CN104882613A - Preparation method for flexible and highly-conductive composite carbon fiber cloth - Google Patents
Preparation method for flexible and highly-conductive composite carbon fiber cloth Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
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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
- D06M11/73—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 carbon or compounds thereof
- D06M11/74—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 carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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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
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to the field of carbon composite materials, more particularly to a preparation method for the flexible and highly-conductive composite carbon fiber cloth, wherein the pure natural cellulose cloth is adopted as a precursor to be uniformly compounded with carbon nanotubes and/or graphene through the impregnation method. In the protective atmosphere, textile fibers are carbonized through the high-temperature heat treatment, and a carbon fiber interface is strongly bonded with the composite carbon nanotubes or the composite graphene. In this way, during the carbonizing process, a strong bonding action is formed between carbon fibers, carbon nanotubes and/or grapheme, so that a coaxial carbon fiber cloth composite structure is formed. According to the invention, the structure and the performance of the composite material are regulated at different treatment temperatures, different treatment times and different compound quantities of carbon nanotubes. In this way, by means of the flexible and highly-conductive composite carbon fiber cloth, the problem that conventional carbon materials do not have the advantages of flexibility, high specific surface area and high electrical conductivity at the same time can be solved.
Description
Technical field
The present invention relates to carbon composite field, particularly a kind of preparation method of flexible high connductivity composite construction carbon cloth.
Background technology
Carbon fiber because of the features such as the mechanical property of its excellence, good chemical stability and high-strength light from appearance since enjoy favor, it is applied widely in fields such as automobile, Aero-Space, military project national defence as composite material reinforcement body.There is significant difference in mechanics, the electric property of the carbon fiber obtained by different precursor power, the two-dimentional conductive network become by carbon fiber knit has potential application in all many-sides.Carbon nano-tube, Graphene are the Novel Carbon Nanomaterials be found in recent years, and because it has unique nanostructure, theoretical and experimental study shows that carbon nano-tube and Graphene have the physical and chemical performance more excellent than micron order carbon fiber.If carbon nano-tube, Graphene and carbon fiber are carried out compound, effectively can reduce resistance further, and strengthen structural strength, and research is in this respect relatively less.
Up to the present, both at home and abroad the report of flexible carbon fiber composite structure is mainly concentrated in the following areas: [document 1, Wang HQ, Chen ZX, Liu HK, Guo, ZP.Rsc Advances 4,110,65074-65080 (2014)] there is researcher to be used for lithium-sulfur cell by after cotton carbonization, but be formed by weaving by line stock due to cotton, very closely knit between carbon fiber, cause the effective interface of material very little, limit the application in the composite of carbonized cotton cloth material.In carbon cloth composite construction, current research mainly contains the following aspects, [patent 1, the method of carbon nano-tube in carbon cloth substrate, (2006) CN 1868869A] applicant discloses the method for a kind of utilization at carbon cloth upper berth catalyst, at high temperature obtains the composite construction of carbon nano-tube and carbon cloth; [patent 2, a kind of preparation method of the flexible super capacitor based on carbon cloth, (2006) CN102509635] discloses one and utilizes on carbon cloth and modify oxide particle or carbon nano-tube, and is applied to the method for flexible capacitor; Because above structure is all utilize the carbon cloth of industrial preparation for raw material, cost is higher, utilizes the process more complicated of the long carbon nano-tube of catalyst regeneration further, is unfavorable for large-scale production and application.In addition, obtaining under high conductivity and flexible prerequisite, how to control Graphene, interface interaction power between carbon nano-tube and carbon fiber is also very crucial.
Therefore, how to realize the simple and easy controlled compound of carbon nano-tube, Graphene and carbon fiber, and effective matter of science and technologys such as its combination property (as: good flexibility, excellent conductivity, stability) that strengthen still await further investigation and solve.
In a word, simultaneously the R&D target of carbon fiber reinforce plastic realizes flexibility good when material has, excellent conductivity, accurate content control and good interface cohesion.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of low cost, easy industrialized flexible high connductivity composite construction carbon cloth, to meet the demand of electrode supporting structure etc. of compliant thermal interface material, flexible electronic device, lithium ion battery.
Technical scheme of the present invention is:
A preparation method for flexible High-conductivity composite carbon fiber cloth, with pure natural fiber silk barathea cloth for presoma, by infusion process by after carbon nano-tube and/or Graphene and the even compound of presoma, carry out high-temperature process and make the carbonization of main fibre element, concrete steps are as follows:
(1) with pure natural fiber silk barathea cloth for presoma, in the solution of second alcohol and water after washing by soaking, dry for standby;
(2) get carbon nano-tube and/or graphene dispersion in the solution, be mixed with the slurry of variable concentrations;
(3) cotton is impregnated in the slurry of variable concentrations, after oven dry, obtains composite precursor;
(4) composite precursor is heated up under protective atmosphere; the gas flow of protective atmosphere is 10sccm ~ 2000sccm; heating rate is 1 ~ 50 DEG C/min; be warming up to 600 ~ 1200 DEG C; be incubated 1 ~ 6h at a set temperature; under protective atmosphere, be annealed to room temperature, obtain flexible carbon fibre cloth composite construction.
The preparation method of described flexible High-conductivity composite carbon fiber cloth, in step (1), selected cotton be 100% native cellulose or by mixing the compounded cotton of chemical fibre.
The preparation method of described flexible High-conductivity composite carbon fiber cloth, in step (1), gets cotton, puts into alcohol respectively, water soaks 1 ~ 24h, to remove surface impurity, dries 5 ~ 24 hours at 60 ~ 100 DEG C.
The preparation method of described flexible High-conductivity composite carbon fiber cloth, in step (2), carbon nano-tube is Single Walled Carbon Nanotube, few-wall carbon nanotube or multi-walled carbon nano-tubes, and its diameter is from 1nm to 300nm, and length is from 100nm to 1000 μm; Graphene is single-layer graphene, minority layer graphene or multi-layer graphene, and size is by 2 μm to 200 μm.
The preparation method of described flexible High-conductivity composite carbon fiber cloth, in the slurry of step (2), comprise the solution of carbon nano-tube and/or Graphene, dispersing Nano carbon tubes and/or Graphene, surfactant, by mass percentage, carbon nano-tube and/or Graphene account for 0.01% ~ 10%, surfactant accounts for 1 ~ 10%, and surplus is the solution of dispersing Nano carbon tubes and/or Graphene.
The preparation method of described flexible High-conductivity composite carbon fiber cloth, the solution of dispersing Nano carbon tubes, Graphene be in deionized water, ethanol, ethylene glycol, acetone, 1-METHYLPYRROLIDONE, polyvinyl alcohol, acetone wherein one or more; Surfactant is one in polyvinylpyrrolidone, neopelex, lauryl sodium sulfate, softex kw, polyethylene glycol or two or more.
The preparation method of described flexible High-conductivity composite carbon fiber cloth, protective atmosphere is argon gas, helium or nitrogen.
The preparation method of described flexible High-conductivity composite carbon fiber cloth, in the process of carbonization, carbon nano-tube and/or form bonding action between Graphene and carbon fiber, obtains the coaxial composite structure that carbon nano-tube and/or graphene uniform are coated on carbon fiber surface; The diameter distribution of its carbon fiber is 3 ~ 500 μm, and length distribution range is 0.1 ~ 2mm.
The preparation method of described flexible High-conductivity composite carbon fiber cloth, the bending angle of carbon cloth composite construction is from 0 ~ 180 degree, and its conductivity improves along with the rising of heat treatment temperature, and its square resistance scope is 0.3 ~ 20K Ω/.
Design philosophy of the present invention is:
The present invention take yarn fabric as raw material; after one or both compounds in carbon nano-tube, Graphene; fabric fibre carbonization is made by high-temperature heat treatment under protective atmosphere; and make the carbon nano-tube of carbon fiber interface and compound or Graphene produce stronger adhesion, and form coaxial composite structure.The present invention utilizes the compound quantity of different heat treatment temperatures, heat treatment time and nano-carbon material to regulate and control the stuctures and properties of composite material, and this flexible carbon fibre cloth composite construction solves the problem that common material with carbon element can not have flexibility, high-ratio surface sum high conductivity concurrently.
Advantage of the present invention and beneficial effect are:
1, the present invention adopts pure natural fiber silk barathea cloth to be precursor material, by the control to heat treatment temperature and heat treatment time, can realize the regulation and control of degree of crystallinity to carbon fiber and conductivity.
2, the present invention can realize the regulation and control of carbon nano-tube in carbon cloth composite construction, Graphene content.
3, the present invention can realize carbon nano-tube, interface binding power good between Graphene and carbon fiber.
4, the present invention can realize carbon cloth composite construction and possesses good flexibility, and its bending angle can realize the change of 0 ~ 180 °, and keeps good conductivity.
5, the present invention is easy and simple to handle, and technical process easily realizes industrialization.
Accompanying drawing explanation
Fig. 1. flood the composite precursor optics picture before heat treatment of different carbon nanotube mass.Wherein, from left to right, carbon nanotube mass is respectively: (a) 0mg, (b) 3.3mg, (c) 6.1mg, (d) 15.8mg, (e) 33.3mg, (f) 75mg.
Fig. 2. flood the composite precursor optics picture before heat treatment of different Graphene quality.Wherein, from left to right, load Graphene quality is respectively: (a) 0mg, (b) 3.3mg, (c) 6.1mg, (d) 15.8mg, (e) 33.3mg, (f) 75mg.
Fig. 3. flood the composite precursor optics picture before heat treatment of different carbon nano-tube and Graphene (mass ratio 1:1) mixing quality.Wherein, from left to right, the quality of load carbon nano-tube and Graphene is respectively: (a) 0mg, (b) 3.3mg, (c) 6.1mg, (d) 15.8mg, (e) 33.3mg, (f) 75mg.
Fig. 4. carbon nano-tube composite precursor optical photograph after heat treatment.Wherein, (a) is pure carbon fiber cloth; B () is 1wt% carbon nano tube composite carbon fiber cloth; C () is 2wt% carbon nano tube composite carbon fiber cloth; D () is 5wt% carbon nano tube composite carbon fiber cloth; E () is 10wt% carbon nano tube composite carbon fiber cloth; F () is 20wt% carbon nano tube composite carbon fiber cloth.
Fig. 5. Graphene composite precursor optical photograph after heat treatment.Wherein, (a) is pure carbon fiber cloth; B () is 1wt% Graphene carbon fibre cloth; C () is 2wt% Graphene carbon fibre cloth; D () is 5wt% Graphene carbon fibre cloth; E () is 10wt% Graphene carbon fibre cloth; F () is 20wt% Graphene carbon fibre cloth.
Fig. 6. carbon nano-tube and Graphene composite precursor optical photograph after heat treated altogether.Wherein, (a) is pure carbon fiber cloth; B () is 1wt% carbon nano-tube and Graphene carbon fibre cloth altogether; C () is 2wt% carbon nano-tube and Graphene carbon fibre cloth altogether; D () is 5wt% carbon nano-tube and Graphene carbon fibre cloth altogether; E () is 10wt% carbon nano-tube and Graphene carbon fibre cloth altogether; F () is 20wt% carbon nano-tube and Graphene carbon fibre cloth altogether.
Fig. 7. the stereoscan photograph of pure carbon fiber cloth under different amplification.Wherein, photo under (a) carbon cloth low power; B () knits exograph X for composition carbon cloth; C () is the single many carbon fiber photos knitted in line; D () is carbon fiber surface photo.
Fig. 8. the stereoscan photograph of carbon nano tube composite carbon fiber cloth under different amplification.Wherein, (a) is photo under carbon nano tube composite carbon fiber cloth low power; B () knits exograph X for carbon nano tube composite carbon fiber cloth; C () is the single many carbon fiber photos knitted in line; D carbon fiber surface photo that () is even enveloped carbon nanometer tube.
Fig. 9. the stereoscan photograph of Graphene carbon fibre cloth under different amplification.Wherein, (a) is photo under Graphene carbon fibre cloth low power; B () knits exograph X for Graphene carbon fibre cloth; C () is the single many carbon fiber photos knitted in line; D () is the carbon fiber surface photo of even coated graphite alkene.
Figure 10. carbon nano-tube and the Graphene stereoscan photograph of carbon fibre cloth under different amplification altogether.Wherein, (a) is photo under carbon nano-tube and Graphene altogether carbon fibre cloth low power; (b) for carbon nano-tube and Graphene altogether carbon fibre cloth knit exograph X; C () is the single many carbon fiber photos knitted in line; D carbon fiber surface photo that () is even enveloped carbon nanometer tube and Graphene.
Figure 11. the Raman collection of illustrative plates contrast collection of illustrative plates of different carbon cloth composite construction.In figure, Raman shift (cm
-1) be Raman shift.
Figure 12. under carbon cloth and carbon nano-tube, Graphene, carbon nano-tube and Graphene three kinds of different composite systems, the square resistance resolution chart of different composite content.
Figure 13. resistance test figure under carbon nano tube composite carbon fiber cloth bending condition.
Embodiment
In a specific embodiment, the present invention for presoma with pure natural fiber silk barathea cloth, by simple infusion process by after carbon nano-tube and/or Graphene and the even compound of presoma, carries out high-temperature heat treatment and makes the carbonization of main fibre element.In the process of carbonization, form stronger bonding between carbon fiber and carbon nano-tube and/or Graphene, the diameter of carbon fiber is 3 ~ 500 μm (being preferably 5 ~ 50 μm), and the length distribution range of carbon fiber is 0.1 ~ 2mm; Carbon fiber surface and carbon nano-tube and/or Graphene form coaxial composite structure, and carbon fiber knit becomes line and obtains three-dimensional macro bluk recombination structure.Its concrete steps are as follows:
(1) with pure natural fiber silk barathea cloth for presoma, in the solution of second alcohol and water after washing by soaking, dry for standby.Get appropriate cotton, put into alcohol respectively, water soaks 1 ~ 24h, remove surface impurity, at 60 ~ 100 DEG C, dry 5 ~ 24h;
(2) get a series of carbon nano-tube and/or graphene dispersion in the solution, be made into the slurry of variable concentrations;
(3) cotton is impregnated in the slurry of variable concentrations, after drying, obtains compound cotton presoma;
(4) presoma is heated up under protective atmosphere (argon gas, helium or nitrogen); protective atmosphere flow is 10 ~ 2000sccm (being preferably 300 ~ 1000sccm); heating rate is 1 ~ 50 DEG C/min; be warming up to 600 ~ 1200 DEG C; be incubated 1 ~ 6h at a set temperature; under protective atmosphere, be annealed to room temperature, flexible carbon fibre cloth composite construction can be obtained.Define stronger adhesion between carbon fiber and Graphene and/or carbon nano-tube in described carbon cloth composite construction, form coaxial composite structure (coaxial composite structure refers to that carbon nano-tube and/or graphene uniform are coated on carbon fiber); Meanwhile, material monolithic shows good flexibility and high conductivity: bending angle is from 0 ~ 180 °, and conductivity improves along with the rising of heat treatment temperature (the square resistance scope weighing electric conductivity is 0.3 ~ 20K Ω/).
Selected cotton is the native cellulose of 100% or by the compounded cotton of chemical fibre, the area of selected cotton is 1cm
2above.Can be Single Walled Carbon Nanotube, few-wall carbon nanotube or multi-walled carbon nano-tubes with the carbon nano-tube of carbon fiber skeleton compound, its diameter distribution is 1 ~ 300nm, and length distribution range is 100nm ~ 1000 μm.Can be single-layer graphene, minority layer graphene or multi-layer graphene with the Graphene of carbon fiber skeleton compound, dimensions length distribution is 2 ~ 200 μm, and number of plies distribution is 1 ~ 100 layer.
In the slurry that infusion process adopts, comprise the solution of carbon nano-tube and/or Graphene, dispersing Nano carbon tubes and/or Graphene, surfactant, carbon nano-tube and/or Graphene account for 0.01 ~ 10wt% and (are preferably 0.02 ~ 2wt%, surfactant accounts for 1 ~ 10wt% (being preferably 1 ~ 5wt%), and surplus is the solution of dispersing Nano carbon tubes and/or Graphene.The solution of dispersing Nano carbon tubes, Graphene is one or more in deionized water, ethanol, ethylene glycol, acetone, 1-METHYLPYRROLIDONE (NMP), polyvinyl alcohol (PVA), acetone etc.; Surfactant is one or more in polyvinylpyrrolidone (PVP), neopelex (SDBS), lauryl sodium sulfate (SDS), softex kw (CTAB), polyethylene glycol etc.
The present invention is described in further detail below by embodiment and accompanying drawing.
In an embodiment, employing length be 11cm, wide for 10.5cm, thickness be 1mm, quality is the cotton of 2.4g, puts into ethanol and water (volume ratio 1:1) soaking and washing 5h, 70 DEG C of drying in oven 6h.
In an embodiment, in the slurry that infusion process adopts, comprise carbon nano-tube and/or Graphene, the solution for dispersing Nano carbon tubes and/or Graphene, surfactant, by mass percentage, carbon nano-tube and/or Graphene account for 0.2wt%, surfactant accounts for 1.5wt%, and surplus is the solution of dispersing Nano carbon tubes and/or Graphene.
Embodiment 1
Get seven, above-mentioned cotton, flood the carbon nano-tube of compound different quality respectively, be followed successively by (a) 0mg, (b) 3.3mg, (c) 6.1mg, (d) 15.8mg, (e) 33.3mg, (f) 75mg, afterwards compound cotton presoma is put in 70 DEG C of baking ovens and dries 12h, corresponding to Fig. 1 (a), (b), (c), (d), (e) and (f), taking-up is put in tube furnace, vacuumize, take argon gas as protection gas (flow is 1000sccm), with the ramp of 10 DEG C/min to 1000 DEG C, heat preservation hot process 2h under argon gas, room temperature is dropped to again in argon shield, gained sample as shown in Figure 4.In six samples, content of carbon nanotubes is respectively: 0,1wt%, 2wt%, 5wt%, 10wt% and 20wt%; Fig. 7 shows, pure carbon fiber cloth, and the electron scanning micrograph in Fig. 8 shows cotton and knits line by regular cotton and be formed by weaving, and carbon fiber surface is evenly coated with carbon nano-tube.
Embodiment 2
Get seven, above-mentioned cotton, flood the Graphene of compound different quality respectively, be followed successively by (a) 0mg, (b) 3.3mg, (c) 6.1mg, (d) 15.8mg, (e) 33.3mg, (f) 75mg, afterwards compound cotton presoma is put in 70 DEG C of baking ovens and dries 12h, corresponding to Fig. 2 (a), (b), (c), (d), (e) and (f), taking-up is put in tube furnace, vacuumize, take argon gas as protection gas (flow is 1000sccm), with the ramp of 10 DEG C/min to 1000 DEG C, under argon gas, heat treatment time is 2h, argon shield drops to room temperature.(as shown in Figure 5) in six samples, Graphene content is respectively: 0,1wt%, 2wt%, 5wt%, 10wt% and 20wt%.Electron scanning micrograph in Fig. 8 illustrates cotton and knits line by regular cotton and be formed by weaving, and carbon fiber surface is evenly coated with Graphene.
Embodiment 3
Get seven, above-mentioned cotton, in the carbon nano-tube of flooding compound quantity respectively and Graphene mixed solution (mass ratio 1:1), be followed successively by (a) 0mg, (b) 3.3mg, (c) 6.1mg, (d) 15.8mg, (e) 33.3mg, (f) 75mg, afterwards compound cotton presoma is put in 70 DEG C of baking ovens and dries 12h, corresponding to Fig. 3 (a), (b), (c), (d), (e) (f), taking-up is put in tube furnace, vacuumize, take argon gas as protection gas (flow is 1000sccm), with the ramp of 10 DEG C/min to 1000 DEG C, under argon gas, heat treatment time is 2h, argon shield drops to room temperature.(as shown in Figure 6) in six samples, carbon nano-tube and Graphene gross mass percentage are respectively: 0,1wt%, 2wt%, 5wt%, 10wt% and 20wt%.Electron scanning micrograph in Fig. 9 illustrates cotton and knits line by regular cotton and be formed by weaving, and carbon fiber surface is evenly coated with carbon nano-tube and Graphene.
Embodiment 4
After high-temperature process, sample size remains on long 8cm, wide 7.5cm, thick 0.8mm substantially, utilizes three-electrode method and universal instrument to carry out conductivity test.With carbon nano-tube and/or Graphene compound after, the conductivity of carbon cloth strengthens (as Figure 12) further, and related data is as follows:
As shown in table 1, the square resistance utilizing four probe method to test pure carbon fiber cloth is 8 Ω/, and to carbon nano tube composite carbon fiber cloth material, when content of carbon nanotubes is 1wt%, square resistance is 6.5 Ω/; Decline further along with content of carbon nanotubes increases square resistance, when content of carbon nanotubes is 20wt%, resistance value is 5.3 Ω/; To Graphene carbon fiber reinforce plastic cloth material, when Graphene content is 1wt%, square resistance is 6.2 Ω/, and along with the increase of Graphene content, square resistance declines further, and when Graphene content is 20wt%, square resistance is 3.8 Ω/; To carbon nano-tube and Graphene carbon fiber reinforce plastic cloth material altogether, when carbon nano-tube and Graphene content are 1wt%, square resistance is 6.3 Ω/, and when content is 20wt%, square resistance is 4.6 Ω/.
Table 1
As shown in Figure 10, can find out that the fiber in the carbon cloth after Graphene compound still maintains the structure of carbon fiber, graphene uniform is coated with carbon fiber, defines coaxial configuration.
As shown in figure 11, can find out that in the sample of carbon cloth and carbon nano-tube, Graphene and carbon nano-tube and Graphene co-blended, sample Raman signal is obvious, indicates and has successfully prepared composite construction.
As shown in figure 12, can find out by after carbon nano-tube and/or Graphene carbon fiber reinforce plastic, surperficial square resistance can be reduced further, namely improve the conductivity of composite construction; Compare known, Graphene is in raising conductivity, and be slightly better than multi-walled carbon nano-tubes, 20wt% Graphene carbon fibre cloth body structure surface resistance can reach 3.8 Ω/.
As shown in figure 13, can find out that carbon nano-tube and/or graphene composite structure still can keep good electric conductivity in a flexed condition according, namely show that carbon fiber reinforced polymers has good flexibility, excellent conductivity.
Embodiment result shows, the present invention can by the preparation controlling different heat treatment temperatures, different complex parameter realizes flexible carbon fibre cloth composite material.Resulting materials shows good flexibility, excellent conductivity and good surface conjunction power, is expected to obtain application in the braiding preparation etc. of the power supply of compliant thermal interface material, wearable device, the catalyst carrier of fuel cell and functional material.
Claims (9)
1. the preparation method of a flexible High-conductivity composite carbon fiber cloth, it is characterized in that, with pure natural fiber silk barathea cloth for presoma, by infusion process by after carbon nano-tube and/or Graphene and the even compound of presoma, carry out high-temperature process and make the carbonization of main fibre element, concrete steps are as follows:
(1) with pure natural fiber silk barathea cloth for presoma, in the solution of second alcohol and water after washing by soaking, dry for standby;
(2) get carbon nano-tube and/or graphene dispersion in the solution, be mixed with the slurry of variable concentrations;
(3) cotton is impregnated in the slurry of variable concentrations, after oven dry, obtains composite precursor;
(4) composite precursor is heated up under protective atmosphere; the gas flow of protective atmosphere is 10sccm ~ 2000sccm; heating rate is 1 ~ 50 DEG C/min; be warming up to 600 ~ 1200 DEG C; be incubated 1 ~ 6h at a set temperature; under protective atmosphere, be annealed to room temperature, obtain flexible carbon fibre cloth composite construction.
2., according to the preparation method of flexible High-conductivity composite carbon fiber cloth according to claim 1, it is characterized in that, in step (1), selected cotton be 100% native cellulose or by mixing the compounded cotton of chemical fibre.
3. according to the preparation method of flexible High-conductivity composite carbon fiber cloth according to claim 1, it is characterized in that, in step (1), get cotton, put into alcohol respectively, water soaks 1 ~ 24h, to remove surface impurity, dry 5 ~ 24 hours at 60 ~ 100 DEG C.
4. according to the preparation method of flexible High-conductivity composite carbon fiber cloth according to claim 1, it is characterized in that, in step (2), carbon nano-tube is Single Walled Carbon Nanotube, few-wall carbon nanotube or multi-walled carbon nano-tubes, its diameter is from 1nm to 300nm, and length is from 100nm to 1000 μm; Graphene is single-layer graphene, minority layer graphene or multi-layer graphene, and size is by 2 μm to 200 μm.
5. according to the preparation method of flexible High-conductivity composite carbon fiber cloth according to claim 1, it is characterized in that, in the slurry of step (2), comprise the solution of carbon nano-tube and/or Graphene, dispersing Nano carbon tubes and/or Graphene, surfactant, by mass percentage, carbon nano-tube and/or Graphene account for 0.01% ~ 10%, and surfactant accounts for 1 ~ 10%, and surplus is the solution of dispersing Nano carbon tubes and/or Graphene.
6. according to the preparation method of flexible High-conductivity composite carbon fiber cloth according to claim 5, it is characterized in that, the solution of dispersing Nano carbon tubes, Graphene be in deionized water, ethanol, ethylene glycol, acetone, 1-METHYLPYRROLIDONE, polyvinyl alcohol, acetone wherein one or more; Surfactant is one in polyvinylpyrrolidone, neopelex, lauryl sodium sulfate, softex kw, polyethylene glycol or two or more.
7. according to the preparation method of flexible High-conductivity composite carbon fiber cloth according to claim 1, it is characterized in that, protective atmosphere is argon gas, helium or nitrogen.
8. according to the preparation method of flexible High-conductivity composite carbon fiber cloth according to claim 1, it is characterized in that, in the process of carbonization, carbon nano-tube and/or form bonding action between Graphene and carbon fiber, obtains the coaxial composite structure that carbon nano-tube and/or graphene uniform are coated on carbon fiber surface; The diameter distribution of its carbon fiber is 3 ~ 500 μm, and length distribution range is 0.1 ~ 2mm.
9. according to the preparation method of flexible High-conductivity composite carbon fiber cloth according to claim 1, it is characterized in that, the bending angle of carbon cloth composite construction is from 0 ~ 180 degree, and its conductivity improves along with the rising of heat treatment temperature, and its square resistance scope is 0.3 ~ 20K Ω/.
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Cited By (24)
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| CN113249961A (en) * | 2021-04-25 | 2021-08-13 | 北京邮电大学 | Flexible device structure based on conductive fiber network and preparation method and application thereof |
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| CN105898981B (en) * | 2016-04-01 | 2018-08-03 | 合肥工业大学 | A kind of stretchable electrode and preparation method thereof based on conductive fabric |
| CN105841601A (en) * | 2016-04-26 | 2016-08-10 | 清华大学 | Flexible wearable strain sensor based on fabrics and preparation method thereof |
| CN105841601B (en) * | 2016-04-26 | 2019-04-23 | 清华大学 | A kind of flexible wearable strain transducer and preparation method based on fabric |
| CN106000300A (en) * | 2016-05-26 | 2016-10-12 | 江苏大学 | Preparation method and use of porous flexible adsorbent |
| WO2017220979A1 (en) * | 2016-06-24 | 2017-12-28 | The University Of Manchester | Graphene-based sensor |
| CN106211388A (en) * | 2016-07-05 | 2016-12-07 | 安徽吉安特种线缆制造有限公司 | A kind of self limiting temperature cable material of good weatherability |
| CN106283610A (en) * | 2016-08-04 | 2017-01-04 | 武汉纺织大学 | A kind of Graphene inductive formation polypyrrole nano line conducing composite material preparation method |
| CN106283610B (en) * | 2016-08-04 | 2018-08-10 | 武汉纺织大学 | A kind of graphene inductive formation polypyrrole nano line conducing composite material preparation method |
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| CN106450258A (en) * | 2016-12-02 | 2017-02-22 | 黑龙江科技大学 | Vanadium oxide and hard carbon fiber cloth combined electrode material preparation method |
| CN106450258B (en) * | 2016-12-02 | 2018-11-13 | 黑龙江科技大学 | A kind of preparation method of vanadium oxide and hard carbon fiber cloth combination electrode material |
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| CN107887181A (en) * | 2017-11-16 | 2018-04-06 | 东华大学 | A kind of preparation method of cotton base carbon fibre flexible electrode |
| CN108253875A (en) * | 2018-01-16 | 2018-07-06 | 清远建滔暖芯技术有限公司 | The detection control method and system of a kind of graphene carbon fiber cloth |
| CN108827136A (en) * | 2018-04-16 | 2018-11-16 | 西南石油大学 | A method of flexible strain transducer is prepared using waste and old thermosetting resin |
| CN108827136B (en) * | 2018-04-16 | 2019-07-02 | 西南石油大学 | A method of flexible strain transducer is prepared using waste and old thermosetting resin |
| CN109183459A (en) * | 2018-07-30 | 2019-01-11 | 嘉兴学院 | A kind of method that graphene is used for cotton products arrangement |
| CN109526077A (en) * | 2018-11-08 | 2019-03-26 | 嘉兴纳科新材料有限公司 | A kind of preparation method based on carbon cloth flexible electric heating sheet |
| CN110323451A (en) * | 2019-04-28 | 2019-10-11 | 中国科学院山西煤炭化学研究所 | A kind of multifunctional composite and its preparation method and application based on graphene and macromolecular fibre |
| CN110957485A (en) * | 2019-12-17 | 2020-04-03 | 东莞理工学院 | Graphene nanosheet coated porous carbon fiber material and preparation method thereof |
| CN111304799A (en) * | 2020-04-10 | 2020-06-19 | 中国科学院苏州纳米技术与纳米仿生研究所 | Argon-free self-protection method for high-temperature electric heating of carbon nanotube fiber and application thereof |
| CN113005548A (en) * | 2021-03-30 | 2021-06-22 | 上海大学 | Carbon nano tube modified antistatic agent for fibers |
| CN113249961A (en) * | 2021-04-25 | 2021-08-13 | 北京邮电大学 | Flexible device structure based on conductive fiber network and preparation method and application thereof |
| CN113307253A (en) * | 2021-05-24 | 2021-08-27 | 盐城金麦穗科技发展有限公司 | Graphene carbon fiber composite urban rail transit electrical carbon slide bar and manufacturing method thereof |
| CN114709429A (en) * | 2022-03-02 | 2022-07-05 | 江苏科技大学 | Cotton carbon cloth/nitrogen-doped nano carbon/carbon nano tube flexible integrated electrode and preparation method and application thereof |
| CN114725390A (en) * | 2022-03-30 | 2022-07-08 | 广西科技大学 | Carbon cloth loaded carbon tube material and preparation method and application thereof |
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