CN104261394B - The preparation method of Graphene - Google Patents
The preparation method of Graphene Download PDFInfo
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- CN104261394B CN104261394B CN201410499792.1A CN201410499792A CN104261394B CN 104261394 B CN104261394 B CN 104261394B CN 201410499792 A CN201410499792 A CN 201410499792A CN 104261394 B CN104261394 B CN 104261394B
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Abstract
The preparation method that the present invention relates to a kind of Graphene, add in carbonate-based solvent including by surfactant, the preparation solution containing surfactant, surfactant at least one in tetramethyl ammonium hydrogen carbonate, tetraethyl ammonium hydrogen carbonate, tetrabutyl ammonium hydrogen carbonate, dodecyl tetramethyl guanidine carbonate and cetyl tetramethylammonium guanidine carbonate；Graphite is added in the solution containing surfactant, centrifugal after carrying out ultrasonic stripping, obtain the supernatant containing Graphene；Supernatant containing Graphene is incubated at 80 DEG C～100 DEG C 0.5h～1h, filters, dry obtain graphene powder crude product；And in protective gas atmosphere, graphene powder crude product is incubated at 200 DEG C～300 DEG C 0.5h～1h and obtains the step of graphene powder.The method can prevent remaining surface activating agent and solvent on Graphene, makes the residual helping remover and solvent less, and the lamella of Graphene is of a size of 3 μm～50 μm, and lamella is larger in size.
Description
Technical field
The present invention relates to technical field of graphene, the preparation method particularly relating to a kind of Graphene.
Background technology
Graphene has fabulous electric conductivity and heat conductivity, and has fabulous intensity and high surface area.Moreover, the special construction of Graphene also gives the band structure of its uniqueness so that it is have perfect tunneling effect and half integral quantum hall effect and its electrical conductivity of never disappearing.The performance of these uniquenesses makes Graphene have great application prospect in material and electronic circuit etc..Therefore, a large amount of preparations of Graphene there is great demand.
The preparation method of traditional Graphene can be divided into two kinds, is Physical and chemical method respectively.The Graphene character that Physical and chemical method obtain is different.Having mechanical stripping method, arc discharge method, ultrasonic dispersion etc. in Physical, the graphene sheet layer ratio obtained is more complete, but mechanical stripping method productivity is too low and unstable product quality；Arc discharge method needs special equipment and high cost；The existence of ultrasonic disperse rule helps remover or solvent can carry out stronger absorption with Graphene, it is difficult to separates Graphene and helps remover, or is difficult to separate Graphene and solvent, thus the problem reducing the performance of Graphene.Chemical method can be divided into organic synthesis method from bottom to top, oxidation-reduction method, solvent-thermal method and chemical vapour deposition technique several.Wherein, organic synthesis method is strict to equipment and ingredient requirement, it is difficult to volume production；Solvent-thermal method cannot stabilized product quality, average quality is poor；The high cost of chemical vapour deposition technique, and cannot large-scale production.On the graphene sheet layer that oxidation-reduction method obtains, defect is many, so that the excellent properties of Graphene cannot be showed fully.Therefore, no matter it is any preparation method, all cannot be sufficiently completed the volume production of Graphene and target that high-quality coexists, so that Graphene technology and goods slowly can not get the popularization of the marketization.
The preparation method of above-mentioned Graphene is considered for the control of graphene sheet layer size override often.The lamella of Graphene is more big, and the contact resistance of its sheet interlayer is more little.Still further aspect, the lamella of Graphene is more big, and its non-void ratio surface area is more big, in the field such as lithium ion battery, desalinization, also more can give play to its value.It addition, the Graphene of big lamella also better can carry out compound by other material of load, obtain the composite of excellent performance.Therefore, several stripping means that can keep graphene sheet layer and structure in Physical, if it is possible to solve to be difficult to separate the problem helping remover, just well can push the Graphene of big lamella to application.
Summary of the invention
Based on this, it is necessary to the preparation method providing a kind of Graphene, help remover with preparation and dissolvent residual is less, the larger-size Graphene of lamella.
The preparation method of a kind of Graphene, comprises the steps:
Surfactant is added in carbonate-based solvent, the preparation solution containing surfactant, wherein, described surfactant at least one in tetramethyl ammonium hydrogen carbonate, tetraethyl ammonium hydrogen carbonate, tetrabutyl ammonium hydrogen carbonate, dodecyl tetramethyl guanidine carbonate and cetyl tetramethylammonium guanidine carbonate；
Graphite is added in the described solution containing surfactant, centrifugal after carrying out ultrasonic stripping, obtain the supernatant containing Graphene；
The described supernatant containing Graphene is incubated at 80 DEG C～100 DEG C 0.5h～1h, then filters, dry, obtain graphene powder crude product；And
In protective gas atmosphere, described graphene powder crude product is incubated at 200 DEG C～300 DEG C 0.5h～1h, obtains graphene powder.
Wherein in an embodiment, in the described solution containing surfactant, the mass percent concentration of described surfactant is 4%～15%.
Wherein in an embodiment, described carbonate-based solvent at least one in Allyl carbonate, Ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate and diphenyl carbonate.
Wherein in an embodiment, described graphite described be 0.1mg/L～1mg/L containing the concentration in the solution in surfactant.
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:
Being added by crystalline flake graphite in the mixed acid of nitric acid and phosphoric acid, after stirring, heating in water bath is to 40 DEG C～60 DEG C, is subsequently adding oxidant, then at 70 DEG C～85 DEG C heating in water bath to 1h～2h, obtains reactant；
Adding deionized water in described reactant, stirring obtains suspension, is centrifuged by described suspension, takes precipitation, washes, dries, obtains expandable sulfur-free graphite；And
In protective gas atmosphere, described expandable sulfur-free graphite is expanded 10s～15s in 800 DEG C～950 DEG C, obtains described expanded graphite.
Wherein in an embodiment, described oxidant at least one in chloric acid, nitric acid, sulphuric acid, persulfate, permanganate, chlorate and perchlorate.
Wherein in an embodiment, the volume ratio of described nitric acid and phosphoric acid is 1:2～5, and described crystalline flake graphite concentration in described mixed 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 surfactant, and use labile carbonate-based solvent as the solvent of surfactant, effectively prevent remaining surface activating agent and solvent on graphene sheet layer, namely graphene sheet layer helps the residual of remover and solvent less, 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 is larger in size.
Accompanying drawing explanation
Fig. 1 is the flow chart 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.
Detailed description of the invention
Understandable for enabling the above-mentioned purpose of the present invention, feature and advantage to become apparent from, below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.Elaborate a lot of detail in the following description so that fully understanding the present invention.But the present invention can implement being much different from alternate manner described here, and those skilled in the art can do similar improvement when without prejudice to intension of the present invention, therefore the present invention is by the following public restriction being embodied as.
Refer to Fig. 1, the preparation method of the Graphene of an embodiment, comprise the steps 110 to step 140.
Step 110: surfactant is added in carbonate-based solvent, the preparation solution containing surfactant, wherein, surfactant at least one in tetramethyl ammonium hydrogen carbonate, tetraethyl ammonium hydrogen carbonate, tetrabutyl ammonium hydrogen carbonate, dodecyl tetramethyl guanidine carbonate and cetyl tetramethylammonium guanidine carbonate.
Carbonate-based solvent, as the solvent of surfactant, also serves as the dispersant of Graphene.Surfactant helps remover as what prepare Graphene, is conducive to maintaining the stability of graphene dispersion, it is to avoid Graphene is reunited.
Above-mentioned surfactant easily decomposes, it is possible to relatively easily remove the surfactant of Graphene absorption in subsequent step so that on Graphene, residual helps remover less.Preferably, above-mentioned surfactant at least one in tetrabutyl ammonium hydrogen carbonate, tetramethyl ammonium hydrogen carbonate and dodecyl tetramethyl guanidine carbonate.
Carbonate-based solvent easily decomposes, and follow-up can being easier to removes.Preferably, carbonate-based solvent at least one in Allyl carbonate, Ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate and diphenyl carbonate.
Being added by surfactant in carbonate-based solvent, ultrasonic agitation makes surfactant and carbonate-based solvent complete miscibility, and preparation obtains the solution containing surfactant.The power of ultrasonic agitation is preferably 180w～320w, and the time of ultrasonic agitation is 1h～3h.
Preferably, in the solution containing surfactant, the mass percent concentration of surfactant is 4%～15%.
Step 120: graphite is added in the solution containing surfactant, centrifugal after carrying out ultrasonic stripping, obtain the supernatant containing Graphene.
Preferably, graphite is expanded graphite.Use expanded graphite to peel off as graphitic source, advantageously ensure that the large scale of graphene sheet layer.
Preferably, the expanded graphite used by step 120 is prepared as follows, and the method comprises the steps 210 to step 230:
Step 210: added by crystalline flake graphite in the mixed acid of nitric acid and phosphoric acid, after stirring, heating in water bath is to 40 DEG C～60 DEG C, is subsequently adding oxidant, then at 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.Crystalline flake graphite concentration in mixed acid is 0.1g/mL～0.2g/mL.Wherein, nitric acid is mass percent concentration is the nitric acid of 68%.
Before crystalline flake graphite is added the step of mixed acid of nitric acid and phosphoric acid, also include the step that crystalline flake graphite is carried out to be washed, dry, pulverize and sieve, the crystalline flake graphite thinner to obtain cleaning, granularity.Preferably, sieve as crossing 200 mesh sieves.
The speed of stirring is preferably 180rpm～300rpm, and mixing time is 1h～5h.
Oxidant at least one in chloric acid, nitric acid, sulphuric acid, persulfate, permanganate, chlorate 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 sulphuric acid is preferably 120%.Persulfate can be sodium peroxydisulfate, potassium peroxydisulfate, Ammonium persulfate. etc., permanganate can potassium permanganate, sodium permanganate, high manganese lithium etc., chlorate can potassium chlorate, sodium chlorate etc., perchlorate can be sodium perchlorate etc..
The mass ratio of crystalline flake graphite and oxidant is preferably 1:0.3～1.
Step 220: adding deionized water in reactant, stirring obtains suspension, is centrifuged by suspension, takes precipitation, washes, dries, obtain expandable sulfur-free graphite.
The volume ratio of reactant and deionized water is 1:10～20.The speed of stirring is preferably 180rpm～300rpm, and mixing time is 1h～5h.Centrifugal speed is 3000rpm～4000rpm, and the centrifugal time is 0.1h～0.5h.
The pH value centrifugal gained precipitation being washed till eluate with deionized water is 5～6.Dry temperature is preferably 60 DEG C～70 DEG C.
Step 230: in protective gas atmosphere, expands 10s～15s by expandable sulfur-free graphite in 800 DEG C～950 DEG C, obtains expanded graphite.
Protective gas can nitrogen or noble gas.
Make the expanded graphite prepared in aforementioned manners ensure that and follow-up obtain the larger-size Graphene of lamella.Further, the defect of the expanded graphite that said method prepares is few, structural integrity.This expanded graphite is used to prepare Graphene as graphitic source, can effectively keep the electronic structure of Graphene, so that to Graphene there is good activity, it is possible to be widely used in material and electronic circuit field, be especially applicable in electrochemical catalysis and battery.
Further, the sheet number of plies making the Graphene that the expanded graphite prepared in aforementioned manners prepares as raw material is less, and directly uses the sheet number of plies of Graphene that crystalline flake graphite prepares as raw material bigger.
Preferably, graphite concentration in the solution containing surfactant is 0.1mg/L～1mg/L.
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 containing Graphene is incubated 0.5h～1h at 80 DEG C～100 DEG C, then filters, dries, obtain graphene powder crude product.
Employing microporous filter membrane is filtered, and then obtains graphene powder crude product after vacuum drying at 30 DEG C～50 DEG C.
Supernatant containing Graphene is incubated at 80 DEG C～100 DEG C 0.5h～1h, makes Graphene and surfactant coagulation, it is easy to filter.
Step 140: in protective gas atmosphere, is incubated graphene powder crude product 0.5h～1h at 200 DEG C～300 DEG C, obtains graphene powder.
Protective gas is nitrogen or noble gas.
Graphene powder crude product is incubated at 200 DEG C～300 DEG C 0.5h～1h, to remove surfactant and the carbonate-based solvent of absorption in graphene powder crude product.A part of surfactant is removed in step 130, and unnecessary surfactant transfers gas in step 140 to, thus being again turned on by graphene sheet layer.Therefore, step 140 can not only completely remove unnecessary surfactant, and also the thickness of graphene sheet layer is also without interference.
Preferably, after being incubated 0.5h～1h at 200 DEG C～300 DEG C, also include the step carrying out ball milling and screening, after ball milling and screening, the lower thickness of Graphene, be conducive to the preparation 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 surfactant, and use labile carbonate-based solvent as the solvent of surfactant, effectively prevent remaining surface activating agent and solvent on graphene sheet layer, namely graphene sheet layer help the residual of remover and solvent less, Graphene will not be produced covalent modification, 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 is larger in size.
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, it is impossible to show the excellent specific property that the electronic structure of single-layer graphene brings, prepare the quality relatively 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, can show the excellent specific property that the electronic structure of single-layer graphene brings preferably, and quality is higher.
The preparation method technique of above-mentioned Graphene is simple, low for equipment requirements, is conducive to carrying out large-scale industry and prepares.
Below by way of specific embodiment, the preparation method of above-mentioned Graphene is expanded on further.
Embodiment 1
1, tetramethyl ammonium hydrogen carbonate adds in Allyl carbonate, ultrasonic agitation 3h under the ultrasonic power of 180w, makes tetramethyl ammonium hydrogen carbonate and Allyl carbonate miscible, and preparation obtains the solution containing surfactant, wherein, the mass percent concentration of tetramethyl ammonium hydrogen carbonate is 4%.
2, crystalline flake graphite is washed, dry, pulverize and cross 200 mesh sieves to process, crystalline flake graphite after process is added in the mixed acid of nitric acid and phosphoric acid 1:2 by volume mixing, crystalline flake graphite concentration in mixed acid is 0.1mg/L, stir 5h with the speed of 180rpm to stir with the mixture by crystalline flake graphite Yu mixed acid, wherein the mass percent concentration of above-mentioned nitric acid is 68%, further heating in water bath is to 40 DEG C, it is subsequently adding the nitric acid that mass percent concentration is 95%, then at 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 is obtained with the mixture 5h of the speed reaction stirred of 180rpm Yu deionized water, by suspension centrifugal 0.5h under 4000rpm, taking precipitation, pH value gained precipitation being washed till eluate with deionized water is 5, and dry in 60 DEG C, obtain expandable sulfur-free graphite；In nitrogen atmosphere, expandable sulfur-free graphite is expanded at 800 DEG C 15s, obtains expanded graphite.
3, expanded graphite is added in the above-mentioned solution containing surfactant, the concentration of expanded graphite is 0.1mg/L, expanded graphite and the mixture containing surfactant are carried out under the power of 300W ultrasonic stripping 4h, then with the centrifugal 5min of the speed of 3000rpm, the supernatant containing Graphene is obtained.
4, the supernatant containing Graphene being incubated 1h at 80 DEG C, then adopt microporous filter membrane to be filtered, take precipitation, at 30 DEG C, vacuum drying obtains graphene powder crude product.
5, in nitrogen atmosphere, graphene powder crude product is incubated at 200 DEG C 1h, 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 monolayer.
Embodiment 2
1, tetrabutyl ammonium hydrogen carbonate adds in Ethyl methyl carbonate, ultrasonic agitation 1h under the ultrasonic power of 320w, makes tetrabutyl ammonium hydrogen carbonate and Ethyl methyl carbonate miscible, and preparation obtains the solution containing surfactant, wherein, the mass percent concentration of tetrabutyl ammonium hydrogen carbonate is 15%.
2, crystalline flake graphite is washed, dry, pulverize and cross 200 mesh sieves to process, crystalline flake graphite after process is added in the mixed acid of nitric acid and phosphoric acid 1:5 by volume mixing, crystalline flake graphite concentration in mixed acid is 0.2mg/L, stir 1h with the speed of 300rpm to stir with the mixture by crystalline flake graphite Yu mixed acid, wherein the mass percent concentration of above-mentioned nitric acid is 68%, further heating in water bath is to 60 DEG C, it is subsequently adding the oleum that mass percent concentration is 120%, then at 85 DEG C of heating in water bath to 1h, obtain reactant, wherein, the mass ratio of crystalline flake graphite and sulphuric acid is 1:1；Deionized water is added in this reactant, wherein, the volume ratio of reactant and deionized water is 1:10, suspension is obtained with the mixture 1h of the speed reaction stirred of 300rpm Yu deionized water, by suspension centrifugal 0.1h under 4000rpm, taking precipitation, pH value gained precipitation being washed till eluate with deionized water is 6, and dry in 70 DEG C, obtain expandable sulfur-free graphite；In nitrogen atmosphere, expandable sulfur-free graphite is expanded at 950 DEG C 10s, obtains expanded graphite.
3, expanded graphite is added in the above-mentioned solution containing surfactant, the concentration of expanded graphite is 1mg/L, expanded graphite and the mixture containing surfactant are carried out under the power of 800W ultrasonic stripping 2h, then with the centrifugal 3min of the speed of 4000rpm, obtains the supernatant containing Graphene.
4, the supernatant containing Graphene being incubated 0.5h at 100 DEG C, then adopt microporous filter membrane to be filtered, take precipitation, at 50 DEG C, vacuum drying obtains graphene powder crude product.
5, in nitrogen atmosphere, graphene powder crude product is incubated at 300 DEG C 0.5h, 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 monolayer.
Embodiment 3
1, dodecyl tetramethyl guanidine carbonate adds in diethyl carbonate, ultrasonic agitation 2h under the ultrasonic power of 220w, make dodecyl tetramethyl guanidine carbonate and diethyl carbonate miscible, preparation obtains the solution containing surfactant, wherein, the mass percent concentration of dodecyl tetramethyl guanidine carbonate is 10%.
2, crystalline flake graphite is washed, dry, pulverize and cross 200 mesh sieves to process, crystalline flake graphite after process is added in the mixed acid of nitric acid and phosphoric acid 1:3 by volume mixing, crystalline flake graphite concentration in mixed acid is 0.15mg/L, stir 3h with the speed of 250rpm to stir with the mixture by crystalline flake graphite Yu mixed acid, wherein the mass percent concentration of above-mentioned nitric acid is 68%, further heating in water bath is to 50 DEG C, it is subsequently adding the chloric acid that mass percent concentration is 10%, then at 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 is obtained with the mixture 2h of the speed reaction stirred of 250rpm Yu deionized water, by suspension centrifugal 0.5h under 4000rpm, taking precipitation, pH value gained precipitation being washed till eluate with deionized water is 5.5, and dry in 65 DEG C, obtain expandable sulfur-free graphite；In nitrogen atmosphere, expandable sulfur-free graphite is expanded at 900 DEG C 12s, obtains expanded graphite.
3, expanded graphite is added in the above-mentioned solution containing surfactant, the concentration of expanded graphite is 0.5mg/L, expanded graphite and the mixture containing surfactant are carried out under the power of 500W ultrasonic stripping 3h, then with the centrifugal 4min of the speed of 3500rpm, the supernatant containing Graphene is obtained.
4, the supernatant containing Graphene being incubated 0.8h at 90 DEG C, then adopt microporous filter membrane to be filtered, take precipitation, at 40 DEG C, vacuum drying obtains graphene powder crude product.
5, in nitrogen atmosphere, graphene powder crude product is incubated at 280 DEG C 0.5h, obtains graphene powder.
Embodiment 4
1, it is that tetrabutyl ammonium hydrogen carbonate and tetramethyl ammonium hydrogen carbonate are added dimethyl carbonate and diphenyl carbonate by volume in the mixed carbonic acid esters solvent of 1:2 mixing by 1:1 in mass ratio, ultrasonic agitation 2h under the ultrasonic power of 280w, make tetrabutyl ammonium hydrogen carbonate, tetramethyl ammonium hydrogen carbonate and mixed carbonic acid esters solvent miscible, preparation obtains the solution containing surfactant, wherein, the gross mass percent concentration of tetrabutyl ammonium hydrogen carbonate and tetramethyl ammonium hydrogen carbonate is 8%.
2, crystalline flake graphite carries out wash, dry, pulverize and cross 200 mesh sieves process, crystalline flake graphite after process is added in the mixed acid of nitric acid and phosphoric acid 1:4 by volume mixing, crystalline flake graphite concentration in mixed acid is 0.2mg/L, stir 4h with the speed of 200rpm to stir with the mixture by crystalline flake graphite Yu mixed acid, wherein the mass percent concentration of above-mentioned nitric acid is 68%, further heating in water bath is to 55 DEG C, it is subsequently adding potassium chlorate, then at 75 DEG C of heating in water bath to 1.5h, obtain reactant, wherein, crystalline flake graphite is 1:0.8 with the mass ratio of potassium chlorate；Deionized water is added in this reactant, wherein, the volume ratio of reactant and deionized water is 1:12, suspension is obtained with the mixture 3h of the speed reaction stirred of 280rpm Yu deionized water, by suspension centrifugal 0.5h under 3000rpm, taking precipitation, pH value gained precipitation being washed till eluate with deionized water is 5.5, and dry in 65 DEG C, obtain expandable sulfur-free graphite；In nitrogen atmosphere, expandable sulfur-free graphite is expanded at 850 DEG C 13s, obtains expanded graphite.
3, expanded graphite is added in the above-mentioned solution containing surfactant, the concentration of expanded graphite is 0.8mg/L, expanded graphite and the mixture containing surfactant are carried out under the power of 600W ultrasonic stripping 2.5h, then with the centrifugal 3.5min of the speed of 3800rpm, the supernatant containing Graphene is obtained.
4, the supernatant containing Graphene being incubated 0.8h at 85 DEG C, then adopt microporous filter membrane to be filtered, take precipitation, at 45 DEG C, vacuum drying obtains graphene powder crude product.
5, in nitrogen atmosphere, graphene powder crude product is incubated at 250 DEG C 0.7h, obtains graphene powder.
Embodiment 5
1, cetyl tetramethylammonium guanidine carbonate adds in diethyl carbonate, ultrasonic agitation 1.8h under the ultrasonic power of 250w, make cetyl tetramethylammonium guanidine carbonate and diethyl carbonate miscible, preparation obtains the solution containing surfactant, wherein, the mass percent concentration of cetyl tetramethylammonium guanidine carbonate is 12%.
2, crystalline flake graphite is washed, dry, pulverize and cross 200 mesh sieves to process, crystalline flake graphite after process is added in the mixed acid of nitric acid and phosphoric acid 1:2.5 by volume mixing, crystalline flake graphite concentration in mixed acid is 0.2mg/L, stir 2.5h with the speed of 280rpm to stir with the mixture by crystalline flake graphite Yu mixed acid, wherein the mass percent concentration of above-mentioned nitric acid is 68%, further heating in water bath is to 45 DEG C, it is subsequently adding potassium permanganate, then at 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 is obtained with the mixture 3.5h of the speed reaction stirred of 220rpm Yu deionized water, by suspension centrifugal 0.5h under 4000rpm, taking precipitation, pH value gained precipitation being washed till eluate with deionized water is 5.5, and dry in 68 DEG C, obtain expandable sulfur-free graphite；In nitrogen atmosphere, expandable sulfur-free graphite is expanded at 880 DEG C 14s, obtains expanded graphite.
3, expanded graphite is added in the above-mentioned solution containing surfactant, the concentration of expanded graphite is 0.3mg/L, expanded graphite and the mixture containing surfactant are carried out under the power of 700W ultrasonic stripping 2.5h, then with the centrifugal 4min of the speed of 3500rpm, the supernatant containing Graphene is obtained.
4, the supernatant containing Graphene being incubated 0.6h at 95 DEG C, then adopt microporous filter membrane to be filtered, take precipitation, at 40 DEG C, vacuum drying obtains graphene powder crude product.
5, in nitrogen atmosphere, graphene powder crude product is incubated at 270 DEG C 0.8h, obtains graphene powder.
Embodiment described above only have expressed the several embodiments 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, it is also possible to making some deformation and improvement, these broadly fall into 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. the preparation method of a Graphene, it is characterised in that comprise the steps:
Surfactant is added in carbonate-based solvent, the preparation solution containing surfactant, wherein, described surfactant at least one in tetramethyl ammonium hydrogen carbonate, tetraethyl ammonium hydrogen carbonate, tetrabutyl ammonium hydrogen carbonate, dodecyl tetramethyl guanidine carbonate and cetyl tetramethylammonium guanidine carbonate；
Graphite is added in the described solution containing surfactant, centrifugal after carrying out ultrasonic stripping, obtain the supernatant containing Graphene；
The described supernatant containing Graphene is incubated at 80 DEG C～100 DEG C 0.5h～1h, then filters, dry, obtain graphene powder crude product；And
In protective gas atmosphere, described graphene powder crude product is incubated at 200 DEG C～300 DEG C 0.5h～1h, obtains graphene powder.
2. the preparation method of Graphene according to claim 1, it is characterised in that in the described solution containing surfactant, the mass percent concentration of described surfactant is 4%～15%.
3. the preparation method of Graphene according to claim 1, it is characterised in that described carbonate-based solvent at least one in Allyl carbonate, Ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate and diphenyl carbonate.
4. the preparation method of Graphene according to claim 1, it is characterised in that described graphite concentration in the described solution containing surfactant is 0.1mg/L～1mg/L.
5. the preparation method of Graphene according to claim 1, it is characterised in that the power of described ultrasonic stripping is 300W～800W, the time of ultrasonic stripping is 2h～4h.
6. the preparation method of Graphene according to claim 1, it is characterised in that described centrifugal speed is 3000rpm～4000rpm, the centrifugal time is 3min～5min.
7. the preparation method of Graphene according to claim 1, it is characterised in that described graphite is expanded graphite.
8. the preparation method of Graphene according to claim 7, it is characterised in that described expanded graphite is prepared as follows:
Being added by crystalline flake graphite in the mixed acid of nitric acid and phosphoric acid, after stirring, heating in water bath is to 40 DEG C～60 DEG C, is subsequently adding oxidant, then at 70 DEG C～85 DEG C heating in water bath to 1h～2h, obtains reactant；
Adding deionized water in described reactant, stirring obtains suspension, is centrifuged by described suspension, takes precipitation, washes, dries, obtains expandable sulfur-free graphite；And
In protective gas atmosphere, described expandable sulfur-free graphite is expanded 10s～15s in 800 DEG C～950 DEG C, obtains described expanded graphite.
9. the preparation method of Graphene according to claim 8, it is characterised in that described oxidant at least one in chloric acid, nitric acid, sulphuric acid, persulfate, permanganate, chlorate and perchlorate.
10. the preparation method of Graphene according to claim 8, it is characterised in that the volume ratio of described nitric acid and phosphoric acid is 1:2～5, described crystalline flake graphite concentration in described mixed acid is 0.1g/mL～0.2g/mL.
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| CN105523549B (en) * | 2016-01-28 | 2017-10-27 | 成都新柯力化工科技有限公司 | A kind of remover and application that graphene is prepared for mechanical stripping method |
| CN105869770B (en) * | 2016-03-30 | 2017-10-27 | 成都新柯力化工科技有限公司 | A kind of mechanical stripping prepares graphene conductive slurry and preparation method thereof |
| 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 |
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| CN102491310A (en) * | 2011-11-18 | 2012-06-13 | 武汉理工大学 | Preparation method of finely squamose sulfur-free expandable graphite |
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