CN101993065A - Method for preparing graphene powder - Google Patents
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Abstract
The invention relates to a method for preparing graphene powder in large scale, which is characterized by comprising the following steps of: firstly, uniformly peeling graphene oxide into a graphene oxide suspension solution; then, atomizing the graphene oxide solution by using the spray drying technology comprising spray pyrolysis drying and spray freeze drying, and removing a solvent to obtain graphene oxide powder; and finally, oxidizing grapheme by using the non-expansion heat treatment process to obtain non-agglomerative graphene powder. The continuous preparation process of the spray technology and the non-expansion heat treatment process ensure the large-scale preparation of the graphene powder. The prepared graphene powder comprising intermediate product graphene oxide powder does not have agglomeration and has good dispersivity in the solvent. The graphene powder is used as a filling material to prepare high strength composite materials, conductive composite materials, novel air-tight flame-retardant composite materials, novel nanodevices and the like.
Description
Technical Field
The invention relates to a method for preparing graphene powder on a large scale, and belongs to the technical field of novel nano materials.
Background
The graphene has excellent electric conduction and heat conduction performance, ultrahigh mechanical strength, unique gas resistance, high specific surface area and surface activity, so that the graphene can be a new-generation functional material beyond a carbon nano tube. The graphene powder can be used as a polymer filler to improve the conductivity of the composite material, so that the graphene powder can be used for antistatic polymers and can also be used for the important industries of the countries such as the electric shielding of wires and cables; the graphene powder as a polymer additive can improve the mechanical strength of a polymer system by hundreds of times, for example, graphene is uniformly dispersed in polyphenylene sulfide, and the polyphenylene sulfide can be used for aircraft manufacturing, so that a graphene powder material can be added into a large aircraft in the future. In view of the huge usage amount of polymer materials in industrial and civil applications, with the continuous development of graphene in different polymers, the demand of graphene will increase in the next few years.
Like other nano materials, the large-scale preparation of the nano material is a key factor for restricting the application and research of the nano material. At present, the price of high-quality graphene powder is $ 1000 per gram, which is more than ten times of the gold price, and the price is a fatal strike for the application research in the industry. The patent and literature search shows that the vast majority of related technologies at home and abroad are to prepare graphene solution, and then obtain blocks by centrifuging or filtering the dispersion in the solution. CN200910193873.8, a method for producing graphene, discloses a method for producing graphene, in which graphite powder is ball-milled by a wet method in an organic solvent; the surface of a grinding ball used for wet ball milling is wrapped with a soft polymer, and the friction force between the soft polymer and graphite is utilized to improve the grinding and stripping effect, but the method has long ball milling time and high energy consumption, and the ball milling product is required to be subjected to complex separation. CN201010179119.1 method for preparing graphene or graphene oxide by high efficiency and low cost mechanical stripping adopts a similar method. CN 200910077131.9 "preparation method of graphene" uses metal sodium and halogenated hydrocarbon as raw materials, and prepares graphene by reacting in a solvent under an inert environment, and there are also reports in literature that graphene is realized by reacting potassium with an organic solvent, and the greatest disadvantage of this preparation route is that chemical properties such as sodium halide and potassium are active, and there is a great risk in storage and preparation processes, and at the same time, the preparation process is difficult to control, so that it is difficult to realize high-yield single-layer graphene. CN200910052042.9 method for preparing graphene-based nanomaterial by electron beam irradiation reduces graphite oxide by using a certain dose of electron beam irradiation to obtain graphene nanomaterial, but graphene is agglomerated in the reduction process, and after drying, the graphene needs to be ground to be converted into powder, and the powder is also agglomerated microscopically. Other methods, such as patent 200910050318.X "a method for preparing single-layer graphene simply and without toxicity", 200910054919.8 "a method for preparing graphene based on ascorbic acid", 200910099595.X "a method for preparing solution phase of graphene", 200910017788.6 "a method for preparing functional nano-graphene", 200910070735.0 "a method for preparing single-layer graphene", and the like, obtain a graphene solution or aggregate, and it is very difficult to uniformly disperse the aggregated graphene flakes having a thickness of only one atomic layer. One of the more currently reported methods is the rapid thermal processing Graphene oxide method, which was published in 2010 on Small for a review of Graphene oxide, high reduced Graphene oxide, and Graphene: versatile building blocks for carbon-based materials only mentions that processing graphene oxide at 1050 ℃ at a heating rate of more than 2000 ℃/min is a main method for preparing graphene powder, and CN200880101275.7, a high-efficiency method for preparing layered exfoliated graphene, directly obtains graphene with a large specific surface area by exfoliating graphite oxide through rapid thermal treatment, but due to the defects of small treatment amount, uneven heating and the like in the rapid thermal treatment process, the finally prepared powder has a high specific surface area but serious agglomeration on a microscopic scale. Another disadvantage of this method is that the rapid expansion of 200 to 500 times the volume makes the process difficult to control and the product difficult to collect. CN201010179339.4 "a method for preparing dry graphene powder", firstly, graphene is prepared into a suspension, and then freeze-dried into a powder. This freeze-drying technique can produce dry powder, but it is time-consuming, and the graphene sheets are connected to each other during the freeze-drying process and need to be re-dispersed.
In conclusion, the existing method for preparing graphene in a micro-scale manner in a laboratory is generally realized by a centrifugation or suction filtration method, and the prepared product is difficult to be uniformly dispersed in a solvent again. There are also areas where improvements in rapid heat treatment processes and freeze drying processes are needed. At present, no simple method for preparing the non-agglomerated graphene powder in a large scale is reported.
Disclosure of Invention
The invention provides a method for preparing graphene powder on a large scale aiming at the defects of the prior art explained in the technical background, which thoroughly solves the agglomeration problem of the graphene powder prepared in the prior art, so that the prepared graphene powder is easily dispersed in a solvent, and the method can realize the large-scale preparation of the graphene powder.
A method for preparing graphene powder in a large scale comprises the following steps: firstly, uniformly stripping graphite oxide into a stable graphene oxide suspension solution; secondly, atomizing the graphene oxide solution prepared in the first step by using a spray drying technology including spray pyrolysis drying and spray freeze drying, and removing a solvent to obtain graphene oxide; and thirdly, under the protection of inert or reducing atmosphere, carrying out expansion-free heat treatment on the graphene oxide to obtain graphene powder.
The graphene oxide has a thickness of a single or several atomic layers, and a characteristic length or width dimension of 500 nanometers to 100 micrometers.
The non-expansion heat treatment refers to that the temperature is gradually increased to a set value, the temperature rise rate is less than 50 ℃/second, and the method is not a method for preparing graphene by rapidly processing graphene oxide reported at present. The problems of dust and difficulty in collection caused by the fact that the volume is rapidly expanded to 200-500 times in the rapid heat treatment process are solved.
In the first step of the preparation method, firstly, the graphite oxide is obtained by carrying out oxidation intercalation on crystalline flake graphite, highly oriented pyrolytic graphite and the like. The oxidative intercalation process may be a Brodie process, Staudenmaier process or Hummers process. Intercalation is realized between each atomic layer, namely first-order intercalation;
and secondly, the method is characterized in that the graphite oxide prepared in the first step is stripped into single or several atomic layers of graphene oxide, so that the prepared graphene oxide is uniformly dispersed and forms a stable suspension solution without any precipitate. The solvent can be water or organic solvent, such as ethanol, acetone, dimethylformamide, ethylene glycol, N-methylpyrrolidone, tetrahydrofuran, or dispersant, such as common surfactant, sodium p-styrene sulfonate, ammonia water, sodium chloride, sodium carbonate, potassium hydroxide, sodium hydroxide, ammonium carbonate, etc.;
③ the concentration of the formed stable graphene oxide suspension is 0.1mg/ml to 2 mg/ml.
In the second step of the preparation method, the spray drying technique includes spray pyrolysis drying and spray freeze drying;
the spray drying equipment comprises spray pyrolysis drying equipment and spray freeze drying equipment, or any similar equipment with the same working principle;
and thirdly, spray pyrolysis drying, namely spraying the graphene oxide suspension solution prepared in the step 1 into fine vaporous liquid beads, and drying the graphene oxide suspension solution into graphene oxide powder in a few seconds by contacting with hot air. Collecting the powder from the bottom of the drying tower and a cyclone separator; the typical air inlet temperature is 150 ℃ and 250 ℃;
and fourthly, spray freeze drying, namely spraying the graphene oxide suspension solution into fine mist liquid beads, contacting with cold air to form fine ice blocks containing graphene oxide sheets, and collecting powder through a freeze drying method. Typical inlet temperatures are-40 ℃ to-10 ℃.
The spraying rate can be 50ml to 5L per hour according to different equipment. The use of industrial equipment can reach 500L per hour or even higher.
In the third step of the preparation method, typical reducing atmosphere is hydrogen and ammonia, and typical inert atmosphere is nitrogen, argon and the like. But are not limited to these gases.
② the heat treatment temperature is 500-1200 ℃.
And the heat treatment time is 30 seconds to 2 hours.
According to the method for preparing the graphene powder, the obtained graphene is powder without agglomeration, and is not a block or a solution.
According to the method for preparing the graphene powder, the specific surface area of the obtained graphene is 300-2600 m2The specific surface area increases with the reduction in the number of graphene layers produced.
According to the method for preparing the graphene powder, the obtained graphene can be rapidly dispersed in the solvent, so that no dispersant is required to be added, and the dispersant can be added to ensure that the dispersion is more uniform.
According to the method for preparing the graphene powder, the obtained graphene can be directly compounded with polymers through an internal mixer or an extruder without being crushed or ground.
According to the method for preparing the graphene powder, the continuous production of the graphene oxide powder can be realized through a continuous spraying process.
According to the method for preparing the graphene powder, a large amount of graphene oxide can be subjected to heat treatment at one time to realize large-scale preparation of graphene, the requirement of rapid expansion stripping of the graphene oxide through rapid heat treatment is not met in the aspect of graphene oxide heat treatment, the problem that the powder is difficult to collect due to rapid expansion and dispersion is also solved, and the amount of heat treatment capable of being performed at one time is only limited by the size of heat treatment equipment.
The present invention solves two key problems: the first key problem is to realize the graphene powder without agglomeration, and the graphene powder also comprises an intermediate product graphene oxide powder. In the spray pyrolysis drying process, the rapid gasification of the solvent is utilized to effectively prevent the graphene oxide flakes from agglomerating. In the spray freeze drying process, the liquid drop containing the graphene oxide is rapidly frozen to form solid powder in a short time, and the graphene oxide powder is obtained along with sublimation of the solvent, compared with the method for preparing the powder by directly using a freeze-drying technology, the method has the advantages that macroscopic solution is firstly dispersed into fine particles, the possibility of agglomeration is greatly reduced, the sublimation speed of the solvent is high, the graphene oxide powder is converted into the graphene powder through treatment of reducing gas, and the agglomeration is avoided, see the comparison of experimental results of example 4 and comparative example 2.
The second key problem is that large-scale preparation is realized, the graphene oxide is treated by spray drying in a large amount, a continuous treatment process can be realized, the graphene oxide powder is uninterruptedly prepared, rapid heat treatment is not needed in the heat treatment process of converting the graphene oxide into the graphene, the problems of rapid volume expansion and difficult powder collection of the graphene oxide powder prepared by the conventional rapid heat treatment of the graphene oxide are avoided, 1 to hundreds of grams of graphene oxide powder is converted into the graphene only within a few minutes according to the size of an annealing furnace, and the test results of example 2 and comparative example 1 are compared. The graphene oxide and graphene powder can be directly compounded with a polymer through an internal mixer or an extruder without crushing or grinding to prepare a polymer composite material, can be dispersed in water or an organic solvent and then compounded with other materials, and can also be directly used for sensors, photocatalysis, adsorption, solar cells, nano devices and the like.
The method for preparing the graphene powder in a large scale is suitable for preparing high-strength composite materials, conductive composite materials, novel air-tightness and flame-retardant composite materials, novel nanometer devices and the like by using the graphene powder as a filler.
Drawings
Fig. 1 is a digital photograph of the graphene oxide powder obtained in example 1 dispersed in deionized water;
FIG. 2 is a scanning electron micrograph of the graphene powder obtained in example 1;
fig. 3 is a scanning electron micrograph of the graphene oxide powder obtained in example 2;
FIG. 4 is a scanning electron micrograph of the graphene powder obtained in example 2;
FIG. 5 is a scanning electron micrograph of the graphene oxide powder obtained in example 3;
fig. 6 is a digital photograph of the graphene powder obtained in example 4 dispersed in acetone;
fig. 7 is a scanning electron micrograph of graphene obtained by rapid thermal treatment of comparative example 1;
fig. 8 is a transmission electron micrograph of the graphene oxide powder obtained by freeze-drying in comparative example 2.
Detailed Description
The essential features and the significant advantages of the invention will be further elucidated below by means of specific examples, which are by no means limiting.
Example 1:
the first step is as follows: preparing a graphene oxide solution. By using an improved Hummer method, 69ml of 98% concentrated sulfuric acid is taken, and 1.5g of natural crystalline flake graphite and 1.5g of NaNO are respectively added into the mixture during stirring3Accurately controlling the temperature of the reaction solution at 0 +/-0.5 ℃, and slowly adding 9g of KMnO4Stirring the powder to react for 1 hour, adding 100ml of deionized water, raising the temperature of reactants to 95 +/-1 ℃, and reacting for 30 minutes. The reaction mixture was diluted with deionized water and 10ml of 30% H was added2O2Filtering while the solution is hot, and fully washing the solution by using ionized water until no SO is contained in the filtrate4 2-. Weighing 100mg of graphite oxide in a beaker, adding deionized water to prepare 1000ml of solution, and then carrying out ultrasonic dispersion on the solution for 5 minutes to obtain a stable 0.1mg/ml graphene oxide suspension solution.
The second step is that: using a conventional spray pyrolysis dryer or the like, the inlet temperature was set at 150 ℃, and the liquid ejection rate was 5000ml per hour. The graphene oxide powder can be dispersed in deionized water by stirring, the photograph is shown in fig. 1, and the transparent brown solution is the result of uniform dispersion of graphene oxide.
The third step: raising the temperature of the graphene oxide powder to 500 ℃ under the protection of nitrogen, and keeping the temperature for one minute to obtain the non-agglomerated graphene powder, as shown in fig. 2. The graphene flakes have a size of 0.5 to 10 microns and are naturally rolled into agglomerates due to only one atomic layer, each agglomerate having a size of about 0.5 to 5 microns, with no significant agglomeration between agglomerates.
Example 2:
firstly, preparing a graphene oxide solution. Adding natural crystalline flake graphite into a mixed solution of 98% concentrated sulfuric acid and nitric acid by using an improved Staudenmaier method, adding potassium nitrate by stirring, controlling the temperature of a reaction solution to be 0-10 ℃, stirring a reactant for 6 hours to obtain graphite oxide, filtering and drying to obtain the graphite oxide. Weighing 300mg of graphite oxide in a beaker, adding deionized water to prepare 500ml of solution, adding 2ml of KOH solution with the concentration of 1M, and then carrying out ultrasonic dispersion on the solution for 20 minutes to obtain the stable 0.6mg/ml graphene oxide suspension solution.
The second step is that: a conventional spray dryer or the like was used, the inlet temperature was set at 200 ℃, the liquid discharge rate was 2000ml per hour, and the nozzle diameter was 2 mm. The graphene oxide powder is collected, and a field emission scanning electron microscope test proves that the graphene oxide powder obtained by the preparation technology is free from agglomeration, as shown in fig. 3.
The third step: raising the temperature of the graphene oxide powder to 1000 ℃ under the protection of argon, and keeping the temperature for one minute to obtain the non-agglomerated graphene powder, as shown in fig. 4.
Example 3:
the first step is as follows: the graphene oxide solution was prepared as in case 2. Weighing 1g of graphite oxide in a beaker, adding deionized water to prepare 500ml of solution, adding 10ml of 1M NaOH solution, and then carrying out ultrasonic dispersion on the solution for 60 minutes to obtain a stable graphene oxide suspension solution with the concentration of 2 mg/ml.
The second step is that: using a conventional spray dryer or similar device, the inlet temperature was set at 300 ℃ and the liquid was sprayed out at a rate of 1000ml per hour. The collected graphene oxide powder is tested by a field emission scanning electron microscope to prove that the graphene oxide powder obtained by the preparation technology is not agglomerated, as shown in fig. 5.
The third step: and (3) raising the temperature of the graphene oxide powder to 600 ℃ under the protection of hydrogen gas, and keeping the temperature for one minute to obtain the non-agglomerated graphene powder, wherein the morphology of the non-agglomerated graphene powder is similar to that of the graphene oxide powder shown in the figure 4.
Example 4:
the first step is as follows: the graphene oxide solution was prepared as in case 2. Weighing 1000mg of graphite oxide in a beaker, adding deionized water to prepare 1L of solution, adding 2ml of ammonia water, and then carrying out ultrasonic dispersion on the solution for 1 minute to obtain a stable 0.1mg/ml graphene oxide suspension solution.
The second step is that: using a conventional spray dryer or similar device, the inlet temperature was set at-40 ℃ and the liquid was sprayed out at a rate of 2500ml per hour. And collecting the graphene oxide powder.
The third step: and (3) heating the oxidized graphene powder to 600 ℃ under the protection of ammonia gas, and preserving the heat for one minute to obtain non-agglomerated graphene powder, wherein the morphology of the obtained graphene powder is similar to that of the graphene powder shown in the figures 2 and 4. 1mg was taken and placed in 10ml acetone and dissolved rapidly to form a stable black solution, as shown in FIG. 6.
Example 5: the temperature of the air inlet is set to be minus 20 ℃, and other preparation processes are the same as those of the embodiment 4. The morphology of the obtained graphene powder is similar to that of the graphene powder shown in figures 2 and 3.
Comparative example 1: comparative experiment of graphene obtained by rapid thermal treatment of graphite oxide. Adding natural crystalline flake graphite into a mixed solution of 98% concentrated sulfuric acid and nitric acid by using an improved Staudenmaier method, adding potassium nitrate by stirring, controlling the temperature of a reaction solution to be 0-10 ℃, stirring a reactant for 6 hours to obtain graphite oxide, filtering and drying to obtain the graphite oxide. 300mg of graphite oxide is weighed into a ceramic boat and quickly pushed into a tube furnace at 1000 ℃, and the heat treatment is carried out for 30 seconds under the protection of nitrogen. The results of the sem examination are shown in fig. 7, where the vermicular graphite, i.e., the graphite flakes that were not exfoliated, were still connected together at some locations to form a porous expanded graphite structure.
Comparative example 2: comparative test of the obtained graphene oxide powder by freeze-drying. By using an improved Hummer method, 98% concentrated sulfuric acid is taken, cooled at low temperature, and a certain amount of natural crystalline flake graphite and NaNO are respectively added into the mixture during stirring3And KMnO4Controlling the temperature of the reaction solution to be 0-10 ℃, stirring for 5 hours, then carrying out high-temperature reaction, controlling the temperature of the reaction solution to be within 100 ℃, and continuing stirring for 30 minutes. Diluting the reaction solution with deionized water, and adding a proper amount of H2O2Filtering while the solution is hot, and fully washing the solution by using ionized water until no SO is contained in the filtrate4 2-. Weighing 500mg of graphite oxide in a beaker, adding deionized water to prepare 1000ml of solution, and then carrying out ultrasonic dispersion on the solution for 5 minutes to obtain a stable 0.5mg/ml graphene oxide solution. The solution was frozen in a refrigerator, and graphene oxide powder was obtained using a freeze dryer, and the transmission electron micrograph of the powder is shown in fig. 8. The graphene oxide sheets with the monoatomic layers still partially agglomerate in the freezing process and the sublimation process of the solvent, and the evidence that the graphene oxide sheets with different shapes at the edges and the folds on the surfaces are mutually overlapped is provided.
Claims (10)
1. A method for preparing graphene powder in a large scale is characterized by comprising the following steps:
a) uniformly stripping graphite oxide into a graphene oxide suspension solution;
b) b, atomizing the suspension solution prepared in the step a by using a spray drying technology, and removing the solvent to obtain graphene oxide powder;
c) and c, under the protection of inert or reducing atmosphere, processing the graphene oxide prepared in the step b by adopting a non-expansion heat treatment method to finally prepare non-agglomeration graphene powder.
2. The method of claim 1, wherein the graphene oxide has a thickness of a single or a few atomic layers and a length or width of 500 nm to 100 μm.
3. The method of claim 1, wherein the graphite oxide is obtained by oxidative intercalation of crystalline flake graphite or highly oriented pyrolytic graphite.
4. The method of claim 1, wherein the solvent used to form the graphene oxide suspension is water or an organic solvent comprising ethanol, acetone, dimethylformamide, ethylene glycol, N-methylpyrrolidone, tetrahydrofuran.
5. The method of claim 4, wherein the suspension solution has a concentration of 0.1mg/ml to 2 mg/ml; in a suspension solution or by adding a dispersant.
6. The method of claim 5 wherein the dispersant is a surfactant, sodium p-styrene sulfonate, aqueous ammonia, sodium chloride, sodium carbonate, potassium hydroxide, sodium hydroxide, or ammonium carbonate.
7. The method of claim 1, wherein said spray drying comprises spray pyrolysis drying or spray freeze drying; wherein,
firstly, spray pyrolysis drying is to spray a graphene oxide suspension solution into fine mist liquid beads, and the graphene oxide suspension solution is contacted with hot air and dried into graphene oxide powder within a few seconds. Collecting the powder from the bottom of the drying tower and a cyclone separator; the temperature of the air inlet is 150 ℃ and 250 ℃;
secondly, spray freeze drying is to spray the graphene oxide suspension solution into fine mist liquid beads, the fine mist liquid beads are contacted with cold air to form fine ice blocks containing graphene oxide sheets, then powder is collected by a freeze drying method, and the temperature of an air inlet is between 40 ℃ below zero and 10 ℃ below zero.
8. The method of claim 1 wherein the non-expansion heat treatment is carried out at a temperature ramp rate of less than 50 ℃/sec.
9. The method according to claim 1 or 8, wherein the reducing atmosphere in the non-expansion heat treatment is hydrogen or ammonia, and the inert atmosphere is nitrogen or argon; the temperature of the non-expansion heat treatment is 500-1200 ℃, and the time of the non-expansion heat treatment is 30 seconds to 2 hours.
10. The process as claimed in claim 1, wherein the graphene obtained has a specific surface area of from 300 to 2600m2The specific surface area increases with the reduction in the number of graphene layers produced.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080258359A1 (en) * | 2007-04-17 | 2008-10-23 | Aruna Zhamu | Low-temperature method of producing nano-scaled graphene platelets and their nanocomposites |
| CN101559944A (en) * | 2009-05-27 | 2009-10-21 | 天津大学 | Conductive graphene film and self-assembly preparation method thereof |
-
2010
- 2010-12-17 CN CN201010593157A patent/CN101993065B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080258359A1 (en) * | 2007-04-17 | 2008-10-23 | Aruna Zhamu | Low-temperature method of producing nano-scaled graphene platelets and their nanocomposites |
| CN101559944A (en) * | 2009-05-27 | 2009-10-21 | 天津大学 | Conductive graphene film and self-assembly preparation method thereof |
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