CN107304490A - A kind of graphene/polyimides is combined the preparation method of carbon fiber - Google Patents
A kind of graphene/polyimides is combined the preparation method of carbon fiber Download PDFInfo
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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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- 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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- 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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- 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
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Abstract
The present invention relates to the preparation method that a kind of graphene/polyimides is combined carbon fiber.Including：（1）Graphene oxide/polyamic acid spinning solution；（2）Prepare graphene oxide/polyimide composite fiber；（3）Prepare graphene/polyimides and be combined carbon fiber and graphite fibre.Instant invention overcomes the problem of polyamic acid spinning technique difficulty, improve the spinnability of polyamic acid solution, the addition of graphene promotes the orientation of composite fibre and carbon fiber, and the carbonization induction of composite fibre and graphitization, the mechanical performance and conductive performance of final compound carbon fiber and graphite fibre are improved, good carbon fiber has good Practical significance to preparing the performances such as high-strength and high-modulus, high heat conduction, conduction.
Description
Technical field
The present invention relates to the preparation method that a kind of graphene/polyimides is combined carbon fiber, belong to the preparation field of functional special carbon fiber.
Background technology
Carbon fiber and its composite are a current most promising class high performance structures materials.Carbon fiber is the material axially arranged along fiber by graphite crystal, the Turbostratic of the plain crystallite of the stepped construction and charcoal with graphite crystal.Carbon fiber has excellent performance, such as high-module high-strength, high-low temperature resistant, heat conduction, biography shake, radiation hardness.Most study and industrialization degree highest are polyacrylonitrile-radical and asphalt base carbon fiber in carbon fiber.But polyacrylonitrile-based carbon fibre heat conductivility is not very high, the production cost of high-performance mesophase pitch-based carbon fibers is high, complex process, low intensity.
As economic continues to develop, people are also being continuously increased to the demand of tencel, and especially high-module high-strength, high heat conduction, conductive fiber are gradually applied to the fields such as reinforcing material, military affairs.
Graphene is by SP between carbon atom2Hydridization bonding, is arranged in the monoatomic layer flat crystal of bi-dimensional cellular shape, with very big specific surface area, there is excellent electricity, calorifics and mechanical property.Using graphene come reinforcing fiber, the nucleus of carbonization can be turned into carbonization, promote the carbonisation of fiber, the stability of composite fibre can be improved, promote the axial orientation of fiber in stretching, the combination property of material can be obviously improved, improve conductive, heat conduction and mechanical property.
Polyimides is the polymer that a class has imide ring, it is an important kind of high-performance fiber, with the excellent properties such as high-module high-strength, high temperature resistant, low temperature resistant, solvent resistant, and also there are good dielectric properties, have broad application prospects in the fields such as Aero-Space, national defense construction, novel building, sports apparatus.Highly oriented Kapton has successfully prepared thermal conductivity up to 1900W/ (mK), high-flexibility carbon film, fast-developing in the high power density electronic product scope such as mobile phone, projecting apparatus.But this carbon film thickness is relatively thin, and heat flux is low, it is difficult to continuously produce and obtain big block elements, limit its application.And carbon fiber using polyimides as the new presoma of carbon fiber, then may prepare high conductance and high performance carbon fiber because can then overcome these difficult with stronger designability.Polyimides has substantial amounts of benzene ring structure and imide ring structure in itself, after polyimide fiber is carbonized, because fiber has very high orientation, can obtain that size is big, defect is few, more perfect graphite lattice structure, so as to produce high performance carbon fiber.The problems such as yet with polyamic acid spinning technique difficulty, high processing costs so that the research of polyimides base carbon fibre is less.This patent solves the problem of spinning moulding is difficult by adding graphene oxide in polyamic acid, carbonization and graphitizing process of the graphene to composite fibre after reduction has good facilitation, can improve orientation, mechanical performance and the conductive performance of final carbon fiber.
Chinese patent CN102605477, which is disclosed, describes polyimides base carbon fibre and preparation method thereof, pass through dianhydride and diamines polycondensation reaction synthesizing polyamides acid, and then prepare polyimide fiber, and polyimides base carbon fibre is prepared using it as presoma, prepared polyimides base carbon fibre has good compactness, defect is few, phosphorus content is high, it is electrically conductive, but the final carburizing temperature of polyimides base carbon fibre prepared by such a method is at 1000 ~ 1600 DEG C, the graphitization processing of the higher temperature of 2000 DEG C and the above is not carried out, in high heat conduction, conductive aspect is not discussed.Chinese patent CN102534870A discloses the preparation method for describing a kind of graphene modified polyacrylonitrile-based carbon fiber, the method by graphene suspension and polyacrylonitrile solution blending by carrying out spinning, then precursor is pre-oxidized and carbonization obtains graphene modified polyacrylonitrile-based carbon fiber, the method is simple and easy to apply, and mechanical property and electric conductivity are significantly improved.Chinese patent CN102534858A, which is disclosed, describes a kind of preparation method of graphene/polyimide composite fibers, the addition of graphene causes the mechanical property of composite fibre to be significantly improved, and this invention is not directed to influence of the graphene to composite fibre induced orientation under drawing-off effect.Chinese patent CN102560453A discloses the method for describing and being carbonized using graphene reinforced polyimide resin and preparing carbonized film, film is prepared in the polyamic acid solution that graphene is added to preparation, then be carbonized obtaining carbonized film, solve to prepare carbonization film method and have that carburizing temperature is high, power consumption is big, carbonization cycle length, carbonized film carbonation rate be low and technical problem of low intensity, with the increase of graphene ratio, the increase of carbon film mechanical property, specific capacitance increase.
Existing data shows to report really in terms of using graphene doped carbon fibre property, but the preparation method and technology that graphene/polyimides is combined carbon fiber but has no report.
The content of the invention
The invention aims to provide to prepare the preparation method that a kind of graphene/polyimides is combined carbon fiber.The spinning solution of graphene oxide and polyamic acid is prepared for using situ aggregation method, the addition of graphene oxide can be with polyamic acid fiber fixed orientation, and inhibits the disorientation of polyamic acid, solves the problem of spinning technique is difficult.The drawing-off of high power is carried out to composite fibre in imidization and carbonisation, the axial orientation of composite fibre can be promoted, the degree of orientation of composite fibre is improved；Meanwhile, graphene plays a part of graphite microcrystal nucleus in carbonisation, so as to be more beneficial for carbonization and graphitizing process, in a word, the addition of graphene causes the conductive performance of the compound carbon fiber and graphite fibre prepared, mechanical property to be improved significantly.
The preparation method that a kind of graphene/polyimides of the present invention is combined carbon fiber comprises the following steps：
（1）By graphene oxide ultrasonic disperse in organic solvent, graphene oxide suspension is produced.
（2）Graphene oxide suspension is added in reactor, inert gas is passed through（Nitrogen or argon gas）, add 4,4'- diaminodiphenyl ethers（ODA）, stir after after its dissolving, pyromellitic acid anhydride (PMDA) be added portionwise, low temperature poly condensation 3-15h are carried out at -15 ~ 25 DEG C, produce graphene oxide/polyamic acid solution, standing, vacuum defoamation.
（3）Graphene oxide/polyamic acid spinning solution is added in spinning kettle, solution-polymerized SBR is carried out under a certain pressure, obtain graphene oxide/polyamic acid as-spun fibre, wherein spinning temperature is 10-40 DEG C, coagulation bath temperature is 10-40 DEG C, spin rate is 0.5-100m/min, and coagulating bath is the mixed liquor of second alcohol and water.Then gradient temperature hot imidization processing is carried out after as-spun fibre is dried in vacuo under certain drawing-off effect, then thermal finalization stretch processing is carried out to fiber with 3-12 times of draw ratio at 300-550 DEG C, obtains graphene oxide/polyimide composite fiber.
（4）Composite fibre obtained above is subjected to carbonization treatment under certain drawing-off effect, graphene/polyimides is obtained and is combined carbon fiber.
（5）By the processing of above-mentioned graphite fiberization, high performance graphene/polyimides composite graphite fiber is obtained.
Above-mentioned organic solvent used can be 1-METHYLPYRROLIDONE（NMP）, N,N-dimethylformamide（DMF）, DMAC N,N' dimethyl acetamide（DMAc）, dimethyl sulfoxide (DMSO)（DMSO）One or more therein.
The solid content of polyamic acid solution described above is 5%-35%.
Graphene oxide doped amount described above is 0.1-10wt%.
The ratio of coagulating bath second alcohol and water described above is ethanol:Water=1:9~9:1.
Hot-imide temperature described above is 100-450 DEG C, 2-10 DEG C of heating rate/min, residence time 1-2h.
Low-temperature carbonization condition described above is：Under the effect of certain drafting force, 800-1600 DEG C, retention time 1-60min, high pure nitrogen atmosphere are warming up to 1-20 DEG C/min.
High temperature graphitization condition described above is：Graphitization temperature is 2400-3200 DEG C, 1-20 DEG C of heating rate, retention time 1-60min, high-purity argon gas atmosphere.
Present invention advantage compared with prior art is：
1st, compared with other carbon fiber precursors, the favorable orientation on the macromolecular chain of polyimide fiber is more easy to be converted into graphite microcrystal size greatly, perfect carbonization structure.
2nd, this method is orientated using graphene oxide anchoring fiber, and it is important that graphene promotes aromatic rings to play the role of in terms of being converted into the higher graphite microcrystal of axial orientation degree in carbonisation as graphite microcrystal nucleus.
3rd, the compound carbon fiber defect obtained by the present invention is few, with higher conductive performance and mechanical property, there is very wide application prospect.
Embodiment
With reference to specific embodiment, the present invention is further elaborated, but the invention is not restricted to following examples.
Embodiment 1
（1）Ultrasonic disperse in organic solvent DMAc is added graphene oxide into, graphene oxide suspension is obtained.
（2）Graphene oxide suspension is added in flask; and flask is placed in ice-water bath; it is passed through nitrogen protection; add 4.840gODA; stirring is after it is completely dissolved; 5.380gPMDA is added portionwise, after persistently stirring 6h after solid dissolving, that is, graphene oxide/polyamic acid spinning solution liquid that solid content is 12% is obtained.
（3）After graphene oxide/polyamic acid spinning solution standing, vacuum defoamation.Then graphene oxide/polyamic acid composite fibre is prepared using dry-wet spinning method, wherein spinning temperature is 20 DEG C, and spin rate 20m/min, coagulation bath temperature is 20 DEG C, and coagulation bath composition is ethanol:Water=4:6.
（4）Gained composite fibre is subjected to hot imidization processing, vacuum environment, using gradient heating, respectively 150,250,1h, 5 DEG C/min of heating rate are handled at a temperature of 300,350 DEG C, fiber after hot imidization is handled is stretched, draft temperature is 300 DEG C, and 5 times of draw ratio obtains graphene oxide/polyimide composite fiber.
（5）Above-mentioned gained fiber is carried out in carbonization treatment, nitrogen environment, under certain drawing-off effect, 500 DEG C are warming up to 3 DEG C/min, then 800 DEG C are warming up to 2 DEG C/min, constant temperature keeps 1h, cooling obtains graphene/polyimides and is combined carbon fiber.
（6）Above-mentioned gained fiber is subjected to graphitization processing, 2800 DEG C of graphitization temperature, heating rate 10 DEG C/min, retention time 1h under ar gas environment.Compound carbon fiber obtained by present implementation is graphite microcrystalline structure, and carbon content is 100%, and intensity is 1.2GPa, thermal conductivity 458W/ (mK).
Embodiment 2
It is 0.5wt% by the increase of graphene oxide doped amount, other conditions are same as Example 1, the compound carbon fiber obtained by present implementation is graphite microcrystalline structure, and carbon content is 100%, intensity is 1.32GPa, thermal conductivity is 562W/ (m K).
Embodiment 3
PMDA and ODA addition is calculated, it is 13% to make the increase of polyamic acid solution solid content, and other conditions are same as Example 1, compound carbon fiber obtained by present implementation is graphite microcrystalline structure, carbon content is 100%, and intensity is 1.58GPa, and thermal conductivity is 571W/ (mK).
Embodiment 4
Organic solvent DMF used is changed to 1-METHYLPYRROLIDONE, other conditions are same as Example 1, compound carbon fiber obtained by present implementation is graphite microcrystalline structure, carbon content is 100%, and intensity is 1.28GPa, and thermal conductivity is 522W/ (mK).
Embodiment 5
Graphene/polyimide composite fibers are prepared using dry-wet spinning, spinning temperature is 25 DEG C, spin rate 5m/min, coagulation bath temperature is 20 DEG C, other conditions are identical with example 1, and the compound carbon fiber obtained by present implementation is graphite microcrystalline structure, and carbon content is 100%, intensity is 1.34GPa, and thermal conductivity is 578W/ (mK).
Embodiment 6
Graphene/polyimide composite fibers are prepared using dry-wet spinning, spinning temperature is 20 DEG C, spin rate 2m/min, coagulation bath temperature is 25 DEG C, other conditions are identical with example 1, and the compound carbon fiber obtained by present implementation is graphite microcrystalline structure, and carbon content is 100%, intensity is 1.31GPa, thermal conductivity 581W/ (mK).
Embodiment 7
The temperature of polycondensation reaction is risen to 5 DEG C, other conditions are same as Example 1, the compound carbon fiber obtained by present implementation is graphite microcrystalline structure, and carbon content is 100%, and intensity is 1.18GPa, thermal conductivity 433W/ (mK).
Embodiment 8
The ratio of coagulating bath second alcohol and water is adjusted to ethanol:Water=2:8, other conditions are same as Example 1, and the compound carbon fiber obtained by present implementation is graphite microcrystalline structure, and carbon content is 100%, and intensity is 1.12GPa, thermal conductivity 492W/ (mK).
Embodiment 9
Gained composite fibre is subjected to hot imidization processing, vacuum environment, using gradient heating, respectively 150,1h is handled at a temperature of 250,300,350 DEG C, the fiber after hot imidization is handled is stretched, draft temperature is 300 DEG C, and 8 times of draw ratio obtains graphene/polyimide composite fibers.Compound carbon fiber obtained by present implementation is graphite microcrystalline structure, and carbon content is 100%, and intensity is 1.55GPa, thermal conductivity 638W/ (mK).
Embodiment 10
Gained composite fibre is subjected to hot imidization processing, vacuum environment, using gradient heating, respectively 150,250,1h, 5 DEG C/min of heating rate are handled at a temperature of 300,350 DEG C, fiber after hot imidization is handled is stretched, draft temperature is 350 DEG C, and 12 times of draw ratio obtains graphene/polyimide composite fibers.Compound carbon fiber obtained by present implementation is graphite microcrystalline structure, and carbon content is 100%, and intensity is 1.77GPa, thermal conductivity 683W/ (mK).
Embodiment 11
The gained graphene/polyimide composite fibers of Example 1, carry out carbonization treatment, in nitrogen environment, 500 DEG C are warming up to 3 DEG C/min, are then warming up to 1000 DEG C with 2 DEG C/min, keep 1h, natural cooling.Other conditions are same as Example 1, and the compound carbon fiber obtained by present implementation is graphite microcrystalline structure, and carbon content is 100%, and intensity is 1.48GPa, thermal conductivity 603W/ (mK).
Embodiment 12
The gained graphene of Example 1/polyimides is combined carbon fiber, and graphitization processing is carried out in ar gas environment, and graphitization temperature is 3200 DEG C, residence time 1h.Compound carbon fiber obtained by present implementation is graphite microcrystalline structure, and carbon content is 100%, and intensity is 1.85GPa, thermal conductivity 848W/ (mK).
Presently preferred embodiments of the present invention is illustrated above, but the present invention is not limited in the embodiment, those skilled in the art can also make a variety of equal modifications and replacement on the premise of without prejudice to spirit of the invention, and these equal modifications and replacement are all contained in the application claims limited range.
Claims (11)
1. the preparation method that a kind of graphene/polyimides is combined carbon fiber comprises the following steps：
（1）By graphene oxide ultrasonic disperse in organic solvent, graphene oxide suspension is produced；
（2）Graphene oxide suspension is added in reactor, inert gas is passed through（Nitrogen or argon gas）, add 4,4'- diaminodiphenyl ethers（ODA）, stir after after its dissolving, pyromellitic acid anhydride be added portionwise（PMDA）, low temperature poly condensation 3-15h is carried out at -15 ~ 25 DEG C, graphene oxide/polyamic acid mixed solution, standing, vacuum defoamation is obtained；
（3）Graphene oxide/polyamic acid spinning solution is added in spinning kettle, solution-polymerized SBR is carried out under a certain pressure, obtain graphene oxide/polyamic acid as-spun fibre, coagulating bath is the mixed liquor of second alcohol and water, as-spun fibre is dried in vacuo then progress hot imidization processing under the effect of certain drafting force, graphene oxide/polyimide composite fiber is obtained；
（4）Composite fibre obtained above is subjected to carbonization treatment, graphene/polyimides is obtained and is combined carbon fiber；
（5）Above-mentioned compound carbon fiber is subjected to graphitization processing, High-performance graphene/polyimides composite graphite fiber is obtained.
2. preparation method according to claim 1, it is characterised in that the particle diameter of graphene oxide is 20-100nm.
3. preparation method according to claim 1, it is characterised in that organic solvent used can be 1-METHYLPYRROLIDONE（NMP）, N,N-dimethylformamide（DMF）, DMAC N,N' dimethyl acetamide（DMAc）, dimethyl sulfoxide (DMSO)（DMSO）One or more therein.
4. preparation method according to claim 1, it is characterised in that mol ratio PMDA: ODA=(1~1.03)
:1, solid content 5%-35%.
5. preparation method according to claim 1, it is characterised in that graphene oxide doped amount is 0.1-10wt%.
6. preparation method according to claim 1, it is characterised in that solution spinning processes parameter：10-40 DEG C of spinning temperature, 10-40 DEG C of coagulation bath temperature, spinning speed 0.5-100m/min.
7. preparation method according to claim 1, it is characterised in that the ratio of coagulating bath second alcohol and water is ethanol:Water=2:8~8:2.
8. preparation method according to claim 1, it is characterised in that hot-imide temperature is 150-450 DEG C, 3-10 DEG C of heating rate/min, residence time 0.5-2h.
9. preparation method according to claim 1, it is characterised in that the draw ratio of fiber is 3-12, draft temperature is 300-550 DEG C.
10. preparation method according to claim 1, it is characterised in that the Carbonization Conditions of composite fibre is are warming up to 800-1200 DEG C, retention time 1-60min, high pure nitrogen atmosphere with 1-20 DEG C/min.
11. preparation method according to claim 1, it is characterised in that graphitization condition is：Graphitization temperature is 2400-3200 DEG C, retention time 1-60min, high-purity argon gas atmosphere.
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Cited By (10)
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| 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 |
| CN110644075A (en) * | 2019-07-19 | 2020-01-03 | 北京化工大学 | Method for preparing carbon fiber by doping polyimide with planar aromatic macromolecules |
| CN110872193A (en) * | 2018-09-04 | 2020-03-10 | 天津大学 | Preparation method of high-thermal-conductivity graphene/chopped carbon fiber composite material |
| 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 |
| CN113233453A (en) * | 2021-06-04 | 2021-08-10 | 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 |
| CN114737318A (en) * | 2022-04-18 | 2022-07-12 | 江西昌大高新能源材料技术有限公司 | Preparation method of polyimide-based high-thermal-conductivity graphite nanofiber membrane |
| CN115286823A (en) * | 2022-08-25 | 2022-11-04 | 上海大学 | High-thermal-conductivity electromagnetic shielding polyimide-based co-carbonized carbon fiber composite material and preparation method thereof |
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| CN110872193A (en) * | 2018-09-04 | 2020-03-10 | 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 |
| CN110644075A (en) * | 2019-07-19 | 2020-01-03 | 北京化工大学 | Method for preparing carbon fiber by doping polyimide with planar aromatic macromolecules |
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| CN113233453A (en) * | 2021-06-04 | 2021-08-10 | 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 |
| WO2023080715A1 (en) * | 2021-11-04 | 2023-05-11 | 한국과학기술연구원 | Method for preparing carbon composite fiber, and carbon nanofiber |
| CN114737318A (en) * | 2022-04-18 | 2022-07-12 | 江西昌大高新能源材料技术有限公司 | Preparation method of polyimide-based high-thermal-conductivity graphite nanofiber membrane |
| 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 |
| CN115286823A (en) * | 2022-08-25 | 2022-11-04 | 上海大学 | High-thermal-conductivity electromagnetic shielding polyimide-based co-carbonized carbon fiber composite material and preparation method thereof |
| CN115286823B (en) * | 2022-08-25 | 2024-05-14 | 上海大学 | High-heat-conductivity electromagnetic shielding polyimide-based co-carbonized carbon fiber composite material and preparation method thereof |
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