CN103213970A - Method for preparing graphene powder and graphene transparent conductive film by oxyhydrogen flame method - Google Patents
Method for preparing graphene powder and graphene transparent conductive film by oxyhydrogen flame method Download PDFInfo
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Abstract
The invention discloses a method for preparing high-quality graphene powder and a graphene transparent conductive film. The method comprises that through an oxyhydrogen flame rapid heating method, organics are decomposed into high-activity carbon atoms; and the high-activity carbon atoms are re-configurated into graphene on an insulating substrate or a catalyst substrate. Through the method, high-quality graphene can directly grow on the insulating substrate, and through an ultrasonic method, high-quality graphene powder without a support substrate is obtained. Compared with the traditional chemical stripping method for preparing graphene, the method has simple processes, a low cost, less defects and good conductivity and can produce high-quality graphene. The method can be used for preparing the graphene transparent conductive film on a catalyst film substrate. The graphene transparent conductive film has quality and conductivity approximate to the optimal values of a graphene transparent conductive film obtained by the traditional CVD method. Graphene obtained by the method has wide application prospects in fields of photoelectric devices such as copper indium gallium diselenide, cadmium telluride and dye-sensitized solar cells, panel displays, super capacitors, field emission materials, and lithium ion batteries.
Description
Technical field
The present invention relates to the method that a kind of oxyhydrogen flame method prepares high-quality Graphene powder and Graphene transparent conductive film.
Technical background
Graphene is the two-dimensional material by the tightly packed one-tenth of monolayer carbon atom.Because unique two-dirnentional structure feature and splendid crystallography quality, it has not only contained abundant and novel physical phenomenon, having important theoretical research is worth, and its particular structure and excellent performance might make it obtain great practical application in a plurality of fields, for economy, the social development in future provides new strong growth point.For example, has high light transmission (people (R.Nair) " science (Science) " 2008 such as R. Nai Er in the visible-near-infrared zone of Graphene, 320,1308), this has been avoided the conventional transparent conductive oxide near infrared photoabsorption, help to utilize the near infrared sun power of 900-1800nm, realize making full use of sun power; Carrier mobility is up to 20,000cm
2V
-1S
-1Be much better than common oxidic transparent conductive film (A. base grace (A.Geim), " nature material (Nat.Mater) " .2007,6,183.), this helps the electric charge fast transferring, improves the electric charge ability, raise the efficiency, thereby have broad application prospects at renewable energy source domains such as lithium ion battery, solar cells.
The preparation of material is its performance of research and prerequisite and the basis of exploring its application.Although the multiple method for preparing Graphene has been arranged at present, the output of Graphene and quality have all had lifting significantly, but how to realize that at different application the magnanimity control of Graphene prepares, and regulates and control to be still the significant challenge of present Graphene research field to its quality, structure.In present preparation method of graphene, micromechanics is peeled off the Graphene that method can prepare the micron size, but its controllability is low, is difficult to extensive synthetic people (K.S.Novoselov) such as (, " science (Science) " 2004,306,666) K.S. Nuo Wosefu; The epitaxially grown Graphene of SiC, though can directly make electron device by photoetching process, but because reconstruct takes place in SiC plane of crystal surface in high-temperature heating process easily, cause surface tissue comparatively complicated, be difficult to obtain the Graphene (people (C.Berger) such as C. Burger of big area, thickness homogeneous, " science (Science) " 2006,312,1191); CVD is considered to prepare the good method of big area Graphene, but its growth substrates process of removing can be destroyed the quality (people (K.Kim) such as K. gold " nature (Nature) " 2009,457,706) of Graphene; Though the chemical stripping method can prepare Graphene in a large number, but its violent redox processes can be destroyed Graphene planar carbon skeleton, produce defective, the Graphene downgrade that causes gained, seriously restricting (the people (D.Li) " natural nanotechnology (Nat.Nanotech.) " 2008 such as Lee D. that applies of Graphene, 3,101).Therefore, how the high-quality graphene powder of preparation of simple controllable magnanimity and transparent conductive film are a big difficult point and focuses of research at present.
Summary of the invention
The object of the present invention is to provide a kind of method that can prepare high quality graphene powder and transparent conductive film simply, fast.Under negative pressure, utilize oxyhydrogen flame rapid heating organic molecule, make its pyrolysis produce a large amount of active carbon sources, these active carbon sources on catalyzer or insulating substrate nucleation, grow into Graphene.
One aspect of the present invention provides a kind of preparation method of Graphene powder, and described method comprises: utilize oxyhydrogen flame rapid heating decomposing organic matter, produce highly active carbon atom; Highly active carbon atom is reconstituted Graphene on insulating substrate, obtain the Graphene powder thus.In a preferred embodiment, the preparation method of described Graphene powder carries out in the encloses container under the negative pressure.More preferably, the pressure range 100-1000Pa of described negative pressure.
In embodiments of the present invention, described organism is one or more the combination in polymethylmethacrylate, polystyrene, polyoxyethylene glycol, polyvinyl alcohol, polyethylene, polypropylene, sucrose, glucose, naphthalene and the fluorenes.In preferred embodiment, described organism is dissolved in the solvent, forms organic solution; Described organism quality concentration is 1.0%-20%.Described solvent can be organic solvent or water, preferred volatile organic solvent or the organic solvent that can dry in baking oven.
In embodiments of the present invention, described insulating substrate is the one or more combination in hexagonal boron nitride, hexagonal carborundum, magnesium oxide, aluminium nitride, sapphire, silicon-dioxide, zinc sulphide, zinc oxide, the titanium dioxide.In preferred embodiment, described insulating substrate is scattered in the organic solution with form of powder, and concentration is 10.0-80.0mg/mL.
In preferred embodiment of the present invention, the preparation method of described graphene powder comprises:
1) it is even to get the insulating substrate powder mixes of the organic solution 100-800mL of 1.0%-20% and 1.0-10.0g, obtains suspension;
2) step 1) gained suspension is placed in the 80-150 ℃ of baking oven insulation 0.5-4 hour, obtain powder;
3) with step 2) the gained powder packs in the silica tube, is evacuated to 100-1000Pa, with oxyhydrogen flame rapid heating silica tube 10-60 second;
4) withdraw oxyhydrogen flame, obtain to grow in the Graphene on the insulating substrate.
In embodiments of the present invention, the preparation method of described graphene powder also comprises: the described Graphene that grows on the insulating substrate was carried out ultrasonic 10-40 minute in power is the ultrasonic wave of 100-600w, obtain pure graphene powder.
On the other hand, the invention provides a kind of preparation method of Graphene nesa coating, described method comprises: utilize oxyhydrogen flame rapid heating decomposing organic matter, produce highly active carbon atom; Highly active carbon atom is reconstituted Graphene on catalyst substrate.In a preferred embodiment, described method is carried out in the encloses container under the negative pressure.More preferably, the pressure range 100-1000Pa of described negative pressure.
In embodiments of the present invention, described organism is one or more the combination in polymethylmethacrylate, polystyrene, polyoxyethylene glycol, polyvinyl alcohol, polyethylene, polypropylene, sucrose, glucose, naphthalene and the fluorenes.More preferably, described organism is dissolved in the solvent, forms organic solution; Described organism quality concentration is 1.0%-20%.Described solvent can be organic solvent or water, preferred volatile organic solvent or the organic solvent that can dry in baking oven.。
Individual in embodiments of the present invention, described catalyst substrate is the one or more combination in copper, nickel, cobalt, the iron.
In the specific embodiment of the present invention, the preparation method of described Graphene transparent conductive film comprises:
1) catalyst film substrate or catalyzer paillon foil substrate are placed atmosphere furnace, under 600-1000 ℃, at H
2Insulation is 5-30 minute in the/Ar gas mixture, wherein, and H
2Content 5-20%;
2) the organic solution 40-200 μ L that gets 1.0%-20% is spun on catalyst film substrate or the catalyzer paillon foil substrate, place the interior insulation of 80-150 ℃ of baking oven after 0.5-4 hour, on catalyst film substrate or catalyzer paillon foil substrate, form the organic thin film that thickness is about 50-400nm, obtain the substrate that organic thin film coats;
3) in the substrate that organic thin film is coated is packed silica tube into, be evacuated to 100-1000Pa, use oxyhydrogen flame rapid heating silica tube 10-30 second;
4) withdraw oxyhydrogen flame, obtain to grow in the Graphene on catalyst substrate surface.
5) with 4) Graphene that obtains transfers on the target substrate, obtains the Graphene transparent conductive film.
In the preferred embodiment of the present invention, the preparation method of described Graphene transparent conductive film also comprises by selecting different catalyst substrate to control the thickness of described organic thin film.
In the present invention, the contriver finds only to need oxyhydrogen flame and common vacuum system can realize a large amount of preparations of graphene powder and transparent conductive film.Compare with traditional chemical stripping method, few, the good conductivity of graphene powder defective that the present invention obtains, and simple to operate, step is few, preparation cost is very low.Be equipped with transparent conductive film with present general CVD legal system and compare, equipment required for the present invention is simple, and preparation time is short; Another important advantage of the present invention be can be on insulating substrate direct growth high quality Graphene, this is that additive method is difficult to realize.
Description of drawings
Fig. 1 is the synoptic diagram that the present invention prepares Graphene.
(a) among Fig. 2 is the transmission electron microscope photo that is directly grown in the Graphene of h-BN, and as can be seen from the figure the Graphene that obtains of the present invention can extend to the growth of h-BN substrate outside.(b) among Fig. 2 is the high-resolution-ration transmission electric-lens photo of Graphene and h-BN substrate interface.(c) among Fig. 2 is the high-resolution electron microscopy photo of graphene edge; As can be seen from the figure the Graphene number of plies that obtains of the present invention is less than 5.(d) among Fig. 2 is the selected area electron diffraction style of Graphene/h-BN.Wherein, can demarcate its Miller crystal indices in conjunction with wherein (b).As can be known, Graphene of growing of the present invention is grown along h-BN (1100) crystal face from Fig. 2 (b) and 2 (d).
Fig. 3 is the organism PMMA of different concns prepares the different concns Graphene on the h-BN substrate Raman figure.
As we know from the figure, the G peak position～1582cm of the Graphene that under PMMA concentration is 2% condition, obtains
-1, the position～2690cm at 2D peak
-1, the G peak obviously is better than D peak (～1350cm
-1), illustrate that the Graphene defective that is obtained by the present invention is few; I
2D/ I
G～1, the number of plies that the Graphene that the present invention obtains is described is a layer 2-3, and this result with the high-resolution-ration transmission electric-lens photo is consistent.Along with the increase of PMMA concentration, the 2D peak position moves on to 2700cm from 2690
-1, the number of plies that Graphene is described is increasing, when still remaining on below 5 layers.And traditional peel off legal system by chemical oxidation and be equipped with gained Graphene (r-GO), its 2D peak is very weak and the D peak is very strong, and the quality that the Graphene that the present invention obtains is described is far above traditional chemical stripping method gained.
Fig. 4 is the XPS collection of illustrative plates of h-BN/ graphene complex; Wherein, (a)-(c) be respectively the 1s figure of C, B and N.C 1s spectrum has three to be positioned at 284.7eV, and the sub-peak of 286.6eV and 288.8eV constitutes, and corresponds respectively to C=C, C-N and O=C-O key.The carbon material that the C=C peak obtains has sp
2Electronic structure; Explanation h-BN substrate appears in the C-N peak has doping effect to Graphene; The appearance at O=C-O peak shows that a little P MMA does not decompose fully in addition.
Fig. 5 is the transmission electron microscope photo of the h-BN/ Graphene of gained when the PMMA mass concentration is 2%.
(a) among Fig. 6 be when the PMMA mass concentration be 4% to be the transmission electron microscope photo of the h-BN/ Graphene of gained, (a) corresponding electron diffraction pattern among (b) among Fig. 6 and Fig. 6.(b) from Fig. 6 can clearly see the hexagonal structure of h-BN and the polycrystalline structure of Graphene.
(a) among Fig. 7 is the transmission electron microscope photo of the Graphene that supports at the linerless end of gained h-BN/ Graphene of the present invention after ultrasonic; (b) in 7 is the high-resolution electron microscopy photo in the middle white dashed line square of (a) in 7, and therefrom as can be seen, the Graphene that the present invention obtains is an individual layer; (c) in 7 and (d) figure be the high-resolution-ration transmission electric-lens photo of graphene edge, as we know from the figure, the Graphene that the present invention obtains is less than 5 layers.
Fig. 8 is that gained of the present invention is transferred to SiO
2The Raman spectrogram of the Graphene transparent conductive film on the substrate.
As we know from the figure, the 2D peak of growth gained Graphene and strength ratio～4 at G peak on the Cu paper tinsel, the peak width at half height at 2D peak is 30cm
-1, the 2D peak position is about 2690cm
-1, these results illustrate that the gained Graphene is an individual layer.In addition, do not have tangible D peak on Raman spectrum, the strength ratio at D peak and G peak is 0.07, and being of high quality of gained Graphene of the present invention is described.When using Ni paper tinsel growth Graphene instead, the Raman spectrogram 2D peak of the Graphene that obtains and strength ratio～1.1 at G peak, the peak width at half height at 2D peak is 45cm
-1, the 2D peak position is about 2695cm
-1, these results illustrate that the gained Graphene is for being bilayer.
Embodiment
Among the present invention, described organic molecule can be the one or more combination in polymethylmethacrylate (PMMA), polystyrene (PS), polyoxyethylene glycol (PEG), polyvinyl alcohol (PVA), polyethylene (PE), polypropylene (PP), sucrose, glucose, naphthalene and the fluorenes etc., and described catalyst substrate is Copper Foil, nickel foil, cobalt paper tinsel, iron film, copper powder, nickel powder, cobalt powder, iron powder; Described insulating substrate is hexagonal boron nitride (h-BN), silicon carbide (SiC), silicon-dioxide (SiO
2), aluminium nitride (AlN), sapphire, magnesium oxide (MgO), zinc sulphide (ZnS), zinc oxide (ZnO), titanium dioxide (TiO
2) in one or more combination.Above-mentioned materials prepares Graphene fast under vacuum.Describe the present invention below in detail.
A) growth Graphene transparent conductive film on catalyst film or paillon foil substrate
One or more combination in organism polymethylmethacrylate (PMMA), polystyrene (PS), polyoxyethylene glycol (PEG), polyvinyl alcohol (PVA), polyethylene (PE), polypropylene (PP), sucrose, glucose, naphthalene and the fluorenes etc. is dissolved in organic solvent or the water, and forming different mass concentration is the solution of 0.1-20%.Organic concentration is different according to the metal catalyst kind.
Get the organic solution of 40-500 μ L, under the rotating speed of 500-3000 rev/min (rpm), be spun on the surface of transition metal Copper Foil, nickel foil, cobalt paper tinsel or iron foil substrate.Afterwards, place 80-120 ℃ of loft drier insulation 1.5-4 hour, fully remove and desolvate.Drying temperature and time are different according to solvent types and quantity.To coat organic catalyst substrate and place in the silica tube, and vacuumize, pressure maintains 10-1000Pa.Open oxyhydrogen flame, the rapid heating silica tube, 10-60 drops back from oxyhydrogen flame second, and the rapid cool to room temperature of silica tube of catalyst substrate is housed, and obtains to grow in the graphene film of catalyst surface thus.Wherein, preparation time and pressure are different according to the kind of organism and catalyzer.
B) transfer of graphene film
Be the methyl-phenoxide solution of 4% PMMA earlier, with the protection graphene film at surperficial spin coating one deck massfraction of Graphene; Subsequently, place the aqueous solution dissolving etching catalyst substrate of the iron trichloride of 0.1-0.5mol/L, obtain graphene film after 30-150 minute.Described etching time is different according to the thickness of catalyst substrate.Obtain floating on the Graphene/PMMA film on the solution after the dissolving etched substrate; With sheet glass with Graphene/PMMA film transfer in deionized water, remove foreign ion, repeat to guarantee for twice that foreign ion removes fully; Graphene/PMMA film transfer on target substrate, is placed in 80 ℃ the loft drier and removes moisture; Place acetone 60 minutes to remove the PMMA film afterwards, obtain transferring to the graphene film of target substrate.
C) at catalyst fines surface growth Graphene powder
Get 100-800mL a) in the organic solution that configures, after one or more combination dispersed with stirring in the copper powder of 0.5-10g, nickel powder, cobalt powder, the iron powder, place 80-120 ℃ of loft drier to remove and desolvate, form the mixture (being catalyzer/organic mixture) of organism coated metal catalyzer.
Catalyzer/organic mixture is packed in the silica tube, vacuumize, make pressure remain on 10-1000Pa.Open oxyhydrogen flame, the rapid heating silica tube, 10-60 drops back from oxyhydrogen flame second, and the rapid cool to room temperature of silica tube of sample is housed, and obtains to grow in the Graphene powder (being Graphene/catalyst powder) of catalyst surface.Wherein, preparation time and pressure are different according to the kind of organism and catalyzer.
D) purification of Graphene powder
In the aqueous solution of the iron trichloride of 0.1-1.0mol/L, dissolving etching catalyst fines obtained graphene powder after 20-120 minute with Graphene/catalyst powder dispersed with stirring.Etching time is different according to the kind of catalyzer.Remove foreign ion by filtering, washing, obtain the pure Graphene powder of self-support (freestanding).
The Graphene powder that is obtained by the present invention can be used as lithium ion battery, electrocondution slurry etc.
E) direct growth Graphene powder on insulating substrate
Get 100-800mL a) in the organic solution that configures, after mixing with the insulating substrate that is selected from the one or more combination in hexagonal boron nitride, silicon carbide, silicon-dioxide, aluminium nitride, sapphire, magnesium oxide, zinc sulphide, zinc oxide, the titanium dioxide, place 80-120 ℃ of loft drier to remove and desolvate, obtain insulating substrate/organic mixture.Organic amount is different according to the metal catalyst kind.
Insulating substrate/organic mixture is packed in the silica tube, vacuumize, allow the pressure in the silica tube maintain 10-1000Pa.Open oxyhydrogen flame, the rapid heating silica tube.10-60 drops back from oxyhydrogen flame second, and the rapid cool to room temperature of silica tube of sample is housed, and directly is longer than the Graphene on the insulating substrate.Preparation time is different according to catalyzer and organic kind.
In a kind of optimal way of the present invention,, can obtain the graphene powder that supports at the linerless end with ultrasonic removal insulating substrate.Wherein, ultrasound intensity is 100-600W, different different according to substrate.Obtain the graphene powder of pure support of the linerless end by centrifugation.
F) pattern of Graphene and structural characterization
To pattern and the growth mechanism of gained Graphene sample of the present invention by scanning electron microscope (SEM, JEOL JSM-6700F) and transmission electron microscope (JEM 2010) observation sample; Characterize the structure of Graphene with Raman spectrum (invia of Reinshaw company type Raman microscope (Renishaw invia Raman Microscope), excitation wavelength is 514nm); Measure the electroconductibility of Graphene with four point probe vanderburg (Van Der Pauw) method (AccentHL5500).Each element relative content ratio and chemical combination attitude thereof with x-ray photoelectron spectroscopy (XPS, PHI 5000CESCA system) analytic sample surface.
Its electroconductibility that compares with Graphene of the present invention and chemical stripping method (being the Hummers method) preparation.
G) the chemical stripping legal system is equipped with Graphene
Prepare the quality and the electroconductibility of Graphene for contrast the present invention, prepare graphene oxide with the Hummers method, promptly obtain graphite oxide with the vitriol oil, SODIUMNITRATE and potassium permanganate oxidation flake graphite, obtain graphene oxide [people (W.S.Hummers) J.Am.Chem.Soc.1958 such as W.S. Han Mosi, 1339] with ultrasonic peeling off again.Redox graphene is come with the method for high temperature pyrolysis in the back.
Introduce embodiments of the invention below, to understanding of the present invention, but the present invention is limited to embodiment absolutely not with further increase.
Embodiment 1:
Direct growth graphene powder on the h-BN insulating substrate
Implementation process prepares massfraction earlier and is the methyl-phenoxide solution 2L of 6% PMMA, for future use as shown in Figure 1.
Get the methyl-phenoxide solution 100mL of 6% PMMA and the h-BN powder of 5g, stir after 30 minutes, place 2 hours abundant solvent flashings of insulation in 120 ℃ the baking oven, obtain the h-BN of PMMA coating.The h-BN that above-mentioned PMMA is coated packs in the silica tube of size φ 25 * 2mm.Be evacuated to 100Pa, use oxyhydrogen flame rapid heating silica tube 20 seconds.Afterwards, withdraw oxyhydrogen flame, allow silica tube be cooled fast to room temperature.Take out sample and obtain the h-BN/ graphene complex.
The graphene conductive property testing of direct growth on the h-BN insulating substrate
Electric conductivity is the important indicator that characterizes the Graphene quality.For the electric conductivity of measuring h-BN/ Graphene, the present invention scrapes the h-BN/ Graphene and paints film, surveys its square resistance with four probe method again.Detailed process is as follows:
Dispose N-Methyl pyrrolidone (NMP) solution of the polyvinylidene difluoride (PVDF) (PVDF) of 10g/L earlier.Toward wherein adding the h-BN/ graphene complex, stirred 40 minutes, be mixed into the homogeneous slurry of 10g/L.Go out 5 * 5cm with the doctor knife coater blade coating
2Thick film, forming thickness 100 ℃ of oven dry is the film of 10 μ m, the silver slurry is used to test its square resistance on the point.
In order to reduce error, each sample is tested three times at least, gets its mean value at last.Test result shows that the average resistance of the h-BN/ graphene complex that the present invention obtains is 27 Ω/sq (ohm-sq), is better than the optimum value 200 Ω/sq (ohm-sq) (people (W.Gao) .Nature Chem. such as W. height, 2009,1,403) of bibliographical information.Illustrate that the Graphene defective that the present invention obtains is few, quality is high.
Another significant advantage of the present invention is to make h-BN become the favorable conductive body from isolator by the coating of Graphene.This has further expanded the range of application of the full-time blind material of this deep ultraviolet response of h-BN.
Pattern and structural performance characterize
From the TEM characterization result (as Fig. 2 a) as can be known the Graphene that obtains of the present invention can not only coat substrate uniformly, and after Graphene covers fully, can break away from the substrate vertical growth on substrate; Observe Graphene and h-BN substrate interface with high-resolution-ration transmission electric-lens (Fig. 2 b), as can be known, Graphene is grown along h-BN substrate (1100) crystal face from Fig. 2 b; HRTEM (Fig. 2 b) can observe its border find that the present invention obtains Graphene less than five layers; Selected area electron diffraction style (Fig. 2 d) can be seen the hexagonal structure of h-BN and the polycrystalline structure of Graphene clearly.
Embodiment 2:
The preparation of unsupported (Freestanding) Graphene
In order to obtain pure Graphene, the present invention with the h-BN/ graphene complex 6.7g that obtains, places the ethanol of 400mL on the basis of embodiment 1, obtains turbid solution at the power ultrasonic of 300w after 15 minutes.After under 1000 rev/mins the rotating speed centrifugal 5 minutes, can obtain pure nothing and support Graphene sample 1.5g.
The unsupported Graphene that is obtained by present embodiment is modulated into electrocondution slurry, scrapes the film of painting 10 μ m by the method among the embodiment 1, silver slurry on the point, and being used to test its average square resistance is 31 Ω sq (ohms/square).
Pattern and structural performance characterize
The nothing that obtains with transmission electron microscope observing supports the pattern of Graphene, as shown in Figure 7.The Graphene that obtains as we know from the figure is of a size of 200nm.With the border of high-resolution-ration transmission electric-lens observation Graphene, shown in Fig. 7 b-d, with the number of plies of statistics Graphene.The Graphene that obtains as we know from the figure is below 5 layers.The high-resolution-ration transmission electric-lens photo (80 of random sampling) that analytic statistics is a large amount of, 94% Graphene is less than 5 layers.
Raman spectrum is one of effective means that characterizes the Graphene quality and the number of plies.Quality with the Graphene that Raman spectrum characterizes, contrast the present invention and chemical stripping method obtain.High-quality Graphene has very strong G peak and 2D peak and weak D peak is arranged.As can be known from Fig. 3, the Graphene that obtains of the present invention has the feature of high quality Graphene.In addition, can judge the number of plies of Graphene from the position at 2D peak, the about 2690cm in 2D peak position of the Graphene that the present invention obtains
-1, this explanation Graphene is less than 5 layers.This sign structure with high-resolution-ration transmission electric-lens is consistent.In Raman spectrum, be positioned at 1360cm
-1Acromion be that the h-BN substrate causes.
And traditional peel off legal system by chemical oxidation and be equipped with gained Graphene (r-GO), its 2D peak is very weak and the D peak is very strong, and the quality that the Graphene that the present invention obtains is described is far above traditional chemical stripping method gained.
Comparative Examples 1:
The electroconductibility and the quality of the Graphene excellence for preparing for outstanding the present invention, we are equipped with Graphene with general chemical stripping legal system, i.e. the Hummers method.Its concrete steps are as follows:
The preparation of graphene oxide
Get the flake graphite of 1.0g, the SODIUMNITRATE (NaNO of 1g
3) and the vitriol oil of 46mL in ice bath, stirred 15 minutes, add the potassium permanganate (KMnO of 6g slowly
4).After the mixing, system transferred in 35 ± 5 ℃ the water-bath, stirred 6 hours, form the mixture of the mud sample of black.
Under agitation condition, add the deionized water of 20mL in the mixture, system temperature is raised to 90 ± 5 ℃.The water dilution that adds 200mL after 30 minutes.The H that adds 2mL
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 wash with a large amount of water (being about 2L).The filter cake that obtains is dispersed in the deionized water again, ultra-sonic dispersion 20 minutes.Earlier 1000 rev/mins of low speed centrifugal 5 minutes down, removing the graphite that does not react completely, the back is at 12000 rev/mins of foreign ions of removing in the graphene oxide at a high speed with whizzer.Promptly get spongiform graphene oxide after 8 hours with lyophilize.
The reduction of Graphene
We adopt the method for at present general redox graphene to come redox graphene.The graphene oxide sponge that obtains is placed the tubular type atmosphere furnace, at H
2/ Ar (contains 5% H
2) be heated to 1000 ℃ in the gas mixture, insulation 6h, reduction obtains Graphene.
By Raman spectrum (as shown in Figure 3) as can be known, the Graphene that obtains far below the present invention of the quality of the Graphene that obtains of traditional chemical stripping method.And, traditional chemical stripping method process complexity, foreign ion is difficult to remove.Review the present invention, method is simple, only needs household microwave oven can realize the preparation of high quality Graphene.
Embodiment 3:
The configuration quality mark is the methyl-phenoxide solution 2L of 4% PMMA, for future use.
Get the methyl-phenoxide solution 200mL of 4% PMMA and the h-BN powder of 5g, stir after 20 minutes, place 3 hours abundant solvent flashings of insulation in 120 ℃ the baking oven, obtain the h-BN of PMMA coating.The h-BN that above-mentioned PMMA is coated packs in the silica tube of size φ 25 * 2mm.Be evacuated to 100Pa, use oxyhydrogen flame rapid heating silica tube 15 seconds.Afterwards, withdraw oxyhydrogen flame, allow silica tube be cooled fast to room temperature.Take out sample and obtain the h-BN/ graphene complex.
In order to obtain pure Graphene, on the basis of above-mentioned h-BN/ graphene complex,, place the ethanol of 800mL with the h-BN/ graphene complex 7.1g that obtains, obtain turbid solution at the power ultrasonic of 400w after 15 minutes.After under 1000 rev/mins the rotating speed centrifugal 5 minutes, can obtain pure nothing and support Graphene sample 1.7g.
The Graphene of the self-support that is obtained by present embodiment is modulated into electrocondution slurry, scrapes the film of painting 10 μ m by the method among the embodiment 1, and testing its average square resistance is 76 Ω/sq (ohms/square).
The electroconductibility of Graphene, structure and pattern characterizing method such as embodiment 1.
Embodiment 4:
The configuration quality mark is the methyl-phenoxide solution 2L of 2% PMMA, for future use.
Get the methyl-phenoxide solution 200mL of 2% PMMA and the h-BN powder of 5g, stir after 20 minutes, place 3 hours abundant solvent flashings of insulation in 120 ℃ the baking oven, obtain the h-BN of PMMA coating.The h-BN that above-mentioned PMMA is coated packs in the silica tube of size φ 25 * 2mm.Be evacuated to 100Pa, use oxyhydrogen flame rapid heating silica tube 15 seconds.Afterwards, withdraw oxyhydrogen flame, allow silica tube be cooled fast to room temperature.Take out sample and obtain the h-BN/ graphene complex.
In order to obtain pure Graphene, on the basis of above-mentioned h-BN/ graphene complex,, place the ethanol of 800mL with the h-BN/ graphene complex 6.4g that obtains, obtain turbid solution at the power ultrasonic of 400w after 15 minutes.After under 1000 rev/mins the rotating speed centrifugal 5 minutes, can obtain pure Graphene powder sample 1.1g.
The Graphene powder that is obtained by present embodiment is modulated into electrocondution slurry, scrapes the film of painting 10 μ m by the method among the embodiment 1, and testing its average square resistance is 126 Ω/sq (ohms/square).
The electroconductibility of Graphene, structure and pattern characterizing method such as embodiment 1.
Embodiment 5:
Getting massfraction is the ethanolic soln 100mL of 8% sucrose and the h-BN powder of 3g, stirs after 40 minutes, places 1 hour abundant solvent flashing of the interior insulation of baking oven of 80 ℃, obtains the h-BN that sucrose coats.The h-BN that above-mentioned sucrose is coated packs in the silica tube of size φ 25 * 2mm.Be evacuated to 100Pa, use oxyhydrogen flame rapid heating silica tube 15 seconds.Afterwards, withdraw oxyhydrogen flame, allow silica tube be cooled fast to room temperature.Take out sample and obtain the h-BN/ graphene complex.
In order to obtain pure Graphene, on the basis of above-mentioned h-BN/ graphene complex,, place the ethanol of 300mL with the h-BN/ graphene complex 4.2g that obtains, obtain turbid solution at the power ultrasonic of 300w after 10 minutes.After under 1000 rev/mins the rotating speed centrifugal 5 minutes, can obtain pure Graphene powder sample 0.76g.
The Graphene that is obtained by present embodiment is modulated into electrocondution slurry, scrapes the film of painting 10 μ m by the method among the embodiment 1, and testing its average square resistance is 154 Ω/sq (ohms/square).
The electroconductibility of Graphene, structure and pattern characterizing method such as embodiment 1.
Embodiment 6:
Getting massfraction is the aqueous solution 400mL of 6% polyvinyl alcohol (PVA) and the h-BN powder of 5g, stirs after 40 minutes, places 2 hours abundant solvent flashings of the interior insulation of baking oven of 90 ℃, obtains the h-BN that PVA coats.The h-BN that above-mentioned PVA is coated packs in the silica tube of size φ 25 * 2mm.Be evacuated to 200Pa, use oxyhydrogen flame rapid heating silica tube 60 seconds.Afterwards, withdraw oxyhydrogen flame, allow silica tube be cooled fast to room temperature.Take out sample and obtain the h-BN/ graphene complex.
In order to obtain pure Graphene, on the basis of above-mentioned h-BN/ graphene complex,, place the ethanol of 600mL with the h-BN/ graphene complex 7.3g that obtains, obtain turbid solution at the power ultrasonic of 500w after 20 minutes.After under 1000 rev/mins the rotating speed centrifugal 5 minutes, can obtain pure from Graphene powder sample 1.9g.
The Graphene that is obtained by present embodiment is modulated into electrocondution slurry, scrapes the film of painting 10 μ m by the method among the embodiment 1, and testing its average square resistance is 64 Ω sq (ohm-sq).
The electroconductibility of Graphene, structure and pattern characterizing method such as embodiment 1.
Embodiment 7:
Get massfraction and be the ethanolic soln 200mL of 20% fluorenes and the h-BN powder of 10g, stir after 60 minutes, place 2 hours abundant solvent flashings of insulation in 80 ℃ the baking oven, obtain the h-BN of fluorenes coating.The h-BN that above-mentioned fluorenes is coated packs in the silica tube of size φ 25 * 2mm.Be evacuated to 100Pa, use oxyhydrogen flame rapid heating silica tube 60 seconds.Afterwards, withdraw oxyhydrogen flame, allow silica tube be cooled fast to room temperature.Take out sample and obtain the h-BN/ graphene complex.
In order to obtain pure Graphene, on the basis of above-mentioned h-BN/ graphene complex,, place the ethanol of 1000mL with the h-BN/ graphene complex 15.9g that obtains, obtain turbid solution at the power ultrasonic of 600w after 10 minutes.After under 1000 rev/mins the rotating speed centrifugal 5 minutes, can obtain pure Graphene powder sample 5.6g.
The Graphene that is obtained by present embodiment is modulated into electrocondution slurry, scrapes the film of painting 10 μ m by the method among the embodiment 1, and testing its average square resistance is 18 Ω/sq (ohms/square).
The electroconductibility of Graphene, structure and pattern characterizing method such as embodiment 1.
Embodiment 8:
Get the methyl-phenoxide solution 200mL of 4% PMMA and the 6H-SiC powder of 8g, stir after 30 minutes, place 3 hours abundant solvent flashings of insulation in 120 ℃ the baking oven, obtain the 6H-SiC of PMMA coating.The 6H-SiC that above-mentioned PMMA is coated packs in the silica tube of size φ 25 * 2mm.Be evacuated to 100Pa, use oxyhydrogen flame rapid heating silica tube 40 seconds.Afterwards, withdraw oxyhydrogen flame, allow silica tube be cooled fast to room temperature.Take out sample and obtain the 6H-SiC/ graphene complex.
In order to obtain pure Graphene, on the basis of above-mentioned 6H-SiC/ graphene complex,, place the ethanol of 600mL with the 6H-SiC/ graphene complex 10.1g that obtains, obtain turbid solution at the power ultrasonic of 300w after 15 minutes.After under 500 rev/mins the rotating speed centrifugal 5 minutes, can obtain pure Graphene powder sample 1.7g.
The Graphene powder that is obtained by present embodiment is modulated into electrocondution slurry, scrapes the film of painting 10 μ m by the method among the embodiment 1, and testing its average square resistance is 46 Ω sq (ohm-sq).
The electroconductibility of Graphene, structure and pattern characterizing method such as embodiment 1.
Embodiment 9:
Get the methyl-phenoxide solution 200mL of 4% PMMA and the AlN powder of 5g, stir after 30 minutes, place 2 hours abundant solvent flashings of insulation in 120 ℃ the baking oven, obtain the AlN of PMMA coating.The AlN that above-mentioned PMMA is coated packs in the silica tube of size φ 25 * 2mm.Be evacuated to 100Pa, use oxyhydrogen flame rapid heating silica tube 60 seconds.Afterwards, withdraw oxyhydrogen flame, allow silica tube be cooled fast to room temperature.Take out sample and obtain the AlN/ graphene complex.
In order to obtain pure Graphene, on the basis of above-mentioned AlN/ graphene complex,, place the ethanol of 1000mL with the AlN/ graphene complex 5.9g that obtains, obtain turbid solution at the power ultrasonic of 600w after 10 minutes.After under 1000 rev/mins the rotating speed centrifugal 5 minutes, can obtain pure Graphene powder sample 0.62g.
The Graphene powder that is obtained by present embodiment is modulated into electrocondution slurry, scrapes the film of painting 10 μ m by the method among the embodiment 1, and testing its average square resistance is 141 Ω/sq (ohms/square).
The electroconductibility of Graphene, structure and pattern characterizing method such as embodiment 1.
Embodiment 10:
Get the methyl-phenoxide solution 100mL of 4% PMMA and the magnesium oxide powder of 3g, stir after 30 minutes, place 2 hours abundant solvent flashings of insulation in 120 ℃ the baking oven, obtain the MgO of PMMA coating.The MgO that above-mentioned PMMA is coated packs in the silica tube of size φ 25 * 2mm.Be evacuated to 100Pa, use oxyhydrogen flame rapid heating silica tube 30 seconds.Afterwards, withdraw oxyhydrogen flame, allow silica tube be cooled fast to room temperature.Take out sample and obtain the MgO/ graphene complex.
In order to obtain pure Graphene, on the basis of above-mentioned MgO/ graphene complex,, place the ethanol of 1000mL with the MgO/ graphene complex 3.2g that obtains, obtain turbid solution at the power ultrasonic of 200w after 10 minutes.After under 1500 rev/mins the rotating speed centrifugal 5 minutes, can obtain pure Graphene sample 0.41g.
The Graphene that is obtained by present embodiment is modulated into electrocondution slurry, scrapes the film of painting 10 μ m by the method among the embodiment 1, and testing its average square resistance is 214 Ω/sq (ohms/square).
The electroconductibility of Graphene, structure and pattern characterizing method such as embodiment 1.
Embodiment 11:
(1) preparation of Graphene transparent conductive film
Another kind of optimal way of the present invention is to prepare high-quality Graphene transparent conductive film, and its concrete grammar is as follows:
The Copper Foil of commercialization is placed 1000 ℃ tube furnace, at H
2/ Ar gas mixture (contains H
25%) insulation is 10 minutes in.This process can not only be gone back the oxidized copper of original surface, and can make the grain growth of copper, reduces crystal boundary, and this catalytic growth to Graphene is very favorable.
The methyl-phenoxide solution 100 μ L spin coatings (1500 rev/mins rotating speed, 40 seconds) of getting 4% PMMA are in 20 thick * 20mm of 25 μ m
2The Cu paper tinsel on.Place abundant solvent flashing in 120 ℃ of baking ovens, on the Cu paper tinsel, obtain the PMMA film that thickness is about 250nm after 30 minutes.
The Cu paper tinsel that above-mentioned PMMA is coated is packed in the silica tube of size φ 25 * 2mm.Be evacuated to 100Pa, use oxyhydrogen flame rapid heating silica tube 15 seconds.Afterwards, withdraw oxyhydrogen flame, allow silica tube be cooled fast to room temperature.Take out the graphene film that sample obtains growing in Cu paper tinsel surface.
(2) transfer of Graphene transparent conductive film
Be the methyl-phenoxide solution of 4% PMMA earlier, with the protection graphene film at surperficial spin coating one deck massfraction of Graphene; Subsequently, with the above-mentioned Cu paper tinsel (20 * 20mm that graphene film is arranged that obtains
2) placing the aqueous solution of the iron trichloride of 0.5mol/L, dissolving etching catalyst substrate obtains floating on the graphene film of solution surface after 60 minutes; With sheet glass with Graphene/PMMA film transfer in deionized water, remove foreign ion, repeat to guarantee for twice that foreign ion removes fully; Graphene/PMMA film transfer to sheet glass, is placed in 80 ℃ the loft drier and removes moisture; Place acetone to soak 120 minutes afterwards, finally obtain the graphene film transparent conductive film fully to remove the PMMA film.
(3) Graphene transparent conductive film photoelectric characteristic characterizes
Light transmission and electroconductibility are to characterize the quality of graphene film and the important indicator of photoelectric characteristic.We characterize the light transmission of graphene film with ultraviolet-visible-near-infrared absorption spectrum.Gained graphene film (20 * 20mm of the present invention
2) be that the light transmission of 550nm is 96.8% at wavelength, in the near infrared fluctuation nearly 99% light transmission is arranged, this explanation gained Graphene of the present invention is an individual layer.
Characterize the electric conductivity and the carrier mobility of graphene film with four probe method.Test result shows that the square resistance of the Graphene transparent conductive film that the present invention obtains is 1450 Ω/sq (ohms/square), and carrier mobility is 910cm
2v
-1s
-1, approach optimum value (～1200 Ω/sq (ohms/square)) with chemical Vapor deposition process gained Graphene.
Characterize the quality of Graphene with Raman spectrum.As shown in Figure 8, the 2D peak of gained Graphene of the present invention and strength ratio～4 at G peak, the peak width at half height at 2D peak is 30cm
-1, the 2D peak position is about 2690cm
-1, these results illustrate that the gained Graphene is an individual layer, this is consistent with the test result of light transmission; In addition, do not have tangible D peak on Raman spectrum, the strength ratio at D peak and G peak is 0.05, and being of high quality of gained Graphene of the present invention is described.
Having the present invention to obtain the high quality monolayer graphene film can be used as transparency electrode and is used for devices such as solar cell, flat pannel display.
Comparative Examples 2:
For outstanding superiority of the present invention, we prepare the Graphene transparent conductive film in contrast with traditional C VD method, and concrete steps are as follows:
The Copper Foil of commercialization is placed 1000 ℃ tube furnace, at H
2/ Ar gas mixture (contains H
2Amount is 5%) in the insulation 10 minutes.
Regulate Ar and H
2Flow, its ratio reach 300: 50 standard milliliter per minutes (sccm); Open methane CH
4, its flow is 10sccm.React after 10 minutes, stop heating.
After temperature is reduced to room temperature, take out sample, obtain the long Copper Foil that graphene film is arranged.
Transfer and characterizing method are as embodiment 12.
Same, characterize CVD method Graphene quality with Raman spectrum.As shown in Figure 8, the basically identical of the Graphene that traditional C VD method gained Raman spectrum and the present invention obtain, this Graphene quality that illustrates that this aspect obtains can be compared with traditional C VD method.But traditional C VD method required equipment complexity, the good energy of high temperature, to the preparation condition harshness, used H
2And CH
4Shortcoming such as inflammable and explosive.And device just household microwave oven involved in the present invention can be realized the preparation of Graphene transparent conductive film, and this proves absolutely superiority of the present invention.
Embodiment 13:
Another optimal way of the present invention is and can regulates Graphene thickness by selecting different substrates.
The Ni paper tinsel of commercialization is placed 1000 ℃ tube furnace, at H
2/ Ar gas mixture (contains H
25%) insulation is 10 minutes in.This process can not only be gone back the oxidized Ni of original surface, and can be the grain growth of Ni, reduces crystal boundary, helps the growth of Graphene.
The methyl-phenoxide solution 50 μ L spin coatings (1500 rev/mins rotating speed, 40 seconds) of getting 4% PMMA are in 20 thick * 20mm of 25 μ m
2The Ni paper tinsel on.Place abundant solvent flashing in 120 ℃ of baking ovens, on the Ni paper tinsel, obtain the PMMA film that thickness is about 80nm after 30 minutes.
The Ni paper tinsel that above-mentioned PMMA is coated is packed in the silica tube of size φ 25 * 2mm.Be evacuated to 200Pa, use oxyhydrogen flame rapid heating silica tube 20 seconds.Afterwards, withdraw oxyhydrogen flame, allow silica tube be cooled fast to room temperature.The taking-up sample obtains growing in the graphene film on the Ni paper tinsel.
The transfer of Graphene, electroconductibility, structure and pattern characterizing method such as embodiment 12.
With the Graphene quality after the transfer of Raman spectrum sign.As shown in Figure 8, the 2D peak of gained Graphene of the present invention and strength ratio～1.0 at G peak, the peak width at half height at 2D peak is 45cm
-1, the 2D peak position is about 2695cm
-1, these results illustrate that the gained Graphene is for double-deck; In addition, do not have tangible D peak on Raman spectrum, the strength ratio at D peak and G peak is 0.05, and being of high quality of gained Graphene of the present invention is described.
Comprehensive embodiment 12 and 13 illustrates that the present invention can obtain the graphene film of different thickness by selecting different substrates.
Table 1 is the h-BN/ Graphene content and the electric conductivity thereof of growing with different PMMA concentration on the h-BN substrate.
Table 1
As can be seen from the table, can obtain the h-BN/ graphene complex of different Graphene content in different PMMA concentration ([PMMA]), with respect to different electric conductivitys.Promptly can be by concentration content and the electroconductibility that can regulate Graphene of control PMMA.This is another advantage place of the present invention.
Claims (17)
1. the preparation method of a Graphene powder, described method comprises:
Utilize oxyhydrogen flame rapid heating decomposing organic matter, produce active atoms of carbon;
Described active atoms of carbon is reconstituted Graphene on insulating substrate or catalyst substrate, obtain the Graphene powder.
2. the preparation method of graphene powder as claimed in claim 1 is characterized in that, described method is carried out in the encloses container under the negative pressure.
3. the preparation method of graphene powder as claimed in claim 2 is characterized in that, the pressure range 100-1000Pa of described negative pressure.
4. the preparation method of graphene powder as claimed in claim 1, it is characterized in that described organism is one or more the combination in polymethylmethacrylate, polystyrene, polyoxyethylene glycol, polyvinyl alcohol, polyethylene, polypropylene, sucrose, glucose, naphthalene and the fluorenes.
5. the preparation method of graphene powder as claimed in claim 4 is characterized in that, described organism is dissolved in the solvent, forms organic solution; Described organic mass concentration is 1.0%-20%.
6. the preparation method of graphene powder as claimed in claim 1, it is characterized in that described insulating substrate is the one or more combination in hexagonal boron nitride, hexagonal carborundum, magnesium oxide, aluminium nitride, sapphire, silicon-dioxide, zinc sulphide, zinc oxide, the titanium dioxide; Described catalyst substrate is the one or more combination in copper, nickel, cobalt, the iron.
7. as the preparation method of each described graphene powder of claim 1-6, it is characterized in that described insulating substrate or catalyst substrate are scattered in the organic solution with form of powder, concentration is 10.0-80.0mg/mL.
8. as the preparation method of each described graphene powder of claim 1-6, it is characterized in that described preparation method comprises:
1) it is even to get insulating substrate or the catalyst substrate powder mixes of the organic solution 100-800mL of 1.0%-20% and 1.0-10.0g, obtains suspension;
2) step 1) gained suspension is placed in the 80-150 ℃ of baking oven insulation 0.5-4 hour, obtain powder;
3) with step 2) the gained powder packs in the silica tube, is evacuated to 100-1000Pa, with oxyhydrogen flame rapid heating silica tube 10-60 second;
4) withdraw oxyhydrogen flame, obtain to grow in the Graphene on insulating substrate or the catalyst substrate.
9. the preparation method of graphene powder as claimed in claim 8, it is characterized in that, described method also comprises: the described Graphene that grows on insulating substrate or the catalyst substrate was carried out ultrasonic 10-40 minute in power is the ultrasonic wave of 100-600w, obtain pure graphene powder.
10. the preparation method of a Graphene nesa coating, described method comprises:
Utilize oxyhydrogen flame rapid heating decomposing organic matter, produce active atoms of carbon;
Described active atoms of carbon is reconstituted Graphene on catalyst film or paillon foil substrate, obtain the Graphene nesa coating.
11. the preparation method of Graphene transparent conductive film as claimed in claim 10 is characterized in that, described method is carried out in the encloses container under the negative pressure.
12. the preparation method of Graphene transparent conductive film as claimed in claim 11 is characterized in that, the pressure range 100-1000Pa of described negative pressure.
13. the preparation method of Graphene transparent conductive film as claimed in claim 10, it is characterized in that described organism is one or more the combination in polymethylmethacrylate, polystyrene, polyoxyethylene glycol, polyvinyl alcohol, polyethylene, polypropylene, sucrose, glucose, naphthalene and the fluorenes.
14. the preparation method of Graphene transparent conductive film as claimed in claim 13 is characterized in that, described organism is dissolved in the solvent, forms organic solution; Described organic mass concentration is 1.0%-20%.
15. the preparation method of Graphene transparent conductive film as claimed in claim 10 is characterized in that, described catalyst substrate is the one or more combination in copper, nickel, cobalt, the iron.
16. the preparation method as each described Graphene transparent conductive film of claim 10-15 is characterized in that, described method comprises:
1) catalyst film substrate or catalyzer paillon foil substrate are placed atmosphere furnace, under 600-1000 ℃, at H
2Insulation is 5-30 minute in the/Ar gas mixture, wherein, and H
2Content 5-20%;
2) the organic solution 40-200 μ L that gets 1.0%-20% is spun on catalyst film substrate or the catalyzer paillon foil substrate, place the interior insulation of 80-150 ℃ of baking oven after 0.5-4 hour, on catalyst film substrate or catalyzer paillon foil substrate, form the organic thin film that thickness is about 50-400nm, obtain the substrate that organic thin film coats;
3) in the substrate that organic thin film is coated is packed silica tube into, be evacuated to 100-1000Pa, use oxyhydrogen flame rapid heating silica tube 10-30 second;
4) withdraw oxyhydrogen flame, obtain to grow in the Graphene on catalyst substrate surface; With
5) Graphene that (4) are obtained is transferred on the target substrate, obtains the Graphene transparent conductive film.
17. the preparation method of Graphene transparent conductive film as claimed in claim 16 is characterized in that, described method also comprises by selecting different catalyst substrate to control the thickness of described organic thin film.
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