CN114974924B - Preparation method of carbon nanofiber with full solid structure - Google Patents
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- 239000002134 carbon nanofiber Substances 0.000 title claims abstract description 75
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000007787 solid Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 18
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 18
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 16
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 13
- 238000009987 spinning Methods 0.000 claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- 238000003763 carbonization Methods 0.000 claims abstract description 8
- 230000003647 oxidation Effects 0.000 claims abstract description 8
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 6
- 150000002815 nickel Chemical class 0.000 claims abstract description 6
- 238000000197 pyrolysis Methods 0.000 claims abstract description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 3
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 claims abstract 3
- 238000010438 heat treatment Methods 0.000 claims description 20
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 12
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical group [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 11
- 229940078494 nickel acetate Drugs 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 238000007711 solidification Methods 0.000 claims description 2
- 230000008023 solidification Effects 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 27
- 239000000047 product Substances 0.000 description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 239000002041 carbon nanotube Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 229910021393 carbon nanotube Inorganic materials 0.000 description 9
- 230000008569 process Effects 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
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- 230000009286 beneficial effect Effects 0.000 description 2
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- 238000001523 electrospinning Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
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- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- -1 i.e. Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
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- 238000001000 micrograph Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/40—Fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to a preparation method of carbon nanofiber with a full solid structure, which is characterized by comprising the following steps of: the preparation method comprises the steps of dissolving polyacrylonitrile PAN and polyvinylpyrrolidone PVP in dimethylformamide DMF, stirring to form a mixed solution, adding nickel salt and magnesium salt, continuously stirring to form a spinning solution, carrying out electrostatic spinning, solidifying a spinning product in a nitrogen atmosphere, carrying out pre-oxidation treatment in air, and finally carrying out pyrolysis carbonization. The preparation method can prepare the composite material composed of two carbon nanofibers with different structures and large diameter difference, so as to remarkably improve the electrochemical performance of the material.
Description
The invention relates to a carbon nanofiber composite material with a three-dimensional hierarchical structure and a preparation method thereof, which are classified applications of patent application No. 202110608762. X.
Technical Field
The invention relates to the technical field of preparation of carbon nanofiber materials, in particular to a preparation method of carbon nanofibers with full solid structures.
Background
Among various types of supercapacitors, electric double layer capacitors play an important role in commercialization because of their low cost and good mechanical stability. The energy storage depends on the electrode material, which should have high conductivity, large ion accessibility, specific surface area and proper pore size distribution. As the electrode material, a carbon-based material having advantages of high specific surface area, light weight, low cost, and the like is generally used. The capacitance of the carbonaceous material is increased by N doping in the carbon nanotube material, and besides the double-layer capacitance provided by the porosity, the N doping can also provide active sites, and pseudo capacitance is provided by oxidation-reduction reaction, so that the carbon material has excellent electrochemical performance as a capacitor. However, because the resistance of the carbonaceous material is too large, high capacitance or high power still cannot be well provided, and the mechanical property of the carbon nanotube is poor, so that the carbon nanotube is easy to break in the use process, and the technical problems of performance attenuation, sharp reduction of service life and the like are solved.
Disclosure of Invention
The invention aims to provide a preparation method of carbon nanofibers with full solid structures, which can prepare a composite material composed of two carbon nanofibers with different structures and large diameter difference, so as to remarkably improve the electrochemical performance of the material.
The aim of the invention is realized by the following technical scheme:
a preparation method of carbon nanofiber with a full solid structure is characterized by comprising the following steps: dissolving Polyacrylonitrile (PAN) and polyvinylpyrrolidone (PVP) in Dimethylformamide (DMF), stirring to form a mixed solution, adding nickel salt and magnesium salt, continuously stirring to form a spinning solution, carrying out electrostatic spinning, solidifying a spinning product in a nitrogen atmosphere, carrying out pre-oxidation treatment in air, and finally carrying out pyrolysis carbonization; the solidification is that the electrostatic spinning product is placed in a tube furnace, and N is introduced into the tube furnace 2 Heating to 260-270 ℃ at a speed of 1-2 ℃/min, preserving heat for 2-3 hours, and cooling to room temperature; the pre-oxidation is to introduce air into a tube furnace, raise the temperature to 180-190 ℃ at 1-1.5 ℃/min, and keep the temperature for 50-70 min; the mass ratio of the PAN to the PVP to the DMF is preferably 3:1:21.4, and stirring is carried out for 1-2 hours at 150-250 rpm; the nickel salt is nickel acetate, the magnesium salt is magnesium nitrate hexahydrate, the mass ratio of the nickel acetate to the magnesium nitrate hexahydrate is 1:1, and the mass ratio of the total sum to the mixed solution is preferably 1:1.5875; the carbon nanofiber with the full solid structure consists of fine solid carbon nanofibers with the diameter of about 10nm and coarse solid carbon nanofibers with the diameter of 80-100 nm and branch structures, wherein the fine solid carbon nanofibers grow on the surfaces of the coarse carbon nanofibers and are communicated with adjacent coarse solid carbon nanofibers.
Carbon nanofibers are carbon fibers with nanoscale, and are classified into solid Carbon Nanofibers (CNFs) and hollow carbon nanofibers, i.e., carbon Nanotubes (CNTs), according to their structures, whereas carbon nanotubes have excellent electrochemical properties, but due to their hollow structures, CNTs prepared by electrospinning have poor mechanical properties, and are easily broken when impacted by external forces, resulting in attenuation of their electrochemical properties and poor stability. Thus, we need to prepare carbon nanofiber CNFs of full solid structure. According to the invention, the structural consistency of the carbon nanofibers with smaller diameters and the carbon nanofibers with larger diameters is kept, so that the carbon nanofibers with larger diameters have excellent performance stability, secondly, the branched structures of the carbon nanofibers with larger diameters provide more channels for electron transmission, the electron transmission efficiency is remarkably improved, thirdly, the carbon nanofibers with smaller diameters provide larger specific surface areas for materials, the specific capacitance value of the carbon nanofibers with smaller diameters is increased, and different binding sites are provided for doping nitrogen together with the carbon nanotubes with larger diameters, so that a very small amount of nitrogen doping introduces more doping form contents which are beneficial to improving electrochemical performance, and finally, the carbon nanofibers with larger diameters adjacent to each other are communicated through the carbon nanofibers with smaller diameters, the impedance of the materials is reduced, the conductivity of the materials is improved, and finally, the carbon nanofiber composite material with excellent electrochemical performance is obtained. Meanwhile, the nickel salt and the magnesium salt are adopted, PVP plays a role of a template in a system, metal ions are effectively dispersed in a spinning process, two metal ions are promoted to generate Ni/MgO which is a composite catalyst with smaller particle size and uniform dispersion in a high-temperature curing process, the Ni/MgO is effectively adsorbed on the surface of a large-diameter carbon nanofiber which is generated, on one hand, the catalyst is influenced by the airflow of a carbon source precursor in the curing process, the activation energy of a crystal face of the catalyst is changed, the growth direction of the carbon nanofiber is changed, a branched structure is generated, on the other hand, the composite catalyst formed by two metals is prevented from being used as a catalyst in a high-temperature curing process, the problem of carbon deposition caused by the adoption of single metal nickel is solved, the dissociation of a carbon source is promoted, on the other hand, the polymer molecular chain is naturally curled to generate physical shrinkage in the high-temperature curing process, the polymer is cyclized to form chemical shrinkage in the curing process, and the fiber adhesion aggregation is restrained at a lower temperature, and the excessive oxidization is prevented, so that the problem of structural rearrangement is solved, the diameter distribution is uneven in the high-temperature carbonization process, and the two carbon nanofibers with extremely small diameter and solid carbon nanofibers with extremely large diameters are finally formed.
As a further optimization, ar and NH are introduced into a tubular furnace for pyrolysis carbonization 3 Heating to 820-860 ℃, preserving heat for 50-80 min, stopping introducing NH 3 Cooled to room temperature under Ar protection and the product was collected.
As a further optimization, ar and NH are as described above 3 The air flow ratio of (2) was 5:1, and the total air flow was 600mm 3 /min。
As a further optimization, after the carbonization is finished, the product is washed by 4-5 mol of hydrochloric acid solution and deionized water in sequence, and then vacuum drying is carried out at 80 ℃.
The preparation method of the carbon nanofiber with the full solid structure is characterized by comprising the following steps of:
(1) Dissolving Polyacrylonitrile (PAN) and polyvinylpyrrolidone (PVP) in Dimethylformamide (DMF), and stirring at 150-250 rpm for 1-2 hours at normal temperature to form a mixed solution, wherein the mass ratio of the PAN to the PVP to the DMF is 3:1:20-22; adding nickel acetate and magnesium nitrate hexahydrate into the mixed solution according to the mass ratio of 1:1, and continuously stirring for 1h, wherein the mass ratio of the sum of the nickel acetate and the magnesium nitrate hexahydrate to the mixed solution is 1:1.5-1.625;
(2) Carrying out electrostatic spinning at room temperature at a speed of 0.1-0.2 mm/min under the voltage of 10-30 KV;
(3) Placing the electrostatic spinning product in a tube furnace, and introducing N into the tube furnace 2 Heating to 260-270 ℃ at a speed of 1-2 ℃/min, preserving heat for 2-3 hours, and cooling to room temperature;
(4) Introducing air into the tube furnace, heating to 180-190 ℃ at 1-1.5 ℃/min, and preserving heat for 50-70 min;
(5) Ar and NH were introduced into a tube furnace 3 Is 600mm in total gas flow 3 /min，Heating to 820-860 ℃, preserving heat for 50-80 min, and stopping introducing NH 3 Cooling to room temperature under Ar protection, collecting a product, washing the product with 4-5 mol of hydrochloric acid solution and deionized water in sequence, and then vacuum drying at 80 ℃, wherein Ar and NH 3 The air flow ratio of (2) was 5:1.
The invention has the following technical effects:
the invention provides a preparation method of carbon nano fibers with a full solid structure, which is used for preparing a composite material composed of carbon nano fibers with two different structures and large diameter difference, wherein the carbon nano fibers with the two solid structures have large diameter difference, the two diameters are distributed uniformly and have excellent structural stability, the composite material has large specific surface area, large and abundant electronic channels and a large number of active centers which are beneficial to improving electrochemical performance, the material has low internal impedance, excellent conductivity and capacitance, the capacitance is 575F/g, the cyclic discharge is 50000 times, the capacitance is still more than 94 percent of the initial value, and the composite material has excellent cyclic stability.
Drawings
Fig. 1: the structure of the carbon nanofiber with the full solid structure prepared by the invention is schematically shown.
Fig. 2: the scanning electron microscope image of the carbon nanofiber with the full solid structure prepared by the invention.
Fig. 3: x-ray diffraction pattern of carbon nanofiber with full solid structure prepared by the invention.
Fig. 4: energy density-power density curve graph of carbon nanofiber with full solid structure prepared by the invention.
Fig. 5: the carbon nanofiber with the full solid structure prepared by the invention circulates for more than 50000 times and has the capacity retention rate.
Fig. 6: performance comparison graph of carbon nanofiber with full solid structure prepared by the invention and carbon nanofiber material with single structure prepared by comparative example 1.
Detailed Description
The present invention is described in detail below by way of examples, which are necessary to be pointed out herein for further illustration of the invention and are not to be construed as limiting the scope of the invention, since numerous insubstantial modifications and adaptations of the invention will be to those skilled in the art in light of the foregoing disclosure.
Example 1
The preparation method of the carbon nanofiber with the full solid structure comprises the following steps:
(1) 1.5g of PAN and 0.5g of PVP are dissolved in 10g of DMF and stirred at 150rpm for 2 hours at normal temperature to form a mixed solution, 4g of nickel acetate and 4g of magnesium nitrate hexahydrate are added into the mixed solution and stirring is continued for 1 hour;
(2) Electrostatic spinning at room temperature at a voltage of 10KV and a speed of 0.2 mm/min;
(3) Placing the electrostatic spinning product in a tube furnace, and introducing N into the tube furnace 2 Heating to 270 ℃ at a speed of 2 ℃/min, preserving heat for 2 hours, and cooling to room temperature;
(4) Introducing air into the tube furnace, heating to 190 ℃ at a speed of 1 ℃/min, and preserving heat for 50min;
(5) Ar and NH were introduced into a tube furnace 3 Is 600mm in total gas flow 3 Heating to 820 ℃, preserving heat for 80min, stopping introducing NH 3 Cooling to room temperature under Ar protection, collecting the product, washing the product with 5mol hydrochloric acid solution and deionized water in sequence, and vacuum drying at 80deg.C, wherein Ar and NH 3 The air flow ratio of (2) was 5:1.
Example 2
The preparation method of the carbon nanofiber with the full solid structure comprises the following steps:
(1) 0.75g PAN and 0.25g PVP are dissolved in 5.5g DMF, and stirred at 250rpm for 1h at normal temperature to form a mixed solution, 2g nickel acetate and 2g magnesium nitrate hexahydrate are added into the mixed solution, and stirring is continued for 1h;
(2) Electrostatic spinning at room temperature at a voltage of 30KV and a speed of 0.15 mm/min;
(3) Placing the electrostatic spinning product in a tube furnace, and introducing N into the tube furnace 2 Heating to 260 ℃ at a speed of 1 ℃/min, preserving heat for 3 hours, and cooling to room temperature;
(4) Introducing air into the tube furnace, heating to 180 ℃ at a speed of 1.5 ℃/min, and preserving heat for 70min;
(5) Ar and NH were introduced into a tube furnace 3 Is 600mm in total gas flow 3 Heating to 860 ℃, preserving heat for 50min, stopping introducing NH 3 Cooling to room temperature under Ar protection, collecting a product, washing the product with 4-5 mol of hydrochloric acid solution and deionized water in sequence, and then vacuum drying at 80 ℃, wherein Ar and NH 3 The air flow ratio of (2) was 5:1.
Example 3
The preparation method of the carbon nanofiber with the full solid structure comprises the following steps:
(1) 0.75g PAN and 0.25g PVP are dissolved in 5.35g DMF, and stirred at 200rpm for 1.5 hours at normal temperature to form a mixed solution, 2g nickel acetate and 2g magnesium nitrate hexahydrate are added into the mixed solution, and stirring is continued for 1 hour;
(2) Electrostatic spinning at room temperature at a voltage of 20KV and a speed of 0.1 mm/min;
(3) Placing the electrostatic spinning product in a tube furnace, and introducing N into the tube furnace 2 Heating to 265 ℃ at a speed of 1.5 ℃/min, preserving heat for 2.5 hours, and cooling to room temperature;
(4) Introducing air into the tube furnace, heating to 180 ℃ at a speed of 1 ℃/min, and preserving heat for 60min;
(5) Ar and NH were introduced into a tube furnace 3 Is 600mm in total gas flow 3 Heating to 850 deg.C, maintaining for 60min, and stopping introducing NH 3 Cooling to room temperature under Ar protection, collecting the product, washing the product with 4.5mol hydrochloric acid solution and deionized water in sequence, and vacuum drying at 80deg.C, wherein Ar and NH 3 The air flow ratio of (2) was 5:1.
The carbon nanofiber with the full solid structure prepared by the invention consists of solid carbon nanofibers with the diameter of about 10nm and solid carbon nanofibers with the diameter of 80-100 nm, wherein thinner carbon nanofibers are longer than the surfaces of thicker carbon nanofibers, and adjacent thicker carbon nanofibers are communicated, as shown in figures 1 and 2. After 5000 times of cyclic charge and discharge, the capacitance retention rate is basically not attenuated, after 10000 times of charge and discharge cycles, the capacitance retention rate is still kept at more than 96% of an initial value, and after 50000 times of cyclic charge and discharge, the capacitance retention rate is still kept at more than 94% of the initial value, so that the carbon nanofiber with the full solid structure prepared by the method has excellent cyclic stability.
Comparative example 1
Unlike example 3, PVP was not added to the spinning solution, and the temperature was directly raised to 250℃at 1℃per minute after electrospinning to perform pre-oxidation for 1 hour. The other steps were the same as in example 3.
The product prepared in comparative example 1 has no hierarchical structure, only a single structure of large-diameter carbon nanofibers having a branched structure exists, and the specific capacitance and the conductive properties are poor.
Comparative example 2
In this comparative example, unlike example 3, only nickel acetate was added as the metal salt in the preparation of the spinning solution, and pre-oxidation was performed for 1 hour by directly heating to 250 c at 1 c/min after the spinning was completed. The other steps were the same as in example 3.
In the product prepared in comparative example 1, the final product in the large-diameter carbon nanofiber has no branched structure, hollow Carbon Nanotubes (CNTs) are grown on the surface of the product instead of Carbon Nanofibers (CNFs) with solid structures, the diameter of the large-diameter carbon nanotube is about 200-300 nm, the diameter of the small-diameter carbon nanotube is 80-100 nm, the diameter difference is small, the diameter distribution range is large, the uniformity is poor, and the structure and the performance stability of the product are poor.
Comparative example 3
After electrostatic spinning was performed with the same spinning solution as in example 3, the temperature was directly raised to 250℃at 1℃per minute without using a curing treatment, and pre-oxidation was performed for 1 hour. The other steps were the same as in example 3.
The carbon nanofibers with two diameters in the product prepared in the comparative example 3 have poor uniformity in diameter distribution, the diameter of the carbon nanotube with a larger diameter is about 180-250 nm, the diameter of the carbon nanofiber with a smaller diameter is 50-80 nm, and the diameter of the carbon nanofiber with a smaller diameter is slightly reduced compared with that of the carbon nanofiber in the comparative example 1, but the overall diameter distribution range is still large, the overall specific surface area of the composite material is reduced, and the capacitance is reduced. The products prepared in example 3 and comparative example 3 were used for capacitor active electrode materials, and as shown in FIG. 6, the specific capacitances of example 3 and comparative example 3 of the present invention were 575F/g and 302F/g, respectively, at a current density of 1A/g.
Claims (5)
1. A preparation method of carbon nanofiber with a full solid structure is characterized by comprising the following steps: dissolving polyacrylonitrile PAN and polyvinylpyrrolidone PVP in dimethylformamide DMF, stirring to form a mixed solution, then adding nickel salt and magnesium salt, continuously stirring to form a spinning solution, carrying out electrostatic spinning, solidifying a spinning product in a nitrogen atmosphere, then carrying out pre-oxidation treatment in air, and finally carrying out pyrolysis carbonization; the solidification is that the electrostatic spinning product is placed in a tube furnace, and N is introduced into the tube furnace 2 Heating to 260-270 ℃ at a speed of 1-2 ℃/min, preserving heat for 2-3 hours, and cooling to room temperature; the pre-oxidation is to introduce air into a tube furnace, raise the temperature to 180-190 ℃ at 1-1.5 ℃/min, and keep the temperature for 50-70 min; the mass ratio of the PAN to the PVP to the DMF is 3:1:21.4, and stirring is carried out for 1-2 h at 150-250 rpm; the nickel salt is nickel acetate, the magnesium salt is magnesium nitrate hexahydrate, the mass ratio of the nickel acetate to the magnesium nitrate hexahydrate is 1:1, and the mass ratio of the total sum to the mixed solution is 1:1.5875; the carbon nanofiber with the full solid structure consists of fine solid carbon nanofibers with the diameter of about 10nm and coarse solid carbon nanofibers with the diameter of 80-100 nm and branch structures, wherein the fine solid carbon nanofibers grow on the surfaces of the coarse carbon nanofibers and are communicated with adjacent coarse solid carbon nanofibers.
2. The method for preparing the carbon nanofiber with the full solid structure according to claim 1, wherein: the pyrolysis carbonization is to introduce Ar and NH into a tube furnace 3 Heating to 820-860 ℃, preserving heat for 50-80 min, stopping introducing NH 3 Cooled to room temperature under Ar protection and the product was collected.
3. A method for preparing the carbon nanofiber with the full solid structure according to claim 2, wherein: ar and NH 3 The air flow ratio of (2) was 5:1, and the total air flow was 600mm 3 /min。
4. A method for producing a carbon nanofiber of an entirely solid structure according to any one of claims 1 to 3, characterized in that: and washing the product with 4-5 mol of hydrochloric acid solution and deionized water in sequence after carbonization is finished, and then drying in vacuum at 80 ℃.
5. The preparation method of the carbon nanofiber with the full solid structure is characterized by comprising the following steps of:
(1) 1.5g of polyacrylonitrile PAN and 0.5g of polyvinylpyrrolidone PVP are dissolved in 10g of dimethylformamide DMF and stirred at 150rpm for 2 hours at normal temperature to form a mixed solution; adding 4g of nickel acetate and 4g of magnesium nitrate hexahydrate into the mixed solution, and continuously stirring for 1h;
(2) Electrostatic spinning at room temperature at a voltage of 10KV and a speed of 0.2 mm/min;
(3) Placing the electrostatic spinning product in a tube furnace, and introducing N into the tube furnace 2 Heating to 270 ℃ at a speed of 2 ℃/min, preserving heat for 2 hours, and cooling to room temperature;
(4) Introducing air into the tube furnace, heating to 190 ℃ at a speed of 1 ℃/min, and preserving heat for 50min;
(5) Ar and NH were introduced into a tube furnace 3 Is 600mm in total gas flow 3 Heating to 820 ℃, preserving heat for 80min, stopping introducing NH 3 Cooling to room temperature under Ar protection, collecting the product, washing the product with 5mol hydrochloric acid solution and deionized water in sequence, and vacuum drying at 80deg.C, wherein Ar and NH 3 The air flow ratio of (2) was 5:1.
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