CN109056118A - A kind of graphene fiber and preparation method thereof - Google Patents
A kind of graphene fiber and preparation method thereof Download PDFInfo
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- CN109056118A CN109056118A CN201810833034.7A CN201810833034A CN109056118A CN 109056118 A CN109056118 A CN 109056118A CN 201810833034 A CN201810833034 A CN 201810833034A CN 109056118 A CN109056118 A CN 109056118A
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- graphene
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- fiber
- oxide
- amino modified
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
Abstract
The present invention provides a kind of preparation methods of graphene fiber, it is modified to graphene oxide by using amino modified ferroso-ferric oxide, wet spinning is carried out under magnetic fields, the elongation of the graphene fiber prepared in the method is up to 50%, it is apparently higher than existing graphene fiber (elongation is 10% or so), and graphene fiber intensity height, conductivity height that method of the invention obtains, there is excellent mechanics electric property.
Description
Technical field
The present invention relates to graphene fiber field of material technology more particularly to a kind of preparation methods of graphene fiber.
Background technique
One-dimensional redox graphene fiber, the electrodynamic performance with more higher than conventional semiconductors flexibility and brilliance,
Its flexible and resistance stability will can be improved after its functionalization.Therefore, one-dimensional redox graphene fiber has caused extensively
General concern, in fields such as wearable electronic, stretch sensor, smart actuation device, supercapacitor and intelligent clothings
With potential effect.
Currently, the methods of the reduction of dry-wet spinning, Chemical assembly, electrophoresis assembling and dry film rolling are applied to synthesize
Using graphene oxide as the fiber of substrate.Mainly draw using the spinning of pure zirconia graphene or in graphene oxide spinning process
Enter Section 3 substance (such as metal ion, high polymer etc.), then by making most with strong acid or highly basic redox graphene fiber
The graphene fiber obtained eventually has excellent mechanics, electricity or electrodynamic performance.
Although metal ion and high polymer are introduced oxidation stone however, these researchs at present have reached prominent achievement
Black alkene solution spun at the elongation of graphene fiber be 10% or so, this is because introduce metal ion and high polymer for
The rule of piling up of lamella influences deficiency in graphene oxide spinning process, cannot preferably regulate and control piling up for graphene sheet layer, from
And cause the flexible degree of prepared fiber to fail the desired value for reaching researcher, and the elasticity of fiber product obtained compared with
Difference, the electrical stability in torsion and drawing process are poor.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of graphene fiber, improve the elongation of graphene fiber,
Enhance its flexible degree, and further increases its electrical stability.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of preparation methods of graphene fiber, comprising the following steps:
By graphene oxide and amino modified ferroso-ferric oxide in 1- (3- dimethylamino-propyl) -3- ethyl carbodiimide salt
Cross-linking reaction is carried out under the catalytic action of hydrochlorate, obtains magnetic oxygenated graphene；
The magnetic oxygenated graphene is subjected to wet spinning under magnetic fields, obtains graphene oxide fiber；
The graphene oxide fiber is restored, graphene fiber is obtained.
Preferably, the mass ratio of the amino modified ferroso-ferric oxide and graphene oxide is 2.5:97.5~30:70.
Preferably, the time of the cross-linking reaction is 15~180min.
Preferably, when the wet spinning, the induction direction in magnetic field at silk direction be in 0~180 ° of angle.
Preferably, the magnetic field strength in the magnetic field is 25~500mT.
Preferably, the speed of the wet spinning is 1~50mL/h, and the time is 1~180s.
Preferably, the temperature of the reduction is 10~100 DEG C, and the time is 1~20h.
Preferably, the amino modified ferroso-ferric oxide preparation method the following steps are included:
By Fe3O4Ammoxidation is carried out after particle, coupling agent and organic solvent mixing, obtains amino modified four oxidation three
Iron；The coupling agent is aminopropyl triethoxysilane.
Preferably, the organic solvent is the mixture of methanol and toluene, and the volume ratio of the methanol and toluene is 1:1.
Preferably, the temperature of the ammoxidation is 100~120 DEG C, and the time is 5~20h.
The present invention provides a kind of preparation methods of graphene fiber, by using amino modified ferroso-ferric oxide to oxidation
Graphene is modified, and obtains magnetic oxygenated graphene；Then fixed magnetic field effect under by the magnetic oxygenated graphene into
Row wet spinning, and the packing structure of fibrous inside lamella can be changed by the induction direction in regulation magnetic field, to improve stone
Mechanics, electricity and the electrodynamic performance of black alkene fiber.
The elongation of graphene fiber prepared by the present invention is up to 50%, hence it is evident that is higher than (the elongation of existing graphene fiber
Rate 10% or so), while the graphene fiber product that method of the invention obtains has excellent elasticity, and is reversing and drawing
There is excellent electrical stability during stretching.
Method of the invention have applicability is wide, easy to operate, process adjustments flexibly, it is lower production costs, high-efficient
Advantage is easy to industrialization production.
Specific embodiment
The present invention provides a kind of preparation methods of graphene fiber, comprising the following steps:
By graphene oxide and amino modified ferroso-ferric oxide in 1- (3- dimethylamino-propyl) -3- ethyl carbodiimide salt
Cross-linking reaction is carried out under the catalytic action of hydrochlorate, obtains magnetic oxygenated graphene；
The magnetic oxygenated graphene is subjected to wet spinning under magnetic fields, obtains graphene oxide fiber；
The graphene oxide fiber is restored, graphene fiber is obtained.
The present invention is by graphene oxide and amino modified ferroso-ferric oxide in 1- (3- dimethylamino-propyl) -3- ethyl carbon two
Cross-linking reaction is carried out under the catalytic action of inferior amine salt hydrochlorate, obtains magnetic oxygenated graphene.In the present invention, described amino modified
The mass ratio of ferroso-ferric oxide and graphene oxide is preferably 2.5:97.5~30:70, more preferably 5:95~15:85.At this
In invention, the time of the cross-linking reaction is preferably 15min~180min, more preferably 50~150min, most preferably 80~
120min.The present invention does not have special restriction to the source of the graphene oxide, selects side well known to those skilled in the art
Prepared by method, in an embodiment of the present invention, specifically using improved Hummer method and according to document (Chen Qi, Tong Na
Pellet, Li Ping wait electric property [J] of graphene layer group copper ammonia fiber to print and dye, 2017 (20): 7-10.) method be prepared
Graphene oxide.
In the present invention, the preparation method of the amino modified ferroso-ferric oxide preferably includes following steps:
By Fe3O4Ammoxidation is carried out after particle, coupling agent and organic solvent mixing, obtains amino modified four oxidation three
Iron；The coupling agent is aminopropyl triethoxysilane.
In the present invention, the organic solvent is preferably the mixture of methanol and toluene, the volume of the methanol and toluene
Than being preferably 1:1.The present invention does not have special restriction to the mixed mode, selects mode well known to those skilled in the art
It is mixed.In the present invention, the temperature of the ammoxidation is preferably 100~120 DEG C, more preferably 110~118
DEG C, the time is preferably 5~20h, more preferably 10~15h.The present invention preferably carries out the ammonia under conditions of oil bath and reflux
Glycosylation reaction.After completing the ammoxidation, present invention preferably employs methanol to carry out cleaning 2~3 to ammoxidation product
It is secondary, then wash products are filtered by vacuum, it then will filter products therefrom and be placed in drying in vacuum oven, after crushed
To amino modified ferroso-ferric oxide.The present invention does not have special restriction to the source of the ferriferrous oxide particles, selects ability
Prepared by preparation method known to field technique personnel, for example use coprecipitation, thermal decomposition method, hydro-thermal method, solvent heat
Method, microemulsion method and air oxidation process prepare ferroso-ferric oxide.
The present invention under catalytic action by amino modified ferroso-ferric oxide covalent cross-linking in graphene oxide on piece, and pass through
Induced by magnetic field drives graphene oxide sheet rotation, can obtain the graphene oxide fiber of compound with regular structure, and then by restoring
To graphene fiber.
After obtaining magnetic oxygenated graphene, the magnetic oxygenated graphene is carried out Wet-spinning by the present invention under magnetic fields
Silk, obtains graphene oxide fiber.The solution of magnetic oxygenated graphene is preferably fitted into plastic injector by the present invention, utilizes note
Pump is penetrated with the speed injection of 10mL/h into acetic acid bath, wet spinning is carried out under magnetic fields.In the present invention, the wet process
When spinning, the induction direction in magnetic field is preferably in 0~180 ° of angle at silk direction with fiber, and more preferably 0~90 °；It is described wet
The speed of method spinning is preferably 1~50mL/h, more preferably 10~30mL/h, and the time is preferably 1~180s, more preferably 50~
150s；The magnetic field strength in the magnetic field is preferably 25-500mT, more preferably 50-300mT.The present invention can by induced by magnetic field
The packing structure for changing fibrous inside lamella, can enhance the flexibility of graphene fiber, improve its elongation, and can be improved stone
The electricity and electrodynamic performance of black alkene fiber.
After obtaining graphene oxide fiber, the present invention restores the graphene oxide fiber, obtains graphene fibre
Dimension.In the present invention, the temperature of the reduction is preferably 10~100 DEG C, and more preferably 30~70 DEG C, the time is preferably 1~
20h, more preferably 5~15h.The present invention does not have special restriction to the mode of the reduction, selects those skilled in the art ripe
That knows is reduced to graphene oxide the mode of graphene, can obtain graphene.In an embodiment of the present invention, specifically
It is that graphene oxide fiber is immersed in hydroiodic acid to restore.
It is described in detail below with reference to preparation method of the embodiment to graphene fiber provided by the invention, but not
They can be interpreted as limiting the scope of the present invention.
Embodiment 1
By 230mL H2SO4、5g NaNO3, 10g graphite powder and 30g potassium permanganate be added in beaker and be uniformly mixed, stirring is anti-
1h is answered, graphite intercalation compound is obtained；After being warming up to 45 DEG C the reaction was continued 30min, 460mL deionized water is added, the reaction was continued
30min；The hydrogen peroxide that 1400mL deionized water and 50mL mass concentration are 30% is sequentially added, solution becomes yellow from brick-red
Color after the reaction was continued 15min, is washed three times with the dilute hydrochloric acid that mass concentration is 3%, is then repeatedly centrifuged and is washed with deionized water
It washs, obtains graphite oxide, graphite oxide is subjected to ultrasonic disperse 4h, obtains graphene oxide；
By 1g Fe3O4Nano particle is scattered in 5.4g silane coupling agent KH-540 (APTMS), remixes with methanol and first
Benzene volume ratio be 1:1 solvent in (methanol and toluene respectively take 50mL), be put into 500mL three-necked flask, under the conditions of 110 DEG C into
Row oil bath simultaneously flows back 10 hours, after reaction, is cleaned reflux product 2~3 times using methanol, and repeatedly by gained wash products
It is filtered by vacuum.After the completion of suction filtration, suction filtration product is placed in vacuum oven and is dried, grind into powder after drying obtains
Amino modified ferroso-ferric oxide；
The amino modified ferroso-ferric oxide of 5g is mixed with 95g graphene oxide and water, in 1- (3- dimethylamino-propyl) -3-
90min is mixed under the catalytic action of ethyl-carbodiimide hydrochloride, carries out cross-linking reaction, it is molten to obtain magnetic oxygenated graphene
Liquid, drying, obtains magnetic oxygenated graphene powder；
The magnetic oxygenated graphene powder is configured to the solution that mass concentration is 2%, is fitted into plastic injector, benefit
With syringe pump with the speed injection of 10mL/h into acetic acid bath, (magnetic field strength 500mT) carries out wet spinning under magnetic fields,
Obtain graphene oxide fiber；The graphene oxide fiber is immersed in hydroiodic acid, reduction 8h is carried out at 95 DEG C, is obtained
Graphene fiber.
Embodiment 2
Graphene fiber is prepared according to 1 the method for embodiment, difference from Example 1 is, ammonia in the present embodiment
The weight ratio of base improved ferroferric oxide and graphene oxide is 7.5:92.5.
Embodiment 3
Graphene fiber is prepared according to 1 the method for embodiment, difference from Example 1 is, ammonia in the present embodiment
The weight ratio of base improved ferroferric oxide and graphene oxide is 10:90.
Embodiment 4
Graphene fiber is prepared according to 1 the method for embodiment, difference from Example 1 is, ammonia in the present embodiment
The weight ratio of base improved ferroferric oxide and graphene oxide is 12.5:87.5.
Embodiment 5
Graphene fiber is prepared according to 1 the method for embodiment, difference from Example 1 is, ammonia in the present embodiment
The weight ratio of base improved ferroferric oxide and graphene oxide is 15:85.
Respectively have magnetic field and without magnetic field condition under graphene fiber that Examples 1 to 5 is prepared carry out performance survey
Examination, concrete outcome are shown in Tables 1 and 2.
Table 1 is the mechanical performance data in the graphene fiber being prepared whether there is or not Examples 1 to 5 under magnetic field condition, by
Table 1 it is found that the elongation for the graphene fiber that the method for the present invention is prepared up to 50%, relative to existing graphene fiber
(elongation 10% or so), significantly improves the elongation of graphene fiber, improves the flexibility of fiber, has excellent mechanics
Performance.
Table 1 is whether there is or not the mechanical performance datas for the graphene fiber being prepared under magnetic field condition
Table 2 is whether there is or not the resistance datas for the graphene fiber being prepared under magnetic field condition
| Case | There is magnetic field (Ω cm) | Without magnetic field (Ω cm) |
| Embodiment 1 | 17.32 | 42.41 |
| Embodiment 2 | 8.85 | 49.71 |
| Embodiment 3 | 7.11 | 83.79 |
| Embodiment 4 | 5.52 | 31.30 |
| Embodiment 5 | 8.94 | 63.37 |
Table 2 is the resistance data in the graphene fiber being prepared whether there is or not Examples 1 to 5 under magnetic field condition, can by table
Know, the graphene fiber electrical stability that the method for the present invention is prepared is excellent.
As seen from the above embodiment, the present invention provides a kind of preparation method of graphene fiber, changed by using amino
Property ferroso-ferric oxide is modified to graphene oxide, wet spinning is carried out under magnetic fields, the graphite prepared in the method
The elongation of alkene fiber is up to 50%, hence it is evident that is higher than existing graphene fiber (elongation 10% or so), and of the invention
The graphene fiber intensity that method obtains is high, conductivity is high, has excellent mechanics electric property.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of graphene fiber, comprising the following steps:
By graphene oxide and amino modified ferroso-ferric oxide in 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride
Catalytic action under carry out cross-linking reaction, obtain magnetic oxygenated graphene；
The magnetic oxygenated graphene is subjected to wet spinning under magnetic fields, obtains graphene oxide fiber；
The graphene oxide fiber is restored, graphene fiber is obtained.
2. preparation method according to claim 1, which is characterized in that the amino modified ferroso-ferric oxide and graphite oxide
The mass ratio of alkene is 2.5:97.5~30:70.
3. preparation method according to claim 1 or 2, which is characterized in that the time of the cross-linking reaction be 15~
180min。
4. preparation method according to claim 1, which is characterized in that when the wet spinning, the induction direction in magnetic field with
It is in 0~180 ° of angle at silk direction.
5. preparation method according to claim 1 or 4, which is characterized in that the magnetic field strength in the magnetic field be 25~
500mT。
6. preparation method according to claim 1 or 4, which is characterized in that the speed of the wet spinning is 1~50mL/
H, time are 1~180s.
7. preparation method according to claim 1, which is characterized in that the temperature of the reduction is 10~100 DEG C, and the time is
1~20h.
8. preparation method according to claim 1 or 2, which is characterized in that the preparation of the amino modified ferroso-ferric oxide
Method the following steps are included:
By Fe3O4Ammoxidation is carried out after particle, coupling agent and organic solvent mixing, obtains amino modified ferroso-ferric oxide；Institute
Stating coupling agent is aminopropyl triethoxysilane.
9. preparation method according to claim 8, which is characterized in that the organic solvent is the mixing of methanol and toluene
The volume ratio of object, the methanol and toluene is 1:1.
10. preparation method according to claim 8, which is characterized in that the temperature of the ammoxidation is 100~120
DEG C, the time is 5~20h.
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Cited By (3)
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| CN112376121A (en) * | 2020-10-27 | 2021-02-19 | 山东科技大学 | Preparation method and application of folded graphene fibers for improving shear orientation of graphene sheets |
| CN114394679A (en) * | 2022-01-19 | 2022-04-26 | 江苏利然环保科技有限公司 | Microbial adsorbent for industrial wastewater and preparation method thereof |
| CN114542990A (en) * | 2020-11-25 | 2022-05-27 | 中国石油化工股份有限公司 | Electro-spinning magnetic nanofiber demulsifier for low-temperature gathering and transportation of crude oil and preparation method thereof |
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