CN106637936A - Graphene-iron composite fiber and preparation method thereof - Google Patents
Graphene-iron composite fiber and preparation method thereof Download PDFInfo
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- CN106637936A CN106637936A CN201611219108.5A CN201611219108A CN106637936A CN 106637936 A CN106637936 A CN 106637936A CN 201611219108 A CN201611219108 A CN 201611219108A CN 106637936 A CN106637936 A CN 106637936A
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- graphene
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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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/20—Electroplating: Baths therefor from solutions of iron
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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 invention discloses a graphene-iron composite fiber and a preparation method thereof. The method comprises the steps of firstly preparing a graphene oxide fiber of which the diameter is 1-50 microns by adopting a wet spinning method, and putting the graphene oxide fiber into a high-temperature furnace for heating and reducing to obtain a continuous pure graphene fiber. Due to a special treatment mode, the fiber surface has multi-stage folds, the pure graphene fiber is fixed on a negative electrode of a plating bath for electroplating, and an iron layer has an extension structure embedded into the folds. The graphene is tightly combined with an iron crystal, and a hole defect is avoided, so that the electrical properties of the material are greatly improved. The fiber is stable in structure and is constant in electric conductivity after being bent for 100 times.
Description
Technical field
The present invention relates to a kind of novel graphite alkene metallic composite, particularly a kind of Graphene-iron composite fibre and its
Preparation method.
Background technology
Metallic iron possesses in fields such as metal alloy, building trade and mould moldings and is widely applied potentiality, relative to
Other metal materials, it shows more excellent ductility, but mechanical strength is not high.In order to improve the practicality of iron and reduce
Cost, the method for generally adopting at present is that its material with carbon element good with more tough and electric conductivity is made into composite, carbon materials
Material such as graphite and CNT have preferable pliability, so the composite made will not be bright while reduces cost
Development rings its processing characteristics and performance.
Relative to graphite and CNT, Graphene has more excellent electric conductivity and more preferably pliability, therefore more
It is adapted to make composite with iron.Plating iron mainly has two kinds of paths of chemical plating and plating, relative to chemical plating, electroplates more environmentally-friendly
Clean and easy to operate, therefore realize that iron plating is a kind of ideal method on Graphene in the way of electroplating.
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 iron.
The content of the invention
For problem above, the invention provides a kind of economical and effective, and a kind of Graphene-iron 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-iron composite fibre, the compound fibre
Tie up and be made up of the iron layer of pure graphene fiber and the pure graphene fiber of cladding；The pure graphene fiber surface has fold,
Iron 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-iron composite fibre, its preparation process is as follows：
(1) graphene oxide fiber (a diameter of 1-50 microns) 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 iron staff 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 in vacuum drying oven, obtains Graphene-iron composite fibre.The electroplate liquid is consisted of, ferric sulfate
Concentration is 300-550g/L, and the volumetric concentration of the concentrated sulfuric acid of 98wt% is 3-10mL/L, and the concentration of potassium sulfate is 100-200g/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 10s.
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, metallic iron layer 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 structural representation of Graphene-iron composite fibre；
Fig. 2 is the multistage pleated structure figure of graphenic surface under different multiplying；
Fig. 3 is the distribution of iron particle and growth conditions when Graphene-iron composite fibre is electroplated；
Fig. 4 is the XRD of Graphene-iron 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-iron composite fibre, the composite fibre by a diameter of 1-50 microns pure graphite
The iron layer composition of alkene fiber and the pure graphene fiber of cladding；The pure graphene fiber surface has fold, and iron layer has embedding
Enter the extended structure of fold.The good physical property of fiber is combined closely from iron layer 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, obtained plating iron graphene fiber stone
Black alkene bulk density is 1.8-5.3g/cm3, Graphene mass fraction is 20-80%, and the mass fraction of iron is 20-80%, fiber
Conductance be 1.1 × 105S/m–3.6×106S/m, thickness of coating is 1-18 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, particle is gradually given birth to for the crystal grain of iron
Long, particle becomes big, and the crack being crimped is fixed, and further, iron crystal grain is along fold homoepitaxial and mutually fusion is until paving
Full whole fiber surface, its growth course is as illustrated, this growth pattern from inside to outside guarantees that final coating can be uniform
It is covered in fiber surface and stably adheres to.On the one hand the fibre structure for obtaining is stablized, such as can bend 100 conductances not
Become；On the other hand, bi-material is combined closely, and is not in hole defect, substantially increases the electric property of material.Tie below
The invention will be further described to close embodiment.
Embodiment 1
A kind of method that galvanoplastic prepare Graphene and iron composite fibre, including procedure below：
(1) a diameter of 4 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 5 microns of graphene oxide (on carbon paddy wish) in dimethylformamide, oxygen
The concentration of graphite alkene is 8mg/mL；The internal diameter of spinneret is 100 microns；Coagulating bath is the mixing of ethyl acetate and dichloromethane
(the two volume ratio is 1 to 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 1000 DEG C, after heating 1.5 hours, is obtained
To a diameter of 4 microns of graphene fiber.
(3) negative pole that graphene fiber is fixed on electroplating bath is electroplated, electroplating bath just extremely high purity iron rod, apply with
Magnitude of voltage is the DC voltage of 0.1V, and electroplate liquid is the dense sulphur of ferrous sulfate (300g/L), potassium sulfate (100g/L) and 98wt%
The mixed aqueous solution of sour (3mL/L), after electroplating 8 seconds, washes the electroplate liquid of fiber surface with water, 1 is dried in vacuum drying oven little
When.Because voltage is relatively low, the time is shorter, obtains coating and is about 3 microns.As shown in figure 4, XRD results show final compound fibre
There is the peak of obvious iron crystal in dimension table face.Jing is tested, and its conductance is 7.3 × 105S/m。
Embodiment 2
A kind of method that galvanoplastic prepare Graphene and iron 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 5 microns of graphene oxide (on carbon paddy wish) 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 dichloromethane
(the two volume ratio is 10 to 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 iron rod, apply with
Magnitude of voltage is the DC voltage of 1.3V, and electroplate liquid is the dense sulphur of ferrous sulfate (450g/L), potassium sulfate (130g/L) and 98wt%
The mixed aqueous solution of sour (3.5mL/L), after electroplating 120 seconds, washes the electroplate liquid of fiber surface with water, is dried in vacuum drying oven
9 hours.Obtain coating and be about 5 microns.Jing is tested, and its conductance is 1.5 × 106S/m。
Embodiment 3
A kind of method that galvanoplastic prepare Graphene and iron composite fibre, including procedure below：
(1) a diameter of 30 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 11mg/mL；The internal diameter of spinneret is 500 microns；Coagulating bath is ethyl acetate and dichloromethane
(the two volume ratio is 200 to mixed 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 2700 DEG C, after heating 1 hour, is obtained
To a diameter of 30 microns of graphene fiber.
(3) negative pole that graphene fiber is fixed on electroplating bath is electroplated, the just extremely pure iron staff of electroplating bath, apply with
Magnitude of voltage is the DC voltage of 20V, and electroplate liquid is ferrous sulfate (500g/L), the concentrated sulfuric acid (10mL/L) of 98wt% and potassium sulfate
(200g/L) mixed aqueous solution, after electroplating 2 seconds, washes the electroplate liquid of fiber surface with water, 5 is dried in vacuum drying oven little
When.After improving supply voltage, the potential of fiber is raised, and is obtained coating and is about 10 microns.Jing test, its conductance be 2.8 ×
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-iron composite fibre, it is characterised in that the composite fibre is by pure graphene fiber and coats pure stone
The iron layer composition of black alkene fiber；The pure graphene fiber surface has fold, and iron layer has the extended structure for being embedded in fold.
2. Graphene according to claim 1-iron 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-iron composite fibre, it is characterised in that its preparation process
It is as follows：
(1) graphene oxide fiber (a diameter of 1-50 microns) 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 iron staff 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-iron composite fibre.The electroplate liquid is consisted of, the concentration of ferric sulfate
For 300-550g/L, the volumetric concentration of the concentrated sulfuric acid of 98wt% is 3-10mL/L, and the concentration of potassium sulfate is 100-200g/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 10s.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108411350A (en) * | 2018-04-08 | 2018-08-17 | 武汉大学苏州研究院 | A kind of preparation method of graphene enhancing iron base composite material |
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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 |
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| CN105648579A (en) * | 2016-03-31 | 2016-06-08 | 浙江大学 | Superfine graphene fibers and method for preparing same |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108411350A (en) * | 2018-04-08 | 2018-08-17 | 武汉大学苏州研究院 | A kind of preparation method of graphene enhancing iron base composite material |
| CN108411350B (en) * | 2018-04-08 | 2020-04-14 | 武汉大学苏州研究院 | Preparation method of graphene reinforced iron-based composite material |
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Effective date of registration: 20190903 Address after: 313100 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 |
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