CN101734650A - Method for preparing graphene-carbon nano tube hybrid composite - Google Patents
Method for preparing graphene-carbon nano tube hybrid composite Download PDFInfo
- Publication number
- CN101734650A CN101734650A CN200910248681A CN200910248681A CN101734650A CN 101734650 A CN101734650 A CN 101734650A CN 200910248681 A CN200910248681 A CN 200910248681A CN 200910248681 A CN200910248681 A CN 200910248681A CN 101734650 A CN101734650 A CN 101734650A
- Authority
- CN
- China
- Prior art keywords
- graphene
- carbon nano
- nano tube
- hybrid composite
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention provides a method for preparing a graphene-carbon nano tube hybrid composite and relates to a method for preparing a functional high molecular material and a device thereof. The method comprises the following steps of: carrying out the stirring and sonic oscillation treatment on graphene and carbon nano tubes to preform an entangled network structure, thoroughly mixing the entangled network structure and polymer particles, and thus obtaining an uniformly-mixed system in which the graphene-carbon nano tube network is coated on the surfaces of the polymer particles after removing the solvent; and putting the uniformly-mixed system in a mould, hot-compacting, and obtaining the graphene-carbon nano tube hybrid composite after cooling and demoulding. By mingling the graphene and the carbon nano tubes in advance to form the communicated network structure, the method realizes the advantage complementation of the graphene and carbon nano tube structures and enables the hybrid composite to have favorable electric conduction and heat conduction properties. The method can be widely used in the fields such as aviation, transportation and communication, electronic industry, civil facilities, construction, chemical industry and the like, can be produced in the industrial scale, and has the advantages of 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102486812A CN101734650B (en) | 2009-12-23 | 2009-12-23 | Method for preparing graphene-carbon nano tube hybrid composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102486812A CN101734650B (en) | 2009-12-23 | 2009-12-23 | Method for preparing graphene-carbon nano tube hybrid composite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101734650A true CN101734650A (en) | 2010-06-16 |
| CN101734650B CN101734650B (en) | 2012-06-20 |
Family
ID=42458766
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009102486812A Expired - Fee Related CN101734650B (en) | 2009-12-23 | 2009-12-23 | Method for preparing graphene-carbon nano tube hybrid composite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101734650B (en) |
Cited By (46)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102127721A (en) * | 2010-11-03 | 2011-07-20 | 映瑞光电科技(上海)有限公司 | Aluminum alloy material and preparation method of aluminum alloy back plate |
| CN102417610A (en) * | 2011-07-13 | 2012-04-18 | 青岛科技大学 | Graphene/carbon nanotube hybrid polymer composite material |
| CN102492280A (en) * | 2011-11-29 | 2012-06-13 | 电子科技大学 | Poly(aryl ether nitrile) composite material and its preparation method |
| CN102532669A (en) * | 2012-01-12 | 2012-07-04 | 上海交通大学 | High polymer-based graphene composite material with positive resistance temperature coefficient and preparation method |
| WO2012088697A1 (en) * | 2010-12-30 | 2012-07-05 | 海洋王照明科技股份有限公司 | Graphene ramification-carbon nanotube composite material and preparation method thereof |
| CN102724620A (en) * | 2011-03-29 | 2012-10-10 | 清华大学 | Thermoacoustic device and electronic device |
| CN102724621A (en) * | 2011-03-29 | 2012-10-10 | 清华大学 | Thermoacoustic device and electronic device |
| CN102724614A (en) * | 2011-03-29 | 2012-10-10 | 清华大学 | A thermal sounding device and an electronic device |
| CN102724617A (en) * | 2011-03-29 | 2012-10-10 | 清华大学 | Thermoacoustic device and electronic device |
| CN102760582A (en) * | 2011-04-26 | 2012-10-31 | 海洋王照明科技股份有限公司 | Graphene/carbon nano tube/nickel electrode and preparation method and application of grapheme/carbon nano tube/nickel electrode |
| CN102795613A (en) * | 2011-05-27 | 2012-11-28 | 清华大学 | Preparation method of graphene-carbon nano tube composite structure |
| WO2012177864A1 (en) * | 2011-06-23 | 2012-12-27 | Designed Nanotubes, LLC | Nanoplate-nanotube composites, methods for production thereof and products obtained therefrom |
| CN102956872A (en) * | 2011-08-29 | 2013-03-06 | 海洋王照明科技股份有限公司 | Preparation method and application of compound electrode slice |
| CN102956864A (en) * | 2011-08-29 | 2013-03-06 | 海洋王照明科技股份有限公司 | Preparation method of nitrogen-doped graphene electrode |
| CN103021663A (en) * | 2012-12-20 | 2013-04-03 | 同济大学 | Novel method for preparing counter electrode material of carbon nanotube thin-film solar cell |
| CN103122075A (en) * | 2013-03-19 | 2013-05-29 | 苏州格瑞丰纳米科技有限公司 | High heat-conducting thin graphene-based composite material, as well as preparation method and application thereof |
| CN103219066A (en) * | 2012-01-19 | 2013-07-24 | 中国科学院上海硅酸盐研究所 | Flexible conductive thin film compositing two-dimensional graphene and one-dimensional nanowire and preparation method thereof |
| CN103241721A (en) * | 2013-05-13 | 2013-08-14 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method of graphene/carbon nanotube composite system |
| CN103241709A (en) * | 2013-04-29 | 2013-08-14 | 中国科学院金属研究所 | Method for adjusting photoelectric property of nanocarbon film by ozone and for graphing nanocarbon film |
| CN103306132A (en) * | 2012-03-15 | 2013-09-18 | 苏州捷迪纳米科技有限公司 | Carbon nano tube fiber-graphene composite material and preparation method of the same |
| US8597526B2 (en) | 2011-05-27 | 2013-12-03 | Tsinghua University | Method for making graphene/carbon nanotube composite structure |
| CN103450381A (en) * | 2013-05-30 | 2013-12-18 | 上海化工研究院 | Nano-carrier catalyst for producing reinforced polyethylene as well as preparation method and application of catalyst |
| CN103811184A (en) * | 2012-11-15 | 2014-05-21 | 海洋王照明科技股份有限公司 | Graphene-carbon nano tube combined electrode and super capacitor manufacturing method |
| CN103849120A (en) * | 2012-11-30 | 2014-06-11 | 合肥杰事杰新材料股份有限公司 | Conductive composite material and its preparation method |
| US8758635B2 (en) | 2011-05-27 | 2014-06-24 | Tsinghua University | Method for making thermoacoustic element |
| CN103965535A (en) * | 2014-04-02 | 2014-08-06 | 芜湖浙鑫新能源有限公司 | Preparation method of heat-conductive plastic adopting ordered space network structure |
| US8811633B2 (en) | 2011-03-29 | 2014-08-19 | Tsinghua University | Thermoacoustic device |
| US8815367B2 (en) | 2011-03-29 | 2014-08-26 | Tsinghua University | Graphene/carbon nanotube composite structure |
| US8920661B2 (en) | 2011-05-27 | 2014-12-30 | Tsinghua University | Method for making graphene/carbon nanotube composite structure |
| CN104393165A (en) * | 2014-11-19 | 2015-03-04 | 国家纳米科学中心 | Nanometer carbon material thin film-based electro-thermal pump type actuator and preparation method thereof |
| US9067795B2 (en) | 2011-05-27 | 2015-06-30 | Tsinghua University | Method for making graphene composite structure |
| CN105084810A (en) * | 2014-05-08 | 2015-11-25 | 劲烯科技股份有限公司 | Composite carbon-material slice and manufacturing method therefor |
| US9205604B2 (en) | 2012-06-19 | 2015-12-08 | Airbus Group Limited | Thermoplastic polymer powder |
| CN106378984A (en) * | 2016-08-29 | 2017-02-08 | 上海复合材料科技有限公司 | Lightweight flexible high-thermal-conductivity nanometer carbon composite film and preparation method thereof |
| CN107286491A (en) * | 2017-06-16 | 2017-10-24 | 青岛大学 | A kind of high conductivity carbon nano tube/graphene aeroge/poly styrene composite material and preparation method thereof |
| CN107312440A (en) * | 2017-07-14 | 2017-11-03 | 合肥思敬齐化工材料有限责任公司 | High-termal conductivity aqueous polyurethane coating and preparation method thereof |
| CN108117743A (en) * | 2018-01-19 | 2018-06-05 | 广州润锋科技有限公司 | A kind of highly conductive nylon composite materials of carbon nano-tube modification and preparation method thereof |
| CN108117684A (en) * | 2018-01-19 | 2018-06-05 | 广州润锋科技有限公司 | A kind of polyolefin/carbon nano tube high-conductivity composite material and preparation method thereof |
| US9997785B2 (en) * | 2011-06-23 | 2018-06-12 | Molecular Rebar Design, Llc | Nanoplate-nanotube composites, methods for production thereof and products obtained therefrom |
| CN108314857A (en) * | 2018-03-07 | 2018-07-24 | 南京苏展智能科技有限公司 | A kind of preparation method of the wear-resistant conductive composite material containing graphene |
| CN109368616A (en) * | 2018-09-11 | 2019-02-22 | 天津大学 | A kind of controllable method for preparing of three-dimensional grapheme carbon nano tube compound material |
| CN110229465A (en) * | 2019-05-16 | 2019-09-13 | 宿迁南航新材料与装备制造研究院有限公司 | A kind of polymer matrix composite of graphene/carbon nano-tube and preparation method thereof |
| US10608282B2 (en) | 2012-06-21 | 2020-03-31 | Molecular Rebar Design, Llc | Binders, electrolytes and separator films for energy storage and collection devices using discrete carbon nanotubes |
| CN112029273A (en) * | 2020-09-07 | 2020-12-04 | 北京航天凯恩化工科技有限公司 | Conductive nylon master batch with graphene-carbon nanotube composite structure and preparation method thereof |
| CN112591741A (en) * | 2020-11-17 | 2021-04-02 | 同济大学 | Preparation method and application of carbon-based composite material |
| CN116003148A (en) * | 2022-12-12 | 2023-04-25 | 山东大学 | High-thermal-conductivity graphene composite film and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1328309C (en) * | 2004-05-26 | 2007-07-25 | 中国科学院金属研究所 | Conductive composite materials with positive temperature coefficient effect and process for making same |
| CN100478392C (en) * | 2005-12-14 | 2009-04-15 | 中国科学院金属研究所 | High-temperature-resisting thermosensitive resistance composite material and its production |
| US7449133B2 (en) * | 2006-06-13 | 2008-11-11 | Unidym, Inc. | Graphene film as transparent and electrically conducting material |
-
2009
- 2009-12-23 CN CN2009102486812A patent/CN101734650B/en not_active Expired - Fee Related
Cited By (76)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8833431B2 (en) | 2010-11-03 | 2014-09-16 | Enraytek Optoelectronics Co., Ltd. | Aluminum alloy material and method of manufacturing aluminum alloy backboard |
| CN102127721A (en) * | 2010-11-03 | 2011-07-20 | 映瑞光电科技(上海)有限公司 | Aluminum alloy material and preparation method of aluminum alloy back plate |
| WO2012058847A1 (en) * | 2010-11-03 | 2012-05-10 | 映瑞光电科技(上海)有限公司 | Aluminium alloy material and method for preparing aluminium alloy back board |
| CN103153843A (en) * | 2010-12-30 | 2013-06-12 | 海洋王照明科技股份有限公司 | Graphene ramification-carbon nanotube composite material and preparation method thereof |
| EP2660192A4 (en) * | 2010-12-30 | 2016-12-07 | Ocean's King Lighting Science&Technology Co Ltd | Graphene ramification-carbon nanotube composite material and preparation method thereof |
| WO2012088697A1 (en) * | 2010-12-30 | 2012-07-05 | 海洋王照明科技股份有限公司 | Graphene ramification-carbon nanotube composite material and preparation method thereof |
| CN103153843B (en) * | 2010-12-30 | 2014-04-02 | 海洋王照明科技股份有限公司 | Graphene ramification-carbon nanotube composite material and preparation method thereof |
| CN102724620A (en) * | 2011-03-29 | 2012-10-10 | 清华大学 | Thermoacoustic device and electronic device |
| US8842857B2 (en) | 2011-03-29 | 2014-09-23 | Tsinghua University | Thermoacoustic device |
| CN102724617A (en) * | 2011-03-29 | 2012-10-10 | 清华大学 | Thermoacoustic device and electronic device |
| CN102724621B (en) * | 2011-03-29 | 2015-07-01 | 清华大学 | Thermoacoustic device and electronic device |
| CN102724620B (en) * | 2011-03-29 | 2015-06-03 | 清华大学 | Thermoacoustic device and electronic device |
| CN102724621A (en) * | 2011-03-29 | 2012-10-10 | 清华大学 | Thermoacoustic device and electronic device |
| US8837753B2 (en) | 2011-03-29 | 2014-09-16 | Tsinghua University | Thermoacoustic device |
| US8831252B2 (en) | 2011-03-29 | 2014-09-09 | Tsinhua University | Thermoacoustic device |
| US8815367B2 (en) | 2011-03-29 | 2014-08-26 | Tsinghua University | Graphene/carbon nanotube composite structure |
| CN102724614A (en) * | 2011-03-29 | 2012-10-10 | 清华大学 | A thermal sounding device and an electronic device |
| CN102724617B (en) * | 2011-03-29 | 2015-06-03 | 清华大学 | Thermoacoustic device and electronic device |
| US8811632B2 (en) | 2011-03-29 | 2014-08-19 | Tsinghua University | Thermoacoustic device |
| US8958579B2 (en) | 2011-03-29 | 2015-02-17 | Tsinghua University | Thermoacoustic device |
| US8811633B2 (en) | 2011-03-29 | 2014-08-19 | Tsinghua University | Thermoacoustic device |
| CN102724614B (en) * | 2011-03-29 | 2015-06-03 | 清华大学 | A thermal sounding device and an electronic device |
| CN102760582B (en) * | 2011-04-26 | 2015-11-25 | 海洋王照明科技股份有限公司 | A kind of graphene/carbon nano-tube/nickel electrode, its preparation method and application |
| CN102760582A (en) * | 2011-04-26 | 2012-10-31 | 海洋王照明科技股份有限公司 | Graphene/carbon nano tube/nickel electrode and preparation method and application of grapheme/carbon nano tube/nickel electrode |
| CN102795613A (en) * | 2011-05-27 | 2012-11-28 | 清华大学 | Preparation method of graphene-carbon nano tube composite structure |
| US8597526B2 (en) | 2011-05-27 | 2013-12-03 | Tsinghua University | Method for making graphene/carbon nanotube composite structure |
| US8920661B2 (en) | 2011-05-27 | 2014-12-30 | Tsinghua University | Method for making graphene/carbon nanotube composite structure |
| US8900390B2 (en) | 2011-05-27 | 2014-12-02 | Tsinghua University | Method for making graphene/carbon nanotube composite structure |
| CN102795613B (en) * | 2011-05-27 | 2014-09-10 | 清华大学 | Preparation method of graphene-carbon nano tube composite structure |
| US9067795B2 (en) | 2011-05-27 | 2015-06-30 | Tsinghua University | Method for making graphene composite structure |
| US8758635B2 (en) | 2011-05-27 | 2014-06-24 | Tsinghua University | Method for making thermoacoustic element |
| JP2014529325A (en) * | 2011-06-23 | 2014-11-06 | モレキュラーレバー デザイン，エルエルシー | Nanoplate-nanotube composite, method for producing the same, and product obtained therefrom |
| US20140127511A1 (en) * | 2011-06-23 | 2014-05-08 | Molecular Rebar Design, Llc | Nanoplate-nanotube composites, methods for production thereof and products obtained therefrom |
| US9475921B2 (en) * | 2011-06-23 | 2016-10-25 | Molecular Rebar Design, Llc | Nanoplate-nanotube composites, methods for production thereof and products obtained therefrom |
| US9997785B2 (en) * | 2011-06-23 | 2018-06-12 | Molecular Rebar Design, Llc | Nanoplate-nanotube composites, methods for production thereof and products obtained therefrom |
| CN103764553A (en) * | 2011-06-23 | 2014-04-30 | 分子钢筋设计有限责任公司 | Nanoplate-nanotube composites, methods for production thereof and products obtained therefrom |
| CN103764553B (en) * | 2011-06-23 | 2016-05-11 | 分子钢筋设计有限责任公司 | Nanometer sheet-nanometer tube composite materials, its production method and the product by its acquisition |
| WO2012177864A1 (en) * | 2011-06-23 | 2012-12-27 | Designed Nanotubes, LLC | Nanoplate-nanotube composites, methods for production thereof and products obtained therefrom |
| CN102417610A (en) * | 2011-07-13 | 2012-04-18 | 青岛科技大学 | Graphene/carbon nanotube hybrid polymer composite material |
| CN102956872A (en) * | 2011-08-29 | 2013-03-06 | 海洋王照明科技股份有限公司 | Preparation method and application of compound electrode slice |
| CN102956864B (en) * | 2011-08-29 | 2015-11-18 | 海洋王照明科技股份有限公司 | A kind of preparation method of nitrating Graphene electrodes |
| CN102956864A (en) * | 2011-08-29 | 2013-03-06 | 海洋王照明科技股份有限公司 | Preparation method of nitrogen-doped graphene electrode |
| CN102956872B (en) * | 2011-08-29 | 2015-06-03 | 海洋王照明科技股份有限公司 | Preparation method and application of compound electrode slice |
| CN102492280B (en) * | 2011-11-29 | 2014-01-29 | 电子科技大学 | Poly(aryl ether nitrile) composite material and its preparation method |
| CN102492280A (en) * | 2011-11-29 | 2012-06-13 | 电子科技大学 | Poly(aryl ether nitrile) composite material and its preparation method |
| CN102532669A (en) * | 2012-01-12 | 2012-07-04 | 上海交通大学 | High polymer-based graphene composite material with positive resistance temperature coefficient and preparation method |
| CN103219066B (en) * | 2012-01-19 | 2016-08-03 | 中国科学院上海硅酸盐研究所 | Flexible conductive film that two-dimensional graphene is compound with one-dimensional nano line and preparation method thereof |
| CN103219066A (en) * | 2012-01-19 | 2013-07-24 | 中国科学院上海硅酸盐研究所 | Flexible conductive thin film compositing two-dimensional graphene and one-dimensional nanowire and preparation method thereof |
| CN103306132A (en) * | 2012-03-15 | 2013-09-18 | 苏州捷迪纳米科技有限公司 | Carbon nano tube fiber-graphene composite material and preparation method of the same |
| US9205604B2 (en) | 2012-06-19 | 2015-12-08 | Airbus Group Limited | Thermoplastic polymer powder |
| US10608282B2 (en) | 2012-06-21 | 2020-03-31 | Molecular Rebar Design, Llc | Binders, electrolytes and separator films for energy storage and collection devices using discrete carbon nanotubes |
| CN103811184A (en) * | 2012-11-15 | 2014-05-21 | 海洋王照明科技股份有限公司 | Graphene-carbon nano tube combined electrode and super capacitor manufacturing method |
| CN103849120A (en) * | 2012-11-30 | 2014-06-11 | 合肥杰事杰新材料股份有限公司 | Conductive composite material and its preparation method |
| CN103021663A (en) * | 2012-12-20 | 2013-04-03 | 同济大学 | Novel method for preparing counter electrode material of carbon nanotube thin-film solar cell |
| CN103122075A (en) * | 2013-03-19 | 2013-05-29 | 苏州格瑞丰纳米科技有限公司 | High heat-conducting thin graphene-based composite material, as well as preparation method and application thereof |
| CN103241709A (en) * | 2013-04-29 | 2013-08-14 | 中国科学院金属研究所 | Method for adjusting photoelectric property of nanocarbon film by ozone and for graphing nanocarbon film |
| CN103241721A (en) * | 2013-05-13 | 2013-08-14 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method of graphene/carbon nanotube composite system |
| CN103241721B (en) * | 2013-05-13 | 2014-12-03 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method of graphene/carbon nanotube composite system |
| CN103450381B (en) * | 2013-05-30 | 2016-03-23 | 上海化工研究院 | Produce nano-carrier Catalysts and its preparation method and the application of enhanced polyethylene |
| CN103450381A (en) * | 2013-05-30 | 2013-12-18 | 上海化工研究院 | Nano-carrier catalyst for producing reinforced polyethylene as well as preparation method and application of catalyst |
| CN103965535A (en) * | 2014-04-02 | 2014-08-06 | 芜湖浙鑫新能源有限公司 | Preparation method of heat-conductive plastic adopting ordered space network structure |
| CN105084810A (en) * | 2014-05-08 | 2015-11-25 | 劲烯科技股份有限公司 | Composite carbon-material slice and manufacturing method therefor |
| CN104393165A (en) * | 2014-11-19 | 2015-03-04 | 国家纳米科学中心 | Nanometer carbon material thin film-based electro-thermal pump type actuator and preparation method thereof |
| CN106378984A (en) * | 2016-08-29 | 2017-02-08 | 上海复合材料科技有限公司 | Lightweight flexible high-thermal-conductivity nanometer carbon composite film and preparation method thereof |
| CN107286491B (en) * | 2017-06-16 | 2020-02-07 | 青岛大学 | High-conductivity carbon nanotube/graphene aerogel/polystyrene composite material and preparation method thereof |
| CN107286491A (en) * | 2017-06-16 | 2017-10-24 | 青岛大学 | A kind of high conductivity carbon nano tube/graphene aeroge/poly styrene composite material and preparation method thereof |
| CN107312440A (en) * | 2017-07-14 | 2017-11-03 | 合肥思敬齐化工材料有限责任公司 | High-termal conductivity aqueous polyurethane coating and preparation method thereof |
| CN108117743A (en) * | 2018-01-19 | 2018-06-05 | 广州润锋科技有限公司 | A kind of highly conductive nylon composite materials of carbon nano-tube modification and preparation method thereof |
| CN108117684A (en) * | 2018-01-19 | 2018-06-05 | 广州润锋科技有限公司 | A kind of polyolefin/carbon nano tube high-conductivity composite material and preparation method thereof |
| CN108314857A (en) * | 2018-03-07 | 2018-07-24 | 南京苏展智能科技有限公司 | A kind of preparation method of the wear-resistant conductive composite material containing graphene |
| CN109368616A (en) * | 2018-09-11 | 2019-02-22 | 天津大学 | A kind of controllable method for preparing of three-dimensional grapheme carbon nano tube compound material |
| CN110229465A (en) * | 2019-05-16 | 2019-09-13 | 宿迁南航新材料与装备制造研究院有限公司 | A kind of polymer matrix composite of graphene/carbon nano-tube and preparation method thereof |
| CN112029273A (en) * | 2020-09-07 | 2020-12-04 | 北京航天凯恩化工科技有限公司 | Conductive nylon master batch with graphene-carbon nanotube composite structure and preparation method thereof |
| CN112029273B (en) * | 2020-09-07 | 2022-04-29 | 北京航天凯恩化工科技有限公司 | Conductive nylon master batch with graphene-carbon nanotube composite structure and preparation method thereof |
| CN112591741A (en) * | 2020-11-17 | 2021-04-02 | 同济大学 | Preparation method and application of carbon-based composite material |
| CN116003148A (en) * | 2022-12-12 | 2023-04-25 | 山东大学 | High-thermal-conductivity graphene composite film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101734650B (en) | 2012-06-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101734650B (en) | Method for preparing graphene-carbon nano tube hybrid composite | |
| An et al. | A polymer-based thermal management material with enhanced thermal conductivity by introducing three-dimensional networks and covalent bond connections | |
| Pan et al. | Vertically aligned silicon carbide nanowires/boron nitride cellulose aerogel networks enhanced thermal conductivity and electromagnetic absorbing of epoxy composites | |
| Wang et al. | 3D Ti3C2Tx MXene/C hybrid foam/epoxy nanocomposites with superior electromagnetic interference shielding performances and robust mechanical properties | |
| Wang et al. | Ultralow electrical percolation in graphene aerogel/epoxy composites | |
| Yang et al. | Improvement of thermal conductivities for PPS dielectric nanocomposites via incorporating NH2-POSS functionalized nBN fillers | |
| Guo et al. | Simultaneous improvement of thermal conductivities and electromagnetic interference shielding performances in polystyrene composites via constructing interconnection oriented networks based on electrospinning technology | |
| Ying et al. | Tailoring highly ordered graphene framework in epoxy for high-performance polymer-based heat dissipation plates | |
| Zhang et al. | Preparation of highly thermally conductive but electrically insulating composites by constructing a segregated double network in polymer composites | |
| Pan et al. | Highly thermally conductive 3D BN/MWCNTs/C spatial network composites with improved electrically insulating and flame retardancy prepared by biological template assisted method | |
| Li et al. | Quick heat dissipation in absorption-dominated microwave shielding properties of flexible poly (vinylidene fluoride)/carbon nanotube/Co composite films with anisotropy-shaped Co (flowers or chains) | |
| Tan et al. | Carbon nanoparticle hybrid aerogels: 3D double-interconnected network porous microstructure, thermoelectric, and solvent-removal functions | |
| Yu et al. | Graphite nanoplatelet− epoxy composite thermal interface materials | |
| CN106459494B (en) | Based on composite material preparation catecholamine-plate shaped graphite polymer composite | |
| Kwon et al. | Fabrication of graphene sheets intercalated with manganese oxide/carbon nanofibers: toward high‐capacity energy storage | |
| Mani et al. | 3D structured graphene fluoride-based epoxy composites with high thermal conductivity and electrical insulation | |
| Wang et al. | Highly deformable thermal interface materials enabled by covalently-bonded carbon nanotubes | |
| Wu et al. | High-performance carbon nanotube/polymer composite fiber from layer-by-layer deposition | |
| Wang et al. | A roadmap review of thermally conductive polymer composites: critical factors, progress, and prospects | |
| Guo et al. | Highly thermally conductive carbon nanotubes pillared exfoliated graphite/polyimide composites | |
| Li et al. | Highly oriented graphite aerogel fabricated by confined liquid-phase expansion for anisotropically thermally conductive epoxy composites | |
| CN107892784B (en) | Polymer-based nanocomposite and preparation method thereof | |
| Fan et al. | Sustainable bacterial cellulose reinforced carbon nanotube buckypaper and its multifunctionality for electromagnetic interference shielding, Joule heating and humidity sensing | |
| Chen et al. | Significant enhancement of thermal conductivity in segregated (GnPs&MWCNTs)@ Polybenzoxazine/(Polyether ether ketone)-based composites with excellent electromagnetic shielding | |
| Yang et al. | Highly thermally conductive and superior electrical insulation polymer composites via in situ thermal expansion of expanded graphite and in situ oxidation of aluminum nanoflakes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120620 Termination date: 20131223 |