CN107217334A - Carbon nano-fiber and preparation method thereof and device - Google Patents
Carbon nano-fiber and preparation method thereof and device Download PDFInfo
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- CN107217334A CN107217334A CN201710301453.1A CN201710301453A CN107217334A CN 107217334 A CN107217334 A CN 107217334A CN 201710301453 A CN201710301453 A CN 201710301453A CN 107217334 A CN107217334 A CN 107217334A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/12—Stretch-spinning methods
- D01D5/14—Stretch-spinning methods with flowing liquid or gaseous stretching media, e.g. solution-blowing
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/76—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres otherwise than in a plane, e.g. in a tubular way
Abstract
The present invention proposes carbon nano-fiber and preparation method thereof and device.The method for preparing carbon nano-fiber includes：(1) precursor solution with spinnability is provided, wherein, the precursor solution contains carbon fiber precursor and solvent；(2) driven liquid solution is stretched as fiber using air-flow, and fiber is collected with collector；(3) fiber being collected into is post-processed, to obtain the carbon nano-fiber.Preparation method proposed by the invention, substantial amounts of high performance carbon nanofiber can fast and efficiently be prepared,, can also be by controlling the diameter of carbon fiber prepared by the viscosity of precursor solution and the speed control of air-flow and this method has that equipment is simple, easy to operate, energy-saving safe advantage compared to the method for existing electrostatic spinning or melt-out spinning.
Description
Technical field
The present invention relates to Materials Science and Engineering field, specifically, the present invention relates to carbon nano-fiber and preparation method thereof
And device.
Background technology
Carbon fiber is reinforcing fiber of new generation, is fibrous carbon materials, is divided into long filament, chopped fiber, chopped strand etc..
Being mainly used for of carbon fiber is combined with the matrix such as resin, metal, ceramics, and structural material is made.Wherein, fibre reinforced epoxy
Resin composite materials, its specific strength, specific modulus overall target are highests in existing structure material.Particularly in density, just
Degree, weight, fatigue properties etc. have the field of strict demand, are requiring the high occasion of high temperature, chemical stability, carbon fiber composite
Material all has much advantage.Carbon nano-fiber is due to its nano level structure, in the presence of skin effect and quantum size effect, its
Obvious change occurs for physical and chemical performance, many novel characteristics occurs, and these special performances are cured for electronic information, biology
The numerous areas such as treatment, environmental energy, Aero-Space have far-reaching influence.
At present, its filament diameter of industrial production carbon fiber is at 5~7 microns, and the carbon fiber of nano-grade size does not have also
The method of batch industrialization production.At this stage, preparing carbon nano-fiber method has based on template, method of electrostatic spinning etc..But,
These methods all in the presence of prepare it is difficult, yield poorly, high cost shortcoming, also limit the production and application of carbon nano-fiber.
Accordingly, it would be desirable to which a kind of inexpensive method that can largely prepare carbon nano-fiber is necessary.
The content of the invention
It is contemplated that at least solving one of technical problem in correlation technique to a certain extent.
The present invention is the following discovery based on inventor and completed：
The present inventor has found in research process, gas spinning process have efficient and convenient, safely cleaning, it is applied widely,
Can magnanimity prepare etc. advantage, it is easy to realize industrialized production.Also, gas spinning is because its yield is greatly and by current-controlled
Feature, further by porous cage modle collection device, the available three-dimensional sponge structure being made up of nanofiber, then by high temperature
The three dimensional elasticity conductive structure of carbon nano-fiber composition can be obtained after carbonization.
The present invention utilizes gas spining technology, by the precursor solution containing carbon fiber precursor and solvent, by quick
Air-flow is drawn into nanofiber, then by the post processing of high temperature, ultimately forms diameter in nano level carbon fibre material.Enter one
Step uses porous cage modle collection device, in this way, a kind of elastic sponge being made up of carbon nano-fiber can be prepared very easily
Structure, available for answering in terms of energy storage, sewage disposal, flexible electronic device and filtering, catalysis, sensor, suction ripple
With.
In view of this, it is an object of the present invention to propose a kind of fast, efficient, safe, energy-conservation or prepare in large quantities
Go out the method for carbon nano-fiber.
In the first aspect of the present invention, the present invention proposes a kind of method for preparing carbon nano-fiber.
Embodiments in accordance with the present invention, methods described includes：(1) precursor solution with spinnability is provided, wherein, institute
State precursor solution and contain carbon fiber precursor and solvent；(2) precursor solution is stretched as fiber using air-flow, be used in combination
Collector collects the fiber；(3) fiber being collected into is post-processed, to obtain the carbon nano-fiber.
Inventor is it was unexpectedly observed that using the preparation method of the embodiment of the present invention, can fast and efficiently prepare substantial amounts of
High performance carbon nanofiber, and this method has equipment simple, easy compared to the method for existing electrostatic spinning or melt-out spinning
Operation, the advantage of energy-saving safe, can also by control precursor solution viscosity and air-flow speed control prepare carbon fiber
Diameter.
In addition, preparation method according to the above embodiment of the present invention, can also have technical characteristic additional as follows：
Embodiments in accordance with the present invention, the carbon fiber precursor is polyacrylonitrile；Weight based on the precursor solution
Amount, the concentration of the carbon fiber precursor is 10~20w/w%.
Embodiments in accordance with the present invention, the solvent includes at least the one of DMF and dimethyl sulfoxide (DMSO)
Kind.
Embodiments in accordance with the present invention, the precursor solution further contains polymeric additive, and the macromolecule adds
Plus agent is PVP；Based on the weight of the precursor solution, the concentration of the polymeric additive for 10~
20w/w%.
Embodiments in accordance with the present invention, the speed of the air-flow is 2~48m/s, and the collector is porous cage modle.
Embodiments in accordance with the present invention, the post processing further comprises：(3-1) carries out pre- oxygen to the fiber of collection
Change is handled；(3-2) carries out carbonization treatment again；(3-3) finally carries out graphitization processing, to obtain the carbon nano-fiber.
Embodiments in accordance with the present invention, the pre-oxidation treatment uses staged temperature-raising method；Wherein, the staged heating
Method is from 230 degrees Celsius to 280 degrees Celsius, often heats up 10 degrees Celsius and be incubated 20~40 minutes.
Embodiments in accordance with the present invention, the temperature of the carbonization treatment is 700~900 degrees Celsius, and the time is 1~3 hour；
The temperature of the graphitization processing is 1200~1600 degrees Celsius, and the time is 1~30 minute.
In the second aspect of the present invention, the present invention proposes a kind of carbon nano-fiber.
Embodiments in accordance with the present invention, the carbon nano-fiber is prepared by above-mentioned method.
Inventor is it was unexpectedly observed that the carbon nano-fiber of the embodiment of the present invention, its fibre diameter is in Nano grade, uniformity
It is good, can also be in three-dimensional sponge structure, so available for energy storage, sewage disposal, flexible electronic device and filtering, catalysis,
Application in terms of sensor, suction ripple.It will be appreciated to those of skill in the art that above for the side for preparing carbon nano-fiber
Feature and advantage described by method, are still applied to the carbon nano-fiber, will not be repeated here.
In the third aspect of the present invention, the present invention proposes a kind of device.
Embodiments in accordance with the present invention, the device includes above-mentioned carbon nano-fiber.
Inventor is it was unexpectedly observed that the part-structure of the device of the embodiment of the present invention, wherein carbon nano-fiber composition is led
Electrical property is good, elastic performance is high, the application available for energy battery, flexible electronic device.Those skilled in the art can manage
Solution, above for the feature and advantage described by carbon nano-fiber and preparation method thereof, is still applied to the device, herein not
Repeat again.
The additional aspect and advantage of the present invention will be set forth in part in the description, and will partly become from the following description
Obtain substantially, or recognized by the practice of the present invention.
Brief description of the drawings
The above-mentioned and/or additional aspect and advantage of the present invention will become from description of the accompanying drawings below to embodiment is combined
Substantially and be readily appreciated that, wherein：
Fig. 1 is the schematic flow sheet for preparing carbon nano-fiber method of one embodiment of the invention；
Fig. 2 is the S300 of the preparation method of one embodiment of the invention schematic flow sheet；
Fig. 3 is the gas spinning schematic diagram (a) of the preparation method of one embodiment of the invention and the photo (b- of each step product
d)；
Fig. 4 is the SEM figures of the carbon nano-fiber of one embodiment of the invention；
Fig. 5 is the Raman figures of the carbon nano-fiber of one embodiment of the invention；
Fig. 6 is the XRD of the carbon nano-fiber of one embodiment of the invention；
Fig. 7 is the compression performance test process figure of the carbon nano-fiber of one embodiment of the invention；
Fig. 8 is the conducting performance test figure of the carbon nano-fiber of one embodiment of the invention.
Embodiment
Embodiments of the invention, those skilled in the art are described below in detail it will be appreciated that example below is intended to be used to solve
The present invention is released, and is not construed as limitation of the present invention.Unless stated otherwise, it is not expressly recited in embodiment below specific
Technology or condition, those skilled in the art can be according to conventional technology in the art or condition or according to product description
Carry out.Agents useful for same or the unreceipted production firm person of instrument, are the conventional products that can be bought by city.
In one aspect of the invention, the present invention proposes a kind of method for preparing carbon nano-fiber.Reference picture 1~3 is right
The preparation method of the present invention is described in detail.Embodiments in accordance with the present invention, reference picture 1, this method includes：
S100：Precursor solution with spinnability is provided.
In this step there is provided precursor solution, wherein, the precursor solution contains carbon fiber precursor and solvent, should
Carbon fiber precursor can make the precursor solution have certain viscosity, so as to meet the preparation requirement of follow-up gas spinning.
Embodiments in accordance with the present invention, the specific species of the carbon fiber precursor is not particularly limited, as long as this kind of material
The carbon fiber precursor of material can make precursor solution meet the viscosity requirement of gas spinning and can be changed into after high-temperature post-treatment
Carbon fiber, those skilled in the art can be selected according to actual preparation situation.In some embodiments of the invention,
Carbon fiber precursor can be polyacrylonitrile (PAN).In this way, selection polyacrylonitrile is as carbon fiber precursor, due to its big point
There is highly polar cyano group (- CN), its special performance has irreplaceability in carbon fiber development and production, shown excellent in son
Good resistance to daylight, weatherability, acid and alkali-resistance, organic solvent resistance, and be easy to mix and bond with matrix resin, be conducive to using
Make composite and reinforcing material etc., while intensity is high, cost and density are relatively low, and resistant to elevated temperatures performance is protruded.
The specific concentration of carbon fiber precursor is not limited particularly in embodiments in accordance with the present invention, the precursor solution
System, as long as the carbon fiber precursor of concentration can make precursor solution meet the viscosity requirement of gas spinning and pass through high-temperature post-treatment
The carbon fiber being changed into afterwards meets use requirement, and those skilled in the art can be according to the use of specific technique and carbon fiber
It is required that being designed and adjusting.In some embodiments of the invention, the weight based on precursor solution, the carbon fiber precursor
Concentration can be 10~20w/w%.In this way, using the carbon fiber precursor of above-mentioned concentration range, precursor solution can be made
Viscosity is more moderate, and the mechanical property for post-processing the carbon fiber obtained through subsequent high temperature is more preferable.
The specific species of solvent in embodiments in accordance with the present invention, the precursor solution is not particularly limited, as long as
The solvent of the species can dissolve above-mentioned carbon fiber precursor and its volatility is good, and those skilled in the art can be fine according to carbon
The specific species of dimension presoma is selected.In some embodiments of the invention, the solvent may include N, N- dimethyl formyls
At least one of amine and dimethyl sulfoxide (DMSO).In this way, above-mentioned carbon fiber precursor can be completely dissolved using above-mentioned solvent, and wave
Hair property is high, can quickly be volatilized in follow-up gas spinning process, so as to promote fast and efficiently to prepare containing carbon fiber precursor
Nanofiber.
Embodiments in accordance with the present invention, precursor solution can also further contain polymeric additive, add in this way, making this
Plus agent can further adjust the viscosity of precursor solution.In some embodiments of the invention, the polymeric additive can be
PVP (PVP), in this way, the PVP can not only reduce the viscosity of precursor solution, so that in precursor solution
The concentration of carbon fiber precursor is improved, and after high-temperature post-treatment, PVP can be sintered, so as to be formed in the carbon fibers many
Pore structure.
The specific concentration of polymeric additive is not limited particularly in embodiments in accordance with the present invention, the precursor solution
System, as long as the polymeric additive of the concentration can make precursor solution meet the viscosity requirement of gas spinning and locate after high temperature
Loose structure can be formed after reason, those skilled in the art can be designed according to the use requirement of carbon fiber.In the present invention
Some embodiments in, the weight based on precursor solution, the concentration of polymeric additive can be 10~20w/w%.In this way,
Polymeric additive in above-mentioned concentration range, can be such that the surface and inside of the carbon nano-fiber finally prepared is respectively formed uniformly
Loose structure so that increasing specific surface area.
S200：Precursor solution is stretched as fiber using air-flow, and fiber is collected with collector.
In this step, after the solute (including carbon fiber precursor and macromolecule) in precursor solution is completely dissolved,
It is transferred in syringe, while syringe pump at the uniform velocity injects precursor solution, will has certain glutinous using quick air-flow
The precursor solution stretching of degree, solvent can volatilize rapidly in drawing process, obtain main by carbon fiber precursor so as to collect
The fiber of composition.
Inventor is it was unexpectedly observed that by the precursor solution containing carbon fiber precursor and solvent, pass through quick air-flow
Nanofiber can be drawn into.Porous cage modle collection device is further used, in this way, one kind can very easily be prepared by rice
The elastic sponge structure of fiber composition.Pass through follow-up high-temperature process, the carbon nano-fiber ultimately formed, available for energy storage again
Deposit, sewage disposal, flexible electronic device and filtering, catalysis, sensor, inhale application in terms of ripple.
Embodiments in accordance with the present invention, the specific speed of the air-flow of gas spinning process is not particularly limited, as long as the speed
The air-flow of degree can stretch above-mentioned precursor solution and form fiber of the diameter in Nano grade, those skilled in the art
It can be selected and be adjusted in actual preparation process.In some embodiments of the invention, the speed of air-flow can for 2~
48m/s.In this way, using said flow speed, precursor solution can be made to be evenly stretched as nanofiber.
Embodiments in accordance with the present invention, the specific species of the air-flow of gas spinning process is not also particularly limited, as long as should
The gas of species can make the solvent in the precursor solution being stretched quickly volatilize, and those skilled in the art can be according to solvent
Specific species selected.In some embodiments of the invention, air, nitrogen and argon gas may be selected extremely in the gas of air-flow
Few one kind.In this way, using the gas of mentioned kind, can quick, inexpensive, efficient ground vapour spinning go out fibre of the diameter in Nano grade
Dimension.
Embodiments in accordance with the present invention, the specific equipment of gas spinning process is not particularly limited, as long as the equipment can lead to
Cross high velocity air and precursor solution is stretched as nanofiber, those skilled in the art can enter according to actual preparation condition
Row design.In some embodiments of the invention, with reference to Fig. 3 .a, the gas spinning equipment includes syringe, elbow needle tubing, supply
Device and collector, wherein, the syringe equipped with precursor solution can evenly inject precursor solution from elbow needle tubing,
Meanwhile, feeder provides quick air-flow along the direction that precursor solution is projected, so that precursor solution is effectively drawn
A diameter of nano level fiber is extended, and precursor solution can effectively volatilize in drawing process, so as to directly be formed main
Fiber containing carbon fiber precursor.In some embodiments of the invention, with reference to Fig. 3 .a, collector can be porous cage modle.
In this way, quickly air-flow can also be such that fiber is wound in porous cage modle, and then it can very easily prepare and be made up of rice fiber
Elastic sponge structure.
S300：The fiber being collected into is post-processed, to obtain carbon nano-fiber.
In this step, the fiber gathered passes through the post processing of high temperature again, ultimately forms diameter fine in nano level carbon
Tie up material.
Embodiments in accordance with the present invention, with reference to Fig. 2, the post processing can further comprise：
S310：Pre-oxidation treatment is carried out to the fiber of collection.
In this step, the pre-oxidation treatment of low temperature is carried out to the fiber of collection first, so that the fibre that gas spinning is formed
Dimension sizing, the size and dimension of fiber will not occur big change or cave in, bond in follow-up processing at higher temperature
Problem.
Embodiments in accordance with the present invention, the specific process parameter of pre-oxidation treatment, such as temperature and time, not by special
Limitation, as long as the pre-oxidation treatment of the technological parameter can make the fiber surface of collection effectively shape, people in the art
Member can be designed according to the specific performance of the fiber of acquisition.In some embodiments of the invention, pre-oxidation treatment can be used
Staged temperature-raising method.Wherein, staged temperature-raising method is from 230 degrees Celsius to 280 degrees Celsius, often heat up 10 degrees Celsius of insulations 20
~40 minutes.In this way, carrying out pre-oxidation treatment using staged temperature-raising method, PAN can be avoided in pre-oxidation engineering because concentration is put
Thermal conductivity causes fibre structure to be destroyed, it is easier to control fiber preoxidation heat release behavior.
S320：Carbonization treatment is carried out again.
In this step, the fiber crossed to pre-oxidation treatment carries out carbonization treatment, so as to obtain carbon fibre material.
Embodiments in accordance with the present invention, such as specific process parameter of carbonization treatment, temperature and time, are not limited particularly
System, as long as carbon fiber precursor effectively can be fully converted into carbon fiber, this area by the carbonization treatment of the technological parameter
Technical staff can be adjusted according to actual vegetation.In some embodiments of the invention, the temperature of carbonization treatment can
Think 700~900 degrees Celsius, the time can be 1~3 hour.In this way, using the carbonization treatment of above-mentioned process conditions, can make pre-
Oxidation-treated fiber is fully changed into carbon fiber.
S330：Graphitization processing is finally carried out, to obtain carbon nano-fiber.
In this step, the carbon fiber after carbonization treatment is also needed to continue graphitization processing at higher temperature, so as to promote
The further raising of the conductance of the carbon nano-fiber.
Embodiments in accordance with the present invention, the specific process parameter of graphitization processing, such as temperature and time, not by special
Limitation, as long as the graphitization processing of the technological parameter improves effectively the conductance of carbon nano-fiber, this area skill
Art personnel can be selected and be adjusted according to actual vegetation.In some embodiments of the invention, graphitization processing
Temperature can be 1200~1600 degrees Celsius, and the time can be 1~30 minute.In this way, using the graphitization of above-mentioned process conditions
Processing, can obtain the carbon nano-fiber that conductance is higher, resistance is lower.
In summary, embodiments in accordance with the present invention, the present invention proposes a kind of method for preparing carbon nano-fiber, the party
Method can fast and efficiently prepare substantial amounts of high performance carbon nanofiber, and this method is compared to existing electrostatic spinning or molten
The method of meltblown silk has that equipment is simple, easy to operate, energy-saving safe advantage, can also by control precursor solution viscosity and
The diameter of carbon fiber prepared by the speed control of air-flow.
In another aspect of the present invention, the present invention proposes a kind of carbon nano-fiber.
Embodiments in accordance with the present invention, the carbon nano-fiber is prepared by above-mentioned method.
In summary, embodiments in accordance with the present invention, the present invention proposes a kind of carbon nano-fiber, and its fibre diameter is being received
Meter level is other, uniformity is good, can also be in three-dimensional sponge structure, so available for energy storage, sewage disposal, flexible electronic device with
And the application in terms of filtering, catalysis, sensor, suction ripple.It will be appreciated to those of skill in the art that above for preparing carbon
Feature and advantage described by the method for nanofiber, are still applied to the carbon nano-fiber, will not be repeated here.
In another aspect of the present invention, the present invention proposes a kind of device.Embodiments in accordance with the present invention, the device bag
Include above-mentioned carbon nano-fiber.
Embodiments in accordance with the present invention, the specific species of the device is not particularly limited, and those skilled in the art can root
It is designed according to the particular use of device.In some embodiments of the invention, the species of the device can be battery afflux liquid,
In this way, using the battery afflux liquid of the excellent carbon nano-fiber formation of above-mentioned electric conductivity, the electronics of its battery constituted is passed
Conductance is higher.
In summary, embodiments in accordance with the present invention, the present invention proposes a kind of device, and wherein carbon nano-fiber is constituted
The electric conductivity of part-structure is good, elastic performance is high, the application available for energy battery, flexible electronic device.This area skill
Art personnel are, it is understood that above for the feature and advantage described by carbon nano-fiber and preparation method thereof, be still applied to
The device, will not be repeated here.
Below with reference to specific embodiment, present invention is described, it is necessary to which explanation, these embodiments are only descriptive
, without limiting the present invention in any way.
Embodiment 1
In this embodiment, the carbon nano-fiber of three-dimensional sponge structure is prepared.Specific steps include：
First, configuration needs the precursor solution of spinning, and PAN is dissolved in DMF, and both mass ratioes are 1:6, heating stirring
6h to PAN is completely dissolved, and solution is in pale yellow transparent shape；
Then, certain solution is extracted in syringe, by topping-up pump, by precursor solution with 1ml/h speed from syringe needle
Outpour, with reference to Fig. 3 .a, air-flow (Gas) is with 25m/s speed from needle point laterally across precursor solution (Solution) is existed
Aerial to be drawn into fiber, solvent also rapid volatilization during this time forms nano level fiber, collected apart from liquid outlet
In 20cm porous cage modle collector, and the mutually sponge of winding composition three-dimensional structure；
PAN nanofibers are put into Muffle furnace, in air atmosphere with 5 DEG C/min heating rates to 230 DEG C, then with
1 DEG C/min heats up, and every 10 DEG C are a heating step and need to be incubated 30min, until being warming up to 280 DEG C, are pre-oxidized.Then
By the fibre migration of pre-oxidation into tube furnace, under inert gas atmosphere, it is warming up to 800 DEG C with 3 DEG C/min and is incubated 2h, enter
Row carbonization.Then under an inert atmosphere, 1400 DEG C of insulation 10min are warming up to 5 DEG C/min, it is good that progress graphitization obtains electric conductivity
Good carbon nano-fiber sponge.
The photo of each step product of the embodiment refer to Fig. 3 .b~d, wherein, Fig. 3 .b are the PAN Nanowires collected
Sponge is tieed up, Fig. 3 .c are PAN nanofiber sponges after pre-oxidation, and Fig. 3 .d are the carbon fiber sponge after carbonization.From figure 3, it can be seen that
The preparation method can prepare the sponge structure being made up of carbon nano-fiber in large quantities.
The scanning electron microscope (SEM) photograph of carbon nano-fiber prepared by the embodiment, with reference to Fig. 4.As can be seen from Figure 4, the carbon nano-fiber
Diameter be evenly distributed in Nano grade, and diameter.
The Raman and XRD of carbon nano-fiber prepared by the embodiment test result figure, please refer to Fig. 5 and Fig. 6 respectively.
As can be seen from Figure 5, the G peaks (G peak) and D peaks (D peak) of the material are respectively in 1587.26cm-1And 1338.89cm-1, say
The bright material finally prepared is carbon fiber.And as can be seen from Figure 6, corresponding 2 θ of characteristic peak of (002) and (100) of the material
Respectively 24.86 ° and 43.68 °, it is carbon fiber also to illustrate the material finally prepared.
The compression performance test result of carbon nano-fiber prepared by the embodiment, refer to Fig. 7.As can be seen from Figure 7, the carbon
The compressive deformation of nanofiber can reach 70%, and compression stress remove after the sponge structure can restore to the original state completely state, illustrate this
The elastic performance of nanofiber is excellent.
The conducting performance test result of carbon nano-fiber prepared by the embodiment, refer to Fig. 8.As can be seen from Figure 8, the carbon
The resistance of nanofiber is only 5.4 Ω, illustrates conducting electricity very well for the nanofiber.
Embodiment 2
In this embodiment, according to method and condition substantially the same manner as Example 1, the carbon for preparing three-dimensional sponge structure is received
Rice fiber.Difference is, in this embodiment, PAN is dissolved in into DMSO, and both mass ratioes are 1:4；Air-flow is with 48m/s speed
From needle point laterally across collection can obtain suitable between two parallel with the airflow direction piece bar apart from liquid outlet 20cm
The fiber of row；Pre-oxidation, is heated up with 1 DEG C/min, and every 10 DEG C are a heating step and need to be incubated 20min；It is warming up to 700 DEG C simultaneously
3h is incubated, is carbonized；1200 DEG C of insulation 30min are warming up to, graphitization is carried out and obtains carbon nano-fiber sea with good conductivity
It is continuous.
Embodiment 3
In this embodiment, according to method and condition substantially the same manner as Example 1, the carbon for preparing three-dimensional sponge structure is received
Rice fiber.Difference is, in this embodiment, PAN, PVP is dissolved in into DMF, three's mass ratio is 1:1:8；Air-flow is with 2m/s's
Speed is from needle point laterally across collection is in the porous cage modle collector apart from liquid outlet 20cm, and mutually winding composition
The sponge of three-dimensional structure；Pre-oxidation, is heated up with 1 DEG C/min, and every 10 DEG C are a heating step and need to be incubated 40min；It is warming up to
900 DEG C and 1h is incubated, is carbonized；1600 DEG C of insulation 1min are warming up to, graphitization is carried out and obtains porous carbon with good conductivity
Nanofiber sponge.
Summarize
Integrated embodiment 1~3 can show that the method for preparing carbon nano-fiber proposed by the invention can be fast and efficiently
Substantial amounts of high performance carbon nanofiber is prepared, and this method has compared to the method for existing electrostatic spinning or melt-out spinning
Equipment is simple, easy to operate, energy-saving safe advantage, can also be by controlling the viscosity of precursor solution and the speed control system of air-flow
The diameter of standby carbon fiber.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means to combine specific features, structure, material or the spy that the embodiment or example are described
Point is contained at least one embodiment of the present invention or example.In this manual, to the schematic representation of above-mentioned term not
Identical embodiment or example must be directed to.Moreover, specific features, structure, material or the feature of description can be with office
Combined in an appropriate manner in one or more embodiments or example.In addition, in the case of not conflicting, the skill of this area
Art personnel can be tied the not be the same as Example or the feature of example and non-be the same as Example or example described in this specification
Close and combine.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changed, replacing and modification.
Claims (10)
1. a kind of method for preparing carbon nano-fiber, it is characterised in that including：
(1) precursor solution with spinnability is provided, wherein, the precursor solution contains carbon fiber precursor and solvent；
(2) precursor solution is stretched as fiber using air-flow, and the fiber is collected with collector；
(3) fiber being collected into is post-processed, to obtain the carbon nano-fiber.
2. according to the method described in claim 1, it is characterised in that the carbon fiber precursor is polyacrylonitrile；
Based on the weight of the precursor solution, the concentration of the carbon fiber precursor is 10~20w/w%.
3. according to the method described in claim 1, it is characterised in that the solvent includes DMF and dimethyl
At least one of sulfoxide.
4. according to the method described in claim 1, it is characterised in that the precursor solution is further added containing macromolecule
Agent, the polymeric additive is PVP；
Based on the weight of the precursor solution, the concentration of the polymeric additive is 10~20w/w%.
5. according to the method described in claim 1, it is characterised in that
The speed of the air-flow is 2~48m/s,
The collector is porous cage modle.
6. according to the method described in claim 1, it is characterised in that the post processing further comprises：
(3-1) carries out pre-oxidation treatment to the fiber of collection；
(3-2) carries out carbonization treatment again；
(3-3) finally carries out graphitization processing, to obtain the carbon nano-fiber.
7. method according to claim 6, it is characterised in that the pre-oxidation treatment uses staged temperature-raising method；Wherein,
The staged temperature-raising method is from 230 degrees Celsius to 280 degrees Celsius, often heats up 10 degrees Celsius and be incubated 20~40 minutes.
8. method according to claim 6, it is characterised in that
The temperature of the carbonization treatment is 700~900 degrees Celsius, and the time is 1~3 hour；
The temperature of the graphitization processing is 1200~1600 degrees Celsius, and the time is 1~30 minute.
9. a kind of carbon nano-fiber, it is characterised in that the carbon nano-fiber is by described in any one of claim 1~8
Prepared by method.
10. a kind of device, it is characterised in that including the carbon nano-fiber described in claim 9.
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| CN109306554A (en) * | 2018-09-10 | 2019-02-05 | 天津大学 | Has abstersive elastic carbon nano-fiber and preparation method thereof |
| CN113943980A (en) * | 2021-10-13 | 2022-01-18 | 清华大学深圳国际研究生院 | Polyimide nanofiber sponge and preparation method thereof |
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| CN104562298A (en) * | 2013-12-21 | 2015-04-29 | 上海大学 | Method for preparing nano fiber |
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