CN105648579A - Superfine graphene fibers and method for preparing same - Google Patents
Superfine graphene fibers and method for preparing same Download PDFInfo
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- CN105648579A CN105648579A CN201610201928.5A CN201610201928A CN105648579A CN 105648579 A CN105648579 A CN 105648579A CN 201610201928 A CN201610201928 A CN 201610201928A CN 105648579 A CN105648579 A CN 105648579A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 101
- 239000000835 fiber Substances 0.000 title claims abstract description 91
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000009987 spinning Methods 0.000 claims abstract description 32
- 230000001112 coagulating effect Effects 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 19
- 239000010439 graphite Substances 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- -1 graphite alkene Chemical class 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 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
- 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
- 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
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 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
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000002356 single layer Substances 0.000 claims description 2
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 239000011358 absorbing material Substances 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 239000004744 fabric Substances 0.000 abstract 1
- 239000002798 polar solvent Substances 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 abstract 1
- 238000010008 shearing Methods 0.000 abstract 1
- 239000007921 spray Substances 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000002166 wet spinning Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 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
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000001590 oxidative effect Effects 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
- 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
-
- 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
-
- 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
- D01F11/16—Chemical after-treatment of artificial filaments or the like during manufacture of carbon by physicochemical methods
Abstract
The invention discloses superfine graphene fibers and a method for preparing the same. The method includes dissolving graphene oxide in polar solvents to obtain graphene oxide liquid crystal spinning solution; enabling the spinning solution to flow into coagulating bath via spray nozzles at fixed speeds and forming gelatinous fibers; sufficiently stretching the as-spun gelatinous fibers under the shearing actions of flow fields of the coagulating bath and continuous traction effects of roll shafts; drying the gelatinous fibers and then collecting the gelatinous fibers to obtain graphene oxide fibers; sequentially carrying out chemical reduction and heat treatment on the graphene oxide fibers to obtain the superfine graphene fibers. The orientation degree of the superfine graphene fibers can reach 80-90%, and the density of the superfine graphene fibers is 1.6-2.2 g/cm<3>. The superfine graphene fibers and the method have the advantages that processes are controllable in integral spinning procedures, and the superfine graphene fibers are excellent in mechanical strength, flexibility and electric conductivity, can be used for preparing graphene braided fabrics and are used in the fields of composite materials, light conducting wires, electromagnetic shielding, wave-absorbing materials and the like.
Description
Technical field
The present invention relates to a kind of graphene fiber, particularly relate to a kind of superfine graphite alkene fiber and preparation method thereof.
Background technology
Graphene (graphene) is a kind of New Two Dimensional crystalline material being made up of single carbon atom layer, there is the best mechanical property of known materials (fracture strength 125GPa, Young's modulus 1100GPa), and the electric property of excellence (under room temperature, electron mobility is up to 2 �� 105cm2/ Vs) and prominent heat conductivility (5000W/mK), it is referred to as the material of mystery. AndreGeim and KonstantinNovoselov is because obtaining Nobel prize for physics in 2010 to the contribution of Graphene research. From native graphite alkene, prepare graphene oxide by oxidizing process, utilize the liquid crystal behavior of graphene oxide solution, in conjunction with wet spinning technology, it is achieved that the preparation (Nat.Commun.2011,2,571) of graphene fiber. The preparation of graphene fiber and functionalization thereof have become as the focus of current research. But, the mechanical strength of current reported graphene fiber is poor, it is difficult to meet application demand. Still have greatly improved space, it is possible to prepared the graphene fiber of high intensity by methods such as raw material and the optimization of spinning technique, fiber fine-denier, optimization aftertreatment technologys.
It is known that fiber is more thin, its defect is more few, and therefore intensity is more high. Preparing the technological difficulties that superfine fibre is this area, for carbon fiber, the limit diameter of preparation is also at about 5-7um at present.
Summary of the invention
It is an object of the invention to overcome the deficiency of existing graphene fiber, it is provided that a kind of superfine graphite alkene fiber and preparation method thereof.
It is an object of the invention to be achieved through the following technical solutions: a kind of superfine graphite alkene fiber, this fiber is formed by Graphene axially ordered arrangement, and fibre diameter is 1��4 ��m, and the degree of orientation is 80��90%, and density is 1.6��2.2g/cm3, it is possible to continuously prepared by scale.
The preparation method of a kind of superfine graphite alkene fiber, comprises the following steps:
(1) by the graphene oxide of 1 weight portion, the solvent mixing of 100��1000 weight portions, obtain graphene oxide dispersion after ultrasonic disperse;
(2) graphene oxide dispersion that step (1) is obtained, under the vacuum of 0.001��0.1Pa, degassed process 10��60min, obtain graphene oxide spinning liquid;
(3) the graphene oxide spinning liquid that step (2) is obtained, the spinning nozzle being 20��80 ��m by aperture with the flow velocity of 100��200mL/h, enter coagulating bath, the coagulating bath of 10��60 DEG C stops 5��60s, obtain nascent gelatinous fibre; By nascent gelatinous fibre by rotating speed be 200��500rpm/min roll shaft draw stretching continuously, dry with the infrared lamp that power is 100��300W simultaneously, collect obtain graphene oxide fiber;
(4) being placed in by the graphene oxide fiber of gained in step (3) in reducing agent and reduce, washing is dry, obtains continuous print graphene fiber;
(5) graphene fiber of gained in step (4) is placed in the tube furnace of 600��1300 DEG C, heat treatment 0.5��2h in atmosphere, obtain high intensity continuous graphite alkene fiber.
Further, the solvent in described step (1) is mainly made up of according to the mixing of any proportioning one or more in water, dimethyl sulfoxide, DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone, oxolane.
Further, the coagulating bath in described step (3) is made up of according to the mixing of any proportioning one or more in methanol, ethanol, ethyl acetate, n-butyl alcohol, ethylene glycol, glycerol, butyl acetate, n-propyl acetate, acetic acid, acetone.
Further, the reducing agent in described step (4) is made up of according to the mixing of any proportioning one or more in hydrazine hydrate, sodium borohydride, hydrobromic acid, hydroiodic acid, acetic acid, trifluoroacetic acid.
Further, atmosphere used in described step (5) is that one or more in hydrogen, argon, nitrogen are according to any proportioning mixing composition.
Further, in described step (1), described graphene oxide is the single-layer graphene oxide of radial dimension 10��20 ��m.
The present invention has following technical effect that
1, the primary raw materials of graphene oxide is graphite, raw material sources extensively, be easy to get, with low cost;
2, classical wet spinning technology is adopted to be prepared for graphene oxide fiber, easy and simple to handle, it may be achieved to prepare continuously;
3, have employed in spinning process and draw drawing process continuously, be conducive to the orientations of graphene oxide, prepared graphene oxide fiber has good mechanical strength;
4, by electronation and heat treatment, the structure having recovered Graphene of part, enhance the interaction force between graphene sheet layer, prepared graphene fiber has the mechanical strength of excellence, has the electric conductivity of excellence simultaneously.
Detailed description of the invention
The invention provides the graphene fiber of a kind of ultra-fine high intensity, this fiber is formed by Graphene axially ordered arrangement, and fibre diameter is 1��4 ��m, and the degree of orientation is 80��90%, and density is 1.6��2.2g/cm3, it is possible to continuously prepared by scale. The preparation method that the present invention also provides for a kind of ultra-fine high strength graphite alkene fiber, the method by rotating speed be 200��500rpm/min roll shaft draw stretching continuously, make graphene oxide ordered arrangement vertically, drying of the infrared lamp that auxiliary is 100��300W with power, partly recover the structure of Graphene, enhance the interaction force between graphene sheet layer, it is achieved that graphene sheet layer is tightly packed. The diameter of the graphene oxide fiber first prepared is 5��10 ��m, and hot strength is 800��1000MPa, and elongation at break is 0.3��10%.The diameter of the graphene fiber obtained after carrying out reduction is 1��4 ��m, and hot strength is 1200��2200MPa, and elongation at break is 0.5��2%, and conductivity is higher than 10000S/m.
Below in conjunction with embodiment, the invention will be further described. The present embodiment is served only for that the present invention is described further, it is impossible to being interpreted as limiting the scope of the invention, those skilled in the art makes some nonessential change and adjustment according to the content of foregoing invention, 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 is the known general knowledge of this area.
Embodiment 1:
(1) 1g graphene oxide and 100g deionized water are mixed, in 20 DEG C of supersound process 1h with 50KHz, obtain graphene oxide dispersion.
(2) by the graphene oxide dispersion water circulating pump of (1) gained under the vacuum condition of 0.1Pa, degassed 10min, obtain graphene oxide spinning liquid.
(3) the graphene oxide spinning liquid of (2) gained is taken, the spinning nozzle being 80 ��m by internal diameter with the extruded velocity of 200mL/h, in the ethyl acetate coagulating bath of 25 DEG C, stop 10s become gelatinous fibre, by nascent gelatinous fibre by rotating speed be 500rpm/min roll shaft draw stretching continuously, dry with the infrared lamp that power is 100W simultaneously, collect and obtain continuous print graphene oxide fiber;
(4) the graphene oxide fiber (3) obtained is in 20% hydriodic acid aqueous solution at mass fraction, and heating, to 90 DEG C, fully reduces 12h, and washing is dry obtains graphene fiber.
(5) graphene fiber (4) obtained, in argon, 3000 DEG C process 0.5h, obtain ultra-fine high-strength graphite alkene fiber.
Through above step, obtaining the graphene oxide spinning liquid of stable homogeneous, graphene oxide spinning liquid has good Shear Flow, it can be seen that obvious liquid crystal stripe texture under polarizing microscope. The graphene oxide tensile strength of fiber of preparation is 800��1000MPa, and elongation at break is 1��3%, has good compliance simultaneously. The diameter of the superfine graphite alkene fiber that reduction is formed is 1��4 ��m, and hot strength is 1600��2200MPa, and elongation at break is 0.5��2%, and conductivity is more than 10000S/m.
Embodiment 2:
(1) 1g graphene oxide and 500gN, N-dimethyl acetylamide are mixed, in 25 DEG C of supersound process 2h with 60KHz, obtain graphene oxide dispersion.
(2) by the graphene oxide dispersion water circulating pump of (1) gained under the vacuum condition of 0.01Pa, degassed 30min, obtain graphene oxide spinning liquid.
(3) the graphene oxide spinning liquid of (2) gained is taken, the spinning nozzle being 60 ��m by internal diameter with the extruded velocity of 150mL/h, in the ethyl acetate coagulating bath of 25 DEG C, stop 60s become gelatinous fibre, by nascent gelatinous fibre by rotating speed be 300rpm/min roll shaft draw stretching continuously, dry with the infrared lamp that power is 200W simultaneously, collect and obtain continuous print graphene oxide fiber; .
(4) being placed in the hydrazine hydrate that mass fraction is 35% by the graphene oxide fiber that (3) obtain, heating, to 90 DEG C, fully reduces 1h, and washing is dry obtains graphene fiber.
(5) graphene fiber (4) obtained, in argon, 3000 DEG C process 0.5h, obtain ultra-fine high-strength graphite alkene fiber.
Through above step, obtaining the graphene oxide spinning liquid of stable homogeneous, graphene oxide spinning liquid has good Shear Flow, it can be seen that obvious liquid crystal stripe texture under polarizing microscope.The graphene oxide tensile strength of fiber of preparation is 800��1000MPa, and elongation at break is 1��3%, has good compliance simultaneously. The diameter of the superfine graphite alkene fiber that reduction is formed is 1��4 ��m, and hot strength is 1400��1800MPa, and elongation at break is 0.5��2%, and conductivity is more than 10000S/m.
Embodiment 3
(1) DMF of 1g graphene oxide and 1000g is mixed, in 20 DEG C of supersound process 2h with 60KHz, obtain graphene oxide dispersion.
(2) by the graphene oxide dispersion water circulating pump of (1) gained under the vacuum condition of 0.001Pa, degassed 1h, obtain graphene oxide spinning liquid.
(3) the graphene oxide spinning liquid of (2) gained is taken, the spinning nozzle being 20 ��m by internal diameter with the extruded velocity of 100mL/h, stops 10s in the ethyl acetate of 25 DEG C and the mixing of acetone bathe (both volume ratios are 1:1) admittedly and becomes gelatinous fibre; By nascent gelatinous fibre by rotating speed be 200rpm/min roll shaft draw stretching continuously, dry with the infrared lamp that power is 100W simultaneously, collect obtain continuous print graphene oxide fiber.
(4) being placed in the mixed solution of hydroiodic acid and acetic acid by the graphene oxide fiber that (3) obtain, heating, to 90 DEG C, fully reduces 12h, and washing is dry obtains graphene fiber.
(5) graphene fiber (4) obtained, in argon, 3000 DEG C process 0.5h, obtain ultra-fine high-strength graphite alkene fiber.
Through above step, obtaining the graphene oxide spinning liquid of stable homogeneous, graphene oxide spinning liquid has good Shear Flow, it can be seen that obvious liquid crystal stripe texture under polarizing microscope. The graphene oxide tensile strength of fiber of preparation is 800��1000MPa, and elongation at break is 1��3%, has good compliance simultaneously. The diameter of the superfine graphite alkene fiber that reduction is formed is 1��4 ��m, and hot strength is 1200��1500MPa, and elongation at break is 0.5��2%, and conductivity is more than 10000S/m.
It should be understood that concentration of dope selected by the present invention, spinning nozzle diameter, extruded velocity and hauling speed to match each other. If concentration of dope is too high, spinning nozzle diameter is excessive, extruded velocity is excessively slow, hauling speed is too low, then the diameter of prepared graphene fiber will more than 5 ��m, and the degree of orientation of fiber is relatively low, and the mechanical strength of fiber is relatively low; If concentration of dope is too low, spinning nozzle diameter is too small, extruded velocity is too fast, hauling speed is too high, then the continuous preparation of superfine graphite alkene fiber cannot be realized, fracture of wire phenomenon occurs.
In embodiment 1, if the concentration of spinning liquid is 2%, other conditions are constant, then the diameter of prepared fiber will more than 10 ��m, and fibre orientation degree also can reduce. In embodiment 2, if spinning nozzle diameter is 80 ��m, other conditions are constant, then the diameter of prepared fiber is about 10 ��m. In embodiment 3, if the hauling speed of roll shaft is 300rpm/min, other conditions are constant, then arise that fracture of wire phenomenon in spinning process, it is impossible to collect graphene fiber continuously.
Above-described embodiment is used for illustrating the present invention, rather than limits the invention, in the spirit and scope of the claims of the present invention, and any amendment that the present invention is made and change, both fall within protection scope of the present invention.
Claims (7)
1. a superfine graphite alkene fiber, it is characterised in that this fiber is formed by Graphene axially ordered arrangement, fibre diameter is 1��4 ��m, and the degree of orientation is 80��90%, and density is 1.6��2.2g/cm3��
2. the preparation method of a superfine graphite alkene fiber, it is characterised in that comprise the following steps:
(1) by the graphene oxide of 1 weight portion, the solvent mixing of 100��1000 weight portions, obtain graphene oxide dispersion after ultrasonic disperse;
(2) graphene oxide dispersion that step (1) is obtained, under the vacuum of about 0.001��0.1Pa, degassed process 10��60min, obtain graphene oxide spinning liquid.
(3) the graphene oxide spinning liquid that step (2) is obtained, the spinning nozzle being 20��80 ��m by aperture with the flow velocity of 100��200mL/h, enter coagulating bath, the coagulating bath of 10��60 DEG C stops 5��60s, obtain nascent gelatinous fibre; By nascent gelatinous fibre by rotating speed be 200��500rpm/min roll shaft draw stretching continuously, dry with the infrared lamp that power is 100��300W simultaneously, collect obtain graphene oxide fiber;
(4) being placed in by the graphene oxide fiber of gained in step (3) in reducing agent and reduce, washing is dry, obtains continuous print graphene fiber;
(5) graphene fiber of gained in step (4) is placed in the tube furnace of 2000��3000 DEG C, heat treatment 0.5��2h in atmosphere, obtain high intensity continuous graphite alkene fiber.
3. method according to claim 2, it is characterized in that, solvent in described step (1) mainly by water, dimethyl sulfoxide, DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone, etc. in one or more according to any proportioning mixing form.
4. method according to claim 2, it is characterized in that, the coagulating bath in described step (3) is made up of according to the mixing of any proportioning one or more in methanol, ethanol, ethyl acetate, n-butyl alcohol, ethylene glycol, glycerol, butyl acetate, n-propyl acetate, acetic acid, acetone.
5. method according to claim 2, it is characterised in that the reducing agent in described step (4) is made up of according to the mixing of any proportioning one or more in hydrazine hydrate, sodium borohydride, hydroiodic acid, acetic acid, trifluoroacetic acid.
6. method according to claim 2, it is characterised in that atmosphere used in described step (5) is that one or more in hydrogen, argon, nitrogen are according to any proportioning mixing composition.
7. method according to claim 2, it is characterised in that in described step (1), described graphene oxide is the single-layer graphene oxide of radial dimension 10��20 ��m.
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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 |
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