CN114229830A - Preparation method of single-walled carbon nanotube powder - Google Patents
Preparation method of single-walled carbon nanotube powder Download PDFInfo
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- CN114229830A CN114229830A CN202010940636.XA CN202010940636A CN114229830A CN 114229830 A CN114229830 A CN 114229830A CN 202010940636 A CN202010940636 A CN 202010940636A CN 114229830 A CN114229830 A CN 114229830A
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- C01B32/00—Carbon; Compounds thereof
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- C01B32/159—Carbon nanotubes single-walled
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- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/36—Diameter
Abstract
A method for preparing single-walled carbon nanotube powder. The present invention belongs to the field of carbon nanotube and its preparation technology. The invention solves the technical problems of low purity and uneven pipe diameter distribution of the existing single-walled carbon nanotube. The invention relates to a preparation method of single-walled carbon nanotube powder, which comprises the following steps: firstly, heating the reaction cavity to 600-1200 ℃ under the protection of inert gas, and preserving heat for 30-60 min; and secondly, continuously introducing mixed gas of inert gas, hydrogen and gaseous carbon-containing organic matters into the reaction cavity, and simultaneously injecting transition metal plasma into the reaction cavity for 0.2-10 h to obtain the single-walled carbon nanotube powder. The single-walled carbon nanotube of the invention does not need further purification treatment, and keeps the good structure thereof to the maximum extent so as to ensure the performance. It can be used as conductive additive for various materials, and has mechanical property enhancing effect.
Description
Technical Field
The invention belongs to the technical field of carbon nanotubes and preparation thereof, and particularly relates to a preparation method of single-walled carbon nanotube powder.
Background
The carbon nanotube is a one-dimensional cylindrical hollow structure, and can also be understood as being formed by curling a graphite sheet structure, and is divided into a single-walled carbon nanotube and a multi-walled carbon nanotube. The diameter of the carbon nanotube is about several to hundreds of nanometers, the length of the carbon nanotube is generally in a micron order, and the carbon nanotube is several times or even tens of thousands of times of the diameter, so that the carbon nanotube has a larger length-diameter ratio. From the performance, the carbon nano tube has good heat conduction, electric conduction and mechanical strength, and can be used for composite materials, additives and the like, and the strength, the electric conductivity and the like of the materials are enhanced. From the aspect of preparation, methods for preparing carbon nanotubes include arc discharge, laser evaporation, chemical vapor deposition, and the like. At present, the known single-walled carbon nanotube manufacturers mainly adopt an arc discharge method to prepare or produce the single-walled carbon nanotubes in batches, and although the arc discharge method is simple, the product is complex, so that the defects of low purity, high energy consumption, poor economy and the like are caused.
Compared with the multi-wall carbon nanotube, the single-wall carbon nanotube has obvious advantages in the using process, has low addition amount, and has wider application range than the multi-wall carbon nanotube in certain directions with color requirements.
Application publication No. CN 101941691A discloses a method for preparing single-walled carbon nanotubes, 1) preparing iron-containing catalyst carbon electrode rods; 2) using a prepared electrode bar as an anode and a pure carbon electrode as a cathode; 3) in hydrogen or mixed gas of hydrogen and other inert gases, in static or dynamic atmosphere, discharging in a direct current or alternating current mode to generate electric arc to evaporate the electrode, and obtaining the product, namely the single-walled carbon nanotube, in the cavity of the electric arc equipment. However, the purity of the carbon nanotube obtained by the method is generally lower, further acidification purification or high-temperature purification is needed, the structure of the carbon nanotube is irreversibly damaged, and the method is not beneficial to environmental protection and consumption reduction; on the other hand, the method is not suitable for batch preparation and production from the energy consumption perspective.
Application publication No. CN 110980891A discloses a macroscopic preparation method of single-walled carbon nanotubes with controllable diameter and high purity, which is a conventional floating catalyst chemical vapor deposition method, hydrogen is used as carrier gas, a compound of transition metal is used as catalyst, sulfur is used as growth promoter, and the preparation of the single-walled carbon nanotubes is realized by adjusting the thermodynamic and kinetic conditions of a reaction system. However, the carrier gas is pure hydrogen, the danger coefficient is extremely high, the pipe diameter distribution of the grown single-walled carbon nano-tubes is not uniform, the pipe diameter of the single-walled carbon nano-tubes is distributed between 1.5nm and 2nm, the pipe diameter of the carbon nano-tubes prepared by the method is about 3nm to 15nm, and the performance of the carbon nano-tubes is 30 to 50 percent different from that of the pure single-walled carbon nano-tubes.
Disclosure of Invention
The invention solves the technical problems of low purity and uneven pipe diameter distribution of the existing single-walled carbon nanotube, and provides a preparation method of single-walled carbon nanotube powder.
The preparation method of the single-walled carbon nanotube powder comprises the following steps:
firstly, heating the reaction cavity to 600-1200 ℃ under the protection of inert gas, and preserving heat for 30-60 min;
and secondly, continuously introducing mixed gas of inert gas, hydrogen and gaseous carbon-containing organic matters into the reaction cavity, and simultaneously injecting transition metal plasma into the reaction cavity for 0.2-10 h to obtain the single-walled carbon nanotube powder.
Further limiting, in the step one, the temperature of the reaction cavity is increased to 600-1200 ℃ at the temperature increasing rate of 3-7 ℃/min.
Further limiting, in the first step, the temperature of the reaction cavity is increased to 700 ℃ at a temperature increasing rate of 5 ℃/min.
Further limiting, in the step one, the reaction cavity is a vertical tubular furnace or a horizontal tubular furnace.
Further, in the first step, the inert gas is nitrogen, argon or helium.
Further limiting, in the second step, the inert gas is nitrogen, argon or helium, and the gaseous carbon-containing organic matter is carbon-containing organic gas or gasified organic liquid.
Further limiting, the carbon-containing organic gas is one or a mixture of several of methane, natural gas, ethane, ethylene, acetylene, propane and propylene in any ratio.
Further limiting, the gasified organic liquid is one or a mixture of several of absolute methanol, absolute ethanol, benzene, toluene and xylene according to any ratio.
Further limiting, the gasification temperature of the organic liquid is 100-300 ℃.
Further limiting, the flow ratio of the inert gas, the hydrogen and the gaseous carbon-containing organic matter in the mixed gas in the second step is (0.5-10): (2-8): 1.
further limiting, in the second step, the transition metal plasma is one or a mixture of several of iron, cobalt, nickel, copper, zinc, manganese, chromium and vanadium in any ratio.
Further limiting, the current of the emitting transition metal plasma in the second step is 3 mA-200 mA.
Further, the current of the transition metal plasma emission in the second step is 20 mA.
Further limiting, the reaction time in step two is 0.5 h.
The micro-morphology of the single-walled carbon nanotube powder prepared by the invention is a tube bundle with orientation, the tube diameter of the single-walled carbon nanotube powder is 1.5-3 nm, the carbon content is more than 85%, and the carbon content is preferably more than 90%.
Compared with the prior art, the invention has the advantages that:
the high-quality single-walled carbon nanotube prepared by the invention has the tube diameter of 1.5-3 nm and the carbon content of more than 85 percent, can be used as a final product without further purification treatment, and keeps the good structure to the maximum extent so as to ensure the performance. It can be used as conductive additive for various materials, and has mechanical property enhancing effect.
Drawings
FIG. 1 is an SEM image of single-walled carbon nanotube powder according to a first embodiment;
fig. 2 is an SEM image of the single-walled carbon nanotube powder according to the second embodiment.
Detailed Description
The first embodiment is as follows: the preparation method of the single-walled carbon nanotube powder of the embodiment comprises the following steps:
at one, in N2Heating the reaction cavity to 660 ℃ at the heating rate of 5 ℃/min under protection, and keeping the temperature for 45 min;
secondly, continuously introducing N into the reaction cavity2、H2And C3H6The iron plasma is injected into the reaction cavity by the emission current of 5mA at the same time, the reaction time is 0.25h, and black powder 232mg, namely single-walled carbon nanotube powder, with the tube diameter of 2.3nm, the carbon content of 88.50% and the purity of 86.45%, is obtained; wherein N is contained in the mixed gas2、H2And C3H6The flow ratio of (3): 4: 1. the SEM image of the obtained single-walled carbon nanotube powder is shown in FIG. 1.
The second embodiment is as follows: the preparation method of the single-walled carbon nanotube powder of the embodiment comprises the following steps:
firstly, heating a reaction cavity to 710 ℃ at a heating rate of 5 ℃/min under the protection of Ar, and preserving heat for 50 min;
secondly, continuously introducing Ar and H into the reaction cavity2And C3H8The cobalt plasma is injected into the reaction cavity by the emission current of 8mA at the same time, the reaction time is 35min, and black powder 315mg, namely single-walled carbon nanotube powder, with the tube diameter of 1.8nm, the carbon content of 86.50% and the purity of 84.25% is obtained; wherein Ar and H in the mixed gas2And C3H8The flow ratio of (1.5): 2: 1. the SEM image of the obtained single-walled carbon nanotube powder is shown in FIG. 2.
The third concrete implementation mode: the preparation method of the single-walled carbon nanotube powder of the embodiment comprises the following steps:
firstly, heating a reaction cavity to 850 ℃ at a heating rate of 5 ℃/min under the protection of Ar, and preserving heat for 40 min;
secondly, continuously introducing Ar and H into the reaction cavity2Mixing with anhydrous ethanol gas gasified at 150 deg.C, injecting iron plasma into the reaction cavity with 10mA emission current for 40min to obtain black powder 504mg, which is single-walled carbon nanotube powder or tubeThe diameter is 2.35nm, the carbon content is 89.35%, and the purity is 86.55%; wherein Ar and H in the mixed gas2And absolute ethanol gasified at 150 ℃ in a flow ratio of 1.5: 2: 1.
the fourth concrete implementation mode: the preparation method of the single-walled carbon nanotube powder of the embodiment comprises the following steps:
firstly, heating a reaction cavity to 750 ℃ at a heating rate of 5 ℃/min under the protection of Ar, and preserving heat for 35 min;
secondly, continuously introducing Ar and H into the reaction cavity2And C2H4Simultaneously injecting a mixture of iron plasma and cobalt plasma (the mass ratio of Fe to Co is 3: 1) into the reaction cavity by an emission current of 15mA, and reacting for 35min to obtain 457mg of black powder, namely single-walled carbon nanotube powder, wherein the diameter of the tube is 1.95nm, the carbon content is 88.65%, and the purity is 87.35%; wherein Ar and H in the mixed gas2And C3H8The flow ratio of (2): 4: 1.
the fifth concrete implementation mode: the preparation method of the single-walled carbon nanotube powder of the embodiment comprises the following steps:
firstly, heating the reaction cavity to 790 ℃ at the heating rate of 5 ℃/min under the protection of Ar, and preserving the temperature for 45 min;
secondly, continuously introducing Ar and H into the reaction cavity2And CH4Simultaneously injecting a mixture of iron plasma and cobalt plasma (the mass ratio of Fe to Co is 1: 2) into the reaction cavity by using 20mA emission current, and reacting for 30min to obtain 256mg of black powder, namely single-walled carbon nanotube powder, wherein the diameter of the tube is 1.5nm, the carbon content is 86.35%, and the purity is 85.25%; wherein Ar and H in the mixed gas2And C3H8The flow ratio of (1): 2: 1.
Claims (10)
1. the preparation method of the single-walled carbon nanotube powder is characterized by comprising the following steps of:
firstly, heating the reaction cavity to 600-1200 ℃ under the protection of inert gas, and preserving heat for 30-60 min;
and secondly, continuously introducing mixed gas of inert gas, hydrogen and gaseous carbon-containing organic matters into the reaction cavity, and simultaneously injecting transition metal plasma into the reaction cavity for 0.2-10 h to obtain the single-walled carbon nanotube powder.
2. The method for preparing single-walled carbon nanotube powder according to claim 1, wherein in the first step, the temperature of the reaction cavity is increased to 600-1200 ℃ at a rate of 3-7 ℃/min.
3. The method of claim 1, wherein in the first step, the temperature of the reaction chamber is increased to 700 ℃ at a rate of 5 ℃/min.
4. The method of claim 1, wherein the reaction chamber in step one is a vertical tube furnace or a horizontal tube furnace, and the inert gas in step one is nitrogen, argon or helium.
5. The method for preparing single-walled carbon nanotube powder according to claim 1, wherein the inert gas in the second step is nitrogen, argon or helium, the gaseous carbon-containing organic substance is carbon-containing organic gas or gasified organic liquid, and the gasification temperature of the organic liquid is 100-300 ℃.
6. The method for preparing single-walled carbon nanotube powder according to claim 5, wherein the carbon-containing organic gas is one or a mixture of several of methane, natural gas, ethane, ethylene, acetylene, propane and propylene, and the gasified organic liquid is one or a mixture of several of absolute methanol, absolute ethanol, benzene, toluene and xylene.
7. The method for preparing single-walled carbon nanotube powder according to claim 1, wherein the flow ratio of the inert gas, the hydrogen gas and the gaseous carbon-containing organic matter in the mixed gas in the second step is (0.5-10): (2-8): 1.
8. the method for preparing single-walled carbon nanotube powder according to claim 1, wherein the transition metal plasma in the second step is one or a mixture of several of iron, cobalt, nickel, copper, zinc, manganese, chromium and vanadium.
9. The method for preparing single-walled carbon nanotube powder according to claim 1, wherein the current for emitting transition metal plasma in the second step is 3 mA-200 mA.
10. The method of claim 1, wherein the obtained single-walled carbon nanotube powder has a microscopic morphology of tube bundles with orientation, a tube diameter of 1.5nm to 3nm, and a carbon content of 85% or more.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030211030A1 (en) * | 2002-05-09 | 2003-11-13 | Smiljanic Olivier | Method and apparatus for producing single-wall carbon nanotubes |
| CN101941691A (en) * | 2010-09-21 | 2011-01-12 | 上海大学 | Preparation method of single-walled carbon nanotube |
| CN109970046A (en) * | 2019-05-07 | 2019-07-05 | 江西铜业技术研究院有限公司 | A kind of preparation method of slim pipe diameter carbon nanotube |
| CN110790259A (en) * | 2019-12-23 | 2020-02-14 | 哈尔滨金纳科技有限公司 | Method for preparing single-walled carbon nanotubes in batches |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030211030A1 (en) * | 2002-05-09 | 2003-11-13 | Smiljanic Olivier | Method and apparatus for producing single-wall carbon nanotubes |
| CN101941691A (en) * | 2010-09-21 | 2011-01-12 | 上海大学 | Preparation method of single-walled carbon nanotube |
| CN109970046A (en) * | 2019-05-07 | 2019-07-05 | 江西铜业技术研究院有限公司 | A kind of preparation method of slim pipe diameter carbon nanotube |
| CN110790259A (en) * | 2019-12-23 | 2020-02-14 | 哈尔滨金纳科技有限公司 | Method for preparing single-walled carbon nanotubes in batches |
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