CN101993065B - 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 present invention relates to a kind of method of scale preparation Graphene powder, belong to the novel nano-material technical field.
Background technology
Vapour lock property, high-specific surface area and the surfactivity of the mechanical strength of conduction that Graphene is excellent and heat conductivility, superelevation, uniqueness make it can surmount carbon nanotube becomes new functional.The Graphene powder can be used as the conductivity that polymer carrier improves matrix material, therefore can be used for antistatic macromolecule, also can be used for the great industry of the countries such as electric shielding of electric wire; The Graphene powder can hundreds and thousands of times improve the mechanical strength of Polymer Systems as high molecular additive; Like homodisperse Graphene in polyphenylene sulfide; And polyphenylene sulfide can be used for aircraft manufacturing, and therefore following big aircraft also may be used and add the Graphene powder body material.And in view of macromolecular material industry with civilian aspect huge usage quantity, continually develop along with what Graphene was used in different polymers, the demand of interior Graphene will grow with each passing day the coming years.
The same with other nano materials, can prepare on a large scale be the key factor of its applied research of restriction.Present high-quality Graphene powder price is 1000 dollars of every grams, is more than ten times of the price of gold, and this is a deathblow for the applied research of industry member.Patent searching and document find that domestic and international most correlation techniques all are preparation Graphene solution at present, then the dispersion-s in the solution are obtained block through centrifugal or filtration.CN200910193873.8 " a kind of method of producing Graphene " discloses a kind of method of producing Graphene, in organic solvent, Graphite Powder 99 is carried out wet ball grinding; The abrading-ball that wet ball grinding is used be coated with soft polymkeric substance, utilize the frictional force between soft polymer and the graphite to improve mill stripping effect, but this method ball milling time is long, energy consumption is high, also will carry out the separation of complicacy to milled product.CN201010179119.1 " high-efficiency and low-cost mechanical stripping prepares the method for Graphene or graphene oxide " has adopted similar method.CN 200910077131.9 " preparation method of graphene " is a raw material with sodium Metal 99.5 and halohydrocarbon; Through under inert environments, in solvent, carrying out the prepared in reaction Graphene; Also have bibliographical information to use potassium and organic solvent reaction to realize Graphene, the maximum shortcoming of this preparation route is that chemical property such as halogen sodium and potassium are active, and all there are very big danger in storage and preparation process; Prepare process simultaneously and also be difficult to control not, therefore be difficult to realize the single-layer graphene of high yield.CN200910052042.9 " method of preparing graphite alkenyl nanometer materials by electron beam irradiation method " uses the electron beam irradiation of doses that graphite oxide is reduced; Obtain the graphene nano material; But Graphene is reunited in reduction process; Need after the drying just to change powder into, and this powder is still reunited on microcosmic through grinding.Additive method; Like patent 200910050318.X " a kind of method of simple innoxiously preparing single-layer graphene ", 200910054919.8 " based on the graphene preparation methods of xitix ", 200910099595.X " a kind of solution phase preparation method of Graphene ", 200910017788.6 " a kind of preparing methods of functional nano-graphene " and 200910070735.0 " preparing methods of single-layer graphene " etc.; Also be Graphene solution or coacervate, and the homodisperse very difficulty that comes again after wanting to make this graphene platelet that has only an atomic layer level thickness to reunite.The more a kind of method of report is a rapid thermal process graphene oxide method at present; Be published in Small in 2010 and go up summary Graphene oxide about Graphene; Highly reduced graphene oxide; And graphene:Versatile building blocks for carbon-based materials; Only mentioned that be preparation Graphene powder main method at 1050 ℃ to handle graphene oxide greater than the temperature rise rate of 2000 ℃/min; Same CN200880101275.7 " highly efficient process of preparation exfoliated graphene " utilizes rapid thermal process to peel off the Graphene that graphite oxide directly obtains bigger serface, owing to have the few and shortcoming such as inhomogeneous of being heated of treatment capacity, the serious agglomeration on the microcosmic though the powder specific surface area of final preparation is very high in the rapid thermal treatment process.Another shortcoming of this method is that the rapid expansion of 200 to 500 times of volumes makes process be difficult to control, and product is difficult to collect.CN201010179339.4 " a kind of method for preparing dry graphene powder " at first is prepared into suspension-s with Graphene, and lyophilize becomes powder again.This cryodesiccated technology can access the dry state powder, but consuming time very long, and graphene platelet still will be connected to each other in the freeze-drying process, needs to disperse again.
To sum up visible, the micropreparation Graphene is generally realized through centrifugal or suction filtration method in the laboratory at present, and prepared product is difficult in solvent homodisperse again.And rapid thermal process method and freeze-drying also have the improved place of needs.At present also there is not simple scale preparation not have the report of reunion Graphene powder method.
Summary of the invention
The deficiency of the existing technology of preparing that the present invention is directed in the technical background to be set forth; A kind of method of scale preparation Graphene powder is provided; Thoroughly solve the agglomeration traits of preparation Graphene powder in the prior art; Make the prepared graphene powder be easy to be distributed in the solvent, and the method that is provided can realize the mass preparation of Graphene powder.
A kind of method of scale preparation Graphene powder: the first step, graphite oxide is evenly peeled off into stable graphene oxide aaerosol solution; Second step, utilize spray drying technology, comprise spray pyrolysis drying and atomizing freeze drying, remove solvent behind the graphene oxide solution atomization that the first step is prepared and obtain graphene oxide; In the 3rd step, under the atmosphere protection of inertia or reductibility, adopt no swelling heat to handle graphene oxide and obtain the Graphene powder.
Described graphene oxide, its thickness are single or several atomic shells, and characteristic length or width dimensions are 500 nanometers to 100 micron.
Described no swelling heat is handled, and is meant that temperature progressively is elevated to set(ting)value, and temperature rise rate is less than 50 ℃/second, rather than the fast processing graphene oxide of reporting at present prepares the method for Graphene.Overcome in the rapid thermal treatment process dust that doubly brings to 200-500 owing to the volume rapid expansion and be difficult to problem such as collection.
In said preparing method's the first step, it is characterized in that 1. graphite oxide is to obtain through crystalline flake graphite or highly oriented pyrolytic graphite etc. is carried out the oxidation intercalation.Oxidation intercalation technology can be Brodie method, Staudenmaier method or Hummers method.Intercalation realizes between each atomic shell, i.e. the single order intercalation;
2. it is characterized in that the graphite oxide that 1. step makes is peeled off into the graphene oxide of single or several atomic shells, make prepared graphene oxide homodisperse, and form stable aaerosol solution to have no deposition.Solvent can be water or organic solvent, like ethanol, and acetone, N, terepthaloyl moietie, N-Methyl pyrrolidone; THF also can add dispersion agent, as tensio-active agent, sodium p styrene sulfonate, ammoniacal liquor; Sodium-chlor, yellow soda ash, Pottasium Hydroxide, sodium hydroxide, volatile salt etc.;
The concentration of the stable graphene oxide aaerosol solution that 3. forms is that 0.1mg/ml is to 2mg/ml.
In said preparing method's second step, 1. spray drying technology comprises spray pyrolysis drying and atomizing freeze drying;
2. spray drying device comprises spray pyrolysis drying plant and atomizing freeze drying equipment, or any similar devices with identical principle of work;
3. the spray pyrolysis drying is that step 1 preparation graphene oxide aaerosol solution is sprayed into trickle vaporific liquid pearl, and contacting at several seconds time inner drying with warm air is the graphene oxide powder.Powder is collected by drying tower bottom and cyclonic separator; Typical intake air temperature is 150-250 ℃;
4. atomizing freeze drying is that the graphene oxide aaerosol solution is sprayed into trickle vaporific liquid pearl, contacts with freezing air to form the tiny ice cube that contains the graphene oxide thin slice, collects powder through freeze-drying method then.Typical intake air temperature is-40 ℃ to-10 ℃.
5. different according to equipment, spray rate can for 50ml per hour to 5L.Adopt industrial equipment per hour can reach 500L, in addition higher.
In the 3rd step, 1. the atmosphere of said typical reductibility is hydrogen and ammonia in said preparation method, and typical inert atmosphere is nitrogen and argon gas etc.But be not limited to these gas.
2. said thermal treatment temp is 500-1200 ℃.
3. said heat treatment time is 30 seconds to 2 hours.
By the above-mentioned method for preparing the Graphene powder, the powder of resulting Graphene for not having to reunite, but not block or solution.
By the above-mentioned method for preparing the Graphene powder, resulting Graphene specific surface area is 300 to 2600m
2/ g, the size of specific surface area increases along with reducing of the preparation Graphene number of plies.
By the above-mentioned method for preparing the Graphene powder, resulting Graphene can disperse in solvent fast, thereby can not need add any dispersion agent, also can add dispersion agent, makes dispersion more even.
By the above-mentioned method for preparing the Graphene powder, resulting Graphene can be directly compound through Banbury mixer or forcing machine with polymer, do not need again through pulverizing or grinding.
By the above-mentioned method for preparing the Graphene powder, can realize the continuous production of graphene oxide powder through the successive spray process.
By the above-mentioned method for preparing the Graphene powder; Can be once a large amount of thermal treatment graphene oxides are realized the mass preparation of Graphenes; Aspect graphene oxide thermal treatment; Do not have rapid thermal process to realize the requirement that rapid expansion is peeled off, thereby the problem that does not also have powder sharply to expand and fly away and be difficult to collect once can heat treated amount only be subject to the size of HTFX.
The invention solves two key issues: first key issue is to have realized not having the Graphene powder of reunion, also comprises intermediate product graphene oxide powder.In the spray pyrolysis drying process, utilize the quick gasification of solvent to hinder the reunion of graphene oxide thin slice effectively.In the atomizing freeze drying process; Quick freezing makes the drop that contains graphene oxide in very short time, become solid powder, and along with the distillation of solvent obtains the graphene oxide powder, this prepares powder with direct use freeze drying technology and compares; Advantage is at first macroscopic solution to be dispersed into tiny particle; Greatly reduce the possibility of reunion, and the solvent rate of sublimation is fast, the graphene oxide powder changes the Graphene powder into through the processing of reducing gas; Same do not reunite, relatively referring to the experimental result of embodiment 4 and Comparative Examples 2.
Second key issue is to have realized scale preparation; Spraying drying is very big to the treatment capacity of graphene oxide; Can realize the successive treating processes; Prepare the graphene oxide powder incessantly, and do not need rapid thermal process, the volume of having avoided present rapid thermal process graphite oxide to prepare the Graphene powder problem with the difficult collection of powder that sharply expands in the heat treatment process that graphene oxide changes Graphene into; According to the size of lehre only the time chien shih 1 of the several minutes graphene oxide powder that restrains several hectograms change Graphene into, referring to the test result of embodiment 2 and Comparative Examples 1 relatively.Graphene oxide that the present invention realized and Graphene powder; Can be directly and polymer directly compound through Banbury mixer or forcing machine; And do not need again through pulverizing or grinding; The preparation polymer composite can disperse back and other materials compound in water or organic solvent, also can directly be used for transmitter, photochemical catalysis, absorption, solar cell and nano-device etc.
The method of scale preparation Graphene powder provided by the invention is applicable to and comprises as filler and prepare high strength composite, conducing composite material, novel resistance to air loss and flame retardant resistance matrix material and novel nano device etc.
Description of drawings
Fig. 1 is that the graphene oxide powder that embodiment 1 obtains is dispersed in the digital photograph in the deionized water;
Fig. 2 is the stereoscan photograph of the Graphene powder that obtains of embodiment 1;
Fig. 3 is the stereoscan photograph of the graphene oxide powder that obtains of embodiment 2;
Fig. 4 is the stereoscan photograph of the Graphene powder that obtains of embodiment 2;
Fig. 5 is the stereoscan photograph of the graphene oxide powder that obtains of embodiment 3;
Fig. 6 is that the Graphene powder that embodiment 4 obtains is dispersed in the digital photograph in the acetone;
Fig. 7 is the stereoscan photograph of the Graphene that obtains of Comparative Examples 1 rapid thermal process;
Fig. 8 is the transmission electron microscope photo of the graphene oxide powder that obtains of Comparative Examples 2 lyophilizes.
Embodiment
Describe through specific embodiment below, further set forth substantive distinguishing features of the present invention and marked improvement, but the present invention only is confined to embodiment by no means.
Embodiment 1:
The first step: preparation graphene oxide solution.Utilize improved Hummer method, get 98% vitriol oil 69ml, add 1.5g natural flake graphite and 1.5g NaNO in the stirring respectively
3, accurately control reacting liquid temperature at 0 ± 0.5 ℃, slowly add 9gKMnO
4Powder, stirring reaction 1 hour adds the 100ml deionized water, and temperature of charge is brought up to 95 ± 1 ℃, reacts 30 minutes.With deionized water with the H that adds 10ml 30% after the reaction solution dilution again
2O
2, filtered while hot, the ionized water thorough washing does not have SO in filtrating
4 2-Take by weighing the 100mg graphite oxide in beaker, add deionized water and be made into 1000ml solution, with solution ultra-sonic dispersion 5 minutes, obtain stable 0.1mg/ml graphene oxide aaerosol solution again.
Second step: use general spray pyrolysis moisture eliminator or similar devices, intake air temperature is set to 150 ℃, and the ejection speed of liquid is 5000ml per hour.The stirring of graphene oxide powder can be dispersed in the deionized water, and photo is as shown in Figure 1, and transparent brown solution is the homodisperse result of graphene oxide.
The 3rd step: the graphene oxide powder is risen to the Graphene powder that 500 ℃ of insulations promptly obtained not having reunion in a minute under nitrogen protection, as shown in Figure 2.Graphene platelet is of a size of 0.5 to 10 micron, owing to have only an atomic shell, curls into bulk naturally, and each bulk particulate size is about 0.5 to 5 micron, does not significantly unite between the bulk particle.
Embodiment 2:
The first step, the preparation of graphene oxide solution.Utilize improved Staudenmaier method in the mixed solution of 98% the vitriol oil and nitric acid, to add natural flake graphite, stir and add saltpetre, 0-10 ℃ of control reacting liquid temperature, reaction stirred obtained graphite oxide in 6 hours, and filtration drying obtains graphite oxide.Take by weighing the 300mg graphite oxide in beaker, add deionized water and be made into 500ml solution, adding 2ml concentration is the KOH solution of 1M, with solution ultra-sonic dispersion 20 minutes, obtains stable 0.6mg/ml graphene oxide aaerosol solution again.
Second step: use general spray-dryer or similar devices, intake air temperature is set to 200 ℃, and the ejection speed of liquid is 2000ml per hour, and the shower nozzle diameter is 2mm.Collect the graphene oxide powder, the graphene oxide powder that this technology of preparing of field emission scanning electron microscope test test proof obtains is not reunited, and is as shown in Figure 3.
The 3rd step: the graphene oxide powder is risen to the Graphene powder that 1000 ℃ of insulations promptly obtained not having reunion in a minute under argon shield, as shown in Figure 4.
Embodiment 3:
The first step: the preparation of graphene oxide solution is with case 2.Take by weighing the 1g graphite oxide in beaker, add deionized water and be made into 500ml solution, add the NaOH solution of 10ml 1M, with solution ultra-sonic dispersion 60 minutes, obtain stable 2mg/ml graphene oxide aaerosol solution again.
Second step: use general spray-dryer or similar devices, intake air temperature is set to 300 ℃, and the ejection speed of liquid is 1000ml per hour.Collect graphene oxide powder field emission scanning electron microscope test test and prove that the graphene oxide powder that this technology of preparing obtains does not have to reunite, as shown in Figure 5.
The 3rd step: the graphene oxide powder is risen to the Graphene powder that 600 ℃ of insulations promptly obtained not having reunion in a minute under the hydrogen gas shiled, its pattern is similar with Fig. 4.
Embodiment 4:
The first step: the preparation of graphene oxide solution is with case 2.Take by weighing the 1000mg graphite oxide in beaker, add deionized water and be made into 1L solution, add 2ml ammoniacal liquor, with solution ultra-sonic dispersion 1 minute, obtain stable 0.1mg/ml graphene oxide aaerosol solution again.
Second step: use general spray-dryer or similar devices, intake air temperature is set to subzero 40 ℃, and the ejection speed of liquid is 2500ml per hour.Collect the graphene oxide powder.
The 3rd step: the graphene oxide powder is risen to 600 ℃ of insulations promptly obtained not having the Graphene powder of reunion in one minute under protection of ammonia, the Graphene morphology microstructure that obtains and Fig. 2,4 similar.Get 1mg and put into 10ml acetone, dissolving forms stable dark solution rapidly, and is as shown in Figure 6.
Embodiment 5: intake air temperature is set to subzero 20 ℃, and other preparation processes are with embodiment 4.The Graphene morphology microstructure that obtains and Fig. 2,3 similar.
Comparative Examples 1: the rapid thermal process graphite oxide obtains the simultaneous test of Graphene.Utilize improved Staudenmaier method in the mixed solution of 98% the vitriol oil and nitric acid, to add natural flake graphite, stir and add saltpetre, 0-10 ℃ of control reacting liquid temperature, reaction stirred obtained graphite oxide in 6 hours, and filtration drying obtains graphite oxide.Take by weighing the 300mg graphite oxide and in ceramic boat, be pushed into fast in 1000 ℃ the tube furnace, thermal treatment is 30 seconds under nitrogen protection.The result is as shown in Figure 7 for its sem test, worm graphite, and the graphite flake of promptly not peeling away still links together at some position, forms porous expanded graphite structure.
Comparative Examples 2: the cryodesiccated simultaneous test that obtains the graphene oxide powder.Utilize improved Hummer method, get 98% the vitriol oil, subcooling adds a certain amount of natural flake graphite, NaNO respectively in the stirring
3And KMnO
4, 0-10 ℃ of control reacting liquid temperature, stirring reaction carries out pyroreaction after 5 hours, and the control reacting liquid temperature continues to stir 30 minutes in 100 ℃.Add an amount of H with deionized water again with after the reaction solution dilution
2O
2, filtered while hot, the ionized water thorough washing does not have SO in filtrating
4 2-Take by weighing the 500mg graphite oxide in beaker, add deionized water and be made into 1000ml solution, with solution ultra-sonic dispersion 5 minutes, obtain stable 0.5mg/ml graphene oxide solution again.In refrigerator that solution is freezing, utilize Freeze Drying Equipment to obtain the graphene oxide powder, the transmission electron microscope photo of powder is as shown in Figure 8.The graphene oxide thin slice of monoatomic layer still has part to reunite in the sublimation process of refrigerating process and solvent, and the fold on edge different-shape and surface all is that the multi-disc graphene oxide overlaps on proof together each other.
Claims (5)
1. the method for a scale preparation Graphene powder is characterized in that comprising:
A) graphite oxide is evenly peeled off into the graphene oxide aaerosol solution;
B) utilize spray drying technology, the aaerosol solution atomizing back that step a is made is removed solvent and is obtained the graphene oxide powder;
C) under the atmosphere protection of inertia or reductibility, adopt the no prepared graphene oxide powder of swelling heat disposal methods step b and make no reunion Graphene powder at last;
Described spraying drying comprises spray pyrolysis drying or atomizing freeze drying; Wherein,
1. the spray pyrolysis drying is that the graphene oxide aaerosol solution is sprayed into trickle vaporific liquid pearl, and contacting at several seconds time inner drying with warm air is the graphene oxide powder, and powder is collected by drying tower bottom and cyclonic separator; Intake air temperature is 150-250 ℃;
2. atomizing freeze drying is that the graphene oxide aaerosol solution is sprayed into trickle vaporific liquid pearl, contacts with freezing air to form the tiny ice cube that contains the graphene oxide thin slice, collects powder through freeze-drying method then, and intake air temperature is-40 ℃ to-10 ℃;
Described nothing expands heat treated temperature rise rate less than 50 ℃/second;
The atmosphere of described reductibility was hydrogen or ammonia when described no swelling heat was handled, and described inert atmosphere is nitrogen or argon gas; No swelling heat treatment temp is 500-1200 ℃, and the said no swelling heat treatment time is 30 seconds to 2 hours.
2. by the described method of claim 1, it is characterized in that graphite oxide carries out the oxidation intercalation through crystalline flake graphite or highly oriented pyrolytic graphite and obtains.
3. by the described method of claim 1, the solvent that it is characterized in that forming the graphene oxide aaerosol solution is water or the organic solvent that comprises ethanol, acetone, N, terepthaloyl moietie, N-Methyl pyrrolidone, THF.
4. by the described method of claim 3, the concentration that it is characterized in that described aaerosol solution is 0.1mg/ml-2mg/ml; In aaerosol solution, add dispersion agent.
5. by the described method of claim 4, it is characterized in that described dispersion agent is tensio-active agent, sodium p styrene sulfonate, ammoniacal liquor, sodium-chlor, yellow soda ash, Pottasium Hydroxide, sodium hydroxide or volatile salt.
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