CN109095454A - A kind of carbon nanotube and its purification process - Google Patents
A kind of carbon nanotube and its purification process Download PDFInfo
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- CN109095454A CN109095454A CN201710470706.8A CN201710470706A CN109095454A CN 109095454 A CN109095454 A CN 109095454A CN 201710470706 A CN201710470706 A CN 201710470706A CN 109095454 A CN109095454 A CN 109095454A
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Abstract
The present invention relates to carbon nanotube preparation fields, and in particular to a kind of carbon nanotube and its purification process.The invention discloses a kind of methods of purifying carbon nano-tube, this method comprises: (1) is under an inert atmosphere, the metal oxide in the carbon nanotube containing metal oxide and/or metal impurities is carried out reduction reaction；(2) under an inert atmosphere, the carbon nanotube and cyclopentadiene step (1) obtained carries out haptoreaction, generates metallocene；(3) metallocene generated in step (2) is removed.Also disclose the carbon nanotube that the above method purifies.Purification process of the invention can not destroy carbon nano tube structure while farthest remove metal impurities.
Description
Technical field
The present invention relates to carbon nanotube preparation fields, and in particular to a kind of carbon nanotube and its purification process.
Background technique
The existing industrialized preparation method of carbon nanotube is generally chemical gaseous phase cracking process (also known as CVD method), this system
One problem of Preparation Method is that product impurity is more, and main impurity is metal and metal oxide.Traditional at present removes metal
Or the method for metal oxide impurities is mainly acid cleaning process, i.e., using one or more mixed acid such as nitric acid, hydrochloric acid and sulfuric acid
It is impregnated, the metal impurities adulterated in carbon nanotube reaction is generated into soluble metallic salt, it will be golden by repeatedly washing
Belong to salt removal, obtains the less carbon nanotube product of impurity after dry.
But the problem that above-mentioned pickling impurity removal technique is main are as follows: 1, carbon nanotube caliber it is superfine small, or even only several receive
Rice, liquid should not enter inside carbon nanotube, and the impurity inside carbon nanotube should not remove；2, the acid that removal of impurities uses all has one
Fixed oxidisability is easily destroyed the state of carbon nano tube surface, reduces the characteristic (such as electric conductivity, thermal conductivity etc.) of carbon nanotube；
3, the post-processing of the acidic cleaning solution containing metal ion is cumbersome.
Therefore, it is badly in need of a kind of method that can effectively remove the metal impurities in carbon nanotube obtained now.
Summary of the invention
The purpose of the invention is to overcome purification process of the existing technology easily lead to carbon nano tube surface destroy and
It is not easy to remove the defect of the metal class impurity in carbon nanotube, a kind of carbon nanotube and its purification process, this method purifying is provided
The metals content impurity of obtained carbon nanotube is lower and the resistivity of the carbon nanotube is lower.
To achieve the goals above, one aspect of the present invention provides a kind of method of purifying carbon nano-tube, this method comprises:
(1) under an inert atmosphere, by the metal oxide in the carbon nanotube containing metal oxide and/or metal impurities
Carry out reduction reaction；
(2) under an inert atmosphere, the carbon nanotube and cyclopentadiene step (1) obtained carries out haptoreaction, generates cyclopentadienyl
Metal；
(3) metallocene generated in step (2) is removed.
Second aspect of the present invention provides the carbon nanotube that the above method purifies.
The present invention uses cyclopentadiene, and cyclopentadiene metallization can be generated with the metal reaction in carbon nanotube obtained
It closes object (i.e. metallocene), this substance is easy to volatilize or be easily soluble in organic solvent, is easy to pass through physics or chemical method
Removing.In addition, purification process of the invention will not destroy carbon nano tube surface property, enable to the resistivity of carbon nanotube compared with
Low, i.e., the electric conductivity for the carbon nanotube that purifying of the invention obtains is preferable.In short, purification process of the invention can not destroy carbon
Nano tube structure farthest removes metal impurities simultaneously.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
One aspect of the present invention provides a kind of method of purifying carbon nano-tube, this method comprises:
(1) under an inert atmosphere, by the metal oxide in the carbon nanotube containing metal oxide and/or metal impurities
Carry out reduction reaction；
(2) under an inert atmosphere, the carbon nanotube and cyclopentadiene step (1) obtained carries out haptoreaction, generates cyclopentadienyl
Metal；
(3) metallocene generated in step (2) is removed.
The step of method of purifying carbon nano-tube of the present invention (1) to (3), carries out in the reactor, which is high temperature
Tank reactor.
Method according to the present invention, the carbon nanotube containing metal oxide impurities can be various using this field
Carbon nanotube made from conventional method.Such as the method for preparing the carbon nanotube containing metal oxide impurities is chemical vapor deposition
At least one of area method, laser evaporization method and graphite acr method method, preferably chemical vapour deposition technique.Wherein, chemical gas
The specific method of phase sedimentation may include: that catalyst is fitted into fixed bed reactors, be heated to 500- under an inert atmosphere
1000 DEG C, carbon source is passed through into reactor, then reaction time 5-60min is cooled to room temperature under an inert atmosphere, obtains carbon
Nanotube.Wherein, the carbon source can be selected from C1-C5Hydrocarbon, C1-C8Pure and mild inorganic carbonaceous compound, it is preferable that C1-C5Hydrocarbon
For at least one of methane, ethane, ethylene, propylene and acetylene；Preferably, C1-C8Alcohol be methanol, ethyl alcohol and propyl alcohol in extremely
Few one kind, more preferably ethyl alcohol；Preferably, the inorganic carbonaceous compound is carbon monoxide.In the method, carbon obtained is received
The metal oxide contained in mitron catalyst as used in preparation process introduces.Catalyst used in the preparation method can
Think the various conventional method preparations in this field or commercially available catalyst.The preparation method of catalyst may include: to adopt first
Fe is prepared with the precipitation method2O3/ NiO/MgO catalyst.According to Fe:Ni:Mg=0.1-1:0.1-1:1 (with mole of metallic element
Than meter) proportion weigh analytically pure Fe (NO3)3.9H2O、 Ni(NO3)2·6H2O and Mg (NO3)2·6H2O, then by Mg
(NO3)2·6H2O is put into ultrasonic disperse in the aqueous solution of ferric nitrate and nickel nitrate, is slowly added to while stirring above-mentioned solution
The ammonium carbonate (relative to metallic element excess) of 1.5-4mol/L proportion, dries after the filtering of gained turbid solution, is ground into fine powder,
It is finally calcined at 500-1000 DEG C, has thus obtained the Fe of precipitation method preparation2O3/ NiO/MgO catalyst.
In the present invention, when using laser evaporization method or graphite acr method preparation carbon nanotube, it may lead in preparation process
It crosses Preparation equipment and raw material introduces metal and/or metal oxide impurities.
Method according to the present invention, in step (1), the metal in the metal oxide can be transition metal,
Preferably, the metal is at least one of iron, cobalt, nickel, copper, platinum, vanadium, niobium, tungsten, chromium, iridium, titanium and molybdenum, further,
The metal is iron and/or nickel, so that the content of metal impurities is reduced to 60ppm or less in carbon nanotube.
Method according to the present invention, in step (1), reducing agent used in reduction reaction can for it is various can
The reducing agent that impurity in metal oxide is restored, such as can be hydrogen, carbon monoxide, nitric oxide and three oxidations
At least one of two phosphorus, preferably hydrogen, so that metal oxide restores completely and then further remove the gold
Belong to impurity.
Method according to the present invention, in step (1), the condition of reduction reaction is preferably included: temperature 300-1500
DEG C, more preferably 800-1200 DEG C；Time is 10min-2h, more preferably 30min-1h, so that metal oxide
The metal impurities are restored and then further removed completely.
Method according to the present invention, in step (2), the catalytic condition is preferably included: temperature 210-
800 DEG C, more preferably 300-600 DEG C；Time is 5min-2h, more preferably 0.3-0.5h, so that reduction obtained
Metal sufficiently reacts with cyclopentadiene and then further removes the metal impurities.
Method according to the present invention, as long as the dosage of cyclopentadiene and carbon nanotube makes cyclopentadiene relative to carbon
Metal impurities excess in nanotube, when the total content of the various metal impurities in the carbon nanotube as made from detection
When (with elemental metal) is 2000-10000ppm, relative to the carbon nanotube of 100g, the dosage of cyclopentadiene can be
0.6-2.6g。
Method according to the present invention, in step (2), cyclopentadiene can be passed through in the form of a vapor.Such as it can be with
It is passed through the carbon nanotube haptoreaction obtained in reactor with step (1) again after cyclopentadiene is heated to 40 DEG C or more gasifications.
Method according to the present invention, in step (3), the mode for removing metallocene is preferably included: using inert gas
Metallocene is blown out into reactor, the mixture for perhaps vacuumizing to reactor or obtaining step (2) haptoreaction
It is passed through in organic solvent and removes after cooling, so as to the cyclopentadienyl gold by physics or chemical method removing containing metal impurities
Belong to, thoroughly the metal impurities in removing carbon nanotube.
In a kind of specific embodiment of the invention, the mode for removing metallocene is to be blown metallocene using inert gas
Out when reactor, carbon nanotube to be purified is heated to 150-500 DEG C, then using high temperature inert gas by metallocene from anti-
It answers in device and blows out, the time for being passed through high temperature inert gas can be 10-90min, and the temperature of high temperature inert gas can be 150-
500℃。
In another specific embodiment of the invention, the mode for removing metallocene is to vacuumize to reactor
When, use vaccum-pumping equipment that the pressure in final reactor can be made for 10-6-10-3MPa。
In another specific embodiment of the invention, the mode for removing metallocene is to obtain step (2) haptoreaction
To mixture it is cooling after be passed through removed in organic solvent when, the organic solvent can remove having for metallocene to be various
Solvent, such as can be at least one of carbon tetrachloride, acetone, ethyl alcohol and ether, preferably in acetone, ethyl alcohol and ether
At least one.Wherein, the cooling so that temperature be reduced to 50 DEG C hereinafter, so that generate metallocene be cooled to liquid
State.
In the present invention, the inert atmosphere can be provided by inert gas, and the inert gas can be nitrogen and/or dilute
There is gas, wherein the rare gas can be at least one in helium (He), neon (Ne), argon (Ar), krypton (Kr) and xenon (Xe)
Kind.
Second aspect of the present invention provides the carbon nanotube that the above method purifies.
In carbon nanotube of the invention the gross mass content of metal impurities be greater than 0 and be less than 60ppm, preferably greater than 0 and
Less than 40ppm；Resistivity be 10-20 Ω cm, preferably 13-15 Ω cm, thermal conductivity 0.6-1W/mK, preferably
0.7-0.8W/m·K。
The present invention will be described in detail by way of examples below.
Preparation example
Fe is prepared using the precipitation method2O3/ NiO/MgO catalyst: according to matching for Fe: Ni:Mg=0.5:0.5:1 (molar ratio)
Than weighing analytically pure Fe (NO3)3.9H2O、Ni(NO3)2·6H2O and Mg (NO3)2·6H2O, then by Mg (NO3)2·6H2O is put
Enter ultrasonic disperse in the aqueous solution of ferric nitrate and nickel nitrate, the carbon of 3mol/L proportion is slowly added to while stirring above-mentioned solution
Sour ammonium (relative to metallic element excess), dries after the filtering of gained turbid solution, is ground into fine powder, finally calcine at 650 DEG C, this
Sample has just obtained the Fe of precipitation method preparation2O3/ NiO/MgO catalyst.
Then, it takes the above-mentioned catalyst of about 100mg to be fitted into fixed bed reactors, is heated to 800 DEG C under an ar atmosphere, then
It is passed through methane, 20min is reacted, is finally cooled to room temperature under an argon atmosphere, just obtains carbon nanotube product
Detecting Fe content in the carbon nanotube product obtained is 2150ppm, and Ni content is 1980ppm.
Embodiment 1
The present embodiment is for illustrating carbon nanotube and its purification process of the invention.
(1) it takes carbon nanotube made from 100g preparation example to be fitted into reactor, argon gas is passed through into reactor, so that reaction
It is full of argon gas in device, is then passed through hydrogen treat 30min into 800 DEG C of reactor；
(2) it will warm up 50 DEG C of gaseous state cyclopentadiene (dosage 1.2g) to be passed through in the reactor full of argon gas 300
Carbon nanotube 30min is handled at DEG C；
(3) carbon nanotube that step (2) obtains is heated to 300 DEG C, then with 300 DEG C of nitrogen by metallocene from reaction
It is blown out in device, the time for being passed through nitrogen can be 10min, then cool to room temperature, obtain carbon nanotube A1 after purification.
Embodiment 2
The present embodiment is for illustrating carbon nanotube and its purification process of the invention.
(1) it takes carbon nanotube made from 100g preparation example to be fitted into reactor, argon gas is passed through into reactor, so that reaction
It is full of argon gas in device, is then passed through hydrogen treat 50min into 1000 DEG C of reactor；
(2) it will warm up 60 DEG C of gaseous state cyclopentadiene (dosage 1.2g) to be passed through in the reactor full of argon gas 600
Carbon nanotube 20min is handled at DEG C；
(3) carbon nanotube that step (2) obtains is heated to 500 DEG C, then with 500 DEG C of nitrogen by metallocene from reaction
It is blown out in device, the time for being passed through nitrogen can be 50min, then cool to room temperature, obtain carbon nanotube A2 after purification.
Embodiment 3
The present embodiment is for illustrating carbon nanotube and its purification process of the invention.
(1) it takes carbon nanotube made from 100g preparation example to be fitted into reactor, argon gas is passed through into reactor, so that reaction
It is full of argon gas in device, is then passed through hydrogen treat 60min into 900 DEG C of reactor；
(2) it will warm up 60 DEG C of gaseous state cyclopentadiene (dosage 2.6g) to be passed through in the reactor full of argon gas 400
Carbon nanotube 25min is handled at DEG C；
(3) carbon nanotube that step (2) obtains is heated to 150 DEG C, then with 150 DEG C of nitrogen by metallocene from reaction
It is blown out in device, the time for being passed through nitrogen can be 90min, then cool to room temperature, obtain carbon nanotube A3 after purification.
Embodiment 4
The present embodiment is for illustrating carbon nanotube and its purification process of the invention.
(1) it takes carbon nanotube made from preparation example to be fitted into reactor, argon gas is passed through into reactor, so that in reactor
Full of argon gas, hydrogen treat 60min then is passed through into 900 DEG C of reactor；
(2) it will warm up 60 DEG C of gaseous state cyclopentadiene and be passed through in the reactor full of argon gas and handle carbon at 400 DEG C and receive
Mitron 30min；
(3) temperature of reactor is reduced to 40 DEG C, then takes out carbon nanotube, be dipped into acetone solvent
10min obtains carbon nanotube A4 after purification after taking out drying.
Embodiment 5
The present embodiment is for illustrating carbon nanotube and its purification process of the invention.
Purifying carbon nano-tube A5 according to the method for embodiment 1, unlike, in step (2), carbon is handled at 210 DEG C and is received
Mitron 40min.
Embodiment 6
The present embodiment is for illustrating carbon nanotube and its purification process of the invention.
Purifying carbon nano-tube A6 according to the method for embodiment 1, unlike, in step (2), carbon is handled at 800 DEG C and is received
Mitron 10min.
Embodiment 7
The present embodiment is for illustrating carbon nanotube and its purification process of the invention.
According to the method purifying carbon nano-tube A7 of embodiment 4, the difference is that, in step (3), acetone solvent is replaced with four
Chlorination carbon.
Comparative example 1
Carbon nanotube made from preparation example is used to the mixed liquor (molar ratio 1:1) of hydrochloric acid and nitric acid at 25 DEG C of room temperature
30min is impregnated, takes out and is rinsed to pH value using deionized water greater than 6, obtain carbon nanotube D1 after purification after dry.
Test case 1
LiFePO 4, binder, solvent and embodiment 1-7 and comparative example 1 are purified obtained carbon nanotube to mix respectively
It closes uniformly, weight ratio 100:3:100:1.The film at 200um thickness, drying are smeared on polyimides (PI), wherein
Binder is PVDF, and solvent is N- Jia base Bi Ka Wan ketone (NMP), then tests electricity using the test method of GB/T 6615-1986
Resistance rate, test result see the table below 1.
Test case 2
Organic siliconresin, calcium carbonate are purified obtained carbon nanotube with embodiment 1-7 and comparative example 1 and mixed respectively
Even, weight ratio 25:70:5 measures the thermal conductivity of mixed paste, test knot according to ASTM D5470 standard method
Fruit see the table below 1.
Test case 3
Obtained carbon nanotube is purified using the test method testing example 1-7 and comparative example 1 of GB/T 9723-2007
In metal impurities Fe and Ni content, test result see the table below 1.
Table 1
As the result of table 1 can be seen that purification process of the invention enable to made from carbon nanotube metal it is miscellaneous
The gross mass content of matter is greater than 0 and to be less than 60ppm, and the surface state of the carbon nanotube obtained after purification is kept preferably, thus
The resistivity for enabling to carbon nanotube after purification is 10-20 Ω cm, thermal conductivity 0.6-1W/mK.Present invention purifying
The metals content impurity of obtained carbon nanotube is lower, extends the application range of the carbon nanotube, such as can apply in electricity
To reduce influence of the metal impurities to battery life in pond.In addition, the surface breakdown due to carbon nanotube is few, carbon nanotube properties
Preferably retained, ensure that good electric conductivity and thermal conductivity, such as can be used as conductive agent using in the battery with more
The internal resistance of cell is reduced to big degree, reduce power loss and improve circulating ratio etc..
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (10)
1. a kind of method of purifying carbon nano-tube, which is characterized in that this method comprises:
(1) under an inert atmosphere, the metal oxide in the carbon nanotube containing metal oxide and/or metal impurities is carried out
Reduction reaction；
(2) under an inert atmosphere, the carbon nanotube and cyclopentadiene step (1) obtained carries out haptoreaction, generates metallocene；
(3) metallocene generated in step (2) is removed.
2. according to the method described in claim 1, wherein, in step (1), the metal in the metal oxide is transition gold
Belong to, it is preferable that the metal is at least one of iron, cobalt, nickel, copper, platinum, vanadium, niobium, tungsten, chromium, iridium, titanium and molybdenum, further
Ground, the metal are iron and/or nickel.
3. according to the method described in claim 1, wherein, in step (1), reducing agent used in reduction reaction be hydrogen,
At least one of carbon monoxide, nitric oxide and diphosphorus trioxide, preferably hydrogen.
4. method described in any one of -3 according to claim 1, wherein in step (1), the condition of reduction reaction includes:
Temperature is 300-1500 DEG C, preferably 800-1200 DEG C；Time is 10min-2h, preferably 30min-1h.
5. according to the method described in claim 1, wherein, in step (2), the catalytic condition includes: that temperature is
210-800 DEG C, preferably 300-600 DEG C；Time is 5min-2h, preferably 0.3-0.5h.
6. according to the method described in claim 1, wherein, in step (3), the mode for removing metallocene includes:
Metallocene is blown out by reactor using inert gas, perhaps reactor is vacuumized or is contacted step (2) anti-
It is passed through in organic solvent and removes after the mixture that should be obtained is cooling.
7. according to the method described in claim 6, wherein, in step (3), the organic solvent is carbon tetrachloride, acetone, ethyl alcohol
At least one of with ether, preferably at least one of acetone, ethyl alcohol and ether.
8. method according to any one of claims 1-7, wherein carbon nanometer of the preparation containing metal oxide impurities
The method of pipe is at least one of chemical vapour deposition technique, laser evaporization method and graphite acr method method, preferably chemical gas
Phase sedimentation；
Preferably, the inert atmosphere is provided by inert gas, and the inert gas is nitrogen and/or rare gas.
9. the carbon nanotube that method described in any one of claim 1-8 purifies.
10. carbon nanotube according to claim 9, wherein the gross mass content of the metal impurities in the carbon nanotube is
Greater than 0 and be less than 60ppm, preferably greater than 0 and be less than 40ppm；Resistivity be 10-20 Ω cm, preferably 13-15 Ω cm,
Thermal conductivity is 0.6-1W/mK, preferably 0.7-0.8W/mK.
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Cited By (1)
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| CN112551512A (en) * | 2020-11-27 | 2021-03-26 | 宁波埃氪新材料科技有限公司 | Method for purifying iron impurities in carbon nano tube by taking cyclopentadiene as medium |
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