CN108660546A - A kind of environment-friendly preparation method thereof of cobalt, the porous carbon composite nano-fiber of N doping - Google Patents
A kind of environment-friendly preparation method thereof of cobalt, the porous carbon composite nano-fiber of N doping Download PDFInfo
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- CN108660546A CN108660546A CN201810552008.7A CN201810552008A CN108660546A CN 108660546 A CN108660546 A CN 108660546A CN 201810552008 A CN201810552008 A CN 201810552008A CN 108660546 A CN108660546 A CN 108660546A
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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
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Abstract
The invention discloses a kind of cobalt, the environment-friendly preparation method thereofs of the porous carbon composite nano-fiber of N doping.Include the following steps：1）Chitosan, cobalt acetate, polyethylene glycol oxide, polyethyleneimine, TritonX 100, acetic acid is miscible in certain proportion in water, obtain water phase spinning solution；2）Electrostatic spinning is carried out to water phase spinning solution；3）Sample obtained by spinning is first pre-oxidized in air, temperature programming isothermal pyrolysis carbonization is then carried out in an inert atmosphere, obtains the porous carbon composite nano-fiber of cobalt, N doping.The present invention prepares the porous carbon composite nano-fiber of cobalt, N doping with aqueous phase system electrostatic spinning technique combination heat treating process, can keep the fiber morphology of precursor after pyrolysis substantially, as electrode material, has application potential in electrode of super capacitor, fuel battery negative pole.The method of the present invention is using water soluble polymer as presoma, and using water as solvent, in spinning process, there is no noxious materials to discharge, and environmental-friendly, simple process is not related to complicated post-processing.
Description
Technical field
The present invention relates to porous carbon nanofiber technical field of material, and in particular to a kind of cobalt, N doping porous carbon
The environment-friendly preparation method thereof of composite nano fiber.
Background technology
Based on sustainable development for the demand of clean energy resource, conversion, utilization and the storage of new energy to lithium ion battery,
The performance of the equipment such as fuel cell, ultracapacitor proposes increasingly higher demands.In these energy conversions and storage facilities,
Electrode material is its core.Carbon-based electrode material can increase solid and liquid with higher surface area and excellent electric conductivity
Interfacial area between body or solid and gas, while shortening diffusion length, to promote electronics or ion to transmit and improve electricity
Chemical property causes extensive concern and research.In the different carbon material of pattern, the carbon nano-fiber with one-dimentional structure,
Since pattern is continuously uniform, there is excellent conductivity, great surface area and structural stability, have in electrode material wide
General application.
Electrostatic spinning technique is since can to spin the pulp freeness that substance classes are various, technique is controllable, prepared big for it
The advantages that, it is a kind of high efficiency method for manufacturing nano-fiber material, nanofiber prepared by method of electrostatic spinning passes through high temperature cabonization
Afterwards, you can obtain carbon nano-fiber.For the ease of spinning and convenient for high production carbon rate, generally use thermostabilization can be obtained after carbonization
The strong ring-like polymer of property can be in the linear macromolecule of pre-oxidizing the stage cyclization（Such as PAN）To carry out spinning.However, these are high
Molecule is generally free of hydrophilic group, is only soluble in highly polar organic solvent, such as n,N-Dimethylformamide（DMF）, tetrahydrochysene
Furans（THF）, chloroform（CHCl3）, dimethylacetylamide（DMAc）Deng, and electrostatic spinning is one and solvent is constantly made to volatilize and make
Fiber solidifying process, long operational time, so, using the organic solvents of these strong toxicities, there are bigger environmental pollution is hidden
Suffer from, if not taking strict vent gas treatment measure, these organic steams for the personnel that go in for the study or produce and near
The health of resident has great harm.Therefore, a kind of carbon nano-fiber conduct prepared by water system electrostatic spinning is developed
Electrode material has the significances such as green, environmental protection.
Invention content
Problem of environmental pollution existing for carbon nano-fiber is prepared to solve existing organic phase electrostatic spinning technique, it is of the invention
It is designed to provide the environment-friendly preparation method thereof of a kind of cobalt, the porous carbon composite nano-fiber of N doping, this method uses water phase body
The electrostatic spinning combination heat treatment technics of system, has many advantages, such as green, safe and environment-friendly, at low cost, efficient.
The purpose of the present invention is realized by following technical solution.
The environment-friendly preparation method thereof of a kind of cobalt, the porous carbon composite nano-fiber of N doping, using the electrostatic spinning of aqueous phase system
In conjunction with heat treatment technics, following steps are specifically included:
1）The preparation of water phase spinning solution：Carbon source is first dissolved in aqueous acetic acid respectively, spinning-aid agent is dissolved in deionized water, nitrogen source and network
Cobalt source is added after being diluted with deionized water in mixture, obtains three kinds of solution；Then three kinds of solution are uniformly mixed, add surface work
Property agent, stirring, obtain water phase spinning solution；
2）Electrostatic spinning：Condition to water phase spinning solution in electrostatic spinning carries out electrostatic spinning；
3）Heat treatment：Sample obtained by electrostatic spinning is placed in tube furnace, is first pre-oxidized in air；Then in inert atmosphere
Under, temperature-programmed pyrolysis carbonization obtains the porous carbon composite nano-fiber of cobalt, N doping.
Further, carbon source be chitosan, cobalt source be cobalt acetate, spinning-aid agent is polyethylene glycol oxide, nitrogen source and complexing agent is
Polyethyleneimine, surfactant are Triton X-100 TritonX-100.
Further, the average molecular weight of the chitosan is 50 ~ 600,000, the average molecular weight of polyethylene glycol oxide is 30 ~
1000000.
Further, the step 1）In, the mass concentration that cobalt source accounts for water phase spinning solution is 0.1 ~ 0.5wt%.
Further, the step 1）In, the mass concentration that carbon source accounts for water phase spinning solution is 1 ~ 3 wt%, and acetic acid accounts for water phase
The mass concentration of spinning solution is 0.3 ~ 1.5wt%, and the mass concentration that spinning-aid agent accounts for water phase spinning solution is 1.4 ~ 3 wt%, nitrogen source and network
Mixture account for water phase spinning solution mass concentration be 0.3 ~ 1.3wt%, surfactant account for water phase spinning solution mass concentration be 0.4 ~
0.8wt%。
Further, step 1）Middle whipping temp is 25 ~ 40 DEG C, and the time is 8 ~ 24 hours.
Further, step 2）Described in the condition of electrostatic spinning be：Spinning distance is 10 ~ 20cm；The flow velocity of spinning solution
For 0.3 ~ 0.9mL/h；Spinning voltage is 15 ~ 25kV.
Further, step 3）Described in Pre oxidation be 120 ~ 150 DEG C, the time be 2 ~ 6 hours.
Further, step 3）Described in temperature programming be：In tube furnace, under an inert atmosphere, with 1 ~ 3 DEG C/min liters
Temperature is to 200 ~ 300 DEG C, constant temperature 0.5 ~ 4 hour；300 ~ 400 DEG C are warming up to 1 ~ 3 DEG C/min again, constant temperature 0.5 ~ 2 hour；Then
3-10 DEG C/min rises to 700 ~ 900 DEG C, constant temperature 1 ~ 3 hour.
Further, the inert atmosphere is one or more of nitrogen or argon gas.
Compared with prior art, the present invention has the following advantages and beneficial effect：
1）The present invention prepares the porous carbon composite nano-fiber of cobalt, N doping, spinning material ring using water phase electrostatic spinning technique
It protects nontoxic, is safe from harm to environment and human body, technological process is easy to control, and is not related to complicated post-processing：
2）The porous carbon composite nano-fiber of gained cobalt, N doping keeps the cross-linked network structure of fibrinogen substantially, large specific surface area,
The contacting efficiency for being conducive to improve electro catalytic activity site and reactant has high activity to electrocatalytic oxidation reduction reaction.
3）This method has universality, and the electrode of different function can be prepared by changing the type or content of salt in solution
Material or catalysis material.
Description of the drawings
Fig. 1 is the flow diagram of preparation method of the present invention.
Fig. 2 is the scanning electron microscope (SEM) photograph of 5 macromolecule mixture fiber of the embodiment of the present invention.
Fig. 3 is the scanning electron microscope (SEM) photograph of 3 cobalt of the embodiment of the present invention, the porous carbon composite nano-fiber of N doping.
Fig. 4 is the transmission electron microscope picture of 1 cobalt of the embodiment of the present invention, the porous carbon composite nano-fiber of N doping.
Fig. 5 is the BET test result figures of 3 cobalt of the embodiment of the present invention, the porous carbon composite nano-fiber of N doping.
Fig. 6 is the oxygen of 4 cobalt of the embodiment of the present invention, the porous carbon composite nano-fiber of N doping in 0.1mol/L KOH solutions
Restore LSV curve graphs.
Fig. 7 is that ultracapacitor working electrode is made in 5 cobalt of the embodiment of the present invention, the porous carbon composite nano-fiber of N doping
Afterwards, the constant current charge-discharge curve graph in 6 mol/L KOH solutions.
Specific implementation mode
With reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.It is noted that if the following process for having not special detailed description, is that those skilled in the art can refer to the prior art
Realize or understand.
Fig. 1 is the flow diagram of preparation method of the present invention.Detailed process is as follows：Chitosan is taken to be dissolved in the water-soluble of acetic acid
Liquid takes polyethylene glycol oxide to be dissolved in deionized water, and cobalt acetate is added after taking polyethyleneimine to be diluted with deionized water, by three of the above
Solution is mixed evenly, and TritonX-100 is added, obtains mixed solution.Only by chitosan use acetate dissolution, then with it is other
Polymer Solution mixes, and is because dissolving the excessive acetic acid of chitosan needs, and polyethylene glycol oxide is dissolved to transparent be also required to less
Acetic acid is measured, excessive acetic acid can meet polyethylene glycol oxide and is dissolved to the needs of transparent just when chitosan dissolves, and spinning solution
In acetic acid can excessively reduce the spinnability of solution.Mixed solution is stirred, then ultrasound or standing are defoamed to transparent clear
After clear, take mixed solution to carry out electrostatic spinning by electrospinning device, obtain macromolecule mixture fiber.Fig. 2 is the present invention
The scanning electron microscope (SEM) photograph of 5 macromolecule mixture fiber of embodiment, as can be seen from Figure the method for the present invention can obtain smooth even and
Crosslinked nanofiber.The fiber is placed in tube furnace, first pre-oxidizes, then carries out at temperature programming heat in air
Reason, the at this time fibers carbonization obtained by electrospinning, labile element volatilization leave abundant micropore and mesoporous；Finally obtain cobalt, nitrogen
Adulterate porous carbon composite nano-fiber.Fig. 3 is the scanning electricity of 3 cobalt of the embodiment of the present invention, the porous carbon composite nano-fiber of N doping
Mirror figure, Fig. 4 are the transmission electron microscope pictures of 1 cobalt of the embodiment of the present invention, the porous carbon composite nano-fiber of N doping, as can be seen from Figure 4, cobalt gold
The reunion of metal particles is grown up has obtained certain inhibition under this temperature program；From the comparison of Fig. 2 and Fig. 3, Fig. 4 it is found that quiet
The obtained fiber morphology of Electrospun has obtained good holding under temperature program appropriate, and hole is formed in pyrolytic process
With finely dispersed particle.The temperature program is to maintain an important factor for carbon nano-fiber pattern, and control is improper, cannot keep
Complete fiber morphology.
Embodiment 1
A kind of cobalt, the preparation process of the porous carbon composite nano-fiber of N doping are as follows：
1）Preparation of spinning solution：The chitosan that average molecular weight is 53.5 ten thousand is dissolved in the aqueous solution of acetic acid, and average molecular weight of making even is 100
Ten thousand polyethylene glycol oxide is dissolved in deionized water, and four hydration cobalt acetates are added after taking polyethyleneimine to be diluted with deionized water, will be with
Upper three kinds of solution is mixed evenly, be added TritonX-100, obtain spinning solution, wherein chitosan it is a concentration of
2.4wt%, acetate concentration 0.7wt%, a concentration of 1.4wt% of polyethylene glycol oxide, a concentration of 0.3wt% of polyethyleneimine, vinegar
A concentration of 0.5wt% of a concentration of 0.1wt% of sour cobalt, TritonX-100；It is small that mixed solution stirs 24 in 30 DEG C of water-baths
When.2）Electrostatic spinning：Gained spinning solution is fitted into syringe and carries out electrostatic spinning, wherein spinning distance is 15 cm, solution
Flow is 0.6mL/h, and application voltage is 25kV.3）Heat treatment：Mixing macromolecular fibre obtained by spinning is placed in tube furnace, is first existed
It is pre-oxidized 6 hours for 130 DEG C in air, then under inert atmosphere, is first warming up to 300 DEG C with 3 DEG C/min, constant temperature 2 hours, then with 1
DEG C/min is warming up to 400 DEG C, constant temperature 0.5 hour, then 10 DEG C/min rises to 900 DEG C, and constant temperature 0.5 hour finally obtains cobalt, nitrogen
Adulterate porous carbon composite nano-fiber.
Embodiment 2
A kind of cobalt, the preparation process of the porous carbon composite nano-fiber of N doping are as follows：
1）Preparation of spinning solution：The chitosan that average molecular weight of making even is 53.5 ten thousand is dissolved in the aqueous solution of acetic acid, and average molecular weight of making even is
300000 polyethylene glycol oxide is dissolved in deionized water, and four hydration cobalt acetates are added after taking polyethyleneimine to be diluted with deionized water, will
Three of the above solution is mixed evenly, be added TritonX-100, obtain spinning solution, wherein chitosan it is a concentration of
1wt%, acetate concentration 0.3wt%, a concentration of 3wt% of polyethylene glycol oxide, a concentration of 0.3wt% of polyethyleneimine, cobalt acetate
A concentration of 0.1wt%, a concentration of 0.4wt% of TritonX-100；Mixed solution stirs 24 hours in 40 DEG C of water-baths.2）
Electrostatic spinning：Gained spinning solution is fitted into syringe and carries out electrostatic spinning, wherein spinning distance is 20 cm, and liquid inventory is
0.8mL/h, application voltage are 20kV.3）Heat treatment：Mixing macromolecular fibre obtained by spinning is placed in tube furnace, first in air
120 DEG C pre-oxidize 3 hours, then under inert atmosphere, are first warming up to 300 DEG C with 1 DEG C/min, constant temperature 0.5 hour, then with 1 DEG C/
Min is warming up to 400 DEG C, constant temperature 1 hour, and then 6 DEG C/min rises to 800 DEG C, and it is porous to finally obtain cobalt, N doping for constant temperature 1 hour
Carbon composite nano-fiber.
Embodiment 3
A kind of cobalt, N doping porous carbon receive composite rice fiber preparation process it is as follows：
1）Preparation of spinning solution：The chitosan that average molecular weight is 600,000 is dissolved in the aqueous solution of acetic acid, and average molecular weight of making even is 1,000,000
Polyethylene glycol oxide be dissolved in deionized water, after taking polyethyleneimine to be diluted with deionized water be added four hydration cobalt acetates, will more than
Three kinds of solution are mixed evenly, and TritonX-100 is added, obtains spinning solution, wherein a concentration of 2.9wt% of chitosan,
Acetate concentration is 1.1wt%, a concentration of 2.4wt% of polyethylene glycol oxide, a concentration of 0.5wt% of polyethyleneimine, cobalt acetate it is dense
Degree is 0.2wt%, a concentration of 0.8wt% of TritonX-100；Mixed solution stirs 8 hours in 30 DEG C of water-baths.2）Static Spinning
Silk：Gained spinning solution is fitted into syringe and carries out electrostatic spinning, wherein spinning distance is 10 cm, liquid inventory 0.3mL/
H, application voltage are 15kV.3）Heat treatment：Mixing macromolecular fibre obtained by spinning is placed in tube furnace, first 150 DEG C in air
Pre-oxidation 4 hours then under inert atmosphere, is first warming up to 240 DEG C with 3 DEG C/min, constant temperature 2 hours, then is heated up with 3 DEG C/min
To 340 DEG C, constant temperature 2 hours, then 3 DEG C/min rise to 800 DEG C, it is compound to finally obtain cobalt, N doping porous carbon for constant temperature 2 hours
Nanofiber.
Fig. 5 be 3 cobalt of embodiment, the porous carbon composite nano-fiber of N doping BET test result figures exist as seen from the figure
The hysteresis loop of open-wire line, it was demonstrated that the presence of its central hole structure obtains cobalt, N doping porous carbon nanofiber according to data in figure
Specific surface area is 563.4m2/ g, Kong Rongwei 0.59cm3/g。
Embodiment 4
A kind of cobalt, the preparation process of the porous carbon composite nano-fiber of N doping are as follows：
1）Preparation of spinning solution：The chitosan that average molecular weight is 53.5 ten thousand is dissolved in the aqueous solution of acetic acid, and average molecular weight of making even is 100
Ten thousand polyethylene glycol oxide is dissolved in deionized water, and four hydration cobalt acetates are added after taking polyethyleneimine to be diluted with deionized water, will be with
Upper three kinds of solution is mixed evenly, be added TritonX-100, obtain spinning solution, wherein chitosan it is a concentration of
1.3wt%, acetate concentration 1.5wt%, a concentration of 2.5wt% of polyethylene glycol oxide, a concentration of 1.3wt% of polyethyleneimine, vinegar
A concentration of 0.4wt% of a concentration of 0.1wt% of sour cobalt, TritonX-100；It is small that mixed solution stirs 24 in 25 DEG C of water-baths
When.2）Electrostatic spinning：Gained spinning solution is fitted into syringe and carries out electrostatic spinning, wherein spinning distance is 13 cm, solution
Flow is 0.9mL/h, and application voltage is 18kV.3）Heat treatment：Mixing macromolecular fibre obtained by spinning is placed in tube furnace, is first existed
It is pre-oxidized 3 hours for 120 DEG C in air, then under inert atmosphere, is first warming up to 200 DEG C with 1 DEG C/min, constant temperature 0.5 hour, then with
1 DEG C/min is warming up to 400 DEG C, constant temperature 2 hours, and then 10 DEG C/min rises to 800 DEG C, and constant temperature 2 hours finally obtains cobalt, nitrogen is mixed
Miscellaneous porous carbon receives composite rice fiber.
Fig. 6 is the porous carbon composite nano-fiber of cobalt, N doping that is prepared of embodiment 4 through 2mol/L HCl pickling, 800
DEG C annealing after, in 0.1mol/L KOH solutions carry out hydrogen reduction LSV curves.It will be appreciated from fig. 6 that cobalt, N doping porous carbon are multiple
Close nanofiber catalytic oxidation-reduction reaction take-off potential be -0.04V, half wave potential be -0.13V, this illustrate the present invention cobalt,
The porous carbon composite nano-fiber of N doping has high catalytic activity to oxygen reduction reaction.
Embodiment 5
A kind of cobalt, the preparation process of the porous carbon composite nano-fiber of N doping are as follows：
1）Water phase preparation of spinning solution：The chitosan that average molecular weight of making even is 500,000 is dissolved in the aqueous solution of acetic acid, average molecular weight of making even
It is dissolved in deionized water for 600,000 polyethylene glycol oxide, four hydration cobalt acetates are added after taking polyethyleneimine to be diluted with deionized water,
Three of the above solution is mixed evenly, be added TritonX-100, obtain spinning solution, wherein chitosan it is a concentration of
1.9wt%, acetate concentration 0.6wt%, a concentration of 1.5wt% of polyethylene glycol oxide, a concentration of 0.8wt% of polyethyleneimine, vinegar
A concentration of 0.6wt% of a concentration of 0.5wt% of sour cobalt, TritonX-100；It is small that mixed solution stirs 12 in 40 DEG C of water-baths
When.2）Electrostatic spinning：Gained spinning solution is fitted into syringe and carries out electrostatic spinning, wherein spinning distance is 15 cm, solution
Flow is 0.48mL/h, and application voltage is 19kV.3）Heat treatment：Mixing macromolecular fibre obtained by spinning is placed in tube furnace, first
It pre-oxidizes 2 hours for 140 DEG C in air, then under inert atmosphere, is first warming up to 200 DEG C with 3 DEG C/min, constant temperature 4 hours, then with
2 DEG C/min is warming up to 300 DEG C, and then constant temperature 2 hours rises to 700 DEG C with 5 DEG C/min, constant temperature 3 hours finally obtains cobalt, nitrogen is mixed
Miscellaneous porous carbon composite nano-fiber.
In embodiment 5, the content of cobalt acetate is 0.5wt% in spinning solution, and obtained cobalt, N doping porous carbon are compound
After high temperature pyrolysis, unstable substance volatilizees nanofiber substantially, and cobalt element almost all retains, therefore cobalt, the nitrogen generated
It adulterates porous carbon composite nano-fiber and contains more cobalt-based fake capacitance material.
The porous carbon composite nano-fiber of cobalt, N doping and conductive black, adhesion agent will be obtained through this embodiment（PTFE）
Ultracapacitor working electrode is made in mixing back loading in nickel foam, and Fig. 7 is the ultracapacitor working electrode in 6 mol/L
Constant current charge-discharge curve graph in KOH solution, as seen from the figure, under the current density of 1A/g, which is
94.9F/g。
Claims (10)
1. a kind of environment-friendly preparation method thereof of the porous carbon composite nano-fiber of cobalt, N doping, which is characterized in that using aqueous phase system
Electrostatic spinning combination heat treatment technics, specifically includes following steps:
The preparation of water phase spinning solution：Carbon source is first dissolved in aqueous acetic acid respectively, spinning-aid agent is dissolved in deionized water, nitrogen source and complexing
Cobalt source is added after being diluted with deionized water in agent, obtains three kinds of solution；Then three kinds of solution are uniformly mixed, add surface-active
Agent, stirring, obtains water phase spinning solution；
2）Electrostatic spinning：Electrostatic spinning is carried out under conditions of electrostatic spinning to water phase spinning solution；
3）Heat treatment：Sample obtained by electrostatic spinning is placed in tube furnace, is first pre-oxidized in air；Then in inert atmosphere
Under, temperature-programmed pyrolysis carbonization obtains the porous carbon composite nano-fiber of cobalt, N doping.
2. the environment-friendly preparation method thereof of a kind of cobalt according to claim 1, the porous carbon composite nano-fiber of N doping, feature
It is:The step 1）Carbon source is chitosan, and cobalt source is cobalt acetate, and spinning-aid agent is polyethylene glycol oxide, and nitrogen source and complexing agent are poly-
Aziridine, surfactant are Triton X-100 TritonX-100.
3. the environment-friendly preparation method thereof of a kind of cobalt according to claim 2, the porous carbon composite nano-fiber of N doping, feature
It is:The average molecular weight of the chitosan is 50 ~ 600,000, and the average molecular weight of polyethylene glycol oxide is 30 ~ 1,000,000.
4. the environment-friendly preparation method thereof of a kind of cobalt according to claim 1, the porous carbon composite nano-fiber of N doping, feature
It is:The step 1）In, the mass concentration that cobalt source accounts for water phase spinning solution is 0.1 ~ 0.5wt%.
5. the environment-friendly preparation method thereof of a kind of cobalt according to claim 1, the porous carbon composite nano-fiber of N doping, feature
It is:The step 1）In, the mass concentration that carbon source accounts for water phase spinning solution is 1 ~ 3 wt%, and acetic acid accounts for the quality of water phase spinning solution
A concentration of 0.3 ~ 1.5wt%, the mass concentration that spinning-aid agent accounts for water phase spinning solution are 1.4 ~ 3 wt%, and nitrogen source and complexing agent account for water phase spinning
The mass concentration of silk liquid is 0.3 ~ 1.3wt%, and the mass concentration that surfactant accounts for water phase spinning solution is 0.4 ~ 0.8wt%.
6. the environment-friendly preparation method thereof of a kind of cobalt according to claim 1, the porous carbon composite nano-fiber of N doping, feature
It is:The step 1）Middle whipping temp is 25 ~ 40 DEG C, and the time is 8 ~ 24 hours.
7. the environment-friendly preparation method thereof of a kind of cobalt according to claim 1, the porous carbon composite nano-fiber of N doping, feature
It is:Step 2）Described in the condition of electrostatic spinning be：Spinning distance is 10 ~ 20cm；The flow velocity of spinning solution is 0.3 ~ 0.9mL/
h；Spinning voltage is 15 ~ 25kV.
8. the environment-friendly preparation method thereof of a kind of cobalt according to claim 1, the porous carbon composite nano-fiber of N doping, feature
It is:Step 3）Described in Pre oxidation be 120 ~ 150 DEG C, the time be 2 ~ 6 hours.
9. the environment-friendly preparation method thereof of a kind of cobalt according to claim 1, the porous carbon composite nano-fiber of N doping, feature
It is:Step 3）Described in temperature programming be：In tube furnace, under an inert atmosphere, 200 ~ 300 are warming up to 1 ~ 3 DEG C/min
DEG C, constant temperature 0.5 ~ 4 hour；300 ~ 400 DEG C are warming up to 1 ~ 3 DEG C/min again, constant temperature 0.5 ~ 2 hour；Then 3-10 DEG C/min liters
To 700 ~ 900 DEG C, constant temperature 1 ~ 3 hour.
10. a kind of environment-friendly preparation method thereof of the porous carbon composite nano-fiber of cobalt, N doping according to claim 1 or 9,
It is characterized in that：The inert atmosphere is one or more of nitrogen or argon gas.
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| CN110474031A (en) * | 2019-08-20 | 2019-11-19 | 齐鲁工业大学 | A method of Copper-cladding Aluminum Bar mangano-manganic oxide composite material is prepared using polymeric complexing agent |
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| CN110474031A (en) * | 2019-08-20 | 2019-11-19 | 齐鲁工业大学 | A method of Copper-cladding Aluminum Bar mangano-manganic oxide composite material is prepared using polymeric complexing agent |
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