CN104030265B - Nitrogen-doped carbon nanometer pipe and preparation method thereof - Google Patents
Nitrogen-doped carbon nanometer pipe and preparation method thereof Download PDFInfo
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- CN104030265B CN104030265B CN201310068923.6A CN201310068923A CN104030265B CN 104030265 B CN104030265 B CN 104030265B CN 201310068923 A CN201310068923 A CN 201310068923A CN 104030265 B CN104030265 B CN 104030265B
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- carbon nanotube
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 42
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000007789 gas Substances 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 239000012265 solid product Substances 0.000 claims abstract description 17
- 230000004048 modification Effects 0.000 claims abstract description 16
- 238000012986 modification Methods 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 230000000802 nitrating effect Effects 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000010792 warming Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 26
- 229910052786 argon Inorganic materials 0.000 claims description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 239000004202 carbamide Substances 0.000 claims description 11
- 239000001307 helium Substances 0.000 claims description 11
- 229910052734 helium Inorganic materials 0.000 claims description 11
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000000034 method Methods 0.000 abstract description 13
- 239000004568 cement Substances 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000004146 energy storage Methods 0.000 description 8
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
Abstract
The present invention relates to a kind of nitrogen-doped carbon nanometer pipe and preparation method thereof, the method comprises the following steps: to be placed in by carbon nanotube under reactor plasma body 1 ~ 2 hour, to obtain the carbon nanotube of modification; The carbon nanotube of described modification is mixed with nitrating agent, dry after fully stirring, in reactor, pass into rare gas element, after making to form inert atmosphere in reactor, be warming up to 800 ~ 900 ° of C, after keeping 0.5 ~ 1h reaction, be down to room temperature; Cleaning is carried out and drying to the solid product of gained, obtains described nitrogen-doped carbon nanometer pipe.In nitrogen-doped carbon nanometer pipe of the present invention and preparation method thereof, the carbon nanotube defect through Cement Composite Treated by Plasma is more, and when carrying out N doping, nitrogen content is higher.And preparation method's cost of the present invention is low, easily realizes large-scale industrial production.
Description
Technical field
The present invention relates to chemical material synthesis field, particularly relate to a kind of nitrogen-doped carbon nanometer pipe and preparation method thereof.
Background technology
Nineteen nineties, carbon material has promoted ultracapacitor, the greatly developing of lithium ion battery as the use of energy storage material.And carbon nanotube is as a kind of carbon material of one dimension, there is very high specific conductivity, and carbon nanotube is very easy to derivatize, so its derivative is also subject to the extensive concern of investigator.
Carbon nano tube derivative mainly contains nitrogen-doped carbon nanometer pipe and boron doped carbon nanometer pipe.Wherein, the many electronics more outer than carbon atom of the nitrogen-atoms in nitrogen-doped carbon nanometer pipe, adulterates in N-type, compare the carbon nanotube not carrying out adulterating and there is better energy-storage property, and the nitrogen content of nitrogen-doped carbon nanometer pipe is higher, energy storage site is more, and its energy-storage property is also better.
At present, the method that the heavy industrialization easily realized prepares nitrogen-doped carbon nanometer pipe is high-temperature hot doping method, but the maximum at present problem of this method to be prepared nitrogen-doped carbon nanometer pipe nitrogen content lower.From the mechanism of N doping, N doping preferentially carries out at unordered place.Therefore, the disordered structure increased on carbon nanotube can have very great help to N doping.
Summary of the invention
The object of the invention is to solve above-mentioned prior art Problems existing and deficiency, provide a kind of nitrogen-doped carbon nanometer pipe and preparation method thereof, the carbon nanotube defect through Cement Composite Treated by Plasma is more, can reach higher nitrogen content when carrying out N doping reaction.
The present invention is directed to above-mentioned technical problem and the technical scheme proposed is: a kind of preparation method of nitrogen-doped carbon nanometer pipe, comprises the steps:
Carbon nanotube to be placed under reactor plasma body 1 ~ 2 hour, to obtain the carbon nanotube of modification;
The carbon nanotube of described modification is mixed with nitrating agent, dry after fully stirring, in reactor, pass into rare gas element, after making to form inert atmosphere in reactor, be warming up to 800 ~ 900 ° of C, after keeping 0.5 ~ 1h reaction, be down to room temperature;
Cleaning is carried out and drying to the solid product of gained, obtains described nitrogen-doped carbon nanometer pipe.
The purity of described carbon nanotube is 99%.
The power that sends of described helium gas plasma is 100 ~ 300W.
Described plasma body is argon plasma or helium gas plasma.
Described nitrating agent is ammoniacal liquor or urea, and the carbon nanotube of described modification and the mass ratio of nitrating agent are 1:1 ~ 1:5.
The time of described stirring is 2 hours, and temperature dry after described stirring is 80 DEG C, the dry time is 6h.
Described rare gas element is argon gas, nitrogen or helium, and flow velocity when described rare gas element passes into is 400ml/min.
The speed of described intensification is 5 ~ 20 DEG C/min.
The operation also dry to described solid product cleaning is as follows: described solid product being added concentration is filter after stirring 4 hours in the hydrochloric acid soln of 10%, cleaner with deionized water wash, is then placed in 60 ° of dry 12h of C vacuum drying oven.
The present invention also comprises the nitrogen-doped carbon nanometer pipe utilizing above-mentioned preparation method to obtain.
Compared with prior art, there is following advantage in nitrogen-doped carbon nanometer pipe of the present invention and preparation method thereof:
1. the carbon nanotube defect through Cement Composite Treated by Plasma is more, and when carrying out N doping, nitrogen content is higher.
2. preparation method's cost of the present invention is low, easily realizes large-scale industrial production.
3., compared with other preparation methods, equipment used of the present invention and technique are simple, convenient operation.
Embodiment
Below in conjunction with embodiment, elaboration is further given to the present invention.
Preparation technology's flow process of nitrogen-doped carbon nanometer pipe of the present invention is roughly as follows: carbon nanotube → modified carbon nano-tube → nitrogen-doped carbon nanometer pipe.
Particularly, the preparation process of nitrogen-doped carbon nanometer pipe of the present invention is divided into following steps:
(1) modified carbon nano-tube: by purity be 99% carbon nanotube be placed in that to send power be under the plasma body of 100 ~ 300W, reaction obtains the carbon nanotube of modification for 1 ~ 2 hour;
Wherein, plasma body is hydrogen plasma, argon plasma or helium gas plasma.
(2) nitrogen-doped carbon nanometer pipe is prepared: joined by the carbon nanotube of modification (carbon nanotube of modification and the mass ratio of nitrating agent are 1:1 ~ 1:5) in the reactor of the ethanol solution being dissolved with urea, abundant stirring after 2 hours at 80 DEG C dry 6h, being placed in flow velocity is heat up (temperature rise rate is 5 ~ 20 DEG C/min) to 800 ~ 900 ° of C after the inert gas atmosphere of 400ml/min, is down to room temperature after keeping 0.5 ~ 1h; The selection of reactor is not limited, is preferably test tube;
Wash away the impurity in gained solid product with the hydrochloric acid that concentration is 10% and filter, with solid product described in washed with de-ionized water, in the vacuum drying oven under 60 ° of C, drying 12 hours, obtains nitrogen-doped carbon nanometer pipe.
Wherein, nitrating agent is ammoniacal liquor or urea.
After the process of step (1) (by carbon nanotube through Cement Composite Treated by Plasma), carbon nanotube can produce more defect, follow-up carry out N doping reaction time, the nitrogen content of carbon nanotube can be improved.Nitrating agent urea can be reaction provides nitrogenous source, at high temperature reacts, better can improve the nitrogen content of nitrogen-doped carbon nanometer pipe through the carbon nanotube of modification and nitrogenous source, thus increases the energy storage site of nitrogen-doped carbon nanometer pipe, greatly improves its energy-storage property.
Below be specifically described with the preparation method of embodiment 1 ~ 4 to nitrogen-doped carbon nanometer pipe of the present invention again.
Embodiment 1
(1) modified carbon nano-tube: by purity be 99% carbon nanotube be placed in helium gas plasma under, power is adjusted to 100W, processes 2 hours, obtains modified carbon nanotube;
(2) nitrogen-doped carbon nanometer pipe is prepared: added by the carbon nanotube of modification (mass ratio of carbon nanotube and urea is 1:2) in the test tube of the ethanol solution being dissolved with ammoniacal liquor, stir 2 hours, drying 6 hours at being placed in 80 DEG C, be placed in the argon gas that flow velocity is 400ml/min again, form argon gas atmosphere, 800 ° of C are warming up to 20 ° of C/min temperature rise rates, and keep 1 hour, the argon gas atmosphere being 400ml/min at flow velocity drops to room temperature, the solid product of gained being added concentration is in the HCl solution of 10%, stir 4 hours, filter rear deionized water wash, solid product is placed in 60 ° of C vacuum drying ovens after dry 12 hours, obtain nitrogen-doped carbon nanometer pipe.
Embodiment 2
(1) modified carbon nano-tube: by purity be 99% carbon nanotube be placed in argon plasma under, power is adjusted to 150W, processes 1 hour, obtains modified carbon nanotube;
(2) nitrogen-doped carbon nanometer pipe is prepared: added by the carbon nanotube of modification and be dissolved with (mass ratio of carbon nanotube and urea is 1:3) in the ethanol solution of urea, stir 2 hours, drying 6 hours at being placed in 80 DEG C, be placed in the nitrogen that flow velocity is 400ml/min again, form nitrogen atmosphere, 850 ° of C are warming up to 10 ° of C/min temperature rise rates, and keep 0.5 hour, the nitrogen atmosphere being 400ml/min at flow velocity drops to room temperature, the solid product of gained being added concentration is in the HCl solution of 10%, stir 4 hours, filter rear deionized water wash, solid product is placed in 60 ° of C vacuum drying ovens after dry 12 hours, obtain nitrogen-doped carbon nanometer pipe.
Embodiment 3
(1) modified carbon nano-tube: by purity be 99% carbon nanotube be placed in helium gas plasma under, power is adjusted to 200W, processes 2 hours, obtains modified carbon nanotube;
(2) nitrogen-doped carbon nanometer pipe is prepared: added by the carbon nanotube of modification (mass ratio of carbon nanotube and urea is 1:5) in the test tube of the ethanol solution being dissolved with urea, stir 2 hours, drying 6 hours at being placed in 80 DEG C, be placed in the helium that flow velocity is 400ml/min again, form helium atmosphere, 800 ° of C are warming up to 5 ° of C/min temperature rise rates, and keep 0.5 hour, the helium atmosphere being 400ml/min at flow velocity drops to room temperature, the solid product of gained being added concentration is in the HCl solution of 10%, stir 4 hours, filter rear deionized water wash, solid product is placed in 60 ° of C vacuum drying ovens after dry 12 hours, obtain nitrogen-doped carbon nanometer pipe.
Embodiment 4
(1) modified carbon nano-tube: by purity be 99% carbon nanotube be placed in argon plasma under, power is adjusted to 300W, processes 1.5 hours, obtains modified carbon nanotube;
(2) nitrogen-doped carbon nanometer pipe is prepared: added by the carbon nanotube of modification and be dissolved with (mass ratio of carbon nanotube and urea is 1:1) in the ethanol solution of ammoniacal liquor, stir 2 hours, drying 6 hours at being placed in 80 DEG C, be placed in the argon gas that flow velocity is 400ml/min again, form argon gas atmosphere, 900 ° of C are warming up to 15 ° of C/min temperature rise rates, and keep 1 hour, the argon gas atmosphere being 400ml/min at flow velocity drops to room temperature, the solid product of gained being added concentration is in the HCl solution of 10%, stir 4 hours, filter rear deionized water wash, solid product is placed in 60 ° of C vacuum drying ovens after dry 12 hours, obtain nitrogen-doped carbon nanometer pipe.
Elemental composition analysis is carried out to nitrogen-doped carbon nanometer pipe obtained in above embodiment 1 to 4, draws the per-cent composition data of each principal element content in following table 1.
Table 1
| Carbon (%) | Nitrogen element (%) | Oxygen element (%) | |
| Embodiment 1 | 89 | 8.9 | 2.1 |
| Embodiment 2 | 87.7 | 10.4 | 1.9 |
| Embodiment 3 | 84.6 | 13.2 | 2.2 |
| Embodiment 4 | 90.3 | 8.1 | 1.6 |
Known from the data above table, higher according to the nitrogen content of the nitrogen-doped carbon nanometer pipe prepared by method of the present invention, all more than 8%, be up to 13.2%.This illustrates, nitrogen-doped carbon nanometer pipe energy storage site of the present invention is many, and energy-storage property is high.
Nitrogen-doped carbon nanometer pipe of the present invention and preparation method thereof, there is following advantage: the carbon nanotube defect through Cement Composite Treated by Plasma is more, when carrying out N doping, nitrogen content is higher, and preparation method's cost is low, easily realize large-scale industrial production, equipment and process used is simple, convenient operation.
Foregoing; be only preferred embodiment of the present invention; not for limiting embodiment of the present invention; those of ordinary skill in the art are according to central scope of the present invention and spirit; can carry out corresponding flexible or amendment very easily, therefore protection scope of the present invention should be as the criterion with the protection domain required by claims.
Claims (6)
1. a preparation method for nitrogen-doped carbon nanometer pipe, is characterized in that, comprises the steps:
Carbon nanotube to be placed under reactor plasma body 1 ~ 2 hour, to obtain the carbon nanotube of modification;
The carbon nanotube of described modification is mixed with nitrating agent, dry after fully stirring, in reactor, pass into rare gas element, after making to form inert atmosphere in reactor, be warming up to 800 ~ 900 DEG C, after keeping 0.5 ~ 1h reaction, be down to room temperature;
Cleaning is carried out and drying to the solid product of gained, obtains described nitrogen-doped carbon nanometer pipe;
Wherein, described plasma body is argon plasma or helium gas plasma, and the power that sends of described plasma body is 100 ~ 300W;
Described nitrating agent is ammoniacal liquor or urea, and the carbon nanotube of described modification and the mass ratio of nitrating agent are 1:1 ~ 1:5.
2. according to preparation method according to claim 1, it is characterized in that, the purity of described carbon nanotube is 99%.
3. preparation method according to claim 1, is characterized in that, the time of described stirring is 2 hours, and temperature dry after described stirring is 80 DEG C, the dry time is 6h.
4. preparation method according to claim 1, is characterized in that, described rare gas element is argon gas, nitrogen or helium, and flow velocity when described rare gas element passes into is 400mL/min.
5. preparation method according to claim 1, is characterized in that, the speed of described intensification is 5 ~ 20 DEG C/min.
6. preparation method according to claim 1, it is characterized in that, the operation also dry to described solid product cleaning is as follows: described solid product being added concentration is filter after stirring 4 hours in the hydrochloric acid soln of 10%, clean with deionized water wash again, be then placed in 60 DEG C of dry 12h of vacuum drying oven.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105399077A (en) * | 2015-12-09 | 2016-03-16 | 中南大学 | Preparation method of atom doped carbon material in physical field |
| CN106348277A (en) * | 2016-08-23 | 2017-01-25 | 石河子大学 | Heteroatom-doped carbon material and preparation method thereof |
| CN109529901A (en) * | 2018-11-12 | 2019-03-29 | 东莞理工学院 | Preparation method of nitrogen-doped carbon nanotube composite titanium dioxide composite material |
| CN110048128A (en) * | 2019-04-19 | 2019-07-23 | 江苏师范大学 | A kind of nitrogen-doped carbon nanometer pipe oxygen reduction electro-catalyst and preparation method thereof |
| CN117199282A (en) * | 2023-09-04 | 2023-12-08 | 中能鑫储(北京)科技有限公司 | Preparation method of nitrogen-doped high-conductivity nano composite material for aluminum ion battery |
| CN119890342A (en) * | 2025-03-27 | 2025-04-25 | 山东海化集团有限公司 | Preparation method and application of composite bipolar plate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1994875A (en) * | 2006-01-05 | 2007-07-11 | 三星电子株式会社 | Method for forming nitrogen-doped single-walled carbon nanotubes |
| CN102745679A (en) * | 2012-07-19 | 2012-10-24 | 南京邮电大学 | Method for preparing three-dimensional graphene-carbon nitrogen nanotube composite |
| CN102790224A (en) * | 2012-08-23 | 2012-11-21 | 上海第二工业大学 | Bamboo-joint-shaped nitrogen-doped carbon nano tube material and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1994875A (en) * | 2006-01-05 | 2007-07-11 | 三星电子株式会社 | Method for forming nitrogen-doped single-walled carbon nanotubes |
| CN102745679A (en) * | 2012-07-19 | 2012-10-24 | 南京邮电大学 | Method for preparing three-dimensional graphene-carbon nitrogen nanotube composite |
| CN102790224A (en) * | 2012-08-23 | 2012-11-21 | 上海第二工业大学 | Bamboo-joint-shaped nitrogen-doped carbon nano tube material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| "Production of graphene from graphite oxide using urea as expansion-reduction agent";Stephen Wakeland, et al.;《CARBON》;20100526;第48卷;Page3463-3470 * |
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