CN102408107B - Method for preparing high-quality graphene - Google Patents
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- CN102408107B CN102408107B CN201010291891.2A CN201010291891A CN102408107B CN 102408107 B CN102408107 B CN 102408107B CN 201010291891 A CN201010291891 A CN 201010291891A CN 102408107 B CN102408107 B CN 102408107B
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Abstract
The invention discloses a method for preparing high-quality graphene, which is characterized by comprising the following steps of: reacting active metals with low-carbon halogenated hydrocarbons or absolute ethyl alcohols in a certain time at a certain temperature so as to generate new ecological carbon; then, restructuring the new ecological carbon so as to obtain graphene; and finally, carrying out purification on the obtained graphene so as to obtain high-quality graphene. Compared with the traditional chemical stripping method for preparing graphene, the method disclosed by the invention is simple in operation and low in cost, and can prepare less-defect, good-electroconductivity and high-quality graphene. The graphene prepared by using the method disclosed by the invention can have a broad application prospect in the fields of photoelectric devices such as CIGS (copper indium gallium selenide), CdTe(cadmium telluride) and dye sensitized solar cells and the like, flat-panel displays, super capacitors, field emission materials, lithium ion batteries, and the like.
Description
Technical field
The present invention relates to a kind of graphene preparation method, belong to materials chemistry preparing technical field.
Background technology
Graphene (graphene) is the monoatomic layer material with bi-dimensional cellular shape structure taking phenyl ring as elementary cell being made up of carbon atom, is the elementary cell that builds other dimension carbonaceous material (as zero dimension soccerballene, one dimension carbon nanotube and three-dimensional graphite).Graphene has excellent electricity, calorifics and mechanical property, and for example, Graphene has 10 times of high carrier mobilities to commercial silicon chip and (reaches 15000cm
2v
- 1s
-1), and current carrier shows the ballistic transport characteristic of obvious ambipolar field performance characteristic and room temperature submicron-scale, and high and continuously adjustable carrier concentration (can reach 10
13cm
-2); The intensity of Graphene can reach 130GPa, is more than 100 times of steel; The thermal conductivity of Graphene can reach 5000W/mK, is 3 times of pure diamond under room temperature; Graphene all has excellent perviousness etc. near infrared, visible ray and UV-light.Therefore, Graphene is expected to obtain widespread use in fields such as high-performance nanometer electronic device, matrix material, field emmision material, display device, gas sensor and stored energies.Due to its unique two-dirnentional structure and excellent crystallography quality, Graphene has contained abundant and novel physical phenomenon, and therefore, Graphene becomes rapidly chemistry, Materials science and Condensed Matter Physics field study hotspot in recent years.
At present, the application of Graphene relates generally to two fields of physics and chemistry, and physical study mainly concentrates on characteristic electron and mechanical characteristics, and chemical research mainly contains preparation, surface and chemically modified.And the large-scale application of Graphene need badly realize extensive, can repeatedly prepare smooth, even, thickness and the controlled high-quality graphene material of size.People's original adoptions such as Geim " micromechanical forces disintegrating method ", by mechanical force from graphite crystal sur-face peeling graphene sheet layer and transfer to the carrier surfaces such as silicon oxide.Although this method can be prepared the Graphene of micron size, its poor controllability, yields poorly.By heating SiC (0001) single-crystal surface extending and growing graphene structure, this Graphene supporting can directly be made electron device by photoetching process.But because reconstruct easily occurs on SiC plane of crystal surface in high-temperature heating process, cause surface tissue comparatively complicated, be difficult to obtain the Graphene of big area, thickness homogeneous.Chemical Vapor deposition process (CVD) is taking metal single crystal or Polycrystalline Metals film as substrate, expose in its surface and pyrolytic decomposition carbon compound can generate graphene-structured, but the metal substrate difficulty of growing graphene is removed.Prepare at present Graphene application maximum be chemical stripping method, by strong oxidizer graphite oxidation, form graphene oxide, then with strong reductive agent, graphene oxide is reduced into Graphene again.The strong oxidizer using in the process of chemical stripping, can destroy the carbon skeleton of Graphene plane, produces defect, causes the graphene conductive degradation of gained.Therefore, how the high-quality Graphene of preparation of simple controlled magnanimity is large difficult point and a focus of research at present.
Summary of the invention
The object of the present invention is to provide a kind of method that can preparation in macroscopic quantity high-quality graphene.The basic ideas of invention are: utilize active metal and dehydrated alcohol or low-carbon (LC) halohydrocarbons reaction to generate the carbon of nascent state, the carbon of nascent state reconstitutes Graphene.For compared with Graphene method, Graphene defect that the present invention obtains is few, good conductivity with traditional chemical stripping legal system, and simple to operate, step is few, preparation cost is very low, can preparation in macroscopic quantity.
The present invention is with one or more the combination in active metal lithium, potassium, sodium, magnesium, calcium, strontium, barium, lanthanum etc.; low-carbon (LC) halohydrocarbon is the one or more combination raw material in trichloromethane, tetracol phenixin, carbon tetrabromide, Perchlorobenzene, hexachloroethane, heptachloropropane and dehydrated alcohol; under inert atmosphere protection, adopt solvent thermal synthesizing graphite alkene.Describe the present invention below in detail.
A) Graphene is synthetic
One or more combination in the combination of one or more in active metal lithium, sodium, potassium, magnesium, calcium, strontium, barium, lanthanum and low-carbon (LC) halohydrocarbon tetracol phenixin, carbon tetrabromide, trichloromethane, Perchlorobenzene, hexachloroethane, heptachloropropane or dehydrated alcohol be raw material inert atmosphere as argon gas, nitrogen etc. in reaction, reaction times is 0.5-60 hour, temperature is 60-500 DEG C, reaction times and temperature are all different according to the kind of metal and carbon source, and the mol ratio of active metal and carbon source is 0.5-6.
Reaction vessel is the high voltage bearing closed reactor of energy, reactor will be tightened, in case the gas leakage relating in reaction process before reaction.
After contacting with halohydrocarbon, metal should be rapidly heated (within about 60min) to temperature required and be incubated 5-50h.
B) purification of Graphene
After reaction finishes, the by products such as the metal halide that contains unreacted halohydrocarbon and generation in the Graphene obtaining.Therefore, need to purify to the Graphene obtaining.
1. in the mixture first obtaining toward reaction, add a large amount of acetone, and fully stir 0.5-1h to make acetone fully dissolve halohydrocarbon.The amount of required acetone changes according to the amount of added halohydrocarbon in reaction process.
2. in filtration step mixed solution 1., obtain filter cake, and filter cake is washed out with deionized water.
3. the hydrochloric acid that is 10%-35% toward the molar fraction that adds 20-200mL in 2., is heated to 60-80 DEG C, fully stirs.The object that adds hydrochloric acid is herein the alkali metal halide in order better to remove the generation in reaction process.
4. 3. mixed solution is filtered, and with a large amount of deionized water wash.
5. vacuum-drying obtains Graphene sample, and vacuum-drying temperature is 60-100 DEG C, vacuum-drying time 6-10h.
6. step 5. gained sample ultrasonic 10-60min disperse after obtain Graphene product.
In order to characterize the feature of Graphene prepared by method provided by the invention, spy has carried out performance characterization and has prepared Graphene with chemical peeling and carry out the work of performance test:
(1) pattern of Graphene and structural characterization
Gained Graphene sample of the present invention is observed to the pattern of sample by scanning electron microscope (SEM, LEO-1530VP) and transmission electron microscope (JEM 2010); Observe surface and the thickness of graphene platelet by atomic force microscope (AFM, Japanese Seiko II SPI3800V & spa300HV type).
Characterize the structure of Graphene with Raman spectrum (Renishaw invia Raman Microscope, excitation wavelength is 514.5nm).
By each element relative content ratio and the chemical combination state thereof on x-ray photoelectron spectroscopy (XPS) analytic sample surface.Instrument is the PHI 5000C ESCA System of PHI company of the U.S.; Employing condition is magnesium target, high pressure 14.0kV, and power 250W, vacuum is better than 1 × 10
-8torr.Adopt RBD147 data collecting card and the AugerScan3.21 software full scan spectrum (logical can be 93.9eV) of 0～1200eV of collected specimens respectively of RBD company of the U.S., then gather the narrow scan spectrum (logical can be 23.5eV) of each element related track, and adopt AugerScan3.21 software to carry out data analysis.Carrying out combination can proofread and correct taking C1s=284.6eV as benchmark.
Characterize the electric property of Graphene with electrochemical workstation (CHI 660B) test cross flow impedance.
Its electroconductibility that compares of preparing by Graphene of the present invention and chemical stripping method (being Hummers method).
(2) chemical stripping legal system is for Graphene
Prepare the electroconductibility of Graphene for contrasting the present invention, prepare graphene oxide by Hummers method, obtain graphite oxide with the vitriol oil, SODIUMNITRATE and potassium permanganate oxidation flake graphite, obtain graphene oxide [W.S.Hummers, etc.J.Am.Chem.Soc. (1958) 1339] with ultrasonic peeling off again.Carry out redox graphene by the method for high temperature pyrolysis afterwards.As accompanying drawing 7[D.Li, etc.Nature Nanotech.3 (2008) 101-105.] (referring to embodiment 1).
The present invention has simple to operate, with low cost, can obtain that defect is few, good conductivity, Graphene that quality is high.The Graphene that the present invention prepares can, at photoelectric device as solar cells such as copper-indium-galliun-selenium, cadmium telluride, dye sensitizations, have broad application prospects in the fields such as flat pannel display, ultracapacitor, field emmision material, lithium ion battery.
Brief description of the drawings
The stereoscan photograph of Fig. 1 Graphene is as can be seen from the figure to spend the same sheet structure.
Fig. 2 atomic force microscope (AFM) figure, the structure that Fig. 2 (a) is large stretch of Graphene, its size, between 15-20 μ m, can find out that from Fig. 2 (b) its thickness of Graphene obtaining is 0.8nm left and right, is single-layer graphene.
Fig. 3 transmission electron microscope photo, from figure (a) (c) the known sample obtaining be sheet structure, Fig. 3 (b) is high-resolution electron microscopy photo, therefrom can find out the Graphene number of plies n < 3 obtaining.
Fig. 4 Raman spectrum, the Raman spectrogram of the Graphene that Fig. 4 (a) chemical stripping method obtains, ratio IG/ID～1.1 of G peak and D peak intensity.The Raman spectrogram that figure (b) is the Graphene that obtains for the present invention.
Fig. 5 is the narrow scan spectrum of carbon 1s track.
The alternating-current impedance figure that the Graphene that Fig. 6 the present invention obtains and the Graphene obtaining by chemical stripping method contrast.The Graphene alternating-current impedance curve that curve 1 obtains for chemical stripping, the 2 Graphene alternating-current impedance curves that make for the present invention.
Fig. 7 diagram Hummer legal system is for graphene oxide and be further reduced to Graphene.
Embodiment
Introduce embodiments of the invention below, further to increase understanding of the present invention, but the present invention is limited to absolutely not embodiment.
Embodiment 1:
Synthesizing of Graphene
In kerosene, take out potassium metal, put into the glove box of anhydrous and oxygen-free (containing H
2o < 0.1ppm, O
2< 0.1ppm) in, to use after facilitating.In glove box, get the potassium of 2.0g, that puts into volume and be 30mL has a teflon-lined stainless steel cauldron, adds the tetracol phenixin of 10mL.Tighten rapidly sealing.Reactor is put into baking oven, in 60min, be warming up to rapidly 120 DEG C, insulation 8h.
The purifying of Graphene
After reaction finishes, naturally cool to room temperature.Open reactor, add the acetone of 100mL toward inside liner, reaction product is all washed out to 200mL beaker, fully stir 30min.Filter.Filter cake is washed out with deionized water, add 10% the hydrochloric acid soln of 100mL, be heated to 60 DEG C, fully stir 30min.Filter, and with the deionized water wash of about 1L, fully to remove the by product Repone K producing in reaction process.By the product obtaining vacuum-drying 8h at 80 DEG C, and obtain Graphene product 1.2g through the ultrasonic dispersion of 30min.
The pattern of Graphene and structural characterization
What can obtain Graphene sample from SEM and TEM characterization result (respectively as shown in accompanying drawing 1 and 3) is sheet structure.After ultrasonic 40min, characterize its thickness with AFM (as shown in Figure 2), be about 0.8nm, be single-layer graphene.Raman spectrum is one of effective means characterizing Graphene quality, and high-quality Graphene has very strong G peak and 2D peak and has weak D peak.As can be known from Fig. 4, the Graphene that the present invention obtains has the feature of high-quality graphene, and the Graphene obtaining with chemical stripping has very strong D peak, illustrates that Graphene quality that the present invention obtains obtains far above traditional chemical stripping method.The Graphene that known the present invention obtains from the narrow spectrum scanning of C (1s) (accompanying drawing 5) of XPS is to be reconstituted and formed by the carbon of nascent state.
The sign of chemical property
We characterize the conductivity of product by test alternating-current impedance.For making alternating-current impedance working electrode, we are uniformly mixed graphene powder and N-Methyl pyrrolidone (NMP) to become the homogeneous of 50mg/ml slurry, are coated on and produce isolation region (1cm with adhesive tape with glass stick
2) conductive glass FTO (15 Ω/square) upper, drying and forming thickness is the film of 4 μ m, starches and draws wire with silver.Test is when EIS, and taking Pt electrode as to electrode, saturated calomel electrode (SCE) is reference electrode, with the K of the 10mmol/L in the KCl solution of 0.1mol/L
3[Fe (CN)
6]/K
4[Fe (CN)
6] (1: 1) be redox probe, perturbation condition is 5mV, 100mHz～100KHz.
Chemical stripping legal system is for the preparation of Graphene
The excellent electroconductibility of the Graphene preparing for outstanding the present invention, the application also uses chemical stripping legal system for Graphene, i.e. Hummers method, its preparating mechanism is as shown in Figure 7.Preparation process comprises following four steps:
The first step, gets the flake graphite of 1.0g, the SODIUMNITRATE (NaNO of 1g
3) and the vitriol oil of 46ml in ice bath, stir 15min, add slowly the potassium permanganate (KMnO of 6g
4).After mixing, system is transferred in the water-bath of 35 ± 5 DEG C, stirred 6 hours, form the mixture of the mud sample of black.
Second step, under agitation condition, toward the deionized water that adds 20ml in mixture, system temperature is raised to 90 ± 5 DEG C.After 30min, add the water dilution of 200ml.Add the H of 6ml
2o
2(30%) reduce excessive KMnO
4, system color is glassy yellow by brown stain.
The 3rd step, by solution filter obtained above, and washs with a large amount of water (being about 2L).The filter cake obtaining is dispersed in deionized water again, ultrasonic dispersion 20min.With first centrifugal 5min under low speed 1000rpm of whizzer, to remove the graphite not reacting completely, after remove the water in graphene oxide at high speed 12000rpm.After 100 DEG C of dry 8h of vacuum, obtain graphene oxide again.
The 4th step, by the graphene oxide obtaining at H
2/ Ar is (containing 5% H
2) be heated to 1000 DEG C in gas mixture, insulation 6h, reduction obtains Graphene.
Can find out the ratio I with G peak intensity the standby Graphene of chemical stripping legal system from Fig. 4 (a)
g/ I
d～1.1; And the Raman spectrogram of the Graphene of preparing from Fig. 4 (b) the present invention can be found out G peak position～1580cm
-1, the position～2700cm at 2D peak
-1, G peak is obviously better than D peak (～1350cm
-1), intensity ratio IG/ID～2.5, illustrate that the Graphene defect being obtained by the present invention is few.
As can be seen from Figure 5, it is in conjunction with being 284.5eV, and this can be consistent with the combination of carbon atom in Graphene.What can further prove thus that the present invention obtains is Graphene.
From Fig. 6 alternating-current impedance figure, wherein 1 Graphene obtaining for chemical stripping method, the alternating-current impedance figure of 2 Graphenes that obtain for the present invention.Region corresponding to semicircle in figure be corresponding to the alternating-current impedance of Graphene sample, and this resistance that shows the Graphene that the present invention obtains is less than the Graphene that chemical stripping method obtains, and illustrates that the Graphene defect that the present invention obtains is few, quality is high.
Embodiment 2:
In glove box, get the carbon tetrabromide (CBr of 4.5g
4) be dissolved in the benzene of 20mL, put into the polytetrafluoroethyllining lining that volume is 30mL, get the potassium of 2.0g.Put into rapidly stainless steel cauldron, tighten sealing.Reactor is put into baking oven, in 60min, be warming up to rapidly 160 DEG C, insulation 12h.
Edulcoration purification and electrochemical property test process are as embodiment 1.
Embodiment 3:
In glove box, get the trichloromethane of 8mL, put into the polytetrafluoroethyllining lining that volume is 30mL, get the potassium of 2.0g.Put into rapidly stainless steel cauldron, tighten sealing.Reactor is put into baking oven, be warming up to rapidly 60 DEG C, insulation 10h.
Edulcoration purification and electrochemical property test process are as embodiment 1.
Embodiment 4:
In glove box, get the sodium of 2.0g and the carbon tetrabromide of 4.5g, put into the polytetrafluoroethyllining lining that volume is 30mL.Put into rapidly stainless steel cauldron, tighten sealing.Reactor is put into baking oven, in 60min, be warming up to rapidly 250 DEG C, insulation 60h.
Edulcoration purification and electrochemical property test process are as embodiment 1.
Embodiment 5
Potassium in embodiment 1 changes calcium into, and difference is that temperature of reaction is 160 DEG C, and the reaction times is 12h.Edulcoration purification and electrochemical property test process are as embodiment 1.
Embodiment 6
Potassium in embodiment 2 changes calcium into, and difference is that temperature of reaction is 200 DEG C, and the time is 12h.Purifying to product and electrochemical property test process are as embodiment 1.
Embodiment 7
In glove box, get potassium and the 1.5g sodium of 1.0g, that puts into volume and be 30mL has a teflon-lined stainless steel cauldron, adds the tetracol phenixin of 10mL.Tighten rapidly sealing.Reactor is put into baking oven, in 60min, be warming up to rapidly 140 DEG C, insulation 10h.
Edulcoration purification and electrochemical property test process are as embodiment 1.
Embodiment 8
In glove box, get the potassium of 2.0g, that puts into volume and be 30mL has a teflon-lined stainless steel cauldron, adds 5.0mL to be dissolved with the carbon tetrachloride solution of the carbon tetrabromide of 3.0g.Tighten rapidly sealing.Reactor is put into baking oven, in 60min, be warming up to rapidly 180 DEG C, insulation 18h.
Edulcoration purification and electrochemical property test process are as embodiment 1.
Embodiment 9
In glove box, get potassium and the 1.0g sodium of 1.5g, that puts into volume and be 30mL has a teflon-lined stainless steel cauldron, adds 5.0mL to be dissolved with the carbon tetrachloride solution of the carbon tetrabromide of 2.0g.Tighten rapidly sealing.Reactor is put into baking oven, in 60min, be warming up to rapidly 200 DEG C, insulation 24h.
Edulcoration purification and electrochemical property test process are as embodiment 1.
Embodiment 10
In glove box, get the lithium of 1.5g, put into the stainless steel cauldron that volume is 30mL, add the carbon tetrachloride solution of 5.0mL.Tighten rapidly sealing.Reactor is put into retort furnace, in 100min, be warming up to 400 DEG C, insulation 8h.
Edulcoration purification and electrochemical property test process are as embodiment 1.
Embodiment 11
In glove box, get the potassium of 2.0g, put into the stainless steel cauldron that volume is 30mL, add the Perchlorobenzene of 4.0g.Tighten rapidly sealing.Reactor is put into retort furnace, in 100min, be warming up to rapidly 400 DEG C, insulation 14h.
Edulcoration purification and electrochemical property test process are as embodiment 1.
Embodiment 12
Get the Perchlorobenzene (C of 2.5g
6cl
6) be dissolved in the benzene of 20mL, transfer in 30mL stainless steel cauldron the past potassium metal that wherein adds 2.5g in glove box.Reactor is put into retort furnace, in 100min, be warming up to rapidly 350 DEG C, insulation 8h.
Edulcoration purification and electrochemical property test process are as embodiment 1.
Embodiment 13
In glove box, get the sodium of 2.0g, put into the stainless steel cauldron that volume is 30mL, add the dehydrated alcohol of 5mL.Tighten rapidly sealing.Reactor is put into retort furnace, in 60min, be warming up to rapidly 300 DEG C, insulation 60h.
Edulcoration purification and electrochemical property test process are as embodiment 1.
Embodiment 14
In glove box, get 1.0g magnesium powder, put into the stainless steel cauldron that volume is 30mL, add the dehydrated alcohol of 10mL.Tighten rapidly sealing.Reactor is put into retort furnace, in 100min, be warming up to rapidly 500 DEG C, insulation 12h.
Edulcoration purification and electrochemical property test process are as embodiment 1.
Embodiment 15
In glove box, get 2.0g magnesium powder, put into the stainless steel cauldron that volume is 30mL, add the tetracol phenixin of 4.5mL.Tighten rapidly sealing.Reactor is put into retort furnace, in 60min, be warming up to rapidly 500 DEG C, insulation 16h.
Edulcoration purification and electrochemical property test process are as embodiment 1.
Embodiment 16
Get the hexachloroethane (C of 0.6g
2cl
6) be dissolved in the benzene of 20mL, transfer in 30mL stainless steel cauldron the past barium metal that wherein adds 2.0g in glove box.Reactor is put into retort furnace, in 60min, be warming up to rapidly 100 DEG C, insulation 3h.
Edulcoration purification and electrochemical property test process are as embodiment 1.
Embodiment 17
Get the heptachloropropane (C of 1.0g
3hCl
7) be dissolved in the CCl of 15mL
4in, transfer in the stainless steel cauldron of 30mL the past lanthanum that wherein adds 2.8g in glove box.Reactor is put into rapidly to the retort furnace that has been warming up to 500 DEG C, insulation 0.5h.
Edulcoration purification and electrochemical property test process are as embodiment 1.
Embodiment 18:
In kerosene, take out sodium Metal 99.5, after with filter paper, kerosene being blotted, put into glove box, for future use.In glove box, get the sodium of 2.0g, put into the polytetrafluoroethyllining lining that volume is 30mL, add the tetracol phenixin of 5mL.Put into rapidly stainless steel cauldron, tighten sealing.Reactor is put into baking oven, in 60min, be warming up to rapidly 300 DEG C, insulation 48h.
Edulcoration purification and electrochemical property test process are as embodiment 1.
Claims (3)
1. a preparation method for Graphene, is characterized in that the large step of purification two of the synthetic and synthetic Graphene of point Graphene:
A) Graphene is synthetic
1. one or more combination or the dehydrated alcohol in the combination of one or more in active metal lithium, sodium, potassium, magnesium, calcium, strontium, barium, lanthanum and low-carbon (LC) halohydrocarbon tetracol phenixin, carbon tetrabromide, trichloromethane, Perchlorobenzene, hexachloroethane, heptachloropropane is raw material, in argon gas or nitrogen inert atmosphere, react, temperature is 60-500 DEG C, and reaction times and temperature are all different according to the kind of metal and carbon source;
2. reaction vessel is high voltage bearing closed reactor, before reaction, reactor is tightened, in case the gas leakage relating in reaction process; After contacting with halohydrocarbon, metal is rapidly heated to temperature required and insulation;
B) purification of synthetic Graphene
1. in the mixture first obtaining toward reactions steps a, add a large amount of acetone, and fully stir 0.5-1h to make acetone fully dissolve unreacted low-carbon (LC) halohydrocarbon; The amount of required acetone changes according to the amount of added halohydrocarbon in reaction process;
2. filtration step mixed solution 1. obtains filter cake, and filter cake is washed out with deionized water;
3. the hydrochloric acid that the molar fraction that adds 20-200mL toward step in is 2. 10%-35%, is heated to 60-80 DEG C, stirs, to remove the alkali metal halide of the generation in reaction process;
4. mixed solution 3. of step is filtered, and with deionized water wash;
5. vacuum-drying obtains Graphene, and vacuum-drying temperature is 60-100 DEG C;
6. by step 5. the Graphene of gained make Graphene through ultrasonic dispersion.
2. by method claimed in claim 1, it is characterized in that in Graphene synthesis step:
A) the step reaction times is 1. 0.5-60 hour;
B) step 2. in the time of being rapidly heated be in 60min;
C) to be warming up to temperature required soaking time in be 2. 5-50 hour to step.
3. by method claimed in claim 2, it is characterized in that in the purification step of Graphene:
A) the 3. middle time 0.5-1h stirring of step;
B) 5. the middle vacuum-drying time is 6-10 hour to step;
C) step 6. in ultrasonic jitter time be 10-60min.
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| CN110422839B (en) * | 2019-08-07 | 2021-03-16 | 清华大学 | Synthetic method of graphene |
| CN112993075B (en) * | 2021-02-07 | 2022-08-16 | 西安交通大学 | Intercalated graphene/silicon Schottky junction photoelectric detector and preparation process thereof |
| CN114572969B (en) * | 2022-02-11 | 2023-08-18 | 中国科学技术大学先进技术研究院 | Microfluidic reaction system and method for preparing reduced graphene oxide |
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| CN101285175A (en) * | 2008-05-29 | 2008-10-15 | 中国科学院化学研究所 | Process for preparing graphenes by chemical vapour deposition method |
| CN101462719A (en) * | 2009-01-16 | 2009-06-24 | 北京大学 | Preparation of graphene |
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| CN101462719A (en) * | 2009-01-16 | 2009-06-24 | 北京大学 | Preparation of graphene |
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