CN105544017B - A kind of highly conductive graphene fiber and preparation method thereof - Google Patents
A kind of highly conductive graphene fiber and preparation method thereof Download PDFInfo
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- CN105544017B CN105544017B CN201610054970.9A CN201610054970A CN105544017B CN 105544017 B CN105544017 B CN 105544017B CN 201610054970 A CN201610054970 A CN 201610054970A CN 105544017 B CN105544017 B CN 105544017B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 143
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 133
- 239000000835 fiber Substances 0.000 title claims abstract description 97
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000009987 spinning Methods 0.000 claims abstract description 21
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 11
- 239000010439 graphite Substances 0.000 claims abstract description 11
- 238000012545 processing Methods 0.000 claims abstract description 6
- 230000001112 coagulating effect Effects 0.000 claims abstract description 5
- 238000007711 solidification Methods 0.000 claims abstract description 3
- 230000008023 solidification Effects 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 239000011591 potassium Substances 0.000 claims description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 239000002019 doping agent Substances 0.000 claims description 6
- 229940071870 hydroiodic acid Drugs 0.000 claims description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 238000005660 chlorination reaction Methods 0.000 claims description 5
- 239000011630 iodine Substances 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 5
- 239000010410 layer Substances 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
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 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
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- NNYBQONXHNTVIJ-UHFFFAOYSA-N etodolac Chemical compound C1COC(CC)(CC(O)=O)C2=C1C(C=CC=C1CC)=C1N2 NNYBQONXHNTVIJ-UHFFFAOYSA-N 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- 229940063718 lodine Drugs 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 230000031709 bromination Effects 0.000 claims description 2
- 238000005893 bromination reaction Methods 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- -1 graphite Alkene Chemical class 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
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum 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
- 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
- 230000005611 electricity Effects 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 238000002166 wet spinning Methods 0.000 abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 2
- 239000010949 copper Substances 0.000 abstract description 2
- 230000005540 biological transmission Effects 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- 239000010453 quartz Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000003708 ampul Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 5
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000138 intercalating agent Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 208000002925 dental caries Diseases 0.000 description 1
- 238000011161 development Methods 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
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Classifications
-
- 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
- D01F11/127—Metals
Abstract
The invention discloses a kind of highly conductive graphene fiber and preparation method thereof, using wet spinning technology, the graphene oxide spinning solution that mass fraction is 1~10% is squeezed into coagulating bath from spinneret and obtains graphene oxide gel fiber, fully after solidification, it is collected on graphite roller bearing, obtains graphene oxide fiber.Electronation, high-temperature heat treatment processing and chemical doping are sequentially passed through again, and prepared graphene fiber has very high conductance, and the conductance than general graphene fiber is higher by an order of magnitude.Whole process technique is simply controllable, realizes the lifting of graphene fiber electric conductivity.Resulting graphene fiber has very excellent mechanical property and excellent electrical and thermal conductivity performance.This highly conductive graphene fiber can be used for preparing flexible solar battery, ultracapacitor, wearable device；For ultralight electric wire, substituted metal copper cash can be expected to, for power transmission of new generation as lightweight wire.
Description
Technical field
The present invention relates to a kind of graphene fiber, more particularly to a kind of highly conductive graphene 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, and graphene is single carbon
Atomic layer graphite, it has a series of superior functions beyond imagination.Such as, highest mechanical property, modulus is 1.1TPa, intensity
For 180GPa；Highest carrier transport speed, up to 150000cm2/ Vs, is 100 times of monocrystalline silicon；Highest thermal conductivity
5000W/mK, is more than 10 times of copper；Highest electrical conductivity (108S/m) and superelevation current loading density.Go out from native graphite
Hair, graphene oxide is prepared by oxidizing process, using the liquid crystal behavior of graphene oxide solution, real with reference to wet spinning technology
The preparation (Nat.Commun.2011,2,571) of graphene fiber is showed.The preparation of graphene fiber and its functionalization into
There is good development prospect for the focus of current research, especially graphene fiber as lightweight wire.But, reported at present
The electric conductivity of the graphene fiber in road is unsatisfactory, and conductance is only 10000S/m, it is difficult to meet actual application demand.Can
With by optimizing spinning technique, the technology such as follow-up high-temperature heat treatment, chemical doping prepare the excellent graphene of electric conductivity
Fiber.
The content of the invention
The purpose of the present invention is to overcome the shortcomings of that existing graphene fiber technology of preparing is fine there is provided a kind of highly conductive graphene
Dimension and preparation method thereof.
The purpose of the present invention is achieved through the following technical solutions：A kind of highly conductive graphene fiber, the fiber by
Axially ordered arrangement is formed graphene, graphene layer spacing about 0.3~0.4nm, has bromine, iodine, bromine between graphene sheet layer
Change the dopants such as iodine, lodine chloride, potassium, calcium, iron chloride, molybdenum chloride, aluminium chloride or copper chloride, the quality of dopant is graphene matter
The 10~30% of amount；The degree of orientation of graphene fiber is 80~90%.
A kind of preparation method of highly conductive graphene fiber, comprises the following steps：
(1) by the graphene oxide of 1 parts by weight, the solvent of 10~100 parts by weight is mixed, and obtains aoxidizing stone after ultrasonic disperse
Black alkene spinning solution；
(2) the graphene oxide spinning solution for obtaining step (1), with 1~100mL/h extruded velocity, be by aperture
30~300 μm of spinneret, stops 5~60s or so in 10~50 DEG C of coagulating bath, and collection obtains continuous graphene oxide
Fiber；
(3) the graphene oxide fiber of gained in step (2) is placed in reducing agent and reduced, washed drying, obtain primary
Graphene fiber；
(4) the primary graphene fiber of gained in step (3) is placed in 1000~3000 DEG C of graphite furnace, in atmosphere
1~4h is heat-treated, high-quality graphene fiber is obtained.
(5) high-quality graphene fiber resulting in step (4) is placed in 1~24h of processing in dopant steam, obtained
Highly conductive graphene fiber.
Further, in the step (1) solvent is main by dimethyl sulfoxide, DMF, N, N- diformazans
It is one or more kinds of according to any proportioning mixing composition in yl acetamide, 1-METHYLPYRROLIDONE, tetrahydrofuran.
Further, in the step (2) solidification liquid it is main by methanol, ethanol, ethyl acetate, n-butanol, ethylene glycol,
It is one or more according to any proportioning mixing composition in butyl acetate, n-propyl acetate, acetic acid, acetone.
Further, in the step (3) reducing agent is main by hydrazine hydrate, hydrobromic acid, hydroiodic acid, acetic acid, trifluoro second
It is one or more according to any proportioning mixing composition in acid.
Further, atmosphere used in the step (4) is one or more according to appointing in hydrogen, argon gas, nitrogen
Meaning proportioning mixing composition.
Further, dopant steam is bromine vapor, iodine vapor, bromination iodine steam, lodine chloride steaming in the step (5)
The metal chloride steam such as vapour, potassium steam, calcium steam, iron chloride steam, molybdenum chloride steam, aluminium chloride vapour, copper chloride steam.
Further, in the step (1), the graphene oxide is the mono-layer graphite oxide of 15~35 μm of radial dimension
Alkene.
The present invention has following technique effect：
1st, the primary raw materials of graphene oxide be graphite, raw material sources extensively, be easy to get, it is with low cost；
2nd, graphene oxide fiber is prepared for using wet spinning technology, it is easy to operate；
3rd, by electronation and high-temperature heat treatment, the perfect structure of graphene has been recovered, gained graphene fiber has
Good electric conductivity and mechanical property.
4. being handled by chemical doping, the conductance of graphene fiber has the lifting of the order of magnitude.
Brief description of the drawings
Fig. 1 is the quartz ampoule schematic diagram for doing intercalation；
Fig. 2 is the I-V curve of graphene fiber before and after doping.
Embodiment
The conductance of graphene fiber is brought up to 1 × 10 by the present invention by chemical doping6More than S/m, than general stone
The conductance of black alkene fiber is higher by an order of magnitude.Whole process technique is simply controllable, realizes graphene fiber electric conductivity
Lifting.Resulting graphene fiber has very excellent mechanical property and excellent electrical and thermal conductivity performance.
It should be noted that in the present invention, intercalation steam treatment mode is specially：Intercalator and high-quality graphene is fine
Dimension is respectively placed in double end quartz container, then quartz container is heated, vacuumize process so that intercalator is by thermosetting
Steam, intercalation is realized by vapor form；The double end quartz container is to include the quartz ampoule of two spherical cavitys.
In addition, 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.
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.
Embodiment 1：
(1) 1g graphene oxides and 50g DMAs are mixed, in 25 DEG C with the ultrasonically treated of 70KHz
1h, obtains graphene oxide spinning solution.
(2) take the graphene oxide spinning solution obtained by step (1), using 10mL/h extruded velocity by internal diameter as 200 μm
Spinneret, fully solidified in 25 DEG C of ethyl acetate coagulating bath, then sequentially pass through collection and drying process, obtain aoxidize stone
Black alkene fiber.
(3) the graphene oxide fiber for obtaining step (2) is placed in mass fraction in 37% hydriodic acid aqueous solution, in 90
Reductase 12 4h at DEG C, washing is dried to obtain primary graphene fiber.
(4) the primary graphene fiber for obtaining step (3), in argon gas atmosphere, in handling 2h at 1000 DEG C, obtains height
Quality graphene fiber.
(5) the high-quality graphene fiber for obtaining step (4) is placed in quartz ampoule, and 12h is handled in bromine vapor, is obtained
The highly conductive graphene fiber of bromine doping.
By above step, the graphene oxide spinning solution of stable homogeneous is obtained, it can be seen that liquid under petrographic microscope
Brilliant stripe texture.A diameter of 10~150 μm of the highly conductive graphene fiber of the bromine doping prepared, elongation at break is 1
~10%, tensile strength is 300~600MPa, and conductance is more than 1000000S/m.
Embodiment 2：
(1) 1g graphene oxides and 100g dimethyl sulfoxides are mixed, in 20 DEG C of ultrasonically treated 1h with 40KHz, obtains oxygen
Graphite alkene spinning solution.
(2) take the graphene oxide spinning solution obtained by step (1), using 1mL/h extruded velocity by internal diameter as 80 μm
Spinneret, in 25 DEG C of n-butanols and ethylene glycol according to volume ratio 1:Fully solidified in the coagulating bath of 1 composition, obtain graphite oxide
Alkene fiber.
(3) the graphene oxide fiber for obtaining step (2) is placed in the hydrazine hydrate that mass fraction is 10%, at 90 DEG C
12h is reduced, washing is dried to obtain primary graphene fiber.
(4) the primary graphene fiber for obtaining step (3), in argon gas atmosphere, in handling 1.5h at 2000 DEG C, is obtained
High-quality graphene fiber.
(5) the high-quality graphene fiber for obtaining step (4) is placed in quartz ampoule, and 24h is handled in iron chloride steam,
Obtain the highly conductive graphene fiber of chlorination Fe2O3 doping.
By above step, the graphene oxide spinning solution of stable homogeneous is obtained, it can be seen that liquid under petrographic microscope
Brilliant stripe texture.A diameter of 30~100 μm of the highly conductive graphene fiber of the chlorination Fe2O3 doping prepared, elongation at break
For 1~10%, tensile strength is 300~600MPa, and conductance is more than 1000000S/m.
Embodiment 3
(1) 2g graphene oxides and 20g DMAs are mixed, in 30 DEG C with the ultrasonically treated of 40KHz
2h, obtains graphene oxide spinning solution.
(2) take the graphene oxide spinning solution obtained by step (1), using 100mL/h extruded velocity by internal diameter as 300 μm
Spinneret, in 25 DEG C of acetone are bathed admittedly stop 1min become gelatinous fibre, obtain graphene oxide fiber.
(3) the graphene oxide fiber for obtaining step (2) is placed in the mixed solvent of hydroiodic acid and trifluoroacetic acid, is heated
To 90 DEG C, 1h is reduced, washing is dried to obtain primary graphene fiber.
(4) the primary graphene fiber for obtaining step (3), in argon gas atmosphere, 3000 DEG C of processing 1h obtain high-quality
Graphene fiber.
(5) the high-quality graphene fiber for obtaining step (4) is placed in quartz ampoule, under vacuum, uses metallic potassium
Steam treatment 1h, obtains the highly conductive graphene fiber of potassium doping.
By above step, the graphene oxide spinning solution of stable homogeneous is obtained, it can be seen that bright under petrographic microscope
Aobvious liquid crystal stripe texture.A diameter of 30~30 μm of the highly conductive graphene fiber of potassium doping prepared, 500~
800MPa, elongation at break is 1~10%, and conductance is better than 1000000S/m.
Embodiment 4
(1) 2g graphene oxides and 20g DMFs are mixed, in 30 DEG C with the ultrasonically treated of 40KHz
2h, obtains graphene oxide spinning solution.
(2) take the graphene oxide spinning solution obtained by step (1), using 100mL/h extruded velocity by internal diameter as 150 μm
Spinneret, in 25 DEG C of ethyl acetate are bathed admittedly stop 1min become gelatinous fibre, obtain graphene oxide fiber.
(3) the graphene oxide fiber for obtaining step (2) is placed in the mixed solvent of hydroiodic acid and trifluoroacetic acid, is heated
To 90 DEG C, 1h is reduced, washing is dried to obtain primary graphene fiber.
(4) the primary graphene fiber for obtaining step (3), in argon gas atmosphere, 3000 DEG C of processing 1h obtain high-quality
Graphene fiber.
(5) the high-quality graphene fiber for obtaining step (4) is placed in quartz ampoule, under vacuum, uses aluminium chloride
Steam treatment 1h, obtains the highly conductive graphene fiber of aluminium chloride doping.
By above step, the graphene oxide spinning solution of stable homogeneous is obtained, it can be seen that bright under petrographic microscope
Aobvious liquid crystal stripe texture.A diameter of 30~30 μm of the highly conductive graphene fiber of potassium doping prepared, 500~
800MPa, elongation at break is 1~10%, and conductance is better than 1000000S/m.
Embodiment 5
(1) 2g graphene oxides and 20g DMAs are mixed, in 30 DEG C with the ultrasonically treated of 40KHz
2h, obtains graphene oxide spinning solution.
(2) take the graphene oxide spinning solution obtained by step (1), using 100mL/h extruded velocity by internal diameter as 300 μm
Spinneret, in 25 DEG C of acetone are bathed admittedly stop 1min become gelatinous fibre, obtain graphene oxide fiber.
(3) the graphene oxide fiber for obtaining step (2) is placed in the mixed solvent of hydroiodic acid and trifluoroacetic acid, is heated
To 90 DEG C, 1h is reduced, washing is dried to obtain primary graphene fiber.
(4) the primary graphene fiber for obtaining step (3), in argon gas atmosphere, 3000 DEG C of processing 1h obtain high-quality
Graphene fiber.
(5) the high-quality graphene fiber for obtaining step (4) is placed in quartz ampoule, under vacuum, uses molybdenum chloride
Steam treatment 1h, obtains the highly conductive graphene fiber of chlorination molybdenum doping.
By above step, the graphene oxide spinning solution of stable homogeneous is obtained, it can be seen that bright under petrographic microscope
Aobvious liquid crystal stripe texture.A diameter of 30~30 μm of the highly conductive graphene fiber of potassium doping prepared, 500~
800MPa, elongation at break is 1~10%, and conductance is better than 1000000S/m.
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, any modifications and changes made to the present invention both fall within protection scope of the present invention.
Claims (8)
1. a kind of highly conductive graphene fiber, it is characterised in that axially ordered arrangement is formed the fiber by graphene, graphite
Doped with bromine, iodine, IBr, lodine chloride, potassium, calcium, iron chloride, chlorination between alkene 0.3 ~ 0.4nm of interlamellar spacing, graphene sheet layer
Molybdenum, aluminium chloride or copper chloride, the quality of dopant are the 10 ~ 30% of graphene quality；The degree of orientation of graphene fiber be 80 ~
90%。
2. the preparation method of the highly conductive graphene fiber described in a kind of claim 1, 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
Spinning solution；
（2）By step（1）Obtained graphene oxide spinning solution, with 1 ~ 100 mL/h extruded velocity, by aperture be 30 ~
300 μm of spinneret, stops 5 ~ 60s in 10 ~ 50 DEG C of coagulating bath, and collection obtains continuous graphene oxide fiber；
（3）By step（2）The graphene oxide fiber of middle gained is placed in reducing agent and reduced, and washs drying, obtains primary graphite
Alkene fiber；
（4）By step（3）The primary graphene fiber of middle gained is placed in 1000 ~ 3000 DEG C of graphite furnace, in atmosphere at heat
1 ~ 4h is managed, high-quality graphene fiber is obtained；
（5）By step（4）In obtained by high-quality graphene fiber be placed in dopant steam 1 ~ 24h of processing, obtain height and lead
The graphene fiber of electricity.
3. the preparation method of highly conductive graphene fiber according to claim 2, it is characterised in that the step（1）In
Solvent is by dimethyl sulfoxide, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, 1-METHYLPYRROLIDONE, tetrahydrofuran
It is one or more kinds of to be constituted according to any proportioning mixing.
4. the preparation method of highly conductive graphene fiber according to claim 2, it is characterised in that the step（2）In
Solidification liquid is main by methanol, ethanol, ethyl acetate, n-butanol, ethylene glycol, butyl acetate, n-propyl acetate, acetic acid, acetone
It is one or more according to any proportioning mixing composition.
5. the preparation method of highly conductive graphene fiber according to claim 2, it is characterised in that the step（3）In
Reducing agent is made up of the one or more in hydrazine hydrate, hydrobromic acid, hydroiodic acid, acetic acid, trifluoroacetic acid according to any proportioning mixing.
6. the preparation method of highly conductive graphene fiber according to claim 2, it is characterised in that the step（4）Middle institute
Atmosphere is that one or more mixed according to any proportioning in hydrogen, argon gas, nitrogen constitutes.
7. the preparation method of highly conductive graphene fiber according to claim 2, it is characterised in that the step（5）In mix
Miscellaneous dose of steam is bromine vapor, iodine vapor, bromination iodine steam, chlorination iodine steam, potassium steam, calcium steam, iron chloride steam, molybdenum chloride
Steam, aluminium chloride vapour, copper chloride steam.
8. the preparation method of highly conductive graphene fiber according to claim 2, it is characterised in that the step（1）In, institute
State the single-layer graphene oxide that graphene oxide is 15 ~ 35 μm of radial dimension.
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