CN106676875B - A kind of graphene-nickel composite fibre and preparation method thereof - Google Patents
A kind of graphene-nickel composite fibre and preparation method thereof Download PDFInfo
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- CN106676875B CN106676875B CN201611217920.4A CN201611217920A CN106676875B CN 106676875 B CN106676875 B CN 106676875B CN 201611217920 A CN201611217920 A CN 201611217920A CN 106676875 B CN106676875 B CN 106676875B
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- 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
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- 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
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Abstract
The present invention illustrates a kind of graphene-nickel 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 nickel layer has the extended structure for being embedded in fold.Graphene is combined closely with nickel 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-nickel composite fibre and its
Preparation method.
Background technique
Metallic nickel is in smelting iron and steel, and nickel-base alloy, the fields such as energy industry and electro-catalysis, which have, is widely applied potentiality,
Relative to other metal materials, superior corrosion-resistant, high temperature resistant and rustless property are shown.In order to improve the practicability of nickel
And cost is reduced, the method generallyd use at present is that it is made into composite wood with carbon material more flexible and with good conductivity
Material, carbon material such as graphite and carbon nanotube have preferable flexibility, so the composite material being made into is reducing the same of cost
Shi Buhui significantly affects 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 nickel.Nickel plating 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 electronickelling 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 nickel.
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-nickel 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-nickel composite fibre, the compound fibre
Dimension is made of the nickel layer of pure graphene fiber and the pure graphene fiber of cladding；The pure graphene fiber surface has fold,
Nickel layer 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-nickel 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 nickel stick 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-nickel composite fibre.The composition of the electroplate liquid are as follows: nickel sulfate
Concentration is 150-350g/L, and the volumetric concentration of 98wt% sulfuric acid is 3-10mL/L, and the concentration of sodium chloride is 4-10g/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 20s.
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 nickel 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 the structure chart of graphene-nickel composite fibre；
Fig. 2 is the graphene surface multistage pleated structure figure under different multiplying；
Fig. 3 is the distribution of nickel particle and growth conditions when graphene-nickel composite fibre is electroplated；
Fig. 4 is the XRD diagram of graphene-nickel composite fibre；
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-nickel composite fibre, the pure graphite that the composite fibre is 1-50 microns by diameter
The nickel layer composition of alkene fiber and the pure graphene fiber of cladding；The pure graphene fiber surface has fold, and nickel layer has embedding
Enter the extended structure of fold.The good physical property of fiber is combined closely from nickel layer 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 Ni-coated graphite alkene graphite fiber
Alkene bulk density is 1.7-6.8g/cm3, graphene mass fraction is 30-90%, and the mass fraction of nickel is 10-70%, fiber
Conductivity is 1.1 × 105S/m–7.4×106S/m, thickness of coating are 1-13 microns.
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 nickel is preferentially nucleated here and apposition growth, and with the progress of plating, cobalt granule is gradually
Growth, particle becomes larger, and the crack being crimped is fixed, further, nickel crystallite along fold homoepitaxial and mutually fusion up to
It is paved with entire fiber surface, growth course is as shown, this growth pattern from inside to outside ensures that final coating can be
It is even to be covered on fiber surface and stablize attachment.On the one hand the fibre structure obtained is stablized, for example can be bent 100 conductivities
It is constant；On the other hand, two kinds of material tights combine, and there is no hole defects, substantially increase the electric property of material.Below
The invention will be further described in conjunction with the embodiments.
Embodiment 1
A kind of method that galvanoplastic prepare graphene and nickel composite fiber, including following procedure:
(1) the graphene oxide fiber that diameter is 3 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 4mg/mL；The internal diameter of spinneret is 60 microns；Coagulating bath is the mixing of ethyl acetate and methylene chloride
Solution (the two volume ratio is 1:1), 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 1000 DEG C, after heating 1.5 hours, is obtained
The graphene fiber for being 3 microns to diameter.
(3) cathode that graphene fiber is fixed on electroplating bath is electroplated, electroplating bath just extremely high purity nickel stick, apply with
Voltage value is the DC voltage of 0.1V, and electroplate liquid is nickel sulfate (300g/L), and sodium chloride (4g/L) and mass fraction are 98wt%
The concentrated sulfuric acid (3mL/L) mixed aqueous solution, plating 8 seconds after, the electroplate liquid of fiber surface is washed off with water, in vacuum drying oven do
Dry 1 hour.Since voltage is lower, the time is shorter, and obtaining coating is about 3 microns, answers as shown in figure 4, XRD is final as the result is shown
There is the peak of apparent nickel crystal on condensating fiber surface.After tested, conductivity is 9.3 × 105S/m。
Embodiment 2
A kind of method that galvanoplastic prepare graphene and nickel composite fiber, 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 nickel stick, apply with
Voltage value is the DC voltage of 1V, and electroplate liquid is nickel sulfate (350g/L), and sodium chloride (8g/L) and mass fraction are 98wt%'s
The electroplate liquid of fiber surface is washed off with water after plating 120 seconds in the mixed aqueous solution of the concentrated sulfuric acid (4mL/L), does in vacuum drying oven
Dry 9 hours.Obtaining coating is about 5 microns.After tested, conductivity is 2.1 × 106S/m。
Embodiment 3
A kind of method that galvanoplastic prepare graphene and nickel composite fiber, 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 2700 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 nickel stick of electroplating bath, apply with
Voltage value is the DC voltage of 20V, and electroplate liquid is nickel sulfate (150g/L), and sodium chloride (10g/L) and mass fraction are 98wt%
The concentrated sulfuric acid (10mL/L) mixed aqueous solution, plating 2 seconds after, the electroplate liquid of fiber surface is washed off with water, in vacuum drying oven
It is 5 hours dry.After improving supply voltage, the potential of fiber is increased, and obtaining coating is about 12 microns.After tested, conductivity
It is 6.8 × 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 preparation method of graphene-nickel composite fibre, the composite fibre is by pure graphene fiber and the pure stone of cladding
The nickel layer of black alkene fiber forms；The pure graphene fiber surface has fold, and nickel layer has the extended structure for being embedded in fold,
It 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 nickel stick 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-nickel composite fibre；The composition of the electroplate liquid are as follows: the concentration of nickel sulfate
For 150-350 g/L, the volumetric concentration of 98wt% sulfuric acid is 3-10 mL/L, and the concentration of sodium chloride is 4-10g/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 5s.
4. the method according to claim 1, wherein in the step 3, when voltage is 1V, required electroplating time
For 20s.
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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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| CN105063687A (en) * | 2015-09-22 | 2015-11-18 | 太仓市金鹿电镀有限公司 | Nickel-magnesium alloy electroplating technique |
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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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| 纳米碳材料在可穿戴柔性导电材料中的应用研究进展;夏凯伦;《物理化学学报》;20161031;第32卷(第10期);第2427-2446页 |
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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: 310058 Xihu District, Zhejiang, Yuhang Tong Road, No. 866, No. Patentee before: Zhejiang University |