CN107304490B - Preparation method of graphene/polyimide composite carbon fiber - Google Patents
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/24—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
Abstract
The invention relates to a preparation method of graphene/polyimide composite carbon fibers. The method comprises the following steps: (1) graphene oxide/polyamic acid spinning solution; (2) preparing graphene oxide/polyimide composite fibers; (3) preparing the graphene/polyimide composite carbon fiber and the graphite fiber. The method overcomes the problem of difficult polyamide acid spinning forming, improves the spinnability of polyamide acid solution, promotes the orientation of the composite fiber and the carbon fiber by adding the graphene, induces the carbonization and graphitization of the composite fiber, improves the mechanical properties and the conductivity of the final composite carbon fiber and graphite fiber, and has good practical significance for preparing the carbon fiber with high strength, high modulus, high heat conductivity, good electric conductivity and the like.
Description
Technical Field
The invention relates to a preparation method of graphene/polyimide composite carbon fibers, and belongs to the field of preparation of functional special carbon fibers.
Background
Carbon fibers and their composites are currently the most promising class of high performance structural materials. The carbon fiber is a substance in which graphite crystals are arranged in the fiber axis direction, and has a layered structure of graphite crystals and a disordered layer structure of carbon crystallites. The carbon fiber has excellent performances such as high modulus, high strength, high and low temperature resistance, heat conduction, shock transmission, radiation resistance and the like. Among the most studied and most industrialized carbon fibers are polyacrylonitrile-based and pitch-based carbon fibers. However, the polyacrylonitrile-based carbon fiber has not very high heat conductivity, and the high-performance mesophase pitch-based carbon fiber has high production cost, complex process and low strength.
With the continuous development of economy, the demand of people on novel fibers is also continuously increased, and particularly, the high-modulus, high-strength, high-heat-conductivity and high-electric-conductivity fibers are gradually applied to the fields of reinforcing materials, military affairs and the like.
Graphene is a SP between carbon atoms2The crystal has the advantages of hybridization into bonds, arrangement into a two-dimensional honeycomb-shaped monoatomic layer planar crystal, large specific surface area, and excellent electrical, thermal and mechanical properties. The graphene is utilized to reinforce the fiber, the fiber can become a carbonized crystal nucleus during carbonization, the carbonization process of the fiber is promoted, the stability of the composite fiber can be improved, the axial orientation of the fiber is promoted during stretching, the comprehensive performance of the material can be obviously improved, and the electric conduction, the heat conduction and the mechanical properties are improved.
Polyimide is a polymer with imide rings, is an important variety of high-performance fibers, has excellent properties such as high modulus, high strength, high temperature resistance, low temperature resistance, solvent resistance and the like, also has good dielectric properties, and has wide application prospects in the fields of aerospace, national defense construction, novel buildings, sports equipment and the like. The high-flexibility carbon film with thermal conductivity up to 1900W/(m.K) is successfully prepared from the high-orientation polyimide film, and is rapidly developed in the fields of high-power density electronic products such as mobile phones, projectors and the like. However, such carbon films are thin and have low heat flux, which makes it difficult to continuously produce and obtain large bulk products, and limits the range of applications. The carbon fiber can overcome the difficulties due to the strong designability, and the polyimide can be used as a new precursor of the carbon fiber, so that the carbon fiber with high conductivity and high performance can be prepared. Polyimide has a large number of benzene ring structures and imide ring structures, and after polyimide fibers are carbonized, the graphite lattice structure which is large in size, few in defects and more complete can be obtained due to high orientation of the fibers, so that high-performance carbon fibers are produced. However, the research on polyimide-based carbon fibers is relatively rare due to the problems of difficult spinning and forming of polyamic acid, high processing cost and the like. This patent solves the difficult problem of spinning shaping through adding graphite oxide in polyamic acid, and graphite alkene after the reduction has fine promotion effect to composite fiber's carbonization and graphitization process, can improve final carbon fiber's orientation, mechanical properties and conductivity.
Chinese patent CN102605477 discloses a polyimide-based carbon fiber and a preparation method thereof, which synthesizes polyamic acid through condensation polymerization of dianhydride and diamine to prepare polyimide fiber, and prepares the polyimide-based carbon fiber by using the polyimide-based carbon fiber as a precursor, the prepared polyimide-based carbon fiber has good compactness, few defects, high carbon content and electrical conductivity, but the final carbonization temperature of the polyimide-based carbon fiber prepared by the method is 1000-1600 ℃, graphitization treatment at a temperature of 2000 ℃ or above is not performed, and no discussion is made on the aspects of high thermal conductivity and electrical conductivity. Chinese patent CN102534870A discloses a preparation method of graphene modified polyacrylonitrile-based carbon fibers, which is characterized in that a graphene suspension and a polyacrylonitrile solution are blended for spinning, and then protofilaments are pre-oxidized and carbonized to obtain the graphene modified polyacrylonitrile-based carbon fibers. Chinese patent CN102534858A discloses a preparation method of graphene/polyimide composite fiber, the mechanical property of the composite fiber is obviously improved by adding graphene, and the invention does not relate to the influence of graphene on the induced orientation of the composite fiber under the drafting action. Chinese patent CN102560453A discloses a method for preparing a carbonized film by carbonizing graphene reinforced polyimide resin, which comprises the steps of adding graphene into a prepared polyamic acid solution to prepare a film, and then carbonizing the film to obtain the carbonized film.
The existing data show that the performance of the carbon fiber doped with graphene is really reported, but the preparation method and the process of the graphene/polyimide composite carbon fiber are not reported.
Disclosure of Invention
The invention aims to provide a preparation method of graphene/polyimide composite carbon fibers. The spinning solution of graphene oxide and polyamic acid is prepared by an in-situ polymerization method, the polyamic acid fiber can be fixed and oriented by adding the graphene oxide, the de-orientation of the polyamic acid is inhibited, and the problem of difficult spinning formation is solved. The composite fiber is highly drafted in the imidization and carbonization processes, so that the axial orientation of the composite fiber can be promoted, and the orientation degree of the composite fiber is improved; meanwhile, the graphene plays a role of a graphite microcrystal crystal nucleus in the carbonization process, so that the carbonization and graphitization processes are facilitated, and in a word, the addition of the graphene obviously improves the conductivity and mechanical properties of the prepared composite carbon fiber and graphite fiber.
The preparation method of the graphene/polyimide composite carbon fiber comprises the following steps:
(1) and ultrasonically dispersing the graphene oxide in an organic solvent to obtain a graphene oxide suspension.
(2) Adding the graphene oxide suspension into a reactor, introducing inert gas (nitrogen or argon), adding 4, 4' -diaminodiphenyl ether (ODA), stirring until the graphene oxide suspension is dissolved, adding pyromellitic dianhydride (PMDA) in batches, carrying out low-temperature polycondensation reaction at the temperature of minus 15-25 ℃ for 3-15h to obtain a graphene oxide/polyamide acid solution, standing and carrying out vacuum defoaming.
(3) Adding the graphene oxide/polyamic acid spinning solution into a spinning kettle, and carrying out solution spinning under a certain pressure to obtain the graphene oxide/polyamic acid nascent fiber, wherein the spinning temperature is 10-40 ℃, the coagulation bath temperature is 10-40 ℃, the spinning speed is 0.5-100m/min, and the coagulation bath is a mixed solution of ethanol and water. And then carrying out vacuum drying on the nascent fiber under the action of certain drafting, carrying out gradient temperature thermal imidization treatment, and then carrying out heat setting and stretching treatment on the fiber at the stretching ratio of 3-12 times at the temperature of 300-550 ℃ to obtain the graphene oxide/polyimide composite fiber.
(4) And carbonizing the obtained composite fiber under a certain drafting action to obtain the graphene/polyimide composite carbon fiber.
(5) And graphitizing the fiber to obtain the high-performance graphene/polyimide composite graphite fiber.
The organic solvent may be one or more of N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), and dimethyl sulfoxide (DMSO).
The solid content of the polyamic acid solution is 5-35%.
The doping amount of the graphene oxide is 0.1-10 wt%.
The ratio of ethanol to water in the coagulation bath is 1: 9-9: 1.
The thermal imidization temperature is 100-450 ℃, the heating rate is 2-10 ℃/min, and the retention time is 1-2 h.
The low-temperature carbonization conditions are as follows: under the action of a certain stretching force, the temperature is raised to 800-1600 ℃ at the speed of 1-20 ℃/min, the holding time is 1-60min, and the atmosphere is high-purity nitrogen.
The high-temperature graphitization conditions are as follows: the graphitization temperature is 2400-3200 ℃, the heating rate is 1-20 ℃, the holding time is 1-60min, and the atmosphere is high-purity argon.
Compared with the prior art, the invention has the advantages that:
1. compared with other carbon fiber precursors, the polyimide fiber has good orientation on a polymer chain, and is easier to be converted into a graphitized structure with large graphite crystallite dimension and perfection.
2. According to the method, the fiber orientation is fixed by using the graphene oxide, and the graphene serves as a graphite microcrystal crystal nucleus in the carbonization process to promote the aromatic ring to be converted into the graphite microcrystal with higher axial orientation degree.
3. The composite carbon fiber obtained by the invention has few defects, higher conductivity and mechanical property and wide application prospect.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples.
Example 1
(1) And adding graphene oxide into an organic solvent DMAc for ultrasonic dispersion to obtain a graphene oxide suspension.
(2) Adding the graphene oxide suspension into a flask, placing the flask in an ice-water bath, introducing nitrogen for protection, adding 4.840g of ODA, stirring until the graphene oxide suspension is completely dissolved, adding 5.380g of PMDA in batches, and continuously stirring for 6 hours after the solid is dissolved to obtain the graphene oxide/polyamic acid spinning solution with the solid content of 12%.
(3) And standing the graphene oxide/polyamic acid spinning solution and defoaming in vacuum. And then preparing the graphene oxide/polyamic acid composite fiber by using a dry-wet spinning method, wherein the spinning temperature is 20 ℃, the spinning speed is 20m/min, the coagulation bath temperature is 20 ℃, and the coagulation bath composition is ethanol and water =4: 6.
(4) And (3) carrying out thermal imidization treatment on the obtained composite fiber, respectively treating the composite fiber at the temperatures of 150, 250, 300 and 350 ℃ for 1h in a vacuum environment by adopting a gradient heating method, wherein the heating rate is 5 ℃/min, and stretching the fiber after the thermal imidization treatment at the stretching temperature of 300 ℃ by 5 times to obtain the graphene oxide/polyimide composite fiber.
(5) And carbonizing the obtained fiber, heating to 500 ℃ at a speed of 3 ℃/min under the action of a certain drafting in a nitrogen environment, heating to 800 ℃ at a speed of 2 ℃/min, keeping the constant temperature for 1h, and cooling to obtain the graphene/polyimide composite carbon fiber.
(6) Graphitizing the obtained fiber in an argon environment at 2800 ℃ at a heating rate of 10 ℃/min for 1 h. The composite carbon fiber obtained by the implementation method has a graphite microcrystalline structure, the carbon content is 100%, the strength is 1.2GPa, and the thermal conductivity is 458W/(m.K).
Example 2
The amount of doped graphene oxide was increased to 0.5wt%, and the other conditions were the same as in example 1, but the composite carbon fiber obtained by the present method had a graphite crystallite structure, a carbon content of 100%, a strength of 1.32GPa, and a thermal conductivity of 562W/(m · K).
Example 3
The amount of PMDA and ODA added was calculated to increase the solid content of the polyamic acid solution to 13%, and the other conditions were the same as in example 1, and the composite carbon fiber obtained by the present embodiment was of a graphite crystallite structure, with a carbon content of 100%, a strength of 1.58GPa, and a thermal conductivity of 571W/(m · K).
Example 4
The organic solvent N, N-dimethylformamide used was changed to N-methylpyrrolidone, and the other conditions were the same as in example 1, and the composite carbon fiber obtained by the present embodiment was of a graphite crystallite structure, with a carbon content of 100%, a strength of 1.28GPa, and a thermal conductivity of 522W/(m · K).
Example 5
The graphene/polyimide composite fiber is prepared by dry-wet spinning, the spinning temperature is 25 ℃, the spinning speed is 5m/min, the coagulation bath temperature is 20 ℃, other conditions are the same as those of example 1, the composite carbon fiber obtained by the implementation method is of a graphite microcrystalline structure, the carbon content is 100%, the strength is 1.34GPa, and the thermal conductivity is 578W/(m.K).
Example 6
The graphene/polyimide composite fiber is prepared by dry-wet spinning, the spinning temperature is 20 ℃, the spinning speed is 2m/min, the coagulation bath temperature is 25 ℃, other conditions are the same as those of example 1, the composite carbon fiber obtained by the implementation method is of a graphite microcrystalline structure, the carbon content is 100%, the strength is 1.31GPa, and the thermal conductivity is 581W/(m.K).
Example 7
The temperature of the polycondensation reaction was raised to 5 ℃ under the same conditions as in example 1, and the composite carbon fiber obtained by the present embodiment had a graphite crystallite structure, a carbon content of 100%, a strength of 1.18GPa, and a thermal conductivity of 433W/(m · K).
Example 8
The ratio of ethanol to water in the coagulation bath was adjusted to =2:8, and the other conditions were the same as in example 1, and the composite carbon fiber obtained by the present embodiment had a graphite crystallite structure, a carbon content of 100%, a strength of 1.12GPa, and a thermal conductivity of 492W/(m · K).
Example 9
And (3) carrying out thermal imidization treatment on the obtained composite fiber, respectively treating the composite fiber at the temperatures of 150, 250, 300 and 350 ℃ for 1h in a vacuum environment by adopting a gradient heating method, and stretching the fiber after the thermal imidization treatment at the stretching temperature of 300 ℃ by 8 times to obtain the graphene/polyimide composite fiber. The composite carbon fiber obtained by the implementation method has a graphite microcrystalline structure, the carbon content is 100%, the strength is 1.55GPa, and the thermal conductivity is 638W/(m.K).
Example 10
And (3) carrying out thermal imidization treatment on the obtained composite fiber, respectively treating the composite fiber at the temperatures of 150, 250, 300 and 350 ℃ for 1h in a vacuum environment by adopting a gradient heating method, wherein the heating rate is 5 ℃/min, and stretching the fiber after the thermal imidization treatment at the stretching temperature of 350 ℃ by the stretching multiple of 12 times to obtain the graphene/polyimide composite fiber. The composite carbon fiber obtained by the implementation method has a graphite microcrystalline structure, the carbon content is 100%, the strength is 1.77GPa, and the thermal conductivity is 683W/(m.K).
Example 11
Taking the graphene/polyimide composite fiber obtained in the example 1, carrying out carbonization treatment, heating to 500 ℃ at a speed of 3 ℃/min in a nitrogen environment, then heating to 1000 ℃ at a speed of 2 ℃/min, keeping for 1h, and naturally cooling. The composite carbon fiber obtained by the present embodiment had a graphite crystallite structure, a carbon content of 100%, a strength of 1.48GPa, and a thermal conductivity of 603W/(m · K) under the same conditions as in example 1.
Example 12
The graphene/polyimide composite carbon fiber obtained in example 1 is graphitized in an argon atmosphere at 3200 ℃ for 1 h. The composite carbon fiber obtained by the implementation method has a graphite microcrystalline structure, the carbon content is 100%, the strength is 1.85GPa, and the thermal conductivity is 848W/(m.K).
While the preferred embodiments of the present invention have been illustrated and described, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (8)
1. A preparation method of graphene/polyimide composite carbon fibers comprises the following steps:
(1) ultrasonically dispersing graphene oxide in an organic solvent to obtain a graphene oxide suspension;
(2) adding the graphene oxide suspension into a reactor, introducing inert gas nitrogen or argon, adding 4, 4' -diaminodiphenyl ether (ODA), stirring until the graphene oxide suspension is dissolved, adding pyromellitic dianhydride (PMDA) in batches, carrying out low-temperature polycondensation reaction for 3-15h at the temperature of-15-25 ℃ to obtain a graphene oxide/polyamide acid mixed solution, standing and carrying out vacuum defoaming;
(3) adding the graphene oxide/polyamide acid spinning solution into a spinning kettle, carrying out solution spinning under certain pressure to obtain graphene oxide/polyamide acid nascent fiber, carrying out vacuum drying on the nascent fiber under the action of certain drawing force and then carrying out thermal imidization treatment, and then carrying out thermal setting and drawing treatment on the fiber at the temperature of 300-550 ℃ and with the drawing multiple of 3-12 times to obtain the graphene oxide/polyimide composite fiber;
(4) carbonizing the obtained composite fiber to obtain graphene/polyimide composite carbon fiber;
(5) graphitizing the composite carbon fiber to obtain high-performance graphene/polyimide composite graphite fiber;
the particle size of the graphene oxide is 20-100 nm; the doping amount of the graphene oxide is 0.1-0.5 wt%.
2. The preparation method according to claim 1, wherein the organic solvent is one or more of N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc) and Dimethylsulfoxide (DMSO).
3. The preparation method according to claim 1, wherein the molar ratio of PMDA to ODA = (1-1.03) = (1): 1, and the solid content is 5-35%.
4. The method of claim 1, wherein the solution spinning process parameters are as follows: the spinning temperature is 10-40 ℃, the coagulating bath temperature is 10-40 ℃, and the spinning speed is 0.5-100 m/min.
5. The preparation method according to claim 1, wherein the ratio of the ethanol to the water in the coagulation bath is 2:8 to 8: 2.
6. The method according to claim 1, wherein the thermal imidization temperature is 150-450 ℃, the heating rate is 3-10 ℃/min, and the retention time is 0.5-2 h.
7. The preparation method as claimed in claim 1, wherein the carbonization condition of the composite fiber is that the temperature is raised to 800-.
8. The method according to claim 1, wherein the graphitization conditions are: the graphitization temperature is 2400-3200 ℃, the holding time is 1-60min, and the atmosphere is high-purity argon.
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| CN110872193B (en) * | 2018-09-04 | 2021-09-28 | 天津大学 | Preparation method of high-thermal-conductivity graphene/chopped carbon fiber composite material |
| CN109390534A (en) * | 2018-09-10 | 2019-02-26 | 中原工学院 | A kind of nano fibrous membrane and preparation method thereof for lithium ion battery separator |
| CN110644075B (en) * | 2019-07-19 | 2020-09-22 | 北京化工大学 | Method for preparing graphite fiber by doping polyimide with planar aromatic macromolecules |
| CN113215685A (en) * | 2021-04-29 | 2021-08-06 | 北京化工大学 | Method for in-situ growth of graphite crystal cone on fiber surface without catalysis |
| CN113233453B (en) * | 2021-06-04 | 2022-12-02 | 四川大学 | High-electric-conductivity heat-conduction graphite material and preparation method thereof |
| CN113402288A (en) * | 2021-06-16 | 2021-09-17 | 江苏集萃碳纤维及复合材料应用技术研究院有限公司 | Preparation method of carbon fiber reinforced high-strength and high-heat-conductivity composite film |
| CN113737310A (en) * | 2021-08-26 | 2021-12-03 | 南通强生石墨烯科技有限公司 | Graphene polyimide composite fiber and preparation method thereof |
| KR20230064984A (en) * | 2021-11-04 | 2023-05-11 | 한국과학기술연구원 | Producing method of polyimide based carbon composite fibers |
| CN114737318B (en) * | 2022-04-18 | 2023-11-17 | 江西昌大高新能源材料技术有限公司 | Preparation method of polyimide-based high-heat-conductivity graphite nanofiber membrane |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102534858A (en) * | 2012-01-09 | 2012-07-04 | 东华大学 | Method for preparing graphene/polyimide composite fibers |
| CN102560453A (en) * | 2012-03-08 | 2012-07-11 | 哈尔滨工业大学 | Method for preparing carbide film by carbonizing graphene reinforced polyimide resin |
| CN105113088A (en) * | 2015-06-08 | 2015-12-02 | 江西先材纳米纤维科技有限公司 | High thermal conductivity polyimide-based graphite nanometer fiber film material and preparation method thereof |
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| US9156700B2 (en) * | 2013-02-25 | 2015-10-13 | Nanotek Instruments, Inc. | Process for producing unitary graphene materials |
| US9359208B2 (en) * | 2014-03-20 | 2016-06-07 | Nanotek Instruments, Inc. | Production process for highly conductive graphitic films |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102534858A (en) * | 2012-01-09 | 2012-07-04 | 东华大学 | Method for preparing graphene/polyimide composite fibers |
| CN102560453A (en) * | 2012-03-08 | 2012-07-11 | 哈尔滨工业大学 | Method for preparing carbide film by carbonizing graphene reinforced polyimide resin |
| CN105113088A (en) * | 2015-06-08 | 2015-12-02 | 江西先材纳米纤维科技有限公司 | High thermal conductivity polyimide-based graphite nanometer fiber film material and preparation method thereof |
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