Catalyst for synthesizing multi-wall carbon nanotubes, method for producing catalyst, and multi-wall carbon nanotubes synthesized by catalyst

Abstract

The present invention relates to a catalyst for synthesizing multi-wall carbon nanotubes and, more specifically, to a catalyst for synthesizing multi-wall carbon nanotubes, capable of easily disperse the synthesized multi-wall carbon nanotubes and significantly improving conductivity, to a method for producing the catalyst, and to multi-wall carbon nanotubes synthesized by the catalyst.

Claims

1. A multi-wall carbon nanotube wherein the value obtained by dividing the volume of a carbon nanotube grown per 1 g of the catalyst expressed by the following formula (1), by the volume of 1 g of the catalyst is over 120, wherein
V.sub.t/c=(W.sub.t??.sub.t)/(W.sub.c??.sub.c)Formula (1) (in the formula (1), ?.sub.t=1/?.sub.t, ?.sub.c=1/?.sub.c, and W.sub.t is the weight of the carbon nanotube which can be grown with the unit catalyst (1 g), and W.sub.c is 1 g which means the weight of the unit catalyst, and ?.sub.t is the apparent density of the carbon nanotube, and ?.sub.c is the apparent density of the catalyst), wherein the surface area of the multi-wall carbon nanotube is 400-1,000 m.sup.2/g.

2. The multi-wall carbon nanotube of claim 1 wherein the diameter of the multi-wall carbon nanotube is 3-10 nm, and the number of walls is 3-10.

3. The multi-wall carbon nanotube of claim 1 wherein the purity of the multi-wall carbon nanotube is over 98%.

4. The multi-wall carbon nanotube of claim 1, wherein the value obtained by dividing the volume of the carbon nanotube grown per 1 g of the catalyst expressed by formula (1), by the volume of 1 g of the catalyst is over 160.

5. A composite that includes a multi-wall carbon nanotube of claim 1.

6. An energy storage device formed of a multi-wall carbon nanotube of claim 1.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is an image showing a catalyst taken by a scanning electron microscope (SEM), which is produced according to a first embodiment of the present invention;

(2) FIG. 2 is an image showing a multi-wall carbon nanotube taken by a SEM and a transmission electron microscope (TEM), which is produced according to a first embodiment of the present invention;

(3) FIG. 3 is an image showing a multi-wall carbon nanotube taken by a SEM and a TEM, which is produced according to a second embodiment of the present invention;

(4) FIG. 4 is a graph showing a surface resistance based on the content of a multi-wall carbon nanotube (MWNT); and

(5) FIG. 5 is a schematic view for describing a method for producing a catalyst to synthesize a multi-wall carbon nanotube.

DETAILED DESCRIPTION

(6) The implementations and embodiments of the present invention will be described in detail with reference to the accompanying drawings so that a person having ordinary skill in the art can easily implement the present invention. It, however, it noted that the present invention may be implemented into various different forms, which are not limited to the implementations and embodiments disclosed herein. Moreover, the portions which are not directly related with the descriptions of the present invention will be omitted for the sake of clarified descriptions of the present invention.

(7) Throughout the specification of the present invention, unless otherwise stated herein, the term comprise may represent that another component may be further included, not excluding the aforementioned another component.

(8) The term approximate used throughout the specification may be used to represent that a thing is close at a predetermined value or to the value if a predetermined tolerance is suggested for an inherent manufacturing and substance and may be used to prevent the disclosure, which contains an accurate or absolute value provided to assist the better understanding of the present invention, from being unfairly used by an unconscious person. Moreover, the terms a step of ?ing or a step of ? used throughout the specification should not interpreted as representing a step for ?ing.

(9) The implementations and embodiments of the present invention will be described with reference to the accompanying drawings, and it is obvious that the present invention is not limited to such implementations and embodiments.

(10) According to an aspect of the present invention, a multi-wall carbon nanotube is provided, wherein the value obtained by dividing the volume of a multi-wall carbon nanotube grown per 1 g of the catalyst expressed by the following formula (1) by the volume of 1 g of the catalyst is over 30.
V.sub.t/c=(W.sub.t??.sub.t)/(W.sub.c??.sub.c)Formula (1)

(11) (in the formula 1, ?.sub.t=1/?.sub.t, ?.sub.c=1/?.sub.c, and

(12) W.sub.t is the weight of the carbon nanotube which can be grown with the unit catalyst (1 g), and

(13) W.sub.c is 1 g which means the weight of the unit catalyst, and

(14) ?.sub.t is the apparent density of the carbon nanotube, and ?.sub.c is the apparent density of the catalyst).

(15) According to another aspect of the present invention, a multi-wall carbon nanotube is provided, wherein the surface area is 400?1,000 m.sup.2/g. The surface area of the multi-wall carbon nanotube is, for example, 400?1,000 m.sup.2/g, and is preferably 500?1,000 m.sup.2/g, and is more preferably 600?1,000 m.sup.2/g, and the aforementioned values are not limited thereto. The aforementioned surface area is a wide surface area which has not been ever observed at the multi-wall carbon nanotube, except for the single wall carbon nanotube (SWNT). This surface area is available since the carbon nanotube grown using the catalyst of the present invention has a multi-wall structure wherein the number of walls is less, and the diameter of the carbon nanotube is small.

(16) An implementation of the present invention is characterized in that the diameter of the multi-wall carbon nanotube is 3?10 nm, and the number of the walls is 3?10, but the aforementioned features are not limited thereto. For example, the diameter of the multi-wall nanotube may be 3?10 nm, and may be preferably 3?6 nm and may be more preferably 3?5 nm, and the number of the multi-wall nanotubes may be, for example, 3?10 and may be preferably 3?6 and may be more preferably 3?5.

(17) According to an implementation of the present invention, the purity of the multi-wall carbon nanotube is, for example, over 98%, but it is not limited thereto.

(18) According to another aspect of the present invention, a composite formed of a multi-wall carbon nanotube is provided, wherein the composite contains more than 0.5% by weight of the multi-wall carbon nanotube. For this reason, it may have a conductivity, and the matrix of the composite may be any of a polymer, a ceramic, a metal and a combination of them. The aforementioned polymer may be any of a thermoplastic polymer and a thermosetting polymer, but it is not limited thereto.

(19) The thermoplastic resin is a plasticity or transmutability polymer material. The thermoplastic resin can be dissolved into liquid, and can be remolded even after it has been hardened. For example, the thermoplastic resin may be any of an acrylic resin, a polyvinyl chloride resin, a polyvinyl acetate resin, a vinyl acetyl resin, a methylmethacrylic resin, a styrene resin, a polypropylene resin, a polyethylene resin, and a polyamide resin (nylon), but it is not limited thereto.

(20) The thermosetting resin is a polymer material which can be more hardened when a predetermined energy is supplied to the thermosetting resin. Once the thermosetting resin is hardened, it no longer can be heated or molded. For example, the thermosetting resin may be any of a phenol resin, a urea resin, a melamine resin, a unsaturated polyester resin, an epoxy resin, a polyurethane resin, a polyamide resin, an alkyd resin and a silicon resin, but it is not limited thereto.

(21) As for the electric conductivity of a carbon nanotube conductive composite, an electrical percolation, in general, may occur at the content of about 1?2% by weight in case of a multi-wall carbon nanotube. The multi-wall carbon nanotube according to the present invention is able to have a conductivity even at 0.5% by weight which corresponds to a very low concentration. The conductive composite using the present invention may be applied, for example, to a bulk type composite, a thin film type composite, an energy sector and an electric electronic sector. More specifically, the conductive composite of the present invention may be applied, for example, to a plastic for an electronic device antistatic and static electricity distribution, a plastic which has the functions of an electromagnetic wave shielding and a heat radiation, a conductive transparent electrode used at an OLED and a solar battery, a lithium ion battery additive, and a carbon nanotube composite for a concrete enforcement and heat radiation, but it is not limited thereto.

(22) According to another aspect of the present invention, an energy storage device formed of a multi-wall carbon nanotube is provided. The carbon material containing a multi-wall carbon nanotube is a very important substance which has effect on the performance of such an energy storage device. The energy storage device using the same may be any of a primary cell, a secondary cell, a super-capacitor, a fuel cell, and a solar battery, but it is not limited thereto.

(23) According to another aspect of the present invention, a plate type catalyst for the growth of a carbon nanotube is provided, wherein it may contain one or more components (preferably, two or more components) selected from the group consisting of Fe, Co, Ca, Ni and Mo, and it may contain one or more components (preferably two or more components) selected from the group consisting of Mn, Al, Mg and Si, and it may has a composition ratio which can be expressed by the following chemical formula (1), and the apparent density is 0.05?0.07 g/ml, and the value obtained by dividing the volume of the multi-wall carbon nanotube grown per 1 g of the catalyst which can be expressed by the following formula (2), by the volume of 1 g of the catalyst is over 30.
[Fe.sub.a, Co.sub.b, Ca.sub.c, Ni.sub.d, Mo.sub.e][Mn.sub.w, Al.sub.x, Mg.sub.y, Si.sub.z][Chemical formula 1]

(24) (in the aforementioned chemical formula (1), a, b, c, d, e, w, x, y and z mean the molar fractions of each element, and 0?a?10, 0?b?10, 0?c?10, 0?d?10, 0?e?10, 0?w?30, 0?x?30, 0?y?30, 0?z?30, and 2?a+b+c+d+e+w+x+y+z?170, 2?a+b+c+d+e?50, 2?w+x+y+z?50).
V.sub.t/c=(W.sub.t??.sub.t)/(W.sub.c??.sub.c)(2)

(25) (in the aforementioned formula (2), ?.sub.t=1/?.sub.t, ?.sub.c=1/?.sub.c, and

(26) W.sub.t is the weight of the carbon nanotube which can be grown with the unit catalyst (1 g), and

(27) W.sub.c is 1 g which means the weight of the unit catalyst, and

(28) ?.sub.t is the apparent density of the carbon nanotube, and ?.sub.c is the apparent density of the catalyst).

(29) In an implementation of the present invention, the catalyst, for example, may be any one selected from the group consisting of Iron(II) chloride tetrahydrate, Iron(II) sulfate heptahydrate, Iron(III) chloride anhydrous, Iron(III) nitrate nonahydrate, Ammonium iron(III) sulfate dodecahydrate (all of which contain a Fe component), Cobalt(II) acetate tetrahydrate, Cobalt(II) chloride hexahydrate, Cobalt(II) nitrate hexahydrate, Cobalt(II) sulfate heptahydrate (all of which contain a Co component), Calcium acetate monohydrate, Calcium chloride anhydrous, Calcium nitrate tetrahydrate, Calcium sulfate dihydrate (all of which contain a Ca component), Nickel(II) chloride hexahydrate, Nickel(II) nitrate hexahydrate, Nickel(II) sulfate hexahydrate, Ammonium molybdate tetrahydrate (all of which contain a Ni component), Manganese(II) acetate tetrahydrate, Manganese(II) chloride tetrahydrate, Manganese(II) nitrate hexahydrate, Manganese(II) sulfate monohydrate (all of which contain a Mn component), Aluminium chloride hexahydrate, Aluminium hydroxide, Aluminium isopropoxide, Aluminium nitrate nonahydrate (all of which contain an Al component), Magnesium acetate tetrahydrate, Magnesium chloride hexahydrate, Magnesium hydroxide, Magnesium nitrate hexahydrate, Magnesium sulfate anhydrous (all of which contain a Mg component), Silicon dioxide, Silicon carbide, Silicon, Silicon(IV) chloride (all of which contain a Si component) and a combination of them, but it is not limited thereto.

(30) According to another aspect of the present invention, a plate type catalyst for the growth of a carbon nanotube the specific surface area of which is over 120 m.sup.2/g is provided. The carbon nanotube the specific surface area of which is wide can be mass-produced in such a way to increase an active reaction surface area by using a plate type catalyst for the growth of a carbon nanotube wherein the value obtained by dividing the volume of a multi-wall carbon nanotube grown per 1 g of the catalyst, by the volume of 1 g of the catalyst is over 30. The carbon nanotube synthesized by using the catalyst the specific surface area of which is wide according to the present invention, so the carbon nanotube can have a low dispersion energy and a high conductivity.

(31) According to another aspect of the present invention, a carbon nanotube containing a plate type catalyst is provided. In case of the plate type catalyst, it has a wider surface area than that of a spherical or needle-shaped type catalyst, and the carbon nanotube can concurrently grow on the upper and lower surfaces of the catalyst, whereupon it is advantageously possible to enhance the productivity of the carbon nanotubes.

(32) According to another aspect of the present invention, a method for a plate type catalyst for the growth of a carbon nanotube, which may include a mixing step (a) wherein one or more components selected from the reaction precursors formed of Fe, Co, Ca, Ni and Mo and one or more components selected from the reaction precursors formed of Mn, Al, Mg and Si are mixed, thus producing a mixture; and a step (b) wherein the mixture is plasticized while being sprayed in the form of liquid droplets at a temperature of 400?900? C. The step (b) is carried out following the step (a). The range of a high temperature at which the mixture is sprayed in the form of liquid droplets is, for example, 400?900? C., it is preferably 400?700? C., and it is more preferably 400?500? C.

(33) The present invention will be described in detail below in conjunction with the embodiments, and it is noted that the present invention is not limited thereby.

(34) TABLE-US-00001 Embodiments Metal catalyst Carbon nanotube Apparent Synthesized Sum of moles Sum of moles density of amount(g) Apparent of compound of compound catalyst of carbon density Diameter Purity(wt %) Specific (group 1) (group2) (g/ml) nanotubes per (g/ml) distribu- Ash content surface Volume- Classi- Fe.sub.aCO.sub.bCa.sub.cNi.sub.dMO.sub.e = Mn.sub.wAl.sub.xMg.sub.ySi.sub.z = KS M unit catalyst KS M tion(nm) KS M area(m.sup.2/g) weight fication a + b + c + d + e w + x + y + z ISO 1306 (1 g) ISO 1306 TEM ISO 1125 BET ratio(V.sub.t/c) Embodi- a + b = 5 x + y = 16 0.05 90 0.01 5~8 >98 600 450 ment 1 Embodi- a + b = 5 x + y = 20 0.02 80 0.01 5~8 >98 600 160 ment 2

Embodiment 1

(35) Mg(NO.sub.3).sub.2.6H.sub.2O and AlCl.sub.3.6H.sub.2O were added to 100 ml of water for the sum of moles of Al and Mg to be 16 and were agitated, and Fe(NO.sub.3).sub.2.9H.sub.2O and Co(NO.sub.3).sub.2.6H.sub.2O were added for the sum of moles of Fe and Co to be 5 and were agitated. Thereafter, the mixture was sprayed in the form of liquid droplets within a temperature range of 400?900? C. and then was plasticized, thus producing a catalyst.

Embodiment 2

(36) The same producing method as the method described in conjunction with the embodiment 1 was used, and a metal catalyst was produced after changing the sum of moles of Al and Mg 20.

Production Example 1

(37) A carbon nanotube was produced using the catalyst obtained in the embodiment 1 based on the vapor deposition method wherein the temperature of a reactor was increased to 400?1200? C. under a carbon source gas and inert gas environment.

Production Example 2

(38) A carbon nanotube was produced using the catalyst obtained in the embodiment 2 based on the vapor deposition method wherein the temperature of the reactor was increased to 400?1200? C. under a carbon source gas and inert gas environment.

(39) The reactor used to produce the carbon nanotubes in the production examples 1 and 2 was, for example, any of a batch reactor, a fluidized bed type reactor, a rotary Kilin reactor, and the fluidized bed type reactor might be a roof type fluidized bed reactor, but it was not limited thereto.

(40) The plate type catalyst containing the particles the specific surface areas of which were maximized, was produced based on the embodiments 1 and 2.

(41) FIG. 1 is an image showing the catalyst produced based on the embodiment 1, wherein the image was taken by the SEM. A result of the BET (Brunauer Emmett Teller) specific surface area measurement was 142 m.sup.2/g, and the apparent density of the catalyst was measured in compliance with the Korean Standard (KS M ISO 1306).

(42) More specifically, when measuring the apparent density, a catalyst was inputted through the center of a cylinder type container from a portion which was not over 50 mm higher than the edge of the container the diameter of which was 100?10 mm, and which was not equipped with any spout at a vertical wall at a predetermined height, and the container had a storing volume of 1,000 cm.sup.3 when it was filled full. An excessive amount of the catalyst was used to form a conical shape which was higher than the edges of the container. The upper surface of the catalyst filled in the container was arranged flat using a straight edge or a paddle in a state that they were contacted with the edges of the container without leaving any space between them. The weight of the container including the catalyst was measured. The mass of the catalyst was determined based on the nearest weight of gram after the weight of the cylinder was subtracted.

(43) The apparent densities of the catalysts produced by the embodiments 1 and 2 of the present invention were 0.05 g/ml and 0.02 g/ml.

(44) The multi-wall carbon nanotubes of the production examples 1 and 2 were produced using the catalyst which was produced based on the embodiments 1 and 2. The amounts of the carbon nanotubes synthesized per 1 g of the catalyst were 90 g and 80 g.

(45) The apparent densities (measured in compliance with the KS M ISO 1306) of the multi-wall carbon nanotubes synthesized based on the production examples 1 and 2 were 0.01 g/ml, and the diameters of the carbon nanotubes measured by the TEM were 5?8 nm.

(46) The purity was over 98%, and the measurement of the purity was carried out in compliance with the Ash Content KS M ISO 1125.

(47) More specifically, a crucible was heated in an electric furnace at a temperature of 550?25? C. for one hour with the lid close so as to measure the purity, and the crucible and the lid were inputted in a desiccator. It was cooled to a room temperature, and the weight was measured up to the weight unit of 0.1 mg. The carbon nanotube of slightly over 2 g was dried for one hour in a dryer of 125? C., and it was cooled to a room temperature and was inputted into the crucible which had been used when measuring the weight of the carbon nanotube, and the weight thereof was measured up to the weight unit of 0.1 mg, and it was heated in the electric furnace of 800?25? C. with the lid open for the same to become a predetermined amount. Subsequently, the lid was closed, and it was moved into the desiccator and was cooled to a room temperature, and the weight thereof was measured up to the weight unit of 0.1 mg. The crucible and the lid were washed and dried in the dryer of 125? C., and the weight thereof was measured again up to the weight unit of 0.1 mg.

(48) The BET specific surface areas of the multi-wall carbon nanotubes synthesized by the production examples 1 and 2 were all 600 m.sup.2/g, and each volume-weight ratio (V.sub.t/c) thereof was 450 and 160, respectively. In the multi-wall carbon nanotube produced by the production example 1, what the volume-weight ratio (V.sub.t/c) of the carbon nanotube which had grown using the unit catalyst (1 g) was 450, represented that the volume of the multi-wall carbon nanotube grown as compared to the volume that 1 g of the catalyst had was 450 times.

(49) More specifically, since the volume of 1 g of the unit catalyst was 20 ml, it meant that the volume of the multi-wall carbon nanotube which had grown using the plate type catalyst was 9,000 ml (9 Liter).

(50) FIGS. 2 and 3 are images showing the carbon nanotubes produced by the production examples 1 and 2 wherein the images were taken by the SEM and the TEM. As shown therein, it is possible to confirm the carbon nanotubes which were measured using the scale bars of 500 ?m, 50 ?m, 1 ?m and 20 nm.

(51) FIG. 4 is a graph showing the surface resistance of the composite based on the content of the multi-wall carbon nanotube (MWNT) which was grown using the catalyst of the present invention. The measurement was carried out to confirm conductivity. The nylon 66/MWNT composite was produced in such a way to differentiate the contents of the multi-wall carbon nanotubes produced using a twin screw extruder.

(52) As illustrated in FIG. 4, the composite may have a conductivity from when it contains the content of 0.5% by weight of the multi-wall carbon nanotube (MWNT), and as the content of the multi-wall carbon nanotube increases, the conductivity of the composite sharply increases (whereas as the content of the multi-wall carbon nanotube increases, the surface resistance sharply decreases).

(53) The multi-wall carbon nanotube which has a high dispersibility and is synthesized using the catalyst of the present invention, has a high conductivity in a polymer matrix and at a low content (0.5% by weight).

(54) FIG. 5 is a schematic view for describing a method for producing a catalyst for the synthesis of a multi-wall carbon nanotube.

(55) As described above, the catalyst (a plate type catalyst) produced by the catalyst production method according to the present invention has a very low apparent density. Since the surface area is very wide as compared to its weight, the production amount of the multi-wall carbon nanotube can be increased, and the multi-wall carbon nanotube synthesized using the aforementioned catalyst may need less dispersion energy and is able to maintain a high conductivity since the length may be damaged much less during the dispersion procedure.

(56) Moreover, a high purity multi-wall carbon nanotube synthesized using the catalyst produced by the production method of the present invention has a diameter which is similar to that of a single wall carbon nanotube (SWNT). The number of walls is 3?10 which means a very even quality. Since the surface area is large, the multi-wall carbon nanotube according to the present invention has a very high conductivity.

(57) The above description of the present invention is provided for illustrative purposes, and it is understood that a person having ordinary skill in the art is able to easily modify it into various forms without changing the technical idea or necessary features of the present invention. For this reason, the disclosed embodiments are provided for illustrative purposes in all aspects, not limiting to the disclosures.

(58) The scope of the present invention may be determined by the subsequent claims rather than the descriptions, and it is noted that all changes or modifications derived from the meaning and scope and equivalents of the present invention are included in the scope of the present invention.