CN101462719A - Preparation of graphene - Google Patents
Preparation of graphene Download PDFInfo
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- CN101462719A CN101462719A CNA2009100771319A CN200910077131A CN101462719A CN 101462719 A CN101462719 A CN 101462719A CN A2009100771319 A CNA2009100771319 A CN A2009100771319A CN 200910077131 A CN200910077131 A CN 200910077131A CN 101462719 A CN101462719 A CN 101462719A
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Abstract
The invention discloses a method for preparing graphene, which belongs to the technical field of chemical synthesis. The method is characterized in that sodium metal and halogenated hydrocarbon are taken as raw materials to react in a solvent in inert atmosphere so as to prepare the grapheme; reaction temperature is preferably between 120 and 400 DEG C, and is more preferably between 160 and 360 DEG C; the molar ratio of the sodium metal to the halogenated hydrocarbon is preferably between 1:1 and 100:1, wherein the halogenated hydrocarbon can be added before reaction or during the reaction; and the halogenated hydrocarbon is preferably halogenated C1-4 aliphatic hydrocarbon and halogenated benzene, such as tetrachloroethylene, hexachlorobenzene, trichloroethylene, bromobenzene, ethylenetetrabromide and the like. The method also preferably performs post-treatment on the prepared graphene so as to improve purity. The method has the advantages of simple equipment, easy operation, low cost, high yield and good product properties, can play an important role in the industrial production of graphene and related products such as lithium ion batteries and the like, and is broad in application prospects.
Description
Technical field
The present invention relates to Graphene, relate in particular to preparation method of graphene, belong to chemosynthesis technical field.
Background technology
Graphene (Graphene) is a kind of new carbon of broad research in recent years.It can be counted as the two-dimension plane structure that is made of carbon atom.The appearance of Graphene has caused global research boom.
Graphene particular structure characteristics have been brought a series of novelties, special nature to it, have been the focus of scientists study since it is found always.At first, Graphene has highly stable structure, makes that its mechanical property is very excellent.Graphene is present the thinnest a kind of material, and each carbon atom is perfectly arranged in Graphene, and when applying external force, the carbon atom face can flexural deformation under the effect of external force, adapts to external force thereby carbon atom needn't be rearranged, and has also just kept Stability Analysis of Structures.On the plane of Graphene, the arrangement of carbon atom makes it very firmly hard in addition; Its tensile strength can reach 50-200GPa, is 100 times of steel, and density has only 1/6 of steel; In addition, its Young's modulus can reach 1TPa, and is suitable with adamantine Young's modulus, is about 5 times of steel.It is the material that to prepare at present with high specific strength.Simultaneously, Graphene can also be compound with other material as the mechanics strongthener, and prepared matrix material has mechanical strength, elasticity, fatigue resistance and many other excellent properties of superelevation.At present, studying maximum is Graphene enhanced macromolecular material, this matrix material for original macromolecular material not only mechanical property improve greatly, and has good electroconductibility, can make flexible conductive film material, radiowave is also had certain screening ability, can be applicable to the defence and military field and prepare antistatic coating, radar absorbing, and the stealth material of submarine aircraft.
Secondly, Graphene has peculiar electrical properties.Electronic motion speed has reached 1/300 of the light velocity in the Graphene, considerably beyond the movement velocity of electronics in general conductor, has outstanding electroconductibility.Because the perfect crystalline network of Graphene, electronics when mobile, can or do not introduced foreign atom because of lattice imperfection scattering takes place in track.Because reactive force is very strong between atom, at normal temperatures, even carbon atom telescopes on every side, the interference that electronics is subjected in the Graphene is also very little.When Graphene was cut into the Graphene band, its energy band structure was different and different with cut direction, can show metallicity or semiconductive.Graphene has different electron spinning passages in addition, makes it that reasonable application prospect be arranged on the spintronics device.Modify by suitable end group, Graphene can all be a semiconductive, can be as preparation nano-electron field-effect transistor.And because the two dimensional structure of Graphene makes that the technology when preparing electricity device is simpler based on the electricity device of Graphene than making.After the together a lot of interactions of molecules of Graphene, its electrical properties can change, thereby Graphene can be used as the transmitter that detects these molecules.Graphene has also shown unusual integer quantum Hall behavior.Its Hall electricity is led=2e2/h, 6e2/h, and the odd-multiple that 10e2/h.... leads for the quantum electricity, and can at room temperature observe, can be used as the quantum electricity device.
Aspect the energy, the shared status of Graphene also more shows important.At first,, make it have very big specific surface area, than activated carbon of sorbent commonly used bigger hydrogen adsorption ability is arranged, thereby be suitable as very much the material of Chu Qing because Graphene has unique two-dimension plane structure.The specific surface area that Graphene is bigger makes it adsorb more multi-catalyst particle as the carrier of good catalyzer, thereby makes activity of such catalysts and selectivity greatly obtain significantly to improve, and will bring huge economic benefit for industrial production.Because the rock steady structure of Graphene is more stable when it is used as support of the catalyst, can use for a long time.The good electric conductivity of Graphene makes when it is used as electrochemical catalysis that excellent performance is also arranged.In addition, Graphene also can be used as the cathode material of lithium ion battery, and its constructional feature is very beneficial for Li
+Embedding with move out, be expected to become a kind of novel lithium ion battery material.
In addition, because Graphene has than high thermal in its plane, therefore, Graphene also is good thermal conducting material; Simultaneously, and the interplanar thermal conductivity is lower, therefore, also Graphene can be made anisotropic thermally conductive material.
In sum, Graphene is as present high, the thinnest two-dimensional nano carbon material of intensity, have unique mechanical, chemistry and electronics performance, can be used as strongthener and prepare high strength composite, the inherent nature of existing carbon fibre material has the heat-resisting and stable of the conduction of metallic substance and thermal conductivity, stupalith again, the softness of textile materials and braiding property, and the workability of macromolecular material, be with a wide range of applications and have the application prospect of potentiality.
At present, the production method of Graphene mainly contains mechanically peel method and thermal expansion graphite method.
Wherein, the mechanically peel method is that the high orientation pyrolytic graphite with costliness bonds repeatedly with adhesive plaster and peels off, and transfers on the substrate material surface at last.This method efficient is low, output is little, cost is high, can only be limited to Laboratory Production.And it is thermal expansion graphite method step complexity, and big to the broken ring of graphene-structured.
Summary of the invention
The objective of the invention is to overcome problems of the prior art, a kind of simple to operate, with low cost, method for preparing Graphene that transformation efficiency is higher is provided.
The inventive method is a raw material with sodium Metal 99.5 and halohydrocarbon, by carry out the prepared in reaction Graphene in solvent under inert environments.
Wherein, temperature of reaction can be set according to reaction solvent, and wherein synthesizing graphite alkene is comparatively suitable in 120-400 ℃ temperature range, and preferred temperature range is 160-360 ℃; And temperature is high more, and speed of response is fast more.Be to improve combined coefficient, be preferably in 1-120 minute and temperature brought up to required temperature of reaction.
In the reactant, the mol ratio of sodium Metal 99.5 and halohydrocarbon is preferably between 1:1-100:1;
Particularly, the present invention preferably takes following two kinds of reaction methods to react, first kind: earlier raw material and reaction solvent are placed reactor, the volume ratio of described raw material and reaction solvent can be selected (such as between 1:1000-1:1) in the scope of broad, feed shielding gas then, the gases of getting rid of in the reaction system such as oxygen obtain the inert reaction environment, react for some time (such as 0.1-48 hour) under temperature of reaction, obtain Graphene;
Second kind: earlier sodium Metal 99.5 and reaction solvent are placed reactor, the volume ratio of described raw material and reaction solvent can be selected (such as between 1:1000-1:1) equally in the scope of broad, halohydrocarbon is introduced reaction system by Bubbling method then, under temperature of reaction, react for some time (such as 0.1-48 hour), obtain Graphene.
In above-mentioned preparation method of graphene, the range of choice of described halohydrocarbon is comparatively extensive, is preferably halo C1-4 aliphatic hydrocarbon and halogeno-benzene, as zellon, Perchlorobenzene, trieline, bromobenzene, ethylene tetrabromide etc., or their mixture all can, most preferably be zellon.
The selection of described reaction solvent also is diversified, so long as do not react with raw material sodium and halohydrocarbon and boiling point be higher than 120 ℃ solvent and all can, as long chain alkane, ethers or acetals solvent etc., specifically, can be paraffin oil, phenyl ether, methyl-phenoxide, eicosane, trimethylbenzene etc., or their mixture.
Described reactor requirement and sodium and halohydrocarbon all do not react, and can the tolerance response temperature.
Described inert environments mainly obtains by feed rare gas element in reaction system, and the selection of rare gas element also is widely, and all can not use with the gas that sodium, halohydrocarbon and reaction solvent react, as nitrogen, argon gas etc.
For obtaining the higher Graphene of purity, also comprise the step of the synthetic Graphene being carried out purifying among the described preparation method, to remove impurity such as the reaction solvent that contained in the synthetic Graphene and unreacted sodium, described purification process can may further comprise the steps:
1) with the synthetic Graphene with can with the reagent mix of sodium Metal 99.5 reaction, remove remaining a small amount of sodium by chemical reaction;
2) with can the Graphene that step 1) obtains being washed, to remove remaining reaction solvent with the organic solvent that reaction solvent dissolves each other;
3) with deionized water to step 2) Graphene that obtains washs, to remove remaining NaCl;
4) oven dry obtains purified Graphene.
In above-mentioned purification process, can be ethanol, propyl alcohol, Virahol, methyl alcohol etc. with the reagent of sodium Metal 99.5 reaction in the step 1).
Step 2) organic solvent in can be sherwood oil, acetone, ether, DMF etc.
Compare with the ordinary method of preparation Graphene, the preparation of Graphene of the present invention has the following advantages:
1. equipment is simple, operation easily, and production stage is few, is easy to carry out large-scale industrial production;
2. raw materials cost is cheap, and solvent can recycle;
3. productive rate higher (more than 65%), and metallic impurity are less in the product, are easy to purify;
4. temperature of reaction is low, and can be prepared under normal pressure, and energy consumption is low;
5. the synthetic Graphene has bigger specific surface area;
6. the Graphene of using as support of the catalyst and electrode often needs Graphene to have more defective, and had more defective with the Graphene itself that the inventive method makes, therefore need not it is carried out oxide treatment, promptly can be used as support of the catalyst or electrode materials;
Based on above-mentioned advantage, the present invention will play a significant role in the suitability for industrialized production of Graphene and related products (as lithium ion battery etc.), have a extensive future.
Description of drawings
Fig. 1 is the photo of the Graphene of embodiment 1 preparation
The TEM that Fig. 2 A and Fig. 2 B are respectively the Graphene of embodiment 2 and embodiment 3 preparations characterizes detected result
Fig. 3 is the Raman spectral detection result of the Graphene of embodiment 1 preparation
Fig. 4 is that the TGA of the Graphene of embodiment 2 preparations characterizes detected result
Embodiment
Below in conjunction with the drawings and specific embodiments the present invention is described in further details.
Method therefor is ordinary method if no special instructions among the following embodiment.
Present embodiment prepares the device that Graphene adopts and comprises: ground there-necked flask (250mL, reactor), spherical condenser, electrically heated cover, high pure nitrogen steel cylinder (nitrogen is provided), glass capillary, thermowell, rubber tubing and thermometer (0-400 ℃).
The method concrete grammar that present embodiment prepares Graphene may further comprise the steps:
1, Graphene is synthetic
Oven dry ground there-necked flask in baking oven adds the 50mL paraffin oil therein earlier, dries the impurity on sodium Metal 99.5 surface, is placed on then to weigh in the balance on the watch-glass and gets 2.0g sodium, and it is directly put into there-necked flask, adds zellon 1.0mL, stirs; Then thermometer and thermowell are connected; fill on the bottleneck of there-necked flask side; the bead of thermometer bottom just enters into below the reaction solution liquid level; spherical condenser is connected with rubber tubing one end; the rubber tubing the other end is connected with there-necked flask intermediary bottleneck; one end that will have the ventpipe of stopper again is connected to the remaining bottleneck of there-necked flask; the ventpipe the other end is connected with nitrogengas cylinder; open the nitrogengas cylinder reducing valve; feed low discharge as the nitrogen of shielding gas 5 minutes, with the O in the system
2Drive out of; Subsequently, connect the water coolant of the spherical condenser that is connected with the ground there-necked flask, the electricity consumption heating jacket begins heating to there-necked flask, and simultaneously system is stirred at a slow speed, make sodium to stir with integral body, 20 minutes post-heating to 250 ℃ (power by control electrically heated cover is regulated and control temperature) are kept this thermotonus stopped reaction after 2 hours, obtain Graphene.Can observe in the reaction process in the there-necked flask liquid color by original transparent become to add to be deep to gradually become black, liquid also becomes muddy gradually in the bottle, finally can find to have in the there-necked flask a large amount of black solid materials to generate, these atraments are Graphene.
2, the purifying of Graphene
Contain impurity such as reaction solvent and unreacted sodium in the Graphene of step 1 preparation, therefore, for improving the purity of Graphene, also need it is carried out purifying, concrete grammar may further comprise the steps:
1) cooling adds ethanol in there-necked flask, removes residual little metal sodium by chemical reaction, when bubble not had is emitted, shows that unreacted sodium is removed fully;
2) by the decant method solvent is separated with solid matter (Graphene), use sherwood oil (60-90) (the recyclable recycling of sherwood oil) that solid matter is washed again, repeat 3 times, to remove remaining reaction solvent paraffin oil;
3) with deionized water solid matter is washed again, repeat 3 times, to remove remaining NaCl;
4) in 100 ℃ baking oven, the solid matter of black is dried, obtain purified Graphene.
After testing, the productive rate with aforesaid method synthetic Graphene is about 85%.
Embodiment 2---the preparation of Graphene
Prepare Graphene with the experimental installation identical with embodiment 1, concrete preparation method may further comprise the steps:
1, Graphene is synthetic
In the ground there-necked flask of drying, add the 50mL phenyl ether, dry the impurity on sodium Metal 99.5 surface, be placed on then to weigh in the balance on the watch-glass and get 2.3g (0.1 mole) sodium, it is directly put into there-necked flask, add zellon 0.016g (0.001 mole), stir; Open the nitrogengas cylinder reducing valve, feed low discharge N
25min, subsequently, connect the water coolant of the spherical condenser that is connected with the ground there-necked flask, the electricity consumption heating jacket begins heating to there-necked flask, and simultaneously system is stirred at a slow speed, make sodium to stir, 20min post-heating to 160 ℃ (power by control electrically heated cover is regulated and control temperature) with integral body, keep this thermotonus stopped reaction after 2 hours, obtain it is directly put into there-necked flask.
2, the purifying of Graphene
With the method identical the synthetic Graphene is carried out purifying, obtain purified Graphene with embodiment 1.
After testing, the productive rate with aforesaid method synthetic Graphene is about 80%.
Embodiment 3---the preparation of Graphene
Present embodiment prepares the device that Graphene adopts and comprises: ground there-necked flask (250mL, reactor), spherical condenser, electrically heated cover, high pure nitrogen steel cylinder (nitrogen is provided), glass capillary, thermowell, rubber tubing and thermometer (0-400 ℃), bubbling device.Concrete preparation method may further comprise the steps:
1, Graphene is synthetic
Add the 50mL paraffin oil in the ground there-necked flask of in baking oven, drying earlier, dry the impurity on sodium Metal 99.5 surface, be placed on then to weigh in the balance on the watch-glass and get 2.0g sodium, it is directly put into there-necked flask.In bubbling device, add the 2ml zellon, open the nitrogengas cylinder reducing valve, speed with about 100 bubbles of per minute blasts nitrogen, subsequently, connect the water coolant of the spherical condenser that is connected with the ground there-necked flask, the electricity consumption heating jacket begins heating to there-necked flask, 20 minutes post-heating to 360 ℃ (power by control electrically heated cover is regulated and control temperature), keep this thermotonus stopped reaction after 2 hours, obtain Graphene.
2, the purifying of Graphene
With the method identical the synthetic Graphene is carried out purifying, obtain purified Graphene with embodiment 1.
After testing, the productive rate with aforesaid method synthetic Graphene is about 80%.
Embodiment 4---the preparation of Graphene
Prepare Graphene with the experimental installation identical with embodiment 1, concrete preparation method may further comprise the steps:
1, Graphene is synthetic
In the ground there-necked flask of drying, add the 100mL paraffin oil, dry the impurity on sodium Metal 99.5 surface, be placed on then to weigh in the balance on the watch-glass and get 2.3g (0.1 mole) sodium, it is directly put into there-necked flask, add zellon 16.6g (0.1 mole), stir; Open the nitrogengas cylinder reducing valve, feed low discharge N
25min, subsequently, connect the water coolant of the spherical condenser that is connected with the ground there-necked flask, the electricity consumption heating jacket begins heating to there-necked flask, and simultaneously system is stirred at a slow speed, make sodium to stir with integral body, 20min post-heating to 400 ℃ (power by control electrically heated cover is regulated and control temperature) is kept this thermotonus stopped reaction after 6 minutes.
2, the purifying of Graphene
With the method identical the synthetic Graphene is carried out purifying, obtain purified Graphene with embodiment 1.
After testing, the productive rate with aforesaid method synthetic Graphene is about 65%.
Embodiment 5---the preparation of Graphene
Present embodiment adopts and prepares Graphene with embodiment 1 identical apparatus and method, difference only is, behind 10 minutes internal heating to 120 ℃, react, reaction times is 48 hours, the equal-volume that the halohydrocarbon of participation reaction replaces with Perchlorobenzene and trieline is than mixture, and its cumulative volume is similarly 1.0ml.
Behind the purification step identical, can make Graphene equally with embodiment 1.
Embodiment 6---the detection of Graphene
With following method embodiment 1-3 is detected with the Graphene of preparation:
One, TEM characterizes and detects
Graphene to embodiment 1-3 preparation carries out the detection of transmission electron microscope (TEM) sign, method is: the Graphene black powder takes a morsel, ultra-sonic dispersion in dehydrated alcohol, get 1-2 then and drip on the copper mesh side China film, use transmission electron microscope (JEOL-100CX) to observe the two-dimension plane structure of prepared graphene then.Fig. 2 A and 2B have provided the transmission electron microscope photo of the Graphene of embodiment 2 and embodiment 3 preparations respectively, and as can be seen, the Graphene for preparing with the inventive method is a two dimensional structure, and size can reach tens microns.
Two, Raman spectral detection
Graphene to embodiment 1-3 preparation carries out Raman spectral detection (JobinYvon HR800, excitation wavelength 632.8nm).Fig. 4 has provided the Raman spectrogram (X-coordinate is a wave number, and ordinate zou is an intensity) of the Graphene of embodiment 1 preparation, as can be seen, and at 1347cm
-1And 1584cm
-1There is a strong peak respectively in two positions, wherein, and at 1584cm
-1The existence of graphite-structure near the strong cutting edge of a knife or a sword explanation Graphene is at 1347cm
-1Contain more defective near the strong cutting edge of a knife or a sword explanation Graphene.
Three, BET specific surface test
Adopt N
2As adsorbed gas, the Graphene that embodiment 1-3 is prepared carries out BET specific surface test (ASAP2010).Wherein, the specific surface of the Graphene that makes of embodiment 1 is 584m
2/ g illustrates the bigger specific surface that has with the Graphene of the inventive method preparation.
Four, TGA characterizes and detects
Rate of heating with 10 ℃/min is carried out TGA sign detection (the Thermal Analysis SDT2960 of company) to the Graphene of embodiment 1-3 preparation in nitrogen gas stream.Fig. 6 has provided the detected result of the Graphene that embodiment 2 is made, and (X-coordinate is a temperature, ordinate zou is a rate of weight loss), as can be seen, the decomposition temperature of Graphene in nitrogen with the inventive method preparation is about 600 ℃, rate of weight loss in the time of about 750 ℃ is 100%, illustrates that the Graphene with the inventive method preparation has certain thermostability.
Claims (10)
1, a kind of preparation method of graphene is characterized in that, by being that raw material reacts in solvent under inert environments and prepares Graphene with sodium Metal 99.5 and halohydrocarbon.
2, preparation method as claimed in claim 1 is characterized in that, described halohydrocarbon is halo C1-4 aliphatic hydrocarbon and halogeno-benzene.
3, preparation method as claimed in claim 2 is characterized in that, described halohydrocarbon is selected from one or more in zellon, Perchlorobenzene, trieline, bromobenzene or the ethylene tetrabromide.
4, preparation method as claimed in claim 1 is characterized in that, described solvent is selected from one or more in paraffin oil, phenyl ether, methyl-phenoxide, eicosane, the trimethylbenzene.
5, preparation method as claimed in claim 1 is characterized in that, carries out under the described temperature that is reflected in 120 ℃ to 400 ℃ the scope.
6, preparation method as claimed in claim 5 is characterized in that, carries out under the described temperature that is reflected in 160 ℃ to 360 ℃ the scope.
7, preparation method as claimed in claim 1 is characterized in that, the reaction times of described reaction is in 0.1 hour to 48 hours scope.
8, preparation method as claimed in claim 1 is characterized in that, the mol ratio between described sodium Metal 99.5 and the halohydrocarbon is in 1:1 arrives the scope of 100:1.
9, preparation method as claimed in claim 1 is characterized in that, described halohydrocarbon before reaction, add reaction system or along with the reaction carrying out add reaction system gradually.
10, preparation method as claimed in claim 1 is characterized in that, also comprises by following method the Graphene that makes is carried out aftertreatment:
A) remove remaining sodium Metal 99.5 by one or more the sodium removing agent that is selected from ethanol, propyl alcohol, Virahol or the methyl alcohol;
B) by being selected from one or more the reaction solvent of washing composition eccysis remnants among sherwood oil, acetone, ether or the DMF;
C) NaCl by deionized water eccysis remnants; Oven dry.
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