CN106637937A - Graphene-cobalt composite fiber and preparation method thereof - Google Patents
Graphene-cobalt composite fiber and preparation method thereof Download PDFInfo
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- CN106637937A CN106637937A CN201611219143.7A CN201611219143A CN106637937A CN 106637937 A CN106637937 A CN 106637937A CN 201611219143 A CN201611219143 A CN 201611219143A CN 106637937 A CN106637937 A CN 106637937A
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- graphene
- fiber
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- microns
- composite fibre
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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
-
- 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
-
- 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
- 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 a graphene-cobalt composite fiber and a preparation method thereof. The method comprises the steps as follows: a graphene oxide fiber with diameter being 1-50 microns is prepared with a wet spinning method and is put in a high-temperature furnace for heating reduction, and the continuous pure graphene fiber is obtained. Due to the special treatment manner, the fiber surface has multi-stage wrinkles, the pure graphene fiber is fixed to a negative electrode in a plating tank for plating, and the cobalt layer has an extension structure embedded in the wrinkles. Graphene and cobalt are integrated closely without the defect of holes, thus, electrical properties of the material are greatly improved. The fiber is stable in structure and has the constant conductivity after being bent a hundred times.
Description
Technical field
The present invention relates to a kind of novel graphite alkene metallic composite, particularly a kind of Graphene-cobalt composite fibre and its
Preparation method.
Background technology
Metallic cobalt possesses in fields such as electro-catalysis and is widely applied potentiality, and relative to other catalyst, its is cheap, holds
Easily it is worth.In order to further reduce its application cost, the method for generally adopting at present is that it is made into composite wood with material with carbon element
Material, material with carbon element such as graphite and CNT have good electric conductivity, so the composite made is in the same of reduces cost
Shi Buhui substantially reduces its electrocatalysis characteristic.
Relative to graphite and CNT, Graphene has more excellent electric conductivity, therefore is more suitable for being made again with cobalt
Condensation material.Cobalt plating mainly has two kinds of paths of chemical plating and plating, relative to chemical plating, electroplate more environmentally-friendly cleaning and operation side
Just, therefore in the way of electroplating realize that plating cobalt is a kind of ideal method on Graphene.
However, being different from other material with carbon elements, there is super lubrication between Graphene and metal, adhesive force therebetween
Very weak, this brings huge challenge to grapheme material directly electroplating on surface cobalt.
The content of the invention
For problem above, the invention provides a kind of economical and effective, and a kind of Graphene-cobalt of energy large-scale application is multiple
Condensating fiber and preparation method thereof, composite fibre good stability obtained in the method, density is low, and conductance is high, and pliability is good.
The purpose of the present invention is achieved through the following technical solutions：A kind of Graphene-cobalt composite fibre, the compound fibre
Tie up and be made up of the cobalt layers of pure graphene fiber and the pure graphene fiber of cladding；The pure graphene fiber surface has fold,
Cobalt 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-cobalt composite fibre, its preparation process is as follows：
(1) graphene oxide fiber (fibre diameter 1-50 micron) is prepared using the method for wet spinning；
(2) graphene oxide fiber is placed in high temperature furnace plus thermal reduction again, temperature is 800-3000 DEG C, the recovery time is
1-24 hours, obtain pure graphene fiber.
(3) negative pole that pure graphene fiber is fixed on electroplating bath is electroplated, electroplating bath just extremely cobalt rod applies with electricity
Pressure value is the DC voltage of 0.1-20V, after electroplating the 2-120 seconds in electroplate liquid, takes out fiber, and deionized water washes fiber table off
The electroplate liquid in face, is dried 1-12 hours in vacuum drying oven, obtains Graphene-cobalt composite fibre.The electroplate liquid is cobaltous sulfate
With the mixed aqueous solution of the concentrated sulfuric acid (98wt%), wherein, the concentration of cobaltous sulfate is 100-250g/L, and the volumetric concentration of the concentrated sulfuric acid is
3-8mL/L。
Further, in the step 1, the spinning solution of wet spinning is：Piece diameter is the oxidation stone of 1-50 microns
Dispersion liquid of the black alkene in dimethylformamide, the concentration of graphene oxide is 1～10mg/mL；The internal diameter of spinning pipeline is 60-
500 microns；Coagulating bath is that (the two volume ratio is 1 for the mixed solution of ethyl acetate and dichloromethane：1-50：1) it is, outer during receipts silk
Boundary's heating-up 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 8s.
The beneficial effects of the present invention is：Preparation process of the present invention is simple and safe controllable, and time consumption and energy consumption is few, raw material sources
Extensively.Because graphenic surface has many folds, layer of metal cobalt can be made closely to be combined with graphene fiber surface, be obtained
Complex structure of filament is fine and close, functional.
Description of the drawings
Fig. 1 is the structure chart of Graphene-cobalt composite fibre；
Fig. 2 is the multistage pleated structure figure of graphenic surface under different multiplying；
Fig. 3 is electroplating process figure；
Fig. 4 is the XRD of Graphene-cobalt composite fibre；
Fig. 5 a, b, c are respectively the state that smooth graphenic surface plates metal.
Specific embodiment
As shown in figure 1, a kind of Graphene-cobalt composite fibre, the composite fibre by a diameter of 1-50 microns pure graphite
The cobalt layers composition of alkene fiber and the pure graphene fiber of cladding；The pure graphene fiber surface has fold, and cobalt layers have embedding
Enter the extended structure of fold.The good physical property of fiber is combined closely from cobalt layers and graphene fiber surface, solution
Determine and the problem for electroplating modification has been difficult between Graphene and metallic particles.On the one hand the fibre structure for obtaining is stablized, such as can be with
Bend 100 conductances constant；On the other hand, bi-material is combined closely, and is not in hole defect, substantially increases material
The electric property of material.
As shown in Fig. 2 the width of the fold is 20 nanometers to 5 microns.Jing is tested, and the Graphene bulk density is
1.8-6.9g/cm3, Graphene mass fraction is 30-90%, and the mass fraction of cobalt is 10-70%, and the conductance of fiber is 1.1
×105S/m–8.7×106S/m, thickness of coating is 1-25 microns.
As shown in figure 3, in the plating starting stage, due to graphene fiber surface irregularity, electronics is in radius of curvature ratio
Larger plication region aggregation, preferentially in nucleation herein and apposition growth, with the carrying out of plating, cobalt granule is gradually for the crystal grain of cobalt
Growth, particle becomes big, and the crack being crimped is fixed, further, along the fold homoepitaxial and mutually fusion of cobalt crystal grain up to
Whole fiber surface is paved with, this growth pattern from inside to outside guarantees that final coating energy uniform fold is in fiber surface and steady
Fixed attachment.On the one hand the fibre structure for obtaining is stablized, such as can bend 100 conductances constant；On the other hand, two kinds of materials
Material is combined closely, and is not in hole defect, substantially increases the electric property of material.With reference to embodiment to present invention work
Further illustrate.
Embodiment 1
A kind of method that galvanoplastic prepare Graphene and cobalt composite fibre, including procedure below：
(1) a diameter of 7 microns of graphene oxide fiber is prepared using the method for wet spinning, specially：Wet spinning
Spinning solution be：Piece diameter is the dispersion liquid of 50 microns of graphene oxide (on carbon paddy wish) in dimethylformamide,
The concentration of graphene oxide is 1mg/mL；The internal diameter of spinneret is 60 microns；Coagulating bath is the mixed of ethyl acetate and dichloromethane
(the two volume ratio is 1 to close solution：1) extraneous heating-up temperature when, receiving silk is 200 DEG C.
(2) graphene oxide fiber is placed in high temperature furnace plus thermal reduction, temperature is 800 DEG C, after heating 24 hours, is obtained
A diameter of 7 microns of graphene fiber.
(3) negative pole that graphene fiber is fixed on electroplating bath is electroplated, electroplating bath just extremely high-purity cobalt rod, apply with
Magnitude of voltage for 1V DC voltage, electroplate liquid is the concentrated sulfuric acid (3mL/L) that cobaltous sulfate (200g/L) and mass fraction are 98wt%
Mixed aqueous solution, plating 8 seconds after, wash the electroplate liquid of fiber surface with water, in vacuum drying oven be dried 1 hour.Due to electricity
Pressure is relatively low, and the time is shorter, obtains coating and is about 3 microns.As shown in figure 4, XRD results show that final composite fiber surface has bright
The peak of aobvious cobalt crystal.Jing is tested, and its conductance is 1.3 × 106S/m。
Embodiment 2
A kind of method that galvanoplastic prepare Graphene and cobalt composite fibre, including procedure below,
(1) a diameter of 10 microns of graphene oxide fiber is prepared using the method for wet spinning, specially：Wet spinning
Spinning solution be：Piece diameter is the dispersion liquid of 1 micron of graphene oxide (on carbon paddy wish) in dimethylformamide, oxygen
The concentration of graphite alkene is 10mg/mL；The internal diameter of spinneret is 500 microns；Coagulating bath is the mixed of ethyl acetate and dichloromethane
(the two volume ratio is 50 to close solution：1) extraneous heating-up temperature when, receiving silk is 80 DEG C.
(2) graphene oxide fiber is placed in high temperature furnace again and adds thermal reduction, temperature is 2200 DEG C, after heating 3 hours, is obtained
To a diameter of 10 microns of graphene fiber；
(3) negative pole that graphene fiber is fixed on electroplating bath is electroplated, electroplating bath just extremely high-purity cobalt rod, apply with
Magnitude of voltage for 20V DC voltage, electroplate liquid is the concentrated sulfuric acid (4mL/L) that cobaltous sulfate (100g/L) and mass fraction are 98wt%
Mixed aqueous solution, plating 2 seconds after, wash the electroplate liquid of fiber surface with water, in vacuum drying oven be dried 10 hours.It is electric herein
The plating time is longer, obtains coating and is about 5 microns.Jing is tested, and its conductance is 2.4 × 106S/m。
Embodiment 3
A kind of method that galvanoplastic prepare Graphene and cobalt composite fibre, including procedure below：
(1) a diameter of 48 microns of graphene oxide fiber is prepared using the method for wet spinning, specially：Wet spinning
Spinning solution be：Piece diameter is the dispersion liquid of 30 microns of graphene oxide (on carbon paddy wish) in dimethylformamide,
The concentration of graphene oxide is 6mg/mL；The internal diameter of spinneret is 100 microns；Coagulating bath is the mixed of ethyl acetate and dichloromethane
(the two volume ratio is 20 to close solution：1) extraneous heating-up temperature when, receiving silk is 100 DEG C.
(2) graphene oxide fiber is placed in high temperature furnace again and adds thermal reduction, temperature is 3000 DEG C, after heating 1 hour, is obtained
To a diameter of 48 microns of graphene fiber.
(3) negative pole that graphene fiber is fixed on electroplating bath is electroplated, the just extremely pure cobalt rod of electroplating bath, apply with
Magnitude of voltage for 0.1V DC voltage, electroplate liquid is the concentrated sulfuric acid (3mL/ that cobaltous sulfate (250g/L) and mass fraction are 98wt%
L mixed aqueous solution), after electroplating 120 seconds, washes the electroplate liquid of fiber surface with water, is dried 5 hours in vacuum drying oven.Carry
After high power supply voltage, the potential of fiber is raised, and is obtained coating and is about 8 microns.Jing is tested, and its conductance is 4.1 × 106S/m。
Embodiment 4
It is using the fold of smooth graphenic surface checking graphenic surface for the importance of metal plating including following
Process：
(1) as shown in Figure 5 a, smooth graphene film is taken, is conventionally electroplated, the metal for obtaining is answered
Close film as shown in Figure 5 b, coating is relatively thin and very uneven.
(2) metallic graphite carbon alkene composite membrane is slightly rinsed in water, the result for obtaining as shown in Figure 5 c, shell completely by coating
Fall, show the adhesion and stability of extreme difference.
Claims (6)
1. a kind of Graphene-cobalt composite fibre, it is characterised in that the composite fibre is by pure graphene fiber and coats pure stone
The cobalt layers composition of black alkene fiber；The pure graphene fiber surface has fold, and cobalt layers have the extended structure for being embedded in fold.
2. Graphene according to claim 1-cobalt composite fibre, it is characterised in that the width of the fold is 20 nanometers
To 5 microns.
3. a kind of preparation method of the Graphene described in claim 1-cobalt composite fibre, it is characterised in that its preparation process
It is as follows：
(1) graphene oxide fiber (fibre diameter 1-50 micron) is prepared using the method for wet spinning；
(2) graphene oxide fiber is placed in high temperature furnace again and adds thermal reduction, obtain pure graphene fiber.
(3) negative pole that pure graphene fiber is fixed on electroplating bath is electroplated, electroplating bath just extremely cobalt rod applies with magnitude of voltage
For the DC voltage of 0.1-20V, after electroplating the 2-120 seconds in electroplate liquid, fiber is taken out, deionized water washes fiber surface off
Electroplate liquid, is dried in vacuum drying oven, obtains Graphene-cobalt composite fibre.The electroplate liquid is cobaltous sulfate and the concentrated sulfuric acid
(98wt%) mixed aqueous solution, wherein, the concentration of cobaltous sulfate is 100-250g/L, and the volumetric concentration of the concentrated sulfuric acid is 3-8mL/L.
4. method according to claim 3, it is characterised in that in the step 1, the spinning solution of wet spinning is：Piece is straight
Footpath size for 1-50 microns dispersion liquid of the graphene oxide in dimethylformamide, the concentration of graphene oxide is 1～
10mg/mL；The internal diameter of spinning pipeline is 60-500 microns；Coagulating bath is mixed solution (the two of ethyl acetate and dichloromethane
Volume ratio is 1：1-50：1) extraneous heating-up temperature when, receiving silk is 80-200 DEG C.
5. method according to claim 3, it is characterised in that in the step 3, when voltage is 20V, required electroplating time
For 2s.
6. method according to claim 3, it is characterised in that in the step 3, when voltage is 1V, required electroplating time
For 8s.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108896215A (en) * | 2018-05-21 | 2018-11-27 | 福建师范大学 | Pressure sensor preparation method and its pressure sensor of preparation |
| CN111701565A (en) * | 2020-06-28 | 2020-09-25 | 南京工业大学 | Preparation method and application of carbon nitride-loaded graphene-based flexible fiber |
| CN114942262A (en) * | 2022-02-25 | 2022-08-26 | 南京农业大学 | Laser-induced graphene electrode for detecting phosphate ions and preparation method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108896215A (en) * | 2018-05-21 | 2018-11-27 | 福建师范大学 | Pressure sensor preparation method and its pressure sensor of preparation |
| CN111701565A (en) * | 2020-06-28 | 2020-09-25 | 南京工业大学 | Preparation method and application of carbon nitride-loaded graphene-based flexible fiber |
| CN114942262A (en) * | 2022-02-25 | 2022-08-26 | 南京农业大学 | Laser-induced graphene electrode for detecting phosphate ions and preparation method |
| CN114942262B (en) * | 2022-02-25 | 2024-03-08 | 南京农业大学 | Laser-induced graphene electrode for phosphate ion detection and preparation method 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 |