CN105544017A - High-conductivity graphene fiber and preparation method thereof - Google Patents
High-conductivity graphene fiber and preparation method thereof Download PDFInfo
- Publication number
- CN105544017A CN105544017A CN201610054970.9A CN201610054970A CN105544017A CN 105544017 A CN105544017 A CN 105544017A CN 201610054970 A CN201610054970 A CN 201610054970A CN 105544017 A CN105544017 A CN 105544017A
- Authority
- CN
- China
- Prior art keywords
- graphene
- fiber
- graphene fiber
- steam
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 151
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 145
- 239000000835 fiber Substances 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000009987 spinning Methods 0.000 claims abstract description 22
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 6
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 6
- 239000010439 graphite Substances 0.000 claims abstract description 6
- 230000001112 coagulating effect Effects 0.000 claims abstract description 5
- 239000007788 liquid Substances 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
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-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
- 238000002156 mixing Methods 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 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
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052794 bromium 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
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 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
- 229940071870 hydroiodic acid Drugs 0.000 claims description 6
- 239000010410 layer Substances 0.000 claims description 6
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-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
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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 class Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- NNYBQONXHNTVIJ-UHFFFAOYSA-N etodolac Chemical compound C1COC(CC)(CC(O)=O)C2=C1C(C=CC=C1CC)=C1N2 NNYBQONXHNTVIJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 229940063718 lodine 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
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 3
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- 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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-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
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 229910001510 metal chloride Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000002356 single layer Substances 0.000 claims description 2
- 238000007711 solidification Methods 0.000 claims description 2
- 230000008023 solidification Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 20
- 239000000126 substance Substances 0.000 abstract description 4
- 238000002166 wet spinning Methods 0.000 abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 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
- 238000006722 reduction reaction Methods 0.000 abstract 1
- 238000005096 rolling process Methods 0.000 abstract 1
- 238000007669 thermal treatment Methods 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
- 238000001035 drying Methods 0.000 description 6
- 239000004973 liquid crystal related substance Substances 0.000 description 6
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000000138 intercalating agent Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 208000002925 dental caries Diseases 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
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 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 high-conductivity graphene fiber and a preparation method thereof. By the adoption of the wet spinning technology, oxidized graphene spinning liquid with the mass percentage being 1-10% is extruded from a spinning head into a coagulating bath to obtain an oxidized graphene gel fiber, the oxidized graphene gel fiber is collected on a graphite rolling shaft after being fully solidified, the oxidized graphene fiber is obtained, and the oxidized graphene fiber is sequentially subjected to chemical reduction, high-temperature thermal treatment and chemical doping. The prepared graphene fiber has high conductivity, and the conductivity of the prepared graphene fiber is one magnitude order higher than that of a common graphene fiber. The whole process is simple and controllable in technology, and conductivity of the graphene fiber is improved. The obtained graphene fiber has excellent mechanical property and excellent electrical conductivity and thermal conductivity. The high-conductivity graphene fiber can be used for preparing soft solar batteries, supercapacitors and wearable devices and can serve as a light wire to be used in ultra-light wires and cables, and it is hopeful to replace a metal copper wire with the graphene fiber for new-generation power transmission.
Description
Technical field
The present invention relates to a kind of graphene fiber, particularly relate to a kind of high connductivity graphene fiber and preparation method thereof.
Background technology
Graphene (graphene) is a kind of New Two Dimensional crystalline material be made up of single carbon atom layer, and Graphene and single carbon atom layer graphite, it has a series of superior function beyond imagination.As, the highest mechanical property, modulus is 1.1TPa, and intensity is 180GPa; The highest carrier transport speed, up to 150000cm
2/ Vs is 100 times of monocrystalline silicon; The highest thermal conductivity 5000W/mK is more than 10 times of copper; The highest electrical conductivity (10
8and the current loading density of superelevation S/m).From native graphite, prepare graphene oxide by oxidizing process, utilize the liquid crystal behavior of graphene oxide solution, in conjunction with wet spinning technology, achieve the preparation (Nat.Commun.2011,2,571) of graphene fiber.The preparation of graphene fiber and functionalization thereof have become the focus of current research, and especially graphene fiber has good development prospect as lightweight wire.But the electric conductivity of current reported graphene fiber is unsatisfactory, and conductance is only 10000S/m, be difficult to meet actual application demand.The graphene fiber of electric conductivity excellence can be prepared by optimizing the technology such as spinning technique, follow-up high-temperature heat treatment, chemical doping.
Summary of the invention
The object of the invention is the deficiency overcoming existing graphene fiber technology of preparing, a kind of high connductivity graphene fiber and preparation method thereof is provided.
The object of the invention is to be achieved through the following technical solutions: a kind of high connductivity graphene fiber, this fiber by Graphene axially ordered arrangement form, graphene layer spacing about 0.3 ~ 0.4nm, have the adulterants such as bromine, iodine, IBr, lodine chloride, potassium, calcium, iron chloride, molybdenum chloride, aluminium chloride or copper chloride between graphene sheet layer, the quality of adulterant is 10 ~ 30% of Graphene quality; The degree of orientation of graphene fiber is 80 ~ 90%.
A preparation method for high connductivity graphene fiber, comprises the following steps:
(1) by the graphene oxide of 1 weight portion, the solvent of 10 ~ 100 weight portions, obtains graphene oxide spinning solution after ultrasonic disperse;
(2) by graphene oxide spinning solution that step (1) obtains, with the extruded velocity of 1 ~ 100mL/h, by the spinneret that aperture is 30 ~ 300 μm, in the coagulating bath of 10 ~ 50 DEG C, stop about 5 ~ 60s, collect and obtain continuous print graphene oxide fiber;
(3) the graphene oxide fiber of gained in step (2) is placed in reductant to reduce, washing is dry, obtains elementary graphene fiber;
(4) the elementary graphene fiber of gained in step (3) is placed in the graphite furnace of 1000 ~ 3000 DEG C, heat treatment 1 ~ 4h in atmosphere, obtains high-quality graphene fiber.
(5) the high-quality graphene fiber obtained in step (4) is placed in adulterant steam process 1 ~ 24h, obtains the graphene fiber of high connductivity.
Further, the solvent in described step (1) forms according to any proportioning mixing primarily of one or more in methyl-sulfoxide, DMF, DMA, 1-METHYLPYRROLIDONE, oxolane.
Further, the solidification liquid in described step (2) forms according to any proportioning mixing primarily of one or more in methyl alcohol, ethanol, ethyl acetate, n-butanol, ethylene glycol, butyl acetate, n-propyl acetate, acetic acid, acetone.
Further, the reductant in described step (3) forms according to any proportioning mixing primarily of one or more in hydrazine hydrate, hydrobromic acid, hydroiodic acid, acetic acid, trifluoroacetic acid.
Further, in described step (4), atmosphere used is that one or more in hydrogen, argon gas, nitrogen are according to any proportioning mixing composition.
Further, in described step (5), adulterant steam is the metal chloride steam such as bromine vapor, iodine vapor, IBr steam, lodine chloride steam, potassium steam, calcium steam, iron chloride steam, molybdenum chloride steam, aluminium chloride vapour, copper chloride steam.
Further, in described step (1), described graphene oxide is the single-layer graphene oxide of radial dimension 15 ~ 35 μm.
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, wet spinning technology is adopted to prepare graphene oxide fiber, easy and simple to handle;
3, by electronation and high-temperature heat treatment, recovered the perfect structure of Graphene, gained graphene fiber has good electric conductivity and mechanical property.
4., by chemical doping process, the conductance of graphene fiber has the lifting of the order of magnitude.
Accompanying drawing explanation
Fig. 1 is the quartz ampoule schematic diagram doing intercalation;
Fig. 2 is the I-V curve of graphene fiber before and after doping.
Detailed description of the invention
The conductance of graphene fiber, by chemical doping, is brought up to 1 × 10 by the present invention
6more than S/m, exceeds an order of magnitude than the conductance of general graphene fiber.Whole process is simply controlled, achieves the lifting of graphene fiber electric conductivity.The graphene fiber obtained 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 fiber are placed in double end quartz container respectively, then heat quartz container, vacuumize process, make intercalator be subject to thermosetting steam, realize intercalation by vapor form; Described double end quartz container is the quartz ampoule comprising two spherical cavitys.
In addition, in the present invention, for the reductant of redox graphene, comprise hydrazine hydrate, sodium borohydride, hydrobromic acid, hydroiodic acid, acetic acid, trifluoroacetic acid etc., its concentration range is the common practise of this area.
Below in conjunction with drawings and Examples, the invention will be further described.The present embodiment is only for the present invention is described further, and can not be 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, all belongs to protection scope of the present invention.
Embodiment 1:
(1) by 1g graphene oxide and the mixing of 50gN, N-dimethylacetylamide, in 25 DEG C with the ultrasonic process 1h of 70KHz, graphene oxide spinning solution is obtained.
(2) the graphene oxide spinning solution of step (1) gained is got, be the spinneret of 200 μm by internal diameter with the extruded velocity of 10mL/h, fully solidify in the ethyl acetate coagulating bath of 25 DEG C, more successively through collecting and dry process, obtain graphene oxide fiber.
(3) the graphene oxide fiber that step (2) obtains being placed in mass fraction is 37% hydriodic acid aqueous solution, reductase 12 4h at 90 DEG C, and washing drying obtains elementary graphene fiber.
(4) by the elementary graphene fiber that step (3) obtains, in argon gas atmosphere, at 1000 DEG C, process 2h, obtain high-quality graphene fiber.
(5) the high-quality graphene fiber that step (4) obtains is placed in quartz ampoule, in bromine vapor, processes 12h, obtain the high connductivity graphene fiber of bromine doping.
Through above step, obtain the graphene oxide spinning solution of stable homogeneous, liquid crystal stripe texture can be seen under petrographic microscope.The diameter of the high connductivity graphene fiber of the bromine doping prepared is 10 ~ 150 μm, and elongation at break is 1 ~ 10%, and TENSILE STRENGTH is 300 ~ 600MPa, and conductance is greater than 1000000S/m.
Embodiment 2:
(1) by 1g graphene oxide and the mixing of 100g methyl-sulfoxide, in 20 DEG C with the ultrasonic process 1h of 40KHz, graphene oxide spinning solution is obtained.
(2) the graphene oxide spinning solution of step (1) gained is got, be the spinneret of 80 μm by internal diameter with the extruded velocity of 1mL/h, fully solidify in the coagulating bath that the n-butanols of 25 DEG C and ethylene glycol form according to volume ratio 1:1, obtain graphene oxide fiber.
(3) the graphene oxide fiber that step (2) obtains is placed in the hydrazine hydrate that mass fraction is 10%, reduces 12h at 90 DEG C, washing drying obtains elementary graphene fiber.
(4) by the elementary graphene fiber that step (3) obtains, in argon gas atmosphere, at 2000 DEG C, process 1.5h, obtain high-quality graphene fiber.
(5) the high-quality graphene fiber that step (4) obtains is placed in quartz ampoule, in iron chloride steam, processes 24h, obtain the high connductivity graphene fiber of iron chloride doping.
Through above step, obtain the graphene oxide spinning solution of stable homogeneous, liquid crystal stripe texture can be seen under petrographic microscope.The diameter of the high connductivity graphene fiber of the iron chloride doping prepared is 30 ~ 100 μm, and elongation at break is 1 ~ 10%, and TENSILE STRENGTH is 300 ~ 600MPa, and conductance is greater than 1000000S/m.
Embodiment 3
(1) by 2g graphene oxide and the mixing of 20gN, N-dimethylacetylamide, in 30 DEG C with the ultrasonic process 2h of 40KHz, graphene oxide spinning solution is obtained.
(2) get the graphene oxide spinning solution of step (1) gained, be the spinneret of 300 μm by internal diameter with the extruded velocity of 100mL/h, in the acetone of 25 DEG C are bathed admittedly, stop 1min become gelatinous fibre, obtain graphene oxide fiber.
(3) the graphene oxide fiber that step (2) obtains is placed in the mixed solvent of hydroiodic acid and trifluoroacetic acid, is heated to 90 DEG C, reduction 1h, washing drying obtains elementary graphene fiber.
(4) by the elementary graphene fiber that step (3) obtains, in argon gas atmosphere, 3000 DEG C of process 1h, obtain high-quality graphene fiber.
(5) the high-quality graphene fiber that step (4) obtains is placed in quartz ampoule, under vacuum, with metallic potassium steam treatment 1h, obtains the high connductivity graphene fiber of potassium doping.
Through above step, obtain the graphene oxide spinning solution of stable homogeneous, obvious liquid crystal stripe texture can be seen under petrographic microscope.The diameter of the potassium doping high connductivity graphene fiber prepared is 30 ~ 30 μm, and 500 ~ 800MPa, elongation at break is 1 ~ 10%, and conductance is better than 1000000S/m.
Embodiment 4
(1) by 2g graphene oxide and 20gN, dinethylformamide mixes, and in 30 DEG C with the ultrasonic process 2h of 40KHz, obtains graphene oxide spinning solution.
(2) get the graphene oxide spinning solution of step (1) gained, be the spinneret of 150 μm by internal diameter with the extruded velocity of 100mL/h, in the ethyl acetate of 25 DEG C are bathed admittedly, stop 1min become gelatinous fibre, obtain graphene oxide fiber.
(3) the graphene oxide fiber that step (2) obtains is placed in the mixed solvent of hydroiodic acid and trifluoroacetic acid, is heated to 90 DEG C, reduction 1h, washing drying obtains elementary graphene fiber.
(4) by the elementary graphene fiber that step (3) obtains, in argon gas atmosphere, 3000 DEG C of process 1h, obtain high-quality graphene fiber.
(5) the high-quality graphene fiber that step (4) obtains is placed in quartz ampoule, under vacuum, with aluminium chloride vapour process 1h, obtains the high connductivity graphene fiber of aluminium chloride doping.
Through above step, obtain the graphene oxide spinning solution of stable homogeneous, obvious liquid crystal stripe texture can be seen under petrographic microscope.The diameter of the potassium doping high connductivity graphene fiber prepared is 30 ~ 30 μm, and 500 ~ 800MPa, elongation at break is 1 ~ 10%, and conductance is better than 1000000S/m.
Embodiment 5
(1) by 2g graphene oxide and the mixing of 20gN, N-dimethylacetylamide, in 30 DEG C with the ultrasonic process 2h of 40KHz, graphene oxide spinning solution is obtained.
(2) get the graphene oxide spinning solution of step (1) gained, be the spinneret of 300 μm by internal diameter with the extruded velocity of 100mL/h, in the acetone of 25 DEG C are bathed admittedly, stop 1min become gelatinous fibre, obtain graphene oxide fiber.
(3) the graphene oxide fiber that step (2) obtains is placed in the mixed solvent of hydroiodic acid and trifluoroacetic acid, is heated to 90 DEG C, reduction 1h, washing drying obtains elementary graphene fiber.
(4) by the elementary graphene fiber that step (3) obtains, in argon gas atmosphere, 3000 DEG C of process 1h, obtain high-quality graphene fiber.
(5) the high-quality graphene fiber that step (4) obtains is placed in quartz ampoule, under vacuum, with molybdenum chloride steam treatment 1h, obtains the high connductivity graphene fiber of molybdenum chloride doping.
Through above step, obtain the graphene oxide spinning solution of stable homogeneous, obvious liquid crystal stripe texture can be seen under petrographic microscope.The diameter of the potassium doping high connductivity graphene fiber prepared is 30 ~ 30 μm, and 500 ~ 800MPa, elongation at break is 1 ~ 10%, and conductance is better than 1000000S/m.
Above-described embodiment is used for explaining and the present invention is described, instead of limits the invention, and in the protection domain of spirit of the present invention and claim, any amendment make the present invention and change, all fall into protection scope of the present invention.
Claims (8)
1. a high connductivity graphene fiber, it is characterized in that, this fiber by Graphene axially ordered arrangement form, graphene layer spacing about 0.3 ~ 0.4nm, doped with adulterants such as bromine, iodine, IBr, lodine chloride, potassium, calcium, iron chloride, molybdenum chloride, aluminium chloride or copper chlorides between graphene sheet layer, the quality of adulterant is 10 ~ 30% of Graphene quality; The degree of orientation of graphene fiber is 80 ~ 90%.
2. a preparation method for high connductivity graphene fiber according to claim 1, is characterized in that, comprise the following steps:
(1) by the graphene oxide of 1 weight portion, the solvent of 10 ~ 100 weight portions, obtains graphene oxide spinning solution after ultrasonic disperse;
(2) by graphene oxide spinning solution that step (1) obtains, with the extruded velocity of 1 ~ 100mL/h, by the spinneret that aperture is 30 ~ 300 μm, in the coagulating bath of 10 ~ 50 DEG C, stop about 5 ~ 60s, collect and obtain continuous print graphene oxide fiber;
(3) the graphene oxide fiber of gained in step (2) is placed in reductant to reduce, washing is dry, obtains elementary graphene fiber.
(4) the elementary graphene fiber of gained in step (3) is placed in the graphite furnace of 1000 ~ 3000 DEG C, heat treatment 1 ~ 4h in atmosphere, obtains high-quality graphene fiber.
(5) the high-quality graphene fiber obtained in step (4) is placed in adulterant steam process 1 ~ 24h, obtains the graphene fiber of high connductivity.
3. the preparation method of high connductivity graphene fiber according to claim 1, it is characterized in that, solvent in described step (1) is by methyl-sulfoxide, N, one or more in the materials such as dinethylformamide, DMA, 1-METHYLPYRROLIDONE, oxolane are according to any proportioning mixing composition.
4. the preparation method of high connductivity graphene fiber according to claim 1, it is characterized in that, the solidification liquid in described step (2) forms according to any proportioning mixing primarily of one or more in methyl alcohol, ethanol, ethyl acetate, n-butanol, ethylene glycol, butyl acetate, n-propyl acetate, acetic acid, acetone etc.
5. the preparation method of high connductivity graphene fiber according to claim 1, it is characterized in that, the reductant in described step (3) is generally made up of according to any proportioning mixing one or more in hydrazine hydrate, hydrobromic acid, hydroiodic acid, acetic acid, trifluoroacetic acid.
6. the preparation method of high connductivity graphene fiber according to claim 1, is characterized in that, atmosphere used in described step (4) can be that one or more in hydrogen, argon gas, nitrogen are according to any proportioning mixing composition.
7. the preparation method of high connductivity graphene fiber according to claim 1, it is characterized in that, in described step (5), adulterant steam is the metal chloride steam such as bromine vapor, iodine vapor, IBr steam, lodine chloride steam, potassium steam, calcium steam, iron chloride steam, molybdenum chloride steam, aluminium chloride vapour, copper chloride steam.
8. the preparation method of high connductivity graphene fiber according to claim 1, it is characterized in that, in described step (1), described graphene oxide is the single-layer graphene oxide of radial dimension 15 ~ 35 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610054970.9A CN105544017B (en) | 2016-01-27 | 2016-01-27 | A kind of highly conductive graphene fiber and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610054970.9A CN105544017B (en) | 2016-01-27 | 2016-01-27 | A kind of highly conductive graphene fiber and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105544017A true CN105544017A (en) | 2016-05-04 |
| CN105544017B CN105544017B (en) | 2017-07-14 |
Family
ID=55823565
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610054970.9A Active CN105544017B (en) | 2016-01-27 | 2016-01-27 | A kind of highly conductive graphene fiber and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105544017B (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106006608A (en) * | 2016-05-12 | 2016-10-12 | 哈尔滨工业大学 | Method for preparing graphene nanobelt fibers with 3D solution printing technology |
| CN106120025A (en) * | 2016-07-02 | 2016-11-16 | 苏州大学 | A kind of graphene fiber and preparation method thereof |
| CN106653150A (en) * | 2017-01-13 | 2017-05-10 | 广安市华蓥山领创电子有限公司 | Graphene wire |
| CN106987925A (en) * | 2017-05-05 | 2017-07-28 | 南京工业大学 | A kind of functionalization graphene preparation method based on ion exchange |
| CN107059160A (en) * | 2017-04-01 | 2017-08-18 | 卜庆革 | Graphene fiber of nanometer modified by silver and preparation method thereof |
| CN107268120A (en) * | 2017-07-28 | 2017-10-20 | 合肥泓定科技有限公司 | A kind of preparation method of doped graphene fiber |
| CN108221370A (en) * | 2018-01-23 | 2018-06-29 | 浙江大学 | A kind of compound alkene fiber of the highly conductive graphite of ambient stable and preparation method thereof |
| CN109967735A (en) * | 2019-05-07 | 2019-07-05 | 河北科技师范学院 | The method for preparing copper fiber felt as template using graphene |
| DE102018200236A1 (en) | 2018-01-09 | 2019-07-11 | Robert Bosch Gmbh | Process for producing graphene fibers, graphene fiber, yarn, electrical component and electrical conductor |
| CN110184671A (en) * | 2018-04-12 | 2019-08-30 | 济南开发区星火科学技术研究院 | A kind of graphene composite fibre |
| CN111535011A (en) * | 2020-06-08 | 2020-08-14 | 北京石墨烯研究院 | Method for preparing graphene fibers through joule heat flash evaporation |
| CN111719212A (en) * | 2020-01-13 | 2020-09-29 | 中原工学院 | Preparation method of flexible graphene conductive yarn capable of being woven |
| WO2021004692A1 (en) | 2019-07-10 | 2021-01-14 | Robert Bosch Gmbh | Method for producing graphene fibres |
| WO2021115669A1 (en) | 2019-12-09 | 2021-06-17 | Robert Bosch Gmbh | Electrical conductor made of graphene and/or carbon nanotubes having coated joints |
| CN113122948A (en) * | 2021-04-29 | 2021-07-16 | 南通强生石墨烯科技有限公司 | Flexible radiation-proof fiber based on graphene composite material and preparation method thereof |
| DE102021210974A1 (en) | 2021-09-30 | 2023-03-30 | Robert Bosch Gesellschaft mit beschränkter Haftung | Electrical machine and method for inserting at least one electrical conductor assembly into at least one slot of a stator or rotor for an electrical machine |
| DE102022203207A1 (en) | 2022-03-31 | 2023-10-05 | Robert Bosch Gesellschaft mit beschränkter Haftung | Process for producing a graphene film |
| CN116994943A (en) * | 2023-09-27 | 2023-11-03 | 之江实验室 | Preparation method of N-type tellurium alkene based on iodine vapor doping method |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102534865A (en) * | 2012-01-05 | 2012-07-04 | 浙江大学 | Ion-enhanced graphene fiber and preparation method thereof |
| CN102534869A (en) * | 2012-01-05 | 2012-07-04 | 浙江大学 | Method for preparing high-strength conductive graphene fiber by large-size graphene oxide sheet |
| US20130115462A1 (en) * | 2011-11-03 | 2013-05-09 | Baker Hughes Incorporated | Polarizable nanoparticles and electrorheological fluid comprising same |
| CN103477418A (en) * | 2010-12-13 | 2013-12-25 | 挪威科技大学 | Nanowire epitaxy on a graphitic substrate |
| CN104099687A (en) * | 2013-04-10 | 2014-10-15 | 华为技术有限公司 | Graphene fiber and preparation method thereof |
| CN104746180A (en) * | 2015-03-31 | 2015-07-01 | 东华大学 | Method for preparing molybdenum disulfide-doped graphene fibers |
| CN104894692A (en) * | 2015-06-03 | 2015-09-09 | 东华大学 | Preparation method of high-strength graphene fibers |
-
2016
- 2016-01-27 CN CN201610054970.9A patent/CN105544017B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103477418A (en) * | 2010-12-13 | 2013-12-25 | 挪威科技大学 | Nanowire epitaxy on a graphitic substrate |
| US20130115462A1 (en) * | 2011-11-03 | 2013-05-09 | Baker Hughes Incorporated | Polarizable nanoparticles and electrorheological fluid comprising same |
| CN102534865A (en) * | 2012-01-05 | 2012-07-04 | 浙江大学 | Ion-enhanced graphene fiber and preparation method thereof |
| CN102534869A (en) * | 2012-01-05 | 2012-07-04 | 浙江大学 | Method for preparing high-strength conductive graphene fiber by large-size graphene oxide sheet |
| CN104099687A (en) * | 2013-04-10 | 2014-10-15 | 华为技术有限公司 | Graphene fiber and preparation method thereof |
| CN104746180A (en) * | 2015-03-31 | 2015-07-01 | 东华大学 | Method for preparing molybdenum disulfide-doped graphene fibers |
| CN104894692A (en) * | 2015-06-03 | 2015-09-09 | 东华大学 | Preparation method of high-strength graphene fibers |
Non-Patent Citations (1)
| Title |
|---|
| 吴其胜: "单轴应变对石墨烯掺杂硼、氮、铝、硅、磷的影响与调控", 《化学学报》 * |
Cited By (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106006608A (en) * | 2016-05-12 | 2016-10-12 | 哈尔滨工业大学 | Method for preparing graphene nanobelt fibers with 3D solution printing technology |
| CN106006608B (en) * | 2016-05-12 | 2018-03-06 | 哈尔滨工业大学 | A kind of method for preparing graphene nanobelt fiber using 3D solution printing techniques |
| CN106120025A (en) * | 2016-07-02 | 2016-11-16 | 苏州大学 | A kind of graphene fiber and preparation method thereof |
| CN106653150B (en) * | 2017-01-13 | 2018-04-17 | 广安市华蓥山领创电子有限公司 | A kind of graphene electric wire |
| CN106653150A (en) * | 2017-01-13 | 2017-05-10 | 广安市华蓥山领创电子有限公司 | Graphene wire |
| CN107059160A (en) * | 2017-04-01 | 2017-08-18 | 卜庆革 | Graphene fiber of nanometer modified by silver and preparation method thereof |
| CN107059160B (en) * | 2017-04-01 | 2019-04-30 | 卜庆革 | The graphene fiber and preparation method thereof of nanometer modified by silver |
| CN106987925B (en) * | 2017-05-05 | 2020-06-12 | 南京工业大学 | Functionalized graphene preparation method based on ion exchange |
| CN106987925A (en) * | 2017-05-05 | 2017-07-28 | 南京工业大学 | A kind of functionalization graphene preparation method based on ion exchange |
| CN107268120A (en) * | 2017-07-28 | 2017-10-20 | 合肥泓定科技有限公司 | A kind of preparation method of doped graphene fiber |
| DE102018200236A1 (en) | 2018-01-09 | 2019-07-11 | Robert Bosch Gmbh | Process for producing graphene fibers, graphene fiber, yarn, electrical component and electrical conductor |
| CN108221370A (en) * | 2018-01-23 | 2018-06-29 | 浙江大学 | A kind of compound alkene fiber of the highly conductive graphite of ambient stable and preparation method thereof |
| CN108221370B (en) * | 2018-01-23 | 2020-04-14 | 长兴德烯科技有限公司 | Environment-stable high-conductivity graphene composite fiber and preparation method thereof |
| CN110184671A (en) * | 2018-04-12 | 2019-08-30 | 济南开发区星火科学技术研究院 | A kind of graphene composite fibre |
| CN109967735B (en) * | 2019-05-07 | 2021-01-26 | 河北科技师范学院 | Method for preparing copper fiber felt by taking graphene as template |
| CN109967735A (en) * | 2019-05-07 | 2019-07-05 | 河北科技师范学院 | The method for preparing copper fiber felt as template using graphene |
| CN114096701A (en) * | 2019-07-10 | 2022-02-25 | 罗伯特·博世有限公司 | Method for preparing graphene fiber |
| WO2021004692A1 (en) | 2019-07-10 | 2021-01-14 | Robert Bosch Gmbh | Method for producing graphene fibres |
| US11939703B2 (en) | 2019-07-10 | 2024-03-26 | Robert Bosch Gmbh | Method for producing graphene fibres |
| WO2021115669A1 (en) | 2019-12-09 | 2021-06-17 | Robert Bosch Gmbh | Electrical conductor made of graphene and/or carbon nanotubes having coated joints |
| US11875913B2 (en) | 2019-12-09 | 2024-01-16 | Robert Bosch Gmbh | Electrical conductor made of graphene and/or carbon nanotubes having coated joints |
| CN111719212A (en) * | 2020-01-13 | 2020-09-29 | 中原工学院 | Preparation method of flexible graphene conductive yarn capable of being woven |
| CN111535011A (en) * | 2020-06-08 | 2020-08-14 | 北京石墨烯研究院 | Method for preparing graphene fibers through joule heat flash evaporation |
| CN113122948A (en) * | 2021-04-29 | 2021-07-16 | 南通强生石墨烯科技有限公司 | Flexible radiation-proof fiber based on graphene composite material and preparation method thereof |
| DE102021210974A1 (en) | 2021-09-30 | 2023-03-30 | Robert Bosch Gesellschaft mit beschränkter Haftung | Electrical machine and method for inserting at least one electrical conductor assembly into at least one slot of a stator or rotor for an electrical machine |
| WO2023052116A1 (en) | 2021-09-30 | 2023-04-06 | Robert Bosch Gmbh | Electric machine and method for placing at least one electrical composite conductor into at least one groove of a stator or rotor for an electric machine |
| DE102022203207A1 (en) | 2022-03-31 | 2023-10-05 | Robert Bosch Gesellschaft mit beschränkter Haftung | Process for producing a graphene film |
| WO2023186456A1 (en) | 2022-03-31 | 2023-10-05 | Robert Bosch Gmbh | Method for producing a graphene film |
| CN116994943A (en) * | 2023-09-27 | 2023-11-03 | 之江实验室 | Preparation method of N-type tellurium alkene based on iodine vapor doping method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105544017B (en) | 2017-07-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105544017A (en) | High-conductivity graphene fiber and preparation method thereof | |
| CN105648579A (en) | Superfine graphene fibers and method for preparing same | |
| CN104882613B (en) | A kind of preparation method of flexible High-conductivity composite carbon fiber cloth | |
| CN108251076B (en) | Carbon nanotube-graphene composite heat dissipation film, and preparation method and application thereof | |
| CN109256535B (en) | Silicon @ carbon composite material with yolk shell structure and preparation and application thereof | |
| JP6360252B2 (en) | Nano-sulfur cathode composite coated with nitrogen-doped graphene, its preparation method and application | |
| CN105603582A (en) | High-strength continuous graphene fiber and preparing method thereof | |
| CN104445153B (en) | A kind of method being prepared charcoal nanometer roll by Graphene magnanimity | |
| Zhang et al. | 3D hierarchical microspheres constructed by ultrathin MoS2-C nanosheets as high-performance anode material for sodium-ion batteries | |
| CN107658447B (en) | Nitrogen-doped carbon layer coated flower ball-shaped V2O5Preparation method of (1) | |
| Guo et al. | Vertically aligned ultrathin MoS2 nanosheets grown on graphene-wrapped hollow carbon microtubes derived from loofah sponge as advanced anodes for highly reversible lithium storage | |
| CN103420352A (en) | High-fluoride-content graphite fluoride and preparation method thereof | |
| CN105514434A (en) | Preparation method of whisker-shaped carbon nano tube film | |
| Kong et al. | Synthesis of natural nitrogen-rich soybean pod carbon with ion channels for low cost and large areal capacitance supercapacitor | |
| Oh et al. | Highly integrated and interconnected CNT hybrid nanofibers decorated with α-iron oxide as freestanding anodes for flexible lithium polymer batteries | |
| CN104036970A (en) | Preparation method for flexible graphite fibre-based asymmetric super capacitor | |
| CN111276679A (en) | Double-carbon composite molybdenum sulfide composite material for sodium ion battery cathode material and preparation method thereof | |
| CN106711409A (en) | Preparation method of tin-dioxide-supported carbon nanorod material | |
| Yang et al. | Self-assembled FeF3 nanocrystals clusters confined in carbon nanocages for high-performance Li-ion battery cathode | |
| CN105097130A (en) | Preparation method of high-strength and high-conductivity copper or copper alloy lead containing graphene | |
| CN107658148A (en) | A kind of method for preparing graphene tin dioxide composite material and its application in terms of energy storage | |
| Cao et al. | Sb&Sb 2 O 3@ C-enhanced flexible carbon cloth as an advanced self-supporting anode for sodium-ion batteries | |
| Singh et al. | Fabrication of high energy density symmetric polyaniline/functionalized multiwalled carbon nanotubes supercapacitor device with swift charge transport in different electrolytic mediums | |
| Chen et al. | Two-step thermal treatment of electrochemical graphene oxide films for high-performance electrical heating and electromagnetic interference shielding | |
| Yu et al. | Advancements and Prospects of Graphite Anode for Potassium‐Ion Batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190904 Address after: 313199 Room 830, 8th Floor, Changxing World Trade Building, 1278 Mingzhu Road, Changxing Economic Development Zone, Huzhou City, Zhejiang Province Patentee after: Changxin de Technology Co., Ltd. Address before: 310027 Hangzhou, Zhejiang Province, Xihu District, Zhejiang Road, No. 38, No. Patentee before: Zhejiang University |
|
| TR01 | Transfer of patent right |