CN106116580B - A kind of flexibility carbon film and preparation method thereof - Google Patents

A kind of flexibility carbon film and preparation method thereof Download PDF

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CN106116580B
CN106116580B CN201610503903.0A CN201610503903A CN106116580B CN 106116580 B CN106116580 B CN 106116580B CN 201610503903 A CN201610503903 A CN 201610503903A CN 106116580 B CN106116580 B CN 106116580B
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graphite flake
carbon film
polyacrylonitrile
monomer
graphite
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CN106116580A (en
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李凤美
王彪
郑迎迎
王华平
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Donghua University
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    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
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    • C04B35/62218—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining ceramic films, e.g. by using temporary supports
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
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Abstract

The present invention relates to a kind of flexible carbon films and preparation method thereof, which is made of height-oriented graphite flake and graphite microcrystal；Graphite flake there is inducing action, the graphite microcrystal that induction generates to be orientated along graphite flake surface alignment the formation of graphite microcrystal；The carbon film has the characteristics that compact structure, order degree are big, defect is few and average grain size is small；The carbon film is prepared through casting film, high drafting and sintering processes by graphite flake/polyacrylonitrile composite solution.The rigid softness of flexible carbon film prepared by the present invention is 10‑4~10mNcm, resistivity 10‑3~100 Ω cm, intensity are 5~500MPa, and thermal coefficient is 0.5~50W/mk, and the structural behaviour of carbon film can be substantially improved, and has very high market application value, can be widely applied to the fields such as electrode material, functional material and energy and material.

Description

A kind of flexibility carbon film and preparation method thereof
Technical field
The invention belongs to technology of composite film preparation field, it is related to a kind of flexible carbon film and preparation method thereof, more particularly to one The method that kind prepares high-performance flexible carbon film using conventional polypropylene nitrile as raw material.
Background technology
Carbon film is a kind of new material for having very much development and application prospect, has many excellent performances, such as high hardness, Chemical inertness, low frictional factor, high impedance, good heat transfer and excellent electric conductivity etc., be widely used in electrode material, The fields such as Magnetic Memory device, high temperature semiconductors material, machine tool.The method for preparing carbon film at present can substantially be divided into physics gas Phase sedimentation and chemical vapour deposition technique, these methods need to use large scale equipment, and production cost is high, low output, and gas phase Sedimentation is difficult to obtain the pure single carbon film for completely stripping substrate.Also, there are brittleness, flexible differences to lack for common carbon film Point, which also limits the application developments of carbon film.
With economic continuous development, the carbon film material with high flexibility, electric conductivity, thermal conductivity is gradually explored and is applied to The fields such as functional material, electromagnetic field, communication, the energy, electrode material.Graphene is a kind of two-dimentional carbon materials rapidly developed in recent years Material has extra specific surface area, and the performances such as excellent electricity, calorifics and mechanics, this makes it be rapidly developed in every field, especially Be be widely used in terms of polymer modification it is general.Polyacrylonitrile is important one of three big carbon fiber precursors, by it Carbon fiber can be prepared by carrying out pre-oxidation and carbonization treatment.But the research at present about polyacrylonitrile-radical carbon film is less, wherein Major part pays close attention to its thermal conductivity, and the performances such as electric conductivity are less for flexible carbon film and its performance study.
The method of the invention is compound with graphite flake by polyacrylonitrile, prepares a kind of novel carbon film, which has Compact structure, order degree are big, defect is few and the feature of superpower flexibility, while having the advantages that high conductivity and high-termal conductivity, It can be widely applied to the fields such as electrode material, functional material and energy and material.
Invention content
It is flexible its object is to improve the brittleness of conventional carbon film the present invention relates to a kind of flexible carbon film and preparation method thereof Difference, the shortcomings that being not easily stripped substrate, the flexible carbon film in the present invention are made of height-oriented graphite flake and graphite microcrystal；Graphite Piece there is inducing action, the graphite microcrystal that induction generates to be orientated along graphite flake surface alignment the formation of graphite microcrystal；Through this Flexible carbon film prepared by invention has the characteristics that compact structure, order degree are big, defect is few and average grain size is small, has height The performances such as flexibility, high conductivity, high intensity and high-termal conductivity.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes：
A kind of flexibility carbon film, the flexibility carbon film are made of height-oriented graphite flake and graphite microcrystal；The graphite flake There is inducing action, the graphite microcrystal that induction generates to be orientated along graphite flake surface alignment the formation of graphite microcrystal；The height It refers to being less than 30 ° at the angle of orientation more than the graphite plate plane of graphite flake additive amount 70% and flexible carbon film plane institute that degree, which is orientated,；Institute The average grain size for stating graphite microcrystal is 1~5nm, and the porosity of the flexibility carbon film is 0~4%, in JIS L 1096 Slide methods measure flexible carbon film rigid softness be 10-4~10mNcm.
A kind of flexible carbon film as described above, the resistivity of the flexibility carbon film is 10-3~100 Ω cm, the flexibility Carbon film strength is 5~500MPa, and the thermal coefficient of the flexibility carbon film is 0.5~50W/mk；The thickness of the carbon film is 0.1~100 μm.
A kind of preparation method of flexibility carbon film, includes the following steps：
1) by blending method or situ aggregation method, graphite flake/polyacrylonitrile composite solution is prepared；
2) graphite flake/polyacrylonitrile composite solution is handled through casting film, forms graphite flake/polyacrylonitrile laminated film；
3) graphite flake/polyacrylonitrile laminated film handles through high drafting, pressure pre-oxidation and scale pressure carbonization and flexibility is made Carbon film；
The pressure pre-oxidation temperature is 200~300 DEG C, and the time is 30~200 minutes；The scale pressure carbonization temperature is 600~2000 DEG C, the time is 1~60 minute；The pressure size applied in the pressurization is 0.2~50MPa.
As optimal technical scheme：
A kind of flexible carbon film as described above, the graphite flake is graphene microchip, graphene, graphene oxide or reduction One or more of graphene oxide；
The pressure pre-oxidation is identical with the pressuring method and pressure size in scale pressure carbonization stage, and the mode of pressurization is logical It crosses 1-4 group hot-pressing rollers application pressure or is passed through atmosphere gas and apply one or more of pressure；Gas in the pressure pre-oxidation Atmosphere is air atmosphere, and the atmosphere in the scale pressure carbonization is inert atmosphere, and the inert atmosphere is nitrogen or argon gas.
A kind of preparation method of flexible carbon film as described above, the blending method refer to by graphite flake dispersion liquid with contain it is identical molten The polyacrylonitrile solution of agent is mixed by mechanical agitation, and it is multiple that solution is then carried out deaeration processing acquisition graphite flake/polyacrylonitrile Close solution；
The graphite flake dispersion liquid using preceding need by ultrasonic disperse, magnetic agitation dispersion or mechanical agitation decentralized processing in More than one, processing time be 0.5~12 hour, temperature be 10~40 DEG C；
The polyacrylonitrile is or further, also to contain second comonomer or second comonomer including at least the first monomer And Third monomer；
First monomer is acrylonitrile, and the first single phase is 80~100% to the mass fraction of total monomer；
The second comonomer is acrylamide, methyl acrylate, methyl methacrylate, methacrylonitrile or vinyl acetate Ester, second comonomer are 1~20% with respect to the mass fraction of total monomer；
The Third monomer is itaconic acid, sodium allylsulfonate, methylpropene sodium sulfonate, metering system benzene sulfonic acid sodium salt, ethylene Yl pyridines or dimethylaminoethyl acrylate methyl base aminoethyl, Third monomer are 1~3% with respect to the mass fraction of total monomer；
The solvent is dimethylformamide, dimethyl sulfoxide (DMSO), dimethylacetylamide or sodium thiocyanate water solution；The sulphur A concentration of 50~60wt% of cyanic acid sodium water solution；
A concentration of 0.5~5wt% of the graphite flake dispersion liquid；A concentration of the 10 of the polyacrylonitrile solution~ 40wt%；
The time of mechanical agitation mixing is 1~for 24 hours, rotating speed is 50-1500 revs/min, and temperature is 10~50 DEG C；
The mode of the deaeration processing is vacuum defoamation, ultrasonic deaeration or standing and defoaming, and the time is 0.5~12h；
A concentration of 9~39wt% of polyacrylonitrile in the graphite flake/polyacrylonitrile composite solution, graphite flake relatively poly- third The mass fraction of alkene nitrile is 0.1~80%.
A kind of preparation method of flexible carbon film as described above, the situ aggregation method refers to by monomer, initiator and graphite Piece dispersion liquid is separately added into solvent identical with contained solvent in graphite flake dispersion liquid, is uniformly mixed and polymeric solution is made；Often Pressure, at 50~70 DEG C polymerize 1~for 24 hours, then by solution progress deaeration handle to obtain graphite flake/polyacrylonitrile composite solution；
The monomer includes at least the first monomer, or further, also contains second comonomer or second comonomer and third Monomer；
First monomer is acrylonitrile, and the first single phase is 80~100% to the mass fraction of total monomer；
The second comonomer is acrylamide, methyl acrylate, methyl methacrylate, methacrylonitrile or vinyl acetate Ester, second comonomer are 1~20% with respect to the mass fraction of total monomer；
The Third monomer is itaconic acid, sodium allylsulfonate, methylpropene sodium sulfonate, metering system benzene sulfonic acid sodium salt, ethylene Yl pyridines or dimethylaminoethyl acrylate methyl base aminoethyl, Third monomer are 1~3% with respect to the mass fraction of total monomer；
The initiator be azodiisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, dilauroyl peroxide or Di-isopropyl peroxydicarbonate；
The solvent is dimethylformamide, dimethyl sulfoxide (DMSO), dimethylacetylamide or sodium thiocyanate water solution；The sulphur A concentration of 50~60wt% of cyanic acid sodium water solution；
The graphite flake dispersion liquid using preceding need by ultrasonic disperse, magnetic agitation dispersion or mechanical agitation decentralized processing in More than one, processing time be 0.5~12 hour, temperature be 10~40 DEG C；
A concentration of 0.5~5wt% of the graphite flake dispersion liquid；
The mode of the deaeration processing is vacuum defoamation, ultrasonic deaeration or standing and defoaming, and the time is 0.5~12h；
In the polymeric solution, a concentration of 10~40wt% of monomer, the mass fraction of initiator relative monomer is 0.3~ 1.5%；The mass fraction of graphite flake relative monomer is 0.1~80%；
The conversion ratio of monomer is 70~99% in the graphite flake/polyacrylonitrile composite solution.
A kind of preparation method of flexible carbon film, the method for the casting film are the tape casting, squeeze out pulling method, hot pressing as described above Method, swelling pulling method or cement-dipping method；The graphite flake/polyacrylonitrile laminated film thickness is 1~200 μm.
A kind of preparation method of flexible carbon film, the super drawing refer to that hot steam super drawing or boiling water are high as described above It stretches again；Draw ratio in the super drawing is 1~50 times；In the casting film and super drawing technique, graphite flake is along film Level is orientated, and forms orientation texture.
The preparating mechanism of flexible carbon film is：
(1) pre-oxidizing the stage, at pre-oxidation initial stage, as temperature increases, polyacrylonitrile film reaches vitrifying in temperature When more than transition temperature, molecule segment setting in motion, film gradually softens, in the case where being acted on perpendicular to the pressure of membrane plane, due to Film uniform force makes its macro morphology keep smooth, and edge gradually takes graphite flake perpendicular to pressure direction under the effect of the pressure To, meanwhile, graphite flake drives polyacrylonitrile strand that a degree of orientation occurs along its differently- oriented directivity during the motion；With It temperature to continue to increase, dehydrocyclization reaction occurs for polyacrylonitrile strand, and polyacrylonitrile is gradually converted by linear macromolecule There is trapezoidal six-membered ring structure, reacts the H of generation2Or H2The small-molecule substances such as O are excluded outside film under pressure, and gas generates The hole generated in preparation process with the hole and raw material film formed inside film in discharge process is acted in pressure Under, since molecular chain movement is gradually filled and led up, and under pressure, graphite flake centainly takes with the holding of polyacrylonitrile strand To making deorientation weaken, form orderly fine and close orientation texture；As temperature continues to increase, oxidation cross-linked reaction starts Occur, oxygen molecule is more easy to enter inside film under pressure, makes oxygen molecule and polyacrylonitrile molecule Rapid contact, can To promote the progress of oxidation cross-linked reaction.When using graphene or graphene microchip as raw material, since graphene or graphene are micro- Piece existing defects itself generate segmental defect during heat treatment, and in graphene or graphene microchip fault location, there are parts May participate in the carbon atom of reaction, these carbon atoms under heat effect and oxygen occur oxidation reaction, and then with polyacrylonitrile molecule In functional group crosslink reaction, form cross-linked structure；When use graphene oxide or redox graphene as raw material When, since certain oxygen-containing functional group, oxygen and oxygen-containing functional group are contained in the surface of graphene oxide or redox graphene Oxidation reaction occurs with functional groups such as carbon-carbon double bonds at a certain temperature, polycondensation reaction can also occur between oxygen-containing functional group, make Between polyacrylonitrile molecule, between polyacrylonitrile molecule and graphene oxide or redox graphene, graphene oxide it Between or redox graphene between crosslink, generate more regular cross-linked structure, polyacrylonitrile macromolecular is converted into heat-resisting Trapezium structure.
(2) carbonation stage, with the raising of carburizing temperature, the ring molecule and graphite flake that are formed in preoxidation process are into one Step is crosslinked, is cyclized and polycondensation reaction, reacts the CO of generation2、NH3、N2Equal small-molecule substances are in the pressure perpendicular to membrane plane It is excluded outside film under effect, gas is generated with the hole that is formed inside film in discharge process under pressure, due to molecule Chain movement is gradually filled and led up, and under pressure, and graphite flake keeps certain with polyacrylonitrile strand and is orientated, and disorientation is made to make With decrease, more orderly fine and close orientation texture is formed；As carburizing temperature continues to increase, graphite flake as nucleation agent and Template, makes the graphite microcrystal that polyacrylonitrile is formed along the further aligned growth in carbon-based face of graphite flake, and induction is generated along graphite The graphite microcrystalline structure that piece surface alignment is orientated；Also, since graphite flake has two dimensional height orderly hexatomic ring carbon structure surface, So that the graphite microcrystal being formed on its surface is by template growth, the average grain size of the graphite microcrystal of generation is smaller, is arranged with Sequence is higher.
Meanwhile in carbonisation, when using graphene oxide or redox graphene as raw material, graphene oxide or Oxygen-containing functional group on redox graphene surface such as carbonyl, hydroxyl, carboxyl etc., under high temperature inert atmosphere participate in reaction or by Removing is decomposed, graphene oxide or redox graphene is made to be reduced.
There is height-oriented graphite flake and graphite microcrystalline structure just because of prepared carbon film so that it has higher Flexibility.
Advantageous effect：
1. the present invention provides a kind of flexible carbon film and preparation method thereof, this method is easy to operate, and raw material sources are extensive, can Significantly improve the flexibility of carbon film, while making carbon film that there is high conductivity and high-termal conductivity.
2. the present invention can utilize conventional or discarded polyacrylonitrile raw material, there is very high market application value.
3. the present invention improves the brittleness of carbon film by adding graphite flake in polyacrylonitrile matrix, flexibility is made it have. This is because in casting film and super drawing technique, graphite flake is height-oriented along membrane plane, forms orientation texture.It was pre-oxidizing Cheng Zhong, graphite flake can promote cross-linking reaction to carry out, advantageously form cross-linked network structure；In carbonisation, graphite flake conduct Nucleation agent and template can induce graphite microcrystal to be orientated along graphite flake surface alignment, and the crystallite dimension of formation is small, structure Dense regular and the few graphite microcrystalline structure of defect, therefore be formed by carbon film there is high flexibility.
Description of the drawings
Fig. 1 is flexible carbon film profile scanning electron microscope, and amplification factor is 10000 times；
Fig. 2 is flexible carbon film profile scanning electron microscope, and amplification factor is 50000 times.
Specific implementation mode
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Fixed range.
Embodiment 1
A kind of preparation method of flexibility carbon film, by blending method, by the graphene oxide dispersion of a concentration of 0.5wt% with Polyacrylonitrile (polyacrylonitrile for including the first monomers acrylonitrile) solution of a concentration of 9wt% is mixed by mechanical agitation；Oxidation For graphene dispersing solution using preceding needing to handle by ultrasonic disperse, processing time is 0.5 hour, and temperature is 10 DEG C, graphene oxide Dispersion liquid contains identical solvent with polyacrylonitrile solution, and solvent is dimethylformamide；The time of mechanical agitation mixing is 1h, Rotating speed is 50 revs/min, and temperature is 10 DEG C；Then solution is subjected to vacuum defoamation and handles 0.5h, obtain graphene oxide/poly- third Alkene nitrile composite solution；A concentration of 20wt% of polyacrylonitrile in graphene oxide obtained/polyacrylonitrile composite solution aoxidizes stone The mass fraction of black alkene vs polypropylene nitrile is 10%；Then graphene oxide/polyacrylonitrile composite solution is cast through the tape casting Film；Form graphene oxide/polyacrylonitrile laminated film that thickness is 20 μm；Again by graphene oxide/polyacrylonitrile THIN COMPOSITE Film is handled through hot steam super drawing, and draw ratio is 2 times；Continue pressure pre-oxidation processing, pressure pre-oxidation temperature is 250 DEG C, the time is 60 minutes, and atmosphere is air atmosphere, and the mode of pressurization is to apply the pressure of 20MPa by 1 group of hot-pressing roller；After Continuous to carry out scale pressure carbonization processing, scale pressure carbonization temperature is 1300 DEG C, and the time is 1 minute, and atmosphere is nitrogen atmosphere, the mode of pressurization To apply the pressure of 10MPa by 1 group of hot-pressing roller；The flexible carbon film that thickness is 10 μm is made.
Flexibility carbon film obtained is made of height-oriented redox graphene and graphite microcrystal；Height-oriented refers to more It is less than 30 ° at the angle of orientation with flexible carbon film plane institute in the redox graphene plane of graphene oxide additive amount 70%；Such as Shown in Fig. 1, average grain size is that the graphite microcrystal of 2.7nm is orientated along redox graphene surface alignment, as shown in Figure 2； The porosity of the flexibility carbon film is 0.5%；The rigid softness of flexible carbon film measured with the slide methods in JIS L 1096 is 0.01mNcm, resistivity are 7 × 10-3Ω cm, intensity 85MPa, thermal coefficient 26W/mk.
Embodiment 2
A kind of preparation method of flexibility carbon film, by situ aggregation method, by the monomer of a concentration of 10wt%, (monomer includes the One monomers acrylonitrile) solution, initiator azodiisobutyronitrile and a concentration of 0.5wt% graphene dispersing solution be uniformly mixed be made Polymeric solution；Graphene dispersing solution is using preceding needing by magnetic agitation decentralized processing, and processing time is 12 hours, temperature 40 DEG C, graphene dispersing solution contains identical solvent with polyacrylonitrile solution, and solvent is dimethyl sulfoxide (DMSO)；Initiator relative monomer Mass fraction is 0.3%；The mass fraction of graphene relative monomer is 0.1%；Then it polymerize 1h at normal pressure, 50 DEG C, then Solution is subjected to vacuum defoamation and handles 12h, obtains graphene/polyacrylonitrile composite solution；Graphene/polyacrylonitrile obtained is multiple The conversion ratio for closing monomer in solution is 70%；Then by the extruded pulling method casting film of graphene/polyacrylonitrile composite solution；It is formed Graphene/polyacrylonitrile laminated film that thickness is 1 μm；Again by graphene/polyacrylonitrile laminated film through boiling water super drawing Processing, draw ratio are 1 times；Continuing pressure pre-oxidation processing, pressure pre-oxidation temperature is 200 DEG C, and the time is 30 minutes, Atmosphere is air atmosphere, and the mode of pressurization is to apply the pressure that size is 0.2MPa by 1 group of hot-pressing roller；Continue pressurized carbon Change is handled, and scale pressure carbonization temperature is 600 DEG C, and the time is 1 minute, and atmosphere is nitrogen atmosphere, and the mode of pressurization is to pass through 1 group of hot pressing Roller applies the pressure of pressure 0.2MPa；The flexible carbon film that thickness is 0.5 μm is made.
Flexibility carbon film obtained is made of height-oriented graphene and graphite microcrystal；Height-oriented refers to being more than graphene The graphene planes of additive amount 70% are less than 30 ° with flexible carbon film plane institute at the angle of orientation；Average grain size is the graphite of 5nm For crystallite along graphene surface oriented, the porosity of the flexibility carbon film is 4%；It is measured with the slide methods in JIS L 1096 Flexible carbon film rigid softness be 10mNcm, resistivity be 100 Ω cm, intensity 5MPa, thermal coefficient 0.5W/m k。
Embodiment 3
A kind of preparation method of flexibility carbon film, by blending method, by the graphene dispersing solution of a concentration of 5wt% with it is a concentration of The polyacrylonitrile of 39wt% (includes the polyacrylonitrile of the first monomers acrylonitrile and second comonomer acrylamide, wherein acrylonitrile phase Mass fraction to total monomer is 80%, and acrylamide is that 20%) solution passes through mechanical agitation with respect to the mass fraction of total monomer Mixing；Graphene dispersing solution is using preceding needing by mechanical agitation decentralized processing, and processing time is 10 hours, and temperature is 35 DEG C, stone Black alkene dispersion liquid contains identical solvent with polyacrylonitrile solution, and solvent is dimethylacetylamide；Graphene dispersing solution and poly- third The time that alkene nitrile solution movement is stirred is that for 24 hours, rotating speed is 1500 revs/min, and temperature is 50 DEG C；Then solution is surpassed Sound deaeration 10h obtains graphene/polyacrylonitrile composite solution；Polyacrylonitrile in graphene obtained/polyacrylonitrile composite solution A concentration of 39wt%, the mass fraction of graphene vs polypropylene nitrile is 80%；Then graphene/polyacrylonitrile is compound molten Liquid is through pressure sintering casting film；Form graphene/polyacrylonitrile laminated film that thickness is 200 μm；It is again that graphene/polyacrylonitrile is multiple It closes film to handle through hot steam super drawing, draw ratio is 50 times；Pressure pre-oxidation processing is then proceeded by, pressurize pre- oxygen It is 300 DEG C to change temperature, and the time is 200 minutes, and atmosphere is air atmosphere, and the mode of pressurization is to apply 50MPa by 4 groups of hot-pressing rollers Pressure；Continuing scale pressure carbonization processing, scale pressure carbonization temperature is 2000 DEG C, and the time is 60 minutes, and atmosphere is argon atmosphere, The mode of pressurization is to apply the pressure of 50MPa by 4 groups of hot-pressing rollers, and the flexible carbon film that thickness is 4 μm is made.
Flexibility carbon film obtained is made of height-oriented graphene and graphite microcrystal；Height-oriented refers to being more than graphene The graphene planes of additive amount 70% are less than 30 ° with flexible carbon film plane institute at the angle of orientation；Average grain size is the graphite of 1nm For crystallite along graphene surface oriented, the porosity of the flexibility carbon film is 0%；It is measured with the slide methods in JIS L 1096 Flexible carbon film rigid softness be 10-4MNcm, resistivity 10-3Ω cm, intensity 500MPa, thermal coefficient 50W/ m·k。
Embodiment 4
A kind of preparation method of flexibility carbon film, by situ aggregation method, by the monomer of a concentration of 40wt%, (monomer includes the One monomers acrylonitrile and second comonomer methyl acrylate, wherein acrylonitrile are 90% with respect to the mass fraction of total monomer, acrylic acid Methyl esters is micro- with respect to the graphene that the mass fraction of total monomer is 10%) solution, initiator azobisisoheptonitrile and a concentration of 4wt% Piece dispersion liquid is uniformly mixed and polymeric solution is made；Graphene microchip dispersion liquid is using preceding needing to handle by ultrasonic disperse, when processing Between be 8 hours, temperature is 30 DEG C, and graphene microchip dispersion liquid and polyacrylonitrile solution contain identical solvent, and solvent is concentration Mass fraction for 52wt% sodium thiocyanate water solutions, initiator relative monomer is 1.5%；The matter of graphene microchip relative monomer It is 80% to measure score；Then it polymerize at normal pressure, 70 DEG C for 24 hours, solution, which is then carried out standing and defoaming, handles 8h, obtains graphene Microplate/polyacrylonitrile composite solution；The conversion ratio of monomer is 99% in graphene microchip obtained/polyacrylonitrile composite solution； Then by graphene microchip/polyacrylonitrile composite solution through being swollen pulling method casting film；It is micro- to form the graphene that thickness is 190 μm Piece/polyacrylonitrile laminated film；Graphene microchip/polyacrylonitrile laminated film is handled through boiling water super drawing again, is stretched again Number is 2 times；Continue pressure pre-oxidation processing, pressure pre-oxidation temperature is 225 DEG C, and the time is 180 minutes, and atmosphere is air Atmosphere, the mode of pressurization are to apply the pressure of pressure 0.9MPa by 4 groups of hot-pressing rollers；Continue scale pressure carbonization processing, pressurization Carburizing temperature is 800 DEG C, and the time is 50 minutes, and atmosphere is argon atmosphere, and the mode of pressurization is to apply pressure by 1 group of hot-pressing roller The pressure of 0.8MPa；The flexible carbon film that thickness is 100 μm is made.
Flexibility carbon film obtained is made of height-oriented graphene microchip and graphite microcrystal；Height-oriented refers to being more than stone The graphene microchip plane of black alkene microplate additive amount 70% is less than 30 ° with flexible carbon film plane institute at the angle of orientation；Average crystal grain ruler The very little graphite microcrystal for 4.2nm is orientated along graphene microchip surface alignment, and the porosity of the flexibility carbon film is 3.5%；With JIS L The rigid softness for the flexible carbon film that slide methods in 1096 measure is 2 × 10-4MNcm, resistivity are 7 Ω cm, and intensity is 460MPa, thermal coefficient 25W/mk.
Embodiment 5
A kind of preparation method of flexibility carbon film, by blending method, by the graphene oxide dispersion of a concentration of 3wt% with it is dense Degree is that the polyacrylonitrile of 20wt% (includes the polyacrylonitrile of the first monomers acrylonitrile and second comonomer methacrylonitrile, wherein third Alkene nitrile is 88% with respect to the mass fraction of total monomer, and methacrylonitrile is that 12%) solution passes through with respect to the mass fraction of total monomer Mechanical agitation mixes；For graphene oxide dispersion using preceding needing to disperse by magnetic agitation, processing time is 1 hour, and temperature is 15 DEG C, graphene oxide dispersion contains identical solvent with polyacrylonitrile solution, and solvent is a concentration of 50wt% sodium sulfocyanates Aqueous solution；The time that graphene oxide dispersion is mixed with polyacrylonitrile solution mechanical agitation is 10h, and rotating speed is 1000 revs/min Clock, temperature are 30 DEG C；Then solution is subjected to ultrasonic deaeration 6h, obtains graphene oxide/polyacrylonitrile composite solution；It is obtained A concentration of 9wt% of polyacrylonitrile in graphene oxide/polyacrylonitrile composite solution, the matter of graphene oxide vs polypropylene nitrile It is 0.1% to measure score；Then by graphene oxide/polyacrylonitrile composite solution through cement-dipping method casting film；It is 180 μm to form thickness Graphene oxide/polyacrylonitrile laminated film；At again by graphene oxide/polyacrylonitrile laminated film through hot steam super drawing Reason, draw ratio are 5 times；Continuing pressure pre-oxidation processing, pressure pre-oxidation temperature is 235 DEG C, and the time is 160 minutes, Atmosphere is air atmosphere, and the mode of pressurization is to be passed through air to apply the pressure that size is 1MPa；Continue scale pressure carbonization processing, Scale pressure carbonization temperature is 1000 DEG C, and the time is 6 minutes, and atmosphere is argon atmosphere, and the mode of pressurization is to be passed through argon gas to apply 5MPa Pressure；The flexible carbon film that thickness is 16 μm is made.
Flexibility carbon film obtained is made of height-oriented redox graphene and graphite microcrystal；Height-oriented refers to more It is less than 30 ° at the angle of orientation with flexible carbon film plane institute in the redox graphene plane of graphene oxide additive amount 70%；It is flat The graphite microcrystal that equal crystallite dimension is 1.2nm is orientated along redox graphene surface alignment, and the porosity of the flexibility carbon film is 3.1%；The rigid softness of the flexible carbon film measured with the slide methods in JIS L 1096 is 9.5mNcm, and resistivity is 95 Ω Cm, intensity 7MPa, thermal coefficient 0.6W/mk.
Embodiment 6
A kind of preparation method of flexibility carbon film, by blending method, by the graphene dispersing solution of a concentration of 2wt% with it is a concentration of The polyacrylonitrile of 30wt% (includes the polyacrylonitrile of the first monomers acrylonitrile and second comonomer methyl methacrylate, wherein third Alkene nitrile is 93% with respect to the mass fraction of total monomer, and methyl methacrylate is logical for 7%) solution with respect to the mass fraction of total monomer Cross mechanical agitation mixing；Graphene dispersing solution is using preceding needing by mechanical agitation decentralized processing, and processing time is 5 hours, temperature It it is 25 DEG C, graphene dispersing solution contains identical solvent with polyacrylonitrile solution, and solvent is dimethylformamide；Graphene dispersion The time that liquid is mixed with polyacrylonitrile solution mechanical agitation is 4h, and rotating speed is 500 revs/min, and temperature is 25 DEG C；Then by solution It carries out vacuum defoamation 4h and obtains graphene/polyacrylonitrile composite solution；Poly- third in graphene obtained/polyacrylonitrile composite solution The mass fraction of a concentration of 25wt% of alkene nitrile, graphene vs polypropylene nitrile are 58%；Then graphene/polyacrylonitrile is multiple Solution is closed through the tape casting casting film；Form graphene/polyacrylonitrile laminated film that thickness is 160 μm；Again by graphene/polypropylene Nitrile laminated film is handled through boiling water super drawing, and draw ratio is 25 times；Pressure pre-oxidation processing is then proceeded by, pressurization is pre- Oxidizing temperature is 255 DEG C, and the time is 160 minutes, and atmosphere is air atmosphere, and the mode of pressurization is to be applied greatly by 2 groups of hot-pressing rollers The small pressure for 10MPa；Continue scale pressure carbonization processing, scale pressure carbonization temperature is 1200 DEG C, and the time is 30 minutes, and atmosphere is Nitrogen atmosphere, the mode of pressurization are to apply the pressure that size is 15MPa by 2 groups of hot-pressing rollers；The flexible carbon that thickness is 5 μm is made Film.
Flexibility carbon film obtained is made of height-oriented graphene and graphite microcrystal；Height-oriented refers to being more than graphene The graphene planes of additive amount 70% are less than 30 ° with flexible carbon film plane institute at the angle of orientation；Average grain size is the stone of 2.9nm For black crystallite along graphene surface oriented, the porosity of the flexibility carbon film is 2.4%；With the slide methods in JIS L 1096 The rigid softness of the flexible carbon film of measurement is 2 × 10-3MNcm, resistivity are 0.02 Ω cm, intensity 380MPa, thermal coefficient For 22W/mk.
Embodiment 7
A kind of preparation method of flexibility carbon film, by situ aggregation method, by the monomer of a concentration of 10wt%, (monomer includes the One monomers acrylonitrile, second comonomer vinylacetate and Third monomer dimethylaminoethyl acrylate methyl base aminoethyl, wherein acrylonitrile The mass fraction of opposite total monomer is 81%, and vinylacetate is 16% with respect to the mass fraction of total monomer, methacrylic acid two Methylamino ethyl ester is 3%) solution, initiator dibenzoyl peroxide and a concentration of 1wt% with respect to the mass fraction of total monomer Graphene oxide dispersion is uniformly mixed and polymeric solution is made；Graphene oxide dispersion is using preceding needing to disperse by mechanical agitation Processing is handled 4 hours for 0.5 hour with ultrasonic disperse, and temperature is 20 DEG C, and graphene oxide dispersion contains with polyacrylonitrile solution Identical solvent, solvent are dimethylformamide；The mass fraction of initiator relative monomer is 1%；Graphene oxide is relatively single The mass fraction of body is 20%；Then it polymerize 10h at normal pressure, 55 DEG C, solution, which is then carried out ultrasonic deaeration, handles 2h, obtains Graphene oxide/polyacrylonitrile composite solution；The conversion ratio of monomer is in graphene oxide obtained/polyacrylonitrile composite solution 90%；Then by graphene oxide/polyacrylonitrile composite solution through being swollen pulling method casting film；It is 150 μm of oxidation stones to form thickness Black alkene/polyacrylonitrile laminated film；Graphene oxide/polyacrylonitrile laminated film is handled through hot steam super drawing again, is drawn It is 35 times to stretch multiple；Pressure pre-oxidation processing is then proceeded by, pressure pre-oxidation temperature is 275 DEG C, and the time is 150 minutes, Atmosphere is air atmosphere, and the mode of pressurization is to be passed through air to apply the pressure that size is 20MPa；Continue at scale pressure carbonization Reason, scale pressure carbonization temperature are 1400 DEG C, and the time is 40 minutes, and atmosphere is nitrogen atmosphere, and the mode of pressurization is to be passed through nitrogen application Size is the pressure of 25MPa；The flexible carbon film that thickness is 4 μm is made.
Flexibility carbon film obtained is made of height-oriented redox graphene and graphite microcrystal；Height-oriented refers to more It is less than 30 ° at the angle of orientation with flexible carbon film plane institute in the redox graphene plane of graphene oxide additive amount 70%；It is flat The graphite microcrystal that equal crystallite dimension is 2.3nm is orientated along redox graphene surface alignment, and the porosity of the flexibility carbon film is 1.8%；The rigid softness of the flexible carbon film measured with the slide methods in JIS L 1096 is 0.6mNcm, and resistivity is 8 × 10-3 Ω cm, intensity 200MPa, thermal coefficient 27W/mk.
Embodiment 8
A kind of preparation method of flexibility carbon film, by situ aggregation method, by the monomer of a concentration of 40wt%, (monomer includes the One monomers acrylonitrile, second comonomer methyl methacrylate and Third monomer itaconic acid, wherein matter of the acrylonitrile with respect to total monomer It is 97% to measure score, and methyl methacrylate is 2% with respect to the mass fraction of total monomer, quality point of the itaconic acid with respect to total monomer Number is the redox graphene dispersion liquid and 20wt% of 1%) solution, initiator azodiisobutyronitrile and a concentration of 0.8wt% It is uniformly mixed and polymeric solution is made；Redox graphene dispersion liquid using preceding needing by magnetic agitation decentralized processing 1 hour and Ultrasonic disperse is handled 2 hours, and temperature is 22 DEG C, and redox graphene dispersion liquid contains identical molten with polyacrylonitrile solution Agent, solvent are dimethyl sulfoxide (DMSO)；The mass fraction of initiator relative monomer is 1%；The matter of redox graphene relative monomer It is 30% to measure score；Then it polymerize 5h at normal pressure, 60 DEG C, solution, which is then carried out vacuum defoamation, handles 0.5h, is restored Graphene oxide/polyacrylonitrile composite solution；The conversion of monomer in redox graphene obtained/polyacrylonitrile composite solution Rate is 80%；Then by redox graphene/extruded pulling method of polyacrylonitrile composite solution and pressure sintering casting film；It is formed thick Redox graphene/polyacrylonitrile laminated film that degree is 120 μm；Again by redox graphene/polyacrylonitrile THIN COMPOSITE Film is handled through hot steam super drawing, and draw ratio is 45 times；Continue pressure pre-oxidation processing, pressure pre-oxidation temperature is 285 DEG C, the time is 120 minutes, and atmosphere is air atmosphere, and the mode of pressurization is by 2 groups of hot-pressing rollers and to be passed through air application The pressure of 30MPa；Continue scale pressure carbonization processing, scale pressure carbonization temperature is 1600 DEG C, and the time is 25 minutes, and atmosphere is nitrogen Atmosphere；The mode of pressurization be by 3 groups of hot-pressing rollers and be passed through nitrogen apply 35MPa pressure；The flexible carbon that thickness is 2 μm is made Film.
Flexibility carbon film obtained is made of height-oriented redox graphene and graphite microcrystal；Height-oriented refers to more It is less than at the angle of orientation with flexible carbon film plane institute in the redox graphene plane of redox graphene additive amount 70% 30°；Average grain size is that the graphite microcrystal of 1.8nm is orientated along redox graphene surface alignment, the hole of the flexibility carbon film Gap rate is 1.2%；The rigid softness of the flexible carbon film measured with the slide methods in JIS L 1096 is 0.08mNcm, resistivity It is 6 × 10-3Ω cm, intensity 245MPa, thermal coefficient 34W/mk.
Embodiment 9
A kind of preparation method of flexibility carbon film, by blending method, by the graphite flake (graphene microchip of a concentration of 1.5wt% With the mass ratio 2 of graphene oxide:1) polyacrylonitrile of dispersion liquid and a concentration of 20wt% (include the first monomers acrylonitrile, the The mass fraction that the polyacrylonitrile of two monomeric acrylamides and Third monomer sodium allylsulfonate, wherein acrylonitrile account for total monomer is 92%, the mass fraction that acrylamide accounts for total monomer is 5%, and it is logical for 3%) solution that sodium allylsulfonate accounts for the mass fraction of total monomer Cross mechanical agitation mixing；Graphite flake dispersion liquid is using preceding needing by magnetic agitation decentralized processing 1 hour and mechanical agitation dispersion Reason 9 hours, temperature are 32 DEG C, and graphite flake dispersion liquid contains identical solvent with polyacrylonitrile solution, and solvent is dimethylacetamide Amine；The time that graphite flake dispersion liquid is mixed with polyacrylonitrile solution mechanical agitation is 5h, and rotating speed is 800 revs/min, temperature 20 ℃；Then solution is subjected to standing and defoaming, time 1.5h obtains graphite flake/polyacrylonitrile composite solution；Graphite obtained A concentration of 30wt% of polyacrylonitrile in piece/polyacrylonitrile composite solution, the mass fraction of graphite flake vs polypropylene nitrile are 40%；Then by graphite flake/polyacrylonitrile composite solution through pressure sintering casting film；Form graphite flake/polypropylene that thickness is 100 μm Nitrile laminated film；Graphite flake/polyacrylonitrile laminated film is handled through boiling water super drawing again, draw ratio is 10 times；Continue Pressure pre-oxidation processing is carried out, pressure pre-oxidation temperature is 295 DEG C, and the time is 100 minutes, and atmosphere is air atmosphere, pressurization Mode be by 2 groups of hot-pressing rollers and be passed through air apply 40MPa pressure；Continue scale pressure carbonization processing, scale pressure carbonization temperature Degree is 1800 DEG C, and the time is 15 minutes, and atmosphere is argon atmosphere, and the mode of pressurization is by 1 group of hot-pressing roller and to be passed through argon gas and apply Add the pressure of 45MPa；The flexible carbon film that thickness is 10 μm is made.
Flexibility carbon film obtained is made of height-oriented graphite flake and graphite microcrystal；Height-oriented refers to being more than graphite flake The graphite plate plane of additive amount 70% is less than 30 ° with flexible carbon film plane institute at the angle of orientation；Average grain size is the stone of 1.5nm Black crystallite is orientated along graphite flake surface alignment, and the porosity of the flexibility carbon film is 0.3%；With the slide methods in JIS L 1096 The rigid softness of the flexible carbon film of measurement is 0.03mNcm, and resistivity is 3 × 10-3Ω cm, intensity 290MPa, thermal coefficient For 42W/mk.
Embodiment 10
A kind of preparation method of flexibility carbon film, by situ aggregation method, by the monomer of a concentration of 30wt%, (monomer includes the One monomers acrylonitrile, second comonomer methacrylonitrile and Third monomer methylpropene sodium sulfonate, wherein acrylonitrile accounts for total monomer Mass fraction is 98%, and the mass fraction that methacrylonitrile accounts for total monomer is 1%, and methylpropene sodium sulfonate accounts for the quality of total monomer Score is graphite flake (graphene oxide and the oxygen reduction of 1%) solution, initiator dibenzoyl peroxide and a concentration of 2.5wt% The mass ratio of graphite alkene is 1:3) dispersion liquid is uniformly mixed and polymeric solution is made；Graphite flake dispersion liquid is using preceding needing by machinery It is dispersed with stirring processing, processing time is 3 hours, and temperature is 18 DEG C, and graphite flake dispersion liquid contains identical with polyacrylonitrile solution Solvent, solvent are dimethylacetylamide；The mass fraction of initiator relative monomer is 1%；The quality of graphite flake relative monomer point Number is 50%；Then polymerize 12h at normal pressure, 65 DEG C, solution, which is then carried out ultrasonic deaeration, handles 3.5h, obtain graphite flake/ Polyacrylonitrile composite solution；The conversion ratio of monomer is 89% in graphite flake obtained/polyacrylonitrile composite solution；Then by graphite Piece/polyacrylonitrile composite solution is through cement-dipping method casting film；Form graphite flake/polyacrylonitrile laminated film that thickness is 80 μm；Again will Graphite flake/polyacrylonitrile laminated film is handled through hot steam super drawing, and draw ratio is 4 times；Continue pressure pre-oxidation Processing, pressure pre-oxidation temperature are 210 DEG C, and the time is 80 minutes, and atmosphere is air atmosphere, and the mode of pressurization is by 3 groups of heat Pressure roller applies the pressure that size is 50MPa；Continue scale pressure carbonization processing, scale pressure carbonization temperature is 650 DEG C, and the time is 55 points Clock, atmosphere are argon atmosphere, and the mode of pressurization is to apply the pressure that size is 2MPa by 3 groups of hot-pressing rollers；It is 20 μ that thickness, which is made, The flexible carbon film of m.
Flexibility carbon film obtained is made of height-oriented graphite flake and graphite microcrystal；Height-oriented refers to being more than graphite flake The graphite plate plane of additive amount 70% is less than 30 ° with flexible carbon film plane institute at the angle of orientation；Average grain size is the stone of 4.7nm Black crystallite is orientated along graphite flake surface alignment, and the porosity of the flexibility carbon film is 0.7%；With the slide methods in JIS L 1096 The rigid softness of the flexible carbon film of measurement is 4 × 10-3MNcm, resistivity are 58 Ω cm, intensity 350MPa, and thermal coefficient is 0.8W/m·k。
Embodiment 11
A kind of preparation method of flexibility carbon film, by blending method, by the graphite flake of a concentration of 3.5wt% (graphene and also The mass ratio of former graphene oxide is 2:5) dispersion liquid and a concentration of 35wt% polyacrylonitrile (comprising the first monomers acrylonitrile, The polyacrylonitrile of second comonomer methyl methacrylate and Third monomer metering system benzene sulfonic acid sodium salt, wherein acrylonitrile account for total monomer Mass fraction be 89%, methyl methacrylate with respect to total monomer mass fraction be 9%；Metering system benzene sulfonic acid sodium salt is opposite The mass fraction of total monomer is that 2%) solution is mixed by mechanical agitation；Graphite flake dispersion liquid is using preceding needing by mechanical agitation point It dissipates processing 1 hour, magnetic agitation decentralized processing 2 hours and ultrasonic disperse to handle 5 hours, temperature is 25 DEG C, graphite flake dispersion liquid Contain identical solvent with polyacrylonitrile solution, solvent is a concentration of 57wt% sodium thiocyanate water solutions, graphite flake dispersion liquid with The time of polyacrylonitrile solution mechanical agitation mixing is 8h, and rotating speed is 700 revs/min, and temperature is 35 DEG C；Then solution is carried out Vacuum defoamation 5.5h obtains graphite flake/polyacrylonitrile composite solution；Poly- third in graphite flake obtained/polyacrylonitrile composite solution The mass fraction of a concentration of 18wt% of alkene nitrile, graphite flake vs polypropylene nitrile are 60%；Then graphite flake/polyacrylonitrile is multiple Solution is closed through pressure sintering casting film；Form graphite flake/polyacrylonitrile laminated film that thickness is 50 μm；Again by graphite flake/polypropylene Nitrile laminated film is handled through hot steam super drawing, and draw ratio is 3 times；Then proceed by pressure pre-oxidation processing, pressurization Pre oxidation is 230 DEG C, and the time is 60 minutes, and atmosphere is air atmosphere, and the mode of pressurization is to be passed through air application size to be The pressure of 4MPa；Continue scale pressure carbonization processing, scale pressure carbonization temperature is 700 DEG C, and the time is 45 minutes, and atmosphere is nitrogen atmosphere It encloses, the mode of pressurization is to be passed through nitrogen to apply the pressure that size is 6MPa；The flexible carbon film that thickness is 17 μm is made.
Flexibility carbon film obtained is made of height-oriented graphite flake and graphite microcrystal；Height-oriented refers to being more than graphite flake The graphite plate plane of additive amount 70% is less than 30 ° with flexible carbon film plane institute at the angle of orientation；Average grain size is the stone of 4.4nm Black crystallite is orientated along graphite flake surface alignment, and the porosity of the flexibility carbon film is 3.2%；With the slide methods in JIS L 1096 The rigid softness of the flexible carbon film of measurement is 1 × 10-3MNcm, resistivity are 32 Ω cm, intensity 410MPa, and thermal coefficient is 0.9W/m·k。
Embodiment 12
A kind of preparation method of flexibility carbon film, by situ aggregation method, by the monomer of a concentration of 30wt%, (monomer includes the One monomers acrylonitrile, second comonomer methyl acrylate and Third monomer vinylpyridine, wherein acrylonitrile account for the quality of total monomer Score is 85%, and the mass fraction that methyl acrylate accounts for total monomer is 13%, and the mass fraction that vinylpyridine accounts for total monomer is 2%) the graphene microchip dispersion liquid of solution, initiator dilauroyl peroxide and a concentration of 4.5wt% is uniformly mixed and polymerization is made Solution；Graphene microchip dispersion liquid is using preceding needing by magnetic agitation decentralized processing, and processing time is 7 hours, and temperature is 20 DEG C, Graphene microchip dispersion liquid contains identical solvent with polyacrylonitrile solution, and solvent is that a concentration of 60wt% sodium sulfocyanates are water-soluble Liquid；The mass fraction of initiator relative monomer is 1%；The mass fraction of graphene microchip relative monomer is 70%；Then normal It presses, polymerize 20h at 57 DEG C, solution, which is then carried out standing and defoaming, handles 7.5h, and it is compound molten to obtain graphene microchip/polyacrylonitrile Liquid；The conversion ratio of monomer is 85% in graphene microchip obtained/polyacrylonitrile composite solution；Then by graphene microchip/poly- Acrylonitrile composite solution is through pressure sintering casting film；Form graphene microchip/polyacrylonitrile laminated film that thickness is 30 μm；Again by stone Black alkene microplate/polyacrylonitrile laminated film is handled through hot steam super drawing, and draw ratio is 2 times；Continue the pre- oxygen that pressurizes Change is handled, and pressure pre-oxidation temperature is 240 DEG C, and the time is 50 minutes, and atmosphere is air atmosphere, and the mode of pressurization is to be passed through air Apply the pressure that size is 10MPa；Continuing scale pressure carbonization processing, scale pressure carbonization temperature is 900 DEG C, and the time is 35 minutes, Atmosphere is argon atmosphere；The mode of pressurization is to be passed through argon gas to apply the pressure that size is 10MPa；The flexibility that thickness is 15 μm is made Carbon film.
Flexibility carbon film obtained is made of height-oriented graphene microchip and graphite microcrystal；Height-oriented refers to being more than stone The graphene microchip plane of black alkene microplate additive amount 70% is less than 30 ° with flexible carbon film plane institute at the angle of orientation；Average crystal grain ruler The very little graphite microcrystal for 3.7nm is orientated along graphene microchip surface alignment, and the porosity of the flexibility carbon film is 2.9%；With JIS L The rigid softness for the flexible carbon film that slide methods in 1096 measure is 7 × 10-4MNcm, resistivity are 0.4 Ω cm, and intensity is 450MPa, thermal coefficient 8W/mk.
Embodiment 13
A kind of preparation method of flexibility carbon film, by blending method, by the graphite flake of a concentration of 4.1wt% (graphene microchip, The mass ratio 1 of graphene oxide and graphene:1:1) polyacrylonitrile of dispersion liquid and a concentration of 30wt% (includes the first monomer third The polyacrylonitrile of alkene nitrile, second comonomer vinylacetate and Third monomer dimethylaminoethyl acrylate methyl base aminoethyl, wherein propylene The mass fraction that nitrile accounts for total monomer is 90%, and the mass fraction that vinylacetate accounts for total monomer is 8%, dimethylaminoethyl acrylate methyl base The mass fraction that aminoethyl accounts for total monomer is that 2%) solution is mixed by mechanical agitation；Graphite flake dispersion liquid using preceding need by Ultrasonic disperse processing, processing time are 10 hours, and temperature is 25 DEG C, and graphite flake dispersion liquid contains identical with polyacrylonitrile solution Solvent, solvent are dimethylformamide；The time that graphite flake dispersion liquid is mixed with polyacrylonitrile solution mechanical agitation is 15h, is turned Speed is 900 revs/min, and temperature is 35 DEG C；Then solution is subjected to ultrasonic deaeration 9.5h, it is compound obtains graphite flake/polyacrylonitrile Solution；A concentration of 15wt% of polyacrylonitrile in graphite flake obtained/polyacrylonitrile composite solution, graphite flake vs polypropylene nitrile Mass fraction be 16%；Then by graphite flake/polyacrylonitrile composite solution through pressure sintering casting film；Form the stone that thickness is 10 μm Ink sheet/polyacrylonitrile laminated film；Graphite flake/polyacrylonitrile laminated film is handled through hot steam super drawing again, is stretched again Number is 1 times；Pressure pre-oxidation processing is then proceeded by, pressure pre-oxidation temperature is 250 DEG C, and the time is 140 minutes, and atmosphere is Air atmosphere, the mode of pressurization are to be passed through air to apply the pressure that size is 20MPa；Continue scale pressure carbonization processing, pressurization Carburizing temperature is 1100 DEG C, and the time is 10 minutes, and atmosphere is nitrogen atmosphere；The mode of pressurization is to be passed through nitrogen application size to be The pressure of 20MPa；The flexible carbon film that thickness is 12 μm is made.
Flexibility carbon film obtained is made of height-oriented graphite flake and graphite microcrystal；Height-oriented refers to being more than graphite flake The graphite plate plane of additive amount 70% is less than 30 ° with flexible carbon film plane institute at the angle of orientation；Average grain size is the stone of 3.1nm Black crystallite is orientated along graphite flake surface alignment, and the porosity of the flexibility carbon film is 2.1%；With the slide methods in JIS L 1096 The rigid softness of the flexible carbon film of measurement is 0.9mNcm, and resistivity is 0.05 Ω cm, intensity 140MPa, and thermal coefficient is 20W/m·k。
Embodiment 14
A kind of preparation method of flexibility carbon film, by situ aggregation method, by the monomer of a concentration of 35wt%, (monomer includes the One monomers acrylonitrile, second comonomer methyl methacrylate and Third monomer dimethylaminoethyl acrylate methyl base aminoethyl, wherein third The mass fraction that alkene nitrile accounts for total monomer is 90%, and the mass fraction that methyl methacrylate accounts for total monomer is 7%, methacrylic acid The mass fraction that dimethyl amido ethyl ester accounts for total monomer is 3%) solution, initiator di-isopropyl peroxydicarbonate and a concentration of 1wt% graphite flake (graphene microchip, graphene oxide, redox graphene and graphene mass ratio 1:3:1:1) divide Dispersion liquid is uniformly mixed and polymeric solution is made；For graphite flake dispersion liquid using preceding needing to handle by ultrasonic disperse, processing time is 5 small When, temperature is 10 DEG C, and graphite flake dispersion liquid contains identical solvent with polyacrylonitrile solution, and solvent is dimethyl sulfoxide (DMSO)；Cause The mass fraction of agent relative monomer is 1%；The mass fraction of graphite flake relative monomer is 64%；Then gather at normal pressure, 67 DEG C 15h is closed, solution, which is then carried out vacuum defoamation, handles 11.5h, obtains graphite flake/polyacrylonitrile composite solution；Graphite obtained The conversion ratio of monomer is 89% in piece/polyacrylonitrile composite solution；Then by graphite flake/polyacrylonitrile composite solution through the tape casting Casting film；Form graphite flake/polyacrylonitrile laminated film that thickness is 200 μm；Again by graphite flake/polyacrylonitrile laminated film through boiling Water super drawing is handled, and draw ratio is 6 times；Continuing pressure pre-oxidation processing, pressure pre-oxidation temperature is 215 DEG C, when Between be 130 minutes, atmosphere is air atmosphere, and the mode of pressurization is that apply pressure sizes by 3 groups of hot-pressing rollers be 30MPa；Continue Scale pressure carbonization processing is carried out, scale pressure carbonization temperature is 1900 DEG C, and the time is 5 minutes, and atmosphere is nitrogen atmosphere, and the mode of pressurization is It is 30MPa to apply pressure size by 4 groups of hot-pressing rollers；The flexible carbon film that thickness is 38 μm is made.
Flexibility carbon film obtained is made of height-oriented graphite flake and graphite microcrystal；Height-oriented refers to being more than graphite flake The graphite plate plane of additive amount 70% is less than 30 ° with flexible carbon film plane institute at the angle of orientation；Average grain size is the stone of 1.2nm Black crystallite is orientated along graphite flake surface alignment, and the porosity of the flexibility carbon film is 0.7%；With the slide methods in JIS L 1096 The rigid softness of the flexible carbon film of measurement is 2.1 × 10-3MNcm, resistivity are 2 × 10-3Ω cm, intensity 420MPa, lead Hot coefficient is 47W/mk.
Embodiment 15
A kind of preparation method of flexibility carbon film, by blending method, by the graphene oxide dispersion of a concentration of 3.2wt% with The polyacrylonitrile of a concentration of 25wt% (includes the first monomers acrylonitrile, second comonomer acrylamide and Third monomer metering system The mass fraction that the polyacrylonitrile of sour dimethyl amido ethyl ester, wherein acrylonitrile account for total monomer is 80%, and acrylamide accounts for total list The mass fraction of body is 18%, and the mass fraction that dimethylaminoethyl acrylate methyl base aminoethyl accounts for total monomer is that 2%) solution passes through machine Tool is stirred；Graphene oxide dispersion is using preceding needing by magnetic agitation decentralized processing, and processing time is 8 hours, temperature It it is 30 DEG C, graphene oxide dispersion contains identical solvent with polyacrylonitrile solution, and solvent is dimethylacetylamide；Aoxidize stone The time that black alkene dispersion liquid is mixed with polyacrylonitrile solution mechanical agitation is 20h, and rotating speed is 900 revs/min, and temperature is 40 DEG C； Then solution is subjected to ultrasonic deaeration, the time is that 11h obtains graphene oxide/polyacrylonitrile composite solution；Oxidation stone obtained A concentration of 35wt% of polyacrylonitrile in black alkene/polyacrylonitrile composite solution, the quality point of graphene oxide vs polypropylene nitrile Number is 27%；Then by graphene oxide/polyacrylonitrile composite solution through the tape casting casting film；Form the oxidation stone that thickness is 1 μm Black alkene/polyacrylonitrile laminated film；Graphene oxide/polyacrylonitrile laminated film is handled through hot steam super drawing again, is drawn It is 10 times to stretch multiple；Continue pressure pre-oxidation processing, pressure pre-oxidation temperature is 260 DEG C, and the time is 160 minutes, atmosphere For air atmosphere, the mode of pressurization is to apply the pressure that size is 40MPa by 2 groups of hot-pressing rollers；Continue at scale pressure carbonization Reason, scale pressure carbonization temperature are 1300 DEG C, and the time is 50 minutes, and atmosphere is argon atmosphere, and the mode of pressurization is to pass through 2 groups of hot-pressing rollers Apply the pressure that size is 40MPa；The flexible carbon film that thickness is 0.1 μm is made.
Flexibility carbon film obtained is made of height-oriented redox graphene and graphite microcrystal；Height-oriented refers to more It is less than 30 ° at the angle of orientation with flexible carbon film plane institute in the redox graphene plane of graphene oxide additive amount 70%；It is flat The graphite microcrystal that equal crystallite dimension is 2.5nm is orientated along redox graphene surface alignment, and the porosity of the flexibility carbon film is 0.5%；The rigid softness of the flexible carbon film measured with the slide methods in JIS L 1096 is 0.4mNcm, and resistivity is 9 × 10-3 Ω cm, intensity 230MPa, thermal coefficient 24W/mk.
Embodiment 16
A kind of preparation method of flexibility carbon film, by situ aggregation method, by the monomer of a concentration of 28wt%, (monomer includes the One monomers acrylonitrile, second comonomer methyl acrylate and Third monomer sodium allylsulfonate, wherein acrylonitrile account for the quality of total monomer Score is 82%, and the mass fraction that methyl acrylate accounts for total monomer is 16%, and the mass fraction that sodium allylsulfonate accounts for total monomer is 2%) solution, initiator dibenzoyl peroxide and a concentration of 5wt% redox graphenes dispersion liquid be uniformly mixed be made it is poly- Close solution；For redox graphene dispersion liquid using preceding needing to handle by ultrasonic disperse, processing time is 8.5 hours, and temperature is 28 DEG C, redox graphene dispersion liquid contains identical solvent with polyacrylonitrile solution, and solvent is a concentration of 55wt% sulphur cyanogen The mass fraction of acid sodium aqueous solution, initiator relative monomer is 1%；The mass fraction of redox graphene relative monomer is 38%；Then polymerize 8h at normal pressure, 55 DEG C, solution, which is then carried out ultrasonic deaeration, handles 9h, obtain redox graphene/ Polyacrylonitrile composite solution；The conversion ratio of monomer is 79% in redox graphene obtained/polyacrylonitrile composite solution；So Afterwards by the extruded pulling method casting film of redox graphene/polyacrylonitrile composite solution；Form the reduction-oxidation that thickness is 110 μm Graphene/polyacrylonitrile laminated film；At again by redox graphene/polyacrylonitrile laminated film through hot boiling water super drawing Reason, draw ratio are 50 times；Pressure pre-oxidation processing is then proceeded by, pressure pre-oxidation temperature is 270 DEG C, the time 170 Minute, atmosphere is air atmosphere, and the mode of pressurization is to be passed through air to apply the pressure that size is 25MPa；Continue pressurized carbon Change is handled, and scale pressure carbonization temperature is 1500 DEG C, and the time is 2 minutes, and atmosphere is nitrogen atmosphere, and the mode of pressurization is to be passed through nitrogen to apply Increase the small pressure for 25MPa；The flexible carbon film that thickness is 5 μm is made.
Flexibility carbon film obtained is made of height-oriented redox graphene and graphite microcrystal；Height-oriented refers to more It is less than at the angle of orientation with flexible carbon film plane institute in the redox graphene plane of redox graphene additive amount 70% 30°；Average grain size is that the graphite microcrystal of 2.2nm is orientated along redox graphene surface alignment, the hole of the flexibility carbon film Gap rate is 1.5%；The rigid softness of the flexible carbon film measured with the slide methods in JIS L 1096 is 6 × 10-2MNcm, resistance Rate is 5 × 10-3Ω cm, intensity 280MPa, thermal coefficient 23W/mk.
Embodiment 17
A kind of preparation method of flexibility carbon film, by blending method, by the graphite flake (graphene oxide of a concentration of 1.6wt% Mass ratio with redox graphene is 2:1) polyacrylonitrile of dispersion liquid and a concentration of 15wt% (includes the first monomer propylene The polyacrylonitrile of nitrile, second comonomer vinylacetate and Third monomer itaconic acid, wherein acrylonitrile account for the mass fraction of total monomer It is 87%, the mass fraction that vinylacetate accounts for total monomer is 12%, and itaconic acid accounts for the mass fraction of total monomer as 1%) solution It is mixed by mechanical agitation；Graphite flake dispersion liquid is using preceding needing by mechanical agitation decentralized processing, and processing time is 9 hours, temperature Degree is 25 DEG C, and graphite flake dispersion liquid contains identical solvent with polyacrylonitrile solution, and solvent is a concentration of 51.3wt% thiocyanic acids Sodium water solution, then by solution carry out vacuum defoamation 7h, graphite flake dispersion liquid mixed with polyacrylonitrile solution mechanical agitation when Between for for 24 hours, rotating speed is 50 revs/min, and temperature is 10 DEG C；Obtain graphite flake/polyacrylonitrile composite solution；Graphite flake obtained/ The mass fraction of a concentration of 26wt% of polyacrylonitrile in polyacrylonitrile composite solution, graphite flake vs polypropylene nitrile are 45%； Then by graphite flake/polyacrylonitrile composite solution through pressure sintering casting film；It is multiple to form graphite flake/polyacrylonitrile that thickness is 195 μm Close film；Graphite flake/polyacrylonitrile laminated film is handled through hot steam super drawing again, draw ratio is 3 times；It then proceedes to Pressure pre-oxidation processing is carried out, pressure pre-oxidation temperature is 290 DEG C, and the time is 90 minutes, and atmosphere is air atmosphere, the side of pressurization Formula is to be passed through air to apply the pressure that pressure size is 36MPa；Continue scale pressure carbonization processing, scale pressure carbonization temperature is 1700 DEG C, the time is 3 minutes, and atmosphere is nitrogen atmosphere, and the mode of pressurization is to be passed through nitrogen to apply the pressure that pressure size is 36MPa； The flexible carbon film that thickness is 63 μm is made.
Flexibility carbon film obtained is made of height-oriented graphite flake and graphite microcrystal；Height-oriented refers to being more than graphite flake The graphite plate plane of additive amount 70% is less than 30 ° with flexible carbon film plane institute at the angle of orientation；Average grain size is the stone of 1.6nm Black crystallite is orientated along graphite flake surface alignment, and the porosity of the flexibility carbon film is 0.4%；With the slide methods in JIS L 1096 Rigid soft the 1 of the flexible carbon film of measurement is 8 × 10-3MNcm, resistivity are 3 × 10-3Ω cm, intensity 330MPa, heat conduction system Number is 36W/mk.

Claims (8)

1. a kind of flexibility carbon film, characterized in that the flexibility carbon film is made of height-oriented graphite flake and graphite microcrystal；It is described Graphite flake there is inducing action, the graphite microcrystal that induction generates to be orientated along graphite flake surface alignment the formation of graphite microcrystal； It is described it is height-oriented refer to more than the graphite plate plane of graphite flake additive amount 70% and flexible carbon film plane be less than at the angle of orientation 30°；The average grain size of the graphite microcrystal is 1~5nm, and the porosity of the flexibility carbon film is 0~4%, with JIS L The rigid softness for the flexible carbon film that slide methods in 1096 measure is 10-4~10mNcm.
2. a kind of flexible carbon film according to claim 1, which is characterized in that the resistivity of the flexibility carbon film is 10-3~ 100 Ω cm, the flexibility carbon film strength is 5~500MPa, and the thermal coefficient of the flexibility carbon film is 0.5~50W/m k；The thickness of the carbon film is 0.1~100 μm.
3. preparing such as a kind of preparation method of flexible carbon film of claim 1~2 any one of them, characterized in that including following Step：
1) by blending method or situ aggregation method, graphite flake/polyacrylonitrile composite solution is prepared；
2) graphite flake/polyacrylonitrile composite solution is handled through casting film, forms graphite flake/polyacrylonitrile laminated film；
3) graphite flake/polyacrylonitrile laminated film is handled through high drafting, pressure pre-oxidation and scale pressure carbonization is made flexible carbon film；
The pressure pre-oxidation temperature is 200~300 DEG C, and the time is 30~200 minutes；The scale pressure carbonization temperature be 600~ 2000 DEG C, the time is 1~60 minute；The pressure size applied in the pressurization is 0.2~50MPa.
4. preparation method according to claim 3, which is characterized in that the graphite flake is graphene microchip, graphene, oxygen One or more of graphite alkene or redox graphene；
The pressure pre-oxidation is identical with the pressuring method and pressure size in scale pressure carbonization stage, and the mode of pressurization is to pass through 1- 4 groups of hot-pressing rollers, which apply pressure or are passed through atmosphere gas, applies one or more of pressure；Atmosphere in the pressure pre-oxidation is Air atmosphere, the atmosphere in the scale pressure carbonization are inert atmosphere, and the inert atmosphere is nitrogen or argon gas.
5. preparation method according to claim 3, which is characterized in that the blending method refer to by graphite flake dispersion liquid with contain The polyacrylonitrile solution of same solvent is mixed by mechanical agitation, and solution, which is then carried out deaeration processing, obtains graphite flake/poly- third Alkene nitrile composite solution；
The graphite flake dispersion liquid using preceding need by ultrasonic disperse, magnetic agitation dispersion or mechanical agitation decentralized processing in one Kind or more, processing time is 0.5~12 hour, and temperature is 10~40 DEG C；
The polyacrylonitrile is or further, also to contain second comonomer or second comonomer and the including at least the first monomer Three monomers；
First monomer is acrylonitrile, and the first single phase is 80~100% to the mass fraction of total monomer；
The second comonomer be acrylamide, methyl acrylate, methyl methacrylate, methacrylonitrile or vinylacetate, Second comonomer is 1~20% with respect to the mass fraction of total monomer；
The Third monomer is itaconic acid, sodium allylsulfonate, methylpropene sodium sulfonate, metering system benzene sulfonic acid sodium salt, vinylpyridine Pyridine or dimethylaminoethyl acrylate methyl base aminoethyl, Third monomer are 1~3% with respect to the mass fraction of total monomer；
The solvent is dimethylformamide, dimethyl sulfoxide (DMSO), dimethylacetylamide or sodium thiocyanate water solution；The thiocyanic acid A concentration of 50~60wt% of sodium water solution；
A concentration of 0.5~5wt% of the graphite flake dispersion liquid；A concentration of 10~40wt% of the polyacrylonitrile solution；
The time of mechanical agitation mixing is 1~for 24 hours, rotating speed is 50-1500 revs/min, and temperature is 10~50 DEG C；
The mode of the deaeration processing is vacuum defoamation, ultrasonic deaeration or standing and defoaming, and the time is 0.5~12h；
A concentration of 9~39wt% of polyacrylonitrile in the graphite flake/polyacrylonitrile composite solution, graphite flake vs polypropylene nitrile Mass fraction be 0.1~80%.
6. preparation method according to claim 3, which is characterized in that the situ aggregation method refers to by monomer, initiator Be separately added into solvent identical with contained solvent in graphite flake dispersion liquid with graphite flake dispersion liquid, be uniformly mixed be made polymerization it is molten Liquid；Under normal pressure, it polymerize 1 at 50~70 DEG C~for 24 hours, it then handles the solution progress deaeration to obtain graphite flake/polyacrylonitrile compound Solution；
The monomer includes at least the first monomer, or further, also contains second comonomer or second comonomer and third list Body；
First monomer is acrylonitrile, and the first single phase is 80~100% to the mass fraction of total monomer；
The second comonomer be acrylamide, methyl acrylate, methyl methacrylate, methacrylonitrile or vinylacetate, Second comonomer is 1~20% with respect to the mass fraction of total monomer；
The Third monomer is itaconic acid, sodium allylsulfonate, methylpropene sodium sulfonate, metering system benzene sulfonic acid sodium salt, vinylpyridine Pyridine or dimethylaminoethyl acrylate methyl base aminoethyl, Third monomer are 1~3% with respect to the mass fraction of total monomer；
The initiator is azodiisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, dilauroyl peroxide or peroxide Change two diisopropyl carbonates；
The solvent is dimethylformamide, dimethyl sulfoxide (DMSO), dimethylacetylamide or sodium thiocyanate water solution；The thiocyanic acid A concentration of 50~60wt% of sodium water solution；
The graphite flake dispersion liquid using preceding need by ultrasonic disperse, magnetic agitation dispersion or mechanical agitation decentralized processing in one Kind or more, processing time is 0.5~12 hour, and temperature is 10~40 DEG C；
A concentration of 0.5~5wt% of the graphite flake dispersion liquid；
The mode of the deaeration processing is vacuum defoamation, ultrasonic deaeration or standing and defoaming, and the time is 0.5~12h；
In the polymeric solution, a concentration of 10~40wt% of monomer, the mass fraction of initiator relative monomer is 0.3~ 1.5%；The mass fraction of graphite flake relative monomer is 0.1~80%；
The conversion ratio of monomer is 70~99% in the graphite flake/polyacrylonitrile composite solution.
7. preparation method according to claim 3, which is characterized in that the method for the casting film is the tape casting, squeezes out stretching Method, pressure sintering, swelling pulling method or cement-dipping method；The graphite flake/polyacrylonitrile laminated film thickness is 1~200 μm.
8. preparation method according to claim 3, which is characterized in that the super drawing refer to hot steam super drawing or Boiling water super drawing；Draw ratio in the super drawing is 1~50 times.
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