CN107934935A - A kind of nitrogen-doped carbon nano-fiber and its preparation method and application - Google Patents

A kind of nitrogen-doped carbon nano-fiber and its preparation method and application Download PDF

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CN107934935A
CN107934935A CN201711176718.6A CN201711176718A CN107934935A CN 107934935 A CN107934935 A CN 107934935A CN 201711176718 A CN201711176718 A CN 201711176718A CN 107934935 A CN107934935 A CN 107934935A
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fiber
carbon nano
nitrogen
doped carbon
salt
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易清风
余亮
李广
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Hunan University of Science and Technology
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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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    • B82—NANOTECHNOLOGY
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    • 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
    • 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
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    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • 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
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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    • 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

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Abstract

The invention discloses a kind of preparation method of nitrogen-doped carbon nano-fiber, including step：（1）Material precursor prepares and high temperature cabonization；（2）It is prepared by nitrogen-doped carbon nano-fiber.The present invention is using nickel salt and cobalt salt as catalyst, using glucose as carbon source, using melamine and dicyandiamide as nitrogen source, by their mixture by simple high temperature pyrolysis, prepares the carbon nano-fiber of N doping.The caliber of this carbon nano-fiber is small, and while high temperature pyrolysis forms carbon nano-fiber, nitrogen is also adulterated into inside carbon structure.The carbon nano-fiber of this N doping has excellent property as the electrode material of electric chemical super capacitor, and its preparation process is simple, and operation is easy；The cost of material used is low, is readily available.The method of the carbon nano-fiber for preparing N doping of the present invention cannot be only used for laboratory research, it can also be used to which industrial large-scale production, has important research and application value.

Description

A kind of nitrogen-doped carbon nano-fiber and its preparation method and application
Technical field
The invention belongs to new carbon technical field, and in particular to a kind of nitrogen-doped carbon nano-fiber and its preparation side Method.
Background technology
Carbon nano-fiber（Carbon nano-fibers, abbreviation CNFs）It is a kind of discontinuous graphite line, and standard one The new carbon of dimension, has been subject to the extensive concern of scientific worker since nearest more than ten years.The diameter of CNFs is generally received more than ten Rice is to nanometers up to a hundred, and length is typically up to tens microns, and aspect ratio distribution is 100~500.CNFs is between graphite and ball Material between carbon, is formed by the graphite flake layer of nano-scale in space and the axial of fiber into different angle accumulation.People are led to Further investigation is crossed, it is found that carbon nano-fiber has unique fibre structure, not only with defects count is few, specific surface area is big, long Footpath than it is big the advantages that, also have the spy such as low-density, high ratio modulus, high specific strength, high conductivity, high-termal conductivity and compact structure Property, this new carbon material storage material, electrode material, catalyst and catalyst carrier, high-efficiency adsorbent, point
Have broad application prospects from agent and composite material etc..
The preparation method of CNFs is relatively more, but mainly has so several：（1）Matrix method：Utilize ceramics or SiO2Fiber is made Matrix, then by catalyst granules（The mostly transition metal such as Fe, Co, Ni）Nanometer particle is separated into, and makes it It is dispersed on matrix, catalyst deposits on matrix in the reactor all the time in reaction process, according to catalyst activity Difference select suitable reaction temperature, be passed through hydrocarbon gas and be pyrolyzed and decompose, Carbon deposition growth, which obtains, has nanoscale Carbon fiber.（2）Spray process：Nano-catalyst particles, such as lemel, ferrocene are prepared first, then by nano-catalytic Agent particle is sufficiently mixed with liguid organic solvents such as benzene according to a certain percentage, finally controls certain pressure, and this mixing is molten Liquid is sprayed into pyroreaction room, obtains carbon nano tube/carbon fiber.（3）Gas phase flows catalysis method：By some metallorganics, such as two Luxuriant iron etc. is mixed with hydrocarbon, then is heated to gaseous state, and is concomitantly introduced into pyroreaction with some hydrocarbon gas Room, completes catalysis and the decomposition of hydrocarbon gas at high temperature, and the metallic particles of generation is dispersed in whole reative cell as catalyst Space, and the pyrogenous origin carbon atom of hydrocarbon gas grows into carbon nano-fiber under nm-class catalyst catalysis.（4）Plasma Body enhancing chemical vapour deposition technique (PECVD):First a certain amount of pure inert gas is filled with the reative cell being evacuated, Then plasma electrical source is connected, while imports various reacting gas and protective gas, reaction system quilt within the extremely short time Plasma high-temperature flame stream heats and reaches the temperature for triggering corresponding chemical reaction, promotes the chemical reaction between gas, so that Whisker is deposited under lower temperature and obtains carbon fiber product.（5）Method of electrostatic spinning：Continuous Nano carbon fibers can be made in this way Dimension.（6）Arc process：This method is also one of main method for preparing carbon nano-fiber material.（7）Laser ablation/radio frequency Magnetic control method：Catalyst and target are closed into powder briquet, after high temperature degassing, target is heated to 1200 °C or so, is used Beam of laser ablation target forms aerosol, while is blown into traffic protection gas（He or Ar）, under certain air pressure, going out Gas port is nearby collected by water cooling collector and carbon nano-fiber is made.
The content of the invention
The object of the present invention is to provide a kind of nitrogen-doped carbon nano-fiber, the purpose of the present invention additionally provides a kind of N doping The preparation method of carbon nano-fiber.
Embodiment of the present invention is：A kind of preparation method of nitrogen-doped carbon nano-fiber, comprises the following steps：
（1）It is prepared by material precursor：
Nickel salt or the salt-mixture of cobalt salt or nickel salt and cobalt salt, glucose, melamine and dicyandiamide are added in deionized water, It is sufficiently stirred at room temperature, forms uniform dispersion；Then, by the dispersion liquid 80OHeating in vacuum in C water-baths, removes moisture content, By obtained solid in 40OIt is dried in vacuo under C, obtained solid is material precursor；
The nickel salt or cobalt salt or salt-mixture, glucose, melamine, the mass ratio of dicyandiamide are：Nickel salt or cobalt salt are mixed Close salt：Glucose：Melamine：Dicyandiamide=1~15：1~30：5~100：10~150；
（2）It is prepared by material precursor high temperature cabonization：
By above-mentioned material presoma in a nitrogen atmosphere, with 4oC min-1Programming rate be heated to 550OC, and keep the temperature Spend certain time；Then with 2oC min-1Programming rate continue to be warming up to 820OC, and kept for temperature certain time；Finally Room temperature is naturally cooled under nitrogen atmosphere, obtains black solid particle, is collected, it is pending；
（3）It is prepared by nitrogen-doped carbon nano-fiber：
Above-mentioned black solid particle is placed in 2 mol L-1H2SO4In, it is slowly stirred at room temperature, filters, be washed till with pure water Neutrality, is finally washed with absolute ethyl alcohol, by obtained solid in 400It is dried in vacuo under C, obtains nitrogen-doped carbon nano-fiber；
The nickel salt is nickel acetate（Ni(CH3COO)2×4H2O）, nickel nitrate (Ni (NO3)2×6H2) or nickel chloride (NiCl O2× 6H2O)。
The cobalt salt is cobalt acetate（Co(CH3COO)2×4H2O）, cobalt nitrate (Co (NO3)2×6H2) or cobalt chloride O (CoCl2×6H2O)。
In the salt-mixture, the mass ratio of nickel salt and cobalt salt is（1 ~ 100）：（0.1 ~ 50）.
Nitrogen-doped carbon nano-fiber prepared by the preparation method described in a kind of basis.
Application of the nitrogen-doped carbon nano-fiber prepared according to the preparation method in terms of electrode.
（4）In common three-electrode system, the electrochemical capacitor characteristic of product is measured in different electrolyte solutions. The nitrogen-doped carbon nano-fiber is mixed with absolute ethyl alcohol, adds the Nafion solution that mass percent is 5%, then will Mixture forms pastel after being ultrasonically treated, and the pastel finally is coated in carbon paper surface, working electrode is used as after dry, with platinum Piece is that saturated calomel electrode is reference electrode, using common cyclic voltammetric technology or cycle charge discharge power technology, in electrode Property electrolyte solution in measure gained nitrogen-doped carbon nano-fiber capacitance characteristic.
The neutral electrolyte solution is 0.1 mol L-1K2SO4, or 0.1 mol L-1KNO3;
The present invention uses nickel salt and cobalt salt, using glucose as carbon source, nitrogen to be used as using melamine and dicyandiamide as catalyst Source, by their mixture by simple high temperature pyrolysis, prepares the carbon nano-fiber of N doping.Carbon material passes through N doping Afterwards, its various physical and chemical performances are greatly improved.The caliber of this carbon nano-fiber is small, and in high temperature pyrolysis shape While into carbon nano-fiber, nitrogen is also adulterated into inside carbon structure.The carbon nano-fiber of this N doping surpasses as electrochemistry The electrode material of level capacitor has excellent property, and its preparation process is simple, and operation is easy；The cost of material used It is low, it is readily available.The method of the carbon nano-fiber for preparing N doping of the present invention cannot be only used for laboratory research, it can also be used to Industrial large-scale production, has important research and application value.
Embodiment
Embodiment 1：
（1）It is prepared by material precursor
By 1 g nickel acetate Ni (CH3COO)2×4H2O）, 1 g glucose, 5 g melamines and 10 g dicyandiamides be added to 80mL In deionized water, it is sufficiently stirred at room temperature, forms uniform dispersion；Then, which is transferred in Rotary Evaporators, 80OHeating in vacuum in C water-baths, removes moisture content, obtained solid is placed in vacuum drying chamber again, 40OWhen drying 24 is small under C, obtain The solid arrived is material precursor.
（2）It is prepared by material precursor high temperature cabonization
Above-mentioned material presoma is transferred in tube furnace, in a nitrogen atmosphere, with 4oC min-1Programming rate be heated to 550OC, and at this temperature keep 2.5 it is small when；Then with 2oC min-1Programming rate continue to be warming up to 820OC, and herein At a temperature of keep 2 it is small when；Room temperature is finally naturally cooled under nitrogen atmosphere, obtains black solid particle, is collected, it is pending.
（3）It is prepared by nitrogen-doped carbon nano-fiber
Above-mentioned black solid particle is placed in 2 mol L-1H2SO4In, be slowly stirred at room temperature 3 it is small when, filter afterwards, use A large amount of pure water are washed till neutrality, are finally washed three times, obtained solid are put in vacuum drying chamber, in 40 with absolute ethyl alcohol0Done under C It is dry 24 it is small when, obtain nitrogen-doped carbon nano-fiber, its caliber is 30 ~ 35nm, and length is 4 ~ 4.5mm.
（4）The specific capacitance test process of nitrogen-doped carbon nano-fiber：In common three-electrode system, in different electrolysis The electrochemical capacitor characteristic of product is measured in matter solution.The nitrogen-doped carbon nano-fiber is mixed with absolute ethyl alcohol, adds matter The Nafion solution that percentage is 5% is measured, pastel is formed after then mixture is ultrasonically treated, finally applies the pastel In glassy carbon electrode surface, working electrode is used as after dry, using platinized platinum as to electrode, saturated calomel electrode is reference electrode, is used Common cyclic voltammetric technology or cycle charge discharge power technology, the nitrogen-doped carbon Nanowire in neutral electrolyte solution obtained by measure The capacitance characteristic of dimension.
The specific capacitance test result of nitrogen-doped carbon nano-fiber：In 0.1 mol L-1K2SO4In solution, electric current 0.1 A g-1When specific capacitance be 310 F g-1, electric current is 0.5 A g-1When specific capacitance be 290 F g-1；In 0.1 mol L-1's KNO3In solution, electric current is 0.1 A g-1When specific capacitance be 305F g-1, electric current is 0.5 A g-1When specific capacitance be 288 F g-1。
Embodiment 2：
（1）It is prepared by material precursor
By 8 g nickel acetate Ni (CH3COO)2×4H2O）, 15 g glucose, 50 g melamines and 80 g dicyandiamides are added to In 1200mL deionized waters, it is sufficiently stirred at room temperature, forms uniform dispersion；Then, which is transferred to rotary evaporation In instrument, 80OHeating in vacuum in C water-baths, removes moisture content, obtained solid is placed in vacuum drying chamber again, 40ODry 24 under C Hour, obtained solid is material precursor.
（2）It is prepared by material precursor high temperature cabonization
The step of with embodiment 1（2）It is identical.
（3）It is prepared by nitrogen-doped carbon nano-fiber
Above-mentioned black solid particle is placed in 2 mol L-1H2SO4In, be slowly stirred at room temperature 3 it is small when, filter afterwards, use A large amount of pure water are washed till neutrality, are finally washed three times, obtained solid are put in vacuum drying chamber, in 40 with absolute ethyl alcohol0Done under C It is dry 24 it is small when, obtain nitrogen-doped carbon nano-fiber, its caliber is 29 ~ 32nm, and length is 4 ~ 4.4mm.
（4）The specific capacitance test process of nitrogen-doped carbon nano-fiber：The step of with embodiment 1（4）It is identical.
The specific capacitance test result of nitrogen-doped carbon nano-fiber：In 0.1 mol L-1K2SO4In solution, electric current 0.1 A g-1When specific capacitance be 322 F g-1, electric current is 0.5 A g-1When specific capacitance be 291 F g-1；In 0.1 mol L-1's KNO3In solution, electric current is 0.1 A g-1When specific capacitance be 315F g-1, electric current is 0.5 A g-1When specific capacitance be 292F g-1。
Embodiment 3：
（1）It is prepared by material precursor
By 15g nickel acetate Ni (CH3COO)2×4H2O）, 30 g glucose, 100 g melamines and 150 g dicyandiamides are added to In 2400mL deionized waters, it is sufficiently stirred at room temperature, forms uniform dispersion；Then, which is transferred to rotary evaporation In instrument, 80OHeating in vacuum in C water-baths, removes moisture content, obtained solid is placed in vacuum drying chamber again, 40ODry 24 under C Hour, obtained solid is material precursor.
（2）It is prepared by material precursor high temperature cabonization
The step of with embodiment 1（2）It is identical.
（3）It is prepared by nitrogen-doped carbon nano-fiber
Above-mentioned black solid particle is placed in 2 mol L-1H2SO4In, be slowly stirred at room temperature 3 it is small when, filter afterwards, use A large amount of pure water are washed till neutrality, are finally washed three times, obtained solid are put in vacuum drying chamber, in 40 with absolute ethyl alcohol0Done under C It is dry 24 it is small when, obtain nitrogen-doped carbon nano-fiber, its caliber is 33 ~ 38nm, and length is 3.3 ~ 3.8mm.
（4）The specific capacitance test process of nitrogen-doped carbon nano-fiber：The step of with embodiment 1（4）It is identical.
The specific capacitance test result of nitrogen-doped carbon nano-fiber：In 0.1 mol L-1K2SO4In solution, electric current 0.1 A g-1When specific capacitance be 312 F g-1, electric current is 0.5 A g-1When specific capacitance be 290 F g-1；In 0.1 mol L-1's KNO3In solution, electric current is 0.1 A g-1When specific capacitance be 319F g-1, electric current is 0.5 A g-1When specific capacitance be 294F g-1。
Embodiment 4：
（1）It is prepared by material precursor
By 1 nickel nitrate (Ni (NO3)2×6H2O), 1 g glucose, 5 g melamines and 10 g dicyandiamides be added to 80mL go from In sub- water, it is sufficiently stirred at room temperature, forms uniform dispersion；Then, which is transferred in Rotary Evaporators, 80OC Heating in vacuum in water-bath, removes moisture content, obtained solid is placed in vacuum drying chamber again, 40OWhen drying 24 is small under C, obtain Solid be material precursor.
（2）It is prepared by material precursor high temperature cabonization
The step of with embodiment 1（2）It is identical.
（3）It is prepared by nitrogen-doped carbon nano-fiber
Above-mentioned black solid particle is placed in 2 mol L-1H2SO4In, be slowly stirred at room temperature 3 it is small when, filter afterwards, use A large amount of pure water are washed till neutrality, are finally washed three times, obtained solid are put in vacuum drying chamber, in 40 with absolute ethyl alcohol0Done under C It is dry 24 it is small when, obtain nitrogen-doped carbon nano-fiber, its caliber is 30 ~ 34nm, and length is 3.9 ~ 4.5mm.
（4）The specific capacitance test process of nitrogen-doped carbon nano-fiber：The step of with embodiment 1（4）It is identical.
The specific capacitance test result of nitrogen-doped carbon nano-fiber：In 0.1 mol L-1K2SO4In solution, electric current 0.1 A g-1When specific capacitance be 311 F g-1, electric current is 0.5 A g-1When specific capacitance be 289 F g-1；In 0.1 mol L-1's KNO3In solution, electric current is 0.1 A g-1When specific capacitance be 304F g-1, electric current is 0.5 A g-1When specific capacitance be 289 F g-1。
Embodiment 5：
（1）It is prepared by material precursor
By 8 g nickel nitrates (Ni (NO3)2×6H2O), 15 g glucose, 50 g melamines and 80 g dicyandiamides are added to In 1200mL deionized waters, it is sufficiently stirred at room temperature, forms uniform dispersion；Then, which is transferred to rotary evaporation In instrument, 80OHeating in vacuum in C water-baths, removes moisture content, obtained solid is placed in vacuum drying chamber again, 40ODry 24 under C Hour, obtained solid is material precursor.
（2）It is prepared by material precursor high temperature cabonization
The step of with embodiment 1（2）It is identical.
（3）It is prepared by nitrogen-doped carbon nano-fiber
Above-mentioned black solid particle is placed in 2 mol L-1H2SO4In, be slowly stirred at room temperature 3 it is small when, filter afterwards, use A large amount of pure water are washed till neutrality, are finally washed three times, obtained solid are put in vacuum drying chamber, in 40 with absolute ethyl alcohol0Done under C It is dry 24 it is small when, obtain nitrogen-doped carbon nano-fiber, its caliber is 29 ~ 33nm, and length is 4 ~ 4.2mm.
（4）The specific capacitance test process of nitrogen-doped carbon nano-fiber：The step of with embodiment 1（4）It is identical.
The specific capacitance test result of nitrogen-doped carbon nano-fiber：In 0.1 mol L-1K2SO4In solution, electric current 0.1 A g-1When specific capacitance be 320 F g-1, electric current is 0.5 A g-1When specific capacitance be 290 F g-1；In 0.1 mol L-1's KNO3In solution, electric current is 0.1 A g-1When specific capacitance be 312F g-1, electric current is 0.5 A g-1When specific capacitance be 290F g-1。
Embodiment 6：
（1）It is prepared by material precursor
By 15g nickel nitrates (Ni (NO3)2×6H2O), 30 g glucose, 100 g melamines and 150 g dicyandiamides are added to In 2400mL deionized waters, it is sufficiently stirred at room temperature, forms uniform dispersion；Then, which is transferred to rotary evaporation In instrument, 80OHeating in vacuum in C water-baths, removes moisture content, obtained solid is placed in vacuum drying chamber again, 40ODry 24 under C Hour, obtained solid is material precursor.
（2）It is prepared by material precursor high temperature cabonization
The step of with embodiment 1（2）It is identical.
（3）It is prepared by nitrogen-doped carbon nano-fiber
Above-mentioned black solid particle is placed in 2 mol L-1H2SO4In, be slowly stirred at room temperature 3 it is small when, filter afterwards, use A large amount of pure water are washed till neutrality, are finally washed three times, obtained solid are put in vacuum drying chamber, in 40 with absolute ethyl alcohol0Done under C It is dry 24 it is small when, obtain nitrogen-doped carbon nano-fiber, its caliber is 30 ~ 33nm, and length is 3.8 ~ 4.2mm.
（4）The specific capacitance test process of nitrogen-doped carbon nano-fiber：The step of with embodiment 1（4）It is identical.
The specific capacitance test result of nitrogen-doped carbon nano-fiber：In 0.1 mol L-1K2SO4In solution, electric current 0.1 A g-1When specific capacitance be 314 F g-1, electric current is 0.5 A g-1When specific capacitance be 294 F g-1；In 0.1 mol L-1's KNO3In solution, electric current is 0.1 A g-1When specific capacitance be 316F g-1, electric current is 0.5 A g-1When specific capacitance be 298F g-1。
Embodiment 7：
（1）It is prepared by material precursor
By 1 nickel chloride (NiCl2×6H2O), 1 g glucose, 5 g melamines and 10 g dicyandiamides are added to 80mL deionizations In water, it is sufficiently stirred at room temperature, forms uniform dispersion；Then, which is transferred in Rotary Evaporators, 80OC water Heating in vacuum in bath, removes moisture content, obtained solid is placed in vacuum drying chamber again, 40OWhen drying 24 is small under C, obtain Solid is material precursor.
（2）It is prepared by material precursor high temperature cabonization
The step of with embodiment 1（2）It is identical.
（3）It is prepared by nitrogen-doped carbon nano-fiber
Above-mentioned black solid particle is placed in 2 mol L-1H2SO4In, be slowly stirred at room temperature 3 it is small when, filter afterwards, use A large amount of pure water are washed till neutrality, are finally washed three times, obtained solid are put in vacuum drying chamber, in 40 with absolute ethyl alcohol0Done under C It is dry 24 it is small when, obtain nitrogen-doped carbon nano-fiber, its caliber is 38 ~ 42nm, and length is 2.9 ~ 3.5mm.
（4）The specific capacitance test process of nitrogen-doped carbon nano-fiber：The step of with embodiment 1（4）It is identical.
The specific capacitance test result of nitrogen-doped carbon nano-fiber：In 0.1 mol L-1K2SO4In solution, electric current 0.1 A g-1When specific capacitance be 301 F g-1, electric current is 0.5 A g-1When specific capacitance be 280 F g-1；In 0.1 mol L-1's KNO3In solution, electric current is 0.1 A g-1When specific capacitance be 294F g-1, electric current is 0.5 A g-1When specific capacitance be 278 F g-1。
Embodiment 8：
（1）It is prepared by material precursor
By 8 g nickel chlorides (NiCl2×6H2O), 15 g glucose, 50 g melamines and 80 g dicyandiamides are added to 1200mL In deionized water, it is sufficiently stirred at room temperature, forms uniform dispersion；Then, which is transferred in Rotary Evaporators, 80OHeating in vacuum in C water-baths, removes moisture content, obtained solid is placed in vacuum drying chamber again, 40OWhen drying 24 is small under C, obtain The solid arrived is material precursor.
（2）It is prepared by material precursor high temperature cabonization
The step of with embodiment 1（2）It is identical.
（3）It is prepared by nitrogen-doped carbon nano-fiber
Above-mentioned black solid particle is placed in 2 mol L-1H2SO4In, be slowly stirred at room temperature 3 it is small when, filter afterwards, use A large amount of pure water are washed till neutrality, are finally washed three times, obtained solid are put in vacuum drying chamber, in 40 with absolute ethyl alcohol0Done under C It is dry 24 it is small when, obtain nitrogen-doped carbon nano-fiber, its caliber is 33 ~ 39nm, and length is 3.7 ~ 4.2mm.
（4）The specific capacitance test process of nitrogen-doped carbon nano-fiber：The step of with embodiment 1（4）It is identical.
The specific capacitance test result of nitrogen-doped carbon nano-fiber：In 0.1 mol L-1K2SO4In solution, electric current 0.1 A g-1When specific capacitance be 312 F g-1, electric current is 0.5 A g-1When specific capacitance be 288 F g-1；In 0.1 mol L-1's KNO3In solution, electric current is 0.1 A g-1When specific capacitance be 305F g-1, electric current is 0.5 A g-1When specific capacitance be 287F g-1。
Embodiment 9：
（1）It is prepared by material precursor
By 15g nickel chlorides (NiCl2×6H2O), 30 g glucose, 100 g melamines and 150 g dicyandiamides are added to In 2400mL deionized waters, it is sufficiently stirred at room temperature, forms uniform dispersion；Then, which is transferred to rotary evaporation In instrument, 80OHeating in vacuum in C water-baths, removes moisture content, obtained solid is placed in vacuum drying chamber again, 40ODry 24 under C Hour, obtained solid is material precursor.
（2）It is prepared by material precursor high temperature cabonization
The step of with embodiment 1（2）It is identical.
（3）It is prepared by nitrogen-doped carbon nano-fiber
Above-mentioned black solid particle is placed in 2 mol L-1H2SO4In, be slowly stirred at room temperature 3 it is small when, filter afterwards, use A large amount of pure water are washed till neutrality, are finally washed three times, obtained solid are put in vacuum drying chamber, in 40 with absolute ethyl alcohol0Done under C It is dry 24 it is small when, obtain nitrogen-doped carbon nano-fiber, its caliber is 35 ~ 38nm, and length is 3.2 ~ 4.0mm.
（4）The specific capacitance test process of nitrogen-doped carbon nano-fiber：The step of with embodiment 1（4）It is identical.
The specific capacitance test result of nitrogen-doped carbon nano-fiber：In 0.1 mol L-1K2SO4In solution, electric current 0.1 A g-1When specific capacitance be 310 F g-1, electric current is 0.5 A g-1When specific capacitance be 290 F g-1；In 0.1 mol L-1's KNO3In solution, electric current is 0.1 A g-1When specific capacitance be 311F g-1, electric current is 0.5 A g-1When specific capacitance be 292F g-1。
Embodiment 10：
（1）It is prepared by material precursor
By 1 g cobalt acetates（Co(CH3COO)2×4H2O）, 1 g glucose, 5 g melamines and 10 g dicyandiamides be added to 80mL In deionized water, it is sufficiently stirred at room temperature, forms uniform dispersion；Then, which is transferred in Rotary Evaporators, 80OHeating in vacuum in C water-baths, removes moisture content, obtained solid is placed in vacuum drying chamber again, 40OWhen drying 24 is small under C, obtain The solid arrived is material precursor.
（2）It is prepared by material precursor high temperature cabonization
Above-mentioned material presoma is transferred in tube furnace, in a nitrogen atmosphere, with 4oC min-1Programming rate be heated to 550OC, and at this temperature keep 2.5 it is small when；Then with 2oC min-1Programming rate continue to be warming up to 820OC, and herein At a temperature of keep 2 it is small when；Room temperature is finally naturally cooled under nitrogen atmosphere, obtains black solid particle, is collected, it is pending.
（3）It is prepared by nitrogen-doped carbon nano-fiber
Above-mentioned black solid particle is placed in 2 mol L-1H2SO4In, be slowly stirred at room temperature 3 it is small when, filter afterwards, use A large amount of pure water are washed till neutrality, are finally washed three times, obtained solid are put in vacuum drying chamber, in 40 with absolute ethyl alcohol0Done under C It is dry 24 it is small when, obtain nitrogen-doped carbon nano-fiber, its caliber is 50 ~ 65nm, and length is 1 ~ 2mm.
（4）The specific capacitance test process of nitrogen-doped carbon nano-fiber：In common three-electrode system, in different electrolysis The electrochemical capacitor characteristic of product is measured in matter solution.The nitrogen-doped carbon nano-fiber is mixed with absolute ethyl alcohol, adds matter The Nafion solution that percentage is 5% is measured, pastel is formed after then mixture is ultrasonically treated, finally applies the pastel In glassy carbon electrode surface, working electrode is used as after dry, using platinized platinum as to electrode, saturated calomel electrode is reference electrode, is used Common cyclic voltammetric technology or cycle charge discharge power technology, the nitrogen-doped carbon Nanowire in neutral electrolyte solution obtained by measure The capacitance characteristic of dimension.
The specific capacitance test result of nitrogen-doped carbon nano-fiber：In 0.1 mol L-1K2SO4In solution, electric current 0.1 A g-1When specific capacitance be 322 F g-1, electric current is 0.5 A g-1When specific capacitance be 287 F g-1；In 0.1 mol L-1's KNO3In solution, electric current is 0.1 A g-1When specific capacitance be 309F g-1, electric current is 0.5 A g-1When specific capacitance be 289 F g-1。
Embodiment 11：
（1）It is prepared by material precursor
By 8 g cobalt acetates（Co(CH3COO)2×4H2O）, 15 g glucose, 50 g melamines and 80 g dicyandiamides are added to In 1200mL deionized waters, it is sufficiently stirred at room temperature, forms uniform dispersion；Then, which is transferred to rotary evaporation In instrument, 80OHeating in vacuum in C water-baths, removes moisture content, obtained solid is placed in vacuum drying chamber again, 40ODry 24 under C Hour, obtained solid is material precursor.
（2）It is prepared by material precursor high temperature cabonization
The step of with embodiment 1（2）It is identical.
（3）It is prepared by nitrogen-doped carbon nano-fiber
Above-mentioned black solid particle is placed in 2 mol L-1H2SO4In, be slowly stirred at room temperature 3 it is small when, filter afterwards, use A large amount of pure water are washed till neutrality, are finally washed three times, obtained solid are put in vacuum drying chamber, in 40 with absolute ethyl alcohol0Done under C It is dry 24 it is small when, obtain nitrogen-doped carbon nano-fiber, its caliber is 51 ~ 62nm, and length is 1.1 ~ 2.4mm.
（4）The specific capacitance test process of nitrogen-doped carbon nano-fiber：The step of with embodiment 1（4）It is identical.
The specific capacitance test result of nitrogen-doped carbon nano-fiber：In 0.1 mol L-1K2SO4In solution, electric current 0.1 A g-1When specific capacitance be 321 F g-1, electric current is 0.5 A g-1When specific capacitance be 290 F g-1；In 0.1 mol L-1's KNO3In solution, electric current is 0.1 A g-1When specific capacitance be 313F g-1, electric current is 0.5 A g-1When specific capacitance be 293F g-1。
Embodiment 12：
（1）It is prepared by material precursor
By 15g cobalt acetates（Co(CH3COO)2×4H2O）, 30 g glucose, 100 g melamines and 150 g dicyandiamides are added to In 2400mL deionized waters, it is sufficiently stirred at room temperature, forms uniform dispersion；Then, which is transferred to rotary evaporation In instrument, 80OHeating in vacuum in C water-baths, removes moisture content, obtained solid is placed in vacuum drying chamber again, 40ODry 24 under C Hour, obtained solid is material precursor.
（2）It is prepared by material precursor high temperature cabonization
The step of with embodiment 1（2）It is identical.
（3）It is prepared by nitrogen-doped carbon nano-fiber
Above-mentioned black solid particle is placed in 2 mol L-1H2SO4In, be slowly stirred at room temperature 3 it is small when, filter afterwards, use A large amount of pure water are washed till neutrality, are finally washed three times, obtained solid are put in vacuum drying chamber, in 40 with absolute ethyl alcohol0Done under C It is dry 24 it is small when, obtain nitrogen-doped carbon nano-fiber, its caliber is 53 ~ 68nm, and length is 1.3 ~ 2.8mm.
（4）The specific capacitance test process of nitrogen-doped carbon nano-fiber：The step of with embodiment 1（4）It is identical.
The specific capacitance test result of nitrogen-doped carbon nano-fiber：In 0.1 mol L-1K2SO4In solution, electric current 0.1 A g-1When specific capacitance be 310 F g-1, electric current is 0.5 A g-1When specific capacitance be 291 F g-1；In 0.1 mol L-1's KNO3In solution, electric current is 0.1 A g-1When specific capacitance be 315F g-1, electric current is 0.5 A g-1When specific capacitance be 290F g-1。
Embodiment 13：
（1）It is prepared by material precursor
By 1 cobalt nitrate (Co (NO3)2×6H2O), 1 g glucose, 5 g melamines and 10 g dicyandiamides be added to 80mL go from In sub- water, it is sufficiently stirred at room temperature, forms uniform dispersion；Then, which is transferred in Rotary Evaporators, 80OC Heating in vacuum in water-bath, removes moisture content, obtained solid is placed in vacuum drying chamber again, 40OWhen drying 24 is small under C, obtain Solid be material precursor.
（2）It is prepared by material precursor high temperature cabonization
The step of with embodiment 1（2）It is identical.
（3）It is prepared by nitrogen-doped carbon nano-fiber
Above-mentioned black solid particle is placed in 2 mol L-1H2SO4In, be slowly stirred at room temperature 3 it is small when, filter afterwards, use A large amount of pure water are washed till neutrality, are finally washed three times, obtained solid are put in vacuum drying chamber, in 40 with absolute ethyl alcohol0Done under C It is dry 24 it is small when, obtain nitrogen-doped carbon nano-fiber, its caliber is 45 ~ 69nm, and length is 1.9 ~ 2.5mm.
（4）The specific capacitance test process of nitrogen-doped carbon nano-fiber：The step of with embodiment 1（4）It is identical.
The specific capacitance test result of nitrogen-doped carbon nano-fiber：In 0.1 mol L-1K2SO4In solution, electric current 0.1 A g-1When specific capacitance be 310 F g-1, electric current is 0.5 A g-1When specific capacitance be 285 F g-1；In 0.1 mol L-1's KNO3In solution, electric current is 0.1 A g-1When specific capacitance be 301F g-1, electric current is 0.5 A g-1When specific capacitance be 282 F g-1。
Embodiment 14：
（1）It is prepared by material precursor
By 8 g cobalt nitrates (Co (NO3)2×6H2O), 15 g glucose, 50 g melamines and 80 g dicyandiamides are added to In 1200mL deionized waters, it is sufficiently stirred at room temperature, forms uniform dispersion；Then, which is transferred to rotary evaporation In instrument, 80OHeating in vacuum in C water-baths, removes moisture content, obtained solid is placed in vacuum drying chamber again, 40ODry 24 under C Hour, obtained solid is material precursor.
（2）It is prepared by material precursor high temperature cabonization
The step of with embodiment 1（2）It is identical.
（3）It is prepared by nitrogen-doped carbon nano-fiber
Above-mentioned black solid particle is placed in 2 mol L-1H2SO4In, be slowly stirred at room temperature 3 it is small when, filter afterwards, use A large amount of pure water are washed till neutrality, are finally washed three times, obtained solid are put in vacuum drying chamber, in 40 with absolute ethyl alcohol0Done under C It is dry 24 it is small when, obtain nitrogen-doped carbon nano-fiber, its caliber be 67 ~ 71, length is 1.1 ~ 2.2mm.
（4）The specific capacitance test process of nitrogen-doped carbon nano-fiber：The step of with embodiment 1（4）It is identical.
The specific capacitance test result of nitrogen-doped carbon nano-fiber：In 0.1 mol L-1K2SO4In solution, electric current 0.1 A g-1When specific capacitance be 321 F g-1, electric current is 0.5 A g-1When specific capacitance be 292 F g-1；In 0.1 mol L-1's KNO3In solution, electric current is 0.1 A g-1When specific capacitance be 315F g-1, electric current is 0.5 A g-1When specific capacitance be 288F g-1。
Embodiment 15：
（1）It is prepared by material precursor
By 15g cobalt nitrates (Co (NO3)2×6H2O), 30 g glucose, 100 g melamines and 150 g dicyandiamides are added to In 2400mL deionized waters, it is sufficiently stirred at room temperature, forms uniform dispersion；Then, which is transferred to rotary evaporation In instrument, 80OHeating in vacuum in C water-baths, removes moisture content, obtained solid is placed in vacuum drying chamber again, 40ODry 24 under C Hour, obtained solid is material precursor.
（2）It is prepared by material precursor high temperature cabonization
The step of with embodiment 1（2）It is identical.
（3）It is prepared by nitrogen-doped carbon nano-fiber
Above-mentioned black solid particle is placed in 2 mol L-1H2SO4In, be slowly stirred at room temperature 3 it is small when, filter afterwards, use A large amount of pure water are washed till neutrality, are finally washed three times, obtained solid are put in vacuum drying chamber, in 40 with absolute ethyl alcohol0Done under C It is dry 24 it is small when, obtain nitrogen-doped carbon nano-fiber, its caliber is 56 ~ 67nm, and length is 1.8 ~ 2.2mm.
（4）The specific capacitance test process of nitrogen-doped carbon nano-fiber：The step of with embodiment 1（4）It is identical.
The specific capacitance test result of nitrogen-doped carbon nano-fiber：In 0.1 mol L-1K2SO4In solution, electric current 0.1 A g-1When specific capacitance be 311 F g-1, electric current is 0.5 A g-1When specific capacitance be 292 F g-1；In 0.1 mol L-1's KNO3In solution, electric current is 0.1 A g-1When specific capacitance be 313F g-1, electric current is 0.5 A g-1When specific capacitance be 294F g-1。
Embodiment 16：
（1）It is prepared by material precursor
By 1 cobalt chloride (CoCl2×6H2O), 1 g glucose, 5 g melamines and 10 g dicyandiamides are added to 80mL deionizations In water, it is sufficiently stirred at room temperature, forms uniform dispersion；Then, which is transferred in Rotary Evaporators, 80OC water Heating in vacuum in bath, removes moisture content, obtained solid is placed in vacuum drying chamber again, 40OWhen drying 24 is small under C, obtain Solid is material precursor.
（2）It is prepared by material precursor high temperature cabonization
The step of with embodiment 1（2）It is identical.
（3）It is prepared by nitrogen-doped carbon nano-fiber
Above-mentioned black solid particle is placed in 2 mol L-1H2SO4In, be slowly stirred at room temperature 3 it is small when, filter afterwards, use A large amount of pure water are washed till neutrality, are finally washed three times, obtained solid are put in vacuum drying chamber, in 40 with absolute ethyl alcohol0Done under C It is dry 24 it is small when, obtain nitrogen-doped carbon nano-fiber, its caliber is 55 ~ 68nm, and length is 1.9 ~ 2.5mm.
（4）The specific capacitance test process of nitrogen-doped carbon nano-fiber：The step of with embodiment 1（4）It is identical.
The specific capacitance test result of nitrogen-doped carbon nano-fiber：In 0.1 mol L-1K2SO4In solution, electric current 0.1 A g-1When specific capacitance be 311 F g-1, electric current is 0.5 A g-1When specific capacitance be 285 F g-1；In 0.1 mol L-1's KNO3In solution, electric current is 0.1 A g-1When specific capacitance be 295F g-1, electric current is 0.5 A g-1When specific capacitance be 279 F g-1。
Embodiment 17：
（1）It is prepared by material precursor
By 8 g cobalt chlorides (CoCl2×6H2O), 15 g glucose, 50 g melamines and 80 g dicyandiamides are added to 1200mL In deionized water, it is sufficiently stirred at room temperature, forms uniform dispersion；Then, which is transferred in Rotary Evaporators, 80OHeating in vacuum in C water-baths, removes moisture content, obtained solid is placed in vacuum drying chamber again, 40OWhen drying 24 is small under C, obtain The solid arrived is material precursor.
（2）It is prepared by material precursor high temperature cabonization
The step of with embodiment 1（2）It is identical.
（3）It is prepared by nitrogen-doped carbon nano-fiber
Above-mentioned black solid particle is placed in 2 mol L-1H2SO4In, be slowly stirred at room temperature 3 it is small when, filter afterwards, use A large amount of pure water are washed till neutrality, are finally washed three times, obtained solid are put in vacuum drying chamber, in 40 with absolute ethyl alcohol0Done under C It is dry 24 it is small when, obtain nitrogen-doped carbon nano-fiber, its caliber is 52 ~ 69nm, and length is 1.7 ~ 2.2mm.
（4）The specific capacitance test process of nitrogen-doped carbon nano-fiber：The step of with embodiment 1（4）It is identical.
The specific capacitance test result of nitrogen-doped carbon nano-fiber：In 0.1 mol L-1K2SO4In solution, electric current 0.1 A g-1When specific capacitance be 310 F g-1, electric current is 0.5 A g-1When specific capacitance be 289 F g-1；In 0.1 mol L-1's KNO3In solution, electric current is 0.1 A g-1When specific capacitance be 308F g-1, electric current is 0.5 A g-1When specific capacitance be 289F g-1。
Embodiment 18：
（1）It is prepared by material precursor
By 15g cobalt chlorides (CoCl2×6H2O), 30 g glucose, 100 g melamines and 150 g dicyandiamides are added to In 2400mL deionized waters, it is sufficiently stirred at room temperature, forms uniform dispersion；Then, which is transferred to rotary evaporation In instrument, 80OHeating in vacuum in C water-baths, removes moisture content, obtained solid is placed in vacuum drying chamber again, 40ODry 24 under C Hour, obtained solid is material precursor.
（2）It is prepared by material precursor high temperature cabonization
The step of with embodiment 1（2）It is identical.
（3）It is prepared by nitrogen-doped carbon nano-fiber
Above-mentioned black solid particle is placed in 2 mol L-1H2SO4In, be slowly stirred at room temperature 3 it is small when, filter afterwards, use A large amount of pure water are washed till neutrality, are finally washed three times, obtained solid are put in vacuum drying chamber, in 40 with absolute ethyl alcohol0Done under C It is dry 24 it is small when, obtain nitrogen-doped carbon nano-fiber, its caliber is 55 ~ 68nm, and length is 1.2 ~ 2.0mm.
（4）The specific capacitance test process of nitrogen-doped carbon nano-fiber：The step of with embodiment 1（4）It is identical.
The specific capacitance test result of nitrogen-doped carbon nano-fiber：In 0.1 mol L-1K2SO4In solution, electric current 0.1 A g-1When specific capacitance be 304 F g-1, electric current is 0.5 A g-1When specific capacitance be 278 F g-1；In 0.1 mol L-1's KNO3In solution, electric current is 0.1 A g-1When specific capacitance be 305F g-1, electric current is 0.5 A g-1When specific capacitance be 287F g-1。
Embodiment 19：
（1）It is prepared by material precursor
By 4 g nickel acetates（Ni(CH3COO)2×4H2O）, 4 g cobalt acetates（Co(CH3COO)2×4H2O）, 15 g glucose, 50 g Melamine and 80 g dicyandiamides are added in 1200mL deionized waters, are sufficiently stirred at room temperature, form uniform dispersion；With Afterwards, which is transferred in Rotary Evaporators, 80OHeating in vacuum in C water-baths, removes moisture content, and obtained solid is placed in again In vacuum drying chamber, 40OWhen drying 24 is small under C, obtained solid is material precursor.
（2）It is prepared by material precursor high temperature cabonization
The step of with embodiment 1（2）It is identical.
（3）It is prepared by nitrogen-doped carbon nano-fiber
Above-mentioned black solid particle is placed in 2 mol L-1H2SO4In, be slowly stirred at room temperature 3 it is small when, filter afterwards, use A large amount of pure water are washed till neutrality, are finally washed three times, obtained solid are put in vacuum drying chamber, in 40 with absolute ethyl alcohol0Done under C It is dry 24 it is small when, obtain nitrogen-doped carbon nano-fiber, its caliber is 25 ~ 30nm, and length is 6.7 ~ 8.2mm.
（4）The specific capacitance test process of nitrogen-doped carbon nano-fiber：The step of with embodiment 1（4）It is identical.
The specific capacitance test result of nitrogen-doped carbon nano-fiber：In 0.1 mol L-1K2SO4In solution, electric current 0.1 A g-1When specific capacitance be 365 F g-1, electric current is 0.5 A g-1When specific capacitance be 289 F g-1；In 0.1 mol L-1's KNO3In solution, electric current is 0.1 A g-1When specific capacitance be 378F g-1, electric current is 0.5 A g-1When specific capacitance be 282F g-1。
Embodiment 20：
（1）It is prepared by material precursor
By 8 g nickel acetates（Ni(CH3COO)2×4H2O）, 5 g cobalt acetates（Co(CH3COO)2×4H2O）, 15 g glucose, 50 g Melamine and 80 g dicyandiamides are added in 1200mL deionized waters, are sufficiently stirred at room temperature, form uniform dispersion；With Afterwards, which is transferred in Rotary Evaporators, 80OHeating in vacuum in C water-baths, removes moisture content, and obtained solid is placed in again In vacuum drying chamber, 40OWhen drying 24 is small under C, obtained solid is material precursor.
（2）It is prepared by material precursor high temperature cabonization
The step of with embodiment 1（2）It is identical.
（3）It is prepared by nitrogen-doped carbon nano-fiber
Above-mentioned black solid particle is placed in 2 mol L-1H2SO4In, be slowly stirred at room temperature 3 it is small when, filter afterwards, use A large amount of pure water are washed till neutrality, are finally washed three times, obtained solid are put in vacuum drying chamber, in 40 with absolute ethyl alcohol0Done under C It is dry 24 it is small when, obtain nitrogen-doped carbon nano-fiber, its caliber is 24 ~ 28nm, and length is 6.8 ~ 8.1mm.
（4）The specific capacitance test process of nitrogen-doped carbon nano-fiber：The step of with embodiment 1（4）It is identical.
The specific capacitance test result of nitrogen-doped carbon nano-fiber：In 0.1 mol L-1K2SO4In solution, electric current 0.1 A g-1When specific capacitance be 368 F g-1, electric current is 0.5 A g-1When specific capacitance be 288 F g-1；In 0.1 mol L-1's KNO3In solution, electric current is 0.1 A g-1When specific capacitance be 377F g-1, electric current is 0.5 A g-1When specific capacitance be 285F g-1。

Claims (6)

1. a kind of preparation method of nitrogen-doped carbon nano-fiber, it is characterized in that, comprise the following steps：
（1）It is prepared by material precursor：
Nickel salt or the salt-mixture of cobalt salt or nickel salt and cobalt salt, glucose, melamine and dicyandiamide are added in deionized water, It is sufficiently stirred at room temperature, forms uniform dispersion；Then, by the dispersion liquid 80OHeating in vacuum in C water-baths, removes moisture content, By obtained solid in 40OIt is dried in vacuo under C, obtained solid is material precursor；
The nickel salt or cobalt salt or salt-mixture, glucose, melamine, the mass ratio of dicyandiamide are：Nickel salt or cobalt salt are mixed Close salt：Glucose：Melamine：Dicyandiamide=1~15：1~30：5~100：10~150；
In the salt-mixture, the mass ratio of nickel salt and cobalt salt is（1 ~ 100）：（0.1 ~ 50）；
（2）It is prepared by material precursor high temperature cabonization：
By above-mentioned material presoma in a nitrogen atmosphere, with 4oC min-1Programming rate be heated to 550OC, and keep the temperature Certain time；Then with 2oC min-1Programming rate continue to be warming up to 820OC, and kept for temperature certain time；Finally exist Room temperature is naturally cooled under blanket of nitrogen, obtains black solid particle, is collected, it is pending；
（3）It is prepared by nitrogen-doped carbon nano-fiber：
Above-mentioned black solid particle is placed in 2 mol L-1H2SO4In, it is slowly stirred, filters, in being washed till with pure water at room temperature Property, finally washed with absolute ethyl alcohol, by obtained solid in 400It is dried in vacuo under C, obtains nitrogen-doped carbon nano-fiber.
2. the preparation method of nitrogen-doped carbon nano-fiber according to claim 1, it is characterized in that, the nickel salt is nickel acetate （Ni(CH3COO)2×4H2O）, nickel nitrate (Ni (NO3)2×6H2) or nickel chloride (NiCl O2×6H2O)。
3. the preparation method of nitrogen-doped carbon nano-fiber according to claim 1, it is characterized in that, the cobalt salt is cobalt acetate （Co(CH3COO)2×4H2O）, cobalt nitrate (Co (NO3)2×6H2) or cobalt chloride (CoCl O2×6H2O)。
4. the preparation method of nitrogen-doped carbon nano-fiber according to claim 1, it is characterized in that, in the salt-mixture, nickel The mass ratio of salt and cobalt salt is（1 ~ 100）：（0.1 ~ 50）.
A kind of 5. nitrogen-doped carbon nano-fiber prepared by preparation method according to claim 1.
6. the application of nitrogen-doped carbon nano-fiber prepared by preparation method according to claim 1 in terms of electrode.
CN201711176718.6A 2017-11-22 2017-11-22 A kind of nitrogen-doped carbon nano-fiber and its preparation method and application Pending CN107934935A (en)

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