CN103253647B - Preparation method for directly growing high density carbon nanotube array on carbon fiber paper base bottom - Google Patents
Preparation method for directly growing high density carbon nanotube array on carbon fiber paper base bottom Download PDFInfo
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- CN103253647B CN103253647B CN201210448832.0A CN201210448832A CN103253647B CN 103253647 B CN103253647 B CN 103253647B CN 201210448832 A CN201210448832 A CN 201210448832A CN 103253647 B CN103253647 B CN 103253647B
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Abstract
The invention discloses a preparation method for directly growing high density carbon nanotube array on carbon fiber paper base bottom. The method is a chemical vapor deposition method. Firstly, iron (Fe), cobalt (Co) and nickel (Ni) element containing sol is prepared and coated on carbon fiber paper after pretreatment. The carbon fiber paper base bottom formed with catalyst precursor is placed in the vacuum furnace chamber, and the substrate is heated to a first temperature and maintained for a predetermined time; with the protection gas, the reduction gas is let into the reacting furnace, and the substrate formed with catalyst precursor is heated to a second temperature and maintained for a predetermined time; the mixture of protection gas and carbon source gas is let into the reacting furnace, and is heated to a third temperature, and the high density carbon nanotube array is grown on the surface of the substrate catalyst. The carbon nanotube array can be directly grown on the carbon fiber paper base bottom according to the method, and can be used as electrode material of green energy storage device fuel cell and super capacitor.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, particularly a kind of method of direct growth carbon nano pipe array in carbon fiber paper substrate.
Background technology
Carbon nanotube is typical monodimension nanometer material, receives much concern due to the structure of its uniqueness, excellent physics, chemical property and wide application prospect.Carbon nanotube has good charge transport properties, and the electrode materials that can be used as green energy storage device promotes transfer transport, as fuel cell, ultracapacitor, all-vanadium flow battery and organic solar batteries, is with a wide range of applications.
Usually the carbon nanotube prepared is non-orientation, in being wound around shape, the caliber of carbon nanotube excellence when specific surface area is all had a greatly reduced quality, and the excellent properties of many one-dimensional materials can not get effectively playing, and has had a strong impact on character research and the practical application of carbon nanotube.Therefore, explore the method for the carbon nano pipe array of preparation favorable orientation, tool is of great significance.At present, many investigators grow carbon nano pipe array in silicon base, quartz substrate and other metal coating substrate.Ren ZF (Science 1998; 282:1105-7) with Fan SS (Science 1999; Array of multi-walled carbon nanotubes is grown on 283:512-4) respectively at the bottom of glass and porous silicon-base.But catalyst preparation process is complicated, substrate is nonconducting board-like material, needs the electrode materials that just can be applied as the energy storage devices such as fuel cell through transfer.Chinese patent (2008201367639) discloses a kind of novel array electrode, and conducting base relates to titanium, aluminium, copper, tantalum, tungsten, conductive plastics or conductive rubber etc., does not relate to carbon paper substrate.Chinese patent (200710118930.7) discloses a kind of preparation method of high-orientation carbon nanotube film, and carbon nano-tube solution spreads on substrate by the method, applies high-voltage electric field simultaneously.The method preparation process requires harsh, and wayward, cost is high.Chinese patent (200710118930.7) discloses a kind of method preparing carbon nano pipe array based on chemical vapour deposition, adopts synthetic gas as carbon source, carbon nano-tube on non-conductive matrix.Although this method reduce the cost preparing carbon nanotube, be unfavorable for producing high-quality carbon nano pipe array.Non-conductive matrix can not directly as the electrode materials of the energy storage device such as fuel cell, ultracapacitor.
Therefore, provide that a kind of operation is simple, high-density, can directly to grow on conductive substrates carbon paper, the preparation method being adapted at the carbon nano pipe array of industrial large-scale mass production is very necessary.
Summary of the invention
Using carbon fiber paper as substrate; Form catalyst precursor at substrate surface, described catalyzer can contain Fe, Co, Ni element respectively; The described carbon fiber paper substrate being formed with catalyst precursor is placed in Reaktionsofen, heats described substrate to the first temperature and keep the scheduled time, to remove the organism in catalyst precursor; Under a shielding gas, in Reaktionsofen, pass into reducing gas, the described substrate being formed with catalyst precursor is heated to the second temperature and keeps the scheduled time, to make Fe, Co, Ni element reduction in catalyst precursor; In Reaktionsofen, pass into the gas mixture of shielding gas and carbon-source gas, and be heated to the 3rd temperature, grow high-density carbon nano-tube array at the catalyst surface of described substrate.
The invention has the advantages that the preparation method of proposition is the caliber being controlled carbon nanotube by the catalyst particle size of control deposition of carbon nanotubes, the catalyst particle size of deposition of carbon nanotubes can be controlled by the processing parameter preparing sol solution.Compared to prior art, catalyst precursor prepared by sol-gel method directly can be coated in carbon paper surface, and this method is simple, easily controls, and cost is low, is conducive to big area, production in enormous quantities, is easy to later use.Make this carbon nanotube/carbon paper complex body have larger range of application, as the electrode materials of fuel cell, ultracapacitor and all-vanadium flow battery, and be adapted at industrial batch production.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the carbon nano pipe array of the inventive method
Embodiment
The ultrasonic cleaning dry stand-by one by one of carbon paper dilute hydrochloric acid, acetone, alcohol, deionized water.Fe, Co, Ni acid salt solution of different concns and organic solvent are mixed with out colloidal sol.Spin-coating method or dip-coating method is adopted to be deposited on carbon fiber paper substrate the colloidal sol prepared.The spin coating rotating speed of spin-coating method is 4000-5000 rev/min, and spin-coating time is 30 seconds-2 minutes.The pull rate of dip-coating method is 10-20cm/ minute.Wet film is repeated impregnations lift after 100 DEG C of thermal treatment, and lift number of times is 3-10 time.
The described carbon fiber paper substrate being formed with catalyst precursor is placed in Reaktionsofen, direct growth carbon nano pipe array in chemical gas-phase deposition system: concrete preparation comprises the following steps:
(1) be placed in the chamber of chemical gas-phase deposition system by the carbon fiber paper scribbling colloidal sol, start to heat up, target temperature is 300-500 DEG C, and the hold-time is 10-120 minute.
(2) furnace temperature rises to 400 DEG C-600 DEG C, passes into shielding gas and reducing gas, and the hold-time is 30-120 minute.Shielding gas is nitrogen, argon gas or their mixture.Reducing gas is hydrogen.
(3) furnace temperature is continued to rise to 750-900 DEG C, pass into carbon-source gas, as methane, ethane, acetylene, ethene or their mixture.Hold-time is 15-90 minute.Wherein the volume ratio of shielding gas and carbon-source gas is 1-1: 10.
Be described below in conjunction with concrete enforcement.
Example 1
By the ultrasonic cleaning dry stand-by one by one of carbon paper dilute hydrochloric acid, acetone, alcohol, deionized water.With 2M Fe (NO
3)
3solution and tetraethoxy prepare colloidal sol, and adopt spin-coating method colloidal sol to be coated in equably carbon fiber paper surface preparation, spin coating rotating speed preferably 4000 revs/min in this example, spin-coating time is preferably 1 minute.Be placed in the chamber of chemical gas-phase deposition system by scribbling containing the carbon fiber paper of Fe elemental sols, start to heat up, target temperature is 300 DEG C, and the hold-time is 1 hour; Furnace temperature continues to rise to 500 DEG C, passes into reducing gas hydrogen, and the hold-time is 60 minutes; Furnace temperature continues to rise to 900 DEG C, passes into methane and nitrogen simultaneously.Hydrogen: methane: nitrogen ratios is 1: 4: 10.Control the closed degree of vacuum butterfly valve, guarantee that the air pressure of whole reaction process is at about 400Pa; React after 30 minutes, grow complete.Stop gas passing into, be cooled to less than 100 DEG C, take out sample and preserved.
Example 2
Carbon paper preprocessing process is with example 1.With 1.5M Fe (NO
3)
3solution and tetraethoxy prepare colloidal sol, and adopt dip-coating method colloidal sol to be coated in equably carbon fiber paper surface preparation, in this example, pull rate is 10cm/ minute.Wet film is repeated impregnations lift after 100 DEG C of thermal treatment, and lift number of times is 5 times.Be placed in the chamber of chemical gas-phase deposition system by scribbling containing the carbon fiber paper of Fe elemental sols, start to heat up, target temperature is 300 DEG C, and the hold-time is 1 hour; Furnace temperature continues to rise to 500 DEG C, passes into reducing gas hydrogen, and the hold-time is 60 minutes; Furnace temperature continues to rise to 900 DEG C, passes into methane and nitrogen simultaneously.Hydrogen: methane: nitrogen ratios is 1: 4: 10.Control the closed degree of vacuum butterfly valve, guarantee that the air pressure of whole reaction process is at about 400Pa; React after 30 minutes, grow complete.Stop gas passing into, be cooled to less than 100 DEG C, take out sample and preserved.
Example 3
Carbon paper preprocessing process is with example 1.With 1M Ni (NO
3)
3prepare colloidal sol with methyl silicate, adopt spin-coating method that colloidal sol is coated in carbon fiber paper surface equably.Spin coating rotating speed preferably 5000 revs/min in this example, spin-coating time is preferably 30 seconds.Be placed in the chamber of chemical gas-phase deposition system by scribbling containing the carbon fiber paper of Ni elemental sols, start to heat up, target temperature is 300 DEG C, and the hold-time is 1 hour; Furnace temperature continues to rise to 400 DEG C, passes into reducing gas hydrogen, and the hold-time is 90 minutes; Furnace temperature continues to rise to 750 DEG C, passes into methane and nitrogen simultaneously.Hydrogen: methane: nitrogen ratios is 1: 4: 10.Control the closed degree of vacuum butterfly valve, guarantee that the air pressure of whole reaction process is at about 400Pa; React after 30 minutes, grow complete.Stop gas passing into, be cooled to less than 100 DEG C, take out sample and preserved.
Example 4
Carbon paper preprocessing process is with example 1.Use 1.5M FeSO
4prepare colloidal sol with methyl silicate, adopt spin-coating method that colloidal sol is coated in carbon fiber paper surface equably.Spin coating rotating speed preferably 4000 revs/min in this example, spin-coating time is preferably 60 seconds.Be placed in the chamber of chemical gas-phase deposition system by scribbling containing the carbon fiber paper of Fe elemental sols, start to heat up, target temperature is 300 DEG C, and the hold-time is 1 hour; Furnace temperature continues to rise to 500 DEG C, passes into reducing gas hydrogen, and the hold-time is 90 minutes; Furnace temperature continues to rise to 900 DEG C, passes into acetylene and nitrogen simultaneously.Hydrogen: acetylene: nitrogen ratios is 1: 2: 10.Control the closed degree of vacuum butterfly valve, guarantee that the air pressure of whole reaction process is at about 400Pa; React after 60 minutes, grow complete.Stop gas passing into, be cooled to less than 100 DEG C, take out sample and preserved.
Example 5
Carbon paper preprocessing process is with example 1.Use 1M CoSO
4prepare colloidal sol with tetraethoxy, adopt spin-coating method that colloidal sol is coated in carbon fiber paper surface equably.Spin coating rotating speed preferably 5000 revs/min in this example, spin-coating time is preferably 60 seconds.Be placed in the chamber of chemical gas-phase deposition system by scribbling containing the carbon fiber paper of Co elemental sols, start to heat up, target temperature is 400 DEG C, and the hold-time is 1 hour; Furnace temperature continues to rise to 450 DEG C, passes into reducing gas hydrogen, and the hold-time is 60 minutes; Furnace temperature continues to rise to 800 DEG C, passes into acetylene and argon gas simultaneously.Hydrogen: acetylene: argon gas ratio is 1: 2: 8.Control the closed degree of vacuum butterfly valve, guarantee that the air pressure of whole reaction process is at about 400Pa; React after 60 minutes, grow complete.Stop gas passing into, be cooled to less than 100 DEG C, take out sample and preserved.
Example 6
Carbon paper preprocessing process is with example 1.Use 0.5M NiSO
4prepare colloidal sol with tetraethoxy, adopt dip-coating method that colloidal sol is coated in carbon fiber paper surface equably.In this example, pull rate is 15cm/ minute.Repeated impregnations lift after wet film 100 DEG C of thermal treatments, lift number of times is 10 times.Be placed in the chamber of chemical gas-phase deposition system by scribbling containing the carbon fiber paper of Ni elemental sols, start to heat up, target temperature is 300 DEG C, and the hold-time is 1 hour; Furnace temperature continues to rise to 450 DEG C, passes into reducing gas hydrogen, and the hold-time is 60 minutes; Furnace temperature continues to rise to 750 DEG C, passes into ethane and nitrogen simultaneously.Hydrogen: ethane: nitrogen ratios is 1: 4: 10.Control the closed degree of vacuum butterfly valve, guarantee that the air pressure of whole reaction process is at about 400Pa; React after 90 minutes, grow complete.Stop gas passing into, be cooled to less than 100 DEG C, take out sample and preserved.
Example 7
Carbon paper preprocessing process is with example 1.With 0.2M Fe (NO
3)
3prepare colloidal sol with methyl silicate, adopt dip-coating method that colloidal sol is coated in carbon fiber paper surface equably.In this example, pull rate is 20cm/ minute.Repeated impregnations lift after wet film 100 DEG C of thermal treatments, lift number of times is 10 times.Be placed in the chamber of chemical gas-phase deposition system by scribbling containing the carbon fiber paper of Fe elemental sols, start to heat up, target temperature is 300 DEG C, and the hold-time is 1 hour; Furnace temperature continues to rise to 550 DEG C, passes into reducing gas hydrogen, and the hold-time is 120 minutes; Furnace temperature continues to rise to 900 DEG C, passes into acetylene simultaneously, shielding gas is argon gas and nitrogen mixed gas.Hydrogen: methane: nitrogen: argon gas ratio is 1: 2: 8: 8.Control the closed degree of vacuum butterfly valve, guarantee that the air pressure of whole reaction process is at about 400Pa; React after 90 minutes, grow complete.Stop gas passing into, be cooled to less than 100 DEG C, take out sample and preserved.
All can the carbon nano pipe array of acquisition according to above-described embodiment, pattern is as shown in Figure 1.The technical program is by changing concentration, coating time, the coating speed as Fe, Co, Ni element in catalyst precursor; the condition such as throughput ratio, temperature of reaction, reaction times of shielding gas and carbon-source gas, can control to grow the diameter, length and the ratio that obtain carbon nano pipe array.Catalyst precursor wide material sources in the technical program, cost is low, carbon-source gas involved in process of growth and shielding gas cheap, make the cost of whole process of growth lower, be applicable to industrial scale operation.
Claims (6)
1. the preparation method of a high-density carbon nano-tube array, it is characterized in that: Fe, Co, Ni acid salt solution and organic solvent are mixed with out colloidal sol and are coated on carbon fiber-based bottom material, described base material is the carbon fiber paper material with electroconductibility, heat described substrate to the first temperature and keep the scheduled time, described first temperature is 300-500 DEG C, hold-time is 10-120 minute, to remove the organism in catalyst precursor; Under a shielding gas, in Reaktionsofen, pass into reducing gas, the described substrate being formed with catalyst precursor is heated to the second temperature and keeps the scheduled time, described second temperature is 400-600 DEG C, hold-time is 30-120 minute, reduces to make the metallic element in catalyst precursor; In Reaktionsofen, pass into the gas mixture of shielding gas and carbon-source gas, and be heated to the 3rd temperature, described 3rd temperature is 750-900 DEG C, and the hold-time is 15-90 minute, grows high-density carbon nano-tube array at the catalyst surface of described substrate.
2. the preparation method of carbon nano pipe array as claimed in claim 1, is characterized in that, the acid salt solution of described preparation Fe, Co, Ni colloidal sol is the Fe (NO of different concns
3)
3, Co (NO
3)
2, Ni (NO
3)
2, Fe
2(SO
4)
3, FeSO
4, NiSO
4, CoSO
4solution, described in be used for preparing colloidal sol organic solvent be one or both mixtures of tetraethoxy, methyl silicate.
3. the preparation method of carbon nano pipe array as claimed in claim 1, is characterized in that, adopt spin-coating method and dip-coating method to apply in carbon fiber paper substrate, the spin coating rotating speed adopting spin-coating method is 4000-5000 rev/min, and spin-coating time is 30 seconds-2 minutes; The pull rate adopting dip-coating method is 10-20cm/ minute, and wet film is repeated impregnations lift after 100 DEG C of thermal treatment, and lift number of times is 3-10 time.
4. the preparation method of carbon nano pipe array as claimed in claim 1, is characterized in that, passing into shielding gas gas is one or more of nitrogen, argon gas or other rare gas elementes.
5. the preparation method of carbon nano pipe array as claimed in claim 1, is characterized in that, pass into one or more mixtures that carbon-source gas is methane, ethane, acetylene and ethene.
6. the preparation method of carbon nano pipe array as claimed in claim 1, it is characterized in that, prepared carbon nano-pipe array is classified as the one in single-wall carbon nanotube array, array of multi-walled carbon nanotubes.
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| CN104310372B (en) * | 2014-09-30 | 2016-11-16 | 张映波 | A kind of method of direct growth carbon nano pipe array in fibrous substrate |
| CN104831252B (en) * | 2015-04-02 | 2017-04-12 | 中南大学 | Preparation method for one-surface in situ gas phase growth of carbon nanofiber composite structure on carbon fiber paper, and application of composite structure |
| CN105375041A (en) * | 2015-11-18 | 2016-03-02 | 华南理工大学 | Carbon nanotube-transition metal-carbon fiber composite material and preparation method and application therefor |
| CN105421084A (en) * | 2015-12-04 | 2016-03-23 | 镇江奥立特机械制造有限公司 | Novel fiber liquid-immersing method |
| CN107445641A (en) * | 2016-10-12 | 2017-12-08 | 平顺县西沟龙鼎新材料科技有限公司 | A kind of preparation method of carbon brake disc |
| CN107651666A (en) * | 2017-03-27 | 2018-02-02 | 江苏超电新能源科技发展有限公司 | A kind of preparation method and applications of high density horizontal orientation CNT |
| CN109285992B (en) * | 2017-07-19 | 2020-07-14 | 中国科学院过程工程研究所 | Molybdenum sulfide flexible electrode material and preparation method and application thereof |
| FR3085161B1 (en) * | 2018-08-21 | 2023-05-12 | Nawatechnologies | METHOD FOR GROWING CARBON NANOTUBES ON THE SURFACE AND IN THE VOLUME OF A POROUS CARBON SUBSTRATE AND USE FOR PREPARING AN ELECTRODE |
| CN110756163A (en) * | 2019-10-31 | 2020-02-07 | 上海师范大学 | Nano CoFe2O4Carbon fiber felt composite material and preparation method and application thereof |
| CN114068959B (en) * | 2021-11-23 | 2023-10-27 | 成都先进金属材料产业技术研究院股份有限公司 | Method for improving activity of carbon fiber felt for vanadium battery |
| CN114597428B (en) * | 2022-03-10 | 2022-11-29 | 湖南金博氢能科技有限公司 | Flexible carbon paper, preparation method thereof, gas diffusion layer and fuel cell |
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