CN107268120A - A kind of preparation method of doped graphene fiber - Google Patents
A kind of preparation method of doped graphene fiber Download PDFInfo
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- CN107268120A CN107268120A CN201710628362.9A CN201710628362A CN107268120A CN 107268120 A CN107268120 A CN 107268120A CN 201710628362 A CN201710628362 A CN 201710628362A CN 107268120 A CN107268120 A CN 107268120A
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- acid
- fiber
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- graphene fiber
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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
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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
- 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
Abstract
The invention discloses a kind of preparation method of doped graphene fiber, including step 1：Prepare graphene spinning solution；Step 2：By in graphene spinning solution inhalation syringe, using wet spinning technology, spinning solution obtains kish alkene fiber after spinneret orifice in coagulating bath；Step 3：Kish alkene fiber is handled through supersolidification, is wound up into after drying on bobbin, spontaneously dries, obtains graphene fiber；Step 4：Graphene fiber is put on the substrate in anoxic reactor, heats and carbon and the material of doped chemical are added in backward reactor, obtain doped graphene fiber.Preparation method of the invention is simple and easy to apply, flow is short, easy controlled operation, and production efficiency is high, suitable for promoting the use of, the possibility with large-scale production, and obtained doped graphene fiber can be used for the fields such as superconduction, energy stores, opto-electronic conversion.The carrier concentration of graphene fiber can be significantly improved, so that its conductance has the lifting of the order of magnitude.
Description
Technical field
The present invention relates to graphene fiber preparation method technical field, more particularly to a kind of preparation of doped graphene fiber
Method.
Background technology
Carbon fiber excellent in mechanical performance, chemical stability is higher, it is considered to be a kind of very excellent reinforcing material.Gao Mo
Carbon fiber (also known as graphite fibre) is measured, is an important kind in carbon fiber.Graphite fibre is in national defense construction and national economy
In have extensive purposes.For Spacecraft Material, requirement of the people to structural material performance just concentrates on high-modulus, height
Intensity, thermal coefficient of expansion are small, high temperature resistant and it is low it is close in terms of, be this high mould and high strength carbon graphite fibre just turn into manufacture universe fly
Ship, aerospace craft, satellite, the indispensable original of dual-use composite of military aircraft and the various high-grade products for civilian use
One of material.Polyacrylonitrile fibril, by pre-oxidizing process, by low-temperature carbonization process, by high temperature cabonization process, passes through
Graphitizing process, can produce the high modulus and strength graphite fibre of surface smooth regular.Generally for increase graphite fibre
The layer shear strength of composite, will be surface-treated to graphite fibre, usually using anodizing.This method needs to allow
Graphite fibre passes through electrolytic cell.More floating dust and impurity is usually contained in the electrolytic cell of large-scale production, can adsorb fine in graphite
Dimension table face, is polluted to graphite fibre, even if by washing, can not also ensure the cleaning on graphite fibre surface, have impact on stone
Black fiber is prepared into the performance after composite.Therefore, study one kind and do not pollute graphite fibre, and graphene can be significantly improved
The carrier concentration of fiber is that graphene fiber preparation method is that those skilled in the art thirst for solution always, but is not yet solved so far
Technical barrier certainly.
The content of the invention
It is an object of the invention to provide a kind of preparation for the doped graphene fiber that compact structure is regular and conductance is high
Method.
In order to realize above-mentioned technical purpose, above-mentioned technique effect is reached, the present invention is achieved through the following technical solutions：
A kind of preparation method of doped graphene fiber, comprises the following steps：
Step 1：At a temperature of 30~70 DEG C, concentration is sufficiently stirred for for 10~30mg/ml graphene solution, stone is made
Black alkene spinning solution；
Step 2：In the graphene spinning solution that the step 1 is obtained, inhalation syringe, spinning speed is controlled with flow pump
Degree, using wet spinning technology, spinning solution obtains kish alkene fiber after spinneret orifice in coagulating bath；
Step 3：Kish alkene fiber is handled through supersolidification, then is wound up into after drying processing on bobbin, is done naturally
It is dry, obtain graphene fiber；
Step 4：It is blended with the graphene fiber of catalyst to be put on the substrate in the reactor of anaerobic, is heated to 800
~1500 DEG C, carbon and the material of doped chemical then are added to the reactor, doped graphene fiber is obtained.
Further, the step of step 4 also includes purifying doped graphene, to remove the catalyst.
Further, described coagulating bath includes acid and alcohol, and the pH value of coagulating bath is adjusted with acid, control coagulating bath
PH value is 3<pH<7.
Further, the catalyst is metal or metallic compound.
Further, the solvent of step 1 graphene oxide solution is the one or more in water, ethanol and methanol.
Further, the internal diameter of spinneret orifice is 0.8~3mm in the step 2.
Further, the acid in the coagulating bath is hydrochloric acid, sulfuric acid, nitric acid, glacial acetic acid, formic acid, hypochlorous acid, carbonic acid, phosphorus
One or more in acid, ethanedioic acid；Alcohol is methanol or ethanol.
Further, the spinning speed of the spinning technique is 0.5~5ml/min.
Further, the material containing carbon and doped chemical can be by least one change containing carbon
Compound and at least one compound group containing doped chemical into compound or a kind of contain carbon and doping member
The compound of element.
Further, the compound containing carbon be ethanol, acetylene, in benzene, toluene, methane, carbon monoxide
One or more of combinations.
Further, the doped chemical can be any one in bromine, potassium, iron.
The beneficial effects of the invention are as follows：
A kind of preparation method of doped graphene fiber of the present invention, the equal abundance of material therefor of the present invention, valency
Lattice are cheap, environmental protection；Due to carrying out effective control to the pH value of coagulating bath, obtained graphene fiber fibre-forming performance is good,
Compound with regular structure, meanwhile, fracture strength is improved.The graphene fiber prepared using wet spinning technology, preparation method letter
Single easy, flow is short, easy controlled operation, and production efficiency is high, and suitable for promoting the use of, the possibility with large-scale production is obtained
Graphene fiber can be used for the fields such as superconduction, energy stores, opto-electronic conversion.Because doping molecule or ion are deposited with graphene fiber
In electric charge transfer interaction, the carrier concentration of graphene fiber can be significantly improved, so that its conductance has the order of magnitude
Lifting.
Embodiment
To enable the purpose of the present invention, feature, advantage more obvious and understandable, below in the embodiment of the present invention
Technical scheme is clearly and completely described, it is clear that the embodiments described below are only a part of embodiment of the invention,
And not all embodiments.Based on the embodiment in the present invention, the every other embodiment that those skilled in the art is obtained, all
Belong to the scope of protection of the invention.
Embodiment 1
A kind of preparation method of doped graphene fiber, comprises the following steps
Step 1：By the graphene oxide water solution that concentration is 15mg/ml, at 20 DEG C, with 400r/min speed magnetic force
1h is stirred, graphene oxide spinning solution is obtained.
Step 2：Spinning solution is filled into 10ml syringes, it is 0.5ml/h, spinneret orifice that spinning speed is controlled with flow pump
Internal diameter be 0.8mm, spin to pH value for 2.35 coagulating bath in.
Step 3：Natural coagulation 1min.Fiber is slowly pulled out, drying system, at 20 DEG C, 10min is dried, with 1r/
Min speed is wound up on bobbin, and is spontaneously dried.
Step 4：The substrate that deposition has zinc sulphide is placed in the middle part of the quartz ampoule of cleaning, catalyst is then blended with
Graphene fiber is put on the silicon substrate in the reactor of anaerobic, and the mixed gas conduct of hydrogen and argon gas is passed through in quartz ampoule
Carrier gas, reactor center region is heated to 800 DEG C, then adds carbon and the material of doped chemical, reaction to the reaction
Carry out 10 minutes, be continually fed into hydrogen and argon gas until dropping to room temperature, obtain doped graphene fiber.
The hydrochloric acid that the above method also includes the substrate that deposition has doped graphene fiber being put into 0.1 mole every liter is molten
Soaked in liquid 60 minutes and remove zinc sulphide, net rear drying is then washed with deionized water.
PH hydrochloric acid, sulfuric acid, nitric acid, glacial acetic acid, formic acid, hypochlorous acid, carbonic acid, phosphoric acid, ethanedioic acid in the coagulating bath
In one or more regulated and controled；The present embodiment regulates and controls the pH value of coagulating bath with formic acid, and the solvent of coagulating bath is methanol.
The silicon substrate is dried after being cleaned by ultrasonic successively with deionized water, ethanol, acetone, then passes through physical vapour deposition (PVD)
Technology is used as catalyst in the zinc sulphide that the surface of silicon deposits one layer about 100 nanometers.
The elongation at break of the doped graphene fiber prepared by the test present invention is 5.75%, and fracture strength is
80.95MPa, the elongation at break of graphene fiber is 3.33%, and fracture strength is 118.10MPa.
Embodiment 2
Step 1：By the graphene oxide water solution that concentration is 8mg/ml, at 45 DEG C, with 500r/min speed magnetic force
Stirring 8 hours, obtains graphene oxide spinning solution.
Step 2：Obtained spinning solution is filled into 10ml syringes, it is 1ml/h that spinning speed is controlled with flow pump, spun
The internal diameter in silk hole is 1mm, is spinned to pH value as in 5 coagulating bath.
Step 3：Natural coagulation 5min.Fiber is slowly pulled out, drying system, at 40 DEG C, 10min is dried, with 2r/
Min speed is wound up on bobbin, and is spontaneously dried.By the graphene oxide fiber of preparation.
Step 4：The substrate that deposition has iron chloride is placed in the middle part of the quartz ampoule of cleaning, catalyst is then blended with
Graphene fiber is put on the silicon substrate in the reactor of anaerobic, and the mixed gas conduct of hydrogen and argon gas is passed through in quartz ampoule
Carrier gas, reactor center region is heated to 900 DEG C, then adds carbon and the material of doped chemical, reaction to the reaction
Carry out 15 minutes, be continually fed into hydrogen and argon gas until dropping to room temperature, obtain doped graphene fiber.
The hydrochloric acid that the above method also includes the substrate that deposition has doped graphene fiber being put into 0.1 mole every liter is molten
Soaked in liquid 50 minutes and remove iron chloride, net rear drying is then washed with deionized water.
PH hydrochloric acid, sulfuric acid, nitric acid, glacial acetic acid, formic acid, hypochlorous acid, carbonic acid, phosphoric acid, ethanedioic acid in the coagulating bath
In one or more regulated and controled；The present embodiment regulates and controls the pH value of coagulating bath with formic acid, and the solvent of coagulating bath is methanol.
The silicon substrate is dried after being cleaned by ultrasonic successively with deionized water, ethanol, acetone, then passes through physical vapour deposition (PVD)
Technology is used as catalyst in the zinc sulphide that the surface of silicon deposits one layer about 100 nanometers.
The elongation at break of the doped graphene fiber prepared by the test present invention is 6.25%, and fracture strength is
83.61MPa, the elongation at break of graphene fiber is 3.21%, and fracture strength is 119.23MPa.
Embodiment 3
Step 1：By the graphene oxide ethanol solution that concentration is 20mg/ml, at 80 DEG C, with 800r/min speed magnetic
Power is stirred 1 hour, obtains graphene oxide spinning solution.
Step 2：Spinning solution is filled into 10ml syringes, it is 5ml/min, spinneret orifice that spinning speed is controlled with flow pump
Internal diameter be 3mm, spin to pH value for 6 coagulating bath in.
Step 3：Natural coagulation 1h.Fiber is slowly pulled out, drying system, at 20 DEG C, 10min is dried, with 10r/min
Speed be wound up on bobbin, and spontaneously dry, obtained graphene fiber.
Step 4：The substrate that deposition has Nano Silver is placed in the middle part of the quartz ampoule of cleaning, catalyst is then blended with
Graphene fiber is put on the silicon substrate in the reactor of anaerobic, and the mixed gas conduct of hydrogen and argon gas is passed through in quartz ampoule
Carrier gas, reactor center region is heated to 900 DEG C, then adds carbon and the material of doped chemical, reaction to the reaction
Carry out 8 minutes, be continually fed into hydrogen and argon gas until dropping to room temperature, obtain doped graphene fiber..
PH hydrochloric acid, sulfuric acid, nitric acid, glacial acetic acid, formic acid, hypochlorous acid, carbonic acid, phosphoric acid, ethanedioic acid in the coagulating bath
In one or more regulated and controled；The present embodiment regulates and controls the pH value of coagulating bath with formic acid, and the solvent of coagulating bath is methanol.
The silicon substrate is dried after being cleaned by ultrasonic successively with deionized water, ethanol, acetone, then passes through physical vapour deposition (PVD)
Technology is used as catalyst in the zinc sulphide that the surface of silicon deposits one layer about 100 nanometers.
The elongation at break of the doped graphene fiber prepared by the test present invention is 6.47%, and fracture strength is
86.33MPa, the elongation at break of graphene fiber is 3.17%, and fracture strength is 120.25MPa.
Although the above-mentioned embodiment to the present invention is described, not to the limit of the scope of the present invention
System, one of ordinary skill in the art should be understood that on the basis of technical scheme those skilled in the art need not pay
Go out various modifications or deform still within the scope of the present invention that creative work can make.
Claims (9)
1. a kind of preparation method of doped graphene fiber, it is characterised in that comprise the following steps：
Step 1：At a temperature of 30~70 DEG C, concentration is sufficiently stirred for for 10~30mg/ml graphene solution, graphene is made
Spinning solution；
Step 2：In the graphene spinning solution that the step 1 is obtained, inhalation syringe, spinning speed is controlled with flow pump, is adopted
With wet spinning technology, spinning solution obtains kish alkene fiber after spinneret orifice in coagulating bath；
Step 3：Kish alkene fiber is handled through supersolidification, then is wound up into after drying processing on bobbin, spontaneously dries, obtains
To graphene fiber；
Step 4：The graphene fiber of catalyst is blended with to be put on the substrate in the reactor of anaerobic, it is heated to 800~
1500 DEG C, carbon and the material of doped chemical then are added to the reactor, doped graphene fiber is obtained.
2. the preparation method of doped graphene fiber according to claim 1, it is characterised in that the step 4 also includes
The step of being purified to the doped graphene of preparation, to remove the catalyst.
3. the preparation method of doped graphene fiber according to claim 1, it is characterised in that described coagulating bath includes
Acid and alcohol, the pH value of coagulating bath are adjusted with acid, and the pH value for controlling coagulating bath is 3<pH<7.
4. the Chinese medicine preparation for the treatment of lung cancer according to claim 1, it is characterised in that the catalyst is metal or metal
Compound.
5. the Chinese medicine preparation for the treatment of lung cancer according to claim 1, it is characterised in that step 1 graphene oxide is molten
The solvent of liquid is the one or more in water, ethanol and methanol.
6. the Chinese medicine preparation for the treatment of lung cancer according to claim 1, it is characterised in that the acid in the coagulating bath is salt
One or more in acid, sulfuric acid, nitric acid, glacial acetic acid, formic acid, hypochlorous acid, carbonic acid, phosphoric acid, ethanedioic acid；Alcohol is methanol or second
Alcohol.
7. the Chinese medicine preparation for the treatment of lung cancer according to claim 1, it is characterised in that described to contain carbon and doping member
The material of element can be by least one compound containing carbon and at least one compound group containing doped chemical into
Compound or a kind of compound containing carbon and doped chemical.
8. the Chinese medicine preparation for the treatment of lung cancer according to claim 1, it is characterised in that the compound containing carbon
For ethanol, acetylene, one or more of combinations in benzene, toluene, methane, carbon monoxide.
9. it is according to claim 1 treatment lung cancer Chinese medicine preparation, it is characterised in that the doped chemical can for bromine, potassium,
Any one in iron.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710628362.9A CN107268120A (en) | 2017-07-28 | 2017-07-28 | A kind of preparation method of doped graphene fiber |
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| CN201710628362.9A CN107268120A (en) | 2017-07-28 | 2017-07-28 | A kind of preparation method of doped graphene fiber |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110424069A (en) * | 2019-08-11 | 2019-11-08 | 武汉中科先进技术研究院有限公司 | A kind of biomass-based carbon nitrogen phosphorus complex fiber material and preparation method thereof |
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| CN106120025A (en) * | 2016-07-02 | 2016-11-16 | 苏州大学 | A kind of graphene fiber and preparation method thereof |
| US20170204271A1 (en) * | 2016-01-20 | 2017-07-20 | Honda Motor Co., Ltd. | Alteration of carbon fiber surface properties via growing of carbon nanotubes |
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2017
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101289181B (en) * | 2008-05-29 | 2010-09-01 | 中国科学院化学研究所 | Doped graphene and method for preparing same |
| US20170204271A1 (en) * | 2016-01-20 | 2017-07-20 | Honda Motor Co., Ltd. | Alteration of carbon fiber surface properties via growing of carbon nanotubes |
| CN105544017A (en) * | 2016-01-27 | 2016-05-04 | 浙江大学 | High-conductivity graphene fiber and preparation method thereof |
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Cited By (2)
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| CN110424069A (en) * | 2019-08-11 | 2019-11-08 | 武汉中科先进技术研究院有限公司 | A kind of biomass-based carbon nitrogen phosphorus complex fiber material and preparation method thereof |
| CN110424069B (en) * | 2019-08-11 | 2021-07-23 | 武汉中科先进技术研究院有限公司 | Biomass-based carbon nitrogen phosphorus composite fiber material and preparation method thereof |
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