CN101570329B - Method for preparing carbon nanofiber - Google Patents
Method for preparing carbon nanofiber Download PDFInfo
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- CN101570329B CN101570329B CN2009100626419A CN200910062641A CN101570329B CN 101570329 B CN101570329 B CN 101570329B CN 2009100626419 A CN2009100626419 A CN 2009100626419A CN 200910062641 A CN200910062641 A CN 200910062641A CN 101570329 B CN101570329 B CN 101570329B
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Abstract
The invention relates to a method for preparing carbon nanofibers (CNFs). The method is to control the diameter size of the carbon nanofiber by an external direct current electric field in a chemical vapor deposition system. The method comprises the following steps: firstly, plating a nickel nanocrystal film on the surface of a prepared substrate by numerical control double-pulsing electrodeposition technology; secondly, placing the electrodeposited substrate and an electrode in a uniform temperature zone of a furnace chamber of the chemical vapor deposition system, and sealing the furnace chamber; thirdly, introducing Ar gas; fourthly, heating the furnace chamber to 600 DEG C; and finally, preparing the carbon nanofibers with uniform diameter under the action of the external direct current electric field. The carbon nanofiber is synthesized by a common CVD system, and has strong practicality; the external electric field is a simple device, and can be operated and controlled easily. Furthermore, the method not only can effectively control the diameter size of the carbon nanofibers (CNFs), but also can lead the diameter size of the carbon nanofibers to be more uniform.
Description
Technical field
The invention belongs to field of inorganic material preparing technology, particularly a kind of method for preparing carbon nanofiber (CNFs).
Background technology
Diameter is a kind of new nano material at the carbon nanofiber (CNFs) of 10-100nm.It beyond performances such as low density, high specific strength, high ratio modulus, high conduction and heat conduction, also has advantages such as defects count is few, specific surface area big, compact structure except having the characteristic of general micron order carbon fiber.Under the situation of present still difficult a large amount of preparation graphite whiskers, carbon nanofiber (CNFs) provide the ideal surrogate.In addition, carbon nanofiber (CNFs) is with a wide range of applications in fields such as catalyzer, support of the catalyst, lithium-ion secondary cell anode material, electrical double layer capacitor electrodes, high-efficiency adsorbent, separating agent, superpower matrix material, hydrogen storage material, absorbing materials.And the controllable growth of carbon nanofiber (CNFs) is the basis and the prerequisite of its large-scale application.The diameter of carbon nanofiber (CNFs) has directly and significantly influence its physics, chemistry and mechanical property etc., therefore if can control the diameter of carbon nanofiber (CNFs) effectively, just can regulate and control its performance effectively.
At present, mainly adopt chemical Vapor deposition process (CVD) preparation carbon nanofiber (CNFs).It is to be catalyzer with magnesium-yttrium-transition metal Fe, Co, Ni and alloy ultra-fine grain thereof, is carbon source with the hydrocarbon polymer, and hydrogen is carrier gas, is prepared under 600-1200 ℃ with synthetic.The general method of having controlled the diameter of one-dimensional carbon nano material in the CVD method is: by changing, come the control catalyst size such as synthesis temperature, catalyst calcination temperature and synthesis gas flow velocity etc., and then the diameter of control CNFs.Therefore the size of granules of catalyst is the principal element of decision one-dimensional carbon nano material diameter.Because these methods that change growth conditions all are the remote effect granules of catalyst, its suitability and validity are limited, are difficult to accomplish accurately to control the diameter of CNFs, and also can cause problems such as the change of diameter Distribution scope is big sometimes when changing diameter.
Summary of the invention
Purpose of the present invention is exactly to solve the problems referred to above that prior art exists, and overcomes the defective that the carbon nanomaterial diameter need rely on the catalyst particle size size, and the diameter of the carbon nanofiber that effectively makes.The invention provides a kind of method for preparing carbon nano fiber (CNFs), especially a kind of method of utilizing applying direct current electric field effectively to control carbon nanofiber (CNFs) diameter in gas-phase deposition system, it can control the diameter of carbon nanofiber (CNFs) effectively by simple method, and the distribution that makes carbon nanofiber (CNFs) diameter uniformity more.
Technical scheme of the present invention is: a kind of method for preparing carbon nanofiber is characterized in that: in chemical gas-phase deposition system, utilize the diameter of applying direct current electric field control carbon nanofiber.This method comprises the steps:
1) metal substrate is carried out the polishing of mechanical mill and flannelette and obtain the smooth smooth minute surface of use face; Then, the substrate plating surface last layer nickel nano-crystal film that is preparing with numerical control two pulse electro-deposition techniques;
2) with behind the uniform temperature zone in substrate after the galvanic deposit and the electrode placement chemical gas-phase deposition system furnace chamber, the sealing furnace chamber, the flow velocity feeding Ar gas with 200sccm is heated to 600 ℃;
3) introduce external electric field, substrate connects the electric field negative pole, and two electrodes carry out the preparation of carbon nanofiber at a distance of being 6mm, apply an applying direct current electric field between substrate and another electrode, and keeps electric field stable; Flow velocity with 30sccm feeds C
2H
2Gas reacts;
4) after reaction is finished, turn-off C
2H
2Air valve and external electric field are taken out after being cooled to room temperature under the Ar gas shiled, promptly get the uniform carbon nanofiber of diameter.
The time of described numerical control two pulse galvanic deposit is 1min; Described metal substrate is copper, copper alloy, steel or aluminium.
The intensity of described applying direct current electric field is 25000-50000V/m.
Adopt the present invention can control the diameter of carbon nanofiber (CNFs) effectively, and have the following advantages: 1) use common chemical vapor deposition (CVD) system to synthesize, suitability is very strong; 2) the extra electric field device is simple, easily operates and controls; 3) this method can not only effectively be controlled the diameter of CNFs, can also make its size uniformity more.
Description of drawings
Fig. 1 is transmission electron microscope (TEM) photo and the diameter Distribution figure that does not prepare carbon nanofiber during added electric field;
Fig. 2 is transmission electron microscope (TEM) photo and the diameter Distribution figure that extra electric field prepares carbon nanofiber during for 25000V/m;
Fig. 3 is transmission electron microscope (TEM) photo and the diameter Distribution figure that extra electric field prepares carbon nanofiber during for 50000V/m.
Embodiment
1. basic equipment and instrument: CVD system, galvanic deposit (plating) power supply, direct supply;
2. galvanic deposit anode material: pure nickel (Ni) sheet
3. gas: acetylene, argon gas;
4. metal substrate (negative electrode) material: metal (as: copper or copper alloy, steel, aluminium etc.) substrate;
5. Preparation of Catalyst: with numerical control two pulse galvanic deposit power supply, preparation one deck nickel nano-crystal film on metal substrate.The tinsel size is approximately 10 * 20mm, and the processes such as mechanical mill and flannelette polishing of at first carrying out before carrying out pulse electrodeposition are to obtain bright and clean smooth minute surface.Electrodeposition time is about 1min.
6. the introducing of external electric field: adopt the conventional DC power supply that external electric field is provided, the voltage change scope is 0～700V.Introduced in the CVD furnace chamber by two copper rods, and connect substrate and another electrode, two electrodes are about 6mm apart.
7. the preparation of carbon nanofiber (CNFs): 1) with behind the uniform temperature zone in substrate after the galvanic deposit and the electrode placement furnace chamber, the sealing furnace chamber; 2) flow velocity with 200sccm feeds Ar gas; 4) begin to be heated to 600 ℃ behind the 40min; 5) introduce external electric field this moment, substrate connects the electric field negative pole, and adopting intensity is that (the carbon nanofiber mean diameter is 19.2nm to the steady electric field of the 25000-50000V/m carbon nanofiber that can make specific mean diameter during as added electric field not, and standard error is 8.6nm; The electric field that adds 25000V/m can be prepared mean diameter 13.8nm, standard error is the carbon nanofiber of 4.7nm; When adding the electric field of 50000V/m, the carbon nanofiber mean diameter that obtains is 8.0nm, and standard error is 2.4nm), add in the external electric field process and to keep electric field stable; 6) flow velocity with 30sccm feeds C
2H
2Gas, the reaction beginning continues 3min; 7) reaction is finished, and turn-offs C
2H
2Air valve removes external electric field then, takes out after being cooled to room temperature under the Ar gas shiled.
Below in conjunction with drawings and Examples the present invention is further set forth, but therefore do not limit the present invention within the described scope of embodiments.
The copper sheet substrate that at first prepares 10 * 20mm is some, carries out mechanical mill and flannelette polishing etc. subsequently to obtain bright and clean smooth minute surface, carries out electric deposition nickel film 1min then, and numbering M1-Mn (n 〉=3).
Embodiment 1: after will depositing the good substrate that is numbered M2 and being positioned over the CVD uniform temperature zone, the sealing furnace chamber begins to be heated to 600 ℃ after feeding Ar gas, 40min with the flow velocity of 200sccm afterwards.Introduce external electric field this moment, and substrate connects the electric field negative pole, and strength of electric field is 25000V/m, keeps constant.Flow velocity with 30sccm feeds C
2H
2Gas, the reaction beginning continues 3min; After reaction is finished, turn-off C
2H
2Air valve removes external electric field, takes out after being cooled to room temperature under the Ar gas shiled.Transmission electron microscope (TEM) photo and the diameter Distribution figure of the carbon nanofiber that obtains see Fig. 2, and as shown in Figure 2, mean diameter is that 13.8nm, standard error are 4.7nm.
Embodiment 2: will deposit the electric field (other experiment condition is identical with embodiment 1) that the good substrate that is numbered M3 adds 50000V/m.Transmission electron microscope (TEM) photo and the diameter Distribution figure of the carbon nanofiber that obtains see Fig. 3, and as shown in Figure 3, mean diameter is that 8.0nm, standard error are 2.4nm.
Embodiment 3: as a comparison, the substrate that is numbered M1 that deposition is good is also put into CVD, and experiment condition is identical with embodiment 1, but does not add electric field in the preparation process.Transmission electron microscope (TEM) photo and the diameter Distribution figure of the carbon nanofiber that obtains see Fig. 1, and as shown in Figure 1, mean diameter is that 19.2nm, standard error are 8.6nm.
The mean diameter of CNFs and diameter Distribution scope thereof are all progressively being dwindled as can be seen along with the increase of extra electric field from last, have promptly reached the purpose of control CNFs diameter.
Claims (3)
1. a method for preparing carbon nanofiber in chemical gas-phase deposition system, is utilized the diameter of applying direct current electric field control carbon nanofiber, it is characterized in that: comprise the steps:
1) metal substrate is carried out the polishing of mechanical mill and flannelette and obtain the smooth smooth minute surface of use face; Then, the substrate plating surface last layer nickel nano-crystal film that is preparing with numerical control two pulse electro-deposition techniques;
2) with behind the uniform temperature zone in substrate after the galvanic deposit and the electrode placement chemical gas-phase deposition system furnace chamber, the sealing furnace chamber, the flow velocity feeding Ar gas with 200sccm is heated to 600 ℃;
3) introduce external electric field, substrate connects the electric field negative pole, and two electrodes carry out the preparation of carbon nanofiber at a distance of being 6mm, apply an applying direct current electric field between substrate and another electrode, and keeps electric field stable; Flow velocity with 30sccm feeds C
2H
2Gas reacts;
4) after reaction is finished, turn-off C
2H
2Air valve and external electric field are taken out after being cooled to room temperature under the Ar gas shiled, promptly get the uniform carbon nanofiber of diameter.
2. prepare the method for carbon nanofiber according to claim 1, it is characterized in that: the time of described numerical control two pulse galvanic deposit is 1min; Described metal substrate is copper, copper alloy, steel or aluminium.
3. prepare the method for carbon nanofiber as claimed in claim 1 or 2, it is characterized in that: the intensity of described applying direct current electric field is 25000-50000V/m.
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| CN101570329B true CN101570329B (en) | 2011-05-11 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101845750B (en) * | 2010-04-30 | 2011-12-21 | 冯静 | Manufacturing method of carbon nano tube modified fiber line and manufacturing device thereof |
| CN102121191B (en) * | 2010-04-30 | 2012-02-22 | 冯静 | Method for producing reinforced carbon nano pipeline adopting fiber yarns as carriers |
| CN102623192A (en) * | 2011-02-01 | 2012-08-01 | 林钲絖 | Negative electrode aluminum and carbon foil structure of solid aluminum electrolytic capacitor and forming method thereof |
| CN102070141A (en) * | 2011-03-10 | 2011-05-25 | 武汉大学 | Method for preparing graphene |
| CN103014917B (en) * | 2012-12-24 | 2014-09-24 | 青岛科技大学 | Preparation method of multi-branched carbon fiber |
| CN108070903A (en) * | 2016-11-16 | 2018-05-25 | 北京大学 | A kind of device that regulation and control thin-film material growth is powered up to substrate |
| CN107119347B (en) * | 2017-04-07 | 2019-05-03 | 西北大学 | A kind of preparation method of carbon nano-fiber |
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