CN105603585B - A kind of preparation method of the controllable hollow carbon fiber of yardstick - Google Patents
A kind of preparation method of the controllable hollow carbon fiber of yardstick Download PDFInfo
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- CN105603585B CN105603585B CN201610079960.0A CN201610079960A CN105603585B CN 105603585 B CN105603585 B CN 105603585B CN 201610079960 A CN201610079960 A CN 201610079960A CN 105603585 B CN105603585 B CN 105603585B
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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
-
- 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
A kind of preparation method of the controllable hollow carbon fiber of yardstick, is related to the preparing technical field of carbon fiber.First hydro-thermal method prepares metal oxide nanorods, then metal oxide nanorods and high polymer are miscible in organic solvent, stirs；Metal oxide (MO is obtained through electrostatic spinningX)/high polymer（MP）Blending precursor；Subsequent blending precursor is through pre-oxidizing, and the heat treatment technics such as carbonization obtains MOX/ CNF is combined carbon fiber, then through pickling, filters, and drying produces hollow carbon fiber.The yardstick controllability of metal oxide hard mould agent prepared by hydro-thermal method is good, can prepare the carbon fiber of different scale hollow structure while overcoming current coaxial electrostatic spinning prepares the problem of ectonexine solution during hollow carbon fiber dissolves each other；The use of electrostatic spinning technique can effectively regulate and control the yardstick of fiber, and can realize the purpose largely produced.
Description
Technical field
The present invention relates to the preparing technical field of carbon fiber.
Technical background
Common carbon fibers have high specific surface area due to it, and heat endurance is good, anticorrosive, the spy such as excellent conductive and heat-conductive
Property, by extensive concern.Hollow carbon fiber is compared with common carbon fibers, in addition to having the advantages that common carbon fibers, due to hollow knot
The presence of structure, adds extra inner surface, its performance in terms of absorption, mass transfer, catalysis is greatly improved, from
And had a good application prospect in fields such as hydrogen storage industry, environmental protection and the purifications of water body.
The technology of preparing of traditional hollow carbon fiber mainly has molecular self-assembling method, chemical vapour deposition technique.Molecule is from group
Hollow carbon fiber diameter prepared by dress method is smaller, is usually no more than 10nm；And chemical vapour deposition technique prepares hollow carbon fiber
Technology then causes expensive because yield is relatively low.Compared with first two method, though method of electrostatic spinning prepares hollow carbon fiber
Right starting evening, but because its equipment is simple, a large amount of productions, the advantages of fibre dimensions controllability is strong by extensive concern.So far, utilize
The technique that electrostatic spinning prepares hollow carbon fiber is all the precursor that coaxial electrostatic spinning obtains core/shell structure, by solvent or water
The operation such as wash and remove internal layer（Stratum nucleare）Material, the final carbon fibre material for obtaining hollow structure.For example, Chinese patent
201210172307.0 invent a kind of method that coaxial electrostatic spinning prepares polyacrylonitrile-radical Porous hollow carbon fiber.It is by
The mixed liquor of polyacrylonitrile and certain pore creating material regard the degradable high polymeric solution of certain high temperature as internal layer as outer layer, carries out
Coaxial electrical spinning, it is then thermally treated to remove pore creating material and degradable high polymer to prepare Porous hollow carbon fiber；Science and techniques of defence
The Sun Liangkui of university（Macromolecule journal, 1,2009,61-65）Using polyacrylonitrile as outer layer, using methyl-silicone oil as internal layer, using same
Axle electrostatic spinning is prepared for PAN base hollow carbon fibers through two-step thermal processing again.But, coaxial spinning prepares hollow carbon fiber spinning
Condition harshness is, it is necessary to strictly control the flow velocity of ectonexine, operational stability is poor；The feelings such as dissolved each other in addition, being also easy to occur solution
Condition, is difficult to realize large-scale production.
The content of the invention
The purpose of the present invention is a kind of preparation method of the controllable hollow carbon fiber material of yardstick.
The present invention comprises the following steps：
1）Hydro-thermal method prepares metal oxide nanorods；
2）Metal oxide nanorods and high polymer are miscible in organic solvent, obtain spinning solution；
3）Metal oxide/high polymer precursor is made through electrostatic spinning in spinning solution；
4）By metal oxide/high polymer precursor after pre-oxidation, carbonization, compound carbon fiber is obtained；
5）By compound carbon fiber through pickling, drying, hollow carbon fiber is obtained.
The present invention is that the joint of the technologies such as a kind of controllable preparation, electrostatic spinning and the subsequent heat treatment of hydro-thermal method template should
With.The present invention is made as the metal oxide nanorods of hollow carbon fiber hard mould agent by hydro-thermal method, and hard mould agent makes
With the shortcoming that solution dissolves each other in coaxial spinning can be overcome, almost no requirement (NR) is set for flow velocity, strengthens the operability of spinning；
By adjusting hydrothermal procedure parameter, so that metal oxide nanorods yardstick is effectively controlled, it can be achieved to prepare in difference
The hollow carbon fiber of hollow structure；And the stability and ease for operation of the blending technology of conventional method of electrostatic spinning, then it can effectively improve
The operability and controllability of whole process；Cheap metal precursor then advantageously reduces being prepared into for hollow carbon fiber
This, improves process economics, suitable for large-scale production.
The present invention has the advantage that and good effect is：
1st, hydro-thermal method prepares metal oxide nanorods, is used as the hard mould agent for subsequently preparing hollow carbon fiber, its yardstick
Controllability is good, can prepare the carbon fiber of different scale hollow structure.
2nd, method of electrostatic spinning can realize a large amount of productions of carbon fiber, and regulation and control spinning condition also can control the chi of carbon fiber
Degree.
3rd, the preparation process of whole hollow carbon fiber is simple, workable, experiment condition temperature and environment-friendly.
4th, economically, the use of cheap metal precursor can reduce preparation cost, improve the economic benefit of process.
Further, metal oxide nanorods of the present invention are MnO2。MnO2For cheap metal oxide, Ke Yiti
High process economics；And it is easy to pickling, improve operability.
The Hydrothermal Synthesiss temperature that the hydro-thermal method prepares metal oxide nanorods is 160 DEG C, and the time is 12~24h.Water
The extension of hot time can increase the yardstick of metal oxide nanorods, and different scale can be prepared in this, as hard template
Hollow carbon fiber.
The high polymer is PAN, or PVP.PAN and PVP is the high polymer of easy spinning, improves grasping for spinning process
The property made.
The organic solvent is DMF.DMF can preferably dissolve PAN and PVP, be easy to spinning.
The environment temperature of the electrostatic spinning is≤40 DEG C, ambient humidity≤30%；Spinning voltage is 15kV, receives distance
25cm, spinning flow velocity 2.5mm/min, the angle of inclination of syringe is 15 °.The spinning under this temperature and humidity, helps to spin
The volatilization of solvent, is easy into silk during silk；And under this pressure, reception distance, spinning flow velocity and syringe angle of inclination,
Spinning process is more easy to carry out, and fiber precursor Size Distribution is evenly.
The environment temperature of the pre-oxidation is 250 DEG C, and the time of pre-oxidation is 2h.It is former to fiber in this temperature and time
Silk pre-oxidation so that macromolecule is converted into resistant to elevated temperatures trapezium structure by cyclodehydrogenation in precursor, so as in pyrocarbon
Change the lower original fiber morphology of holding, improve stability of the precursor in carbonisation.
The carbonization is carried out in nitrogen, and heating rate is 5 DEG C/min, the constant temperature 2h under the conditions of temperature is 800 DEG C.Carbonization
Process can remove the non-carbon element in fiber, the high carbon fiber of generation phosphorus content.Carbonization can be made more abundant on this condition.
Concentration is used during the pickling for 3mol/L aqueous solution of nitric acid.Aqueous solution of nitric acid can preferably remove MnO2。
Brief description of the drawings
Fig. 1 be embodiment 1 in prepare MnO2During the hydro-thermal time be 12h when hollow carbon fiber SEM figure.
Fig. 2 be embodiment 2 in prepare MnO2During the hydro-thermal time be 18h when hollow carbon fiber SEM figure.
Fig. 3 be embodiment 3 in prepare MnO2During the hydro-thermal time be 24h when hollow carbon fiber SEM figure.
Fig. 4 is the SEM figures of the hollow carbon fiber prepared by spinning solution of PVP in embodiment 4.
Embodiment
First, preparation technology：
Embodiment 1：
A. 0.45g MnSO are weighed4·H2O and 1g KMnO4It is dissolved in respectively in 30mL deionized waters, magnetic agitation, until solid
Body is completely dissolved.By MnSO4H2O solution pours into KMnO4In solution, continue to stir, until mixed liquor gradually becomes brown color and hanged
Turbid liquid.Then brown color suspension is transferred in 100mL stainless steel hydrothermal reaction kettles, the isothermal reaction 12h at 160 DEG C.Instead
Sediment in kettle is depressurized into suction filtration after should terminating, and with respectively cleaning 3 times of distilled water and absolute ethyl alcohol, dries, that is, obtains MnO2Gold
Belong to oxide nano-rod.
B. PAN 1.5g are weighed, are dissolved in 15g DMF, magnetic agitation is until be completely dissolved.It is subsequently placed into 0.5g
MnO2Metal oxide nanorods, continue to stir, are well mixed, produce spinning solution.
C. the environment temperature of electrostatic spinning is≤40 DEG C, ambient humidity≤30%.Spinning solution is loaded into electrostatic spinning apparatus
Middle carry out spinning, spinning voltage is 15kV, and it is 25cm to receive distance, and spinning flow velocity is 2.5mm/min, the inclination angle of syringe
Spend for 15 °.MnO is obtained through electrostatic spinning2/ PAN blending precursor.
D. by MnO2/ PAN blending precursor pre-oxidizes 2h with 5 DEG C/min heating rate at 250 DEG C in atmosphere；Then
In N2In be carbonized with 5 DEG C/min heating rate at 800 DEG C 2h, produce MnO/CNF and be combined carbon fiber.
E. MnO/CNF is combined carbon fiber and is put into 3mol/L nitric acid and soak 2h, filtered, drying produces hollow carbon fiber.
Embodiment 2：
A. 0.45g MnSO are weighed4·H2O and 1g KMnO4It is dissolved in respectively in 30mL deionized waters, magnetic agitation, until solid
Body is completely dissolved.By MnSO4H2O solution pours into KMnO4In solution, continue to stir, until mixed liquor gradually becomes brown color and hanged
Turbid liquid.Then brown color suspension is transferred in 100mL stainless steel hydrothermal reaction kettles, the isothermal reaction 18h at 160 DEG C.Instead
Sediment in kettle is depressurized into suction filtration after should terminating, and with respectively cleaning 3 times of distilled water and absolute ethyl alcohol, dried, you can obtain MnO2
Metal oxide nanorods.
B. PAN 1.5g are weighed, are dissolved in 15g DMF, magnetic agitation is until be completely dissolved.It is subsequently placed into 0.5g
MnO2Metal oxide nanorods, continue to stir, are well mixed, produce spinning solution.
C. the environment temperature of electrostatic spinning is≤40 DEG C, ambient humidity≤30%.Spinning solution is loaded into electrostatic spinning apparatus
Middle carry out spinning, spinning voltage is 15kV, and it is 25cm to receive distance, and spinning flow velocity is 2.5mm/min, the inclination angle of syringe
Spend for 15 °.MnO is obtained through electrostatic spinning2/ PAN blending precursor.
D. by MnO2/ PAN blending precursor pre-oxidizes 2h with 5 DEG C/min heating rate at 250 DEG C in atmosphere；Then
In N2In be carbonized with 5 DEG C/min heating rate at 800 DEG C 2h, produce MnO/CNF and be combined carbon fiber.
E. MnO/CNF is combined carbon fiber and is put into 3mol/L nitric acid and soak 2h, filtered, drying produces hollow carbon fiber.
Embodiment 3：
A. 0.45g MnSO are weighed4·H2O and 1g KMnO4It is dissolved in respectively in 30mL deionized waters, magnetic agitation, until solid
Body is completely dissolved.By MnSO4H2O solution pours into KMnO4In solution, continue to stir, until mixed liquor gradually becomes brown color and hanged
Turbid liquid.Then brown color suspension is transferred in 100mL stainless steel hydrothermal reaction kettles, the isothermal reaction 24h at 160 DEG C.Instead
Sediment in kettle is depressurized into suction filtration after should terminating, and with respectively cleaning 3 times of distilled water and absolute ethyl alcohol, dried, you can obtain MnO2
Metal oxide nanorods.
B. PAN 1.5g are weighed, are dissolved in 15g DMF, magnetic agitation is until be completely dissolved.It is subsequently placed into 0.5g
MnO2Metal oxide nanorods, continue to stir, are well mixed, produce spinning solution.
C. the environment temperature of electrostatic spinning is≤40 DEG C, ambient humidity≤30%.Spinning solution is loaded into electrostatic spinning apparatus
Middle spinning, spinning voltage is 15kV, and it is 25cm to receive distance, and spinning flow velocity is 2.5mm/min, and the angle of inclination of syringe is
15°.MnO is obtained through electrostatic spinning2/ PAN blending precursor.
D. by MnO2/ PAN blending precursor pre-oxidizes 2h with 5 DEG C/min heating rate at 250 DEG C in atmosphere；Then
In N2In be carbonized with 5 DEG C/min heating rate at 800 DEG C 2h, produce MnO/CNF and be combined carbon fiber.
E. MnO/CNF is combined carbon fiber and is put into 3mol/L nitric acid and soak 2h, filtered, drying produces hollow carbon fiber.
Embodiment 4：
A. 0.45g MnSO are weighed4·H2O and 1g KMnO4It is dissolved in respectively in 30mL deionized waters, magnetic agitation, until solid
Body is completely dissolved.By MnSO4H2O solution pours into KMnO4In solution, continue to stir, until mixed liquor gradually becomes brown color and hanged
Turbid liquid.Then brown color suspension is transferred in 100mL stainless steel hydrothermal reaction kettles, the isothermal reaction 24h at 160 DEG C.Instead
Sediment in kettle is depressurized into suction filtration after should terminating, and with respectively cleaning 3 times of distilled water and absolute ethyl alcohol, dried, you can obtain MnO2
Metal oxide nanorods.
B. PVP is weighed（Polyvinylpyrrolidone）1.5g, is dissolved in 15g DMF, and magnetic agitation is until be completely dissolved；
It is subsequently placed into 0.5g MnO2Metal oxide nanorods, continue to stir, are well mixed, produce spinning solution.
C. the environment temperature of electrostatic spinning is≤40 DEG C, ambient humidity≤30%.Spinning solution is loaded into electrostatic spinning apparatus
Middle spinning, spinning voltage is 15kV, and it is 25cm to receive distance, and spinning flow velocity is 2.5mm/min, and the angle of inclination of syringe is
15°.MnO is obtained through electrostatic spinning2/ PVP blending precursor.
D. by MnO2/ PVP blending precursor pre-oxidizes 2h with 5 DEG C/min heating rate at 250 DEG C in atmosphere；Then
In N2In be carbonized with 5 DEG C/min heating rate at 800 DEG C 2h, produce MnO/CNF and be combined carbon fiber.
E. MnO/CNF is combined carbon fiber and is put into 3mol/L nitric acid and soak 2h, filtered, drying produces hollow carbon fiber.
2nd, the SEM figures of the hollow carbon fiber that each example is made more than are as shown in Figures 1 to 4.
Compare Fig. 1,2,3 as can be seen that preparing MnO2During, with the increase of hydro-thermal time, the hollow carbon of preparation
The hollow yardstick of fiber has increased.This is due to the increase of hydro-thermal time, MnO2The yardstick of nanometer rods is increasing to be made
Into.Comparison diagram 3 and Fig. 4, it can be seen that the pattern of fiber does not have in Fig. 3 that fiber morphology is good in Fig. 4, and this is mainly due to PVP
It is heated easily to decompose what is caused.
Claims (7)
1. a kind of preparation method of the controllable hollow carbon fiber of yardstick, comprises the following steps：
1）Metal oxide nanorods are prepared using hydro-thermal method；
2）Metal oxide nanorods and high polymer are miscible in organic solvent, obtain spinning solution；
3）Metal oxide/high polymer precursor is made through electrostatic spinning in spinning solution；
4）By metal oxide/high polymer precursor after pre-oxidation, carbonization, compound carbon fiber is obtained；
5）By compound carbon fiber through pickling, drying, hollow carbon fiber is obtained；
The metal oxide nanorods are MnO2Nanometer rods；The hydro-thermal method prepares the Hydrothermal Synthesiss of metal oxide nanorods
Temperature is 160 DEG C, and the time is 12~24h.
2. preparation method according to claim 1, it is characterised in that：The high polymer is PAN or PVP.
3. preparation method according to claim 1, it is characterised in that：The organic solvent is DMF.
4. preparation method according to claim 1, it is characterised in that：The environment temperature of the electrostatic spinning is≤40 DEG C, ring
Border humidity≤30%；Spinning voltage is 15kV, is received apart from 25cm, spinning flow velocity 2.5mm/min, the angle of inclination of syringe
For 15 °.
5. preparation method according to claim 1, it is characterised in that：The environment temperature of the pre-oxidation is 250 DEG C, pre-oxidation
Time be 2h.
6. preparation method according to claim 1, it is characterised in that：The carbonization is carried out in nitrogen, and heating rate is 5
DEG C/min, the constant temperature 2h under the conditions of temperature is 800 DEG C.
7. preparation method according to claim 1, it is characterised in that：Concentration is used during the pickling for 3mol/L nitric acid aqueous solution
Solution.
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| CN106192081B (en) * | 2016-06-30 | 2018-07-13 | 天津工业大学 | A kind of preparation method of graphene skeletal porous nanofiber |
| CN105926085B (en) * | 2016-07-06 | 2019-05-03 | 天津工业大学 | A kind of preparation method of carbon nano-fiber/nano particle composite material |
| CN106811833B (en) * | 2017-02-16 | 2019-10-25 | 济南大学 | A kind of SnO2The preparation method of micro nanometer fiber |
| 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 |
| CN107297103B (en) * | 2017-07-28 | 2020-05-15 | 中材科技膜材料（山东）有限公司 | Dust filtering base material, preparation method and application thereof |
| CN108385209A (en) * | 2018-03-02 | 2018-08-10 | 河南工程学院 | The preparation method of porous filamentous nanocarbon |
| 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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| CN103225135B (en) * | 2013-05-09 | 2015-12-23 | 中国科学院化学研究所 | Porous carbon fiber and preparation method thereof and application |
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