CN103253647A - 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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- CN103253647A CN103253647A CN2012104488320A CN201210448832A CN103253647A CN 103253647 A CN103253647 A CN 103253647A CN 2012104488320 A CN2012104488320 A CN 2012104488320A CN 201210448832 A CN201210448832 A CN 201210448832A CN 103253647 A CN103253647 A CN 103253647A
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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 the nano material preparation technical field, particularly a kind of on carbon fiber paper substrate the method for direct growth carbon nano pipe array.
Background technology
Carbon nanotube is typical monodimension nanometer material, owing to its particular structure, excellent physics, chemical property and wide application prospect receive much concern.Carbon nanotube has charge transport properties preferably, can promote transfer transport as the electrode materials of green energy-storing device, as fuel cell, ultracapacitor, all-vanadium flow battery and organic solar batteries, is with a wide range of applications.
Usually the carbon nanotube for preparing is non-orientation, be the winding 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 bringing into play effectively, has had a strong impact on property research and the practical application of carbon nanotube.Therefore, explore the method for the carbon nano pipe array of preparation favorable orientation, have very important meaning.At present, many investigators grow carbon nano pipe array in silicon base, quartz substrate and other metal coating substrate.(Science 1998 for Ren ZF; 282:1105-7) (Science 1999 with Fan SS; 283:512-4) at the bottom of glass and porous silicon-base, grow array of multi-walled carbon nanotubes respectively.But catalyst preparation process complexity, substrate are nonconducting board-like material, need the electrode materials that just can be applied as energy storage devices such as fuel cell through shifting.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 this method spreads over carbon nano-tube solution on the substrate, applies high-voltage electric field simultaneously.This method preparation process requires harsh, and is wayward, the cost height.Chinese patent (200710118930.7) discloses and has a kind ofly prepared the method for carbon nano pipe array based on chemical vapour deposition, adopts synthetic gas as carbon source, carbon nano-tube on non-conductive matrix.Though this method has reduced the cost of preparation carbon nanotube, is unfavorable for producing high-quality carbon nano pipe array.Can not directly the act as a fuel electrode materials of energy storage devices such as battery, ultracapacitor of non-conductive matrix.
Therefore, provide that a kind of operation is simple, high-density, can directly grow at the conductive substrates carbon paper, the preparation method who is adapted at the carbon nano pipe array of industrial large-scale mass production is very necessary.
Summary of the invention
With 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 that is formed with catalyst precursor is placed in the Reaktionsofen, heat described substrate to the first temperature and keep the scheduled time, to remove the organism in the catalyst precursor; Under shielding gas, in Reaktionsofen, feed reducing gas, the described substrate that is formed with catalyst precursor is heated to second temperature and keeps the scheduled time, so that the Fe in the catalyst precursor, Co, Ni element reduction; Feed the gas mixture of shielding gas and carbon-source gas in the Reaktionsofen, and be heated to the 3rd temperature, grow high-density carbon nano-tube array at the catalyst surface of described substrate.
The preparation method who the invention has the advantages that proposition controls the caliber of 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 of control preparation sol solution.Compared to prior art, the catalyst precursor of Prepared by Sol Gel Method can directly be coated in the carbon paper surface, and this method is simple, control easily, 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 that bigger range of application be arranged, as the electrode materials of fuel cell, ultracapacitor and all-vanadium flow battery, and be adapted at industrial batch process.
Description of drawings
Fig. 1 is the SEM figure of the carbon nano pipe array of the inventive method system
Embodiment
Carbon paper is with the ultrasonic cleaning and dry stand-by one by one of dilute hydrochloric acid, acetone, alcohol, deionized water.Fe, Co, Ni acid salt solution and the organic solvent of different concns are mixed with out colloidal sol.Adopt spin-coating method or dip-coating method to be deposited on carbon fiber paper substrate the colloidal sol for preparing.The spin coating rotating speed of spin-coating method is 4000-5000 rev/min, and the spin coating time is 30 seconds-2 minutes.The pull rate of dip-coating method is 10-20cm/ minute.Wet film repeated impregnations after 100 ℃ of thermal treatment lifts, and lifting number of times is 3-10 time.
The described carbon fiber paper substrate that is formed with catalyst precursor is placed in the Reaktionsofen direct growth carbon nano pipe array in chemical gas-phase deposition system: concrete preparation may further comprise the steps:
(1) carbon fiber paper that will scribble colloidal sol places in the chamber of chemical gas-phase deposition system, begins to heat up, and target temperature is 300-500 ℃, and the hold-time is 10-120 minute.
(2) furnace temperature rises to 400 ℃-600 ℃, feeds 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 ℃, feed 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.
Describe below in conjunction with concrete enforcement.
Example 1
With carbon paper with the ultrasonic cleaning and dry stand-by one by one of dilute hydrochloric acid, acetone, alcohol, deionized water.With 2M Fe (NO
3)
3Solution and tetraethoxy prepare colloidal sol, adopt spin-coating method that colloidal sol is coated in the carbon fiber paper surface preparation equably, and the spin coating rotating speed is preferred 4000 rev/mins in this example, and the spin coating time is preferably 1 minute.Place in the chamber of chemical gas-phase deposition system scribbling the carbon fiber paper that contains Fe element colloidal sol, begin to heat up, target temperature is 300 ℃, and the hold-time is 1 hour; Furnace temperature continues to rise to 500 ℃, feeds reducing gas hydrogen, and the hold-time is 60 minutes; Furnace temperature continues to rise to 900 ℃, feeds methane and nitrogen simultaneously.Hydrogen: methane: nitrogen ratios is 1: 4: 10.The closed degree of control vacuum butterfly valve guarantees that the air pressure of entire reaction course is about 400Pa; React after 30 minutes, growth finishes.Stop gas and feed, be cooled to below 100 ℃, take out sample and preserved.
Example 2
The carbon paper preprocessing process is with example 1.With 1.5M Fe (NO
3)
3Solution and tetraethoxy prepare colloidal sol, adopt dip-coating method that colloidal sol is coated in the carbon fiber paper surface preparation equably, and pull rate is 10cm/ minute in this example.Wet film repeated impregnations after 100 ℃ of thermal treatment lifts, and lifting number of times is 5 times.Place in the chamber of chemical gas-phase deposition system scribbling the carbon fiber paper that contains Fe element colloidal sol, begin to heat up, target temperature is 300 ℃, and the hold-time is 1 hour; Furnace temperature continues to rise to 500 ℃, feeds reducing gas hydrogen, and the hold-time is 60 minutes; Furnace temperature continues to rise to 900 ℃, feeds methane and nitrogen simultaneously.Hydrogen: methane: nitrogen ratios is 1: 4: 10.The closed degree of control vacuum butterfly valve guarantees that the air pressure of entire reaction course is about 400Pa; React after 30 minutes, growth finishes.Stop gas and feed, be cooled to below 100 ℃, take out sample and preserved.
Example 3
The 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 the carbon fiber paper surface equably.The spin coating rotating speed is preferred 5000 rev/mins in this example, and the spin coating time is preferably 30 seconds.Place in the chamber of chemical gas-phase deposition system scribbling the carbon fiber paper that contains Ni element colloidal sol, begin to heat up, target temperature is 300 ℃, and the hold-time is 1 hour; Furnace temperature continues to rise to 400 ℃, feeds reducing gas hydrogen, and the hold-time is 90 minutes; Furnace temperature continues to rise to 750 ℃, feeds methane and nitrogen simultaneously.Hydrogen: methane: nitrogen ratios is 1: 4: 10.The closed degree of control vacuum butterfly valve guarantees that the air pressure of entire reaction course is about 400Pa; React after 30 minutes, growth finishes.Stop gas and feed, be cooled to below 100 ℃, take out sample and preserved.
Example 4
The 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 the carbon fiber paper surface equably.The spin coating rotating speed is preferred 4000 rev/mins in this example, and the spin coating time is preferably 60 seconds.Place in the chamber of chemical gas-phase deposition system scribbling the carbon fiber paper that contains Fe element colloidal sol, begin to heat up, target temperature is 300 ℃, and the hold-time is 1 hour; Furnace temperature continues to rise to 500 ℃, feeds reducing gas hydrogen, and the hold-time is 90 minutes; Furnace temperature continues to rise to 900 ℃, feeds acetylene and nitrogen simultaneously.Hydrogen: acetylene: nitrogen ratios is 1: 2: 10.The closed degree of control vacuum butterfly valve guarantees that the air pressure of entire reaction course is about 400Pa; React after 60 minutes, growth finishes.Stop gas and feed, be cooled to below 100 ℃, take out sample and preserved.
Example 5
The 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 the carbon fiber paper surface equably.The spin coating rotating speed is preferred 5000 rev/mins in this example, and the spin coating time is preferably 60 seconds.Place in the chamber of chemical gas-phase deposition system scribbling the carbon fiber paper that contains Co element colloidal sol, begin to heat up, target temperature is 400 ℃, and the hold-time is 1 hour; Furnace temperature continues to rise to 450 ℃, feeds reducing gas hydrogen, and the hold-time is 60 minutes; Furnace temperature continues to rise to 800 ℃, feeds acetylene and argon gas simultaneously.Hydrogen: acetylene: the argon gas ratio is 1: 2: 8.The closed degree of control vacuum butterfly valve guarantees that the air pressure of entire reaction course is about 400Pa; React after 60 minutes, growth finishes.Stop gas and feed, be cooled to below 100 ℃, take out sample and preserved.
Example 6
The 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 the carbon fiber paper surface equably.Pull rate is 15cm/ minute in this example.Repeated impregnations lifts after 100 ℃ of thermal treatments of wet film, and lifting number of times is 10 times.Place in the chamber of chemical gas-phase deposition system scribbling the carbon fiber paper that contains Ni element colloidal sol, begin to heat up, target temperature is 300 ℃, and the hold-time is 1 hour; Furnace temperature continues to rise to 450 ℃, feeds reducing gas hydrogen, and the hold-time is 60 minutes; Furnace temperature continues to rise to 750 ℃, feeds ethane and nitrogen simultaneously.Hydrogen: ethane: nitrogen ratios is 1: 4: 10.The closed degree of control vacuum butterfly valve guarantees that the air pressure of entire reaction course is about 400Pa; React after 90 minutes, growth finishes.Stop gas and feed, be cooled to below 100 ℃, take out sample and preserved.
Example 7
The 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 the carbon fiber paper surface equably.Pull rate is 20cm/ minute in this example.Repeated impregnations lifts after 100 ℃ of thermal treatments of wet film, and lifting number of times is 10 times.Place in the chamber of chemical gas-phase deposition system scribbling the carbon fiber paper that contains Fe element colloidal sol, begin to heat up, target temperature is 300 ℃, and the hold-time is 1 hour; Furnace temperature continues to rise to 550 ℃, feeds reducing gas hydrogen, and the hold-time is 120 minutes; Furnace temperature continues to rise to 900 ℃, feeds acetylene simultaneously, shielding gas is argon gas and nitrogen mixture body.Hydrogen: methane: nitrogen: the argon gas ratio is 1: 2: 8: 8.The closed degree of control vacuum butterfly valve guarantees that the air pressure of entire reaction course is about 400Pa; React after 90 minutes, growth finishes.Stop gas and feed, be cooled to below 100 ℃, take out sample and preserved.
According to the carbon nano pipe array that above-described embodiment all can obtain, pattern as shown in Figure 1.The technical program is by changing concentration, coating time, the coating speed as the Fe in the catalyst precursor, Co, Ni element; conditions such as the throughput ratio of shielding gas and carbon-source gas, temperature of reaction, reaction times can be controlled diameter, length and ratio that growth obtains carbon nano pipe array.Catalyst precursor wide material sources in the technical program, cost is low, and carbon-source gas and shielding gas related in the process of growth are cheap, make that the cost of whole growth process is lower, are fit to industrial scale operation.
Claims (10)
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 the carbon fiber substrates material.Heat described substrate to the first temperature and keep the scheduled time, to remove the organism in the catalyst precursor; Under shielding gas, in Reaktionsofen, feed reducing gas, the described substrate that is formed with catalyst precursor is heated to second temperature and keeps the scheduled time, so that the reduction of the metallic element in the catalyst precursor; Feed the gas mixture of shielding gas and carbon-source gas in the Reaktionsofen, and be heated to the 3rd temperature, grow 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, described base material is the carbon fiber paper material with electroconductibility.
3. 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.The described organic solvent that is used for preparing colloidal sol is one or both mixtures of tetraethoxy, methyl silicate.
4. the preparation method of carbon nano pipe array as claimed in claim 1 is characterized in that, adopts spin-coating method and dip-coating method to apply in carbon fiber paper substrate.Adopting the spin coating rotating speed of spin-coating method is 4000-5000 rev/min, and the spin coating time is 30 seconds-2 minutes; Adopting the pull rate of dip-coating method is 10-20cm/ minute.Wet film repeated impregnations after 100 ℃ of thermal treatment lifts, and lifting number of times is 3-10 time.
5. the preparation method of the described carbon nano pipe array of claim 1 is characterized in that, described first temperature is 300-500 ℃, and the hold-time is 10-120 minute.
6. the preparation method of carbon nano pipe array as claimed in claim 1 is characterized in that, feeding shielding gas gas is one or more of nitrogen, argon gas or other rare gas elementes.
7. the preparation method of carbon nano pipe array as claimed in claim 1 is characterized in that, described second temperature is 400-600 ℃, and the hold-time is 30-120 minute.
8. the preparation method of carbon nano pipe array as claimed in claim 1 is characterized in that, the feeding carbon-source gas is one or more mixtures of methane, ethane, acetylene and ethene.
9. the preparation method of carbon nano pipe array as claimed in claim 1 is characterized in that, described the 3rd temperature is 750-900 ℃, and the hold-time is 15-90 minute.
10. the preparation method of carbon nano pipe array as claimed in claim 1 is characterized in that, prepared carbon nano-pipe array is classified a kind of in single-wall carbon nanotube array, the array of multi-walled carbon nanotubes as.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104310372A (en) * | 2014-09-30 | 2015-01-28 | 张映波 | Method for directly growing carbon nano tube array on fiber substrate |
| CN104831252A (en) * | 2015-04-02 | 2015-08-12 | 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 |
| CN109285992A (en) * | 2017-07-19 | 2019-01-29 | 中国科学院过程工程研究所 | A kind of molybdenum sulfide flexible electrode material and its preparation method and application |
| 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 |
| CN113490639A (en) * | 2018-08-21 | 2021-10-08 | 纳瓦科技公司 | Method for growing carbon nanotubes on the surface and in the bulk of a porous carbonaceous substrate and use for preparing an electrode |
| CN114068959A (en) * | 2021-11-23 | 2022-02-18 | 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 |
| CN114597428A (en) * | 2022-03-10 | 2022-06-07 | 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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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104310372A (en) * | 2014-09-30 | 2015-01-28 | 张映波 | Method for directly growing carbon nano tube array on fiber substrate |
| CN104831252A (en) * | 2015-04-02 | 2015-08-12 | 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 |
| CN109285992A (en) * | 2017-07-19 | 2019-01-29 | 中国科学院过程工程研究所 | A kind of molybdenum sulfide flexible electrode material and its preparation method and application |
| 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 |
| CN113490639A (en) * | 2018-08-21 | 2021-10-08 | 纳瓦科技公司 | Method for growing carbon nanotubes on the surface and in the bulk of a porous carbonaceous substrate and use for preparing an electrode |
| CN113490639B (en) * | 2018-08-21 | 2024-03-08 | 纳瓦科技公司 | Method for growing carbon nanotubes on the surface and bulk of a porous carbonaceous substrate and use for preparing electrodes |
| 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 |
| CN114068959A (en) * | 2021-11-23 | 2022-02-18 | 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 |
| 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 |
| CN114597428A (en) * | 2022-03-10 | 2022-06-07 | 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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