CN110857217A - Boron-doped carbon nanotube film and preparation method and application thereof - Google Patents
Boron-doped carbon nanotube film and preparation method and application thereof Download PDFInfo
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- 239000002238 carbon nanotube film Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000243 solution Substances 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 239000011259 mixed solution Substances 0.000 claims abstract description 17
- 229930192474 thiophene Natural products 0.000 claims abstract description 17
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004327 boric acid Substances 0.000 claims abstract description 15
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002347 injection Methods 0.000 claims abstract description 15
- 239000007924 injection Substances 0.000 claims abstract description 15
- 238000000889 atomisation Methods 0.000 claims abstract description 10
- 239000012495 reaction gas Substances 0.000 claims abstract description 9
- 238000007789 sealing Methods 0.000 claims abstract description 8
- 238000005303 weighing Methods 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 31
- 239000002041 carbon nanotube Substances 0.000 claims description 23
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 230000001681 protective effect Effects 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000001307 helium Substances 0.000 claims description 5
- 229910052734 helium Inorganic materials 0.000 claims description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 38
- 229910052796 boron Inorganic materials 0.000 description 38
- 239000003054 catalyst Substances 0.000 description 6
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- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 239000010408 film Substances 0.000 description 5
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- 238000003917 TEM image Methods 0.000 description 2
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- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
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- 150000002736 metal compounds Chemical class 0.000 description 2
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- 239000002994 raw material Substances 0.000 description 2
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- 239000012847 fine chemical Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/162—Preparation characterised by catalysts
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
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Abstract
The invention discloses a boron-doped carbon nanotube film and a preparation method and application thereof, wherein the preparation method comprises the following steps: 1) weighing ethanol, ferrocene and thiophene according to the mass ratio of (90-100) to (1.3-1.7) to (0.5-1.5) to obtain a mixed solution, adding 1-3 wt.% of boric acid into the mixed solution, and uniformly dispersing at 40-60 ℃ to obtain a precursor solution; 2) completely sealing the CVD furnace, continuously introducing 100-; 3) closing Ar, and continuously introducing H of 700-900sccm2As reaction gas to H2And (2) filling the whole hearth, then injecting the precursor solution obtained in the step (1) into the furnace in uniformly dispersed mist-like liquid drops through an ultrasonic atomization device at the liquid injection rate of 8-15mL/h, and after 10-30min, doping the carbon nanotube film at the bottom of the hearth, wherein the mass specific capacitance can reach 65.6F/g.
Description
Technical Field
The invention relates to the technical field of carbon nanotube-based thin film materials, in particular to a boron-doped carbon nanotube thin film and a preparation method and application thereof.
Background
The carbon nano tube is used as a unique one-dimensional material, has excellent conductivity and good ion and electron transmission capability, and is widely applied to the preparation of electrochemical modified electrodes. However, the carbon nanotube directly used as the cathode material still has disadvantages, mainly including large first irreversible capacity, potential hysteresis, etc., which limits the practical application of the carbon nanotube. The hetero-atom doping of the carbon nanotube can effectively control the crystal and electronic structure of the carbon nanotube and improve the electrochemical performance of the pure carbon nanotube. Among various doping elements, boron can activate sp in a carbon structure because of only three valence electrons2Inert electrons generate a large amount of freely moving pi electrons, and the conductivity and the electrochemical performance of the carbon nano tube are effectively improved. At present, methods for compounding boron and carbon nanotubes mainly comprise a template method, a chemical vapor deposition method and a hydrothermal/solvothermal method combined with later-stage heat treatment, and the process is complex and time-consuming.
Disclosure of Invention
The invention aims to provide a boron-doped carbon nanotube film and a preparation method and application thereof, aiming at the technical defects in the prior art, the modification of the structure of a carbon nanotube is realized by effectively introducing a boron source, specifically, the one-step preparation method is realized by floating cracking, an organic metal compound is used as a catalyst, thiophene is used as a reaction promoter, the organic metal compound and the thiophene are dissolved in ethanol to form a precursor solution, the precursor solution and the precursor solution are injected into a vertical chemical vapor deposition furnace (CVD furnace) together, and catalyst particles float in a reaction gas H2In the carrier gas, a film-shaped product can be finally collected at the bottom of the hearth, so that the preparation is continuous and large-scale.
The technical scheme adopted for realizing the purpose of the invention is as follows:
a boron-doped carbon nanotube film comprises a bent short and thick tube with the diameter of 50-80nm and a long and straight carbon nanotube with the diameter of 15-25nm, wherein the bent short and thick tube is formed by stacking closely attached carbon cages;
the boron-doped carbon nanotube film is prepared by the following method:
In the above technical scheme, the inert protective gas is nitrogen, argon or helium. Preferably 100-.
In the above technical scheme, H is introduced in the step 32The speed of (1) is 700-900 sccm.
In the above technical scheme, the reaction time of step 3 is 10-30min, and the boron-doped carbon nanotube film is in the form of a cylindrical film.
In the technical scheme, the mass ratio of the ethanol, the ferrocene and the thiophene in the step 1 is 95:1.5:1, the boric acid in the step 1 is 3% of the mass of the mixed solution, and the injection rate in the step 3 is 10 mL/h.
In another aspect of the present invention, a method for preparing a boron-doped carbon nanotube film is further provided, which comprises the following steps:
In the above technical scheme, the inert protective gas is nitrogen, argon or helium. Preferably 100-.
In the above technical scheme, H is introduced in the step 32The speed of (1) is 700-900 sccm.
In the above technical scheme, the reaction time of step 3 is 10-30min, and the boron-doped carbon nanotube film is in the form of a cylindrical film.
In the technical scheme, the CVD furnace is sealed in a water seal or oil seal mode.
In the technical scheme, the CVD furnace is a vertical CVD furnace with an ultrasonic atomization device arranged at the top of a hearth.
In another aspect of the invention, the application of the boron-doped carbon nanotube film in a supercapacitor electrode is also included.
In the technical scheme, the mass specific capacitance of the boron-doped carbon nanotube film is 27.5-65.6F/g.
In the above technical solution, when the mass of the boric acid in the step 1 is 3 wt.% of the mixed solution, and the injection rate in the step 2 is 10mL/h, the mass specific capacitance of the boron-doped carbon nanotube film is 63-66F/g.
Compared with the prior art, the invention has the beneficial effects that:
1. the boron-doped carbon nanotube film is prepared by using ethanol as a carbon source, ferrocene as a catalyst, thiophene as an accelerator and boric acid as a boron source for reaction, so that the electrochemical performance of the carbon nanotube is improved.
2. Compared with the existing method for preparing the boron-doped carbon nanotube, the method has the advantages of simple process and low cost, and the obtained product is a membrane material, has good self-supporting property and can realize large-scale and continuous production.
3. The ultrasonic atomization device enables the precursor to be well dispersed, and contributes to the boron source to better participate in the growth of the carbon nano tube, so that the boron doping is effectively realized to improve the electrochemical performance of the carbon nano tube.
Drawings
Fig. 1 is a high power SEM image of a boron doped carbon nanotube film with a boron source content of 1 wt.% in example 1;
fig. 2 is a high power SEM image of a boron doped carbon nanotube film with a boron source content of 2 wt.% in example 2;
fig. 3 is a high power SEM image of a boron doped carbon nanotube film with a boron source content of 3 wt.% in example 3;
fig. 4 is a high power TEM image of a boron doped carbon nanotube film with a boron source content of 3 wt.% in example 3;
fig. 5 is a CV cyclic voltammogram of boron doped carbon nanotube films with boron source content of 1 wt.%, 2 wt.% and 3 wt.% in examples 1, 2 and 3, respectively, at a scan rate of 5 mv/s.
Fig. 6 is a constant current charge and discharge curve of boron doped carbon nanotube films with boron source content of 1 wt.%, 2 wt.% and 3 wt.% in examples 1, 2 and 3, respectively.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The ferrocene and the thiophene are produced by Tianjin photoresistive fine chemical research institute and are analytical pure reagents; the ethanol is produced by a Fochen chemical reagent factory in Tianjin, and is a high-grade pure reagent; the boric acid is produced by chemical reagents of Tianjin three factories, and the purity is 99.5 percent.
Example 1
(1) Completely sealing the vertical CVD furnace, continuously introducing 100sccm of Ar to completely remove the air in the furnace, heating the vertical CVD furnace to 1150 ℃ through a temperature controller, and preserving the temperature for 3 hours to provide a constant temperature environment for the subsequent growth of the carbon nanotube film;
(2) weighing ethanol, ferrocene and thiophene according to the mass ratio of 95:1.5:1, and mixing to obtain a solution, wherein the ethanol is used as a carbon source, the ferrocene is used as a catalyst, and the thiophene is used as an accelerator; adding 1 wt.% of boric acid as a boron source for reaction on the basis of the mixed solution, and continuously performing ultrasonic dispersion on the solution at the temperature of 50 ℃ for 30min to obtain uniform dispersion liquid, and transferring the uniform dispersion liquid to an injector to be used as a precursor solution;
(3) after the steps (1) and (2) are finished, Ar is closed, and H of 800sccm is continuously introduced2As reaction gas, up to H2The whole hearth is filled with the precursor solution, the injection speed is controlled at 10mL/h by an injection pump, and the precursor solution is injected into the furnace in uniformly dispersed mist-shaped liquid drops through an ultrasonic atomization device at the top of the vertical CVD furnace. And collecting a cylindrical film, namely the boron-doped carbon nanotube film, at the bottom of the hearth within 10min after the reaction starts.
Fig. 1 is a high power SEM image of a boron doped carbon nanotube film with a boron source content of 1 wt.% in example 1. As can be seen from the figure, the introduction of boron has a great influence on the structure of the carbon nanotube, and the bent short and thick tube accounts for the main part of the structure.
Example 2
(1) Completely sealing the vertical CVD furnace, continuously introducing 100sccm of Ar to completely remove the air in the furnace, heating the vertical CVD furnace to 1150 ℃ through a temperature controller, and preserving the temperature for 3 hours to provide a constant temperature environment for the subsequent growth of the carbon nanotube film;
(2) weighing ethanol, ferrocene and thiophene according to the mass ratio of 95:1.5:1, and mixing to obtain a solution, wherein the ethanol is used as a carbon source, the ferrocene is used as a catalyst, and the thiophene is used as an accelerator; adding 2 wt.% of boric acid as a boron source for reaction on the basis of the mixed solution, and continuously performing ultrasonic dispersion on the solution at the temperature of 50 ℃ for 30min to obtain uniform dispersion liquid, and transferring the uniform dispersion liquid to an injector to be used as a precursor solution;
(3) after the steps (1) and (2) are finished, Ar is closed, and H of 800sccm is continuously introduced2As reaction gas, up to H2Filling the whole hearth, and controlling the liquid injection speed by an injection pumpThe rate is 10mL/h, and the precursor solution is injected into the furnace in the form of uniformly dispersed mist drops through an ultrasonic atomization device at the top of the vertical CVD furnace. And collecting a cylindrical film, namely the boron-doped carbon nanotube film, at the bottom of the hearth within 10min after the reaction starts.
Fig. 2 is a high power SEM image of a boron doped carbon nanotube film with a boron source content of 2 wt.% in example 2. As can be seen from the figure, the number of bent short and thick tubes similar to that in example 1 is increased in proportion to the introduced amount of the boron source, and it is confirmed that the structure is indeed a change of the structure of the carbon nanotube caused by boron.
Example 3
(1) Completely sealing the vertical CVD furnace, continuously introducing 100sccm of Ar to completely remove the air in the furnace, heating the vertical CVD furnace to 1150 ℃ through a temperature controller, and preserving the temperature for 3 hours to provide a constant temperature environment for the subsequent growth of the carbon nanotube film;
(2) weighing ethanol, ferrocene and thiophene according to the mass ratio of 95:1.5:1, and mixing to obtain a solution, wherein the ethanol is used as a carbon source, the ferrocene is used as a catalyst, and the thiophene is used as an accelerator; adding 3 wt.% of boric acid as a boron source for reaction on the basis of the mixed solution, and continuously performing ultrasonic dispersion on the solution at the temperature of 50 ℃ for 30min to obtain uniform dispersion liquid, and transferring the uniform dispersion liquid to an injector to be used as a precursor solution;
(3) after the steps (1) and (2) are finished, Ar is closed, and H of 800sccm is continuously introduced2As reaction gas, up to H2The whole hearth is filled with the precursor solution, the injection speed is controlled at 10mL/h by an injection pump, and the precursor solution is injected into the furnace in uniformly dispersed mist-shaped liquid drops through an ultrasonic atomization device at the top of the vertical CVD furnace. And collecting a cylindrical film, namely the boron-doped carbon nanotube film, at the bottom of the hearth within 10min after the reaction starts.
Fig. 3 is a high power SEM image of a boron doped carbon nanotube film with a boron source content of 3 wt.% in example 3. It can be seen from the figure that, compared with the examples 1 and 2, in addition to a large number of bent short and thick tubes with the diameter of 50-80nm, the number of the thin long and straight carbon nanotubes (with the diameter of about 20 nm) is increased, which shows that the improvement of the introduction amount of the boron source has the promotion effect on the growth of the carbon nanotubes, and the existence of the long and straight carbon nanotubes also improves the mechanical strength of the membrane material, thereby being beneficial to continuous production.
Fig. 4 is a high power TEM image of a boron doped carbon nanotube film with a boron source content of 3 wt.%, and it can be seen that the curved stubby tube in the structure is actually formed by stacking closely adjacent carbon cages.
Fig. 5 shows CV cyclic voltammetry curves of the boron-doped carbon nanotube film at a scanning rate of 5mv/s after introduction of boron sources with different contents, and it can be seen that the boron-doped carbon nanotube film with a boron source content of 3 wt.% has the highest mass-to-capacitance, and can be calculated to be 65.6F/g by combining with the constant current charge-discharge curve of fig. 6, compared with 1 wt.% (27.5F/g) and 2 wt.% (34.5F/g), it can be known that the specific mass capacity of the boron-doped carbon nanotube film is improved with the increase of the boron introduction amount, which also indicates that the introduction of boron has a good influence on the electrochemical performance of the material.
The method for preparing the boric acid doped carbon nanotube film in one step by adopting the floating cracking in the vertical CVD furnace is suitable for all boron-containing carbon nanotube film materials in the system.
All the raw materials listed in the invention can realize the invention, and the upper and lower limit values and interval values of the raw materials can realize the invention, which are not illustrated in the specification.
The foregoing description of the embodiments is provided to facilitate an understanding and appreciation of the invention by those skilled in the art. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art should make improvements and modifications to the present invention based on the disclosure of the present invention within the protection scope of the present invention.
Claims (10)
1. The boron-doped carbon nanotube film is characterized in that the carbon nanotubes comprise bent short and thick tubes with the diameter of 50-80nm and long and straight carbon nanotubes with the diameter of 15-25nm, wherein the bent short and thick tubes are formed by stacking closely attached carbon cages;
the boron-doped carbon nanotube film is prepared by the following method:
step 1, weighing ethanol, ferrocene and thiophene according to the mass ratio of (90-100) to (1.3-1.7) to (0.5-1.5) to obtain a mixed solution, adding 1-3 wt.% of boric acid into the mixed solution, and uniformly dispersing at 40-60 ℃ to obtain a precursor solution;
step 2, completely sealing the CVD furnace, continuously introducing inert protective gas to exhaust air in the furnace, regulating the temperature of the CVD furnace to 1100-1200 ℃, and preserving the temperature for 2-5h to provide a constant temperature environment for the subsequent growth of the carbon nanotube film;
step 3, closing the inert protective gas and continuously introducing H2As reaction gas to H2Filling the whole hearth, injecting the precursor solution obtained in the step 1 into the furnace in the form of uniformly dispersed fog-like liquid drops through an ultrasonic atomization device at the liquid injection rate of 8-15mL/h, reacting at the temperature of 1100-.
2. The boron-doped carbon nanotube film of claim 1, wherein the inert shielding gas is nitrogen, argon or helium.
3. The boron-doped carbon nanotube film of claim 1, wherein the inert shielding gas is nitrogen, argon or helium, and H is introduced in the step 32The reaction time in the step 3 is 10-30min, and the boron-doped carbon nanotube film is in a cylindrical shape.
4. The boron-doped carbon nanotube film according to claim 1, wherein the mass ratio of ethanol, ferrocene and thiophene in the step 1 is 95:1.5:1, the boric acid in the step 1 is 3% of the mass of the mixed solution, and the injection rate in the step 3 is 10 mL/h.
5. The use of the boron-doped carbon nanotube film of claim 1 in a supercapacitor electrode, wherein the boron-doped carbon nanotube film has a mass specific capacitance of 27.5-65.6F/g.
6. The use of claim 5, wherein when the mass of the boric acid in the step 1 is 3 wt.% of the mixed solution, and the injection rate in the step 2 is 10mL/h, the mass specific capacitance of the boron-doped carbon nanotube film is 63-66F/g.
7. The preparation method of the boron-doped carbon nanotube film is characterized by comprising the following steps of:
step 1, weighing ethanol, ferrocene and thiophene according to the mass ratio of (90-100) to (1.3-1.7) to (0.5-1.5) to obtain a mixed solution, adding 1-3 wt.% of boric acid into the mixed solution, and uniformly dispersing at 40-60 ℃ to obtain a precursor solution;
step 2, completely sealing the CVD furnace, continuously introducing inert protective gas to exhaust air in the furnace, regulating the temperature of the CVD furnace to 1100-1200 ℃, and preserving the temperature for 2-5h to provide a constant temperature environment for the subsequent growth of the carbon nanotube film;
step 3, closing the inert protective gas and continuously introducing H2As reaction gas to H2Filling the whole hearth, injecting the precursor solution obtained in the step 1 into the furnace in the form of uniformly dispersed fog-like liquid drops through an ultrasonic atomization device at the liquid injection rate of 8-15mL/h, and collecting the boron-doped carbon nanotube film at the bottom of the hearth after the reaction is finished.
8. The method of claim 7, wherein the inert shielding gas is nitrogen, argon, or helium.
9. The method according to claim 7, wherein H is introduced in the step 32The reaction time in the step 3 is 10-30min, and the boron-doped carbon nanotube film is in a cylindrical shape.
10. The method according to claim 7, wherein the CVD furnace is a vertical CVD furnace having an ultrasonic atomizer at the top of the furnace chamber, and is sealed by water seal or oil seal.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112875681A (en) * | 2021-01-27 | 2021-06-01 | 常州大学 | Preparation method of modified carbon nanotube film/sulfur composite flexible positive electrode material and application of modified carbon nanotube film/sulfur composite flexible positive electrode material in flexible lithium-sulfur battery |
| CN115079338A (en) * | 2022-07-08 | 2022-09-20 | 湖北工业大学 | Nitrogen-doped carbon nanotube micro-nano optical fiber and gas sensor comprising same |
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