CN105603582B - A kind of high intensity continuous graphite alkene fiber and preparation method thereof - Google Patents
A kind of high intensity continuous graphite alkene fiber and preparation method thereof Download PDFInfo
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- CN105603582B CN105603582B CN201610056302.XA CN201610056302A CN105603582B CN 105603582 B CN105603582 B CN 105603582B CN 201610056302 A CN201610056302 A CN 201610056302A CN 105603582 B CN105603582 B CN 105603582B
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- 239000000835 fiber Substances 0.000 title claims abstract description 76
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 18
- 239000010439 graphite Substances 0.000 title claims abstract description 18
- -1 graphite alkene Chemical class 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 96
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 94
- 238000009987 spinning Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 16
- 230000001112 coagulating effect Effects 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- 238000007872 degassing Methods 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 229940071870 hydroiodic acid Drugs 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000004575 stone Substances 0.000 claims description 4
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 3
- 239000001828 Gelatine Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 229920000159 gelatin Polymers 0.000 claims description 3
- 235000019322 gelatine Nutrition 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000002356 single layer Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims 1
- 229940113088 dimethylacetamide Drugs 0.000 claims 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims 1
- 235000011187 glycerol Nutrition 0.000 claims 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims 1
- 238000006197 hydroboration reaction Methods 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 239000011358 absorbing material Substances 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 239000003960 organic solvent Substances 0.000 abstract 1
- 239000003495 polar organic solvent Substances 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- 238000007711 solidification Methods 0.000 abstract 1
- 230000008023 solidification Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000010410 layer Substances 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 210000005239 tubule Anatomy 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000002166 wet spinning Methods 0.000 description 3
- QEWYKACRFQMRMB-UHFFFAOYSA-N fluoroacetic acid Chemical compound OC(=O)CF QEWYKACRFQMRMB-UHFFFAOYSA-N 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
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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
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
-
- 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
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
- D01F11/12—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with inorganic substances ; Intercalation
- D01F11/121—Halogen, halogenic acids or their salts
-
- 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
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
- D01F11/12—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with inorganic substances ; Intercalation
- D01F11/128—Nitrides, nitrogen carbides
-
- 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
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
- D01F11/14—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with organic compounds, e.g. macromolecular compounds
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Inorganic Fibers (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of high intensity continuous graphite alkene fiber and preparation method thereof, first graphene oxide is scattered in polar organic solvent, spinning solution is made, then spinning solution is continuously squeezed into coagulating bath from spinneret capillary with fixed speed, the gelatinous fibre of solidification is by continuous traction stretching and drying process, it is finally collected on graphite roll shaft, obtains graphene oxide fiber.Pass through electronation and heat treatment successively again, obtain the degree of orientation and be up to 70~80%, density is 1.3~2g/cm3Graphene fiber.Spinning technique is simple, with water or organic solvent, realizes the continuous preparation of graphene fiber with collecting.Resulting graphene fiber has excellent mechanical property and good conductance.Continuous high strength graphite alkene fiber can be used for preparing graphene braid, used in fields such as electromagnetic shielding, absorbing materials；Available in polymer composites, as reinforcer.
Description
Technical field
The present invention relates to a kind of graphene fiber, more particularly to a kind of high intensity continuous graphite alkene fiber and its preparation side
Method.
Background technology
Graphene (graphene) is a kind of New Two Dimensional crystalline material being made up of single carbon atom layer, has known materials
Best mechanical property (fracture strength 125GPa, Young's modulus 1100GPa), and excellent electric property (electronics at room temperature
Mobility is up to 2 × 105cm2/ Vs) and prominent heat conductivility (5000W/mK), it is referred to as magical material.Andre Geim
With Konstantin Novoselov because the contribution to graphene research obtains Nobel prize for physics in 2010.From natural stone
Black alkene is set out, and graphene oxide is prepared by oxidizing process, using the liquid crystal behavior of graphene oxide solution, with reference to wet spinning skill
Art, realize the preparation (Nat.Commun.2011,2,571) of graphene fiber.The preparation of graphene fiber and its functionalization are
Through the focus as current research.But the mechanical strength for the graphene fiber reported at present is still than relatively low (500MPa),
Still have greatly improved space, can prepare high intensity by the methods of optimization, post processing of raw material and spinning technique
Graphene fiber.
The content of the invention
The purpose of the present invention is to overcome the shortcomings of existing graphene fiber technology of preparing, there is provided a kind of high intensity continuous graphite
Alkene fiber and preparation method thereof.
The purpose of the present invention is achieved through the following technical solutions：A kind of high intensity continuous graphite alkene fiber, the fibre
By graphene, axially ordered arrangement forms dimension, and the degree of orientation is 70~80%, and density is 1.3~2g/cm3。
A kind of preparation method of high intensity continuous graphite alkene fiber, comprises the following steps：
(1) graphene oxide of 1 parts by weight, the solvent of 10~100 parts by weight are mixed, obtains aoxidizing stone after ultrasonic disperse
Black alkene dispersion liquid；
(2) graphene oxide dispersion for obtaining step (1), under 0.001~0.1Pa vacuum, degassing process
10~60min, obtain graphene oxide spinning solution；
(3) the graphene oxide spinning solution for obtaining step (2), with 1~100mL/h extruded velocity, it is by aperture
After 60~300 μm of spinneret capillary extrusion, into coagulating bath, 5~60s is stopped in 10~60 DEG C of coagulating bath, is obtained
Gelatine silk；Gelatine silk is passed through to the roll shaft continuously run that rotating speed is 50~100rpm/min and 60~300rpm/min successively,
And the rotating speed of second roll shaft is 1.1~2.5 times of the rotating speed of first roll shaft, while the infrared lamp with power for 20~200W
Dry, collection obtains continuous graphene oxide fiber；
(4) the graphene oxide fiber of gained in step (3) is placed in reducing agent and reduced, wash drying, obtained continuous
Graphene fiber；
(5) graphene fiber of gained in step (4) is placed in 600~1300 DEG C of tube furnace, in atmosphere at heat
0.5~2h is managed, obtains high intensity continuous graphite alkene fiber.
Further, the solvent in the step (1) is mainly by water, dimethyl sulfoxide, DMF, N, N- bis-
It is one or more kinds of according to any proportioning mixing composition in methylacetamide, 1-METHYLPYRROLIDONE, tetrahydrofuran.
Further, the coagulating bath in the step (3) is by methanol, ethanol, ethyl acetate, n-butanol, ethylene glycol, the third three
It is one or more according to any proportioning mixing composition in alcohol, butyl acetate, n-propyl acetate, acetic acid, acetone.
Further, the reducing agent in the step (4) is by hydrazine hydrate, sodium borohydride, hydrobromic acid, hydroiodic acid, acetic acid, three
It is one or more according to any proportioning mixing composition in fluoroacetic acid.
Further, atmosphere used in the step (5) is one or more according to appointing in hydrogen, argon gas, nitrogen
Meaning proportioning mixing composition.
Further, in the step (1), the graphene oxide is the mono-layer graphite oxide of 10~20 μm of radial dimension
Alkene.
The present invention has following technique effect：
1st, the primary raw materials of graphene oxide is graphite, raw material sources extensively, be easy to get, cost it is cheap；
2nd, graphene oxide fiber is prepared for using the wet spinning technology of classics, it is easy to operate；
3rd, continuous traction drawing process is employed in spinning process, is advantageous to the orientations of graphene oxide, it is obtained
Graphene oxide fiber has good mechanical strength；
4th, by electronation and heat treatment, the structure for having recovered graphene of part, enhance graphene sheet layer it
Between interaction force, obtained graphene fiber has excellent mechanical strength, while has excellent electric conductivity.
Brief description of the drawings
Fig. 1 is the schematic diagram of wet spinning device.
Embodiment
The invention provides a kind of high intensity continuous graphite alkene fiber, the fiber by graphene axially ordered arrangement and
Into the degree of orientation is up to 70~80%, and density is 1.3~2g/cm3, it is of the invention that a kind of high intensity continuous graphite alkene fiber is also provided
Preparation method, this method by rotating speed be 50~100rpm/min and 60~300rpm/min the roll shaft continuously run company
Continuous traction stretching so that graphene oxide ordered arrangement vertically, aid in the drying using power as 20~200W infrared lamp, portion
Divide ground to recover the structure of graphene, enhance the interaction force between graphene sheet layer；It is close to realize graphene sheet layer
Accumulation.A diameter of 3~200 μm of the graphene oxide fiber being prepared first, tensile strength are 300~600MPa, fracture
Elongation is 0.3~10%.A diameter of 3~200 μm of the graphene fiber obtained after carrying out reduction, tensile strength be 600~
1000MPa, elongation at break are 0.1~10%, and conductance is higher than 10000S/m.
Below in conjunction with the accompanying drawings and embodiment the invention will be further described.The present embodiment be served only for being the present invention into
The explanation of one step, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art is according in foregoing invention
Appearance makes some nonessential changes and adjustment, belongs to protection scope of the present invention.
It should be noted that in the present invention, for the reducing agent of redox graphene, including hydrazine hydrate, sodium borohydride,
Hydrobromic acid, hydroiodic acid, acetic acid, trifluoroacetic acid etc., its concentration range are the common knowledge of this area.
Embodiment 1：
(1) 1g graphene oxides and 10g deionized waters are mixed, in 20 DEG C of supersound process 1h with 50KHz, aoxidized
Graphene dispersing solution.
(2) by the graphene oxide dispersion water circulating pump obtained by (1) under 0.1Pa vacuum condition, degassing
10min, obtain graphene oxide spinning solution.
(3) take the graphene oxide spinning solution obtained by (2), using 10mL/h extruded velocity by internal diameter as 60 μm of spinning
Capillus tubule, stop 10s becomes gelatinous fibre in 25 DEG C of ethyl acetate coagulating bath, is by rotating speed successively by gelatinous fibre
The 55rpm/min and 60rpm/min roll shaft continuously run, now corresponding draw ratio is 1.1 (and rotating speeds of second roll shaft
For 1.1 times of the rotating speed of first roll shaft), while the infrared lamp for being 20W with power is dried, collection obtains continuously aoxidizing stone
Black alkene fiber；
(4) the graphene oxide fiber that (3) obtain is heated to 90 in mass fraction is 20% hydriodic acid aqueous solution
DEG C, 12h is fully reduced, washing is dried to obtain graphene fiber.
(5) graphene fiber for obtaining (4), handles 0.5h in 700 DEG C of tube furnaces of applying argon gas atmosphere, obtains high-strength
Spend continuous graphite alkene fiber.
By above step, the graphene oxide spinning solution of stable homogeneous is obtained, graphene oxide spinning solution has good
Shear Flow, it can be seen that obvious liquid crystal stripe texture under petrographic microscope.The fiber being prepared it is a diameter of
20~30 μm, axial direction arrangement of the graphene film along fiber.The graphene oxide tensile strength of fiber of preparation is 300~600MPa,
Elongation at break is 1~3%, while has good compliance.The high strength graphite alkene tensile strength of fiber that reduction is formed is 600
~700MPa, elongation at break are 8~10%, and conductance is more than 10000S/m.
Embodiment 2：
(1) 0.5g graphene oxides and 20g DMAs are mixed, in 25 DEG C of supersound process with 60KHz
2h, obtain graphene oxide dispersion.
(2) by the graphene oxide dispersion water circulating pump obtained by (1) under 0.01Pa vacuum condition, degassing
30min, obtain graphene oxide spinning solution.
(3) take the graphene oxide spinning solution obtained by (2), using 40mL/h extruded velocity by internal diameter as 130 μm of spinning
Silk capillus tubule, stop 60s becomes gelatinous fibre in 25 DEG C of acetone coagulating bath, is by rotating speed successively by gelatinous fibre
The 200rpm/min and 300rpm/min roll shaft continuously run, now corresponding draw ratio is 1.5, while is 200W with power
Infrared lamp dry, collection obtain continuous graphene oxide fiber；.
(4) the graphene oxide fiber that (3) obtain is placed in the hydrazine hydrate that mass fraction is 35%, is heated to 90 DEG C,
Fully reduction 1h, washing are dried to obtain graphene fiber.
(5) graphene fiber for obtaining (4), in hydrogen-argon-mixed atmosphere, 600 DEG C of processing 2h, it is continuous to obtain high intensity
Graphene fiber.
By above step, the graphene oxide spinning solution of stable homogeneous is obtained, graphene oxide spinning solution has good
Shear Flow, it can be seen that obvious liquid crystal stripe texture under petrographic microscope.The fiber being prepared it is a diameter of
20~30 μm, axial direction arrangement of the graphene film along fiber.The graphene oxide tensile strength of fiber of preparation is 300~600MPa,
Elongation at break is 1~2%, while has good toughness.The graphene fiber tensile strength that reduction is formed for 700~
800MPa, elongation at break are 7~8%, and conductance is more than 10000S/m.
Embodiment 3
(1) 2g graphene oxides and 100g DMF are mixed, in 20 DEG C of supersound process with 60KHz
2h, obtain graphene oxide dispersion.
(2) by the graphene oxide dispersion water circulating pump obtained by (1) under 0.001Pa vacuum condition, deaerate 1h,
Obtain graphene oxide spinning solution.
(3) take the graphene oxide spinning solution obtained by (2), using 0mL/h extruded velocity by internal diameter as 200 μm of spinning
Capillus tubule, bathes that (both volume ratios are 1 in the mixing of 25 DEG C of ethyl acetate and acetone admittedly:1) 10s is stopped in and becomes gel
Fiber；By gelatinous fibre successively by the roll shaft continuously run that rotating speed is 100rpm/min and 250rpm/min, now correspond to
Draw ratio be 2.5, while with power be 100W infrared lamp dry, collection obtain continuous graphene oxide fiber.
(4) the graphene oxide fiber that (3) obtain is placed in the mixed solution of hydroiodic acid and acetic acid, is heated to 90 DEG C,
Fully reduction 12h, washing are dried to obtain graphene fiber.
(5) graphene fiber for obtaining (4), in hydrogen-argon-mixed atmosphere, 1300 DEG C of processing 0.5h, high intensity company is obtained
Continuous graphene fiber.
By above step, the graphene oxide spinning solution of stable homogeneous is obtained, graphene oxide spinning solution has good
Shear Flow, it can be seen that obvious liquid crystal stripe texture under petrographic microscope.The fiber being prepared it is a diameter of
20~60 μm, axial direction arrangement of the graphene film along fiber.The graphene oxide tensile strength of fiber of preparation is 500~600MPa,
Elongation at break is 8~10%, while has good toughness.The graphene fiber tensile strength that reduction is formed for 800~
1000MPa, elongation at break are 1~2%, and conductance is more than 10000S/m.
It should be noted that：Rotating speed selected by the present invention is optimized rotating speed, i.e., optimal draw ratio, if two roll shafts turn
Speed does not regulate, then the fiber mechanicses intensity of preparation is than relatively low, or can not continuously prepare.
In embodiment 1, if the roll shaft rotating speed continuously run is all 45rpm/min, i.e., draw ratio is 1, and other conditions are not
Become, then the intensity of prepared fiber only has 100~200MPa.In embodiment 2, if the roll shaft rotating speed difference continuously run
For 250rpm/min and 300rpm/min, i.e. draw ratio is 1.2, and other conditions are constant, then the intensity of prepared fiber is only
There is 250~350MPa.In embodiment 3, if the roll shaft rotating speed continuously run is respectively 100rpm/min and 200rpm/min, i.e.,
Draw ratio is 2.0, and other conditions are constant, then the intensity of prepared fiber only has 300~450MPa.
Above-described embodiment is used for illustrating the present invention, rather than limits the invention, the present invention spirit and
In scope of the claims, to any modifications and changes of the invention made, protection scope of the present invention is both fallen within.
Claims (6)
1. a kind of preparation method of high intensity continuous graphite alkene fiber, it is characterised in that comprise the following steps：
（1）By the graphene oxide of 1 parts by weight, the solvent of 10 ~ 100 parts by weight is mixed, and graphene oxide is obtained after ultrasonic disperse
Dispersion liquid；
（2）By step（1）Obtained graphene oxide dispersion, under 0.001 ~ 0.1 Pa vacuum, degassing process 10 ~ 60
Min, obtain graphene oxide spinning solution；
（3）By step（2）Obtained graphene oxide spinning solution, with 1 ~ 100 mL/h extruded velocity, by aperture be 60 ~
After 300 μm of spinneret capillary extrusion, into coagulating bath, 5 ~ 60s is stopped in 10 ~ 60 DEG C of coagulating bath, obtains gel
Silk；By gelatine silk successively by the roll shaft continuously run that rotating speed is 50 ~ 100 rpm/min and 60 ~ 300 rpm/min, and the
The rotating speed of two roll shafts is 1.1 ~ 2.5 times of the rotating speed of first roll shaft, while is dried with the infrared lamp that power is 20 ~ 200 W,
Collection obtains continuous graphene oxide fiber；
（4）By step（3）The graphene oxide fiber of middle gained, which is placed in reducing agent, to reduce, and washs drying, obtains continuous stone
Black alkene fiber；
（5）By step（4）The graphene fiber of middle gained is placed in 600 ~ 1300 DEG C of tube furnace, in atmosphere be heat-treated 0.5 ~
2 h, obtain high intensity continuous graphite alkene fiber.
2. according to the method for claim 1, it is characterised in that the step（1）In solvent by water, dimethyl sulfoxide, N,
It is one or more kinds of according to appointing in dinethylformamide, DMAC N,N' dimethyl acetamide, 1-METHYLPYRROLIDONE, tetrahydrofuran
Meaning proportioning mixing composition.
3. according to the method for claim 1, it is characterised in that the step（3）In coagulating bath by methanol, ethanol, second
It is one or more according to appointing in acetoacetic ester, n-butanol, ethylene glycol, glycerine, butyl acetate, n-propyl acetate, acetic acid, acetone
Meaning proportioning mixing composition.
4. according to the method for claim 1, it is characterised in that the step（4）In reducing agent by hydrazine hydrate, hydroboration
It is one or more according to any proportioning mixing composition in sodium, hydrobromic acid, hydroiodic acid, acetic acid, trifluoroacetic acid.
5. according to the method for claim 1, it is characterised in that the step（5）In used atmosphere be hydrogen, argon gas,
It is one or more according to any proportioning mixing composition in nitrogen.
6. according to the method for claim 1, it is characterised in that the step（1）In, the graphene oxide is radially
The single-layer graphene oxide that 10 ~ 20 μm of size.
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