CN108660546B - Green preparation method of cobalt and nitrogen doped porous carbon composite nanofiber - Google Patents
Green preparation method of cobalt and nitrogen doped porous carbon composite nanofiber Download PDFInfo
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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
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0092—Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields
Abstract
The invention discloses a green preparation method of cobalt and nitrogen doped porous carbon composite nanofibers. The method comprises the following steps: 1) mixing and dissolving chitosan, cobalt acetate, polyethylene oxide, polyethyleneimine, TritonX-100 and acetic acid in water according to a certain proportion to obtain an aqueous phase spinning solution; 2) carrying out electrostatic spinning on the aqueous phase spinning solution; 3) and (3) pre-oxidizing a sample obtained by spinning in the air, and then carrying out temperature programming-constant temperature pyrolysis carbonization in an inert atmosphere to obtain the cobalt and nitrogen doped porous carbon composite nanofiber. The cobalt and nitrogen doped porous carbon composite nanofiber prepared by combining the water phase system electrostatic spinning technology with the heat treatment method can basically keep the fiber morphology of protofilaments after pyrolysis, and has application potential in super capacitor electrodes and fuel cell cathodes as electrode materials. The method of the invention adopts water-soluble polymer as precursor and water as solvent, no toxic substance is discharged in the spinning process, the method is environment-friendly, the process is simple and convenient, and no complicated post-treatment is involved.
Description
Technical Field
The invention relates to the technical field of preparation of porous carbon nanofiber materials, in particular to a green preparation method of cobalt and nitrogen doped porous carbon composite nanofibers.
Background
Based on the demand for clean energy in sustainable development, the conversion, utilization and storage of new energy put increasing demands on the performance of devices such as lithium ion batteries, fuel cells, supercapacitors and the like. In these energy conversion and storage devices, the electrode material is the core. The carbon-based electrode material has a high surface area and excellent electrical conductivity, can increase the interfacial area between a solid and a liquid or between a solid and a gas, and simultaneously shortens the diffusion distance, thereby promoting the electron or ion transmission and improving the electrochemical performance, and has attracted extensive attention and research. Among carbon materials with different shapes, the carbon nanofiber with a one-dimensional structure has excellent conductivity, extremely large surface area and structural stability due to continuous and uniform shapes, and is widely applied to electrode materials.
The electrostatic spinning technology is an efficient method for manufacturing the nanofiber material due to the advantages of various spinnable substances, adjustable process, large specific surface area of the prepared fiber and the like, and the carbon nanofiber can be obtained after the nanofiber prepared by the electrostatic spinning method is carbonized at high temperature. In order to facilitate spinning and to obtain a high carbon yield after carbonization, a cyclic polymer having high thermal stability or a linear polymer (e.g., PAN) capable of being cyclized at a pre-oxidation stage is usually used for spinning. However, these polymers generally do not contain hydrophilic groups and are only soluble in strongly polar organic solvents, such as N, N-Dimethylformamide (DMF), Tetrahydrofuran (THF), chloroform (CHCl)3) And dimethylacetamide (DMAc), etc., and electrospinning is a process of continuously volatilizing a solvent to solidify fibers, and has a long running time, so that there is a great environmental pollution risk when using these highly toxic organic solvents, and if rigorous exhaust gas treatment measures are not taken, these organic vapors are extremely harmful to the health of research or production personnel and nearby residents. Therefore, the carbon nanofiber prepared by water-based electrostatic spinning is developed to be used as an electrode material, and has important significance in environmental protection and the like.
Disclosure of Invention
In order to solve the problem of environmental pollution in the preparation of carbon nanofibers by the existing organic phase electrostatic spinning technology, the invention aims to provide a green preparation method of cobalt and nitrogen doped porous carbon composite nanofibers, and the method adopts the electrostatic spinning of a water phase system in combination with a heat treatment technology, and has the advantages of being green, safe, environment-friendly, low in cost, high in efficiency and the like.
The object of the present invention is achieved by the following means.
A green preparation method of cobalt and nitrogen doped porous carbon composite nanofibers adopts an electrostatic spinning and heat treatment technology of a water phase system, and specifically comprises the following steps:
1) preparing a water-phase spinning solution: respectively dissolving a carbon source in an acetic acid aqueous solution, dissolving a spinning aid in deionized water, diluting a nitrogen source and a complexing agent with the deionized water, and adding a cobalt source to obtain three solutions; then uniformly mixing the three solutions, adding a surfactant, and stirring to obtain a water-phase spinning solution;
2) electrostatic spinning: carrying out electrostatic spinning on the aqueous phase spinning solution under the condition of electrostatic spinning;
3) and (3) heat treatment: placing a sample obtained by electrostatic spinning in a tubular furnace, and pre-oxidizing in air; and then, under the inert atmosphere, carrying out temperature programming pyrolysis carbonization to obtain the cobalt and nitrogen doped porous carbon composite nanofiber.
Further, the carbon source is chitosan, the cobalt source is cobalt acetate, the spinning aid is polyethylene oxide, the nitrogen source and complexing agent is polyethyleneimine, and the surfactant is polyethylene glycol octyl phenyl ether TritonX-100.
Further, the average molecular weight of the chitosan is 50-60 ten thousand, and the average molecular weight of the polyoxyethylene is 30-100 ten thousand.
Further, in the step 1), the mass concentration of the cobalt source in the aqueous phase spinning solution is 0.1-0.5 wt%.
Further, in the step 1), the mass concentration of the carbon source in the aqueous phase spinning solution is 1-3 wt%, the mass concentration of the acetic acid in the aqueous phase spinning solution is 0.3-1.5 wt%, the mass concentration of the spinning aid in the aqueous phase spinning solution is 1.4-3 wt%, the mass concentration of the nitrogen source and complexing agent in the aqueous phase spinning solution is 0.3-1.3 wt%, and the mass concentration of the surfactant in the aqueous phase spinning solution is 0.4-0.8 wt%.
Further, in the step 1), the stirring temperature is 25-40 ℃ and the stirring time is 8-24 hours.
Further, the electrostatic spinning conditions in the step 2) are as follows: the spinning distance is 10-20 cm; the flow rate of the spinning solution is 0.3-0.9 mL/h; the spinning voltage is 15-25 kV.
Further, in the step 3), the pre-oxidation temperature is 120-150 ℃ and the time is 2-6 hours.
Further, the temperature programming in step 3) is as follows: in a tubular furnace, heating to 200-300 ℃ at a speed of 1-3 ℃/min under an inert atmosphere, and keeping the temperature for 0.5-4 hours; heating to 300-400 ℃ at a speed of 1-3 ℃/min, and keeping the temperature for 0.5-2 hours; then raising the temperature to 700-900 ℃ at a speed of 3-10 ℃/min, and keeping the temperature for 1-3 hours.
Further, the inert atmosphere is more than one of nitrogen or argon.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1) the invention adopts the water-phase electrostatic spinning technology to prepare the cobalt and nitrogen doped porous carbon composite nanofiber, the spinning raw materials are environment-friendly and nontoxic, the environment and the human body are not harmed, the process flow is easy to control, and the complex post-treatment is not involved:
2) the obtained cobalt and nitrogen doped porous carbon composite nanofiber basically keeps a fibril cross-linked network structure, has a large specific surface area, is beneficial to improving the contact efficiency of an electrocatalytic active site and a reactant, and has high activity on electrocatalytic oxygen reduction reaction.
3) The method has universality, and can be used for preparing electrode materials or catalytic materials with different functions by changing the types or the contents of salts in the solution.
Drawings
FIG. 1 is a schematic flow diagram of the preparation process of the present invention.
FIG. 2 is a scanning electron micrograph of a polymer blend fiber according to example 5 of the present invention.
Fig. 3 is a scanning electron microscope image of cobalt and nitrogen doped porous carbon composite nanofibers according to example 3 of the present invention.
FIG. 4 is a transmission electron microscope image of the cobalt and nitrogen doped porous carbon composite nanofiber in example 1 of the present invention.
FIG. 5 is a BET test result of the cobalt and nitrogen doped porous carbon composite nanofiber according to example 3 of the present invention.
FIG. 6 is the LSV curve of the cobalt and nitrogen doped porous carbon composite nanofibers in 0.1mol/L KOH solution in accordance with example 4 of the present invention.
FIG. 7 is a constant current charging/discharging curve diagram of a supercapacitor made of cobalt and nitrogen doped porous carbon composite nanofibers in a 6 mol/L KOH solution in example 5 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art.
FIG. 1 is a schematic flow diagram of the preparation process of the present invention. The specific process is as follows: dissolving chitosan in an aqueous solution of acetic acid, dissolving polyoxyethylene in deionized water, diluting polyethyleneimine with deionized water, adding cobalt acetate, mixing the three solutions, stirring uniformly, and adding TritonX-100 to obtain a mixed solution. Only the chitosan is dissolved by using acetic acid and then is mixed with other high molecular solution, because excessive acetic acid is needed for dissolving the chitosan, a small amount of acetic acid is needed for dissolving the polyoxyethylene until the polyoxyethylene is transparent, the excessive acetic acid just can meet the requirement for dissolving the polyoxyethylene until the polyoxyethylene is transparent when the chitosan is dissolved, and the excessive acetic acid in the spinning solution can reduce the spinnability of the solution. And fully and uniformly stirring the mixed solution, performing ultrasonic treatment or standing for defoaming until the mixed solution is transparent and limpid, and performing electrostatic spinning on the mixed solution through electrostatic spinning equipment to obtain the polymer mixture fiber. FIG. 2 is a scanning electron micrograph of a polymer blend fiber according to example 5 of the present invention, from which it can be seen that smooth, uniform and crosslinked nanofibers can be obtained by the method of the present invention. Placing the fiber in a tubular furnace, pre-oxidizing in air, then carrying out temperature programmed heat treatment, carbonizing the fiber obtained by electrospinning, volatilizing unstable components, and leaving rich micropores and mesopores; finally obtaining the cobalt and nitrogen doped porous carbon composite nanofiber. Fig. 3 is a scanning electron microscope image of cobalt and nitrogen-doped porous carbon composite nanofibers according to example 3 of the present invention, fig. 4 is a transmission electron microscope image of cobalt and nitrogen-doped porous carbon composite nanofibers according to example 1 of the present invention, and it can be seen from fig. 4 that the agglomeration growth of cobalt metal particles is suppressed to a certain extent by this temperature increasing process; as can be seen from the comparison of fig. 2 with fig. 3 and fig. 4, the morphology of the fiber obtained by electrospinning is well maintained under a proper temperature-raising procedure, and pores and uniformly dispersed particles are formed during pyrolysis. The temperature rise program is an important factor for keeping the morphology of the carbon nanofibers, and the complete morphology of the fibers cannot be kept if the temperature rise program is controlled improperly.
Example 1
The preparation method of the cobalt and nitrogen doped porous carbon composite nanofiber comprises the following steps:
1) preparing a spinning solution: dissolving chitosan with the average molecular weight of 53.5 ten thousand in an aqueous solution of acetic acid, dissolving polyoxyethylene with the average molecular weight of 100 ten thousand in deionized water, diluting polyethyleneimine with the deionized water, adding cobalt acetate tetrahydrate, mixing and stirring the three solutions uniformly, and adding TritonX-100 to obtain a spinning solution, wherein the concentration of the chitosan is 2.4wt%, the concentration of the acetic acid is 0.7wt%, the concentration of the polyoxyethylene is 1.4wt%, the concentration of the polyethyleneimine is 0.3wt%, the concentration of the cobalt acetate is 0.1wt%, and the concentration of the TritonX-100 is 0.5 wt%; the mixed solution was stirred in a 30 ℃ water bath for 24 hours. 2) Electrostatic spinning: and (3) filling the obtained spinning solution into an injector for electrostatic spinning, wherein the spinning distance is 15 cm, the solution flow rate is 0.6mL/h, and the applied voltage is 25 kV. 3) And (3) heat treatment: placing the mixed polymer fiber obtained by spinning in a tubular furnace, pre-oxidizing for 6 hours at 130 ℃ in the air, then heating to 300 ℃ at 3 ℃/min under an inert atmosphere, keeping the temperature for 2 hours, heating to 400 ℃ at 1 ℃/min, keeping the temperature for 0.5 hour, then heating to 900 ℃ at 10 ℃/min, keeping the temperature for 0.5 hour, and finally obtaining the cobalt and nitrogen doped porous carbon composite nanofiber.
Example 2
The preparation method of the cobalt and nitrogen doped porous carbon composite nanofiber comprises the following steps:
1) preparing a spinning solution: taking chitosan with the average molecular weight of 53.5 ten thousand to be dissolved in an aqueous solution of acetic acid, taking polyethylene oxide with the average molecular weight of 30 ten thousand to be dissolved in deionized water, taking polyethyleneimine to be diluted by the deionized water, adding cobalt acetate tetrahydrate, mixing and stirring the three solutions uniformly, and adding TritonX-100 to obtain a spinning solution, wherein the concentration of the chitosan is 1wt%, the concentration of the acetic acid is 0.3wt%, the concentration of the polyethylene oxide is 3wt%, the concentration of the polyethyleneimine is 0.3wt%, the concentration of the cobalt acetate is 0.1wt%, and the concentration of the TritonX-100 is 0.4 wt%; the mixed solution was stirred in a 40 ℃ water bath for 24 hours. 2) Electrostatic spinning: and (3) filling the obtained spinning solution into an injector for electrostatic spinning, wherein the spinning distance is 20cm, the solution flow is 0.8mL/h, and the applied voltage is 20 kV. 3) And (3) heat treatment: placing the mixed polymer fiber obtained by spinning in a tubular furnace, pre-oxidizing for 3 hours at 120 ℃ in the air, then heating to 300 ℃ at 1 ℃/min under an inert atmosphere, keeping the temperature for 0.5 hour, heating to 400 ℃ at 1 ℃/min, keeping the temperature for 1 hour, then heating to 800 ℃ at 6 ℃/min, keeping the temperature for 1 hour, and finally obtaining the cobalt and nitrogen doped porous carbon composite nanofiber.
Example 3
The preparation method of the cobalt and nitrogen doped porous carbon nano composite nanofiber comprises the following steps:
1) preparing a spinning solution: dissolving chitosan with the average molecular weight of 60 ten thousand in an aqueous solution of acetic acid, dissolving polyoxyethylene with the average molecular weight of 100 ten thousand in deionized water, diluting polyethyleneimine with the deionized water, adding cobalt acetate tetrahydrate, mixing and stirring the three solutions uniformly, and adding TritonX-100 to obtain a spinning solution, wherein the concentration of the chitosan is 2.9wt%, the concentration of the acetic acid is 1.1wt%, the concentration of the polyoxyethylene is 2.4wt%, the concentration of the polyethyleneimine is 0.5wt%, the concentration of the cobalt acetate is 0.2wt%, and the concentration of the TritonX-100 is 0.8 wt%; the mixed solution was stirred in a 30 ℃ water bath for 8 hours. 2) Electrostatic spinning: and (3) filling the obtained spinning solution into an injector for electrostatic spinning, wherein the spinning distance is 10 cm, the solution flow is 0.3mL/h, and the applied voltage is 15 kV. 3) And (3) heat treatment: placing the mixed polymer fiber obtained by spinning in a tubular furnace, pre-oxidizing for 4 hours at 150 ℃ in the air, then heating to 240 ℃ at 3 ℃/min under an inert atmosphere, keeping the temperature for 2 hours, heating to 340 ℃ at 3 ℃/min, keeping the temperature for 2 hours, then heating to 800 ℃ at 3 ℃/min, keeping the temperature for 2 hours, and finally obtaining the cobalt and nitrogen doped porous carbon composite nanofiber.
FIG. 5 is a BET test result of the cobalt and nitrogen doped porous carbon composite nanofiber in example 3, wherein the BET test result indicates the existence of the cobalt and nitrogen doped porous carbon composite nanofiberA bright-line hysteresis loop which proves the existence of a pore structure, and the specific surface area of the cobalt and nitrogen doped porous carbon nanofiber is 563.4m according to the data in the figure2Per g, pore volume of 0.59cm3/g。
Example 4
The preparation method of the cobalt and nitrogen doped porous carbon composite nanofiber comprises the following steps:
1) preparing a spinning solution: dissolving chitosan with the average molecular weight of 53.5 ten thousand in an aqueous solution of acetic acid, dissolving polyoxyethylene with the average molecular weight of 100 ten thousand in deionized water, diluting polyethyleneimine with the deionized water, adding cobalt acetate tetrahydrate, mixing and stirring the three solutions uniformly, and adding TritonX-100 to obtain a spinning solution, wherein the concentration of the chitosan is 1.3wt%, the concentration of the acetic acid is 1.5wt%, the concentration of the polyoxyethylene is 2.5wt%, the concentration of the polyethyleneimine is 1.3wt%, the concentration of the cobalt acetate is 0.1wt%, and the concentration of the TritonX-100 is 0.4 wt%; the mixed solution was stirred in a 25 ℃ water bath for 24 hours. 2) Electrostatic spinning: and (3) filling the obtained spinning solution into an injector for electrostatic spinning, wherein the spinning distance is 13 cm, the solution flow rate is 0.9mL/h, and the applied voltage is 18 kV. 3) And (3) heat treatment: placing the mixed polymer fiber obtained by spinning in a tubular furnace, pre-oxidizing for 3 hours at 120 ℃ in the air, then heating to 200 ℃ at 1 ℃/min under an inert atmosphere, keeping the temperature for 0.5 hour, heating to 400 ℃ at 1 ℃/min, keeping the temperature for 2 hours, then heating to 800 ℃ at 10 ℃/min, keeping the temperature for 2 hours, and finally obtaining the cobalt and nitrogen doped porous carbon nano composite fiber.
FIG. 6 is an LSV curve of the cobalt and nitrogen doped porous carbon composite nanofiber prepared in example 4, which is subjected to 2mol/L HCl pickling, 800 ℃ annealing and then oxygen reduction in 0.1mol/L KOH solution. As can be seen from fig. 6, the initial potential of the cobalt and nitrogen doped porous carbon composite nanofiber for catalyzing the oxygen reduction reaction is-0.04V, and the half-wave potential is-0.13V, which indicates that the cobalt and nitrogen doped porous carbon composite nanofiber of the present invention has high catalytic activity for the oxygen reduction reaction.
Example 5
The preparation method of the cobalt and nitrogen doped porous carbon composite nanofiber comprises the following steps:
1) preparing an aqueous phase spinning solution: dissolving chitosan with the average molecular weight of 50 ten thousand in an aqueous solution of acetic acid, dissolving polyoxyethylene with the average molecular weight of 60 ten thousand in deionized water, diluting polyethyleneimine with the deionized water, adding cobalt acetate tetrahydrate, mixing and stirring the three solutions uniformly, and adding TritonX-100 to obtain a spinning solution, wherein the concentration of the chitosan is 1.9wt%, the concentration of the acetic acid is 0.6wt%, the concentration of the polyoxyethylene is 1.5wt%, the concentration of the polyethyleneimine is 0.8wt%, the concentration of the cobalt acetate is 0.5wt%, and the concentration of the TritonX-100 is 0.6 wt%; the mixed solution was stirred in a 40 ℃ water bath for 12 hours. 2) Electrostatic spinning: and (3) filling the obtained spinning solution into an injector for electrostatic spinning, wherein the spinning distance is 15 cm, the solution flow rate is 0.48mL/h, and the applied voltage is 19 kV. 3) And (3) heat treatment: placing the mixed polymer fiber obtained by spinning in a tubular furnace, pre-oxidizing for 2 hours at 140 ℃ in the air, then heating to 200 ℃ at 3 ℃/min under an inert atmosphere, keeping the temperature for 4 hours, heating to 300 ℃ at 2 ℃/min, keeping the temperature for 2 hours, then heating to 700 ℃ at 5 ℃/min, keeping the temperature for 3 hours, and finally obtaining the cobalt and nitrogen doped porous carbon composite nanofiber.
In example 5, the content of cobalt acetate in the spinning solution was 0.5wt%, and after the obtained cobalt and nitrogen-doped porous carbon composite nanofiber was pyrolyzed at high temperature, unstable substances were substantially volatilized, and cobalt elements were almost completely retained, so that the generated cobalt and nitrogen-doped porous carbon composite nanofiber contained more cobalt-based pseudocapacitive materials.
The cobalt and nitrogen-doped porous carbon composite nanofiber obtained by the embodiment is mixed with conductive carbon black and a bonding agent (PTFE) and then loaded on foamed nickel to prepare the working electrode of the supercapacitor, fig. 7 is a constant current charge-discharge curve diagram of the working electrode of the supercapacitor in 6 mol/L KOH solution, and as can be seen from the graph, the capacitance of the mixed material is 94.9F/g under the current density of 1A/g.
Claims (6)
1. The green preparation method of the cobalt and nitrogen doped porous carbon composite nanofiber is characterized by adopting an electrostatic spinning and heat treatment technology of a water phase system, and specifically comprises the following steps:
1) preparing a water-phase spinning solution: respectively dissolving a carbon source in an acetic acid aqueous solution, dissolving a spinning aid in deionized water, diluting a nitrogen source and a complexing agent with the deionized water, and adding a cobalt source to obtain three solutions; then uniformly mixing the three solutions, adding a surfactant, and stirring to obtain a water-phase spinning solution; the mass concentration of the cobalt source in the aqueous phase spinning solution is 0.1-0.5 wt%; the mass concentration of the carbon source in the aqueous-phase spinning solution is 1-3 wt%, the mass concentration of the acetic acid in the aqueous-phase spinning solution is 0.3-1.5 wt%, the mass concentration of the spinning aid in the aqueous-phase spinning solution is 1.4-3 wt%, the mass concentration of the nitrogen source and complexing agent in the aqueous-phase spinning solution is 0.3-1.3 wt%, and the mass concentration of the surfactant in the aqueous-phase spinning solution is 0.4-0.8 wt%;
2) electrostatic spinning: carrying out electrostatic spinning on the aqueous phase spinning solution under the condition of electrostatic spinning;
3) and (3) heat treatment: placing a sample obtained by electrostatic spinning in a tubular furnace, and pre-oxidizing in air; then, under the inert atmosphere, carrying out temperature programming pyrolysis carbonization to obtain cobalt and nitrogen doped porous carbon composite nanofibers; the pre-oxidation temperature is 120-150 ℃, and the time is 2-6 hours; the temperature programming is as follows: in a tubular furnace, heating to 200-300 ℃ at a speed of 1-3 ℃/min under an inert atmosphere, and keeping the temperature for 0.5-4 hours; heating to 300-400 ℃ at a speed of 1-3 ℃/min, and keeping the temperature for 0.5-2 hours; then raising the temperature to 700-900 ℃ at a speed of 3-10 ℃/min, and keeping the temperature for 1-3 hours.
2. The green preparation method of the cobalt and nitrogen doped porous carbon composite nanofiber according to claim 1, wherein the carbon source in the step 1) is chitosan, the cobalt source is cobalt acetate, the spinning aid is polyethylene oxide, the nitrogen source and complexing agent is polyethyleneimine, and the surfactant is polyethylene glycol octyl phenyl ether TritonX-100.
3. The green preparation method of the cobalt and nitrogen doped porous carbon composite nanofiber as claimed in claim 2, wherein the average molecular weight of the chitosan is 50-60 ten thousand, and the average molecular weight of the polyethylene oxide is 30-100 ten thousand.
4. The green preparation method of the cobalt and nitrogen doped porous carbon composite nanofiber according to claim 1, wherein the stirring temperature in the step 1) is 25-40 ℃ and the stirring time is 8-24 hours.
5. The green preparation method of the cobalt and nitrogen doped porous carbon composite nanofiber according to claim 1, wherein the electrostatic spinning conditions in the step 2) are as follows: the spinning distance is 10-20 cm; the flow rate of the spinning solution is 0.3-0.9 mL/h; the spinning voltage is 15-25 kV.
6. The green preparation method of the cobalt and nitrogen doped porous carbon composite nanofiber according to claim 1 or 5, characterized in that: the inert atmosphere is more than one of nitrogen or argon.
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