CN111321487A - Preparation method of carbon nanofiber with graphene structure on surface - Google Patents
Preparation method of carbon nanofiber with graphene structure on surface Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 114
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000002134 carbon nanofiber Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 55
- 239000004917 carbon fiber Substances 0.000 claims abstract description 50
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 49
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 31
- 238000009987 spinning Methods 0.000 claims abstract description 31
- 238000005406 washing Methods 0.000 claims abstract description 27
- 239000002253 acid Substances 0.000 claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 14
- 239000002105 nanoparticle Substances 0.000 claims abstract description 13
- 230000002308 calcification Effects 0.000 claims abstract description 12
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 11
- 239000010439 graphite Substances 0.000 claims abstract description 11
- 238000010000 carbonizing Methods 0.000 claims abstract description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- 238000005554 pickling Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 18
- 238000003763 carbonization Methods 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 11
- 229920001732 Lignosulfonate Polymers 0.000 claims description 10
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 229910001868 water Inorganic materials 0.000 claims description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 3
- 229910052925 anhydrite Inorganic materials 0.000 claims description 3
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 3
- OOCMUZJPDXYRFD-UHFFFAOYSA-L calcium;2-dodecylbenzenesulfonate Chemical compound [Ca+2].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O OOCMUZJPDXYRFD-UHFFFAOYSA-L 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000004146 energy storage Methods 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 239000002121 nanofiber Substances 0.000 description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 229920005610 lignin Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 229920005552 sodium lignosulfonate Polymers 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 2
- 238000001523 electrospinning Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- PQMFVUNERGGBPG-UHFFFAOYSA-N (6-bromopyridin-2-yl)hydrazine Chemical compound NNC1=CC=CC(Br)=N1 PQMFVUNERGGBPG-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000001674 calcium compounds Chemical class 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- ZPIRTVJRHUMMOI-UHFFFAOYSA-N octoxybenzene Chemical compound CCCCCCCCOC1=CC=CC=C1 ZPIRTVJRHUMMOI-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
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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
- D01F9/16—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate
- D01F9/17—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate from lignin
-
- 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
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
- D01F11/12—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with inorganic substances ; Intercalation
-
- 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
- D01F9/21—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
Abstract
The invention relates to the technical field of carbon nanofiber preparation, and provides a preparation method of carbon nanofibers with graphene structures on the surfaces, which comprises the following steps: 1) preparing polymer spinning solution added with calcification, and 2) preparing a carbon fiber precursor through electrostatic spinning; 3) pre-oxidizing and carbonizing to prepare carbon nanofiber with the surface coated with a graphite carbon layer and compounded with calcium sulfide nano particles; 4) and (3) washing or pickling the calcium sulfide composite carbon nanofiber to prepare the carbon nanofiber only with the graphene structure on the surface. The invention skillfully utilizes the catalytic action of the calcification through the calcification or CaSO-containing calcification3Carbon fibers made of polymers of the formula-R having on their surface calcium sulfide coated with a graphitic carbon layerAfter the calcium sulfide particles of the nano particles are removed by acid washing, the graphite carbon layer on the surface of the nano particles is reserved, so that the conductivity of the carbon fiber is increased; the prepared carbon nanofiber with the graphene structure on the surface can be applied to the fields of energy storage, catalysis, adsorption and the like, and is wide in application range.
Description
Technical Field
The invention relates to the technical field of carbon nanofiber preparation, in particular to a preparation method of carbon nanofiber with a graphene structure on the surface.
Background
The carbon nanofiber is a carbon fiber with a nanoscale, and has the advantages of excellent conductivity, good chemical stability, ultra-high specific surface area and the like, so that the carbon nanofiber has wide application in the fields of energy storage, catalysis, adsorption and the like.
Carbon nanofibers are produced by electrospinning, which generally comprises subjecting a high polymer solution to high-voltage electrospinning to obtain nanofibers, and then stabilizing and carbonizing the nanofibers to obtain carbon nanofibers. Among them, polyacrylonitrile is the most common precursor for preparing carbon nanofibers, and has the characteristics of high carbon content and good spinnability. However, polyacrylonitrile is a petroleum-based raw material, which is not only limited in reserves and expensive, but also causes pollution to the environment to a certain extent when petrochemical resources are exploited. In view of the above, there is a need to select an alternative precursor.
Lignin is a natural polymer which is inferior to cellulose in quantity, and is considered as a suitable raw material for preparing a carbon material because the molecular chain of lignin has a large number of benzene ring structures and the carbon content of the lignin exceeds 60%. And compared with lignin, the lignosulfonate has more sulfonate on the fatty carbon of the phenylpropyl alkyl structural unit, so that the lignosulfonate is easily soluble in water, and the post-treatment process is further simplified.
The invention discloses a method for preparing a lignin-based carbon fiber hydrogen storage material by an electrostatic spinning method (with the publication number being CN104947246A), wherein sodium lignosulfonate/polyacrylonitrile/nickel acetate/boric acid is used as a precursor spinning solution, and sodium lignosulfonate/polyacrylonitrile composite carbon fiber containing a Ni-B catalyst is prepared by subsequent heat treatment, wherein Ni-B plays a role in catalyzing graphitization. The invention discloses a method for preparing activated carbon nanofibers by taking sodium lignosulfonate as a precursor (the publication number is CN108707999A), wherein a certain amount of sodium lignosulfonate, polyvinyl alcohol and polyethylene glycol octyl phenyl ether are taken as precursor spinning solutions, and the activated carbon nanofibers with high specific surface area and high porosity are prepared after pre-oxidation and high-temperature carbonization. However, the graphene structure is not generated on the surface of the carbon fiber finally formed by the methods.
Disclosure of Invention
In view of the above problems in the prior art, the present invention provides a method for preparing a carbon nanofiber having a graphene structure on the surface thereof, in which a carbon fiber having a graphene structure is prepared by adding a calcification compound to a polymer precursor.
The invention adopts the following technical scheme:
a preparation method of carbon nanofibers with graphene structures on the surfaces comprises the following steps:
(1) preparing a carbon fiber precursor by electrostatic spinning:
a. preparing a spinning solution:
dissolving a spinning aid in a solvent, and fully stirring to obtain a spinning solution;
b. adding calcine or CaSO-containing spinning liquid3The polymer of the-R is fully stirred to obtain a precursor spinning solution;
c. injecting the precursor spinning solution into a needle tube, and preparing a carbon fiber precursor by utilizing electrostatic spinning;
(2) pre-oxidizing a carbon fiber precursor at the pre-oxidation temperature of 150-300 ℃ for 60-180 min;
(3) carbonizing the pre-oxidized carbon fiber precursor to prepare carbon nanofiber with the surface provided with calcium sulfide nano-particles coated by the graphite carbon layer;
(4) and washing or pickling the carbonized carbon fibers with water to prepare the carbon nanofibers with the graphene structures on the surfaces.
Further, the spinning aid is mixed with a calcification compound or CaSO3The mass ratio of the polymer of-R is 5:1 to 1: 5.
Further, the calcification is CaS, Ca (HSO)3)2、CaSO3Or CaSO4。
Further, the CaSO3The polymer of-R is a lignosulfonate or a phenyl or alkyl sulfonate of calcium dodecylbenzenesulfonate.
Further, the spinning aid is polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), polyethylene oxide (PEO), or Polyacrylonitrile (PAN).
Further, the mass ratio of the spinning aid to the solvent is 1: 10-1: 20; the solvent is H2O or DMF.
Further, the voltage of the electrostatic spinning is 15-25 kV, the receiving distance is 10-20 cm, and the injection speed is 0.2-1.0 mL/h.
Further, the pre-oxidation of the carbon fiber precursor is carried out by placing the carbon fiber precursor in a muffle furnace.
Further, the carbon fiber precursor after preoxidation is carbonized in a tubular furnace, inert gas is continuously introduced for protection, the carbonization temperature is 600-1800 ℃, and the carbonization time is 1-3 h.
Further, the inert gas is argon or nitrogen.
Further, in the step (4), if the acid washing is performed, the acid washing solution is a 0.1-1 mol/L diluted hydrochloric acid solution, the acid washing time is 2-24 hours, and the acid washing temperature is 30-60 ℃.
The invention has the beneficial effects that:
skillfully utilizes the catalytic action of the calcification through the calcification or the CaSO-containing calcification3The surface of the carbon fiber prepared by the polymer of the-R is provided with calcium sulfide nano particles coated by a graphite carbon layer, and after the calcium sulfide particles are removed by acid washing, the graphite carbon layer on the surface of the carbon fiber is reserved, so that the conductivity of the carbon fiber is increased; the prepared carbon nanofiber with the graphene structure on the surface can be applied to energy storage, catalysis and absorptionAnd the application range is wide.
Drawings
FIG. 1 is a scanning electron microscope and a high-resolution transmission electron microscope, wherein a is a scanning electron microscope of carbon nanofibers carbonized at 1400 ℃; b is a high-resolution transmission electron microscope image of the carbonized carbon nanofiber at 1400 ℃; c is a scanning electron microscope image of the carbon nanofiber after acid cleaning; d is a high-resolution transmission electron microscope image of the carbon nanofiber after acid cleaning;
FIG. 2 is a Raman diagram in which a is a Raman diagram of a carbon nanofiber after carbonization at 1400 ℃ and b is a Raman diagram of a carbon nanofiber after acid washing.
Detailed Description
The present invention will be described in detail with reference to the following examples:
a preparation method of carbon nanofibers with graphene structures on the surfaces comprises the following steps:
1) preparing a carbon fiber precursor by electrostatic spinning;
2) pre-oxidizing a carbon fiber precursor;
3) carbonizing the pre-oxidized carbon fiber precursor to prepare the carbon nanofiber with the graphite carbon layer-coated calcium sulfide nano-particles on the surface;
4) and washing or pickling the carbonized carbon fibers with water to prepare the carbon nanofibers with the graphene structures on the surfaces.
As one example thereof, specifically, the step 1) includes the steps of:
a. adding calcium compound or CaSO3Dissolving the polymer of the-R and the spinning aid in a solvent, and stirring for 4-8 hours to obtain a precursor spinning solution;
b. and injecting the precursor spinning solution into a needle tube, and preparing a carbon fiber precursor by utilizing electrostatic spinning.
Specifically, the solvent is water or DMF.
In particular, the spinning aid is mixed with a calcification or CaSO-containing3The mass ratio of the polymer of-R is 5:1 to 1: 5.
Specifically, the calcification is CaS, Ca (HSO)3)2、CaSO3Or CaSO4。
In particular, the CaSO-containing3The polymer of-R is a lignosulfonate or a phenyl or alkyl sulfonate of calcium dodecylbenzenesulfonate.
Specifically, the spinning aid is polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), polyethylene oxide (PEO), or Polyacrylonitrile (PAN).
Specifically, the mass ratio of the spinning aid to the solvent is 1: 10-1: 20.
Specifically, the voltage of the electrostatic spinning is 15-25 kV, the receiving distance is 10-20 cm, and the injection speed is 0.2-1.0 mL/h.
As one example thereof, specifically, the step 2) includes the steps of:
c. and placing the carbon fiber precursor in a muffle furnace for pre-oxidation.
Specifically, the pre-oxidation temperature is 150-300 ℃, and the pre-oxidation time is 60-180 min.
As one example thereof, specifically, the step 3) includes the steps of:
d. and placing the pre-oxidized carbon fiber precursor into a tubular furnace for carbonization, and continuously introducing inert gas for protection.
Specifically, the carbonization temperature is 600-1800 ℃, and the carbonization time is 1-3 h.
Specifically, the inert gas is argon or nitrogen.
Specifically, the sodium salt in the carbon fiber precursor is separated in a gas phase during carbonization, and calcium sulfide can be formed at 600 ℃ or above.
As one example, specifically, the step 4) includes the following steps:
e. and (3) washing or pickling the carbonized carbon fiber with water. If the acid washing is carried out, the acid washing solution is 0.1-1 mol/L of dilute hydrochloric acid solution, the acid washing time is 2-24 h, and the acid washing temperature is 30-60 ℃.
Example 1
The preparation method of the carbon nanofiber with the graphene structure on the surface comprises the following steps:
1) preparation of carbon fiber precursor by electrostatic spinning
a. Dissolving 0.7g of PVA in 10g of deionized water, and stirring at the constant temperature of 90 ℃ for 2h to obtain a colorless transparent solution;
b. adding 1.4g of lignosulfonate into the solution, and stirring at the constant temperature of 90 ℃ for 2 hours to obtain an electrostatic spinning precursor solution;
c. preparing a carbon fiber precursor by electrostatic spinning: carrying out electrostatic spinning under the conditions of voltage of 15kV, receiving distance of 15cm and advancing speed of 1.0mL/h, wherein the spinning time is 6 h.
2) Pre-oxidizing a carbon fiber precursor, namely putting the lignosulfonate precursor fiber prepared by the electrostatic spinning method into a muffle furnace, heating to 180 ℃ for pre-oxidizing treatment, wherein the pre-oxidizing time is 2 hours.
3) And (3) placing the preoxidized nano-fiber in a tubular furnace, carbonizing the nano-fiber under the protection of high-purity argon at the heating rate of 5 ℃/min at the carbonization temperature of 1200 ℃ for 2h, and cooling the nano-fiber to room temperature to obtain the carbon nano-fiber with the calcium sulfide nano-particles coated by the graphite carbon layer on the surface.
4) And (3) soaking the carbon nanofiber prepared in the step in 0.2mol/L hydrochloric acid solution for 6 hours at 50 ℃, and then washing the carbon nanofiber with deionized water until the solution is neutral, thereby preparing the carbon nanofiber with the graphene structure on the surface.
Example 2
The preparation method of the carbon nanofiber with the graphene structure on the surface comprises the following steps:
1) preparation of carbon fiber precursor by electrostatic spinning
a. Dissolving 0.7g of PVA in 10g of deionized water, and stirring at the constant temperature of 90 ℃ for 2h to obtain a colorless transparent solution;
b. and adding 1.75g of lignosulfonate into the solution, and stirring at the constant temperature of 90 ℃ for 3 hours to obtain an electrostatic spinning precursor solution.
c. Preparing a carbon fiber precursor by electrostatic spinning: carrying out electrostatic spinning under the conditions of voltage of 15kV, receiving distance of 15cm and advancing speed of 0.8mL/h, wherein the spinning time is 6 h.
2) Pre-oxidizing a carbon fiber precursor: putting the lignosulfonate precursor fiber prepared by the electrostatic spinning method into a muffle furnace, heating to 200 ℃ for pre-oxidation treatment, wherein the pre-oxidation time is 2 h.
3) And (3) placing the preoxidized nano-fiber in a tubular furnace, carbonizing the nano-fiber under the protection of high-purity argon at the heating rate of 5 ℃/min at the carbonization temperature of 1400 ℃ for 2h, and cooling the nano-fiber to room temperature to obtain the carbon nano-fiber with the calcium sulfide nano-particles coated by the graphite carbon layer on the surface.
4) And (3) soaking the carbon nanofiber prepared in the step in 0.2mol/L hydrochloric acid solution for 6 hours at 50 ℃, and then washing the carbon nanofiber with deionized water until the solution is neutral, thereby preparing the carbon nanofiber with the graphene structure on the surface.
And (3) observing the carbonized carbon nanofibers by using a scanning electron microscope (see fig. 1(a)) and a high-resolution transmission electron microscope (see fig. 1(b)), and observing the carbon nanofibers subjected to acid washing by using a scanning electron microscope (see fig. 1(c)) and a high-resolution transmission electron microscope (see fig. 1(d)), wherein the results show that calcium sulfide nanoparticles coated with a carbon layer are generated in situ on the fiber surfaces after carbonization, the graphene carbon layer structure on the surfaces of the particles subjected to acid washing is retained, and finally the carbon nanofibers with the graphene structures on the surfaces are prepared.
In order to further verify the obtained calcium sulfide nanoparticles coated by the carbon layer, the carbonized carbon nanofibers and the carbon nanofibers after the acid washing were subjected to raman characterization, and the results are shown in fig. 2, wherein the wave number is 1340cm-1，1600cm-1And 2700cm-1The peaks appearing nearby respectively correspond to a D band, a G band and a 2D band of carbon in the carbon nanofiber, and the appearance of the 2D peak also proves that a thin-layer graphene structure is generated on the surface of the carbon fiber, and the graphene structure is still retained after acid washing.
Example 3
The preparation method of the carbon nanofiber with the graphene structure on the surface comprises the following steps:
1) preparation of carbon fiber precursor by electrostatic spinning
a. Dissolving 1.0g of PVA in 10g of deionized water, and stirring at the constant temperature of 90 ℃ for 2 hours to obtain a colorless transparent solution;
b. 0.2g of Ca (HSO)3)2Adding the solution into the solution, and stirring the solution at a constant temperature of 90 ℃ for 4 hours to obtain an electrostatic spinning precursor solution.
c. Preparing a carbon fiber precursor by electrostatic spinning: carrying out electrostatic spinning under the conditions of voltage of 15kV, receiving distance of 15cm and advancing speed of 0.6mL/h, wherein the spinning time is 6 h.
2) Pre-oxidizing a carbon fiber precursor: putting the lignosulfonate precursor fiber prepared by the electrostatic spinning method into a muffle furnace, heating to 220 ℃ for pre-oxidation treatment, wherein the pre-oxidation time is 2 h.
3) And (3) placing the preoxidized nano-fiber in a tubular furnace, carbonizing the nano-fiber under the protection of high-purity argon at the heating rate of 5 ℃/min at the carbonization temperature of 1500 ℃ for 2h, and cooling the nano-fiber to room temperature to obtain the carbon nano-fiber with the calcium sulfide nano-particles coated by the graphite carbon layer on the surface.
4) And (3) soaking the carbon nanofiber prepared in the step in deionized water for 24 hours at 50 ℃, so as to prepare the carbon nanofiber with the graphene structure on the surface.
Example 4
The preparation method of the carbon nanofiber with the graphene structure on the surface comprises the following steps:
1) preparation of carbon fiber precursor by electrostatic spinning
a. Dissolving 0.8g of PAN in 10g of DMF, and stirring for 4 hours at room temperature to obtain a colorless transparent solution;
b. and adding 0.2g of CaS into the solution, and stirring at room temperature for 4 hours to obtain an electrostatic spinning precursor solution.
c. Preparing a carbon fiber precursor by electrostatic spinning: carrying out electrostatic spinning under the conditions of voltage of 15kV, receiving distance of 15cm and advancing speed of 0.4mL/h, wherein the spinning time is 6 h.
2) Pre-oxidizing a carbon fiber precursor: and (3) putting the precursor fiber prepared by the electrostatic spinning method into a muffle furnace, heating to 280 ℃ for pre-oxidation treatment, wherein the pre-oxidation time is 2 h.
3) And (3) placing the preoxidized nano-fiber in a tubular furnace, carbonizing the nano-fiber under the protection of high-purity argon at the heating rate of 5 ℃/min at the carbonization temperature of 1000 ℃ for 2h, and cooling the nano-fiber to room temperature to obtain the carbon nano-fiber with the calcium sulfide nano-particles coated by the graphite carbon layer on the surface.
4) And (3) soaking the carbon nanofiber prepared in the step in 0.2mol/L hydrochloric acid solution for 6 hours at 50 ℃, and then washing the carbon nanofiber with deionized water until the solution is neutral, thereby preparing the carbon nanofiber with the graphene structure on the surface.
It is to be understood that the above description is not intended to limit the present invention, and the present invention is not limited to the above examples, and those skilled in the art may make modifications, alterations, additions or substitutions within the spirit and scope of the present invention.
Claims (10)
1. A preparation method of carbon nanofibers with graphene structures on the surfaces is characterized by comprising the following steps:
(1) preparing a carbon fiber precursor by electrostatic spinning:
a. preparing a spinning solution:
dissolving a spinning aid in a solvent, and fully stirring to obtain a spinning solution;
b. adding calcine or CaSO-containing spinning liquid3The polymer of the-R is fully stirred to obtain a precursor spinning solution;
c. injecting the precursor spinning solution into a needle tube, and preparing a carbon fiber precursor by utilizing electrostatic spinning;
(2) pre-oxidizing a carbon fiber precursor at the pre-oxidation temperature of 150-300 ℃ for 60-180 min;
(3) carbonizing the pre-oxidized carbon fiber precursor to prepare carbon nanofiber with the surface provided with calcium sulfide nano-particles coated by the graphite carbon layer;
(4) and (3) washing or pickling the carbonized carbon fibers with water to prepare the carbon nanofibers with the graphene structures on the surfaces.
2. The method for preparing the carbon nanofiber with the graphene structure on the surface according to claim 1, wherein the spinning aid is mixed with a calcification compound or CaSO3The mass ratio of the polymer of-R is 5:1 to 1: 5.
3. The method according to claim 1 or 2, wherein the calcification is CaS or Ca (HSO)3)2、CaSO3Or CaSO4。
4. The method for preparing the carbon nanofiber with the graphene structure on the surface according to claim 1 or 2, wherein the CaSO3The polymer of-R is a lignosulfonate or a phenyl or alkyl sulfonate of calcium dodecylbenzenesulfonate.
5. The method for preparing the carbon nanofiber with the graphene structure on the surface according to claim 1, wherein the spinning aid is polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide or polyacrylonitrile.
6. The preparation method of the carbon nanofiber with the graphene structure on the surface according to claim 1 or 5, wherein the mass ratio of the spinning aid to the solvent is 1: 10-1: 20; the solvent is H2O or DMF.
7. The method for preparing the carbon nanofiber with the graphene structure on the surface according to claim 1, wherein the electrostatic spinning voltage is 15-25 kV, the receiving distance is 10-20 cm, and the injection speed is 0.2-1.0 mL/h.
8. The method for preparing the carbon nanofiber with the graphene structure on the surface according to claim 1, wherein the pre-oxidation of the carbon fiber precursor is carried out by placing the carbon fiber precursor in a muffle furnace.
9. The method for preparing the carbon nanofiber with the graphene structure on the surface according to claim 1, wherein the carbonization of the pre-oxidized carbon fiber precursor is carried out by placing the pre-oxidized carbon fiber precursor in a tube furnace, and continuously introducing inert gas for protection, wherein the carbonization temperature is 600-1800 ℃ and the carbonization time is 1-3 h.
10. The method for preparing the carbon nanofiber with the graphene structure on the surface according to claim 1, wherein in the step (4), if the carbon nanofiber is subjected to acid washing, the acid washing solution is a 0.1-1 mol/L diluted hydrochloric acid solution, the acid washing time is 2-24 hours, and the acid washing temperature is 30-60 ℃.
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