CN103935979B - The preparation method of graphene nanobelt - Google Patents
The preparation method of graphene nanobelt Download PDFInfo
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- CN103935979B CN103935979B CN201310019285.9A CN201310019285A CN103935979B CN 103935979 B CN103935979 B CN 103935979B CN 201310019285 A CN201310019285 A CN 201310019285A CN 103935979 B CN103935979 B CN 103935979B
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Abstract
A preparation method for graphene nanobelt, comprises the steps: to prepare carbon nanometer wall; Under anaerobic, be that carbon nanometer wall mixes with metal intercalation agent by 1 ~ 5:1 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, metal intercalation agent is at least one in lithium, sodium, magnesium, potassium, calcium, rubidium, strontium and barium; It is 1 gram: 10 milliliters ~ 100 milliliters according to mass volume ratio, the intercalation carbon nanometer wall of metal is mixed with ionic liquid, and the supersound process 0.5 minute ~ 30 minutes using power to be 2000W ~ 10000W, obtain reaction solution, filtering reacting liquid obtains graphene nanobelt.Graphene nanobelt prepared by the preparation method of above-mentioned graphene nanobelt has higher specific conductivity.
Description
Technical field
The present invention relates to the synthesis 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), the carbon nanotube, carbon nanofiber etc. of one dimension, the Graphene of two dimension, three-dimensional graphite, diamond etc., carbon nanometer wall (carbonnanowall, 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-like 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 just begin 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 are early stage preparation method or nearest preparation method, all can relate to and react under plasma atmosphere, certain destruction can be caused to the structure of CNW.
Graphene nanobelt not only has the performance of Graphene, also possesses the performance that some are special, such as its length-to-diameter ratio is larger, can up to thousands of times, and the specific conductivity of graphene nanobelt is higher, can copper conductor be replaced at integrated circuit connection, improve integrated level further, 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 defect, cause its specific conductivity lower.
Summary of the invention
Given this, be necessary to provide a kind of preparation method with the graphene nanobelt of high conductance.
A preparation method for graphene nanobelt, comprises the steps:
Metal substrate is placed in concentration be 0.01mol/L ~ 1mol/L acid solution etching 0.5 minute ~ 10 minutes; Under anaerobic, the described metal substrate after etching is heated to 600 DEG C ~ 900 DEG C, uses metal substrate surface described in UV-irradiation, and pass into carbonaceous gas and protection gas, keep 30 minutes ~ 300 minutes, after reaction, obtain carbon nanometer wall on the surface of described metal substrate; Wherein, the flow passing into described carbonaceous gas is 10sccm ~ 1000sccm, and the throughput ratio of described carbonaceous gas and described protection gas is 2 ~ 10:1;
Under anaerobic, be that described carbon nanometer wall mixes with metal intercalation agent by 1 ~ 5:1 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 intercalation agent is at least one in lithium, sodium, magnesium, potassium, calcium, rubidium, strontium and barium; And
Be 1 gram: 10 milliliters ~ 100 milliliters according to mass volume ratio, the intercalation carbon nanometer wall of described metal is mixed with ionic liquid, and the supersound process 0.5 minute ~ 30 minutes using power to be 2000W ~ 10000W, obtain graphene nanobelt after filtration.
Wherein in an embodiment, before to the described metal substrate heating after etching, also comprise the step that the described metal substrate after to etching adopts deionized water, ethanol and acetone to clean successively.
Wherein in an embodiment, 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.
Wherein in an embodiment, described metal substrate is the one in iron foil, nickel foil and cobalt paper tinsel.
Wherein in an embodiment, described carbonaceous gas is the one in methane, ethane, propane, acetylene and alcohol vapour.
Wherein in an embodiment, described protection gas is at least one in helium, nitrogen and argon gas.
Wherein 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.
Wherein in an embodiment, the vacuum tightness of described vacuum environment is 10 handkerchief ~ 1000 handkerchiefs.
Wherein in an embodiment, also comprise the step of cleaning to described graphene nanobelt and drying: in described graphene nanobelt, refilter 3 times ~ 6 times through adding organic solvent, adding deionized water again filters until the pH value of filtrate is in neutral, then by filter residue in 60 DEG C ~ 100 DEG C vacuum-dryings to constant weight.
Wherein in an embodiment, described organic solvent is 1-Methyl-2-Pyrrolidone or DMF.
The preparation method of above-mentioned graphene nanobelt, by preparing carbon nanometer wall first voluntarily as starting material, namely the carbon nanometer wall by adopting etching metal substrate and photochemical catalysis chemical gaseous phase deposition two steps to prepare, prepare carbon nanometer wall under effectively can avoiding traditional using plasma atmosphere and cause it destructurized, and the carbon nanometer wall prepared has uniform thickness, structure is more complete, then lithium is used, sodium, magnesium, potassium, calcium, rubidium, at least one in strontium and barium is as metal intercalation agent, after being prepared into the intercalation carbon nanometer wall of metal, ionic liquid is adopted 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 a large amount of heat release in ultrasonication of the intercalation carbon nanometer wall of metal, make the graphene nanobelt structural integrity prepared, effectively can also prevent the reunion again of graphene nanobelt, thus make above-mentioned preparation method prepare graphene nanobelt there is higher specific conductivity.
Accompanying drawing explanation
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 carbon nanometer wall prepared by embodiment 1;
Fig. 3 is the scanning electron microscope (SEM) photograph (SEM) of graphene nanobelt prepared by 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 concentration be 0.01mol/L ~ 1mol/L acid solution etching 0.5 minute ~ 10 minutes; Under anaerobic, the metal substrate after etching is heated to 600 DEG C ~ 900 DEG C, uses 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 passing 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, carbon nanometer wall is obtained on the surface of metal substrate.Finally, the carbon nanometer wall of metal substrate surface is scraped, just obtain carbon nanometer wall powder.
By to metal substrate etching, make the etched surfaces of metal substrate produce defect, effectively can improve the surface tissue of metal substrate, carbon nanometer wall energy is enough grown at this metal substrate surface.Wherein, acid solution is the dilute acid soln that this area is commonly used, and 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 is preferably 60 seconds ~ 180 seconds.Preferred etching condition, can reach good etching effect, can improve the growth efficiency of carbon nanometer wall.
The carbon source that the growth needs of carbon nanometer wall is more; 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; carbonaceous gas can be diluted to a certain extent, be conducive to the growth of carbon nanometer wall.
Wherein, the metal substrate that metal substrate can be commonly used for this area, is preferably the one in iron foil, nickel foil and cobalt paper tinsel.
Prepare carbon nanometer wall in the absence of oxygen, be in order to avoid oxygen participates in reaction, and have influence on the growth of carbon nanometer wall, thus provide a stable environment to the growth of carbon nanometer wall.
By adopting UV-light to irradiate metal substrate surface, thus playing light-catalysed effect, effectively can reduce the temperature of reaction, reducing energy consumption, reducing production cost.Preferably, the instrument of UV-irradiation is provided to be ultraviolet source equipment.Preferably, the wavelength of UV-light is 200 nanometer ~ 400 nanometers.
By the carbon nanometer wall adopting etching metal substrate and photochemical catalysis chemical gaseous phase deposition two steps to prepare, prepare carbon nanometer wall under effectively can avoiding traditional using plasma atmosphere and cause it destructurized, and the carbon nanometer wall prepared has uniform thickness, structure is more complete.And the carbon nanometer wall energy of preparation enough vertically grows in the metal substrate of etching, preparation technology is simple, and preparation condition is easy to control, and shortens etching period, thus improves production efficiency.
Preferably, before to the metal substrate heating after etching, the step that the metal substrate after to etching adopts deionized water, ethanol and acetone to clean successively is also comprised.
Wherein, the carbonaceous gas that carbonaceous gas can be commonly used for this area, is preferably the one in methane, ethane, propane, acetylene and alcohol vapour.This several carbonaceous gas structure is simple, is easy to cracking and deposition.
Wherein, the rare gas element that protection gas can be commonly used for this area, is preferably at least one in helium, nitrogen and argon gas.
Step S120: under anaerobic, is that carbon nanometer wall mixes with metal intercalation agent by 1 ~ 5:1 according to mol ratio, is then placed in vacuum environment and is 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, such as, under inert gas environment, under being preferably the environment of nitrogen, argon gas or helium.Wherein, metal intercalation agent is at least one in lithium, sodium, magnesium, potassium, calcium, rubidium, strontium and barium.These metals are adopted to make preparation technology simple as intercalator, and low to the requirement of equipment, decrease preparation cost.
By first carbon nanometer wall and metal intercalation agent being mixed with the intercalation carbon nanometer wall of metal, carbon-coating spacing can be made to increase, thus the reactive force of graphite layers is reduced, be conducive to follow-up stripping.And be the destruction in order to avoid carbon nano wall structure by the intercalation carbon nanometer wall being first prepared into metal, be conducive to the integrity obtaining the structure of graphene nanobelt after peeling off.
Preferably, the vacuum tightness of vacuum environment is 10 handkerchiefs (Pa) ~ 1000 handkerchief.This vacuum ranges avoids that vacuum tightness is too high can increase preparation cost on the one hand; Ensure that certain vacuum degree carries out smoothly to avoid above-mentioned metal intercalation agent to be oxidized and to be conducive to intercalation on the other hand.
In the particular embodiment, load in heat-resistant glass tube after carbon nanometer wall is mixed with metal intercalation agent, then Glass tubing is vacuumized, make the vacuum tightness in Glass tubing be 10Pa ~ 1000Pa.
Step S130: be 1 gram: 10 milliliters ~ 100 milliliters according to mass volume ratio, mixes the intercalation carbon nanometer wall of metal with ionic liquid, and the supersound process 0.5 minute ~ 30 minutes using power to be 2000W ~ 10000W, obtain graphene nanobelt after filtration.
Preferably, the device of supersound process is ultrasonic disintegrator.The intercalation carbon nanometer wall of employing ultrasonic disintegrator supersound process metal and the mixture of ionic liquid are to realize the intercalation carbon nanometer wall of quick stripping metal.
Power is that metal intercalation carbon nanometer wall can be peeled off into graphene nanobelt by 2000W ~ 10000W fast, and is scattered in ionic liquid, and can complete stripping fast, required time is short, and technique is simple.And this power can also be avoided ultrasonic to graphene nanobelt structural damage for a long time, to prepare high-quality graphene nanobelt.
Because basic metal or alkaline-earth metal are comparatively active, when itself and carbon nanometer wall are prepared into the intercalation carbon nanometer wall of metal, if adopt water to peel off as solvent, violent reaction can be there is with water, thus the problem causing heat release too fast, and adopt ethanol etc. to make solvent well can not to solve the too fast problem of heat release, mix with the intercalation carbon nanometer wall of metal as solvent by using ionic liquid, the problem that heat release is too fast can well be solved, thus effectively avoid a large amount of heat releases of intercalation carbon nanometer wall in the stripping process of supersound process of metal, make preparation process more safe and reliable, further increase the integrity of the graphene nano band structure prepared, 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 the step to graphene nanobelt cleaning and drying: in graphene nanobelt, refilter 3 times ~ 6 times through adding organic solvent, adding deionized water again filters until the pH value of filtrate is in neutral, then by filter residue in 60 DEG C ~ 100 DEG C vacuum-dryings to constant weight.Preferably, the organic solvent that organic solvent can be commonly used for this area, be preferably 1-Methyl-2-Pyrrolidone (NMP) or N, dinethylformamide (DMF), 1-Methyl-2-Pyrrolidone (NMP) or DMF (DMF) can remove ionic liquid effectively.
The preparation method of above-mentioned graphene nanobelt, by preparing carbon nanometer wall first voluntarily as starting material, namely the carbon nanometer wall by adopting etching metal substrate and photochemical catalysis chemical gaseous phase deposition two steps to prepare, prepare carbon nanometer wall under effectively can avoiding traditional using plasma atmosphere and cause it destructurized, and the carbon nanometer wall prepared has uniform thickness, structure is more complete, then lithium is used, sodium, magnesium, potassium, calcium, rubidium, at least one in strontium and barium is as metal intercalation agent, after being prepared into the intercalation carbon nanometer wall of metal, ionic liquid is adopted 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 a large amount of heat release in ultrasonication of the intercalation carbon nanometer wall of metal, make the graphene nanobelt structural integrity prepared, effectively can also prevent the reunion again of graphene nanobelt, thus make above-mentioned preparation method prepare graphene nanobelt 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 be 1mol/L hydrochloric acid soln etching 0.5 minute, clean with deionized water, ethanol, acetone successively after etching, b nickel foil after cleaning is put into reaction chamber by (), and after getting rid of the air in reaction chamber, nickel foil is heated to 900 DEG C, then ultraviolet source equipment is opened, make UV-irradiation on nickel foil surface, then methane and nitrogen is passed into, keep 100 minutes, wherein, the flow passing 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 heating nickel foil, and close light source, after question response room is cooled to room temperature, stop passing into nitrogen, the carbon nanometer wall of the present embodiment is obtained on nickel foil surface, it is scraped from nickel foil surface, just carbon nanometer wall powder is obtained.
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) of carbon nanometer wall prepared by the present embodiment.As can be seen from the figure, carbon nanometer wall prepared by the present embodiment is perpendicular to nickel foil dense growth, and thickness is even, is about 30 nanometer ~ 60 nanometers.
(2) under the environment being full of helium, carbon nanometer wall step (1) prepared for 5:1 in molar ratio mixes with lithium, loads in heat-resistant glass tube, then be evacuated to 10Pa to Glass tubing, 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 joined 1-ethyl-3-methylimidazole Tetrafluoroboric acid (EtMeImBF is housed
4) container in, supersound process 30 minutes under power is 2000W ultrasonic disintegrator, obtain reaction solution, filtering reacting liquid obtains the graphene nanobelt of the present embodiment, graphene nanobelt is filtered 6 times through adding 1-Methyl-2-Pyrrolidone (NMP), then the pH value being filtered to filtrate with deionized water is in neutral; Then the filter residue cleaned up to be put in vacuum drying oven dry constant weight at 60 DEG C, to obtain pure graphene nanobelt.And the specific conductivity of the graphene nanobelt of the present embodiment obtained, in table 1.
Fig. 3 is the scanning electron microscope (SEM) photograph (SEM) of graphene nanobelt prepared by the present embodiment.As can be seen from the figure, the width distribution of graphene nanobelt prepared by the present embodiment is concentrated, and be about 20 nanometer ~ 40 nanometers, 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 be 0.5mol/L sulphuric acid soln etching 4 minutes, etching after with cleaning with deionized water, ethanol, acetone successively, b iron foil after cleaning is put into reaction chamber by (), and after getting rid of the air in reaction chamber, iron foil is heated to 600 DEG C, then ultraviolet source equipment is opened, make UV-irradiation on iron foil surface, then ethane steam and argon gas is passed into, keep 200 minutes, wherein, the flow passing 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 heating iron foil, and close light source, after question response room is cooled to room temperature, stop passing into argon gas, the carbon nanometer wall of the present embodiment is obtained on iron foil surface, it is scraped from iron foil surface, just carbon nanometer wall powder is obtained.
(2) under the environment being full of nitrogen, carbon nanometer wall step (1) prepared for 2:1 in molar ratio mixes with potassium, loads in heat-resistant glass tube, then be evacuated to 100Pa to Glass tubing, 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 joined 1-ethyl-3-methylimidazole fluoroform sulfimide (EtMeImN (CF is housed
3sO
2)
2) container in, supersound process 0.5 minute under power is 10000W ultrasonic disintegrator, obtain reaction solution, filtering reacting liquid, obtain the graphene nanobelt of the present embodiment, by graphene nanobelt through adding DMF (DMF) filter 23 time, then the pH value being filtered to filtrate with deionized water is in neutral; Then the filter residue cleaned up to be put in vacuum drying oven dry constant weight at 80 DEG C, to obtain pure graphene nanobelt.And the specific conductivity of the graphene nanobelt of the present embodiment obtained, 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 be 0.01mol/L salpeter solution etching 10 minutes, etching after with cleaning with deionized water, ethanol, acetone successively, b cobalt paper tinsel after cleaning is put into reaction chamber by (), and after getting rid of the air in reaction chamber, cobalt paper tinsel is heated to 700 DEG C, then ultraviolet source equipment is opened, make UV-irradiation on cobalt paper tinsel surface, then acetylene steam and argon gas is passed into, keep 300 minutes, wherein, the flow passing 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 heating cobalt paper tinsel, and close light source, after question response room is cooled to room temperature, stop passing into helium, the carbon nanometer wall of the present embodiment is obtained on cobalt paper tinsel surface, it is scraped from cobalt paper tinsel surface, just carbon nanometer wall powder is obtained.
(2) under the environment being full of argon gas, carbon nanometer wall step (1) prepared for 1:1 in molar ratio mixes with sodium, loads in heat-resistant glass tube, then be evacuated to 500Pa to Glass tubing, 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 joined 1-ethyl-3-methylimidazole trifluoromethanesulfonic acid (EtMeImCF is housed
3sO
3) container in, supersound process 1 minute under power is 8000W ultrasonic disintegrator, obtain reaction solution, filtering reacting liquid, obtain the graphene nanobelt of the present embodiment, graphene nanobelt is filtered 5 times through adding 1-Methyl-2-Pyrrolidone (NMP), then the pH value being filtered to filtrate with deionized water is in neutral; Then the filter residue cleaned up to be put in vacuum drying oven dry constant weight at 100 DEG C, to obtain pure graphene nanobelt.And the specific conductivity of the graphene nanobelt of the present embodiment obtained, 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 be 0.2mol/L hydrochloric acid soln etching 2 minutes, etching after with cleaning with deionized water, ethanol, acetone successively, b nickel foil after cleaning is put into reaction chamber by (), and after getting rid of the air in reaction chamber, nickel foil is heated to 750 DEG C, then ultraviolet source equipment is opened, make UV-irradiation on nickel foil surface, then propane vapor and nitrogen and argon gas mixed gas is passed into, keep 30 minutes, wherein, the flow passing 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 heating nickel foil, and close light source, after question response room is cooled to room temperature, stop passing into nitrogen and argon gas mixed gas, the carbon nanometer wall of the present embodiment is obtained on nickel foil surface, it is scraped from nickel foil surface, just carbon nanometer wall powder is obtained.
(2) under the environment being full of helium, carbon nanometer wall, rubidium and strontium mixing step (1) prepared for 3:1 in molar ratio, loads in heat-resistant glass tube, then be evacuated to 1000Pa to Glass tubing, 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 joined 1-ethyl-3-methylimidazole trifluoroacetic acid (EtMeImN (CN) is housed
2) container in, supersound process 2 minutes under power is 6000W ultrasonic disintegrator, obtain reaction solution, filtering reacting liquid, obtain the graphene nanobelt of the present embodiment, by graphene nanobelt through adding DMF (DMF) filter 23 time, then the pH value being filtered to filtrate with deionized water is in neutral; Then the filter residue cleaned up to be put in vacuum drying oven dry constant weight at 90 DEG C, to obtain pure graphene nanobelt.And the specific conductivity of the graphene nanobelt of the present embodiment obtained, 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 be 0.1mol/L sulphuric acid soln etching 5 minutes, etching after with cleaning with deionized water, ethanol, acetone successively, b iron foil after cleaned is put into reaction chamber by (), and after getting rid of the air in reaction chamber, iron foil is heated to 800 DEG C, then ultraviolet source equipment is opened, make UV-irradiation on iron foil surface, then alcohol vapour and argon gas is passed into, keep 50 minutes, wherein, the flow passing 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 heating iron foil, and close light source, after question response room is cooled to room temperature, stop passing into argon gas, the carbon nanometer wall of the present embodiment is obtained on iron foil surface, it is scraped from iron foil surface, just carbon nanometer wall powder is obtained.
(2) under the environment being full of nitrogen, carbon nanometer wall step (1) prepared for 5:1 in molar ratio mixes with magnesium, loads in heat-resistant glass tube, then be evacuated to 200Pa to Glass tubing, 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 joined 1-ethyl-3-methylimidazole fluoroform sulphonyl carbon (EtMeImC (CF is housed
3sO
2)
3) container in, supersound process 12 minutes under power is 5000W ultrasonic disintegrator, obtain reaction solution, filtering reacting liquid, obtain the graphene nanobelt of the present embodiment, graphene nanobelt is filtered 4 times through adding 1-Methyl-2-Pyrrolidone (NMP), then the pH value being filtered to filtrate with deionized water is in neutral; Then the filter residue cleaned up to be put in vacuum drying oven dry constant weight at 70 DEG C, to obtain pure graphene nanobelt.And the specific conductivity of the graphene nanobelt of the present embodiment obtained, 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 be 0.4mol/L salpeter solution etching 8 minutes, etching after with cleaning with deionized water, ethanol, acetone successively, b cobalt paper tinsel after cleaning is put into reaction chamber by (), and after getting rid of the air in reaction chamber, cobalt paper tinsel is heated to 850 DEG C, then ultraviolet source equipment is opened, make UV-irradiation on cobalt paper tinsel surface, then steam methane and helium is passed into, keep 90 minutes, wherein, the flow passing 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 heating cobalt paper tinsel, and close light source, after question response room is cooled to room temperature, stop passing into helium, the carbon nanometer wall of the present embodiment is obtained on cobalt paper tinsel surface, it is scraped from cobalt paper tinsel surface, just carbon nanometer wall powder is obtained.
(2) under the environment being full of argon gas, carbon nanometer wall step (1) prepared for 1:1 in molar ratio mixes with calcium, loads in heat-resistant glass tube, then be evacuated to 600Pa to Glass tubing, 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 joined 1-ethyl-3-methylimidazole trifluoromethanesulfonic acid (EtMeImCF is housed
3sO
3) container in, supersound process 25 minutes under power is 3000W ultrasonic disintegrator, obtain reaction solution, filtering reacting liquid, obtain the graphene nanobelt of the present embodiment, graphene nanobelt is filtered 5 times through adding DMF (DMF), then the pH value being filtered to filtrate with deionized water is in neutral; Then the filter residue cleaned up to be put in vacuum drying oven dry constant weight at 60 DEG C, to obtain pure graphene nanobelt.And the specific conductivity of the graphene nanobelt of the present embodiment obtained, 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 be 0.25mol/L hydrochloric acid soln etching 3 minutes, clean with deionized water, ethanol, acetone successively after etching, b nickel foil after cleaning is put into reaction chamber by (), and after getting rid of the air in reaction chamber, nickel foil is heated to 900 DEG C, then ultraviolet source equipment is opened, make UV-irradiation on nickel foil surface, then ethane steam and nitrogen is passed into, keep 120 minutes, wherein, the flow passing 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 heating nickel foil, and close light source, after question response room is cooled to room temperature, stop passing into nitrogen, the carbon nanometer wall of the present embodiment is obtained on nickel foil surface, it is scraped from nickel foil surface, just carbon nanometer wall powder is obtained.
(2) under the environment being full of nitrogen, carbon nanometer wall step (1) prepared for 4:1 in molar ratio mixes with barium, loads in heat-resistant glass tube, then be evacuated to 800Pa to Glass tubing, 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 joined 1-ethyl-3-methylimidazole two cyaniding nitrogen (EtMeImN (CN) is housed
2) container in, supersound process 4 minutes under power is 2000W ultrasonic disintegrator, obtain reaction solution, filtering reacting liquid, obtain the graphene nanobelt of the present embodiment, by graphene nanobelt through adding 1-Methyl-2-Pyrrolidone (NMP) filter 23 time, then the pH value being filtered to filtrate with deionized water is in neutral; Then the filter residue cleaned up to be put in vacuum drying oven dry constant weight at 100 DEG C, to obtain pure graphene nanobelt.And the specific conductivity of the graphene nanobelt of the present embodiment obtained, 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 be 1mol/L hydrochloric acid soln etching 4 minutes, etching after with cleaning with deionized water, ethanol, acetone successively, b iron foil after cleaning is put into reaction chamber by (), and after getting rid of the air in reaction chamber, iron foil is heated to 650 DEG C, then ultraviolet source equipment is opened, make UV-irradiation on iron foil surface, then acetylene steam and argon gas is passed into, keep 180 minutes, wherein, the flow passing 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 heating iron foil, and close light source, after question response room is cooled to room temperature, stop passing into argon gas, the carbon nanometer wall of the present embodiment is obtained on iron foil surface, it is scraped from iron foil surface, just carbon nanometer wall powder is obtained.
(2) under the environment being full of helium, carbon nanometer wall step (1) prepared for 5:1 in molar ratio mixes with strontium, loads in heat-resistant glass tube, then be evacuated to 100Pa to Glass tubing, 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 joined 1-ethyl-3,5-methylimidazole fluoroform sulfimide (1-Et-3,5-Me are housed
2imN (CF
3sO
2)
2) container in, supersound process 15 minutes under power is 5000W ultrasonic disintegrator, obtain reaction solution, filtering reacting liquid, obtain the graphene nanobelt of the present embodiment, graphene nanobelt is filtered 6 times through adding DMF (DMF), then the pH value being filtered to filtrate with deionized water is in neutral; Then the filter residue cleaned up to be put in vacuum drying oven dry constant weight at 80 DEG C, to obtain pure graphene nanobelt.And the specific conductivity of the graphene nanobelt of the present embodiment obtained, 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 be 0.3mol/L sulphuric acid soln etching 2 minutes, etching after with cleaning with deionized water, ethanol, acetone successively, b cobalt paper tinsel after cleaning is put into reaction chamber by (), and after getting rid of the air in reaction chamber, cobalt paper tinsel is heated to 700 DEG C, then ultraviolet source equipment is opened, make UV-irradiation on cobalt paper tinsel surface, then propane vapor and helium is passed into, keep 240 minutes, wherein, the flow passing 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 heating cobalt paper tinsel, and close light source, after question response room is cooled to room temperature, stop passing into helium, the carbon nanometer wall of the present embodiment is obtained on cobalt paper tinsel surface, it is scraped from cobalt paper tinsel surface, just carbon nanometer wall powder is obtained.
(2) under the environment being full of nitrogen, carbon nanometer wall step (1) prepared for 3:1 in molar ratio mixes with potassium, loads in heat-resistant glass tube, then be evacuated to 50Pa to Glass tubing, 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 joined 1,3-diethyl-4-methylimidazole fluoroform sulfimide (1,3-Et is housed
2-4-MeImN (CF
3sO
2)
2) container in, supersound process 5 minutes under power is 8000W ultrasonic disintegrator, obtain reaction solution, filtering reacting liquid, obtain the graphene nanobelt of the present embodiment, by graphene nanobelt through adding 1-Methyl-2-Pyrrolidone (NMP) filter 23 time, then the pH value being filtered to filtrate with deionized water is in neutral; Then the filter residue cleaned up to be put in vacuum drying oven dry constant weight at 90 DEG C, to 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 be 0.5mol/L salpeter solution etching 5 minutes, clean with deionized water, ethanol, acetone successively after etching, b nickel foil after cleaning is put into reaction chamber by (), and after getting rid of the air in reaction chamber, nickel foil is heated to 800 DEG C, then ultraviolet source equipment is opened, make UV-irradiation on nickel foil surface, then alcohol vapour and nitrogen is passed into, keep 300 minutes, wherein, the flow passing 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 heating nickel foil, and close light source, after question response room is cooled to room temperature, stop passing into nitrogen, the carbon nanometer wall of the present embodiment is obtained on nickel foil surface, it is scraped from nickel foil surface, just carbon nanometer wall powder is obtained.
(2) under the environment being full of nitrogen, carbon nanometer wall step (1) prepared for 4:1 in molar ratio mixes with sodium, loads in heat-resistant glass tube, then be evacuated to 10Pa to Glass tubing, 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 joined 1,3-diethyl-5-Methylimidazole fluoroform sulfimide (1,3-Et is housed
2-5-MeImN (CF
3sO
2)
2) container in, supersound process 10 minutes under power is 10000W ultrasonic disintegrator, obtain reaction solution, filtering reacting liquid, obtain the graphene nanobelt of the present embodiment, graphene nanobelt is filtered 4 times through adding DMF (DMF), then the pH value being filtered to filtrate with deionized water is in neutral; Then the filter residue cleaned up to be put in vacuum drying oven dry constant weight at 70 DEG C, to obtain pure graphene nanobelt.And the specific conductivity of the graphene nanobelt of the present embodiment obtained, 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 be 0.05mol/L hydrochloric acid soln etching 1 minute, etching after with cleaning with deionized water, ethanol, acetone successively; B cobalt paper tinsel after cleaning is put into reaction chamber by (), and after getting rid of 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 passing 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 heating cobalt paper tinsel, and close light source, after question response room is cooled to room temperature, stop passing into argon gas, obtain the carbon nanometer wall of the present embodiment on cobalt paper tinsel surface, it is scraped from cobalt paper tinsel surface, just obtains carbon nanometer wall powder.
(2) under the environment being full of helium, carbon nanometer wall step (1) prepared for 2:1 in molar ratio mixes with calcium, loads in heat-resistant glass tube, then be evacuated to 100Pa to Glass tubing, 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 joined 1-ethyl-3-methylimidazole two cyaniding nitrogen (EtMeImN (CN) is housed
2) container in, supersound process 15 minutes under power is 8000W ultrasonic disintegrator, obtain reaction solution, filtering reacting liquid, obtain the graphene nanobelt of the present embodiment, graphene nanobelt is filtered 5 times through adding 1-Methyl-2-Pyrrolidone (NMP), then the pH value being filtered to filtrate with deionized water is in neutral; Then the filter residue cleaned up to be put in vacuum drying oven dry constant weight at 100 DEG C, to obtain pure graphene nanobelt.And the specific conductivity of the graphene nanobelt of the present embodiment obtained, in table 1.
What table 1 represented is the specific conductivity of graphene nanobelt prepared by embodiment 1 ~ embodiment 11.
Table 1
Can learn from table 1, 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, the specific conductivity (10 of graphene nanobelt prepared by the method preparing graphene nanobelt higher than tradition
4s/m), this illustrates that the graphene nanobelt adopting the preparation method of graphene nanobelt of the present invention to prepare has good integrity.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not 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 (9)
1. a preparation method for graphene nanobelt, is characterized in that, comprises the steps:
Metal substrate is placed in concentration be 0.01mol/L ~ 1mol/L acid solution etching 0.5 minute ~ 10 minutes; Under anaerobic, the described metal substrate after etching is heated to 600 DEG C ~ 900 DEG C, uses metal substrate surface described in UV-irradiation, and pass into carbonaceous gas and protection gas, keep 30 minutes ~ 300 minutes, after reaction, obtain carbon nanometer wall on the surface of described metal substrate; Wherein, the flow passing into described carbonaceous gas is 10sccm ~ 1000sccm, and the throughput ratio of described carbonaceous gas and described protection gas is 2 ~ 10:1;
Under anaerobic, be that described carbon nanometer wall mixes with metal intercalation agent by 1 ~ 5:1 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 intercalation agent is at least one in lithium, sodium, magnesium, potassium, calcium, rubidium, strontium and barium; And
Be 1 gram: 10 milliliters ~ 100 milliliters according to mass volume ratio, the intercalation carbon nanometer wall of described metal is mixed with ionic liquid, and the supersound process 0.5 minute ~ 30 minutes using power to be 2000W ~ 10000W, obtain graphene nanobelt after filtration;
Described metal substrate is the one in iron foil, nickel foil and cobalt paper tinsel.
2. the preparation method of graphene nanobelt according to claim 1, it is characterized in that, before to the described metal substrate heating after etching, also comprise the step that the described metal substrate after to etching adopts deionized water, ethanol and acetone to clean successively.
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 carbonaceous gas is the one in methane, ethane, propane, acetylene and alcohol vapour.
5. 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.
6. 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.
7. 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.
8. the preparation method of graphene nanobelt according to claim 1, it is characterized in that, also comprise the step to described graphene nanobelt cleaning and drying: in described graphene nanobelt, refilter 3 times ~ 6 times through adding organic solvent, adding deionized water again filters until the pH value of filtrate is in neutral, then by filter residue in 60 DEG C ~ 100 DEG C vacuum-dryings to constant weight.
9. the preparation method of graphene nanobelt according to claim 8, is characterized in that, described organic solvent is 1-Methyl-2-Pyrrolidone or DMF.
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