CN108221370A - A kind of compound alkene fiber of the highly conductive graphite of ambient stable and preparation method thereof - Google Patents
A kind of compound alkene fiber of the highly conductive graphite of ambient stable and preparation method thereof Download PDFInfo
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- CN108221370A CN108221370A CN201810061944.8A CN201810061944A CN108221370A CN 108221370 A CN108221370 A CN 108221370A CN 201810061944 A CN201810061944 A CN 201810061944A CN 108221370 A CN108221370 A CN 108221370A
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- graphene
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- highly conductive
- composite fibre
- potassium
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
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- 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
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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
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/08—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with halogenated hydrocarbons
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
Abstract
The invention discloses compound alkene fibers of the highly conductive graphite of a kind of ambient stable and preparation method thereof.Using wet spinning technology, graphene oxide fiber is prepared with graphene oxide first, then prepare the graphene fiber of high conductivity through reduction treatment and chemical doping successively.Further by Surface grafting reaction, molecule protective layer is formed in doped graphene fiber surface situ-formed graft.Preparation process is simply controllable, and obtained graphene fiber has very excellent mechanical property and electric conductivity.It is this that there is the graphene composite fibre for stablizing high conductivity can be used as conducting wire, for fields such as light weight electric motor, flexible wearable equipment, electromagnetic protection clothes.
Description
Technical field
The present invention relates to a kind of highly conductive graphene composite fibres more particularly to a kind of highly conductive graphene of ambient stable to answer
Condensating fiber and preparation method thereof.
Background technology
Graphene has highest mechanical property, modulus 1.1TPa, intensity 180GPa；Highest carrier transport speed
Rate, up to 150000cm2/Vs；Highest conductivity (108) and the current loading density of superelevation S/m.Using graphene oxide liquid
Brilliant wet spinning technology, prepares High-performance graphene fiber, is expected to the excellent specific property on graphene micro-scale being converted into
Performance in macro-scale.Studies have shown that graphene fiber has good development prospect as lightweight wire.But at present
The electric conductivity of pure graphene fiber reported is up to 0.8MS/m, although after chemical doping conductivity can improve to
22MS/m, but in air and unstable, it is difficult to meet practical application demand (Advanced Materials 2016,
28,7941).Therefore there is an urgent need for explore new method to improve the stability of doped graphene fiber.
Invention content
The purpose of the present invention is overcoming the shortcomings of that existing chemical doping graphene fiber conductivity stabilization is poor, one is provided
Kind highly conductive graphene composite fibre of ambient stable and preparation method thereof.
The purpose of the present invention is achieved through the following technical solutions：A kind of compound fibre of highly conductive graphene of ambient stable
Dimension, including graphene inner core and molecule protective layer, by graphene, axially ordered arrangement forms the graphene inner core, graphite
Alkene interlamellar spacing about 0.3~0.4nm, doped with potassium ion between graphene sheet layer, the molecule protective layer is by halogenated hydrocarbon molecule structure
Into halogenated hydrocarbon molecule and the graphene covalent bond on graphene inner core surface layer.
Further, in the graphene inner core, the content of potassium is 10~30wt%；The degree of orientation of graphene fiber is 80
~90%.
A kind of preparation method of the highly conductive graphene composite fibre of ambient stable, includes the following steps：
(1) by the graphene oxide spinning solution of 10mg/mL, with the extruded velocity of 1~100mL/h, by aperture for 30~
300 μm of spinneret, stops 5~60s in 10~50 DEG C of coagulating bath, and collection obtains continuous graphene oxide fiber；
(2) the graphene oxide fiber of gained in step (1) is placed in 1000~3000 DEG C of graphite furnace, in atmosphere
0.5~1.5h is heat-treated, obtains high-quality graphene fiber.
(3) high-quality graphene fiber obtained in step (2) is placed in potassium steam processing 1~for 24 hours, obtains height and lead
Electric potassium doped graphene fiber.
(4) potassium doped graphene fiber obtained in step (2) is placed in halogenated hydrocarbons, holding 12~for 24 hours, after taking-up
Obtain the highly conductive graphene composite fibre of ambient stable.
Further, in the step (4) halogenated hydrocarbons mainly by chloro n-hexane, iodo n-hexane, fluoro n-hexane, complete
One or more of fluorine n octyl iodide alkane, perfluoro decyl iodine alkane, 1,1,2,2- tetrahydrochysene perfluoro-hexyl iodides etc. are according to arbitrary proportioning
Mixing composition.
The present invention has following technique effect：
1. graphene fiber is prepared using wet spinning technology, it is easy to operate；
2. by high-temperature heat treatment and chemical doping, the conductivity of graphene fiber is significantly improved.
3. forming molecule protective layer by surface grafting, prevent oxygen and water from entering fibrous inside, ensure that
Its conductivity can remain stable in a long time.
Description of the drawings
The compound alkene fibre structure schematic diagram of the highly conductive graphite of Fig. 1 ambient stables；
Fig. 2 is the electric conductivity appraisal curve of graphene fiber before and after grafting molecules protective layer.
Specific embodiment
It should be noted that in the present invention, potassium doped graphene fiber need to be only immersed in halogenated hydrocarbon solvent, it is halogenated
Hydrocarbon compound graphene electronegative with surface layer occurs covalence graft and reacts, and forms hydrophobic protective layers, whole process is simple
Controllably.After reaction, graphene composite fibre is with good stability in air, and electric conductivity, which is substantially better than, does not carry out surface
The potassium doped graphene fiber of modification.
The invention will be further described with reference to the accompanying drawings and embodiments.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, all belongs to the scope of protection of the present invention.
Embodiment 1：
(1) by the graphene oxide spinning solution of 10mg/mL, with the extruded velocity of 1mL/h, pass through the spinning that aperture is 30 μm
Head, stops 60s or so in 10 DEG C of coagulating bath, and collection obtains continuous graphene oxide fiber；
(2) the graphene oxide fiber of gained in step (1) is placed in 1000 DEG C of graphite furnace, is heat-treated in atmosphere
0.5h obtains high-quality graphene fiber.
(3) obtained graphene fiber in step (2) is placed in potassium steam and handles 1h, obtain highly conductive potassium doping stone
Black alkene fiber.
(4) potassium doped graphene fiber obtained in step (2) is placed in perfluoro octyl iodide alkane, keeps 12h, taken out
After obtain the highly conductive graphene composite fibre of ambient stable.
By above step, the highly conductive graphene composite fibre of ambient stable is obtained, a diameter of 5~150 μm of fiber, is wrapped
Graphene inner core and molecule protective layer are included, axially ordered arrangement forms the graphene inner core by graphene, and the degree of orientation is
90%；Graphene layer spacing about 0.3~0.4nm, doped with potassium ion between graphene sheet layer, the content of potassium is 10wt%；Institute
Molecule protective layer is stated to be made of halogenated hydrocarbon molecule.By Raman spectrum analyses, in 1350cm-1There is stronger D peaks, table in place
The halogenated hydrocarbon molecule of light fibers surface grafting.Equally, from x-ray photoelectron spectroscopy, halogenated hydrocarbon molecule and fibre can also be analyzed
Covalence graft reaction has occurred in dimension table layer graphene.After tested, elongation at break is 2~8%, tensile strength for 200~
800MPa, conductivity can maintain 1000000S/m for a long time in air.
Embodiment 2：
(1) it is 300 μm by aperture with the extruded velocity of 100mL/h by the graphene oxide spinning solution of 10mg/mL
Spinneret, stops 5s or so in 50 DEG C of coagulating bath, and collection obtains continuous graphene oxide fiber；
(2) the graphene oxide fiber of gained in step (1) is placed in 2000 DEG C of graphite furnace, is heat-treated in atmosphere
1h obtains high-quality graphene fiber.
(3) obtained graphene fiber in step (2) is placed in potassium steam and handles 16h, obtain highly conductive potassium doping
Graphene fiber.
(4) potassium doped graphene fiber obtained in step (2) is placed in perfluoro decyl iodine alkane, keeps 18h, taken out
After obtain the highly conductive graphene composite fibre of ambient stable.
By above step, the highly conductive graphene composite fibre of ambient stable is obtained, a diameter of 5~150 μm of fiber, is wrapped
Graphene inner core and molecule protective layer are included, axially ordered arrangement forms the graphene inner core by graphene, and the degree of orientation is
90%, graphene layer spacing about 0.3~0.4nm, doped with potassium ion between graphene sheet layer, the content of potassium is 24wt%；Institute
Molecule protective layer is stated to be made of halogenated hydrocarbon molecule.By Raman spectrum analyses, occur stronger D peaks, table at 1350cm-1
The halogenated hydrocarbon molecule of light fibers surface grafting.Equally, from x-ray photoelectron spectroscopy, halogenated hydrocarbon molecule and fibre can also be analyzed
Covalence graft reaction has occurred in dimension table layer graphene.After tested, elongation at break is 1~6%, tensile strength for 200~
800MPa, conductivity can maintain 4000000S/m for a long time in air.
Embodiment 3
(1) by the graphene oxide spinning solution of 10mg/mL, with the extruded velocity of 80mL/h, pass through the spinning that aperture is 100 μm
Silk head, stops 30s or so in 40 DEG C of coagulating bath, and collection obtains continuous graphene oxide fiber；
(2) the graphene oxide fiber of gained in step (1) is placed in 3000 DEG C of graphite furnace, is heat-treated in atmosphere
1.5h obtains high-quality graphene fiber.
(3) obtained graphene fiber in step (2) is placed in potassium steam and handled for 24 hours, obtain highly conductive potassium doping
Graphene fiber.
(4) potassium doped graphene fiber obtained in step (2) is placed in 1,1,2,2- tetrahydrochysene perfluoro-hexyl iodide, protected
It holds for 24 hours, the highly conductive graphene composite fibre of ambient stable is obtained after taking-up.
By above step, the highly conductive graphene composite fibre of ambient stable is obtained, a diameter of 5~150 μm of fiber, is wrapped
Graphene inner core and molecule protective layer are included, axially ordered arrangement forms the graphene inner core by graphene, and the degree of orientation is
86%；Graphene layer spacing about 0.3~0.4nm, doped with potassium ion between graphene sheet layer, the content of potassium is 30wt%；Institute
Molecule protective layer is stated to be made of halogenated hydrocarbon molecule.By Raman spectrum analyses, occur stronger D peaks, table at 1350cm-1
The halogenated hydrocarbon molecule of light fibers surface grafting.Equally, from x-ray photoelectron spectroscopy, halogenated hydrocarbon molecule and fibre can also be analyzed
Covalence graft reaction has occurred in dimension table layer graphene.After tested, elongation at break is 0.5~3%, tensile strength for 600~
1000MPa, conductivity can maintain more than 15000000S/m for a long time in air, as shown in Figure 2.
Above-described embodiment be used for illustrate the present invention rather than limit the invention, the present invention spirit and
In scope of the claims, to any modifications and changes that the present invention makes, protection scope of the present invention is both fallen within.
Claims (5)
1. a kind of highly conductive graphene composite fibre of ambient stable, which is characterized in that including graphene inner core and molecule protective layer,
By graphene, axially ordered arrangement forms the graphene inner core, graphene layer spacing about 0.3~0.4nm, graphene film
It is made of between layer doped with potassium ion, the molecule protective layer halogenated hydrocarbon molecule, halogenated hydrocarbon molecule and graphene inner core surface layer
Graphene covalent bond.
2. composite fibre according to claim 1, which is characterized in that in the graphene inner core, the content of potassium for 10~
30wt%.
3. composite fibre according to claim 1, which is characterized in that in the graphene inner core, graphene fiber takes
It is 80~90% to degree.
A kind of 4. preparation method of the highly conductive graphene composite fibre of ambient stable described in claim 1, which is characterized in that packet
Include following steps：
(1) it is 30~300 μm by aperture with the extruded velocity of 1~100mL/h by the graphene oxide spinning solution of 10mg/mL
Spinneret, in 10~50 DEG C of coagulating bath stop 5~60s, collection obtain continuous graphene oxide fiber；
(2) the graphene oxide fiber of gained in step (1) is placed in 1000~3000 DEG C of graphite furnace, in atmosphere at heat
0.5~1.5h is managed, obtains high-quality graphene fiber.
(3) high-quality graphene fiber obtained in step (2) is placed in potassium steam processing 1~for 24 hours, obtains highly conductive potassium
Doped graphene fiber.
(4) potassium doped graphene fiber obtained in step (2) is placed in halogenated hydrocarbons, holding 12~for 24 hours, it is obtained after taking-up
The highly conductive graphene composite fibre of ambient stable.
5. the preparation method of the highly conductive graphene composite fibre of ambient stable according to claim 1, which is characterized in that described
Halogenated hydrocarbons is mainly by chloro n-hexane, iodo n-hexane, fluoro n-hexane, perfluoro octyl iodide alkane, perfluoro decyl iodine in step (4)
One or more of alkane, 1,1,2,2- tetrahydrochysene perfluoro-hexyl iodides etc. are according to arbitrary proportioning mixing composition.
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| CN201810061944.8A CN108221370B (en) | 2018-01-23 | 2018-01-23 | Environment-stable high-conductivity graphene composite fiber and preparation method thereof |
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| CN201810061944.8A CN108221370B (en) | 2018-01-23 | 2018-01-23 | Environment-stable high-conductivity graphene composite fiber and preparation method thereof |
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| CN108221370A true CN108221370A (en) | 2018-06-29 |
| CN108221370B CN108221370B (en) | 2020-04-14 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109260765A (en) * | 2018-10-30 | 2019-01-25 | 蔡菁菁 | A kind of preparation method of the polyvinyl formal oil suction sponge for water-oil separating |
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| CN102926020A (en) * | 2012-11-14 | 2013-02-13 | 浙江大学 | Preparation method for polymer-grafted graphene laminated fiber with electrical conductivity and high-strength |
| EP2687626A2 (en) * | 2011-03-15 | 2014-01-22 | IUCF-HYU (Industry-University Cooperation Foundation Hanyang University) | Graphene fiber and method for manufacturing same |
| CN104099687A (en) * | 2013-04-10 | 2014-10-15 | 华为技术有限公司 | Graphene fiber and preparation method thereof |
| CN105544017A (en) * | 2016-01-27 | 2016-05-04 | 浙江大学 | High-conductivity graphene fiber and preparation method thereof |
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Patent Citations (5)
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| EP2687626A2 (en) * | 2011-03-15 | 2014-01-22 | IUCF-HYU (Industry-University Cooperation Foundation Hanyang University) | Graphene fiber and method for manufacturing same |
| CN102586922A (en) * | 2012-01-18 | 2012-07-18 | 浙江大学 | Preparation method for macroscopic fiber of polyacrylonitrile grafted graphene |
| CN102926020A (en) * | 2012-11-14 | 2013-02-13 | 浙江大学 | Preparation method for polymer-grafted graphene laminated fiber with electrical conductivity and high-strength |
| CN104099687A (en) * | 2013-04-10 | 2014-10-15 | 华为技术有限公司 | Graphene fiber and preparation method thereof |
| CN105544017A (en) * | 2016-01-27 | 2016-05-04 | 浙江大学 | High-conductivity graphene fiber and preparation method thereof |
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| CN109260765A (en) * | 2018-10-30 | 2019-01-25 | 蔡菁菁 | A kind of preparation method of the polyvinyl formal oil suction sponge for water-oil separating |
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