CN104882613B - A kind of preparation method of flexible High-conductivity composite carbon fiber cloth - Google Patents
A kind of preparation method of flexible High-conductivity 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 carbon composite field, particularly a kind of preparation method of flexible highly conductive composite construction carbon cloth.Using pure natural fiber silk barathea cloth as presoma; after CNT and/or graphene are uniformly combined with presoma by infusion process; fabric fibre is carbonized by high-temperature heat treatment under protective atmosphere, and carbon fiber interface is produced stronger adhesion with compound CNT or graphene.Formed during carbonization, between carbon fiber and CNT and/or graphene it is stronger be bonded, form coaxial carbon fibre cloth.The present invention regulates and controls the structure and performance of composite using different treatment temperatures, processing time and Nano Carbon amount, and the flexible High-conductivity composite carbon fiber cloth solves the problem of common carbon material can not have flexible, high-specific surface area and high conductivity concurrently.
Description
Technical field
The present invention relates to carbon composite field, particularly a kind of preparation side of flexible highly conductive composite construction carbon cloth
Method.
Background technology
The features such as carbon fiber is because of its excellent mechanical property, good chemical stability and high-strength light since the advent of the world
Favor is enjoyed, 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 prepared by different presomas, the two dimension being woven into by carbon fiber
Conductive network has potential application in all many-sides.CNT, graphene are the Novel Carbon Nanomaterials being found in recent years,
Because it has unique nanostructured, theoretical and experimental study shows that CNT and graphene have than micron grade carbon fiber more
Excellent physical and chemical performance.If CNT, graphene and carbon fiber are combined, can effectively further it reduce
Resistance, and enhancing structure intensity, and research in this respect is relatively fewer.
Up to the present, following aspect is concentrated mainly on to the report of flexible carbon fiber composite structure both at home and abroad：[document 1,
Wang HQ, Chen ZX, Liu HK, Guo, ZP.Rsc Advances 4,110,65074-65080 (2014)] there is researcher will
It is used for lithium-sulfur cell after cotton carbonization, but is due to that cotton is formed by weaving by strands, it is very closely knit between carbon fiber, cause
The effective interface very little of material, limits the application of carbonization cloth material in the composite.In carbon cloth composite construction side
Face, at present research mainly has the following aspects, [patent 1, grows the method for CNT in carbon cloth substrate,
(2006) CN 1868869A] applicant disclose it is a kind of using carbon cloth upper berth catalyst method, obtain at high temperature
The composite construction of CNT and carbon cloth；[patent 2, a kind of preparation of the flexible super capacitor based on carbon cloth
Method, (2006) CN102509635] one kind is disclosed using modification oxide particle or CNT on carbon cloth, and
Method applied to flexible capacitor；It using the carbon cloth that industrially prepares is raw material to be all due to above structure, cost compared with
Height, further the process using catalyst regrowth CNT is more complicated, is unfavorable for mass producing and applies.In addition,
On the premise of obtaining high conductivity and be flexible, the interface interaction power between graphene, CNT and carbon fiber how is controlled
Also it is very crucial.
Therefore, the simple controllable compound of CNT, graphene and carbon fiber how is realized, and it is comprehensive effectively to strengthen its
Can (such as：Good flexible, excellent electric conductivity, stability) etc. matter of science and technology still await furtheing investigate and solving.
In a word, the R＆D target for being combined carbon fiber be and meanwhile realize when material has good flexible, excellent electric conductivity,
Accurate content control and good interface cohesion.
The content of the invention
It is an object of the invention to provide a kind of inexpensive, easy industrialized flexible highly conductive composite construction carbon cloth
Preparation method, the demand of the electrode supporting structure to meet compliant thermal interface material, flexible electronic device, lithium ion battery etc..
The technical scheme is that：
A kind of preparation method of flexible High-conductivity composite carbon fiber cloth, using pure natural fiber silk barathea cloth as presoma, passes through
After CNT and/or graphene are uniformly combined by infusion process with presoma, carrying out high-temperature process makes main fibre element carbonization, tool
Body step is as follows：
(1) using pure natural fiber silk barathea cloth as presoma, in the solution of second alcohol and water after washing by soaking, dry for standby；
(2) CNT and/or graphene dispersion are taken in a solvent, the slurry of various concentrations is configured to；
(3) cotton is impregnated into the slurry of various concentrations, impregnates corresponding cotton in various concentrations slurry respectively, dried
After obtain composite precursor；
(4) composite precursor is heated up under protective atmosphere, the gas flow of protective atmosphere for 10sccm~
2000sccm, heating rate is 1~50 DEG C/min, is warming up to 600~1200 DEG C of 1~6h of insulation, is annealed under protective atmosphere
Room temperature, obtains flexible High-conductivity composite carbon fiber cloth.
In the preparation method of described flexible High-conductivity composite carbon fiber cloth, step (1), cotton is taken, second alcohol and water is put into
Solution in soak 1~24h, to remove surface impurity, at 60~100 DEG C dry 5~24 hours.
In the preparation method of described flexible High-conductivity composite carbon fiber cloth, step (2), CNT is single
Pipe, few-wall carbon nanotube or multi-walled carbon nanotube, its diameter is from 1nm to 300nm, and length is from 100nm to 1000 μm；Graphene is
Single-layer graphene, a small number of layer graphenes or multi-layer graphene, size is by 2 μm to 200 μm.
In the preparation method of described flexible High-conductivity composite carbon fiber cloth, the slurry of step (2), including CNT
And/or graphene, the solvent of dispersing Nano carbon tubes and/or graphene, surfactant, based on weight/mass percentage composition, carbon nanometer
Pipe and/or graphene account for 0.01%~10%, and surfactant accounts for 1~10%, and surplus is dispersing Nano carbon tubes and/or graphene
Solvent.
The preparation method of described flexible High-conductivity composite carbon fiber cloth, dispersing Nano carbon tubes, the solvent of graphene are to go
One of which or two or more in ionized water, ethanol, ethylene glycol, acetone, 1-METHYLPYRROLIDONE, polyvinyl alcohol；Live on surface
Property agent be polyvinylpyrrolidone, it is neopelex, lauryl sodium sulfate, cetyl trimethylammonium bromide, poly-
It is more than the one or two kinds of in ethylene glycol.
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, during carbonization, CNT and/or stone
Bonding action is formed between black alkene and carbon fiber, CNT is obtained and/or graphene uniform is coated on the same of carbon fiber surface
Axle composite construction；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 fibre cloth is from 0~180
Degree, its electric conductivity is improved with the rise of heat treatment temperature, and its square resistance scope is 0.3~20K Ω/.
The present invention design philosophy be：
The present invention is using yarn fabric as raw material, after being combined with one or both of CNT, graphene, in protectiveness
Fabric fibre is carbonized by high-temperature heat treatment under atmosphere, and carbon fiber interface is produced with compound CNT or graphene
Stronger adhesion, and form coaxial composite structure.The present invention utilizes different heat treatment temperatures, heat treatment time and nano-sized carbon
The compound quantity of material regulates and controls the structure and performance of composite, and the flexible carbon fibre cloth composite construction solves common carbon material
The problem of flexible, high-specific surface area and high conductivity can not be had concurrently.
Advantages of the present invention and beneficial effect are：
1st, the present invention uses pure natural fiber silk barathea cloth for precursor material, by heat treatment temperature and heat treatment time
Control, the regulation and control to the crystallinity and electric conductivity of carbon fiber can be achieved.
2nd, CNT, the regulation and control of graphene content in the achievable carbon cloth composite construction of the present invention.
3rd, interface binding power good between CNT, graphene and carbon fiber can be achieved in the present invention.
4th, the achievable carbon cloth composite construction of the present invention possesses good flexibility, and its bending angle can realize 0~180 °
Change, and keep good electric conductivity.
5th, the present invention is easy to operate, and technical process easily realizes industrialization.
Brief description of the drawings
Fig. 1 impregnate the optics picture of the composite precursor of different carbon nanotube mass before heat treatment.Wherein, from a left side to
The right side, carbon nanotube mass is respectively：(a)0mg、(b)3.3mg、(c)6.1mg、(d)15.8mg、(e)33.3mg、(f)75mg.
Fig. 2 impregnate the optics picture of the composite precursor of different graphene quality before heat treatment.Wherein, from left to right,
Loading graphene quality is respectively：(a)0mg、(b)3.3mg、(c)6.1mg、(d)15.8mg、(e)33.3mg、(f)75mg.
Fig. 3 impregnate different CNTs and graphene (mass ratio 1:1) composite precursor of mixing quality is before heat treatment
Optics picture.Wherein, from left to right, the quality of load CNT and graphene is respectively：(a)0mg、(b)3.3mg、(c)
6.1mg、(d)15.8mg、(e)33.3mg、(f)75mg。
The optical photograph of Fig. 4 CNTs composite precursor after heat treatment.Wherein, (a) is pure carbon fiber cloth；(b) it is
1wt% carbon nano tube composite carbon fiber cloths；(c) it is 2wt% carbon nano tube composite carbon fiber cloths；(d) answered for 5wt% CNTs
Close carbon cloth；(e) it is 10wt% carbon nano tube composite carbon fiber cloths；(f) it is 20wt% carbon nano tube composite carbon fiber cloths.
The optical photograph of Fig. 5 graphenes composite precursor after heat treatment.Wherein, (a) is pure carbon fiber cloth；(b) it is
1wt% graphene carbon fibre cloths；(c) it is 2wt% graphene carbon fibre cloths；(d) it is fine for 5wt% graphenes composite carbon
Wei Bu；(e) it is 10wt% graphene carbon fibre cloths；(f) it is 20wt% graphene carbon fibre cloths.
Fig. 6 CNTs and the thermally treated rear optical photograph of the common composite precursor of graphene.Wherein, (a) is that pure carbon is fine
Wei Bu；(b) it is 1wt% CNTs and the common carbon fibre cloth of graphene；(c) it is multiple altogether for 2wt% CNTs and graphene
Close carbon cloth；(d) it is 5wt% CNTs and the common carbon fibre cloth of graphene；(e) it is 10wt% CNTs and graphite
The common carbon fibre cloth of alkene；(f) it is 20wt% CNTs and the common carbon fibre cloth of graphene.
Stereoscan photograph of Fig. 7 pure carbon fibers cloth under different amplification.Wherein, shone under (a) carbon cloth low power
Piece；(b) exograph X is knitted for composition carbon cloth；(c) it is the single many carbon fiber photos knitted in line；(d) it is carbon fiber surface
Face photo.
Stereoscan photograph of Fig. 8 carbon nano tube composite carbons fiber cloths under different amplification.Wherein, (a) receives for carbon
Photo under mitron carbon fibre cloth low power；(b) exograph X is knitted for carbon nano tube composite carbon fiber cloth；(c) line is knitted to be single
Many interior carbon fiber photos；(d) it is the carbon fiber surface photo of uniform enveloped carbon nanometer tube.
Stereoscan photograph of Fig. 9 graphenes carbon fibre cloths under different amplification.Wherein, (a) is graphene
Photo under carbon fibre cloth low power；(b) exograph X is knitted for graphene carbon fibre cloth；(c) for it is single knit in line it is many
Root carbon fiber photo；(d) it is the carbon fiber surface photo of uniform coated graphite alkene.
Figure 10 CNTs and common stereoscan photograph of the carbon fibre cloth under different amplification of graphene.Its
In, (a) is photo under CNT and the common carbon fibre cloth low power of graphene；(b) it is that CNT and graphene are combined altogether
Carbon cloth knits exograph X；(c) it is the single many carbon fiber photos knitted in line；(d) it is uniform enveloped carbon nanometer tube and stone
The carbon fiber surface photo of black alkene.
The Raman collection of illustrative plates contrast collection of illustrative plates of Figure 11 difference carbon cloth composite constructions.In figure, Raman shift (cm-1) it is to draw
Graceful displacement.
Under Figure 12 carbon cloths and CNT, graphene, three kinds of different composite systems of CNT and graphene, no
With the square resistance test chart of compound content.
Resistance test figure under Figure 13 carbon nano tube composite carbon fiber cloth bending conditions.
Embodiment
In a specific embodiment, the present invention, will by simple infusion process using pure natural fiber silk barathea cloth as presoma
After CNT and/or graphene are uniformly combined with presoma, carrying out high-temperature heat treatment makes main fibre element carbonization.In carbonization
During, formed between carbon fiber and CNT and/or graphene it is stronger be bonded, a diameter of 3~500 μm of carbon fiber
(being preferably 5~50 μm), the length distribution range of carbon fiber is 0.1~2mm；Carbon fiber surface and CNT and/or graphite
Alkene formation coaxial composite structure, carbon fiber is woven into line and obtains three-dimensional macro bluk recombination structure.It is comprised the following steps that：
(1) using pure natural fiber silk barathea cloth as presoma, in the solution of second alcohol and water after washing by soaking, dry for standby.
Appropriate cotton is taken, 1~24h of immersion is put into the solution of second alcohol and water, removes surface impurity, dry 5 at 60~100 DEG C~
24h；
(2) a series of CNT and/or graphene dispersion are taken in a solvent, the slurry of various concentrations is made into；
(3) cotton is impregnated into the slurry of various concentrations, impregnates corresponding cotton in various concentrations slurry respectively, dried
Compound cotton presoma is obtained afterwards；
(4) presoma is heated up under protective atmosphere (argon gas, helium or nitrogen), protective atmosphere flow be 10~
2000sccm (be preferably 300~1000sccm), heating rate is 1~50 DEG C/min, be warming up to 600~1200 DEG C of insulations 1~
6h, room temperature is annealed under protective atmosphere, you can obtain flexible High-conductivity composite carbon fiber cloth.Carbon in the carbon fibre cloth
Stronger adhesion is formd between fiber and graphene and/or CNT, coaxial composite structure (coaxial composite structure is formed
Refer to that CNT and/or graphene uniform are coated on carbon fiber)；Meanwhile, material general performance goes out good flexible and height
Electric conductivity：Bending angle is from 0~180 °, and electric conductivity is improved with the rise of heat treatment temperature (weighs the square electricity of electric conductivity
Resistance scope is 0.3~20K Ω/).
The area of selected cotton is 1cm2More than.The CNT being combined with carbon fiber skeleton can be single
Pipe, few-wall carbon nanotube or multi-walled carbon nanotube, its diameter distribution is 1~300nm, length distribution range be 100nm~
1000μm.The graphene being combined with carbon fiber skeleton can be single-layer graphene, a small number of layer graphenes or multi-layer graphene, and size is long
It is 2~200 μm to spend distribution, and number of plies distribution is 1~100 layer.
In the slurry that infusion process is used, including CNT and/or graphene, dispersing Nano carbon tubes and/or graphene
It (is preferably 0.02~2wt%, surface-active that solvent, surfactant, CNT and/or graphene, which account for 0.01~10wt%,
Agent accounts for 1~10wt% (being preferably 1~5wt%), and surplus is the solvent of dispersing Nano carbon tubes and/or graphene.Scattered carbon nanometer
Pipe, the solvent of graphene are deionized water, ethanol, ethylene glycol, acetone, 1-METHYLPYRROLIDONE (NMP), polyvinyl alcohol (PVA)
One or more in；Surfactant is polyvinylpyrrolidone (PVP), neopelex (SDBS), 12
One or more in sodium alkyl sulfate (SDS), cetyl trimethylammonium bromide (CTAB), polyethylene glycol etc..
The present invention is described in further detail below by embodiment and accompanying drawing.
In embodiment, use length for the cotton that 11cm, a width of 10.5cm, thickness are that 1mm, quality are 2.4g, be put into
Ethanol and water (volume ratio 1:1) soaking and washing 5h, 70 DEG C of drying in oven 6h.
In embodiment, in the slurry that infusion process is used, including CNT and/or graphene, for disperseing carbon nanometer
Solvent, the surfactant of pipe and/or graphene, based on weight/mass percentage composition, CNT and/or graphene account for 0.2wt%,
Surfactant accounts for 1.5wt%, and surplus is the solvent of dispersing Nano carbon tubes and/or graphene.
Embodiment 1
Take above-mentioned seven, cotton, the CNT of compound different quality impregnated respectively, be followed successively by (a) 0mg, (b) 3.3mg,
(c) compound cotton presoma, is put in 70 DEG C of baking ovens dries afterwards by 6.1mg, (d) 15.8mg, (e) 33.3mg, (f) 75mg
12h, corresponding to Fig. 1 (a), (b), (c), (d), (e) and (f), taking-up is put in tube furnace, vacuumized, using argon gas as protection gas
(flow is 1000sccm), 1000 DEG C are warming up to 10 DEG C/min speed, insulation heat treatment 2h under argon gas, then at argon gas protection
Drop to room temperature, gained sample is as shown in Figure 4.Content of carbon nanotubes is respectively in six samples：0th, 1wt%, 2wt%,
5wt%, 10wt% and 20wt%；Fig. 7 shows, pure carbon fiber cloth, and the electron scanning micrograph in Fig. 8 shows cotton
Cloth is knitted line by regular cotton and is formed by weaving, and carbon fiber surface is uniformly coated with CNT.
Embodiment 2
Above-mentioned seven, cotton is taken, the graphene of compound different quality is impregnated respectively, (a) 0mg, (b) 3.3mg, (c) is followed successively by
Compound cotton presoma, is put in 70 DEG C of baking ovens dries 12h afterwards by 6.1mg, (d) 15.8mg, (e) 33.3mg, (f) 75mg,
Corresponding to Fig. 2 (a), (b), (c), (d), (e) and (f), taking-up is put in tube furnace, vacuumized, using argon gas as protection gas (flow
For 1000sccm), 1000 DEG C are warming up to 10 DEG C/min speed, heat treatment time is 2h under argon gas, argon gas protection drops to
Room temperature.Graphene content is respectively in (as shown in Figure 5) six samples：0th, 1wt%, 2wt%, 5wt%, 10wt% and
20wt%.Electron scanning micrograph in Fig. 8, which illustrates cotton, to be knitted line by regular cotton and is formed by weaving, and carbon fiber surface is equal
It is even to be coated with graphene.
Embodiment 3
Above-mentioned seven, cotton is taken, (mass ratio 1 in the CNT and graphene mixed solution of compound quantity is impregnated respectively:1),
(a) 0mg, (b) 3.3mg, (c) 6.1mg, (d) 15.8mg, (e) 33.3mg, (f) 75mg are followed successively by, afterwards by compound cotton forerunner
Body is put in 70 DEG C of baking ovens and dries 12h, corresponding to Fig. 3 (a), (b), (c), (d), (e) (f), and taking-up is put in tube furnace, takes out true
Sky, using argon gas as protection gas (flow is 1000sccm), is warming up to when being heat-treated under 1000 DEG C, argon gas with 10 DEG C/min speed
Between be 2h, argon gas protection drops to room temperature.CNT and graphene gross mass percentage score in (as shown in Figure 6) six samples
It is not：0th, 1wt%, 2wt%, 5wt%, 10wt% and 20wt%.Electron scanning micrograph in Fig. 9 illustrates cotton
Cloth is knitted line by regular cotton and is formed by weaving, and carbon fiber surface is uniformly coated with CNT and graphene.
Embodiment 4
Sample size substantially remains in long 8cm, width 7.5cm, thickness 0.8mm after high-temperature process, using three-electrode method with
And universal meter carries out conductivity test.After being combined with CNT and/or graphene, the electric conductivity of carbon cloth further increases
By force (such as Figure 12), related data is as follows：
As shown in table 1, the square resistance for testing pure carbon fiber cloth using four probe method is 8 Ω/, compound to CNT
Carbon fiber cloth material, when content of carbon nanotubes is 1wt%, square resistance is 6.5 Ω/；As content of carbon nanotubes increases
Square resistance further declines, and when content of carbon nanotubes is 20wt%, resistance value is 5.3 Ω/；It is fine to graphene composite carbon
Cloth material is tieed up, when graphene content is 1wt%, square resistance is 6.2 Ω/, with the increase of graphene content, square electricity
Resistance further declines, and when graphene content is 20wt%, square resistance is 3.8 Ω/；It is multiple altogether to CNT and graphene
Carbon fiber cloth material is closed, when CNT and graphene content are 1wt%, square resistance is 6.3 Ω/, when content is
During 20wt%, square resistance is 4.6 Ω/.
Table 1
As shown in Figure 10, it can be seen that the fiber in carbon cloth after graphene is compound has remained in that the knot of carbon fiber
Structure, graphene uniform is coated with carbon fiber, forms coaxial configuration.
As shown in figure 11, it can be seen that carbon cloth is blended with CNT, graphene and CNT and graphene
Sample Raman signal substantially, indicates and is successfully prepared composite construction in the sample of conjunction.
As shown in figure 12, it can be seen that be combined after carbon fiber, can further reduced by CNT and/or graphene
Surface square resistance, that is, improve the electric conductivity of composite construction；Compare and understand, graphene is slightly better than in terms of electric conductivity is improved
Multi-walled carbon nanotube, 20wt% graphene carbon fibre cloth body structure surface resistance can reach 3.8 Ω/.
As shown in figure 13, it can be seen that CNT and/or graphene composite structure still are able to keep in a flexed condition according
Good electric conductivity, that is, show that carbon fiber reinforced polymers possess good flexible, excellent electric conductivity.
Embodiment result shows that the complex parameter that the present invention can be by controlling different heat treatment temperatures, different is realized
The preparation of flexible carbon fibre cloth composite.Resulting materials show good flexible, excellent electric conductivity and good table
Face adhesion, is expected in compliant thermal interface material, the power supply of wearable device, the catalyst carrier of fuel cell and function material
The braiding of material is applied in terms of preparing.
Claims (5)
1. a kind of preparation method of flexible High-conductivity composite carbon fiber cloth, it is characterised in that using pure natural fiber silk barathea cloth before
Body is driven, after being uniformly combined CNT and/or graphene with presoma by infusion process, carrying out high-temperature process makes main fibre
Element carbonization, is comprised the following steps that：
(1) using pure natural fiber silk barathea cloth as presoma, in the solution of second alcohol and water after washing by soaking, dry for standby；
(2) CNT and/or graphene dispersion are taken in a solvent, the slurry of various concentrations is configured to；
(3) cotton is impregnated into the slurry of various concentrations, obtained after impregnating corresponding cotton, drying respectively in various concentrations slurry
Obtain 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, is warming up to 600~1200 DEG C of 1~6h of insulation, room temperature is annealed under protective atmosphere, is obtained
Flexible High-conductivity composite carbon fiber cloth；
In step (2), CNT be single-walled carbon nanotube, few-wall carbon nanotube or multi-walled carbon nanotube, its diameter from 1nm to
300nm, length is from 100nm to 1000 μm；Graphene is single-layer graphene, a small number of layer graphenes or multi-layer graphene, and size is by 2
μm to 200 μm；
In the slurry of step (2), including CNT and/or graphene, the solvent of dispersing Nano carbon tubes and/or graphene, table
Face activating agent, based on weight/mass percentage composition, CNT and/or graphene account for 0.01%~10%, and surfactant accounts for 1~
10%, surplus is the solvent of dispersing Nano carbon tubes and/or graphene；
During carbonization, bonding action is formed between CNT and/or graphene and carbon fiber, CNT is obtained
And/or graphene uniform is coated on the coaxial composite structure of carbon fiber surface；The diameter distribution of its carbon fiber is 3~500 μ
M, length distribution range is 0.1~2mm.
2. according to the preparation method of the flexible High-conductivity composite carbon fiber cloth described in claim 1, it is characterised in that step (1)
In, cotton is taken, 1~24h of immersion is put into the solution of second alcohol and water, to remove surface impurity, dry 5 at 60~100 DEG C~
24 hours.
3. according to the preparation method of the flexible High-conductivity composite carbon fiber cloth described in claim 1, it is characterised in that scattered carbon is received
Mitron, graphene solvent be deionized water, ethanol, ethylene glycol, acetone, 1-METHYLPYRROLIDONE, polyvinyl alcohol in wherein
It is one or more kinds of；Surfactant is polyvinylpyrrolidone, neopelex, lauryl sodium sulfate, ten
It is more than the one or two kinds of in six alkyl trimethyl ammonium bromides, polyethylene glycol.
4. according to the preparation method of the flexible High-conductivity composite carbon fiber cloth described in claim 1, it is characterised in that protectiveness gas
Atmosphere is argon gas, helium or nitrogen.
5. according to the preparation method of the flexible High-conductivity composite carbon fiber cloth described in claim 1, it is characterised in that composite carbon is fine
The bending angle of cloth is tieed up from 0~180 degree, its electric conductivity is improved with the rise of heat treatment temperature, its square resistance scope is 0.3
~20K Ω/.
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| CN110323451B (en) * | 2019-04-28 | 2022-03-22 | 中国科学院山西煤炭化学研究所 | Multifunctional composite material based on graphene and polymer fibers and preparation method and application thereof |
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| CN111304799B (en) * | 2020-04-10 | 2022-05-31 | 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 |
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| 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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| CN101462889A (en) * | 2009-01-16 | 2009-06-24 | 南开大学 | Graphene and carbon fiber composite material, and preparation thereof |
| CN102509635A (en) * | 2011-10-31 | 2012-06-20 | 华中科技大学 | Preparation method of flexible super capacitor based on carbon cloth |
| CN103437158B (en) * | 2013-09-11 | 2016-06-01 | 常州第六元素材料科技股份有限公司 | A kind of carbon-fibre composite and its preparation method |
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