CN102602925A - Method for preparing graphene by virtue of high-pressure reduction - Google Patents
Method for preparing graphene by virtue of high-pressure reduction Download PDFInfo
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Abstract
The invention relates to a method for preparing graphene by virtue of high-pressure reduction. In the method, high-temperature high-pressure reduction processing is performed on graphene oxide in an inert atmosphere so as to completely remove the oxygen-containing functional groups in graphene oxide, and the structural defects of graphene are repaired at the same time, so as to obtain high-quality graphene. The method can be used for avoiding the excessive use of chemical reagents, brings less pollution to environment and can be applied to the reduction of various powder of graphene oxide prepared by various methods.
Description
Technical field
The present invention relates to the grapheme material preparation field, more particularly, relate to a kind of technology that graphene oxide is reduced into the high quality Graphene through hot, high pressure reductive technology.
Background technology
Graphene, English name Graphene after 2004 are found by the scientist of University of Manchester, just becomes the focus of scientific circles and industry member concern.The thickness of Graphene has only 0.335 nanometer, be not only in the known materials the thinnest a kind of, unusual rigid also; As simple substance, the speed that it at room temperature transmits electronics than known all conductor and semi-conductor all fast (in the Graphene travelling speed of electronics reached the light velocity 1/300).Because the weird atom structure of Graphene, wherein the behavior of current carrier (electronics and hole) must use relativistic quantum mechanics (Relativistic Quantum Mechanics) just can describe.Specifically, Graphene is a kind of two-dimensional material of monoatomic layer, i.e. monolayer carbon lattice plane material, and (theoretical specific surface area is up to 2630m to have the specific surface area of super large
2/ g), excellent conduction and heat conductivility, and good chemicalstability.These good properties make the material based on Graphene become a kind of ideal energy storage material, comprise that super capacitance electrode material, lithium ion battery electrode material, hydrogen storage material, fuel cell are with material etc.
At present, the method for preparing Graphene mainly comprises following four kinds: mechanically peel method, graphite oxide reduction method, epitaxial growth method and chemical Vapor deposition process.Wherein, the resulting Graphene lamella of mechanically peel method is less, and is difficult to realize widespread adoption.Though epitaxial growth method can prepare the big area single-layer graphene, agents useful for same costs an arm and a leg, and is also relatively more difficult.
The Graphene of chemical Vapor deposition process preparation is of high quality, but the preparation process depends on catalytic metal.The graphite oxide reduction method is earlier graphite to be carried out oxide treatment; Obtaining the equal appendix in top layer and side has the graphite oxide of a large amount of oxy radicals; Then in the water equal solvent, utilize mechanical effects such as ultrasonic concussion with its peel off dissociate obtain graphene oxide (Graphite Oxide, GO).It is generally acknowledged that the GO two-dimensional layered structure that is as the criterion, interlayer contain a large amount of hydroxyls and the acid reactive group of carbonyl, and ultimate analysis finds that the ratio of the C of GO: H: O was at 6: 2.33: 1.2-6: between 3.7: 2.83.In the preparation process of GO, the introducing of Sauerstoffatom has destroyed the conjugated structure of original graphite, makes the graphene oxide of peeling off lose electroconductibility, thereby has limited it at the store energy active material, the especially application of compositing conducting nano-complex aspect.
At present, can pass through method of reducing, make the GO deoxidation realize that heavy greying obtains Graphene, thereby the conductivity of graphene oxide is enlarged markedly.To GO reduce the preparation Graphene be unique can mass production the technology of grapheme material.Graphite oxide reduction method reductive method comprises thermal reduction, the chemical reduction of Hydrazine Hydrate 80 class and microwave reduction.Thermal reduction is that graphene oxide is heated to more than 1000 ℃, makes it lose oxygen-containing functional group and forms Graphene.The resulting Graphene of this method, the residual a small amount of oxygen-containing functional group of meeting, electric conductivity is not high.The chemical reduction of Hydrazine Hydrate 80 class is to adopt chemical reducing agent to make graphene oxide be reduced into Graphene, and reductive agent is a hydrazine class compound, like Hydrazine Hydrate 80, dimethylhydrazine etc.Because hydrazine class compound has inflammable, explosive, hypertoxic performance, a large amount of use meetings cause severe contamination to environment, and the safety of using can be very poor.Microwave reduction utilizes that microwave heating is concentrated, high-power characteristics, makes graphite oxide instantaneously heating reduction, expands rapidly and discharges a large amount of gases.This method blast process is comparatively violent, and the product loss is uncontrollable, and resulting Graphene defective is more.
It is little how to develop a kind of environmental pollution, and reduction reaction is thorough, and the time, short graphene oxide reduction reaction was the problem that this area need solve.
Summary of the invention
To the deficiency of prior art, one of the object of the invention is to provide a kind of high pressure reduction to prepare the method for Graphene.Said method is under the inert gas pressure environment, and graphene oxide is carried out pyroprocessing, removes oxygen-containing functional group, repairs the textural defect in the Graphene simultaneously, thereby makes high-quality Graphene.
The present invention realizes through following technical scheme:
Preparation method of graphene of the present invention is: in inert atmosphere, graphene oxide high temperature, high pressure reduction are handled, prepared Graphene, said pyritous temperature >=900 ℃; Said highly compressed pressure >=1MPa.
The present invention is through in inert protective atmosphere, under high-temperature and high-pressure conditions, with GO reductive method, does not therefore have concrete qualification for graphene oxide, and the graphene oxide that every oxidized graphite obtains all can be used for the present invention.In the prior art, the preparation of graphite oxide mainly contains Brodie method, Hummers method or three kinds of method for oxidation of Staudenmaier method.
The Brodie method is at first with the HNO of being fuming
3Handle natural micro powder graphite, when graphite was oxidized, nitrate ion was invaded between people's graphite flake layer, and then dropped into KClO
4Further oxidation is thrown reactant in National People's Congress's water gaging subsequently, filters, and washing to filtrating is near after the neutrality, and drying obtains graphite oxide.
The Staudemaier method is with the vitriol oil and nitrosonitric acid mixing acid Graphite Powder 99 to be handled, and equally also is with KClO
4Be oxygenant.
The Hummers method is with Graphite Powder 99 and anhydrous nitric acid sodium (NaNO
3) joining the vitriol oil that places in the ice bath, the powerful stirring adds KMnO down
4, and use volume(tric)fraction 3%H
2O
2Reduce remaining potassium permanganate and MnO
2, make its soluble MnSO that becomes colorless
4Under the processing of ydrogen peroxide 50, suspension-s becomes glassy yellow.Filter, wash 3 times, vacuum hydro-extraction obtains then.Resulting oxidized graphite flake layer has pleat beryllium type structure, and oxygen level is bigger, and functional group is than horn of plenty, but in pure water good distribution.
Graphene oxide of the present invention is selected from graphite after peroxo-obtains graphite oxide, obtains graphene oxide through peeling off.
Preferably, preferred any one in Brodie method, Hummers method or Staudenmaier method of the preparation method of said graphite oxide.
Preferably, the method that the method for peeling off of said graphite oxide is well known to those skilled in the art, for example pyrolysis expand peel off, ultra-sonic dispersion etc.The present invention does not do qualification to the means of peeling off, and all can access the method for graphene oxide (GO), all can be used for the present invention.
Method of reducing of the present invention need carry out in inert atmosphere, and purpose is to prevent airborne oxidizing gas, and for example oxygen is incited somebody to action reductive Graphene reoxidation, thereby hinders the carrying out of reduction reaction.Inert atmosphere of the present invention is realized through charging into rare gas element; Said rare gas element be not with the gas of graphene oxide and Graphene reaction; 1 kind or at least 2 kinds combination in nitrogen, helium, neon, argon gas, krypton gas, xenon, the radon gas; Said combination is nitrogen/argon gas, helium/radon gas, neon/argon gas/krypton gas etc. for example, further nitrogen and/or argon gas, and most preferably purity is that 99.999% nitrogen and/or purity are 99.99% argon gas.
Described inert atmosphere be embodied as technology well-known to those skilled in the art, for example can be earlier disposable reaction vessel be evacuated to the vacuum of condition of high vacuum degree, feed rare gas element then; Also can earlier reaction vessel be vacuumized, feed rare gas element then, carry out said step repeatedly, until the oxidizing gas in the reaction vessel is drained only.The residual quantity of oxidizing gas directly influences last graphene oxide reductive effect in the said inert atmosphere, and residual oxidizing gas is few more, and the oxidisability Graphene reduces thoroughly more.
The present invention under high pressure carries out; Said highly compressed pressure is 1-100MPa; For example 1MPa, 2MPa, 3MPa, 9MPa, 12MPa, 30MPa, 50MPa, 60MPa, 80MPa, 88MPa, 90MPa, 93MPa, 96MPa, 99MPa, 100MPa etc.; Further preferred 10-50MPa, preferred especially 10-40MPa.
Thus; In the highly compressed rare gas element, carry out during reduction reaction of the present invention; Described high-pressure inert gas condition form experimental implementation well-known to those skilled in the art; The most simply form high pressure and in reaction vessel, feed rare gas element, till reaching needed reaction pressure for continuing.The formation of high-pressure inert gas can realize that also other any operations that can form the high-pressure inert gas condition all can realize the present invention through the volume that dwindles reaction vessel.
The present invention at high temperature carries out; Said pyritous temperature is 900-2000 ℃; For example 900 ℃, 905 ℃, 930 ℃, 980 ℃, 1100 ℃, 1300 ℃, 1500 ℃, 1700 ℃, 1800 ℃, 1900 ℃, 1950 ℃, 1990 ℃, 2000 ℃ etc.; Further preferred 1000-2000 ℃, preferred 1100-1500 ℃ especially.
Preferably; High temperature according to the invention, high pressure reduction treatment time are >=1min; For example 1min, 2min, 5min, 10min, 22min, 35min, 49min, 60min, 80min, 120min etc., the preferably treatment time is 1-60min, further preferred 2-10min.
As optimal technical scheme, the method for preparing Graphene of the present invention comprises the steps:
(1) the graphene oxide powder is placed in the high temperature reaction stove, sealing vacuumizes;
(2) in high temperature reaction stove, feed rare gas element, the pressure and temperature that pressurizes, is warming up to regulation reacts;
(3) reacted after, be cooled to room temperature naturally, obtain Graphene.
Preferably, graphene oxide of the present invention is that the graphite of oxidation obtains after peeling off, and the equal appendix in top layer and side of said graphite through oxidation has a large amount of oxy radicals, i.e. graphite oxide.
High temperature reaction stove of the present invention is for realizing that (closed reaction vessel of pressure >=1MPa), those skilled in the art can select according to physical condition according to the expertise and the relevant information of own grasp for high temperature (temperature >=900 ℃) and high pressure.Preferably, high temperature reaction stove of the present invention is selected from vacuum sintering furnace and/or calcining furnace.The type of heating of described vacuum sintering furnace can be selected from resistive heating, induction heating, microwave heating etc.; Said calcining furnace has can-type calcine furnace, electric calciner etc.Preferably; High temperature reaction stove according to the invention is selected from any one in discharge plasma sintering stove, resistive heating vacuum sintering furnace, induction heating vacuum sintering furnace, microwave heating vacuum sintering furnace and the calcining furnace, further preferred self-discharge plasma agglomeration stove and/or calcining furnace.
Method provided by the present invention does not adopt any poisonous and hazardous chemical reagent; Preparation technology is simple; Each node can accurately be controlled in the flow process; Can realize efficient, the high-quality reduction of graphene oxide material, solve problems such as the environmental pollution, the reduction that exist in the prior art are not thorough, recovery time length.
Two of the object of the invention provides a kind of Graphene; Said Graphene is to prepare the Graphene that the method for Graphene prepares through high pressure reduction; The carbon of said Graphene and the atomic ratio of oxygen element >=9; For example 9,10,15,30,40,55,69,80,90,95,100 etc., the atomic ratio 9-90 of the carbon of preferred said Graphene and oxygen element, further preferred 9-50.
Preferably, the electronic mobility of said Graphene is 800-1200cm
2/ VS, for example 800cm
2/ VS, 820cm
2/ VS, 850cm
2/ VS, 890cm
2/ VS, 910cm
2/ VS, 970cm
2/ VS, 1060cm
2/ VS, 1140cm
2/ VS, 1200cm
2/ VS etc.The specific conductivity of said Graphene is 200-500S/m, for example 200S/m, 205S/m, 240S/m, 260S/m, 380S/m, 420S/m, 480S/m, 500S/m etc.
Three of the object of the invention provides a kind of purposes for preparing the Graphene that the method for Graphene prepares through high pressure reduction; Said Graphene is used for the store energy active material; Be preferred for Chu Qing, lithium ion battery, ultracapacitor or fuel cell, and nanometer electronic device, high frequency circuit, photon sensor, the order-checking of gene electronics and minimizing noise.
Compared with prior art, the present invention has following beneficial effect:
(1) the present invention removes the oxygen-containing functional group in the graphene oxide fully with under the graphene oxide high-temperature and high-pressure conditions, repairs the textural defect in the Graphene simultaneously, thereby makes high-quality Graphene;
(2) technology of the present invention has been avoided a large amount of use chemical reagent, and environmental pollution is little, is applicable to the reduction based on the various powders of graphene oxide of prepared in various methods;
(3) recovery time of the present invention short (the shortest 1min), reduction thoroughly, and is simple to operate, and condition is prone to control;
(4) the present invention can realize the efficient high-quality reduction of graphene oxide material, and the ratio minimum of C: O is 9, according to residual quantity different of pressure, temperature, time and the oxidizing gas of reaction, can oxygen-containing functional group be removed fully in theory;
(5) electronic mobility of grapheme material provided by the present invention is higher than the Graphene that prior art for preparing obtains far away.
Embodiment
For ease of understanding the present invention, it is following that the present invention enumerates embodiment.Those skilled in the art should understand, and said embodiment helps to understand the present invention, should not be regarded as concrete restriction of the present invention.
Embodiment 1:
Get the graphite oxide of Hummers method preparation, after microwave is peeled off, obtain the graphene oxide powder; Weighing 500mg graphene oxide powder places in the discharge plasma sintering stove, 6 * 10 then
-4Under the vacuum condition of Pa, feed argon gas and make protection gas, be pressurized to 10MPa, calcining is 10 minutes under 2000 ℃ of high temperature, and heating is cooled to room temperature after accomplishing naturally.Reduction back gained grapheme material specific conductivity is 185S/m.
Graphene oxide carbon and oxygen element atomic ratio (the carbon Sauerstoffatom is than C/O) are merely 4.28 before the reduction, and the reduction back is because a large amount of oxygen-containing functional groups is removed, and C/O rises to 9.27, and the C/O of the Graphene of Hydrazine Hydrate 80 chemical process reduction preparation is 6.2.
Embodiment 2
At first be equipped with graphite oxide, after thermal expansion is peeled off, obtain the graphene oxide powder, take by weighing 500mg and place in the high-temperature calcination stove according to the Staudenmaier legal system.6 * 10
-4Under the vacuum condition of Pa, feed nitrogen and make protection gas, be pressurized to 20MPa, calcining is 6 minutes under 1500 ℃ of high temperature, and heating is cooled to room temperature after accomplishing naturally.Reduction back gained grapheme material specific conductivity is 205S/m.Graphene oxide carbon and oxygen element atomic ratio (the carbon Sauerstoffatom is than C/O) are lower before the reduction, are merely 5.10.The reduction back is superior to the Graphene of Hydrazine Hydrate 80 chemical process reduction preparation because a large amount of oxygen-containing functional groups is removed, and C/O rises to 13.97.
Embodiment 3
At first be equipped with graphite oxide, after ultrasonic and thermal reduction, obtain the graphene oxide powder, take by weighing this graphene oxide powder 500mg then and place in the high-temperature calcination stove according to the Brodie legal system.6 * 10
-4Under the vacuum condition of Pa, feed helium and make protection gas, be pressurized to 40MPa, calcining is 3 minutes under 1200 ℃ of high temperature, and heating is cooled to room temperature after accomplishing naturally.Reduction back gained grapheme material specific conductivity is 278S/m.Graphene oxide carbon and oxygen element atomic ratio (the carbon Sauerstoffatom is than C/O) are lower before the reduction, are merely 6.34.The reduction back is superior to the Graphene of Hydrazine Hydrate 80 chemical process reduction preparation because a large amount of oxygen-containing functional groups is removed, and C/O rises to 37.4.
Embodiment 4
At first be equipped with graphite oxide, after thermal expansion is peeled off, obtain the graphene oxide powder, take by weighing this graphene oxide powder 500mg then and place wire spiral heat-agglomerating stove according to the Brodie legal system.Sintering oven is evacuated to 6 * 10
-4Pa, feeding purity is that 99.999% nitrogen is made protection gas, is pressurized to 1MPa, and calcining is 60 minutes under 2000 ℃ of high temperature, and heating is cooled to room temperature after accomplishing naturally.Reduction back gained grapheme material specific conductivity is 237S/m.Graphene oxide carbon and oxygen element atomic ratio (the carbon Sauerstoffatom is than C/O) are lower before the reduction, are merely 6.34.The reduction back is superior to the Graphene of Hydrazine Hydrate 80 chemical process reduction preparation because a large amount of oxygen-containing functional groups is removed, and C/O rises to 31.5.
Embodiment 4
At first be equipped with graphite oxide, after ultrasonic peeling off, obtain the graphene oxide powder, take by weighing this graphene oxide powder 500mg then and place the microwave heating sintering oven according to the Staudenmaier legal system.Sintering oven is evacuated to 6 * 10
-4Pa, logical purity is that 99.99% argon gas is made protection gas, is pressurized to 100MPa, and calcining is 1 minute under 900 ℃ of high temperature, and heating is cooled to room temperature after accomplishing naturally.Reduction back gained grapheme material specific conductivity is 201S/m.Graphene oxide carbon and oxygen element atomic ratio (the carbon Sauerstoffatom is than C/O) are lower before the reduction, are merely 6.34.The reduction back is superior to the Graphene of Hydrazine Hydrate 80 chemical process reduction preparation because a large amount of oxygen-containing functional groups is removed, and C/O rises to 22.6.
Applicant's statement; The present invention explains detailed process equipment of the present invention and technical process through the foregoing description; But the present invention is not limited to above-mentioned detailed process equipment and technical process, does not mean that promptly the present invention must rely on above-mentioned detailed process equipment and technical process could be implemented.The person of ordinary skill in the field should understand, and to any improvement of the present invention, to the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (9)
1. a high pressure reduction prepare method of Graphene, it is characterized in that said method is in inert atmosphere, to graphene oxide high temperature, high pressure reduction processing, prepares Graphene;
Said pyritous temperature >=900 ℃; Said highly compressed pressure >=1MPa.
2. the method for claim 1 is characterized in that, said graphene oxide is selected from graphite and peels off the product that obtains through oxidation;
Preferably, preferred any one in Brodie method, Hummers method or Staudenmaier method of said mode of oxidizing.
Said peel off mode preferably expand from pyrolysis peel off, ultra-sonic dispersion any a kind in peeling off.
3. according to claim 1 or claim 2 method; It is characterized in that; Said inert atmosphere realizes through charging into rare gas element, and said rare gas element be the gas that does not react with graphene oxide and Graphene, a kind or at least 2 kinds combination in nitrogen, helium, neon, argon gas, krypton gas, xenon, the radon gas; Further nitrogen and/or argon gas, most preferably purity is that 99.999% nitrogen and/or purity are 99.99% argon gas.
4. like the described method of one of claim 1-3, it is characterized in that said highly compressed pressure is 1-100MPa, further preferred 10-50MPa, preferred especially 10-40MPa;
Preferably, said high pressure is realized pressure atmosphere through rare gas element.
5. like the described method of one of claim 1-4, it is characterized in that said pyritous temperature is 900-2000 ℃, further preferred 1000-2000 ℃, preferred 1100-1500 ℃ especially;
Preferably, said high temperature, high pressure reduction treatment time are >=1min that the preferably treatment time is 1-60min, further preferred 2-10min.
6. like the described method of one of claim 1-5, it is characterized in that said method comprises the steps:
(1) the graphene oxide powder is placed in the high temperature reaction stove, sealing vacuumizes;
(2) in high temperature reaction stove, feed rare gas element, the pressure and temperature that pressurizes, is warming up to regulation reacts;
(3) reacted after, be cooled to room temperature naturally, obtain Graphene.
7. method as claimed in claim 6; It is characterized in that; Said high temperature reaction stove is selected from vacuum sintering furnace and/or calcining furnace; In preferred self-discharge plasma agglomeration stove, resistive heating vacuum sintering furnace, induction heating vacuum sintering furnace, microwave heating vacuum sintering furnace and the calcining furnace any one, further preferred self-discharge plasma agglomeration stove and/or calcining furnace.
One kind like the described high pressure of one of claim 1-7 reduction prepares the Graphene that the method for Graphene prepares; It is characterized in that; The carbon of said Graphene and the atomic ratio of oxygen element >=9; The atomic ratio 9-90 of the carbon of preferred said Graphene and oxygen element, further preferred 9-50;
Preferably, the electronic mobility of said Graphene is 800-1200cm
2/ VS, specific conductivity is 200-500S/m.
9. the purposes of a Graphene as claimed in claim 8; It is characterized in that; Said Graphene is used for the store energy active material; Be preferred for Chu Qing, lithium ion battery, ultracapacitor or fuel cell, and nanometer electronic device, high frequency circuit, photon sensor, the order-checking of gene electronics and minimizing noise.
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| CN109264702A (en) * | 2018-12-07 | 2019-01-25 | 四川聚创石墨烯科技有限公司 | A kind of graphene preparation method, graphene and its preparation system |
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