CN102627275B - Method for preparing graphene by melting carbon-containing alloy to separate out carbon in solidification process - Google Patents
Method for preparing graphene by melting carbon-containing alloy to separate out carbon in solidification process Download PDFInfo
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Abstract
The invention discloses a method for preparing graphene by melting carbon-containing alloy to separate out carbon in the solidification process. The method comprises the following steps of: firstly, preparing carbon-containing metal or alloy, wherein the content of carbon in the metal or the alloy is less than or equal to 10 percent; secondly, heating to melt or partially melt the carbon-containing metal or alloy; and thirdly, cooling at the speed of 0.1 to 109DEG C/s, solidifying the metal or the alloy and separating out the grapheme on the surface. The invention particularly discloses a single-roll preparation method similar to a preparation method for preparing amorphous metal or alloy. The melt carbon-containing metal or alloy melt is sprayed to the rotary metal roll surface, so that the melt is quickly cooled to obtain the grapheme. According to the method disclosed by the invention, the grapheme can be prepared in a large scale, high quality, high speed and low cost; and the method has important application for realizing industrialization and real application obtaining of the grapheme.
Description
technical field:
the present invention relates to field of preparation of graphene, particularly relate to and a kind ofly in process of setting, separate out by melting phosphorus-containing alloy the method that carbon prepares Graphene.
background technology:
Geim study group of Univ Manchester UK (Novoselov KS in 2004, et al, Science, 2004,306:666) obtain mono-layer graphite-Graphene (Graphene) by mechanically peel highly oriented pyrolytic graphite, this work before having broken perfect two-dirnentional structure that is theoretical and that experimentally think cannot to obtain the Nobel Prize in physics of 2010 in the understanding of non-zero absolute temperature stable existence.Graphene is by individual layer sp
2the bi-dimensional cellular shape structure of the tightly packed one-tenth of hydbridized carbon atoms, the two-dirnentional structure of its uniqueness and splendid crystallography quality make Graphene have a lot of special character (Virendra S, et al, Progress in Materials Science, 2011,56:1178), as the high capacity of heat transmission (5000Wm
-1k
-1), outstanding mechanical property (Young's modulus reaches 1TPa), very high carrier mobility (250,000 cm
2/ Vs); High-specific surface area (2600m
2/ g); Because the electrical type in Graphene is like the quantum hall effect of the exception shown without quality dirac fermion; Complete single-layer graphene is not by atom larger than helium etc.These special character of Graphene make it can obtain potential application in a lot, the performance of some materials or device is obtained and greatly improves or create brand-new materials and devices.Such as, complete single-layer graphene, not by the characteristic of the atom larger than helium, can be used for the electrode materials, heat dissipation film, the desirable barrier film (Barrier Film) that manufacture battery; High carrier mobility characteristic may be used for preparation ultra-high speed field-effect transistor and laser apparatus; High transparent and high conductivity, make it may become nesa coating as well and substitute the ITO material generally used at present, for aspects such as touch panel, flexible liquid crystal panel, solar cells; High specific surface area, can improve the output power density of store battery and ultracapacitor; And the mechanical property of its excellence, then make it can manufacture high performance composite, elevator stretching into space etc.
Graphene excellent properties and outstanding potential using value, excite the research enthusiasm of people.Efficiently, conveniently, prepare on a large scale at an easy rate high-quality Graphene and can to its carry out composition, structure, shape regulation and control be realize its application basis.So far, the method preparing Graphene (appoints literary talent etc., novel charcoal material, 2011, 26 (1): 71) mainly contain: mechanically peel (Novoselov KS, et al, Science, 2004, 306:666), chemical stripping (Park S, Ruoff RS, Nature Nanotechnol, 2009, 4:217) or chemosynthesis (Cai JM, et al, Nature, 2010, 466:470), SiC epitaxy (Berger C, et al, Science, 2006, 312:1191), single-crystal metal surface epitaxy (Kevin FM, et al, Carbon, 2009, 47:1806), chemical vapour deposition (CVD method, Li XS, et al, Science, 2009, 324:1312) etc.These methods respectively have quality, and mechanically peel method can obtain the high-quality graphene film be more difficult to get when adopting additive method, and apparatus and process is simple, but not easily accomplishes scale production; Chemical peeling easily realizes the mass-producing of Graphene, but the standby Graphene of this legal system contains more defect, loaded down with trivial details with a large amount of chemical functional groups, subsequent disposal; Chemical synthesis is not easy to obtain the larger Graphene of area; SiC epitaxy can obtain the single-layer graphene of big area better quality, but growth conditions is harsh and be difficult to transfer, significantly limit the popularization of this preparation method; Single-crystal metal epitaxial growth method prepares the method for graphite flake layer in early days, but the making metal epitaxial process cost intensive and be difficult to mass-producing of single-crystal metal substrate and high vacuum; CVD method; first in high temperature carbon-containing atmosphere, carburizing is carried out to metal; afterwards cooling is fast carried out to metal and prepare a kind of method of Graphene; the method preparation condition is simple, controlled; the Graphene quality obtained is high, area is large; being easy to transfer on required substrate, is therefore a kind of method that Graphene is prepared in more promising mass-producing, but at present still needs development to improve preparing in the scale of Graphene, quality and controllability.Therefore, to can the research invention of the efficient method of large-scale production Graphene, remaining rich challenge and urgently to be resolved hurrily, be also realize its key finally applied.
The mechanism of Graphene is prepared from CVD method, wherein Ni etc. have the metal of higher solubility to carbon, the difference utilizing carbon solubleness in a metal under high and low temperature, separate out oversaturated carbon at low temperature and form Graphene, under high temperature, carburizing is then under being in carbon-containing atmosphere for a long time under making metallic high temperature, and carbon progressively infiltrates metal and completes cementation process.High temperature carburizing process time is wherein longer, but its meaning is just metallic surface and shallow top layer infiltrates a small amount of carbon, this cementation process, completely can prefabricated carbon containing alloy and obtain.Simultaneously, although research shows, when adopting CVD method to produce Graphene on Ni tinsel, if cooling rate is too large, would not Graphene be obtained, but, the precipitation of this carbon is diffused as basis with carbon atom in solid metal, if carbon atom spreads in liquid or liquid and solid-state mixed state, carbon atom will be separated out at faster speed and can generate Graphene in the shorter time, therefore can with the Graphene of speed of cooling acquisition faster.Obtaining in large speed of cooling, the preparation method of non-crystaline amorphous metal provides good reference, such as single rod preparation method and two roller preparation method, hammer anvil method, is similar to single rod method, is suitable for the molten drop method of high-meltiing alloy fusing and cooling, centrifuging, injection method, melt is stained with method (Wang Juanjuan, non-crystalline solids and technology of preparing (courseware) thereof) etc., can provide very high speed of cooling.And certain methods wherein, as single-roller method, become industrialized ordinary method.Therefore, if adopt similar technique means, likely develop a kind of extensive, method that high quality, high speed, low cost prepare Graphene.
summary of the invention:
In view of this, the object of the present invention is to provide and a kind ofly in process of setting, separate out by melting phosphorus-containing alloy the method that carbon prepares Graphene, phosphorus-containing alloy by molten state cools, and makes it directly to produce Graphene in process of setting, can realize extensive continuous production Graphene.
For achieving the above object, the present invention by the following technical solutions:
In process of setting, separate out by melting phosphorus-containing alloy the method that carbon prepares Graphene, it is characterized in that: comprise the steps: the first step, prepare carbon containing metal or alloy, carbon content≤10% in metal or alloy; Second step, heating, makes carbon containing metal or alloy melt or partial melting; 3rd step, cooling, speed of cooling is 0.1 DEG C/s-10
9dEG C/s, metal or alloy solidifies and at surperficial indigenous graphite alkene.
Described metal and alloy can make it melt by various method, comprise medium, high frequency heating, and irradiated heat, the heating of use resistance furnace, direct-electrifying heats, and Heating temperature should at least make metal or alloy part occur fusing.
The cooling of described metal and alloy melt, comprise at present institute and use the melt supercooled method of manufacture amorphous metal or alloy, as prepared the methods such as single rod method of amorphous metal or alloy and two roller methods, metal or alloy melt-coating process that the present invention proposes specially etc.; Also comprise the method that other can make melt cooling, such as, under room temperature naturally cooling, putting into holding furnace, to carry out stove according to certain speed of cooling cold, adopts alloy or alloy melt to spray to form powder, melt evaporative condenser etc.The speed of cooling, can from from 0.1 DEG C/s to 10 according to requiring
9dEG C/s, mainly 10
2-10
7dEG C/s scope, particularly 10
3-10
7dEG C/s within the scope of best results.
Various method is adopted to make in metal melt process of cooling the carbon containing metal or alloy of molten state, no matter by alloy melting, or cooling, can carry out under vacuum state or particular pressure, can carry out under inert atmosphere, reducing atmosphere, also can directly carry out under air.
Further, described carbon containing metal or alloy mainly comprises magnesium-yttrium-transition metal, or the binary alloy that forms of magnesium-yttrium-transition metal and other elements or multicomponent alloy.
Described melting phosphorus-containing alloy, for having the metal or alloy of certain solubility, the phosphorus-containing alloy formed together with carbon to carbon.These have the metal or alloy of certain solubility to carbon, mainly comprise magnesium-yttrium-transition metal, or the binary alloy that forms of magnesium-yttrium-transition metal and other elements or multicomponent alloy, such as Ni, Fe, Pt, Ru, the metals and alloy etc. such as Cu/Ni.Carbon is had to the metal or alloy of certain solubility, can also contain the elements such as nitrogen (N), boron (B), phosphorus (P), sulphur (S), these elements equally also can be separated out in the process of Graphite Precipitation, thus realize the doping of Graphene.
Further, the raw material prepared, when heating, can be put into the inorganic chemical property management of crucible or band nozzle, then add hot smelting carbon containing metal or alloy by described second step.
Nozzle can be designed to circular hole, strip, perforate (array is lined up in multiple hole) etc. on request, and size is according to the design such as width, thickness of the sheet metal strip that will obtain.Further, when cooling in described 3rd step, by the carbon containing metal or alloy melt jet of melting on the metal roll surface rotated, make melt cooling and obtain Graphene; The processing parameter used is: metallic roll diameter 1-200 centimetre, metallic roll rotating speed 1-10000 rev/min; Distance 0.1-10 centimetre between metallic roll and nozzle.
Further, when cooling in described 3rd step, first by between carbon containing metal or alloy melt jet to two the metal roll surfaces rotated, melt is cooled by metallic roll and rolls as sheet metal strip, the spontaneous formation Graphene on the two sides of band; The processing parameter used is: metallic roll diameter 1-200 centimetre, metallic roll rotating speed 1-10000 rev/min, described two the distance 0.1-10 centimetre between metallic roll and nozzle.
Further, the cooling in the heating in described second step or the 3rd step is carried out in rare gas element or reducing gas, and the pressure of described gas is 10
-6between Pa to 10MPa.The gas that described rare gas element or reducing gas use can be Ar, He, N
2, H
2, the gas such as CO and composition thereof.
Further, when cooling in described 3rd step, by phosphorus-containing alloy coating or to be injected on the metallic strip surface of motion and to make it cooling, Graphene is separated out from the alloy surface that solidifies in the process; The movement velocity of described metal strip is 0.1-100m/s.
Further, the metal strip of described motion adopts the mode of folding and unfolding metal coil tape that metal strip is moved, and phosphorus-containing alloy melt directly sprays or is coated on metal strip, forms phosphorus-containing alloy film thereon, and in alloy film forming process, also form Graphene on its surface simultaneously.
Further, when cooling in described 3rd step, carbon containing metal or alloy melt adopted spray method or the solid surface that mode is coated to high heat conduction such as to topple over, carbon containing metal or alloy melt solidifies and indigenous graphite alkene at this solid surface.
Further, when cooling in described 3rd step, carbon containing metallic alloy melt is dropped in two relative movement and between the good metallic surface of heat conduction, cool rapidly after melt is squeezed and be pressed into sheet or specific shape, in the process, from the metal or alloy surface indigenous graphite alkene solidified.
Further, when cooling in described 3rd step, by the internal surface of the carbon containing metal or alloy melt jet in silica tube middle for the cylinder being in high speed rotating to cylinder, and by the metal or alloy band that melt obtains at cylinder inner wall curl along the axial-movement of cylinder, at the spiral helicine metal or alloy strip surface indigenous graphite alkene that this solidifies; Described drum diameter 1-100 centimetre, velocity of rotation is 1-2000 rev/min, silica tube lift velocity 1-500 cm per minute.
Further, when cooling in described 3rd step, tinsel is skimmed over carbon containing metal or alloy melt, or by rosette along carbon containing metal or alloy bath surface high speed rotating, melt is stained with skim by tinsel or disk thus carbon containing metal or alloy is cooled rapidly, is stained with at this skim phosphorus-containing alloy indigenous graphite alkene on the surface.
Beneficial effect of the present invention is:
Advantage of the present invention be mainly can on a large scale, high quality, high speed, low cost prepare Graphene, to realizing the industrialization of Graphene and real obtain application there is important effect.Wherein prepare single roller method of amorphous metal or alloy strip steel rolled stock and two these class methods of roller method for similar, be characterized in making molten metal or the condensation of alloy high speed get off and become solid metal or alloy by rapid quenching, and in this condensation process, carbon will be separated out from metal or alloy surface and be formed Graphene, in the present invention, the graphene preparation method of the spontaneous precipitation of molten metal fast quenching carbon (Molten melt quenched-induced carbon self segregation-MMQCSS) is referred to as.For single rod method, its speed of cooling is 10
5dEG C/s magnitude, maximumly reach 10
6dEG C/s, determined by the rotating speed of copper rod to a great extent.Single roller method and two roller preparation method are the methods of ripe preparation of industrialization non-crystaline amorphous metal, product is thickness tens microns, width number centimetre arrives several tens cm, length then can reach the metal thin strip of dozens of kilometres according to the amount of raw material, and the preparation speed of band can reach tens of meter per second, therefore can obtain large-sized Graphene fast, it prepares speed is adopt conventional CVD process to prepare thousands of times of the speed of Graphene at present.And when adopting metal or alloy melt jet or be coated in the sheet metal strip of high-speed motion, melt to be laid on sheet metal strip and cooling fast, in process of cooling, indigenous graphite alkene.This kind of method, prepare except the advantage of Graphene except having single roller method and two roller method, the Graphene that width is higher can also be prepared, because the width of the sheet metal strip for carrying carbon containing metal or alloy own can very greatly (more than 100 centimetres), therefore can obtain the very large coat of width, the coat that this width is very large then can separate out the very large Graphene of width.And for the phosphorus-containing alloy particle sprayed, then indigenous graphite alkene in the process of solidifying, forms the alloying pellet being coated with Graphene.
accompanying drawing illustrates:
The similar device schematic diagram of preparing the single roller method of amorphous metal or alloy strip steel rolled stock of Fig. 1 for using in embodiment 1-3 in the present invention;
The similar device of preparing the two roller methods of amorphous metal or alloy strip steel rolled stock of Fig. 2 for using in embodiment in the present invention 4;
Fig. 3 is scanning electronic microscope (SEM) image on the Ni/C alloy strip steel rolled stock surface adopting single-roller method to prepare in the embodiment of the present invention 1;
Fig. 4 is that the Raman on the Ni/C alloy strip steel rolled stock surface adopting single-roller method to prepare in the embodiment of the present invention 1 detects collection of illustrative plates;
Fig. 5 is by metal or alloy melt jet or the schematic diagram of the metal foil roll coil of strip being coated in folding and unfolding in the embodiment of the present invention 5;
Fig. 6 applies the schematic diagram that centrifuging prepares Graphene in the embodiment of the present invention 7.
embodiment:
Below in conjunction with accompanying drawing and embodiment, technical scheme of the present invention is further described:
Embodiment 1:
As shown in Figure 1, the single roller apparatus preparing amorphous metal or alloy strip steel rolled stock (foil) is used to prepare Graphene.The nickel block of certain mass proportioning and carbon (carbon containing 1.5wt%) are put into the quartz test tube with nozzle, hot smelting is added by ruhmkorff coil, obtaining Ni/C alloy melt and being ejected into velocity of rotation at about 1500 DEG C is on the Ni metal roller of 2000 revs/min, Ni metal roller diameter 32 centimetres, by the high speed rotating of metallic roll, melt quenching is solidified, obtain long Ni/C alloy foil, its speed of cooling is 10
5dEG C/s magnitude, maximumly reach 10
6dEG C/s, determined by the rotating speed of copper rod to a great extent.In this foil, the spontaneous precipitation of carbon generates Graphene, and this method the present invention preparing Graphene is referred to as the spontaneous separation method of molten metal quenching carbon.From scanning electronic microscope (SEM) figure on Fig. 3 Ni/C alloy strip steel rolled stock surface, it there is translucent membranoid substance, membranoid substance has fold; Fig. 4 is then that the Raman on Ni/C alloy strip steel rolled stock surface detects collection of illustrative plates, only has G peak (about 1583cm as seen
-1) and 2D peak (about 2699cm
-1) and without D peak (about 1350cm
-1) and 2D peak height in G peak, this membranoid substance obtained not is amorphous carbon but Graphene or Multi-layer graphite sheet, but because 2D peak height is in G peak, may be the more less Graphene of individual layer or the number of plies.
Embodiment 2:
The nickel block of certain mass proportioning and carbon (carbon containing 1.0wt%) are put into the quartz test tube with nozzle, hot smelting is added by ruhmkorff coil, obtaining Ni/C alloy melt and being ejected into velocity of rotation at about 1550 DEG C is on the Ni metal roller of 3500 revs/min, quenching is realized by the high speed rotating of metallic roll, obtain long Ni/C alloy foil, in this foil, also obtain translucent membranoid substance, membranoid substance has fold; The Raman on alloy strip steel rolled stock surface also only have G peak and 2D peak and without D peak and 2D peak height in G peak, this membranoid substance obtained not is amorphous carbon but single-layer graphene or the less Graphene of the number of plies.
Embodiment 3:
The nickel by powder of certain mass proportioning, copper powder and carbon dust mix by a certain percentage (carbon containing 1.0wt%, cupric 9.0wt%), adopt hydropress make green compact and under high temperature reducing atmospheres anneal (1000 DEG C, 5 hours; Hydrogen and argon gas total flux 300sccm-standard cubic centimeter per minute, volume ratio 1:9), obtain the base substrate of Ni/Cu/C, in this base substrate, Ni and Cu and C has certain diffusion.This base substrate is put into the quartz test tube with nozzle, also can select the inorganic chemical property management such as carbon tube, ZrO pipe.Being added hot smelting acquisition Ni/Cu/C alloy melt by ruhmkorff coil and be ejected into velocity of rotation at about 1550 DEG C is on the Ni metal roller of 3000 revs/min, quenching is realized by the high speed rotating of metallic roll, obtain long Ni/Cu/C alloy foil, in this foil, also obtain translucent membranoid substance, membranoid substance has fold; The Raman on alloy strip steel rolled stock surface also only has G peak and 2D peak and without D peak, and this membranoid substance obtained not is amorphous carbon but the less Graphene of the number of plies.
Embodiment 4:
As shown in Figure 2, the two roller apparatus preparing amorphous metal or alloy strip steel rolled stock are used.The nickel of certain mass proportioning, Ni/C alloy are mixed by a certain percentage, puts into quartz test tube with nozzle, hot smelting is added by ruhmkorff coil, obtaining Ni/C alloy melt (carbon containing 1.2wt%) and being ejected into velocity of rotation at about 1500 DEG C is 2000 revs/min, but turning direction contrary two Ni metal rollers between, two Ni metal roller diameters are 20 centimetres, and the gap between two Cu rollers is 300 microns.Phosphorus-containing alloy melt realizes quenching and ejection downwards by the high speed rotating of metallic roll, obtains long Ni/C alloy foil.In this foil, also obtain translucent membranoid substance, membranoid substance has fold; The Raman on alloy strip steel rolled stock surface also only have G peak and 2D peak and without D peak and 2D peak height in G peak, this membranoid substance obtained not is amorphous carbon but Graphene.
Embodiment 5:
Ni, Fe, Ni/C master alloy is melted, adopts plumbago crucible fusing and 1600 DEG C of insulations, make the weight ratio of Ni, Fe, C in alloy reach 92:7.6:0.4.Brought to the Cu that high-speed motion (20m/s), width are 50 centimetres by phosphorus-containing alloy melt jet, Cu band is moved by draw off gear, and Fig. 5 is shown in by device schematic diagram, and obtaining thickness is 30 microns, the Ni/Fe/C alloy coat (film) of width more than 30 centimetres.On this metallic film, SEM picture shows to separate out translucent membranaceous material, and Raman spectrum shows equally, and alloy firm has been separated out single-layer graphene or multi-layer graphene.
Embodiment 6:
By Co, Ni/C master alloy fusing (weight ratio of Ni, Co, C is 87.5:11.7:0.8), and adopt spray method Ar to be ejected into by phosphorus-containing alloy in the reaction chamber of Ar atmosphere, obtain Ni/Co/C nano particle, around nano particle, define graphite linings.Because be adopt spray method, speed of cooling is very high, and speed of cooling is 10
3-10
7dEG C/s, metal or alloy solidifies and at surperficial indigenous graphite alkene.
Embodiment 7:
The nickel of certain mass proportioning, Ni/C alloy are mixed by a certain percentage, (but its nozzle direction is not downward vertically in ground to the quartz test tube putting into nozzle, but be parallel to ground) in, hot smelting is added by ruhmkorff coil, obtain Ni/C alloy melt (carbon containing 0.5wt%) and adopt centrifuging to prepare spiral sheet metal strip at about 1500 DEG C, Fig. 6 is shown in by device schematic diagram.In preparation process, drum diameter 50 centimetres, velocity of rotation is 120 revs/min, silica tube lift velocity 100 cm per minute.The sheet metal strip obtained also can see translucent membranaceous material by SEM photo, and Raman spectrum also shows simultaneously, obtains Graphene.
Embodiment 8:
Ni, Fe, Ni/C master alloy is melted, adopts plumbago crucible fusing under vacuo and 1650 DEG C of insulations, make the weight ratio of Ni, Fe, C in alloy reach 96:4.5:0.5.Be on the Ni metal plate of 20 degree by its rapid dumps with ground afterwards, the metal melt of trickling forms banded film, and SEM observes and shows, on this metallic membrane, also obtain translucent membranoid substance, and Raman spectrum shows equally, obtains Graphene.
Embodiment 9:
Similar to the hammer anvil method making metal and alloy melt cool fast, phosphorus-containing alloy (Ni:C weight ratio is 99.7:0.3) is dropped in (squares that the length of side is 50 centimetres) on Ni metal plate surface, the onesize Cu plate of another block is pressed in rapidly on the Cu plate that drips and have molten drop, be rapidly cooled after melt is squeezed and be pressed into the thin slice that thickness is less than 100 microns, speed of cooling is 10
5dEG C/s magnitude.In the process, Graphene has been separated out from the phosphorus-containing alloy slice surfaces solidified.
Embodiment 10:
The alloy melt (Pt content 99wt%) of melting Pt, C, immerses alloy melt by Pt plate (2 millimeters) afterwards and takes out rapidly, on this Pt plate, obtaining the semitransparent thin film of one deck carbon containing Pt alloy.Research shows, the film of this carbon containing Pt alloy has also separated out Graphene.
Embodiment 11:
Be the Ni/Fe/C(weight ratio 80:29.2:0.8 of 100 microns by rolling) alloy sheet, in high vacuum conditions 1050 DEG C heating 1 hour, afterwards adopt 50 DEG C/s speed cooling.SEM observes and can find to separate out semitransparent thin film on alloy sheet.Raman shows, this film is Graphene.
Embodiment 12:
The iron block of certain mass proportioning and carbon (carbon containing 3wt%) are put into the ZrO with nozzle
2in test tube, add hot smelting by ruhmkorff coil, obtaining Fe/C alloy melt and being ejected into velocity of rotation at about 1600 DEG C is on the Ni metal roller of 4000 revs/min, Ni metal roller diameter 50 centimetres, make melt quenching by the high speed rotating of metallic roll, speed of cooling is approximately 10
5dEG C/s magnitude, obtain long Fe/C alloy foil, in this foil, the spontaneous precipitation of carbon generates Graphene.
Embodiment 13:
The nickel block of certain mass proportioning and carbon (carbon containing 1wt%) are put into the plumbago crucible with nozzle, by resistive heating melting, obtaining Ni/C alloy melt and being ejected into velocity of rotation at about 1550 DEG C is on the Ni metal roller of 1500 revs/min, Ni metal roller diameter 50 centimetres, melt quenching is made by the high speed rotating of metallic roll, obtain long Ni/C alloy foil, in this foil, the spontaneous precipitation of carbon generates Graphene.
Embodiment 14:
The nickel block of certain mass proportioning, silver bullion and carbon (carbon containing 0.8wt%, argentiferous 10wt%) put into plumbago crucible with nozzle, by resistive heating melting, obtaining Ni/Ag/C alloy melt and being ejected into velocity of rotation at about 1525 DEG C is on the Ni metal roller of 150 revs/min, Ni metal roller diameter 5 centimetres, melt quenching is made by the high speed rotating of metallic roll, speed of cooling is approximately 1000 DEG C/s magnitude, obtain long Ni/C alloy foil, in this foil, the spontaneous precipitation of carbon generates Graphene.
Embodiment 15:
Certain mass first by the Ni/C(carbon containing 5wt% of arc melting gained) put into graphite test tube with nozzle, by resistive heating melting, obtaining Ni/C alloy melt and being ejected into velocity of rotation at about 1570 DEG C is on the Ni metal roller of 500 revs/min, Ni metal roller diameter 50 centimetres, make melt quenching by the high speed rotating of metallic roll, speed of cooling is approximately 10
5dEG C/s magnitude, obtain Ni/C alloy foil, in this foil, the spontaneous precipitation of carbon generates Graphene.
Embodiment 16:
As shown in Figure 2, the two roller apparatus preparing amorphous metal or alloy strip steel rolled stock are used.The nickel of certain mass proportioning, platinum, Ni/C alloy are mixed by a certain percentage, puts into ZrO with nozzle
2in crucible, hot smelting is added by ruhmkorff coil, obtain Ni/Pt/C alloy melt (carbon containing 1.2wt%, platiniferous 3.8wt%) and to be ejected into velocity of rotation at about 1600 DEG C be 3000 revs/min, but turning direction contrary two Ni metal rollers between, two Ni metal roller diameters are 20 centimetres, and the gap between two Cu rollers is 300 microns.Phosphorus-containing alloy melt realizes quenching and ejection downwards by the high speed rotating of metallic roll, obtains long Ni/Pt/C alloy foil.In this foil, also obtain translucent membranoid substance, membranoid substance has fold; The Raman on alloy strip steel rolled stock surface also only has G peak and 2D peak and without D peak, this membranoid substance obtained not is amorphous carbon but Graphene.
Claims (10)
1. in process of setting, separate out by melting phosphorus-containing alloy the method that carbon prepares Graphene, it is characterized in that: comprise the steps:
The first step, prepares carbon containing metal or alloy, carbon content≤10% in metal or alloy;
Second step, heating, makes carbon containing metal or alloy melt or partial melting;
3rd step, cooling, speed of cooling is 10
2dEG C/s-10
9dEG C/s, metal or alloy solidifies and at surperficial indigenous graphite alkene; During cooling, by the carbon containing metal or alloy melt jet of melting on the metal roll surface rotated, make melt cooling and obtain Graphene; The processing parameter used is: metallic roll diameter 1-200 centimetre, metallic roll rotating speed 1-10000 rev/min; Distance 0.1-10 centimetre between metallic roll and nozzle.
2. a kind ofly as claimed in claim 1 in process of setting, separate out by melting phosphorus-containing alloy the method that carbon prepares Graphene, it is characterized in that: speed of cooling is 10
2-10
7dEG C/s.
3. a kind ofly as claimed in claim 1 in process of setting, separate out by melting phosphorus-containing alloy the method that carbon prepares Graphene, it is characterized in that: speed of cooling is 10
3-10
7dEG C/s.
4. a kind ofly as claimed in claim 1 in process of setting, separate out by melting phosphorus-containing alloy the method that carbon prepares Graphene, it is characterized in that: when cooling in described 3rd step, first by between carbon containing metal or alloy melt jet to two the metal roll surfaces rotated, melt is cooled by metallic roll and rolls as sheet metal strip, the spontaneous formation Graphene on the two sides of band; The processing parameter used is: metallic roll diameter 1-200 centimetre, metallic roll rotating speed 1-10000 rev/min, described two the distance 0.1-10 centimetre between metallic roll and nozzle.
5. a kind ofly as claimed in claim 1 in process of setting, separate out by melting phosphorus-containing alloy the method that carbon prepares Graphene, it is characterized in that: when cooling in described 3rd step, by phosphorus-containing alloy coating or be injected in motion metallic strip surface on and make it cooling, Graphene is separated out from the alloy surface solidified in the process; The movement velocity of described metal strip is 0.1-100m/s.
6. a kind ofly as claimed in claim 5 in process of setting, separate out by melting phosphorus-containing alloy the method that carbon prepares Graphene, it is characterized in that: the metal strip of described motion adopts the mode of folding and unfolding metal coil tape that metal strip is moved, phosphorus-containing alloy melt directly sprays or is coated on metal strip, form phosphorus-containing alloy film thereon, and in alloy film forming process, also form Graphene on its surface simultaneously.
7. a kind of as described in claim 1 separates out by melting phosphorus-containing alloy the method that carbon prepares Graphene in process of setting, it is characterized in that: when cooling in described 3rd step, adopt spray method or the mode of toppling over to be coated to the solid surface of high heat conduction carbon containing metal or alloy melt, carbon containing metal or alloy melt solidifies and indigenous graphite alkene at this solid surface.
8. a kind ofly as claimed in claim 1 in process of setting, separate out by melting phosphorus-containing alloy the method that carbon prepares Graphene, it is characterized in that: when cooling in described 3rd step, carbon containing metallic alloy melt is dropped in two relative movement and between the good metallic surface of heat conduction, cool rapidly after melt is squeezed and be pressed into sheet or specific shape, in the process, from the metal or alloy surface indigenous graphite alkene solidified.
9. a kind of as described in claim 1 or 4 separates out by melting phosphorus-containing alloy the method that carbon prepares Graphene in process of setting, it is characterized in that: when cooling in described 3rd step, by the internal surface of the carbon containing metal or alloy melt jet cylinder in silica tube middle for the cylinder being in high speed rotating, and by the metal or alloy band that melt obtains at cylinder inner wall curl along the axial-movement of cylinder, at the spiral helicine metal or alloy strip surface indigenous graphite alkene that this solidifies; Described drum diameter 1-100 centimetre, velocity of rotation is 1-2000 rev/min, silica tube lift velocity 1-500 cm per minute.
10. a kind of as described in claim 1 or 4 separates out by melting phosphorus-containing alloy the method that carbon prepares Graphene in process of setting, it is characterized in that: when cooling in described 3rd step, tinsel is skimmed over carbon containing metal or alloy melt, or by rosette along carbon containing metal or alloy bath surface high speed rotating, melt is stained with skim by tinsel or disk thus carbon containing metal or alloy is cooled rapidly, is stained with at this skim phosphorus-containing alloy indigenous graphite alkene on the surface.
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| CN103508450B (en) * | 2013-09-11 | 2015-05-20 | 清华大学 | Laser preparation method for large-area patterned graphene |
| CN103466609B (en) * | 2013-09-25 | 2015-02-18 | 电子科技大学 | Preparation method of double-layer graphene films |
| JP6506738B2 (en) * | 2014-09-09 | 2019-04-24 | 株式会社 東北テクノアーチ | Method for producing porous graphite and porous graphite |
| CN105016329A (en) * | 2015-07-06 | 2015-11-04 | 兰州大学 | Preparation method for graphene |
| CN105399089B (en) * | 2015-12-15 | 2018-11-30 | 深圳市国创新能源研究院 | Graphene generation method, device and equipment based on any substrate |
| CN107364846A (en) * | 2017-09-06 | 2017-11-21 | 蚌埠玻璃工业设计研究院 | A kind of device in substrate surface growth graphene film |
| CN108751167A (en) * | 2018-05-12 | 2018-11-06 | 深圳莱必德科技股份有限公司 | A kind of graphene solution preparation method |
| CN110668432B (en) * | 2019-09-27 | 2021-05-14 | 北京碳垣新材料科技有限公司 | Device for growing graphene by taking metal powder liquid phase as substrate |
| CN112620640B (en) * | 2020-12-09 | 2023-01-31 | 温州宏丰电工合金股份有限公司 | Preparation method of AgNi electrical contact material based on recycling of AgC scrap |
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