CN103935979A - Preparation method of graphene nanoribbon - Google Patents
Preparation method of graphene nanoribbon Download PDFInfo
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- CN103935979A CN103935979A CN201310019285.9A CN201310019285A CN103935979A CN 103935979 A CN103935979 A CN 103935979A CN 201310019285 A CN201310019285 A CN 201310019285A CN 103935979 A CN103935979 A CN 103935979A
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Abstract
A preparation method of a graphene nanoribbon comprises the following steps: preparing a carbon nanowall; mixing the carbon nanowall with a metal intercalation agent in a mol ratio of 1-5:1 in an oxygen-free environment and heating the mixture to 200-1000 DEG C in a vacuum environment, maintaining the temperature, and carrying out reactions for 12-120 hours, so as to obtain a metal intercalation carbon nanowall, wherein the metal intercalation agent is at least one of lithium, sodium, potassium, magnesium, calcium, rubidium, strontium and barium; mixing the metal intercalation carbon nanowall with an ionic liquid in a mass volume ratio of 1 g:10-100 ml, treating the mixture with ultrasonic wave with the power of 2000-10000 W for 0.5-30 minutes, so as to obtain a reaction liquid; and filtering the reaction liquid to obtain the graphene nanoribbon. The graphene nanoribbon prepared by the preparation method has relatively high conductivity.
Description
Technical field
The present invention relates to the synthetic field of nano-carbon material, particularly a kind of preparation method of graphene nanobelt.
Background technology
The kind of carbon material has the soccerballene (C of zero dimension
60deng), carbon nanotube, the carbon nanofiber etc. of one dimension, the Graphene of two dimension, three-dimensional graphite, diamond etc., carbon nanometer wall (carbon nanowall, CNW) is the carbon nano structure with two-dimensional diffusion, its most typical pattern is just perpendicular to substrate material surface growth, thickness is greater than the wall shape structure of Graphene, completely different from the feature of soccerballene, carbon nanotube, Graphene etc., can be used as the raw material of other carbon material of preparation.
Before finding early than Graphene, people have just begun one's study the preparation of carbon nanometer wall.Just there were preparation and the related application thereof of reported in literature carbon nanometer wall in 2002, but no matter be early stage preparation method or nearest preparation method, all can relate under plasma atmosphere and react, can cause certain destruction to the structure of CNW.
Graphene nanobelt not only has the performance of Graphene, also possess some special performances, for example its length-to-diameter ratio is larger, can be up to thousands of times, and the specific conductivity of graphene nanobelt is higher, can replace copper conductor at integrated circuit connection, further improve integrated level, also can carry out modification to its structure and be prepared into switch device.But at present because graphene nanobelt still exists a lot of defects, cause its specific conductivity lower.
Summary of the invention
Given this, be necessary to provide a kind of preparation method of the graphene nanobelt with high conductance.
A preparation method for graphene nanobelt, comprises the steps:
Metal substrate is placed in to the acid solution etching 0.5 minute～10 minutes that concentration is 0.01mol/L～1mol/L; Under oxygen free condition, the described metal substrate after etching is heated to 600 DEG C～900 DEG C, use metal substrate surface described in UV-irradiation, and pass into carbonaceous gas and protect gas, keep 30 minutes～300 minutes, after reaction, obtain carbon nanometer wall on the surface of described metal substrate; Wherein, the flow that passes into described carbonaceous gas is 10sccm～1000sccm, and the throughput ratio of described carbonaceous gas and described protection gas is 2～10:1;
Under oxygen free condition, be that 1～5:1 mixes described carbon nanometer wall with metal intercalator according to mol ratio, be then placed in vacuum environment and be heated to 200 DEG C～1000 DEG C insulation reaction 12 hours～120 hours, obtain the intercalation carbon nanometer wall of metal; Wherein, described metal intercalator is at least one in lithium, sodium, magnesium, potassium, calcium, rubidium, strontium and barium; And
Be 1 gram according to mass volume ratio: 10 milliliters～100 milliliters, the intercalation carbon nanometer wall of described metal is mixed with ionic liquid, and use the supersound process 0.5 minute～30 minutes that power is 2000W～10000W, after filtration, obtain graphene nanobelt.
In an embodiment, before the described metal substrate heating to after etching, also comprise the step that adopts successively deionized water, ethanol and acetone to clean to the described metal substrate after etching therein.
In an embodiment, described acid solution is hydrochloric acid soln, sulphuric acid soln or salpeter solution therein; The concentration of described acid solution is 0.1mol/L～0.5mol/L; The etching period of described metal substrate in described acid solution is 60 seconds～180 seconds.
In an embodiment, described metal substrate is the one in iron foil, nickel foil and cobalt paper tinsel therein.
In an embodiment, described carbonaceous gas is the one in methane, ethane, propane, acetylene and alcohol vapour therein.
In an embodiment, described protection gas is at least one in helium, nitrogen and argon gas therein.
Therein in an embodiment, described ionic liquid is 1-ethyl-3-methylimidazole Tetrafluoroboric acid, 1-ethyl-3-methylimidazole fluoroform sulfimide, 1-ethyl-3-methylimidazole trifluoromethanesulfonic acid, 1-ethyl-3-methylimidazole trifluoroacetic acid, 1-ethyl-3-methylimidazole fluoroform sulphonyl carbon, 1-ethyl-3-methylimidazole five acetyl fluoride imines, 1-ethyl-3-methylimidazole two cyaniding nitrogen, 1-ethyl-3, 5-methylimidazole fluoroform sulfimide, 1, 3-diethyl-4-methylimidazole fluoroform sulfimide and 1, at least one in 3-diethyl-5-Methylimidazole fluoroform sulfimide.
In an embodiment, the vacuum tightness of described vacuum environment is 10 handkerchief～1000 handkerchiefs therein.
Therein in an embodiment, also comprise cleaning to described graphene nanobelt and dry step: in described graphene nanobelt through adding organic solvent to refilter 3 times～6 times, add again deionized water filter until the pH value of filtrate be neutrality, then by filter residue in 60 DEG C～100 DEG C vacuum-dryings to constant weight.
In an embodiment, described organic solvent is 1-Methyl-2-Pyrrolidone or DMF therein.
The preparation method of above-mentioned graphene nanobelt, by preparing first voluntarily carbon nanometer wall as starting material, by the carbon nanometer wall that adopts etching metal substrate and two steps of photochemical catalysis chemical gaseous phase deposition to prepare, can effectively avoid preparing carbon nanometer wall and causing it destructurized under traditional using plasma atmosphere, and the carbon nanometer wall of preparing has uniform thickness, and structure is more complete, then use lithium, sodium, magnesium, potassium, calcium, rubidium, at least one in strontium and barium is as metal intercalator, be prepared into after the intercalation carbon nanometer wall of metal, adopt ionic liquid to make solvent, and by under the effect of supersound process, not only can realize the intercalation carbon nanometer wall of quick stripping metal to obtain graphene nanobelt, prevent intercalation carbon nanometer wall a large amount of heat releases in supersound process process of metal, make the graphene nanobelt structural integrity preparing, can also effectively prevent the reunion again of graphene nanobelt, thereby make above-mentioned preparation method prepare graphene nanobelt and there is higher specific conductivity.
Brief description of the drawings
Fig. 1 is preparation method's schema of the graphene nanobelt of an embodiment;
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) of the carbon nanometer wall prepared of embodiment 1;
Fig. 3 is the scanning electron microscope (SEM) photograph (SEM) of the graphene nanobelt prepared of embodiment 1.
Embodiment
Mainly in conjunction with the drawings and the specific embodiments the preparation method of graphene nanobelt is described in further detail below.
As shown in Figure 1, the preparation method of the graphene nanobelt of an embodiment, comprises the steps:
Step S110: metal substrate is placed in to the acid solution etching 0.5 minute～10 minutes that concentration is 0.01mol/L～1mol/L; Under oxygen free condition, the metal substrate after etching is heated to 600 DEG C～900 DEG C, use UV-irradiation metal substrate surface, and pass into carbonaceous gas and protection gas, keep 30 minutes～300 minutes, after reaction, obtain carbon nanometer wall on the surface of metal substrate; Wherein, the flow that passes into carbonaceous gas is 10sccm(standard state milliliter per minute)～1000sccm, and the throughput ratio of carbonaceous gas and protection gas is 2～10:1.After having reacted, stop passing into carbonaceous gas, stop heating and UV-irradiation, to be cooled to room temperature, obtain carbon nanometer wall on the surface of metal substrate.Finally, the carbon nanometer wall on metal substrate surface is scraped, just obtained carbon nanometer wall powder.
By to metal substrate etching, make the etched surfaces of metal substrate produce defect, can effectively improve the surface tissue of metal substrate, make carbon nanometer wall energy enough in this metal substrate surface growth.Wherein, acid solution is the conventional dilute acid soln in this area, is preferably hydrochloric acid soln, sulphuric acid soln or salpeter solution.The concentration of acid solution is preferably 0.1mol/L～0.5mol/L; And the etching period of metal substrate in acid solution be preferably 60 seconds～and 180 seconds.Preferred etching condition, can reach good etching effect, can improve the growth efficiency of carbon nanometer wall.
The more carbon source of growth needs of carbon nanometer wall; carbonaceous gas is 2～10:1 with the throughput ratio of protection gas, not only has more carbon source, and adopts the protection gas of this ratio as carrier gas; can dilute to a certain extent carbonaceous gas, be conducive to the growth of carbon nanometer wall.
Wherein, metal substrate can be the conventional metal substrate in this area, is preferably the one in iron foil, nickel foil and cobalt paper tinsel.
Under the condition of anaerobic, preparing carbon nanometer wall, is to participate in reaction for fear of oxygen, and has influence on the growth of carbon nanometer wall, thereby a stable environment is provided to the growth of carbon nanometer wall.
By adopting UV-light to irradiate metal substrate surface, thereby play light-catalysed effect, can effectively reduce the temperature of reaction, reduce energy consumption, reduce production costs.Preferably, providing the instrument of UV-irradiation is ultraviolet source equipment.Preferably, ultraviolet light wavelength is 200 nanometer～400 nanometers.
By the carbon nanometer wall that adopts etching metal substrate and two steps of photochemical catalysis chemical gaseous phase deposition to prepare, can effectively avoid preparing carbon nanometer wall and causing it destructurized under traditional using plasma atmosphere, and the carbon nanometer wall of preparing has uniform thickness, and structure is more complete.And preparation carbon nanometer wall energy be enough vertically grown in etched metal substrate, preparation technology is simple, and preparation condition be easy to control, shortened etching period, thereby improved production efficiency.
Preferably, before the metal substrate heating to after etching, also comprise the step that adopts successively deionized water, ethanol and acetone to clean to the metal substrate after etching.
Wherein, carbonaceous gas can be the conventional carbonaceous gas in this area, is preferably the one in methane, ethane, propane, acetylene and alcohol vapour.These several carbonaceous gass are simple in structure, are easy to cracking and deposition.
Wherein, protection gas can be the conventional rare gas element in this area, is preferably at least one in helium, nitrogen and argon gas.
Step S120: under oxygen free condition, be that 1～5:1 mixes carbon nanometer wall with metal intercalator according to mol ratio, be then placed in vacuum environment and be heated to 200 DEG C～1000 DEG C insulation reaction 12 hours～120 hours, obtain the intercalation carbon nanometer wall of metal.Oxygen free condition can be under the environment of protective gas, for example, under inert gas environment, be preferably under the environment of nitrogen, argon gas or helium.Wherein, metal intercalator is at least one in lithium, sodium, magnesium, potassium, calcium, rubidium, strontium and barium.Adopt these metals to make preparation technology simple as intercalator, and to equipment require lowly, reduced preparation cost.
By first carbon nanometer wall and metal intercalator being mixed with to the intercalation carbon nanometer wall of metal, can make carbon-coating spacing increase, thereby the reactive force of graphite layers is reduced, be conducive to follow-up peeling off.And be the destruction for fear of carbon nano wall structure by the intercalation carbon nanometer wall that is first prepared into metal, be conducive to obtain after peeling off the integrity of the structure of graphene nanobelt.
Preferably, the vacuum tightness of vacuum environment is 10 handkerchiefs (Pa)～1000 handkerchiefs.This vacuum ranges avoids the too high meeting of vacuum tightness to increase preparation cost on the one hand; Ensure that on the other hand certain vacuum degree carries out smoothly to avoid above-mentioned metal intercalator oxidation and to be conducive to intercalation.
In specific embodiment, after being mixed with metal intercalator, carbon nanometer wall packs in heat-resistant glass tube, then Glass tubing is vacuumized, making the vacuum tightness in Glass tubing is 10Pa～1000Pa.
Step S130: be 1 gram according to mass volume ratio: 10 milliliters～100 milliliters, the intercalation carbon nanometer wall of metal is mixed with ionic liquid, and use the supersound process 0.5 minute～30 minutes that power is 2000W～10000W, after filtration, obtain graphene nanobelt.
Preferably, the device of supersound process is ultrasonic disintegrator.Adopt the intercalation carbon nanometer wall of ultrasonic disintegrator supersound process metal and the mixture of ionic liquid to realize the intercalation carbon nanometer wall of quick stripping metal.
Power is that 2000W～10000W can peel off into graphene nanobelt by metal intercalation carbon nanometer wall fast, and is scattered in ionic liquid, can complete and peel off fast, and required time is short, and technique is simple.And it is long-time ultrasonic to graphene nanobelt structural damage that this power can also be avoided, to prepare high-quality graphene nanobelt.
Due to basic metal or alkaline-earth metal comparatively active, when itself and carbon nanometer wall are prepared into the intercalation carbon nanometer wall of metal, if adopting water peels off as solvent, can there is violent reacting with water, thereby cause the too fast problem of heat release, and employing ethanol etc. makees solvent and can not well solve the too fast problem of heat release, by using ionic liquid to mix with the intercalation carbon nanometer wall of metal as solvent, can well solve the too fast problem of heat release, thereby a large amount of heat releases of the intercalation carbon nanometer wall of effectively avoiding metal in the stripping process of supersound process, make preparation process more safe and reliable, further improve the integrity of the graphene nano band structure preparing, make it have higher specific conductivity.Preferably, ionic liquid is 1-ethyl-3-methylimidazole Tetrafluoroboric acid (EtMeImBF
4), 1-ethyl-3-methylimidazole fluoroform sulfimide (EtMeImN (CF
3sO
2)
2), 1-ethyl-3-methylimidazole trifluoromethanesulfonic acid (EtMeImCF
3sO
3), 1-ethyl-3-methylimidazole trifluoroacetic acid (EtMeImN (CN)
2), 1-ethyl-3-methylimidazole fluoroform sulphonyl carbon (EtMeImC (CF
3sO
2)
3), 1-ethyl-3-methylimidazole five acetyl fluoride imines (EtMeImN (C
2f
5sO
2)
2), 1-ethyl-3-methylimidazole two cyaniding nitrogen (EtMeImN (CN)
2), 1-ethyl-3,5-methylimidazole fluoroform sulfimide (1-Et-3,5-Me
2imN (CF
3sO
2)
2), 1,3-diethyl-4-methylimidazole fluoroform sulfimide (1,3-Et
2-4-MeImN (CF
3sO
2)
2) and 1,3-diethyl-5-Methylimidazole fluoroform sulfimide (1,3-Et
2-5-MeImN (CF
3sO
2)
2) at least one.
Preferably, after step S130, also comprise to graphene nanobelt clean and dry step: in graphene nanobelt through adding organic solvent to refilter 3 times～6 times, add again deionized water filter until the pH value of filtrate be neutrality, then by filter residue in 60 DEG C～100 DEG C vacuum-dryings to constant weight.Preferably, organic solvent can be the conventional organic solvent in this area, be preferably 1-Methyl-2-Pyrrolidone (NMP) or N, dinethylformamide (DMF), 1-Methyl-2-Pyrrolidone (NMP) or DMF (DMF) can be removed ionic liquid effectively.
The preparation method of above-mentioned graphene nanobelt, by preparing first voluntarily carbon nanometer wall as starting material, by the carbon nanometer wall that adopts etching metal substrate and two steps of photochemical catalysis chemical gaseous phase deposition to prepare, can effectively avoid preparing carbon nanometer wall and causing it destructurized under traditional using plasma atmosphere, and the carbon nanometer wall of preparing has uniform thickness, and structure is more complete, then use lithium, sodium, magnesium, potassium, calcium, rubidium, at least one in strontium and barium is as metal intercalator, be prepared into after the intercalation carbon nanometer wall of metal, adopt ionic liquid to make solvent, and by under the effect of supersound process, not only can realize the intercalation carbon nanometer wall of quick stripping metal to obtain graphene nanobelt, prevent intercalation carbon nanometer wall a large amount of heat releases in supersound process process of metal, make the graphene nanobelt structural integrity preparing, can also effectively prevent the reunion again of graphene nanobelt, thereby make above-mentioned preparation method prepare graphene nanobelt and there is higher specific conductivity.
The preparation method of above-mentioned graphene nanobelt is simple, and required equipment is all common chemical industry equipment, saves research and development equipment cost, is applicable to scale operation.
Be below specific embodiment part:
Embodiment 1
Being prepared as follows of the graphene nanobelt of the present embodiment:
(1) prepare carbon nanometer wall: (a) nickel foil is put into concentration and be the hydrochloric acid soln etching 0.5 minute of 1mol/L, after etching, clean with deionized water, ethanol, acetone successively, (b) nickel foil after cleaning is put into reaction chamber, and get rid of after the air in reaction chamber, nickel foil is heated to 900 DEG C, then open ultraviolet source equipment, make UV-irradiation on nickel foil surface, then pass into methane and nitrogen, keep 100 minutes, wherein, the flow that passes into steam methane is 200sccm, the throughput ratio of steam methane and nitrogen is 2:1, after having reacted, stop passing into steam methane, stop nickel foil heating, and close light source, question response chamber is cooled to after room temperature, stop passing into nitrogen, obtain the carbon nanometer wall of the present embodiment on nickel foil surface, it is scraped from nickel foil surface, just obtain carbon nanometer wall powder.
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) of the carbon nanometer wall prepared of the present embodiment.As can be seen from the figure, carbon nanometer wall prepared by the present embodiment is perpendicular to the intensive growth of nickel foil, and even thickness, is about 30 nanometer～60 nanometers.
(2) under the environment that is full of helium, the carbon nanometer wall of for 5:1 being prepared by step (1) in molar ratio mixes with lithium, packs in heat-resistant glass tube, then Glass tubing is evacuated to 10Pa, sealing, is heated to 200 DEG C, insulation reaction 12 hours, obtains the intercalation carbon nanometer wall of lithium.
(3) be 1g:10ml according to mass volume ratio, the intercalation carbon nanometer wall of lithium is joined 1-ethyl-3-methylimidazole Tetrafluoroboric acid (EtMeImBF is housed
4) container in, be supersound process 30 minutes under 2000W ultrasonic disintegrator at power, obtain reaction solution, filtering reacting liquid obtains the graphene nanobelt of the present embodiment, graphene nanobelt, through adding 1-Methyl-2-Pyrrolidone (NMP) to filter 6 times, then is to neutrality by the pH value that deionized water is filtered to filtrate; Then the filter residue cleaning up is put in vacuum drying oven and at 60 DEG C, is dried constant weight, obtain pure graphene nanobelt.And the specific conductivity of the graphene nanobelt of the present embodiment obtaining, in table 1.
Fig. 3 is the scanning electron microscope (SEM) photograph (SEM) of the graphene nanobelt prepared of the present embodiment.As can be seen from the figure, the width distribution of graphene nanobelt prepared by the present embodiment is concentrated, and is about 20 nanometer～40 nanometers, and length is about 2 microns～20 microns, and length-to-diameter ratio is 50～1000.
Embodiment 2
Being prepared as follows of the graphene nanobelt of the present embodiment:
(1) prepare carbon nanometer wall: (a) iron foil is put into concentration and is the sulphuric acid soln etching 4 minutes of 0.5mol/L, after etching with cleaning with deionized water, ethanol, acetone successively, (b) iron foil after cleaning is put into reaction chamber, and get rid of after the air in reaction chamber, iron foil is heated to 600 DEG C, then open ultraviolet source equipment, make UV-irradiation on iron foil surface, then pass into ethane steam and argon gas, keep 200 minutes, wherein, the flow that passes into ethane steam is 100sccm, ethane steam is 5:1 with the throughput ratio ratio of argon gas, after having reacted, stop passing into ethane steam, stop iron foil heating, and close light source, question response chamber is cooled to after room temperature, stop passing into argon gas, obtain the carbon nanometer wall of the present embodiment on iron foil surface, it is scraped from iron foil surface, just obtain carbon nanometer wall powder.
(2) under the environment that is full of nitrogen, the carbon nanometer wall of for 2:1 being prepared by step (1) in molar ratio mixes with potassium, packs in heat-resistant glass tube, then Glass tubing is evacuated to 100Pa, sealing, is heated to 250 DEG C, insulation reaction 20 hours, obtains the intercalation carbon nanometer wall of potassium.
(3) be 1g:100ml according to mass volume ratio, the intercalation carbon nanometer wall of potassium is joined 1-ethyl-3-methylimidazole fluoroform sulfimide (EtMeImN (CF is housed
3sO
2)
2) container in, be supersound process 0.5 minute under 10000W ultrasonic disintegrator at power, obtain reaction solution, filtering reacting liquid, obtain the graphene nanobelt of the present embodiment, graphene nanobelt, through adding DMF (DMF) filter 23 time, then is to neutrality by the pH value that deionized water is filtered to filtrate; Then the filter residue cleaning up is put in vacuum drying oven to dry constant weight at 80 DEG C, obtains pure graphene nanobelt.And the specific conductivity of the graphene nanobelt of the present embodiment obtaining, in table 1.
Embodiment 3
Being prepared as follows of the graphene nanobelt of the present embodiment:
(1) prepare carbon nanometer wall: (a) cobalt paper tinsel is put into concentration and is the salpeter solution etching 10 minutes of 0.01mol/L, after etching with cleaning with deionized water, ethanol, acetone successively, (b) the cobalt paper tinsel after cleaning is put into reaction chamber, and get rid of after the air in reaction chamber, cobalt paper tinsel is heated to 700 DEG C, then open ultraviolet source equipment, make UV-irradiation on cobalt paper tinsel surface, then pass into acetylene steam and argon gas, keep 300 minutes, wherein, the flow that passes into acetylene steam is 10sccm, the throughput ratio of acetylene steam and helium is 8:1, after having reacted, stop passing into acetylene steam, stop cobalt paper tinsel to heat, and close light source, question response chamber is cooled to after room temperature, stop passing into helium, obtain the carbon nanometer wall of the present embodiment on cobalt paper tinsel surface, it is scraped from cobalt paper tinsel surface, just obtain carbon nanometer wall powder.
(2) under the environment that is full of argon gas, the carbon nanometer wall of for 1:1 being prepared by step (1) in molar ratio mixes with sodium, packs in heat-resistant glass tube, then Glass tubing is evacuated to 500Pa, sealing, is heated to 300 DEG C, insulation reaction 36 hours, obtains the intercalation carbon nanometer wall of sodium.
(3) be 1g:50ml according to mass volume ratio, the intercalation carbon nanometer wall of sodium is joined 1-ethyl-3-methylimidazole trifluoromethanesulfonic acid (EtMeImCF is housed
3sO
3) container in, be supersound process 1 minute under 8000W ultrasonic disintegrator at power, obtain reaction solution, filtering reacting liquid, obtain the graphene nanobelt of the present embodiment, graphene nanobelt, through adding 1-Methyl-2-Pyrrolidone (NMP) to filter 5 times, then is to neutrality by the pH value that deionized water is filtered to filtrate; Then the filter residue cleaning up is put in vacuum drying oven and at 100 DEG C, is dried constant weight, obtain pure graphene nanobelt.And the specific conductivity of the graphene nanobelt of the present embodiment obtaining, in table 1.
Embodiment 4
Being prepared as follows of the graphene nanobelt of the present embodiment:
(1) prepare carbon nanometer wall: (a) nickel foil is put into concentration and is the hydrochloric acid soln etching 2 minutes of 0.2mol/L, after etching with cleaning with deionized water, ethanol, acetone successively, (b) nickel foil after cleaning is put into reaction chamber, and get rid of after the air in reaction chamber, nickel foil is heated to 750 DEG C, then open ultraviolet source equipment, make UV-irradiation on nickel foil surface, then pass into propane vapor and nitrogen and argon gas mixed gas, keep 30 minutes, wherein, the flow that passes into propane vapor is 1000sccm, the throughput ratio of propane vapor and nitrogen and argon gas mixed gas is 10:1, after having reacted, stop passing into propane vapor, stop nickel foil heating, and close light source, question response chamber is cooled to after room temperature, stop passing into nitrogen and argon gas mixed gas, obtain the carbon nanometer wall of the present embodiment on nickel foil surface, it is scraped from nickel foil surface, just obtain carbon nanometer wall powder.
(2), under the environment that is full of helium, carbon nanometer wall, rubidium and the strontium for 3:1 prepared by step (1) in molar ratio mix, and pack in heat-resistant glass tube, then Glass tubing is evacuated to 1000Pa, sealing, is heated to 220 DEG C, insulation reaction 50 hours, obtains the intercalation carbon nanometer wall of rubidium strontium.
(3) be 1g:20ml according to mass volume ratio, the intercalation carbon nanometer wall of rubidium strontium is joined 1-ethyl-3-methylimidazole trifluoroacetic acid (EtMeImN (CN) is housed
2) container in, be supersound process 2 minutes under 6000W ultrasonic disintegrator at power, obtain reaction solution, filtering reacting liquid, obtain the graphene nanobelt of the present embodiment, graphene nanobelt, through adding DMF (DMF) filter 23 time, then is to neutrality by the pH value that deionized water is filtered to filtrate; Then the filter residue cleaning up is put in vacuum drying oven and at 90 DEG C, is dried constant weight, obtain pure graphene nanobelt.And the specific conductivity of the graphene nanobelt of the present embodiment obtaining, in table 1.
Embodiment 5
Being prepared as follows of the graphene nanobelt of the present embodiment:
(1) prepare carbon nanometer wall: (a) iron foil is put into concentration and is the sulphuric acid soln etching 5 minutes of 0.1mol/L, after etching with cleaning with deionized water, ethanol, acetone successively, (b) iron foil after cleaned is put into reaction chamber, and get rid of after the air in reaction chamber, iron foil is heated to 800 DEG C, then open ultraviolet source equipment, make UV-irradiation on iron foil surface, then pass into alcohol vapour and argon gas, keep 50 minutes, wherein, the flow that passes into alcohol vapour is 500sccm, the throughput ratio of alcohol vapour and argon gas is 6:1, after having reacted, stop passing into argon gas, stop iron foil heating, and close light source, question response chamber is cooled to after room temperature, stop passing into argon gas, obtain the carbon nanometer wall of the present embodiment on iron foil surface, it is scraped from iron foil surface, just obtain carbon nanometer wall powder.
(2) under the environment that is full of nitrogen, the carbon nanometer wall of for 5:1 being prepared by step (1) in molar ratio mixes with magnesium, packs in heat-resistant glass tube, then Glass tubing is evacuated to 200Pa, sealing, is heated to 800 DEG C, insulation reaction 80 hours, obtains the intercalation carbon nanometer wall of magnesium.
(3) be 1g:80ml according to mass volume ratio, the intercalation carbon nanometer wall of magnesium is joined 1-ethyl-3-methylimidazole fluoroform sulphonyl carbon (EtMeImC (CF is housed
3sO
2)
3) container in, be supersound process 12 minutes under 5000W ultrasonic disintegrator at power, obtain reaction solution, filtering reacting liquid, obtain the graphene nanobelt of the present embodiment, graphene nanobelt, through adding 1-Methyl-2-Pyrrolidone (NMP) to filter 4 times, then is to neutrality by the pH value that deionized water is filtered to filtrate; Then the filter residue cleaning up is put in vacuum drying oven and at 70 DEG C, is dried constant weight, obtain pure graphene nanobelt.And the specific conductivity of the graphene nanobelt of the present embodiment obtaining, in table 1.
Embodiment 6
Being prepared as follows of the graphene nanobelt of the present embodiment:
(1) prepare carbon nanometer wall: (a) cobalt paper tinsel is put into concentration and is the salpeter solution etching 8 minutes of 0.4mol/L, after etching with cleaning with deionized water, ethanol, acetone successively, (b) the cobalt paper tinsel after cleaning is put into reaction chamber, and get rid of after the air in reaction chamber, cobalt paper tinsel is heated to 850 DEG C, then open ultraviolet source equipment, make UV-irradiation on cobalt paper tinsel surface, then pass into steam methane and helium, keep 90 minutes, wherein, the flow that passes into steam methane is 800sccm, the throughput ratio of steam methane and helium is 4:1, after having reacted, stop passing into steam methane, stop cobalt paper tinsel to heat, and close light source, question response chamber is cooled to after room temperature, stop passing into helium, obtain the carbon nanometer wall of the present embodiment on cobalt paper tinsel surface, it is scraped from cobalt paper tinsel surface, just obtain carbon nanometer wall powder.
(2) under the environment that is full of argon gas, the carbon nanometer wall of for 1:1 being prepared by step (1) in molar ratio mixes with calcium, packs in heat-resistant glass tube, then Glass tubing is evacuated to 600Pa, sealing, is heated to 900 DEG C, insulation reaction 100 hours, obtains the intercalation carbon nanometer wall of calcium.
(3) be 1g:60ml according to mass volume ratio, the intercalation carbon nanometer wall of calcium is joined 1-ethyl-3-methylimidazole trifluoromethanesulfonic acid (EtMeImCF is housed
3sO
3) container in, be supersound process 25 minutes under 3000W ultrasonic disintegrator at power, obtain reaction solution, filtering reacting liquid, obtain the graphene nanobelt of the present embodiment, graphene nanobelt, through adding DMF (DMF) to filter 5 times, then is to neutrality by the pH value that deionized water is filtered to filtrate; Then the filter residue cleaning up is put in vacuum drying oven and at 60 DEG C, is dried constant weight, obtain pure graphene nanobelt.And the specific conductivity of the graphene nanobelt of the present embodiment obtaining, in table 1.
Embodiment 7
Being prepared as follows of the graphene nanobelt of the present embodiment:
(1) prepare carbon nanometer wall: (a) nickel foil is put into concentration and be the hydrochloric acid soln etching 3 minutes of 0.25mol/L, after etching, clean with deionized water, ethanol, acetone successively, (b) nickel foil after cleaning is put into reaction chamber, and get rid of after the air in reaction chamber, nickel foil is heated to 900 DEG C, then open ultraviolet source equipment, make UV-irradiation on nickel foil surface, then pass into ethane steam and nitrogen, keep 120 minutes, wherein, the flow that passes into ethane steam is 300sccm, the throughput ratio of ethane steam and nitrogen is 3:1, after having reacted, stop passing into ethane steam, stop nickel foil heating, and close light source, question response chamber is cooled to after room temperature, stop passing into nitrogen, obtain the carbon nanometer wall of the present embodiment on nickel foil surface, it is scraped from nickel foil surface, just obtain carbon nanometer wall powder.
(2) under the environment that is full of nitrogen, the carbon nanometer wall of for 4:1 being prepared by step (1) in molar ratio mixes with barium, packs in heat-resistant glass tube, then Glass tubing is evacuated to 800Pa, sealing, is heated to 1000 DEG C, insulation reaction 120 hours, obtains the intercalation carbon nanometer wall of barium.
(3) be 1g:40ml according to mass volume ratio, the intercalation carbon nanometer wall of barium is joined 1-ethyl-3-methylimidazole two cyaniding nitrogen (EtMeImN (CN) is housed
2) container in, be supersound process 4 minutes under 2000W ultrasonic disintegrator at power, obtain reaction solution, filtering reacting liquid, obtain the graphene nanobelt of the present embodiment, graphene nanobelt, through adding 1-Methyl-2-Pyrrolidone (NMP) filter 23 time, then is to neutrality by the pH value that deionized water is filtered to filtrate; Then the filter residue cleaning up is put in vacuum drying oven and at 100 DEG C, is dried constant weight, obtain pure graphene nanobelt.And the specific conductivity of the graphene nanobelt of the present embodiment obtaining, in table 1.
Embodiment 8
Being prepared as follows of the graphene nanobelt of the present embodiment:
(1) prepare carbon nanometer wall: (a) iron foil is put into concentration and is the hydrochloric acid soln etching 4 minutes of 1mol/L, after etching with cleaning with deionized water, ethanol, acetone successively, (b) iron foil after cleaning is put into reaction chamber, and get rid of after the air in reaction chamber, iron foil is heated to 650 DEG C, then open ultraviolet source equipment, make UV-irradiation on iron foil surface, then pass into acetylene steam and argon gas, keep 180 minutes, wherein, the flow that passes into acetylene steam is 200sccm, the throughput ratio of acetylene steam and argon gas is 2:1, after having reacted, stop passing into acetylene steam, stop iron foil heating, and close light source, question response chamber is cooled to after room temperature, stop passing into argon gas, obtain the carbon nanometer wall of the present embodiment on iron foil surface, it is scraped from iron foil surface, just obtain carbon nanometer wall powder.
(2) under the environment that is full of helium, the carbon nanometer wall of for 5:1 being prepared by step (1) in molar ratio mixes with strontium, packs in heat-resistant glass tube, then Glass tubing is evacuated to 100Pa, sealing, is heated to 950 DEG C, insulation reaction 60 hours, obtains the intercalation carbon nanometer wall of strontium.
(3) be 1g:30ml according to mass volume ratio, the intercalation carbon nanometer wall of strontium is joined 1-ethyl-3 are housed, 5-methylimidazole fluoroform sulfimide (1-Et-3,5-Me
2imN (CF
3sO
2)
2) container in, be supersound process 15 minutes under 5000W ultrasonic disintegrator at power, obtain reaction solution, filtering reacting liquid, obtain the graphene nanobelt of the present embodiment, graphene nanobelt, through adding DMF (DMF) to filter 6 times, then is to neutrality by the pH value that deionized water is filtered to filtrate; Then the filter residue cleaning up is put in vacuum drying oven and at 80 DEG C, is dried constant weight, obtain pure graphene nanobelt.And the specific conductivity of the graphene nanobelt of the present embodiment obtaining, in table 1.
Embodiment 9
Being prepared as follows of the graphene nanobelt of the present embodiment:
(1) prepare carbon nanometer wall: (a) cobalt paper tinsel is put into concentration and is the sulphuric acid soln etching 2 minutes of 0.3mol/L, after etching with cleaning with deionized water, ethanol, acetone successively, (b) the cobalt paper tinsel after cleaning is put into reaction chamber, and get rid of after the air in reaction chamber, cobalt paper tinsel is heated to 700 DEG C, then open ultraviolet source equipment, make UV-irradiation on cobalt paper tinsel surface, then pass into propane vapor and helium, keep 240 minutes, wherein, the flow that passes into propane vapor is 50sccm, the throughput ratio of propane vapor and helium is 5:1, after having reacted, stop passing into propane vapor, stop cobalt paper tinsel to heat, and close light source, question response chamber is cooled to after room temperature, stop passing into helium, obtain the carbon nanometer wall of the present embodiment on cobalt paper tinsel surface, it is scraped from cobalt paper tinsel surface, just obtain carbon nanometer wall powder.
(2) under the environment that is full of nitrogen, the carbon nanometer wall of for 3:1 being prepared by step (1) in molar ratio mixes with potassium, packs in heat-resistant glass tube, then Glass tubing is evacuated to 50Pa, sealing, is heated to 500 DEG C, insulation reaction 30 hours, obtains the intercalation carbon nanometer wall of potassium.
(3) be 1g:100ml according to mass volume ratio, the intercalation carbon nanometer wall of potassium is joined 1,3-diethyl-4-methylimidazole fluoroform sulfimide (1,3-Et is housed
2-4-MeImN (CF
3sO
2)
2) container in, be supersound process 5 minutes under 8000W ultrasonic disintegrator at power, obtain reaction solution, filtering reacting liquid, obtain the graphene nanobelt of the present embodiment, graphene nanobelt, through adding 1-Methyl-2-Pyrrolidone (NMP) filter 23 time, then is to neutrality by the pH value that deionized water is filtered to filtrate; Then the filter residue cleaning up is put in vacuum drying oven and at 90 DEG C, is dried constant weight, obtain pure graphene nanobelt.And obtain the specific conductivity of the graphene nanobelt of the present embodiment, in table 1.
Embodiment 10
Being prepared as follows of the graphene nanobelt of the present embodiment:
(1) prepare carbon nanometer wall: (a) nickel foil is put into concentration and be the salpeter solution etching 5 minutes of 0.5mol/L, after etching, clean with deionized water, ethanol, acetone successively, (b) nickel foil after cleaning is put into reaction chamber, and get rid of after the air in reaction chamber, nickel foil is heated to 800 DEG C, then open ultraviolet source equipment, make UV-irradiation on nickel foil surface, then pass into alcohol vapour and nitrogen, keep 300 minutes, wherein, the flow that passes into alcohol vapour is 20sccm, the throughput ratio of alcohol vapour and nitrogen is 8:1, after having reacted, stop passing into alcohol vapour, stop nickel foil heating, and close light source, question response chamber is cooled to after room temperature, stop passing into nitrogen, obtain the carbon nanometer wall of the present embodiment on nickel foil surface, it is scraped from nickel foil surface, just obtain carbon nanometer wall powder.
(2) under the environment that is full of nitrogen, the carbon nanometer wall of for 4:1 being prepared by step (1) in molar ratio mixes with sodium, packs in heat-resistant glass tube, then Glass tubing is evacuated to 10Pa, sealing, is heated to 400 DEG C, insulation reaction 12 hours, obtains the intercalation carbon nanometer wall of sodium.
(3) be 1g:10ml according to mass volume ratio, the intercalation carbon nanometer wall of sodium is joined 1,3-diethyl-5-Methylimidazole fluoroform sulfimide (1,3-Et is housed
2-5-MeImN (CF
3sO
2)
2) container in, be supersound process 10 minutes under 10000W ultrasonic disintegrator at power, obtain reaction solution, filtering reacting liquid, obtain the graphene nanobelt of the present embodiment, graphene nanobelt, through adding DMF (DMF) to filter 4 times, then is to neutrality by the pH value that deionized water is filtered to filtrate; Then the filter residue cleaning up is put in vacuum drying oven and at 70 DEG C, is dried constant weight, obtain pure graphene nanobelt.And the specific conductivity of the graphene nanobelt of the present embodiment obtaining, in table 1.
Embodiment 11
Being prepared as follows of the graphene nanobelt of the present embodiment:
(1) prepare carbon nanometer wall: (a) cobalt paper tinsel is put into concentration and is the hydrochloric acid soln etching 1 minute of 0.05mol/L, after etching with cleaning with deionized water, ethanol, acetone successively; (b) the cobalt paper tinsel after cleaning is put into reaction chamber, and get rid of after the air in reaction chamber, cobalt paper tinsel is heated to 900 DEG C, then open ultraviolet source equipment, make UV-irradiation on cobalt paper tinsel surface, then pass into steam methane and argon gas, wherein, the flow that passes into steam methane is 100sccm, and the throughput ratio of steam methane and argon gas is 10:1, keeps 30 minutes; After having reacted, stop passing into steam methane, stop cobalt paper tinsel to heat, and close light source, question response chamber is cooled to after room temperature, stops passing into argon gas, the carbon nanometer wall that obtains the present embodiment on cobalt paper tinsel surface, scrapes it from cobalt paper tinsel surface, just obtain carbon nanometer wall powder.
(2) under the environment that is full of helium, the carbon nanometer wall of for 2:1 being prepared by step (1) in molar ratio mixes with calcium, packs in heat-resistant glass tube, then Glass tubing is evacuated to 100Pa, sealing, is heated to 250 DEG C, insulation reaction 20 hours, obtains the intercalation carbon nanometer wall of calcium.
(3) be 1g:50ml according to mass volume ratio, the intercalation carbon nanometer wall of calcium is joined 1-ethyl-3-methylimidazole two cyaniding nitrogen (EtMeImN (CN) is housed
2) container in, be supersound process 15 minutes under 8000W ultrasonic disintegrator at power, obtain reaction solution, filtering reacting liquid, obtain the graphene nanobelt of the present embodiment, graphene nanobelt, through adding 1-Methyl-2-Pyrrolidone (NMP) to filter 5 times, then is to neutrality by the pH value that deionized water is filtered to filtrate; Then the filter residue cleaning up is put in vacuum drying oven and at 100 DEG C, is dried constant weight, obtain pure graphene nanobelt.And the specific conductivity of the graphene nanobelt of the present embodiment obtaining, in table 1.
The specific conductivity of what table 1 represented is graphene nanobelt prepared by embodiment 1～embodiment 11.
Table 1
From table 1, can learn, the specific conductivity of graphene nanobelt prepared by the preparation method of the graphene nanobelt of embodiment 1～embodiment 11 is at least 0.9 × 10
5s/m, prepares the specific conductivity (10 of graphene nanobelt prepared by the method for graphene nanobelt higher than tradition
4s/m) graphene nanobelt that, this explanation adopts the preparation method of graphene nanobelt of the present invention to prepare has good integrity.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a preparation method for graphene nanobelt, is characterized in that, comprises the steps:
Metal substrate is placed in to the acid solution etching 0.5 minute～10 minutes that concentration is 0.01mol/L～1mol/L; Under oxygen free condition, the described metal substrate after etching is heated to 600 DEG C～900 DEG C, use metal substrate surface described in UV-irradiation, and pass into carbonaceous gas and protect gas, keep 30 minutes～300 minutes, after reaction, obtain carbon nanometer wall on the surface of described metal substrate; Wherein, the flow that passes into described carbonaceous gas is 10sccm～1000sccm, and the throughput ratio of described carbonaceous gas and described protection gas is 2～10:1;
Under oxygen free condition, be that 1～5:1 mixes described carbon nanometer wall with metal intercalator according to mol ratio, be then placed in vacuum environment and be heated to 200 DEG C～1000 DEG C insulation reaction 12 hours～120 hours, obtain the intercalation carbon nanometer wall of metal; Wherein, described metal intercalator is at least one in lithium, sodium, magnesium, potassium, calcium, rubidium, strontium and barium; And
Be 1 gram according to mass volume ratio: 10 milliliters～100 milliliters, the intercalation carbon nanometer wall of described metal is mixed with ionic liquid, and use the supersound process 0.5 minute～30 minutes that power is 2000W～10000W, after filtration, obtain graphene nanobelt.
2. the preparation method of graphene nanobelt according to claim 1, it is characterized in that, before the described metal substrate heating to after etching, also comprise the step that adopts successively deionized water, ethanol and acetone to clean to the described metal substrate after etching.
3. the preparation method of graphene nanobelt according to claim 1, is characterized in that, described acid solution is hydrochloric acid soln, sulphuric acid soln or salpeter solution; The concentration of described acid solution is 0.1mol/L～0.5mol/L; The etching period of described metal substrate in described acid solution is 60 seconds～180 seconds.
4. the preparation method of graphene nanobelt according to claim 1, is characterized in that, described metal substrate is the one in iron foil, nickel foil and cobalt paper tinsel.
5. the preparation method of graphene nanobelt according to claim 1, is characterized in that, described carbonaceous gas is the one in methane, ethane, propane, acetylene and alcohol vapour.
6. the preparation method of graphene nanobelt according to claim 1, is characterized in that, described protection gas is at least one in helium, nitrogen and argon gas.
7. the preparation method of graphene nanobelt according to claim 1, it is characterized in that, described ionic liquid is 1-ethyl-3-methylimidazole Tetrafluoroboric acid, 1-ethyl-3-methylimidazole fluoroform sulfimide, 1-ethyl-3-methylimidazole trifluoromethanesulfonic acid, 1-ethyl-3-methylimidazole trifluoroacetic acid, 1-ethyl-3-methylimidazole fluoroform sulphonyl carbon, 1-ethyl-3-methylimidazole five acetyl fluoride imines, 1-ethyl-3-methylimidazole two cyaniding nitrogen, 1-ethyl-3, 5-methylimidazole fluoroform sulfimide, 1, 3-diethyl-4-methylimidazole fluoroform sulfimide and 1, at least one in 3-diethyl-5-Methylimidazole fluoroform sulfimide.
8. the preparation method of graphene nanobelt according to claim 1, is characterized in that, the vacuum tightness of described vacuum environment is 10 handkerchief～1000 handkerchiefs.
9. the preparation method of graphene nanobelt according to claim 1, it is characterized in that, also comprise described graphene nanobelt cleaned and dry step: in described graphene nanobelt through adding organic solvent to refilter 3 times～6 times, add again deionized water filter until the pH value of filtrate be neutrality, then by filter residue in 60 DEG C～100 DEG C vacuum-dryings to constant weight.
10. the preparation method of graphene nanobelt according to claim 9, is characterized in that, described organic solvent is 1-Methyl-2-Pyrrolidone or DMF.
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