CN104310370B - Method for directly preparing carbon nanotube on surface of carbon carrier - Google Patents
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Abstract
The invention provides a method for directly preparing a carbon nanotube on the surface of a carbon carrier. The method comprises the following steps: (1) attaching a catalyst or a precursor of the catalyst onto the surface of the modified carbon carrier; and (2) enabling the modified carbon carrier with the catalyst or the precursor of the catalyst obtained in the step (1) to contact the mixed gas of reduction gas and carbon-source gas. The invention also provides a carbon nanotube prepared by the method.
Description
Technical field
The present invention relates to the preparation field of CNT, relate more specifically to one kind directly in carbonaceous carrier superficial growth carbon
The improved substrate method of nano-tube array, it belongs to the directly chemical vapor deposition in carbonaceous carrier superficial growth CNT
Method.
Background technology
CNT (Carbon Nanotube, CNT) makes it have because of its unique geometry and electronic band structure
The performances such as the mechanics of superelevation, conduction and heat conduction.Experiment records the tensile strength of multi-walled carbon nano-tubes more than 100GPa, and, reason
300GPa may be up to about by calculating the tensile strength predicting some CNTs.Young's moduluss extend more than 1.0TPa, maximum
Rate is up to 10～12%.In addition, CNT electrical conductivity is up to 105Scm-1, it is 1000 times of carbon fiber.The heat conduction of CNT
Rate is up to 3000Wm-1K-1So as to become excellent Heat Conduction Material.The aerial heat stability of CNT is (in atmosphere
Less than 500 DEG C are substantially not oxidized) make it become excellent fire-retardant (Flame Retardant) material.
At present, many researcheres are in sapphire substrates, silicon base, quartz substrate, substrate of glass, metal coating substrate
And carbon nano pipe array is grown on carbon fiber paper substrate.Wherein it is possible to by chemical vapour deposition technique (CVD) directly in carbon
Fiber surface prepares CNT, specifically can be carried out using substrate method or flow method.
Substrate method, also known as the seed law, is that catalyst particle is supported on carbon fiber reinforced substrate, and the kind becoming vapor phase growth is brilliant
(seeding), the carbon fiber being attached with catalyst precursor is placed in stove, then high temperature leads to hydrogen by catalyst precursor also
Originally it was catalyst granules, then was passed through carbon source to grow CNT under the catalytic action of catalyst.Flow method is also referred to as floating catalytic
Agent method, refers to that catalyst particle swims in reactor, contacts with raw material carbon source gas, by the reduction step of catalyst and carbon nanometer
The growth step of pipe unites two into one, using shorten catalyst and the method for carbon fiber directly contact time reduce catalyst component and
The amount of the phase counterdiffusion of carbon in carbon fiber.
In this area, reduction for carbonaceous carrier mechanical performance degree of injury and directly preparing on carbonaceous carrier surface
The modified chemical vapor deposition process (MCVD) of CNT still suffers from demand.
Content of the invention
The invention provides a kind of method directly preparing CNT on carbonaceous carrier surface, comprise the following steps：
1) catalyst or its precursor is made to be attached to modified carbonaceous carrier surface；
2) make step 1) the modified carbonaceous carrier contact reducibility gas being attached with catalyst or its precursor of gained
Gaseous mixture with carbon-source gas.
In embodiments of the invention, described modified carbonaceous carrier surface preferably has such pore-size distribution：
Wherein at least 50%, more preferably at least 60%, even more desirably at least 70% hole, such as at least 75% hole, there is 50nm-10
μm, particularly 0.5-2 μm of aperture.
In one embodiment of the invention, preferably up to 50%, more preferably up to 40%, even more preferably at most
30% hole, such as at most 25% hole, there is the aperture less than 50nm.
Generally, it is preferred to such modified carbonaceous carrier, wherein minimum hole is at least than the nano-sized carbon growing wherein
Big 10 times of the diameter of structure.
In one embodiment of the invention, described modified carbonaceous carrier attached catalyst or its precursor it
Before, also through pretreatment, such as acid treatment.
Described acid treatment includes for described carbonaceous carrier impregnating such as 1 minute to 12 hours in acid, such as 5 minutes to 5
Hour, such as 5 minutes, 10 minutes, 15 minutes, 20 minutes, 30 minutes, 1,2,3,4 or 5 hours.
Described acid can be selected from hydrochloric acid, sulphuric acid, nitric acid, acetic acid, oxalic acid, sulfonic acid, selenic acid, or its two or more mixing
Thing.For example, one of concentrated hydrochloric acid, concentrated sulphuric acid, concentrated nitric acid or its two or more mixed acid, such as concentrated hydrochloric acid and concentrated nitric acid
Mixed acid of mixed acid, concentrated sulphuric acid and concentrated nitric acid etc..
In described mixed acid, the volume ratio of each acid can be arbitrary proportion, for example, when described mixed acid is concentrated nitric acid and dense
The mixture of sulphuric acid, or for concentrated hydrochloric acid and concentrated nitric acid mixture when, the wherein volume ratio of concentrated nitric acid and concentrated sulphuric acid or concentrated hydrochloric acid
Volume ratio with concentrated nitric acid can be 1:10 to 10:1, such as 1:1、2:1、3:1、4:1、5:1 or 1:2、1:3、1:4、1:5.
In a specific embodiment, by carbonaceous carrier in mixed acid (concentrated nitric acid:Concentrated sulphuric acid=3:1) 30 points of dipping in
Clock.
In a specific embodiment, step 1) include for modified carbonaceous carrier being immersed in catalyst or its precursor
Solution in, be then dried.
Preferably, the solution concentration of described catalyst or its precursor be 0.05-500mM, such as 0.1-300mM or 1 to
200mM, dip time is such as 1 minute to 12 hours, such as 1 minute to 5 hours, such as 5 minutes, 10 minutes, 15 minutes, 20 points
Clock, 30 minutes, 1,2,3 or 4 hours.
The temperature of described drying is such as 50 DEG C to 140 DEG C, preferably 60 DEG C to 120 DEG C, such as 70 DEG C to 110 DEG C, 80 DEG C
To 100 DEG C.Preferably 1 hour to 20 hours drying time, more preferably 3 to 15 hours, such as 5 hours to 10 hours.
In embodiments of the invention, step 2) include at 500 to 1000 DEG C, such as 600 DEG C, 650 DEG C, 700 DEG C,
It is passed through reducibility gas (such as hydrogen) and carbon-source gas (such as acetylene) at a temperature of 750 DEG C, 800 DEG C or 900 DEG C, make catalysis
Agent reduction process and carbon nanotube growth process are carried out simultaneously.
In one embodiment of the invention, each lead into reducibility gas and carbon-source gas, wherein said also
The flow-rate ratio of originality gas and carbon-source gas is 200:30 to 200:100, such as 200:50 to 200:80.
In one embodiment of the invention, the precursor of described catalyst can be metal-oxide, metal nitrogen
Compound, metal carbides, the inorganic acid salt of metal, the acylate of metal, the acetylacetonate of metal or its mixture, example
As being selected from nitrate, acetate, acetylacetonate, oxalates or citrate.Preferably Fe (III), the nitric acid of Co or Ni
Salt, acetate or its mixture, such as ferric nitrate.
In embodiments of the invention, described modified carbonaceous carrier by porous carrier materials (as plant origin
Activated carbon), through crushing or pulverizing, screen and calcining step preparation；Or, by vegetable active charcoal raw material (as palm kernel shell
Itself), through crushing or pulverizing, screen, extracting and carburising step preparation.
For example, described modified carbonaceous carrier can be by following method A) or B) preparation：
Method A)：
The activated carbon of porous carrier materials, particularly plant origin
- optionally crushed or pulverizing
- optionally through size selecting step as screened, to obtain particle diameter distribution evenly (e.g., from about 0.5mm, about
0.45mm), and
- calcining, at preferred 300-700 DEG C, more preferably 350-500 DEG C preferably in moving air, such as 450 DEG C of temperature
Under；Calcination time preferably 1 hour to 20 hours, more preferably 3 to 15 hours, such as 5 hours to 10 hours.
Method B)：
From the beginning of the raw material of vegetable active charcoal, such as palm kernel shell itself.These shells
- preferably crushed or pulverizing
- and then step is selected as screened by preferred size, to obtain particle diameter distribution evenly,
- so that the shell granule obtaining is processed through leach step in the presence of nitrogen or metal hydroxidess in the basic conditions,
The hydroxide such as NaOH of described metal hydroxidess preferred as alkali.
Described ammonia or alkali metal hydroxide preferably use (such as 6N to have at least centinormal 1 aqueous solution of 1N
NH3、6N NaOH).Described leach step is preferably carried out, more preferably at 40-80 DEG C at room temperature or higher than at a temperature of room temperature.
Depending on the temperature using, suitable extraction time is 30 minutes -1 day, preferably 1 hour -10 hours.Recommend described in quick stirring
Mixture.The volume range of carbon source/leaching agent is preferably 1:0.1-1:10, particularly 1:0.8-1:7 (such as 1:5).
Carry out following washing step preferably by suitable equipment, preferably by apparatus,Soxhlet'ses in a long time
(such as 1 hour, one week, such as 24 hours).Can be molten in suitable aromatic series (as dimethylbenzene) or alcohols after this washing step
Carry out the second washing step, it all preferably heats before use in agent (as ethanol).
- carry out following carburising step in stove in noble gases.Preferably described noble gases are flowings.Suitable bar
Part includes the N of such as 200ml/min2.With the rate of heat addition of preferred 3K-7K/min by stove heat to preferred 300-430 DEG C, more excellent
Select 330-400 DEG C of final temperature, and be maintained at final temperature for a period of time, preferably 1 hour to 20 hours, more preferably 3 to 15
Hour, such as 5 hours to 10 hours.
Using said method A) or the purpose of size selecting step B) be to separate be situated between sight or nano-carrier.For example, lead to
Cross containing in the water as flotation aid or aliphatic alcohol (such as ethanol) for the suitable surfactant, divided by flotation step
From these parts.
The present invention also provides the CNT being prepared by said method.
The beneficial effects of the present invention is：
1) method of the present invention had both expanded the specific surface area of catalyst layer, improve carbonaceous carrier to catalyst premise again
Adhesion property, significantly improve coverage rate and the coverage speed of catalyst precarsor.
3) method of the present invention carries out the growth of CNT while reducing catalyst, reduces catalyst and carbonaceous carries
The phase counterdiffusion of body.
4) method of the present invention reduces the damage of carbonaceous carrier, directly carbonaceous carrier surface prepare even compact and
The carbon nano pipe array that directionality are preferable, defect is less, and hence improve the performance of nano-sized carbon.
5) method of the present invention is simple, is easily controlled, low cost, be conducive to large area, production in enormous quantities it is easy to after
Continuous utilization.
Specific embodiment
Embodiment 1
1) will buy from the catalysis/carrier activated carbon pulverizing of Shanghai Xi Tan Environmental Protection Technology Co., Ltd, screening to be put down
All particle diameter is the activated carbon of about 0.45mm.Calcine 5 hours at 450 DEG C in atmosphere, to obtain pore volume as 0.6cm3/ g's
Modified activated carbon.
2) use the modified activated carbon of gained to prepare modified carbonaceous carrier, and put it into dipping in concentrated sulphuric acid
20min, washing, it is dried 1 hour at 100 DEG C.By the nitrogen adsorption methods under 77K (using Gao Bo as precise and tiny in Beijing science
The analyser of Technology Co., Ltd.) measure its pore-size distribution, wherein about 80% hole has 0.5-2 μm of an aperture, and at most 20%
Hole there is the aperture less than 50nm.By the carbonaceous carrier of drying 100mM Fe (NO3)3Aqueous solution in impregnate 3 hours.
Subsequently, it is dried 5 hours at a temperature of 80 DEG C in atmosphere.Measure its surface area by the BET under 77K, nitrogen to be about
3000m2/g.
3) dried carbonaceous carrier is lain in quartz ampoule, heat under inert gas atmosphere；When temperature is increased to
It is incubated half an hour after 750 DEG C, is passed through 200sCCm hydrogen and 50sCCm acetylene simultaneously, keep quartzy intraductal pressure to be 3KPa；30 points
After clock, hydrogen and acetylene are entered gas circuit to close, quartz ampoule drops to room temperature in the protection of noble gases.Described step effectively drops
The low damage of carbonaceous carrier, directly in the carbon that even compact is prepared on carbonaceous carrier surface and directionality are preferable, defect is less
Nano-tube array, and hence improve the performance (being shown in Table 2) of CNT.
Comparative example 1
Carried out according to embodiment 1, except that not carrying out step 1) and in step 2) in using non-modified work
Property charcoal prepares carbonaceous carrier.
Embodiment 2-4
Carried out according to embodiment 1, difference is listed in Table 1 below.
Table 1
The performance test results of the CNT obtained by the embodiment of the present invention and comparative example are listed in Table 2 below.
The mechanical property of table 2 carbon nano-tube material
Claims (51)
1. a kind of method directly preparing CNT on carbonaceous carrier surface, comprises the following steps：
1) catalyst or its precursor is made to be attached to modified carbonaceous carrier surface；
2) make step 1) the modified carbonaceous carrier contact reducibility gas and the carbon that are attached with catalyst or its precursor of gained
The gaseous mixture of source gas；
Wherein, described modified carbonaceous carrier, by the activated carbon of plant origin, through crushing or pulverizing, screens and calcining step
Preparation；
Described modified carbonaceous carrier surface has such pore-size distribution：The hole of wherein at least 70% has 50nm-10 μm
Aperture.
2. method according to claim 1 is it is characterised in that described modified carbonaceous carrier surface has such hole
Footpath is distributed：The hole of wherein at least 75% has 0.5-2 μm of aperture.
3. method according to claim 2 is it is characterised in that at most 40% hole has the aperture less than 50nm.
4. method according to claim 2 is it is characterised in that at most 30% hole has the aperture less than 50nm.
5. method according to claim 2 is it is characterised in that at most 25% hole has the aperture less than 50nm.
6., it is characterised in that described modified carbonaceous carrier, wherein minimum hole is extremely for method according to claim 5
Few bigger than the diameter of the carbon structural nano growing wherein 10 times.
7. method according to claim 6 it is characterised in that described modified carbonaceous carrier attached catalyst or its
Before precursor, also through peracid treatment.
8. method according to claim 7 is it is characterised in that described acid treatment includes soaking described carbonaceous carrier in acid
Stain 1 minute to 12 hours.
9. method according to claim 7 is it is characterised in that described acid treatment includes soaking described carbonaceous carrier in acid
Stain 5 minutes to 5 hours.
10. method according to claim 7 is it is characterised in that described acid treatment is included described carbonaceous carrier in acid
Dipping 5 minutes, 10 minutes, 15 minutes, 20 minutes, 30 minutes, 1,2,3 or 4 hours.
11. methods according to any one of claim 7-10 it is characterised in that described acid selected from hydrochloric acid, sulphuric acid, nitric acid,
Acetic acid, oxalic acid, sulfonic acid, selenic acid, or its two or more mixture.
12. methods according to claim 11 are it is characterised in that described acid is in concentrated hydrochloric acid, concentrated sulphuric acid, concentrated nitric acid
A kind of or its two or more mixed acid.
13. methods according to claim 11 it is characterised in that described acid selected from concentrated hydrochloric acid and concentrated nitric acid mixed acid or
Concentrated sulphuric acid and the mixed acid of concentrated nitric acid.
14. methods according to claim 13 it is characterised in that the volume ratio of concentrated nitric acid and concentrated sulphuric acid or concentrated hydrochloric acid with
The volume ratio of concentrated nitric acid is 1:10 to 10:1.
15. methods according to claim 13 it is characterised in that the volume ratio of concentrated nitric acid and concentrated sulphuric acid or concentrated hydrochloric acid with
The volume ratio of concentrated nitric acid is 1:1、2:1、3:1、4:1、5:1 or 1:2、1:3、1:4、1:5.
16. methods according to claim 15 are it is characterised in that described acid treatment is included carbonaceous carrier in concentrated nitric acid:
Concentrated sulphuric acid=3:Impregnate 30 minutes in 1 mixed acid.
17. methods according to claim 1-10 and any one of 12-16 are it is characterised in that step 1) including will be modified
Carbonaceous carrier be immersed in catalyst or the solution of its precursor, be then dried.
18. methods according to claim 11 are it is characterised in that step 1) include being immersed in modified carbonaceous carrier
In the solution of catalyst or its precursor, then it is dried.
19. methods according to claim 17 are it is characterised in that the solution concentration of described catalyst or its precursor is
0.05-500mM.
20. methods according to claim 18 are it is characterised in that the solution concentration of described catalyst or its precursor is
0.05-500mM.
21. methods according to claim 19 or 20 are it is characterised in that the solution concentration of described catalyst or its precursor is
0.1-300mM.
22. methods according to claim 21 it is characterised in that described catalyst or its precursor solution concentration be 1 to
200mM.
23. methods according to claim 22 are it is characterised in that the dip time of described catalyst or its precursor is 1 point
Clock was to 12 hours.
24. methods according to claim 22 are it is characterised in that the dip time of described catalyst or its precursor is 1 point
Clock was to 5 hours.
25. methods according to claim 22 are it is characterised in that the dip time of described catalyst or its precursor is 5 points
Clock, 10 minutes, 15 minutes, 20 minutes, 30 minutes, 1,2,3 or 4 hours.
26. methods according to any one of claim 23-25 are it is characterised in that the temperature of described drying is 50 DEG C to 140
℃.
27. methods according to claim 26 are it is characterised in that the temperature of described drying is 60 DEG C to 120 DEG C.
28. methods according to claim 26 are it is characterised in that the temperature of described drying is 70 DEG C to 110 DEG C.
29. methods according to claim 26 are it is characterised in that the temperature of described drying is 80 DEG C to 100 DEG C.
30. methods according to claim 29 are it is characterised in that drying time is 1 hour to 20 hours.
31. methods according to claim 29 are it is characterised in that drying time is 3 to 15 hours.
32. methods according to claim 29 are it is characterised in that drying time is 5 to 10 hours.
33. methods according to claim 1-10,12-16, any one of 18-20,22-25 and 27-32 it is characterised in that
The precursor of catalyst be metal-oxide, metal nitride, metal carbides, the inorganic acid salt of metal, the acylate of metal,
The acetylacetonate of metal or its mixture.
34. methods according to claim 11 are it is characterised in that the precursor of catalyst is metal-oxide, nitride metal
Thing, metal carbides, the inorganic acid salt of metal, the acylate of metal, the acetylacetonate of metal or its mixture.
35. methods according to claim 17 are it is characterised in that the precursor of catalyst is metal-oxide, nitride metal
Thing, metal carbides, the inorganic acid salt of metal, the acylate of metal, the acetylacetonate of metal or its mixture.
36. methods according to claim 21 are it is characterised in that the precursor of catalyst is metal-oxide, nitride metal
Thing, metal carbides, the inorganic acid salt of metal, the acylate of metal, the acetylacetonate of metal or its mixture.
37. methods according to claim 26 are it is characterised in that the precursor of catalyst is metal-oxide, nitride metal
Thing, metal carbides, the inorganic acid salt of metal, the acylate of metal, the acetylacetonate of metal or its mixture.
38. methods according to claim 33 are it is characterised in that the precursor of catalyst is Fe (III), the nitric acid of Co or Ni
Salt, acetate or its mixture.
39. methods according to any one of claim 34-37 are it is characterised in that the precursor of catalyst is Fe (III), Co
Or the nitrate of Ni, acetate or its mixture.
40. methods according to claim 38 are it is characterised in that the precursor of catalyst is ferric nitrate.
41. methods according to claim 39 are it is characterised in that the precursor of catalyst is ferric nitrate.
42. methods according to claim 40 or 41 are it is characterised in that step 2) temperature that includes at 500 to 1000 DEG C
Under be passed through reducibility gas and carbon-source gas, so that catalyst reduction process and carbon nanotube growth process is carried out simultaneously.
43. methods according to claim 42 are it is characterised in that step 2) include 600 DEG C, 650 DEG C, 700 DEG C, 750
DEG C, be passed through reducibility gas and carbon-source gas at a temperature of 800 DEG C or 900 DEG C, make catalyst reduction process and CNT life
Growth process is carried out simultaneously.
44. methods according to claim 42 it is characterised in that described reducibility gas be hydrogen, described carbon-source gas
For acetylene.
45. methods according to claim 43 it is characterised in that described reducibility gas be hydrogen, described carbon-source gas
For acetylene.
46. methods according to claim 44 or 45 it is characterised in that each leading into reducibility gas and carbon-source gas,
The flow-rate ratio of wherein said reducibility gas and carbon-source gas is 200:30 to 200:100.
47. methods according to claim 46 are it is characterised in that the flow-rate ratio of described reducibility gas and carbon-source gas is
200:50 to 200:80.
48. methods according to claim 47 are it is characterised in that described modified carbonaceous carrier is with by following method
A) prepare：
Method A)：
Porous carrier materials
- crushed or pulverizing
- through screening, to obtain particle diameter distribution evenly, and
- calcining, in moving air at a temperature of 350-500 DEG C；Calcination time is 1 hour to 20 hours.
49. methods according to claim 48 are it is characterised in that method A) calcining heat be 450 DEG C, calcination time is
3 to 15 hours.
50. methods according to claim 48 are it is characterised in that method A) calcination time be 5 to 10 hours.
A kind of 51. CNTs, its method described in any one of claim 1-50 prepares.
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| CN107195876B (en) * | 2017-04-27 | 2019-11-12 | 华中科技大学 | A kind of preparation method and sodium-ion battery of Nanoscale Iron selenium sulfide |
| CN109560270B (en) * | 2018-11-19 | 2022-04-05 | 肇庆市华师大光电产业研究院 | Se @ CNT/CP self-supporting flexible electrode material, preparation method and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101329924A (en) * | 2008-07-30 | 2008-12-24 | 中国科学院山西煤炭化学研究所 | Method for preparing high performance electrode material |
| CN101671951A (en) * | 2009-09-23 | 2010-03-17 | 北京航空航天大学 | Method of carbon nanotube for modifying polyacrylonitrile-based carbon fiber interface produced in China |
| CN102145884A (en) * | 2010-11-25 | 2011-08-10 | 中国科学院山西煤炭化学研究所 | Method for preparing composite carbon material with high specific surface area |
| CN103121674A (en) * | 2013-01-28 | 2013-05-29 | 江苏国正新材料科技有限公司 | Preparation method of high-strength and low ash content palm shell activated carbon |
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| FR2949075B1 (en) * | 2009-08-17 | 2013-02-01 | Arkema France | FE / MO SUPPORTED CATALYST, PROCESS FOR PREPARING THE SAME, AND USE IN THE MANUFACTURE OF NANOTUBES |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101329924A (en) * | 2008-07-30 | 2008-12-24 | 中国科学院山西煤炭化学研究所 | Method for preparing high performance electrode material |
| CN101671951A (en) * | 2009-09-23 | 2010-03-17 | 北京航空航天大学 | Method of carbon nanotube for modifying polyacrylonitrile-based carbon fiber interface produced in China |
| CN102145884A (en) * | 2010-11-25 | 2011-08-10 | 中国科学院山西煤炭化学研究所 | Method for preparing composite carbon material with high specific surface area |
| CN103121674A (en) * | 2013-01-28 | 2013-05-29 | 江苏国正新材料科技有限公司 | Preparation method of high-strength and low ash content palm shell activated carbon |
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Effective date of registration: 20210902 Address after: 201207 first floor, 276 Edison Road, pilot Free Trade Zone, Pudong New Area, Shanghai Patentee after: 4MICRO TECHNOLOGY Co.,Ltd. Address before: 100070 2-1102, zeliu, Yihai Garden, Fengtai District, Beijing Patentee before: Zhang Yingbo |