CN113363083B - Carbon nanofiber composite material with three-dimensional hierarchical structure and preparation method thereof - Google Patents

Carbon nanofiber composite material with three-dimensional hierarchical structure and preparation method thereof Download PDF

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CN113363083B
CN113363083B CN202110608762.XA CN202110608762A CN113363083B CN 113363083 B CN113363083 B CN 113363083B CN 202110608762 A CN202110608762 A CN 202110608762A CN 113363083 B CN113363083 B CN 113363083B
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composite material
hierarchical structure
carbon nanofiber
nanofiber composite
carbon nanofibers
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CN113363083A (en
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周永生
靳盼
杨娇娇
秦宇
陈君华
郭雨
丁志杰
王彦平
牛斐洱
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Anhui University of Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • 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
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

A carbon nanofiber composite material of a three-dimensional hierarchical structure, characterized in that: the carbon nanofiber is composed of fine solid carbon nanofibers with the diameter of about 10nm and coarse solid carbon nanofibers with the diameter of 80-100 nm and a branched structure, wherein the fine solid carbon nanofibers grow on the surfaces of the coarse carbon nanofibers and are connected with adjacent coarse solid carbon nanofibers. The composite material has large specific surface area, large and abundant electronic channels, a large number of active centers which are beneficial to improving the electrochemical performance, low internal impedance of the material, and excellent conductive performance and capacitance, wherein the capacitance is 575F/g, the capacitance is still kept to be more than 94% of the initial value after 50000 times of cyclic discharge. The carbon nanofibers with two solid structures of the nitrogen-doped hierarchical structure carbon nanofibers prepared by the method have large diameter difference and excellent distribution uniformity of the two diameters.

Description

Carbon nanofiber composite material with three-dimensional hierarchical structure and preparation method thereof
Technical Field
The invention relates to the technical field of carbon nanofibers, in particular to a carbon nanofiber composite material with a three-dimensional hierarchical structure and a preparation method thereof.
Background
Super capacitors have received much attention due to their advantages of high power density, long cycle stability, and fast charge and discharge rates. Among various types of supercapacitors, electric double layer capacitors play an important role in commercialization because of their low cost and good mechanical stability. When a potential difference is applied between the electrodes, the electric double layer capacitor stores charge and releases energy by reversibly adsorbing ions in the electrolyte. Therefore, the energy storage depends on the electrode material, which has high conductivity, large ion accessible specific surface area and appropriate pore size distribution. An electrode material generally used for an electric double layer capacitor is a carbon-based material, and has advantages of high specific surface area, light weight, low cost, and the like.
The capacitance of the carbon material is increased by N doping in the carbon nanotube material, the N doping can provide active sites in addition to double-layer capacitance provided by porosity, pseudo capacitance is provided by redox reaction, and therefore the carbon material has excellent electrochemical performance as a capacitor. However, since the carbonaceous material itself has too large resistance, it still cannot provide high capacitance or high power well, and the carbon nanotubes have poor mechanical properties, and are easily damaged during use, resulting in performance degradation and greatly reduced service life.
Disclosure of Invention
In view of the above technical problems, the present invention aims to provide a carbon nanofiber composite material having a three-dimensional hierarchical structure. The composite material is formed by two carbon nanofibers with different structures and large diameter difference, so that the electrochemical performance of the material is remarkably improved.
The invention also aims to provide a preparation method of the carbon nanofiber composite material with the three-dimensional hierarchical structure. The method effectively reduces the self resistance of the carbon nano tube and improves the capacitance and the power.
The purpose of the invention is realized by the following technical scheme:
a carbon nanofiber composite material of a three-dimensional hierarchical structure, characterized in that: the carbon nanofiber is composed of fine solid carbon nanofibers with the diameter of about 10nm and coarse solid carbon nanofibers with the diameter of 80-100 nm and a branched structure, wherein the fine solid carbon nanofibers grow on the surfaces of the coarse carbon nanofibers and are connected with adjacent coarse solid carbon nanofibers.
The invention is composed of the solid carbon nanofiber with smaller diameter and the solid carbon nanofiber with larger diameter, keeps the structural consistency and ensures that the performance stability is excellent, secondly, the branched structure of the carbon nano fiber with larger diameter provides more channels for electron transmission, which obviously improves the electron transmission efficiency, thirdly, the carbon nano fiber with smaller diameter provides larger specific surface area for the material, increases the specific capacitance value, and provides different binding sites for nitrogen doping together with the carbon nanotubes with larger diameter, so that a very small amount of nitrogen doping introduces more content of doping forms which are beneficial to improving the electrochemical performance, and finally, the carbon nanofiber composite material with excellent electrochemical performance is finally obtained by communicating the carbon nanofibers with smaller diameters with the carbon nanofibers with adjacent large-diameter branch structures, so that the impedance of the material is reduced, and the conductivity of the material is improved.
The preparation method of the carbon nanofiber composite material with the three-dimensional hierarchical structure is characterized by comprising the following steps of: dissolving Polyacrylonitrile (PAN) and polyvinylpyrrolidone (PVP) in Dimethylformamide (DMF), stirring to form a mixed solution, adding nickel salt and magnesium salt to form a spinning solution, continuously stirring to form a spinning solution, carrying out electrostatic spinning, carrying out solidification treatment on a spinning product in a nitrogen gas component, carrying out preoxidation treatment in air, and finally carrying out pyrolysis carbonization.
The carbon nanofibers are carbon fibers with nanoscale, and are divided into solid Carbon Nanofibers (CNFs) and hollow carbon nanofibers, namely Carbon Nanotubes (CNTs), according to the structure of the carbon fibers, and although the carbon nanotubes have excellent electrochemical properties, due to the hollow structure of the carbon nanotubes, the CNTs prepared by electrostatic spinning have poor mechanical properties, are easily broken when being impacted by external force, and thus have poor electrochemical properties and stability. Therefore, we need to prepare carbon nanofiber CNFs with an all solid structure.
Further, the above-mentioned solidification is that the electrostatic spinning product is placed in a tube furnace, and N is introduced into the tube furnace2Heating to 260-270 ℃ at the speed of 1-2 ℃/min, preserving the heat for 2-3 h, and cooling to room temperature.
Further, the pre-oxidation is to introduce air into the tubular furnace, heat the tubular furnace to 180-190 ℃ at a speed of 1-1.5 ℃/min, and keep the temperature for 50-70 min.
The invention adopts nickel salt, magnesium salt and PVP to play a template role in a system, effectively disperses metal ions in the spinning process, promotes the two metal ions to generate composite catalyst Ni/MgO with smaller particle size and uniform dispersion in the high-temperature curing process, and effectively adsorbs the composite catalyst Ni/MgO on the surface of the generated carbon nano fiber with large diameter, on one hand, the catalyst is influenced by carbon source precursor airflow in the curing process, changes the crystal face activation energy of the catalyst, and changes the growth direction of the carbon nano fiber so as to generate a branched structure, on the other hand, the composite catalyst formed by the two metals overcomes the carbon deposition problem when single metal nickel is adopted as the catalyst in the high-temperature curing process, promotes the carbon source to be dissociated, on the other hand, the high-temperature curing enables the polymer molecular chain to naturally curl to generate physical shrinkage, and the polymer to cyclize to form chemical shrinkage in the curing process, and then, by pre-oxidation treatment, fiber adhesion and aggregation are inhibited at a lower temperature, and excessive oxidation is prevented, so that the problem of uneven diameter distribution caused by structural rearrangement in the high-temperature carbonization process is solved, solid carbon nanofibers with extremely small diameters and good uniformity are generated, and finally two kinds of all-solid carbon nanofibers CNFs with extremely large diameter difference are formed.
Further, the mass ratio of the PAN to the PVP to the DMF is 3:1: 20-22, and the mixture is stirred at 150-250 rpm for 1-2 hours.
Further, 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 to the mixed solution is 1: 1.5-1.625.
Preferably, the mass ratio of the PAN, the PVP and the DMF is 3:1:21.4, and the mass ratio of the total mass of the nickel acetate and the magnesium nitrate hexahydrate to the mixed solution is 1: 1.5875.
Go toStep, the pyrolysis carbonization is to introduce Ar and NH into a tubular furnace3Heating the mixed gas to 820-860 ℃, preserving the temperature for 50-80 min, and stopping introducing NH3And cooling to room temperature under the protection of Ar, and collecting the product.
Further, Ar and NH3The ratio of the gas flow rates of (1) to (5) and the total gas flow rate of 600mm3/min。
And after carbonization, washing the product with 4-5 mol of hydrochloric acid solution and deionized water in sequence, and then drying in vacuum at 80 ℃.
Most specifically, the preparation method of the carbon nanofiber composite material with the three-dimensional hierarchical structure is characterized by comprising the following steps of:
step (I): electrostatic spinning
(1) Dissolving Polyacrylonitrile (PAN) and polyvinylpyrrolidone (PVP) in Dimethylformamide (DMF), stirring at the normal temperature at 150-250 rpm for 1-2 h to form a mixed solution, wherein the mass ratio of PAN to PVP to 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 1 hour, wherein the mass ratio of the total of the nickel acetate and the magnesium nitrate hexahydrate to the mixed solution is 1: 1.5-1.625;
(2) electrostatic spinning at the room temperature at the speed of 0.1-0.2 mm/min under the voltage of 10-30 KV;
step (II): curing treatment
Placing the electrostatic spinning product in a tubular furnace, and introducing N into the tubular furnace2Heating to 260-270 ℃ at the speed of 1-2 ℃/min, preserving the heat for 2-3 h, and cooling to room temperature;
step (three): low temperature pre-oxidation
Introducing air into the tubular furnace, heating to 180-190 ℃ at a speed of 1-1.5 ℃/min, and preserving heat for 50-70 min;
step (IV): pyrolysis carbonization
Ar and NH are introduced into the tube furnace3The total gas flow of the mixed gas of (2) is 600mm3Heating to 820-860 deg.C for 50-80 min, and stopping NH introduction3Cooling to room temperature under the protection of Ar, collecting a product, and sequentially using 4-5 mol of hydrochloric acid solution and deionized waterWashed and then dried under vacuum at 80 deg.C, wherein Ar and NH3The air flow ratio of (2) is 5: 1.
The invention has the following technical effects:
the nitrogen-doped three-dimensional hierarchical carbon nanofiber composite material has the advantages of large specific surface area, large and abundant electronic channels, a large number of active centers beneficial to improving electrochemical performance, low internal impedance of the material, excellent conductivity and capacitance, capacity of 575F/g, capacity of 50000 times of cyclic discharge, capacity of still more than 94% of the initial value, and excellent cyclic stability; the carbon nanofibers with two solid structures of the nitrogen-doped hierarchical structure carbon nanofibers prepared by the method have large diameter difference, excellent distribution uniformity of the two diameters and excellent structural stability.
Drawings
FIG. 1: the structure schematic diagram of the three-dimensional hierarchical carbon nanofiber composite material prepared by the invention.
FIG. 2: the scanning electron microscope image of the three-dimensional grading carbon nanofiber composite material prepared by the invention.
FIG. 3: the X-ray diffraction pattern of the three-dimensional grading carbon nanofiber composite material prepared by the invention.
FIG. 4: the energy density-power density curve diagram of the three-dimensional grading carbon nanofiber composite material prepared by the invention.
FIG. 5: the capacitance retention rate of the three-dimensional grading carbon nanofiber composite material prepared by the invention is circulated for more than 50000 times.
FIG. 6: the performance comparison graph of the three-dimensional hierarchical carbon nanofiber composite material prepared by the invention and the single-structure carbon nanofiber material prepared by the comparative example 1 is shown.
Detailed Description
The present invention is described in detail below by way of examples, it should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and those skilled in the art can make some insubstantial modifications and adaptations of the present invention based on the above-mentioned disclosure.
Example 1
A preparation method of a carbon nanofiber composite material with a three-dimensional hierarchical structure comprises the following steps:
step (I): electrostatic spinning
(1) Dissolving 1.5g of PAN and 0.5g of PVP in 10g of DMF, stirring at the normal temperature at 150rpm for 2 hours to form a mixed solution, adding 4g of nickel acetate and 4g of magnesium nitrate hexahydrate into the mixed solution, and continuing stirring for 1 hour;
(2) electrostatic spinning at the room temperature at the speed of 0.2mm/min under the voltage of 10 KV;
step (II): curing treatment
Placing the electrostatic spinning product in a tubular furnace, and introducing N into the tubular furnace2Heating to 270 ℃ at the speed of 2 ℃/min, preserving the heat for 2h, and cooling to room temperature;
step (three): low temperature pre-oxidation
Introducing air into the tubular furnace, heating to 190 ℃ at a speed of 1 ℃/min, and keeping the temperature for 50 min;
step (IV): pyrolysis carbonization
Ar and NH are introduced into the tube furnace3The total gas flow of the mixed gas of (2) is 600mm3Min, heating to 820 deg.C, maintaining for 80min, and stopping NH introduction3Cooling to room temperature under the protection of Ar, collecting a product, washing the product with 5mol of hydrochloric acid solution and deionized water in sequence, and then drying the product in vacuum at 80 ℃, wherein Ar and NH3The air flow ratio of (2) is 5: 1.
Example 2
A preparation method of a carbon nanofiber composite material with a three-dimensional hierarchical structure comprises the following steps:
step (I): electrostatic spinning
(1) 0.75g of PAN and 0.25g of PVP are dissolved in 5.5g of DMF, the mixture is stirred at the normal temperature for 1 hour at the rpm of 250 to form a mixed solution, 2g of nickel acetate and 2g of magnesium nitrate hexahydrate are added into the mixed solution, and the stirring is continued for 1 hour;
(2) electrostatic spinning at the room temperature at the speed of 0.15mm/min under the voltage of 30 KV;
step (II): curing treatment
Placing the electrostatic spinning product in a tubular furnace, and introducing N into the tubular furnace2Heating to 260 ℃ at the speed of 1 ℃/min, preserving the heat for 3h, and cooling to room temperature;
step (three): low temperature pre-oxidation
Introducing air into the tubular furnace, heating to 180 ℃ at a speed of 1.5 ℃/min, and keeping the temperature for 70 min;
step (IV): pyrolysis carbonization
Ar and NH are introduced into the tube furnace3The total gas flow of the mixed gas of (2) is 600mm3Min, heating to 860 deg.C, maintaining for 50min, and stopping NH introduction3Cooling to room temperature under the protection of Ar, collecting a product, washing the product with 4-5 mol of hydrochloric acid solution and deionized water in sequence, and then drying in vacuum at 80 ℃, wherein Ar and NH3The air flow ratio of (2) is 5: 1.
Example 3
A preparation method of a carbon nanofiber composite material with a three-dimensional hierarchical structure comprises the following steps:
step (I): electrostatic spinning
(1) Dissolving 0.75g of PAN and 0.25g of PVP in 5.35g of DMF, stirring at normal temperature for 1.5h at 200rpm to form a mixed solution, adding 2g of nickel acetate and 2g of magnesium nitrate hexahydrate into the mixed solution, and continuing stirring for 1 h;
(2) electrostatic spinning at the room temperature at the speed of 0.1mm/min under the voltage of 20 KV;
step (II): curing treatment
Placing the electrostatic spinning product in a tubular furnace, and introducing N into the tubular furnace2Heating to 265 ℃ at the speed of 1.5 ℃/min, preserving the heat for 2.5h, and cooling to room temperature;
step (three): low temperature pre-oxidation
Introducing air into the tubular furnace, heating to 180 ℃ at the speed of 1 ℃/min, and keeping the temperature for 60 min;
step (IV): pyrolysis carbonization
Ar and NH are introduced into the tube furnace3The total gas flow of the mixed gas of (2) is 600mm3Min, heating to 850 deg.C, maintaining for 60min, and stopping NH introduction3At Ar protectionCooling to room temperature under protection, collecting the product, washing the product with 4.5mol hydrochloric acid solution and deionized water in sequence, and then drying the product in vacuum at 80 ℃, wherein Ar and NH3The air flow ratio of (2) is 5: 1.
The three-dimensional hierarchical structure carbon nanofiber composite material prepared by the invention is composed of solid carbon nanofibers with the diameter of about 10nm and solid carbon nanofibers with the diameter of 80-100 nm, wherein the thinner carbon nanofibers grow on the surface of the thicker carbon nanofibers and are communicated with the adjacent thicker carbon nanofibers, as shown in fig. 1 and fig. 2. After 5000 times of cyclic charge and discharge, the capacitance retention rate is not basically attenuated, after 10000 times of charge and discharge cycles, the capacitance retention rate is still kept above 96% of the initial value, and after 50000 times of cyclic charge and discharge, the capacitance retention rate is still kept above 94% of the initial value, so that the carbon nanofiber composite material with the three-dimensional hierarchical structure prepared by the method has excellent cyclic stability.
Comparative example 1
Different from the example 3, the PVP is not added in the spinning solution, and the temperature is raised to 250 ℃ at 1 ℃/min directly after electrostatic spinning for pre-oxidation for 1 h. The other steps were the same as in example 3.
The product prepared in comparative example 1 had no hierarchical structure, and only a single structure of the large-diameter carbon nanofiber having a branched structure existed, and both the specific capacitance and the conductivity were poor.
Comparative example 2
Unlike example 3, in this comparative example, only nickel acetate was added as a metal salt at the time of preparing the spinning solution, and pre-oxidation was performed by raising the temperature to 250 ℃ at 1 ℃/min for 1 hour directly after the completion of spinning. The other steps were the same as in example 3.
In the product prepared in the comparative example 1, the final product in the large-diameter carbon nanofiber has no branched structure, hollow Carbon Nanotubes (CNTs) grow on the surface of the large-diameter carbon nanofiber instead of Carbon Nanofibers (CNFs) with solid structures, the diameter of the carbon nanotube with larger diameter is about 200-300 nm, the diameter of the carbon nanotube with smaller diameter is 80-100 nm, the diameter difference is smaller, the diameter distribution range is large, the uniformity is poor, and the structure and performance stability is poor.
Comparative example 3
After the same spinning solution as in example 3 was electrospun, the temperature was raised to 250 ℃ at 1 ℃/min without curing treatment, and pre-oxidation was carried out for 1 hour. The other steps were the same as in example 3.
The diameter distribution uniformity of the carbon nanofibers with two diameters in the product prepared in the comparative example 3 is poor, 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 is slightly smaller than that of the carbon nanotube with a smaller diameter in the comparative example 1, but the whole diameter distribution range is still large, the whole specific surface area of the composite material is reduced, and the capacitance is reduced. When the products prepared in example 3 and comparative example 3 were used for capacitor active electrode materials, as shown in FIG. 6, the specific capacitances of example 3 and comparative example 3 according to the present invention were 575F/g and 302F/g, respectively, at a current density of 1A/g.

Claims (9)

1. A carbon nanofiber composite material of a three-dimensional hierarchical structure, characterized in that: the carbon nanofiber is composed of fine solid carbon nanofibers with the diameter of about 10nm and coarse solid carbon nanofibers with the diameter of 80-100 nm and a branched structure, wherein the fine solid carbon nanofibers grow on the surface of the coarse carbon nanofibers and are communicated with the adjacent coarse solid carbon nanofibers.
2. A method for preparing the carbon nanofiber composite material of the three-dimensional hierarchical structure according to claim 1, wherein: dissolving Polyacrylonitrile (PAN) and polyvinylpyrrolidone (PVP) in dimethyl formamide (DMF), stirring to form a mixed solution, adding nickel salt and magnesium salt, continuously stirring to form a spinning solution, carrying out electrostatic spinning, curing a spinning product in a nitrogen atmosphere, carrying out pre-oxidation treatment in air, and finally carrying out pyrolysis carbonization.
3. The method of preparing a carbon nanofiber composite material of a three-dimensional hierarchical structure according to claim 2, wherein: the solidification treatment is to place the electrostatic spinning product in a tubular furnace, and to introduce N into the tubular furnace2Heating to 260-270 ℃ at a rate of 1-2 ℃/min and keeping the temperature for 2 DEG CAnd cooling to room temperature for 3 h.
4. The method for preparing a carbon nanofiber composite material of a three-dimensional hierarchical structure according to claim 2 or 3, wherein: and the pre-oxidation is to introduce air into the tubular furnace, heat the tubular furnace to 180-190 ℃ at a speed of 1-1.5 ℃/min, and keep the temperature for 50-70 min.
5. The method for preparing a carbon nanofiber composite material of a three-dimensional hierarchical structure according to claim 2 or 3, wherein: the mass ratio of the PAN to the PVP to the DMF is 3:1: 20-22, and the mixture is stirred at 150-250 rpm for 1-2 hours.
6. The method of preparing a carbon nanofiber composite material of a three-dimensional hierarchical structure according to claim 4, wherein: the mass ratio of the PAN to the PVP to the DMF is 3:1: 20-22, and the mixture is stirred at 150-250 rpm for 1-2 hours.
7. The method of preparing a carbon nanofiber composite material of a three-dimensional hierarchical structure according to claim 6, wherein: 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 to the mixed solution is 1: 1.5-1.625.
8. The method of preparing a carbon nanofiber composite material of a three-dimensional hierarchical structure according to claim 7, wherein: the pyrolysis carbonization is to introduce Ar and NH into a tubular furnace3Heating the mixed gas to 820-860 ℃, preserving the temperature for 50-80 min, and stopping introducing NH3And cooling to room temperature under the protection of Ar, and collecting the product.
9. A preparation method of a carbon nanofiber composite material with a three-dimensional hierarchical structure is characterized by comprising the following steps:
step (I): electrostatic spinning
(1) Dissolving Polyacrylonitrile (PAN) and polyvinylpyrrolidone (PVP) in Dimethylformamide (DMF), stirring at the normal temperature at 150-250 rpm for 1-2 h to form a mixed solution, wherein the mass ratio of PAN to PVP to 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 1 hour, wherein the mass ratio of the total of the nickel acetate and the magnesium nitrate hexahydrate to the mixed solution is 1: 1.5-1.625;
(2) electrostatic spinning at the room temperature at the speed of 0.1-0.2 mm/min under the voltage of 10-30 KV;
step (II): curing treatment
Placing the electrostatic spinning product in a tubular furnace, and introducing N into the tubular furnace2Heating to 260-270 ℃ at the speed of 1-2 ℃/min, preserving the heat for 2-3 h, and cooling to room temperature;
step (three): low temperature pre-oxidation
Introducing air into the tubular furnace, heating to 180-190 ℃ at a speed of 1-1.5 ℃/min, and preserving heat for 50-70 min;
step (IV): pyrolysis carbonization
Ar and NH are introduced into the tube furnace3Heating the mixed gas to 820-860 ℃, preserving the temperature for 50-80 min, and stopping introducing NH3And cooling to room temperature under the protection of Ar, collecting a product, washing the product with 4-5 mol of hydrochloric acid solution and deionized water in sequence, and then drying in vacuum at 80 ℃.
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