KR20160003403A - Method of manufacturing vertically aligned carbon nanotubes - Google Patents

Abstract

The present invention relates to a manufacturing method of vertically aligned carbon nanotube aggregation and, more particularly, to a manufacturing method of vertically aligned carbon nanotube aggregation applicable by a wet processing, which comprises: (A) a step of forming a buffer layer by applying a buffer layer solution, which includes a metal compound containing Zirconium and an organic solvent, on at least one side of a substrate; (B) a step of manufacturing a solution for forming a catalyst layer, including a catalyst precursor compound which has one metal selected from groups of iron, cobalt, and nickel, and an organic solvent; (C) a step of forming a catalyst layer by applying the solution for forming a catalyst layer on the top of the buffer layer; and (D) a step of forming carbon nanotube aggregation on the top of the catalyst layer.

Description

TECHNICAL FIELD [0001] The present invention relates to a method of manufacturing a vertically aligned carbon nanotube aggregate,

The present invention relates to a method for producing a vertically-aligned carbon nanotube aggregate, and more particularly, to a method for producing a vertically-oriented carbon nanotube aggregate with high productivity.

Carbon nanotubes (CNTs) are carbon structures whose lengths are very long compared to their diameter, with one atomic layer of graphite being cylindrical and dried.

Since CNT is conductive and has high strength and is chemically stable, it is prepared in the form of powder, paste, yarn, thin film or sheet and exhibits excellent characteristics when applied to electric, electronic, electrochemical and energy related devices.

CNT can be divided into two types: a technique to make a powder that does not have a large orientation and a technique to form a vertically oriented shape on a substrate. As a representative technique of making the powder form, there is a fluidized bed chemical vapor deposition method.

In order to produce the vertically aligned CNTs, a thin layer of catalyst material is formed on a silicon or metal substrate having a ceramic buffer layer. The catalyst layer is applied by vacuum coating using sputtering or e-beam, a solution containing a catalyst element And spin coating and dip coating are mainly used as the coating method in the wet coating method.

The vertical orientation CNT can be divided into two types. One is that when a part of the vertically oriented CNT is horizontally pulled in the substrate surface, the surrounding CNTs are collectively connected and can be made into a thin and light transmissive CNT sheet. When the CNTs are rotated, they are made into carbon CNTs CNT (drawable CNT), which can be drawn, and CNT sheets or CNT yarns that can not be drawn.

Drawable CNT is advantageous for application because CNT sheet and CNT thread can be easily made by dry method.

However, in order to manufacture drawable CNTs, the thickness of the buffer layer and the catalyst layer must be thinly and uniformly applied. However, manufacturing costs are high since they are manufactured by a sputtering process requiring high vacuum or a dry process using an e-beam. For example, there have been known examples of successfully producing drawable CNTs by applying amorphous silicon oxide on a stainless metal substrate and applying an iron catalyst layer thereon in high-vacuum (Xavier Lepro et al., &Quot; Spinable carbon nanotube forests grown on thin, flexible metallic substrates ", CARBON 48 (2010) 3621-3627).

Xavier Lepro et al., &Quot; Spinable carbon nanotube forests grown on thin, flexible metallic substrates ", CARBON 48 (2010) 3621-3627)

The present invention aims to provide a method for producing a vertically aligned carbon nanotube aggregate through a wet process with high productivity.

It is another object of the present invention to provide a wet process for preparing a vertically aligned carbon nanotube aggregate which can be drawn in a horizontal direction.

1. A method for forming a buffer layer, comprising: (A) applying a solution for forming a buffer layer containing a metal compound containing zirconium and an organic solvent to at least one side of a substrate to form a buffer layer; (B) preparing a catalyst layer-forming solution comprising a catalyst precursor compound comprising at least one metal selected from the group consisting of iron, cobalt and nickel and an organic solvent; (C) applying the solution for forming a catalyst layer on the buffer layer to form a catalyst layer; And (D) forming a vertically aligned carbon nanotube aggregate on the catalyst layer.

2. The method according to item 1, wherein the metal compound containing zirconium is a metal organic compound containing zirconium, a metal salt containing zirconium, or a mixture thereof.

3. The method according to item 1, wherein the metal compound comprising zirconium is selected from the group consisting of zirconium pentanedionate, zirconium acetate, zirconium acrylate, zirconium acetylacetonate, Zirconium hydroxide, or a mixture thereof. 2. The method of claim 1, wherein the carbon nanotube aggregate is at least one selected from the group consisting of zirconium hydroxide and zirconium hydroxide.

4. The method according to item 1, wherein the organic solvent in steps (A) and (B) independently of each other is at least one selected from the group consisting of an alcohol, acetone, dimethylformamide and n-methylpyrrolidone, A method for producing a carbon nanotube aggregate.

5. The method for producing a vertically aligned carbon nanotube aggregate according to item 1, wherein the concentration of the metal cation in the buffer layer forming solution is 0.01 to 0.2 M.

6. The method of manufacturing a vertically aligned carbon nanotube aggregate according to item 1, wherein the step (A) further comprises a heat treatment step after application of a buffer layer forming solution.

7. The method of manufacturing a vertically-aligned carbon nanotube aggregate according to item 6, wherein the buffer layer formed in step (A) is a layer comprising amorphous zirconium oxide.

8. The method according to item 1, wherein the catalyst precursor compound is a metal organic compound containing at least one metal selected from the group consisting of iron, cobalt and nickel, a metal salt or a mixture thereof. .

9. The catalyst precursor compound according to item 1, wherein the catalyst precursor compound is at least one selected from the group consisting of at least one pentanedionate, nitrate, sulfate, hydrochloride, , A method for producing a vertically aligned carbon nanotube aggregate.

10. The method for producing a vertically-aligned carbon nanotube aggregate according to item 1, wherein the catalyst layer-forming solution further comprises a catalyst carrier-forming compound which is a metal organic compound or metal salt including aluminum or zirconium.

11. The catalyst carrier support according to item 10, wherein the catalyst carrier-supporting compound is at least one selected from the group consisting of aluminum or zirconium pentanedionate, nitrate, sulfate, hydrochloride, acetate and formate. A method for producing an aggregate.

12. The catalyst precursor composition according to item 10, wherein the molar ratio of the metal of at least one of iron, cobalt and nickel of the catalyst precursor compound to the aluminum or zirconium of the catalyst carrier-forming compound is 1: 5 to 5: A method for producing a vertically aligned carbon nanotube aggregate.

13. The method for producing a vertically aligned carbon nanotube aggregate according to item 1, wherein the concentration of the metal cation in the solution for forming a catalyst layer is 0.01 to 0.2 M.

14. The method of manufacturing a vertically aligned carbon nanotube aggregate according to item 1, wherein the step (C) further comprises a heat treatment step after application of a solution for forming a catalyst layer.

15. The method of manufacturing a vertically aligned carbon nanotube aggregate according to item 1, wherein the application of the buffer layer forming solution and the catalyst layer forming solution in the steps (A) and (C) is performed by a wet method.

16. The method of producing a vertically-aligned carbon nanotube aggregate according to item 15, wherein the wet method is a spin coating method or a dip coating method.

17. The method according to item 1, wherein the step (D) is performed by chemical vapor deposition.

18. A vertically-aligned carbon nanotube aggregate produced by the method according to any one of items 1 to 17.

19. The vertically-aligned carbon nanotube aggregate according to item 18, wherein the vertically-oriented carbon nanotube aggregate is horizontally drawable.

20. A carbon nanotube thin film prepared from the vertically-oriented carbon nanotube aggregate of item 18.

21. A carbon nanotube yarn produced from the vertically-oriented carbon nanotube aggregate of item 18.

Since the vertically-oriented carbon nanotube aggregate can be produced by a wet method such as a spin coating method or a dip coating method under atmospheric pressure, it can be introduced into a continuous process such as a roll-to-toll process, A vertically aligned carbon nanotube aggregate can be produced with productivity.

When a part of the vertically aligned carbon nanotube aggregate produced by the manufacturing method of the present invention is pulled in a horizontal direction on the surface of the substrate, the surrounding carbon nanotubes are collectively connected and pulled out, whereby a thin and light transmissive carbon nanotube sheet And it can be made into a carbon nanotube yarn by giving rotation at the time of drawing. These carbon nanotube sheets and carbon nanotube seals have high electric conductivity and high strength and can be very useful for transparent electrodes, battery collectors, and supercapacitors.

1 is a schematic view of a substrate, a buffer layer, a catalyst layer and a vertically aligned CNT aggregate according to the production method of the present invention.
2 is a scanning electron micrograph of the surface of the buffer layer according to Example 1. Fig.
3 is a scanning electron microscope (SEM) image of the vertically aligned CNT aggregate prepared according to Example 1. Fig.
4 is a scanning electron microscope (SEM) image of a CNT yarn produced by drawing and rotating a vertically oriented CNT aggregate produced according to Example 1;
5 is a photograph of a CNT sheet produced by drawing a part of a vertically aligned CNT aggregate prepared according to Example 1. FIG.

(A) applying a buffer layer-forming solution containing a zirconium-containing metal compound and an organic solvent to at least one surface of a substrate to form a buffer layer; (B) preparing a catalyst layer-forming solution comprising a catalyst precursor compound comprising at least one metal selected from the group consisting of iron, cobalt and nickel and an organic solvent; (C) applying the solution for forming a catalyst layer on the buffer layer to form a catalyst layer; And (D) forming a carbon nanotube aggregate on the catalyst layer. The present invention also relates to a method for producing a vertically aligned carbon nanotube aggregate to which a wet process can be applied.

Hereinafter, one embodiment of the manufacturing method of the present invention will be described in more detail.

First, a buffer layer forming solution containing a zirconium-containing metal compound and an organic solvent is applied to at least one surface of a substrate to form a buffer layer (step (A)).

The substrate can be used without particular limitation as long as it has durability to withstand the formation of the buffer layer, the catalyst layer and the carbon nanotube aggregate, and it is preferable that the substrate can maintain its shape even at a high temperature of about 800 ° C. Examples of such substrates include glass, polymers, and organic and inorganic thin films and metals. Examples of such substrates include polymers, silicones, quartz, glass, mica, graphite, diamond, ceramics, iron, nickel, The metal may be selected from the group consisting of a metal alone or an oxide, and two or more metals selected from the group consisting of tantalum, tungsten, titanium, aluminum, manganese, cobalt, copper, silver, gold, platinum, niobium, tantalum, lead, Can be used. In the case of applying to a roll-to-roll process or the like, a metal thin film can be used since it is preferably flexible.

The metal compound containing zirconium contained in the buffer layer-forming solution is a main component for forming a buffer layer. The buffer layer is formed stably through a wet process, and the vertically-aligned carbon nanotubes formed later can be horizontally drawn.

Metal organic compounds including zirconium, metal salts including zirconium, and mixtures thereof. More specifically, zirconium pentanedionate, zirconium acetate, zirconium acrylate, zirconium acrylate, At least one selected from the group consisting of zirconium acetylacetonate and zirconium hydroxide is exemplified.

The organic solvent is not particularly limited as long as it is an organic solvent capable of dissolving / dispersing a metal compound including zirconium. Examples of the organic solvent include alcohols, acetone, dimethylformamide, n-methylpyrrolidone, etc., Can be mixed and used.

The metal cation concentration of the buffer layer forming solution is preferably 0.01 to 0.2M. Within this concentration, the buffer layer may be formed to have an appropriate thickness. The thickness of the buffer layer is preferably 2 to 30 nm. The thickness of the buffer layer can be controlled by controlling the application speed, the number of application times, etc. in addition to the concentration of the buffer layer forming solution.

The buffer layer according to the present invention is formed through a wet process in which the above-mentioned buffer layer forming solution is applied to a substrate. The method of applying the buffer layer forming solution to the substrate is not particularly limited as long as it is a wet coating process known in the art, and examples thereof include, but are not limited to, a spin coating method or a dip coating method.

After the solution for forming the buffer layer is applied to the substrate, a buffer layer is formed through natural drying or a heat treatment process for applying a predetermined heat.

When the heat treatment is performed, the metal compound including zirconium is thermally decomposed and the buffer layer contains amorphous zirconium oxide, which is more preferable in view of the productivity of the carbon nanotube and the stability of the buffer layer. The condition of the heat treatment is not particularly limited as long as it can produce an amorphous zirconium oxide, and can be carried out at a temperature of, for example, 250 to 500 DEG C for 5 to 30 minutes.

Next, a solution for forming a catalyst layer containing a catalyst precursor compound including at least one metal selected from the group consisting of iron, cobalt and nickel and an organic solvent is prepared (step (B)).

The catalyst precursor compound forms a catalyst for growing vertically aligned carbon nanotubes. In the present invention, a metal organic compound, a metal salt, or a mixture thereof containing at least one metal selected from the group consisting of iron, cobalt and nickel is used .

More specific examples of the catalyst precursor compound include at least one pentanedionate, nitrate, sulfate, hydrochloride, acetate, and formate salt selected from the group consisting of iron, cobalt and nickel, have.

The organic solvent is not particularly limited as long as it is an organic solvent capable of dissolving / dispersing the catalyst precursor compound, and examples thereof include alcohols, acetone, dimethylformamide, n-methylpyrrolidone, etc., .

Optionally, the catalyst layer-forming solution may further comprise a catalyst carrier-forming compound, which is a metal organic compound or metal salt including aluminum or zirconium. The catalyst carrier may prevent the catalyst from aggregating and promote uniform dispersion, and thus may be more preferable for uniform growth of the vertically-aligned carbon nanotubes.

More specific examples of the catalyst carrier-forming compound include aluminum, zirconium pentanedionate, nitrate, sulfate, hydrochloride, acetate and formate, each of which may be used singly or as a mixture of two or more thereof.

In the case of using the catalyst carrier according to the present invention, the molar ratio of the metal of at least one of iron, cobalt and nickel of the catalyst precursor compound to the aluminum or zirconium of the catalyst carrier- 5: 1. In this range, dispersion of the catalyst can be most effectively performed.

The metal cation concentration of the catalyst layer-forming solution is preferably 0.01 to 0.2M. Within this concentration, the catalyst layer may be formed to have an appropriate thickness. In this case, the metal cation includes both the metal of the catalyst precursor compound and the metal of the catalyst carrier. The thickness of the catalyst layer is preferably 2 to 30 nm. The thickness of the catalyst layer can be controlled by controlling the application speed, the number of times of application, etc., in addition to the concentration of the catalyst layer forming solution.

Next, the catalyst layer forming solution is applied on the buffer layer to form a catalyst layer (step (C)).

The catalyst layer according to the present invention is formed through a wet process in which the above-described solution for forming a catalyst layer is applied on the buffer layer in the same manner as the buffer layer. There is no particular limitation on the applicable wet coating process, and examples thereof include, but not limited to, a spin coating method or a dip coating method.

After the solution for forming the catalyst layer is applied on the buffer layer, the catalyst layer is formed through natural drying or a heat treatment process for applying a predetermined heat.

It may be preferable to perform the heat treatment in consideration of the catalyst layer formation time, efficiency, stability of the catalyst layer, and the like. The conditions of the heat treatment are not particularly limited, but may be carried out at a temperature of, for example, 100 to 800 ° C for 5 to 30 minutes.

Next, a vertically-oriented carbon nanotube aggregate is formed on the catalyst layer (step (D)).

The method of forming the vertically aligned carbon nanotube aggregate on the catalyst layer may be a method known in the art without any particular limitation, and preferably a chemical vapor deposition method can be used.

Taking the chemical vapor deposition method as an example, a vertically-oriented carbon nanotube aggregate can be obtained by injecting a substrate formed up to the catalyst layer into a carbon nanotube growth furnace. As the carbon nanotube growth, acetylene or ethylene gas is used as a carbon source , Nitrogen or argon gas is used as a carrier gas, and hydrogen is used as a catalyst reducing gas.

When the substrate is placed in a portion of the growth furnace and heated to 730 to 830 캜 while flowing the gas, a vertically aligned carbon nanotube aggregate can be produced. The heating rate can be performed at 40 to 700 占 폚 per minute.

FIG. 5 is a schematic view showing a metal layer, a cladding layer, a catalyst layer, and grown CNTs together.

The vertically aligned carbon nanotube aggregate prepared according to the method of the present invention can be formed into a carbon nanotube thin film (paper, sheet, film) by a method known in the art. In particular, the vertically-oriented carbon nanotube aggregate according to the present invention can be drawn in a horizontal direction, so that a sheet produced by drawing or spinning at the time of drawing can have high electrical conductivity and high strength, supercapacitors, and the like.

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to be illustrative of the invention and are not intended to limit the scope of the claims. It will be apparent to those skilled in the art that such variations and modifications are within the scope of the appended claims.

Example  One

Zirconium acetate was dissolved in a 200 cc solution of methyl alcohol so that the metal cation concentration was 0.09 mole. An STS 304 stainless steel thin film having a thickness of 100 탆 was immersed in the solution and held for 5 seconds, and then pulled up at a temperature of 25 캜 at a room temperature of 6 cm / min. After the application, the substrate was heat-treated at 300 ° C for 10 minutes and then cooled to room temperature to prepare a metal substrate coated with the buffer layer. In the heat-treated substrate, the buffer layer applied on the surface was stable even after several months. FIG. 2 shows a scanning electron microscope photograph of the surface of the fully formed layer thus prepared.

Next, aluminum pentane dionate and cobalt nitrate were weighed so that the atomic ratio of aluminum to cobalt was 1: 2 and dissolved in ethyl alcohol to a metal cation concentration of 0.05 mole to prepare a catalyst layer forming solution. The stainless steel substrate coated with the buffer layer at room temperature of 25 ° C was immersed in the solution for forming a catalyst layer and held for 5 seconds and then pulled up at a rate of 6 cm / min at 25 ° C using a dip coater. After the application, the substrate was heat-treated at 300 ° C for 10 minutes and then cooled to room temperature to prepare a metal substrate having a catalyst layer formed thereon. After the heat treatment, the catalyst layer applied on the surface was stable even after several months.

After the substrate coated with the catalyst layer was placed at the center of the growth furnace having an inner diameter of 5 cm at room temperature, the growth furnace was heated to 750 캜 for 2 minutes while introducing 450 sccm of argon gas, 10 sccm of hydrogen gas and 120 sccm of ethylene gas simultaneously. For 5 minutes. Then, the atmosphere in the growth furnace was changed to argon, and then cooled to room temperature to prepare a vertically aligned CNT aggregate. FIG. 3 shows a scanning electron microscope photograph of the CNT thus produced.

FIG. 4 is a scanning electron microscope (SEM) image of the CNT yarn produced by drawing and spinning the CNT aggregates produced.

FIG. 5 shows a photograph of the CNT sheet produced by drawing a part of the vertically aligned CNT aggregate manufactured.

Example  2

Zirconium acetate was dissolved in a 200 cc solution of methyl alcohol so that the metal cation concentration was 0.09 mole. An STS 304 stainless steel thin film having a thickness of 100 탆 was immersed in the solution and held for 5 seconds, and then pulled up at a temperature of 25 캜 at a room temperature of 6 cm / min. After the application, the substrate was heat-treated at 400 ° C for 10 minutes, and then cooled to room temperature to prepare a metal substrate coated with a buffer layer. In the heat-treated substrate, the buffer layer applied on the surface was stable even after several months.

Next, aluminum pentane dionate and iron nitrate were weighed so that the atomic ratio of aluminum and iron was 10: 8, and the solution was dissolved in ethyl alcohol so as to have a metal cation concentration of 0.09 mole, thereby preparing a catalyst layer forming solution. The stainless steel substrate coated with the buffer layer was immersed in a solution for forming a catalyst layer and maintained for 5 seconds. Then, the substrate was lifted at a temperature of 40 ° C at a rate of 6 cm / min using a dip coater. After the application, the substrate was heat-treated at 300 ° C for 10 minutes and then cooled to room temperature to prepare a metal substrate coated with the catalyst layer. After the heat treatment, the catalyst layer applied on the surface was stable even after several months.

After the substrate coated with the buffer layer and the catalyst layer was placed at the center of the growth furnace having an inner diameter of 5 cm at room temperature, the growth furnace was heated to 770 캜 for 20 minutes while injecting 450 sccm of argon gas, 150 sccm of hydrogen gas and 60 sccm of ethylene gas simultaneously After growing at 750 DEG C for 1 minute, the atmosphere in the growth furnace was changed to argon and then cooled to room temperature to prepare a vertically aligned CNT aggregate.

Example  3

Zirconium acetate was dissolved in 200 cc of methyl alcohol so that the metal cation concentration was 0.1 mole. A 100 μm thick STS 304 stainless steel thin film was immersed in the solution and held for 5 seconds, and then pulled up at a temperature of 25 ° C. at a room temperature of 6 cm / min. After the application, the substrate was heat-treated at 400 ° C for 10 minutes and then cooled to prepare a metal substrate coated with a buffer layer.

Next, aluminum pentanedionate and nickel nitrate were weighed so that the atomic ratio of aluminum and nickel was 1: 1, and the solution was dissolved in an ethyl alcohol metal solution so that the cation concentration was 0.05 mole to prepare a catalyst layer forming solution. The stainless steel substrate coated with the buffer layer was immersed in a solution for forming a catalyst layer and maintained for 5 seconds. Then, the substrate was lifted at a temperature of 40 ° C at a rate of 6 cm / min using a dip coater. After the application, it was heat-treated at 300 ° C for 10 minutes and then cooled. After the heat treatment, the catalyst layer applied on the surface was stable even after several months.

After the substrate coated with the buffer layer and the catalyst layer was placed at the center of the growth furnace having an inner diameter of 5 cm, the growth furnace was heated to 750 DEG C for 10 minutes while introducing 450 sccm of argon gas, 100 sccm of hydrogen gas and 50 sccm of ethylene gas simultaneously Grown at 760 ° C for 2 minutes, and then the atmosphere in the growth furnace was changed to argon, and then cooled to room temperature to prepare a vertically aligned CNT aggregate.

Example  4

Zirconium acetate was dissolved in a 200 cc solution of methyl alcohol so that the metal cation concentration was 0.09 mole. A 100 μm thick STS 304 stainless steel thin film was immersed in the solution and held for 5 seconds, and then pulled up at a temperature of 25 ° C. at a room temperature of 6 cm / min. After the application, the substrate was heat-treated at 300 ° C for 10 minutes and then cooled to room temperature to prepare a metal substrate coated with the buffer layer. In the heat-treated substrate, the buffer layer applied on the surface was stable even after several months.

Next, zirconium pentanedionate and cobalt nitrate were weighed so that the atomic ratio of zirconium and cobalt was 1: 2, and dissolved in ethyl alcohol solution so as to have a cation concentration of 0.05 mole, thereby preparing a catalyst layer forming solution. The stainless steel substrate coated with the buffer layer at room temperature of 25 ° C was immersed in the solution for forming a catalyst layer and held for 5 seconds and then pulled up at a rate of 6 cm / min at 25 ° C using a dip coater. After the application, the substrate was heat-treated at 300 ° C for 10 minutes and then cooled to room temperature to prepare a metal substrate coated with the catalyst layer. After the heat treatment, the catalyst layer applied on the surface was stable even after several months.

After the substrate coated with the catalyst layer was placed at the center of the growth furnace having an inner diameter of 5 cm at room temperature, the growth furnace was heated to 750 ° C for 2 minutes while introducing 450 sccm of argon gas, 20 sccm of hydrogen gas and 120 sccm of ethylene gas, For 5 minutes. Then, the atmosphere in the growth furnace was changed to argon, and then cooled to room temperature to prepare a vertically aligned CNT aggregate.

110: substrate 120: buffer layer
130: catalyst layer 140: vertically aligned carbon nanotube aggregate

Claims (21)

(A) applying a solution for forming a buffer layer containing a metal compound containing zirconium and an organic solvent to at least one side of a substrate to form a buffer layer;
(B) preparing a catalyst layer-forming solution comprising a catalyst precursor compound comprising at least one metal selected from the group consisting of iron, cobalt and nickel and an organic solvent;
(C) applying the solution for forming a catalyst layer on the buffer layer to form a catalyst layer; And
(D) forming a vertically aligned carbon nanotube aggregate on the catalyst layer
Wherein the carbon nanotube aggregate has a thickness of 100 nm or less.
The method according to claim 1, wherein the metal compound containing zirconium is a metal organic compound containing zirconium, a metal salt containing zirconium, or a mixture thereof.
The method of claim 1, wherein the metal compound comprising zirconium is selected from the group consisting of zirconium pentanedionate, zirconium acetate, zirconium acrylate, zirconium acetylacetonate and zirconium hydroxide zirconium hydroxide, and zirconium hydroxide.
[4] The method of claim 1, wherein the organic solvent in steps (A) and (B) is at least one selected from the group consisting of alcohols, acetone, dimethylformamide, and n-methylpyrrolidone, A method of manufacturing a tube assembly.
The method for producing a vertically aligned carbon nanotube aggregate according to claim 1, wherein the concentration of the metal cation in the buffer layer forming solution is 0.01 to 0.2 M.
[4] The method of claim 1, wherein the step (A) further comprises a heat treatment step after application of the buffer layer forming solution.
7. The method of claim 6, wherein the buffer layer formed in step (A) is a layer comprising amorphous zirconium oxide.
The method of claim 1, wherein the catalyst precursor compound is a metal organic compound, a metal salt, or a mixture thereof containing at least one metal selected from the group consisting of iron, cobalt, and nickel.
The catalyst precursor compound according to claim 1, wherein the catalyst precursor compound is at least one selected from the group consisting of at least one pentanedionate, nitrate, sulfate, hydrochloride, A method for producing an oriented carbon nanotube aggregate.
The method for producing a vertically-aligned carbon nanotube aggregate according to claim 1, wherein the catalyst layer-forming solution further comprises a catalyst carrier-supporting compound, which is a metal organic compound or metal salt including aluminum or zirconium.
The catalyst carrier supporting structure according to claim 10, wherein the catalyst carrier supporting compound is at least one selected from the group consisting of aluminum or zirconium pentanedionate, nitrate, sulfate, hydrochloride, acetate and formate. Gt;
[Claim 11] The method according to claim 10, wherein the molar ratio of the metal of at least one of iron, cobalt and nickel of the catalyst precursor compound to aluminum or zirconium of the catalyst carrier-forming compound is 1: 5 to 5: A method for producing a carbon nanotube aggregate.
The method for producing a vertically aligned carbon nanotube aggregate according to claim 1, wherein the metal cation concentration of the solution for forming a catalyst layer is 0.01 to 0.2 M.
[4] The method of claim 1, wherein the step (C) further comprises a heat treatment step after application of the catalyst layer forming solution to the vertically aligned carbon nanotube aggregate.
The method according to claim 1, wherein the coating of the buffer layer forming solution and the catalyst layer forming solution is performed by a wet process in the steps (A) and (C).
16. The method according to claim 15, wherein the wet process is a spin coating process or a dip coating process.
[2] The method of claim 1, wherein the step (D) is performed by chemical vapor deposition.
A vertically-aligned carbon nanotube aggregate produced by the method according to any one of claims 1 to 17.
The vertically-aligned carbon nanotube aggregate according to claim 18, wherein the vertically-aligned carbon nanotube aggregate is capable of drawing in a horizontal direction.
The carbon nanotube thin film produced from the vertically-oriented carbon nanotube aggregate of claim 18.
A carbon nanotube yarn produced from the vertically-oriented carbon nanotube aggregate according to claim 18.

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