CN104003375B - A kind of preparation method of small size Graphene - Google Patents
A kind of preparation method of small size Graphene Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of small size Graphene, the steps include: one, by graphite powder and solvent, obtain graphite mixing solutions; Two, solution is put into container, the homogeneous head of the rotor-stator device of rotor-stator mixing tank is fixed on below liquid level simultaneously; Three, unlatching cooling system and rotor-stator mixing tank process; Four, carrying out leaving standstill process or the complete lift-off particles of centrifugation removal preparing solution, collecting supernatant liquor and obtaining stable small size graphene dispersing solution.The present invention is the rotor carry fluid high-speed motion together by high speed rotating, produce high-speed gradient, high shear force, the boss generation high-speed impact of high-velocity fluid and stator hole wall makes graphite flake peel off and refinement simultaneously, and prepared Graphene size is little and distribution is concentrated, individual layer ratio is high.The method facility investment is few, and raw materials cost is low, easy to operation, and output is considerable, is not only applicable to laboratory study, and is more applicable to large-scale industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of small size Graphene, specifically relate to the technology that a kind of hydrokinetics utilizing high speed rotating rotor to produce prepares Graphene in the solution, belong to technical field of graphene preparation.
Background technology
Grapheme material is since Novselove and Geim obtains 2010 annual Nobel Prizes in physics, obtain unprecedented development, because it is at unique excellent properties of each side such as physics, chemistry, electricity, mechanics, expose huge application prospect in field exhibitions such as novel material, new forms of energy, microelectronics.But the most important prerequisite realizing Graphene large-scale application is, develops low-costly and in high volume, free of contamination graphene preparation technology.Equally, the low-cost and pollution-less technology of preparing in enormous quantities of Graphene is also study and one of key problem of commercial application about this material foundation.
Novoselov and Geim, at employing micromechanics cleaving technique in 2004, namely separates graphene film with adhesive tape sticking technology from highly oriented pyrolytic graphite (HOPG).Although the method can prepare the high-quality graphene that lateral dimension reaches tens microns, efficiency and output are extremely low, are only limitted to the fundamental research in laboratory.Main stream approach prepared by current Graphene belongs to chemical technology category, mainly comprise the methods such as substrate grown, substrate extension, chemical vapour deposition and redox graphene, first three methods shows advantage in electronic devices and components application, but have that temperature pressure control overflow is high, high quality substrate, Graphene and substrate separation are difficult to severe condition such as controlling, be difficult to the object reaching a large amount of simple and easy production Graphene, especially cannot meet the commercial application demand of grapheme material.In addition, based on the graphene oxide method of reducing of liquid phase process, although be the effective way of macroscopic preparation of graphene, the method complex process, condition is wayward, preparation cost is higher, repeatability is poor, the graphene oxide of reduction and pure Graphene still difference to some extent in performance, and reduction efficiency is lower, chemical reagent used is mostly poisonous, is difficult to meet low cost green application needs.And directly peel off the method for common crystal preparing graphite alkene in the liquid phase, cheap with its crystalline graphite powder raw material, related solvents and mechanical stripping equipment, solvent can the feature of green non-pollution, shows simple and easy green, low cost, high-level efficiency, prepares the advantage of Graphene in enormous quantities.In this respect, what extensively adopt at present is ultrasonic cavitation technology, namely utilizes the stripping of liquid cavitation realization to graphite of ultrasonic generation.But this method, with the rigorous process also having localized hyperthermia's high pressure of cavitation, can cause the defect of Graphene comparatively large, reduce the quality of Graphene prepared by it, have impact on the performance of Graphene.In addition, the time that ultrasonic cavitation technology is prepared required for Graphene is longer, and capacity usage ratio is lower.Therefore, develop the preparation method of the Graphene that can realize large-scale industrial production, seem particularly important.
At present, although big size graphene is considered to the ideal material preparing transparent conductive film, nanoelectronic components and parts and matrix material etc., small size Graphene is too in biomaterial, chemical/biological sensors, the aspect such as optoelectronic device, transparent conductive film presents huge application potential, especially utilizing Graphene inkjet technology (usual Graphene size is below 1 micron) to manufacture novel conductive film, is the most promising technology of Graphene industrial applications.There is larger difficulty in preparation and the separation of current small size Graphene, preparation method mainly comprises the methods such as chemical tailoring, mechanical mill, high speed centrifugation, but these methods all have larger shortcoming, prepared Graphene defect is comparatively large, performance lower (especially electric property), yield poorly, preparation cost is high.Therefore, exploitation can realize the small size graphene preparation technology of large-scale industrial production, has very important significance equally.
Summary of the invention
Object: the preparation method that the object of the present invention is to provide a kind of small size Graphene, the hydrokinetics that the method mainly utilizes high speed rotating rotor to produce processes Graphite Powder 99, prepared Graphene size is little and distribution is concentrated, individual layer ratio is higher, quality product is high, is the excellent process of a kind of simple and easy, low cost, high-level efficiency, preparation small size Graphene in enormous quantities.
Technical scheme: above-mentioned purpose of the present invention is achieved by following technical solution:
The preparation method of a kind of small size Graphene of the present invention, the method concrete steps are as follows:
Step one, by graphite powder and solvent, obtains graphite mixing solutions;
Step 2, puts into container by solution, the homogeneous head of the rotor-stator device of rotor-stator mixing tank (also claiming high-shear homogenizer, high-shear emulsion machine) is fixed on below liquid level simultaneously;
Step 3, opens cooling system and makes solution remain on certain temperature, opens rotor-stator mixing tank simultaneously and carries out high speed processing;
Step 4, carrying out leaving standstill process or centrifugation preparing solution, removing the particle do not peeled off completely, collect supernatant liquor thus obtain stable small size graphene dispersing solution.
Wherein, in above-mentioned steps one, described solvent is one or more mixing in water and organic solvent, the preferably mixture of ethanol, acetone, Virahol and water, wherein organic solvent ratio is 10%-90% (note: prepare two-dimensional nano powder number of patent application in water and organic solvent mixing solutions and be respectively: 201210177012.2,2012100148902.2);
Wherein, in above-mentioned steps one, described graphite raw material is not limit, preferably micro crystal graphite, crystalline flake graphite, expansible black lead, high orientation pyrolytic graphite;
Wherein, in above-mentioned steps one, the starting point concentration of described graphite mixing solutions is not limit, and preferred concentration is 1-30mg/ml;
Wherein, in above-mentioned steps two, in described rotor-stator device, the hole shape of stator surface is not limit, preferably circular hole;
Wherein, in above-mentioned steps two, described rotor-stator device rotor shape is not limit, preferably blade type;
Wherein, in above-mentioned steps two, the rotor in described rotor-stator device and the gap size between stator are 0.1 millimeter to 30 centimetres, and preferably gap is 0.5-10 millimeter;
Wherein, in above-mentioned steps two, the homogeneous head of described rotor-stator device needs to be fixed on below liquid level, and preferred position is below liquid level central position;
Wherein, in above-mentioned steps three, described unlatching rotor-stator mixing tank carries out high speed processing; The rotating speed of its treating processes rotor-stator mixing tank is that 2000-25000 turns, and preferred rotating speed is that 8000-15000 turns;
Wherein, in above-mentioned steps three, described cooling system is the one that circulating liquid cooling, air cooling and electricity freeze but, preferably circulating water;
Wherein, in above-mentioned steps three, described treating processes solution maintains the temperature at 0-80 DEG C, and preferred solution temperature is 15-35 DEG C;
Wherein, in above-mentioned steps four, described time of repose 0.5-20 hour, described centrifugal treating acceleration is 25-5000g, centrifugation time 30-200 minute, and preferred time of repose is 0.5-5 hour, preferred centrifugal acceleration is 35-500g, and preferred centrifugation time is 30-60 minute.
The invention has the beneficial effects as follows:
(1) hydrodynamic method that the present invention utilizes high speed rotating rotor to produce prepares small size Graphene.First-selected electric motor rotor driven makes high speed rotating relative to stator, and then rotor promotes graphite mixing solutions high speed rotating together, produces high-speed gradient and high shear force stripping graphite in the gap between stators and rotators; The boss generation high-speed impact etc. of high-velocity fluid and stator hole wall simultaneously, makes graphite flake peel off and refinement further.Maximum beneficial effect of the present invention is, the almost whole Graphene lateral dimensions prepared by case study on implementation 1 are all less than 1 μm, and lamellar spacing is less than 3nm, and distribution of sizes is concentrated, and individual layer ratio is high.
(2) the method preparation process is relatively gentle, high-quality graphene can be obtained, and overcome the destruction of current main preparation methods to laminated structure, graphene-structured is easily destroyed, as chemical graft method introduces oxy radical in graphene-structured as ultrasonic cavitation creates the environment such as High Temperature High Pressure at tiny area.
(3) the method prepares Graphene, efficient fast, technique is simple, easy and simple to handle, with low cost, short without the need to accurate Controlling Technology parameter, preparation time, do not pollute, easily expand scale, the suitability for industrialized production of high-quality graphene can be realized.
Accompanying drawing explanation
Fig. 1 is the FB(flow block) of the inventive method.
Fig. 2 (a) is not for assembling pictorial diagram completely for generation of the small―gap suture rotor-stator device of high speed rotating fluid in case study on implementation 1.
Fig. 2 (b) is not for assembling pictorial diagram completely for generation of the wide arc gap rotor-stator device of high speed rotating fluid in case study on implementation 1.
Fig. 3 (a) is the rotor-stator internal mixer section of structure for generation of high rotating fluid in case study on implementation 2.
Fig. 3 (b) is the rotor-stator mixing tank force diagram for generation of high rotating fluid in case study on implementation 2.
The atomic force microscopy of the Graphene of Fig. 4 (a) prepared by the inventive method small―gap suture rotor-stator device.
The transmission electron microscope photo of the Graphene of Fig. 4 (b) prepared by the inventive method small―gap suture rotor-stator device.
The graphene film layer thickness statistical graph of Fig. 5 (a) prepared by the inventive method small―gap suture rotor-stator device.(data add up 1000 graphene sheet layers altogether)
The graphene sheet layer mean sizes statistical graph of Fig. 5 (b) prepared by the inventive method small―gap suture rotor-stator device.(data add up 1000 graphene sheet layers altogether)
The atomic force microscopy of the Graphene of Fig. 6 (a) prepared by the inventive method wide arc gap rotor-stator device.
The transmission electron microscope photo of the Graphene of Fig. 6 (b) prepared by the inventive method wide arc gap rotor-stator device.
The graphene film layer thickness statistical graph of Fig. 7 (a) prepared by the inventive method wide arc gap rotor-stator device.Data add up 1000 graphene sheet layers altogether.
The graphene sheet layer mean sizes statistical graph of Fig. 7 (b) prepared by the inventive method wide arc gap rotor-stator device.Data add up 1000 graphene sheet layers altogether.
Embodiment
See Fig. 1, below in conjunction with embodiment, the present invention will be further described.
Embodiment 1, with in the mixed solvent of 30% volume ratio Virahol and water, utilizes present method to prepare small size Graphene for embodiment.It is in kind as shown in Fig. 2 (a) to be used for the small―gap suture rotor-stator device of the rotor-stator mixing tank producing high speed rotating fluid, and concrete technology step is as follows:
Step one: take the crystalline graphite powder 3.5g that particle diameter is less than 100 microns, is dispersed in the 30% volume ratio Virahol of 700mL and the mixed solvent of water, obtains the graphite dispersing solution that concentration is 5mg/ml;
Step 2: it is in the cylindrical tank of 10 centimetres that the graphite dispersing solution prepared is loaded diameter, the rotor-stator device of rotor-stator mixing tank is put into the central position of below liquid level of solution;
Step 3: ON cycle cooling water system, makes the graphite dispersing solution in container remain on room temperature about 25 DEG C; With present method process graphite dispersing solution 1 hour, rotor speed was 9000 turns; Dispersion liquid is after treatment left standstill 1 hour, then upper strata dispersion liquid is taken out;
Step 4: the upper strata dispersion liquid taken out is loaded in tophan pot, then with the centrifugal acceleration centrifugal treating 30min of 45g; After centrifuging treatment, collect supernatant liquid, namely obtain small size Graphene stable dispersions.
The atomic force microscope of the small size Graphene obtained and transmission electron microscope photo are as shown in Fig. 4 (a), (b), and lamellar spacing and lamella size statistic figure are as shown in Fig. 5 (a), (b).
Embodiment 2, with in the mixing solutions of water and ethanol, present method is utilized to prepare small size Graphene for embodiment, it is in kind as shown in Fig. 2 (b) to be used for the rotor-stator device of the wide arc gap rotor-stator mixing tank producing high speed rotating fluid, Fig. 3 (a), (b) in case study on implementation 2 for generation of the rotor-stator internal mixer section of structure of high rotating fluid and force diagram.
Concrete technology step is as follows:
Step one: the mixing solutions 700mL of configuration water and ethanol, ethanol massfraction is 40%, and all the other are deionized water, and crystalline graphite powder 7g particle diameter being less than 100 microns is scattered in wherein, obtains the graphite dispersing solution that concentration is 5mg/ml,
Step 2: the graphite dispersing solution prepared being transferred to diameter is in the cylindrical tank of 9.5 centimetres, rotor-stator device is fixed on the central position of below liquid level;
Step 3: ON cycle cooling water system, makes the graphite dispersing solution in container remain on room temperature about 25 DEG C; With present method process graphite dispersing solution 1 hour, rotor speed was 9000 turns; Dispersion liquid is after treatment left standstill 1 hour, then upper strata dispersion liquid is taken out;
Step 4: the upper strata dispersion liquid taken out is loaded in tophan pot, then with the centrifugal acceleration centrifugal treating 30min of 64g; After centrifuging treatment, collect supernatant liquid, namely obtain small size Graphene stable dispersions.
The atomic force microscopy of the small size Graphene obtained is as shown in Fig. 6 (a), (b), and lamellar spacing and lamella size statistic figure are as shown in Fig. 7 (a), (b).
From above-described embodiment, lesser trochanter and small―gap suture are more suitable for preparation small size Graphene.
Obviously, above-mentioned case study on implementation of the present invention is only used to clearly demonstrate example of the present invention, and the restriction not to embodiments of the present invention.For the those of ordinary skill in described field, other multi-form change or variations can also be made on the basis of the above description.Here cannot give exhaustive to all embodiments, every belong to technical scheme of the present invention the apparent change of amplifying out or variation be still in the row of protection scope of the present invention.
Claims (1)
1. a preparation method for small size Graphene, is characterized in that: the method concrete steps are as follows:
Step one, by graphite powder and solvent, obtains graphite mixing solutions;
Step 2, puts into container by solution, the homogeneous head of the rotor-stator device of rotor-stator mixing tank is fixed on below liquid level simultaneously;
Step 3, opens cooling system and makes solution remain on certain temperature, opens rotor-stator mixing tank simultaneously and carries out high speed processing;
Step 4, carrying out leaving standstill process or centrifugation preparing solution, removing the particle do not peeled off completely, collect supernatant liquor thus obtain stable small size graphene dispersing solution;
Wherein, Graphene lateral dimension is all less than 1 μm, and lamellar spacing is less than 3nm;
Wherein, the solvent described in step one is one or more of the mixture of ethanol, acetone, Virahol and water; Wherein organic solvent ratio is 10%-90%; Graphite powder described in step one is micro crystal graphite, crystalline flake graphite, expansible black lead or high orientation pyrolytic graphite;
Wherein, the graphite mixing solutions starting point concentration described in step one is 1-30mg/mL;
Wherein, in the device of rotor-stator described in step 2, the hole shape of stator surface is circular hole; Rotor-stator device rotor shape is blade type;
Wherein, the rotor in the device of rotor-stator described in step 2 and the gap size between stator are 0.5-10 millimeter;
Wherein, the homogeneous head of the device of rotor-stator described in step 2 needs to be fixed on below liquid level central position;
Wherein, open rotor-stator mixing tank described in step 3 and carry out high speed processing;
Wherein, cooling system described in step 3 is the one that circulating liquid cooling, air cooling and electricity freeze but;
Wherein, in treating processes described in step 3, solution temperature is 15-35 DEG C;
Wherein, time of repose described in step 4 is 0.5-5 hour, and centrifugal acceleration is 35-500g, and centrifugation time is 30-60 minute.
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| CN108358196A (en) * | 2018-04-21 | 2018-08-03 | 广东明路电力电子有限公司 | Graphene sorting process |
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