CN101314466A - Method for preparing carbon nanotube - Google Patents
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- CN101314466A CN101314466A CNA2007100997053A CN200710099705A CN101314466A CN 101314466 A CN101314466 A CN 101314466A CN A2007100997053 A CNA2007100997053 A CN A2007100997053A CN 200710099705 A CN200710099705 A CN 200710099705A CN 101314466 A CN101314466 A CN 101314466A
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Abstract
The invention discloses a method for preparing a carbon nanotube. The preparation method comprises the following steps that: metal sodium and halogenated non-aromatic hydrocarbon are used as raw materials; a molar ratio of the metal sodium to the halogenated non-aromatic hydrocarbon is 1-5 to 5-1; firstly, the raw materials and a reaction solvent are put into a reaction kettle; a volume ratio of the metal sodium and the halogenated non-aromatic hydrocarbon is 1-5 to 20-1; secondly, shielding gas is passed through the reaction kettle; a middle nozzle of the reaction kettle is connected with a condensing and reflowing device and finally communicated with condensed water; and the reaction is carried out for 0.5 to 24 hours at a temperature of between 120 and 400 DEG C, thereby producing the carbon nanotube. The method plays an important role in industrialized production of the carbon nanotube and related products (such as a lithium ion battery, etc.) and has wide application prospect.
Description
Technical field
The present invention relates to the preparation method of carbon nanotube, particularly relate to a kind of method of chemosynthesis carbon nanotube.
Background technology
Carbon nanotube (Carbon nanotube) is a kind of novel carbon structure that Japanese scientist Iijima in 1991 finds during arc-over between the research Graphite Electrodes, the same with common graphite, diamond and decolorizing carbon, carbon nanotube is a kind of nano-carbon material that is made of carbon.The ideal CNT (carbon nano-tube) is seamless, the hollow tube body that is rolled into by the Graphene lamella that carbon atom forms.The Graphene lamella generally can wherein, contain the Single Walled Carbon Nanotube that is called of one deck Graphene lamella from one deck to layer up to a hundred, and what contain the multi-layer graphene lamella then is called multi-walled carbon nano-tubes.The diameter of Single Walled Carbon Nanotube is generally 1-3nm, and minimum diameter is about 0.5nm, with C
36The diameter of molecule is suitable, and its length in particular cases also can prepare other overlength pipe of millimeter level generally from the hundreds of nanometer to several micron.Because the minimum diameter and the fullerene molecule of Single Walled Carbon Nanotube are similar, so also the someone is called Baji-tube or Fu Leguan.The interlamellar spacing of multi-walled carbon nano-tubes is about 0.34nm, diameter generally in several nanometers to tens nanometers, length is generally in micron dimension, the longlyest also can reach several millimeters.Because CNT (carbon nano-tube) has bigger length-to-diameter ratio, is quasi-one-dimensional nanometer material so can regard it as.
Carbon nanotube particular structure characteristics have been brought a series of novelties, special nature to it, have been the focus of scientists study since it is found always.At first, carbon nanotube has excellent mechanical property, and its tensile strength can reach 50-200GPa, is 100 times of steel, and density but has only 1/6 of steel; In addition, its Young's modulus can reach 1TPa, and is suitable with adamantine Young's modulus, is about 5 times of steel.Carbon nanotube is the material with high specific strength that can prepare at present.Simultaneously, carbon nanotube can also be compound with other material as the mechanics strongthener, and prepared matrix material has mechanical strength, elasticity, fatigue resistance and many other excellent properties of superelevation.At present, studying maximum is carbon nanotube enhanced macromolecular material, this matrix material for original macromolecular material not only mechanical property improve greatly, and has good electroconductibility, radiowave also there is certain screening ability, can be applicable to the defence and military field and prepare antistatic coating, radar absorbing, and the stealth material of submarine aircraft.Wherein, use cement to do good, the anti-electrostatic, wear-resistant, stable high of carbon nano tube compound material shock-resistance of matrix, be difficult for environment is impacted.The intensity of carbon nanotube enhanced ceramic composite is then higher, and toughness and shock resistance are also very excellent.
Secondly, carbon nanotube has peculiar electrical properties, and the metal mold carbon nanotube can be as the lead of nanoscale, and semiconductor type carbon nano-tube can be used for preparing nanometer electronic devices such as field-effect transistor.Between the carbon nanotube of semiconductor property and metalline, can form heterojunction with rectification function.The researchist has made the heterojunction structure between Single Walled Carbon Nanotube and carbide, and the interface size of this structure is a nanometer scale, has represented the heterojunction of the minimum that can reach at present, will play an important role in the mixing nano-device in future.Experimental observation is the result show, the point defect on the carbon nanotube can cause the carbon nanotube part to be Schottky barrier or heterojunction situation.Utilize this characteristic can make the very little nano electron device of yardstick.The researchist has made the unit molecule field-effect transistor of working under the room temperature, and its gain and speed are determined by contact resistance basically.If the contact resistance amount of reducing to is in limit 6h Ω, switching speed just can reach 10THZ.The size of this device can reach below 30 nanometers.Also have scientist that the electronics of spin polarization(SP) is injected into from ferromagnetic material in the multi-walled carbon nano-tubes, find the associated transport of electron spinning.This means that carbon nanotube very likely develops into practical spin electric device.It is quantized that the electricity of carbon nanotube is led, and its electrical conduction mechanism is a ballistic transport, not heat dissipation.Size that the quantum electricity of the typical working and room temperature of carbon nanotube quantum conductance ratio is led and stable high several magnitude, and after the together a lot of interactions of molecules of carbon nanotube, its electrical properties can change, thereby carbon nanotube can also be used as the transmitter that detects these molecules.
Aspect the energy, the shared status of carbon nanotube also more shows important.At first,, make it have very big specific surface area, than activated carbon of sorbent commonly used bigger hydrogen adsorption ability is arranged, thereby be suitable as very much the material of Chu Qing because carbon nanotube has unique nano-grade size and hollow structure.At present, hydrogen is with generally being considered as following clean energy, and still, because hydrogen density is low, it is very inconvenient to be compressed into fluid storage, thereby has limited applying of hydrogen.The carbon nanotube own wt is light, has the structure of hollow, not only can be used as the good container of storage of hydrogen, and the hydrogen density that stores even also higher than the density of liquid state or solid hydrogen.Suitably heating, hydrogen just can slow release come out.The researchist is attempting to make of carbon nanotube the hydrogen storage vessel of portable portable.At present, hydrogen Storage in Carbon Nanotubes research is in the starting stage, and the storage hydrogen condition mostly is low temperature or high pressure, or haves both at the same time, and the storage hydrogen time was generally several hours to tens hours.Carbon nanotube has remarkable advantages at Chu Qing aspect leading, especially carbon material have cheap, stable chemical performance, the advantage that density is little, thereby the application prospect of carbon nanotube aspect Chu Qing is good.In addition, aspect battery, carbon nanotube also can be used as the cathode material of lithium ion battery, the interlamellar spacing of multi-walled carbon nano-tubes is slightly larger than the interlamellar spacing of graphite, these characteristics are very beneficial for the embedding of Li+ and move out, experimental result show with carbon nanotube do negative electrode lithium ion battery embedding Li+ capacity and discharge and recharge stability and all improve much than conventional graphite base lithium ion battery, therefore, carbon nanotube is expected to become a kind of novel lithium ion battery material.
In addition, because carbon nanotube has very large length-to-diameter ratio, have than high thermal along its tube axial direction, therefore, carbon nanotube also is good thermal conducting material; Simultaneously, its thermal conductivity perpendicular to tube axial direction is but very low, therefore, also carbon nanotube can be made anisotropic thermally conductive material.Carbon nanotube also has excellent field emission performance, and its emission threshold values is low, emission big, stability is high, can be used for making the high-performance flat-panel monitor.The Samsung Electronics of Korea S has showed the flat-panel monitor made from carbon nanotube.The specific surface area that carbon nanotube is bigger makes it adsorb more multi-catalyst particle as good support of the catalyst, thereby makes activity of such catalysts and selectivity greatly obtain significantly to improve, and will bring huge economic benefit for industrial production.
In sum, CNT (carbon nano-tube) is as the present 1-dimention nano carbon material that intensity is the highest, diameter is the thinnest, have unique mechanical, chemistry and electronics performance, can be used as strongthener and prepare high strength composite, the inherent nature of existing carbon fibre material has the heat-resisting and stable of the conduction of metallic substance and thermal conductivity, stupalith again, the softness of textile materials and braiding property, and the workability of macromolecular material, be with a wide range of applications and have the application prospect of potentiality.
At present, the production method of carbon nanotube mainly contains arc process, laser ablation method and catalytic pyrolysis method, and other method also has pyrolytic polymer method, flame method, ionizing radiation method, electrolytic process, cryogenic solid pyrolysis method and ball milled.
Wherein, arc process is under the protection of rare gas element, will pass to big electric current, two interpolar geseous discharges between two root graphite electrodes.1991, Iijima was preparing C with arc-over exactly
60Shi Faxian carbon nanotube.Preparing carbon nano tube by arc process is subjected to following condition effect, is respectively the rare gas element kind, chamber pressure, the composition of catalyzer and content in the Graphite Electrodes, the character of electric current (direct current or interchange), voltage, relative dimension of electrode or the like.Preparing carbon nano tube by arc process, because temperature of reaction is higher, so the degree of graphitization of carbon pipe is higher, structural integrity, diameter Distribution is even, but it is more to contain impurity, restive growth, and also output is less, complex process, power consumption is high, and circulation ratio is poor, can't carry out large-scale industrial production.
Laser ablation method is to prepare carbon nanotube by intense laser beam evaporation graphite target.Laser evaporation method and arc process exist power consumption high equally, can't carry out the shortcoming that heavy industrialization is used.
Mode according to adding catalyzer can be divided into catalytic pyrolysis method matrix method, spraying process and mobile catalysis method, and catalyzer generally adopts Fe, Co, Ni or its combination.The matrix method be with catalyst carrier on matrix, feed carbon-source gas then and make it to decompose, the matrix method is decomposed carbon source and is generally adopted chemical Vapor deposition process, this method can be prepared the higher carbon pipe of purity, and can realize the controllable growth of carbon pipe.In addition, fluidized bed process is to make unstripped gas flow through gas distribution grid, and the activatory catalyzer is moving always, and mutual spacing is from much larger than the fixed substrate, as in boiling.Spraying process be with catalyst dissolution in the liquid carbon source, make the temperature of Reaktionsofen reach growth temperature, and then the carbon source that will be dissolved with catalyzer is sprayed onto in the stove.Mobile catalysis method is that the gasiform catalyst precursor is together introduced reaction chamber with carbon-source gas, finishes the decomposition of presoma and carbon-source gas at different warm areas.Output in the catalytic pyrolysis method unit time is very high, and all has good industrial prospect.Though chemical Vapor deposition process can carry out suitability for industrialized production, but its output far can not satisfy the requirement that heavy industrialization is used, and the carbon nanotube that makes often contains impurity such as decolorizing carbon and granules of catalyst, these impurity are difficult to remove fully by purifying, thereby have limited its range of application.
In addition, there is the people under lower temperature, to make carbon nanotube in recent years by solvent thermal method.But the transformation efficiency of carbon nanotube is very low, and contains a large amount of granules of catalyst, and reaction also needs high pressure vessel, and is very high to the requirement of plant and instrument, is unsuitable for large-scale industrial production.
Summary of the invention
The purpose of this invention is to provide a kind of simple to operate, with low cost, method for preparing carbon nanotube that transformation efficiency is higher.
For solving the problems of the technologies described above; the present invention takes following technical scheme: a kind of method for preparing carbon nanotube; be to be raw material with sodium Metal 99.5 and halo non-aromatic hydrocarbon; the mol ratio of described sodium Metal 99.5 and halo non-aromatic hydrocarbon is 1-5: 5-1; earlier raw material and reaction solvent are placed reactor; the volume ratio of described halo non-aromatic hydrocarbon and reaction solvent is 1-5: 20-1; feed shielding gas then; get rid of the oxygen in the reaction system; middle mouth of pipe place (top of reaction liquid level) with reactor connects condensation reflux unit again, makes it and the reactor internal communication, connects water of condensation at last; reacted 0.5-24 hour down at 120-400 ℃, obtain carbon nanotube.
In the preparation method of above-mentioned carbon nanotube, the selection of described halo non-aromatic hydrocarbon is widely, as zellon, trieline, Ethylene Dichloride, ethylene tetrabromide, tribromo-ethylene or sym-dibromoethane etc., is preferably zellon.
The selection of described reaction solvent also is diversified, so long as do not react with raw material sodium and halo non-aromatic hydrocarbon and boiling point be higher than 120 ℃ solvent and all can, as long chain alkane, ethers or acetals solvent etc., specifically can be paraffin oil, phenyl ether, methyl-phenoxide, decane, undecane, dodecane, tridecane, the tetradecane, pentadecane, n-Hexadecane or heptadecane etc.
Described reactor requirement and sodium and halo non-aromatic hydrocarbon all do not react, and can the tolerance response temperature.
The selection of described shielding gas also is widely, and all not can be used as reaction protection gas with the gas that sodium, halo non-aromatic hydrocarbon and reaction solvent react, as nitrogen, argon gas or helium etc.
Described condensation reflux unit requires not react with the halo non-aromatic hydrocarbon and be insoluble to used reaction solvent, and halo non-aromatic hydrocarbon and reaction solvent can be cooled to the temperature below the boiling point.
Described temperature of reaction can be set according to reaction solvent, but in 120-400 ℃ temperature range equal synthesizing carbon nanotubes, and temperature is high more, speed of response is fast more.For improving combined coefficient, be preferably in the 1-240min temperature is brought up to required temperature of reaction.
For obtaining the higher carbon nanotube of purity, also comprise the step of the synthetic carbon nanotube being carried out purifying among the described preparation method, to remove impurity such as the reaction solvent that contained in the synthetic carbon nanotube and unreacted sodium, described purification process can may further comprise the steps:
1) with the synthetic carbon nanotube with can with the reagent mix of sodium Metal 99.5 reaction, remove remaining a small amount of sodium by chemical reaction;
2) with can the carbon nanotube of washing that step 1) obtains being washed, to remove remaining reaction solvent with the organic solvent that reaction solvent dissolves each other;
3) with deionized water to step 2) carbon nanotube that obtains washs, to remove remaining NaCl;
4) oven dry obtains purified carbon nanotube.
In above-mentioned purification process, can be methyl alcohol, ethanol, propyl alcohol or Virahol etc. with the reagent of sodium Metal 99.5 reaction in the step 1).
Step 2) organic solvent in can be sherwood oil, hexanaphthene, hexane, pentane, heptane, ethanol, Virahol, ether, tetrahydrofuran (THF), DMF, methyl alcohol, propyl alcohol, acetone, chloroform or toluene etc.
Carbon nanotube with method for preparing also is that the present invention will protect.
The invention provides a kind of method for preparing carbon nanotube.Compare with the ordinary method (as arc process, laser evaporation method and catalyse pyrolysis etc.) of preparation carbon nanotube, the preparation of carbon nanotube of the present invention has the following advantages:
1. equipment is simple, operation easily, and production stage is few, is easy to carry out large-scale industrial production;
2. raw materials cost is cheap, and solvent can recycle;
3. productive rate higher (more than 65%), and metallic impurity are less in the product, are easy to purify;
4. temperature of reaction is low, and can be prepared under normal pressure, and energy consumption is low;
5. the synthetic carbon nanotube has bigger specific surface area;
6. the carbon nanotube of using as support of the catalyst and electrode often needs carbon nanotube to have more defective, and had more defective with the carbon nanotube itself that the inventive method makes, therefore need not it is carried out oxide treatment, promptly can be used as support of the catalyst or electrode materials;
7. the interlamellar spacing of carbon nanotube, helps ionic and embeds and shift out apart from big slightly than graphite layers.
Based on above-mentioned advantage, the present invention will play a significant role in the suitability for industrialized production of carbon nanotube and related products (as lithium ion battery etc.), have a extensive future.
Below in conjunction with specific embodiment the present invention is described in further details.
Description of drawings
Fig. 1 is the structural representation of the experimental installation of preparation carbon nanotube
Fig. 2 A and Fig. 2 B are the TEM sign detected result with the carbon nanotube of the inventive method preparation
Fig. 3 is the HRTEM sign detected result with the carbon nanotube of the inventive method preparation
Fig. 4 is the Raman spectral detection result with the carbon nanotube of the inventive method preparation
Fig. 5 is the infrared spectra detected result with the carbon nanotube of the inventive method preparation
Fig. 6 is the TGA sign detected result with the carbon nanotube of the inventive method preparation
Fig. 7 is the XRD sign detected result with the carbon nanotube of the inventive method preparation
Embodiment
Method therefor is ordinary method if no special instructions among the following embodiment.
Adopt the experimental installation of routine as shown in Figure 1 to prepare carbon nanotube, this device comprises: ground there-necked flask (250mL, (reactor requirement and sodium and halo non-aromatic hydrocarbon all do not react reactor, and can the tolerance response temperature)), spherical condenser, electrically heated cover, high pure nitrogen steel cylinder (nitrogen is provided), glass capillary, thermowell, rubber tubing and thermometer (0-400 ℃).
Prepare carbon nanotube with method of the present invention, concrete grammar may further comprise the steps:
1, carbon nanotube is synthetic
Add the 50mL paraffin oil in the ground there-necked flask of in baking oven, drying earlier, dry the impurity on sodium Metal 99.5 surface, be placed on then to weigh in the balance on the watch-glass and get 6.0g sodium, put into there-necked flask after being cut into fritter, add zellon 4.0mL, stir; Then thermometer and thermowell are connected; fill on the bottleneck of there-necked flask side; the bead of thermometer bottom just enters into below the reaction solution liquid level; spherical condenser is connected with rubber tubing one end; the rubber tubing the other end is connected with there-necked flask intermediary bottleneck, and an end that will have the ventpipe of stopper again is connected to the remaining bottleneck of there-necked flask, and the ventpipe the other end is connected with nitrogengas cylinder; open the nitrogengas cylinder reducing valve, feed the N of low discharge as shielding gas
25min is with the O in the system
2Drive out of; Subsequently, connect the water coolant of the spherical condenser that is connected with the ground there-necked flask, the electricity consumption heating jacket begins heating to there-necked flask, 40min post-heating to 250 ℃ (power by control electrically heated cover is regulated and control temperature), keep this thermotonus stopped reaction after 2 hours, obtain carbon nanotube.Can observe in the reaction process in the there-necked flask liquid color by original transparent become to add to be deep to gradually become black, liquid also becomes muddy gradually in the bottle, finally can find to have in the there-necked flask a large amount of black solid materials to generate, these atraments are carbon nanotube.
2, the purifying of carbon nanotube
Contain impurity such as reaction solvent and unreacted sodium in the carbon nanotube of step 1 preparation, therefore, for improving the purity of carbon nanotube, also need it is carried out purifying, concrete grammar may further comprise the steps:
1) cooling adds ethanol in there-necked flask, removes residual little metal sodium by chemical reaction, when bubble not had is emitted, shows that unreacted sodium is removed fully;
2) solvent is separated with solid matter (carbon nanotube) by the decant method, use sherwood oil (60-90) that solid matter is washed again, repeat 3 times, each 30 minutes (3 minutes-48 hours all can) be to remove the reaction solvent paraffin oil of remnants;
3) with deionized water solid matter is washed again, repeat 3 times, each 10 minutes (3 minutes-48 hours all can) be to remove remaining NaCl;
4) in 100 ℃ baking oven, the solid matter of black is dried, obtain purified carbon nanotube.
After testing, the productive rate with aforesaid method synthetic carbon nanotube is about 65%.
Embodiment 2, preparation carbon nanotube
Prepare carbon nanotube with the experimental installation identical with embodiment 1, concrete preparation method may further comprise the steps:
1, carbon nanotube is synthetic
Add the 50mL phenyl ether in the ground there-necked flask of in baking oven, drying earlier, dry the impurity on sodium Metal 99.5 surface, be placed on then to weigh in the balance on the watch-glass and get 6.0g sodium, put into there-necked flask after being cut into fritter, add trieline 10mL, stir; Open the helium tank reducing valve, feed low discharge helium 5min, subsequently, connect the water coolant of the spherical condenser be connected with the ground there-necked flask, the electricity consumption heating jacket begins to heat to there-necked flask, 20min post-heating to 140 ℃, keep this thermotonus stopped reaction after 10 hours, obtain carbon nanotube.
2, the purifying of carbon nanotube
Contain impurity such as reaction solvent and unreacted sodium in the carbon nanotube of step 1 preparation, therefore, for improving the purity of carbon nanotube, also need it is carried out purifying, concrete grammar may further comprise the steps:
1) cooling adds propyl alcohol in there-necked flask, removes residual little metal sodium by chemical reaction, when bubble not had is emitted, shows that unreacted sodium is removed fully;
2) by the decant method solvent is separated with solid matter (carbon nanotube), use acetone (the recyclable recycling of acetone) that solid matter is washed again, repeat 2 times, each 60 minutes (3 minutes-24 hours all can) be to remove remaining reaction solvent phenyl ether;
3) with deionized water solid matter is washed again, repeat 3 times, each 10 minutes (3 minutes-24 hours all can) be to remove remaining NaCl;
4) in 100 ℃ baking oven, the solid matter of black is dried, obtain purified carbon nanotube.
After testing, the productive rate with aforesaid method synthetic carbon nanotube is about 75%.
Embodiment 3, preparation carbon nanotube
Prepare carbon nanotube with the experimental installation identical with embodiment 1, concrete preparation method may further comprise the steps:
1, carbon nanotube is synthetic
Add the 50mL methyl-phenoxide in the ground there-necked flask of in baking oven, drying earlier, dry the impurity on sodium Metal 99.5 surface, be placed on then to weigh in the balance on the watch-glass and get 6.0g sodium, put into there-necked flask after being cut into fritter, add ethylene tetrabromide 15mL, stir; Open the argon bottle reducing valve, feed low discharge argon gas 5min, subsequently, connect the water coolant of the spherical condenser be connected with the ground there-necked flask, the electricity consumption heating jacket begins to heat to there-necked flask, 80min post-heating to 350 ℃, keep this thermotonus stopped reaction after 0.5 hour, obtain carbon nanotube.
2, the purifying of carbon nanotube
Contain impurity such as reaction solvent and unreacted sodium in the carbon nanotube of step 1 preparation, therefore, for improving the purity of carbon nanotube, also need it is carried out purifying, concrete grammar may further comprise the steps:
1) cooling adds Virahol in there-necked flask, removes residual little metal sodium by chemical reaction, when bubble not had is emitted, shows that unreacted sodium is removed fully;
2) by the decant method solvent is separated with solid matter (carbon nanotube), use tetrahydrofuran (THF) (the recyclable recycling of tetrahydrofuran (THF)) that solid matter is washed again, repeat 3 times, each 10 minutes, to remove remaining reaction solvent methyl-phenoxide;
3) with deionized water solid matter is washed again, repeat 2 times, each 15 minutes, to remove remaining NaCl;
4) in 100 ℃ baking oven, the solid matter of black is dried, obtain purified carbon nanotube.
After testing, the productive rate with aforesaid method synthetic carbon nanotube is about 70%.
Embodiment 4, preparation carbon nanotube
Prepare carbon nanotube with the experimental installation identical with embodiment 1, concrete preparation method may further comprise the steps:
1, carbon nanotube is synthetic
Add the 50mL n-Hexadecane in the ground there-necked flask of in baking oven, drying earlier, dry the impurity on sodium Metal 99.5 surface, be placed on then to weigh in the balance on the watch-glass and get 6.0g sodium, put into there-necked flask after being cut into fritter, add tribromo-ethylene 25mL, stir; Open the helium tank reducing valve, feed low discharge helium 5min, subsequently, connect the water coolant of the spherical condenser be connected with the ground there-necked flask, the electricity consumption heating jacket begins to heat to there-necked flask, 120min post-heating to 400 ℃, keep this thermotonus stopped reaction after 4 hours, obtain carbon nanotube.
2, the purifying of carbon nanotube
Contain impurity such as reaction solvent and unreacted sodium in the carbon nanotube of step 1 preparation, therefore, for improving the purity of carbon nanotube, also need it is carried out purifying, concrete grammar may further comprise the steps:
1) cooling adds methyl alcohol in there-necked flask, removes residual little metal sodium by chemical reaction, when bubble not had is emitted, shows that unreacted sodium is removed fully;
2) by the decant method solvent is separated with solid matter (carbon nanotube), use heptane (the recyclable recycling of heptane) that solid matter is washed again, repeat 3 times, each 5 minutes, to remove remaining reaction solvent n-Hexadecane;
3) with deionized water solid matter is washed again, repeat 3 times, each 5 minutes, to remove remaining NaCl;
4) in 100 ℃ baking oven, the solid matter of black is dried, obtain purified carbon nanotube.
After testing, the productive rate with aforesaid method synthetic carbon nanotube is about 73%.
The detection of embodiment 5, carbon nanotube
With following method embodiment 1-4 is detected with the carbon nanotube of the inventive method preparation:
One, TEM characterizes and detects
Carbon nanotube to embodiment 1-3 preparation carries out the detection of transmission electron microscope (TEM) sign, and method is; The carbon nanotube black powder that takes a morsel, ultra-sonic dispersion in dehydrated alcohol is got 1-2 then and is dripped on the copper mesh side China film, uses the tubular nanometer structure of the carbon nanotube of transmission electron microscope (JEOL-100CX) observation post preparation then.With the transmission electron microscope photo of the carbon nanotube of the inventive method preparation as Fig. 2 A (ratio: 588nm) and Fig. 2 B (ratio: 100nm), as can be seen, carbon nanotube with the inventive method preparation is a hollow tubular structure, caliber is about 10-20nm, diameter Distribution is narrower, the longest hundreds of micron that reaches of length.
Two, HRTEM characterizes and detects
Carbon nanotube to embodiment 1-4 preparation carries out the detection of high resolution transmission electron microscopy (HRTEM) sign, and method is; The carbon nanotube black powder that takes a morsel behind the ultra-sonic dispersion, is got 1-2 and is dripped on little grid in dehydrated alcohol, uses the tubular nanometer structure of the carbon nanotube of high resolution transmission electron microscopy (H9000) observation post preparation then.With the high resolution transmission electron microscopy photo of the carbon nanotube of the inventive method preparation as shown in Figure 3, as can be seen, imperfect with the structural pipe wall of the carbon nanotube of the inventive method preparation, thickness of pipe is 1.5-3.0nm.
Three, Raman spectral detection
Carbon nanotube to embodiment 1-4 preparation carries out Raman spectral detection (Renishaw 1000, excitation wavelength 632.8nm), and detected result is (X-coordinate is the Raman displacement, and ordinate zou is a Raman intensity) as shown in Figure 4, as can be seen, and at 1334.4cm
-1And 1582.7cm
-1There is a strong peak respectively in two positions, wherein, and at 1582.7cm
-1The existence of graphite-structure near the strong cutting edge of a knife or a sword explanation carbon nanotube is at 1334.4cm
-1Contain more defective near the strong cutting edge of a knife or a sword explanation carbon nanotube.
Four, infrared spectra (IR) detects
The method of employing KBr compressing tablet is carried out infrared spectra (IR) detection to the carbon nanotube of embodiment 1-4 preparation, (X-coordinate is a wave number to detected result as shown in Figure 5, ordinate zou is a transmitance), to scheme to compare with the infrared spectrogram of purified multi-walled carbon nano-tubes sample (available from nanometer port, Shenzhen), the result is almost as broad as long, and at 1600cm
-1Near a very strong absorption peak is arranged, prove absolutely in the carbon nanotube with the inventive method preparation to have graphene-structured.
Five, BET specific surface test
Adopt N
2As adsorbed gas, the carbon nanotube that embodiment 1-4 is prepared carries out BET specific surface test (ASAP2010).Specific surface average out to 496m as a result
2/ g illustrates that the carbon nanotube with the inventive method preparation has bigger specific surface.
Six, TGA characterizes and detects
Rate of heating with 10 ℃/min is carried out TGA sign detection (the Thermal Analysis SDT2960 of company) to the carbon nanotube of embodiment 1-3 preparation in airflow.(X-coordinate is a temperature to detected result as shown in Figure 6, ordinate zou is a rate of weight loss), as can be seen, the aerial decomposition temperature of carbon nanotube with the inventive method preparation is about 370 ℃, rate of weight loss in the time of about 480 ℃ is 100%, illustrates that the carbon nanotube with the inventive method preparation has certain thermostability.
Seven, the sodium content of ICP sign
Measure the sodium amount that contains of the carbon nanotube of embodiment 1-4 preparation, concrete grammar is: the 0.122g carbon nanotube is cleared up with the pure concentrated nitric acid of 20mL top grade (available from Beijing chemical reagents corporation), add 2% (volume/volume percentage concentration) nitric acid then and be settled to 50mL, measure the sodium amount that contains with plasma emission spectrometer (ICP, model is S4-Explorer).The result contains sodium amount average out to 9.83 μ g/mL, calculates the mass percentage content average out to 0.4% of sodium in the carbon nanotube of the inventive method preparation, shows that the content of sodium element is lower in the product, has obtained the higher carbon nanotube of purity.
Eight, XRD characterizes and detects
Carbon nanotube to embodiment 1-4 preparation carries out the detection of X-ray diffraction (XRD, the model DMAX-2400 of x ray diffractometer x) sign.(X-coordinate is 2 θ to detected result as shown in Figure 7, ordinate zou is an intensity), main peak is to be positioned at about 21.0 ℃ broad peak, and the interlamellar spacing that draws the carbon nanotube for preparing with the inventive method as calculated helps ionic and embeds and shift out than the approximately big 0.085nm of graphite layers distance.
Claims (10)
1, a kind of method for preparing carbon nanotube; be to be raw material with sodium Metal 99.5 and halo non-aromatic hydrocarbon; the mol ratio of described sodium Metal 99.5 and halo non-aromatic hydrocarbon is 1-5: 5-1; earlier raw material and reaction solvent are placed reactor, the volume ratio of described halo non-aromatic hydrocarbon and reaction solvent is 1-5: 20-1, feeds shielding gas then; middle mouth of pipe place with reactor connects condensation reflux unit again; connect water of condensation at last, reacted 0.5-24 hour down, obtain carbon nanotube at 120-400 ℃.
2, preparation method according to claim 1 is characterized in that: described halo non-aromatic hydrocarbon is zellon, trieline, Ethylene Dichloride, ethylene tetrabromide, tribromo-ethylene or sym-dibromoethane.
3, preparation method according to claim 1 is characterized in that: described reaction solvent is long chain alkane, ethers or acetals solvent.
4, preparation method according to claim 3 is characterized in that: described reaction solvent is paraffin oil, phenyl ether, methyl-phenoxide, decane, undecane, dodecane, tridecane, the tetradecane, pentadecane, n-Hexadecane or heptadecane.
5, preparation method according to claim 1 is characterized in that: described shielding gas is nitrogen, argon gas or helium.
6, preparation method according to claim 1 is characterized in that: in 1-240min temperature of reaction is increased to 120-400 ℃.
7, according to each described preparation method of claim 1-6, it is characterized in that: also comprise the step of the synthetic carbon nanotube being carried out purifying among the preparation method of described carbon nanotube, described purification process may further comprise the steps:
1) with the synthetic carbon nanotube with can with the reagent mix of sodium Metal 99.5 reaction;
2) with can the carbon nanotube of washing that step 1) obtains being washed with the organic solvent that reaction solvent dissolves each other;
3) with deionized water to step 2) carbon nanotube that obtains washs;
4) oven dry obtains purified carbon nanotube.
8, preparation method according to claim 7 is characterized in that: in described purification process, can be methyl alcohol, ethanol, propyl alcohol or Virahol with the reagent of sodium Metal 99.5 reaction in the step 1).
9, preparation method according to claim 7, it is characterized in that: in described purification process, step 2) in the organic solvent that can dissolve each other with reaction solvent be sherwood oil, hexanaphthene, hexane, pentane, heptane, ethanol, Virahol, ether, tetrahydrofuran (THF), DMF, methyl alcohol, propyl alcohol, acetone, chloroform or toluene.
10, the carbon nanotube for preparing with each described method of claim 1-9.
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| CN102145883A (en) * | 2011-04-29 | 2011-08-10 | 清华大学 | Directly-prepared ultrahigh-purity carbon nanotube and preparation method thereof |
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| CN102485647A (en) * | 2010-12-02 | 2012-06-06 | 中国科学院上海硅酸盐研究所 | Method for preparing boron doped graphene |
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| CN102145883A (en) * | 2011-04-29 | 2011-08-10 | 清华大学 | Directly-prepared ultrahigh-purity carbon nanotube and preparation method thereof |
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| CN102849725B (en) * | 2012-10-15 | 2014-03-05 | 黑龙江大学 | Method for preparing carbon nano tube by sunflower seed skin |
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