KR20120075706A - Process for preparing highly dispersed and concentrated carbon nanotube aqueous solution - Google Patents
Process for preparing highly dispersed and concentrated carbon nanotube aqueous solution Download PDFInfo
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Abstract
The present invention relates to a method for preparing a highly dispersed high concentration carbon nanotube solution through a high density treatment using carbon nanotube powder particles having a low apparent density, more specifically, a low apparent range of 0.01 to 0.06 g / cc. A nonionic dispersant was adsorbed and mixed in a carbon nanotube powder having a density in an aqueous solution state, and the mixed solution thus obtained was dried and powdered, and then, a dispersion solution was added to the dried carbon nanotube powder to obtain high dispersion by high speed rotation dispersion. It relates to a method for preparing a high concentration carbon nanotube solution. In addition, the obtained high-dispersion high-concentration carbon nanotube solution may be applied to the antistatic electromagnetic shielding high thermal conductivity field in the form of paste, ink.
Description
The present invention relates to a method for preparing a highly dispersed high concentration carbon nanotube solution through a high density treatment using carbon nanotube powder particles having a low apparent density, more specifically, a low apparent range of 0.01 to 0.06 g / cc. A nonionic dispersant was adsorbed and mixed in a carbon nanotube powder having a density in an aqueous solution state, and the mixed solution thus obtained was dried and powdered, and then, a dispersion solution was added to the dried carbon nanotube powder to obtain high dispersion by high speed rotation dispersion. It relates to a method for preparing a high concentration carbon nanotube solution. In addition, the obtained highly dispersed high concentration carbon nanotube solution may be applied to antistatic electromagnetic shielding, high thermal conductivity, etc. in the form of a paste or ink.
The discovery of carbon nanotubes by Dr. S.Iijima, Nature, 354 (1991) in 1991 attracted more and more interest in nanocarbon materials and the diverse researches of nanocarbon materials. Due to the recent development of structural control technology, the beneficial physical and chemical properties are pursuing new material values in the field of polymer reinforcement, pharmaceutical, energy storage, and polymer catalyst support.
On the other hand, the study of the crystal structure analysis of nano carbon material was conducted in detail by Baker and NM Rodriguez research group in the United States ( J. Mater. Res. , Vol 8: 3233 ~ 3250, 1993). As a method of manufacturing carbon nanotubes, an arc discharge method, a laser vaporization method, a catalyst growth method, a plasma synthesis method, and the like are mentioned in various documents as follows. RE Smalley et al ., J. Phs. Chem. , 243, 49 (1995); M. Endo et al ., Carbon , 33, 873 (1995); US Patent No. 5,424,054; Chem. Phys. Lett. , 243, 1-12 (1995); Science , 273: 483-487 (1996); Reference is made to US Pat. No. 6,210,800 and the like.
The method for preparing carbon nanotube catalysts mentioned in a number of academic and patent literature related to carbon nanotube production technology can be determined by the size shape of transition metal and support or carrier particles and the composition ratio between them. References to catalyst preparation have already been made by PE Anderson et al. , J. Mater. Res. , 14 (7), 2912 (1999) and RJ Best, WW Russell, J. Am. Chem. Soc. , 76, 838 (1954), etc., but the improvement of catalytic activity and structural characteristics of carbon nanotubes have been continuously developed through the control of numerous catalyst synthesis parameters.
Most carbon nanotube catalyst particles have a spherical or pulverized fine powder. Recently, methods using hollow type spherical particles have been proposed as a fluidization catalyst concept. On the other hand, vertical growth of oriented carbon nanotubes using a semiconductor process has been attempted, but it is not an economical synthesis process suitable for coating solution or polymer compounding.
In order to disperse the entangled carbon nanotube aggregates into individual fibers, it is necessary to improve the dispersing force through chemical surface modification or to apply high energy shearing force. However, in the process, deterioration mechanisms such as grinding and cutting are simultaneously generated. It is difficult to make use of the original characteristics.
The Hada Research Group in Japan introduced a vertical orientation technique based on super-growth CNTs on a limited medium surface. It is assumed that such oriented type carbon nanotube bundles will be advantageous in terms of dispersion than entangled CNT particles.
These oriented carbon nanotubes have a lower apparent density than the entangled type and generally fall in the range of 0.01 to 0.04 g / cc. These apparently low carbon nanotube powders have a swelling effect after strong solvent adsorption at the same time as contact with the solvent, so that the dispersion efficiency is sharply lowered due to an increase in viscosity, thereby making it impossible to prepare a desired dispersion.
Surface modification of chemical carbon nanotubes by strong acid, which is a conventional technical method, has a high possibility of structural defects such as cutting and pulverization in a dispersion process, thereby limiting the utilization of inherent high conductivity properties of carbon nanotubes.
Therefore, the present inventors adsorbed and infiltrated and dried the nonionic dispersant in the aqueous solution state on the surface of the carbon nanotube particles having a low apparent density in order to solve the above problem, and then obtained the carbon nanotube aggregate powder with increased apparent density, the carbon The present invention was completed by preparing a highly dispersed high concentration carbon nanotube solution by redispersing the nanotube aggregate powder in a dispersion solution.
The problem to be solved by the present invention is to obtain a carbon nanotube aggregate powder having an apparent density increased by adsorbing and drying the nonionic dispersant in the aqueous solution state on the surface of the carbon nanotube particles having a low apparent density, the carbon nano It was intended to develop a highly dispersed high carbon nanotube solution by redispersing the tube agglomerated powder in a dispersion solution.
SUMMARY OF THE INVENTION
a) 0.001 to 0.1% by weight of a nonionic dispersant was added to the surface of the carbon nanotube particles in an aqueous solution containing 1 to 10% by weight of carbon nanotube powder having an apparent density of 0.01 g / cc to 0.06 g / cc. Preparing a dispersion;
b) dry powdering the dispersion containing the obtained carbon nanotubes;
c) adding a dispersion solution containing 1-5 parts by weight of a nonionic dispersant to 100 parts by weight of the obtained dry carbon nanotube aggregate powder to prepare a high-concentration carbon nanotube dispersion solution by high-speed rotation dispersion;
Method for producing highly dispersed high concentration carbon nanotube solution
To provide.
At this time, the apparent density of the first carbon nanotube powder is characterized in that the range of 0.01g / cc ~ 0.04g / cc.
In addition, the apparent density of the dry carbon nanotube agglomerated powder is characterized in that the 0.05 ~ 0.1g / cc range.
Meanwhile, the content of the nonionic dispersant added to the first low density carbon nanotube powder is in the range of 0.1 to 1.0 wt% based on the weight of the carbon nanotubes.
In addition, the solid content of the carbon nanotubes in the obtained high concentration carbon nanotube dispersion solution is characterized in that the range of 1.0 to 5.0% by weight relative to the weight of the solution.
The nonionic dispersant is benzene, naphthalene, acenaphthalene, acenaphthene, anthracene, phenanthrene, pyrene, benzanthracene, or a mixture thereof, in which the head portion of the nonionic dispersant is an aromatic hydrocarbon group, and the terminal portion connected to the head portion is a hydrophilic repeating unit. It is characterized in that the polymer chain consisting of a polymer or copolymer of phosphorus ethylene oxide, propylene oxide.
In addition, in order to mix the dry carbon nanotube agglomerated powder into a dispersion solution, it is characterized by using a rotary ring mill (rotate ring mill) method using a bead of 0.1 ~ 1mm diameter of zirconia.
Still another object of the present invention is to provide a highly dispersed, highly concentrated carbon nanotube solution prepared according to the above method.
Still another object of the present invention is to provide a method for using the highly dispersed high-concentration carbon nanotube solution in the form of a paste or ink for antistatic electromagnetic shielding, high thermal conductivity, and the like.
An effect of the present invention is to provide a highly dispersed high concentration carbon nanotube solution which can be used in the field of antistatic electromagnetic shielding high thermal conductivity in paste or ink form. In addition, the carbon nanotube solution is a high concentration carbon nanotube solution is applicable to the electrode coating solution.
1 is a manufacturing process diagram of a highly dispersed high concentration carbon nanotube solution prepared in an embodiment of the present invention. Explanation of the symbols a), b) and c) in the figure is as follows.
a) shows that the nonionic dispersant in distilled water is 0.1? It is a low concentration dispersion solution dissolved within the range of 1% by weight. b) shows that the nonionic dispersant in distilled water is 1 to the weight of the solution. It is a high concentration dispersion solution dissolved within the range of 5% by weight. c) is simply a solution of low density carbon nanotube powder and low concentration dispersion solution.
In general, when dispersing the surface of carbon nanotubes using a water-soluble or alcoholic and organic dispersant such as a surfactant rather than a chemical method such as a strong acid, dispersibility of carbon nanotubes is used according to the dispersion concentration. However, it depends a lot on the processing time.
When using a horn or tip type ultrasonic disperser, it is possible to prepare a small amount of dispersion of less than 100 cc, but it is difficult to prepare a high concentration solution because the dispersion efficiency is low when the carbon nanotube solid content is 1% or more. it's difficult.
It is very important in terms of industrial use to disperse highly oriented carbon nanotube powders having an apparent density of 0.01 to 0.06 g / cc in terms of carbon nanotube particles. The high concentration of carbon nanotube dispersion of 1% or more has a high technical and economical advantage that can shorten and simplify the electrode coating process for the production of highly conductive carbon nanotube paste or conductive ink.
Therefore, in order to solve this problem, the present inventors have found that dispersion is more effective in the same dispersion solvent base when the powder density of the synthesized carbon nanotubes is lower than that of the synthesized carbon nanotubes, especially in the preparation of high concentration carbon nanotube dispersions of 1% or more. Recognizing the fact, the company has developed a carbon nanotube dispersion solution manufacturing process that enables high concentration while maintaining high dispersion by increasing the apparent density of carbon nanotubes.
The present invention relates to a method for producing a high-dispersion, high-concentration carbon nanotube solution by densifying carbon nanotubes having a low apparent density, and more particularly, having a carbon nanotube apparent density in a range of 0.01 to 0.06 g / cc. Mixing carbon nanotube powder and nonionic dispersant at the same time in an aqueous solution, dry powdering the mixed solution containing carbon nanotube, and adding a predetermined dispersion solution to the dried carbon nanotube powder at a high speed for a predetermined time. It relates to a highly dispersed high concentration carbon nanotube solution manufacturing method comprising the step of rotating dispersion to prepare a high concentration solution.
At this time, the carbon nanotube solids content is in the range of 0.1 to 5.0% by weight, and the ionic or nonionic dispersant is to provide a high dispersion high concentration carbon nanotube solution composition, characterized in that the range. The water-soluble high-dispersion high-concentration carbon nanotube solution thus prepared may be used in the antistatic, electromagnetic shielding, high thermal conductivity, etc. in the form of a paste or ink.
The present invention will be described in more detail as follows.
The present invention relates to a method for preparing a highly dispersed, highly concentrated carbon nanotube solution prepared by the following process steps: a) Aqueous solution containing 1-10 wt% of carbon nanotube powder having an apparent density of 0.01 g / cc? 0.06 g / cc Preparing a dispersion liquid adsorbed on the surface of the carbon nanotube particles by adding 0.001 to 0.1% by weight of a nonionic dispersant; b) dry powdering the dispersion containing the obtained carbon nanotubes; c) adding a dispersion solution containing 1-5 parts by weight of a nonionic dispersant to 100 parts by weight of the obtained dry carbon nanotube aggregated powder to prepare a high-concentration carbon nanotube dispersion solution by high-speed rotation dispersion. It relates to a method for producing a highly dispersed high concentration carbon nanotube solution.
In order to manufacture a high functional coating solution using carbon nanotubes, a high dispersion technology of carbon nanotubes capable of maximizing the inherent high electrical conductivity, high thermal conductivity, and strength reinforcing characteristics of carbon nanotubes is required.
When carbon nanotubes are synthesized by a common thermochemical deposition method, the carbon nanotube particles have a powder form in agglomerated form, and the apparent density is in the range of 0.01? 0.1 g / cc. The Hada Research Group in Japan introduced a vertical alignment technique based on rapid growth techniques on a limited medium surface.
The carbon nanotubes of this orientation type are estimated to be advantageous in terms of dispersion rather than the entanglement type. If such an orientation type can be mass-produced in the form of powder particles by thermochemical vapor deposition, it is expected that the dispersion energy will be much smaller in the application of polymer composites or solution dispersion.
Characteristic characteristics of the carbon nanotube particles having a strong orientation is that the apparent density of the powder is 0.01 ~ 0.04g / cc range has a very low value. In general, when dispersing the surface of carbon nanotubes using a water-soluble or alcoholic and organic dispersant such as a surfactant, which is not a chemical method such as a strong acid, disperser treatment in which the dispersibility of carbon nanotubes is used according to the dispersion concentration. It depends a lot on the method and the time of dispersion.
When using a horn or tip type ultrasonic disperser, it is possible to prepare a small amount of dispersion of less than 100 cc, but when the carbon nanotube solid content is 1% by weight or more, it is impossible to prepare a high concentration solution due to low dispersion efficiency. High dispersion of carbon nanotube powders having high orientation with low apparent density is very important in terms of industrial use.
High concentration carbon nanotube dispersion of more than 1% by weight has a high technical and economic advantage to shorten and simplify the electrode coating process in the production of high conductivity carbon nanotube paste or conductive ink.
Therefore, the present inventors have been contemplated to solve this problem, especially in the production of high-density carbon nanotube dispersion of more than 1% by weight, the powder density of the synthesized carbon nanotubes is higher than the case where the powder density is higher than the same dispersion solvent base We found that dispersion is effective, and came up with a process to increase the apparent density of carbon nanotubes.
In order to achieve high dispersion of carbon nanotubes having an apparent density in the range of 0.01 to 0.06 g / cc, carbon nanotube particles are preferably used to disperse carbon nanotube particles having an apparent density in the range of 0.01 to 0.04 g / cc. In the range of 0.1 to 2.0% by weight, preferably 0.1 to 1.0% by weight of the nonionic dispersant solution is impregnated to mix the carbon nanotube powder to be sufficiently adsorbed and penetrated into the dispersion.
At this time, preferred examples of the aromatic hydrocarbon group which may be the head portion of the nonionic dispersant may be aromatic hydrocarbon groups such as benzene, naphthalene, acenaphthalene, acenaphthene, anthracene, phenanthrene, pyrene, benzanthracene, but are not necessarily limited thereto.
The distal end connected to the head may be appropriately selected depending on the type of solvent. For example, the distal end is preferably composed of a monomer raw material of ethylene oxide and propylene oxide which are hydrophilic repeating units, and both dispersants in which the two monomer raw materials are composed in a constant ratio are possible.
For example, triton X series, Koremul NP series, Pluronic series, Brij series and the like can be used. The carbon nanotube solution obtained by simply mixing with a low concentration dispersion liquid was obtained by using a filter press. The powder obtained was dried for 24 hours at 100 ° C. for moisture drying using a general oven. At this time, the moisture content was adjusted to 2% by weight or less.
The dried carbon nanotube powders showed agglomerates in the form of agglomerates. The dry powder was pulverized using a dry pulverizer composed of zirconia blades capable of rotating at high speeds with a particle diameter of 5 mm or less for the next step. At this time, particles that are 5 mm or more after dry grinding were regrinded to control the particle size to 5 mm or less.
The apparent density of the dried carbon nanotube aggregate powder can be controlled by changing the initial dispersion addition concentration, and the powder density was in the range of 0.05-0.1 g / cc. Preferably, the apparent density is in the range of 0.05 to 0.08 g / cc.
In order to disperse the dried carbon nanotube aggregates, the dried carbon nanotube powder was added to a predetermined volume of a predetermined dispersant solution, and then dispersed at a high speed by using a rotate ring mill.
At this time, the concentration of the dispersant solution is 1 to 8% by weight of the solution, preferably 1 to 5%. The total volume of the dispersion was 500 to 2000 ml, preferably 800 to 1500 ml, and the dispersion time was 2 to 10 hours, preferably 2 to 6 hours.
At this time, the operating conditions of the dispersion vessel speed in the vessel is 500 ~ 3,000 rpm, preferably 1,000 ~ 1,600rpm, the external rotor rotational speed is 30 ~ 200rpm, preferably 50 ~ 150rpm. The dispersion vessel was filled with 500-1,000 g of stabilized zirconia beads having a diameter of 0.2-1 mm, preferably 0.2-0.8 mm, preferably 600-900 g.
The concentration of the carbon nanotube solution was adjusted in the range of 1 to 5% by weight, preferably 1 to 4% by weight, of the carbon nanotube solid content relative to the total solution used.
Hereinafter, the present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
Example 1 Preparation of Highly Dispersed High Concentration Carbon Nanotube Solution of the Present Invention
(High Density Treatment Process of Carbon Nanotube Powder)
36 g of carbon nanotube powder having an apparent density of 0.016 g / cc was prepared and placed in a quartz beaker container containing 1,500 ml of distilled water and mixed by using a magnetic bar for 1 hour. 0.072 g of a nonionic dispersant NP 10 (Koremul NP series) was added and mixed and dispersed for 2 hours. The prepared mixed solution was filtered using a filter press to obtain a cake solid slurry in which carbon nanotube particles were agglomerated. This solid slurry was dried for 24 hours at 100 degrees in air using a normal oven. The dry powder was treated in the form of particles having a particle diameter of 5 mm or less using a dry mill (2000 rpm, 2 minutes). Particles larger than 5 mm were repeatedly milled to control particle size.
The apparent density of the dry powder was measured according to the STM D 1895 standard. The characteristics of the prepared carbon nanotube aggregate powder are shown in Table 1.
(Preparation of High Dispersion High Concentration Carbon Nanotube Solution Using Carbon Nanotube Powder)
12 g of dried carbon nanotube agglomerated powder having an apparent density of 0.058 g / cc was mixed in a 1,200 ml container containing a 1% dispersant, and then dispersed for 3 hours using a rotate ring mill. At this time, the operating conditions of the dispersion vessel speed inside the vessel was 1,600 rpm, the outer rotor rotation speed was 120 rpm. At this time, the vessel was filled with 810 g of stabilized zirconia beads having a diameter of 0.8 mm, and the dispersion process was performed. When the control of the carbon nanotube concentration was 2%, a dry carbon nanotube aggregate powder 24g and a dispersion solution 2% solution was used. When the carbon nanotube solid content concentration is 3% was prepared by putting the dried carbon nanotube aggregate powder 36g. At this time, the dispersion solution was used 3% solution. The remaining manufacturing process conditions were performed similarly. Evaluation of the prepared solution is shown in Table 1.
Example 2 Preparation of Highly Dispersed High Concentration Carbon Nanotube Solution of the Present Invention
(High Density Treatment Process of Carbon Nanotube Powder)
36 g of carbon nanotube powder having an apparent density of 0.016 g / cc was prepared and placed in a quartz beaker container containing 1,500 ml of distilled water and mixed by using a magnetic bar for 1 hour. NP10 (Koremul NP series), a nonionic dispersant, was added and dispersed for 2 hours by adding 0.144 g. The prepared mixed solution was filtered using a filter press to obtain a cake solid slurry in which carbon nanotube particles were agglomerated. This solid slurry was dried in air at a temperature of 100 degrees for 24 hours using a normal oven. The dry powder was treated in the form of particles having a particle diameter of 5 mm or less using a dry mill (2000 rpm, 2 minutes). Particles larger than 5 mm were repeatedly milled to control particle size.
The apparent density of the dry powder was measured according to the STM D 1895 standard. The characteristics of the prepared carbon nanotube aggregate powder are shown in Table 1.
(Preparation of High Dispersion High Concentration Carbon Nanotube Solution Using Carbon Nanotube Powder)
12 g of dried carbon nanotube agglomerated powder having an apparent density of 0.065 g / cc was mixed in a 1,200 ml container containing a 1% dispersant, and then dispersed for 3 hours using a rotate ring mill. At this time, the operating conditions of the dispersion vessel speed inside the vessel was 1,600 rpm, and the outer rotor rotation speed was 120 rpm. At this time, 810 g of stabilized zirconia beads having a diameter of 0.8 mm were filled in the vessel, and the dispersion process was performed. When the control of the carbon nanotube concentration is 2%, a dry carbon nanotube aggregate powder 24g and a dispersion solution 2% solution was used. When the carbon nanotube solid content concentration is 3%, 36g of dried carbon nanotube aggregated powder was added thereto. At this time, the dispersion solution was used 3% solution. Evaluation of the prepared solution is shown in Table 1.
Example 3 Preparation of Highly Disperse High Concentration Carbon Nanotube Solution of the Present Invention
(High Density Treatment Process of Carbon Nanotube Powder)
36 g of carbon nanotube powder having an apparent density of 0.016 g / cc was prepared and placed in a quartz beaker container containing 1,500 ml of distilled water and mixed by using a magnetic bar for 1 hour. 0.210 g of nonionic dispersant NP 10 (Koremul NP series) was added and mixed for 2 hours. The prepared mixed solution was filtered using a filter press to obtain a cake solid slurry in which carbon nanotube particles were agglomerated. Using this solid slurry general oven, it was dried in air at a temperature of 100 degrees for 24 hours. The dry powder was treated in the form of particles having a particle diameter of 5 mm or less using a dry mill (2000 rpm, 2 minutes). Particles larger than 5 mm were repeatedly milled to control particle size.
The apparent density of the dry powder was measured according to the STM D 1895 standard. The characteristics of the prepared carbon nanotube aggregate powder are shown in Table 1.
(Preparation of High Dispersion High Concentration Carbon Nanotube Solution Using Carbon Nanotube Powder)
12 g of dried carbon nanotube agglomerated powder having an apparent density of 0.065 g / cc was mixed in a 1,200 ml container containing a 1% dispersant, and then dispersed for 3 hours using a rotate ring mill. At this time, the operating conditions of the dispersion vessel speed inside the vessel was 1,600 rpm, and the outer rotor rotation speed was 120 rpm. At this time, 810 g of stabilized zirconia beads having a diameter of 0.8 mm were filled in the vessel, and the dispersion process was performed. When the control of the carbon nanotube concentration is 2%, 24g of dried carbon nanotube agglomerated powder and the dispersion solution was used as a 2% solution. When the carbon nanotube solid content concentration is 3% was prepared by putting the dried carbon nanotube aggregate powder 36g. At this time, the dispersion solution was used 3% solution. The remaining manufacturing process conditions were performed similarly. Evaluation of the prepared solution is shown in Table 1.
Example 4 Preparation of Highly Dispersed High Concentration Carbon Nanotube Solution of the Present Invention
(High Density Treatment Process of Carbon Nanotube Powder)
36 g of carbon nanotube powder having an apparent density of 0.016 g / cc was prepared and placed in a quartz beaker container containing 1,500 ml of distilled water and mixed by using a magnetic bar for 1 hour. 0.360 g of a nonionic dispersant NP 10 (Koremul NP series) was added and mixed and dispersed for 2 hours. The prepared mixed solution was filtered using a filter press to obtain a cake solid slurry in which carbon nanotube particles were agglomerated. Using this solid slurry general oven, it was dried in air at a temperature of 100 degrees for 24 hours. The dry powder was treated in the form of particles having a particle diameter of 5 mm or less using a dry mill (2000 rpm, 2 minutes). Particles larger than 5 mm were repeatedly milled to control particle size.
The apparent density of the dry powder was measured according to the STM D 1895 standard. The characteristics of the prepared carbon nanotube aggregate powder are shown in Table 1.
(Preparation of High Dispersion High Concentration Carbon Nanotube Solution Using Carbon Nanotube Powder)
12 g of dried carbon nanotube agglomerated powder having an apparent density of 0.065 g / cc was mixed in a 1,200 ml container containing a 1% dispersant, and then dispersed for 3 hours using a rotate ring mill. At this time, the operating conditions of the dispersion vessel speed inside the vessel was 1,600 rpm, and the outer rotor rotation speed was 120 rpm. At this time, 810 g of stabilized zirconia beads having a diameter of 0.8 mm were filled in the vessel, and the dispersion process was performed. When the control of the carbon nanotube concentration is 2%, 24g of dried carbon nanotube agglomerated powder and the dispersion solution was used as a 2% solution. When the carbon nanotube solid content concentration is 3% was prepared by putting the dried carbon nanotube aggregate powder 36g. At this time, the dispersion solution was used 3% solution. The remaining manufacturing process conditions were performed similarly. Evaluation of the prepared solution is shown in Table 1.
Comparative Example 1 Preparation of Carbon Nanotube Solution (Excluding High Density Treatment Process)
A carbon nanotube solution was prepared by excluding the "densification process of carbon nanotube powder" by the method described in Example 1. The apparent density of the dry powder was measured according to the STM D 1895 standard. The characteristics of the prepared carbon nanotube aggregate powder are shown in Table 1.
(Preparation of High Dispersion High Concentration Carbon Nanotube Solution Using Carbon Nanotube Powder)
12 g of carbon nanotube aggregated powder having an apparent density of 0.016 g / cc was mixed in a 1,200 ml container containing a 1% dispersant, and then dispersed for 3 hours using a rotate ring mill. At this time, the operating conditions of the dispersion vessel speed inside the vessel was 1,600 rpm, and the outer rotor rotation speed was 120 rpm. At this time, 810 g of stabilized zirconia beads having a diameter of 0.8 mm were filled in the vessel, and the dispersion process was performed. When the control of the carbon nanotube concentration is 2%, 24g of the dried carbon nanotube agglomerated powder and the dispersion solution used a 2% solution. When the carbon nanotube solid content concentration is 3% was prepared by putting the dried carbon nanotube aggregate powder 36g. At this time, the dispersion solution was used 3% solution. The rest of manufacturing process conditions were performed similarly to the Example. Dispersion proceeded smoothly when the solid content of carbon nanotubes was 1%, but swelling of carbon nanotube powders and solvents occurred rapidly within 10 minutes of dispersion. It was. Evaluation results of the prepared solution are shown in Table 1.
Comparative Example 2 Preparation of Carbon Nanotube Solution (Excluding Dispersant in High Density Treatment Process)
In the "densification process of carbon nanotube powder" according to the method described in Example 1, carbon nanotube aggregated powder was prepared by simply mixing in distilled water without adding a dispersant. 36 g of carbon nanotube powder having an apparent density of 0.016 g / cc was prepared, placed in a quartz beaker container containing 1,500 ml of distilled water, and mixed and dispersed for 2 hours using a magnetic bar for 1 hour. The prepared mixed solution was filtered using a filter press to obtain a cake solid slurry in which carbon nanotube particles were agglomerated. Using this solid slurry general oven, it was dried in air at a temperature of 100 degrees for 24 hours. The dry powder was treated in the form of particles having a particle diameter of 5 mm or less using a dry mill (2000 rpm, 2 minutes). Particles larger than 5 mm were repeatedly milled to control particle size.
The apparent density of the dry powder was measured according to the STM D 1895 standard. The characteristics of the prepared carbon nanotube aggregate powder are shown in Table 1.
(Preparation of High Dispersion High Concentration Carbon Nanotube Solution Using Carbon Nanotube Powder)
12 g of carbon nanotube aggregated powder having an apparent density of 0.041 g / cc was mixed in a 1,200 ml container containing a 1% dispersant, and then dispersed for 3 hours using a rotate ring mill. At this time, the operating conditions of the dispersion vessel speed inside the vessel was 1,600 rpm, and the outer rotor rotation speed was 120 rpm. At this time, 810 g of stabilized zirconia beads having a diameter of 0.8 mm were filled in the vessel, and the dispersion process was performed. When the control of the carbon nanotube concentration is 2%, 24g of the dried carbon nanotube agglomerated powder and the dispersion solution used a 2% solution. When the carbon nanotube solid content concentration is 3% was prepared by putting the dried carbon nanotube aggregate powder 36g. At this time, the dispersion solution was used 3% solution. The rest of manufacturing process conditions were performed similarly to the Example. Dispersion proceeded smoothly when the content of carbon nanotubes was 1%, but swelling of carbon nanotube powder and solvent occurred rapidly in 15 minutes after the start of dispersion. It was. Evaluation results of the prepared solution are shown in Table 1.
Comparative Example 3 Preparation of Carbon Nanotube Solution (Excluding Dispersant in High Density Treatment Process)
In the "densification process of carbon nanotube powder" according to the method described in Example 1, carbon nanotube aggregated powder was prepared by mixing in distilled water without adding a dispersant. 36 g of carbon nanotube powder having an apparent density of 0.016 g / cc was prepared, placed in a quartz beaker container containing 1,500 ml of distilled water, and mixed and dispersed for 2 hours using a magnetic bar for 1 hour. The prepared mixed solution was filtered using a filter press to obtain a cake solid slurry in which carbon nanotube particles were agglomerated. This solid slurry was dried in air at a temperature of 100 degrees for 24 hours using a normal oven. The dry powder was treated in the form of particles having a particle diameter of 5 mm or less using a dry mill (2000 rpm, 2 minutes). Particles larger than 5 mm were repeatedly milled to control particle size.
The apparent density of the dry powder was measured according to the STM D 1895 standard. The characteristics of the prepared carbon nanotube aggregate powder are shown in Table 1.
(Preparation of High Dispersion High Concentration Carbon Nanotube Solution Using Carbon Nanotube Powder)
12 g of carbon nanotube agglomerated powder having an apparent density of 0.059 g / cc was mixed in a 1,200 ml container containing a 1% dispersant, and then dispersed for 3 hours using a rotate ring mill. At this time, the operating conditions of the dispersion vessel speed inside the vessel was 1,600 rpm, and the outer rotor rotation speed was 120 rpm. At this time, 810 g of stabilized zirconia beads having a diameter of 0.8 mm were filled in the vessel, and the dispersion process was performed. When the control of the carbon nanotube concentration is 2%, 24g of the dried carbon nanotube agglomerated powder and the dispersion solution used a 2% solution. When the carbon nanotube solid content concentration is 3% was prepared by putting the dried carbon nanotube aggregate powder 36g. At this time, the dispersion solution was used 3% solution. The rest of manufacturing process conditions were performed similarly to the Example. Dispersion proceeded smoothly when the content of carbon nanotubes was 1% .However, when swelling of carbon nanotube powders and solvents occurred suddenly after 20 minutes of dispersion, the solution viscosity gradually dropped, resulting in dispersion. Some advanced results were obtained. Evaluation results of the prepared solution are shown in Table 1.
* After dispersing for 3 hours using a rotating ring mill, the solution state was evaluated, and marked with "○" if the solution was very good, "■" if the solution could not be prepared, and "△" if the swelling state.
Claims (9)
b) dry powdering the dispersion containing the obtained carbon nanotubes;
c) adding a dispersion solution containing 1-5 parts by weight of a nonionic dispersant to 100 parts by weight of the obtained dry carbon nanotube aggregate powder to prepare a high-concentration carbon nanotube dispersion solution by high-speed rotation dispersion;
Method for producing highly dispersed high concentration carbon nanotube solution
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101414560B1 (en) * | 2013-01-09 | 2014-07-04 | 한화케미칼 주식회사 | method for producing conductive film |
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| CN104822781A (en) * | 2012-11-26 | 2015-08-05 | 韩华石油化学株式会社 | Ink composition, and anti-static film prepared therefrom |
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| WO2014109570A1 (en) * | 2013-01-09 | 2014-07-17 | Hanwha Chemical Corporation | Method for producing conductive film |
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| KR101965975B1 (en) * | 2017-10-19 | 2019-04-04 | 숭실대학교산학협력단 | Electromagnetic interference (EMI) shielding carbon nanotube(CNT) non-woven fabric high strength using the water-soluble hyperbranched supramolecular linker and Fabrication method of the same |
| WO2019146982A1 (en) * | 2018-01-29 | 2019-08-01 | 주식회사 엘지화학 | Method for preparing carbon nanotube dispersion solution |
| KR20190091833A (en) * | 2018-01-29 | 2019-08-07 | 주식회사 엘지화학 | Method for preparing carbon nanotube dispersion |
| CN111094180A (en) * | 2018-01-29 | 2020-05-01 | Lg化学株式会社 | Method for producing carbon nanotube dispersions |
| EP3640202A4 (en) * | 2018-01-29 | 2020-12-09 | LG Chem, Ltd. | Method for preparing carbon nanotube dispersion solution |
| US11453592B2 (en) | 2018-01-29 | 2022-09-27 | Lg Chem, Ltd. | Method for preparing carbon nanotube dispersion |
| CN111094180B (en) * | 2018-01-29 | 2023-03-31 | Lg化学株式会社 | Method for producing carbon nanotube dispersions |
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