CN104860298A - Method for preparing graphene by using molten state reaction bed - Google Patents
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Abstract
The present invention provides a method for preparing graphene by using a molten state reaction bed. The method comprises: 1) forming a molten state reaction bed, 2) making a cracked gas-state carbon source continuously pass through the surface of the molten state reaction bed, and 3) making the carbon be subjected to supersaturated precipitation in the molten state reaction bed so as to form graphene on the molten state reaction bed, or comprises: 1) mixing a solid-state or liquid-state carbon source and a reaction bed substance to form a mixture, 2) melting the mixture to make the solid-state or liquid-state carbon source be cracked so as to form a carbon-containing molten state reaction bed, and 3) making the carbon be subjected to supersaturated precipitation in the molten state reaction bed so as to form graphene on the molten state reaction bed. According to the present invention, the method has characteristics of low cost, high efficiency and low pollution, the prepared graphene has the good quality, and the difficult problem of the graphene peeling and transfer in the engineering technology can be solved.
Description
Technical field
The present invention relates to field of new material preparation, specifically, relate to a kind of preparation method of Graphene.
Background technology
Graphene be a kind of by carbon atom with sp
2hydridization and the two dimensional crystal with honeycomb lattice formed.2004, An Deliehaimu and the Constantine Nuo Woxiaoluofu of Univ Manchester UK successfully isolated Graphene from graphite, and therefore obtain 2010 years Nobel Prizes in physics.
Graphene has excellent performance.First, the specific surface area of Graphene is very large, can reach 2630m
2/ g.Secondly, the carbon atom in Graphene is with sp
2mode hydridization, three carbon atoms that each carbon atom is adjacent form stable C-C by σ key, and thus make Graphene have high mechanical property, its Young's modulus can reach 1100GPa, and breaking tenacity can reach 130GPa.Again, the π-electron delocalization in Graphene forms large π key, and π-electron can move freely, and therefore Graphene has excellent conductivity, and its carrier mobility speed can up to 2 × 10
5cm
2v
-1s
-1, and resistivity only has 10
-8Ω m.In addition, Graphene also has good optical property, thermal property and magnetic performance etc.Therefore, Graphene has huge potential using value, is considered to one of contemporary most important novel material.
At present, the preparation method of Graphene can be divided into method and from bottom to top method from top to bottom, and wherein, graphite oxide reduction method is the main method from top to bottom in method.The method is, first graphite is carried out Strong oxdiative process and obtains graphite oxide, then carries out stripping to graphite oxide and obtain graphene oxide, finally carries out reduction to graphene oxide and obtains Graphene.In the method, the structure of Strong oxdiative process meeting havoc graphene sheet layer, and the electron conjugated structure of graphene sheet layer partly can only be recovered after reduction treatment, the Graphene therefore obtained is of low quality.In addition, the oxidising process of graphite needs a large amount of strong acid (as the vitriol oil, concentrated nitric acid) or other strong oxidizer (as potassium permanganate solution) usually, and in reduction process, also need the toxic substance such as hydrazine hydrate or sodium borohydride, therefore the method efficiency is low, cost is high, energy consumption is large, seriously polluted.
Chemical vapour deposition (CVD) epitaxial growth method is the main method from bottom to top in method.The method method is, is at high temperature filled with carbon-source gas (as methane, ethane, acetylene etc.), and carbon-source gas decomposes and form Graphene on substrate.This method can form high-quality graphene on substrate (such as copper substrate), but requires strict, long reaction time, low yield, with high costs because using a large amount of hazardous gas to device and working condition.Particularly, be difficult to peel off from substrate at the Graphene of the upper growth of substrate (as copper, nickel, silicon carbide etc.) by this method.Often need during stripping to adopt the radical approach such as strong acid burn into high-temperature gasification, this just causes, and cost is high, environmental pollution large, and can damage Graphene finished product.
Summary of the invention
The present invention makes to solve the problems of the technologies described above, its objective is, a kind of method utilizing molten state reaction bed to prepare Graphene is provided, the method cost is low, efficiency is high, pollute less, preparation Graphene quality good, and can solve perplex engineering technological Graphene stripping and transport difficulties.
To achieve these goals, in one aspect of the invention, provide a kind of method utilizing molten state reaction bed to prepare Graphene, it comprises the steps: 1) form molten state reaction bed; 2) gaseous carbon source after cracking is made to continue through the surface of described molten state reaction bed; 3) make carbon supersaturation in described molten state reaction bed separate out, thus form Graphene on described molten state reaction bed.
Preferably, the material forming described molten state reaction bed is water-soluble substances or the material dissolving in weak acid and weak base at normal temperatures.Specifically, described water-soluble substances or the material that dissolves in weak acid and weak base can comprise from water miscible or dissolve in one or more materials selected the inorganic salt of weak acid and weak base, mineral alkali, oxide compound, nitride, carbide.Further preferably, in above-mentioned steps 3) after can also comprise the steps: 4) temperature of described molten state reaction bed is down to normal temperature, thus form deposited on silicon and have the material of Graphene; 5) there is by described deposited on silicon the material of Graphene to immerse wash-out in water or weak acid and weak base, thus obtain Graphene.
In addition, preferably, described gaseous carbon source can comprise one or more carbonaceous materials selected from aliphatic hydrocarbon, aromatic hydrocarbon, hydrocarbon derivative, carbon containing high molecular polymer.Further, described gaseous carbon source can be made to carry out cracking or described gaseous carbon source can be made to carry out cracking by preheating forming the gaseous carbon source after described cracking by the high temperature of described molten state reaction bed.Further again, carry out cracking making described gaseous carbon source or make carbon from the process that described molten state reaction bed is separated out, one or more in copper, copper-bearing alloy, nickel, nickel-containing alloys, platinum, platinum rhodium can be used as catalyzer.
Moreover, preferably, in above-mentioned steps 2) in can pass into one or more gases selected from nitrogen, argon gas, hydrogen, ammonia, as shielding gas simultaneously.
In addition, preferably, in above-mentioned steps 3) before, the solid substrate inserted for graphene growth can also be included in described molten state reaction bed, thus when making carbon in described molten state reaction bed during supersaturation precipitation, deposited graphite alkene while of in described solid substrate.
In addition, preferably, in above-mentioned steps 1) in, Graphene seed crystal can be added in described molten state reaction bed.
In another aspect of this invention, provide a kind of method utilizing molten state reaction bed to prepare Graphene, it comprises the steps: 1. solid-state or liquid carbon source to be mixed with reaction bed material, forms mixture; 2. by described mixture melt, make described solid-state or liquid carbon source cracking, and form the molten state reaction bed of carbon containing; 3. make carbon supersaturation in described molten state reaction bed separate out, thus form Graphene on described molten state reaction bed.
Preferably, described solid-state or liquid carbon source can comprise one or more carbonaceous materials selected from aliphatic hydrocarbon, aromatic hydrocarbon, hydrocarbon derivative, carbon containing high molecular polymer, phthalocyanines material.
Preferably, described reaction bed material is water-soluble substances or the material dissolving in weak acid and weak base at normal temperatures.Specifically, described water-soluble substances or the material that dissolves in weak acid and weak base can comprise from water miscible or dissolve in one or more materials selected the inorganic salt of weak acid and weak base, mineral alkali, oxide compound, nitride, carbide.Further, can also comprise the steps: 4. the temperature of described molten state reaction bed to be down to normal temperature after step 3., thus form the material that deposited on silicon has Graphene; 5. there is by described deposited on silicon the material of Graphene to immerse wash-out in water or weak acid and weak base, thus obtain Graphene.
Preferably, in described mixture, one or more catalyzer of separating out from described molten state reaction bed as described solid-state or liquid carbon source cracking or carbon in copper, copper-bearing alloy, nickel, nickel-containing alloys, platinum, platinum rhodium can be added.
Preferably, step 2. in can pass into one or more gases selected from nitrogen, argon gas, hydrogen, ammonia, as shielding gas simultaneously.
Preferably, before step is 3., the solid substrate inserted for graphene growth can also be included in described molten state reaction bed, thus when making carbon in described molten state reaction bed during supersaturation precipitation, deposited graphite alkene while of in described solid substrate.
Preferably, step 1. in, Graphene seed crystal can be added in described mixture.
From description above with put into practice, the present invention utilizes molten state reaction bed to prepare Graphene, can think the breakthrough of vapour deposition Graphene method in solid substrate to routine.The present invention's facility investment used is little, simple, cost is low, efficiency is high.Prepare in the process of Graphene of the present invention, do not need to use strong acid and other strong oxidizer, do not need to use toxic substance, therefore pollute less, little on the impact of Graphene performance.By dragging for away the Graphene of precipitation or have the material of Graphene to immerse wash-out in water or weak acid and weak base by the deposited on silicon formed after the molten state reaction bed of carbon containing is cooled to normal temperature to obtain Graphene from molten state reaction bed, the Graphene that easily can solve puzzlement engineering technological is peeled off and transport difficulties.If necessary, graphene growth also can be made usually to be difficult on the substrate grown, thus to be convenient to manufacture device.In addition, Graphene quality prepared by the present invention is good, cost performance is high, not high to the raw-material purity requirement preparing Graphene.
Accompanying drawing explanation
Fig. 1 prepares the schema of the method for Graphene for the molten state reaction bed that utilizes described in one aspect of the present invention;
Fig. 2 is the schematic arrangement of Nickel Phthalocyanine;
Fig. 3 for described in one embodiment of the present of invention be reaction bed material with cupric chloride, be carbon source with methane, take Copper Foil as catalyzer and solid substrate and the photo of the Graphene prepared;
Fig. 4 for described in one embodiment of the present of invention be reaction bed material with sodium-chlor, be carbon source with benzene and transmission electron microscope (TEM) photo of the Graphene prepared;
Fig. 5 for described in one embodiment of the present of invention be reaction bed material with Repone K, be carbon source with Nickel Phthalocyanine and X-ray diffraction (XRD) collection of illustrative plates of the Graphene prepared;
Fig. 6 for described in one embodiment of the present of invention be reaction bed material with Repone K, be carbon source with Nickel Phthalocyanine and transmission electron microscope (TEM) photo of the Graphene prepared.
Embodiment
The embodiment utilizing molten state reaction bed to prepare the method for Graphene of the present invention is described below with reference to the accompanying drawings.Those of ordinary skill in the art can recognize, when without departing from the spirit and scope of the present invention, can revise by various different mode to described embodiment.Therefore, accompanying drawing is illustrative with being described in essence, instead of for limiting the protection domain of claim.
Fig. 1 prepares the schema of the method for Graphene for the molten state reaction bed that utilizes described in one aspect of the present invention.As shown in Figure 1, the method utilizing molten state reaction bed to prepare Graphene described in one embodiment of the present of invention comprises following step:
First, in step sl, molten state reaction bed is formed.Then, in step s 2, the gaseous carbon source after cracking is made to continue through the surface of described molten state reaction bed.Finally, in step s3, carbon supersaturation in described molten state reaction bed is separated out, thus form Graphene on described molten state reaction bed.
In the present invention, described molten state reaction bed is used as liquid substrate and the carbon solvent of growing graphene, and after gaseous carbon source cracking, carbon dissolution is in molten state reaction bed.By making carbon supersaturation in molten state reaction bed separate out, carbon can be made to separate out on molten state reaction bed, thus form Graphene.
The material forming described molten state reaction bed can adopt the material having water miscible material at normal temperatures or dissolve in weak acid and weak base.Specifically, described water-soluble substances or the material dissolving in weak acid and weak base can comprise from inorganic salt that are water miscible or that dissolve in weak acid and weak base (such as, villaumite, vitriol, nitrate, carbonate, phosphoric acid salt, silicate, manganate, nickelate, cobaltates etc.), mineral alkali (such as, the metal hydroxides such as potassium hydroxide, sodium hydroxide, calcium hydroxide), one or more materials of selecting in oxide compound, nitride, carbide.But the present invention is not limited thereto.If directly dragged for away by Graphene after indigenous graphite alkene on described molten state reaction bed, the material so forming molten state reaction bed needs not to be the material having water miscible material or dissolve in weak acid and weak base.The fusing point forming the material of molten state reaction bed can in the scope of 500 DEG C to 1500 DEG C.
Described gaseous carbon source can comprise one or more carbonaceous materials selected from aliphatic hydrocarbon, aromatic hydrocarbon, hydrocarbon derivative, carbon containing high molecular polymer, such as, methane, ethane, propane, butane, ethene, propylene, acetylene, naphthenic hydrocarbon, benzene, toluene, naphthalene, methyl alcohol, ethanol, carbohydrate.Selected gaseous carbon source should easily cracking, to enable carbon be dissolved in molten state reaction bed.
The cracking of gaseous carbon source can be realized by two kinds of methods, in first method, directly can pass into gaseous carbon source, and this gaseous carbon source, when high-temperature molten-state reaction bed surperficial, can carry out cracking under the high temperature action of this molten state reaction bed.In the second approach, gaseous carbon source can be made first to carry out cracking by the method for preheating, the carbon source then after cracking through molten state reaction bed, and is dissolved in wherein.Reducing to make cracking temperature, making lysis efficiency improve and carbon precipitation efficiency is improved, carry out cracking making gaseous carbon source or make carbon from the process that molten state reaction bed is separated out, one or more in copper, copper-bearing alloy, nickel, nickel-containing alloys, platinum, platinum rhodium can be used as catalyzer.These catalyzer can make foil-like, netted, spumescence, and are placed on the place of gaseous carbon source generation cracking, as being placed on the top of molten state reaction bed.
While gaseous carbon source after making cracking continues through the surface of molten state reaction bed, one or more gases selected from nitrogen, argon gas, hydrogen, ammonia can be passed into, as shielding gas.
The carbon method that supersaturation is separated out in described molten state reaction bed can be comprised: the carbon source after passing into excessive cracking, or reduce the supersaturation solubleness of carbon in described molten state reaction bed by change temperature and/or pressure, thus carbon can be separated out to form Graphene from molten state reaction bed in supersaturation.But the present invention is not limited thereto.
In addition, in order to improve the crystalline rate of Graphene, Graphene seed crystal can be added in molten state reaction bed.
In one embodiment, after Graphene is formed on the surface of molten state reaction bed, can be shifted in time, thus the forming process of Graphene is carried out continuously.
In another embodiment, make carbon in molten state reaction bed supersaturation separate out before, the solid substrate being used for graphene growth can also be inserted in molten state reaction bed, thus when making carbon in molten state reaction bed during supersaturation precipitation, deposited graphite alkene while of in described solid substrate.Described solid substrate can comprise silicon chip, germanium wafer, sapphire, silicon carbide, aluminum oxide, aluminium nitride, tinsel, ceramic plate etc.
In yet another embodiment, when the material forming molten state reaction bed be water-soluble substances or the material dissolving in weak acid and weak base, the temperature of the molten state reaction bed of carbon containing can be down to normal temperature, after the molten state reaction bed of carbon containing solidifies, form the material that deposited on silicon has Graphene.Then, there is by described deposited on silicon the material of Graphene to immerse wash-out in water or weak acid and weak base, thus obtain Graphene.
In another aspect of this invention, solid-state or liquid carbon source can be used, utilize molten state reaction bed to prepare Graphene.The method utilizing molten state reaction bed to prepare Graphene described in the present invention on the other hand comprises the steps: 1. solid-state or liquid carbon source to be mixed with reaction bed material, forms mixture; 2. by described mixture melt, make described solid-state or liquid carbon source cracking, and form the molten state reaction bed of carbon containing; 3. make carbon supersaturation in described molten state reaction bed separate out, thus form Graphene on described molten state reaction bed.
Similar with description above, described solid-state or liquid carbon source comprises one or more carbonaceous materials selected from aliphatic hydrocarbon, aromatic hydrocarbon, hydrocarbon derivative, carbon containing high molecular polymer, phthalocyanines material.Wherein, phthalocyanines material is a class macrocylc compound, and Phthalocyanine center is a 18-π system be made up of carbon nitrogen conjugated double bond, has a cavity in ring.Two hydrogen atoms in cavity can be replaced by 70 multiple elements, and comprise nearly all metallic element and a part of non-metallic element and metal oxide etc., Fig. 2 shows the schematic arrangement of Nickel Phthalocyanine.
Described reaction bed material can adopt the material having water miscible material at normal temperatures or dissolve in weak acid and weak base.Specifically, described water-soluble substances or the material dissolving in weak acid and weak base can comprise from inorganic salt that are water miscible or that dissolve in weak acid and weak base (such as, villaumite, vitriol, nitrate, carbonate, phosphoric acid salt, silicate, manganate, nickelate, cobaltates etc.), mineral alkali (such as, the metal hydroxides such as potassium hydroxide, sodium hydroxide, calcium hydroxide), one or more materials of selecting in oxide compound, nitride, carbide.But the present invention is not limited thereto.If directly dragged for away by Graphene after indigenous graphite alkene on described molten state reaction bed, the material so forming molten state reaction bed needs not to be the material having water miscible material or dissolve in weak acid and weak base.The fusing point forming the material of molten state reaction bed can in the scope of 500 DEG C to 1500 DEG C.
In described mixture, one or more catalyzer of separating out from molten state reaction bed as described solid-state or liquid carbon source cracking or carbon in copper, copper-bearing alloy, nickel, nickel-containing alloys, platinum, platinum rhodium can be added, the temperature of molten state reaction bed can be reduced like this, or the lysis efficiency of carbon source can be improved, or improve the efficiency of carbon precipitation.
At the described mixture of fusing simultaneously, one or more gases selected from nitrogen, argon gas, hydrogen, ammonia can be passed into, as shielding gas.
The carbon method that supersaturation is separated out in described molten state reaction bed can be comprised: make carbon source excessive, or reduce the supersaturation solubleness of carbon in described molten state reaction bed by change temperature and/or pressure, thus carbon can be separated out to form Graphene from molten state reaction bed in supersaturation.But the present invention is not limited thereto.
In addition, in order to improve the crystalline rate of Graphene, Graphene seed crystal can be added in molten state reaction bed.
In one embodiment, after Graphene is formed on the surface of molten state reaction bed, can be shifted in time, thus the forming process of Graphene is carried out continuously.
In another embodiment, before reducing the supersaturation solubleness of carbon in molten state reaction bed, the solid substrate being used for graphene growth can also be inserted in molten state reaction bed, thus when making carbon in molten state reaction bed during supersaturation precipitation, deposited graphite alkene while of in described solid substrate.Described solid substrate can comprise silicon chip, germanium wafer, sapphire, silicon carbide, aluminum oxide, aluminium nitride, tinsel, ceramic plate etc.
In yet another embodiment, when the material forming molten state reaction bed be water-soluble substances or the material dissolving in weak acid and weak base, the temperature of the molten state reaction bed of carbon containing can be down to normal temperature, after the molten state reaction bed of carbon containing solidifies, form the material that deposited on silicon has Graphene.Then, there is by described deposited on silicon the material of Graphene to immerse wash-out in water or weak acid and weak base, thus obtain Graphene.
The method utilizing molten state reaction bed to prepare Graphene of the present invention is further described below in conjunction with object lesson.
example 1:
The material forming molten state reaction bed is cupric chloride, is loaded plumbago crucible and is placed in high-temperature vacuum pipe formula stove.Be warming up to 900 DEG C, be then warming up to 925 DEG C further and keep 1 hour, continue to pass into high purity (purity is more than 99.99%) methane and hydrogen gas mixture when 925 DEG C of insulations, wherein, methane and hydrogen volume are than being 95:1.Copper Foil is placed in molten state reaction bed, at the end of insulation, Copper Foil is taken out.On Copper Foil, Direct precipitation has high purity graphite alkene.Fig. 3 shows the photo of the Copper Foil being formed with Graphene.The specific surface area data of this grapheme material is shown in Table 1.
example 2:
The material forming molten state reaction bed is cupric chloride, is loaded plumbago crucible and is placed in high-temperature vacuum pipe formula stove.Be warming up to 1300 DEG C, be then cooled to 1250 DEG C and keep 1 hour, continue to pass into high purity (purity is more than 99.99%) methane and hydrogen gas mixture when 1250 DEG C of insulations, wherein, methane and hydrogen volume are than being 95:1.Sapphire sheet is placed in molten state reaction bed, in sapphire sheet, Direct precipitation has high purity graphite alkene material.The specific surface area data of this grapheme material is shown in Table 1.
example 3:
The material forming molten state reaction bed is potassium hydroxide, is loaded plumbago crucible and is placed in high-temperature vacuum pipe formula stove.Be warming up to 1100 DEG C, be then cooled to 1050 DEG C and keep 20 minutes, continue to pass into high purity (purity is more than 99.99%) acetylene and hydrogen gas mixture when 1050 DEG C of insulations, wherein, acetylene and hydrogen volume are than being 99:1.Then, the temperature of molten state reaction bed is down to room temperature.Solidification products is immersed in the water wash-out, obtains high purity graphite alkene material.The specific surface area data of this grapheme material is shown in Table 1.
example 4:
The material forming molten state reaction bed is potassium hydroxide, and be mixed into single-layer graphene powder wherein and do seed crystal, wherein, the volume ratio of potassium hydroxide and Graphene seed crystal is 999999:1.Loaded plumbago crucible and be placed in high-temperature vacuum pipe formula stove.Be warming up to 1100 DEG C, be then cooled to 1050 DEG C and keep 20 minutes, continue to pass into high purity (purity is more than 99.99%) acetylene and hydrogen gas mixture when 1050 DEG C of insulations, wherein, acetylene and hydrogen volume are than being 99:1.Then, the temperature of molten state reaction bed is down to room temperature.Solidification products is immersed in the water wash-out, obtains high purity graphite alkene material.The specific surface area data of this grapheme material is shown in Table 1.
Example 5:
The material forming molten state reaction bed is potassium hydroxide, is loaded plumbago crucible and is placed in high-temperature vacuum pipe formula stove.Be warming up to 1000 DEG C, be then cooled to 950 DEG C and keep 20 minutes, continue high purity (purity is more than 99.99%) acetylene and hydrogen gas mixture to pass into after nickel foam when 950 DEG C of insulations, wherein, acetylene and hydrogen volume are than being 99:1.Then, the temperature of molten state reaction bed is down to room temperature.Solidification products is immersed in the water wash-out, obtains high purity graphite alkene material.The specific surface area data of this grapheme material is shown in Table 1.
Example 6:
The material forming molten state reaction bed is potassium hydroxide, is loaded the plumbago crucible that is loaded with nickel foam and is placed in high-temperature vacuum pipe formula stove.Be warming up to 1000 DEG C, be then cooled to 950 DEG C and keep 20 minutes, continue to pass into high purity (purity is more than 99.99%) acetylene and hydrogen gas mixture when 950 DEG C of insulations, wherein, acetylene and hydrogen volume are than being 99:1.Then, the temperature of molten state reaction bed is down to room temperature.Solidification products is immersed in the water wash-out, obtains high purity graphite alkene material.The specific surface area data of this grapheme material is shown in Table 1.
example 7:
The material forming molten state reaction bed is sodium-chlor, is loaded plumbago crucible and is placed in high-temperature vacuum pipe formula stove.Be warming up to 1200 DEG C, be then cooled to 1150 DEG C and keep 0.5 hour.Continue to pass into high purity (purity is more than 99.99%) benzene vapor and hydrogen gas mixture when 1150 DEG C of insulations, wherein, benzene vapor and hydrogen volume are than being 99:1.Then, the temperature of molten state reaction bed is down to room temperature.Solidification products is immersed in the water wash-out, obtains highly purified grapheme material.The transmission electron microscope photo of this grapheme material is shown in Fig. 4, and its specific surface area data is shown in Table 1.
example 8:
The material forming molten state reaction bed is Repone K, and solid-state carbon source is the Nickel Phthalocyanine (NiPc) of 30.0 grams of laboratory synthesis, and the mass ratio of Nickel Phthalocyanine and Repone K is 1:99, is mixed by Nickel Phthalocyanine, and be placed in quartz tube furnace with Repone K.Under high-purity argon gas protection, (argon gas flow velocity is 50cm
3min
-1), be warming up to 800 DEG C, then at 800 DEG C, stablize 8 hours, last Temperature fall is to room temperature.Solidification products is immersed in the water and carries out wash-out, obtain grapheme material.X-ray diffraction (XRD) collection of illustrative plates of this grapheme material is shown in Fig. 5, and its transmission electron microscope photo is shown in Fig. 6, and its specific surface area data is shown in table 1.
example 9:
The material forming molten state reaction bed is Repone K, and liquid carbon source is 20.0 grams of liquid toluene, and the mass ratio of toluene and Repone K is 1:99.Toluene is mixed with Repone K, and is placed in quartz tube furnace.Under high-purity argon gas protection, be warming up to 900 DEG C, then at 900 DEG C, stablize 4 hours, last Temperature fall is to room temperature.Solidification products be immersed in the water and carry out wash-out, obtain grapheme material, its specific surface area data is shown in table 1.
Table 1:
| Example | Reaction bed material | Carbon source | Graphene specific surface area (㎡ g -1) |
| 1 | CuCl 2 | CH 4(being deposited on Copper Foil) | 1190.5 |
| 2 | CuCl 2 | CH 4(being deposited on sapphire) | 513.6 |
| 3 | KOH | C 2H 2 | 815.1 |
| 4 | KOH | C 2H 2(being added with seed crystal) | 1006.4 |
| 5 | KOH | C 2H 2(adding nickel foam) | 901.2 |
| 6 | KOH | C 2H 2(adding nickel foam) | 899.7 |
| 7 | NaCl | C 6H 6 | 402.3 |
| 8 | KCl | NiPc | 490.8 |
| 9 | KOH | Toluene | 815.1 |
From description above with put into practice, the present invention utilizes molten state reaction bed to prepare Graphene, can think the breakthrough of vapour deposition Graphene method in solid substrate to routine.The present invention's facility investment used is little, simple, cost is low, efficiency is high.Prepare in the process of Graphene of the present invention, do not need to use strong acid and other strong oxidizer, do not need to use toxic substance, therefore pollute less, little on the impact of Graphene performance.By dragging for away the Graphene of precipitation or have the material of Graphene to immerse wash-out in water or weak acid and weak base by the deposited on silicon formed after the molten state reaction bed of carbon containing is cooled to normal temperature to obtain Graphene from molten state reaction bed, the Graphene that easily can solve puzzlement engineering technological is peeled off and transport difficulties.If necessary, graphene growth also can be made usually to be difficult on the substrate grown, thus to be convenient to manufacture device.In addition, Graphene quality prepared by the present invention is good, cost performance is high, not high to the raw-material purity requirement preparing Graphene.
It will be appreciated by those skilled in the art that the molten state reaction bed that utilizes proposed for the invention described above prepares the method for Graphene, various improvement and combination can also be made on the basis not departing from content of the present invention.Therefore, protection scope of the present invention should be determined by the content of appending claims.
Claims (19)
1. utilize molten state reaction bed to prepare a method for Graphene, comprise the steps:
1) molten state reaction bed is formed;
2) gaseous carbon source after cracking is made to continue through the surface of described molten state reaction bed;
3) make carbon supersaturation in described molten state reaction bed separate out, thus form Graphene on described molten state reaction bed.
2. utilize molten state reaction bed to prepare the method for Graphene as claimed in claim 1, wherein, the material forming described molten state reaction bed is water-soluble substances or the material dissolving in weak acid and weak base at normal temperatures.
3. utilize molten state reaction bed to prepare the method for Graphene as claimed in claim 2, wherein, described water-soluble substances or the material that dissolves in weak acid and weak base comprise from water miscible or dissolve in one or more materials selected the inorganic salt of weak acid and weak base, mineral alkali, oxide compound, nitride, carbide.
4. utilize molten state reaction bed to prepare the method for Graphene, wherein, in step 3 as claimed in claim 2) after also comprise the steps:
4) temperature of described molten state reaction bed is down to normal temperature, thus forms the material that deposited on silicon has Graphene;
5) there is by described deposited on silicon the material of Graphene to immerse wash-out in water or weak acid and weak base, thus obtain Graphene.
5. utilize molten state reaction bed to prepare the method for Graphene as claimed in claim 1, wherein, described gaseous carbon source comprises one or more carbonaceous materials selected from aliphatic hydrocarbon, aromatic hydrocarbon, hydrocarbon derivative, carbon containing high molecular polymer.
6. utilize molten state reaction bed to prepare the method for Graphene as claimed in claim 5, wherein, described gaseous carbon source is made to carry out cracking or make described gaseous carbon source carry out cracking by preheating forming the gaseous carbon source after described cracking by the high temperature of described molten state reaction bed.
7. utilize molten state reaction bed to prepare the method for Graphene as claimed in claim 6, wherein, carry out cracking making described gaseous carbon source and at carbon from the process that molten state reaction bed is separated out, use copper, copper-bearing alloy, nickel, nickel-containing alloys, platinum, one or more in platinum rhodium as catalyzer.
8. utilize molten state reaction bed to prepare the method for Graphene, wherein, in step 2 as claimed in claim 1) in pass into one or more gases selected from nitrogen, argon gas, hydrogen, ammonia, as shielding gas simultaneously.
9. utilize molten state reaction bed to prepare the method for Graphene as claimed in claim 1, wherein, in step 3) before, also be included in described molten state reaction bed the solid substrate inserted for graphene growth, thus when the supersaturation making carbon in described molten state reaction bed is separated out, deposited graphite alkene while of in described solid substrate.
10. utilize molten state reaction bed to prepare the method for Graphene, wherein, in step 1 as claimed in claim 1) in, in described molten state reaction bed, add Graphene seed crystal.
11. 1 kinds of methods utilizing molten state reaction bed to prepare Graphene, comprise the steps:
1. solid-state or liquid carbon source are mixed with reaction bed material, form mixture;
2. by described mixture melt, make described solid-state or liquid carbon source cracking, and form the molten state reaction bed of carbon containing;
3. make carbon supersaturation in described molten state reaction bed separate out, thus form Graphene on described molten state reaction bed.
12. utilize molten state reaction bed to prepare the method for Graphene as claimed in claim 11, wherein, described solid-state or liquid carbon source comprises one or more carbonaceous materials selected from aliphatic hydrocarbon, aromatic hydrocarbon, hydrocarbon derivative, carbon containing high molecular polymer, phthalocyanines material.
13. utilize molten state reaction bed to prepare the method for Graphene as claimed in claim 11, and wherein, described reaction bed material is water-soluble substances or the material dissolving in weak acid and weak base at normal temperatures.
14. utilize molten state reaction bed to prepare the method for Graphene as claimed in claim 13, wherein, described water-soluble substances or the material that dissolves in weak acid and weak base comprise from water miscible or dissolve in one or more materials selected the inorganic salt of weak acid and weak base, mineral alkali, oxide compound, nitride, carbide.
15. utilize molten state reaction bed to prepare the method for Graphene as claimed in claim 13, wherein, also comprise the steps: after step 3.
4) temperature of described molten state reaction bed is down to normal temperature, thus forms the material that deposited on silicon has Graphene;
5) there is by described deposited on silicon the material of Graphene to immerse wash-out in water or weak acid and weak base, thus obtain Graphene.
16. utilize molten state reaction bed to prepare the method for Graphene as claimed in claim 11, wherein, in described mixture, add one or more catalyzer of separating out from described molten state reaction bed as described solid-state or liquid carbon source cracking or carbon in copper, copper-bearing alloy, nickel, nickel-containing alloys, platinum, platinum rhodium.
17. utilize molten state reaction bed to prepare the method for Graphene as claimed in claim 11, wherein, step 2. in pass into one or more gases selected from nitrogen, argon gas, hydrogen, ammonia, as shielding gas simultaneously.
18. utilize molten state reaction bed to prepare the method for Graphene as claimed in claim 11, wherein, before step 3., also be included in described molten state reaction bed the solid substrate inserted for graphene growth, thus when making carbon in described molten state reaction bed during supersaturation precipitation, deposited graphite alkene while of in described solid substrate.
19. utilize molten state reaction bed to prepare the method for Graphene as claimed in claim 11, wherein, step 1. in, in described mixture, add Graphene seed crystal.
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