CN102633244B - Carbon material and preparation method thereof - Google Patents
Carbon material and preparation method thereof Download PDFInfo
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- CN102633244B CN102633244B CN201110036862.6A CN201110036862A CN102633244B CN 102633244 B CN102633244 B CN 102633244B CN 201110036862 A CN201110036862 A CN 201110036862A CN 102633244 B CN102633244 B CN 102633244B
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 165
- 238000000034 method Methods 0.000 claims abstract description 60
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 59
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 53
- 239000002131 composite material Substances 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 25
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 25
- 150000003624 transition metals Chemical class 0.000 claims abstract description 25
- 239000007769 metal material Substances 0.000 claims abstract description 16
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 9
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 7
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 238000007599 discharging Methods 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 30
- 239000010439 graphite Substances 0.000 claims description 30
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 17
- 239000004917 carbon fiber Substances 0.000 claims description 17
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 17
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 229910052734 helium Inorganic materials 0.000 claims description 7
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 3
- 229910052691 Erbium Inorganic materials 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052689 Holmium Inorganic materials 0.000 claims description 3
- 229910052765 Lutetium Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052771 Terbium Inorganic materials 0.000 claims description 3
- 229910052775 Thulium Inorganic materials 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 3
- 229910052743 krypton Inorganic materials 0.000 claims description 3
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 3
- 150000002602 lanthanoids Chemical class 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- 239000011295 pitch Substances 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- 239000007789 gas Substances 0.000 description 33
- 239000002041 carbon nanotube Substances 0.000 description 24
- 229910021393 carbon nanotube Inorganic materials 0.000 description 24
- 238000001069 Raman spectroscopy Methods 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 230000005540 biological transmission Effects 0.000 description 10
- 239000005011 phenolic resin Substances 0.000 description 9
- 230000001105 regulatory effect Effects 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000010891 electric arc Methods 0.000 description 6
- 238000012423 maintenance Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910000480 nickel oxide Inorganic materials 0.000 description 6
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 6
- 239000002356 single layer Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000004567 concrete Substances 0.000 description 5
- -1 amino, carboxyl Chemical group 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-M hexadecanoate Chemical compound CCCCCCCCCCCCCCCC([O-])=O IPCSVZSSVZVIGE-UHFFFAOYSA-M 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229940049920 malate Drugs 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Abstract
Disclose by the method preparing Graphene and carbon mano-tube composite of discharging in-between the electrodes, its Anodic comprises carbon material and metallic material, described metallic material is selected from the oxide compound of transition metal or rare earth element, inorganic salt or organic salt or its mixture, or by one or more mixtures formed in above-mentioned one or more and metal Fe, Ni, Mo, Cr or Y.Also disclose the Graphene and carbon mano-tube composite prepared according to the inventive method.
Description
Technical field
The present invention relates to carbon nano-composite material and preparation method thereof.
Background technology
Carbon has multiple existence form, the carbon 60, carbon nanotube and the Graphene that comprise common graphite, diamond, agraphitic carbon and in recent years find.Although these materials are all made up of carbon, structures and characteristics very different.Wherein Graphene is the mono-layer graphite or Multi-layer graphite material that are made up of monolithic graphite.Carbon nanotube is the tubular structure of the curling formation of single-layer graphene, can be Single Walled Carbon Nanotube and multi-walled carbon nano-tubes.Graphene and carbon nano-tube material have much excellent character, such as have high conductive capability and mechanical property, and both will have more excellent character than single-material in some aspects at the matrix material of Nano grade.Therefore be all badly in need of a kind of large-scale producing method of simple possible from research and industrial application aspect, propose the present invention thus.
Summary of the invention
An aspect of of the present present invention provides by the method preparing Graphene and carbon mano-tube composite of discharging in-between the electrodes, its Anodic comprises carbon material and metallic material, described metallic material is selected from the oxide compound of transition metal or rare earth element, inorganic salt or organic salt or its mixture, or by one or more mixtures formed in above-mentioned one or more and metal Fe, Ni, Mo, Cr or Y.
Another aspect provides the Graphene and carbon mano-tube composite that are obtained by above method.
Detailed Description Of The Invention
In the following description, some concrete details is comprised to provide comprehensive understanding to each disclosed embodiment.But those skilled in the relevant art will appreciate that, do not adopt these concrete details one or more, and adopt when other method, parts, material etc. and can realize embodiment.
Unless other requirement in the application, in whole specification sheets and claims thereafter, word " comprises " should be interpreted as meaning that is open, that include formula, namely " includes but not limited to ".
" embodiment " mentioned in whole specification sheets or " embodiment " or " in another embodiment " or " in certain embodiments " mean to comprise and relevant concrete reference feature, structure or the feature described in this embodiment at least one embodiment.Therefore, the phrase " in one embodiment " that different positions occurs in whole specification sheets or " in embodiments " or " in another embodiment " or " in certain embodiments " need not all refer to same embodiment.In addition, concrete key element, structure or feature can combine in any suitable manner in one or more embodiment.
Term " Graphene " used in the present invention refers to single or multiple lift (the being generally 1-30 layer) graphite material of serving as reasons its molecular composition unit " mono-layer graphite " being formed, and is respectively " single-layer graphene " and " multi-layer graphene ".Term " mono-layer graphite " refers to that its monolithic size is at 10nm by the former molecular two dimensional surface molecular skeleton of monolayer carbon
2to 1000 μm
2between, single-sheet thickness is between 0.34nm to 2nm.
The carbon atom of the layer edge section in " Graphene " also can be connected different functional groups, as hydroxyl, amino, carboxyl, epoxide group or hydrogen atom etc. according to concrete preparation method with the difference of preparation condition.
An aspect of of the present present invention provides by the method preparing Graphene and carbon mano-tube composite of discharging in-between the electrodes, its Anodic comprises carbon material and metallic material, described metallic material is selected from the oxide compound of transition metal or rare earth element, inorganic salt or organic salt or its mixture, or by one or more mixtures formed in above-mentioned one or more and metal Fe, Ni, Mo, Cr or Y.
The transition metal used in the present invention is selected from Fe, Ni, Mo or Cr.
The rare earth element used in the present invention is selected from La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu in Sc, Y and group of the lanthanides.
The inorganic salt of the transition metal or rare earth element that can be used in the inventive method comprise the inorganic acid salt of transition metal or rare earth element, include but not limited to carbonate, nitrate, vitriol and phosphoric acid salt.
The organic salt of the transition metal or rare earth element that can be used in the inventive method comprises the organic acid salt of transition metal or rare earth element, includes but not limited to oxalate, Citrate trianion, malate, succinate, stearate and palmitate.
In embodiments of the invention, based on the integral molar quantity of described metallic material and described carbon material, the molar content of described metallic material is 0.1-8%, preferred 1-5%, more preferably 1-4%, most preferably 0.8-3.5%, the mol ratio of described transition metal and described rare earth element is 8: 1 to 1: 2, preferably 6: 1 to 4: 1, more preferably 5: 1 to 4: 1, most preferably 4.5: 1 to 4: 1.
The present invention's carbon material used is graphite, coal, pitch or carbon fiber, or their mixture, the mixture of preferred carbon fiber or carbon fiber and graphite.
In a preferred embodiment of the invention, discharge and to carry out comprising in rare gas element and mixed-gas atmosphere carbon to necessarily other gas reactive, described rare gas element is selected from N
2, He, Ne, Ar, Kr or Xe, be preferably He or Ar or its mixture, described have necessarily other gas reactive to carbon and be selected from NH
3, H
2, CO
2, air or O
2, be preferably NH
3or H
2.
In the preferred embodiment of the present invention, the dividing potential drop having necessarily other gas reactive to carbon in mixed gas is 5% to 80%, preferably 8% to 70%, more preferably 10% to 60%, most preferably 12.5% to 50%.The total gas pressure of mixed gas is 400-760mmHg, is preferably 450-700mmHg, is more preferably 500-600mmHg, most preferably is 500-550mmHg.
In the preferred embodiment of the present invention, sparking voltage is 10-40V, preferred 15-35V, more preferably 20-30V, most preferably 22-28V, and electric current is 60-200A, preferred 80-150A, more preferably 100-140A, most preferably 110-130A.
In a preferred embodiment of the invention, in discharge process, add the magnetic field of magneticstrength >=0.5T, to obtain Graphene and the carbon mano-tube composite of orientation.
In certain embodiments, method of the present invention comprises
1) by transition metal and rare earth element mol ratio be 6: 1 to 4: 1 transition metal oxide and rare earth oxide Homogeneous phase mixing in a mixer, wherein said transition metal is selected from Fe, Ni, Mo or Cr, and described rare earth element is selected from La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu in Sc, Y and group of the lanthanides;
2) said mixture is mixed with carbon material, described carbon material is graphite, coal, pitch or carbon fiber, or their mixture, wherein based on the integral molar quantity of described transition metal, described rare earth element and described carbon material, the molar content of described transition metal and described rare earth element is 1-5%, add water soluble phenol resin, after mixing, be pressed into graphite rod, then at 1000-1200 DEG C, within 24 hours, make sacrificial electrode in roasting;
3) using Graphite Electrodes as negative electrode, using described sacrificial electrode as anode, be placed in electric discharge stove;
4) be filled with comprising rare gas element in described electric discharge stove with mixed gas carbon to necessarily other gas reactive, described rare gas element is selected from N
2, He, Ne, Ar, Kr or Xe, described have necessarily other gas reactive to carbon and be selected from NH
3, H
2, CO
2, air or O
2the wherein said dividing potential drop having necessarily other gas reactive to carbon is 8% to 70%, pressure in stove is made to be 450-700mmHg, arranging outward current is 80-150A, by regulating interelectrode distance to make voltage remain on 15-35V after electric discharge starting, maintaining pressure in stove and, near 450-700mmHg, after anode consumption, stopping electric discharge, collect the cotton-shaped black product in stove, be Graphene and carbon mano-tube composite product.
In certain embodiments, method of the present invention comprises
1) by transition metal and rare earth element mol ratio be 5: 1 to 4: 1 transition metal oxide and rare earth oxide Homogeneous phase mixing in a mixer, wherein said transition metal is Ni, and described rare earth element is Y;
2) said mixture is mixed with carbon material, described carbon material is the mixture of carbon fiber or carbon fiber and graphite, wherein based on the integral molar quantity of Ni, Y and described carbon material, the molar content of Ni and Y is 1-4%, add water soluble phenol resin, be pressed into graphite rod after mixing, then at 1000-1200 DEG C, roasting makes sacrificial electrode in 24 hours;
3) using Graphite Electrodes as negative electrode, using described sacrificial electrode as anode, be placed in electric discharge stove;
4) be filled with in described electric discharge stove by comprising rare gas element with the mixed gas having necessarily other gas reactive to carbon, described rare gas element is selected from He or Ar or its mixture, and described to have necessarily other gas reactive to carbon be NH
3or H
2the wherein said dividing potential drop having necessarily other gas reactive to carbon is 10% to 60%, pressure in stove is made to be 500-600mmHg, arranging outward current is 100-140A, by regulating interelectrode distance to make voltage remain on 20-30V after electric discharge starting, maintaining pressure in stove and, at 500-600mmHg, after anode consumption, stopping electric discharge, collect the cotton-shaped black product in stove, be Graphene and carbon mano-tube composite product.
In certain embodiments, method of the present invention comprises
1) by transition metal and rare earth element mol ratio be 4.5: 1 to 4: 1 transition metal oxide and rare earth oxide Homogeneous phase mixing in a mixer, wherein said transition metal is Ni, and described rare earth element is Y;
2) said mixture is mixed with carbon material, described carbon material is the mixture of carbon fiber or carbon fiber and graphite, wherein based on the integral molar quantity of transition metal, rare earth element and carbon material, the molar content of transition metal and rare earth element is 0.8-3.5%, add water soluble phenol resin, be pressed into graphite rod after mixing, then at 1000-1200 DEG C, roasting makes sacrificial electrode in 24 hours;
3) using Graphite Electrodes as negative electrode, using described sacrificial electrode as anode, be placed in electric discharge stove;
4) be filled with in described electric discharge stove by comprising rare gas element with the mixed gas having necessarily other gas reactive to carbon, described rare gas element is selected from He or Ar or its mixture, and described to have necessarily other gas reactive to carbon be NH
3or H
2the wherein said dividing potential drop having necessarily other gas reactive to carbon is 12.5% to 50%, pressure in stove is made to be 500-550mmHg, arranging outward current is 110-130A, by regulating interelectrode distance to make voltage remain on 22-28V after electric discharge starting, maintaining pressure in stove and, at 500-550mmHg, after anode consumption, stopping electric discharge, collect the cotton-shaped black product in stove, be Graphene and carbon mano-tube composite product.
Another aspect provides the Graphene and carbon mano-tube composite produced according to the method described above.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope(TEM) figure of Graphene and the carbon mano-tube composite obtained according to the method for the embodiment of the present invention 1.
Fig. 2 is the Raman spectrogram of Graphene and the carbon mano-tube composite obtained according to the method for the embodiment of the present invention 1.
Fig. 3 is the transmission electron microscope(TEM) figure of Graphene and the carbon mano-tube composite obtained according to the method for the embodiment of the present invention 2.
Fig. 4 is the enlarged view of part in Fig. 3 frame.
Fig. 5 is the Raman spectrogram of Graphene and the carbon mano-tube composite obtained according to the method for the embodiment of the present invention 2.
Fig. 6 is the transmission electron microscope(TEM) figure of Graphene and the carbon mano-tube composite obtained according to the method for the embodiment of the present invention 3.
Fig. 7 is the enlarged view of part in Fig. 6 frame.
Fig. 8 is the Raman spectrogram of Graphene and the carbon mano-tube composite obtained according to the method for the embodiment of the present invention 3.
Fig. 9 is the transmission electron microscope(TEM) figure of Graphene and the carbon mano-tube composite obtained according to the method for the embodiment of the present invention 4.
Figure 10 is the Raman spectrogram of Graphene and the carbon mano-tube composite obtained according to the method for the embodiment of the present invention 4.
Figure 11 is the transmission electron microscope(TEM) figure of Graphene and the carbon mano-tube composite obtained according to the method for the embodiment of the present invention 5.
Figure 12 is the Raman spectrogram (100cm of Graphene and the carbon mano-tube composite obtained according to the method for the embodiment of the present invention 5
-1~ 3200cm
-1).
Figure 13 is the Raman spectrogram (100cm of Graphene and the carbon mano-tube composite obtained according to the method for the embodiment of the present invention 5
-1~ 300cm
-1).
In all of the figs, label 1 refers to Graphene, and 2 refer to carbon nanotube.
Embodiment
Below by embodiment, the present invention is specifically described; the present embodiment is only for being further detailed the present invention; limiting the scope of the invention can not be interpreted as; those skilled in the art makes some nonessential improvement and adjustment according to the content of the invention described above, all belongs to scope.
Embodiment 1
Take 3.48g carbon fiber; 68g crystalline flake graphite; 3.1g nickel oxide powder; 1.11g yttrium oxide powder, and 34g water soluble phenol resin (according to " coalescence benzene nano particle and polypropylene composite materials prepare novel antistatic fire retardant material ", SCI; method synthesis described in Vol.29 No.6 1276 ~ 1281) binding agent; stir with mixing tank, be then pressed into electrode (12 × 200mm) in a mold, 1100 DEG C of roastings make sacrificial electrode in 24 hours.Do anode with this sacrificial electrode, Graphite Electrodes does negative electrode, and anode and cathode axis, to relative, pass into H in electric arc furnace
2with the gas mixture (H of He
2account for the dividing potential drop of 16%) be 520mmHg to pressure in stove, arranging outward current is 120A.By regulating interelectrode distance to make voltage remain near 25V after electric discharge starts, in maintenance stove, pressure is near 520mmHg, and anode consumption is complete, and reaction terminates.Collect product in furnace chamber.
Graphene obtained according to the method described above and the transmission electron microscope(TEM) figure of carbon mano-tube composite are as shown in Figure 1.Being mostly carbon nanotube and metallic material as seen from the figure, is Graphene on a small quantity.
Graphene obtained according to the method described above and the Raman spectrogram of carbon mano-tube composite are as shown in Figure 2.As seen from the figure at 180cm
-1near there is the characteristic peak of carbon nanotube, illustrate in product to there is carbon nanotube.In addition, at 2692cm
-1the neighbouring 2D peak existed is higher than the intensity of simple carbon nanotube, shows have Graphene to exist.
Embodiment 2
Take 3.48g carbon fiber, 68g crystalline flake graphite, 3.1g nickel oxide powder, 1.11g yttrium oxide powder, 34g water soluble phenol resin (preparation method is with embodiment 1) binding agent, stir with mixing tank, be then pressed into electrode (12 × 200mm) in a mold, 1100 DEG C of roastings make sacrificial electrode in 24 hours.Do anode with this sacrificial electrode, Graphite Electrodes does negative electrode, and anode and cathode axis, to relative, pass into H in electric arc furnace
2with the gas mixture (H of He
2account for the dividing potential drop of 20%) be 520mmHg to pressure in stove, arranging outward current is 120A.By regulating interelectrode distance to make voltage remain near 25V after electric discharge starts, in maintenance stove, pressure is near 520mmHg, and anode consumption is complete, and reaction terminates.Collect product in furnace chamber.
Graphene obtained according to the method described above and the transmission electron microscope(TEM) figure of carbon mano-tube composite are as shown in Figure 3.Product is the hydridization of Graphene and carbon nanotube as seen from the figure.Fig. 4 is the enlarged view of part in Fig. 3 frame.
Graphene obtained according to the method described above and the Raman spectrogram of carbon mano-tube composite are as shown in Figure 5.As seen from the figure at 180cm
-1near there is the characteristic peak of carbon nanotube, illustrate in product to there is carbon nanotube.At 2704cm
-1the neighbouring 2D peak existed is higher than the intensity of simple carbon nanotube, shows have Graphene to exist.
Embodiment 3
Take 3.48g carbon fiber, 68g crystalline flake graphite, 6.18g nickel oxide powder, 2.22g yttrium oxide powder, 34g water soluble phenol resin (preparation method is with embodiment 1) binding agent, stir with mixing tank, be then pressed into electrode (12 × 200mm) in a mold, 1100 DEG C of roastings make sacrificial electrode in 24 hours.Do anode with this sacrificial electrode, Graphite Electrodes does negative electrode, and anode and cathode axis, to relative, pass into H in electric arc furnace
2with the gas mixture (H of He
2account for the dividing potential drop of 25%) be 520mmHg to pressure in stove, arranging outward current is 120A.By regulating interelectrode distance to make voltage remain near 25V after electric discharge starts, in maintenance stove, pressure is near 520mmHg, and anode consumption is complete, and reaction terminates.Collect product in furnace chamber.
Graphene obtained according to the method described above and the transmission electron microscope(TEM) figure of carbon mano-tube composite are as shown in Figure 6.As seen from the figure, carbon nanotube is entrained between Graphene.
Fig. 7 is the enlarged view of part in Fig. 6 frame, there is carbon nano-tube bundle and Graphene as seen.
Graphene obtained according to the method described above and the Raman spectrogram of carbon mano-tube composite are as shown in Figure 8.183cm as seen from the figure
-1there is the RBM characteristic peak of carbon nanotube, illustrate in product to there is carbon nanotube.At 2689cm
-1the neighbouring 2D peak existed is higher than the intensity of simple carbon nanotube, shows have Graphene to exist.
Embodiment 4
Take 3.48g carbon fiber, 68g crystalline flake graphite, 12.36g nickel oxide powder, 4.44g yttrium oxide powder, 34g water soluble phenol resin (preparation method is with embodiment 1) binding agent, stir with mixing tank, be then pressed into electrode (12 × 200mm) in a mold, 1100 DEG C of roastings make sacrificial electrode in 24 hours.Do anode with this sacrificial electrode, Graphite Electrodes does negative electrode, and anode and cathode axis, to relative, pass into H in electric arc furnace
2with the gas mixture (H of He
2account for the dividing potential drop of 12.5%) be 520mmHg to pressure in stove, arranging outward current is 120A.By regulating interelectrode distance to make voltage remain near 25V after electric discharge starts, in maintenance stove, pressure is near 520mmHg, and anode consumption is complete, and reaction terminates.Collect product in furnace chamber.
The transmission electron microscope(TEM) figure of the Graphene obtained according to aforesaid method and carbon mano-tube composite as shown in Figure 9.Graphene and the carbon nanotube with its compound as seen from the figure.
The Graphene obtained according to aforesaid method and the Raman spectrogram of carbon mano-tube composite are as shown in Figure 10.162cm as seen from the figure
-1there is the RBM characteristic peak of carbon nanotube, illustrate in product to there is carbon nanotube.Because content of carbon nanotubes is higher, at 2650 ~ 2750cm
-12D peak do not show the due intensity of Graphene.
Embodiment 5
Take 3.48g carbon fiber, 68g crystalline flake graphite, 6.18g nickel oxide powder, 2.22g yttrium oxide powder, 34g water soluble phenol resin (preparation method is with embodiment 1) binding agent, stir with mixing tank, be then pressed into electrode (12 × 200mm) in a mold, 1100 DEG C of roastings make sacrificial electrode in 24 hours.Do anode with this sacrificial electrode, Graphite Electrodes does negative electrode, and anode and cathode axis, to relative, pass into H in electric arc furnace
2with the gas mixture (H of He
2account for the dividing potential drop of 50%) be 520mmHg to pressure in stove, arranging outward current is 120A.By regulating interelectrode distance to make voltage remain near 25V after electric discharge starts, in maintenance stove, pressure is near 520mmHg, and anode consumption is complete, and reaction terminates.Collect product in furnace chamber.
The transmission electron microscope(TEM) figure of the Graphene obtained according to aforesaid method and carbon mano-tube composite as shown in figure 11.Graphene and the carbon nanotube with its compound as seen from the figure.
The Graphene obtained according to aforesaid method and the Raman spectrogram of carbon mano-tube composite are as shown in Figures 12 and 13.189cm as seen from Figure 13
-1there is the RBM characteristic peak of carbon nanotube, illustrate in product to there is carbon nanotube.Because Graphene content is higher, the RBM peak in the Raman of Figure 12 is composed entirely is more weak, and 2720cm
-1the 2D peak at place is very strong.
Embodiment 6
Take 3.48g carbon fiber, 68g crystalline flake graphite, 12.36g nickel oxide powder, 4.44g yttrium oxide powder, 34g water soluble phenol resin (preparation method is with embodiment 1) binding agent, stir with mixing tank, be then pressed into electrode (12 × 200mm) in a mold, 1100 DEG C of roastings make sacrificial electrode in 24 hours.Do anode with this sacrificial electrode, Graphite Electrodes does negative electrode, and anode and cathode axis, to relative, pass into H in electric arc furnace
2with the gas mixture (H of He
2account for the dividing potential drop of 12.5%) be 520mmHg to pressure in stove, arranging outward current is 120A.Contain at electrical discharge zone the high-intensity magnetic field that magneticstrength is 0.5T, by regulating interelectrode distance to make voltage remain near 25V after electric discharge starts, in maintenance stove, pressure is near 520mmHg, and anode consumption is complete, and product is in field region orientation deposition, and reaction terminates.Collect product in furnace chamber.
Claims (22)
1. by the method preparing Graphene and carbon mano-tube composite of discharging in-between the electrodes, it is characterized in that anode comprises carbon material and metallic material, described metallic material is selected from oxide compound, the transition metal that the form of inorganic salt or organic salt exists with oxide compound, the mixture of the rare earth element of the form existence of inorganic salt or organic salt, or by above-mentioned one or more and metal Fe, Ni, Mo, the mixture of one or more compositions in Cr or Y, described method is carried out comprising in rare gas element and mixed-gas atmosphere carbon to other gas reactive,
Described carbon material is graphite, coal, pitch or carbon fiber, or their mixture;
Wherein said transition metal is selected from Fe, Ni, Mo or Cr, and described rare earth element is selected from La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu in Sc, Y and group of the lanthanides;
Described rare gas element is selected from N
2, He, Ne, Ar, Kr or Xe;
Described have other gas reactive to carbon and be selected from NH
3, H
2, CO
2, air or O
2;
Based on the integral molar quantity of described metallic material and described carbon material, the molar content of described metallic material is 0.1-8%, and the mol ratio of described transition metal and described rare earth element is 8:1 to 1:2.
2. the method for claim 1, the molar content of described metallic material is 1-5%.
3. method as claimed in claim 2, the molar content of described metallic material is 1-4%.
4. method as claimed in claim 2, the molar content of described metallic material is 0.8-3.5%.
5. the method for claim 1, the mol ratio of described transition metal and described rare earth element is 6:1 to 4:1.
6. method as claimed in claim 5, the mol ratio of described transition metal and described rare earth element is 5:1 to 4:1.
7. method as claimed in claim 6, the mol ratio of described transition metal and described rare earth element is 4.5:1 to 4:1.
8. the method as described in claim 1 claim, described carbon material is the mixture of carbon fiber or carbon fiber and graphite.
9. the method for claim 1, described rare gas element is selected from He or Ar or its mixture, and described to have other gas reactive to carbon be NH
3or H
2.
10. the method for claim 1, in described mixed gas, the described dividing potential drop having other gas reactive to carbon is 5% to 80%.
11. methods as claimed in claim 10, the described dividing potential drop having other gas reactive to carbon is 8% to 70%.
12. methods as claimed in claim 11, the described dividing potential drop having other gas reactive to carbon is 10% to 60%.
13. methods as claimed in claim 12, the described dividing potential drop having other gas reactive to carbon is 12.5% to 50%.
14. methods as described in claim 1 or 10, the total gas pressure of described mixed gas is 400-760mmHg.
15. methods as claimed in claim 14, the total gas pressure of described mixed gas is 450-700mmHg.
16. methods as claimed in claim 15, the total gas pressure of described mixed gas is 500-600mmHg.
17. methods as claimed in claim 16, the total gas pressure of described mixed gas is 500-550mmHg.
18. the method for claim 1, sparking voltage is 10-40V, and electric current is 60-200A.
19. methods as claimed in claim 18, sparking voltage is 15-35V, and electric current is 80-150A.
20. methods as claimed in claim 19, sparking voltage is 20-30V, and electric current is 100-140A.
21. methods as claimed in claim 20, sparking voltage is 22-28V, and electric current is 110-130A.
22. the method for claim 1, add the magnetic field of magneticstrength >=0.5T in discharge process, to obtain Graphene and the carbon mano-tube composite of orientation.
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| Carbon Nanotube Hybrid Materials for High-Performance Transparent Conductors.《NANO LETTERS》.2009,第9卷(第5期),第1949-1955页. * |
| Simple Method of Preparing Graphene Flakes by an Arc-Discharge Method;K. S. Subrahmanyam,et.al.;《J. Phys. Chem. C》;20090220;第113卷(第11期);第4257–4259页 * |
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