CN102583340B - High-conductivity graphene material with low-temperature gas-phase reduction and preparation method thereof - Google Patents
High-conductivity graphene material with low-temperature gas-phase reduction and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method of high-conductivity graphene material with low-temperature gas-phase reduction. The preparation method comprises the following steps of: heating a low-temperature zone with graphene oxide and a high-temperature zone with a reducing agent to a certain temperature by utilizing multi-temperature zone heating equipment with the high-temperature zone and the low-temperature zone, and reducing out high-conductivity graphene. The preparation method provided by the utility model has the advantages that under the low-temperature condition, fast and high-efficiency reduction of the graphene oxide is realized, and low-temperature gas-phase reaction maintains the more complete structure of the graphene oxide, so that high-conductivity graphene powder or graphene paper and a high-transmittance and high-conductivity graphene film is prepared. The prepared graphene material has the advantages that the conductivity, the mechanical strength and the flexibility are good, and the bottleneck problem that the existing high-temperature heat treatment or low-temperature liquid-phase chemical reduction method damages the graphene structure can be effectively solved.
Description
Technical field
The present invention relates to the preparing technical field of grapheme material, be specifically related to high conductive graphene material of a kind of low-temperature gaseous phase reduction and preparation method thereof.
Background technology
Graphene is a kind of carbonaceous novel material by the tightly packed one-tenth bi-dimensional cellular of monolayer carbon atom shape crystalline network, is the elementary cell that makes up other dimension carbonaceous material (such as zero dimension soccerballene, one dimension carbon nanotube, three-dimensional graphite).Because its unique two-dirnentional structure and perfect crystalline structure, Graphene has contained abundant and novel physical phenomenon, for the research of quantum electrodynamics phenomenon provides desirable platform, has important theoretical investigation and is worth; Simultaneously, Graphene has the thickness of atom level, excellent electric property, outstanding chemical stability and thermodynamic stability, be expected to obtain widespread use in fields such as high-performance nanometer electronic device, sensor, nano composite material, battery and ultracapacitor, field emmision materials, become the focus of present condensed matter physics and materials science research.It is an important channel of present low cost, macroscopic preparation of graphene that graphene oxide is reduced.Graphene oxide is to contain the Graphene derivative that enriches oxygen-containing functional group, can peel off cheap graphite by chemical oxidation and get, and processes the Graphene that can be made into high conduction performance by reduction subsequently.Can obtain magnanimity Graphene and big area graphene film by reduction based on various powders and the thin-film material of graphene oxide, the magnanimity that promotes Graphene is used be had great importance.Yet present key is how to remove the graphene oxide surface oxygen functional group by reduction, improves its electroconductibility.The method of reducing of the graphene oxide of report mainly contains two classes at present: high-temperature heat treatment and low temperature liquid phase chemical reduction.These methods need to be introduced various chemical substances, ionogen, toxic gas or heat usually.High-temperature heat treatment is carried out in the inertia more than 1000 ℃ or reducing atmosphere usually, and the reduction cost is higher, easily causes the decay of device performance.Cryochemistry reduction can be carried out being lower than under 100 ℃ the condition, is a kind of low-cost method of reducing; But the reduction effect of the best hydrazine class reductive agent (hydrazine, dimethylhydrazine etc.) of effect and metal hydride class reductive agent (sodium borohydride, lithium aluminium hydride etc.) is still undesirable in the chemical reduction method of having reported, and not only cost is high for hydrazine class reductive agent, or highly toxic substance.Up-to-date report (patent publication No.: CN102275902A) proposed to utilize the halogenide such as hydroiodic acid HI, Hydrogen bromide by the method for liquid-phase reduction graphene oxide.Although the method has realized graphene oxide reduction at a lower temperature,, its used reductive agent is stable and resistance of oxidation is poor, strong toxicity, reducing process complicated operation, harsh to the environmental requirement of operation.
Therefore, efficient in the urgent need to developing, low-cost, free of contamination low-temperature reduction method.
Summary of the invention
The problems referred to above in the face of the prior art existence, the inventor recognizes under cold condition, utilize nontoxic gaseous reducing agent solid-state or commonly used, effectively capture oxygen-containing functional group in the graphene oxide by gas-phase reaction, can realize quick, the efficient reduction under the lesser temps, prepare the Graphene of electroconductibility, light transmission excellence, the problems such as environmental pollution, the cost that solution pyroprocessing or low temperature liquid phase chemical reduction technology easily cause is high, destruction graphene-structured.
At this, the invention provides a kind of high conductive graphene material preparation method of low-temperature gaseous phase reduction, described preparation method's utilization has many warm areas heating installation of high-temperature zone and cold zone, be heated to certain temperature by the cold zone that will have graphene oxide and the high-temperature zone with reductive agent, restore high conductive graphene.
The present invention does not relate to the chemical reagent such as any strong acid, highly basic in the whole technological process of redox graphene, and Graphene sample end temperature of reaction is very low, effectively keeps the complete structure of Graphene.Solved the bottleneck problem that existing high-temperature heat treatment or cryochemistry method of reducing destroy the grapheme material structure.
Preferably, described cold zone is heated to 50-500 ℃, described high-temperature zone is heated to 400-1200 ℃.More preferably described cold zone is heated to 80-300 ℃, described high-temperature zone is heated to 600-1000 ℃.
Among the present invention, preferably can before described heating, extract first base vacuum to 0.5Pa-10Pa, and sealing.
Preferably, can also after described heating, make insulation 30-600min, be cooled to again afterwards room temperature.
Heating installation of the present invention for example can use process furnace.
Described reductive agent can be the metal simple-substance that comprises basic metal, alkaline-earth metal, rare earth metal, transition metal-type, non-metal simple-substance, and hydride, or contain the compound of low valence metal ion, also can be the compound that contains low valency element.
Described alkali-metal metal simple-substance can be K, Na, Li, and the metal simple-substance of alkaline-earth metal can be Mg, Ca, Sr, Ba, and the metal simple-substance of transition metal can be Sc, Ti, V, Cr, Fe, Co, Ni, Zn, Y, Zr, Nb, Ta, Mo, W, A.
Described non-metal simple-substance can be H
2, B, C, Si.
Described hydride represents with M/H, and wherein M is basic metal, alkaline-earth metal or rare earth, and H is hydrogen atom.
The described compound that contains low valence metal ion can be FeCl
2, SnCl
2Deng or its combination.
The compound that contains low valency element can be H
2S, NaxS, HI, NH
3, CO, SO
2, Na
2SO
3Or its several combinations.
In addition, desirable above one or more are used as the reductive agent among the preparation method of the present invention simultaneously.
Among the present invention, described graphene oxide is powder, " Buckie paper " or film.
The preparation technology of described graphene oxide powder can comprise: flake graphite and strong oxidizer reacted in the concentrated acid environment and makes the operation A of graphene oxide, and the process B that the graphene oxide that operation A obtains is obtained the graphene oxide powder after lyophilize.
The preparation technology of described " Buckie paper " can comprise: flake graphite and strong oxidizer are reacted in the concentrated acid environment and make the operation A of graphene oxide, and after being mixed with the water-sol with the described graphene oxide that operation A obtains, vacuum filtration obtains the operation C of " Buckie paper ".The thickness of described " the Buckie paper " made by this technique is 0.5-20 μ m, and density is 1.4-2.5g/cm
3
Described thin film technology technique can comprise: flake graphite and strong oxidizer are reacted in the concentrated acid environment and make the operation A of graphene oxide, and after the graphene oxide that operation A obtains was mixed with the water-sol, the method that lifts by dipping was made the step D of film.The described film thickness of making by this technique is 2-100nm.
In the technique of above-mentioned preparation graphene oxide powder, " Buckie paper " or film, described operation A preferably can may further comprise the steps: make the reaction of flake graphite, SODIUMNITRATE and the vitriol oil and potassium permanganate in 35 ± 5 ℃ water-bath, form mixture; Make system temperature be raised to 90 ± 5 ℃ of insulation certain hours, add afterwards the entry dilution; With the excessive potassium permanganate of reductive agent reduction, obtain solution; After obtaining filter cake from described solution, described filter cake is dispersed in the deionized water again, removes the graphite and the foreign ion that do not react completely, obtain the operation of graphene oxide.
The present invention also provides a kind of high conductive graphene material that is made by preparation method of the present invention: graphene powder, Graphene paper or graphene film.Described graphene powder square resistance behind compressing tablet of making by preparation method of the present invention is 0.5-20 Ω sq
-1Described Graphene paper square resistance is 0.5-100 Ω sq
-1The transmittance of described graphene film is 60%-96%, and square resistance is 30-1000 Ω sq
-1And prepared Graphene paper and membrane structure are fine and close, and the bonding force between the graphene sheet layer is strong, and electroconductibility, mechanical strength and snappiness are good.
High conductive graphene material provided by the invention can be applicable to the fields such as photovoltaic, plane demonstration, semiconductor electronic and energy storage device.
High conductive graphene material preparation method of the present invention, under cold condition, utilize metal or non-metal simple-substance, compound or gas, effectively capture oxygen-containing functional group in the graphene oxide by gas-phase reaction, realize quick under lower temperature, the efficient reduction of graphene oxide, the low-temperature gaseous phase reaction has kept the more complete structure of graphene oxide, thereby prepares the graphene film that the high Graphene powder that conducts electricity or Graphene paper and high printing opacity, height conduct electricity.Grapheme material electroconductibility, mechanical strength and the snappiness of the present invention's preparation are good, can effectively solve the bottleneck problem that existing high-temperature heat treatment or low temperature liquid phase chemical reduction method destroy graphene-structured.
Description of drawings
Fig. 1 illustrates according to the graphene oxide paper of the embodiment of the invention 1 and 2 respectively at the X-ray diffractograms of 100 ℃ and the 200 ℃ Graphenes before and after the reduction in 3 hours of Al powder;
Fig. 2 illustrates according to the graphene oxide paper of the embodiment of the invention 1 and 2 respectively at the Raman spectrograms of 100 ℃ and the 200 ℃ Graphenes before and after the reduction in 3 hours of Al powder;
Fig. 3 illustrates photoelectron spectrum (XPS) spectrum according to the graphene oxide paper of the embodiment of the invention 1 and 2;
Fig. 4 illustrates according to the graphene oxide paper of the embodiment of the invention 1 and composes at the photoelectron spectrum (XPS) of 100 ℃ of Graphenes after the reduction in 3 hours of Al powder;
Fig. 5 illustrates according to the graphene oxide paper of the embodiment of the invention 2 and composes at the photoelectron spectrum (XPS) of 200 ℃ of Graphenes after the reduction in 3 hours of Al powder.
Embodiment
Below, with reference to accompanying drawing, and further specify with the following embodiments the present invention.Should be understood that the drawings and the specific embodiments or embodiment only are exemplary, but not be used for restriction the present invention.The test method of unreceipted actual conditions in the following example, usually according to normal condition, or the condition of advising according to manufacturer.Except as otherwise noted, all per-cent and umber are by weight.
The high conductive graphene material preparation method of low-temperature gaseous phase reduction of the present invention specifically comprises: adopt the furnace apparatus of many warm areas, the feed oxygen functionalized graphene is placed low-temperature end, the solid phase reduction agent is placed temperature end or passes into the vapour phase reduction agent from temperature end; Utilize mechanical pump to extract base vacuum to a certain degree, for example to 0.5Pa-10Pa, stop to vacuumize sealing; Begin process furnace two ends to many warm areas again and be heated to respectively temperature requiredly, for example cold zone is heated to 50-500 ℃, the high-temperature zone is heated to 400-1200 ℃, and stopped heating behind the insulation certain hour naturally cools to room temperature, obtains high conductive graphene material.The reaction soaking time can be 30-600min.
The present invention does not relate to the chemical reagent such as any strong acid, highly basic in the whole technological process of redox graphene, and Graphene sample end temperature of reaction is very low, effectively keeps the complete structure of Graphene.The Graphene paper of preparation and membrane structure are fine and close after the reduction, and the bonding force between the graphene sheet layer is strong, and electroconductibility, mechanical strength and snappiness are good, have solved the bottleneck problem that existing high-temperature heat treatment or cryochemistry method of reducing destroy the grapheme material structure.
Reductive agent of the present invention can comprise following one or more:
Metal simple-substance: basic metal (such as K, Na, Li), alkaline-earth metal (such as Mg, Ca, Sr, Ba), rare earth metal, transition metal (such as Sc, Ti, V, Cr, Fe, Co, Ni, Zn, Y, Zr, Nb, Ta, Mo, W, Al) etc. or its combination;
Non-metal simple-substance: H
2, B, C, Si etc. or its combination;
Hydride: represent with M/H, wherein M is basic metal, alkaline-earth metal or rare earth, and H is hydrogen atom;
The compound that contains low valence metal ion: FeCl
2, SnCl
2Deng or its combination;
The compound that contains low valency element: H
2S, Na
2S, HI, NH
3, CO, SO
2, Na
2SO
3Deng or its combination.
Among the present invention, being used for reduction can be as powder, " Buckie paper " or film take the graphene oxide for preparing high conductive graphene, its preparation technology can may further comprise the steps, and should understand in the following steps certain also can omit or use other alternative steps that can reach with texts, and each feature in each step neither be necessary or replaceable regularly and not, here just example ground explanation:
(1) preparation of graphene oxide: flake graphite, SODIUMNITRATE and an amount of vitriol oil of getting mass ratio and being 1: 1 stirs certain hour in ice bath after, slowly add the KMnO of 6 times of quality
4, after the mixing, system transferred in 35 ± 5 ℃ the water-bath, stirred 4-8 hour, form the mixture of the mud sample of black;
Under agitation condition, in mixture, add a small amount of deionized water, system temperature is raised to 90 ± 5 ℃, adds the water dilution of 10 times of amounts behind the 30min again, adds an amount of H
2O
2(30%) the excessive KMnO of reduction
4, the system color is glassy yellow by brown stain;
With solution filter obtained above, and with a large amount of water washings, the filter cake that obtains is dispersed in the deionized water again, ultra-sonic dispersion 10-30min.With the centrifugal under the low speed 5-10min of whizzer elder generation, to remove the graphite that does not react completely, under high speed, remove afterwards the foreign ion in the graphene oxide, obtain graphene oxide;
(2) preparation of graphene oxide powder: with the graphene oxide of (1) gained, after lyophilize, namely get the graphene oxide powder;
(3) preparation of " Buckie paper " (graphene oxide paper): with the graphene oxide of (1) gained, behind ultra-sonic dispersion, be mixed with the water-sol of graphene oxide, on millipore filtration, vacuum filtration namely gets graphene oxide paper, control the thickness of graphene oxide paper by the volume of regulating the water-sol, thickness range is 0.5-20 μ m; Control the density of graphene oxide paper by regulating the suction filtration time, density range is 1.4-2.5g/cm
3
(4) preparation of graphene oxide transparent film: the transparent film for preparing graphene oxide with crystal pulling method, concrete steps are: the graphene oxide configuration concentration with (1) gained is the graphene oxide water-sol of 0.2-1.5g/L, put into sheet glass or quartz plate, behind the dipping 5-10min, with the vertical pulling film forming of the speed of 2-20mm/min, film thickness is regulated by lifting number of times, pull rate and graphene oxide concentration, and thickness range is adjustable continuously at 2-100nm.
Preparation method of the present invention not only can realize a large amount of efficient reduction to graphene oxide powder, Graphene " Buckie paper ", and is very suitable for graphene oxide film is carried out direct-reduction.Be 0.5-20 Ω sq by reducing rear gained graphene powder square resistance behind compressing tablet
-1Graphene " Buckie paper " electroconductibility is very good, and square resistance is 0.5-100 Ω sq
-1, the minimum 0.5 Ω sq that reaches
-1The transmittance of graphene film is adjustable between 60%-96%, and square resistance is 30-1000 Ω sq
- 1, surface resistivity is less than 1000 ohm.These excellent performances are that Graphene is laid a good foundation in the widespread use in the fields such as high-performance nanometer electronic device, sensor, nano composite material, battery and ultracapacitor, field emmision material.
The below further illustrates the high conductive graphene material preparation method of low-temperature gaseous phase reduction of the present invention.
Embodiment 1
Sample to be restored is the graphene oxide paper through vacuum filtration, and thickness is 5 microns, and density is 1.8g/cm
3, diameter is 10cm.Also original reagent is high-purity Al powder; Feed oxygen functionalized graphene paper is placed the low-temperature end of the process furnace of many warm areas, high-purity Al powder places temperature end, and the temperature of temperature end is 700 ℃, and the temperature of low-temperature end is 100 ℃.Utilize mechanical pump to extract base vacuum to the 1Pa, stop to vacuumize sealing.Begin again process furnace two ends to many warm areas be heated to respectively temperature required, insulation reduction 3 hours, stopped heating, natural stove is cold.
The pattern of Graphene and structural characterization
Characterize the structure of Graphene with Raman spectrum (Renishaw invia Raman Microscope, excitation wavelength is 514.5nm).By X-ray powder diffraction instrument (XRD) analysed film phase.Each element relative content ratio and chemical combination attitude thereof with x-ray photoelectron spectroscopy (XPS) analytic sample surface.Instrument is the PHI 5000C ESCA System of U.S. PHI company; The employing condition is the magnesium target, high pressure 14.0kV, and power 250W, vacuum is better than 1 * 10
-8Holder.The RBD147 data collecting card of employing U.S. RBD company and AugerScan3.21 software is the full scan spectrum (lead to and can be 93.9eV) of the 0-1200eV of collected specimens respectively, then gather the narrow scan spectrum (lead to and to be 23.5eV) of each element related track, and adopt AugerScan3.21 software to carry out data analysis.Carrying out combination can proofread and correct take C1s=284.6eV as benchmark.The film that the present invention is obtained is with the transmitance of ultraviolet-visible-near infrared spectrometer testing film.The film that the present invention is obtained carries out conductivity evaluation (comprising square resistance, specific conductivity, carrier concentration, carrier mobility etc.) with the vanderburg four probe method.
Fig. 1 shows the X-ray diffractogram of the Graphene after the reduction in 3 hours of Al powder.As can be seen from FIG., original graphene oxide is main along the growth of (002) high preferred orientation, and the sample after reduction then shows stronger Graphene (001) characteristic peak.Fig. 2 is the Raman spectrogram of the Graphene after reduction.As shown in the figure, compare with graphene oxide, the obvious step-down of halfwidth at the sample characteristic peak after reduction proves that further the crystallization of Graphene improves.Fig. 3 and Fig. 4 show respectively original graphene oxide paper and the photoelectron xps energy spectrum of sample after reduction.Test result shows, and the carbon on GO Graphene surface and oxygen element atomic ratio before the reduction (carbon Sauerstoffatom ratio: C/O) lower, only be 2.14.C/O is increased to 10.8 after reduction.Electric performance test is the result show: be low to moderate under 100 ℃ the reduction temperature, the square resistance of sample is down to 12 Ω sq
-1This shows, prepare Graphene under 100 ℃ the low reduction temperature and have good crystallinity and electric property being low to moderate.
Embodiment 2
Sample to be restored is the graphene oxide paper through vacuum filtration, and thickness range is 5 microns, and density range is 1.8g/cm
3, diameter is 10cm.Also original reagent is high-purity Al powder; Feed oxygen functionalized graphene paper is placed the low-temperature end of the process furnace of many warm areas, high-purity Al powder places temperature end, and the temperature of temperature end is 700 ℃, and the temperature of low-temperature end is 200 ℃.Utilize mechanical pump to extract base vacuum to the 1Pa, stop to vacuumize sealing.Begin again process furnace two ends to many warm areas be heated to respectively temperature required, insulation reduction 3 hours, stopped heating, natural stove is cold.
X-ray diffractogram and the Raman spectrogram of the Graphene after reduction still are shown in Fig. 1 and Fig. 2.As shown in the figure, compare with embodiment 1, the obvious step-down of halfwidth at the sample characteristic peak after 200 ℃ of reduction, peak height grow prove that the crystallization of Graphene improves.Fig. 5 is the photoelectron xps energy spectrum of the rear sample of reduction.Test result shows, sample surfaces C/O is increased to 11.99 after 200 ℃ of reduction.The electric performance test result shows that the square resistance of sample is down to 6 Ω sq
-1This shows, compare with embodiment 1, under 200 ℃ low reduction temperature, prepare Graphene and have better crystallinity and electric property.
Embodiment 3
Sample to be restored is the graphene oxide paper through vacuum filtration, and thickness is 10 microns, and density range is 2.5g/cm
3, diameter is 30cm.Also original reagent is high-purity N a
2The S powder; Feed oxygen functionalized graphene paper is placed the low-temperature end of the process furnace of many warm areas, high-purity N a
2The S powder places temperature end, and the temperature of temperature end is 400 ℃, and the temperature of low-temperature end is 150 ℃.Utilize mechanical pump to extract base vacuum to the 0.5Pa, stop to vacuumize sealing.Begin again process furnace two ends to many warm areas be heated to respectively temperature required, insulation reduction 30 minutes, stopped heating, natural stove is cold.Graphene paper after reduction still keeps compact and complete structure, the well-crystallized, and square resistance is 92 Ω sq
-1
Embodiment 4
Sample to be restored is that thickness is 10nm with the graphene oxide transparent film of crystal pulling method preparation, and substrate is common soda-lime glass, is of a size of 2.5 * 7.5cm
2Also original reagent is high-purity Mg powder; The graphene oxide transparent film is placed the low-temperature end of the process furnace of many warm areas, high-purity Mg powder places temperature end, and the temperature of temperature end is 800 ℃, and the temperature of low-temperature end is 100 ℃.Utilize mechanical pump to extract base vacuum to the 3Pa, stop to vacuumize sealing.Begin again process furnace two ends to many warm areas be heated to respectively temperature required, insulation reduction 5 hours, stopped heating, natural stove is cold.Graphene well-crystallized after reduction demonstrates good light transmission at visible and near-infrared band, and transmittance corresponding to 550nm place reaches 94.3%, and square resistance is 307 Ω sq
- 1
Embodiment 5
Sample to be restored is that thickness is 20nm with the graphene oxide transparent film of crystal pulling method preparation, and substrate is common soda-lime glass, is of a size of 2.5 * 7.5cm
2Also original reagent is high-purity FeCl
2With SnCl
2Mixed powder; The graphene oxide transparent film is placed the low-temperature end of the process furnace of many warm areas, high-purity FeCl
2With SnCl
2Powder mix places temperature end, and the temperature of temperature end is 1000 ℃, and the temperature of low-temperature end is 50 ℃.Utilize mechanical pump to extract base vacuum to the 10Pa, stop to vacuumize sealing.Begin again process furnace two ends to many warm areas be heated to respectively temperature required, insulation reduction 3 hours, stopped heating, natural stove is cold.Graphene well-crystallized after reduction demonstrates good light transmission at visible and near-infrared band, and transmittance corresponding to 550nm place reaches 87.6%, and square resistance is 152 Ω sq
-1
Embodiment 6
Sample to be restored is that thickness is 100nm with the graphene oxide transparent film of crystal pulling method preparation, and substrate is common soda-lime glass, is of a size of 2.5 * 7.5cm
2Also original reagent is high-purity Co powder and Ta powder; The graphene oxide transparent film is placed the low-temperature end of the process furnace of many warm areas, high-purity Co powder and Ta powder place temperature end, and the temperature of temperature end is 1100 ℃, and the temperature of low-temperature end is 500 ℃.Utilize mechanical pump to extract base vacuum to the 1Pa, stop to vacuumize sealing.Begin again process furnace two ends to many warm areas be heated to respectively temperature required, insulation reduction 5 hours, stopped heating, natural stove is cold.Graphene well-crystallized after reduction demonstrates good light transmission at visible and near-infrared band, and transmittance corresponding to 550nm place reaches 84.3%, and square resistance is 702 Ω sq
-1
Embodiment 7
Sample to be restored is through cryodesiccated graphene oxide powder, and going back original reagent is B powder and CO gas; Feed oxygen fossil ink powder is placed the low-temperature end of the process furnace of many warm areas, high-purity B powder places temperature end, and the temperature of temperature end is 500 ℃, and the temperature of low-temperature end is 200 ℃.Utilize mechanical pump to extract base vacuum to the 1Pa, stop to vacuumize.Begin to pass into CO gas from temperature end, begin simultaneously process furnace two ends to many warm areas be heated to respectively temperature required, insulation reduction 6 hours, stopped heating, natural stove is chilled to room temperature, stops passing into CO gas again.Graphene powder well-crystallized after reduction, (thickness is 5 microns) square resistance is 3 Ω sq behind the compressing tablet
-1
Embodiment 8
Sample to be restored is the graphene oxide paper through vacuum filtration, and thickness is 0.5 micron, and density is 1.4g/cm
3, diameter is 2.5cm.Also original reagent is C powder and H
2Gas; Feed oxygen functionalized graphene paper is placed the low-temperature end of the process furnace of many warm areas, high-purity C powder places temperature end, and the temperature of temperature end is 900 ℃, and the temperature of low-temperature end is 100 ℃.Utilize mechanical pump to extract base vacuum to the 1Pa, stop to vacuumize.Begin to pass into H from temperature end
2Gas, begin simultaneously process furnace two ends to many warm areas be heated to respectively temperature required, insulation reductase 12 hour, stopped heating, natural stove is chilled to room temperature, stops passing into H again
2Gas.Graphene paper after reduction still keeps compact and complete structure, the well-crystallized, and square resistance is 56 Ω sq
-1
Embodiment 9
Sample to be restored is that thickness is 80nm with the graphene oxide transparent film of crystal pulling method preparation, and substrate is quartzy, is of a size of 5 * 10cm
2Also original reagent is high-purity Sc, Ti and Ni powder; Feed oxygen functionalized graphene paper is placed the low-temperature end of the process furnace of many warm areas, high-purity Sc, Ti and Ni powder place temperature end, and the temperature of temperature end is 600 ℃, and the temperature of low-temperature end is 80 ℃.Utilize mechanical pump to extract base vacuum to the 1Pa, stop to vacuumize sealing.Begin again process furnace two ends to many warm areas be heated to respectively temperature required, insulation reduction 1 hour, stopped heating, natural stove is cold.Graphene film crystallization after reduction is better, all demonstrates certain light transmission at visible and near-infrared band, and transmittance corresponding to 550nm place reaches 63.5%, and square resistance is 921 Ω sq
-1
Embodiment 10
Sample to be restored is that thickness is 5nm with the graphene oxide transparent film of crystal pulling method preparation, and substrate is quartzy, is of a size of 2.5 * 7.5cm
2Also original reagent is Si powder and H
2S gas; Feed oxygen functionalized graphene paper is placed the low-temperature end of the process furnace of many warm areas, the high-purity Si powder places temperature end, and the temperature of temperature end is 800 ℃, and the temperature of low-temperature end is 100 ℃.Utilize mechanical pump to extract base vacuum to the 1Pa, stop to vacuumize.Begin to pass into H from temperature end
2S gas, begin simultaneously process furnace two ends to many warm areas be heated to respectively temperature required, insulation reduction 3 hours, stopped heating, natural stove is chilled to room temperature, stops passing into H again
2S gas.Graphene film well-crystallized after reduction demonstrates good light transmission at visible and near-infrared band, and transmittance corresponding to 550nm place reaches 95.6%, and square resistance is 512 Ω sq
-1
Embodiment 11
Sample to be restored is the graphene oxide paper through vacuum filtration, and thickness is 20 microns, and density is 2.5g/cm
3, diameter is 5.1cm.Also original reagent is high-purity Fe powder and Ca powder; Feed oxygen functionalized graphene paper is placed the low-temperature end of the process furnace of many warm areas, high-purity Fe powder and Ca powder place temperature end, and the temperature of temperature end is 1200 ℃, and the temperature of low-temperature end is 200 ℃.Utilize mechanical pump to extract base vacuum to the 1Pa, stop to vacuumize sealing.Begin again process furnace two ends to many warm areas be heated to respectively temperature required, insulation reduction 5 hours, stopped heating, natural stove is cold.Graphene paper after reduction still keeps compact and complete structure, the well-crystallized, and square resistance is 0.5 Ω sq
-1
Industrial applicability: it is low that high conductive graphene material of the present invention and preparation method thereof has a preparation cost, the good advantage of grapheme material electroconductibility, light transmission, mechanical strength and snappiness of making can be in field widespread uses such as high-performance nanometer electronic device, sensor, nano composite material, battery and ultracapacitor, field emmision materials.
Claims (20)
1. the high conductive graphene material preparation method of low-temperature gaseous phase reduction, it is characterized in that, described preparation method's utilization has many warm areas heating installation of high-temperature zone and cold zone, be heated to certain temperature by the cold zone that will have graphene oxide and the high-temperature zone with reductive agent, restore high conductive graphene;
Wherein described cold zone is heated to 50-500 ℃, described high-temperature zone is heated to 400-1200 ℃, and before described heating, extract first base vacuum to 0.5Pa-10Pa, and sealing.
2. preparation method according to claim 1 is characterized in that, is incubated 30-600min after described heating, is cooled to afterwards room temperature.
3. preparation method according to claim 1 and 2, it is characterized in that, described reductive agent is for comprising basic metal, alkaline-earth metal, rare earth metal, Sc, Ti, V, Cr, Fe, Co, Ni, Zn, Y, Zr, Nb, Ta, Mo, W, non-metal simple-substance, hydride, and among the Al one or more.
4. preparation method according to claim 3 is characterized in that,
Described alkali-metal metal simple-substance is K, Na, Li, and the metal simple-substance of alkaline-earth metal is Mg, Ca, Sr, Ba;
Described non-metal simple-substance is: H
2, B, C, Si or its several combinations;
Described hydride is: represent with M/H, wherein M is basic metal, alkaline-earth metal or rare earth, and H is hydrogen atom.
5. preparation method according to claim 1 and 2 is characterized in that, described reductive agent is the compound that contains low valence metal ion.
6. preparation method according to claim 5 is characterized in that, the described compound that contains low valence metal ion is FeCl
2, SnCl
2Or its combination.
7. preparation method according to claim 1 and 2 is characterized in that, described reductive agent is the compound that contains low valency element.
8. preparation method according to claim 7 is characterized in that, the described compound that contains low valency element is H
2S, Na
2S, HI, NH
3, CO, SO
2, Na
2SO
3Or its several combination.
9. preparation method according to claim 1 and 2 is characterized in that, described graphene oxide is powder, " Buckie paper " or film.
10. preparation method according to claim 9, it is characterized in that, the preparation technology of the powder of described graphene oxide comprises: flake graphite and strong oxidizer reacted in the concentrated acid environment and makes the operation A of graphene oxide, and the process B that the graphene oxide that operation A obtains is obtained the graphene oxide powder after lyophilize.
11. preparation method according to claim 9, it is characterized in that, the preparation technology of described " Buckie paper " comprising: flake graphite and strong oxidizer are reacted in the concentrated acid environment and make the operation A of graphene oxide, and after being mixed with the water-sol with the described graphene oxide that operation A obtains, vacuum filtration obtains the operation C of " Buckie paper ".
12. preparation method according to claim 11 is characterized in that, the thickness of described " Buckie paper " is 0.5-20 μ m, and density is 1.4-2.5g/cm
3
13. preparation method according to claim 9, it is characterized in that, described thin film technology technique comprises: flake graphite and strong oxidizer are reacted in the concentrated acid environment and make the operation A of graphene oxide, and after the graphene oxide that operation A obtains was mixed with the water-sol, the method that lifts by dipping was made the step D of film.
14. preparation method according to claim 13 is characterized in that, described film thickness is 2-100nm.
15. arbitrary described preparation method in 14 is characterized in that according to claim 10, described operation A comprises: make the reaction of flake graphite, SODIUMNITRATE and the vitriol oil and potassium permanganate in 35 ± 5 ℃ water-bath, form mixture; Make system temperature be raised to 90 ± 5 ℃ of insulation certain hours, add afterwards the entry dilution; With the excessive potassium permanganate of reductive agent reduction, obtain solution; After obtaining filter cake from described solution, described filter cake is dispersed in the deionized water again, removes the graphite and the foreign ion that do not react completely, obtain the operation of graphene oxide.
16. a high conductive graphene material for preparing to 15 described methods according to claim 1, described grapheme material is graphene powder, Graphene paper or graphene film.
17. high conductive graphene material according to claim 16 is characterized in that, described graphene powder square resistance behind compressing tablet is 0.5-20 Ω sq
-1
18. high conductive graphene material according to claim 16 is characterized in that, described Graphene paper square resistance is 0.5-100 Ω sq
-1
19. high conductive graphene material according to claim 16 is characterized in that the transmittance of described graphene film is 60%-96%, square resistance is 30-1000 Ω sq
-1
20. according to claim 16-19 each described high conductive graphene material application in photovoltaic, plane demonstration, semiconductor electronic and energy storage device.
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| CN103779571A (en) * | 2012-10-25 | 2014-05-07 | 海洋王照明科技股份有限公司 | Boron-doped graphene thin film, and preparation method and application thereof |
| CN103833027A (en) * | 2012-11-27 | 2014-06-04 | 海洋王照明科技股份有限公司 | Preparation method of graphene paper |
| CN103011147B (en) * | 2012-12-27 | 2014-10-15 | 中南大学 | Method for preparing graphene through thermal reduction |
| CN103145124B (en) * | 2013-03-27 | 2015-01-14 | 北京大学 | High-performance graphene paper and preparation method thereof |
| CN105764849B (en) * | 2013-10-31 | 2018-10-02 | 华东理工大学 | It is used to prepare the method and system of graphene |
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| CN105366663A (en) * | 2014-08-27 | 2016-03-02 | 中国石油化工股份有限公司 | Method for doping synthesized sulfur with graphene |
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| US10784516B2 (en) | 2015-06-25 | 2020-09-22 | Semiconductor Energy Laboratory Co., Ltd. | Conductor, power storage device, electronic device, and method for forming conductor |
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