CN114481368B - Hollow carbon nanofiber and preparation method thereof - Google Patents
Hollow carbon nanofiber and preparation method thereof Download PDFInfo
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- CN114481368B CN114481368B CN202210134380.2A CN202210134380A CN114481368B CN 114481368 B CN114481368 B CN 114481368B CN 202210134380 A CN202210134380 A CN 202210134380A CN 114481368 B CN114481368 B CN 114481368B
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- polyacrylonitrile
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- polystyrene
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- carbon nanofiber
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000002134 carbon nanofiber Substances 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 83
- 239000002243 precursor Substances 0.000 claims abstract description 82
- 238000009987 spinning Methods 0.000 claims abstract description 64
- 239000004793 Polystyrene Substances 0.000 claims abstract description 39
- 229920002223 polystyrene Polymers 0.000 claims abstract description 39
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 36
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 36
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 35
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 35
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000000835 fiber Substances 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 238000010000 carbonizing Methods 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 230000003647 oxidation Effects 0.000 claims description 20
- 238000007254 oxidation reaction Methods 0.000 claims description 20
- 238000003763 carbonization Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 16
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 39
- 238000010438 heat treatment Methods 0.000 description 29
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 24
- 238000010041 electrostatic spinning Methods 0.000 description 20
- 238000001878 scanning electron micrograph Methods 0.000 description 20
- 229920000049 Carbon (fiber) Polymers 0.000 description 19
- 239000004917 carbon fiber Substances 0.000 description 19
- 230000001590 oxidative effect Effects 0.000 description 13
- 229910052786 argon Inorganic materials 0.000 description 12
- 238000011049 filling Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- 238000005191 phase separation Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000011258 core-shell material Substances 0.000 description 4
- 230000000149 penetrating effect Effects 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000001523 electrospinning Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000011232 storage material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007833 carbon precursor Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 210000005239 tubule Anatomy 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/08—Addition of substances to the spinning solution or to the melt for forming hollow filaments
-
- 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
-
- 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
- D01F9/245—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 from polyurethanes
Abstract
The application discloses a hollow carbon nanofiber and a preparation method thereof, wherein the method comprises the following steps: (1) Mixing polyacrylonitrile, a sacrificial phase and a solvent to obtain a spinning solution; (2) Spinning the spinning solution so as to obtain a precursor fiber; (3) Pre-oxidizing the precursor fiber to obtain a pre-oxidized precursor; (4) Carbonizing the pre-oxidized precursor so as to obtain hollow carbon nanofibers; wherein in step (1), the sacrificial phase comprises at least two of polymethyl methacrylate, polystyrene, and polyvinylpyrrolidone. Therefore, the method for preparing the hollow carbon nanofiber is simple and convenient to operate, high in production efficiency and high in shape controllability, and can be used for large-scale production.
Description
Technical Field
The application belongs to the technical field of carbon nano materials, and particularly relates to a hollow carbon nanofiber and a preparation method thereof.
Background
The carbon nanofiber is an ultrafine carbon material with carbon content of more than 90%, wherein compared with solid carbon nanofiber, the hollow penetrating carbon nanofiber has the advantages of being lower in density, larger in specific surface area, good in chemical resistance and the like, and has better application in the aspects of filtration and adsorption, super capacitors, fuel cells, catalyst carriers, hydrogen storage materials, intelligent clothes and the like.
For the last decade, coaxial electrospinning techniques have been commonly used to produce hollow carbon nanofibers. The spray head is two coaxial metal tubules, wherein shell layer liquid and nuclear layer liquid materials are split-packed in two channels and are respectively connected with two liquid reservoirs to provide two different channels for inner liquid and outer liquid. Preparing a solution of a carbon precursor polymer into a shell layer liquid storage device, placing a pyrolyzed polymer into a core layer liquid storage device, carrying out electrostatic spinning to obtain a core-shell structure with an outer layer of the carbon precursor polymer and an inner layer of the pyrolyzed polymer which can be thermally degraded, and removing the pyrolyzed polymer through pre-oxidation and carbonization to obtain the hollow carbon fiber. However, the coaxial electrostatic spinning method is used to obtain the complete core-shell structure fiber, and thus the hollow penetrating carbon nanofiber, and a series of harsh experimental parameters including the concentration, molecular weight, viscosity, conductivity, surface tension, core-shell flow rate and flow rate ratio of the core-shell solution need to be controlled. In addition, the coaxial electrostatic spinning device has lower production efficiency, cannot meet the requirement of large-scale production and application, and is difficult to realize in large-scale production of spinning.
Therefore, the method for searching the hollow penetrating carbon nanofiber has the advantages of simple operation, high production efficiency and imperative mass production.
Disclosure of Invention
The present application aims to solve at least one of the technical problems in the related art to some extent. Therefore, an object of the present application is to provide a hollow carbon nanofiber and a preparation method thereof, wherein the hollow carbon nanofiber is prepared by the method, and the method has the advantages of simple operation, high production efficiency, high shape controllability and large-scale production.
In a first aspect of the present application, the present application provides a method of preparing hollow carbon nanofibers. According to an embodiment of the application, the method comprises:
(1) Mixing polyacrylonitrile, a sacrificial phase and a solvent to obtain a spinning solution;
(2) Spinning the spinning solution so as to obtain a precursor fiber;
(3) Pre-oxidizing the precursor fiber to obtain a pre-oxidized precursor;
(4) Carbonizing the pre-oxidized precursor so as to obtain hollow carbon nanofibers;
wherein in step (1), the sacrificial phase comprises at least two of polymethyl methacrylate, polystyrene, and polyvinylpyrrolidone.
According to the method for preparing the hollow carbon nanofiber, the spinning solution can be obtained by mixing polyacrylonitrile, a sacrificial phase and a solvent, wherein the sacrificial phase comprises at least two of polymethyl methacrylate, polystyrene and polyvinylpyrrolidone, and the inventor finds that when at least two sacrificial phases are adopted, the whole spinning solution is obviously separated from the sacrificial phase, and a hollow structure of the polyacrylonitrile surrounding the sacrificial phase is easy to form in the following spinning process. Meanwhile, as the solubility parameter differences between different sacrificial phases and polyacrylonitrile are different, hollow carbon fibers with more abundant pores can be formed after heat treatment, and the specific surface area of the carbon fibers is increased; and spinning the spinning solution to obtain a precursor fiber, and sequentially performing pre-oxidation treatment and carbonization treatment on the obtained precursor fiber to remove a sacrificial phase in the precursor fiber, thereby obtaining the hollow carbon nanofiber. Compared with the existing coaxial electrostatic spinning, the method for preparing the hollow carbon nanofiber has the advantages of simpler and more convenient operation, high production efficiency and high shape controllability, and can be used for large-scale production.
In addition, the method of preparing hollow carbon nanofibers according to the above embodiments of the present application may further have the following additional technical features:
in some embodiments of the application, the polyacrylonitrile has a molecular weight of 5 to 30 ten thousand. Thus, the obtained hollow carbon nanofiber has a good appearance and a good hollow structure.
In some embodiments of the application, the sacrificial phase has a molecular weight of 3 to 10 tens of thousands. Thus, the obtained hollow carbon nanofiber has a good appearance and a good hollow structure.
In some embodiments of the application, in step (1), the mixing is performed under stirring at a speed of 200 to 400rpm for a period of 12 to 24 hours. Thus, the obtained hollow carbon nanofiber has a good appearance and a good hollow structure.
In some embodiments of the application, in step (1), the sacrificial phase comprises polymethyl methacrylate and polystyrene, the mass ratio of polymethyl methacrylate to polystyrene being (1-2): (1-2). Thus, the obtained hollow carbon nanofiber has a good appearance and a good hollow structure.
In some embodiments of the application, in step (1), the sacrificial phase comprises polymethyl methacrylate and polyvinylpyrrolidone, the mass ratio of polymethyl methacrylate to polyvinylpyrrolidone being (1-2): (1-2). Thus, the obtained hollow carbon nanofiber has a good appearance and a good hollow structure.
In some embodiments of the application, in step (1), the sacrificial phase comprises polystyrene and polyvinylpyrrolidone, the mass ratio of polystyrene to polyvinylpyrrolidone being (1-2): (1-2). Thus, the obtained hollow carbon nanofiber has a good appearance and a good hollow structure.
In some embodiments of the application, in step (1), the sacrificial phase comprises polymethyl methacrylate, polystyrene, and polyvinylpyrrolidone, the mass ratio of polymethyl methacrylate, polystyrene, and polyvinylpyrrolidone being (1-2): (1-2): (1-2). Thus, the obtained hollow carbon nanofiber has a good appearance and a good hollow structure.
In some embodiments of the application, the polyacrylonitrile is 20 to 90 parts by weight and the sacrificial phase is 10 to 80 parts by weight based on 100 parts by weight of the total mass of the polyacrylonitrile and the sacrificial phase. Thus, the obtained hollow carbon nanofiber has a good appearance and a good hollow structure.
In some embodiments of the application, the mass concentration of the spinning solution is 8-20%. Thus, the obtained hollow carbon nanofiber has a good appearance and a good hollow structure.
In some embodiments of the application, in step (3), the pre-oxidation process is performed under an atmosphere of dry air, the pre-oxidation being performed at a temperature of 200 to 300 ℃ for a time of 2 to 5 hours.
In some embodiments of the application, in step (4), the carbonization treatment is performed in an inert atmosphere, the carbonization treatment being performed at a temperature of 1000 to 2000 degrees celsius for a time of 1 to 3 hours.
In a second aspect of the application, the application provides a hollow carbon nanofiber. According to the embodiment of the application, the hollow carbon nanofiber is prepared by adopting the method. Therefore, the hollow carbon nanofiber has good appearance and a good hollow structure, can be produced in a large scale, and has wide application prospects in the aspects of filtration and adsorption, supercapacitors, fuel cells, catalyst carriers, hydrogen storage materials, intelligent clothes and the like.
Additional aspects and advantages of the application will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the application.
Drawings
The foregoing and/or additional aspects and advantages of the application will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 is a schematic flow diagram of a method of preparing hollow carbon nanofibers according to one embodiment of the present application;
FIG. 2 is an SEM image of hollow carbon nanofibers produced in example 1;
FIG. 3 is a TEM image of the hollow carbon nanofiber prepared in example 1;
FIG. 4 is an SEM image of hollow carbon nanofibers produced in example 2;
FIG. 5 is an SEM image of hollow carbon nanofibers produced in example 3;
FIG. 6 is an SEM image of hollow carbon nanofibers produced in example 4;
FIG. 7 is an SEM image of hollow carbon nanofibers produced in example 5;
FIG. 8 is an SEM image of hollow carbon nanofibers produced in example 6;
FIG. 9 is an SEM image of hollow carbon nanofibers produced in example 7;
fig. 10 is an SEM image of the hollow carbon nanofibers produced in example 8.
Detailed Description
The embodiments described below by referring to the drawings are illustrative and intended to explain the present application and should not be construed as limiting the application.
In a first aspect of the present application, the present application provides a method of preparing hollow carbon nanofibers. Referring to fig. 1, according to an embodiment of the present application, the method includes:
s100: mixing polyacrylonitrile, sacrificial phase and solvent
In the step, polyacrylonitrile, a sacrificial phase and a solvent are mixed, and because the solubility parameter difference of the polyacrylonitrile and the sacrificial phase is large and the molecular structure of the polyacrylonitrile and the sacrificial phase are different, the polyacrylonitrile is used for wrapping the sacrificial phase, so that the spinning solution of the polyacrylonitrile-wrapped sacrificial phase is obtained, wherein the sacrificial phase comprises at least two of polymethyl methacrylate, polystyrene and polyvinylpyrrolidone, and the inventor finds that when at least two sacrificial phases are adopted, the whole spinning solution is obviously separated from the sacrificial phase, and a hollow structure of the polyacrylonitrile for wrapping the sacrificial phase is easy to form in the subsequent spinning process. Meanwhile, as the solubility parameter difference values between different sacrificial phases and polyacrylonitrile are different, hollow carbon fibers with richer pores can be formed after heat treatment, and the specific surface area of the carbon fibers is increased.
Further, the molecular weight of the polyacrylonitrile is 5 to 30 ten thousand. The inventor finds that if the molecular weight of the polyacrylonitrile is too low, the solubility parameters of the polyacrylonitrile and the sacrificial phase are similar, the two polymers are uniformly dispersed, a structure that the polyacrylonitrile completely wraps the sacrificial phase cannot be formed during spinning, and the hollow carbon nanofiber cannot be obtained after heat treatment; if the molecular weight of the polyacrylonitrile is too high, the solubility parameter difference between the polyacrylonitrile and the sacrificial phase becomes large, the polyacrylonitrile is entangled together due to the too high molecular weight, the sacrificial phase is difficult to dissolve into, and the structure of mostly polyacrylonitrile and little sacrificial phase is mainly formed during spinning, and the structure of little and little sacrificial phase and little polyacrylonitrile is also formed. The former forms porous carbon fibers with a small amount of pores after heat treatment, and the latter is mostly burned off, leaving pure polyacrylonitrile fibers. Therefore, the polyacrylonitrile molecular weight is favorable for obtaining the carbon nanofiber with a hollow structure. And the molecular weight of the sacrificial phase is 3-10 ten thousand. The inventors found that if the molecular weight of the sacrificial phase is too low, the sacrificial phase is uniformly dispersed in polyacrylonitrile to form porous carbon fibers containing nanopores or micropores; if the molecular weight of the sacrificial phase is too high, the molecular chains of the sacrificial phase are entangled together and cannot form a structure in which the polyacrylonitrile encapsulates the sacrificial phase. Therefore, the carbon nanofiber with the hollow structure is beneficial to obtaining by adopting the molecular weight of the sacrificial phase.
According to one embodiment of the application, the sacrificial phase comprises any two of polymethyl methacrylate, polystyrene, and polyvinylpyrrolidone, and the sacrificial phase comprises a combination of polymethyl methacrylate and polystyrene, or a combination of polymethyl methacrylate and polyvinylpyrrolidone, or a combination of polystyrene and polyvinylpyrrolidone. According to one embodiment of the present application, the sacrificial phase includes polymethyl methacrylate and polystyrene, and the mass ratio of polymethyl methacrylate to polystyrene is (1-2): (1-2); the sacrificial phase comprises polymethyl methacrylate and polyvinylpyrrolidone, and the mass ratio of the polymethyl methacrylate to the polyvinylpyrrolidone is (1-2): (1-2); the sacrificial phase comprises polystyrene and polyvinylpyrrolidone, and the mass ratio of the polystyrene to the polyvinylpyrrolidone is (1-2): (1-2). Therefore, the sacrificial phase with the mixing proportion is favorable for forming the hollow carbon fiber with large specific surface area and good morphology.
According to still another embodiment of the present application, the above-mentioned sacrificial phase includes three combinations of polymethyl methacrylate, polystyrene and polyvinylpyrrolidone, and the mass ratio of polymethyl methacrylate, polystyrene and polyvinylpyrrolidone is (1 to 2): (1-2): (1-2). Therefore, the sacrificial phase with the mixing ratio of polymethyl methacrylate, polystyrene and polyvinylpyrrolidone is favorable for forming the hollow carbon fiber with large specific surface area and good appearance.
Further, the total mass of the polyacrylonitrile and the sacrificial phase is 20 to 90 parts by weight, and the total mass of the polyacrylonitrile and the sacrificial phase is 10 to 80 parts by weight. And the mass concentration of the spinning solution is 8-20%. The inventor finds that if the mass concentration of the spinning solution is too small, the viscosity of the spinning solution is too low, serious beading phenomenon can occur, so that the performance of the carbon fiber is affected; if the mass concentration of the spinning solution is too high, the viscosity of the spinning solution is too high, and the spinning solution cannot form a Taylor cone after being extruded from a needle, so that the nanofiber cannot be formed. Thus, the nanofiber with better performance can be obtained by adopting the mass concentration of the application. The mixing is carried out under stirring (such as magnetic stirring) at 200-400 rpm for 12-24 h. The specific type of the above solvent is not particularly limited, and those skilled in the art may select according to actual needs, and for example, the solvent includes at least one of N, N-dimethylformamide, chlorobenzene, chloroform, dichloromethane, and tetrahydrofuran.
S200: spinning the spinning solution
In this step, the spinning solution is spun to obtain a fibril. Specifically, the spinning mode may be conventional electrospinning, more specifically, the spinning solution is charged into an injector, electrospinning is performed by pushing with a pusher, and precursor filaments are collected by rotating a cylindrical receiver, thereby obtaining a precursor fiber. The inventor finds that because of the large difference of solubility parameters of the polyacrylonitrile and the sacrificial phase and the difference of molecular structures of the polyacrylonitrile and the sacrificial phase, the polyacrylonitrile and the sacrificial phase have poor compatibility, so that phase separation can occur in the electrostatic spinning process, and small drops similar to a purse-string egg of the polyacrylonitrile wrapping the sacrificial phase are elongated under the action of electrostatic force, so that the elongated fibers, namely the fibril fibers, of which the sacrificial phase mainly exists in the fibers are formed. Meanwhile, as the diameter of the fiber obtained by electrostatic spinning is in the range of hundreds of nanometers, the phase separation is limited in the microscopic field, namely, polyacrylonitrile and a sacrificial phase are subjected to microscopic phase separation in single electrostatic spinning, and the sacrificial phase is removed along with the follow-up pre-oxidation and carbonization, so that the original solid carbon nanofiber can be changed into a hollow penetrating carbon nanofiber. It should be noted that, the distance between the needle and the receiver, the syringe advancing speed and the spinning voltage in the spinning process are all conventional techniques in the art, and are not repeated here.
S300: preoxidation treatment of the fibril
In the step, pre-oxidizing treatment is carried out on the precursor fiber, the polyacrylonitrile molecular structure is crosslinked to form a heat-resistant trapezoid structure, and simultaneously, a pre-oxidized precursor can be obtained along with the removal of part of sacrificial phase. Specifically, the above-mentioned pre-oxidation treatment process is performed in a tube furnace. Further, the pre-oxidation process is carried out in the atmosphere of dry air, the pre-oxidation temperature is 200-300 ℃, and the pre-oxidation time is 2-5 hours. The inventor finds that the water molecules are small molecules, and the existence of the small molecules can influence phase separation, so that the pre-oxidation process is preferably performed in the atmosphere of dry air, and in addition, if the pre-oxidation temperature is too low, polyacrylonitrile cannot form a trapezoid structure, so that a three-dimensional network structure cannot be formed in the carbonization process, and finally, carbon fibers cannot be formed; if the pre-oxidation temperature is too high, the polyacrylonitrile is decomposed after forming the trapezoid structure due to the too high temperature, and the carbon fiber cannot be formed. Meanwhile, if the pre-oxidation time is too short, polyacrylonitrile cannot be completely converted into a trapezoid structure and is decomposed in the subsequent carbonization process; if the pre-oxidation time is too long, the polyacrylonitrile is completely converted into a trapezoid structure, and the production efficiency is reduced if the pre-oxidation time is prolonged. Thus, the use of the pre-oxidation conditions of the present application facilitates the formation of carbon fibers.
S400: carbonizing the pre-oxidized precursor
In the step, the precursor is carbonized after pre-oxidation, and the sacrificial phase is completely removed, so that the hollow carbon nanofiber can be obtained. Specifically, the carbonization process is performed in a tube furnace. Further, the carbonization treatment is carried out in an inert atmosphere, the temperature of the carbonization treatment is 1000-2000 ℃ and the time is 1-3 h. The inventor finds that if the carbonization temperature is too low, polyacrylonitrile with a trapezoid structure cannot be converted into a three-dimensional network structure, so that carbon fibers cannot be formed; if the carbonization temperature is too high, the polyacrylonitrile is decomposed due to the too high temperature after forming the trapezoid structure, and the carbon fiber cannot be formed. Meanwhile, if the carbonization time is too short, the polyacrylonitrile cannot be completely converted into a three-dimensional network structure; if the carbonization time is too long, the polyacrylonitrile is completely converted into carbon fibers, and the production efficiency is reduced if the carbonization time is prolonged. Thus, the carbonization treatment conditions according to the present application are advantageous for the formation of carbon fibers. The specific type of the inert atmosphere is not particularly limited, and may be selected by those skilled in the art according to actual needs.
The inventors have found that by mixing polyacrylonitrile, a sacrificial phase comprising at least two of polymethyl methacrylate, polystyrene and polyvinylpyrrolidone, and a solvent, a spinning solution is obtained, and have found that when at least two sacrificial phases are used, the whole spinning solution produces a significant phase separation of the polyacrylonitrile from the sacrificial phases, which is easy to form a hollow structure of the polyacrylonitrile surrounding the sacrificial phases in the subsequent spinning process. Meanwhile, as the solubility parameter differences between different sacrificial phases and polyacrylonitrile are different, hollow carbon fibers with more abundant pores can be formed after heat treatment, and the specific surface area of the carbon fibers is increased; and spinning the spinning solution, and sequentially performing pre-oxidation treatment and carbonization treatment on the obtained precursor fiber to obtain the hollow carbon nanofiber. Compared with the existing coaxial electrostatic spinning, the method for preparing the hollow carbon nanofiber has the advantages of simpler and more convenient operation, high production efficiency and high shape controllability, and can be used for large-scale production.
In a second aspect of the application, the application provides a hollow carbon nanofiber. According to the embodiment of the application, the hollow carbon nanofiber is prepared by adopting the method. Therefore, the hollow carbon nanofiber has good appearance and a good hollow structure, can be produced in a large scale, and has wide application prospects in the aspects of filtration and adsorption, supercapacitors, fuel cells, catalyst carriers, hydrogen storage materials, intelligent clothes and the like. It should be noted that the features and advantages described above for the method for preparing the hollow carbon nanofiber are equally applicable to the hollow carbon nanofiber, and are not described herein.
The scheme of the present application will be explained below with reference to examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the present application and should not be construed as limiting the scope of the application. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
Step 1: mixing polyacrylonitrile (the molecular weight is 10-20 ten thousand), a sacrificial phase (the mass ratio of polymethyl methacrylate to polystyrene is 1:1, the molecular weight of both is 3-10 ten thousand) and N, N-dimethylformamide (the mass ratio of the polyacrylonitrile to the sacrificial phase is 6:4, and the stirring speed is 300rpm, and the time is 12 hours) to obtain spinning solution with the mass concentration of 15%;
step 2: filling the spinning solution into an injector for electrostatic spinning, using a cylinder receiver to rotationally collect precursor filaments, adjusting the distance between a needle head and the receiver and the advancing speed of the injector, and setting the voltage to obtain precursor filaments;
step 3: putting the precursor fiber into a tubular heating furnace, and pre-oxidizing for 2 hours at 250 ℃ in the atmosphere of dry air to obtain a pre-oxidized precursor;
step 4: and (3) placing the pre-oxidized precursor into a tubular heating furnace, and carbonizing at 1150 ℃ for 1 hour in an argon gas atmosphere to obtain the hollow through carbon nanofiber. The SEM image of the hollow through carbon nanofiber is shown in fig. 2, and the tem image is shown in fig. 3, and it can be seen that the hollow through carbon nanofiber has a good hollow structure.
Example 2
Step 1: mixing polyacrylonitrile (the molecular weight is 10-20 ten thousand), a sacrificial phase (the mass ratio of polymethyl methacrylate to polystyrene is 1:1, the molecular weight of both is 3-10 ten thousand) and N, N-dimethylformamide (the mass ratio of the polyacrylonitrile to the sacrificial phase is 5:5, the stirring speed is 300rpm, and the time is 12 h), so as to obtain spinning solution with the mass concentration of 15%;
step 2: filling the spinning solution into an injector for electrostatic spinning, using a cylinder receiver to rotationally collect precursor filaments, adjusting the distance between a needle head and the receiver and the advancing speed of the injector, and setting the voltage to obtain precursor filaments;
step 3: putting the precursor fiber into a tubular heating furnace, and pre-oxidizing for 2 hours at 200 ℃ in the atmosphere of dry air to obtain a pre-oxidized precursor;
step 4: and (3) placing the pre-oxidized precursor into a tubular heating furnace, and carbonizing at 1200 ℃ for 1 hour in an argon gas atmosphere to obtain the hollow through carbon nanofiber. The SEM image of the hollow through carbon nanofiber is shown in fig. 4, and it can be seen that the hollow through carbon nanofiber has a good hollow structure.
Example 3
Step 1: mixing polyacrylonitrile (the molecular weight is 10-20 ten thousand), a sacrificial phase (the mass ratio of polymethyl methacrylate to polyvinylpyrrolidone is 1:1, the molecular weight of both is 3-10 ten thousand) and N, N-dimethylformamide (the mass ratio of polyacrylonitrile to the sacrificial phase is 7:3, the stirring speed is 300rpm, and the time is 12 hours) to obtain spinning solution with the mass concentration of 15%;
step 2: filling the spinning solution into an injector for electrostatic spinning, using a cylinder receiver to rotationally collect precursor filaments, adjusting the distance between a needle head and the receiver and the advancing speed of the injector, and setting the voltage to obtain precursor filaments;
step 3: putting the precursor fiber into a tubular heating furnace, and pre-oxidizing for 2 hours at 220 ℃ in the atmosphere of dry air to obtain a pre-oxidized precursor;
step 4: and (3) placing the pre-oxidized precursor into a tubular heating furnace, and carbonizing at 1180 ℃ for 1 hour in an argon gas atmosphere to obtain the hollow through carbon nanofiber. The SEM image of the hollow through carbon nanofiber is shown in fig. 5, and it can be seen that the hollow through carbon nanofiber has a good hollow structure.
Example 4
Step 1: mixing polyacrylonitrile (the molecular weight is 10-20 ten thousand), a sacrificial phase (the mass ratio of polymethyl methacrylate to polyvinylpyrrolidone is 1:1, the molecular weight of both is 3-10 ten thousand) and N, N-dimethylformamide (the mass ratio of polyacrylonitrile to the sacrificial phase is 4:6, the stirring speed is 300rpm, and the time is 12 hours) to obtain spinning solution with the mass concentration of 15%;
step 2: filling the spinning solution into an injector for electrostatic spinning, using a cylinder receiver to rotationally collect precursor filaments, adjusting the distance between a needle head and the receiver and the advancing speed of the injector, and setting the voltage to obtain precursor filaments;
step 3: putting the precursor fiber into a tubular heating furnace, and pre-oxidizing for 2 hours at 240 ℃ in the atmosphere of dry air to obtain a pre-oxidized precursor;
step 4: and (3) placing the pre-oxidized precursor into a tubular heating furnace, and carbonizing at 1160 ℃ for 1 hour in an argon gas atmosphere to obtain the hollow through carbon nanofiber. The SEM image of the hollow through carbon nanofiber is shown in fig. 6, and it can be seen that the hollow through carbon nanofiber has a good hollow structure.
Example 5
Step 1: mixing polyacrylonitrile (molecular weight is 10-20 ten thousand), a sacrificial phase (the mass ratio of polystyrene to polyvinylpyrrolidone is 1:1, and the molecular weight of both is 3-10 ten thousand) with N, N-dimethylformamide (the mass ratio of polyacrylonitrile to the sacrificial phase is 3:7, and stirring speed is 300rpm, and time is 12 h), so as to obtain spinning solution with mass concentration of 15%;
step 2: filling the spinning solution into an injector for electrostatic spinning, using a cylinder receiver to rotationally collect precursor filaments, adjusting the distance between a needle head and the receiver and the advancing speed of the injector, and setting the voltage to obtain precursor filaments;
step 3: placing the precursor fiber into a tubular heating furnace, and pre-oxidizing at 260 ℃ for 2 hours in the atmosphere of dry air to obtain a pre-oxidized precursor;
step 4: and (3) placing the pre-oxidized precursor into a tubular heating furnace, and carbonizing at 1140 ℃ for 1 hour in an argon gas atmosphere to obtain the hollow through carbon nanofiber. The SEM image of the hollow through carbon nanofiber is shown in fig. 7, and it can be seen that the hollow through carbon nanofiber has a good hollow structure.
Example 6
Step 1: mixing polyacrylonitrile (molecular weight is 10-20 ten thousand), a sacrificial phase (the mass ratio of polystyrene to polyvinylpyrrolidone is 1:1, and the molecular weight of both is 3-10 ten thousand) with N, N-dimethylformamide (the mass ratio of polyacrylonitrile to the sacrificial phase is 8:2, and stirring speed is 300rpm, and time is 12 h), so as to obtain spinning solution with mass concentration of 15%;
step 2: filling the spinning solution into an injector for electrostatic spinning, using a cylinder receiver to rotationally collect precursor filaments, adjusting the distance between a needle head and the receiver and the advancing speed of the injector, and setting the voltage to obtain precursor filaments;
step 3: putting the precursor fiber into a tubular heating furnace, and pre-oxidizing for 2 hours at 280 ℃ in the atmosphere of dry air to obtain a pre-oxidized precursor;
step 4: and (3) placing the pre-oxidized precursor into a tubular heating furnace, and carbonizing at 1120 ℃ for 1 hour in an argon gas atmosphere to obtain the hollow through carbon nanofiber. The SEM image of the hollow through carbon nanofiber is shown in fig. 8, and it can be seen that the hollow through carbon nanofiber has a good hollow structure.
Example 7
Step 1: mixing polyacrylonitrile (molecular weight is 20-30 ten thousand), a sacrificial phase (the mass ratio of polymethyl methacrylate, polystyrene and polyvinylpyrrolidone is 1:1:1, the molecular weight of the three is 3-7 ten thousand) and N, N-dimethylformamide (the mass ratio of the polyacrylonitrile to the sacrificial phase is 6:4, the stirring speed is 300rpm, and the time is 12 h) to obtain spinning solution with the mass concentration of 15%;
step 2: filling the spinning solution into an injector for electrostatic spinning, using a cylinder receiver to rotationally collect precursor filaments, adjusting the distance between a needle head and the receiver and the advancing speed of the injector, and setting the voltage to obtain precursor filaments;
step 3: placing the precursor fiber into a tubular heating furnace, and pre-oxidizing for 2 hours at 300 ℃ in the atmosphere of dry air to obtain a pre-oxidized precursor;
step 4: and (3) placing the pre-oxidized precursor into a tubular heating furnace, and carbonizing at 1000 ℃ for 1 hour in an argon gas atmosphere to obtain the hollow through carbon nanofiber. The SEM image of the hollow through carbon nanofiber is shown in fig. 9, and it can be seen that the hollow through carbon nanofiber has a good hollow structure.
Example 8
Step 1: mixing polyacrylonitrile (molecular weight is 5-10 ten thousand), a sacrificial phase (the mass ratio of polymethyl methacrylate, polystyrene and polyvinylpyrrolidone is 1:2:2, the molecular weight of the three is 3-10 ten thousand) and N, N-dimethylformamide (the mass ratio of the polyacrylonitrile to the sacrificial phase is 6:4, the stirring speed is 300rpm, and the time is 12 h) to obtain spinning solution with the mass concentration of 15%;
step 2: filling the spinning solution into an injector for electrostatic spinning, using a cylinder receiver to rotationally collect precursor filaments, adjusting the distance between a needle head and the receiver and the advancing speed of the injector, and setting the voltage to obtain precursor filaments;
step 3: putting the precursor fiber into a tubular heating furnace, and pre-oxidizing for 2 hours at 200 ℃ in the atmosphere of dry air to obtain a pre-oxidized precursor;
step 4: and (3) placing the pre-oxidized precursor into a tubular heating furnace, and carbonizing at 1000 ℃ for 1 hour in an argon gas atmosphere to obtain the hollow through carbon nanofiber. The SEM image of the hollow through carbon nanofiber is shown in fig. 10, and it can be seen that the hollow through carbon nanofiber has a good hollow structure.
Comparative example 1
Step 1: mixing polyacrylonitrile (with the molecular weight of 10-20 ten thousand) and polymethyl methacrylate (with the molecular weight of 3-10 ten thousand) with N, N-dimethylformamide (the mass ratio of the polyacrylonitrile to the polymethyl methacrylate is 5:5, the stirring speed is 300rpm, and the time is 12 h), so as to obtain spinning solution with the mass concentration of 15%;
step 2: filling the spinning solution into an injector for electrostatic spinning, using a cylinder receiver to rotationally collect precursor filaments, adjusting the distance between a needle head and the receiver and the advancing speed of the injector, and setting the voltage to obtain precursor filaments;
step 3: putting the precursor fiber into a tubular heating furnace, and pre-oxidizing for 2 hours at 250 ℃ in the atmosphere of dry air to obtain a pre-oxidized precursor;
step 4: and (3) placing the pre-oxidized precursor into a tubular heating furnace, and carbonizing at 1150 ℃ for 1 hour in an argon gas atmosphere to obtain the carbon nanofiber. It can be seen from the SEM image of the carbon nanofiber that it does not have a hollow structure but has a porous structure.
Comparative example 2
Step 1: mixing polyacrylonitrile (molecular weight is 5-10 ten thousand), polystyrene (molecular weight is 3-10 ten thousand) and N, N-dimethylformamide (the mass ratio of the polyacrylonitrile to the polystyrene is 4:6, and stirring speed is 300rpm, and time is 12 h), so as to obtain spinning solution with mass concentration of 15%;
step 2: filling the spinning solution into an injector for electrostatic spinning, using a cylinder receiver to rotationally collect precursor filaments, adjusting the distance between a needle head and the receiver and the advancing speed of the injector, and setting the voltage to obtain precursor filaments;
step 3: putting the precursor fiber into a tubular heating furnace, and pre-oxidizing for 2 hours at 250 ℃ in the atmosphere of dry air to obtain a pre-oxidized precursor;
step 4: and (3) placing the pre-oxidized precursor into a tubular heating furnace, and carbonizing at 1150 ℃ for 1 hour in an argon gas atmosphere to obtain the carbon nanofiber. It can be seen from the SEM image of the carbon nanofiber that it does not have a hollow structure but has a porous structure.
Comparative example 3
Step 1: mixing polyacrylonitrile (molecular weight is 20-30 ten thousand), polyvinylpyrrolidone (molecular weight is 3-10 ten thousand) and N, N-dimethylformamide (the mass ratio of the polyacrylonitrile to the polyvinylpyrrolidone is 7:3, stirring speed is 300rpm, and time is 12 h) to obtain spinning solution with mass concentration of 15%;
step 2: filling the spinning solution into an injector for electrostatic spinning, using a cylinder receiver to rotationally collect precursor filaments, adjusting the distance between a needle head and the receiver and the advancing speed of the injector, and setting the voltage to obtain precursor filaments;
step 3: putting the precursor fiber into a tubular heating furnace, and pre-oxidizing for 2 hours at 250 ℃ in the atmosphere of dry air to obtain a pre-oxidized precursor;
step 4: and (3) placing the pre-oxidized precursor into a tubular heating furnace, and carbonizing at 1150 ℃ for 1 hour in an argon gas atmosphere to obtain the carbon nanofiber. It can be seen from the SEM image of the carbon nanofiber that it does not have a hollow structure but has a porous structure.
Comparative example 4
Step 1: mixing polyacrylonitrile (molecular weight is 30-40 ten thousand), a sacrificial phase (the mass ratio of polymethyl methacrylate to polystyrene is 1:1, and the molecular weight of both is 3-10 ten thousand) with N, N-dimethylformamide (the mass ratio of polyacrylonitrile to the sacrificial phase is 5:5, and stirring speed is 300rpm, and time is 12 h), so as to obtain spinning solution with mass concentration of 15%;
step 2: filling the spinning solution into an injector for electrostatic spinning, using a cylinder receiver to rotationally collect precursor filaments, adjusting the distance between a needle head and the receiver and the advancing speed of the injector, and setting the voltage to obtain precursor filaments;
step 3: putting the precursor fiber into a tubular heating furnace, and pre-oxidizing for 2 hours at 200 ℃ in the atmosphere of dry air to obtain a pre-oxidized precursor;
step 4: and (3) placing the pre-oxidized precursor into a tubular heating furnace, and carbonizing at 1200 ℃ for 1 hour in an argon gas atmosphere to obtain the carbon nanofiber. It can be seen from the SEM image of the carbon nanofiber that it does not have a hollow structure but has a porous structure.
As can be seen from the comparison of the carbon nanofibers produced in examples 1 to 8 with those produced in comparative examples 1 to 4, the carbon nanofibers produced in examples 1 to 8 by using at least two sacrificial phases have a good hollow structure, and the carbon nanofibers produced in comparative examples 1 to 3 by using only one sacrificial phase have too large molecular weight of polyacrylonitrile in comparative example 4 have no hollow structure but have a porous structure. The hollow structure is easy to load metal ions for catalysis or load sulfur for lithium-sulfur batteries due to the pipeline structure with the through middle, and has wider application in the aspect of energy. The porous structure is generally not a communicated pore and is not easy to load other materials.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present application. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present application have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the application, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the application.
Claims (6)
1. A method of making hollow carbon nanofibers comprising:
(1) Mixing polyacrylonitrile, a sacrificial phase and a solvent to obtain a spinning solution;
(2) Spinning the spinning solution so as to obtain a precursor fiber;
(3) Pre-oxidizing the precursor fiber to obtain a pre-oxidized precursor;
(4) Carbonizing the pre-oxidized precursor so as to obtain hollow carbon nanofibers;
in the step (1), the sacrificial phase comprises polymethyl methacrylate and polystyrene, wherein the mass ratio of the polymethyl methacrylate to the polystyrene is (1-2): (1-2) the molecular weight of the polyacrylonitrile is 5-30 ten thousand, the molecular weight of polymethyl methacrylate and polystyrene in the sacrificial phase is 3-10 ten thousand, and the total mass of the polyacrylonitrile and the sacrificial phase is 100 parts by mass, 20-50 parts by weight of the polyacrylonitrile and 50-80 parts by weight of the sacrificial phase;
or,
the sacrificial phase comprises polystyrene and polyvinylpyrrolidone, and the mass ratio of the polystyrene to the polyvinylpyrrolidone is (1-2): (1-2) wherein the molecular weight of the polyacrylonitrile is 5-30 ten thousand, the molecular weights of the polystyrene and the polyvinylpyrrolidone in the sacrificial phase are 3-10 ten thousand, and the total mass of the polyacrylonitrile and the sacrificial phase is 100 parts by mass, 20-50 parts by weight of the polyacrylonitrile and 50-80 parts by weight of the sacrificial phase;
still alternatively, or in addition to the above,
the sacrificial phase comprises polymethyl methacrylate, polystyrene and polyvinylpyrrolidone, wherein the mass ratio of the polymethyl methacrylate to the polystyrene to the polyvinylpyrrolidone is 1:1:1, wherein the molecular weight of the polyacrylonitrile is 20-30 ten thousand, the molecular weights of polymethyl methacrylate, polystyrene and polyvinylpyrrolidone in the sacrificial phase are 3-7 ten thousand, and 60 parts by weight of the polyacrylonitrile and 40 parts by weight of the sacrificial phase are calculated by taking the total mass of the polyacrylonitrile and the sacrificial phase as 100 parts by weight.
2. The method according to claim 1, wherein in the step (1), the mixing is performed under stirring, and the stirring speed is 200 to 400rpm for 12 to 24 hours.
3. The method according to claim 1, wherein in the step (1), the mass concentration of the spinning solution is 8-20%.
4. The method according to claim 1, wherein in the step (3), the pre-oxidation is performed in a dry air atmosphere, the pre-oxidation is performed at a temperature of 200 to 300 ℃ for a time of 2 to 5 hours.
5. The method according to claim 1, wherein in the step (4), the carbonization treatment is performed in an inert atmosphere, the temperature of the carbonization treatment is 1000-2000 ℃ and the time is 1-3 hours.
6. A hollow carbon nanofiber, characterized in that the hollow carbon nanofiber is prepared by the method of any one of claims 1 to 5.
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