CN102583340A - 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 vapour 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 blacking (like zero dimension soccerballene, one dimension carbon nanotube, three-dimensional graphite).Because its unique two-dirnentional structure has contained abundant and novel physical phenomenon with perfect crystalline structure, Graphene,, have important theoretical research and be worth for the quantum electrodynamics phenomenon Study provides ideal platform; Simultaneously; Graphene has the thickness of atom level, excellent electric property, outstanding chemicalstability and thermodynamic stability; Be expected to obtain widespread use, become the focus of present Condensed Matter Physics and Materials science research in fields such as high-performance nanometer electronic device, transmitter, nano composite material, battery and ultracapacitor, field emmision materials.With the graphene oxide reduction is the important channel that present low cost, magnanimity prepare Graphene.Graphene oxide is to contain the Graphene verivate that enriches oxygen-containing functional group, can peel off cheap graphite through chemical oxidation and get, and handles the Graphene that can be made into high conduction performance through reduction subsequently.Can obtain magnanimity Graphene and big area graphene film through reduction based on various powders and the thin-film material of graphene oxide, the magnanimity application of promotion Graphene is had great importance.Yet present key is how to remove the graphene oxide surface oxygen functional group through reduction, improves its electroconductibility.The method of reducing of the graphene oxide of report mainly contains two types at present: high-temperature heat treatment and low temperature liquid phase chemical reduction.These methods need be introduced various chemical substances, ionogen, toxic gas or heat usually.High-temperature heat treatment is carried out in inertia more than 1000 ℃ or reducing atmosphere usually, and the reduction cost is higher, is prone to cause 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 best hydrazine class reductive agent (hydrazine, dimethylhydrazine etc.) of effect and metal hydride class reductive agent (Peng Qinghuana, lithium aluminium hydride etc.) is still undesirable in the chemical reduction method of having reported, and hydrazine class reductive agent not only cost is high, or highly toxic substance.Up-to-date report (patent publication No.: CN102275902A) proposed to utilize the method for halogenide such as hydroiodic acid HI, Hydrogen bromide through the liquid-phase reduction graphene oxide.Though this 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, press for efficient, low-cost, the free of contamination low-temperature reduction method developed.
Summary of the invention
The problems referred to above in the face of the prior art existence; The inventor recognizes under coldcondition; Utilize nontoxic gaseous reducing agent solid-state or commonly used, capture the oxygen-containing functional group in the graphene oxide effectively, can realize quick, the efficient reduction under the lesser temps through gas-phase reaction; Prepare the Graphene of electroconductibility, light transmission excellence, problems such as the environmental pollution that solution pyroprocessing or low temperature liquid phase chemical reduction technology are prone to cause, cost height, destruction graphene-structured.
At this; The present invention provides a kind of high conductive graphene preparation methods of low temperature vapour phase reduction; Said preparing method's utilization has many warm areas heating installation of high-temperature zone and cold zone; Be heated to certain temperature through cold zone that will have graphene oxide and high-temperature zone, restore high conductive graphene with reductive agent.
The present invention does not relate to 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, keeps the complete structure of Graphene effectively.Solved the bottleneck problem that existing high-temperature heat treatment or cryochemistry method of reducing destroy the grapheme material structure.
Preferably, said cold zone is heated to 50-500 ℃, said high-temperature zone is heated to 400-1200 ℃.More preferably said cold zone is heated to 80-300 ℃, said high-temperature zone is heated to 600-1000 ℃.
Among the present invention, preferably can before said heating, extract base vacuum earlier to 0.5Pa-10Pa, and sealing.
Preferably, can also after said heating, make insulation 30-600min, be cooled to room temperature afterwards again.
Heating installation of the present invention for example can use process furnace.
Said reductive agent can be the metal simple-substance that comprises basic metal, earth alkali metal, rare earth metal, transition metal-type, non-metal simple-substance, and hydrogenate, or contain the compound of low valence metal ion, also can be the compound that contains low valency element.
Said alkali-metal metal simple-substance can be K, Na, Li, and the metal simple-substance of earth alkali 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.
Said non-metal simple-substance can be H
2, B, C, Si.
Said hydrogenate representes that with M/H wherein M is basic metal, earth alkali metal or rare earth, and H is a Wasserstoffatoms.
The said 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 kinds combinations.
In addition, desirable one or more above whiles use as the reductive agent among the preparation method of the present invention.
Among the present invention, said graphene oxide is powder, " Buckie paper " or film.
The preparation technology of said graphene oxide powder can comprise: flake graphite and strong oxidizer are reacted in the concentrated acid environment and process the operation A of graphene oxide, and the graphene oxide that operation A obtains is obtained the process B of graphene oxide powder after lyophilize.
The preparation technology of said " Buckie paper " can comprise: flake graphite and strong oxidizer are reacted in the concentrated acid environment and process the operation A of graphene oxide; And after being mixed with the water-sol with the said graphene oxide that operation A obtains, vacuum filtration obtains the operation C of " Buckie paper ".The thickness of said " the Buckie paper " processed through this technology is 0.5-20 μ m, and density is 1.4-2.5g/cm
3
The preparation technology of said film can comprise: flake graphite and strong oxidizer are reacted in the concentrated acid environment and process 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 through dipping was processed the step D of film.The said film thickness of processing through this technology is 2-100nm.
In the technology of above-mentioned preparation graphene oxide powder, " Buckie paper " or film, said operation A preferably can may further comprise the steps: in 35 ± 5 ℃ water-bath, make the reaction of flake graphite, SODIUMNITRATE and the vitriol oil and potassium permanganate, form mixture; Make system temperature be raised to 90 ± 5 ℃ of insulation certain hours, add the entry dilution afterwards; With the excessive potassium permanganate of reductive agent reduction, obtain solution; After obtaining filter cake from said solution, said 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.Said Graphene powder square resistance behind compressing tablet of processing through preparation method of the present invention is 0.5-20 Ω sq
-1Said Graphene paper square resistance is 0.5-100 Ω sq
-1The transmittance of said 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 lamella is strong, and electroconductibility, mechanical strength and snappiness are good.
High conductive graphene material provided by the invention can be applicable to fields such as photovoltaic, plane demonstration, semiconductor electronic and energy storage device.
High conductive graphene preparation methods of the present invention; Under coldcondition; Utilize metal or non-metal simple-substance, compound or gas, capture the oxygen-containing functional group in the graphene oxide effectively, realize quick under lower temperature, the efficient reduction of graphene oxide through gas-phase reaction; The low temperature gas-phase reaction has kept the more complete structure of graphene oxide, thereby prepares the graphene film that 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 solve the bottleneck problem that existing high-temperature heat treatment or low temperature liquid phase chemical reduction method destroy graphene-structured effectively.
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 combine following embodiment to further specify the present invention.Should be understood that accompanying drawing and embodiment or embodiment only are exemplary, but not be used to limit the present invention.The TP 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 preparation methods of low temperature vapour phase reduction of the present invention specifically comprises: adopt the furnace apparatus of many warm areas, the raw material graphene oxide is placed low-temperature end, the solid phase reduction agent is placed temperature end or feeds the vapour phase reduction agent from temperature end; Utilize mechanical pump to extract base vacuum, for example to 0.5Pa-10Pa, stop to vacuumize sealing to a certain degree; Begin process furnace two ends to many warm areas again and be heated to temperature requiredly respectively, for example cold zone is heated to 50-500 ℃, the high-temperature zone is heated to 400-1200 ℃, stops 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 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, keeps the complete structure of Graphene effectively.The Graphene paper and the membrane structure of the preparation of reduction back are fine and close, and the bonding force between the Graphene lamella 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 (like K, Na, Li), earth alkali metal (like Mg, Ca, Sr, Ba), rare earth metal, transition metal (like Sc, Ti, V, Cr, Fe, Co, Ni, Zn, Y, Zr, Nb, Ta, Mo, W, Al) grade or its combination;
Non-metal simple-substance: H
2, B, C, Si etc. or its combination;
Hydrogenate: represent that with M/H wherein M is basic metal, earth alkali metal or rare earth, H is a Wasserstoffatoms;
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 to reduce with the graphene oxide for preparing high conductive graphene can be powder, " Buckie paper " or film; 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 equal effect, and each characteristic in each step neither or replaceable regularly and not, just example ground explanation here:
(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 appearance of black;
Under agitation condition, in mixture, add small quantity 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 a glassy yellow by brown stain;
The above-mentioned solution that obtains is filtered, 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 5-10min under low speed of whizzer elder generation, to remove the graphite that does not react completely, the foreign ion in the graphene oxide is removed in the back under at a high speed, obtains graphene oxide;
(2) preparation of graphene oxide powder:, after lyophilize, promptly get the graphene oxide powder with the graphene oxide of (1) gained;
(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 promptly gets graphene oxide paper, comes the thickness of controlled oxidation Graphene paper through the volume of regulating the water-sol, and thickness range is 0.5-20 μ m; Through regulating the density of suction filtration time controlled oxidation Graphene paper, 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.
Preparing 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 directly reduced.Through gained Graphene powder square resistance behind compressing tablet after reducing is 0.5-20 Ω sq
-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 extensive applications such as high-performance nanometer electronic device, transmitter, nano composite material, battery and ultracapacitor, field emmision materials.
Further illustrate the high conductive graphene preparation methods of low temperature vapour phase reduction of the present invention below.
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; Raw material graphene oxide paper is placed the low-temperature end of the process furnace of many warm areas, and 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 process furnace two ends to many warm areas again and be heated to temperature requiredly respectively, insulation reduction 3 hours stops heating, and 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).Through X-ray powder diffraction appearance (XRD) analysed film thing 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 superior to 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.With C1s=284.6eV is that benchmark carries out the bound energy correction.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.Can see that from figure original graphene oxide is main along the growth of (002) high preferred orientation, 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, to 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 original graphene oxide paper respectively 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 (the carbon Sauerstoffatom compares: C/O) lower, be merely 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 reduced 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; Raw material graphene oxide paper is placed the low-temperature end of the process furnace of many warm areas, and 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 process furnace two ends to many warm areas again and be heated to temperature requiredly respectively, insulation reduction 3 hours stops heating, and natural stove is cold.
The 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, to 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 reduction back sample.Test result shows that 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 reduces to 6 Ω sq
-1This shows, compare, under 200 ℃ low reduction temperature, prepare Graphene and have more crystalline property and electric property with embodiment 1.
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; Raw material graphene oxide 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 process furnace two ends to many warm areas again and be heated to temperature requiredly respectively, insulation reduction 30 minutes stops heating, and natural stove is cold.Graphene paper after reduction still keeps the structure of compact and complete, 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, and 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 process furnace two ends to many warm areas again and be heated to temperature requiredly respectively, insulation reduction 5 hours stops heating, and natural stove is cold.Graphene well-crystallized after reduction demonstrates good light transmittance visible with near-infrared band, and the corresponding transmittance in 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 process furnace two ends to many warm areas again and be heated to temperature requiredly respectively, insulation reduction 3 hours stops heating, and natural stove is cold.Graphene well-crystallized after reduction demonstrates good light transmittance visible with near-infrared band, and the corresponding transmittance in 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, and 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 process furnace two ends to many warm areas again and be heated to temperature requiredly respectively, insulation reduction 5 hours stops heating, and natural stove is cold.Graphene well-crystallized after reduction demonstrates good light transmittance visible with near-infrared band, and the corresponding transmittance in 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, and 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 feed CO gas from temperature end, begin process furnace two ends to many warm areas simultaneously and be heated to temperature requiredly respectively, insulation reduction 6 hours stops heating, and natural stove is chilled to room temperature, stops to feed 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; Raw material graphene oxide paper is placed the low-temperature end of the process furnace of many warm areas, and 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 feed H from temperature end
2Gas begins process furnace two ends to many warm areas simultaneously and is heated to temperature requiredly respectively, and insulation reductase 12 hour stops heating, and natural stove is chilled to room temperature, stops to feed H again
2Gas.Graphene paper after reduction still keeps the structure of compact and complete, 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; Raw material graphene oxide paper is placed the low-temperature end of the process furnace of many warm areas, and 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 process furnace two ends to many warm areas again and be heated to temperature requiredly respectively, insulation reduction 1 hour stops heating, and natural stove is cold.Graphene film crystallization after reduction is better, all demonstrates certain light transmission visible with near-infrared band, and the corresponding transmittance in 550nm place reaches 63.5%, and square resistance is 921 Ω sq
-1
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; Raw material graphene oxide paper is placed the low-temperature end of the process furnace of many warm areas, and 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 feed H from temperature end
2S gas begins process furnace two ends to many warm areas simultaneously and is heated to temperature requiredly respectively, and insulation reduction 3 hours stops heating, and natural stove is chilled to room temperature, stops to feed H again
2S gas.Graphene film well-crystallized after reduction demonstrates good light transmittance visible with near-infrared band, and the corresponding transmittance in 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; Raw material graphene oxide paper is placed the low-temperature end of the process furnace of many warm areas, and 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 process furnace two ends to many warm areas again and be heated to temperature requiredly respectively, insulation reduction 5 hours stops heating, and natural stove is cold.Graphene paper after reduction still keeps the structure of compact and complete, 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 processing of grapheme material electroconductibility, light transmission, mechanical strength and snappiness can be in field widespread uses such as high-performance nanometer electronic device, transmitter, nano composite material, battery and ultracapacitor, field emmision materials.
Claims (18)
1. the high conductive graphene preparation methods of a low temperature vapour phase reduction; It is characterized in that; Said preparing method's utilization has many warm areas heating installation of high-temperature zone and cold zone; Be heated to certain temperature through cold zone that will have graphene oxide and high-temperature zone, restore high conductive graphene with reductive agent.
2. preparation method according to claim 1 is characterized in that, said cold zone is heated to 50-500 ℃, and said high-temperature zone is heated to 400-1200 ℃.
3. based on the described preparation method of claim 1, it is characterized in that, before said heating, extract base vacuum earlier to 0.5Pa-10Pa, and sealing.
4. preparation method according to claim 2 is characterized in that, after said heating, is incubated 30-600min, is cooled to room temperature afterwards.
5. according to each described preparation method of claim 1 to 4; It is characterized in that; Said reductive agent is the metal simple-substance that comprises basic metal, earth alkali metal, rare earth metal, transition metal-type, non-metal simple-substance, hydrogenate; Contain the compound of low valence metal ion and contain in the compound of low valency element one or more.
6. preparation method according to claim 5 is characterized in that,
Said alkali-metal metal simple-substance is K, Na, Li, and the metal simple-substance of earth alkali metal is Mg, Ca, Sr, Ba, and the metal simple-substance of transition metal is Sc, Ti, V, Cr, Fe, Co, Ni, Zn, Y, Zr, Nb, Ta, Mo, W, A;
Said non-metal simple-substance is: H
2, B, C, Si or its several kinds combinations;
Said hydrogenate is: represent that with M/H wherein M is basic metal, earth alkali metal or rare earth, H is a Wasserstoffatoms;
The said compound that contains low valence metal ion is FeCl
2, SnCl
2Or its combination;
The said compound that contains low valency element is H
2S, Na
2S, HI, NH
3, CO, SO
2, Na
2SO
3Or its several kinds combinations.
7. according to each described preparation method of claim 1 to 4, it is characterized in that said graphene oxide is powder, " Buckie paper " or film.
8. preparation method according to claim 7; It is characterized in that; The preparation technology of the powder of said graphene oxide comprises: flake graphite and strong oxidizer are reacted in the concentrated acid environment and process the operation A of graphene oxide, and the graphene oxide that operation A obtains is obtained the process B of graphene oxide powder after lyophilize.
9. preparation method according to claim 7; It is characterized in that; The preparation technology of said " Buckie paper " comprising: flake graphite and strong oxidizer are reacted in the concentrated acid environment and process the operation A of graphene oxide; And after being mixed with the water-sol with the said graphene oxide that operation A obtains, vacuum filtration obtains the operation C of " Buckie paper ".
10. preparation method according to claim 9 is characterized in that, the thickness of said " Buckie paper " is 0.5-20 μ m, and density is 1.4-2.5g/cm
3
11. preparation method according to claim 7; It is characterized in that; The preparation technology of said film comprises: flake graphite and strong oxidizer are reacted in the concentrated acid environment and process 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 through dipping was processed the step D of film.
12. preparation method according to claim 11 is characterized in that, said film thickness is 2-100nm.
13. arbitrary described preparation method in 12 is characterized in that said operation A comprises: in 35 ± 5 ℃ water-bath, make the reaction of flake graphite, SODIUMNITRATE and the vitriol oil and potassium permanganate, form mixture according to Claim 8; Make system temperature be raised to 90 ± 5 ℃ of insulation certain hours, add the entry dilution afterwards; With the excessive potassium permanganate of reductive agent reduction, obtain solution; After obtaining filter cake from said solution, said 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.
14. the high conductive graphene material according to the described method preparation of claim 1 to 13, said grapheme material is Graphene powder, Graphene paper or graphene film.
15. high conductive graphene material according to claim 14 is characterized in that, said Graphene powder square resistance behind compressing tablet is 0.5-20 Ω sq
-1
16. high conductive graphene material according to claim 14 is characterized in that, said Graphene paper square resistance is 0.5-100 Ω sq
-1
17. high conductive graphene material according to claim 14 is characterized in that the transmittance of said graphene film is 60%-96%, square resistance is 30-1000 Ω sq
-1
18. according to each described high conductive graphene material application in photovoltaic, plane demonstration, semiconductor electronic and energy storage device of claim 14-17.
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