CN105603582A - High-strength continuous graphene fiber and preparing method thereof - Google Patents
High-strength continuous graphene fiber and preparing method thereof Download PDFInfo
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- CN105603582A CN105603582A CN201610056302.XA CN201610056302A CN105603582A CN 105603582 A CN105603582 A CN 105603582A CN 201610056302 A CN201610056302 A CN 201610056302A CN 105603582 A CN105603582 A CN 105603582A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 97
- 239000000835 fiber Substances 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000009987 spinning Methods 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 230000001112 coagulating effect Effects 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 229910002804 graphite Inorganic materials 0.000 claims description 17
- 239000010439 graphite Substances 0.000 claims description 17
- -1 graphite alkene Chemical class 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- 238000012545 processing Methods 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
- 239000001828 Gelatine Substances 0.000 claims description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 229920000159 gelatin Polymers 0.000 claims description 4
- 235000019322 gelatine Nutrition 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 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
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 229940071870 hydroiodic acid Drugs 0.000 claims description 3
- 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
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 239000002356 single layer Substances 0.000 claims 1
- 238000001132 ultrasonic dispersion Methods 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000003960 organic solvent Substances 0.000 abstract 2
- 239000011358 absorbing material Substances 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000004744 fabric Substances 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 abstract 1
- 239000012763 reinforcing filler Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 16
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000002166 wet spinning Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 241000446313 Lamella Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000002178 crystalline material Substances 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
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000011084 recovery Methods 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 high-strength continuous graphene fiber and a preparing method thereof. The preparing method includes the steps that firstly, graphene oxide is dispersed into a polarity organic solvent, and a spinning solution is prepared; secondly, the spinning solution is continuously extruded into a coagulating bath at a fixed speed from a spinning head capillary tube, and a solidified gel fiber is subjected to continuous traction stretching and drying treatment; finally, the mixture is collected to a graphene roll shaft, and the graphene oxide fiber is obtained; then the graphene fiber with the orientation degree up to 70%-80% and the density of 1.3-2 g /cm<3> is obtained through chemical reduction and heat treatment sequentially. The spinning technology is simple, and continuous preparation and collection of the graphene fiber are achieved through water or an organic solvent. The obtained graphene fiber has the excellent mechanical performance and the good electric conductivity. The continuous high-strength graphene fiber can be used for preparing graphene braided fabric, is used for the electromagnetic shielding field, the wave-absorbing material field and the like, can be used for a polymer composite material and serves as reinforcing filler.
Description
Technical field
The present invention relates to a kind of graphene fiber, relate in particular to a kind of high strength continuous graphite alkene fiber and system thereofPreparation Method.
Background technology
Graphene (graphene) is a kind of New Two Dimensional crystalline material being made up of single carbon atom layer, hasKnow the best mechanical property of material (fracture strength 125GPa, Young's modulus 1100GPa), and excellent(under room temperature, electron mobility can reach 2 × 10 to electric property5cm2/ Vs) and outstanding heat conductivility (5000W/mK), be called as magical material. AndreGeim and KonstantinNovoselov are because to graphiteThe contribution of alkene research has obtained Nobel prize for physics in 2010. From native graphite alkene, by oxidation legal systemFor graphene oxide, utilize the liquid crystal behavior of graphene oxide solution, in conjunction with wet spinning technology, realizeThe preparation (Nat.Commun.2011,2,571) of graphene fiber. The preparation of graphene fiber and functionalization thereof areThrough becoming the focus of current research. But the mechanical strength of current reported graphene fiber still comparesLow (500MPa), the space that still has greatly improved, can by the optimization of raw material and spinning technique,The methods such as post processing are prepared high-intensity graphene fiber.
Summary of the invention
The object of the invention is to overcome the deficiency of existing graphene fiber technology of preparing, provide a kind of high strength to connectContinuous graphene fiber and preparation method thereof.
The object of the invention is to be achieved through the following technical solutions: a kind of high strength continuous graphite alkene fiber,This fiber is formed along axial ordered arrangement by Graphene, and the degree of orientation is 70～80%, and density is 1.3～2g/cm3。
A preparation method for high strength continuous graphite alkene fiber, comprises the following steps:
(1) by the graphene oxide of 1 weight portion, the solvent of 10～100 weight portions, after ultrasonic dispersionTo graphene oxide dispersion liquid;
(2) graphene oxide dispersion liquid step (1) being obtained, under the vacuum of 0.001～0.1Pa,Degassed processing 10～60min, obtains graphene oxide spinning solution;
(3) graphene oxide spinning solution step (2) being obtained, with the extruded velocity of 1～100mL/h,The spinneret capillary that is 60～300 μ m by aperture enters coagulating bath, 10～60 DEG C solidify after extrudingIn bath, stop 5～60s, obtain gelatine silk; By gelatine silk successively through rotating speed be 50～100rpm/min andThe roll shaft of the continuous operation of 60～300rpm/min, and the rotating speed of second roll shaft rotating speed that is first roll shaft1.1～2.5 times, the infrared lamp that is simultaneously 20～200W with power is dry, collects and obtains continuous oxidation stoneChina ink alkene fiber;
(4) the graphene oxide fiber of gained in step (3) is placed in to reducing agent and reduces, washing is dry,Obtain continuous graphene fiber;
(5) graphene fiber of gained in step (4) is placed in to the tube furnace of 600～1300 DEG C, at gasHeat treatment 0.5～2h in atmosphere, obtains high strength continuous graphite alkene fiber.
Further, the solvent in described step (1) is mainly by water, methyl-sulfoxide, N, N-dimethyl formylOne or more in amine, DMA, 1-METHYLPYRROLIDONE, oxolane are according to appointingMeaning proportioning is mixed composition.
Further, the coagulating bath in described step (3) by methyl alcohol, ethanol, ethyl acetate, n-butanol,One or more in ethylene glycol, glycerine, butyl acetate, n-propyl acetate, acetic acid, acetone are according to appointingMeaning proportioning is mixed composition.
Further, the reducing agent in described step (4) is by hydrazine hydrate, sodium borohydride, hydrobromic acid, hydrogen iodineOne or more in acid, acetic acid, trifluoroacetic acid mix composition according to any proportioning.
Further, in described step (5), atmosphere used is a kind of or many in hydrogen, argon gas, nitrogenPlant according to any proportioning and mix composition.
Further, in described step (1), described graphene oxide is the list of radial dimension 10～20 μ mLayer graphene oxide.
The present invention has following technique effect:
1, the primary raw materials of graphene oxide is graphite, raw material sources extensively, be easy to get, with low cost;
2, adopt classical wet spinning technology to prepare graphene oxide fiber, easy and simple to handle;
3, in spinning process, adopt continuous traction drawing process, be conducive to the orientations of graphene oxide,The graphene oxide fiber making has good mechanical strength;
4, by electronation and heat treatment, part recovery the structure of Graphene, strengthened GrapheneInteraction force between lamella, the graphene fiber making has excellent mechanical strength, has excellence simultaneouslyElectric conductivity.
Brief description of the drawings
Fig. 1 is the schematic diagram of wet spinning device.
Detailed description of the invention
The invention provides a kind of high strength continuous graphite alkene fiber, this fiber by Graphene along axially in orderArrangement forms, and the degree of orientation is up to 70～80%, and density is 1.3～2g/cm3, the present invention also provides a kind of high strengthThe preparation method of continuous graphite alkene fiber, the method is 50～100rpm/min and 60～300 by rotating speedThe continuous traction of the roll shaft of the continuous operation of rpm/min stretches, and makes graphene oxide ordered arrangement vertically,Being dried of the auxiliary infrared lamp taking power as 20～200W, has partly recovered the structure of Graphene, has strengthenedInteraction force between graphene sheet layer; Realize graphene sheet layer tightly packed. First prepareThe diameter of graphene oxide fiber is 3～200 μ m, and hot strength is 300～600MPa, and elongation at break is0.3～10%. The diameter of the graphene fiber obtaining after reduction is 3～200 μ m, and hot strength is600～1000MPa, elongation at break is 0.1～10%, conductance is higher than 10000S/m.
Below in conjunction with drawings and Examples, the invention will be further described. The present embodiment is only for to thisBright being described further, can not be interpreted as limiting the scope of the invention, those skilled in the artMake some nonessential change and adjustment according to the content of foregoing invention, all belong to protection scope of the present invention.
It should be noted that, in the present invention, for the reducing agent of redox graphene, comprise hydrazine hydrate,Sodium borohydride, hydrobromic acid, hydroiodic acid, acetic acid, trifluoroacetic acid etc., its concentration range is the public affairs of this areaKnow general knowledge.
Embodiment 1:
(1) 1g graphene oxide and 10g deionized water are mixed, in 20 DEG C of ultrasonic processing with 50KHz1h, obtains graphene oxide dispersion liquid.
(2) use water circulating pump under the vacuum condition of 0.1Pa the graphene oxide dispersion liquid of (1) gained,Degassed 10min, obtains graphene oxide spinning solution.
(3) get the graphene oxide spinning solution of (2) gained, taking the extruded velocity of 10mL/h by internal diameter asThe spinneret capillary of 60 μ m stops 10s and becomes gelatinous fibre in the ethyl acetate coagulating bath of 25 DEG C, willGelatinous fibre is the roll shaft of the continuous operation of 55rpm/min and 60rpm/min through rotating speed successively, now rightThe draw ratio of answering is 1.1 (and the rotating speed of second roll shaft rotating speed that is first roll shaft 1.1 times), withIn time, is 20W with power infrared lamp is dry, collects and obtain continuous graphene oxide fiber;
(4) the graphene oxide fiber (3) being obtained is in 20% hydriodic acid aqueous solution at mass fraction,Be heated to 90 DEG C, fully reduce 12h, the dry graphene fiber that obtains of washing.
(5) graphene fiber (4) being obtained is processed 0.5h in 700 DEG C of tube furnaces of applying argon gas atmosphere,Obtain high strength continuous graphite alkene fiber.
Through above step, obtain the graphene oxide spinning solution of stable homogeneous, graphene oxide spinning solution toolThere is good Shear Flow, under petrographic microscope, can see obvious liquid crystal stripe texture. Be prepared intoTo the diameter of fiber be 20～30 μ m, graphene film is along the axially-aligned of fiber. The graphene oxide of preparationTensile strength of fiber is 300～600MPa, and elongation at break is 1～3%, has good compliance simultaneously. AlsoThe high strength graphite alkene tensile strength of fiber of former formation is 600～700MPa, and elongation at break is 8～10%,Conductance is greater than 10000S/m.
Embodiment 2:
(1) by 0.5g graphene oxide and 20gN, N-dimethylacetylamide mix, in 25 DEG C with 60KHzUltrasonic processing 2h, obtain graphene oxide dispersion liquid.
(2) use water circulating pump under the vacuum condition of 0.01Pa the graphene oxide dispersion liquid of (1) gained,Degassed 30min, obtains graphene oxide spinning solution.
(3) get the graphene oxide spinning solution of (2) gained, taking the extruded velocity of 40mL/h by internal diameter asThe spinneret capillary of 130 μ m stops 60s and becomes gelatinous fibre in the acetone coagulating bath of 25 DEG C, will coagulateGlue fiber is the roll shaft of the continuous operation of 200rpm/min and 300rpm/min through rotating speed successively, now rightThe draw ratio of answering is 1.5, and the infrared lamp that is simultaneously 200W with power is dry, collects and obtains continuous oxidation stoneChina ink alkene fiber; .
(4) it is 35% hydrazine hydrate that the graphene oxide fiber (3) being obtained is placed in mass fraction, addsHeat, to 90 DEG C, is fully reduced 1h, the dry graphene fiber that obtains of washing.
(5) graphene fiber (4) being obtained, in hydrogen-argon-mixed atmosphere, processes 2h, obtains for 600 DEG CHigh strength continuous graphite alkene fiber.
Through above step, obtain the graphene oxide spinning solution of stable homogeneous, graphene oxide spinning solution toolThere is good Shear Flow, under petrographic microscope, can see obvious liquid crystal stripe texture. Be prepared intoTo the diameter of fiber be 20～30 μ m, graphene film is along the axially-aligned of fiber. The graphene oxide of preparationTensile strength of fiber is 300～600MPa, and elongation at break is 1～2%, has good toughness simultaneously. ReductionThe graphene fiber hot strength forming is 700～800MPa, and elongation at break is 7～8%, and conductance is greater than10000S/m.
Embodiment 3
(1) DMF of 2g graphene oxide and 100g is mixed, in 20 DEG C with 60KHzUltrasonic processing 2h, obtain graphene oxide dispersion liquid.
(2) use water circulating pump under the vacuum condition of 0.001Pa the graphene oxide dispersion liquid of (1) gained,Degassed 1h, obtains graphene oxide spinning solution.
(3) get the graphene oxide spinning solution of (2) gained, taking the extruded velocity of 0mL/h by internal diameter asThe spinneret capillary of 200 μ m, bathes (both volume ratios admittedly in the mixing of the ethyl acetate of 25 DEG C and acetoneFor 1:1) in stop 10s become gelatinous fibre; By gelatinous fibre successively through rotating speed be 100rpm/min andThe roll shaft of the continuous operation of 250rpm/min, now corresponding draw ratio is 2.5, is 100W with power simultaneouslyInfrared lamp dry, collect and obtain continuous graphene oxide fiber.
(4) the graphene oxide fiber (3) being obtained is placed in the mixed solution of hydroiodic acid and acetic acid, addsHeat, to 90 DEG C, is fully reduced 12h, the dry graphene fiber that obtains of washing.
(5) graphene fiber (4) being obtained, in hydrogen-argon-mixed atmosphere, processes 0.5h for 1300 DEG C,Obtain high strength continuous graphite alkene fiber.
Through above step, obtain the graphene oxide spinning solution of stable homogeneous, graphene oxide spinning solution toolThere is good Shear Flow, under petrographic microscope, can see obvious liquid crystal stripe texture. Be prepared intoTo the diameter of fiber be 20～60 μ m, graphene film is along the axially-aligned of fiber. The graphene oxide of preparationTensile strength of fiber is 500～600MPa, and elongation at break is 8～10%, has good toughness simultaneously. AlsoThe graphene fiber hot strength of former formation is 800～1000MPa, and elongation at break is 1～2%, conductanceBe greater than 10000S/m.
It should be noted that: the selected rotating speed of the present invention is optimized rotating speed, i.e. optimum draw ratio, if twoIndividual roll shaft rotating speed does not regulate, and the fiber mechanics strength ratio of preparation is lower so, or can not continuous production.
In embodiment 1, if the roll shaft rotating speed of continuous operation is all 45rpm/min, draw ratio is 1, itsHis condition is constant, and the intensity of so prepared fiber only has 100～200MPa. In embodiment 2, if connectedThe roll shaft rotating speed that reforwarding turns is respectively 250rpm/min and 300rpm/min, and draw ratio is 1.2, otherPart is constant, and the intensity of so prepared fiber only has 250～350MPa. In embodiment 3, if transported continuouslyThe roll shaft rotating speed turning is respectively 100rpm/min and 200rpm/min, and draw ratio is 2.0, and other conditions are notBecome, the intensity of so prepared fiber only has 300～450MPa.
Above-described embodiment is used for the present invention that explains, instead of limits the invention, of the present inventionIn the protection domain of spirit and claim, any amendment and change that the present invention is made, all fall into thisBright protection domain.
Claims (7)
1. a high strength continuous graphite alkene fiber, is characterized in that, this fiber is formed along axial ordered arrangement by Graphene, and the degree of orientation is 70～80%, and density is 1.3～2g/cm3, km level preparation continuously.
2. a preparation method for high strength continuous graphite alkene fiber, is characterized in that, comprises the following steps:
(1), by the graphene oxide of 1 weight portion, the solvent of 10～100 weight portions, obtains graphene oxide dispersion liquid after ultrasonic dispersion;
(2) graphene oxide dispersion liquid step (1) being obtained, under the vacuum of 0.001～0.1Pa left and right, degassed processing 10～60min, obtains graphene oxide spinning solution.
(3) graphene oxide spinning solution step (2) being obtained, with the extruded velocity of 1～100mL/h, the spinneret capillary that is 60～300 μ m by aperture enters coagulating bath after extruding, in the coagulating bath of 10～60 DEG C, stop 5～60s, obtain gelatine silk; Be the roll shaft of the continuous operation of 50～100rpm/min and 60～300rpm/min through rotating speed successively by gelatine silk, and 1.1～2.5 times of the rotating speed that the rotating speed of second roll shaft is first roll shaft, the infrared lamp that is simultaneously 20～200W with power is dry, collects and obtains continuous graphene oxide fiber.
(4) the graphene oxide fiber of gained in step (3) is placed in to reducing agent and reduces, washing is dry, just can obtain continuous graphene fiber.
(5) graphene fiber of gained in step (4) is placed in to the tube furnace of 600～1300 DEG C, heat treatment 0.5～2h in atmosphere, obtains high strength continuous graphite alkene fiber.
3. method according to claim 2, it is characterized in that, solvent in described step (1) is by water, methyl-sulfoxide, N, one or more in dinethylformamide, DMA, 1-METHYLPYRROLIDONE, oxolane etc. mix composition according to any proportioning.
4. method according to claim 2, it is characterized in that, the coagulating bath in described step (3) is mixed and forms according to any proportioning by one or more in methyl alcohol, ethanol, ethyl acetate, n-butanol, ethylene glycol, glycerine, butyl acetate, n-propyl acetate, acetic acid, acetone.
5. method according to claim 2, is characterized in that, the reducing agent in described step (4) is mixed and forms according to any proportioning by one or more in hydrazine hydrate, sodium borohydride, hydrobromic acid, hydroiodic acid, acetic acid, trifluoroacetic acid etc.
6. method according to claim 2, is characterized in that, in described step (5), atmosphere used is that one or more in hydrogen, argon gas, nitrogen mix composition according to any proportioning.
7. method according to claim 2, is characterized in that, in described step (1), described graphene oxide is the mono-layer graphite oxide alkene of radial dimension 10～20 μ m.
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| CN201610056302.XA CN105603582B (en) | 2016-01-27 | 2016-01-27 | A kind of high intensity continuous graphite alkene fiber and preparation method thereof |
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| CN201610056302.XA CN105603582B (en) | 2016-01-27 | 2016-01-27 | A kind of high intensity continuous graphite alkene fiber and preparation method thereof |
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