CN106676878B - A kind of graphene-zinc composite fibre and preparation method thereof - Google Patents
A kind of graphene-zinc composite fibre and preparation method thereof Download PDFInfo
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- CN106676878B CN106676878B CN201611220157.0A CN201611220157A CN106676878B CN 106676878 B CN106676878 B CN 106676878B CN 201611220157 A CN201611220157 A CN 201611220157A CN 106676878 B CN106676878 B CN 106676878B
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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
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
- D06M10/06—Inorganic compounds or elements
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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
- 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
Abstract
The present invention illustrates a kind of graphene-zinc 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 zinc layers have the extended structure for being embedded in fold.Graphene is combined closely with zinc 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-zinc composite fibre and its
Preparation method.
Background technique
Metallic zinc is in automobile, and household electrical appliance, the fields such as mechanical and air cell, which have, is widely applied potentiality, relative to
Other metal materials show superior calenderability, corrosion resistance and castability.In order to improve practicability and the reduction of zinc
Cost, the method generallyd use at present are that it is made into composite material, carbon materials with carbon material more flexible and with good conductivity
Expect that such as graphite and carbon nanotube have preferable flexibility, so the composite material being made into while cost is reduced will not be bright
Develop and rings its processing performance and service performance.
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 zinc.It is zinc-plated mainly to there are 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 electrogalvanizing 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 zinc.
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-zinc 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-zinc composite fibre, the compound fibre
Dimension is made of the zinc layers of pure graphene fiber and the pure graphene fiber of cladding；The pure graphene fiber surface has fold,
Zinc layers have 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-zinc 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 zinc bar 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-zinc composite fibre.The composition of the electroplate liquid are as follows: zinc sulfate
Concentration is 80-200g/L, and the volumetric concentration of the concentrated sulfuric acid of 98wt% is 3-10mL/L, and the concentration of sodium sulphate is 15-25g/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 5s.
Further, in the step 3, when voltage is 1V, required electroplating time is 30s.
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, metallic zinc 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-zinc composite fibre structure chart；
Fig. 2 is the graphene surface multistage pleated structure figure under different multiplying；
The distribution of zinc particle and growth conditions when Fig. 3 is graphene-zinc composite fibre plating；
Fig. 4 is graphene-zinc 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-zinc composite fibre, the pure graphite that the composite fibre is 1-50 microns by diameter
The zinc layers composition of alkene fiber and the pure graphene fiber of cladding；The pure graphene fiber surface has fold, and zinc layers have embedding
Enter the extended structure of fold.The good physical property of fiber is combined closely from zinc layers 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, the zinc-plated graphene fiber graphite
Alkene bulk density is 1.7-4.6g/cm3, graphene mass fraction is 10-90%, and the mass fraction of zinc is 10-90%, fiber
Conductivity is 1.2 × 105S/m–1.3×107S/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 zinc 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, zinc 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 zinc 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 10 microns of graphene oxide (carbon Gu Shangxi) in dimethylformamide,
The concentration of graphene oxide is 5mg/mL；The internal diameter of spinneret is 60 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 130 DEG C.
(2) graphene oxide fiber is placed on to heat in high temperature furnace and is restored, temperature is 1300 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 zinc stick, apply with
Voltage value is the DC voltage of 0.1V, and electroplate liquid is zinc sulfate (160g/L), the concentrated sulfuric acid of sodium sulphate (15g/L) and 98wt%
The electroplate liquid of fiber surface is washed off with water after plating 10 seconds in the mixed aqueous solution of (3mL/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 zinc crystal in dimension table face.After tested, conductivity is 1.1 × 106S/m。
Embodiment 2
A kind of method that galvanoplastic prepare graphene and zinc 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 20:1), extraneous heating temperature when receiving silk is 180 DEG C.
(2) again graphene oxide fiber is placed on to heat in high temperature furnace and is restored, temperature is 1500 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 zinc stick, apply with
Voltage value is the DC voltage of 2V, and electroplate liquid is zinc sulfate (200g/L), the concentrated sulfuric acid of sodium sulphate (25g/L) and 98wt%
The electroplate liquid of fiber surface is washed off with water after plating 120 seconds in the mixed aqueous solution of (10mL/L), and dry 9 is small in vacuum drying oven
When.Obtaining coating is about 5 microns.After tested, conductivity is 3.6 × 106S/m。
Embodiment 3
A kind of method that galvanoplastic prepare graphene and zinc composite fibre, including following procedure:
(1) the graphene oxide fiber that diameter is 28 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 13mg/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 200 DEG C.
(2) again graphene oxide fiber is placed on to heat in high temperature furnace and is restored, temperature is 2700 DEG C, after heating 1 hour, is obtained
The graphene fiber for being 28 microns to diameter.
(3) cathode that graphene fiber is fixed on electroplating bath is electroplated, the just extremely pure zinc bar of electroplating bath, apply with
Voltage value is the DC voltage of 20V, and electroplate liquid is zinc sulfate (80g/L), the concentrated sulfuric acid of sodium sulphate (20g/L) and 98wt%
The electroplate liquid of fiber surface is washed off with water after plating 2 seconds in the mixed aqueous solution of (5mL/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 8.6 × 106S/
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-zinc composite fibre preparation method, the composite fibre is by pure graphene fiber and the pure stone of cladding
The zinc layers of black alkene fiber form；The pure graphene fiber surface has fold, and the width of fold is 20 nanometers to 5 microns, zinc
Layer has the extended structure for being embedded in fold, which is characterized in that its preparation step is as follows:
(1) graphene oxide fiber is prepared 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, obtain pure graphene fiber；
(3) cathode that pure graphene fiber is fixed on electroplating bath is electroplated, electroplating bath just extremely zinc bar 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-zinc composite fibre；The composition of the electroplate liquid are as follows: sulfuric acid zinc concentration
For 80-200g/L, the volumetric concentration of the concentrated sulfuric acid of 98wt% is 3-10mL/L, and the concentration of sodium sulphate is 15-25g/L.
2. the method according to claim 1, wherein in the step (1), the spinning solution of wet spinning are as follows: piece
Diameter is the dispersion liquid of 1-50 micron of graphene oxide in dimethylformamide, the concentration of graphene oxide for 1~
10mg/mL；The internal diameter of spinning pipeline is 60-500 microns；Coagulating bath is ethyl acetate and methylene chloride according to volume ratio 1:1-
The mixed solution of 50:1 composition, extraneous heating temperature when receiving silk are 80-200 DEG C.
3. the method according to claim 1, wherein in the step (3), when voltage is 20V, when required plating
Between be 5s.
4. the method according to claim 1, wherein in the step (3), when voltage is 1V, when required plating
Between be 30s.
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| CN110157950B (en) * | 2019-06-28 | 2021-06-25 | 江西理工大学 | Reduced graphene oxide reinforced zinc-based medical material and preparation method thereof |
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| CN104790067A (en) * | 2015-04-17 | 2015-07-22 | 东华大学 | Nano conductive polymer/graphene composite fiber, and preparation method and application thereof |
| CN105484016A (en) * | 2015-12-28 | 2016-04-13 | 宁国市龙晟柔性储能材料科技有限公司 | Preparation method of graphene composite conductive fiber |
| CN105648579A (en) * | 2016-03-31 | 2016-06-08 | 浙江大学 | Superfine graphene fibers and method for preparing same |
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| 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 |
| CN103390507A (en) * | 2013-07-04 | 2013-11-13 | 复旦大学 | Graphene/ platinum nano particle complex fiber electrode material and preparation method thereof |
| CN104210168A (en) * | 2014-09-10 | 2014-12-17 | 浙江碳谷上希材料科技有限公司 | Preparation method for graphene and metal composite electromagnetic shielding film |
| CN104790067A (en) * | 2015-04-17 | 2015-07-22 | 东华大学 | Nano conductive polymer/graphene composite fiber, and preparation method and application thereof |
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Effective date of registration: 20190903 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: 310058 Xihu District, Zhejiang, Yuhang Tong Road, No. 866, No. Patentee before: Zhejiang University |