CN102115078B - Method for preparing graphene by using supercritical fluid - Google Patents
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- CN102115078B CN102115078B CN2011100210330A CN201110021033A CN102115078B CN 102115078 B CN102115078 B CN 102115078B CN 2011100210330 A CN2011100210330 A CN 2011100210330A CN 201110021033 A CN201110021033 A CN 201110021033A CN 102115078 B CN102115078 B CN 102115078B
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Abstract
The invention discloses a method for preparing graphene by using a supercritical fluid, which relates to the technical field of novel nano materials. The graphene is prepared by repeatedly and circularly treating and cooling graphite powder dispersion liquid. Graphene of less than eight layers, prepared by the method, accounts for 90-95 percent and single-layer graphene accounts for over 10 percent; meanwhile, continuous operation is performed, so that mass production can be realized, and the graphene has the advantages of simple process, nontoxicity and lower cost.
Description
Technical field
What the present invention relates to is a kind of graphene preparation method of nanometer new material technology field, specifically is the method that a kind of supercutical fluid prepares Graphene.
Background technology
Since coming to light from Graphene in 2004, just enjoyed generally favor from physics and field of materials investigator always.Graphene is a kind of by the tightly packed bi-dimensional cellular shape crystalline network blacking that forms of monolayer carbon atom.Although Graphene has only a carbon atomic layer thickness, and be the thinnest a kind of in the known materials, however unusual rigid.Graphene also is the outstanding material of present known conductive property.In addition, Graphene also has the performance of many excellences: like higher Young's modulus, thermal conductivity, huge specific surface area or the like.Because the property of Graphene, it will be widely used at aspects such as electronics, optics, magnetics, biomedicine, transmitter, energy storage.In order Graphene to be applied in above-mentioned field, the problem that at first will solve is can prepare high-quality Graphene and realize scale operation.
At present, the preparation Graphene mainly concentrates on following several method: oxidation reduction process, chemical Vapor deposition process, mechanically peel method, epitaxial growth method etc.Mechanically peel method complex operation, each amount that obtains seldom can not mass preparation.Through existing literature retrieval is found, one Chinese patent application number: 200910050318.x, name are called the invention of " a kind of method of simple innoxiously preparing single-layer graphene ", and this invention has realized innoxiously preparing single-layer graphene; One Chinese patent application number: 200910099595.x, name are called the invention of " a kind of solution phase preparation method of Graphene ", and this invention can be prepared the overlarge area Graphene.But above-mentioned two kinds of methods all live through the graphite oxidation process, and Graphite Powder 99 is introduced a large amount of defectives in oxidation, can not repair it fully in the time of reductive, so be difficult to prepare high-quality Graphene.One Chinese patent application number: 200810113596.0, name is called " method of process for preparing graphenes by chemical vapour deposition " and one Chinese patent application number: 200910023384.8, being called " method of 4H-SiC silicon face extending and growing graphene " can both prepare high-quality Graphene; But preparation condition is harsh, complicated operation, apparatus expensive, is difficult to carry out scale operation.
Summary of the invention
The present invention is directed to the above-mentioned deficiency that prior art exists, the method that provides a kind of supercutical fluid to prepare Graphene can be prepared high-quality Graphene; Productive rate is high; Carry out operate continuously simultaneously, can scale operation, and technology is simple, nontoxic, cost is lower.
The present invention realizes through following technical scheme, the present invention includes following steps:
A, a certain amount of Graphite Powder 99 is poured in the container that fills organic solvent, made the Graphite Powder 99 uniform mixing in organic solvent through UW, ultrasonic time is 5～200 minutes;
B, above-mentioned Graphite Powder 99 mixture solution is pumped in the autoclave, in autoclave, material is heated between 200～700 ℃, and the pressure-controlling in the autoclave is between 10～100MPa, and the residence time of material in autoclave is 5～120 minutes;
After c, material came out from autoclave, through cooling off in the pressure piping entering cooling pool, material was cooled to 0～100 ℃ in cooling pool.With pump cooled solution is re-injected in the autoclave then, make material get into high-temperature high-pressure state again.Said process makes material constantly experience HTHP and refrigeration cycle repeatedly;
After d, material experience HTHP and cooling repeatedly circulate, from pipeline, draw, obtain primary products.Simultaneously, add the Graphite Powder 99 mixing solutions again, carry out the preparation of next batch sample, carry out preparation continuously from opening for feed;
E, with primary products with fresh organic solvent clean repeatedly, centrifugal, and further vacuum-drying obtains final powder-product.
The present invention is at first miscible in organic solvent with Graphite Powder 99; The above state of the stagnation point that in autoclave, makes it reach organic solvent; Utilize organic solvent to be in and have high-solvency and high diffusibility under the above-critical state; Graphite Powder 99 is dissolved in the organic solvent fully, and organic solvent inserts between the graphite linings fully, forms graphite-organic solvent intercalation configuration.Cold and hot circulation repeatedly can improve the productive rate of single-layer graphene, and operate continuously can realize scale operation.
The present invention utilizes the high-solvency and the high diffusibility of supercritical fluid, successfully prepares single-layer graphene, and whole technological process is simple; Cost is low, and operation does not relate to deleterious reagent easily; And can realize continuous preparation, and obtain high-quality Graphene easily.Thereby have broad application prospects.
Description of drawings
Fig. 1 is the process flow diagram of the embodiment of the invention 1.
Fig. 2 is the process flow diagram of the embodiment of the invention 2.
Fig. 3 is the process flow diagram of the embodiment of the invention 3.
Embodiment
Elaborate in the face of embodiments of the invention down, present embodiment provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment being to implement under the prerequisite with technical scheme of the present invention.
Embodiment 1
As shown in Figure 1, the preparation facilities that present embodiment relates to mainly comprises: ultrasonic container 1, pump 2, autoclave 3, valve 4, cooling pool 5 etc.Through pipeline successively with ultrasonic container 1, pump 2, autoclave 3, valve 4, cooling pool 5 etc. connects to form a circulation loop, between ultrasonic container 1 and cooling pool 5, is provided with discharge port 6.
Selecting ethanol for use is organic solvent, and a certain amount of Graphite Powder 99 and a certain amount of ethanol are joined in the ultrasonic container 1, and in organic solvent, ultrasonic time is 10 minutes through the ultrasonic Graphite Powder 99 uniform mixing that makes.Above-mentioned Graphite Powder 99 mixing solutions in the ultrasonic container 1 is pumped in the autoclave 3, and the inlet of pump 2 links to each other with ultrasonic container 1 outlet through pipeline, and the outlet of pump 2 links to each other with autoclave 3 imports through pipeline.In autoclave 3, material is heated to 300 ℃, and the pressure-controlling in the autoclave 3 is at 25MPa, and the residence time of material in autoclave 3 is 5 minutes.After material comes out from autoclave 3, get into cooling in the cooling pool 5 through valve 4, material is cooled to 0 ℃ in cooling pool 5, and cooled material comes back in the ultrasonic container 1 through pipeline.With pump 2 material in the ultrasonic container 1 is re-injected in the autoclave 3 then, make material get into high-temperature high-pressure state again, then further cooling in cooling pool 5 again.Said process makes material constantly experience HTHP and refrigeration cycle repeatedly; After the cold and hot repeatedly circulation of material experience, draw, obtain primary products from discharge port 6.Simultaneously, in ultrasonic container 1, add Graphite Powder 99 and organic solvent again, carry out the preparation of next batch sample, carry out preparation continuously.
With primary products with fresh ethanol clean repeatedly, centrifugal, and further vacuum-drying obtains powdered sample, characterizes through test, the Graphene that is less than 8 layers in the sample kind accounts for 90%, wherein single-layer graphene accounts for 10%.
Embodiment 2
As shown in Figure 2, the preparation facilities that present embodiment relates to mainly comprises: ultrasonic container 1, pump 2, autoclave 3, valve 4, cooling pool 5, autoclave 6, valve 7, cooling pool 8 etc.Successively ultrasonic container 1, pump 2, autoclave 3, valve 4, cooling pool 5, autoclave 6, valve 7, cooling pool 8 etc. are connected to form a circulation loop through pipeline, between ultrasonic container 1 and cooling pool 8, discharge port 9 is set.
Selecting N for use is organic solvent, and a certain amount of Graphite Powder 99 and a certain amount of N are joined in the ultrasonic container 1, and in organic solvent, ultrasonic time is 15 minutes through the ultrasonic Graphite Powder 99 uniform mixing that makes.Above-mentioned Graphite Powder 99 mixing solutions in the ultrasonic container 1 is pumped in the autoclave 3, and the inlet of pump 2 links to each other with ultrasonic container 1 outlet through pipeline, and the outlet of pump 2 links to each other with autoclave 3 imports through pipeline.In autoclave 3, material is heated to 250 ℃, and the pressure-controlling in the autoclave 3 is at 25MPa, and the residence time of material in autoclave 3 is 55 minutes.After material comes out from the outlet of autoclave 3, get into cooling in the cooling pool 5 through valve 4, material is cooled to 3 ℃ in cooling pool 5.Cooled material gets in the autoclave 6 through pipeline, and in autoclave 6, material is heated to 420 ℃, and the pressure-controlling in the autoclave 6 is at 40MPa, and the residence time of material in autoclave 6 is 10 minutes.After material comes out from autoclave 6, get into cooling in the cooling pool 8 through valve 7, material is cooled to 0 ℃ in cooling pool 8.The material that comes out from cooling pool 8 comes back to the ultrasonic container 1.With pump the material in the ultrasonic container 1 is re-injected in the autoclave 3 then, make material get into high-temperature high-pressure state again.Said process makes material constantly experience HTHP and refrigeration cycle repeatedly; After the cold and hot repeatedly circulation of material experience, draw, obtain primary products from discharge port 9.Simultaneously, in ultrasonic container 1, add Graphite Powder 99 and organic solvent again, carry out the preparation of next batch sample, carry out preparation continuously.
With primary products with fresh N clean repeatedly, centrifugal, and further vacuum-drying obtains powder-product, characterizes through test, the Graphene that is less than 8 layers in the product accounts for 95%, wherein single-layer graphene accounts for 15%.
As shown in Figure 3, the preparation facilities that present embodiment relates to mainly comprises: ultrasonic container 1, pump 2, autoclave 3, valve 4, cooling pool 5, autoclave 6, valve 7, cooling pool 8, autoclave 9, valve 10, cooling pool 11 etc.Connect ultrasonic container 1, pump 2, autoclave 3, valve 4, cooling pool 5, autoclave 6, valve 7, cooling pool 8, autoclave 9, valve 10 and cooling pool 11 successively through pipeline, be provided with opening for feed at ultrasonic container 1, cooling pool 9 is provided with discharge port.
Selecting N-Methyl pyrrolidone for use is organic solvent, and a certain amount of Graphite Powder 99 and a certain amount of N-Methyl pyrrolidone are joined the ultrasonic container 1 from opening for feed, and in organic solvent, ultrasonic time is 60 minutes through the ultrasonic Graphite Powder 99 uniform mixing that makes.Above-mentioned Graphite Powder 99 mixing solutions in the ultrasonic container 1 is pumped in the autoclave 3, and the inlet of pump 2 links to each other with ultrasonic container 1 outlet through pipeline, and the outlet of pump 2 links to each other with the import of autoclave 3 through pipeline.In autoclave 3, material is heated to 200 ℃, and the pressure-controlling in the autoclave 3 is at 20MPa, and the residence time of material in autoclave 3 is 60 minutes.After material comes out from the outlet of autoclave 3, get into cooling in the cooling pool 5 through valve 4, material is cooled to 2 ℃ in cooling pool 5.Cooled material gets in the autoclave 7 through valve 6, and in autoclave 7, material is heated to 320 ℃, and the pressure-controlling in the autoclave 7 is at 30MPa, and the residence time of material in autoclave 7 is 30 minutes.After material comes out from autoclave 7, get into cooling in the cooling pool 8 through pipeline, material is cooled to 1 ℃ in cooling pool 8.The material that comes out from cooling pool 8 gets into the autoclave 9 through pipeline, and in autoclave 9, material is heated to 410 ℃, and the pressure-controlling in the autoclave 9 is at 40MPa, and the residence time of material in autoclave 9 is 15 minutes.After material comes out from autoclave 9, get into cooling in the cooling pool 11 through valve 10, material is cooled to 0 ℃ in cooling pool 11.Draw material from the discharge port of cooling pool 11, obtain primary products.This system is in when operation, continuously adds Graphite Powder 99 and organic solvent from the opening for feed of ultrasonic container 1, continuously obtains primary sample from the discharge port of cooling pool 11, realizes preparation continuously.
With primary products with fresh N-Methyl pyrrolidone clean repeatedly, centrifugal, and further vacuum-drying obtains powdered sample, characterizes through test, the Graphene that is less than 8 layers in the sample kind accounts for 85%, wherein single-layer graphene accounts for 12%.
Claims (5)
1. a supercutical fluid prepares the method for Graphene, it is characterized in that, comprises the steps:
A, a certain amount of Graphite Powder 99 is poured in the container that fills organic solvent, obtained even Graphite Powder 99 mixture solution through ultrasonic;
B, above-mentioned Graphite Powder 99 mixing solutions is pumped in the autoclave, in autoclave, material is heated to preset temperature, and in autoclave, stops certain hour;
After c, material come out from autoclave; Through cooling off in the pressure piping entering cooling pool; Material is cooled to certain temperature in cooling pool, with pump cooled solution is re-injected in the autoclave then, makes material get into high-temperature high-pressure state again; Said process makes material constantly experience HTHP and refrigeration cycle repeatedly;
After d, material experience HTHP and cooling repeatedly circulate, from pipeline, draw, obtain primary products, simultaneously, add the Graphite Powder 99 mixing solutions again, carry out the preparation of next batch sample, carry out preparation continuously from opening for feed;
E, with primary products with fresh organic solvent clean repeatedly, centrifugal, and further vacuum-drying obtains final powder-product;
Temperature of charge in the autoclave described in the step b is between 200 ~ 700 ℃, and pressure is between 10 ~ 100MPa, and it is 5 ~ 120 minutes that material stops certain hour;
Material described in the step c is cooled to 0 ~ 100 ℃ in cooling pool.
2. prepare the method for Graphene according to the described supercutical fluid of claim l, it is characterized in that, the Graphite Powder 99 described in the step a is natural graphite powder or expansible black lead powder.
3. supercutical fluid according to claim 1 prepares the method for Graphene; It is characterized in that; Organic solvent described in the step a; Refer to peruscabin, ethanol, N-Methyl pyrrolidone, cruel, the N,N-DIMETHYLACETAMIDE, 1 of γ-Ding Nei, any one in 3-dimethyl--2-imidazolone, N-vinyl-2-Pyrrolidone, 1-dodecyl-2-Pyrrolidone, N, dromisol, Virahol, N-octyl group-2-Pyrrolidone, the acetone.
4. prepare the method for Graphene according to the described supercutical fluid of claim l, it is characterized in that the concentration of the Graphite Powder 99 solution described in the step a is 0.5 ~ 20g/L, frequency of ultrasonic is 20 ~ 100KHz, and power is 20W ~ 600W, and ultrasonic time is 5 ~ 200 minutes.
5. supercutical fluid according to claim 1 prepares the method for Graphene, it is characterized in that, the drying process described in the step e is vacuum-drying, and drying temperature is 40 ~ 150 ℃, and be l ~ 30 hour time of drying.
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| CN102515155B (en) * | 2012-01-05 | 2014-01-01 | 上海交通大学 | Method for preparing large-scale graphene through supercritical carbon dioxide exfoliation |
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