KR102041102B1 - Manufacturing method of carbon nanotube-nanofiber cellulose buckypaper - Google Patents

Abstract

The present invention is to prepare a carbon nanotube (carbon nanotube) dispersion, and to prepare a nanofiber cellulose dispersion (nanofiber cellulose), and the carbon nanotube dispersion and the nanofiber cellulose dispersion by mixing the carbon nanotube- Forming a nanofiber cellulose mixed solution, filtering the carbon nanotube-nanofiber cellulose mixed solution, and drying the filtered carbon nanotube-nanofiber cellulose mixed solution to dry the carbon nanotube-nanofibercellulose cellulose paper It relates to a method for producing a carbon nanotube-nanofiber cellulose bucky paper comprising the step of forming a. According to the present invention, it can be easily produced by a wet method, mass production, excellent reproducibility, and can be produced at a relatively low cost, and excellent mechanical strength and nanofiber cellulose (NFC) and Composite with carbon nanotubes having excellent electrical conductivity can produce carbon nanotubes-nanofiber cellulose bucky paper exhibiting excellent electrical conductivity, mechanical strength and flexibility properties.

Description

Manufacturing method of carbon nanotube-nanofiber cellulose buckypaper}

The present invention relates to a method for producing carbon nanotube bucky paper, and more particularly, can be easily produced by a wet method, mass production, excellent reproducibility, can be produced at a relatively low cost In combination with nanofiber cellulose with excellent mechanical strength and carbon nanotube with excellent electrical conductivity, carbon nanotube-nanofiber cellulose bucky paper which exhibits excellent electrical conductivity, mechanical strength and flexibility characteristics is produced. It is about a method.

Carbon nanotubes (carbon nanotube) is a tube formed by combining one carbon atom with three other carbon atoms in a hexagonal honeycomb pattern, and is a very small material with a diameter of about nanometers. Carbon nanotubes have a unique shape in appearance and, depending on their structure, may have the properties of a conductor such as a metal, or may have properties such as a semiconductor. In addition, since it is structurally stable, lighter than steel, and has a strong tensile force, it is in the spotlight as a next generation new material.

Carbon nanotube bucky paper using the carbon nanotubes have characteristics such as optical transparency, mechanical flexibility, excellent electrical conductivity, large surface area, and can be applied to various fields such as optoelectronic devices, nanocomposites, energy conversion and storage.

Republic of Korea Patent Publication No. 10-2017-0090604

The problem to be solved by the present invention can be easily produced by a wet method, mass production, excellent reproducibility, can be produced at a relatively low cost, excellent mechanical strength nanofiber cellulose (nanofiber cellulose) The present invention provides a method of manufacturing carbon nanotubes-nanofiber cellulose bucky paper, which is combined with carbon nanotubes having excellent electrical conductivity and exhibits excellent electrical conductivity, mechanical strength, and flexibility.

The present invention is to prepare a carbon nanotube (carbon nanotube) dispersion, and to prepare a nanofiber cellulose dispersion (nanofiber cellulose), and the carbon nanotube dispersion and the nanofiber cellulose dispersion by mixing the carbon nanotube- Forming a nanofiber cellulose mixed solution, filtering the carbon nanotube-nanofiber cellulose mixed solution, and drying the filtered carbon nanotube-nanofiber cellulose mixed solution to dry the carbon nanotube-nanofibercellulose cellulose paper It provides a method for producing a carbon nanotube-nanofiber cellulose bucky paper comprising the step of forming a.

The preparing of the carbon nanotube dispersion may include mixing a carbon nanotube and a surfactant to form a carbon nanotube-surfactant mixture and ultrasonicating the carbon nanotube-surfactant mixture to disperse the carbon nanotubes. And forming a carbon nanotube dispersion, wherein the surfactant is preferably mixed with 10 to 300 parts by weight based on 100 parts by weight of the carbon nanotubes.

The carbon nanotube dispersion may be a dispersion in which single wall carbon nanotubes and multi wall carbon nanotubes are dispersed, and the single wall carbon nanotubes and the multiwall carbon nanotubes. It is preferable that the tube has a weight ratio of 50:50 to 90:10.

The surfactant may include at least one material selected from the group consisting of sodium dodeclysulfonate, sodium dodeccylbenzensulfonate, and sodium trtrapropylenebenzensulphonate.

The preparing of the carbon nanotube dispersion may include: (a) mixing a single wall carbon nanotube and a surfactant to form a mixture of the single wall carbon nanotube and a surfactant, and (b) Mixing a multiwall carbon nanotube and a surfactant to form a mixture of multiwall carbon nanotubes and a surfactant, and (c) the single wall carbon nanotube and a surfactant mixture and the multiwall. Mixing a mixture of carbon nanotubes and a surfactant to form a carbon nanotube-surfactant mixture, and (d) carbon nanotubes in which the carbon nanotubes are dispersed by sonicating the carbon nanotube-surfactant mixture. Forming a dispersion, wherein in the step (a) the surfactant is mixed 10 to 300 parts by weight based on 100 parts by weight of the single-walled carbon nanotubes Preferably, in the step (b), the surfactant is preferably mixed with 10 to 300 parts by weight based on 100 parts by weight of the multi-walled carbon nanotubes, and in step (c) with the single-walled carbon nanotubes The multi-walled carbon nanotubes are preferably mixed in a weight ratio of 50:50 to 90:10.

The surfactant may include at least one material selected from the group consisting of sodium dodeclysulfonate, sodium dodeccylbenzensulfonate, and sodium trtrapropylenebenzensulphonate.

The step of preparing the nanofiber cellulose dispersion, (e) mixing a raw material, an oxidizing catalyst and an oxidizing agent containing cellulose in a solvent, and mixing a basic material to adjust and react to an alkaline pH, and (f) Selectively separating the nanofiber cellulose obtained by the reaction, and (g) forming the nanofiber cellulose dispersion by sonicating the selectively separated nanofiber cellulose in a solvent.

The oxidation catalyst may include an N-oxyl compound.

The oxidation catalyst is one selected from the group consisting of TEMPO (2,2,6,6, -tetramethylpiperidine-1-oxyl radical), 4-acetamide-TEMPO and 4-phosphonooxy-TEMPO, 4-carboxy-TEMPO It may contain more than one substance.

The oxidant may comprise one or more substances selected from the group consisting of hypohalogenic acid or salts thereof, ahalogenic acid or salts thereof, perhalogenic acid or salts thereof and hydrogen peroxide.

The oxidant may include an alkali metal hypohalogenate, and the alkali metal hypohalogenate may include one or more substances selected from the group consisting of sodium hypochlorite and sodium hypobromite.

In the step (e), sodium bromide (NaBr) may be further mixed.

In step (e), it is preferable to adjust the pH to 9-11.

Mixing the carbon nanotube dispersion and the nanofiber cellulose dispersion so that the content of cellulose contained in the nanofiber cellulose dispersion is 1 to 50 parts by weight based on 100 parts by weight of the carbon nanotube content contained in the carbon nanotube dispersion It is preferable.

According to the present invention, a carbon nanotube-nanofiber cellulose bucky paper which exhibits excellent electrical conductivity, mechanical strength and flexibility by being combined with nanofiber cellulose (NFC) having excellent mechanical strength and carbon nanotube having excellent electrical conductivity It can manufacture.

In addition, according to the present invention, there is an advantage that can be easily produced by a wet method, mass production, excellent reproducibility, and can be produced carbon nanotube-nanofiber cellulose bucky paper at a relatively low cost .

1 is a photograph showing a carbon nanotube dispersion prepared according to Experimental Example 4.
Figure 2 is a photograph showing a carbon nanotube bucky paper prepared according to Experimental Example 4.
3 is a scanning electron microscope (SEM) photograph showing a carbon nanotube bucky paper prepared according to Experimental Example 4. FIG.
Figure 4 is a graph showing the results of measuring the electrical conductivity according to the mixing ratio of SWCNT and MWCNT.
Figure 5 is a photograph showing the NFC dispersion prepared according to Experimental Example 6.
6 is a transmission electron microscope (TEM) photograph showing an NFC dispersion prepared according to Experimental Example 6. FIG.
Figure 7 is a photograph showing an NFC bucky paper prepared according to Experimental Example 6.
8 is a scanning electron microscope (SEM) photograph showing an NFC bucky paper prepared according to Experimental Example 6. FIG.
9 is a view showing a measurement of the transmittance of the NFC bucky paper prepared according to Experimental Example 6.
10 is a photograph showing a CNT-NFC mixed solution prepared according to Experimental Example 10.
11 is a photograph showing a CNT-NFC composite bucky paper prepared according to Experimental Example 10.
12 is a scanning electron microscope (SEM) photograph showing a CNT-NFC composite bucky paper prepared according to Experimental Example 9. FIG.
13 is a scanning electron microscope (SEM) photograph showing a CNT-NFC composite bucky paper prepared according to Experimental Example 10.
14 is a graph showing the measurement of electrical conductivity and density change of CNT-NFC composite bucky paper prepared according to Experimental Example 7 to Experimental Example 10.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the following embodiments are provided to those skilled in the art to fully understand the present invention, and may be modified in various forms, and the scope of the present invention is limited to the embodiments described below. It doesn't happen.

When one component "includes" another component in the description or claims of the invention, unless otherwise stated, it is not to be construed as limited only to the component, and other components are further interpreted. It should be understood that it may include.

Hereinafter, nanofibers are used to mean fibers having a diameter of 1 nm or more and less than 1 μm as the size in nanometer (nm) units.

According to a preferred embodiment of the present invention, a method of preparing carbon nanotube-nanofiber cellulose bucky paper comprises the steps of preparing a carbon nanotube dispersion, preparing a nanofiber cellulose dispersion, Mixing the carbon nanotube dispersion and the nanofiber cellulose dispersion to form a carbon nanotube-nanofiber cellulose mixed solution, filtering the carbon nanotube-nanofiber cellulose mixed solution, and filtering the filtered carbon nanotubes -Drying the nanofiber cellulose mixed solution to form a carbon nanotube-nanofiber cellulose bucky paper.

The preparing of the carbon nanotube dispersion may include mixing a carbon nanotube and a surfactant to form a carbon nanotube-surfactant mixture and ultrasonicating the carbon nanotube-surfactant mixture to disperse the carbon nanotubes. And forming a carbon nanotube dispersion, wherein the surfactant is preferably mixed with 10 to 300 parts by weight based on 100 parts by weight of the carbon nanotubes.

The carbon nanotube dispersion may be a dispersion in which single wall carbon nanotubes and multi wall carbon nanotubes are dispersed, and the single wall carbon nanotubes and the multiwall carbon nanotubes. It is preferable that the tube has a weight ratio of 50:50 to 90:10.

The surfactant may include one or more materials selected from the group consisting of sodium dodeclysulfonate, sodium dodeccylbenzensulfonate, and sodium trtrapropylenebenzensulphonate.

The preparing of the carbon nanotube dispersion may include: (a) mixing a single wall carbon nanotube and a surfactant to form a mixture of the single wall carbon nanotube and a surfactant, and (b) Mixing a multiwall carbon nanotube and a surfactant to form a mixture of multiwall carbon nanotubes and a surfactant, and (c) the single wall carbon nanotube and a surfactant mixture and the multiwall. Mixing a mixture of carbon nanotubes and a surfactant to form a carbon nanotube-surfactant mixture, and (d) carbon nanotubes in which the carbon nanotubes are dispersed by sonicating the carbon nanotube-surfactant mixture. Forming a dispersion, wherein in the step (a) the surfactant is mixed 10 to 300 parts by weight based on 100 parts by weight of the single-walled carbon nanotubes Preferably, in the step (b), the surfactant is preferably mixed with 10 to 300 parts by weight based on 100 parts by weight of the multi-walled carbon nanotubes, and in step (c) with the single-walled carbon nanotubes The multi-walled carbon nanotubes are preferably mixed in a weight ratio of 50:50 to 90:10.

The surfactant may include at least one material selected from the group consisting of sodium dodeclysulfonate, sodium dodeccylbenzensulfonate, and sodium trtrapropylenebenzensulphonate.

The step of preparing the nanofiber cellulose dispersion, (e) mixing a raw material, an oxidizing catalyst and an oxidizing agent containing cellulose in a solvent, and mixing a basic material to adjust and react to an alkaline pH, and (f) Selectively separating the nanofiber cellulose obtained by the reaction, and (g) forming the nanofiber cellulose dispersion by sonicating the selectively separated nanofiber cellulose in a solvent.

The oxidation catalyst may include an N-oxyl compound.

The oxidation catalyst is one selected from the group consisting of TEMPO (2,2,6,6, -tetramethylpiperidine-1-oxyl radical), 4-acetamide-TEMPO and 4-phosphonooxy-TEMPO, 4-carboxy-TEMPO It may contain more than one substance.

The oxidant may comprise one or more substances selected from the group consisting of hypohalogenic acid or salts thereof, ahalogenic acid or salts thereof, perhalogenic acid or salts thereof and hydrogen peroxide.

The oxidant may include an alkali metal hypohalogenate, and the alkali metal hypohalogenate may include one or more substances selected from the group consisting of sodium hypochlorite and sodium hypobromite.

In the step (e), sodium bromide (NaBr) may be further mixed.

In step (e), it is preferable to adjust the pH to 9-11.

Mixing the carbon nanotube dispersion and the nanofiber cellulose dispersion so that the content of cellulose contained in the nanofiber cellulose dispersion is 1 to 50 parts by weight based on 100 parts by weight of the carbon nanotube content contained in the carbon nanotube dispersion It is preferable.

Hereinafter, a method of manufacturing carbon nanotube-nanofiber cellulose bucky paper according to a preferred embodiment of the present invention will be described in more detail.

A carbon nanotube dispersion is prepared.

To this end, the carbon nanotubes and the surfactant are mixed to form a carbon nanotube-surfactant mixture.

As the carbon nanotubes (CNT), single wall carbon nanotubes (SWCNTs) or multiwall carbon nanotubes (MWCNTs) may be used. It is also possible to use a mixture of wall carbon nanotubes. When the single-walled carbon nanotubes and the multi-walled carbon nanotubes are mixed and used, the single-walled carbon nanotubes and the multi-walled carbon nanotubes preferably have a weight ratio of 50:50 to 90:10. In consideration of dispersibility and electrical conductivity, the carbon nanotubes may have an average diameter of 1 to 50 nm, more preferably 5 to 30 nm, and a length of 0.1 to 20 μm, more preferably 0.1 to 10 μm. Can be.

The surfactant may include at least one material selected from the group consisting of sodium dodeclysulfonate, sodium dodeccylbenzensulfonate, and sodium trtrapropylenebenzensulphonate.

The carbon nanotube-surfactant mixture may be formed as follows.

Single wall carbon nanotubes and a surfactant are mixed to form a mixture of single wall carbon nanotubes and a surfactant. The surfactant is preferably mixed 10 to 300 parts by weight based on 100 parts by weight of the single-walled carbon nanotubes.

Multiwall carbon nanotubes and a surfactant are mixed to form a mixture of multiwall carbon nanotubes and a surfactant. The surfactant is preferably mixed 10 to 300 parts by weight based on 100 parts by weight of the multi-walled carbon nanotubes.

The single-walled carbon nanotubes and the surfactant mixture and the mixture of the multi-walled carbon nanotubes and the surfactant are mixed to form a carbon nanotube-surfactant mixture. At this time, the single-walled carbon nanotubes and the multi-walled carbon nanotubes to form a weight ratio of 50:50 ~ 90:10, the mixture of the single-walled carbon nanotubes and surfactant mixture and the multi-walled carbon nanotubes and surfactant It is preferable to mix.

The carbon nanotube-surfactant mixture is sonicated to form a carbon nanotube dispersion in which the carbon nanotubes are dispersed. The ultrasonic treatment is preferably performed by irradiating the ultrasonic waves of about 20kHz to 3MHz. The ultrasonic treatment is preferably performed for 10 minutes to 12 hours, more preferably for about 1 to 6 hours.

A nanofiber cellulose dispersion is prepared.

To this end, a raw material containing cellulose, an oxidizing catalyst, and an oxidizing agent are mixed in a solvent, and basic materials are mixed to adjust and react with an alkaline pH. At this time, sodium bromide (NaBr) may be further mixed.

The solvent may be distilled water, deionized water, alcohol, or the like.

As the raw material containing the cellulose, cellulose itself, wood pulp, non-wood pulp and the like can be used. The non-wood pulp may be straw, reed, flax, bagasse, kenaf, or the like.

The oxidation catalyst may include an N-oxyl compound. Such N-oxyl compounds include TEMPO (2,2,6,6, -tetramethylpiperidine-1-oxyl radical), 4-acetamide-TEMPO and 4-phosphonooxy-TEMPO, 4-carboxy-TEMPO, mixtures thereof And the like. It is preferable to mix the said oxidation catalyst with 0.01-15 weight part with respect to 100 weight part of raw materials containing the said cellulose.

The oxidant may comprise one or more substances selected from the group consisting of hypohalogenic acid or salts thereof, ahalogenic acid or salts thereof, perhalogenic acid or salts thereof and hydrogen peroxide. More preferably, an alkali metal hypohalogenate is used as the oxidizing agent. The alkali metal hypohalogenate may include one or more substances selected from the group consisting of sodium hypochlorite and sodium hypobromite. It is preferable that the said oxidizing agent mix 0.1-30 weight part with respect to 100 weight part of raw materials containing the said cellulose.

The basic material may be a material such as sodium hydroxide (NaOH), potassium hydroxide (KOH). It is preferable to adjust the said pH to 9-11.

The nanofiber cellulose obtained by the above reaction is selectively separated. Selective separation may use centrifugation or the like.

The nanofiber cellulose selectively separated is sonicated in a solvent to form the nanofiber cellulose dispersion. The ultrasonic treatment is preferably performed by irradiating the ultrasonic waves of about 20kHz to 3MHz. The ultrasonic treatment is preferably performed for 10 minutes to 12 hours, more preferably for about 1 to 6 hours.

The carbon nanotube dispersion and the nanofiber cellulose dispersion are mixed to form a carbon nanotube-nanofiber cellulose mixed solution. Mixing the carbon nanotube dispersion and the nanofiber cellulose dispersion so that the content of cellulose contained in the nanofiber cellulose dispersion is 1 to 50 parts by weight based on 100 parts by weight of the carbon nanotube content contained in the carbon nanotube dispersion It is preferable.

The carbon nanotube-nanofiber cellulose mixed solution is filtered. The filtering may be made of a polycarbonate filter or the like, the filter having a pore size of 0.1 to 20 μm, preferably a pore size of 0.1 to 10 μm, more preferably. For example, it is preferable to use a filter having a pore size of 0.1 to 2 mu m.

The filtered carbon nanotube-nanofiber cellulose mixed solution is dried to form a carbon nanotube-nanofiber cellulose bucky paper. The drying is preferably carried out at a temperature of about 40 ~ 120 ℃.

The carbon nanotube-nanofiber cellulose bucky paper produced by the present invention is composed of nanofiber cellulose (NFC) having excellent mechanical strength and carbon nanotube having excellent electrical conductivity, and thus have excellent electrical conductivity, mechanical strength and Flexibility characteristics and the like.

Hereinafter, experimental examples according to the present invention are specifically presented, and the present invention is not limited to the following experimental examples.

Experimental Example 1

1. Carbon nanotube (CNT) dispersion preparation

A carbon nanotube dispersion was prepared by mixing a carbon nanotube and a surfactant.

Specifically, multi-wall carbon nanotubes (hereinafter referred to as 'MWCNT') were prepared as the carbon nanotubes. Sodium dodecylbenzenesulfonate (hereinafter referred to as 'SDBS') was prepared as the surfactant.

1 g of the MWCNT and 0.5 g of the SDBS were mixed to form a carbon nanotube-SDBS mixture.

The carbon nanotube-SDBS mixture was sonicated to prepare a carbon nanotube dispersion in which carbon nanotubes were dispersed. The ultrasonic treatment was performed by irradiating 20 kHz ultrasound for 2 hours at 750W.

2. Filtering

The carbon nanotube dispersion was filtered through a filter made of polycarbonate having a pore size of 0.8 μm.

3. Drying

The filtered result was dried at 70 ° C. for 10 hours to obtain a carbon nanotube bucky paper having a thickness of 31 μm.

Experimental Example 2

1. Carbon nanotube (CNT) dispersion preparation

A carbon nanotube dispersion was prepared by mixing a carbon nanotube and a surfactant.

Specifically, single-wall carbon nanotubes (hereinafter referred to as 'SWCNT') and MWCNTs were prepared as the carbon nanotubes. SDBS was prepared as the surfactant.

After mixing 1 g of the SWCNT and 2 g of the SDBS to form a mixture of SWCNT and SDBS, after mixing 1 g of the MWCNT and 0.5 g of the SDBS to form a mixture of MWCNT and SDBS, the SWCNT and the MWCNT of 25:75 A carbon nanotube-SDBS mixture was formed by mixing the mixture of SWCNT and SDBS and the mixture of MWCNT and SDBS in a weight ratio.

The carbon nanotube-SDBS mixture was sonicated to prepare a carbon nanotube dispersion in which the carbon nanotubes were dispersed. The ultrasonic treatment was performed by irradiating 20 kHz ultrasound for 2 hours at 750W.

2. Filtering

The carbon nanotube dispersion was filtered through a filter made of polycarbonate having a pore size of 0.8 μm.

3. Drying

The filtered result was dried at 70 ° C. for 10 hours to obtain a carbon nanotube bucky paper having a thickness of 31 μm.

Experimental Example 3

1. Carbon nanotube (CNT) dispersion preparation

A carbon nanotube dispersion was prepared by mixing a carbon nanotube and a surfactant.

Specifically, SWCNT and MWCNT were prepared as the carbon nanotubes. SDBS was prepared as the surfactant.

1 g of the SWCNT and 2 g of the SDBS are mixed to form a mixture of SWCNT and SDBS, and 1 g of the MWCNT and 0.5 g of the SDBS are mixed to form a mixture of MWCNT and SDBS, and the SWCNT and the MWCNT are 50:50. A carbon nanotube-SDBS mixture was formed by mixing the mixture of SWCNT and SDBS and the mixture of MWCNT and SDBS in a weight ratio.

The carbon nanotube-SDBS mixture was sonicated to prepare a carbon nanotube dispersion in which carbon nanotubes were dispersed. The ultrasonic treatment was performed by irradiating 20 kHz ultrasound for 2 hours at 750W.

2. Filtering

The carbon nanotube dispersion was filtered through a filter made of polycarbonate having a pore size of 0.8 μm.

3. Drying

The filtered result was dried at 70 ° C. for 10 hours to obtain a carbon nanotube bucky paper having a thickness of 31 μm.

Experimental Example 4

1. Carbon nanotube (CNT) dispersion preparation

A carbon nanotube dispersion was prepared by mixing a carbon nanotube and a surfactant.

Specifically, SWCNT and MWCNT were prepared as the carbon nanotubes. SDBS was prepared as the surfactant.

1 g of the SWCNT and 2 g of the SDBS are mixed to form a mixture of SWCNT and SDBS, and 1 g of the MWCNT and 0.5 g of the SDBS are mixed to form a mixture of MWCNT and SDBS. A carbon nanotube-SDBS mixture was formed by mixing the mixture of SWCNT and SDBS and the mixture of MWCNT and SDBS in a weight ratio.

The carbon nanotube-SDBS mixture was sonicated to prepare a carbon nanotube dispersion in which carbon nanotubes were dispersed. The ultrasonic treatment was performed by irradiating 20 kHz ultrasound for 2 hours at 750W.

2. Filtering

The carbon nanotube dispersion was filtered through a filter made of polycarbonate having a pore size of 0.8 μm.

3. Drying

The filtered result was dried at 70 ° C. for 10 hours to obtain a carbon nanotube bucky paper having a thickness of 31 μm.

Experimental Example 5

1. Carbon nanotube (CNT) dispersion preparation

A carbon nanotube dispersion was prepared by mixing a carbon nanotube and a surfactant.

Specifically, SWCNT was prepared using the carbon nanotubes. SDBS was prepared as the surfactant.

1 g of the SWCNT and 2 g of the SDBS were mixed to form a carbon nanotube-SDBS mixture.

The carbon nanotube-SDBS mixture was sonicated to prepare a carbon nanotube dispersion in which carbon nanotubes were dispersed. The ultrasonic treatment was performed by irradiating 20 kHz ultrasound for 2 hours at 750W.

2. Filtering

The carbon nanotube dispersion was filtered through a filter made of polycarbonate having a pore size of 0.8 μm.

3. Drying

The filtered result was dried at 70 ° C. for 10 hours to obtain a carbon nanotube bucky paper having a thickness of 31 μm.

Experimental Example 6

1. Preparation of nanofiber cellulose (hereinafter referred to as 'NFC') dispersion

78 mg of TEMPO (2,2,6,6, tetramethylpiperidine-1-oxyl radical) was added to 75 ml of deionized water (DI water), and NaBr 514 mg was added to 50 ml of deionized water (DI water). After that, they were mixed to form a mixture of TEMPO and NaBr.

5 g of cellulose was added to the mixture of TEMPO and NaBr.

30 ml of 10-15% NaClO was added to the resultant to which the cellulose was added.

0.5M NaOH was added to the resultant to which NaClO was added, and the reaction was adjusted to pH 10.5.

The result of the reaction was selectively separated by centrifugation, and the result of the selective separation was further centrifuged three times.

The resultant separated by centrifugation selectively was sonicated in DI water to prepare an NFC dispersion. The ultrasonic treatment was performed by irradiating 20 kHz ultrasound for 2 hours at 750W.

2. Filtering

The NFC dispersion was filtered through a filter made of polycarbonate having a pore size of 0.8 μm.

3. Drying

The filtered result was dried at 70 ° C. for 10 hours to obtain an NFC bucky paper having a thickness of 31 μm.

Experimental Example 7

1. Carbon nanotube (CNT) dispersion preparation

A carbon nanotube dispersion was prepared by mixing a carbon nanotube and a surfactant.

Specifically, SWCNT and MWCNT were prepared as the carbon nanotubes. SDBS was prepared as the surfactant.

1 g of the SWCNT and 2 g of the SDBS are mixed to form a mixture of SWCNT and SDBS, and 1 g of the MWCNT and 0.5 g of the SDBS are mixed to form a mixture of MWCNT and SDBS. A carbon nanotube-SDBS mixture was formed by mixing the mixture of SWCNT and SDBS and the mixture of MWCNT and SDBS in a weight ratio.

A carbon nanotube dispersion was prepared by dispersing the carbon nanotubes by sonicating the carbon nanotubes-SDBS mixture. The ultrasonic treatment was performed by irradiating 20 kHz ultrasound for 2 hours at 750W.

2. NFC Dispersion Manufacturing

78 mg of TEMPO (2,2,6,6, tetramethylpiperidine-1-oxyl radical) was added to 75 ml of deionized water (DI water), and NaBr 514 mg was added to 50 ml of DI water. These were then mixed to form a mixture of TEMPO and NaBr.

5 g of cellulose was added to the mixture of TEMPO and NaBr.

30 ml of 10-15% NaClO was added to the resultant to which the cellulose was added.

0.5M NaOH was added to the resultant to which NaClO was added, and the reaction was adjusted to pH 10.5.

The result of the reaction was selectively separated by centrifugation, and the result of the selective separation was further centrifuged three times.

The resultant separated by centrifugation selectively was sonicated in DI water to prepare an NFC dispersion. The ultrasonic treatment was performed by irradiating 20 kHz ultrasound for 2 hours at 750W.

3. Preparation of CNT-NFC Mixed Solution

The NFC dispersion was mixed with the carbon nanotube dispersion to prepare a CNT-NFC mixed solution. Specifically, the NFC dispersion is added to the carbon nanotube dispersion such that the content of cellulose contained in the NFC dispersion is 3 parts by weight based on 100 parts by weight of the carbon nanotubes (SWCNT and MWCNT) contained in the carbon nanotube dispersion. After mixing, the mixture was stirred at 300 rpm for 10 minutes to prepare a CNT-NFC mixed solution.

4. Filtering

The CNT-NFC mixed solution was filtered through a filter of polycarbonate having a pore size of 0.8 μm.

5. Drying

The filtered result was dried at 70 ° C. for 10 hours to obtain a 31 μm thick CNT-NFC composite bucky paper.

Experimental Example 8

1. Carbon nanotube (CNT) dispersion preparation

A carbon nanotube dispersion was prepared by mixing a carbon nanotube and a surfactant.

Specifically, SWCNT and MWCNT were prepared as the carbon nanotubes. SDBS was prepared as the surfactant.

1 g of the SWCNT and 2 g of the SDBS are mixed to form a mixture of SWCNT and SDBS, and 1 g of the MWCNT and 0.5 g of the SDBS are mixed to form a mixture of MWCNT and SDBS. A carbon nanotube-SDBS mixture was formed by mixing the mixture of SWCNT and SDBS and the mixture of MWCNT and SDBS in a weight ratio.

A carbon nanotube dispersion was prepared by dispersing the carbon nanotubes by sonicating the carbon nanotubes-SDBS mixture. The ultrasonic treatment was performed by irradiating 20 kHz ultrasound for 2 hours at 750W.

2. NFC Dispersion Manufacturing

78 mg of TEMPO (2,2,6,6, tetramethylpiperidine-1-oxyl radical) was added to 75 ml of deionized water (DI water), and NaBr 514 mg was added to 50 ml of DI water. These were then mixed to form a mixture of TEMPO and NaBr.

5 g of cellulose was added to the mixture of TEMPO and NaBr.

30 ml of 10-15% NaClO was added to the resultant to which the cellulose was added.

0.5M NaOH was added to the resultant to which NaClO was added, and the reaction was adjusted to pH 10.5.

The result of the reaction was selectively separated by centrifugation, and the result of the selective separation was further centrifuged three times.

The resultant separated by centrifugation selectively was sonicated in DI water to prepare an NFC dispersion. The ultrasonic treatment was performed by irradiating 20 kHz ultrasound for 2 hours at 750W.

3. Preparation of CNT-NFC Mixed Solution

The NFC dispersion was mixed with the carbon nanotube dispersion to prepare a CNT-NFC mixed solution. Specifically, the NFC dispersion is added to the carbon nanotube dispersion so that the content of cellulose contained in the NFC dispersion is 5 parts by weight based on 100 parts by weight of the carbon nanotubes (SWCNT and MWCNT) contained in the carbon nanotube dispersion. After mixing, the mixture was stirred at 300 rpm for 10 minutes to prepare a CNT-NFC mixed solution.

4. Filtering

The CNT-NFC mixed solution was filtered through a filter of polycarbonate having a pore size of 0.8 μm.

5. Drying

The filtered result was dried at 70 ° C. for 10 hours to obtain a 31 μm thick CNT-NFC composite bucky paper.

Experimental Example 9

1. Carbon nanotube (CNT) dispersion preparation

A carbon nanotube dispersion was prepared by mixing a carbon nanotube and a surfactant.

Specifically, SWCNT and MWCNT were prepared as the carbon nanotubes. SDBS was prepared as the surfactant.

1 g of the SWCNT and 2 g of the SDBS are mixed to form a mixture of SWCNT and SDBS, and 1 g of the MWCNT and 0.5 g of the SDBS are mixed to form a mixture of MWCNT and SDBS. A carbon nanotube-SDBS mixture was formed by mixing the mixture of SWCNT and SDBS and the mixture of MWCNT and SDBS in a weight ratio.

A carbon nanotube dispersion was prepared by dispersing the carbon nanotubes by sonicating the carbon nanotubes-SDBS mixture. The ultrasonic treatment was performed by irradiating 20 kHz ultrasound for 2 hours at 750W.

2. NFC Dispersion Manufacturing

78 mg of TEMPO (2,2,6,6, tetramethylpiperidine-1-oxyl radical) was added to 75 ml of deionized water (DI water), and NaBr 514 mg was added to 50 ml of DI water. These were then mixed to form a mixture of TEMPO and NaBr.

5 g of cellulose was added to the mixture of TEMPO and NaBr.

30 ml of 10-15% NaClO was added to the resultant to which the cellulose was added.

0.5M NaOH was added to the resultant to which NaClO was added, and the reaction was adjusted to pH 10.5.

The result of the reaction was selectively separated by centrifugation, and the result of the selective separation was further centrifuged three times.

The resultant separated by centrifugation selectively was sonicated in DI water to prepare an NFC dispersion. The ultrasonic treatment was performed by irradiating 20 kHz ultrasound for 2 hours at 750W.

3. Preparation of CNT-NFC Mixed Solution

The NFC dispersion was mixed with the carbon nanotube dispersion to prepare a CNT-NFC mixed solution. Specifically, the NFC dispersion is added to the carbon nanotube dispersion such that the content of cellulose contained in the NFC dispersion is 20 parts by weight based on 100 parts by weight of the carbon nanotubes (SWCNT and MWCNT) contained in the carbon nanotube dispersion. After mixing, the mixture was stirred at 300 rpm for 10 minutes to prepare a CNT-NFC mixed solution.

4. Filtering

The CNT-NFC mixed solution was filtered through a filter of polycarbonate having a pore size of 0.8 μm.

5. Drying

The filtered result was dried at 70 ° C. for 10 hours to obtain a 31 μm thick CNT-NFC composite bucky paper.

Experimental Example 10

1. Carbon nanotube (CNT) dispersion preparation

A carbon nanotube dispersion was prepared by mixing a carbon nanotube and a surfactant.

Specifically, SWCNT and MWCNT were prepared as the carbon nanotubes. SDBS was prepared as the surfactant.

1 g of the SWCNT and 2 g of the SDBS are mixed to form a mixture of SWCNT and SDBS, and 1 g of the MWCNT and 0.5 g of the SDBS are mixed to form a mixture of MWCNT and SDBS. A carbon nanotube-SDBS mixture was formed by mixing the mixture of SWCNT and SDBS and the mixture of MWCNT and SDBS in a weight ratio.

A carbon nanotube dispersion was prepared by dispersing the carbon nanotubes by sonicating the carbon nanotubes-SDBS mixture. The ultrasonic treatment was performed by irradiating 20 kHz ultrasound for 2 hours at 750W.

2. NFC Dispersion Manufacturing

78 mg of TEMPO (2,2,6,6, tetramethylpiperidine-1-oxyl radical) was added to 75 ml of deionized water (DI water), and NaBr 514 mg was added to 50 ml of DI water. These were then mixed to form a mixture of TEMPO and NaBr.

5 g of cellulose was added to the mixture of TEMPO and NaBr.

30 ml of 10-15% NaClO was added to the resultant to which the cellulose was added.

0.5M NaOH was added to the resultant to which NaClO was added, and the reaction was adjusted to pH 10.5.

The result of the reaction was selectively separated by centrifugation, and the result of the selective separation was further centrifuged three times.

The resultant separated by centrifugation selectively was sonicated in DI water to prepare an NFC dispersion. The ultrasonic treatment was performed by irradiating 20 kHz ultrasound for 2 hours at 750W.

3. Preparation of CNT-NFC Mixed Solution

The NFC dispersion was mixed with the carbon nanotube dispersion to prepare a CNT-NFC mixed solution. Specifically, the NFC dispersion is added to the carbon nanotube dispersion such that the content of cellulose contained in the NFC dispersion is 50 parts by weight based on 100 parts by weight of the carbon nanotubes (SWCNT and MWCNT) contained in the carbon nanotube dispersion. After mixing, the mixture was stirred at 300 rpm for 10 minutes to prepare a CNT-NFC mixed solution.

4. Filtering

The CNT-NFC mixed solution was filtered through a filter of polycarbonate having a pore size of 0.8 μm.

5. Drying

The filtered result was dried at 70 ° C. for 10 hours to obtain a 31 μm thick CNT-NFC composite bucky paper.

1 is a photograph showing a carbon nanotube dispersion prepared according to Experimental Example 4.

As can be seen in Figure 1 it can be seen that the carbon nanotube dispersion prepared by the addition of SDBS shows a high dispersibility.

Figure 2 is a photograph showing a carbon nanotube bucky paper prepared according to Experimental Example 4. 3 is a scanning electron microscope (SEM) photograph showing a carbon nanotube bucky paper prepared according to Experimental Example 4. FIG.

2 and 3, it was confirmed that carbon nanotube bucky paper having a uniform thickness without peeling after filtering was manufactured. In addition, in FIG. 3, the carbon nanotubes were well aligned by van der Waals attraction, and the pores were distributed between the carbon nanotubes.

Figure 4 is a graph showing the results of measuring the electrical conductivity according to the mixing ratio of SWCNT and MWCNT. The thickness, density and electrical conductivity of carbon nanotube bucky paper according to the mixing ratio of SWCNT and MWCNT are shown in Table 1 below. In FIG. 4 and Table 1, 'MW' means MWCNT, and 'SW' means SWCNT.

Thickness (㎛) Density (g / cm 3) Electrical Conductivity (S / cm) Experimental Example 1 (MWCNT 100%) 68 0.89 69.75 Experimental Example 2 (SW: MW = 25: 75) 43 1.41 524 Experimental Example 3 (SW: MW = 50: 50) 33 1.86 1106 Experimental Example 4 (SW: MW = 75: 25) 31 1.95 1574 Experimental Example 5 (SWCNT 100%) 34 1.78 1273.8

Referring to Table 1 and Figure 4, when the mixing ratio of SWCNT and MWCNT is 75:25 it was confirmed that the highest density and electrical conductivity. This was confirmed that the increase in the content of the SWCNT having a fine diameter can achieve a high electrical conductivity due to the excellent isotropy due to entropy.

The mechanical strength characteristics of the carbon nanotube paper prepared according to Experimental Example 4 were evaluated and shown in Table 2 below. Table 2 shows the case where the mixing ratio of SWCNT and MWCNT is 75:25.

Sample Adhesion strength Carbon Nanotube Bucky Paper (SW: MW = 75: 25) 433.2 ± 4.36

5 is a photograph showing an NFC dispersion prepared according to Experimental Example 6, Figure 6 is a transmission electron microscope (TEM) photograph showing an NFC dispersion prepared according to Experimental Example 6.

7 is a photograph showing an NFC bucky paper prepared according to Experimental Example 6, Figure 8 is a scanning electron microscope (SEM) photograph showing an NFC bucky paper prepared according to Experimental Example 6, Figure 9 is according to Experimental Example 6 Figure shows the measured transmittance of the produced NFC bucky paper.

As shown in FIGS. 5, 7 and 9, it was confirmed that the nanocellulose fiber dispersion and the NFC bucky paper have a high transmittance, which indicates that the cellulose fiber bundle is peeled off by ultrasonic waves and has high dispersibility. .

Referring to Figure 8, it was confirmed that the cellulose fiber has a diameter of several tens of nanometers (nm).

The mechanical strength characteristics of the NFC bucky paper prepared according to Experimental Example 6 are shown in Table 3 below.

Sample Adhesion strength NFC Bucky Paper 674.8 ± 6.33

Referring to Table 3, the bonding strength of the NFC bucky paper produced according to Experimental Example 6 is 674.8N, which is about 1.5 times higher than that of the carbon nanotube bucky paper prepared according to Experimental Example 4, and carbon nanotube bucky paper It was confirmed that excellent bonding strength can be expected when applied to.

10 is a photograph showing a CNT-NFC mixed solution prepared according to Experimental Example 10.

Figure 11 is a photograph showing a CNT-NFC composite bucky paper prepared according to Experimental Example 10.

12 is a scanning electron microscope (SEM) photograph showing a CNT-NFC composite bucky paper prepared according to Experimental Example 9, Figure 13 is a scanning electron microscope (CEM) showing a CNT-NFC composite bucky paper prepared according to Experimental Example 10 ) Photo.

12 and 13, in the case of CNT-NFC composite bucky paper prepared according to Experimental Example 10 (when cellulose forms 50 parts by weight based on 100 parts by weight of carbon nanotubes), the nanocellulose fibers are interposed between carbon nanotubes. It was confirmed that the pores of the filling. Due to the increase in surface resistance, the conductivity decreases while the density increases.

In the case of CNT-NFC composite bucket paper prepared according to Experimental Example 9 (when cellulose forms 20 parts by weight with respect to 100 parts by weight of carbon nanotubes), the electrical conductivity and density due to the increase in the contact area of the carbon nanotubes by the nanocellulose fiber All improved.

14 is a graph showing the measurement of electrical conductivity and density change of CNT-NFC composite bucky paper prepared according to Experimental Example 7 to Experimental Example 10.

Referring to Figure 14, when the cellulose is added to 3, 5, 20 parts by weight based on 100 parts by weight of carbon nanotubes to prepare a CNT-NFC composite bucky paper (Experimental Example 7, Experimental Example 8, Experimental Example 9, respectively) ), The electrical conductivity was slightly increased and the density was greatly improved. In the case of preparing CNT-NFC composite bucky paper by adding 50 parts by weight of cellulose to 100 parts by weight of carbon nanotubes (in Experimental Example 10), the electrical conductivity was decreased and the density was increased.

As mentioned above, although preferred embodiment of this invention was described in detail, this invention is not limited to the said embodiment, A various deformation | transformation is possible for a person with ordinary skill in the art.

Claims (13)

Preparing a carbon nanotube dispersion;
Preparing a nanofiber cellulose dispersion;
Mixing the carbon nanotube dispersion and the nanofiber cellulose dispersion to form a carbon nanotube-nanofiber cellulose mixed solution;
Filtering the carbon nanotube-nanofibercellulose mixed solution; And
Drying the filtered carbon nanotube-nanofibercellulose mixed solution to form a carbon nanotube-nanofibercellulose bucky paper,
Preparing the carbon nanotube dispersion,
(a) mixing a single wall carbon nanotube and a surfactant to form a mixture of the single wall carbon nanotube and a surfactant;
(b) mixing the multiwall carbon nanotube and the surfactant to form a mixture of the multiwall carbon nanotube and the surfactant;
(c) mixing the single-walled carbon nanotubes and the surfactant mixture with the multi-walled carbon nanotubes and the surfactant to form a carbon nanotube-surfactant mixture; And
(d) sonicating the carbon nanotube-surfactant mixture to form a carbon nanotube dispersion in which the carbon nanotubes are dispersed,
In the step (a), the surfactant is mixed with 10 to 300 parts by weight based on 100 parts by weight of the single-walled carbon nanotubes,
In the step (b), the surfactant is mixed with 10 to 300 parts by weight based on 100 parts by weight of the multi-walled carbon nanotubes,
In the step (c), the single-walled carbon nanotubes and the multi-walled carbon nanotubes are mixed in a weight ratio of 50:50 to 90:10.
Preparing a carbon nanotube dispersion;
Preparing a nanofiber cellulose dispersion;
Mixing the carbon nanotube dispersion and the nanofiber cellulose dispersion to form a carbon nanotube-nanofiber cellulose mixed solution;
Filtering the carbon nanotube-nanofibercellulose mixed solution; And
Drying the filtered carbon nanotube-nanofibercellulose mixed solution to form a carbon nanotube-nanofibercellulose bucky paper,
Preparing the carbon nanotube dispersion,
Mixing the carbon nanotubes and the surfactant to form a carbon nanotube-surfactant mixture; And
Ultrasonicating the carbon nanotube-surfactant mixture to form a carbon nanotube dispersion in which the carbon nanotubes are dispersed,
The surfactant is mixed with 10 to 300 parts by weight based on 100 parts by weight of the carbon nanotubes,
The carbon nanotube dispersion is a dispersion in which single wall carbon nanotubes and multi wall carbon nanotubes are dispersed.
The single-walled carbon nanotubes and the multi-walled carbon nanotubes of 50: 50 to 90: 10 characterized in that the weight ratio of the carbon nanotubes-nanofiber cellulose bucket paper manufacturing method.
delete The method according to claim 1 or 2, wherein the surfactant is selected from the group consisting of sodium dodeclysulfonate, sodium dodeccylbenzensulfonate, and sodium tetratrapropylenebenzensulphonate. Method for producing a carbon nanotube-nanofiber cellulose bucky paper comprising at least one material.
delete The method of claim 1, wherein preparing the nanofiber cellulose dispersion,
(e) mixing a raw material including cellulose, an oxidation catalyst, and an oxidizing agent in a solvent, and mixing basic materials to adjust and react to an alkaline pH;
(f) selectively separating the nanofiber cellulose obtained by the reaction; And
(g) manufacturing a carbon nanotube-nanofiber cellulose bucky paper comprising the step of ultrasonically treating the nanofiber cellulose selectively separated in a solvent to form the nanofiber cellulose dispersion.
The method of claim 6, wherein the oxidation catalyst comprises an N-oxyl compound.
The method of claim 6, wherein the oxidation catalyst is TEMPO (2,2,6,6, tetramethylpiperidine-1-oxyl radical), 4-acetamide-TEMPO and 4-phosphonooxy-TEMPO, 4-carboxy-TEMPO Method for producing a carbon nanotube-nanofiber cellulose bucky paper comprising at least one material selected from the group consisting of.
The carbon nanotube according to claim 6, wherein the oxidizing agent comprises at least one substance selected from the group consisting of hypohalogenic acid or a salt thereof, ahalogenic acid or a salt thereof, perhalogenic acid or a salt thereof, and hydrogen peroxide. -Nanofiber cellulose bucky paper manufacturing method.
The method of claim 6, wherein the oxidizing agent comprises an alkali metal hypohalogenate,
The alkali metal hypohalogenate is a method for producing carbon nanotube-nanofiber cellulose bucky paper, characterized in that it comprises at least one substance selected from the group consisting of sodium hypochlorite and sodium hypobromite.
The method of claim 6, wherein in the step (e) sodium bromide (NaBr) is further mixed, characterized in that the manufacturing method of carbon nanotube-nanofiber cellulose bucky paper.
The method of claim 6, wherein in step (e), the pH is adjusted to 9-11.
According to claim 1, wherein the carbon nanotube dispersion and the nano to the content of cellulose contained in the nanofiber cellulose dispersion is 1 to 50 parts by weight based on 100 parts by weight of the carbon nanotube content contained in the carbon nanotube dispersion A method for producing a carbon nanotube-nanofiber cellulose bucky paper comprising mixing a fiber cellulose dispersion.

Images