CN111564318A - Ni2CoS4Supercapacitor electrode material of graphitized porous carbon nanofiber and preparation method thereof - Google Patents
Ni2CoS4Supercapacitor electrode material of graphitized porous carbon nanofiber and preparation method thereof Download PDFInfo
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- 239000002133 porous carbon nanofiber Substances 0.000 title claims abstract description 47
- 239000007772 electrode material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 42
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003990 capacitor Substances 0.000 claims abstract description 18
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004005 microsphere Substances 0.000 claims abstract description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 9
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- 238000010041 electrostatic spinning Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 239000002121 nanofiber Substances 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 claims description 5
- 238000001994 activation Methods 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 3
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract description 14
- 239000011148 porous material Substances 0.000 abstract description 10
- 229910003481 amorphous carbon Inorganic materials 0.000 abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000008859 change Effects 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- 238000005530 etching Methods 0.000 abstract description 2
- 238000005054 agglomeration Methods 0.000 abstract 1
- DLAPQHBZCAAVPQ-UHFFFAOYSA-N iron;pentane-2,4-dione Chemical compound [Fe].CC(=O)CC(C)=O DLAPQHBZCAAVPQ-UHFFFAOYSA-N 0.000 abstract 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- -1 transition metal sulfide Chemical class 0.000 description 2
- 239000004966 Carbon aerogel Substances 0.000 description 1
- 229910005949 NiCo2O4 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to the technical field of super capacitors and discloses Ni2CoS4The super capacitor electrode material of the graphitized porous carbon nanofiber comprises the following formula raw materials and components: glycerol, nickel nitrate, cobalt nitrate, graphitized porous carbon nanofiber and thiourea. The one kind of Ni2CoS4The super capacitor electrode material of graphitized porous carbon nanofiber is activated at high temperature by acetylacetone iron to form nano iron oxide, has a catalytic effect on amorphous carbon, and promotes the amorphous carbon to conduct electricityThe graphitized carbon with more excellent performance is converted, the nano iron oxide is removed through nitric acid etching, and rich pore structures, namely porous Ni, are formed in the graphitized porous carbon nanofibers2CoS4The microspheres are uniformly attached to the pores and the matrix of the graphitized porous carbon nanofiber, so that porous Ni is reduced2CoS4Agglomeration of microspheres, graphitizing porous carbon nanofibers in Ni2CoS4The outer layer of the microsphere forms a three-dimensional conductive network and is Ni2CoS4The volume change of (a) provides a buffer layer.
Description
Technical Field
The invention relates to the technical field of super capacitors, in particular to Ni2CoS4-super capacitor electrode material of graphitized porous carbon nanofiber and a preparation method thereof.
Background
With the continuous improvement of the requirements of people on energy storage devices and systems, the traditional static capacitor has high power density but low energy density, while the chemical battery has high energy density but low power density, the super capacitor has the characteristics of quick charge and discharge of the capacitor and the energy storage characteristic of the battery, and the super capacitor becomes a research hotspot due to the advantages of high power density, long cycle life and the like, and the electrochemical performance of the super capacitor is mainly determined by electrode materials.
The current electrode materials of the super capacitor mainly comprise carbon material electrode materials such as graphene, carbon nano tubes, carbon aerogel and the like, and metal oxide electrode materials such as RuO2、Co3O4、NiCo2O4Etc.; conductive polymer electrode material such as polyaniline, polypyrrole, etc., wherein transition metal sulfide such as Co9S8、NiCo2S4、Ni2CoS4The nickel-based composite material can generate more abundant oxidation-reduction reactions, provides higher specific capacitance, and is a super capacitor electrode material with great development potential, but Ni2CoS4Has poor conductivity, is not favorable for electron transmission and diffusion, and Ni2CoS4The volume change is easy to occur in the electrochemical cycle process, and the Ni is greatly reduced2CoS4The actual specific capacitance of the electrode material.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides Ni2CoS4The super capacitor electrode material of-graphitized porous carbon nanofiber and the preparation method thereof solve the problem of Ni2CoS4The problem of poor conductivity is solved, and simultaneously Ni is solved2CoS4The problem of volume change is likely to occur.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: ni2CoS4The super capacitor electrode material of the graphitized porous carbon nanofiber comprises the following raw materials and components: glycerol, nickel nitrate, cobalt nitrate, graphitized porous carbon nanofiber and thiourea in a mass ratio of 120: 20-22:10:2-8:25-30
Preferably, the Ni2CoS4The preparation method of the supercapacitor electrode material of graphitized porous carbon nanofiber comprises the following steps:
(1) adding N, N-dimethylformamide solvent, polyacrylonitrile and ferric acetylacetonate into a reaction bottle, stirring at constant speed for 10-20h at room temperature to form electrostatic spinning solution, carrying out electrostatic spinning, placing the electrostatic spinning nanofiber precursor into an atmosphere furnace, heating to 230-280 ℃ in air atmosphere at the heating rate of 2-5 ℃/min, carrying out heat preservation and activation for 4-6h, then heating to 600-700 ℃ in nitrogen atmosphere, carrying out heat preservation and calcination for 2-4h, placing the calcined product into dilute nitric acid solution, and carrying out stirring reaction at constant speed for 10-15h at 50-70 ℃ to prepare the graphitized porous carbon nanofiber.
(2) Adding an isopropanol solvent, glycerol, nickel nitrate, cobalt nitrate and graphitized porous carbon nanofiber into a reaction bottle, placing the reaction bottle in a constant-temperature ultrasonic dispersion instrument, performing ultrasonic dispersion treatment at the ultrasonic frequency of 25-35KHz at the temperature of 40-80 ℃ for 2-4h, pouring the solution into a hydrothermal reaction kettle, heating to 170-200 ℃, reacting for 5-10h, cooling the solution to room temperature, filtering to remove the solvent, washing with distilled water and ethanol, placing the solid product in an ethanol solvent and adding thiourea, stirring uniformly, pouring the solution into the hydrothermal reaction kettle, heating to 170-200 ℃, reacting for 10-20h, cooling, filtering, washing and drying to obtain the porous Ni2CoS4The microsphere-loaded graphitized porous carbon nanofiber is Ni2CoS4-a supercapacitor electrode material of graphitized porous carbon nanofibers.
Preferably, the mass ratio of the polyacrylonitrile to the ferric acetylacetonate is 1: 0.6-0.8.
Preferably, the constant temperature ultrasonic dispersion instrument in the step (2) comprises a water bath, an ultrasonic device fixedly connected to the upper part of the inside of the water bath, constant temperature heaters fixedly connected to the two sides of the lower part of the inside of the water bath, a rotating device fixedly connected to the lower part of the inside of the water bath, a rotating screw movably connected to the rotating device, a threaded sleeve movably connected to the rotating screw, a supporting rod fixedly connected to the threaded sleeve, and a reaction bottle movably connected to the supporting rod.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the one kind of Ni2CoS4The supercapacitor electrode material of graphitized porous carbon nanofiber is characterized in that iron acetylacetonate forms nano iron oxide in an electrostatic spinning nanofiber precursor in a high-temperature activation process, the nano iron oxide has a catalytic effect on amorphous carbon generated by high-temperature thermal cracking of the electrostatic spinning nanofiber precursor, conversion of the amorphous carbon to graphitized carbon with more excellent conductivity is promoted, the nano iron oxide is removed through nitric acid etching, a rich pore structure is formed on the graphitized porous carbon nanofiber, and glycerol is used as a guiding agent to react with Ni2+And Co2+The formed precursor uniformly grows in the pore structure of the graphitized porous carbon nanofiber, thiourea is used as a sulfur source, and porous Ni prepared by a hot solvent method2CoS4The microspheres are uniformly attached to the pores and the matrix of the graphitized porous carbon nanofiber, so that porous Ni is reduced2CoS4The microspheres are agglomerated, and the abundant pore structures promote the wettability with electrolyte, so that a large number of electrochemical active sites are exposed, and the graphitized porous carbon nanofiber is coated on Ni2CoS4The outer layer of the microsphere forms a three-dimensional conductive network and is Ni2CoS4Providing a buffer layer, making Ni act synergistically2CoS4The super capacitor electrode material of the graphitized porous carbon nanofiber shows ultra-high electrochemical performance.
Drawings
FIG. 1 is a schematic front view of a water bath;
fig. 2 is a Scanning Electron Microscope (SEM) image of graphitized porous carbon nanofibers;
FIG. 3 is porous Ni2CoS4Scanning Electron Microscopy (SEM) of microsphere-loaded graphitized porous carbon nanofibers.
1-water bath; 2-an ultrasonic device; 3-constant temperature heater; 4-a rotating device; 5-rotating the screw; 6-thread bushing; 7-a support bar; 8-reaction flask.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: ni2CoS4The super capacitor electrode material of the graphitized porous carbon nanofiber comprises the following raw materials and components: glycerol, nickel nitrate, cobalt nitrate, graphitized porous carbon nanofiber and thiourea in a mass ratio of 120: 20-22:10:2-8:25-30
Ni2CoS4The preparation method of the supercapacitor electrode material of graphitized porous carbon nanofiber comprises the following steps:
(1) adding N, N-dimethylformamide solvent, polyacrylonitrile and ferric acetylacetonate with the mass ratio of 1:0.6-0.8 into a reaction bottle, stirring at a constant speed for 10-20h at room temperature to form electrostatic spinning solution, carrying out electrostatic spinning, placing an electrostatic spinning nanofiber precursor into an atmosphere furnace, heating at the rate of 2-5 ℃/min to 230-280 ℃ in the air atmosphere, carrying out heat preservation and activation for 4-6h, then heating to 600-700 ℃ in the nitrogen atmosphere, carrying out heat preservation and calcination for 2-4h, placing a calcination product into dilute nitric acid solution, and stirring at a constant speed for reaction for 10-15h at 50-70 ℃ to prepare the graphitized porous carbon nanofiber.
(2) Adding isopropanol solvent, glycerol, nickel nitrate, cobalt nitrate and graphitized porous carbon nanofiber into a reaction bottle, placing the reaction bottle in a constant-temperature ultrasonic disperser, wherein the constant-temperature ultrasonic disperser comprises a water bath, an ultrasonic device fixedly connected to the upper part of the interior of the water bath, constant-temperature heaters fixedly connected to the two sides of the lower part of the interior of the water bath, a rotating device fixedly connected to the lower part of the interior of the water bath, a rotating screw movably connected to the rotating device, a threaded sleeve movably connected to the rotating screw, a supporting rod fixedly connected to the threaded sleeve and a reaction bottle movably connected to the supporting rod, performing ultrasonic dispersion treatment at 40-80 ℃ for 2-4h, pouring the solution into a hydrothermal reaction kettle, heating to 170 ℃ and 200 ℃, reacting for 5-10h, cooling the solution to room temperature, filtering to remove the solvent, washing with distilled water and ethanol, putting the solid product into an ethanol solvent, adding thiourea, uniformly stirring, pouring the solution into a hydrothermal reaction kettle, heating to 170-200 ℃, reacting for 10-20h, cooling, filtering, washingWashing and drying to prepare porous Ni2CoS4The microsphere-loaded graphitized porous carbon nanofiber is Ni2CoS4-a supercapacitor electrode material of graphitized porous carbon nanofibers.
Example 1
(1) Adding N, N-dimethylformamide solvent, polyacrylonitrile and ferric acetylacetonate with the mass ratio of 1:0.6 into a reaction bottle, stirring at a constant speed for 10 hours at room temperature to form electrostatic spinning solution, carrying out electrostatic spinning, putting an electrostatic spinning nanofiber precursor into an atmosphere furnace, heating at the rate of 2 ℃/min to 230 ℃ in the air atmosphere, carrying out heat preservation and activation for 4 hours, then heating to 600 ℃ in the nitrogen atmosphere, carrying out heat preservation and calcination for 2 hours, putting a calcination product into dilute nitric acid solution, and carrying out stirring reaction at a constant speed for 10 hours at 50 ℃ to prepare the graphitized porous carbon nanofiber.
(2) Adding isopropanol solvent, glycerol, nickel nitrate, cobalt nitrate and graphitized porous carbon nanofiber into a reaction bottle, and placing the reaction bottle into a constant-temperature ultrasonic disperser, wherein the constant-temperature ultrasonic disperser comprises a water bath, an ultrasonic device fixedly connected to the upper part of the interior of the water bath, constant-temperature heaters fixedly connected to the two sides of the lower part of the interior of the water bath, a rotating device fixedly connected to the lower part of the interior of the water bath, a rotating screw movably connected to the rotating device, a threaded sleeve movably connected to the rotating screw, a supporting rod fixedly connected to the threaded sleeve and a reaction bottle movably connected to the supporting rod, the ultrasonic frequency is 25KHz, carrying out ultrasonic dispersion treatment at 40 ℃ for 2 hours, pouring the solution into a hydrothermal reaction kettle, heating to 170 ℃, carrying out reaction for 5 hours, cooling the solution to room temperature, filtering to remove the solvent, washing with distilled water and ethanol, placing the solid product into an ethanol, Nickel nitrate, cobalt nitrate, graphitized porous carbon nanofiber and thiourea in a mass ratio of 120:20:10:2:25, uniformly stirring, pouring the solution into a hydrothermal reaction kettle, heating to 170 ℃, reacting for 10 hours, cooling, filtering, washing and drying to prepare porous Ni2CoS4The microsphere-loaded graphitized porous carbon nanofiber is Ni2CoS4 Supercapacitor electrode material 1 of graphitized porous carbon nanofibers.
Example 2
(1) Adding N, N-dimethylformamide solvent, polyacrylonitrile and ferric acetylacetonate with the mass ratio of 1:0.65 into a reaction bottle, stirring at a constant speed for 20 hours at room temperature to form electrostatic spinning solution, carrying out electrostatic spinning, putting an electrostatic spinning nanofiber precursor into an atmosphere furnace, heating at the rate of 5 ℃/min to 230 ℃ in the air atmosphere, carrying out heat preservation and activation for 6 hours, then heating to 700 ℃ in the nitrogen atmosphere, carrying out heat preservation and calcination for 4 hours, putting a calcination product into dilute nitric acid solution, and carrying out stirring reaction at a constant speed for 10 hours at 50 ℃ to prepare the graphitized porous carbon nanofiber.
(2) Adding isopropanol solvent, glycerol, nickel nitrate, cobalt nitrate and graphitized porous carbon nanofiber into a reaction bottle, and placing the reaction bottle into a constant-temperature ultrasonic disperser, wherein the constant-temperature ultrasonic disperser comprises a water bath, an ultrasonic device fixedly connected to the upper part of the interior of the water bath, constant-temperature heaters fixedly connected to the two sides of the lower part of the interior of the water bath, a rotating device fixedly connected to the lower part of the interior of the water bath, a rotating screw movably connected to the rotating device, a threaded sleeve movably connected to the rotating screw, a supporting rod fixedly connected to the threaded sleeve and a reaction bottle movably connected to the supporting rod, the ultrasonic frequency is 35KHz, carrying out ultrasonic dispersion treatment at 40 ℃ for 4 hours, pouring the solution into a hydrothermal reaction kettle, heating to 170 ℃, carrying out reaction for 10 hours, cooling the solution to room temperature, filtering to remove the solvent, washing with distilled water and ethanol, placing the solid product into an ethanol, Nickel nitrate, cobalt nitrate, graphitized porous carbon nanofiber and thiourea in a mass ratio of 140:20.5:10:3:26, uniformly stirring, pouring the solution into a hydrothermal reaction kettle, heating to 200 ℃, reacting for 20 hours, cooling, filtering, washing and drying to prepare porous Ni2CoS4The microsphere-loaded graphitized porous carbon nanofiber is Ni2CoS4 Supercapacitor electrode material 2 of graphitized porous carbon nanofibers.
Example 3
(1) Adding N, N-dimethylformamide solvent, polyacrylonitrile and ferric acetylacetonate with the mass ratio of 1:0.7 into a reaction bottle, stirring at a constant speed for 15h at room temperature to form electrostatic spinning solution, carrying out electrostatic spinning, putting an electrostatic spinning nanofiber precursor into an atmosphere furnace, heating at the rate of 5 ℃/min to 250 ℃ in the air atmosphere, carrying out heat preservation and activation for 5h, then heating to 650 ℃ in the nitrogen atmosphere, carrying out heat preservation and calcination for 3h, putting a calcination product into dilute nitric acid solution, and carrying out stirring reaction at a constant speed for 12h at 60 ℃ to prepare the graphitized porous carbon nanofiber.
(2) Adding isopropanol solvent, glycerol, nickel nitrate, cobalt nitrate and graphitized porous carbon nanofiber into a reaction bottle, and placing the reaction bottle into a constant-temperature ultrasonic disperser, wherein the constant-temperature ultrasonic disperser comprises a water bath, an ultrasonic device fixedly connected to the upper part of the interior of the water bath, constant-temperature heaters fixedly connected to the two sides of the lower part of the interior of the water bath, a rotating device fixedly connected to the lower part of the interior of the water bath, a rotating screw movably connected to the rotating device, a threaded sleeve movably connected to the rotating screw, a supporting rod fixedly connected to the threaded sleeve and a reaction bottle movably connected to the supporting rod, the ultrasonic frequency is 30KHz, carrying out ultrasonic dispersion treatment at 60 ℃ for 3 hours, pouring the solution into a hydrothermal reaction kettle, heating to 180 ℃, carrying out reaction for 8 hours, cooling the solution to room temperature, filtering to remove the solvent, washing with distilled water and ethanol, placing the solid product into an ethanol, Nickel nitrate, cobalt nitrate, graphitized porous carbon nanofiber and thiourea in a mass ratio of 160:21:10:5:28, uniformly stirring, pouring the solution into a hydrothermal reaction kettle, heating to 180 ℃, reacting for 1h, cooling, filtering, washing and drying to prepare porous Ni2CoS4The microsphere-loaded graphitized porous carbon nanofiber is Ni2CoS4-a supercapacitor electrode material 3 of graphitized porous carbon nanofibers.
Example 4
(1) Adding N, N-dimethylformamide solvent, polyacrylonitrile and ferric acetylacetonate with the mass ratio of 1:0.8 into a reaction bottle, stirring at a constant speed for 20 hours at room temperature to form electrostatic spinning solution, carrying out electrostatic spinning, putting an electrostatic spinning nanofiber precursor into an atmosphere furnace, heating at the rate of 5 ℃/min to 280 ℃ in the air atmosphere, carrying out heat preservation and activation for 6 hours, then heating to 700 ℃ in the nitrogen atmosphere, carrying out heat preservation and calcination for 4 hours, putting a calcination product into dilute nitric acid solution, and carrying out stirring reaction at a constant speed for 15 hours at 70 ℃ to prepare the graphitized porous carbon nanofiber.
(2) Adding isopropanol solvent, glycerol, nickel nitrate, cobalt nitrate and graphitized porous carbon nanofiber into a reaction bottle, and placing the reaction bottle into a constant-temperature ultrasonic disperser, wherein the constant-temperature ultrasonic disperser comprises a water bath, an ultrasonic device fixedly connected to the upper part of the interior of the water bath, constant-temperature heaters fixedly connected to the two sides of the lower part of the interior of the water bath, a rotating device fixedly connected to the lower part of the interior of the water bath, a rotating screw movably connected to the rotating device, a threaded sleeve movably connected to the rotating screw, a supporting rod fixedly connected to the threaded sleeve and a reaction bottle movably connected to the supporting rod, the ultrasonic frequency is 35KHz, carrying out ultrasonic dispersion treatment at 80 ℃ for 4 hours, pouring the solution into a hydrothermal reaction kettle, heating to 200 ℃, carrying out reaction for 10 hours, cooling the solution to room temperature, filtering to remove the solvent, washing with distilled water and ethanol, placing the solid product into an ethanol, Nickel nitrate, cobalt nitrate, graphitized porous carbon nanofiber and thiourea in a mass ratio of 200:22:10:8:30, uniformly stirring, pouring the solution into a hydrothermal reaction kettle, heating to 200 ℃, reacting for 20 hours, cooling, filtering, washing and drying to prepare porous Ni2CoS4The microsphere-loaded graphitized porous carbon nanofiber is Ni2CoS4 Supercapacitor electrode material 4 of graphitized porous carbon nanofibers.
Comparative example 1
(1) Adding N, N-dimethylformamide solvent, polyacrylonitrile and ferric acetylacetonate with the mass ratio of 1:0.4 into a reaction bottle, stirring at a constant speed for 20 hours at room temperature to form electrostatic spinning solution, carrying out electrostatic spinning, putting an electrostatic spinning nanofiber precursor into an atmosphere furnace, heating at the rate of 5 ℃/min to 280 ℃ in the air atmosphere, carrying out heat preservation and activation for 4 hours, then heating to 600 ℃ in the nitrogen atmosphere, carrying out heat preservation and calcination for 2 hours, putting a calcination product into dilute nitric acid solution, and carrying out stirring reaction at a constant speed for 15 hours at 70 ℃ to prepare the graphitized porous carbon nanofiber.
(2) Adding isopropanol solvent, glycerol, nickel nitrate, cobalt nitrate and graphitized porous carbon nanofiber into a reaction bottleThe vitamin is placed in a constant-temperature ultrasonic disperser which comprises a water bath, an ultrasonic device fixedly connected with the upper part of the interior of the water bath, constant-temperature heaters fixedly connected with the two sides of the lower part of the interior of the water bath, a rotating device fixedly connected with the lower part of the interior of the water bath, a rotating screw movably connected with the rotating device, a threaded sleeve movably connected with the rotating screw, a supporting rod fixedly connected with the threaded sleeve, a reaction bottle movably connected with the supporting rod, a hydrothermal reaction kettle with the ultrasonic frequency of 35KHz and the ultrasonic frequency of 40 ℃ for ultrasonic dispersion treatment for 4h, the solution is poured into the hydrothermal reaction kettle and heated to 200 ℃ for reaction for 10h, the solution is cooled to room temperature and filtered to remove the solvent, distilled water and ethanol are used for washing, the solid product is placed in the ethanol solvent and thiourea is added, wherein the porous carbon glycerol, the nickel nitrate, the cobalt nitrate, the graphitized nano fiber and the, pouring the solution into a hydrothermal reaction kettle after uniformly stirring, heating to 200 ℃, reacting for 20 hours, cooling, filtering, washing and drying to prepare the porous Ni2CoS4The microsphere-loaded graphitized porous carbon nanofiber is Ni2CoS4Supercapacitor electrode comparative material 1 of graphitized porous carbon nanofibers.
Comparative example 2
(1) Adding N, N-dimethylformamide solvent, polyacrylonitrile and ferric acetylacetonate with the mass ratio of 1:1 into a reaction bottle, stirring at a constant speed for 20 hours at room temperature to form electrostatic spinning solution, carrying out electrostatic spinning, putting an electrostatic spinning nanofiber precursor into an atmosphere furnace, heating at the rate of 5 ℃/min to 230 ℃ in the air atmosphere, carrying out heat preservation and activation for 6 hours, then heating to 700 ℃ in the nitrogen atmosphere, carrying out heat preservation and calcination for 4 hours, putting a calcined product into dilute nitric acid solution, and carrying out stirring reaction at a constant speed for 10 hours at 50 ℃ to prepare the graphitized porous carbon nanofiber.
(2) Adding isopropanol solvent, glycerol, nickel nitrate, cobalt nitrate and graphitized porous carbon nanofiber into a reaction bottle, and placing the reaction bottle in a constant-temperature ultrasonic disperser, wherein the constant-temperature ultrasonic disperser comprises a water bath, an ultrasonic device fixedly connected to the upper part of the interior of the water bath, constant-temperature heaters fixedly connected to the two sides of the lower part of the interior of the water bath, and a rotating device fixedly connected to the lower part of the interior of the water bathPlacing and rotating a device, wherein the rotating device is movably connected with a rotating screw, the rotating screw is movably connected with a threaded sleeve, the threaded sleeve is fixedly connected with a supporting rod, the supporting rod is movably connected with a reaction bottle, the ultrasonic frequency is 35KHz, the solution is subjected to ultrasonic dispersion treatment for 4 hours at 40 ℃, the solution is poured into a hydrothermal reaction kettle, heated to 200 ℃, reacted for 5 hours, cooled to room temperature, filtered to remove the solvent, washed by distilled water and ethanol, the solid product is placed into the ethanol solvent, and thiourea is added, wherein the mass ratio of glycerol, nickel nitrate, cobalt nitrate, graphitized porous carbon nanofiber and thiourea is 210:25:10:10:32, the solution is poured into the hydrothermal reaction kettle after being uniformly stirred, heated to 200 ℃, reacted for 20 hours, cooled, filtered, washed and dried to prepare the porous Ni2CoS4The microsphere-loaded graphitized porous carbon nanofiber is Ni2CoS4Supercapacitor electrode comparative material 2 of graphitized porous carbon nanofibers.
Ni in examples and comparative examples2CoS4Putting the super capacitor electrode material of the graphitized porous carbon nanofiber in an N-methyl pyrrolidone solvent, respectively adding acetylene black polyvinylidene fluoride, uniformly stirring, uniformly coating on a foamed nickel electrode, drying and tabletting to prepare a super capacitor working electrode, taking a platinum sheet as a counter electrode, taking an Hg/HgO electrode as a reference electrode and 2mol/L potassium hydroxide solution as an electrolyte, and performing an electrochemical performance test in a CHI660E electrochemical workstation, wherein the test standard is GB/T34870.1-2017.
In summary, the one Ni2CoS4The method comprises the steps of preparing a nano iron oxide in an electrostatic spinning nanofiber precursor during high-temperature activation of ferric acetylacetonate, wherein the nano iron oxide has a catalytic effect on amorphous carbon generated by high-temperature thermal cracking of the electrostatic spinning nanofiber precursor, promotes conversion of the amorphous carbon to graphitized carbon with more excellent conductivity, and removes nano carbon by nitric acid etchingIron oxide forms rich pore structures on graphitized porous carbon nanofibers, and then glycerol is used as a guiding agent to react with Ni2+And Co2+The formed precursor uniformly grows in the pore structure of the graphitized porous carbon nanofiber, thiourea is used as a sulfur source, and porous Ni prepared by a hot solvent method2CoS4The microspheres are uniformly attached to the pores and the matrix of the graphitized porous carbon nanofiber, so that porous Ni is reduced2CoS4The microspheres are agglomerated, and the abundant pore structures promote the wettability with electrolyte, so that a large number of electrochemical active sites are exposed, and the graphitized porous carbon nanofiber is coated on Ni2CoS4The outer layer of the microsphere forms a three-dimensional conductive network and is Ni2CoS4Providing a buffer layer, making Ni act synergistically2CoS4The super capacitor electrode material of the graphitized porous carbon nanofiber shows ultra-high electrochemical performance.
Claims (4)
1. Ni2CoS4The super capacitor electrode material of the graphitized porous carbon nanofiber comprises the following raw materials and components, and is characterized in that: glycerol, nickel nitrate, cobalt nitrate, graphitized porous carbon nanofiber and thiourea, wherein the mass ratio is 200:20-22:10:2-8: 25-30.
2. Ni according to claim 12CoS4-a supercapacitor electrode material of graphitized porous carbon nanofibers, characterized in that: the Ni2CoS4The preparation method of the supercapacitor electrode material of graphitized porous carbon nanofiber comprises the following steps:
(1) adding polyacrylonitrile and iron acetylacetonate into an N, N-dimethylformamide solvent, stirring for 10-20h to form an electrostatic spinning solution, carrying out an electrostatic spinning process, placing an electrostatic spinning nanofiber precursor in an atmosphere furnace, heating at the rate of 2-5 ℃/min to 230-280 ℃ in the air atmosphere, carrying out heat preservation and activation for 4-6h, then heating to 600-700 ℃ in the nitrogen atmosphere, carrying out heat preservation and calcination for 2-4h, placing a calcination product in a dilute nitric acid solution, and carrying out uniform stirring reaction for 10-15h at the temperature of 50-70 ℃ to prepare the graphitized porous carbon nanofiber;
(2) adding glycerol, nickel nitrate, cobalt nitrate and graphitized porous carbon nanofiber into an isopropanol solvent, placing the isopropanol solvent into a constant-temperature ultrasonic dispersion instrument, performing ultrasonic dispersion treatment at the ultrasonic frequency of 25-35KHz at the temperature of 40-80 ℃ for 2-4h, pouring the solution into a hydrothermal reaction kettle, heating to 170-200 ℃, reacting for 5-10h, cooling, filtering and washing, placing the solid product into an ethanol solvent, adding thiourea, stirring uniformly, pouring the solution into the hydrothermal reaction kettle, heating to 170-200 ℃, reacting for 10-20h, cooling, filtering, washing and drying to obtain porous Ni2CoS4The microsphere-loaded graphitized porous carbon nanofiber is Ni2CoS4-a supercapacitor electrode material of graphitized porous carbon nanofibers.
3. Ni according to claim 22CoS4-a supercapacitor electrode material of graphitized porous carbon nanofibers, characterized in that: the mass ratio of the polyacrylonitrile to the ferric acetylacetonate is 1: 0.6-0.8.
4. Ni according to claim 22CoS4-a supercapacitor electrode material of graphitized porous carbon nanofibers, characterized in that: the constant-temperature ultrasonic dispersion instrument in the step (2) comprises a water bath, a ultrasonic device fixedly connected to the upper portion of the interior of the water bath, constant-temperature heaters fixedly connected to the two sides of the lower portion of the interior of the water bath, a rotating device fixedly connected to the lower portion of the interior of the water bath, a rotating screw movably connected to the rotating device, a threaded sleeve movably connected to the rotating screw, a supporting rod fixedly connected to the threaded sleeve, and a reaction bottle movably connected to the supporting rod.
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