CN106012110A

CN106012110A - Flexible carbon fiber and preparation method thereof

Info

Publication number: CN106012110A
Application number: CN201610498811.8A
Authority: CN
Inventors: 李凤美; 王彪; 郑迎迎; 王华平
Original assignee: Donghua University
Current assignee: Donghua University; National Dong Hwa University
Priority date: 2016-06-30
Filing date: 2016-06-30
Publication date: 2016-10-12
Anticipated expiration: 2036-06-30
Also published as: CN106012110B

Abstract

The invention relates to a flexible carbon fiber and a preparation method thereof. The carbon fiber is prepared by carrying out spinning on a graphite flake/polyacrylonitrile complex solution and carrying out super-high drafting, pre-oxidation and carbonization treatment. The carbon fiber has highly oriented graphite flakes and graphite crystal structures generated through induction of the graphite flakes, wherein graphite crystallite is arranged and oriented along the surfaces of the graphite flakes. The carbon fiber has the characteristics of high order degree, compact structure, small average grain size and few defects. The rigidity/softness, resistivity, strength and axial thermal conductivity of the prepared flexible carbon fiber are respectively 10<-4>-10mN .cm, 10<-3>-100omega .cm, 1000-5000MPa and 0.5-50W/m .k. The prepared flexible carbon fiber has the beneficial effects that the flexible carbon fiber is low in production cost and wide in raw material sources; the structural properties of the carbon fiber can be substantially improved; and the flexible carbon fiber has very high market application values and can be widely applied to the fields of electrode materials, functional materials, energy materials, and the like.

Description

A kind of flexible carbon fiber and preparation method thereof

Technical field

The invention belongs to composite fibre preparing technical field, relate to a kind of flexible carbon fiber and preparation method thereof, especially Relate to a kind of method preparing high-performance flexible carbon fiber for raw material with conventional polypropylene nitrile.

Background technology

Polyacrylonitrile fibre, as one of three big synthetic fibers, is widely used in clothing, decoration and industry neck Territory.Polyacrylonitrile fibril is the important precursor preparing carbon fiber, accounts for more than the 90% of carbon fiber yield.Poly- Acrylonitrile base carbon fiber has high mechanical properties, low-gravity, high temperature resistant, chemical resistance and excellent electricity physics Mechanical performance, in Aeronautics and Astronautics, steamer, automobile, machine-building, chemical industry, electronics, communication, medical treatment The fields such as industrial circle and physical culture such as equipment have wide practical use.But there is fragility, flexibility in carbon fiber The shortcoming of difference, this makes the impact resistance ability of its composite and goods poor.Therefore the research of flexible carbon fiber Develop significant.

Along with economic development, there is high flexibility, electric conductivity, the carbon fibre material of heat conductivity are gradually visited Rope is applied to the fields such as reinforcing material, function dress ornament, electromagnetic field, communication, military affairs.Graphene is the most fast A kind of Two-dimensional Carbon material of speed development, has the performances such as extra specific surface area, excellent electricity, calorifics and mechanics, This makes it develop rapidly in every field, especially applies quite varied in terms of polymer modification.At present about The research major part of polyacrylonitrile-based carbon fibre pays close attention to its performance such as heat conductivity, electric conductivity, for flexible carbon fiber And performance study is less.

There is fragility, the shortcoming of flexible difference more in common carbon fibers, the method for the invention be by polyacrylonitrile with Graphite flake is combined, and a kind of novel carbon fiber of preparation, this carbon fiber has compact structure, and order degree is big, defect Few feature with superpower flexibility, has the advantage such as high conductivity, high-termal conductivity simultaneously, can be widely applied to strengthen The fields such as material and function dress ornament.

Summary of the invention

The present invention relates to a kind of flexible carbon fiber and preparation method thereof, its object is to improve the crisp of conventional carbon fiber Property, flexible poor, shortcoming, it is micro-that this carbon fiber has the graphite by height-oriented graphite flake and induction generation thereof Crystal structure, this graphite microcrystal is orientated along graphite flake surface alignment；This carbon fiber has that order degree is big, structure causes Feature close, that average grain size is little and defect is few, makes this carbon fiber have high flexibility.This carbon fiber also has The feature of high conductivity, high intensity and high-termal conductivity.

For realizing aforementioned invention purpose, the technical solution used in the present invention includes:

The preparation method of a kind of flexible carbon fiber, comprises 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 through solvent spinning, forms graphite flake/polyacrylonitrile composite fiber；

3) flexibility that graphite flake/polyacrylonitrile composite fiber prepares through super-high power drawing-off, pre-oxidation and carbonization treatment Carbon fiber；

Drafting multiple in described super-high power drawing-off is 10～100 times, and described Pre oxidation is 200～300 DEG C, Time is 30～200 minutes, and applying tension force is 0.2～50MPa；Described carburizing temperature is 600～2000 DEG C, time Between be 1～60 minute, apply tension force be 0.2～50MPa.

As preferred technical scheme:

Preparation method as above, described graphite flake is Graphene, graphene microchip, graphene oxide or goes back More than one in former graphene oxide；Described pre-oxidation atmosphere is air atmosphere, and described pre-oxidation applies tension force Mode be by 2～8 roller draft fibers；Described carburizing atmosphere is inert atmosphere, and described inert atmosphere is Nitrogen or argon；It is by 2～8 roller draft fibers that described carbonization applies the mode of tension force.

Preparation method as above, described blending method refers to polyacrylonitrile solution and the graphite containing same solvent Sheet dispersion liquid is mixed by mechanical agitation, then solution carries out deaeration process acquisition graphite flake/polyacrylonitrile multiple Close solution；

Described polyacrylonitrile includes at least the first monomer；Or further, also containing second comonomer, or second is single Body and Third monomer；

Described first monomer is acrylonitrile, and the first monomer is 80～100% relative to the mass fraction of total monomer；

Described second comonomer is acrylamide, acrylic acid methyl ester., methyl methacrylate, methacrylonitrile or vinegar Vinyl acetate, second comonomer is 1～20% relative to the mass fraction of total monomer；

Described Third monomer be itaconic acid, sodium allylsulfonate, methylpropene sodium sulfonate, metering system benzene sulfonic acid sodium salt, Vinylpyridine or dimethylaminoethyl acrylate methyl base aminoethyl, Third monomer relative to the mass fraction of total monomer is 1～3%；

Described solvent is dimethylformamide, dimethyl sulfoxide, dimethyl acetylamide or sodium thiocyanate water solution； The concentration of described sodium thiocyanate water solution is 50～60wt%；

Described graphite flake dispersion liquid needs before using at ultrasonic disperse, magnetic agitation dispersion or mechanical agitation dispersion More than one in reason, the process time is 0.5～12 hour, and temperature is 10～40 DEG C；

The concentration of described graphite flake dispersion liquid is 0.5～5wt%；The concentration of described polyacrylonitrile solution is 10～40wt%；

The time of described mechanical agitation mixing is 1～24h, and rotating speed is 50～1500 revs/min, and temperature is 10～50 DEG C；

The mode that described deaeration processes is vacuum defoamation, ultrasonic deaeration or standing and defoaming, and the time is 0.5～12h；

In described graphite flake/polyacrylonitrile composite solution, the concentration of polyacrylonitrile is 9～39wt%, and graphite flake is relative The mass fraction of polyacrylonitrile is 0.1～80%.

Preparation method as above, described situ aggregation method refers to monomer, initiator and graphite flake dispersion liquid Be separately added into graphite flake dispersion liquid contained by solvent phase with solvent in, mix homogeneously makes polymeric solution；Normal pressure Under, it being polymerized 1～24h at 50～70 DEG C, deaeration obtains graphite flake/polyacrylonitrile composite solution after processing；

Described monomer includes at least the first monomer；Or further, possibly together with second comonomer, or second comonomer And Third monomer；

Described initiator is azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, peroxidating 12 Acyl or di-isopropyl peroxydicarbonate；

The concentration of described graphite flake dispersion liquid is 0.5～5wt%；

In described polymeric solution, the concentration of monomer is 10～40wt%, and the mass fraction of initiator relative monomer is 0.3-1.5%；The mass fraction of graphite flake relative monomer is 0.1～80%；

In described graphite flake/polyacrylonitrile composite solution, the conversion ratio of monomer is 70～99%.

Preparation method as above, the method for described solvent spinning is wet spinning or dry-jet wet spinning；Institute State a diameter of 1～100 μm of graphite flake/polyacrylonitrile composite fiber.

Preparation method as above, described wet spinning technology is that spinning solution enters coagulating bath through spinning head, Then sequentially entering rinsing bowl and stretch bath, rolling machine is collected and is obtained graphite flake/polyacrylonitrile composite fiber； Described dry-jet wet spinning technique is that spinning solution enters air section through spinning head, then sequentially enter coagulating bath, Rinsing bowl and stretch bath, rolling machine is collected and is obtained graphite flake/polyacrylonitrile composite fiber；Described air section A length of 2～20mm；

Described wet spinning is identical with the process conditions of the coagulating bath of dry-jet wet spinning, rinsing bowl and stretch bath；

Solvent species selected by described coagulating bath solvent for use and graphite flake/polyacrylonitrile composite solution is identical, for Concentration is the water of dimethylformamide, dimethyl sulfoxide, dimethyl acetylamide or the sodium rhodanate of 10～40wt% Solution, temperature is 5～25 DEG C；

Described rinsing bowl, solvent is water, and temperature is 50～70 DEG C；

Described stretch bath, solvent is water, and temperature is 90～98 DEG C, and draw ratio is 3～9 times.

Preparation method as above, described super-high power drawing-off refers to vapours super-high power drawing-off or boiling water super-high power Drawing-off.

Using the flexible carbon fiber that above-mentioned preparation method prepares, this flexibility carbon fiber is mainly micro-by graphite flake and graphite Brilliant composition, wherein more than graphite flake addition 70% graphite flake in-plane and carbon fiber axially formed by take To angle less than 30 °, graphite flake induction the graphite microcrystal produced is orientated along graphite flake surface alignment；Described graphite The average grain size of crystallite is 1～5nm；The porosity of flexible carbon fiber is 0～4%.

Flexible carbon fiber as above, a diameter of 0.1～20 μm of described flexible carbon fiber, by JIS L 1096 The firm softness of the flexible carbon fiber that B method measures is 10^-4～10mN cm；The resistivity of flexible carbon fiber is 10^-3～100 Ω cm, intensity is 1000～5000MPa, and the axial heat conductivity of flexible carbon fiber is 0.5～50W/m k.

In the present invention, the preparating mechanism of flexible carbon fiber is as follows:

1) graphite flake plays sliding plasticization, beneficially fiber at super-high power stretching phase and carries out super times drawing-off；

When with Graphene or graphene microchip for raw material, owing to Graphene or graphene microchip surface are without active base Group, and produce without valence link interaction between polyacrylonitrile molecule, in drafting process, along with drafting multiple increases Adding, drafting tension increases, and Graphene or graphene microchip produce at polyacrylonitrile molecule interchain under tension Sliding, Graphene or graphene microchip play plasticization, make polyacrylonitrile strand be easier to motion, in phase With under drafting tension effect, after adding Graphene or graphene microchip, fiber is easy to get bigger drafting multiple, Be conducive to fiber carries out super times drawing-off；Under tension, Graphene or graphene microchip are the highest along fiber Degree orientation；When with graphene oxide or redox graphene for raw material, due in graphene oxide or reduction Surface of graphene oxide contains the oxy radicals such as hydroxyl, carboxyl, ester group, shows electronegativity in a solvent, and poly-third Alkene nitrile molecule contains the group such as ester group, sulfonic group, the most also shows electronegativity, thus polyacrylonitrile molecule with Certain electrostatic repulsion is there is, along with drafting multiple increases between graphene oxide or redox graphene Adding, drafting tension increases, and graphene oxide or redox graphene are at polyacrylonitrile molecule under tension Interchain is more easily generated sliding, graphene oxide or redox graphene and plays plasticization, makes polyacrylonitrile divide Subchain motion is more prone to, and under identical drafting tension effect, adds graphene oxide or redox graphene After, fiber is readily obtained bigger drafting multiple, is conducive to fiber is carried out super-high power drawing-off；In tension force effect Under, graphene oxide or redox graphene are the most height-oriented along fiber；

2) graphite flake is in pre-oxidation stage crosslinking reaction, the cross-linking reaction within beneficially PAN macromolecule；

The pre-oxidation stage, at the pre-oxidation initial stage, along with temperature raises, polyacrylonitrile strand initial ring fluidized dehydrogenation Reaction, polyacrylonitrile is gradually converted into trapezoidal six-membered ring structure, under tension, graphite by linear macromolecule Sheet axially retains certain orientation with polyacrylonitrile strand along fiber, makes deorientation weaken, and is formed and causes in order Close orientation texture；Along with temperature continues to raise, oxidation cross-linked reaction starts to occur, when with Graphene or graphite When alkene microplate is raw material, due to Graphene or the existing defects of graphene microchip own or produce in heat treatment process Segmental defect, may participate in the carbon atom of reaction, these carbon at Graphene or graphene microchip fault location existence part Atom is under heat effect and oxygen generation oxidation reaction, and then crosslinks with the functional group in polyacrylonitrile molecule Reaction, forms cross-linked structure；When using graphene oxide or redox graphene as raw material, due to oxygen Functionalized graphene or redox graphene contain certain oxygen-containing functional group, and oxygen and oxygen-containing functional group are at a constant temperature There is oxidation reaction in the functional groups such as degree time and carbon-carbon double bond, polycondensation reaction also can occur between oxygen-containing functional group, make Obtain between polyacrylonitrile molecule, between polyacrylonitrile molecule and graphene oxide or redox graphene, oxidation Crosslink reaction between Graphene or between redox graphene, generate more regular cross-linked structure, poly-third Alkene nitrile macromole is converted into heat-resisting trapezium structure；

3) graphite flake inductive effect in carbonisation, induction graphite crystallization is also orientated along graphite flake surface alignment；

Carbonation stage, along with the rising of carburizing temperature, the ring molecule and the graphite flake that are formed in preoxidation process enter One step crosslinks, is cyclized and polycondensation reaction, and under tension, graphite flake keeps with polyacrylonitrile strand Certain orientation, makes deorientation weaken, and forms orientation texture fine and close more in order；Along with carburizing temperature continues Height of continuing rising, the graphite flake of orientation, as nucleation agent and template, makes the graphite microcrystal edge that polyacrylonitrile is formed The further aligned growth in carbon back face of graphite flake, induction produces the graphite microcrystal knot along graphite flake surface alignment orientation Structure；Further, due to graphite flake, there is two dimensional height orderly hexatomic ring carbon structure surface so that formed on its surface Graphite microcrystal by template growth, the average grain size of the graphite microcrystal of generation is less, is arranged with sequence higher.

Meanwhile, in carbonisation, when with graphene oxide or redox graphene for raw material, aoxidize stone Ink alkene or the oxygen-containing functional group such as carbonyl, hydroxyl, carboxyl etc. on redox graphene surface, at high temperature inert atmosphere Enclose lower participation to react or the removing that is decomposed, make graphene oxide or redox graphene be reduced.

Just because of prepared carbon fiber, there is height-oriented graphite flake and graphite microcrystalline structure so that its tool There is higher flexibility.

Beneficial effect:

1) present invention is a kind of flexible carbon fiber and preparation method thereof, and this method is simple to operate, and raw material sources are wide General, can significantly improve the flexibility of carbon fiber, make carbon fiber have high conductivity and high-termal conductivity simultaneously.

2) present invention can utilize routine or discarded polyacrylonitrile raw material, has the highest market using value.

3) present invention improves the fragility of carbon fiber by adding graphite flake in polyacrylonitrile matrix so that it is tool There is flexibility, this is because in spinning and super-high power drawing process, owing to graphite flake is intermolecular at polyacrylonitrile Phorogenesis so that it is the most height-oriented along fiber under tension, forms orientation texture, is conducive to fibre Dimension carries out super-high power drawing-off；In preoxidation process, graphite flake can promote that cross-linking reaction is carried out, and advantageously forms Cross-linked network structure；In carbonisation, graphite flake can induce graphite microcrystal to be orientated along graphite flake surface alignment, The graphite microcrystalline structure that crystallite dimension is little, compact structure is orderly and defect is few formed, the carbon fiber therefore formed There is high flexibility.

Detailed description of the invention

Below in conjunction with detailed description of the invention, the present invention is expanded on further.Should be understood that these embodiments are only used for The bright present invention rather than restriction the scope of the present invention.In addition, it is to be understood that reading the content that the present invention lectures Afterwards, the present invention can be made various changes or modifications by those skilled in the art, and these equivalent form of values fall within equally The application appended claims limited range.

Embodiment 1

The preparation method of a kind of flexible carbon fiber, is dissolved in dimethylformamide by Graphene and polyacrylonitrile respectively, Prepared concentration is the graphene dispersing solution of 0.5wt% and concentration is the polyacrylonitrile solution of 10wt%, polyacrylonitrile Containing only the first monomers acrylonitrile, the first monomer is 100% relative to the mass fraction of total monomer, by graphene dispersion Liquid carries out ultrasonic disperse process, and the process time is 0.5 hour, and temperature is 10 DEG C, is subsequently adding polyacrylonitrile molten Liquid carries out mechanical agitation mixing, and the time is 1h, and rotating speed is 50 revs/min, and temperature is 10 DEG C, vacuum defoamation After 0.5h, the concentration obtaining polyacrylonitrile is 9wt%, the mass fraction of Graphene vs polypropylene nitrile is 0.1% Graphene/polyacrylonitrile composite solution；

Graphene/polyacrylonitrile composite solution, through wet spinning, forms the Graphene/polypropylene of a diameter of 100 μm Nitrile composite fibre；Wet spinning technology is that spinning solution enters coagulating bath, rinsing bowl and stretch bath through spinning head, After stretching 3 times, rolling machine is collected and is obtained Graphene/polyacrylonitrile composite fiber, and wherein coagulating bath is temperature 5 DEG C, concentration be the dimethylformamide in water of 10wt%, rinsing bowl is the aqueous solution of temperature 50 C, draws Stretch the bath aqueous solution for temperature 90 DEG C；

Graphene/polyacrylonitrile composite fiber prepares diameter through 10 times of drawing-offs of vapours, pre-oxidation and carbonization treatment Being the flexible carbon fiber of 20 μm, Pre oxidation is 200 DEG C, and the time is 30 minutes, and atmosphere is air atmosphere, The tension force of 0.2MPa is applied by 2 roller draft fibers；Carburizing temperature is 600 DEG C, and the time is 1 minute, Atmosphere is nitrogen, is applied the tension force of 0.2MPa by 2 roller draft fibers.

Test shows that the flexible carbon fiber prepared mainly is made up of Graphene and graphite microcrystal, wherein more than Graphene Axially the formed angle of orientation is less than 30 °, by Graphene for the in-plane of the Graphene of addition 70% and carbon fiber The graphite microcrystal that induction produces is along graphenic surface oriented；The average grain size of graphite microcrystal is 5nm； The porosity of flexible carbon fiber is 4%；Flexible carbon fiber firm measured by JIS L 1096B method i.e. slide method Softness is 10mN cm, and resistivity is 100 Ω cm, and intensity is 1000MPa, flexible axial the leading of carbon fiber Hot coefficient is 0.5W/m k.

Embodiment 2

The preparation method of a kind of flexible carbon fiber, is dissolved in dimethyl sub-respectively by graphene microchip and polyacrylonitrile Sulfone, prepared concentration is the graphene microchip dispersion liquid of 5wt% and concentration is the polyacrylonitrile solution of 40wt%, poly- Acrylonitrile contains the first monomers acrylonitrile and second comonomer acrylamide, and the first monomer is relative to the mass fraction of total monomer Being 80%, second comonomer is 20% relative to the mass fraction of total monomer, and graphene microchip dispersion liquid is carried out magnetic Power dispersed with stirring processes, and the process time is 12 hours, and temperature is 40 DEG C, is subsequently adding polyacrylonitrile solution and enters Row mechanical agitation mixes, and the time is 24h, and rotating speed is 1500 revs/min, and temperature is 50 DEG C, ultrasonic deaeration 1h After, the concentration obtaining polyacrylonitrile is 39wt%, the mass fraction of graphene microchip vs polypropylene nitrile is 80% Graphene microchip/polyacrylonitrile composite solution；

Graphene microchip/polyacrylonitrile composite solution, through wet spinning, forms the graphene microchip of a diameter of 10 μm / polyacrylonitrile composite fiber；Wet spinning technology be spinning solution through spinning head enter coagulating bath, rinsing bowl and Stretch bath, after stretching 9 times, rolling machine is collected and is obtained graphene microchip/polyacrylonitrile composite fiber, wherein Coagulating bath be temperature 25 DEG C, concentration be the dimethyl sulphoxide aqueous solution of 40wt%, rinsing bowl is temperature 70 C Aqueous solution, stretch bath is the aqueous solution of temperature 98 DEG C；

Graphene microchip/polyacrylonitrile composite fiber prepares through 100 times of drawing-offs of boiling water, pre-oxidation and carbonization treatment The flexible carbon fiber of a diameter of 0.1 μm, Pre oxidation is 300 DEG C, and the time is 200 minutes, and atmosphere is empty Atmosphere is enclosed, and is applied the tension force of 50MPa by 8 roller draft fibers；Carburizing temperature is 2000 DEG C, the time Being 60 minutes, atmosphere is argon, is applied the tension force of 50MPa by 8 roller draft fibers.

Test shows that the flexible carbon fiber prepared mainly is made up of graphene microchip and graphite microcrystal, wherein more than stone The in-plane of the graphene microchip of ink alkene microplate addition 70% and the carbon fiber axially formed angle of orientation is less than 30 °, graphene microchip induction the graphite microcrystal produced is orientated along graphene microchip surface alignment；Graphite microcrystal Average grain size be 1nm；The porosity of flexible carbon fiber is 0%；By the JIS L i.e. slide of 1096B method The firm softness of the flexible carbon fiber that method measures is 5 × 10^-4MN cm, resistivity is 10^-3Ω cm, intensity is 5000MPa, the axial heat conductivity of flexible carbon fiber is 50W/m k.

Embodiment 3

The preparation method of a kind of flexible carbon fiber, is dissolved in dimethylacetamide by graphene oxide and polyacrylonitrile respectively Amine, prepared concentration is the graphene oxide dispersion of 0.8wt% and concentration is the polyacrylonitrile solution of 22wt%, Polyacrylonitrile contains the first monomers acrylonitrile and second comonomer acrylic acid methyl ester., and the first monomer is relative to the quality of total monomer Mark is 99%, and second comonomer is 1% relative to the mass fraction of total monomer, graphene oxide dispersion is carried out Mechanical agitation dispersion processes, and the process time is 1 hour, and temperature is 13 DEG C, is subsequently adding polyacrylonitrile solution Carrying out mechanical agitation mixing, the time is 5h, and rotating speed is 165 revs/min, and temperature is 18 DEG C, standing and defoaming 3h After, the concentration obtaining polyacrylonitrile is 20wt%, the mass fraction of graphene oxide vs polypropylene nitrile is 5% Graphene oxide/polyacrylonitrile composite solution；

Graphene oxide/polyacrylonitrile composite solution, through wet spinning, forms the graphene oxide of a diameter of 90 μm / polyacrylonitrile composite fiber；Wet spinning technology be spinning solution through spinning head enter coagulating bath, rinsing bowl and Stretch bath, after stretching 4 times, rolling machine is collected and is obtained graphene oxide/polyacrylonitrile composite fiber, wherein Coagulating bath be temperature 8 DEG C, concentration be the dimethylacetamide amine aqueous solution of 30wt%, rinsing bowl is temperature 54 DEG C Aqueous solution, stretch bath is the aqueous solution of temperature 96 DEG C；

Graphene oxide/polyacrylonitrile composite fiber prepares straight through 11 times of drawing-offs of boiling water, pre-oxidation and carbonization treatment Footpath is the flexible carbon fiber of 18 μm, and Pre oxidation is 215 DEG C, and the time is 40 minutes, and atmosphere is air atmosphere Enclose, applied the tension force of 0.9MPa by 3 roller draft fibers；Carburizing temperature is 1600 DEG C, and the time is 5 Minute, atmosphere is nitrogen, is applied the tension force of 0.8MPa by 3 roller draft fibers.

Test shows that the flexible carbon fiber prepared mainly is made up of redox graphene and graphite microcrystal, Qi Zhongduo In graphene oxide addition 70% redox graphene in-plane and carbon fiber axially formed by take To angle less than 30 °, redox graphene induction the graphite microcrystal produced is arranged along redox graphene surface Row orientation；The average grain size of graphite microcrystal is 3.7nm；The porosity of flexible carbon fiber is 3.8%；By JIS The firm softness of the flexible carbon fiber that L 1096B method i.e. slide method measures is 0.8mN cm, and resistivity is 6×10^-3Ω cm, intensity is 1640MPa, and the axial heat conductivity of flexible carbon fiber is 33W/m k.

Embodiment 4

The preparation method of a kind of flexible carbon fiber, is dissolved in dimethyl by redox graphene and polyacrylonitrile respectively Sulfoxide, prepared concentration be the redox graphene dispersion liquid of 1wt% and the polyacrylonitrile that concentration is 15wt% molten Liquid, polyacrylonitrile contains the first monomers acrylonitrile and second comonomer methyl methacrylate, and the first monomer is relatively total single The mass fraction of body is 90%, and second comonomer is 10% relative to the mass fraction of total monomer, by oxygen reduction fossil Ink alkene dispersion liquid carries out ultrasonic disperse and magnetic agitation dispersion processes, and the process time is 6 hours, and temperature is 20 DEG C, Being subsequently adding polyacrylonitrile solution and carry out mechanical agitation mixing, the time is 8h, and rotating speed is 280 revs/min, temperature Degree is 20 DEG C, and after vacuum defoamation 12h, the concentration obtaining polyacrylonitrile is 11wt%, redox graphene The mass fraction of vs polypropylene nitrile is the redox graphene/polyacrylonitrile composite solution of 10%；

Redox graphene/polyacrylonitrile composite solution, through wet spinning, forms the oxygen reduction of a diameter of 80 μm Functionalized graphene/polyacrylonitrile composite fiber；Wet spinning technology be spinning solution through spinning head enter coagulating bath, Rinsing bowl and stretch bath, after stretching 5 times, it is multiple that the collection of rolling machine obtains redox graphene/polyacrylonitrile Condensating fiber, wherein coagulating bath be temperature 12 DEG C, concentration be the dimethyl sulphoxide aqueous solution of 20wt%, rinsing bowl In be the aqueous solution of temperature 56 DEG C, stretch bath is the aqueous solution of temperature 97 DEG C；

Redox graphene/polyacrylonitrile composite fiber is through 20 times of drawing-offs of boiling water, pre-oxidation and carbonization treatment system Obtaining the flexible carbon fiber of a diameter of 16 μm, Pre oxidation is 250 DEG C, and the time is 50 minutes, and atmosphere is empty Atmosphere is enclosed, and is applied the tension force of 10MPa by 4 roller draft fibers；Carburizing temperature is 600 DEG C, the time Being 10 minutes, atmosphere is argon, is applied the tension force of 15MPa by 5 roller draft fibers.

Test shows that the flexible carbon fiber prepared mainly is made up of redox graphene and graphite microcrystal, Qi Zhongduo Axial with carbon fiber in the in-plane of the redox graphene lamella of redox graphene addition 70% The formed angle of orientation is less than 30 °, redox graphene induction the graphite microcrystal produced is along reduction-oxidation graphite Alkene surface alignment is orientated；The average grain size of graphite microcrystal is 4.9nm；The porosity of flexible carbon fiber is 2.2%；The firm softness of the flexible carbon fiber measured by JIS L 1096B method i.e. slide method is 0.3mN cm, electricity Resistance rate is 85 Ω cm, and intensity is 1300MPa, and the axial heat conductivity of flexible carbon fiber is 7W/m k.

Embodiment 5

The preparation method of a kind of flexible carbon fiber, is dissolved in the sulfur that concentration is 50wt% by Graphene and graphene microchip Sodium cyanate (NaOCN) aqueous solution, prepared concentration is the graphite flake dispersion liquid of 1.5wt%, Graphene and the matter of graphene microchip Amount ratio is 1:1；Polyacrylonitrile is dissolved in the sodium thiocyanate water solution that concentration is 50wt%, and prepared concentration is 25wt% Polyacrylonitrile solution, polyacrylonitrile is containing the first monomers acrylonitrile, second comonomer acrylic acid methyl ester. and Third monomer Itaconic acid, the first monomer is 97% relative to the mass fraction of total monomer, and second comonomer divides relative to the quality of total monomer Number is 2%, and Third monomer is 1% relative to the mass fraction of total monomer, graphite flake dispersion liquid is carried out magnetic force and stirs Mixing dispersion to process, the process time is 2.5 hours, and temperature is 15 DEG C, is subsequently adding polyacrylonitrile solution and carries out machine Tool stirring mixing, the time is 15h, and rotating speed is 400 revs/min, and temperature is 15 DEG C, after vacuum defoamation 8h, The concentration obtaining polyacrylonitrile is 16wt%, the graphite that mass fraction is 18% of graphite flake vs polypropylene nitrile Sheet/polyacrylonitrile composite solution；

Graphite flake/polyacrylonitrile composite solution, through wet spinning, forms the graphite flake/polypropylene of a diameter of 70 μm Nitrile composite fibre；Wet spinning technology is that spinning solution enters coagulating bath, rinsing bowl and stretch bath through spinning head, After stretching 3 times, rolling machine is collected and is obtained graphite flake/polyacrylonitrile composite fiber, and wherein coagulating bath is temperature 12 DEG C, concentration be the sodium thiocyanate water solution of 10wt%, rinsing bowl is the aqueous solution of temperature 58 DEG C, stretching Bath is the aqueous solution of temperature 95 DEG C；

Graphite flake/polyacrylonitrile composite fiber prepares diameter through 22 times of drawing-offs of vapours, pre-oxidation and carbonization treatment Being the flexible carbon fiber of 15 μm, Pre oxidation is 240 DEG C, and the time is 60 minutes, and atmosphere is air atmosphere, The tension force of 1MPa is applied by 5 roller draft fibers；Carburizing temperature is 650 DEG C, and the time is 10 minutes, Atmosphere is nitrogen, is applied the tension force of 5MPa by 5 roller draft fibers.

Test shows that the flexible carbon fiber prepared mainly is made up of graphite flake and graphite microcrystal, wherein more than graphite flake Axially the formed angle of orientation is less than 30 °, by graphite flake for the in-plane of the graphite flake of addition 70% and carbon fiber The graphite microcrystal that induction produces is orientated along graphite flake surface alignment；The average grain size of graphite microcrystal is 4.7nm；The porosity of flexible carbon fiber is 3.5%；The flexibility measured by JIS L 1096B method i.e. slide method The firm softness of carbon fiber is 0.05mN cm, and resistivity is 50 Ω cm, and intensity is 1560MPa, and flexible carbon is fine Tieing up axial heat conductivity is 5W/m k.

Embodiment 6

The preparation method of a kind of flexible carbon fiber, is dissolved in dimethylformamide by graphene microchip and graphene oxide In, prepared concentration is the graphite flake dispersion liquid of 1.8wt%, and the mass ratio of graphene microchip and graphene oxide is 1:2；Being dissolved in dimethylformamide by polyacrylonitrile, prepared concentration is the polyacrylonitrile solution of 12wt%, poly- Acrylonitrile is containing the first monomers acrylonitrile, second comonomer acrylamide and Third monomer acrylic acid dimethyl amido second Ester, the first monomer is 93% relative to the mass fraction of total monomer, and second comonomer relative to the mass fraction of total monomer is 6%, Third monomer is 1% relative to the mass fraction of total monomer, and graphite flake dispersion liquid is carried out ultrasonic disperse and machine Tool dispersed with stirring processes, and the process time is 3 hours, and temperature is 18 DEG C, is subsequently adding polyacrylonitrile solution and enters Row mechanical agitation mixes, and the time is 4h, and rotating speed is 1200 revs/min, and temperature is 20 DEG C, ultrasonic deaeration 6h After, the concentration obtaining polyacrylonitrile is 10wt%, the mass fraction of graphite flake vs polypropylene nitrile is 25% Graphite flake/polyacrylonitrile composite solution；

Graphite flake/polyacrylonitrile composite solution, through wet spinning, forms the graphite flake/polypropylene of a diameter of 60 μm Nitrile composite fibre；Wet spinning technology is that spinning solution enters coagulating bath, rinsing bowl and stretch bath through spinning head, After stretching 4 times, rolling machine is collected and is obtained graphite flake/polyacrylonitrile composite fiber, and wherein coagulating bath is temperature 15 DEG C, concentration be the aqueous solution of dimethylformamide of 12wt%, rinsing bowl is the aqueous solution of temperature 60 C, Stretch bath is the aqueous solution of temperature 94 DEG C；

Graphite flake/polyacrylonitrile composite fiber prepares diameter through 25 times of drawing-offs of vapours, pre-oxidation and carbonization treatment Being the flexible carbon fiber of 12 μm, Pre oxidation is 230 DEG C, and the time is 70 minutes, and atmosphere is air atmosphere, The tension force of 10MPa is applied by 6 roller draft fibers；Carburizing temperature is 700 DEG C, and the time is 14 minutes, Atmosphere is argon, is applied the tension force of 15MPa by 6 roller draft fibers.

Test shows that the flexible carbon fiber prepared mainly is made up of graphite flake and graphite microcrystal, wherein more than graphite flake Axially the formed angle of orientation is less than 30 °, by graphite flake for the in-plane of the graphite flake of addition 70% and carbon fiber The graphite microcrystal that induction produces is orientated along graphite flake surface alignment；The average grain size of graphite microcrystal is 4.5nm；The porosity of flexible carbon fiber is 2.1%；The flexibility measured by JIS L 1096B method i.e. slide method The firm softness of carbon fiber is 0.01mN cm, and resistivity is 18 Ω cm, and intensity is 1640MPa, and flexible carbon is fine Tieing up axial heat conductivity is 8W/m k.

Embodiment 7

The preparation method of a kind of flexible carbon fiber, is dissolved in dimethyl second by graphene oxide and redox graphene In amide, prepared concentration is the graphite flake dispersion liquid of 2wt%, graphene oxide and the matter of redox graphene Amount ratio is 2:1；Being dissolved in dimethyl acetylamide by polyacrylonitrile, prepared concentration is that the polyacrylonitrile of 30wt% is molten Liquid, polyacrylonitrile contains the first monomers acrylonitrile, second comonomer acrylamide and Third monomer sodium allylsulfonate, the One monomer is 91% relative to the mass fraction of total monomer, and second comonomer is 6% relative to the mass fraction of total monomer, Third monomer is 3% relative to the mass fraction of total monomer, graphite flake dispersion liquid is carried out ultrasonic disperse, magnetic force stirs Mixing dispersion and mechanical agitation dispersion processes, the process time is 8 hours, and temperature is 25 DEG C, is subsequently adding poly-third Alkene nitrile solution carries out mechanical agitation mixing, and the time is 20h, and rotating speed is 600 revs/min, and temperature is 25 DEG C, After standing and defoaming 7h, the concentration obtaining polyacrylonitrile is 23wt%, the quality of graphite flake vs polypropylene nitrile is divided Number is the graphite flake/polyacrylonitrile composite solution of 30%；

Graphite flake/polyacrylonitrile composite solution through dry-jet wet spinning, forms the graphite flake of a diameter of 50 μm/poly- Acrylonitrile composite fibre；Dry-jet wet spinning technique is that spinning solution enters the sky of a length of 2mm through spinning head Gas section, then sequentially enters coagulating bath, rinsing bowl and stretch bath, and after stretching 5 times, rolling machine is collected and obtained Graphite flake/polyacrylonitrile composite fiber, wherein coagulating bath be temperature 16 DEG C, concentration be the dimethyl second of 14wt% The aqueous solution of amide, is the aqueous solution of temperature 62 DEG C in rinsing bowl, and stretch bath is the aqueous solution of temperature 93 DEG C；

Graphite flake/polyacrylonitrile composite fiber prepares diameter through 26 times of drawing-offs of vapours, pre-oxidation and carbonization treatment Being the flexible carbon fiber of 10 μm, Pre oxidation is 220 DEG C, and the time is 75 minutes, and atmosphere is air atmosphere, The tension force of 20MPa is applied by 8 roller draft fibers；Carburizing temperature is 750 DEG C, and the time is 20 minutes, Atmosphere is nitrogen, is applied the tension force of 25MPa by 8 roller draft fibers.

Test shows that the flexible carbon fiber prepared mainly is made up of graphite flake and graphite microcrystal, wherein more than graphite flake Axially the formed angle of orientation is less than 30 °, by graphite flake for the in-plane of the graphite flake of addition 70% and carbon fiber The graphite microcrystal that induction produces is orientated along graphite flake surface alignment；The average grain size of graphite microcrystal is 4.4nm；The porosity of flexible carbon fiber is 1.2%；The flexibility measured by JIS L 1096B method i.e. slide method The firm softness of carbon fiber is 9 × 10^-3MN cm, resistivity is 9 Ω cm, and intensity is 2000MPa, and flexible carbon is fine Tieing up axial heat conductivity is 11W/m k.

Embodiment 8

The preparation method of a kind of flexible carbon fiber, by graphene microchip, graphene oxide and redox graphene Being dissolved in dimethyl sulfoxide, prepared concentration is the graphite flake dispersion liquid of 3.1wt%, graphene microchip, oxidation stone The mass ratio of ink alkene and redox graphene is 1:1:1；Polyacrylonitrile is dissolved in dimethyl sulfoxide, prepares Concentration is the polyacrylonitrile solution of 35wt%, and polyacrylonitrile contains the first monomers acrylonitrile, second comonomer vinyl acetate Ester and Third monomer methylpropene sodium sulfonate, the first monomer is 96% relative to the mass fraction of total monomer, and second is single Body is 2% relative to the mass fraction of total monomer, and Third monomer is 2% relative to the mass fraction of total monomer, by stone Ink sheet dispersion liquid carries out ultrasonic disperse process, and the process time is 4 hours, and temperature is 30 DEG C, is subsequently adding poly- Acrylonitrile solution carries out mechanical agitation mixing, and the time is 6h, and rotating speed is 500 revs/min, and temperature is 30 DEG C, After vacuum defoamation 5h, the concentration obtaining polyacrylonitrile is 28wt%, the quality of graphite flake vs polypropylene nitrile is divided Number is the graphite flake/polyacrylonitrile composite solution of 36%；

Graphite flake/polyacrylonitrile composite solution through dry-jet wet spinning, forms the graphite flake of a diameter of 40 μm/poly- Acrylonitrile composite fibre；Dry-jet wet spinning technique is that spinning solution enters the sky of a length of 6mm through spinning head Gas section, then sequentially enters coagulating bath, rinsing bowl and stretch bath, and after stretching 6 times, rolling machine is collected and obtained Graphite flake/polyacrylonitrile composite fiber, wherein coagulating bath be temperature 18 DEG C, concentration be that the dimethyl of 16wt% is sub- The aqueous solution of sulfone, is the aqueous solution of temperature 64 DEG C in rinsing bowl, and stretch bath is the aqueous solution of temperature 92 DEG C；

Graphite flake/polyacrylonitrile composite fiber prepares diameter through 28 times of drawing-offs of vapours, pre-oxidation and carbonization treatment Being the flexible carbon fiber of 8 μm, Pre oxidation is 210 DEG C, and the time is 80 minutes, and atmosphere is air atmosphere, The tension force of 30MPa is applied by 2 roller draft fibers；Carburizing temperature is 800 DEG C, and the time is 22 minutes, Atmosphere is nitrogen, is applied the tension force of 35MPa by 2 roller draft fibers.

Test shows that the flexible carbon fiber prepared mainly is made up of graphite flake and graphite microcrystal, wherein more than graphite flake Axially the formed angle of orientation is less than 30 °, by graphite flake for the in-plane of the graphite flake of addition 70% and carbon fiber The graphite microcrystal that induction produces is orientated along graphite flake surface alignment；The average grain size of graphite microcrystal is 4.2nm；The porosity of flexible carbon fiber is 0.62%；The flexibility measured by JIS L 1096B method i.e. slide method The firm softness of carbon fiber is 6.4 × 10^-3MN cm, resistivity is 1.2 Ω cm, and intensity is 2200MPa, flexible The axial heat conductivity of carbon fiber is 16W/m k.

Embodiment 9

The preparation method of a kind of flexible carbon fiber, by Graphene, graphene microchip, graphene oxide and oxygen reduction Functionalized graphene is dissolved in dimethylformamide, and prepared concentration is the graphite flake dispersion liquid of 2.2wt%, Graphene, stone Ink alkene microplate, graphene oxide are 1:1:1:1 with the mass ratio of redox graphene；Polyacrylonitrile is dissolved in two Methylformamide, prepared concentration is the polyacrylonitrile solution of 36wt%, polyacrylonitrile containing the first monomers acrylonitrile, Second comonomer methacrylonitrile and Third monomer metering system benzene sulfonic acid sodium salt, the first monomer is relative to the quality of total monomer Mark is 80%, and second comonomer is 17% relative to the mass fraction of total monomer, and Third monomer is relative to total monomer Mass fraction is 3%, and graphite flake dispersion liquid carries out magnetic agitation dispersion process, and the process time is 4.5 hours, Temperature is 30 DEG C, is subsequently adding polyacrylonitrile solution and carries out mechanical agitation mixing, and the time is 8h, and rotating speed is 600 Rev/min, temperature is 36 DEG C, and after standing and defoaming 9h, the concentration obtaining polyacrylonitrile is 32wt%, graphite The mass fraction of sheet vs polypropylene nitrile is the graphite flake/polyacrylonitrile composite solution of 50%；

Graphite flake/polyacrylonitrile composite solution through dry-jet wet spinning, forms the graphite flake of a diameter of 30 μm/poly- Acrylonitrile composite fibre；Dry-jet wet spinning technique is that spinning solution enters the sky of a length of 8mm through spinning head Gas section, then sequentially enters coagulating bath, rinsing bowl and stretch bath, and after stretching 7 times, rolling machine is collected and obtained Graphite flake/polyacrylonitrile composite fiber, wherein coagulating bath be temperature 20 DEG C, concentration be the dimethyl methyl of 18wt% Amide aqueous solution, is the aqueous solution of temperature 66 DEG C in rinsing bowl, and stretch bath is the aqueous solution of temperature 91 DEG C；

Graphite flake/polyacrylonitrile composite fiber prepares diameter through 30 times of drawing-offs of vapours, pre-oxidation and carbonization treatment Being the flexible carbon fiber of 6 μm, Pre oxidation is 200 DEG C, and the time is 90 minutes, and atmosphere is air atmosphere, The tension force of 40MPa is applied by 3 roller draft fibers；Carburizing temperature is 850 DEG C, and the time is 25 minutes, Atmosphere is or argon, is applied the tension force of 45MPa by 3 roller draft fibers.

Test shows that the flexible carbon fiber prepared mainly is made up of graphite flake and graphite microcrystal, wherein more than graphite flake Axially the formed angle of orientation is less than 30 °, by graphite flake for the in-plane of the graphite flake of addition 70% and carbon fiber The graphite microcrystal that induction produces is orientated along graphite flake surface alignment；The average grain size of graphite microcrystal is 3.5nm；The porosity of flexible carbon fiber is 0.11%；The flexibility measured by JIS L 1096B method i.e. slide method The firm softness of carbon fiber is 3.2 × 10^-3MN cm, resistivity is 1 Ω cm, and intensity is 2400MPa, flexible carbon The axial heat conductivity of fiber is 25W/m k.

Embodiment 10

The preparation method of a kind of flexible carbon fiber, is dissolved in dimethyl sulfoxide by Graphene and polyacrylonitrile, system respectively Concentration is the graphene dispersing solution of 4.5wt% and concentration is the polyacrylonitrile solution of 18wt%, polyacrylonitrile contains First monomers acrylonitrile, second comonomer vinylacetate and Third monomer vinylpyridine, the first monomer is the most total The mass fraction of monomer is 85%, and second comonomer is 13% relative to the mass fraction of total monomer, Third monomer phase Mass fraction to total monomer is 2%, and graphene dispersing solution carries out mechanical agitation dispersion process, processes the time Being 5 hours, temperature is 35 DEG C, is subsequently adding polyacrylonitrile solution and carries out mechanical agitation mixing, and the time is 10h, Rotating speed is 800 revs/min, and temperature is 40 DEG C, and after ultrasonic deaeration 0.5h, the concentration obtaining polyacrylonitrile is 15wt%, the mass fraction of Graphene vs polypropylene nitrile are the Graphene/polyacrylonitrile composite solution of 60%；

Graphene/polyacrylonitrile composite solution through dry-jet wet spinning, forms the Graphene of a diameter of 20 μm/poly- Acrylonitrile composite fibre；Dry-jet wet spinning technique is that spinning solution enters the sky of a length of 10mm through spinning head Gas section, then sequentially enters coagulating bath, rinsing bowl and stretch bath, and after stretching 8 times, rolling machine is collected and obtained Graphene/polyacrylonitrile composite fiber, wherein coagulating bath be temperature 21 DEG C, concentration be that the dimethyl of 22wt% is sub- Sulfone aqueous solution, is the aqueous solution of temperature 68 DEG C in rinsing bowl, and stretch bath is the aqueous solution of temperature 96 DEG C；

Graphene/polyacrylonitrile composite fiber prepares diameter through 32 times of drawing-offs of vapours, pre-oxidation and carbonization treatment Being the flexible carbon fiber of 3 μm, Pre oxidation is 205 DEG C, and the time is 95 minutes, and atmosphere is air atmosphere, The tension force of 50MPa is applied by 3 roller draft fibers；Carburizing temperature is 900 DEG C, and the time is 28 minutes, Atmosphere is nitrogen, is applied the tension force of 2MPa by 3 roller draft fibers.

Test shows that the flexible carbon fiber prepared mainly is made up of Graphene and graphite microcrystal, wherein more than Graphene Axially the formed angle of orientation is less than 30 °, by Graphene for the in-plane of the Graphene of addition 70% and carbon fiber The graphite microcrystal that induction produces is along graphenic surface oriented；The average grain size of graphite microcrystal is 3.8nm；The porosity of flexible carbon fiber is 1.5%；The flexibility measured by JIS L 1096B method i.e. slide method The firm softness of carbon fiber is 1.2 × 10^-3MN cm, resistivity is 0.06 Ω cm, and intensity is 2500MPa, flexible The axial heat conductivity of carbon fiber is 3.6W/m k.

Embodiment 11

The preparation method of a kind of flexible carbon fiber, is dissolved in dimethyl acetylamide by Graphene and polyacrylonitrile respectively, Prepared concentration is the graphene dispersing solution of 2.5wt% and concentration is the polyacrylonitrile solution of 24wt%, polyacrylonitrile Containing the first monomers acrylonitrile, second comonomer vinylacetate and Third monomer dimethylaminoethyl acrylate methyl base amido second Ester, the first monomer is 90% relative to the mass fraction of total monomer, and second comonomer relative to the mass fraction of total monomer is 7%, Third monomer is 3% relative to the mass fraction of total monomer, and graphene dispersing solution is carried out ultrasonic disperse process, The process time is 5.5 hours, and temperature is 40 DEG C, is subsequently adding polyacrylonitrile solution and carries out mechanical agitation mixing, Time is 12h, and rotating speed is 1000 revs/min, and temperature is 45 DEG C, after ultrasonic deaeration 11h, obtains polypropylene Graphene/polyacrylonitrile that the concentration of nitrile is 19wt%, the mass fraction of Graphene vs polypropylene nitrile is 70% Composite solution；

Graphene/polyacrylonitrile composite solution through dry-jet wet spinning, forms the Graphene of a diameter of 10 μm/poly- Acrylonitrile composite fibre；Dry-jet wet spinning technique is that spinning solution enters the sky of a length of 12mm through spinning head Gas section, then sequentially enters coagulating bath, rinsing bowl and stretch bath, and after stretching 9 times, rolling machine is collected and obtained Graphene/polyacrylonitrile composite fiber, wherein coagulating bath be temperature 23 DEG C, concentration be the dimethyl second of 24wt% Amide aqueous solution, is the aqueous solution of temperature 70 C in rinsing bowl, and stretch bath is the aqueous solution of temperature 95 DEG C；

Graphene/polyacrylonitrile composite fiber prepares a diameter of through 35 times of drawing-offs of boiling water, pre-oxidation and carbonization treatment The flexible carbon fiber of 1 μm, Pre oxidation is 220 DEG C, and the time is 100 minutes, and atmosphere is air atmosphere, The tension force of 4MPa is applied by 4 roller draft fibers；Carburizing temperature is 950 DEG C, and the time is 30 minutes, Atmosphere is nitrogen, is applied the tension force of 6MPa by 4 roller draft fibers.

Test shows that the flexible carbon fiber prepared mainly is made up of Graphene and graphite microcrystal, wherein more than Graphene Axially the formed angle of orientation is less than 30 °, by Graphene for the in-plane of the Graphene of addition 70% and carbon fiber The graphite microcrystal that induction produces is along graphenic surface oriented；The average grain size of graphite microcrystal is 3.3nm；The porosity of flexible carbon fiber is 3%；The flexible carbon measured by JIS L 1096B method i.e. slide method The firm softness of fiber is 8 × 10^-4MN cm, resistivity is 0.05 Ω cm, and intensity is 2650MPa, flexible carbon The axial heat conductivity of fiber is 10W/m k.

Embodiment 12

The preparation method of a kind of flexible carbon fiber, is dissolved in dimethylformamide by Graphene, carries out at ultrasonic disperse Reason, the process time is 0.5 hour, and temperature is 10 DEG C, obtains the graphene dispersing solution that concentration is 0.5wt%, Then the first monomers acrylonitrile, initiator azodiisobutyronitrile and graphene dispersing solution are separately added into dimethyl methyl In amide, the first monomer is 100% relative to the mass fraction of total monomer, and mix homogeneously makes polymeric solution, poly- Closing the concentration of monomer in solution is 10wt%, and the mass fraction of initiator relative monomer is 0.3%, Graphene phase Mass fraction to monomer is 0.1%, the most at ambient pressure, is polymerized 1h at 50 DEG C, after vacuum defoamation 0.5h, Obtain Graphene/polyacrylonitrile composite solution that monomer conversion is 70%；

Graphene/polyacrylonitrile composite solution, through wet spinning, forms the Graphene/polyacrylonitrile of a diameter of 5 μm Composite fibre；Wet spinning technology is that spinning solution enters coagulating bath, rinsing bowl and stretch bath through spinning head, draws After stretching 3 times, rolling machine is collected and is obtained Graphene/polyacrylonitrile composite fiber, wherein coagulating bath be temperature 5 DEG C, Concentration is the dimethylformamide in water of 26wt%, is the aqueous solution of temperature 60 C in rinsing bowl, stretch bath Aqueous solution for temperature 96 DEG C；

Graphene/polyacrylonitrile composite fiber prepares a diameter of through 36 times of drawing-offs of boiling water, pre-oxidation and carbonization treatment The flexible carbon fiber of 0.4 μm, Pre oxidation is 250 DEG C, and the time is 110 minutes, and atmosphere is air atmosphere, The tension force of 8MPa is applied by 5 roller draft fibers；Carburizing temperature is 1000 DEG C, and the time is 32 minutes, Atmosphere is argon, is applied the tension force of 8MPa by 5 roller draft fibers.

Test shows that the flexible carbon fiber prepared mainly is made up of Graphene and graphite microcrystal, wherein more than Graphene Axially the formed angle of orientation is less than 30 °, by Graphene for the in-plane of the Graphene of addition 70% and carbon fiber The graphite microcrystal that induction produces is along graphenic surface oriented；The average grain size of graphite microcrystal is 4nm； The porosity of flexible carbon fiber is 2.4%；The flexible carbon fiber measured by JIS L 1096B method i.e. slide method Just softness is 9.8mN cm, and resistivity is 0.04 Ω cm, and intensity is 2800MPa, and flexible carbon fiber is axial Heat conductivity is 2W/m k.

Embodiment 13

The preparation method of a kind of flexible carbon fiber, is dissolved in the sodium rhodanate that concentration is 51.3wt% by graphene microchip Aqueous solution, carries out magnetic agitation dispersion process, and the process time is 2 hours, and temperature is 15 DEG C, obtains concentration For the graphene microchip dispersion liquid of 2.8wt%, then by the first monomers acrylonitrile and second comonomer acrylamide, Initiator 2,2'-Azobis(2,4-dimethylvaleronitrile) and graphene microchip dispersion liquid are separately added into the sodium rhodanate that concentration is 51.3wt% In aqueous solution, the first monomer is 80% relative to the mass fraction of total monomer, and second comonomer is relative to the quality of total monomer Mark is 20%, and mix homogeneously makes polymeric solution, and in polymeric solution, the concentration of monomer is 12wt%, causes The mass fraction of agent relative monomer is 0.4%, and the mass fraction of graphene microchip relative monomer is 5%, finally exists Under normal pressure, it is polymerized 24h at 70 DEG C, after ultrasonic deaeration 12h, obtains the Graphene that monomer conversion is 99% micro- Sheet/polyacrylonitrile composite solution；

Graphene microchip/polyacrylonitrile composite solution through wet spinning, formed the graphene microchip of a diameter of 1 μm/ Polyacrylonitrile composite fiber；Wet spinning technology is that spinning solution enters coagulating bath, rinsing bowl through spinning head and draws Stretching bath, after stretching 4 times, rolling machine is collected and is obtained graphene microchip/polyacrylonitrile composite fiber, Qi Zhongning Gu bath is 28wt% sodium thiocyanate water solution for temperature 6 DEG C, concentration, rinsing bowl is the aqueous solution of temperature 61 DEG C, Stretch bath is the aqueous solution of temperature 97 DEG C；

Graphene microchip/polyacrylonitrile composite fiber prepares straight through 38 times of drawing-offs of boiling water, pre-oxidation and carbonization treatment Footpath is the flexible carbon fiber of 0.1 μm, and Pre oxidation is 300 DEG C, and the time is 120 minutes, and atmosphere is air Atmosphere, applies the tension force of 10MPa by 6 roller draft fibers；Carburizing temperature is 1200 DEG C, and the time is 35 minutes, atmosphere was nitrogen, was applied the tension force of 10MPa by 6 roller draft fibers.

Test shows that the flexible carbon fiber prepared mainly is made up of graphene microchip and graphite microcrystal, wherein more than stone The in-plane of the graphene microchip of ink alkene microplate addition 70% and the carbon fiber axially formed angle of orientation is less than 30 °, graphene microchip induction the graphite microcrystal produced is orientated along graphene microchip surface alignment；Graphite microcrystal Average grain size be 2.9nm；The porosity of flexible carbon fiber is 2.2%；By JIS L 1096B method i.e. The firm softness of the flexible carbon fiber that slide method measures is 0.76mN cm, and resistivity is 0.02 Ω cm, and intensity is 1280MPa, the axial heat conductivity of flexible carbon fiber is 4W/m k.

Embodiment 14

The preparation method of a kind of flexible carbon fiber, is dissolved in the sodium rhodanate water that concentration is 57wt% by graphene microchip Solution, carries out mechanical agitation dispersion process, and the process time is 3 hours, and temperature is 20 DEG C, obtains concentration and is The graphene microchip dispersion liquid of 1.5wt%, then by the first monomers acrylonitrile and second comonomer acrylic acid methyl ester., draw Send out agent dibenzoyl peroxide and graphene microchip dispersion liquid is separately added into the sodium rhodanate water that concentration is 57wt% In solution, the first monomer is 99% relative to the mass fraction of total monomer, and second comonomer divides relative to the quality of total monomer Number is 1%, and mix homogeneously makes polymeric solution, and in polymeric solution, the concentration of monomer is 15wt%, initiator phase Mass fraction to monomer is 0.5%, and the mass fraction of graphene microchip relative monomer is 10%, finally often Pressure, is polymerized 2h at 55 DEG C, after standing and defoaming 11h, obtain graphene microchip that monomer conversion is 72%/ Polyacrylonitrile composite solution；

Graphene microchip/polyacrylonitrile composite solution, through wet spinning, forms the graphene microchip of a diameter of 60 μm / polyacrylonitrile composite fiber；Wet spinning technology be spinning solution through spinning head enter coagulating bath, rinsing bowl and Stretch bath, after stretching 4.5 times, rolling machine is collected and is obtained graphene microchip/polyacrylonitrile composite fiber, wherein Coagulating bath be temperature 8 DEG C, concentration be the sodium thiocyanate water solution of 32wt%, rinsing bowl is the water of temperature 62 DEG C Solution, stretch bath is the aqueous solution of temperature 98 DEG C；

Graphene microchip/polyacrylonitrile composite fiber prepares straight through 40 times of drawing-offs of boiling water, pre-oxidation and carbonization treatment Footpath is the flexible carbon fiber of 3.5 μm, and Pre oxidation is 200 DEG C, and the time is 130 minutes, and atmosphere is air Atmosphere, applies the tension force of 15MPa by 7 roller draft fibers；Carburizing temperature is 1300 DEG C, and the time is 36 minutes, atmosphere was nitrogen, was applied the tension force of 15MPa by 7 roller draft fibers.

Test shows that the flexible carbon fiber prepared mainly is made up of graphene microchip and graphite microcrystal, wherein more than stone The in-plane of the graphene microchip of ink alkene microplate addition 70% and the carbon fiber axially formed angle of orientation is less than 30 °, graphene microchip induction the graphite microcrystal produced is orientated along graphene microchip surface alignment；Graphite microcrystal Average grain size be 2.5nm；The porosity of flexible carbon fiber is 2%；By the JIS L i.e. slide of 1096B method The firm softness of the flexible carbon fiber that method measures is 0.28mN cm, and resistivity is 9.8 × 10^-3Ω cm, intensity is 2450MPa, the axial heat conductivity of flexible carbon fiber is 19W/m k.

Embodiment 15

The preparation method of a kind of flexible carbon fiber, is dissolved in dimethylformamide by graphene microchip, carries out ultrasonic point Dissipating and magnetic agitation dispersion processes, the process time is 5 hours, and temperature is 25 DEG C, and obtaining concentration is 2wt%'s Graphene microchip dispersion liquid, then by the first monomers acrylonitrile and second comonomer methyl methacrylate, initiator Dilauroyl peroxide and graphene microchip dispersion liquid are separately added in dimethylformamide, and the first monomer is relatively total single The mass fraction of body is 88%, and second comonomer is 12% relative to the mass fraction of total monomer, and mix homogeneously is made Polymeric solution, in polymeric solution, the concentration of monomer is 20wt%, and the mass fraction of initiator relative monomer is 0.6%, the mass fraction of graphene microchip relative monomer is 15%, the most at ambient pressure, at 56 DEG C of polyase 13 h, After vacuum defoamation 10h, obtain graphene microchip/polyacrylonitrile composite solution that monomer conversion is 75%；

Graphene microchip/polyacrylonitrile composite solution, through wet spinning, forms the graphene microchip of a diameter of 70 μm / polyacrylonitrile composite fiber；Wet spinning technology be spinning solution through spinning head enter coagulating bath, rinsing bowl and Stretch bath, after stretching 5 times, rolling machine is collected and is obtained graphene microchip/polyacrylonitrile composite fiber, wherein Coagulating bath be temperature 10 DEG C, concentration be the dimethylformamide in water of 34wt%, rinsing bowl is temperature 63 DEG C Aqueous solution, stretch bath is the aqueous solution of temperature 95 DEG C；

Graphene microchip/polyacrylonitrile composite fiber prepares straight through 45 times of drawing-offs of boiling water, pre-oxidation and carbonization treatment Footpath is the flexible carbon fiber of 2.5 μm, and Pre oxidation is 210 DEG C, and the time is 140 minutes, and atmosphere is air Atmosphere, applies the tension force of 20MPa by 8 roller draft fibers；Carburizing temperature is 1400 DEG C, and the time is 38 minutes, atmosphere was argon, was applied the tension force of 20MPa by 8 roller draft fibers.

Test test shows that the flexible carbon fiber prepared mainly is made up of graphene microchip and graphite microcrystal, Qi Zhongduo In-plane and the carbon fiber axially formed angle of orientation in the graphene microchip of graphene microchip addition 70% Less than 30 °, graphene microchip induction the graphite microcrystal produced is orientated along graphene microchip surface alignment；Graphite The average grain size of crystallite is 2.3nm；The porosity of flexible carbon fiber is 1.3%；By JIS L 1096B The firm softness of the flexible carbon fiber that method i.e. slide method measures is 0.08mN cm, and resistivity is 6.1 × 10^-3Ω cm, Intensity is 1560MPa, and the axial heat conductivity of flexible carbon fiber is 22W/m k.

Embodiment 16

The preparation method of a kind of flexible carbon fiber, is dissolved in dimethyl sulfoxide by graphene microchip, carries out ultrasonic disperse Processing with mechanical agitation dispersion, the process time is 7 hours, and temperature is 30 DEG C, and obtaining concentration is 3.2wt%'s Graphene microchip dispersion liquid, then by the first monomers acrylonitrile, second comonomer methyl methacrylate, the 3rd list It is sub-that body itaconic acid, initiator di-isopropyl peroxydicarbonate and graphene microchip dispersion liquid are separately added into dimethyl In sulfone, the first monomer is 94% relative to the mass fraction of total monomer, and second comonomer is relative to the mass fraction of total monomer Being 5%, Third monomer is 1% relative to the mass fraction of total monomer, and mix homogeneously makes polymeric solution, polymerization In solution, the concentration of monomer is 32wt%, and the mass fraction of initiator relative monomer is 0.7%, graphene microchip The mass fraction of relative monomer is 20%, the most at ambient pressure, is polymerized 8h at 58 DEG C, after vacuum defoamation 9h, Obtain graphene microchip/polyacrylonitrile composite solution that monomer conversion is 78%；

Graphene microchip/polyacrylonitrile composite solution, through wet spinning, forms the graphene microchip of a diameter of 80 μm / polyacrylonitrile composite fiber；Wet spinning technology be spinning solution through spinning head enter coagulating bath, rinsing bowl and Stretch bath, after stretching 5.5 times, rolling machine is collected and is obtained graphene microchip/polyacrylonitrile composite fiber, wherein Coagulating bath be temperature 12 DEG C, concentration be the dimethyl sulphoxide aqueous solution of 36wt%, rinsing bowl is temperature 64 DEG C Aqueous solution, stretch bath is the aqueous solution of temperature 96 DEG C；

Graphene microchip/polyacrylonitrile composite fiber prepares straight through 50 times of drawing-offs of boiling water, pre-oxidation and carbonization treatment Footpath is the flexible carbon fiber of 4 μm, and Pre oxidation is 220 DEG C, and the time is 150 minutes, and atmosphere is air atmosphere Enclose, applied the tension force of 25MPa by 2 roller draft fibers；Carburizing temperature is 1500 DEG C, and the time is 40 Minute, atmosphere is nitrogen, is applied the tension force of 25MPa by 2 roller draft fibers.

Test shows that the flexible carbon fiber prepared mainly is made up of graphene microchip and graphite microcrystal, wherein more than stone The in-plane of the graphene microchip of ink alkene microplate addition 70% and the carbon fiber axially formed angle of orientation is less than 30 °, graphene microchip induction the graphite microcrystal produced is orientated along graphene microchip surface alignment；Graphite microcrystal Average grain size be 1.8nm；The porosity of flexible carbon fiber is 1%；By the JIS L i.e. slide of 1096B method The firm softness of the flexible carbon fiber that method measures is 0.03mN cm, and resistivity is 5.4 × 10^-3Ω cm, intensity is 2680MPa, the axial heat conductivity of flexible carbon fiber is 25W/m k.

Embodiment 17

The preparation method of a kind of flexible carbon fiber, is dissolved in dimethyl acetylamide by graphene microchip, carries out magnetic force and stir Mixing dispersion and mechanical agitation dispersion processes, the process time is 9 hours, and temperature is 35 DEG C, and obtaining concentration is 1wt% Graphene microchip dispersion liquid, then by the first monomers acrylonitrile, second comonomer methacrylonitrile and Third monomer DMAM, initiator azodiisobutyronitrile and graphene microchip dispersion liquid are separately added into diformazan In yl acetamide, the first monomer is 95% relative to the mass fraction of total monomer, and second comonomer is relative to the matter of total monomer Amount mark is 4%, and Third monomer is 1% relative to the mass fraction of total monomer, and mix homogeneously makes polymeric solution, In polymeric solution, the concentration of monomer is 25wt%, and the mass fraction of initiator relative monomer is 0.8%, Graphene The mass fraction of microplate relative monomer is 30%, the most at ambient pressure, is polymerized 10h, ultrasonic deaeration at 60 DEG C After 8h, obtain graphene microchip/polyacrylonitrile composite solution that monomer conversion is 80%；

Graphene microchip/polyacrylonitrile composite solution is through wet spinning, and the Graphene forming a diameter of 100 μm is micro- Sheet/polyacrylonitrile composite fiber；Wet spinning technology is that spinning solution enters coagulating bath, rinsing bowl through spinning head And stretch bath, after stretching 6 times, rolling machine is collected and is obtained graphene microchip/polyacrylonitrile composite fiber, its Middle coagulating bath be temperature 15 DEG C, concentration be the dimethylacetamide amine aqueous solution of 38wt%, rinsing bowl is temperature The aqueous solution of 65 DEG C, stretch bath is the aqueous solution of temperature 97 DEG C；

Graphene microchip/polyacrylonitrile composite fiber prepares straight through 55 times of drawing-offs of boiling water, pre-oxidation and carbonization treatment Footpath is the flexible carbon fiber of 5 μm, and Pre oxidation is 230 DEG C, and the time is 155 minutes, and atmosphere is air atmosphere Enclose, applied the tension force of 30MPa by 3 roller draft fibers；Carburizing temperature is 1700 DEG C, and the time is 45 Minute, atmosphere is nitrogen, is applied the tension force of 30MPa by 3 roller draft fibers.

Test shows that the flexible carbon fiber prepared mainly is made up of graphene microchip and graphite microcrystal, wherein more than stone The in-plane of the graphene microchip of ink alkene microplate addition 70% and the carbon fiber axially formed angle of orientation is less than 30 °, graphene microchip induction the graphite microcrystal produced is orientated along graphene microchip surface alignment；Graphite microcrystal Average grain size be 1.5nm；The porosity of flexible carbon fiber is 0.7%；By JIS L 1096B method i.e. The firm softness of the flexible carbon fiber that slide method measures is 8 × 10^-3MN cm, resistivity is 3.8 × 10^-3Ω cm, by force Degree is for 3100MPa, and the axial heat conductivity of flexible carbon fiber is 32W/m k.

Embodiment 18

The preparation method of a kind of flexible carbon fiber, is dissolved in dimethyl acetylamide by graphene oxide, carries out ultrasonic point Dissipate, magnetic agitation is disperseed and mechanical agitation dispersion processes, and the process time is 10 hours, and temperature is 40 DEG C, It is the graphene oxide dispersion of 3.6wt% to concentration, then by the first monomers acrylonitrile, second comonomer methyl Acrylonitrile and Third monomer sodium allylsulfonate, initiator 2,2'-Azobis(2,4-dimethylvaleronitrile) and graphene oxide dispersion add respectively Entering in dimethyl acetylamide, the first monomer is 87% relative to the mass fraction of total monomer, and second comonomer is relatively total single The mass fraction of body is 10%, and Third monomer is 3% relative to the mass fraction of total monomer, and mix homogeneously is made poly- Closing solution, in polymeric solution, the concentration of monomer is 28wt%, and the mass fraction of initiator relative monomer is 0.9%, The mass fraction of graphene oxide relative monomer is 40%, the most at ambient pressure, is polymerized 12h at 62 DEG C, stands After deaeration 7h, obtain graphene oxide/polyacrylonitrile composite solution that monomer conversion is 92%；

Graphene oxide/polyacrylonitrile composite solution, through wet spinning, forms the graphene oxide of a diameter of 60 μm / polyacrylonitrile composite fiber；Wet spinning technology be spinning solution through spinning head enter coagulating bath, rinsing bowl and Stretch bath, after stretching 6.2 times, rolling machine is collected and is obtained graphene oxide/polyacrylonitrile composite fiber, wherein Coagulating bath be temperature 16 DEG C, concentration be the dimethylacetamide amine aqueous solution of 35wt%, rinsing bowl is temperature 50 C Aqueous solution, stretch bath is the aqueous solution of temperature 98 DEG C；

Graphene oxide/polyacrylonitrile composite fiber prepares straight through 56 times of drawing-offs of boiling water, pre-oxidation and carbonization treatment Footpath is the flexible carbon fiber of 0.8 μm, and Pre oxidation is 240 DEG C, and the time is 160 minutes, and atmosphere is air Atmosphere, applies the tension force of 32MPa by 4 roller draft fibers；Carburizing temperature is 1800 DEG C, and the time is 50 minutes, atmosphere was argon, was applied the tension force of 32MPa by 4 roller draft fibers.

Test shows that the flexible carbon fiber prepared mainly is made up of redox graphene and graphite microcrystal, Qi Zhongduo In graphene oxide addition 70% redox graphene in-plane and carbon fiber axially formed by take To angle less than 30 °, redox graphene induction the graphite microcrystal produced is arranged along redox graphene surface Row orientation；The average grain size of graphite microcrystal is 1.3nm；The porosity of flexible carbon fiber is 0.6%；By JIS The firm softness of the flexible carbon fiber that L 1096B method i.e. slide method measures is 5 × 10^-3MN cm, resistivity is 3.5×10^-3Ω cm, intensity is 3300MPa, and the axial heat conductivity of flexible carbon fiber is 35W/m k.

Embodiment 19

The preparation method of a kind of flexible carbon fiber, is dissolved in the sodium rhodanate water that concentration is 52wt% by graphene oxide Solution, carries out ultrasonic disperse process, and the process time is 12 hours, and temperature is 12 DEG C, and obtaining concentration is 3.8wt% Graphene oxide dispersion, then by the first monomers acrylonitrile, second comonomer acrylic acid methyl ester. and Third monomer Methylpropene sodium sulfonate, initiator dibenzoyl peroxide and graphene oxide dispersion are separately added into 52wt% Sodium thiocyanate water solution in, the first monomer is 92% relative to the mass fraction of total monomer, and second comonomer is the most total The mass fraction of monomer is 7%, and Third monomer is 1% relative to the mass fraction of total monomer, and mix homogeneously is made Polymeric solution, in polymeric solution, the concentration of monomer is 30wt%, and the mass fraction of initiator relative monomer is 1%, The mass fraction of graphene oxide relative monomer is 50%, the most at ambient pressure, is polymerized 15h at 65 DEG C, ultrasonic After deaeration 6h, obtain graphene oxide/polyacrylonitrile composite solution that monomer conversion is 85%；

Graphene oxide/polyacrylonitrile composite solution, through dry-jet wet spinning, forms the oxidation stone of a diameter of 70 μm Ink alkene/polyacrylonitrile composite fiber；Dry-jet wet spinning technique is that spinning solution enters a length of through spinning head The air section of 15mm, then sequentially enters coagulating bath, rinsing bowl and stretch bath, after stretching 6.5 times, through receiving Volume machine is collected and is obtained graphene oxide/polyacrylonitrile composite fiber, and wherein coagulating bath is that temperature 18 DEG C, concentration are The sodium thiocyanate water solution of 25wt%, is the aqueous solution of temperature 55 DEG C in rinsing bowl, and stretch bath is temperature 95 DEG C Aqueous solution；

Graphene oxide/polyacrylonitrile composite fiber prepares through 58 times of drawing-offs of vapours, pre-oxidation and carbonization treatment The flexible carbon fiber of a diameter of 2 μm, Pre oxidation is 250 DEG C, and the time is 168 minutes, and atmosphere is air Atmosphere, applies the tension force of 35MPa by 5 roller draft fibers；Carburizing temperature is 1900 DEG C, and the time is 55 minutes, atmosphere was argon, was applied the tension force of 35MPa by 5 roller draft fibers.

Test shows that the flexible carbon fiber prepared mainly is made up of redox graphene and graphite microcrystal, Qi Zhongduo In graphene oxide addition 70% redox graphene in-plane and carbon fiber axially formed by take To angle less than 30 °, redox graphene induction the graphite microcrystal produced is arranged along redox graphene surface Row orientation；The average grain size of graphite microcrystal is 1.2nm；The porosity of flexible carbon fiber is 0.4%；By JIS The firm softness of the flexible carbon fiber that L 1096B method i.e. slide method measures is 3 × 10^-3MN cm, resistivity is 2.6×10^-3Ω cm, intensity is 3600MPa, and the axial heat conductivity of flexible carbon fiber is 42W/m k.

Embodiment 20

The preparation method of a kind of flexible carbon fiber, is dissolved in dimethylformamide by graphene oxide, carries out magnetic force and stir Mixing dispersion to process, the process time is 8 hours, and temperature is 27 DEG C, obtains the graphite oxide that concentration is 4.0wt% Alkene dispersion liquid, then by the first monomers acrylonitrile, second comonomer acrylamide and Third monomer metering system benzene sulphur Acid sodium, initiator dilauroyl peroxide and graphene oxide dispersion are separately added in dimethylformamide, and first Monomer is 80% relative to the mass fraction of total monomer, and second comonomer is 17% relative to the mass fraction of total monomer, Third monomer is 3% relative to the mass fraction of total monomer, and mix homogeneously makes polymeric solution, single in polymeric solution The concentration of body is 35wt%, and the mass fraction of initiator relative monomer is 1.1%, graphene oxide relative monomer Mass fraction be 60%, the most at ambient pressure, 66 DEG C be polymerized 18h, after standing and defoaming 5h, obtain list Transformation rate is the graphene oxide/polyacrylonitrile composite solution of 88%；

Graphene oxide/polyacrylonitrile composite solution, through dry-jet wet spinning, forms the oxidation stone of a diameter of 80 μm Ink alkene/polyacrylonitrile composite fiber；Dry-jet wet spinning technique is that spinning solution enters a length of through spinning head The air section of 16mm, then sequentially enters coagulating bath, rinsing bowl and stretch bath, after stretching 7 times, rolling Machine is collected and is obtained graphene oxide/polyacrylonitrile composite fiber, and wherein coagulating bath is that temperature 20 DEG C, concentration are The dimethylformamide in water of 15wt%, is the aqueous solution of temperature 60 C in rinsing bowl, and stretch bath is temperature The aqueous solution of 96 DEG C；

Graphene oxide/polyacrylonitrile composite fiber prepares through 60 times of drawing-offs of vapours, pre-oxidation and carbonization treatment The flexible carbon fiber of a diameter of 0.7 μm, Pre oxidation is 260 DEG C, and the time is 170 minutes, and atmosphere is empty Atmosphere is enclosed, and is applied the tension force of 36MPa by 6 roller draft fibers；Carburizing temperature is 800 DEG C, the time Being 50 minutes, atmosphere is nitrogen, is applied the tension force of 36MPa by 6 roller draft fibers.

Test shows that the flexible carbon fiber prepared mainly is made up of redox graphene and graphite microcrystal, Qi Zhongduo In graphene oxide addition 70% redox graphene in-plane and carbon fiber axially formed by take To angle less than 30 °, redox graphene induction the graphite microcrystal produced is arranged along redox graphene surface Row orientation；The average grain size of graphite microcrystal is 3.7nm；The porosity of flexible carbon fiber is 0.3%；By JIS The firm softness of the flexible carbon fiber that L 1096B method i.e. slide method measures is 10^-3MN cm, resistivity is 0.2 Ω cm, intensity is 4000MPa, and the axial heat conductivity of flexible carbon fiber is 24W/m k.

Embodiment 21

The preparation method of a kind of flexible carbon fiber, is dissolved in dimethyl sulfoxide by redox graphene, carries out machinery Dispersed with stirring processes, and the process time is 8 hours, and temperature is 32 DEG C, obtains the oxygen reduction that concentration is 4.1wt% Functionalized graphene dispersion liquid, then by the first monomers acrylonitrile, second comonomer methacrylonitrile and Third monomer ethylene Yl pyridines, initiator di-isopropyl peroxydicarbonate and redox graphene dispersion liquid are separately added into dimethyl In sulfoxide, the first monomer is 84% relative to the mass fraction of total monomer, and second comonomer divides relative to the quality of total monomer Number is 13%, and Third monomer is 3% relative to the mass fraction of total monomer, and mix homogeneously makes polymeric solution, poly- Closing the concentration of monomer in solution is 40wt%, and the mass fraction of initiator relative monomer is 1.2%, reduction-oxidation The mass fraction of Graphene relative monomer is 70%, the most at ambient pressure, is polymerized 20h, vacuum defoamation at 68 DEG C After 4h, obtain redox graphene/polyacrylonitrile composite solution that monomer conversion is 90%；

Redox graphene/polyacrylonitrile composite solution, through dry-jet wet spinning, forms going back of a diameter of 90 μm Former graphene oxide/polyacrylonitrile composite fiber；Dry-jet wet spinning technique is that spinning solution enters through spinning head The air section of a length of 18mm, then sequentially enters coagulating bath, rinsing bowl and stretch bath, after stretching 8 times, Rolling machine is collected and is obtained redox graphene/polyacrylonitrile composite fiber, wherein coagulating bath be temperature 22 DEG C, Concentration is the dimethyl sulphoxide aqueous solution of 23wt%, is the aqueous solution of temperature 62 DEG C in rinsing bowl, and stretch bath is The aqueous solution that temperature is 97 DEG C；

Redox graphene/polyacrylonitrile composite fiber is through 70 times of drawing-offs of vapours, pre-oxidation and carbonization treatment Preparing the flexible carbon fiber of a diameter of 0.9 μm, Pre oxidation is 280 DEG C, and the time is 180 minutes, atmosphere For air atmosphere, applied the tension force of 40MPa by 7 roller draft fibers；Carburizing temperature is 1000 DEG C, Time is 52 minutes, and atmosphere is nitrogen, is applied the tension force of 40MPa by 7 roller draft fibers.

Test shows that the flexible carbon fiber prepared mainly is made up of redox graphene and graphite microcrystal, Qi Zhongduo In graphene oxide addition 70% redox graphene in-plane and carbon fiber axially formed by take To angle less than 30 °, redox graphene induction the graphite microcrystal produced is arranged along redox graphene surface Row orientation；The average grain size of graphite microcrystal is 2.7nm；The porosity of flexible carbon fiber is 0.2%；By JIS The firm softness of the flexible carbon fiber that L 1096B method i.e. slide method measures is 7.8 × 10^-4MN cm, resistivity is 0.02 Ω cm, intensity is 2700MPa, and the axial heat conductivity of flexible carbon fiber is 18W/m k.

Embodiment 22

The preparation method of a kind of flexible carbon fiber, is dissolved in dimethylacetamide by Graphene and redox graphene Amine, carries out ultrasonic disperse process, and the process time is 5 hours, and temperature is 20 DEG C, and obtaining concentration is 5wt%'s The mass ratio of graphite flake dispersion liquid, Graphene and redox graphene is 3:1；Then by the first monomer propylene Nitrile, second comonomer acrylamide and Third monomer DMAM, initiator azodiisobutyronitrile Being separately added in dimethyl acetylamide with graphite flake dispersion liquid, the first monomer relative to the mass fraction of total monomer is 90%, second comonomer is 7% relative to the mass fraction of total monomer, and Third monomer is relative to the mass fraction of total monomer Being 3%, mix homogeneously makes polymeric solution, and in polymeric solution, the concentration of monomer is 39wt%, and initiator is relative The mass fraction of monomer is 1.5%, and the mass fraction of graphite flake relative monomer is 80%, the most at ambient pressure, It is polymerized 24h at 70 DEG C, after ultrasonic deaeration 3h, obtains graphite flake/polyacrylonitrile that monomer conversion is 99% multiple Close solution；

Graphite flake/polyacrylonitrile composite solution through dry-jet wet spinning, formed the graphite flake of a diameter of 100 μm/ Polyacrylonitrile composite fiber；Dry-jet wet spinning technique is that spinning solution enters a length of 20mm through spinning head Air section, then sequentially enters coagulating bath, rinsing bowl and stretch bath, and after stretching 9 times, rolling machine is collected To graphite flake/polyacrylonitrile composite fiber, wherein coagulating bath be temperature 25 DEG C, concentration be the dimethyl of 33wt% Acetamide aqueous solution, is the aqueous solution of temperature 70 C in rinsing bowl, and stretch bath is the aqueous solution of temperature 98 DEG C；

Graphite flake/polyacrylonitrile composite fiber prepares diameter through 80 times of drawing-offs of vapours, pre-oxidation and carbonization treatment Being the flexible carbon fiber of 1 μm, Pre oxidation is 300 DEG C, and the time is 190 minutes, and atmosphere is air atmosphere Enclose, applied the tension force of 50MPa by 8 roller draft fibers；Carburizing temperature is 1200 DEG C, and the time is 60 Minute, atmosphere is argon, is applied the tension force of 50MPa by 8 roller draft fibers.

Test shows that the flexible carbon fiber prepared mainly is made up of graphite flake and graphite microcrystal, wherein more than oxidation stone Axially the formed angle of orientation is less than 30 °, by stone for the in-plane of the graphite flake of ink alkene addition 70% and carbon fiber The graphite microcrystal that ink sheet induction produces is orientated along graphite flake surface alignment；The average grain size of graphite microcrystal is 1.4nm；The porosity of flexible carbon fiber is 0；The flexible carbon measured by JIS L 1096B method i.e. slide method is fine The firm softness of dimension is 10^-4MN cm, resistivity is 1.2 × 10^-3Ω cm, intensity is 4500MPa, and flexible carbon is fine Tieing up axial heat conductivity is 34W/m k.

Claims

1. a preparation method for flexible carbon fiber, is characterized in that, comprises the following steps:

Drafting multiple in described super-high power drawing-off is 10～100 times, and described Pre oxidation is 200～300 DEG C, the time is 30～200 minutes, and applying tension force is 0.2～50MPa；Described carburizing temperature is 600～2000 DEG C, the time is 1～60 minute, and applying tension force is 0.2～50MPa.

Preparation method the most according to claim 1, it is characterised in that described graphite flake is Graphene, graphite More than one in alkene microplate, graphene oxide or redox graphene；Described pre-oxidation atmosphere is empty Atmosphere is enclosed, and the mode that described pre-oxidation applies tension force is by 2～8 roller draft fibers；Described carbonization Atmosphere is inert atmosphere, and described inert atmosphere is nitrogen or argon；Described carbonization applies the mode of tension force By 2～8 roller draft fibers.

Preparation method the most according to claim 1, it is characterised in that described blending method refers to polyacrylonitrile Solution is mixed by mechanical agitation with the graphite flake dispersion liquid containing same solvent, then solution is carried out deaeration Process and obtain graphite flake/polyacrylonitrile composite solution；

Described polyacrylonitrile includes at least the first monomer；Or further, also containing second comonomer, or the Two monomers and Third monomer；

Described second comonomer is acrylamide, acrylic acid methyl ester., methyl methacrylate, methacrylonitrile Or vinylacetate, second comonomer is 1～20% relative to the mass fraction of total monomer；

Described Third monomer is itaconic acid, sodium allylsulfonate, methylpropene sodium sulfonate, metering system benzene sulphur Acid sodium, vinylpyridine or dimethylaminoethyl acrylate methyl base aminoethyl, Third monomer is relative to the matter of total monomer Amount mark is 1～3%；

Described solvent is that dimethylformamide, dimethyl sulfoxide, dimethyl acetylamide or sodium rhodanate are water-soluble Liquid；The concentration of described sodium thiocyanate water solution is 50～60wt%；

Described graphite flake dispersion liquid needs before using to divide through ultrasonic disperse, magnetic agitation dispersion or mechanical agitation Dissipate process in more than one, the process time is 0.5～12 hour, and temperature is 10～40 DEG C；

In described graphite flake/polyacrylonitrile composite solution, the concentration of polyacrylonitrile is 9～39wt%, graphite flake The mass fraction of vs polypropylene nitrile is 0.1～80%.

Preparation method the most according to claim 1, it is characterised in that described situ aggregation method refer to by monomer, Initiator and graphite flake dispersion liquid be separately added into graphite flake dispersion liquid contained by solvent phase with solvent in, mixed Close and uniformly make polymeric solution；Under normal pressure, being polymerized 1～24h at 50～70 DEG C, deaeration obtains stone after processing Ink sheet/polyacrylonitrile composite solution；

Described monomer includes at least the first monomer；Or further, possibly together with second comonomer, or second Monomer and Third monomer；

Described initiator is azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, peroxidating Lauroyl or di-isopropyl peroxydicarbonate；

In described polymeric solution, the concentration of monomer is 10～40wt%, and the quality of initiator relative monomer is divided Number is 0.3-1.5%；The mass fraction of graphite flake relative monomer is 0.1～80%；

Preparation method the most according to claim 1, it is characterised in that the method for described solvent spinning is wet method Spinning or dry-jet wet spinning；A diameter of 1～100 μm of described graphite flake/polyacrylonitrile composite fiber.

Preparation method the most according to claim 5, it is characterised in that described wet spinning technology is that spinning is former Liquid enters coagulating bath through spinning head, then sequentially enters rinsing bowl and stretch bath, and rolling machine is collected and obtained Graphite flake/polyacrylonitrile composite fiber；Described dry-jet wet spinning technique is that spinning solution enters through spinning head Air section, then sequentially enters coagulating bath, rinsing bowl and stretch bath, and rolling machine is collected and obtained graphite flake / polyacrylonitrile composite fiber；Described air section a length of 2～20mm；

The process conditions phase of described wet spinning and coagulating bath, rinsing bowl and the stretch bath of dry-jet wet spinning With；

Solvent species selected by described coagulating bath solvent for use and graphite flake/polyacrylonitrile composite solution is identical, For dimethylformamide, dimethyl sulfoxide, dimethyl acetylamide or Hydrogen thiocyanate that concentration is 10～40wt% The aqueous solution of sodium, temperature is 5～25 DEG C；

Described rinsing bowl, solvent is water, and temperature is 50～70 DEG C；

Preparation method the most according to claim 1, it is characterised in that described super-high power drawing-off refers to vapours Super-high power drawing-off or boiling water super-high power drawing-off.

8. use the flexible carbon fiber that in claim 1～7, arbitrary preparation method prepares, it is characterized in that, this flexibility carbon Fiber is mainly made up of graphite flake and graphite microcrystal, is wherein more than the graphite flake of graphite flake addition 70% In-plane and the carbon fiber axially formed angle of orientation is less than 30 °, graphite flake induction the graphite produced is micro- Brilliant along graphite flake surface alignment orientation；The average grain size of described graphite microcrystal is 1～5nm；Flexible carbon The porosity of fiber is 0～4%.

Flexible carbon fiber the most according to claim 7, it is characterised in that described flexible carbon fiber a diameter of 0.1～20 μm, JIS L 1096B method the firm softness of the flexible carbon fiber measured is 10^-4～10mN cm； The resistivity of flexible carbon fiber is 10^-3～100 Ω cm, intensity is 1000～5000MPa, flexible carbon fiber Axial heat conductivity is 0.5～50W/m k.