CN106702732B - A kind of graphene-copper composite fibre and preparation method thereof - Google Patents
A kind of graphene-copper composite fibre and preparation method thereof Download PDFInfo
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- CN106702732B CN106702732B CN201611220124.6A CN201611220124A CN106702732B CN 106702732 B CN106702732 B CN 106702732B CN 201611220124 A CN201611220124 A CN 201611220124A CN 106702732 B CN106702732 B CN 106702732B
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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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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0607—Wires
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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 present invention illustrates a kind of graphene-copper composite fibre and preparation method thereof, the graphene oxide fiber that diameter is 1-50 microns is prepared first with the method for wet spinning, again graphene oxide fiber is placed on to heat in high temperature furnace and be restored, obtain continuous pure graphene fiber, since special processing mode makes fiber surface have multistage fold, after the cathode that pure graphene fiber is fixed on electroplating bath is electroplated, so that layers of copper has the extended structure for being embedded in fold.Graphene is combined closely with copper crystal, and hole defect is not present, substantially increases the electric property of material.Fibre structure is stablized, and 100 conductivities of bending are constant.
Description
Technical field
The present invention relates to a kind of novel graphene metallic composite, especially a kind of graphene-copper composite fibre and its
Preparation method.
Background technique
Metallic copper is very proper with our daily life, has widely in the fields such as new industry and electric power energy
Application potential shows superior electric conductivity, thermal conductivity and ductility relative to other metal materials.In order to improve copper
Application value, the method generallyd use at present is that it is made into composite material with carbon material more tough and with good conductivity
Make the reduction of its specific conductivity, carbon material such as graphite and carbon nanotube have preferable flexibility, so the composite material being made into
Its processing performance and service performance will not be significantly affected while cost is reduced.
Relative to graphite and carbon nanotube, graphene has more excellent electric conductivity and more preferably flexibility, therefore more
It is suitble to be made into composite material with copper.Copper facing mainly has two kinds of paths of chemical plating and plating to be electroplated more environmentally-friendly relative to chemical plating
It cleans and easy to operate, therefore realizes that electro-coppering is a kind of ideal method on graphene in a manner of plating.
However, being different from other carbon materials, there is super lubricating action, adhesive force between the two between graphene and metal
Very weak, this brings huge challenge to grapheme material directly electroplating on surface copper.
Summary of the invention
In view of the above problems, the present invention provides a kind of economical and effective, and a kind of graphene-copper of energy large-scale application is multiple
Condensating fiber and preparation method thereof, composite fibre stability made from this method is good, and density is low, and conductivity is high, and flexibility is good.
The purpose of the present invention is what is be achieved through the following technical solutions: a kind of graphene-copper composite fibre, the compound fibre
Dimension is made of the layers of copper of pure graphene fiber and the pure graphene fiber of cladding；The pure graphene fiber surface has fold,
Layers of copper has the extended structure for being embedded in fold.
Further, the width of the fold is 20 nanometers to 5 microns.
A kind of preparation method of graphene-copper composite fibre, its preparation step are as follows:
(1) prepare graphene oxide fiber using the method for wet spinning (diameter is 1-50 microns)；
(2) again graphene oxide fiber is placed on to heat in high temperature furnace and is restored, temperature is 800-3000 DEG C, and the recovery time is
1-24 hours, obtain pure graphene fiber.
(3) cathode that pure graphene fiber is fixed on electroplating bath is electroplated, electroplating bath just extremely copper rod applies with electricity
Pressure value is the DC voltage of 0.1-20V, after being electroplated 2-120 seconds in electroplate liquid, takes out fiber, fiber table is washed with deionized water
The electroplate liquid in face, it is dry in vacuum drying oven, obtain graphene-copper composite fibre.The electroplate liquid composition is as follows: copper sulphate
Concentration is 50-160g/L, and the volumetric concentration of the sulfuric acid of 98wt% is 3-10mL/L, and surfactant Qula is led to for 0.5-2mL/L.
Further, in the step 1, the spinning solution of wet spinning are as follows: the oxidation stone that piece diameter is 1-50 microns
Dispersion liquid of the black alkene in dimethylformamide, the concentration of graphene oxide are 1~10mg/mL；The internal diameter of spinning pipeline is 60-
500 microns；Coagulating bath is the mixed solution (the two volume ratio is 1:1-50:1) of ethyl acetate and methylene chloride, outer when receiving silk
Boundary's heating temperature is 80-200 DEG C.
Further, in the step 3, when voltage is 20V, required electroplating time is 2s.
Further, in the step 3, when voltage is 1V, required electroplating time is 13s.
The beneficial effects of the present invention are: preparation process of the present invention is simple and safe controllable, and time consumption and energy consumption is few, raw material sources
Extensively.Since graphene surface has many folds, metal copper layer and graphene fiber surface can be made closely compound, obtained
Complex structure of filament is fine and close, functional.
Detailed description of the invention
Fig. 1 is graphene-copper composite fibre structural schematic diagram；
Fig. 2 is the graphene surface multistage pleated structure figure under different multiplying；
The distribution of copper particle and growth conditions when Fig. 3 is graphene-copper composite fibre plating；
Fig. 4 is graphene-copper composite fibre XRD diagram；
Fig. 5 a, b, c are respectively the state of smooth graphene surface plating metal.
Specific embodiment
As shown in Figure 1, a kind of graphene-copper composite fibre, the pure graphite that the composite fibre is 1-50 microns by diameter
The layers of copper composition of alkene fiber and the pure graphene fiber of cladding；The pure graphene fiber surface has fold, and layers of copper has embedding
Enter the extended structure of fold.The good physical property of fiber is combined closely from layers of copper and graphene fiber surface, solution
It has determined and has been difficult to the problem of modification is electroplated between graphene and metallic particles.On the one hand obtained fibre structure is stablized, such as can be with
It is constant to be bent 100 conductivities；On the other hand, two kinds of material tights combine, and there is no hole defects, substantially increase material
The electric property of material.
As shown in Fig. 2, the width of the fold is 20 nanometers to 5 microns.After tested, copper-plated graphite alkene cebollite obtained
Black alkene bulk density is 1.8-5.8g/cm3, graphene mass fraction is 10-80%, and the mass fraction of copper is 20-90%, fiber
Conductivity be 1.1 × 105S/m–3.5×107S/m。
As shown in figure 3, due to graphene fiber surface irregularity, electronics is in radius of curvature ratio in the plating initial stage
Biggish plication region aggregation, the crystal grain of copper is preferentially nucleated here and apposition growth, and with the progress of plating, particle is gradually given birth to
Long, particle becomes larger, and the crack being crimped is fixed, and further, copper crystal grain is along fold homoepitaxial and mutually fusion is until paving
Full entire fiber surface, this growth pattern from inside to outside ensure final coating energy uniform fold in fiber surface and stabilization
Attachment.On the one hand obtained fibre structure is stablized, for example can be bent 100 conductivities constant；On the other hand, two kinds of materials
It combines closely, there is no hole defects, substantially increase the electric property of material.Below with reference to embodiment to the present invention make into
One step explanation.
Embodiment 1
A kind of method that galvanoplastic prepare graphene and copper composite fibre, including following procedure:
(1) the graphene oxide fiber that diameter is 5 microns is prepared using the method for wet spinning, specifically: wet spinning
Spinning solution are as follows: piece diameter is the dispersion liquid of 5 microns of graphene oxide (carbon Gu Shangxi) in dimethylformamide, oxygen
The concentration of graphite alkene is 10mg/mL；The internal diameter of spinneret is 100 microns；Coagulating bath is the mixed of ethyl acetate and methylene chloride
Solution (the two volume ratio is 1:1) is closed, extraneous heating temperature when receiving silk is 200 DEG C.
(2) graphene oxide fiber is placed on to heat in high temperature furnace and is restored, temperature is 800 DEG C, after heating 1.5 hours, is obtained
The graphene fiber for being 5 microns to diameter.
(3) cathode that graphene fiber is fixed on electroplating bath is electroplated, electroplating bath just extremely high purity copper stick, apply with
Voltage value is the DC voltage of 0.1V, and electroplate liquid is copper sulphate (160g/L), and the concentrated sulfuric acid (3mL/L) and Qula of 98wt% is logical
The electroplate liquid of fiber surface is washed off with water after plating 10 seconds in the mixed aqueous solution of (0.5mL/L), and dry 1 is small in vacuum drying oven
When.Since voltage is lower, the time is shorter, and obtaining coating is about 3 microns.As shown in figure 4, XRD final compound fibre as the result is shown
There is the peak of apparent copper crystal in dimension table face.Initial map has the signal of cuprous ion, but by going back completely after hydrogen reducing
Original, and it is still able to maintain good stability after the two weeks.After tested, conductivity is 7.3 × 105S/m。
Embodiment 2
A kind of method that galvanoplastic prepare graphene and copper composite fibre, including following procedure,
(1) the graphene oxide fiber that diameter is 10 microns is prepared using the method for wet spinning, specifically: wet spinning
Spinning solution are as follows: piece diameter is the dispersion liquid of 5 microns of graphene oxide (carbon Gu Shangxi) in dimethylformamide, oxygen
The concentration of graphite alkene is 8mg/mL；The internal diameter of spinneret is 250 microns；Coagulating bath is the mixing of ethyl acetate and methylene chloride
Solution (the two volume ratio is 10:1), extraneous heating temperature when receiving silk is 80 DEG C.
(2) again graphene oxide fiber is placed on to heat in high temperature furnace and is restored, temperature is 2200 DEG C, after heating 3 hours, is obtained
The graphene fiber for being 10 microns to diameter；
(3) cathode that graphene fiber is fixed on electroplating bath is electroplated, electroplating bath just extremely high purity copper stick, apply with
Voltage value is the DC voltage of 1V, and electroplate liquid is copper sulphate (100g/L), and the concentrated sulfuric acid (4mL/L) and Qula of 98wt% is logical
The electroplate liquid of fiber surface is washed off with water after plating 120 seconds in the mixed aqueous solution of (0.7mL/L), dry 9 in vacuum drying oven
Hour.Obtaining coating is about 5 microns.After tested, conductivity is 1.5 × 107S/m。
Embodiment 3
A kind of method that galvanoplastic prepare graphene and copper composite fibre, including following procedure:
(1) the graphene oxide fiber that diameter is 30 microns is prepared using the method for wet spinning, specifically: wet spinning
Spinning solution are as follows: piece diameter is the dispersion liquid of 50 microns of graphene oxide (carbon Gu Shangxi) in dimethylformamide,
The concentration of graphene oxide is 11mg/mL；The internal diameter of spinneret is 500 microns；Coagulating bath is ethyl acetate and methylene chloride
Mixed solution (the two volume ratio is 200:1), extraneous heating temperature when receiving silk is 100 DEG C.
(2) again graphene oxide fiber is placed on to heat in high temperature furnace and is restored, temperature is 3000 DEG C, after heating 1 hour, is obtained
The graphene fiber for being 30 microns to diameter.
(3) cathode that graphene fiber is fixed on electroplating bath is electroplated, the just extremely pure copper rod of electroplating bath, apply with
Voltage value is the DC voltage of 20V, and electroplate liquid is copper sulphate (50g/L), and the concentrated sulfuric acid (10mL/L) and Qula of 98wt% is logical
The electroplate liquid of fiber surface is washed off with water after plating 2 seconds in the mixed aqueous solution of (2mL/L), 5 hours dry in vacuum drying oven.
After improving supply voltage, the potential of fiber is increased, and obtaining coating is about 8 microns.After tested, conductivity is 3.1 × 107S/
m。
Embodiment 4
Importance of the fold for metal plating of graphene surface is verified using smooth graphene surface, including following
Process:
(1) as shown in Figure 5 a, smooth graphene film is taken, is conventionally electroplated, obtained metal is multiple
It is as shown in Figure 5 b to close film, coating is relatively thin and very uneven.
(2) metallic graphite carbon alkene composite membrane is slightly rinsed in water, obtained result is as shown in Figure 5 c, and coating is shelled completely
It falls, shows very poor binding force and stability.
Claims (4)
1. a kind of graphene-copper composite fibre preparation method, the composite fibre is by pure graphene fiber and the pure stone of cladding
The layers of copper of black alkene fiber forms；The pure graphene fiber surface has fold, and layers of copper has the extended structure for being embedded in fold；
It is characterized in that, its preparation step is as follows:
(1) the graphene oxide fiber that diameter is 1-50 microns is prepared using the method for wet spinning；
(2) again graphene oxide fiber is placed on to heat in high temperature furnace and is restored, obtain pure graphene fiber；
(3) cathode that pure graphene fiber is fixed on electroplating bath is electroplated, electroplating bath just extremely copper rod applies with voltage value
For the DC voltage of 0.1-20V, after being electroplated 2-120 seconds in electroplate liquid, fiber is taken out, fiber surface is washed with deionized water
Electroplate liquid, it is dry in vacuum drying oven, obtain graphene-copper composite fibre；The electroplate liquid composition is as follows: the concentration of copper sulphate
Volumetric concentration for 50-160g/L, the sulfuric acid of 98wt% is 3-10 mL/L, and surfactant Qula is led to for 0.5-2 mL/L.
2. the method according to claim 1, wherein in the step 1, the spinning solution of wet spinning are as follows: piece is straight
Dispersion liquid of the graphene oxide that diameter size is 1-50 microns in dimethylformamide, the concentration of graphene oxide are 1 ~ 10
mg/mL；The internal diameter of spinning pipeline is 60-500 microns；Coagulating bath is the mixed solution of ethyl acetate and methylene chloride, acetic acid second
Ester and methylene chloride volume ratio are 1:1-50:1, and extraneous heating temperature when receiving silk is 80-200 DEG C.
3. the method according to claim 1, wherein in the step 3, when voltage is 20V, required electroplating time
For 2s.
4. the method according to claim 1, wherein in the step 3, when voltage is 1V, required electroplating time
For 13s.
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| DE102018200236A1 (en) | 2018-01-09 | 2019-07-11 | Robert Bosch Gmbh | Process for producing graphene fibers, graphene fiber, yarn, electrical component and electrical conductor |
| CN108707998A (en) * | 2018-04-11 | 2018-10-26 | 杭州牛墨科技有限公司 | Graphene fiber and graphene fiber non-woven fabrics of a kind of fold and preparation method thereof |
| CN109321951B (en) * | 2018-11-13 | 2019-10-29 | 辽宁工程技术大学 | A kind of preparation method of the high-strength high-conductivity copper based nano composite material based on plating |
| DE102019210211A1 (en) | 2019-07-10 | 2021-01-14 | Robert Bosch Gmbh | Process for the production of graphene fibers |
| CN110777411B (en) * | 2019-11-13 | 2021-09-10 | 中国科学院高能物理研究所 | Preparation method of graphene paper-metal composite material |
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| CN105648579A (en) * | 2016-03-31 | 2016-06-08 | 浙江大学 | Superfine graphene fibers and method for preparing same |
| CN105845218A (en) * | 2016-05-18 | 2016-08-10 | 中天科技装备电缆有限公司 | Light total carbon cable and preparation method |
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