CN105603585A - Preparation method of hollow carbon fibers with controllable scale - Google Patents
Preparation method of hollow carbon fibers with controllable scale Download PDFInfo
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- CN105603585A CN105603585A CN201610079960.0A CN201610079960A CN105603585A CN 105603585 A CN105603585 A CN 105603585A CN 201610079960 A CN201610079960 A CN 201610079960A CN 105603585 A CN105603585 A CN 105603585A
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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
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
- D01F9/225—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles from stabilised polyacrylonitriles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/08—Addition of substances to the spinning solution or to the melt for forming hollow filaments
-
- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- 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
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
The invention provides a preparation method of hollow carbon fibers with a controllable scale and relates to the technical field of preparation of carbon fibers. The preparation method comprises the following steps: firstly preparing a metal oxide nano rod by a hydrothermal method; then mixing and dissolving the metal oxide nano rod and a high polymer in an organic solvent, and uniformly stirring; carrying out electrostatic spinning to obtain metal oxide (MOX)/high polymer (MP) blended proto-filaments; carrying out heat treatment technologies including pre-oxidization, carbonization and the like on the blended proto-filaments to obtain MOX/CNF composite carbon fibers; and carrying out acid washing, filtering and drying to obtain the hollow carbon fibers. A metal oxide hard template agent prepared by the hydrothermal method has good scale controllability and can be used for preparing carbon fibers with different scales and hollow structures; meanwhile, the problem in current coaxial electrostatic spinning that solutions of inner and outer layers are mutually dissolved in a hollow carbon fiber preparation process is overcome; and the scales of the fibers can be effectively regulated and controlled by using an electrostatic spinning technology, and the aim of large-batch production can be realized.
Description
Technical field
The present invention relates to the preparing technical field of carbon fiber.
Technical background
Common carbon fibers is because it has high specific area, Heat stability is good, and anticorrosive, the characteristics such as good conductive and heat-conductive, by extensive concern. Hollow carbon fiber is compared with common carbon fibers; except having the advantage of common carbon fibers; due to the existence of hollow structure; increase extra inner surface; its performance at aspects such as absorption, mass transfer, catalysis is greatly improved, thereby has a good application prospect in fields such as the purifications of storage hydrogen industry, environmental protection and water body.
The technology of preparing of traditional hollow carbon fiber mainly contains molecular self-assembling method, chemical vapour deposition technique. The standby hollow carbon fiber diameter of molecular self-assembling legal system is less, is generally no more than 10nm; The technology that chemical vapour deposition technique is prepared hollow carbon fiber due to output compared with low cause expensive. Compared with first two method, although preparing hollow carbon fiber, method of electrostatic spinning starts to walk evening, because the advantages such as its equipment is simple, produce in a large number, fibre dimensions controllability is strong are by extensive concern. So far, the technique of utilizing electrostatic spinning to prepare hollow carbon fiber is all the precursor that coaxial electrostatic spinning obtains core/shell structure, removes internal layer (stratum nucleare) material by the operation such as solvent or washing, finally obtains the carbon fibre material of hollow structure. For example, Chinese patent 201210172307.0 has been invented a kind of method that coaxial electrostatic spinning is prepared polyacrylonitrile-radical porous hollow carbon fiber. It is using the mixed liquor of polyacrylonitrile and certain pore creating material as skin, and certain high temperature is easily degraded to high polymeric solution as internal layer, carries out coaxial electrical spinning, then removes pore creating material through heat treatment and prepares porous hollow carbon fiber with the high polymer of easily degrading; The Sun Liangkui (macromolecule journal, 1,2009,61-65) of the National University of Defense technology, taking polyacrylonitrile as outer, taking methyl-silicone oil as internal layer, adopts coaxial electrostatic spinning to prepare PAN base hollow carbon fiber through two step heat treatments again. But hollow carbon fiber spinning condition harshness is prepared in coaxial spinning, need internal outer field flow velocity strictly to control, operational stability is poor; In addition, also easily there is the situations such as solution dissolves each other, be difficult to realize large-scale production.
Summary of the invention
The object of the invention is the preparation method of the controlled hollow carbon fiber material of a kind of yardstick.
The present invention includes following steps:
1) hydro-thermal method is prepared metal oxide nanorods;
2) by miscible in organic solvent to metal oxide nanorods and high polymer, obtain spinning solution;
3) spinning solution, through electrostatic spinning, makes metal oxide/high polymer precursor;
4) by metal oxide/high polymer precursor after pre-oxidation, carbonization, obtain carbon fiber reinforce plastic;
5) by carbon fiber reinforce plastic through pickling, dry, obtain hollow carbon fiber.
The present invention is the use in conjunction of the technology such as a kind of controlled preparation, electrostatic spinning and subsequent heat treatment of hydro-thermal method template. The present invention is made as the metal oxide nanorods of hollow carbon fiber hard mould agent by hydro-thermal method, the use of hard mould agent can overcome the shortcoming that in coaxial spinning, solution dissolves each other, and for flow velocity, almost no requirement (NR) is set, and strengthens the operability of spinning; By adjusting hydrothermal procedure parameter, thereby metal oxide nanorods yardstick is effectively controlled, can realizes the hollow carbon fiber of the different hollow structures of preparation; And the stability of the blending technology of routine intravenous electrical spinning method and ease for operation can effectively improve operability and the controllability of whole process; Cheap metal precursor is conducive to reduce the preparation cost of hollow carbon fiber, improves process economy, is suitable for large-scale production.
Advantage and good effect that the present invention has are:
1, hydro-thermal method is prepared metal oxide nanorods, and as the follow-up hard mould agent of preparing hollow carbon fiber, its yardstick controllability is good, can prepare the carbon fiber of different scale hollow structure.
2, method of electrostatic spinning can be realized a large amount of productions of carbon fiber, and regulation and control spinning condition also can be controlled the yardstick of carbon fiber.
3, simple, workable, the experiment condition temperature of the preparation process of whole hollow carbon fiber and environmental friendliness.
4, economically, the use of cheap metal precursor can reduce preparation cost, improves the economic benefit of process.
Further, metal oxide nanorods of the present invention is MnO2。MnO2For cheap metal oxide, can improve process economy; And be easy to pickling, improve operability.
The Hydrothermal Synthesis temperature that described hydro-thermal method is prepared metal oxide nanorods is 160 DEG C, and the time is 12～24h. The prolongation of hydro-thermal time can increase the yardstick of metal oxide nanorods, can prepare the hollow carbon fiber of different scale using this as hard template.
Described high polymer is PAN, or PVP. PAN and PVP are the high polymer of easy spinning, have improved the operability of spinning process.
Described organic solvent is DMF. DMF can better dissolve PAN and PVP, is convenient to spinning.
The environment temperature of described electrostatic spinning is≤40 DEG C, ambient humidity≤30%; Spinning voltage is 15kV, receiving range 25cm, and spinning solution flow velocity 2.5mm/min, the angle of inclination of syringe is 15 °. Spinning under this temperature and humidity, contributes to the volatilization of solvent in spinning process, is convenient to into silk; And under this pressure, receiving range, spinning solution flow velocity and syringe angle of inclination, spinning process is more easily carried out, and fiber precursor distribution of sizes is more even.
The environment temperature of described pre-oxidation is 250 DEG C, and the time of pre-oxidation is 2h. In this temperature and time, to fiber precursor pre-oxidation, make macromolecule in precursor be converted into resistant to elevated temperatures trapezium structure through cyclodehydrogenation, to keep original fiber pattern under high temperature cabonization, improved the stability of precursor in carbonisation.
Described carbonization is carried out in nitrogen, and heating rate is 5 DEG C/min, is constant temperature 2h under 800 DEG C of conditions in temperature. Carbonisation can be removed the non-carbon in fiber, generates the high carbon fiber of phosphorus content. Can make with this understanding carbonization more abundant.
When described pickling, adopting concentration is the aqueous solution of nitric acid of 3mol/L. Aqueous solution of nitric acid can better be removed MnO2。
Brief description of the drawings
Fig. 1 prepares MnO in embodiment 12The SEM of hollow carbon fiber figure when the hydro-thermal time is 12h in process.
Fig. 2 prepares MnO in embodiment 22The SEM of hollow carbon fiber figure when the hydro-thermal time is 18h in process.
Fig. 3 prepares MnO in embodiment 32The SEM of hollow carbon fiber figure when the hydro-thermal time is 24h in process.
Fig. 4 is the SEM figure of the hollow carbon fiber prepared taking PVP as spinning solution in embodiment 4.
Detailed description of the invention
One, preparation technology:
Embodiment 1:
A. take 0.45gMnSO4 ·H2O and 1gKMnO4Be dissolved in respectively in 30mL deionized water, magnetic agitation, until solid dissolves completely. By MnSO4·H2O solution is poured KMnO into4In solution, continue to stir, until mixed liquor becomes brown color suspension gradually. Subsequently brown color suspension is transferred in 100mL stainless steel hydrothermal reaction kettle to isothermal reaction 12h at 160 DEG C. After reaction finishes, by sediment decompress filter in still, and clean 3 times with distilled water and absolute ethyl alcohol are each, oven dry, obtains MnO2Metal oxide nanorods.
B. take PAN1.5g, be dissolved in 15gDMF, magnetic agitation is until dissolve completely. Put into subsequently 0.5gMnO2Metal oxide nanorods, continues to stir, and mixes, and obtains spinning solution.
C. the environment temperature of electrostatic spinning is≤40 DEG C, ambient humidity≤30%. Spinning solution is packed in electrostatic spinning apparatus and carries out spinning, and spinning voltage is 15kV, and receiving range is 25cm, and spinning solution flow velocity is 2.5mm/min, and the angle of inclination of syringe is 15 °. Obtain MnO through electrostatic spinning2/ PAN blending precursor.
D. by MnO2/ PAN blending precursor in air with heating rate pre-oxidation 2h at 250 DEG C of 5 DEG C/min; Then at N2In with heating rate carbonization 2h at 800 DEG C of 5 DEG C/min, obtain MnO/CNF carbon fiber reinforce plastic.
E. MnO/CNF carbon fiber reinforce plastic is put into 3mol/L nitric acid and soak 2h, filter, dry, obtain hollow carbon fiber.
Embodiment 2:
A. take 0.45gMnSO4 ·H2O and 1gKMnO4Be dissolved in respectively in 30mL deionized water, magnetic agitation, until solid dissolves completely. By MnSO4·H2O solution is poured KMnO into4In solution, continue to stir, until mixed liquor becomes brown color suspension gradually. Subsequently brown color suspension is transferred in 100mL stainless steel hydrothermal reaction kettle to isothermal reaction 18h at 160 DEG C. After reaction finishes, by sediment decompress filter in still, and clean 3 times with distilled water and absolute ethyl alcohol are each, oven dry, can obtain MnO2Metal oxide nanorods.
B. take PAN1.5g, be dissolved in 15gDMF, magnetic agitation is until dissolve completely. Put into subsequently 0.5gMnO2Metal oxide nanorods, continues to stir, and mixes, and obtains spinning solution.
C. the environment temperature of electrostatic spinning is≤40 DEG C, ambient humidity≤30%. Spinning solution is packed in electrostatic spinning apparatus and carries out spinning, and spinning voltage is 15kV, and receiving range is 25cm, and spinning solution flow velocity is 2.5mm/min, and the angle of inclination of syringe is 15 °. Obtain MnO through electrostatic spinning2/ PAN blending precursor.
D. by MnO2/ PAN blending precursor in air with heating rate pre-oxidation 2h at 250 DEG C of 5 DEG C/min; Then at N2In with heating rate carbonization 2h at 800 DEG C of 5 DEG C/min, obtain MnO/CNF carbon fiber reinforce plastic.
E. MnO/CNF carbon fiber reinforce plastic is put into 3mol/L nitric acid and soak 2h, filter, dry, obtain hollow carbon fiber.
Embodiment 3:
A. take 0.45gMnSO4 ·H2O and 1gKMnO4Be dissolved in respectively in 30mL deionized water, magnetic agitation, until solid dissolves completely. By MnSO4·H2O solution is poured KMnO into4In solution, continue to stir, until mixed liquor becomes brown color suspension gradually. Subsequently brown color suspension is transferred in 100mL stainless steel hydrothermal reaction kettle to isothermal reaction 24h at 160 DEG C. After reaction finishes, by sediment decompress filter in still, and clean 3 times with distilled water and absolute ethyl alcohol are each, oven dry, can obtain MnO2Metal oxide nanorods.
B. take PAN1.5g, be dissolved in 15gDMF, magnetic agitation is until dissolve completely. Put into subsequently 0.5gMnO2Metal oxide nanorods, continues to stir, and mixes, and obtains spinning solution.
C. the environment temperature of electrostatic spinning is≤40 DEG C, ambient humidity≤30%. Pack spinning solution in electrostatic spinning apparatus spinning, spinning voltage is 15kV, and receiving range is 25cm, and spinning solution flow velocity is 2.5mm/min, and the angle of inclination of syringe is 15 °. Obtain MnO through electrostatic spinning2/ PAN blending precursor.
D. by MnO2/ PAN blending precursor in air with heating rate pre-oxidation 2h at 250 DEG C of 5 DEG C/min; Then at N2In with heating rate carbonization 2h at 800 DEG C of 5 DEG C/min, obtain MnO/CNF carbon fiber reinforce plastic.
E. MnO/CNF carbon fiber reinforce plastic is put into 3mol/L nitric acid and soak 2h, filter, dry, obtain hollow carbon fiber.
Embodiment 4:
A. take 0.45gMnSO4 ·H2O and 1gKMnO4Be dissolved in respectively in 30mL deionized water, magnetic agitation, until solid dissolves completely. By MnSO4·H2O solution is poured KMnO into4In solution, continue to stir, until mixed liquor becomes brown color suspension gradually. Subsequently brown color suspension is transferred in 100mL stainless steel hydrothermal reaction kettle to isothermal reaction 24h at 160 DEG C. After reaction finishes, by sediment decompress filter in still, and clean 3 times with distilled water and absolute ethyl alcohol are each, oven dry, can obtain MnO2Metal oxide nanorods.
B. take PVP(polyvinylpyrrolidone) 1.5g, be dissolved in 15gDMF, magnetic agitation is until dissolve completely; Put into subsequently 0.5gMnO2Metal oxide nanorods, continues to stir, and mixes, and obtains spinning solution.
C. the environment temperature of electrostatic spinning is≤40 DEG C, ambient humidity≤30%. Pack spinning solution in electrostatic spinning apparatus spinning, spinning voltage is 15kV, and receiving range is 25cm, and spinning solution flow velocity is 2.5mm/min, and the angle of inclination of syringe is 15 °. Obtain MnO through electrostatic spinning2/ PVP blending precursor.
D. by MnO2/ PVP blending precursor in air with heating rate pre-oxidation 2h at 250 DEG C of 5 DEG C/min; Then at N2In with heating rate carbonization 2h at 800 DEG C of 5 DEG C/min, obtain MnO/CNF carbon fiber reinforce plastic.
E. MnO/CNF carbon fiber reinforce plastic is put into 3mol/L nitric acid and soak 2h, filter, dry, obtain hollow carbon fiber.
The SEM of the hollow carbon fiber that two, above each example is made schemes as shown in Figures 1 to 4.
Comparison diagram 1,2,3 can be found out, at preparation MnO2In process, along with the increase of hydro-thermal time, the hollow yardstick of the hollow carbon fiber of preparation increases to some extent. This is due to the increase along with the hydro-thermal time, MnO2The yardstick of nanometer rods is increasing to be caused. Comparison diagram 3 and Fig. 4, can see in Fig. 4 that the pattern of fiber does not have in Fig. 3 fiber pattern good, and this mainly easily decomposes and cause because PVP is heated.
Claims (9)
1. a preparation method for the controlled hollow carbon fiber of yardstick, comprises the following steps:
1) adopt hydro-thermal method to prepare metal oxide nanorods;
2) by miscible in organic solvent to metal oxide nanorods and high polymer, obtain spinning solution;
3) spinning solution, through electrostatic spinning, makes metal oxide/high polymer precursor;
4) by metal oxide/high polymer precursor after pre-oxidation, carbonization, obtain carbon fiber reinforce plastic;
5) by carbon fiber reinforce plastic through pickling, dry, obtain hollow carbon fiber.
2. preparation method according to claim 1, is characterized in that: described metal oxide nanorods is MnO2。
3. preparation method according to claim 1, is characterized in that: the Hydrothermal Synthesis temperature that described hydro-thermal method is prepared metal oxide nanorods is 160 DEG C, and the time is 12～24h.
4. preparation method according to claim 1, is characterized in that: described high polymer is PAN or PVP.
5. preparation method according to claim 1, is characterized in that: described organic solvent is DMF.
6. preparation method according to claim 1, is characterized in that: the environment temperature of described electrostatic spinning is≤40 DEG C, ambient humidity≤30%; Spinning voltage is 15kV, receiving range 25cm, and spinning solution flow velocity 2.5mm/min, the angle of inclination of syringe is 15 °.
7. preparation method according to claim 1, is characterized in that: the environment temperature of described pre-oxidation is 250 DEG C, the time of pre-oxidation is 2h.
8. preparation method according to claim 1, is characterized in that: described carbonization is carried out in nitrogen, heating rate is 5 DEG C/min, is constant temperature 2h under 800 DEG C of conditions in temperature.
9. preparation method according to claim 1, is characterized in that: when described pickling, adopting concentration is the aqueous solution of nitric acid of 3mol/L.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105926085A (en) * | 2016-07-06 | 2016-09-07 | 天津工业大学 | Method for preparing carbon nano-fiber/nano-particle composite material |
| CN106192081A (en) * | 2016-06-30 | 2016-12-07 | 天津工业大学 | A kind of preparation method of Graphene skeletal porous nanofiber |
| CN106811832A (en) * | 2017-02-16 | 2017-06-09 | 济南大学 | A kind of pearl-decorated curtain shape BiFeO3The preparation method and products obtained therefrom of micro nanometer fiber |
| CN106811833A (en) * | 2017-02-16 | 2017-06-09 | 济南大学 | A kind of preparation method of SnO2 micro nanometer fibers |
| CN107297103A (en) * | 2017-07-28 | 2017-10-27 | 中材科技膜材料（山东）有限公司 | A kind of dust-filtering base material, its preparation method and application |
| CN108385209A (en) * | 2018-03-02 | 2018-08-10 | 河南工程学院 | The preparation method of porous filamentous nanocarbon |
| CN110273136A (en) * | 2019-06-24 | 2019-09-24 | 大连理工大学 | A kind of self-supporting hollow carbon tunica fibrosa and preparation method thereof and the application in lithium-sulfur cell |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100701627B1 (en) * | 2005-12-22 | 2007-03-29 | 한국생산기술연구원 | Manufacturing method of nano sized activated carbon fiber comprising metal oxide and electrode for super capacitor using the same nano sized activated carbon fiber manufactured thereby |
| CN103225135A (en) * | 2013-05-09 | 2013-07-31 | 中国科学院化学研究所 | Porous carbon fiber, and preparation method and application thereof |
| CN103882559A (en) * | 2014-03-13 | 2014-06-25 | 中国科学院化学研究所 | High-specific surface porous carbon fiber, preparation method and application of carbon fiber |
| CN104071770A (en) * | 2014-07-06 | 2014-10-01 | 太原理工大学 | Method for preparing porous functional carbon fiber cluster from waste cotton textiles |
| CN104342783A (en) * | 2013-07-31 | 2015-02-11 | 国家纳米科学中心 | A nanometer or nanometer porous carbon fiber bundle, a preparing method thereof and applications of the bundle |
-
2016
- 2016-02-05 CN CN201610079960.0A patent/CN105603585B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100701627B1 (en) * | 2005-12-22 | 2007-03-29 | 한국생산기술연구원 | Manufacturing method of nano sized activated carbon fiber comprising metal oxide and electrode for super capacitor using the same nano sized activated carbon fiber manufactured thereby |
| CN103225135A (en) * | 2013-05-09 | 2013-07-31 | 中国科学院化学研究所 | Porous carbon fiber, and preparation method and application thereof |
| CN104342783A (en) * | 2013-07-31 | 2015-02-11 | 国家纳米科学中心 | A nanometer or nanometer porous carbon fiber bundle, a preparing method thereof and applications of the bundle |
| CN103882559A (en) * | 2014-03-13 | 2014-06-25 | 中国科学院化学研究所 | High-specific surface porous carbon fiber, preparation method and application of carbon fiber |
| CN104071770A (en) * | 2014-07-06 | 2014-10-01 | 太原理工大学 | Method for preparing porous functional carbon fiber cluster from waste cotton textiles |
Non-Patent Citations (1)
| Title |
|---|
| 汪满意等: "聚丙烯腈基中空碳纤维的制备及电化学性能研究", 《材料导报》 * |
Cited By (11)
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| CN106192081A (en) * | 2016-06-30 | 2016-12-07 | 天津工业大学 | A kind of preparation method of Graphene skeletal porous nanofiber |
| CN106192081B (en) * | 2016-06-30 | 2018-07-13 | 天津工业大学 | A kind of preparation method of graphene skeletal porous nanofiber |
| CN105926085A (en) * | 2016-07-06 | 2016-09-07 | 天津工业大学 | Method for preparing carbon nano-fiber/nano-particle composite material |
| CN106811832A (en) * | 2017-02-16 | 2017-06-09 | 济南大学 | A kind of pearl-decorated curtain shape BiFeO3The preparation method and products obtained therefrom of micro nanometer fiber |
| CN106811833A (en) * | 2017-02-16 | 2017-06-09 | 济南大学 | A kind of preparation method of SnO2 micro nanometer fibers |
| CN106811832B (en) * | 2017-02-16 | 2019-10-25 | 济南大学 | A kind of pearl-decorated curtain shape BiFeO3The preparation method and products obtained therefrom of micro nanometer fiber |
| CN106811833B (en) * | 2017-02-16 | 2019-10-25 | 济南大学 | A kind of SnO2The preparation method of micro nanometer fiber |
| CN107297103A (en) * | 2017-07-28 | 2017-10-27 | 中材科技膜材料（山东）有限公司 | A kind of dust-filtering base material, its preparation method and application |
| CN108385209A (en) * | 2018-03-02 | 2018-08-10 | 河南工程学院 | The preparation method of porous filamentous nanocarbon |
| CN110273136A (en) * | 2019-06-24 | 2019-09-24 | 大连理工大学 | A kind of self-supporting hollow carbon tunica fibrosa and preparation method thereof and the application in lithium-sulfur cell |
| CN110273136B (en) * | 2019-06-24 | 2021-07-09 | 大连理工大学 | Self-supporting hollow carbon fiber membrane, preparation method thereof and application thereof in lithium-sulfur battery |
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