CN102730676A - Method for preparing graphene - Google Patents
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- CN102730676A CN102730676A CN2012102491371A CN201210249137A CN102730676A CN 102730676 A CN102730676 A CN 102730676A CN 2012102491371 A CN2012102491371 A CN 2012102491371A CN 201210249137 A CN201210249137 A CN 201210249137A CN 102730676 A CN102730676 A CN 102730676A
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Abstract
The invention relates to a method for preparing graphene, belonging to the technical field of materials. The method comprises the steps of: mixing natural flake graphite powder and ionic liquid; carrying out mechanical grinding under the anaerobic condition; then dispersing the obtained mixture in water; carrying out centrifugation to remove by-product; and volatilizing solvent (water) to obtain the graphene which is in an ionic liquid binding state. The method is low in raw material cost, simple in operation, high in efficiency, energy-saving and environment-friendly; and the graphene which is in the ionic liquid binding state and is prepared by the invention has the layer numbers within the range of 1-10, and does not contain oxidation group, so that excellent electric conduction and electrochemical catalytic activity are maintained, and the graphene is especially suitable for preparing a high-performance electrode.
Description
Technical field:
The present invention relates to the material technology field, relate to a kind of graphene preparation method particularly, particularly a kind of ionic liquid combines preparation method of graphene.
Background technology:
When the number of plies of graphite linings is less than 10 layers, be referred to as grapheme material, it shows more common three-dimensional graphite various structure and performance: theoretical specific surface area is up to 2600m
2/ g; Have outstanding heat conductivility (3000W/ (mK)) and mechanical property (1060 GPa); High speed electronic mobility (1 5000cm under the room temperature
2/ (Vs)).Because of a series of specific physiques such as specific conductivity that have perfect quantum tunneling effect, half integral quantum hall effect, never disappear, grapheme material is obtaining extensive studies and application in various fields such as matrix material, nano-device, electronic component, hydrogen storage material and transmitter preparations.
Up to the present, the main method of known preparation Graphene has following several kinds:
(1) micromechanics is peeled off method [Novcselov K.S., et al.Science 306 (2004) 666].This method can only produce the very limited graphene film of quantity, and production efficiency is low, and productive rate receives very big restriction, only as fundamental research.
(2) epitaxial growth method [Berger C., et a1.Science 312 (2006) 1191; Pan Y., et a1.Adv.Mater 21 (2009) 2777].Though this expensive method can obtain high-quality Graphene; For the further investigation of Graphene basis problem and further a kind of novel method and ideal system are provided in the application aspect the device; But in the epitaxial process, Graphene and matrix interact and cause the doping of electronics, cause that difference can appear in the energy of dirac point and Fermi; The graphene platelet of producing is often in uneven thickness, and the bonding characteristic that can influence carbon-coating between Graphene and the matrix.
(3) oxidation reduction process [Tung V.C., et a1.Nature Nanotechn.4 (2009) 25; Sun Xuhui etc. a kind of method for preparing Graphene. patent of invention, application number 201210004009.0; Wu Li pearl etc. a kind of method for preparing Graphene. patent of invention, application number 201110093737.9].Oxidation reduction process is meant natural graphite and strong acid and strong oxidizing property substance reaction generation graphite oxide; Be prepared into graphene oxide through ultra-sonic dispersion; Add reductive agent and remove the oxy radical on graphene oxide surface,, obtain Graphene like carboxyl, epoxy group(ing) and hydroxyl.After oxidation reduction process is suggested, become the easiest method of prepared in laboratory Graphene, obtain vast Graphene investigator's favor with its simple technology.Its shortcoming is that the Graphene of preparation exists certain defective, will cause the loss of finished-product material part electric property, makes to use to be restricted.
(4) chemical Vapor deposition process (CVD) [Kim K.S., et a1.Nature457 (2009) 70; Ningguo's celebrating etc. the preparation method of a kind of Graphene, doped graphene or graphene complex. patent of invention, application number 201110306114.5].The sample that this method makes has guaranteed the perfect crystalline degree of Graphene sample, is expected to obtain the graphene film of high conductivity and strong mechanical performance.And can satisfy the requirement of scale preparation high quality Graphene, but the electronic property of prepared Graphene receives the influence of substrate very big, cost is higher, complex process.
(5) solvent-thermal method [Wang H.L., e t a l.J.Am.Chem.Soc.131 (2009) 9910].Solvent-thermal method is meant and in special closed reactor, adopts organic solvent as reaction medium, through reaction system is heated to critical temperature, in reaction system, self produces high pressure and carries out the method that Graphene prepares.It has solved the problem of scale preparation Graphene, and synthetic Graphene purity is higher, but the reaction times is longer relatively, has also brought the very low negative impact of specific conductivity simultaneously.
(6) electrolytic process [Liu N., et al.J.Adv.Funct.Mater18 (2008) 1518; Zhou Mingjie etc. a kind of graphene preparation method. patent of invention, application number 201010538228.8].The inventive method is low for equipment requirements, and production technique is simple, and is workable, is suitable for suitability for industrialized production, can synthesize a large amount of Graphenes, but the surface of the Graphene that synthesizes all has a large amount of positive ions or negative ion or organism.
(7) solvent is peeled off method [Hamilton C.E., et a1.Nano Lett.9 (2009) 3460].It is that a spot of graphite is scattered in the solvent that solvent is peeled off method, forms the dispersion liquid of lower concentration, utilizes action of ultrasonic waves to destroy the Van der Waals force of graphite layers, and solvent can insert graphite layers and peeled off layer by layer this moment, prepared Graphene.This method can not destroyed the structure of Graphene as oxidation reduction process, can prepare high-quality Graphene.For its application in fields such as microtronics, multifunctional composites provides wide application prospect, but this method productive rate is very low, limits its commercial applications.
Generally speaking, the Graphene technology of preparing is desirable not enough at present.Therefore find a kind of laboratory that both had been applicable to study on a small scale, graphene preparation method that again can large-scale mass production is a problem that urgent need will solve.
Summary of the invention:
The technical problem that the present invention will solve provides a kind of graphene preparation method, thus with solve present Graphene manufacturing cost height, complicated operation, quality product is not high or productivity has lowly limited its problem for commercial applications.
The present invention mixes the natural flake graphite powder with ionic liquid, mechanical mill under oxygen free condition is scattered in the gained mixture in the water then, centrifugal removal by product, and solvent flashing (water) obtains the Graphene of ionic liquid bonding state.The present invention specifically realizes through following steps:
A kind of graphene preparation method may further comprise the steps:
(1), at first with the natural flake graphite powder and the ionic liquid mixed at room temperature of certain mass ratio;
Further, described ionic liquid is N-octyl group pyridine hexafluorophosphate, N-octyl group pyridinium tetrafluoroborate salt, N-octyl group pyridine nitrate salt, N-hexyl pyridine hexafluorophosphate, N-hexyl pyridinium tetrafluoroborate salt or N-hexyl pyridine nitrate salt.
Further, said natural flake graphite powder and ion liquid mass ratio are: 1:2-1:0.6.
(2), above-mentioned steps gained natural flake graphite powder-ionic liquid mixture is ground under oxygen free condition, obtain the mixture of graphitiferous alkene;
Further, described oxygen free condition can adopt nitrogen or rare gas element deoxygenation.
Further, described abradant lapping apparatus material is agate, pottery, glass, stainless steel or tetrafluoroethylene; Rotor is smooth sphere or convex surface centrum; Grinding power is manpower or machinery; Grinding pressure is 1.5 * 10
5-8.0 * 10
5Pascal, the time is 300-900 minute.
(3), the mixture of above-mentioned grinding gained graphitiferous alkene is the ionic liquid combination Graphene that contains small amount of impurities; This state can be used (such as the preparation electrode); The mixture ultra-sonic dispersion that also can the described ionic liquid that contains small amount of impurities be combined Graphene obtains water system and mixes suspension liquid in ultrapure water;
Further, the described ionic liquid that contains small amount of impurities combines the concentration of mixture ultra-sonic dispersion in ultrapure water of Graphene to be not more than 3g/L, and ultrasonic power is 40-60 watt, and the time is 20 minutes.
(4), to mix the suspension liquid centrifuge tube of packing into to water system behind the above-mentioned ultra-sonic dispersion centrifugal, collects the upper strata ionic liquid and combine Graphene to stablize suspension liquid, discards throw out;
Further, described centrifugal rotational speed is 1000-4000 rev/min.
(5), volatilization removes above-mentioned ionic liquid and combines Graphene stablize the moisture in the suspension liquid, obtains high-purity ion liquid combination Graphene powder.
Further, described volatilization is removed above-mentioned ionic liquid and is combined Graphene to stablize the moisture in the suspension liquid, takes nature to dry or reduces pressure (vacuum) method solvent flashing.
The present invention also provides a kind of Graphene that utilizes method for preparing.
The present invention also provides a kind of application that utilizes the Graphene of method for preparing.
The present invention also provides a kind of electrochemical working electrode that utilizes the Graphene manufacturing of method for preparing.
The beneficial effect that the present invention compares with existing method:
1, raw materials cost is low.Natural flake graphite and ionic liquid all are the large-scale commercial prodn commodity, and be cheap and easy to get.Remove and need not other any chemical reagent in addition.
2, simple to operate, energy-efficient, production cost is low.Need not valuable instrument and equipment, both be applicable to that the laboratory studies on a small scale, again can large-scale mass production.Whole process flow takes less; Even be not underhand polish, produce every kilogram of required energy source and power of Graphene also be not more than 12 kilowatts/time.
3, environmental friendliness.Production preparation process does not produce any waste with environmental hazard risk.
4, product is mainly the Graphene of ionic liquid bonding state, and its number of plies is between 1-10, and the oxygen-free group keeps fabulous conductivity and electrochemical catalysis activity, is particularly suitable for being used for preparing high-performance electrode.
Description of drawings:
Fig. 1: Graphene preparation and applicating flow chart thereof.
Fig. 2: OPFP combines the SEM photo (3D) of Graphene.
Fig. 3: the cyclic voltammogram on the paste working electrode (b) that the 1.0mmol/L Tripotassium iron hexacyanide combines the preparation of Graphene powder at OPFP paste working electrode (a) and conventional graphite powder prepare.
Fig. 4: [Bpy] BF
4SEM photo (3D) in conjunction with Graphene.
Fig. 5: 20 μ mol/L malachite greens are at [Bpy] BF
4Cyclic voltammogram on the paste working electrode (b) for preparing in conjunction with the paste working electrode (a) of Graphene powder preparation and conventional graphite powder.
Embodiment:
Combine accompanying drawing to be described in detail technical scheme of the present invention through embodiment below, embodiment makes an explanation to technical scheme of the present invention, and protection scope of the present invention does not receive the restriction of embodiment.
Embodiment 1
A kind of graphene preparation method; The technical scheme synoptic diagram is seen Fig. 1, utilizes the natural flake graphite powder to mix hand-ground under oxygen free condition with N-octyl group pyridine hexafluorophosphate (OPFP) ionic liquid; Be scattered in the gained mixture in the water then; Centrifugal removal by product, solvent flashing (water) obtains the Graphene of ionic liquid bonding state.Concrete steps are following:
Step 1, with natural flake graphite powder and the OPFP mixed at room temperature of mass ratio 1:0.6.
Step 2, mixture is placed in the agate mortar, hand lapping is 2 hours under the nitrogen protection.
Mixture after step 3, the grinding is that the ionic liquid of small amount of impurities combines Graphene can directly be used for preparing or the modification electrochemical working electrode; Also can further handle and obtain highly purified OPFP combination Graphene---be about to mixture 1g and move in the 0.5L water; Disperseed in ultrasonic 20 minutes under the 40W power, obtain water system and mix suspension liquid.
Step 4, water system mixed suspension liquid move into centrifuge tube, 2000 rev/mins centrifugal 10 minutes, get the upper strata ionic liquid and combine Graphene to stablize suspension liquid, discard throw out.
Step 5, volatilization are removed above-mentioned ionic liquid and are combined Graphene to stablize the moisture in the suspension liquid, obtain high-purity ion liquid and combine the Graphene powder, and OPFP combines the SEM photo of Graphene to see Fig. 2.
Step 6, utilize highly purified OPFP to combine Graphene to prepare high performance electrochemical to learn working electrode or be used for modified electrode.Adopt the paste working electrode of Graphite Powder 99 preparation to compare with tradition; Utilize highly purified OPFP to combine the paste working electrode of Graphene powder preparation that the electric active molecule Tripotassium iron hexacyanide is shown significantly higher electron transfer rate and sensitivity (big current-responsive value), its comparison diagram is seen Fig. 3.
Embodiment 2
A kind of graphene preparation method, the technical scheme synoptic diagram is seen Fig. 1, utilizes natural flake graphite powder and N-hexyl pyridinium tetrafluoroborate salt ([Bpy] BF
4) ionic liquid mixes, mechanical mill under oxygen free condition is scattered in the gained mixture in the water then, centrifugal removal by product, and solvent flashing (water) obtains the Graphene of ionic liquid bonding state.Concrete steps are following:
Step 1, with natural flake graphite powder and [Bpy] BF of mass ratio 1:2
4Mixed at room temperature.
Step 2, mixture is placed in the stainless cylinder of steel, under the nitrogen protection, whisking appliance drives diameter 3cm Stainless Steel Ball agitation grinding 5 hours.
Mixture after step 3, the grinding is that the ionic liquid of small amount of impurities combines Graphene can directly be used for preparing or modifying electrochemical working electrode, also can further handle obtaining higher [Bpy] BF of purity
4In conjunction with Graphene---be about to mixture 1g and move in the 0.5L water, disperseed in ultrasonic 20 minutes under the 40W power, obtain water system and mix suspension liquid.
Step 4, water system mixed suspension liquid move into centrifuge tube, 4000 rev/mins centrifugal 5 minutes, get the upper strata ionic liquid and combine Graphene to stablize suspension liquid, discard throw out.
Step 5, volatilization are removed above-mentioned ionic liquid and are combined Graphene to stablize the moisture in the suspension liquid, obtain high purity [Bpy] BF
4Ionic liquid combines Graphene powder, [Bpy] BF
4SEM photo in conjunction with Graphene is seen Fig. 4.
Step 6, utilize highly purified [Bpy] BF
4Preparing high performance electrochemical in conjunction with Graphene learns working electrode or is used for modified electrode.Adopt the paste working electrode of Graphite Powder 99 preparation to compare with tradition, utilize highly purified [Bpy] BF
4Paste working electrode in conjunction with the preparation of Graphene powder shows tangible electro catalytic activity (suboxide overpotential) and higher sensitivity (big current-responsive value) to malachite green, and its comparison diagram is seen Fig. 5.
Embodiment 3
Replace other step of N-octyl group pyridine hexafluorophosphate among the embodiment 1 identical with N-octyl group pyridine nitrate salt, can prepare high-quality Graphene equally with embodiment 1.
Embodiment 4
Replace other step of N-octyl group pyridine hexafluorophosphate among the embodiment 1 identical with N-hexyl pyridine hexafluorophosphate, can prepare high-quality Graphene equally with embodiment 1.
Embodiment 5
Replace other step of N-octyl group pyridine hexafluorophosphate among the embodiment 1 identical with N-hexyl pyridinium tetrafluoroborate salt, can prepare high-quality Graphene equally with embodiment 1.
Embodiment 6
Replace other step of N-octyl group pyridine hexafluorophosphate among the embodiment 1 identical with N-hexyl pyridine nitrate salt, can prepare high-quality Graphene equally with embodiment 1.
Claims (9)
1. graphene preparation method is characterized in that may further comprise the steps:
(1) at first with the natural flake graphite powder and the ionic liquid mixed at room temperature of certain mass ratio;
(2) above-mentioned steps gained natural flake graphite powder-ionic liquid mixture is ground under oxygen free condition, obtain the mixture of graphitiferous alkene;
(3) mixture of above-mentioned grinding gained graphitiferous alkene is the ionic liquid combination Graphene that contains small amount of impurities.
2. a kind of graphene preparation method according to claim 1 is characterized in that described step (1) intermediate ion liquid is a kind of in N-octyl group pyridine hexafluorophosphate, N-octyl group pyridinium tetrafluoroborate salt, N-octyl group pyridine nitrate salt, N-hexyl pyridine hexafluorophosphate, N-hexyl pyridinium tetrafluoroborate salt or the pure solution of N-hexyl pyridine nitrate salt.
3. a kind of graphene preparation method according to claim 1 is characterized in that middle natural flake graphite powder of described step (1) and ion liquid mass ratio are: 1:2-1:1.
4. a kind of graphene preparation method according to claim 1 is characterized in that oxygen free condition adopts nitrogen or rare gas element deoxygenation in the described step (2).
5. a kind of graphene preparation method according to claim 1 is characterized in that abradant lapping apparatus material is agate, pottery, glass, stainless steel or tetrafluoroethylene in the described step (2); Rotor is smooth sphere or convex surface centrum; Grinding power is manpower or machinery; Grinding pressure is 1.5 * 10
5-8.0 * 10
5Pascal, the time is 300-900 minute.
6. graphene preparation method is characterized in that combining the ionic liquid that contains small amount of impurities of the step (3) described in any one described graphene preparation method of claim 1 to 5 Graphene to carry out steps of processing:
(1) combines the described ionic liquid that contains small amount of impurities the Graphene ultra-sonic dispersion in ultrapure water, obtain water system and mix suspension liquid;
(2) it is centrifugal to mix the suspension liquid centrifuge tube of packing into to above-mentioned water system after ultrasonic, collects the upper strata ionic liquid and combines Graphene to stablize suspension liquid, discards throw out;
(3) the above-mentioned ionic liquid of volatilization removal combines Graphene to stablize the moisture in the suspension liquid, obtains high-purity ion liquid and combines Graphene.
7. a kind of graphene preparation method according to claim 6, the ionic liquid that it is characterized in that containing in the described step (1) small amount of impurities combine Graphene to be scattered in concentration ` in the ultrapure water greater than 3g/L, and ultrasonic power is 40-60 watt, and the time is 20 minutes.
8. Graphene that utilizes the preparation of the said method of claim 7.
9. application that utilizes the Graphene of the said method preparation of claim 7.
10 1 kinds of electrochemical working electrodes that utilize the Graphene manufacturing of the said method preparation of claim 7.
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| CN103102514A (en) * | 2013-01-30 | 2013-05-15 | 南京理工大学 | Ionic liquid modified graphene oxide/natural rubber vulcanized rubber and preparation method thereof |
| CN103708442A (en) * | 2013-11-08 | 2014-04-09 | 江苏科技大学 | Method using ionic liquid to prepare high dispersion graphene |
| CN103787310A (en) * | 2012-10-31 | 2014-05-14 | 海洋王照明科技股份有限公司 | Boron-doped graphene composite thin film electrode material and preparation method thereof, and electrochemical capacitor and preparation method of electrochemical capacitor |
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