CN101734650A - Method for preparing graphene-carbon nano tube hybrid composite - Google Patents
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Abstract
一种石墨烯-碳纳米管混杂复合材料的制备方法，涉及一种功能高分子材料及器件的制备方法。将石墨烯和碳纳米管经搅拌、超声振荡处理预先形成缠结的网络结构，将其与聚合物颗粒进行充分混合、去除溶剂后，获得石墨烯-碳纳米管网络包裹于聚合物颗粒表面的均匀混合体系；将其放入模具中，热压成型、冷却脱模后得到石墨烯-碳纳米管混杂复合材料。本方法通过石墨烯与碳纳米管预先混杂形成连通网络结构，实现了石墨烯和碳纳米管结构上的优势互补，使得该混杂复合材料具有较好的导电、导热性能。本发明可以在航空航天、交通运输、电子工业、民用设施、建筑及化工等方面具有广泛的应用，并能够工业化规模生产、成本低廉且环境友好。A method for preparing a graphene-carbon nanotube hybrid composite material relates to a method for preparing a functional polymer material and a device. Graphene and carbon nanotubes are stirred and ultrasonically oscillated to form an entangled network structure in advance. After fully mixing them with polymer particles and removing the solvent, a graphene-carbon nanotube network wrapped on the surface of polymer particles is obtained. A uniform mixing system; put it into a mold, hot press molding, cooling and demoulding to obtain a graphene-carbon nanotube hybrid composite material. In the method, graphene and carbon nanotubes are pre-mixed to form a connected network structure, which realizes the complementary advantages in the structure of graphene and carbon nanotubes, and makes the hybrid composite material have better electrical and thermal conductivity properties. The invention can be widely used in aerospace, transportation, electronic industry, civil facilities, construction, chemical industry, etc., and can be produced on an industrial scale, with low cost and environmental friendliness.
Description
Technical field
The present invention relates to the preparation method in a kind of functional high molecule material and device technology field, particularly relate to a kind of preparation method of graphene-carbon nano tube hybrid composite.
Background technology
Graphene (graphene, see for details: Novoselov K S, et al.Electric field effects inatomically thin carbon films.Science, 2004,306:666-119) be a kind of carbonaceous novel material by the tightly packed one-tenth bi-dimensional cellular of monolayer carbon atom shape crystalline network, it is the elementary cell that makes up other dimension carbonaceous material (as zero dimension soccerballene, one dimension carbon nanotube, three-dimensional graphite).Graphene has excellent electric property and thermal property, and its room temperature electronic mobility can reach 15000cm
2V
-1S
-1, thermal conductivity can reach 3000Wm
-1K
-1In addition, Graphene is cheap, raw material is easy to get, and its unique two-dirnentional structure can carry out effective electric heating transmission, is expected in the acquisition widespread use of fields such as high-performance electronic device, field emmision material, gas sensor and energy storage.But because Graphene has the sheet structure of two dimension, it in use curls and height fold especially easily; When especially adopting melt-blending process to prepare polymer composites, Graphene easier generation under shear action is curled and height fold, is unfavorable for forming in matrix transporting network efficiently.Carbon nanotube (carbon nanotube is a kind of new carbon of being found by Iijima in 1991 CNT), and it can regard the seamless hollow tube that is rolled into by Graphene as, and its length is several microns to several millimeters, diameter in several nanometers between tens nanometers.Because its particular structure, carbon nanotube has significant advantage at aspects such as mechanics enhancing and the transmission of electronics long-range; But there is shortcomings such as being easy to reunion and cost height.
About the existing report of Graphene hybrid polymer thing Composite Preparation technology, for example: Chinese patent, the old Yongsheng of CN200910067708.8 etc., " Graphene and carbon-fibre composite and preparation method thereof ", its principal character comprises: it is to be raw material with Graphene and carbon fibre material, form in carbon fibre material surface-coated Graphene coating preparation by the method that applies, the thickness of coating is 1 nanometer-5 micron.Chinese patent, the old Yongsheng of CN101474897 etc., " Graphene-organic material layered assembling film and preparation method thereof ", its principal character comprises: with grapheme material and organic materials is raw material, utilize the interactions such as static, hydrogen bond, coordinate bond or charge transfer between Graphene and the organic materials, by method for manufacturing thin film such as spin coating, spraying, dipping-the lift film forming that is layering.Chinese patent, the old Yongsheng of CN101474899 etc., " Graphene-inorganic materials composite multi-layer film and preparation method thereof ", its principal character comprises: with grapheme material and inorganic materials is raw material, by typical thin films preparation methods such as spraying, spin coating, dipping, the electroless plating film forming that is layering, every tunic is thick can be controlled at 10 nanometers-2 millimeter as required.In the above method, do not mention that all utilizing Graphene and carbon nano tube hybrid technology to form twines interleaving network, and the spin coating techniques that adopt form laminated film more in the preparation.
Summary of the invention
The objective of the invention is to propose a kind of preparation method of graphene-carbon nano tube hybrid composite, make carbon nanotube and Graphene form by stirring and sonic oscillation in solvent and mix interspersed structure, can prevent curling or wrinkle of Graphene effectively, give full play to the two-dimentional electric heating transport property of Graphene excellence; Mixing of this graphene-carbon nano tube transports network, and it is complementary that Graphene and carbon nanotube are formed in the 26S Proteasome Structure and Function design, when satisfying heat conduction, conducting function, significantly reduces the volume of functional stuffing, the cost of reduction matrix material.In addition, because it transports network structure and can design in advance and make up according to service requirements, has bigger design freedom.
The technical solution adopted in the present invention is:
A kind of preparation method of graphene-carbon nano tube hybrid composite, this preparation method's processing step is as follows:
(1) preparation comprises the suspension system of Graphene, carbon nanotube, dispersion solvent, makes Graphene and carbon nanotube intert, twine the network structure that formation is communicated with mutually through stirring, sonic oscillation;
(2) add polymer beads,, make the polymer beads surface be wrapped up by the graphene-carbon nano tube interleaving network through stirring and sonic oscillation;
(3) behind the removal solvent, form the uniform mixing system that graphene-carbon nano tube is wrapped in the polymer beads surface;
(4) described mixed system is put into mould, make graphene-carbon nano tube hybrid composite after, the cooling and demolding hot-forming through heating up.
The preparation method of described a kind of graphene-carbon nano tube hybrid composite, used Graphene is meant mono-layer graphite sheet, multilayer graphite flake or their mixture; Used carbon nanotube is meant that diameter is that 5-200 nanometer, length are the hollow tubular carbon material of 0.1-100 micron.
The preparation method of described a kind of graphene-carbon nano tube hybrid composite, used dispersion solvent is dehydrated alcohol, acetone, toluene and vinylbenzene.
The preparation method of described a kind of graphene-carbon nano tube hybrid composite makes Graphene and carbon nanotube be pre-formed a kind of network structure that interweaves, twines behind sonic oscillation.。
The preparation method of described a kind of graphene-carbon nano tube hybrid composite, polymer beads is polyethylene, polyvinyl chloride, polypropylene, polymeric amide, polystyrene, polystyrene, polyoxymethylene, tetrafluoroethylene, polycarbonate, polyphenylene oxide, polysulfones.
The preparation method of described a kind of graphene-carbon nano tube hybrid composite removes solvent and realizes by heating or vacuum filtration method.
The preparation method of described a kind of graphene-carbon nano tube hybrid composite, the graphene-carbon nano tube network packet is rolled in the polymer beads surface, forms the connected network along the polymer beads surface arrangement.
The preparation method of described a kind of graphene-carbon nano tube hybrid composite, hot pressing temperature are higher than melting point polymer or softening temperature more than 20 ℃, and forming pressure is greater than 10MPa, and the cooling and demolding temperature is lower than 60 ℃.
The preparation method of described a kind of graphene-carbon nano tube hybrid composite, the initial content proportioning (mass percent) of raw material is:
Graphene 0.1-10 part;
Carbon nanotube 0.1-10 part;
Polymkeric substance: 100 parts;
Dispersion solvent: 100-500 part.
The invention has the beneficial effects as follows:
1. the present invention adopts the graphene-carbon nano tube hybrid technology, make that by sonic oscillation carbon nanotube and Graphene carry out interting mutually and twining, utilize the advantage that the Graphene cost is low, electric property is excellent, the characteristics big by carbon nanotube rigidity, that length-to-diameter ratio is high prevent curling of two-dimentional graphene film; Give full play to constructional feature, the formation of Graphene and carbon nanotube and have complementary advantages, help to form three-dimensional efficiently electric heating and transport network.
2. by designing in advance and structure transports network, can avoid the polymkeric substance that occurs in traditional melt blending preparation process effectively to contact electricity (heat) resistance increases, conduction (heat) performance reduces between the parcel of functional stuffing, filler limitation.Transporting being built with in advance of network among the present invention helps form and effectively has a common boundary, improves the electricity, the heat conduction transmission efficiency that transport network between functional stuffing.
3. in conjunction with the immingling technology of graphene-carbon nano tube network and polymer beads, make the graphene-carbon nano tube network packet be rolled in the polymer beads surface, form the three-dimensional network that transports, significantly improve the effective rate of utilization of filler aspect electric heating transmission enhancing, only need very low volume, hybrid composite just can have conduction (heat) performance preferably, significantly reduces the cost of matrix material.In addition, if adopt the matrix of high crystalline polymkeric substance, hybrid composite can have certain positive temperature coefficient effect, can be widely used at thermistor and devices field.。
4. the present invention prepares hybrid composite with graphene-carbon nano tube conductive network and polymeric matrix by solvent blend, hot-forming mode, equipment is simple, operating process is simple and easy, can be used for the preparation of multiple thermoplastic polymer and graphene-carbon nano tube hybrid composite.Select different matrix material, size distribution and amount of filler, can be according to actual user demand, design in advance and make functional composite material with particular network structure, have great design freedom.
Embodiment
Embodiment 1:
0.01 gram Graphene and 0.01 gram carbon nanotube are scattered in the 10 gram dehydrated alcohols, form steady suspension after ultrasonic 2 hours; 10 gram high density polyethylene(HDPE) ultrafine powder are joined in this suspension, ultrasonic 30 minutes, when treating that graphene-carbon nano tube is wrapped in the high-density polyethylene powder surface and forms the uniform mixing system, be warming up to 60 ℃ and carry out drying with except that desolvating.It is transferred in the mould, is warming up to 170 ℃, and under the 10MPa condition hot-forming 5 minutes, be cooled to room temperature, the demoulding obtains graphene-carbon nano tube hybrid composite.Measure matrix material volume resistance, calculating its resistivity is 7.09 * 10
6Ohmcm.
Embodiment 2:
0.1 gram Graphene and 0.1 gram carbon nanotube are scattered in the 10 gram acetone, form steady suspension after ultrasonic 2 hours; 10 gram polypropylene GRANULES are joined in this suspension, ultrasonic 30 minutes, when treating that graphene-carbon nano tube is wrapped in the high density poly propylene particle surface and forms the uniform mixing system, under normal temperature, carry out vacuum filtration except that desolvating.It is transferred in the mould, is warming up to 200 ℃, and under the 10MPa condition hot-forming 5 minutes, be cooled to the room temperature demoulding, obtain graphene-carbon nano tube hybrid composite.Measure matrix material volume resistance, calculating its resistivity is 2.00 * 10
4Ohmcm.
Embodiment 3:
0.5 gram Graphene and 0.5 gram carbon nanotube are scattered in the 25 gram dehydrated alcohols, form steady suspension after ultrasonic 2 hours; 10 gram poly methyl methacrylate particles are joined in this suspension, ultrasonic 30 minutes, when treating that graphene-carbon nano tube is wrapped in the poly methyl methacrylate particle surface and forms the uniform mixing system, under normal temperature, carry out vacuum filtration and desolvate to remove.It is transferred in the mould, is warming up to 180 ℃, and under the 10MPa condition hot-forming 5 minutes, be cooled to the room temperature demoulding, obtain graphene-carbon nano tube hybrid composite.Measure matrix material volume resistance, calculating its resistivity is 8.84 * 10
2Ohmcm.
Embodiment 4:
1 gram Graphene and 1 gram carbon nanotube are scattered in the 50 gram dehydrated alcohols, form steady suspension after ultrasonic 2 hours; 10 gram granules of polystyrene are joined in this suspension, ultrasonic 30 minutes, when treating that graphene-carbon nano tube is wrapped in granules of polystyrene surface and forms the uniform mixing system, be warming up to 60 ℃ and carry out heat drying and desolvate to remove.Further be transferred in the mould, be warming up to 160 ℃, and under the 10MPa condition hot-forming 5 minutes, be cooled to the room temperature demoulding, obtain graphene-carbon nano tube hybrid composite.Measure matrix material volume resistance, calculating its resistivity is 4.55 * 10
1Ohmcm.
Claims (9)
1. the preparation method of a graphene-carbon nano tube hybrid composite is characterized in that described preparation method's processing step is as follows:
(1) preparation comprises the suspension system of Graphene, carbon nanotube, dispersion solvent, and through stirring, sonic oscillation makes Graphene and carbon nanotube intert, twine the network structure that formation is communicated with mutually;
(2) add polymer beads,, make the polymer beads surface be wrapped up by the graphene-carbon nano tube interleaving network through stirring and sonic oscillation;
(3) behind the removal solvent, form the uniform mixing system that graphene-carbon nano tube is wrapped in the polymer beads surface;
(4) described mixed system is put into mould, make graphene-carbon nano tube hybrid composite after, the cooling and demolding hot-forming through heating up.
2. the preparation method of a kind of graphene-carbon nano tube hybrid composite according to claim 1 is characterized in that used Graphene is meant mono-layer graphite sheet, multilayer graphite flake or their mixture; Used carbon nanotube is meant that diameter is that 5-200 nanometer, length are the hollow tubular carbon material of 0.1-100 micron.
3. the preparation method of a kind of graphene-carbon nano tube hybrid composite according to claim 1 is characterized in that used dispersion solvent is dehydrated alcohol, acetone, toluene and vinylbenzene.
4. the preparation method of a kind of graphene-carbon nano tube hybrid composite according to claim 1 is characterized in that making behind sonic oscillation Graphene and carbon nanotube to be pre-formed a kind of network structure that interweaves, twines.
5. the preparation method of a kind of graphene-carbon nano tube hybrid composite according to claim 1 is characterized in that polymer beads is polyethylene, polyvinyl chloride, polypropylene, polymeric amide, polystyrene, polystyrene, polyoxymethylene, tetrafluoroethylene, polycarbonate, polyphenylene oxide, polysulfones.
6. the preparation method of a kind of graphene-carbon nano tube hybrid composite according to claim 1 is characterized in that removing solvent and realizes by heating or vacuum filtration method.
7. the preparation method of a kind of graphene-carbon nano tube hybrid composite according to claim 1 is characterized in that the graphene-carbon nano tube network packet is rolled in the polymer beads surface, forms the connected network along the polymer beads surface arrangement.
8. the preparation method of a kind of graphene-carbon nano tube hybrid composite according to claim 1 is characterized in that hot pressing temperature is higher than melting point polymer or softening temperature more than 20 ℃, and forming pressure is greater than 10MPa, and the cooling and demolding temperature is lower than 60 ℃.
9. the preparation method of a kind of graphene-carbon nano tube hybrid composite according to claim 1 is characterized in that the mass percent of the initial content proportioning of raw material is:
Graphene: 0.1-10 part;
Carbon nanotube: 0.1-10 part;
Polymkeric substance: 100 parts;
Dispersion solvent: 100-500 part.
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