbon nanotube from the metal catalyst The carbon nanotubes can be directly connected to the carbon support without a separate buffer layer.
Accordingly, it is possible to manufacture a carbon nanostructure having enhanced physical properties by minimizing the thermal and electrical resistance between the hetero-materials that may occur at the interface with the buffer layer.
1 is a flowchart schematically showing a method of manufacturing a carbon nanostructure according to an embodiment of the present invention.
FIG. 2 is a conceptual view schematically showing a state in which a carbon nanostructure is manufactured according to the carbon nanostructure manufacturing method of FIG.
3 is an SEM image showing a state in which a metal catalyst is supported on a carbon support according to a test example of the present invention.
4 is an SEM image of a carbon nanostructure according to a test example of the present invention.
FIG. 5 is a SEM image of a carbon nanostructure according to a test example of the present invention, in which the amount of the metal catalyst supported on the carbon support is changed.
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
A method of fabricating a carbon nanostructure according to an embodiment of the present invention includes the steps of: carrying a metal catalyst for synthesizing carbon nanotubes on the surface of a carbon support using electroless plating; growing carbon nanotubes from the metal catalyst , And growing the metal catalyst so that the metal catalyst is positioned at an upper tip portion of the carbon nanotube.
FIG. 1 is a flow chart schematically showing a method of manufacturing a carbon nanostructure according to an embodiment of the present invention. FIG. 2 is a conceptual view schematically showing a state in which a carbon nanostructure is manufactured according to the carbon nanostructure manufacturing method of FIG. to be. Hereinafter, each step will be described in detail with reference to FIG. 1 and FIG.
(1) Step 1 (S110)
Step 1 is a step of carrying a metal catalyst on the surface of the carbon support using electroless plating. The metal catalyst functions as a seed for synthesis of carbon nanotubes.
The carbon support means a general material containing carbon as a main component, and the carbon nanotube grows in the vertical direction on the surface of the carbon support. Therefore, the structure of the whole carbon nanostructure has a three-dimensional structure.
Examples of the carbon support include graphene, oxide graphene, graphene nanoplate, graphite, expanded graphite, carbon fiber and the like, but not limited thereto (including carbon alloys).
In the method of manufacturing a carbon nano structure according to an embodiment of the present invention, electroless plating is used as a method for supporting a metal catalyst on the surface of a carbon support.
Unlike electroplating, electroless plating is a plating method by chemical reaction of a reducing agent without using electricity. It is a plating method widely applied to components requiring a uniform plating layer and products having a complicated shape. The electroless plating method itself is well known, and a detailed description thereof will be omitted.
The surface of the carbon support needs to be pretreated in order to perform electroless plating. Therefore, the first step (S110) can be divided into the following detailed steps.
Step 1-1 ( S111 )
In the pretreatment step for electroless plating, the surface of the carbon support should be subjected to sensitization treatment and activation treatment sequentially.
Step 1-1 corresponds to the sensitization treatment, and is a step of adsorbing Sn 2 + on the surface of the carbon support. The method of adsorbing Sn 2 + on the surface of the carbon support may be performed by mixing the carbon support with a sensitizing solution containing an Sn salt. The sensitizing solution may comprise water (deionized water), Sn salt and hydrochloric acid. Examples of the Sn salt include, but are not limited to, chloride (stannous), tin oxide, tin fluoride, sodium halide tin stearate, and anthracite. After adsorbing Sn 2 + on the surface of the carbon support, washing (washing) may be performed plural times to remove excess Sn 2 + that has not reacted with the carbon support (S111).
Step 1-2 ( S112 )
Step 1 - 2 corresponds to the activation treatment in the pretreatment step, and is a step of forming Sn 4 + / Pd on the surface of the carbon support by reacting a carbon support adsorbed on the surface of Sn 2 + with a palladium salt. The method of forming Sn 4 + / Pd on the surface of the carbon support may be performed by mixing the carbon support with an activating solution containing a palladium salt and reacting. The reaction formula is as follows.
Sn 2 + + Pd 2 + - & gt ; Pd 0 Sn 4 +
The activation solution may comprise water (deionized water), Pd salt and hydrochloric acid. Examples of the Pd salt include, but are not limited to, palladium chloride, palladium sodium chloride, potassium palladium chloride, palladium ammonium chloride, palladium sulfate, palladium nitrate, palladium acetate and palladium oxide. After forming the Sn 4 + / Pd on carbon support surface through the above reaction may be washed (washing with water) over a plurality of times can be performed to remove the unreacted excess of Pd + 2 (or more S112).
Step 1-3 S113 )
Step 1-3 is a step of supporting the Fe / Co metal catalyst on the surface of the carbon support by electroless plating. The metal catalyst corresponds to a transition metal catalyst for growing carbon nanotubes. In the present specification, examples of the transition metal include Fe and Co, but the transition metal is not limited thereto. In other words, any known metal catalyst that can be used for synthesizing carbon nanotubes can be used. Examples of the metal catalyst include Mo, Ti, V, Cr, Mn, Ni, Cu, Cd, Zn, Ru, Pd, , Or an alloy thereof. On the other hand, it is possible to control the synthesis density of the carbon nanotubes to be grown in the next two steps by controlling the amount of the metal catalyst supported.
The electroless plating may be performed by charging an Fe salt, a Co salt and a reducing agent into a plating bath, and immersing the carbon support in the plating bath.
The Fe salt may be selected from the group consisting of iron chloride, iron sulfate, iron formate, iron acetate, iron citrate, iron oxalate, and hydrates thereof, but is not limited thereto. The Co salt may be selected from the group consisting of cobalt acetate, cobalt carbonate, cobalt chloride, cobalt hydroxide, cobalt nitrate, cobalt sulfate, and hydrates thereof, but is not limited thereto. The reducing agent is not particularly limited as long as it is a compound capable of reducing and precipitating Fe and Co from the Fe salt and the Co salt.
After the Fe / Co metal catalyst is supported on the surface of the carbon support through the electroless plating, washing (rinsing) is performed a plurality of times to remove unreacted excess Fe 2 + , Co 2 + and other impurities (S113).
(2) Step 2 (S120)
The carbon nanotube may be a single wall carbon nanotube, a functionalized single wall carbon nanotube, a double wall carbon nanotube, a functionalized double wall carbon nanotube, a multi wall carbon nanotube, or a functionalized multi wall wall carbon nanotube.
As a method of growing carbon nanotubes, chemical vapor deposition (CVD) may be used. Herein, the chemical vapor deposition may be performed by RTCVD, ICP-CVD, LPCVD, APCVD, MOCVD, MOCVD, ), Chemical vapor deposition (PECVD), and the like.
For example, by introducing the carbon support bearing the metal catalyst into a growth reactor, increasing the temperature of the reactor to 900 ° C to 1000 ° C, and then flowing the reaction gas containing the carbon source (carbon source) Can grow. At this time, it is possible to control the diameter or length of the carbon nanotubes by controlling the pressure of the reactor or the flow rate of the reaction gas. At this time, it is possible to use a known material such as an aliphatic hydrocarbon or an aromatic hydrocarbon as the carbon source. Examples of such carbon sources include, but are not limited to, methane, ethane, propane, butane, ethylene, acetylene, benzene, and the like. The process of growing carbon nanotubes through the chemical vapor deposition process can be performed using known processes, and a detailed description thereof will be omitted.
Meanwhile, when the carbon nanotubes are grown, the contact angle between the carbon support and the metal catalyst is controlled so that the metal catalyst is positioned at the tip of the carbon nanotube. The growth of carbon nanotubes can be classified into two types: the type in which the metal catalyst is located at the upper tip of the carbon nanotube and the type in which the metal catalyst is located at the bottom of the carbon nanotube. will be. The difference between the two forms is determined by the contact angle depending on the surface interaction of the support and the metal catalyst at the growth temperature, and the contact angle may be varied depending on the type of the support and the metal catalyst, the growth temperature, and the like. The inventors of the present invention have found that when the carbon support is a graphene nano plate and the metal catalyst is Co and Fe, the contact angle becomes 80 DEG or more at a growth temperature of about 900 DEG C, And it is possible to grow the carbon nanotubes such that the metal catalyst is positioned at the upper tip portion of the carbon nanotube through the above-described condition setting.
When the metal catalyst is grown to be located at the upper tip region of the carbon nanotube, the carbon support and the carbon nanotube are directly connected to each other without a separate buffer layer. If there is no separate buffer layer, the thermal and electrical resistance between the carbon support and the buffer layer and between the buffer layer and the carbon nanotube can be minimized, so that the physical properties such as electrical and thermal properties of the carbon nanostructure can be enhanced .
The present invention can further provide a carbon nanostructure produced by the above-described method for producing a carbon nanostructure. The carbon nanostructure is grown by directly connecting carbon nanotubes on a carbon material (carbon support) such as graphene, graphite, or carbon fiber. The carbon nanostructure can be used for a solar cell, a field emission device (FED), a capacitor, It can be used in a wide range of fields such as filler and electrode material. In addition, since the carbon nanostructure has a very large specific surface area, the carbon nanostructure can exhibit high physical properties even when a small amount is added to other composite materials.
Hereinafter, specific test examples of the present invention will be described. However, it is apparent that the following test examples do not limit the present invention.
Test Example
(1) Pretreatment process
4 mL of HCl, 3 g of SnCl 2 and 1 g of graphene nanoplate (hereinafter referred to as GNP) were homogeneously mixed for 60 minutes using an ultrasonic grinder to 500 mL of deionized (DI) water to remove excess Sn 2 + not reacted with GNP The sieve (sieve) having a mesh size of 20 μm was used to wash the mixed solution with clean water several times. The washed GNP-Sn 2+ was again homogenized with 500 mL of Deionized (DI) water, 1.25 mL of HCl, and 0.05 g of PdCl 2 through an ultrasonic grinder for 60 min and an excess of Pd that did not react with GNP-Sn 2 + 2+ , the mixture was washed several times by passing the mixture through clean water using a sieve having a mesh size of 20 μm as described above, and then dried at 60 ° C. for one day.
(2) Electroless plating process
Pretreated GNP-Sn 4 + / Pd metal catalyst precursor, 2.55g FeSO 4, CoSO 4 0.45g of a reducing agent and NaH 2 PO 2 · H 2 O 2g, C 6 H 5 O 7 Na 3 6g, H 3 BO 3 3 g of NaOH, 2 g of NaOH, and 500 mL of Deionized (DI) water were stirred at 90 ° C for 30 minutes to be homogeneously mixed to perform electroless plating. Next, excess Fe 2 + , Co 2 +, and other impurities that did not react with GNP-Sn 4 + / Pd were removed several times by passing the mixture through clean water using a sieve having a mesh size of 20 μm Washed and removed. The washed GNP-Fe / Co catalyst support was dried at 60 ° C for one day. 3 is an SEM image (KANC 5.0 Kv, 6.0 mm x 7.00 k SE (U)) showing a state in which an Fe / Co metal catalyst is supported on a graphene nanoplate according to a test example of the present invention.
(3) Growth of Carbon Nanotubes
The GNP-Fe / Co catalyst carrier on which a metal catalyst for synthesizing carbon nanotubes (CNT) was supported on GNP was reacted in a quartz tube through a thermochemical vapor deposition method. Specifically, the GNP-Fe / Co catalyst carrier was reacted in an atmosphere of 900 ° C., Ar (500 sccm) After CNT annealing for 40 minutes, CNTs were synthesized in CH 4 (500 sccm) atmosphere for 60 minutes to fabricate CNTs grown on GNP. At this time, a contact angle of more than 80 ° due to the surface interaction between GNP and the metal catalyst occurs at a synthesis temperature of 900 ° C., and a morphology in which the metal catalyst is finally positioned at the upper tip of the CNT is formed by the synthesis mechanism of CNT. 4 is an SEM image of a carbon nanostructure according to a test example of the present invention (S4800 15.0 Kv, 8.2 mm x 2.00 k SE (U)).
On the other hand, CNTs having various synthetic densities were grown on the GNP by repeating the above tests by varying the amount of the metal catalyst supported on the GNP, which is shown in an SEM image in FIG.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, many modifications and changes may be made by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims. The present invention can be variously modified and changed by those skilled in the art, and it is also within the scope of the present invention.
Claims (5)
And growing the carbon nanotube from the metal catalyst so that the metal catalyst is positioned at an upper tip portion of the carbon nanotube.
Wherein the carbon support is a graphene nanoplate, the metal catalyst is Co and Fe, the growth temperature of the carbon nanotube is 900 ° C, and the contact angle of the graphene nanoplate and the metal catalyst is 80 ° to 90 ° Wherein the carbon nanostructure is a carbon nanostructure.
In the first step,
A step 1-1 of adsorbing Sn 2 + on the surface of the carbon support;
1-2 steps of reacting Sn 2 + with a palladium salt to form Sn 4 + / Pd on the surface of the carbon support; And
The method of claim 1, wherein the carbon support is immersed in a plating bath containing a Fe salt and a Co salt to carry out electroless plating to thereby support the Fe / Co metal catalyst on the surface of the carbon support.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020130157208A KR101545637B1 (en) | 2013-12-17 | 2013-12-17 | Method for preparing carbon nanostructure with 3d structure |
| PCT/KR2014/011718 WO2015093759A1 (en) | 2013-12-17 | 2014-12-02 | Method of manufacturing carbon nanostructure having 3d structure of directly connected carbon supports and carbon nanotubes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020130157208A KR101545637B1 (en) | 2013-12-17 | 2013-12-17 | Method for preparing carbon nanostructure with 3d structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20150074224A KR20150074224A (en) | 2015-07-02 |
| KR101545637B1 true KR101545637B1 (en) | 2015-08-19 |
Family
ID=53403059
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020130157208A KR101545637B1 (en) | 2013-12-17 | 2013-12-17 | Method for preparing carbon nanostructure with 3d structure |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR101545637B1 (en) |
| WO (1) | WO2015093759A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180128611A (en) | 2017-05-24 | 2018-12-04 | 대주전자재료 주식회사 | Graphene-Carbon Nanotube Composites and Manufacturing Method Thereof |
| KR20190076943A (en) | 2019-06-24 | 2019-07-02 | 대주전자재료 주식회사 | Graphene-Carbon Nanotube Composites and Manufacturing Method Thereof |
| KR20200032946A (en) | 2018-09-19 | 2020-03-27 | 전자부품연구원 | Rinsing device for manufacturing carbon material |
| KR20210128176A (en) | 2020-04-16 | 2021-10-26 | 주식회사 그래핀올 | Method for Preparing Graphene-Carbon Nanotube Composite |
| KR20220085691A (en) | 2020-12-14 | 2022-06-22 | 한국전자기술연구원 | Electroless plating apparstus and multidimensional carbon nanostructure manufacturing method using thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050042369A1 (en) * | 2001-08-24 | 2005-02-24 | Nano-Proprietary, Inc. | Catalyst for carbon nanotube growth |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100741762B1 (en) * | 2006-03-28 | 2007-07-24 | 한국에너지기술연구원 | Method of synthesizing carbon nanotubes on graphite thin plate |
| US20100117764A1 (en) * | 2006-04-17 | 2010-05-13 | Board Of Regents, The University Of Texas System | Assisted selective growth of highly dense and vertically aligned carbon nanotubes |
| KR101052614B1 (en) * | 2009-10-07 | 2011-07-29 | 경희대학교 산학협력단 | Method of manufacturing vertically grown carbon nanotubes |
| KR101346321B1 (en) * | 2011-10-19 | 2013-12-31 | 한국과학기술원 | Graphene-carbon nanotubes nanostructure and method of manufacturing the same |
-
2013
- 2013-12-17 KR KR1020130157208A patent/KR101545637B1/en active IP Right Grant
-
2014
- 2014-12-02 WO PCT/KR2014/011718 patent/WO2015093759A1/en active Application Filing
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050042369A1 (en) * | 2001-08-24 | 2005-02-24 | Nano-Proprietary, Inc. | Catalyst for carbon nanotube growth |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180128611A (en) | 2017-05-24 | 2018-12-04 | 대주전자재료 주식회사 | Graphene-Carbon Nanotube Composites and Manufacturing Method Thereof |
| KR20200032946A (en) | 2018-09-19 | 2020-03-27 | 전자부품연구원 | Rinsing device for manufacturing carbon material |
| KR20190076943A (en) | 2019-06-24 | 2019-07-02 | 대주전자재료 주식회사 | Graphene-Carbon Nanotube Composites and Manufacturing Method Thereof |
| KR20210128176A (en) | 2020-04-16 | 2021-10-26 | 주식회사 그래핀올 | Method for Preparing Graphene-Carbon Nanotube Composite |
| KR20220085691A (en) | 2020-12-14 | 2022-06-22 | 한국전자기술연구원 | Electroless plating apparstus and multidimensional carbon nanostructure manufacturing method using thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2015093759A1 (en) | 2015-06-25 |
| KR20150074224A (en) | 2015-07-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101545637B1 (en) | Method for preparing carbon nanostructure with 3d structure | |
| Mallick et al. | On atomic layer deposition: Current progress and future challenges | |
| EP3453062B1 (en) | Electrochemical catalyst for conversion of co2 to ethanol | |
| CN103303897B (en) | Electroless plating is utilized to prepare the method for the nano-sized carbon of nickel coating | |
| Kumaravel et al. | Current progressions in transition metal based hydroxides as bi-functional catalysts towards electrocatalytic total water splitting | |
| KR101213602B1 (en) | Synthesis of the controlled-geometry micro/nano carbon coils using SF6 gas addition | |
| Fan et al. | Atomic layer deposition of cobalt carbide thin films from cobalt amidinate and hydrogen plasma | |
| Chaitoglou et al. | Hybrid nanostructured compounds of Mo2C on vertical graphene nanoflakes for a highly efficient hydrogen evolution reaction | |
| CN112760974B (en) | Carbon nanotube-copper composite fiber and preparation method thereof | |
| Li et al. | Nanostructures and catalytic atoms engineering of tellurium‐based materials and their roles in electrochemical energy conversion | |
| KR101679693B1 (en) | Method for preparing carbon nanotube and hybrid carbon nanotube composite | |
| KR20170137392A (en) | Heat dissipating substrate and manufacturing method thereof | |
| US9028916B2 (en) | Method for synthesizing carbon nanowires on surface of pores or gaps in structure | |
| US9172095B2 (en) | Method for manufacturing electrode for fuel cell comprising nanocarbon and core-shell-structured platinum-carbon composite and the electrode for fuel cell manufactured by the same | |
| Yan et al. | Catalytic growth of carbon nanotubes with large inner diameters | |
| US20100221535A1 (en) | Platelet-type slit-incorporated vapor grown carbon fiber and production method thereof | |
| CN102321876A (en) | Preparation method of carbon nanotube | |
| KR101383821B1 (en) | Direct synthesis method of carbon nanotube using intermetallic nano-catalysts formed on surface of various metal substrates and the structure thereof | |
| KR101809355B1 (en) | 3-dimensional carbon nano structure and preparing method thereof | |
| KR100814677B1 (en) | Surface modifying method of natural graphite by carbon nanofiber | |
| Suda | Chemical Vapor Deposition of Helical Carbon Nanofibers | |
| KR20230011257A (en) | Manufacturing method of carbon and the carbon manufactured therefrom | |
| KR101922333B1 (en) | 3-dimensional carbon nano structure and preparing method thereof | |
| Lawagon et al. | Facile Synthesis of Nickel-carbon Nanotube Composite from Petrochemical Waste Oil | |
| Lee et al. | Preparation and characterization of ZnO nanorods grown on Pd-activated polyacrylonitrile (PAN) fiber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E601 | Decision to refuse application | ||
| AMND | Amendment | ||
| X701 | Decision to grant (after re-examination) | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20180627 Year of fee payment: 4 |
|
| FPAY | Annual fee payment |
Payment date: 20190806 Year of fee payment: 5 |