CN104261394A - Preparation method of graphene - Google Patents
Preparation method of graphene Download PDFInfo
- Publication number
- CN104261394A CN104261394A CN201410499792.1A CN201410499792A CN104261394A CN 104261394 A CN104261394 A CN 104261394A CN 201410499792 A CN201410499792 A CN 201410499792A CN 104261394 A CN104261394 A CN 104261394A
- Authority
- CN
- China
- Prior art keywords
- graphene
- preparation
- carbonate
- graphite
- tensio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention relates to a preparation method of graphene. The preparation method comprises the following steps: adding a surfactant into a carbonate solvent to prepare a solution containing the surfactant; adding graphite to the solution containing the surfactant, carrying out ultrasonic stripping and centrifuging to obtain a supernatant containing graphene; carrying out heat preservation on the supernatant containing graphene at 80 DEG C-100 DEG C for 0.5 hour-1 hour, filtering and drying to obtain crude graphene powder; and carrying out heat preservation on crude graphene powder at 200 DEG C-300 DEG C in a protective gas atmosphere for 0.5 hour-1 hour to obtain graphene powder, wherein the surfactant is selected from at least one of tetramethyl ammonium hydrogen carbonate, tetraethyl l ammonium hydrogen carbonate, tetrabutyl l ammonium hydrogen carbonate, dodecyl tetramethyl guanidine carbonate and hexadecyl tetramethyl guanidine carbonate. By adopting the preparation method, residues of the surfactant and the solvent are prevented, residues of the auxiliary stripping agent and the solvent are less, the size of the lamella of graphene is 3mu m-50mu m which is relatively large.
Description
Technical field
The present invention relates to technical field of graphene, particularly relate to a kind of preparation method of Graphene.
Background technology
Graphene has fabulous electroconductibility and thermal conductivity, and has fabulous intensity and high surface-area.Moreover, the energy band structure of its uniqueness also given by the special construction of Graphene, makes it have the specific conductivity that perfect tunneling effect and half integral quantum hall effect and it never disappear.The performance of these uniquenesses makes Graphene in material and electronic circuit etc., have great application prospect.Therefore, great demand is had to a large amount of preparations of Graphene.
The preparation method of traditional Graphene can be divided into two kinds, is Physical and chemical method respectively.The Graphene proterties that Physical and chemical method obtain is different.Have mechanical stripping method, arc discharge method, ultrasonic dispersion etc. in Physical, the graphene sheet layer obtained is more complete, but the too low and unstable product quality of mechanically peel method productive rate; Arc discharge method needs special equipment, and high cost; The existence of ultrasonic disperse rule helps stripper or solvent can carry out stronger absorption with Graphene, is difficult to be separated Graphene and help stripper, or is difficult to be separated Graphene and solvent, thus reduces the problem of the performance of Graphene.Chemical method can be divided into organic synthesis method, oxidation reduction process, solvent-thermal method and chemical Vapor deposition process from bottom to top several.Wherein, organic synthesis method is strict to equipment and ingredient requirement, is difficult to volume production; Solvent-thermal method cannot stabilized product quality, and average quality is poor; The high cost of chemical Vapor deposition process, and cannot large-scale production.On the graphene sheet layer that oxidation reduction process obtains, defect is many, thus the excellent properties of Graphene cannot be showed fully.Therefore, no matter be any preparation method, all cannot complete the target that the volume production of Graphene and high-quality coexist fully, thus make Graphene technology and goods slowly can not get the popularization of the marketization.
In the preparation method of above-mentioned Graphene for the control of graphene sheet layer size often override be considered.The lamella of Graphene is larger, and the contact resistance of its sheet interlayer is less.In addition on the one hand, the lamella of Graphene is larger, and its non-void ratio surface-area is larger, in the field such as lithium ion battery, sea water desaltination, also more can give play to its value.In addition, the Graphene of large lamella also can better carry out compound by other material of load, obtains the matrix material of excellent performance.Therefore, several stripping means that can keep graphene sheet layer and structure in Physical, if can solve the problem being difficult to be separated and helping stripper, just well can push the Graphene of large lamella to Application Areas.
Summary of the invention
Based on this, be necessary the preparation method that a kind of Graphene is provided, help stripper and dissolvent residual is less, the larger-size Graphene of lamella to prepare.
A preparation method for Graphene, comprises the steps:
Tensio-active agent is added in carbonate-based solvent, the solution of preparation containing tensio-active agent, wherein, described tensio-active agent is selected from least one in tetramethyl ammonium hydrogen carbonate, tetraethyl-bicarbonate of ammonia, tetrabutyl bicarbonate of ammonia, dodecyl tetramethyl-Guanidinium carbonate and cetyl tetramethylammonium Guanidinium carbonate;
Graphite is added described containing in the solution of tensio-active agent, centrifugal after carrying out ultrasonic stripping, obtain the supernatant liquor containing Graphene;
The described supernatant liquor containing Graphene is incubated 0.5h ~ 1h at 80 DEG C ~ 100 DEG C, and then filtration, drying, obtain graphene powder crude product; And
In shielding gas atmosphere, described graphene powder crude product is incubated 0.5h ~ 1h at 200 DEG C ~ 300 DEG C, obtains graphene powder.
Wherein in an embodiment, described containing in the solution of tensio-active agent, the mass percent concentration of described tensio-active agent is 4% ~ 15%.
Wherein in an embodiment, described carbonate-based solvent is selected from least one in propylene carbonate, Methyl ethyl carbonate, diethyl carbonate, methylcarbonate and diphenyl carbonate.
Wherein in an embodiment, the concentration of described graphite in the described solution contained in tensio-active agent is 0.1mg/L ~ 1mg/L.
Wherein in an embodiment, the power of described ultrasonic stripping is 300W ~ 800W, and the time of ultrasonic stripping is 2h ~ 4h.
Wherein in an embodiment, described centrifugal speed is 3000rpm ~ 4000rpm, and the centrifugal time is 3min ~ 5min.
Wherein in an embodiment, described graphite is expanded graphite.
Wherein in an embodiment, described expanded graphite is prepared as follows:
Added by crystalline flake graphite in the mixing acid of nitric acid and phosphoric acid, heating in water bath to 40 DEG C after stirring ~ 60 DEG C, then adds oxygenant, then in 70 DEG C ~ 85 DEG C heating in water bath to 1h ~ 2h, obtains reactant;
In described reactant, add deionized water, stir and obtain suspension liquid, by centrifugal for described suspension liquid, get precipitation, washing, drying, obtain expandable sulfur-free graphite; And
In shielding gas atmosphere, by described expandable sulfur-free graphite in 800 DEG C ~ 950 DEG C expansion 10s ~ 15s, obtain described expanded graphite.
Wherein in an embodiment, described oxygenant is selected from least one in chloric acid, nitric acid, sulfuric acid, persulphate, permanganate, oxymuriate and perchlorate.
Wherein in an embodiment, the volume ratio of described nitric acid and phosphoric acid is 1:2 ~ 5, and the concentration of described crystalline flake graphite in described mixing acid is 0.1g/mL ~ 0.2g/mL.
The preparation method of above-mentioned Graphene is by using the labile alkylammonium salt containing bicarbonate radical or guanidine as tensio-active agent, and use labile carbonate-based solvent as the solvent of tensio-active agent, effectively prevent remaining surface promoting agent and solvent on graphene sheet layer, namely help the residual less of stripper and solvent on graphene sheet layer, maintain the background performance of Graphene preferably.
Further, our experiments show that, the lamella of the preparation-obtained Graphene of preparation method of above-mentioned Graphene is of a size of 3 μm ~ 50 μm, and lamella size is larger.
Accompanying drawing explanation
Fig. 1 is the schema of the preparation method of the Graphene of an embodiment;
Fig. 2 is atomic force microscope (AFM) figure of the graphene powder of embodiment 1;
Fig. 3 is atomic force microscope (AFM) figure of the graphene powder of embodiment 2.
Embodiment
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail the specific embodiment of the present invention below in conjunction with accompanying drawing.Set forth a lot of detail in the following description so that fully understand the present invention.But the present invention can be much different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar improvement when intension of the present invention, therefore the present invention is by the restriction of following public concrete enforcement.
Refer to Fig. 1, the preparation method of the Graphene of an embodiment, comprise the steps 110 to step 140.
Step 110: tensio-active agent is added in carbonate-based solvent, the solution of preparation containing tensio-active agent, wherein, tensio-active agent is selected from least one in tetramethyl ammonium hydrogen carbonate, tetraethyl-bicarbonate of ammonia, tetrabutyl bicarbonate of ammonia, dodecyl tetramethyl-Guanidinium carbonate and cetyl tetramethylammonium Guanidinium carbonate.
Carbonate-based solvent as the solvent of tensio-active agent, also as the dispersion agent of Graphene.Tensio-active agent helps stripper as what prepare Graphene, is conducive to the stability maintaining graphene dispersion, avoids Graphene to reunite.
Above-mentioned tensio-active agent easily decomposes, the tensio-active agent of removing Graphene absorption of comparatively can changing places in subsequent step, to make on Graphene residual to help stripper less.Preferably, above-mentioned tensio-active agent is selected from least one in tetrabutyl bicarbonate of ammonia, tetramethyl ammonium hydrogen carbonate and dodecyl tetramethyl-Guanidinium carbonate.
Carbonate-based solvent easily decomposes, and follow-uply can more easily remove.Preferably, carbonate-based solvent is selected from least one in propylene carbonate, Methyl ethyl carbonate, diethyl carbonate, methylcarbonate and diphenyl carbonate.
Added by tensio-active agent in carbonate-based solvent, ultrasonic agitation makes tensio-active agent and carbonate-based solvent complete miscibility, prepares the solution obtained containing tensio-active agent.The power of ultrasonic agitation is preferably 180w ~ 320w, and the time of ultrasonic agitation is 1h ~ 3h.
Preferably, containing in the solution of tensio-active agent, the mass percent concentration of tensio-active agent is 4% ~ 15%.
Step 120: graphite is added in the solution containing tensio-active agent, centrifugal after carrying out ultrasonic stripping, obtain the supernatant liquor containing Graphene.
Preferably, graphite is expanded graphite.Use expanded graphite to peel off as graphitic source, be conducive to the large size ensureing graphene sheet layer.
Preferably, step 120 expanded graphite used is prepared as follows, and the method comprises the steps 210 to step 230:
Step 210: added by crystalline flake graphite in the mixing acid of nitric acid and phosphoric acid, heating in water bath to 40 DEG C after stirring ~ 60 DEG C, then adds oxygenant, then in 70 DEG C ~ 85 DEG C heating in water bath to 1h ~ 2h, obtains reactant.
Preferably, the volume ratio of nitric acid and phosphoric acid is 1:2 ~ 5.The concentration of crystalline flake graphite in mixing acid is 0.1g/mL ~ 0.2g/mL.Wherein, nitric acid to be mass percent concentration be 68% nitric acid.
Before the step of mixing acid crystalline flake graphite being added nitric acid and phosphoric acid, also comprise crystalline flake graphite carried out wash, dry, the step pulverizing and sieve, to obtain the thinner crystalline flake graphite of cleaning, granularity.Preferably, sieve as crossing 200 mesh sieves.
The speed stirred is preferably 180rpm ~ 300rpm, and churning time is 1h ~ 5h.
Oxygenant is selected from least one in chloric acid, nitric acid, sulfuric acid, persulphate, permanganate, oxymuriate and perchlorate.Wherein, the mass percent concentration of chloric acid is preferably 10%, and the mass percent concentration of nitric acid is preferably 90% ~ 95%, and the mass percent concentration of sulfuric acid is preferably 120%.Persulphate can be Sodium Persulfate, Potassium Persulphate, ammonium persulphate etc., and permanganate can potassium permanganate, sodium permanganate, high manganese lithium etc., and oxymuriate can Potcrate, sodium chlorate etc., and perchlorate can be sodium perchlorate etc.
The mass ratio of crystalline flake graphite and oxygenant is preferably 1:0.3 ~ 1.
Step 220: add deionized water in reactant, stirs and obtains suspension liquid, and suspension liquid is centrifugal, gets precipitation, and washing, drying, obtain expandable sulfur-free graphite.
The volume ratio of reactant and deionized water is 1:10 ~ 20.The speed stirred is preferably 180rpm ~ 300rpm, and churning time is 1h ~ 5h.Centrifugal speed is 3000rpm ~ 4000rpm, and the centrifugal time is 0.1h ~ 0.5h.
With deionized water, centrifugal gained being precipitated the pH value being washed till elutant is 5 ~ 6.Dry temperature is preferably 60 DEG C ~ 70 DEG C.
Step 230: in shielding gas atmosphere, by expandable sulfur-free graphite in 800 DEG C ~ 950 DEG C expansion 10s ~ 15s, obtains expanded graphite.
Shielding gas can nitrogen or rare gas element.
Use the expanded graphite for preparing of aforesaid method can ensure follow-uply to obtain the larger-size Graphene of lamella.Further, the defect of the expanded graphite that aforesaid method prepares is few, structural integrity.This expanded graphite is used to prepare Graphene as graphitic source, effectively can keep the electronic structure of Graphene, thus make the Graphene obtained have good activity, material and electronic circuit field can be widely used in, particularly be applied in electrochemical catalysis and battery.
Further, the sheet number of plies of the Graphene that the expanded graphite using aforesaid method to prepare prepares as raw material is less, and the sheet number of plies of the Graphene directly using crystalline flake graphite to prepare as raw material is larger.
Preferably, graphite is being 0.1mg/L ~ 1mg/L containing the concentration in the solution of tensio-active agent.
The power of ultrasonic stripping is preferably 300W ~ 800W, and the time of ultrasonic stripping is preferably 2h ~ 4h.
Centrifugal speed is preferably 3000rpm ~ 4000rpm, and the centrifugal time is preferably 3min ~ 5min.
Step 130: the supernatant liquor containing Graphene is incubated 0.5h ~ 1h at 80 DEG C ~ 100 DEG C, then filtration, drying, obtain graphene powder crude product.
Adopt millipore filtration to filter, then at 30 DEG C ~ 50 DEG C, obtain graphene powder crude product after vacuum-drying.
Supernatant liquor containing Graphene is incubated 0.5h ~ 1h at 80 DEG C ~ 100 DEG C, makes Graphene and tensio-active agent coagulation, be easy to filter.
Step 140: in shielding gas atmosphere, is incubated 0.5h ~ 1h by graphene powder crude product, obtains graphene powder at 200 DEG C ~ 300 DEG C.
Shielding gas is nitrogen or rare gas element.
Graphene powder crude product is incubated 0.5h ~ 1h at 200 DEG C ~ 300 DEG C, to remove the tensio-active agent and carbonate-based solvent that adsorb in graphene powder crude product.Part tensio-active agent is removed in step 130, and unnecessary tensio-active agent transfers gas in step 140, thus is again opened by graphene sheet layer.Therefore, step 140 can not only remove unnecessary tensio-active agent completely, and also the thickness of graphene sheet layer does not also disturb.
Preferably, after being incubated 0.5h ~ 1h, also comprise the step of carrying out ball milling and screening at 200 DEG C ~ 300 DEG C, after ball milling and screening, the lower thickness of Graphene, is conducive to preparing the less Graphene of the number of plies.
The preparation method of above-mentioned Graphene is by using the labile alkylammonium salt containing bicarbonate radical or guanidine as tensio-active agent, and use labile carbonate-based solvent as the solvent of tensio-active agent, effectively prevent remaining surface promoting agent and solvent on graphene sheet layer, namely the residual less of stripper and solvent is helped on graphene sheet layer, covalent modification can not be produced to Graphene, maintain the background performance of Graphene preferably.
Further, our experiments show that, the lamella of the preparation-obtained Graphene of preparation method of above-mentioned Graphene is of a size of 3 μm ~ 50 μm, and lamella size is larger.
The sheet number of plies of Graphene prepared by traditional ultrasonic stripping method is generally on the high side, be often 5 ~ 8 layers even close to thin layer graphite and nano graphite flakes, the excellent specific property that the electronic structure that can not show single-layer graphene brings, prepares the quality comparatively end of Graphene.And the thickness of Graphene prepared by the preparation method of above-mentioned Graphene is 0.5nm ~ 1.1nm, the number of plies is 1 ~ 3 layer, and the number of plies is less, the excellent specific property that the electronic structure that can show single-layer graphene preferably brings, and quality is higher.
Preparation method's technique of above-mentioned Graphene is simple, low for equipment requirements, is conducive to carrying out large-scale industry preparation.
Below by way of specific embodiment, the preparation method to above-mentioned Graphene sets forth further.
Embodiment 1
1, tetramethyl ammonium hydrogen carbonate adds in propylene carbonate, ultrasonic agitation 3h under the ultrasonic power of 180w, make tetramethyl ammonium hydrogen carbonate and propylene carbonate miscible, prepare the solution that obtains containing tensio-active agent, wherein, the mass percent concentration of tetramethyl ammonium hydrogen carbonate is 4%.
2, crystalline flake graphite is washed, dry, pulverize and cross 200 mesh sieve process, crystalline flake graphite after process is added in the mixing acid of nitric acid and phosphoric acid 1:2 mixing by volume, the concentration of crystalline flake graphite in mixing acid is 0.1mg/L, 5h is stirred to be stirred by the mixture of crystalline flake graphite and mixing acid with the speed of 180rpm, wherein the mass percent concentration of above-mentioned nitric acid is 68%, further heating in water bath to 40 DEG C, then the nitric acid that mass percent concentration is 95% is added, again in 70 DEG C of heating in water bath to 2h, obtain reactant, wherein, the mass ratio of crystalline flake graphite and nitric acid is 1:0.3, deionized water is added in this reactant, wherein, the volume ratio of reactant and deionized water is 1:20, suspension liquid is obtained with the mixture 5h of the speed reaction stirred of 180rpm and deionized water, by suspension liquid centrifugal 0.5h under 4000rpm, getting precipitation, is 5 by the pH value that gained precipitation is washed till elutant by deionized water, and in 60 DEG C of dryings, obtain expandable sulfur-free graphite, in nitrogen atmosphere, expand expandable sulfur-free graphite at 800 DEG C 15s, obtains expanded graphite.
3, expanded graphite is added in the above-mentioned solution containing tensio-active agent, the concentration of expanded graphite is 0.1mg/L, expanded graphite and the mixture containing tensio-active agent are carried out ultrasonic stripping 4h under the power of 300W, then with the centrifugal 5min of the speed of 3000rpm, the supernatant liquor containing Graphene is obtained.
4, the supernatant liquor containing Graphene is incubated 1h at 80 DEG C, then adopt millipore filtration to filter, get precipitation, at 30 DEG C, vacuum-drying obtains graphene powder crude product.
5, in nitrogen atmosphere, graphene powder crude product is incubated 1h at 200 DEG C, obtains graphene powder.
By atomic force microscope (AFM), above-mentioned graphene powder is characterized, as shown in Figure 2.As seen from Figure 2, the preparation-obtained Graphene of embodiment 1 is of a size of 3.11 μm (selected area sizes), and thickness is 0.71nm, and after having deducted substrate and probe thickness, its number of plies visible is individual layer.
Embodiment 2
1, tetrabutyl bicarbonate of ammonia adds in Methyl ethyl carbonate, ultrasonic agitation 1h under the ultrasonic power of 320w, make tetrabutyl bicarbonate of ammonia and Methyl ethyl carbonate miscible, prepare the solution that obtains containing tensio-active agent, wherein, the mass percent concentration of tetrabutyl bicarbonate of ammonia is 15%.
2, crystalline flake graphite is washed, dry, pulverize and cross 200 mesh sieve process, crystalline flake graphite after process is added in the mixing acid of nitric acid and phosphoric acid 1:5 mixing by volume, the concentration of crystalline flake graphite in mixing acid is 0.2mg/L, 1h is stirred to be stirred by the mixture of crystalline flake graphite and mixing acid with the speed of 300rpm, wherein the mass percent concentration of above-mentioned nitric acid is 68%, further heating in water bath to 60 DEG C, then the oleum that mass percent concentration is 120% is added, again in 85 DEG C of heating in water bath to 1h, obtain reactant, wherein, the mass ratio of crystalline flake graphite and sulfuric acid is 1:1, deionized water is added in this reactant, wherein, the volume ratio of reactant and deionized water is 1:10, suspension liquid is obtained with the mixture 1h of the speed reaction stirred of 300rpm and deionized water, by suspension liquid centrifugal 0.1h under 4000rpm, getting precipitation, is 6 by the pH value that gained precipitation is washed till elutant by deionized water, and in 70 DEG C of dryings, obtain expandable sulfur-free graphite, in nitrogen atmosphere, expand expandable sulfur-free graphite at 950 DEG C 10s, obtains expanded graphite.
3, expanded graphite is added in the above-mentioned solution containing tensio-active agent, the concentration of expanded graphite is 1mg/L, expanded graphite and the mixture containing tensio-active agent are carried out ultrasonic stripping 2h under the power of 800W, then with the centrifugal 3min of the speed of 4000rpm, the supernatant liquor containing Graphene is obtained.
4, the supernatant liquor containing Graphene is incubated 0.5h at 100 DEG C, then adopt millipore filtration to filter, get precipitation, at 50 DEG C, vacuum-drying obtains graphene powder crude product.
5, in nitrogen atmosphere, graphene powder crude product is incubated 0.5h at 300 DEG C, obtains graphene powder.
By atomic force microscope (AFM), above-mentioned graphene powder is characterized, as shown in Figure 3.As seen from Figure 3, the preparation-obtained Graphene of embodiment 2 is of a size of 4.12 μm (selected area sizes), and thickness is 0.61nm, and after having deducted substrate and probe thickness, its number of plies visible is individual layer.
Embodiment 3
1, dodecyl tetramethyl-Guanidinium carbonate adds in diethyl carbonate, ultrasonic agitation 2h under the ultrasonic power of 220w, make dodecyl tetramethyl-Guanidinium carbonate and diethyl carbonate miscible, prepare the solution obtained containing tensio-active agent, wherein, the mass percent concentration of dodecyl tetramethyl-Guanidinium carbonate is 10%.
2, crystalline flake graphite is washed, dry, pulverize and cross 200 mesh sieve process, crystalline flake graphite after process is added in the mixing acid of nitric acid and phosphoric acid 1:3 mixing by volume, the concentration of crystalline flake graphite in mixing acid is 0.15mg/L, 3h is stirred to be stirred by the mixture of crystalline flake graphite and mixing acid with the speed of 250rpm, wherein the mass percent concentration of above-mentioned nitric acid is 68%, further heating in water bath to 50 DEG C, then the chloric acid that mass percent concentration is 10% is added, again in 80 DEG C of heating in water bath to 1.5h, obtain reactant, wherein, the mass ratio of crystalline flake graphite and chloric acid is 1:0.5, deionized water is added in this reactant, wherein, the volume ratio of reactant and deionized water is 1:15, suspension liquid is obtained with the mixture 2h of the speed reaction stirred of 250rpm and deionized water, by suspension liquid centrifugal 0.5h under 4000rpm, getting precipitation, is 5.5 by the pH value that gained precipitation is washed till elutant by deionized water, and in 65 DEG C of dryings, obtain expandable sulfur-free graphite, in nitrogen atmosphere, expand expandable sulfur-free graphite at 900 DEG C 12s, obtains expanded graphite.
3, expanded graphite is added in the above-mentioned solution containing tensio-active agent, the concentration of expanded graphite is 0.5mg/L, expanded graphite and the mixture containing tensio-active agent are carried out ultrasonic stripping 3h under the power of 500W, then with the centrifugal 4min of the speed of 3500rpm, the supernatant liquor containing Graphene is obtained.
4, the supernatant liquor containing Graphene is incubated 0.8h at 90 DEG C, then adopt millipore filtration to filter, get precipitation, at 40 DEG C, vacuum-drying obtains graphene powder crude product.
5, in nitrogen atmosphere, graphene powder crude product is incubated 0.5h at 280 DEG C, obtains graphene powder.
Embodiment 4
1, in mass ratio for tetrabutyl bicarbonate of ammonia and tetramethyl ammonium hydrogen carbonate add in methylcarbonate and the mixed carbonic acid esters solvent of diphenyl carbonate by volume for 1:2 mixing by 1:1, ultrasonic agitation 2h under the ultrasonic power of 280w, make tetrabutyl bicarbonate of ammonia, tetramethyl ammonium hydrogen carbonate and mixed carbonic acid esters solvent miscible, prepare the solution obtained containing tensio-active agent, wherein, the total mass percentage concentration of tetrabutyl bicarbonate of ammonia and tetramethyl ammonium hydrogen carbonate is 8%.
2, crystalline flake graphite is washed, dry, pulverize and cross 200 mesh sieve process, crystalline flake graphite after process is added in the mixing acid of nitric acid and phosphoric acid 1:4 mixing by volume, the concentration of crystalline flake graphite in mixing acid is 0.2mg/L, 4h is stirred to be stirred by the mixture of crystalline flake graphite and mixing acid with the speed of 200rpm, wherein the mass percent concentration of above-mentioned nitric acid is 68%, further heating in water bath to 55 DEG C, then Potcrate is added, again in 75 DEG C of heating in water bath to 1.5h, obtain reactant, wherein, the mass ratio of crystalline flake graphite and Potcrate is 1:0.8, deionized water is added in this reactant, wherein, the volume ratio of reactant and deionized water is 1:12, suspension liquid is obtained with the mixture 3h of the speed reaction stirred of 280rpm and deionized water, by suspension liquid centrifugal 0.5h under 3000rpm, getting precipitation, is 5.5 by the pH value that gained precipitation is washed till elutant by deionized water, and in 65 DEG C of dryings, obtain expandable sulfur-free graphite, in nitrogen atmosphere, expand expandable sulfur-free graphite at 850 DEG C 13s, obtains expanded graphite.
3, expanded graphite is added in the above-mentioned solution containing tensio-active agent, the concentration of expanded graphite is 0.8mg/L, expanded graphite and the mixture containing tensio-active agent are carried out ultrasonic stripping 2.5h under the power of 600W, then with the centrifugal 3.5min of the speed of 3800rpm, the supernatant liquor containing Graphene is obtained.
4, the supernatant liquor containing Graphene is incubated 0.8h at 85 DEG C, then adopt millipore filtration to filter, get precipitation, at 45 DEG C, vacuum-drying obtains graphene powder crude product.
5, in nitrogen atmosphere, graphene powder crude product is incubated 0.7h at 250 DEG C, obtains graphene powder.
Embodiment 5
1, cetyl tetramethylammonium Guanidinium carbonate adds in diethyl carbonate, ultrasonic agitation 1.8h under the ultrasonic power of 250w, make cetyl tetramethylammonium Guanidinium carbonate and diethyl carbonate miscible, prepare the solution obtained containing tensio-active agent, wherein, the mass percent concentration of cetyl tetramethylammonium Guanidinium carbonate is 12%.
2, crystalline flake graphite is washed, dry, pulverize and cross 200 mesh sieve process, crystalline flake graphite after process is added in the mixing acid of nitric acid and phosphoric acid 1:2.5 mixing by volume, the concentration of crystalline flake graphite in mixing acid is 0.2mg/L, 2.5h is stirred to be stirred by the mixture of crystalline flake graphite and mixing acid with the speed of 280rpm, wherein the mass percent concentration of above-mentioned nitric acid is 68%, further heating in water bath to 45 DEG C, then potassium permanganate is added, again in 78 DEG C of heating in water bath to 1.2h, obtain reactant, wherein, the mass ratio of crystalline flake graphite and potassium permanganate is 1:0.6, deionized water is added in this reactant, wherein, the volume ratio of reactant and deionized water is 1:18, suspension liquid is obtained with the mixture 3.5h of the speed reaction stirred of 220rpm and deionized water, by suspension liquid centrifugal 0.5h under 4000rpm, getting precipitation, is 5.5 by the pH value that gained precipitation is washed till elutant by deionized water, and in 68 DEG C of dryings, obtain expandable sulfur-free graphite, in nitrogen atmosphere, expand expandable sulfur-free graphite at 880 DEG C 14s, obtains expanded graphite.
3, expanded graphite is added in the above-mentioned solution containing tensio-active agent, the concentration of expanded graphite is 0.3mg/L, expanded graphite and the mixture containing tensio-active agent are carried out ultrasonic stripping 2.5h under the power of 700W, then with the centrifugal 4min of the speed of 3500rpm, the supernatant liquor containing Graphene is obtained.
4, the supernatant liquor containing Graphene is incubated 0.6h at 95 DEG C, then adopt millipore filtration to filter, get precipitation, at 40 DEG C, vacuum-drying obtains graphene powder crude product.
5, in nitrogen atmosphere, graphene powder crude product is incubated 0.8h at 270 DEG C, obtains graphene powder.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a preparation method for Graphene, is characterized in that, comprises the steps:
Tensio-active agent is added in carbonate-based solvent, the solution of preparation containing tensio-active agent, wherein, described tensio-active agent is selected from least one in tetramethyl ammonium hydrogen carbonate, tetraethyl-bicarbonate of ammonia, tetrabutyl bicarbonate of ammonia, dodecyl tetramethyl-Guanidinium carbonate and cetyl tetramethylammonium Guanidinium carbonate;
Graphite is added described containing in the solution of tensio-active agent, centrifugal after carrying out ultrasonic stripping, obtain the supernatant liquor containing Graphene;
The described supernatant liquor containing Graphene is incubated 0.5h ~ 1h at 80 DEG C ~ 100 DEG C, and then filtration, drying, obtain graphene powder crude product; And
In shielding gas atmosphere, described graphene powder crude product is incubated 0.5h ~ 1h at 200 DEG C ~ 300 DEG C, obtains graphene powder.
2. the preparation method of Graphene according to claim 1, is characterized in that, described containing in the solution of tensio-active agent, the mass percent concentration of described tensio-active agent is 4% ~ 15%.
3. the preparation method of Graphene according to claim 1, is characterized in that, described carbonate-based solvent is selected from least one in propylene carbonate, Methyl ethyl carbonate, diethyl carbonate, methylcarbonate and diphenyl carbonate.
4. the preparation method of Graphene according to claim 1, is characterized in that, the concentration of described graphite in the described solution contained in tensio-active agent is 0.1mg/L ~ 1mg/L.
5. the preparation method of Graphene according to claim 1, is characterized in that, the power of described ultrasonic stripping is 300W ~ 800W, and the time of ultrasonic stripping is 2h ~ 4h.
6. the preparation method of Graphene according to claim 1, is characterized in that, described centrifugal speed is 3000rpm ~ 4000rpm, and the centrifugal time is 3min ~ 5min.
7. the preparation method of Graphene according to claim 1, is characterized in that, described graphite is expanded graphite.
8. the preparation method of Graphene according to claim 7, is characterized in that, described expanded graphite is prepared as follows:
Added by crystalline flake graphite in the mixing acid of nitric acid and phosphoric acid, heating in water bath to 40 DEG C after stirring ~ 60 DEG C, then adds oxygenant, then in 70 DEG C ~ 85 DEG C heating in water bath to 1h ~ 2h, obtains reactant;
In described reactant, add deionized water, stir and obtain suspension liquid, by centrifugal for described suspension liquid, get precipitation, washing, drying, obtain expandable sulfur-free graphite; And
In shielding gas atmosphere, by described expandable sulfur-free graphite in 800 DEG C ~ 950 DEG C expansion 10s ~ 15s, obtain described expanded graphite.
9. the preparation method of Graphene according to claim 8, is characterized in that, described oxygenant is selected from least one in chloric acid, nitric acid, sulfuric acid, persulphate, permanganate, oxymuriate and perchlorate.
10. the preparation method of Graphene according to claim 8, is characterized in that, the volume ratio of described nitric acid and phosphoric acid is 1:2 ~ 5, and the concentration of described crystalline flake graphite in described mixing acid is 0.1g/mL ~ 0.2g/mL.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410499792.1A CN104261394B (en) | 2014-09-25 | 2014-09-25 | The preparation method of Graphene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410499792.1A CN104261394B (en) | 2014-09-25 | 2014-09-25 | The preparation method of Graphene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104261394A true CN104261394A (en) | 2015-01-07 |
| CN104261394B CN104261394B (en) | 2016-06-29 |
Family
ID=52153024
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410499792.1A Active CN104261394B (en) | 2014-09-25 | 2014-09-25 | The preparation method of Graphene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104261394B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016045035A1 (en) * | 2014-09-25 | 2016-03-31 | 深圳粤网节能技术服务有限公司 | Method for preparing graphene |
| CN105523549A (en) * | 2016-01-28 | 2016-04-27 | 成都新柯力化工科技有限公司 | Stripping agent for preparation of graphene with mechanical striping method as well as application |
| CN105869770A (en) * | 2016-03-30 | 2016-08-17 | 成都新柯力化工科技有限公司 | Graphene conductive paste prepared by mechanical stripping and preparation method of graphene conductive paste |
| CN107644994A (en) * | 2017-08-21 | 2018-01-30 | 上海空间电源研究所 | A kind of flexible self-supporting graphene composite material film and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102464315A (en) * | 2010-11-18 | 2012-05-23 | 海洋王照明科技股份有限公司 | Preparation method of graphene |
| CN102491310A (en) * | 2011-11-18 | 2012-06-13 | 武汉理工大学 | Preparation method of finely squamose sulfur-free expandable graphite |
-
2014
- 2014-09-25 CN CN201410499792.1A patent/CN104261394B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102464315A (en) * | 2010-11-18 | 2012-05-23 | 海洋王照明科技股份有限公司 | Preparation method of graphene |
| CN102491310A (en) * | 2011-11-18 | 2012-06-13 | 武汉理工大学 | Preparation method of finely squamose sulfur-free expandable graphite |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016045035A1 (en) * | 2014-09-25 | 2016-03-31 | 深圳粤网节能技术服务有限公司 | Method for preparing graphene |
| CN105523549A (en) * | 2016-01-28 | 2016-04-27 | 成都新柯力化工科技有限公司 | Stripping agent for preparation of graphene with mechanical striping method as well as application |
| CN105869770A (en) * | 2016-03-30 | 2016-08-17 | 成都新柯力化工科技有限公司 | Graphene conductive paste prepared by mechanical stripping and preparation method of graphene conductive paste |
| CN107644994A (en) * | 2017-08-21 | 2018-01-30 | 上海空间电源研究所 | A kind of flexible self-supporting graphene composite material film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104261394B (en) | 2016-06-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tao et al. | Scalable exfoliation and dispersion of two-dimensional materials–an update | |
| CN103910354B (en) | Method for preparing graphene through large-scale aqueous phase | |
| CN102502612B (en) | Method for preparing grapheme through oxidation reduction | |
| WO2015109916A1 (en) | Method for preparing graphene | |
| US10472243B2 (en) | Industrial method for preparing large-sized graphene | |
| CN103408000B (en) | Preparation method for oxidized grapheme in large sheet | |
| CN104071784B (en) | Graphene oxide reduction is utilized to prepare the method for Graphene | |
| CN102126720B (en) | Method for synthesizing graphene | |
| CN101786620B (en) | Method for chemical synthesis of graphene | |
| CN104261394A (en) | Preparation method of graphene | |
| CN102874797A (en) | Method for massively preparing high-quality graphene | |
| CN103382028A (en) | Preparation of graphene oxide and post-processing method for waste liquor | |
| CN104211053A (en) | Preparation method of modified graphene aqueous dispersion | |
| CN104386677B (en) | A kind of low-level oxidation Graphene and its preparation method | |
| CN104445169A (en) | Method for preparing grapheme by means of aqueous phase cutting and stripping | |
| CN103058176A (en) | Method for preparing graphene efficiently | |
| CN103072980A (en) | Method for quickly preparing graphene sheets | |
| CN106587046A (en) | Purification method of artificial diamond | |
| CN103011151A (en) | Method for preparing graphene/nickel nanocomposite material by utilizing gamma ray | |
| CN104528708A (en) | Preparation method of large-area few-layer graphene and dispersion solution thereof | |
| CN103130214A (en) | Method of preparing graphene through chemical reduction method | |
| CN106744883B (en) | The preparation method of graphene | |
| CN108640107B (en) | Intercalation agent for rapidly stripping graphite for mass production of high-quality graphene | |
| CN106672957A (en) | Method for preparing graphene oxide according to Fenton oxidation method | |
| CN106477560A (en) | A kind of preparation method of Graphene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20191029 Address after: 518107 Room 202, building a, No. 20, Gaoxin West Road, Dongzhou community, Guangming Street, Guangming New District, Shenzhen City, Guangdong Province Patentee after: Shenzhen Hua Xin new material Co., Ltd. Address before: 518107 C unit 501, building A3, Guangming Science Park, 3009 sightseeing Road, Guangming Road, Guangming District, Guangdong, Shenzhen, China Patentee before: Shenzhen Yuewang Energy-Saving Technology Service Co., Ltd. |
|
| TR01 | Transfer of patent right |