CN108611706A - A kind of graphite level hole ultrafine carbon fiber of self-supporting and preparation method thereof - Google Patents
A kind of graphite level hole ultrafine carbon fiber of self-supporting and preparation method thereof Download PDFInfo
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- CN108611706A CN108611706A CN201810306671.9A CN201810306671A CN108611706A CN 108611706 A CN108611706 A CN 108611706A CN 201810306671 A CN201810306671 A CN 201810306671A CN 108611706 A CN108611706 A CN 108611706A
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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
- D01F9/24—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- D01F9/145—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues
-
- 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
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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
- D01F9/225—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 from stabilised polyacrylonitriles
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- Inorganic Fibers (AREA)
- Artificial Filaments (AREA)
Abstract
The present invention discloses a kind of graphite level hole ultrafine carbon fiber of self-supporting and preparation method thereof, this method is by the way that high molecular weight linear polymer is added into electrostatic spinning presoma and containing the catalyst of transition metal element, is prepared in situ to obtain the graphite level hole ultrafine carbon fiber of self-supporting in one step of carbonisation.Preparation method of the present invention eliminates the need for superhigh temperature and template, convenient and efficient and save cost, is extended to batch and prepares.And, the graphite level hole ultrafine carbon fiber of self-supporting prepared by the present invention has the slabbing form of self-supporting, the hierarchical pore structure that graphite structure, micropore and mesoporous coexist simultaneously makes the fiber have stronger hydrophobicity, larger specific surface area and Kong Rong, can be preferably applied for adsoption catalysis energy storage field.
Description
Technical field
The present invention relates to porous carbon fiber Material Field technologies, and it is ultra-fine to refer in particular to a kind of graphite level hole of self-supporting
Carbon fiber and preparation method thereof.
Background technology
Graphite porous carbon materials are with high-graphitized, chemical thermal stability is good, hydrophobicity is strong and electric conductivity is good
The advantages that, it is a kind of excellent sorbing material, catalytic support material and energy storage material.Graphite porous carbon materials are big at present
It is mostly thermally treated resulting under 2500-3000 DEG C of superhigh temperature, this not only needs a large amount of energy expenditure, while its form is past
It toward being pulverulence, is not easy to directly utilize, engineering usually requires post forming when applying.
Currently, the technology of preparing of porous carbon materials needs to obtain pore structure using template mostly, not only complex procedures, consume
Take the cost of a large amount of time, and template is difficult to recycle.In recent years, method of electrostatic spinning is as a kind of emerging technology, by
It gradually be used to prepare porous carbon fiber.Usual method of electrostatic spinning is under high pressure effect, by single or mixing Polymer Solution shape
At spinneret, organic solvent volatilization is made to obtain high molecular superfine fiber, and by be further carbonized or activate can be prepared it is porous
Carbon fiber.Fiber obtained by this method can self film, eliminate porous carbon materials secondary forming process in practical application.But
The porous carbon fiber that method of electrostatic spinning obtains is often amorphousness, and based on micropore pore structure, Kong Rong is smaller, limits it
Practical application.
Invention content
In view of this, in view of the deficiencies of the prior art, the present invention aims to provide a kind of stones of self-supporting
Black matter level hole ultrafine carbon fiber and preparation method thereof, can effectively solve the porous carbon fiber that existing method of electrostatic spinning obtains
The problem that degree of graphitization is low, pore structure is single and Kong Rong is smaller.
To achieve the above object, the present invention is using following technical solution：
A kind of preparation method of the graphite level hole ultrafine carbon fiber of self-supporting is high by being added into electrostatic spinning presoma
Molecular weight linear polymer and catalyst containing transition metal element, are prepared in situ to obtain the stone of self-supporting in one step of carbonisation
Black matter level hole ultrafine carbon fiber.
As a preferred embodiment, include following steps：
（1）With mass ratio for 1：0.010-0.050：0.020-0.200 respectively gathers electrostatic spinning presoma, high molecular weight linear
It closes object and the catalyst containing transition metal element is dissolved in organic solvent, stirring forms uniform solution；Wherein, electrostatic spinning
A concentration of 20-40wt.% of presoma in organic solvent；
（2）By electrostatic spinning apparatus by above-mentioned solution electrospinning at composite ultrafine fiber；Voltage is 20-30kV, receives distance and is
20-30cm, feed speed 0.5-1.5mL/h；
（3）By step（2）Gained composite ultrafine fiber is progressively heated at 180 DEG C -280 DEG C in air atmosphere and keeps 1-3 small
When；Then carbonization 1-3 hours is carried out under 700-1000 DEG C of inert atmosphere protection, then purifying obtains the graphite layer of self-supporting
Secondary aperture ultrafine carbon fiber.
As a preferred embodiment, the electrostatic spinning presoma is phenolic resin, polyacrylonitrile, polyvinyl alcohol, polyamides
One or more of imines or pitch.
As a preferred embodiment, the high molecular weight linear polymer is polyvinyl butyral, polyvinylpyrrolidine
One or more of alkanone, polyvinyl alcohol and polyacrylonitrile.
As a preferred embodiment, the catalyst containing transition metal element is ferric acetyl acetonade, nickel acetylacetonate, second
The one or more of acyl acetone cobalt, iron chloride, copper chloride, nickel chloride, cobalt chloride, the potassium ferricyanide.
As a preferred embodiment, the organic solvent is ethyl alcohol, methanol, acetone, normal propyl alcohol, N, N- dimethyl formyls
The one or more of amine, DMAC N,N' dimethyl acetamide.
As a preferred embodiment, the inert atmosphere is nitrogen or argon gas or is nitrogen and argon gas mixed atmosphere.
A kind of graphite level hole ultrafine carbon fiber of self-supporting is super using a kind of aforementioned graphite level hole of self-supporting
The preparation method of fine carbon is made, and the graphite level hole ultrafine carbon fiber of the self-supporting has graphite structure and with micropore
The level hole system constituted with mesoporous, specific surface area are more than 500m2/ g, large pore volume is in 0.500cm3/ g, hydrophobic angle are more than 135 °.
The present invention has clear advantage and advantageous effect compared with prior art, specifically, by above-mentioned technical proposal
Known to：
The graphite nanostructure and hierarchical pore structure of the present invention can be obtained by the method in one step of carbonisation original position, and
And the additive amount for changing heat treatment temperature and each mixture of electrostatic spinning presoma can regulate and control gained graphite nanostructure and
Hierarchical pore structure, preparation method eliminate the need for superhigh temperature and template, convenient and efficient and save cost, are extended to batch and make
It is standby.Also, the graphite level hole ultrafine carbon fiber of self-supporting prepared by the present invention has the slabbing form of self-supporting, simultaneously
The hierarchical pore structure that graphite structure, micropore and mesoporous coexist makes the fiber have stronger hydrophobicity, larger specific surface
Product and Kong Rong, can be preferably applied for adsoption catalysis energy storage field.
Description of the drawings
Fig. 1 is the macrograph of 1 gained fiber of embodiments of the present invention；
Fig. 2 is the scanning electron microscope (SEM) photograph of 1 gained fiber of embodiments of the present invention；
Fig. 3 is the transmission electron microscope picture of 1 gained fiber of embodiments of the present invention.
Specific implementation mode
Present invention is disclosed a kind of preparation method of the graphite level hole ultrafine carbon fiber of self-supporting, by Static Spinning
High molecular weight linear polymer and the catalyst containing transition metal element is added in silk presoma, is made in situ in one step of carbonisation
It is standby to obtain the graphite level hole ultrafine carbon fiber of self-supporting.
Specifically, include following steps：
（1）With mass ratio for 1：0.010-0.050：0.020-0.200 respectively gathers electrostatic spinning presoma, high molecular weight linear
It closes object and the catalyst containing transition metal element is dissolved in organic solvent, stirring forms uniform solution；Wherein, electrostatic spinning
A concentration of 20-40wt.% of presoma in organic solvent.The electrostatic spinning presoma is phenolic resin, polyacrylonitrile, gathers
One or more of vinyl alcohol, polyimides or pitch；The high molecular weight linear polymer is polyvinyl butyral, gathers
One or more of vinyl pyrrolidone, polyvinyl alcohol and polyacrylonitrile；The catalyst containing transition metal element
For one kind of ferric acetyl acetonade, nickel acetylacetonate, acetylacetone cobalt, iron chloride, copper chloride, nickel chloride, cobalt chloride, the potassium ferricyanide
Or it is several；The organic solvent is ethyl alcohol, methanol, acetone, normal propyl alcohol, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide
One or more.
（2）By electrostatic spinning apparatus by above-mentioned solution electrospinning at composite ultrafine fiber；Voltage is 20-30kV, receive away from
From for 20-30cm, feed speed 0.5-1.5mL/h.
（3）By step（2）Gained composite ultrafine fiber is progressively heated at 180 DEG C -280 DEG C in air atmosphere and keeps 1-
3 hours；Then carbonization 1-3 hours is carried out under 700-1000 DEG C of inert atmosphere protection, then purifying obtains the graphite of self-supporting
Matter level hole ultrafine carbon fiber.The inert atmosphere is nitrogen or argon gas or is nitrogen and argon gas mixed atmosphere.
The invention also discloses a kind of graphite level hole ultrafine carbon fiber of self-supporting, using a kind of aforementioned self-supporting
The preparation method of graphite level hole ultrafine carbon fiber is made, and the graphite level hole ultrafine carbon fiber of the self-supporting has graphite
Matter structure and the level hole system constituted with micropore and mesoporous, specific surface area are more than 500m2/ g, large pore volume is in 0.500cm3/ g is dredged
Water angle is more than 135 °.
With multiple embodiments, invention is further described in detail below：
Embodiment 1：
A kind of preparation method of the graphite level hole ultrafine carbon fiber of self-supporting is high by being added into electrostatic spinning presoma
Molecular weight linear polymer and catalyst containing transition metal element, are prepared in situ to obtain the stone of self-supporting in one step of carbonisation
Black matter level hole ultrafine carbon fiber.
Specifically, include following steps：
（1）With mass ratio for 1：0.03：0.02 respectively by electrostatic spinning presoma, high molecular weight linear polymer and containing transition gold
The catalyst for belonging to element is dissolved in organic solvent, and stirring forms uniform solution；Wherein, electrostatic spinning presoma is organic molten
A concentration of 22wt.% in agent.The electrostatic spinning presoma is phenolic resin；The high molecular weight linear polymer is poly- second
Enol butyral；The catalyst containing transition metal element is ferric acetyl acetonade；The organic solvent is ethyl alcohol.
（2）By electrostatic spinning apparatus by above-mentioned solution electrospinning at composite ultrafine fiber；Voltage is 25kV, receives distance and is
24cm, feed speed 1mL/h.
（3）By step（2）Gained composite ultrafine fiber is progressively heated at 180 DEG C in air atmosphere and is kept for 2 hours；So
Carbonization 2 hours is carried out under 900 DEG C of inert atmosphere protections afterwards, then purifying obtains the graphite level hole ultrafine carbon fiber of self-supporting
Dimension.The inert atmosphere is nitrogen.
The macroscopic form of the graphite level hole ultrafine carbon fiber of gained self-supporting is as shown in Figure 1, show self-supporting
Macroscopic form has certain flexibility.Its microscopic appearance is as shown in Fig. 2, a diameter of 930nm-1210nm, graphite structure
As shown in Figure 3.The pulp freeness is 1326m2/ g, Micropore volume 0.454cm3/ g, mesopore volume 0.252cm3/ g,
Total pore volume is 0.706cm3/ g, hydrophobic angle are 155 °.
Embodiment 2：
A kind of preparation method of the graphite level hole ultrafine carbon fiber of self-supporting is high by being added into electrostatic spinning presoma
Molecular weight linear polymer and catalyst containing transition metal element, are prepared in situ to obtain the stone of self-supporting in one step of carbonisation
Black matter level hole ultrafine carbon fiber.
Specifically, include following steps：
（1）With mass ratio for 1：0.035：0.05 respectively by electrostatic spinning presoma, high molecular weight linear polymer and containing transition
The catalyst of metallic element is dissolved in organic solvent, and stirring forms uniform solution；Wherein, electrostatic spinning presoma is organic
A concentration of 25wt.% in solvent.The electrostatic spinning presoma is phenolic resin；The high molecular weight linear polymer is poly-
Vinyl pyrrolidone；The catalyst containing transition metal element is nickel acetylacetonate；The organic solvent is methanol.
（2）By electrostatic spinning apparatus by above-mentioned solution electrospinning at composite ultrafine fiber；Voltage is 24kV, receives distance and is
23cm, feed speed 0.8mL/h.
（3）By step（2）Gained composite ultrafine fiber is progressively heated at 180 DEG C in air atmosphere and is kept for 2 hours；So
Carbonization 1.5 hours is carried out under 900 DEG C of inert atmosphere protections afterwards, then purifying obtains the ultra-fine carbon in graphite level hole of self-supporting
Fiber.The inert atmosphere is argon gas.
After tested, a diameter of 1030nm-1380nm of the graphite level hole ultrafine carbon fiber of gained self-supporting, specific surface
Product is 978m2/ g, Micropore volume 0.293cm3/ g, mesopore volume 0.286cm3/ g, total pore volume 0.579cm3/ g, it is hydrophobic
Angle is 147 °.
Embodiment 3：
A kind of preparation method of the graphite level hole ultrafine carbon fiber of self-supporting is high by being added into electrostatic spinning presoma
Molecular weight linear polymer and catalyst containing transition metal element, are prepared in situ to obtain the stone of self-supporting in one step of carbonisation
Black matter level hole ultrafine carbon fiber.
Specifically, include following steps：
（1）With mass ratio for 1：0.04：0.1 respectively by electrostatic spinning presoma, high molecular weight linear polymer and containing transition gold
The catalyst for belonging to element is dissolved in organic solvent, and stirring forms uniform solution；Wherein, electrostatic spinning presoma is organic molten
A concentration of 20wt.% in agent.The electrostatic spinning presoma is polyvinyl alcohol；The high molecular weight linear polymer is poly- second
Enol；The catalyst containing transition metal element is acetylacetone cobalt；The organic solvent is acetone.
（2）By electrostatic spinning apparatus by above-mentioned solution electrospinning at composite ultrafine fiber；Voltage is 20kV, receives distance and is
20cm, feed speed 0.5mL/h.
（3）By step（2）Gained composite ultrafine fiber is progressively heated at 190 DEG C in air atmosphere and is kept for 1 hour；So
Carbonization 1 hour is carried out under 700 DEG C of inert atmosphere protections afterwards, then purifying obtains the graphite level hole ultrafine carbon fiber of self-supporting
Dimension.The inert atmosphere is nitrogen and argon gas mixed atmosphere.
After tested, a diameter of 1090nm-1520nm of the graphite level hole ultrafine carbon fiber of gained self-supporting, specific surface
Product is 883m2/ g, Micropore volume 0.279cm3/ g, mesopore volume 0.246cm3/ g, total pore volume 0.525cm3/ g, it is hydrophobic
Angle is 143 °.
Embodiment 4：
A kind of preparation method of the graphite level hole ultrafine carbon fiber of self-supporting is high by being added into electrostatic spinning presoma
Molecular weight linear polymer and catalyst containing transition metal element, are prepared in situ to obtain the stone of self-supporting in one step of carbonisation
Black matter level hole ultrafine carbon fiber.
Specifically, include following steps：
（1）With mass ratio for 1：0.050：0.200 respectively by electrostatic spinning presoma, high molecular weight linear polymer and containing transition
The catalyst of metallic element is dissolved in organic solvent, and stirring forms uniform solution；Wherein, electrostatic spinning presoma is organic
A concentration of 28wt.% in solvent.The electrostatic spinning presoma is polyimides；The high molecular weight linear polymer is poly-
Acrylonitrile；The catalyst containing transition metal element is iron chloride；The organic solvent is normal propyl alcohol.
（2）By electrostatic spinning apparatus by above-mentioned solution electrospinning at composite ultrafine fiber；Voltage is 23kV, receives distance and is
25cm, feed speed 0.7mL/h.
（3）By step（2）Gained composite ultrafine fiber is progressively heated at 230 DEG C in air atmosphere and is kept for 3 hours；So
Carbonization 2 hours is carried out under 800 DEG C of inert atmosphere protections afterwards, then purifying obtains the graphite level hole ultrafine carbon fiber of self-supporting
Dimension.The inert atmosphere is nitrogen.
After tested, a diameter of 1250nm-1610nm of the graphite level hole ultrafine carbon fiber of gained self-supporting, specific surface
Product is 651m2/ g, Micropore volume 0.209cm3/ g, mesopore volume 0.380cm3/ g, total pore volume 0.589cm3/ g, it is hydrophobic
Angle is 135 °.
Embodiment 5：
A kind of preparation method of the graphite level hole ultrafine carbon fiber of self-supporting is high by being added into electrostatic spinning presoma
Molecular weight linear polymer and catalyst containing transition metal element, are prepared in situ to obtain the stone of self-supporting in one step of carbonisation
Black matter level hole ultrafine carbon fiber.
Specifically, include following steps：
（1）With mass ratio for 1：0.010：0.150 respectively by electrostatic spinning presoma, high molecular weight linear polymer and containing transition
The catalyst of metallic element is dissolved in organic solvent, and stirring forms uniform solution；Wherein, electrostatic spinning presoma is organic
A concentration of 32wt.% in solvent.The electrostatic spinning presoma is pitch；The high molecular weight linear polymer is polyethylene
The mixture of butyral and polyvinylpyrrolidone；The catalyst containing transition metal element is copper chloride；It is described to have
Solvent is N,N-dimethylformamide.
（2）By electrostatic spinning apparatus by above-mentioned solution electrospinning at composite ultrafine fiber；Voltage is 28kV, receives distance and is
28cm, feed speed 1.2mL/h.
（3）By step（2）Gained composite ultrafine fiber is progressively heated at 250 DEG C in air atmosphere and is kept for 2 hours；So
Carbonization 2.5 hours is carried out under 850 DEG C of inert atmosphere protections afterwards, then purifying obtains the ultra-fine carbon in graphite level hole of self-supporting
Fiber.The inert atmosphere is argon gas.
After tested, a diameter of 1030nm-1350nm of the graphite level hole ultrafine carbon fiber of gained self-supporting, specific surface
Product is 1024m2/ g, Micropore volume 0.336cm3/ g, mesopore volume 0.195cm3/ g, total pore volume 0.531cm3/ g, it is hydrophobic
Angle is 139 °.
Embodiment 6：
A kind of preparation method of the graphite level hole ultrafine carbon fiber of self-supporting is high by being added into electrostatic spinning presoma
Molecular weight linear polymer and catalyst containing transition metal element, are prepared in situ to obtain the stone of self-supporting in one step of carbonisation
Black matter level hole ultrafine carbon fiber.
Specifically, include following steps：
（1）With mass ratio for 1：0.02：0.110 respectively by electrostatic spinning presoma, high molecular weight linear polymer and containing transition
The catalyst of metallic element is dissolved in organic solvent, and stirring forms uniform solution；Wherein, electrostatic spinning presoma is organic
A concentration of 40wt.% in solvent.The electrostatic spinning presoma is the mixture of polyvinyl alcohol and polyimides；The high score
Son amount linear polymer is the mixture of polyvinylpyrrolidone and polyvinyl alcohol；The catalyst containing transition metal element
For nickel chloride；The organic solvent is DMAC N,N' dimethyl acetamide.
（2）By electrostatic spinning apparatus by above-mentioned solution electrospinning at composite ultrafine fiber；Voltage is 30kV, receives distance and is
30cm, feed speed 1.5mL/h.
（3）By step（2）Gained composite ultrafine fiber is progressively heated at 280 DEG C in air atmosphere and is kept for 1 hour；So
Carbonization 3 hours is carried out under 1000 DEG C of inert atmosphere protections afterwards, then purifying obtains the ultra-fine carbon in graphite level hole of self-supporting
Fiber.The inert atmosphere is nitrogen and argon gas mixed atmosphere.
After tested, a diameter of 1060nm-1450nm of the graphite level hole ultrafine carbon fiber of gained self-supporting, specific surface
Product is 1028m2/ g, Micropore volume 0.280cm3/ g, mesopore volume 0.276cm3/ g, total pore volume 0.556cm3/ g, it is hydrophobic
Angle is 142 °.
Comparative example 1
According to the methods of embodiment 1, phenolic resin, polyvinyl butyral are dissolved in ethyl alcohol, ferric acetyl acetonade is not added,
Electrostatic spinning solution is formed, porous ultrafine carbon fiber is obtained through electrospinning, carbonization.The ultrafine carbon fiber microscopic appearance does not observe stone
Black matter structure.The addition for illustrating ferric acetyl acetonade plays an important roll the graphitization of carbon fiber.Meanwhile gained fiber is straight
Diameter is 1330nm-1770nm, specific surface area 519m2/ g, Micropore volume 0.225cm3/ g, mesopore volume 0.049cm3/ g,
Total pore volume is 0.274cm3/ g, hydrophobic angle are 121 °.As it can be seen that prepared by being not added with ferric acetyl acetonade carbon fiber, specific surface area
Smaller and hole hold smaller, and hydrophobicity is worse.
The design focal point of the present invention is：The graphite nanostructure and hierarchical pore structure of the present invention can be by being carbonized
The method of one step of process original position obtains, and the additive amount for changing heat treatment temperature and each mixture of electrostatic spinning presoma can be with
Regulation and control gained graphite nanostructure and hierarchical pore structure, preparation method eliminate the need for superhigh temperature and template, it is convenient and efficient simultaneously
And cost is saved, it is extended to batch and prepares.Also, the graphite level hole ultrafine carbon fiber tool of self-supporting prepared by the present invention
There is the slabbing form of self-supporting, while the hierarchical pore structure that graphite structure, micropore and mesoporous coexist makes the fiber have
Stronger hydrophobicity, larger specific surface area and Kong Rong can be preferably applied for adsoption catalysis energy storage field.
The above described is only a preferred embodiment of the present invention, be not intended to limit the scope of the present invention,
Therefore it is every according to the technical essence of the invention to any subtle modifications, equivalent variations and modifications made by above example, still
Belong in the range of technical solution of the present invention.
Claims (8)
1. a kind of preparation method of the graphite level hole ultrafine carbon fiber of self-supporting, it is characterised in that：By to electrostatic spinning
High molecular weight linear polymer and the catalyst containing transition metal element are added in presoma, is prepared in situ in one step of carbonisation
Obtain the graphite level hole ultrafine carbon fiber of self-supporting.
2. a kind of preparation method of the graphite level hole ultrafine carbon fiber of self-supporting according to claim 1, feature
It is：Include following steps：
（1）With mass ratio for 1：0.010-0.050：0.020-0.200 respectively gathers electrostatic spinning presoma, high molecular weight linear
It closes object and the catalyst containing transition metal element is dissolved in organic solvent, stirring forms uniform solution；Wherein, electrostatic spinning
A concentration of 20-40wt.% of presoma in organic solvent；
（2）By electrostatic spinning apparatus by above-mentioned solution electrospinning at composite ultrafine fiber；Voltage is 20-30kV, receives distance and is
20-30cm, feed speed 0.5-1.5mL/h；
（3）By step（2）Gained composite ultrafine fiber is progressively heated at 180 DEG C -280 DEG C in air atmosphere and keeps 1-3 small
When；Then carbonization 1-3 hours is carried out under 700-1000 DEG C of inert atmosphere protection, then purifying obtains the graphite layer of self-supporting
Secondary aperture ultrafine carbon fiber.
3. a kind of preparation method of the graphite level hole ultrafine carbon fiber of self-supporting according to claim 1 or 2, special
Sign is：The electrostatic spinning presoma is one kind in phenolic resin, polyacrylonitrile, polyvinyl alcohol, polyimides or pitch
Or it is several.
4. a kind of preparation method of the graphite level hole ultrafine carbon fiber of self-supporting according to claim 1 or 2, special
Sign is：The high molecular weight linear polymer is polyvinyl butyral, polyvinylpyrrolidone, polyvinyl alcohol and gathers
One or more of acrylonitrile.
5. a kind of preparation method of the graphite level hole ultrafine carbon fiber of self-supporting according to claim 1 or 2, special
Sign is：The catalyst containing transition metal element is ferric acetyl acetonade, nickel acetylacetonate, acetylacetone cobalt, iron chloride, chlorine
Change the one or more of copper, nickel chloride, cobalt chloride, the potassium ferricyanide.
6. a kind of preparation method of the graphite level hole ultrafine carbon fiber of self-supporting according to claim 2, feature
It is：The organic solvent is ethyl alcohol, methanol, acetone, normal propyl alcohol, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide
It is one or more of.
7. a kind of preparation method of the graphite level hole ultrafine carbon fiber of self-supporting according to claim 2, feature
It is：The inert atmosphere is nitrogen or argon gas or is nitrogen and argon gas mixed atmosphere.
8. a kind of graphite level hole ultrafine carbon fiber of self-supporting, it is characterised in that：Using as claimed in claim 1 or 2
A kind of preparation method of the graphite level hole ultrafine carbon fiber of self-supporting is obtained, the ultra-fine carbon in graphite level hole of the self-supporting
The level hole system that fiber is had graphite structure and constituted with micropore and mesoporous, specific surface area are more than 500m2/ g, large pore volume in
0.500cm3/ g, hydrophobic angle are more than 135 °.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810306671.9A CN108611706A (en) | 2018-04-08 | 2018-04-08 | A kind of graphite level hole ultrafine carbon fiber of self-supporting and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201810306671.9A CN108611706A (en) | 2018-04-08 | 2018-04-08 | A kind of graphite level hole ultrafine carbon fiber of self-supporting and preparation method thereof |
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| CN112899821A (en) * | 2021-03-03 | 2021-06-04 | 深圳市翔丰华科技股份有限公司 | Nitrogen-doped narrow mesopore distribution carbon nanofiber and preparation method thereof |
| US11502304B2 (en) * | 2019-11-08 | 2022-11-15 | Enevate Corporation | Catalysts and methods for lowering electrode pyrolysis temperature |
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