CN103879987B - The preparation method of graphene nanobelt - Google Patents
The preparation method of graphene nanobelt Download PDFInfo
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- CN103879987B CN103879987B CN201210555207.6A CN201210555207A CN103879987B CN 103879987 B CN103879987 B CN 103879987B CN 201210555207 A CN201210555207 A CN 201210555207A CN 103879987 B CN103879987 B CN 103879987B
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Abstract
The invention provides a kind of preparation method of graphene nanobelt, utilize UV-light as photocatalyst, carbon source is through photochemical catalysis chemical vapour deposition reaction Formed nanometer wall in the metal substrate through over etching, this carbon nanometer wall is scraped and obtains carbon nanometer wall powder, using this carbon nanometer wall powder as raw material, three-electrode system reaction is adopted to prepare intercalation carbon nanometer wall, be that intercalation carbon nanometer wall to be scattered in ionic liquid and to obtain dispersion liquid by 1g:10 ~ 100ml by mass volume ratio, dispersion liquid is carried out under power 2kW ~ 10kW ultrasonic stripping to filter after 0.5 minute ~ 30 minutes, washing filter residue drying obtains graphene nanobelt.Using the raw material of this carbon nanometer wall powder as graphene nanobelt, carry out ultrasonic stripping and obtain the higher graphene nanobelt of dimensional homogeneity, and this method, preparing in process and can not introducing oxy radical at the graphene nanobelt finally obtained, prepares the good graphene nanobelt of quality.
Description
Technical field
The present invention relates to the synthesis field of nano-carbon material, particularly relate to a kind of preparation method of graphene nanobelt.
Background technology
Graphene nanobelt is on the basis of two-dimensional graphene plane, the zonal structure formed through certain shearing.Graphene nanobelt not only has the performance of Graphene, also possesses the performance that some are special, and such as its length-to-diameter ratio is larger, can up to thousands of times, 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.
At present, the preparation method of graphene nanobelt adopts cutting carbon nanotubes method usually, first carbon nanotube is immersed in sulfuric acid by this method, heats after adding strong oxidizer, utilizes strong oxidizer make carbon nanotube open loop and obtain graphene nanobelt under high temperature action.Usually the introducing oxygen-containing functional group and detrimentally affect is produced to the conductivity of graphene nanobelt of the graphene nanobelt that this side prepares; and the homogeneity of size is difficult to control; make the poor of the graphene nanobelt quality finally obtained, be difficult to practical requirement.
Summary of the invention
Based on this, be necessary the preparation method that a kind of graphene nanobelt is provided, with the good graphene nanobelt of preparation quality.
A preparation method for graphene nanobelt, comprises the steps:
Dilute acid soln is used to etch metal substrate;
Under the atmosphere of anaerobic and shielding gas, described metal substrate is heated to 600 DEG C ~ 900 DEG C;
Under the irradiation of UV-light, pass into the one in methane, ethane, propane, acetylene and ethanol to described metal substrate surface, through photochemical catalysis chemical vapour deposition reaction 30 minutes ~ 300 minutes, at described metal substrate surface Formed nanometer wall;
After having reacted, under the atmosphere of described shielding gas, the metal substrate with carbon nanometer wall is cooled to room temperature, then described carbon nanometer wall is scraped from the surface of described metal substrate, obtain carbon nanometer wall powder;
Described carbon nanometer wall powder to be positioned on collector and to be pressed into carbon nanometer wall flaps layer and obtain working electrode;
Jointly will be soaked in electrolytic solution, at 5mA/cm electrode, reference electrode and described working electrode
2~ 100mA/cm
2current density, reaction after 1 hour ~ 20 hours under room temperature, reacted electrolytic solution carried out filter, wash filter residue and drying obtains intercalation carbon nanometer wall; And
Be that described intercalation carbon nanometer wall to be scattered in ionic liquid and to obtain dispersion liquid by 1g:10 ~ 100ml by mass volume ratio, described dispersion liquid is carried out under power 2kW ~ 10kW ultrasonic stripping to filter after 0.5 minute ~ 30 minutes, washing filter residue drying obtains graphene nanobelt.
Wherein in an embodiment, described use dilute acid soln is specially the step that metal substrate etches: described metal substrate is put into concentration be 0.01mol/L ~ 1mol/L dilute acid soln etching 0.5 minute ~ 10 minutes.
Wherein in an embodiment, described use dilute acid soln carries out etch step to metal substrate and is specially: described metal substrate is put into concentration be 0.1mol/L ~ 0.5mol/L dilute acid soln etching 1 minute ~ 3 minutes.
Wherein in an embodiment, the wavelength of described UV-light is 200 ~ 400nm.
Wherein in an embodiment, a kind of flow in described methane, ethane, propane, acetylene and ethanol is 10sccm ~ 1000sccm.
Wherein in an embodiment, the volume ratio of a kind of and described shielding gas in described methane, ethane, propane, acetylene and ethanol is 2 ~ 10:1.
Wherein in an embodiment, described electrolytic solution is selected from least one in formic acid, acetic acid, propionic acid, nitric acid, Nitromethane 99Min..
Wherein in an embodiment, described ionic liquid is selected from 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, one in 3-diethyl-5-Methylimidazole fluoroform sulfimide.
Wherein in an embodiment, the described washing filter residue also dry step obtaining graphene nanobelt is specially described filter residue 1-Methyl-2-Pyrrolidone or N, dinethylformamide washing 3 ~ 6 times, be neutral by the pH value that ethanol, acetone and deionized water are filtered to filtrate successively again, then at 60 DEG C ~ 100 DEG C, vacuum-drying obtains graphene nanobelt to constant weight.
Wherein in an embodiment, the described washing filter residue also dry step obtaining intercalation carbon nanometer wall is specially: with filter residue described in deionized water wash, and in 60 DEG C ~ 80 DEG C vacuum-dryings 12 hours ~ 24 hours.
First the preparation method of above-mentioned graphene nanobelt utilizes photochemical catalysis chemical vapour deposition to prepare structural integrity, carbon nanometer wall powder that dimensional homogeneity is higher, using the raw material of this carbon nanometer wall powder as graphene nanobelt, carry out ultrasonic stripping and obtain that dimensional homogeneity is higher, the graphene nanobelt of favorable dispersity, and this method, preparing in process and can not introducing oxy radical at the graphene nanobelt finally obtained, prepares the good graphene nanobelt of quality.
Accompanying drawing explanation
Fig. 1 is preparation method's schema of the graphene nanobelt of an embodiment;
Fig. 2 is the SEM figure of carbon nanometer wall prepared by embodiment 1;
Fig. 3 is the SEM figure of graphene nanobelt prepared by embodiment 1.
Embodiment
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail the specific embodiment of the present invention below in conjunction with accompanying drawing.Set forth a lot of detail in the following description so that fully understand the present invention.But the present invention can be much different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar improvement when intension of the present invention, therefore the present invention is by the restriction of following public concrete enforcement.
Refer to Fig. 1, the preparation method of the graphene nanobelt of an embodiment, comprises the steps:
Step S110: use dilute acid soln to etch metal substrate.
Metal substrate is preferably the one in iron foil, nickel foil and cobalt paper tinsel.
Use dilute acid soln the step that metal substrate etches is specially: metal substrate is put into concentration be 0.01mol/L ~ 1mol/L dilute acid soln etching 0.5 minute ~ 10 minutes.
Dilute acid soln is dilute hydrochloric acid solution, dilution heat of sulfuric acid or dilute nitric acid solution.
Preferably, the concentration of dilute acid soln is 0.1mol/L ~ 0.5mol/L, and the time of etching is 1 minute ~ 3 minutes.
Metal substrate is etched, makes metal substrate surface produce defect, effectively can improve the surface tissue of metal substrate, think that carbon nanometer wall provides a favourable growth substrate, make the enough surface growths in metal substrate of carbon nanometer wall energy.
A kind of metal substrate in iron foil, nickel foil and cobalt paper tinsel is put into the dilute acid soln etching 1 minute ~ 3 minutes that concentration is 0.1mol/L ~ 0.5mol/L, good etching effect can be reached, be conducive to the growth efficiency improving carbon nanometer wall.
Step S120: under the atmosphere of anaerobic and shielding gas, metal substrate is heated to 600 DEG C ~ 900 DEG C.
First the metal substrate through over etching is cleaned up with deionized water, ethanol and acetone and drying successively, for subsequent use.
The metal substrate through over etching after cleaning-drying is put into reaction chamber.The air got rid of in reaction chamber also passes into shielding gas, makes reaction chamber be in anaerobic state completely, and avoid the participation of oxygen and affect the growth of carbon nanometer wall, the growth for carbon nanometer wall provides a stable environment.
Metal substrate is heated to 600 DEG C ~ 900 DEG C, and insulation is to reacting end.
Shielding gas is preferably at least one in helium, nitrogen, argon gas.
Step S130: under the irradiation of UV-light, passes into the one in methane, ethane, propane, acetylene and ethanol to metal substrate surface, through photochemical catalysis chemical vapour deposition reaction 30 minutes ~ 300 minutes, at metal substrate surface Formed nanometer wall.
Ultraviolet source equipment and metal substrate are just right.Open ultraviolet source equipment, make UV-irradiation on the surface of metal substrate.
UV-light is as photocatalyst.The wavelength of UV-light is preferably 200 ~ 400nm.
Under the irradiation of UV-light, in reaction chamber, pass into carbon source, metal substrate is in the atmosphere of carbon source.Carbon source is selected from the one in methane, ethane, propane, acetylene and ethanol.
The flow of carbon source is 10sccm ~ 1000sccm.
Preferably, the volume ratio of carbon source and shielding gas is 2 ~ 10:1.
Under UV-irradiation and in shielding gas atmosphere, the one in methane, ethane, propane, acetylene and ethanol through photochemical catalysis chemical vapour deposition reaction 30 minutes ~ 300 minutes, Formed nanometer wall on the metallic substrate.
Step S140: after having reacted, is cooled to room temperature by the metal substrate with carbon nanometer wall, is then scraped from the surface of metal substrate by carbon nanometer wall, obtain carbon nanometer wall powder under the atmosphere of shielding gas.
React after 30 minutes ~ 300 minutes; stop passing into carbon source, close heating installation and close ultraviolet source equipment, stop passing into shielding gas after question response room and the metal substrate with carbon nanometer wall are cooled to room temperature; the carbon nanometer wall of metal substrate surface is scraped, obtains carbon nanometer wall powder.
Question response room and stop again after being cooled to room temperature with the metal substrate of carbon nanometer wall passing into shielding gas, prevents the carbon nanometer wall generated at high temperature to be oxidized, ensures the quality obtaining carbon nanometer wall powder further.
Step S150: carbon nanometer wall powder to be positioned on collector and to be pressed into carbon nanometer wall flaps layer and obtain working electrode.
Carbon nanometer wall powder and binding agent are positioned on collector, then with mould compacting, make collector to be formed carbon nanometer wall flaps layer, obtain the working electrode of three-electrode system.Collector preferably adopts stainless steel collector.
Carbon nanometer wall flaps layer is of a size of 75*40*7mm
3.
Step S160: jointly will be soaked in electrolytic solution, at 5mA/cm electrode, reference electrode and working electrode
2~ 100mA/cm
2current density, reaction after 1 hour ~ 20 hours under room temperature, reacted electrolytic solution carried out filter, wash filter residue and drying obtains intercalation carbon nanometer wall.
Adopt stereotype as to electrode, Hg/Hg
2sO
4as reference electrode.
Electrolytic solution is selected from least one in formic acid, acetic acid, propionic acid, nitric acid, Nitromethane 99Min..Electrolytic solution also plays the effect of intercalator simultaneously, and under electric field action, electrolytic solution forms potential difference at working electrode surface, constantly overcomes the reactive force between carbon nanowall layer, be inserted between carbon nanowall layer under the driving of potential difference, obtains intercalation carbon nanometer wall.
React after 1 hour ~ 20 hours, reacted electrolytic solution is filtered, the filter residue deionized water wash then will obtained, then by the vacuum-drying 12 hours ~ 24 hours at 60 DEG C ~ 80 DEG C of the filter residue after washing, obtain drying, pure intercalation carbon nanometer wall.
Step S170: be that intercalation carbon nanometer wall to be scattered in ionic liquid and to obtain dispersion liquid by 1g:10 ~ 100ml by mass volume ratio, dispersion liquid is carried out under power 2kW ~ 10kW ultrasonic stripping to filter after 0.5 minute ~ 30 minutes, washing filter residue drying obtains graphene nanobelt.
Intercalation carbon nanometer wall is scattered in ionic liquid is convenient to ultrasonic stripping, and the graphene nanobelt obtained after stripping is also scattered in ionic liquid.Can prevent graphene nanobelt from reuniting with ionic liquid as dispersion liquid, thus improve the productive rate of graphene nanobelt.
In order to reach good dispersion effect, to improve the productive rate of charge stripping efficiency and graphene nanobelt, the mass volume ratio of intercalation carbon nanometer wall and ionic liquid is preferably 1g:10 ~ 100ml.
Ionic liquid is selected from 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 (EtMeImCF
3cO
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-Me2ImN (CF
3sO
2)
2), 1,3-diethyl-4-methylimidazole fluoroform sulfimide (1,3-Et2-4-MeImN (CF
3sO
2)
2) and 1,3-diethyl-5-Methylimidazole fluoroform sulfimide (1,3-Et
2-5-MeImN (CF
3sO
2)
2) in one.
Above-mentioned ionic liquid is liquid at normal temperatures, and to make intercalated graphite be scattered in ionic liquid, to carry out ultrasonic stripping at normal temperatures, energy consumption is low, and preparation cost is low.
Dispersion liquid carries out ultrasonic stripping and filters for the first time after 0.5 minute ~ 30 minutes under power 2kW ~ 10kW, again by filter residue 1-Methyl-2-Pyrrolidone (NMP) or N, dinethylformamide (DMF) washs 3 ~ 6 times, fully to remove the ionic liquid in filter residue.Then, be neutral by the pH value that ethanol, acetone and deionized water are filtered to filtrate successively, then vacuum-drying obtain graphene nanobelt to constant weight at 60 DEG C ~ 100 DEG C.
Under power 2kW ~ 10kW, carry out ultrasonic stripping, ensure certain charge stripping efficiency to facilitate, make splitting time shorter, production efficiency is higher; On the other hand, avoid hyperacoustic power too high, destruction is produced to the structure of graphene nanobelt.
In ultrasonic stripping process, do not introduce impurity, the filtrate obtained of filtration, namely ionic liquid can reclaim and reuse, and is conducive to reducing preparation cost.
The preparation method of above-mentioned graphene nanobelt, first utilize UV-light as photocatalyst, carbon source is through photochemical catalysis chemical vapour deposition reaction Formed nanometer wall in the metal substrate through over etching, this carbon nanometer wall is scraped and obtains carbon nanometer wall powder, using this carbon nanometer wall powder as raw material, adopt three-electrode system reaction to prepare intercalation carbon nanometer wall, ultrasonic stripping is carried out to this intercalation carbon nanometer wall and obtains graphene nano wall.
Utilize UV-light as photocatalyst, carbon source avoids through the method for photochemical catalysis chemical vapour deposition reaction Formed nanometer wall in the metal substrate through over etching that traditional in preparation method, plasma body, can generating structure is comparatively complete, dimensional homogeneity is higher carbon nanometer wall to the destruction of carbon nanometer wall in plasma atmosphere.The carbon nanometer wall utilizing this dimensional homogeneity higher prepares graphene nanobelt as raw material, the dimensional homogeneity of graphene nanobelt can be improved, and, adopt ultrasonic stripping method to peel off intercalation carbon nanometer wall and obtain graphene nanobelt, tradition can be avoided to adopt in the method for oxygenant cutting carbon nanotubes and to introduce oxygen-containing functional group, prepare the good graphene nanobelt of quality.
Preparation method's technique of this graphene nanobelt is simple, and condition is easily controlled, and ultrasonic charge stripping efficiency is high, stripping process is the highest only needs 30 minutes, improves production efficiency, and the graphene nanobelt dispersiveness of preparation is high, photochemical catalysis effectively can reduce temperature of reaction, reduces energy consumption, reduces production cost.
The graphene nanobelt that the method adopts the carbon nanometer wall powder prepared voluntarily to prepare as raw material, the preparation of carbon nanometer wall powder is a kind of as carbon source in methane, ethane, propane, acetylene and ethanol, this several carbon source is comparatively cheap, relative to the raw material adopting commercially available carbon nanotube as graphene nanobelt, its advantage of lower cost.
The method equipment used is all common chemical industry equipment, lower to the requirement of equipment, is applicable to scale operation.
It is below specific embodiment.
Embodiment 1
1. nickel foil is put into the dilute hydrochloric acid solution etching 0.5 minute that concentration is 1mol/L, good rear the deionized water of etching, ethanol, acetone carry out cleaning also drying;
2. get rid of the air in reaction chamber and pass into nitrogen, nickel foil after cleaning-drying is put into the reaction chamber being connected with nitrogen, and nickel foil is heated to 900 DEG C and is incubated, then ultraviolet source equipment is opened, make UV-irradiation on nickel foil surface, the wavelength of UV-light is 250nm, then passes into methane 200sccm, the volume ratio of methane and nitrogen is 2:1, keeps 100 minutes;
3. after having reacted, stop passing into methane, stop nickel foil heating and close ultraviolet source equipment, stop after question response room is cooled to room temperature passing into nitrogen, nickel foil Surface Creation carbon nanometer wall, scrapes it from nickel foil surface, just obtains carbon nanometer wall powder;
4. the preparation of intercalation carbon nanometer wall: adopt stainless steel substrates as collector, put on collector by the above-mentioned carbon nanometer wall powder prepared, being pressed into specification is on a current collector 75*40*7mm
3the carbon nanometer wall flaps layer of (about 2g) as working electrode, using stereotype as to electrode, Hg/Hg
2sO
4as reference electrode, three electrodes, as electrolytic solution, are put into electrolyzer and are fully immersed in electrolytic solution, at 5mA/cm by formic acid
2current density, carry out reaction 20 hours under room temperature, then reacted electrolytic solution is filtered, the filter residue washed with de-ionized water obtained is placed in vacuum drying oven and can obtains pure, dry intercalation carbon nanometer wall after 24 hours in 60 DEG C of dryings;
5. getting intercalation carbon nanometer wall, is that 1g:10ml joins EtMeImBF is housed by mass volume ratio
4in the container of ionic liquid, ultrasonic stripping 30 minutes under power is 2kW ultrasonic disintegrator, then filter for the first time, the filter residue NMP filtration washing obtained 6 times, be neutral by the cleaning such as ethanol, acetone, deionized water to the pH value of filtrate successively again, filter, the filter residue collected is dried to constant weight at vacuum drying oven at 60 DEG C and obtains graphene nanobelt.
Fig. 2 and Fig. 3 is respectively the carbon nanometer wall of embodiment 1 preparation and the SEM figure of graphene nanobelt.As can be seen from Figures 2 and 3, carbon nanometer wall is perpendicular to substrate dense growth, and thickness is even, be about 30 ~ 60nm, concentrated by the graphene nanobelt width distribution of carbon nanometer wall prepared by raw material, be about 20 ~ 40nm, length is about 2 ~ 20um, and length-to-diameter ratio is about 50 ~ 1000.
This graphene nanobelt do not introduce oxygen-containing functional group, and width distribution is comparatively even, and quality is better.
Embodiment 2
1. adopt iron foil as substrate, iron foil is put into the dilution heat of sulfuric acid etching 4 minutes that concentration is 0.5mol/L, good rear the deionized water of etching, ethanol, acetone carry out cleaning also drying;
2. the air in eliminating reaction chamber also passes into argon gas, iron foil after cleaning-drying is put into the reaction chamber being connected with argon gas, and iron foil is heated to 600 DEG C and is incubated, then ultraviolet source equipment is opened, make UV-irradiation on iron foil surface, the wavelength of UV-light is 200nm, then passes into ethane 100sccm, the volume ratio of ethane and argon gas is 5:1, keeps 200 minutes;
3. after having reacted, stop passing into ethane, stop iron foil heating and close ultraviolet source equipment, stop after question response room is cooled to room temperature passing into argon gas, iron foil Surface Creation carbon nanometer wall, scrapes it from iron foil surface, just obtains carbon nanometer wall powder;
4. the preparation of intercalation carbon nanometer wall: adopt stainless steel substrates as collector, put on collector by the above-mentioned carbon nanometer wall powder prepared, being pressed into specification is on a current collector 75*40*7mm
3the carbon nanometer wall flaps layer of (about 2g) as working electrode, using stereotype as to electrode, Hg/Hg
2sO
4as reference electrode, three electrodes, as electrolytic solution, are put into electrolyzer and are fully immersed in electrolytic solution, at 20mA/cm by acetic acid
2current density, carry out reaction 1 hour under room temperature, then reacted electrolytic solution is filtered, the filter residue washed with de-ionized water obtained is placed in vacuum drying oven and can obtains pure, dry intercalation carbon nanometer wall after 20 hours in 70 DEG C of dryings;
5. getting intercalation carbon nanometer wall, is that 1g:100ml joins EtMeImN (CF is housed by mass volume ratio
3sO
2)
2in the container of ionic liquid, ultrasonication 0.5 minute under power is 10kW ultrasonic disintegrator, then filter for the first time, the filter residue DMF filtration washing obtained 3 times, be neutral by the cleaning such as ethanol, acetone, deionized water to the pH value of filtrate successively again, filter, the filter residue collected is dried to constant weight at vacuum drying oven at 80 DEG C and can obtains graphene nanobelt.
Embodiment 3
1. adopt cobalt paper tinsel as substrate, cobalt paper tinsel is put into the dilute nitric acid solution etching 10 minutes that concentration is 0.01mol/L, good rear the deionized water of etching, ethanol, acetone carry out cleaning also drying;
2. the air in eliminating reaction chamber also passes into helium, cobalt paper tinsel after cleaning-drying is put into the reaction chamber being connected with helium, and cobalt paper tinsel is heated to 700 DEG C of insulations, then ultraviolet source equipment is opened, make UV-irradiation on cobalt paper tinsel surface, the wavelength of UV-light is 300nm, then passes into acetylene 10sccm, the volume ratio of acetylene and helium is 8:1, keeps 300 minutes;
3. after having reacted, stop passing into acetylene, stop the heating of cobalt paper tinsel and close ultraviolet source equipment, stop after question response room is cooled to room temperature passing into helium, cobalt paper tinsel Surface Creation carbon nanometer wall, scrapes it from cobalt paper tinsel surface, just obtains carbon nanometer wall powder;
4. the preparation of intercalation carbon nanometer wall: adopt stainless steel substrates as collector, put on collector by the above-mentioned carbon nanometer wall powder prepared, being pressed into specification is on a current collector 75*40*7mm
3the carbon nanometer wall flaps layer of (about 2g) as working electrode, using stereotype as to electrode, Hg/Hg
2sO
4as reference electrode, three electrodes, as electrolytic solution, are put into electrolyzer and are fully immersed in electrolytic solution, at 50mA/cm by propionic acid
2current density, carry out reaction 2 hours under room temperature, then reacted electrolytic solution is filtered, the filter residue washed with de-ionized water obtained is placed in vacuum drying oven and can obtains pure, dry intercalation carbon nanometer wall after 12 hours in 80 DEG C of dryings;
5. getting intercalation carbon nanometer wall, is that 1g:50ml joins EtMeImCF is housed by mass volume ratio
3sO
3in the container of ionic liquid, ultrasonication 1 minute under power is 8kW ultrasonic disintegrator, then filter for the first time, the filter residue NMP filtration washing obtained 5 times, be neutral by the cleaning such as ethanol, acetone, deionized water to the pH value of filtrate successively again, filter, the filter residue collected is dried to constant weight at vacuum drying oven at 100 DEG C and can obtains graphene nanobelt.
Embodiment 4
1. adopt nickel foil as substrate, nickel foil is put into the dilute hydrochloric acid solution etching 2 minutes that concentration is 0.2mol/L, good rear the deionized water of etching, ethanol, acetone carry out cleaning also drying;
2. the air in eliminating reaction chamber also passes into nitrogen, nickel foil after cleaning-drying is put into the reaction chamber being connected with nitrogen, and nickel foil is heated to 750 DEG C and is incubated, then ultraviolet source equipment is opened, make UV-irradiation on nickel foil surface, the wavelength of UV-light is 400nm, then passes into propane 1000sccm, the volume ratio of propane and nitrogen is 10:1, keeps 30 minutes;
3. after having reacted, stop passing into propane, stop nickel foil heating and close ultraviolet source equipment, stop after question response room is cooled to room temperature passing into nitrogen, nickel foil Surface Creation carbon nanometer wall, scrapes it from nickel foil surface, just obtains carbon nanometer wall powder;
4. the preparation of intercalation carbon nanometer wall: adopt stainless steel substrates as collector, put on collector by the above-mentioned carbon nanometer wall powder prepared, being pressed into specification is on a current collector 75*40*7mm
3the carbon nanometer wall flaps layer of (about 2g) as working electrode, using stereotype as to electrode, Hg/Hg
2sO
4as reference electrode, massfraction be the nitric acid of 68% as electrolytic solution, three electrodes are put into electrolyzer and are fully immersed in electrolytic solution, at 100mA/cm
2current density, carry out reaction 5 hours under room temperature, then reacted electrolytic solution is filtered, the filter residue washed with de-ionized water obtained is placed in vacuum drying oven and can obtains pure, dry intercalation carbon nanometer wall after 15 hours in 75 DEG C of dryings;
5. getting intercalation carbon nanometer wall, is that 1g:20ml joins EtMeImCF is housed by mass volume ratio
3cO
3in the container of ionic liquid, ultrasonication 2 minutes under power is 6W ultrasonic disintegrator, then filter for the first time, the filter residue DMF filtration washing obtained 3 times, be neutral by the cleaning such as ethanol, acetone, deionized water to the pH value of filtrate successively again, filter, the filter residue collected is dried to constant weight at vacuum drying oven at 90 DEG C and can obtains graphene nanobelt.
Embodiment 5
1. adopt iron foil as substrate, iron foil is put into the dilution heat of sulfuric acid etching 5 minutes that concentration is 0.1mol/L, good rear the deionized water of etching, ethanol, acetone carry out cleaning also drying;
2. the air in eliminating reaction chamber also passes into argon gas, iron foil after cleaning-drying is put into the reaction chamber being connected with argon gas, and iron foil is heated to 800 DEG C and is incubated, then ultraviolet source equipment is opened, make UV-irradiation on iron foil surface, the wavelength of UV-light is 380nm, then passes into ethanol 500sccm, the volume ratio of ethanol and argon gas is 6:1, keeps 50 minutes;
3. after having reacted, stop passing into ethanol, stop iron foil heating and close ultraviolet source equipment, stop after question response room is cooled to room temperature passing into argon gas, iron foil Surface Creation carbon nanometer wall, scrapes it from iron foil surface, just obtains carbon nanometer wall powder;
4. the preparation of intercalation carbon nanometer wall: adopt stainless steel substrates as collector, put on collector by the above-mentioned carbon nanometer wall powder prepared, being pressed into specification is on a current collector 75*40*7mm
3the carbon nanometer wall flaps layer of (about 2g) as working electrode, using stereotype as to electrode, Hg/Hg
2sO
4as reference electrode, three electrodes, as electrolytic solution, are put into electrolyzer and are fully immersed in electrolytic solution, at 80mA/cm by formic acid
2current density, carry out reaction 10 hours under room temperature, then reacted electrolytic solution is filtered, the filter residue washed with de-ionized water obtained is placed in vacuum drying oven and can obtains pure, dry intercalation carbon nanometer wall after 18 hours in 65 DEG C of dryings;
5. getting intercalation carbon nanometer wall, is that 1g:80ml joins EtMeImC (CF is housed by mass volume ratio
3sO
2)
3in the container of ionic liquid, ultrasonication 12 minutes under power is 5W ultrasonic disintegrator, then filter for the first time, the filter residue NMP filtration washing obtained 4 times, be neutral by the cleaning such as ethanol, acetone, deionized water to the pH value of filtrate successively again, filter, the filter residue collected is dried to constant weight at vacuum drying oven at 70 DEG C and can obtains graphene nanobelt.
Embodiment 6
1. adopt cobalt paper tinsel as substrate, cobalt paper tinsel is put into the dilute nitric acid solution etching 8 minutes that concentration is 0.4mol/L, good rear the deionized water of etching, ethanol, acetone carry out cleaning also drying;
2. the air in eliminating reaction chamber also passes into helium, cobalt paper tinsel after cleaning-drying is put into the reaction chamber being connected with helium, and cobalt paper tinsel is heated to 850 DEG C and is incubated, then ultraviolet source equipment is opened, make UV-irradiation on cobalt paper tinsel surface, the wavelength of UV-light is 200nm, then passes into methane 800sccm, the volume ratio of methane and helium is 4:1, keeps 90 minutes;
3. after having reacted, stop passing into methane, stop the heating of cobalt paper tinsel and close ultraviolet source equipment, stop after question response room is cooled to room temperature passing into helium, cobalt paper tinsel Surface Creation carbon nanometer wall, scrapes it from cobalt paper tinsel surface, just obtains carbon nanometer wall powder;
4. the preparation of intercalation carbon nanometer wall: adopt stainless steel substrates as collector, put on collector by the above-mentioned carbon nanometer wall powder prepared, being pressed into specification is on a current collector 75*40*7mm
3the carbon nanometer wall flaps layer of (about 2g) as working electrode, using stereotype as to electrode, Hg/Hg
2sO
4as reference electrode, three electrodes, as electrolytic solution, are put into electrolyzer and are fully immersed in electrolytic solution, at 40mA/cm by Nitromethane 99Min.
2current density, carry out reaction 15 hours under room temperature, then reacted electrolytic solution is filtered, the filter residue washed with de-ionized water obtained is placed in vacuum drying oven and can obtains pure, dry intercalation carbon nanometer wall after 20 hours in 60 DEG C of dryings;
5. getting intercalation carbon nanometer wall, is that 1g:60ml joins EtMeImN (C is housed by mass volume ratio
2f
5sO
2)
2in the container of ionic liquid, ultrasonication 25 minutes under power is 3W ultrasonic disintegrator, then filter for the first time, the filter residue DMF filtration washing obtained 5 times, be neutral by the cleaning such as ethanol, acetone, deionized water to the pH value of filtrate successively again, filter, the filter residue collected is dried to constant weight at vacuum drying oven at 60 DEG C and can obtains graphene nanobelt.
Embodiment 7
1. adopt nickel foil as substrate, nickel foil is put into the dilute hydrochloric acid solution etching 3 minutes that concentration is 0.25mol/L, good rear the deionized water of etching, ethanol, acetone carry out cleaning also drying;
2. the air in eliminating reaction chamber also passes into nitrogen, nickel foil after cleaning-drying is put into the reaction chamber being connected with nitrogen, and nickel foil is heated to 900 DEG C and is incubated, then ultraviolet source equipment is opened, make UV-irradiation on nickel foil surface, the wavelength of UV-light is 330nm, then passes into ethane 300sccm, the volume ratio of ethane and nitrogen is 3:1, keeps 120 minutes;
3. after having reacted, stop passing into ethane, stop nickel foil heating and close ultraviolet source equipment, stop after question response room is cooled to room temperature passing into nitrogen, nickel foil Surface Creation carbon nanometer wall, scrapes it from nickel foil surface, just obtains carbon nanometer wall powder;
4. the preparation of intercalation carbon nanometer wall: adopt stainless steel substrates as collector, put on collector by the above-mentioned carbon nanometer wall powder prepared, being pressed into specification is on a current collector 75*40*7mm
3the carbon nanometer wall flaps layer of (about 2g) as working electrode, using stereotype as to electrode, Hg/Hg
2sO
4as reference electrode, three electrodes, as electrolytic solution, are put into electrolyzer and are fully immersed in electrolytic solution, at 10mA/cm by the mixed solution of acetic acid and Nitromethane 99Min. 1: 1 mixing by volume
2current density, carry out reaction 6 hours under room temperature, then reacted electrolytic solution is filtered, the filter residue washed with de-ionized water obtained is placed in vacuum drying oven and can obtains pure, dry intercalation carbon nanometer wall after 12 hours in 80 DEG C of dryings;
5. getting intercalation carbon nanometer wall, is that 1g:40ml joins EtMeImN (CN) is housed by mass volume ratio
2in the container of ionic liquid, ultrasonication 4 minutes under power is 2W ultrasonic disintegrator, then filter for the first time, the filter residue NMP filtration washing obtained 3 times, be neutral by the cleaning such as ethanol, acetone, deionized water to the pH value of filtrate successively again, filter, the filter residue collected is dried to constant weight at vacuum drying oven at 100 DEG C and can obtains graphene nanobelt.
Embodiment 8
1. adopt iron foil as substrate, iron foil is put into the dilute hydrochloric acid solution etching 4 minutes that concentration is 1mol/L, good rear the deionized water of etching, ethanol, acetone carry out cleaning also drying;
2. the air in eliminating reaction chamber also passes into argon gas, iron foil after cleaning-drying is put into the reaction chamber being connected with argon gas, and iron foil is heated to 650 DEG C and is incubated, then ultraviolet source equipment is opened, make UV-irradiation on iron foil surface, the wavelength of UV-light is 220nm, then passes into acetylene 200sccm, the volume ratio of acetylene and argon gas is 2:1, keeps 180 minutes;
3. after having reacted, stop passing into acetylene, stop iron foil heating and close ultraviolet source equipment, stop after question response room is cooled to room temperature passing into argon gas, iron foil Surface Creation carbon nanometer wall, scrapes it from iron foil surface, just obtains carbon nanometer wall powder;
4. the preparation of intercalation carbon nanometer wall: adopt stainless steel substrates as collector, put on collector by the above-mentioned carbon nanometer wall powder prepared, being pressed into specification is on a current collector 75*40*7mm
3the carbon nanometer wall flaps layer of (about 2g) as working electrode, using stereotype as to electrode, Hg/Hg
2sO
4as reference electrode, formic acid and massfraction be 68% nitric acid by volume 4:1 mixing mixed solution as electrolytic solution, three electrodes are put into electrolyzer and are fully immersed in electrolytic solution, at 30mA/cm
2current density, carry out reaction 8 hours under room temperature, then reacted electrolytic solution is filtered, the filter residue washed with de-ionized water obtained is placed in vacuum drying oven and can obtains pure, dry intercalation carbon nanometer wall after 15 hours in 70 DEG C of dryings;
5. getting intercalation carbon nanometer wall, is that 1g:30ml joins and 1-Et-3 is housed, 5-Me by mass volume ratio
2imN (CF
3sO
2)
2in the container of ionic liquid, ultrasonication 15 minutes under power is 5W ultrasonic disintegrator, then filter for the first time, the filter residue DMF filtration washing obtained 6 times, be neutral by the cleaning such as ethanol, acetone, deionized water to the pH value of filtrate successively again, filter, the filter residue collected is dried to constant weight at vacuum drying oven at 80 DEG C and can obtains graphene nanobelt.
Embodiment 9
1. adopt cobalt paper tinsel as substrate, cobalt paper tinsel is put into the dilution heat of sulfuric acid etching 2 minutes that concentration is 0.3mol/L, good rear the deionized water of etching, ethanol, acetone carry out cleaning also drying;
2. the air in eliminating reaction chamber also passes into argon gas, cobalt paper tinsel after cleaning-drying is put into the reaction chamber being connected with helium, and cobalt paper tinsel is heated to 700 DEG C and is incubated, then ultraviolet source equipment is opened, make UV-irradiation on cobalt paper tinsel surface, the wavelength of UV-light is 250nm, then passes into propane 50sccm, the volume ratio of propane and helium is 5:1, keeps 240 minutes;
3. after having reacted, stop passing into propane, stop the heating of cobalt paper tinsel and close ultraviolet source equipment, stop after question response room is cooled to room temperature passing into helium, cobalt paper tinsel Surface Creation carbon nanometer wall, scrapes it from cobalt paper tinsel surface, just obtains carbon nanometer wall powder.
4. the preparation of intercalation carbon nanometer wall: adopt stainless steel substrates as collector, put on collector by the above-mentioned carbon nanometer wall powder prepared, being pressed into specification is on a current collector 75*40*7mm
3the carbon nanometer wall flaps layer of (about 2g) as working electrode, using stereotype as to electrode, Hg/Hg
2sO
4as reference electrode, propionic acid and massfraction be 68% nitric acid by volume 1:2 mixing mixed solution as electrolytic solution, three electrodes are put into electrolyzer and are fully immersed in electrolytic solution, at 5mA/cm
2current density, carry out reaction 15 hours under room temperature, then reacted electrolytic solution is filtered, the filter residue washed with de-ionized water obtained is placed in vacuum drying oven and can obtains pure, dry intercalation carbon nanometer wall after 20 hours in 80 DEG C of dryings;
5. getting intercalation carbon nanometer wall, is that 1g:100ml joins 1,3-Et is housed by mass volume ratio
2-4-MeImN (CF
3sO
2)
2in the container of ionic liquid, ultrasonication 5 minutes under power is 8W ultrasonic disintegrator, then filter for the first time, the filter residue NMP filtration washing obtained 3 times, be neutral by the cleaning such as ethanol, acetone, deionized water to the pH value of filtrate successively again, filter, the filter residue collected is dried to constant weight at vacuum drying oven at 90 DEG C and can obtains graphene nanobelt.
Embodiment 10
1. adopt nickel foil as substrate, nickel foil is put into the dilute nitric acid solution etching 5 minutes that concentration is 0.5mol/L, good rear the deionized water of etching, ethanol, acetone carry out cleaning also drying;
2. the air in eliminating reaction chamber also passes into nitrogen, nickel foil after cleaning-drying is put into the reaction chamber being connected with nitrogen, and nickel foil is heated to 800 DEG C and is incubated, then ultraviolet source equipment is opened, make UV-irradiation on nickel foil surface, the wavelength of UV-light is 360nm, then passes into ethanol 20sccm, the volume ratio of ethanol and nitrogen is 8:1, keeps 300 minutes;
3. after having reacted, stop passing into ethanol, stop nickel foil heating and close ultraviolet source equipment, stop after question response room is cooled to room temperature passing into nitrogen, nickel foil Surface Creation carbon nanometer wall, scrapes it from nickel foil surface, just obtains carbon nanometer wall powder;
4. the preparation of intercalation carbon nanometer wall: adopt stainless steel substrates as collector, put on collector by the above-mentioned carbon nanometer wall powder prepared, being pressed into specification is on a current collector 75*40*7mm
3the carbon nanometer wall flaps layer of (about 2g) as working electrode, using stereotype as to electrode, Hg/Hg
2sO
4as reference electrode, three electrodes, as electrolytic solution, are put into electrolyzer and are fully immersed in electrolytic solution, at 100mA/cm by acetic acid
2current density, carry out reaction 2 hours under room temperature, then reacted electrolytic solution is filtered, the filter residue washed with de-ionized water obtained is placed in vacuum drying oven and can obtains pure, dry intercalation carbon nanometer wall after 18 hours in 60 DEG C of dryings;
5. getting intercalation carbon nanometer wall, is that 1g:10ml joins 1,3-Et is housed by mass volume ratio
2-5-MeImN (CF
3sO
2)
2in the container of ionic liquid, ultrasonication 10 minutes under power is 10W ultrasonic disintegrator, then filter for the first time, the filter residue DMF filtration washing obtained 4 times, be neutral by the cleaning such as ethanol, acetone, deionized water to the pH value of filtrate successively again, filter, the filter residue collected is dried to constant weight at vacuum drying oven at 70 DEG C and can obtains graphene nanobelt.
Embodiment 11
1. adopt cobalt paper tinsel as substrate, cobalt paper tinsel is put into the dilute hydrochloric acid solution etching 1 minute that concentration is 0.05mol/L, good rear the deionized water of etching, ethanol, acetone carry out cleaning also drying;
2. the air in eliminating reaction chamber also passes into argon gas, cobalt paper tinsel after cleaning-drying is put into the reaction chamber being connected with argon gas, and cobalt paper tinsel is heated to 900 DEG C and is incubated, then ultraviolet source equipment is opened, make UV-irradiation on cobalt paper tinsel surface, the wavelength of UV-light is 300nm, then passes into methane 100sccm, the volume ratio of methane and argon gas is 10:1, keeps 30 minutes;
3. after having reacted, stop passing into methane, stop the heating of cobalt paper tinsel and close ultraviolet source equipment, stop after question response room is cooled to room temperature passing into argon gas, cobalt paper tinsel Surface Creation carbon nanometer wall, scrapes it from cobalt paper tinsel surface, just obtains carbon nanometer wall powder;
4. the preparation of intercalation carbon nanometer wall: adopt stainless steel substrates as collector, put on collector by the above-mentioned carbon nanometer wall powder prepared, being pressed into specification is on a current collector 75*40*7mm
3the carbon nanometer wall flaps layer of (about 2g) as working electrode, using stereotype as to electrode, Hg/Hg
2sO
4as reference electrode, three electrodes, as electrolytic solution, are put into electrolyzer and are fully immersed in electrolytic solution, at 50mA/cm by Nitromethane 99Min.
2current density, carry out reaction 1 hour under room temperature, then reacted electrolytic solution is filtered, the filter residue washed with de-ionized water obtained is placed in vacuum drying oven and can obtains pure, dry intercalation carbon nanometer wall after 20 hours in 80 DEG C of dryings;
5. getting intercalation carbon nanometer wall, is that 1g:50ml joins EtMeImBF is housed by mass volume ratio
4in the container of ionic liquid, ultrasonication 15 minutes under power is 8W ultrasonic disintegrator, then filter for the first time, the filter residue NMP filtration washing obtained 5 times, be neutral by the cleaning such as ethanol, acetone, deionized water to the pH value of filtrate successively again, filter, the filter residue collected is dried to constant weight at vacuum drying oven at 100 DEG C and can obtains graphene nanobelt.
The processing parameter of embodiment 1 ~ 11 is in table 1.
The processing parameter of table 1 embodiment 1 ~ 11
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:
Use dilute acid soln to etch metal substrate, described metal substrate is the one in iron foil, nickel foil and cobalt paper tinsel;
Under the atmosphere of anaerobic and shielding gas, described metal substrate is heated to 600 DEG C ~ 900 DEG C;
Under the irradiation of UV-light, pass into the one in methane, ethane, propane, acetylene and ethanol to described metal substrate surface, through photochemical catalysis chemical vapour deposition reaction 30 minutes ~ 300 minutes, at described metal substrate surface Formed nanometer wall;
After having reacted, under the atmosphere of described shielding gas, the metal substrate with carbon nanometer wall is cooled to room temperature, then described carbon nanometer wall is scraped from the surface of described metal substrate, obtain carbon nanometer wall powder;
Described carbon nanometer wall powder to be positioned on collector and to be pressed into carbon nanometer wall flaps layer and obtain working electrode;
Jointly will be soaked in electrolytic solution, at 5mA/cm electrode, reference electrode and described working electrode
2~ 100mA/cm
2current density, reaction after 1 hour ~ 20 hours under room temperature, carried out by reacted electrolytic solution filtering, wash filter residue and drying obtains intercalation carbon nanometer wall, described electrolytic solution is selected from least one in formic acid, acetic acid, propionic acid, nitric acid, Nitromethane 99Min.; And
Be that described intercalation carbon nanometer wall to be scattered in ionic liquid and to obtain dispersion liquid by 1g:10 ~ 100mL by mass volume ratio, described dispersion liquid is carried out under power 2kW ~ 10kW ultrasonic stripping to filter after 0.5 minute ~ 30 minutes, washing filter residue drying obtains graphene nanobelt.
2. the preparation method of graphene nanobelt according to claim 1, it is characterized in that, described use dilute acid soln is specially the step that metal substrate etches: described metal substrate is put into concentration be 0.01mol/L ~ 1mol/L dilute acid soln etching 0.5 minute ~ 10 minutes.
3. the preparation method of graphene nanobelt according to claim 2, it is characterized in that, described use dilute acid soln carries out etch step to metal substrate and is specially: described metal substrate is put into concentration be 0.1mol/L ~ 0.5mol/L dilute acid soln etching 1 minute ~ 3 minutes.
4. the preparation method of graphene nanobelt according to claim 1, is characterized in that, the wavelength of described UV-light is 200 ~ 400nm.
5. the preparation method of graphene nanobelt according to claim 1, is characterized in that, a kind of flow in described methane, ethane, propane, acetylene and ethanol is 10sccm ~ 1000sccm.
6. the preparation method of graphene nanobelt according to claim 1, is characterized in that, the volume ratio of a kind of and described shielding gas in described methane, ethane, propane, acetylene and ethanol is 2 ~ 10:1.
7. the preparation method of graphene nanobelt according to claim 1, it is characterized in that, described ionic liquid is selected from 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, one in 3-diethyl-5-Methylimidazole fluoroform sulfimide.
8. the preparation method of graphene nanobelt according to claim 1, it is characterized in that, the described washing filter residue also dry step obtaining graphene nanobelt is specially: by described filter residue 1-Methyl-2-Pyrrolidone or N, dinethylformamide washing 3 ~ 6 times, be neutral by the pH value that ethanol, acetone and deionized water are filtered to filtrate successively again, then at 60 DEG C ~ 100 DEG C, vacuum-drying obtains graphene nanobelt to constant weight.
9. the preparation method of graphene nanobelt according to claim 1, it is characterized in that, the described washing filter residue also dry step obtaining intercalation carbon nanometer wall is specially: with filter residue described in deionized water wash, and in 60 DEG C ~ 80 DEG C vacuum-dryings 12 hours ~ 24 hours.
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