CN109322009A - A kind of graphene fiber and preparation method thereof of wet spinning preparation - Google Patents
A kind of graphene fiber and preparation method thereof of wet spinning preparation Download PDFInfo
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- CN109322009A CN109322009A CN201810993456.0A CN201810993456A CN109322009A CN 109322009 A CN109322009 A CN 109322009A CN 201810993456 A CN201810993456 A CN 201810993456A CN 109322009 A CN109322009 A CN 109322009A
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- Prior art keywords
- graphene
- fiber
- preparation
- graphene oxide
- wet spinning
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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 invention discloses a kind of graphene fibers and preparation method thereof of wet spinning preparation, comprising: (1) by forming the high graphene oxide spinning solution of dispersibility after chemical functionalization；(2) the graphene oxide solute liquid crystal solution of formation is put into single-shaft-rotation spin duct；(3) it will be expressed into the nozzle in spin duct in the coagulation bath of single axial stream；(4) phase transformation is carried out by exchange of solvent coagulation；(5) evaporation solvent cures obtain graphene oxide fiber；(6) graphene fiber is obtained by chemistry or thermal reduction.Available a kind of high performance wet spinning graphene fiber in the present invention, preparation process is simple, environmentally protective, easy to operate, and preparation working hour is few, and obtained graphene fiber structure is uniform, there is excellent in toughness and electric conductivity, can be woven into various functional fabrics.
Description
Technical field
The invention patent relates to graphene fiber manufacturing fields, and in particular to a kind of graphene fiber of wet spinning preparation
And preparation method thereof.
Background technique
Graphene is that carbon atom passes through sp2The two-dimensional structure that hydridization form is formed, it is good with very high specific surface area
Conduction well, heating conduction, and there is high mechanical strength, have become the research hotspot of 21 century Material Field.Mesh
Before, macroscopical assembly of graphene mainly has powder, fiber, film, aeroge etc., and fiber is as a kind of material application shape
Formula is widely used in the fields such as daily life, communications and transportation, industrial production.Therefore, the fiber that graphene is processed into macroscopic view is had
There is very high application value.
Graphene fiber is the one-dimensional carbon material of macroscopic view assembled by two-dimensional graphene, has good electric property
And mechanical property.Graphene fiber has high conductivity and good flexibility.Graphene fiber material has its property special
Property, the preparation and application of graphene fiber are widely studied.In the early time, by by dispersed graphene oxide very well and water-soluble
Property NaTDC be uniformly mixed and obtain graphene oxide/deoxycholic acid sodium gel, inject in micro-pipe and pass through the method to roller
Obtain graphene fiber band (Huang G., Hou C., et al.Scientific Reports, 2013,3,4248)；Pass through tune
The content of graphene oxide, is prepared for porous graphene fiber, and porous in whole graphene oxide/deoxycholic acid sodium gel
Solid electrolyte is immersed in fiber obtains all solid state fibrous supercapacitor (Huang G., Hou C., et al.Nano
Energy, 2015,12,26).Professor Qu Liangti of Beijing Institute of Technology is by carrying out spiral shell in situ to the graphene fiber of preparation
Rotation obtains changing rotary graphene fiber (Cheng H., Liu J., et al.Angewandte with humidity
Chemie-International Edition, 2013,52,10482.) etc..
Currently, the preparation method of graphene fiber has very much, however, the graphene fiber intensity that these methods obtain mostly
Low, structure is uneven, is easily broken off, it is difficult to meet the requirement that reality uses, therefore with regard to how to produce stone with high performance
Black alkene fiber is a current problem urgently to be solved.
The Chinese patent application of Patent No. CN106702535A discloses a kind of graphene fiber and preparation method thereof.
The preparation method includes: that certain density graphene oxide spinning solution is put into device for spinning by (1), then by spinning solution from spinning
It is uniformly squeezed into coagulating bath in spinning spout on head, rotary spinning head while squeezing out, realizes that multiply graphene oxide is fine
The preparation and twisting of dimension；(2) by the multiply graphene oxide fiber reduction after twisting, the multiply graphene fiber twisted.
The invention can prepare single group by adjusting spinning solution component, spinning spout quantity, spinning spout size and rotation speed etc.
Point or the graphene fiber that constitutes of various ingredients, and realize regulation to its component, number of share of stock, diameter, the twist.
The Chinese patent application of Patent No. CN108219139A a kind of functionalized graphite's alkene, functionalized graphite's alkene are
Refer to the graphene of surface grafting one or more bioactive molecule, which includes multiple terminal functionalities, multiple end group
Functional group includes at least two active function groups.Since chemistry can occur for the active function groups instead with the molecule in organic silicone oil
It answers, therefore what functionalized graphite's alkene can be relatively uniform is dissolved in the organic silicone oil, so that utilizing functionalized graphite's alkene
The polysiloxane of preparation has good heating conduction.In addition, this application additionally provides the preparation of functionalized graphite's alkene
Method and corresponding polysiloxane.
A kind of superhigh-flexibility graphene of dry spinning preparation of the Chinese patent application of Patent No. CN108277556A
Fiber and preparation method thereof, the graphene fiber use graphene oxide solution, oxidation are prepared by way of dry spinning
Graphene fiber, then redox graphene fiber is up to the graphene fiber.The present invention breaks through the material of composition fiber
It must be the thinking constraint of long chain macromolecular polymer, for the first time the graphene oxide of nanometer two-dimensional slice, be spun using dry method
Silk, being successfully realized continuous preparation has the graphene oxide fiber of excellent flexibility energy, and is successfully prepared by reduction method
Graphene fiber with excellent flexibility energy.
A kind of preparation method of High-performance graphene fiber of the Chinese patent application of Patent No. CN107893266A, relates to
And graphene oxide is dispersed in pure water by graphene fiber production technical field at room temperature, and uses ultrasonic disperse
2~3h obtains graphene oxide water solution, water-soluble with graphene oxide then using ionic liquid and paraphenylenediamine as coagulator
Liquid prepares graphene oxide fiber as spinning solution, by wet spinning process；Graphene oxide fiber is placed on room temperature environment
Lower drying after dry, with hydroiodic acid reduction treatment, then washed, drying under conditions of temperature is 60~80 DEG C, obtains graphite
Alkene fiber.
Such as above-mentioned several patents, the relevant technical products in this field are disclosed, but how to solve graphene oxide dispersion
Property problem and obtain high-performance and more superior graphene fiber be this field urgent need technical problems to be solved.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of wet spinning preparation graphene fiber and
Preparation method.
In order to solve the above-mentioned technical problem, used technical solution is: a kind of graphene fiber of wet spinning preparation
And preparation method thereof, the wet spinning preparation includes: that (1) is high by forming dispersibility after chemical functionalization and ultrasonic treatment
Graphene oxide spinning solution；(2) the graphene oxide solute liquid crystal solution of formation is put into single-shaft-rotation spin duct；
(3) it will be expressed into the nozzle in spin duct in the coagulation bath of single axial stream；(4) phase transformation is carried out by exchange of solvent coagulation；(5) it steams
Hair solvent cures obtain graphene oxide fiber；(6) graphene fiber is obtained by chemistry or thermal reduction；(7) pass through rotation rolling
Cylinder receives the graphene fiber after reduction.
Further, the graphene oxide is handled by surface grafting, using isocyanates, silane coupling agent, is had
One or more of machine amine, diazonium salt and toluene mix reagent carries out surface-functionalized processing to graphene oxide, is contained
Have the graphene oxide of multiple terminal reactive functional groups, be able to satisfy graphene oxide it is highly uniform be dispersed in water or alcoholic solution
In.
Further, the graphene oxide spinning solution is the functionalization of 0.3%~25% mass fraction by concentration
Graphene oxide, water, methanol and ethyl alcohol composition.
Further, the graphene oxide spinning solution is squeezed from spinning spout with the speed of 0.05mm/s~10mm/s
Out, and from single spinning spout the fibre diameter squeezed out is 0.1 μm~100 μm.
Further, the coagulating bath contain selected from potassium hydroxide, sodium hydroxide, sodium chloride, potassium chloride, iron chloride,
The aqueous solution and/or organic solution of any one or two or more substances in calcium chloride and methanol, setting time meet phase
What is become is thoroughly finished.
Further, the solidification temperature meets the graphene oxide fiber for obtaining regulatory specifications.
Further, the chemistry or thermal reduction method are to pass through the graphene oxide fiber that curing and drying obtains
The chemical solvent of hydrazine hydrate and hydroiodic acid is restored, and is finally carried out thermal degradation method at high temperature and is obtained phosphorus content higher than 99%
Above graphene fiber.
Advantage for present invention: (1) being that graphene oxide is molten in water and alcohol by functionalization processing and ultrasonic treatment
There is extraordinary dispersibility in liquid, be further formed high performance graphene fiber.(2) have preparation process simple, production
It is high-efficient.(3) carbon content of graphene fiber can be made to be increased to by the thermal anneal process under heat/chemical reduction method and high temperature
The graphene fiber structure that 99% or more (4) obtain is uniform, has excellent in toughness and electric conductivity, can be woven into various functionality and knit
Object.
Specific embodiment
Combined with specific embodiments below, the present invention is furture elucidated, it should be understood that these embodiments are merely to illustrate the present invention
Rather than limit the scope of the invention, after the present invention has been read, those skilled in the art are to various equivalences of the invention
It is as defined in the appended claims that the modification of form falls within the application.
Embodiment 1
A kind of graphene fiber and preparation method thereof of wet spinning preparation, the wet spinning preparation include: that (1) is logical
The high graphene oxide spinning solution of dispersibility is formed after crossing chemical functionalization；(2) by the graphene oxide solute liquid crystal of formation
Solution is put into single-shaft-rotation spin duct；(3) it will be expressed into the nozzle in spin duct in the coagulation bath of single axial stream；(4) lead to
It crosses exchange of solvent coagulation and carries out phase transformation；(5) evaporation solvent cures obtain graphene oxide fiber；(6) pass through chemistry or thermal reduction
Obtain graphene fiber；(7) receive the graphene fiber after reduction by rotating cylinder.
Further, the graphene oxide is handled by surface grafting, using organic amine butylamine and toluene mixing examination
Agent carries out surface-functionalized processing to graphene oxide, and three-aminopropyl triethoxysilanes is recycled to obtain with graphite alkene reaction
Graphene oxide containing silicon oxygen bond, is able to satisfy that graphene oxide is highly uniform to be dispersed in water or alcoholic solution.
Further, the graphene oxide spinning solution aoxidizes stone by the functionalization that concentration is 15% mass fraction
Black alkene, water, methanol and ethyl alcohol composition.
Further, the graphene oxide spinning solution is squeezed out from spinning spout with the speed of 5mm/s, and from list
The fibre diameter that a spinning spout squeezes out is 10 μm.
Further, the coagulating bath contains the aqueous solution selected from potassium hydroxide and sodium hydroxide, and setting time meets
Phase transformation is thoroughly finished.
Further, the solidification temperature meets the graphene oxide fiber for obtaining regulatory specifications.
Further, the chemistry or thermal reduction method are to pass through the graphene oxide fiber that curing and drying obtains
The chemical solvent of hydrazine hydrate and hydroiodic acid is restored, and is finally carried out thermal degradation method at high temperature and is obtained phosphorus content higher than 99%
Above graphene fiber.
It above are only the specific embodiment of the present invention, but the design concept of the present invention is not limited to this, all benefits
It is made a non-material change to the present invention with this design, should belong to the behavior for invading the scope of protection of the invention.But it is all
Without departing from the content of technical solution of the present invention, according to the technical essence of the invention any type of letter to the above embodiments
Single modification, equivalent variations and remodeling, still fall within the protection scope of technical solution of the present invention.
Claims (7)
1. a kind of graphene fiber and preparation method thereof of wet spinning preparation, it is characterised in that the wet spinning prepares packet
It includes: (1) by forming the high graphene oxide spinning solution of dispersibility after chemical functionalization and ultrasonic treatment；(2) by formation
Graphene oxide solute liquid crystal solution is put into single-shaft-rotation spin duct；(3) single shaft will be expressed into the nozzle in spin duct
In the coagulation bath of stream；(4) phase transformation is carried out by exchange of solvent coagulation；(5) evaporation solvent cures obtain graphene oxide fiber；
(6) graphene fiber is obtained by chemistry or thermal reduction；(7) receive the graphene fiber after reduction by rotating cylinder.
2. a kind of graphene fiber and preparation method thereof of wet spinning preparation according to claim 1, it is characterised in that
The graphene oxide is handled by surface grafting, using isocyanates, silane coupling agent, organic amine, diazonium salt and toluene
One or more of mix reagent surface-functionalized processing is carried out to graphene oxide, obtain containing multiple terminal reactive functions
The graphene oxide of group, is able to satisfy that graphene oxide is highly uniform to be dispersed in water or alcoholic solution.
3. a kind of graphene fiber and preparation method thereof of wet spinning preparation according to claim 1, it is characterised in that
The graphene oxide spinning solution is functionalization graphene oxide, the water, first of 0.3%~25% mass fraction by concentration
Pure and mild ethyl alcohol composition.
4. a kind of graphene fiber and preparation method thereof of wet spinning preparation according to claim 1, it is characterised in that
The graphene oxide spinning solution is squeezed out from spinning spout with the speed of 0.05mm/s~10mm/s, and from single spinning
The fibre diameter that spout squeezes out is 0.1 μm~100 μm.
5. a kind of graphene fiber and preparation method thereof of wet spinning preparation according to claim 1, it is characterised in that
The coagulating bath contains appointing in potassium hydroxide, sodium hydroxide, sodium chloride, potassium chloride, iron chloride, calcium chloride and methanol
The aqueous solution and/or organic solution of the substance for one or more of anticipating, setting time meet thoroughly being finished for phase transformation.
6. a kind of graphene fiber and preparation method thereof of wet spinning preparation according to claim 1, it is characterised in that
The solidification temperature meets the graphene oxide fiber for obtaining regulatory specifications.
7. a kind of graphene fiber and preparation method thereof of wet spinning preparation according to claim 1, it is characterised in that
The chemistry or thermal reduction method is that the graphene oxide fiber for obtaining curing and drying passes through the change of hydrazine hydrate and hydroiodic acid
It learns solvent to be restored, finally carries out thermal degradation method at high temperature and obtain the graphene fiber that phosphorus content is higher than 99% or more.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110181879A (en) * | 2019-06-27 | 2019-08-30 | 中素新科技有限公司 | Graphene aerogel fiber composite honeycomb aluminum plate and preparation method thereof |
| CN111719212A (en) * | 2020-01-13 | 2020-09-29 | 中原工学院 | Preparation method of flexible graphene conductive yarn capable of being woven |
| CN112030268A (en) * | 2020-07-21 | 2020-12-04 | 南通大学 | Continuous dry-wet combined spinning method for graphene |
| CN112064149A (en) * | 2020-09-22 | 2020-12-11 | 杭州高烯科技有限公司 | Method for graphene wet spinning |
| CN114250529A (en) * | 2021-12-14 | 2022-03-29 | 浙江大学 | Aerogel fiber with specific section morphological characteristics and preparation method and device thereof |
| JP2022531167A (en) * | 2019-04-30 | 2022-07-06 | 青島大学 | Method for producing graphene oxide fiber and obtained fiber |
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| JP2022531167A (en) * | 2019-04-30 | 2022-07-06 | 青島大学 | Method for producing graphene oxide fiber and obtained fiber |
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| CN111719212A (en) * | 2020-01-13 | 2020-09-29 | 中原工学院 | Preparation method of flexible graphene conductive yarn capable of being woven |
| CN112030268A (en) * | 2020-07-21 | 2020-12-04 | 南通大学 | Continuous dry-wet combined spinning method for graphene |
| CN112030268B (en) * | 2020-07-21 | 2023-04-07 | 南通大学 | Continuous dry-wet combined spinning method for graphene |
| CN112064149A (en) * | 2020-09-22 | 2020-12-11 | 杭州高烯科技有限公司 | Method for graphene wet spinning |
| CN114250529A (en) * | 2021-12-14 | 2022-03-29 | 浙江大学 | Aerogel fiber with specific section morphological characteristics and preparation method and device thereof |
| CN114250529B (en) * | 2021-12-14 | 2023-08-22 | 浙江大学 | Aerogel fiber with specific cross-sectional morphological characteristics and preparation method and device thereof |
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