CN111599607B - Hollow carbon nanofiber-CoS2Electrode material of super capacitor and preparation method thereof - Google Patents

Hollow carbon nanofiber-CoS2Electrode material of super capacitor and preparation method thereof Download PDF

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CN111599607B
CN111599607B CN202010497103.9A CN202010497103A CN111599607B CN 111599607 B CN111599607 B CN 111599607B CN 202010497103 A CN202010497103 A CN 202010497103A CN 111599607 B CN111599607 B CN 111599607B
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carbon nanofiber
porous polymer
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CN111599607A (en
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邓新峰
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Guangdong Haizhiyuan New Material Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention relates to the technical field of electrode materials of super capacitors and discloses a hollow carbon nanofiber-CoS2The super capacitor electrode material comprises the following formula raw materials and components: polyvinylpyrrolidone and nano CoS2And amidoximated acrylonitrile-itaconic acid porous nano fiber. Preparing polyacrylonitrile porous polymer by a high internal phase ratio emulsion template method, reacting a nitrile group with hydroxylamine hydrochloride to generate an amidoxime group, and reacting the amidoxime group with nano CoS2Uniformly adsorbing and dispersing the mixture into a matrix of an amidoximated polyacrylonitrile porous polymer, and performing electrostatic spinning treatment, high-temperature preoxidation and thermal cracking to obtain the unique hollow porous carbon nanofiber, namely the nano CoS2Uniformly distributed and attached in the carbon nano fiber, and reduces the nano CoS2The agglomeration phenomenon, the abundant pore structure and the hollow structure are beneficial to the wettability of the electrolyte and promote the transmission and migration of ions.

Description

Hollow carbon nanofiber-CoS2Electrode material of super capacitor and preparation method thereof
Technical Field
The invention relates to the technical field of electrode materials of super capacitors, in particular to hollow carbon nanofiber-CoS2The electrode material of the super capacitor and a preparation method thereof.
Background
The super capacitor is a novel energy storage device, is arranged between the capacitor and the rechargeable battery, and has the characteristics of rapid charging and discharging and energy storage, the super capacitor has the advantages of high power density, long cycle life, wide working temperature limit, environmental protection and the like, but the energy density of the super capacitor is lower, and the research and development of electrode materials with high specific capacitance are effective ways for solving the problems.
The current electrode materials of the super capacitor mainly comprise an active carbon electrode material, a conductive polymer electrode material, a transition metal oxide electrode material and a transition metal sulfide electrode material, and the active carbon electrode material, the conductive polymer electrode material, the transition metal oxide electrode material and the transition metal sulfide electrode material are used as the electrode materialsSulfides of medium transition metals such as Co9S8、CoS2、NiCo2S4、MoS2The composite material has unique physical and electrochemical properties, has excellent pseudocapacitance effect and theoretical specific capacitance, is an ideal electrode material, has important research and application in electrode materials of super capacitors, but transition metal sulfides such as CoS2Has low intrinsic conductivity and low actual specific capacitance, and is nano-CoS2Easy agglomeration in electrode materials, greatly reduced specific surface area and electrochemical active sites, and limited CoS2The application in super capacitor electrode materials.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides the high-efficiency hollow carbon nanofiber-CoS2The super capacitor electrode material and the preparation method thereof solve the problem of CoS2Poor conductivity of electrode material, nano CoS2Easy agglomeration.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: hollow carbon nanofiber-CoS2The electrode material of the super capacitor is characterized in that: comprises the following raw materials and components of polyvinylpyrrolidone and nano CoS2The amidoximated acrylonitrile-itaconic acid porous nanofiber comprises 100:30-60:8-12 mass ratio.
Preferably, the hollow carbon nanofiber-CoS2The preparation method of the supercapacitor electrode material comprises the following steps:
(1) adding distilled water and sodium thiosulfate into a reaction bottle, stirring and dissolving, slowly dropwise adding a cobalt chloride aqueous solution, controlling the mass ratio of the sodium thiosulfate to the cobalt chloride to be 1-1.2:1, uniformly stirring, pouring the solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle into a hydrothermal reaction device, heating to 170-200 ℃, reacting for 10-15h, filtering, washing and drying the solution, and preparing the nano CoS2。
(2) Adding pore-foaming agent cyclohexane, emulsifier span 80, acrylonitrile, methyl acrylate, itaconic acid and initiator azobisisobutyronitrile into a reaction bottle, stirring uniformly, slowly dropwise adding an aqueous solution of calcium chloride, heating to 60-80 ℃, stirring for reacting for 5-10h, carrying out reduced pressure distillation on the solution, and carrying out vacuum drying to prepare the polyacrylonitrile porous polymer.
(3) Adding methanol solvent, polyacrylonitrile porous polymer and hydroxylamine hydrochloride into a reaction bottle, stirring uniformly, standing and swelling for 12-24h, adding sodium hydroxide to adjust the pH value of the solution to 8-9, heating to 65-80 ℃, reacting for 10-20h, and carrying out reduced pressure distillation, distilled water washing and ethanol extraction to prepare the amidoxime polyacrylonitrile porous polymer.
(4) Adding polyvinylpyrrolidone and nano CoS into a reaction bottle2Uniformly dispersing by ultrasonic, adding amidoximated polyacrylonitrile porous polymer, heating to 50-70 ℃, reacting for 12-24h, and preparing the nano CoS-containing material2Modifying polyacrylonitrile porous polymer solution.
(5) To contain nano CoS2Using a solution for modifying polyacrylonitrile porous polymer as an electrostatic spinning solution, preparing a carbon nanofiber precursor through an electrostatic spinning process, placing the carbon nanofiber precursor in an atmosphere resistance furnace, heating the carbon nanofiber precursor to 300-350 ℃ at a heating rate of 5-10 ℃/min in the air atmosphere, carrying out thermal insulation pre-oxidation for 30-90min, heating the carbon nanofiber precursor to 900-1000 ℃ in the nitrogen atmosphere, carrying out thermal insulation calcination and thermal cracking for 1-2h, and preparing the hollow carbon nanofiber-CoS2The supercapacitor electrode material of (1).
Preferably, the hydrothermal reaction device in the step (1) comprises a reaction chamber, a blast heater is arranged below the inner part of the reaction chamber, a pulley block is fixedly connected to the inner wall of the reaction chamber, a guide wheel is movably connected to the pulley block, a guide rail is fixedly connected to the guide wheel, a carrying disc is fixedly connected to the guide rail, and a reaction kettle is arranged above the carrying disc.
Preferably, the mass fraction of the pore-foaming agent cyclohexane in the step (2) is 20-25%, the mass fraction of the emulsifier span 80 is 35-45%, and the mass fraction of the calcium chloride is 0.05-0.5%.
Preferably, the mass ratio of acrylonitrile, methyl acrylate, itaconic acid and azobisisobutyronitrile in the step (2) is 100:30-60:5-15: 2-8.
Preferably, the mass ratio of the polyacrylonitrile porous polymer to the hydroxylamine hydrochloride in the step (3) is 10: 12-18.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the hollow carbon nanofiber-CoS2The supercapacitor electrode material is prepared by taking cyclohexane as a pore-forming agent, span 80 as an emulsifier and calcium chloride as a stabilizer through a high internal phase ratio emulsion template method, a polyacrylonitrile porous polymer is prepared, a nitrile group of the polyacrylonitrile porous polymer is reacted with hydroxylamine hydrochloride to obtain an amidoxime group-containing amidoxime polyacrylonitrile porous polymer, and nitrogen and oxygen atoms in the amidoxime group and nano CoS2The cobalt atom of the cobalt generates chemical bonding action to lead the nano CoS2Uniformly adsorbing and dispersing the mixture into a matrix of an amidoximated polyacrylonitrile porous polymer through a large number of pore structures, taking the polyacrylonitrile porous polymer as a shell core and polyvinylpyrrolidone as a shell layer, performing electrostatic spinning treatment, and performing oxidative crosslinking on oxygen and the polymer in the high-temperature pre-oxidation and thermal cracking processes to generate a large number of ester functional groups with thermal stability, so that the shell core cannot be completely thermally cracked, and further the unique hollow porous carbon nanofiber is obtained.
The hollow carbon nanofiber-CoS2The electrode material of the super capacitor, nano CoS2Uniformly distributed and attached in the porous structure and hollow core of the carbon nanofiber, and reduces the nano CoS2The agglomeration phenomenon is avoided, so that a large number of electrochemical active sites are exposed, the wettability of electrolyte is facilitated due to rich pore structures and hollow structures, the transmission and migration of ions are promoted, the carbon nanofiber is nitrogen-doped carbon, and the carbon nanofiber is formed by nano CoS2The outside forms a three-dimensional conductive network, and the hollow carbon nanofiber-CoS is enabled to be under the synergistic action2The electrode material of the super capacitor shows excellent electrochemical performance and actual specific capacitance.
Drawings
FIG. 1 is a schematic front view of a hydrothermal reaction apparatus;
figure 2 is a schematic top view of a carrier tray.
1-a hydrothermal reaction device; 2-a reaction chamber; 3-a blast heater; 4-a pulley block; 5-a guide wheel; 6-a guide rail; 7-carrying plate; 8-a reaction kettle.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: hollow carbon nanofiber-CoS2The electrode material of the super capacitor is characterized in that: comprises the following raw materials and components of polyvinylpyrrolidone and nano CoS2The amidoximated acrylonitrile-itaconic acid porous nanofiber comprises 100:30-60:8-12 mass ratio.
Hollow carbon nanofiber-CoS2The preparation method of the supercapacitor electrode material comprises the following steps:
(1) adding distilled water and sodium thiosulfate into a reaction bottle, stirring and dissolving, slowly dropwise adding a cobalt chloride aqueous solution, controlling the mass ratio of the sodium thiosulfate to the cobalt chloride to be 1-1.2:1, uniformly stirring, pouring the solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle into a hydrothermal reaction device, wherein the hydrothermal reaction device comprises a reaction chamber, a blast heater is arranged below the inner part of the reaction chamber, a pulley block is fixedly connected to the inner wall of the reaction chamber, a guide wheel is movably connected to the pulley block, a guide rail is fixedly connected to the guide rail, a carrying disc is fixedly connected to the guide rail, the reaction kettle is arranged above the carrying disc, heating is carried out to 170-2。
(2) Adding 20-25% of pore-foaming agent cyclohexane and 35-45% of emulsifier span 80 into a reaction bottle, uniformly stirring acrylonitrile, methyl acrylate, itaconic acid and initiator azobisisobutyronitrile in a mass ratio of 100:30-60:5-15:2-8, slowly dropwise adding 0.05-0.5% of calcium chloride aqueous solution after uniformly stirring, heating to 60-80 ℃, stirring for reaction for 5-10h, carrying out reduced pressure distillation on the solution, and carrying out vacuum drying to prepare the polyacrylonitrile porous polymer.
(3) Adding methanol solvent, polyacrylonitrile porous polymer and hydroxylamine hydrochloride in a mass ratio of 10:12-18 into a reaction bottle, uniformly stirring, standing and swelling for 12-24h, adding sodium hydroxide to adjust the pH value of the solution to 8-9, heating to 65-80 ℃, reacting for 10-20h, carrying out reduced pressure distillation, distilled water washing and ethanol extraction processes, and preparing the amidoxime polyacrylonitrile porous polymer.
(4) Adding polyvinylpyrrolidone and nano CoS into a reaction bottle2Uniformly dispersing by ultrasonic, adding amidoximated polyacrylonitrile porous polymer, heating to 50-70 ℃, reacting for 12-24h, and preparing the nano CoS-containing material2Modifying polyacrylonitrile porous polymer solution.
(5) To contain nano CoS2Using a solution for modifying polyacrylonitrile porous polymer as an electrostatic spinning solution, preparing a carbon nanofiber precursor through an electrostatic spinning process, placing the carbon nanofiber precursor in an atmosphere resistance furnace, heating the carbon nanofiber precursor to 300-350 ℃ at a heating rate of 5-10 ℃/min in the air atmosphere, carrying out thermal insulation pre-oxidation for 30-90min, heating the carbon nanofiber precursor to 900-1000 ℃ in the nitrogen atmosphere, carrying out thermal insulation calcination and thermal cracking for 1-2h, and preparing the hollow carbon nanofiber-CoS2The supercapacitor electrode material of (1).
Example 1
(1) Adding distilled water and sodium thiosulfate into a reaction bottle, stirring and dissolving, slowly dropwise adding a cobalt chloride aqueous solution, controlling the mass ratio of the sodium thiosulfate to the cobalt chloride to be 1:1, pouring the solution into a hydrothermal reaction kettle after uniformly stirring, placing the hydrothermal reaction kettle into a hydrothermal reaction device, wherein the hydrothermal reaction device comprises a reaction chamber, a blast heater is arranged below the inner part of the reaction chamber, a pulley block is fixedly connected to the inner wall of the reaction chamber, a guide wheel is movably connected to the pulley block, a guide rail is fixedly connected to the guide rail, a carrying disc is fixedly connected to the guide rail, the reaction kettle is arranged above the carrying disc, heating is carried out to 170 ℃, reacting for 10 hours, filtering, washing and drying the solution, and preparing the nano CoS2。
(2) Adding 20 mass percent of pore-foaming agent cyclohexane, 35 mass percent of emulsifier span 80, and acrylonitrile, methyl acrylate, itaconic acid and initiator azobisisobutyronitrile in a mass ratio of 100:30:5:2 into a reaction bottle, stirring uniformly, slowly dropwise adding 0.05 mass percent of calcium chloride aqueous solution, heating to 60 ℃, stirring for reaction for 5 hours, carrying out reduced pressure distillation on the solution, and carrying out vacuum drying to prepare the polyacrylonitrile porous polymer.
(3) Adding methanol solvent, polyacrylonitrile porous polymer and hydroxylamine hydrochloride in a mass ratio of 10:12 into a reaction bottle, uniformly stirring, standing and swelling for 12h, adding sodium hydroxide to adjust the pH value of the solution to 8, heating to 65 ℃, reacting for 10h, and carrying out reduced pressure distillation, distilled water washing and ethanol extraction to prepare the amidoxime polyacrylonitrile porous polymer.
(4) Adding polyvinylpyrrolidone and nano CoS into a reaction bottle2Uniformly dispersing by ultrasonic, adding amidoximated polyacrylonitrile porous polymer with the mass ratio of 100:30:8, heating to 50 ℃, reacting for 12h, and preparing the nano CoS-containing porous polymer2Modifying polyacrylonitrile porous polymer solution.
(5) To contain nano CoS2Using a solution for modifying polyacrylonitrile porous polymer as an electrostatic spinning solution, preparing a carbon nanofiber precursor through an electrostatic spinning process, placing the carbon nanofiber precursor in an atmosphere resistance furnace, heating to 300 ℃ at a heating rate of 5 ℃/min in the air atmosphere, carrying out thermal insulation pre-oxidation for 30min, heating to 900 ℃ in the nitrogen atmosphere, carrying out thermal insulation calcination and thermal cracking for 1h, and preparing the hollow carbon nanofiber-CoS2The supercapacitor electrode material 1.
Example 2
(1) Adding distilled water and sodium thiosulfate into a reaction bottle, stirring and dissolving, slowly dropwise adding a cobalt chloride aqueous solution, controlling the mass ratio of the sodium thiosulfate to the cobalt chloride to be 1.05:1, uniformly stirring, pouring the solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle into a hydrothermal reaction device, wherein the hydrothermal reaction device comprises a reaction chamber, a blast heater is arranged below the inner part of the reaction chamber, a pulley block is fixedly connected to the inner wall of the reaction chamber, a guide wheel is movably connected to the pulley block, a guide rail is fixedly connected to the guide rail, a carrying disc is fixedly connected to the guide rail, the reaction kettle is arranged above the carrying disc, heating is carried out to 180 ℃, reacting for 15 hours, filtering, washing and drying the solution, and the nano CoS is prepared2。
(2) Adding 22 mass percent of pore-foaming agent cyclohexane and 37 mass percent of emulsifier span 80 into a reaction bottle, uniformly stirring acrylonitrile, methyl acrylate, itaconic acid and initiator azobisisobutyronitrile, slowly dropwise adding 0.2 mass percent of calcium chloride aqueous solution, heating to 80 ℃, stirring for reaction for 10 hours, distilling the solution under reduced pressure, and drying in vacuum to obtain the polyacrylonitrile porous polymer.
(3) Adding methanol solvent, polyacrylonitrile porous polymer and hydroxylamine hydrochloride in a mass ratio of 10:14 into a reaction bottle, uniformly stirring, standing and swelling for 24h, adding sodium hydroxide to adjust the pH of the solution to 9, heating to 80 ℃, reacting for 10h, and carrying out reduced pressure distillation, distilled water washing and ethanol extraction to prepare the amidoxime polyacrylonitrile porous polymer.
(4) Adding polyvinylpyrrolidone and nano CoS into a reaction bottle2Uniformly ultrasonically dispersing, adding amidoximated polyacrylonitrile porous polymer with the mass ratio of 100:40:9, heating to 70 ℃, reacting for 18 hours, and preparing the nano CoS-containing porous polymer2Modifying polyacrylonitrile porous polymer solution.
(5) To contain nano CoS2Using a solution for modifying polyacrylonitrile porous polymer as an electrostatic spinning solution, preparing a carbon nanofiber precursor through an electrostatic spinning process, placing the carbon nanofiber precursor in an atmosphere resistance furnace, heating to 300 ℃ at a heating rate of 10 ℃/min in the air atmosphere, carrying out thermal insulation pre-oxidation for 90min, heating to 920 ℃ in the nitrogen atmosphere, carrying out thermal insulation calcination and thermal cracking for 2h, and preparing the hollow carbon nanofiber-CoS2The supercapacitor electrode material 2.
Example 3
(1) Adding distilled water and sodium thiosulfate into a reaction bottle, stirring and dissolving, slowly dropwise adding a cobalt chloride aqueous solution, controlling the mass ratio of the sodium thiosulfate to the cobalt chloride to be 1.1:1, uniformly stirring, pouring the solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle into a hydrothermal reaction device, wherein the hydrothermal reaction device comprises a reaction chamber, a blast heater is arranged below the inner part of the reaction chamber, a pulley block is fixedly connected to the inner wall of the reaction chamber, and a guide wheel is movably connected to the pulley blockThe guide wheel is fixedly connected with a guide rail, the guide rail is fixedly connected with a carrying disc, a reaction kettle is arranged above the carrying disc, the reaction kettle is heated to 180 ℃, the reaction kettle reacts for 12 hours, the solution is filtered, washed and dried, and the nano CoS is prepared2。
(2) Adding pore-foaming agent cyclohexane with the mass fraction of 24%, emulsifier span 80 with the mass fraction of 42% into a reaction bottle, uniformly stirring acrylonitrile, methyl acrylate, itaconic acid and initiator azobisisobutyronitrile with the mass ratio of 100:50:12:6, slowly dripping aqueous solution of calcium chloride with the mass fraction of 0.4%, heating to 70 ℃, stirring for reacting for 8 hours, distilling the solution under reduced pressure and drying in vacuum to prepare the polyacrylonitrile porous polymer.
(3) Adding methanol solvent, polyacrylonitrile porous polymer and hydroxylamine hydrochloride in a mass ratio of 10:16 into a reaction bottle, uniformly stirring, standing and swelling for 18h, adding sodium hydroxide to adjust the pH of the solution to 8-9, heating to 75 ℃, reacting for 15h, and carrying out reduced pressure distillation, distilled water washing and ethanol extraction to prepare the amidoxime polyacrylonitrile porous polymer.
(4) Adding polyvinylpyrrolidone and nano CoS into a reaction bottle2Uniformly ultrasonically dispersing, adding amidoximated polyacrylonitrile porous polymer with the mass ratio of 100:50:10, heating to 60 ℃, reacting for 18h, and preparing the nano CoS-containing material2Modifying polyacrylonitrile porous polymer solution.
(5) To contain nano CoS2Using a solution for modifying polyacrylonitrile porous polymer as an electrostatic spinning solution, preparing a carbon nanofiber precursor through an electrostatic spinning process, placing the carbon nanofiber precursor in an atmosphere resistance furnace, heating to 330 ℃ at a heating rate of 8 ℃/min in the air atmosphere, carrying out thermal insulation pre-oxidation for 60min, heating to 960 ℃ in the nitrogen atmosphere, carrying out thermal insulation calcination and thermal cracking for 1.5h, and preparing to obtain the hollow carbon nanofiber-CoS2The supercapacitor electrode material 3.
Example 4
(1) Adding distilled water and sodium thiosulfate into a reaction bottle, stirring to dissolve, slowly dropwise adding cobalt chloride aqueous solution, and controlling substances of the sodium thiosulfate and the cobalt chlorideThe mass ratio of the solution to the water is 1.2:1, the solution is poured into a hydrothermal reaction kettle after being uniformly stirred and is placed in a hydrothermal reaction device, the hydrothermal reaction device comprises a reaction chamber, a blast heater is arranged below the inner part of the reaction chamber, a pulley block is fixedly connected to the inner wall of the reaction chamber, a guide wheel is movably connected to the pulley block, a guide rail is fixedly connected to the guide wheel, a carrying disc is fixedly connected to the guide rail, the reaction kettle is arranged above the carrying disc, the reaction kettle is heated to 200 ℃ for 15 hours, the solution is filtered, washed and dried, and the nano CoS is prepared2。
(2) Adding 25 mass percent of pore-foaming agent cyclohexane, 45 mass percent of emulsifier span 80 into a reaction bottle, uniformly stirring acrylonitrile, methyl acrylate, itaconic acid and initiator azobisisobutyronitrile, slowly dripping 0.5 mass percent of calcium chloride aqueous solution, heating to 80 ℃, stirring for reaction for 10 hours, distilling the solution under reduced pressure, and drying in vacuum to prepare the polyacrylonitrile porous polymer.
(3) Adding methanol solvent, polyacrylonitrile porous polymer and hydroxylamine hydrochloride in a mass ratio of 10:18 into a reaction bottle, stirring uniformly, standing and swelling for 24h, adding sodium hydroxide to adjust the pH of the solution to 9, heating to 80 ℃, reacting for 20h, and carrying out reduced pressure distillation, distilled water washing and ethanol extraction to prepare the amidoxime polyacrylonitrile porous polymer.
(4) Adding polyvinylpyrrolidone and nano CoS into a reaction bottle2Uniformly ultrasonically dispersing, adding amidoximated polyacrylonitrile porous polymer with the mass ratio of 100:60:12, heating to 70 ℃, reacting for 24 hours, and preparing the nano CoS-containing material2Modifying polyacrylonitrile porous polymer solution.
(5) To contain nano CoS2Using a solution for modifying polyacrylonitrile porous polymer as an electrostatic spinning solution, preparing a carbon nanofiber precursor through an electrostatic spinning process, placing the carbon nanofiber precursor in an atmosphere resistance furnace, heating to 350 ℃ at a heating rate of 10 ℃/min in the air atmosphere, carrying out thermal insulation pre-oxidation for 90min, heating to 1000 ℃ in the nitrogen atmosphere, carrying out thermal insulation calcination and thermal cracking for 2h, and preparing the hollow carbon nanofiber-CoS2Is disclosedThe stage capacitor electrode material 4.
Comparative example 1
(1) Adding distilled water and sodium thiosulfate into a reaction bottle, stirring and dissolving, then slowly dropwise adding a cobalt chloride aqueous solution, controlling the mass ratio of the sodium thiosulfate to the cobalt chloride to be 1.3:1, pouring the solution into a hydrothermal reaction kettle after uniformly stirring, placing the hydrothermal reaction kettle into a hydrothermal reaction device, wherein the hydrothermal reaction device comprises a reaction chamber, a blast heater is arranged below the inner part of the reaction chamber, a pulley block is fixedly connected to the inner wall of the reaction chamber, a guide wheel is movably connected to the pulley block, a guide rail is fixedly connected to the guide rail, a carrier plate is fixedly connected to the guide rail, the reaction kettle is arranged above the carrier plate, heating is carried out to 170 ℃, reacting for 15 hours, filtering, washing and drying the solution, thus preparing the nano CoS2。
(2) Adding 18 mass percent of pore-foaming agent cyclohexane, 30 mass percent of emulsifier span 80 into a reaction bottle, uniformly stirring acrylonitrile, methyl acrylate, itaconic acid and initiator azobisisobutyronitrile, slowly dripping 0.7 mass percent of calcium chloride aqueous solution, heating to 80 ℃, stirring for reaction for 5 hours, distilling the solution under reduced pressure, and drying in vacuum to prepare the polyacrylonitrile porous polymer.
(3) Adding methanol solvent, polyacrylonitrile porous polymer and hydroxylamine hydrochloride in a mass ratio of 1:1 into a reaction bottle, stirring uniformly, standing and swelling for 24h, adding sodium hydroxide to adjust the pH of the solution to 8, heating to 80 ℃, reacting for 10h, and carrying out reduced pressure distillation, distilled water washing and ethanol extraction to prepare the amidoxime polyacrylonitrile porous polymer.
(4) Adding polyvinylpyrrolidone and nano CoS into a reaction bottle2Uniformly ultrasonically dispersing, adding amidoximated polyacrylonitrile porous polymer with the mass ratio of 100:20:6, heating to 70 ℃, reacting for 12 hours, and preparing the nano CoS-containing porous polymer2Modifying polyacrylonitrile porous polymer solution.
(5) To contain nano CoS2Using the solution of the modified polyacrylonitrile porous polymer as electrostatic spinning solution, preparing a carbon nanofiber precursor through an electrostatic spinning process, and subjecting carbon nanofibers to electrostatic spinningPlacing the fiber precursor in an atmosphere resistance furnace, heating to 3050 ℃ at a heating rate of 10 ℃/min in an air atmosphere, carrying out thermal insulation and pre-oxidation for 90min, heating to 900 ℃ in a nitrogen atmosphere, carrying out thermal insulation, calcination and thermal cracking for 2h, and preparing to obtain the hollow carbon nanofiber-CoS2Comparative example 1.
The hollow carbon nanofiber-CoS in examples and comparative examples2The electrode material of the super capacitor is placed in an ethanol solvent, acetylene black and polyvinylidene fluoride are heated, the solution is coated on a foamed nickel electrode, drying and tabletting are carried out, a working electrode of the super capacitor is obtained, a platinum sheet is used as a counter electrode, Ag/AgCl is used as a reference electrode, 6mol/L potassium hydroxide solution is used as electrolyte, and an electrochemical performance test is carried out in a CHI760E electrochemical workstation, wherein the test standard is GB/T34870.1-2017.
Testing Current Density (A/g) Specific capacitance (F/g)
Example 1 1 422.8
Example 2 1 508.4
Example 3 1 487.2
Example 4 1 438.2
Comparative example 1 1 323.7

Claims (5)

1. Hollow carbon nanofiber-CoS2The electrode material of the super capacitor is characterized in that: comprises the following raw materials and components of polyvinylpyrrolidone and nano CoS2The amidoximated acrylonitrile-itaconic acid porous nanofiber is prepared by mixing 100:30-60:8-12 by mass;
the hollow carbon nanofiber-CoS2The preparation method of the supercapacitor electrode material comprises the following steps: (1) adding sodium thiosulfate into a distilled water solvent, slowly dropwise adding a cobalt chloride aqueous solution, controlling the mass ratio of the sodium thiosulfate to the cobalt chloride to be 1-1.2:1, uniformly stirring, pouring the solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle into a hydrothermal reaction device, heating to 170-200 ℃, reacting for 10-15h, filtering, washing and drying to prepare the nano CoS2(ii) a (2) Adding pore-foaming agent cyclohexane, emulsifier span 80, acrylonitrile, methyl acrylate, itaconic acid and initiator azobisisobutyronitrile into a reaction bottle, stirring uniformly, slowly dropwise adding an aqueous solution of calcium chloride, heating to 60-80 ℃, reacting for 5-10h, distilling under reduced pressure and drying in vacuum to prepare the polyacrylonitrile porous polymer; (3) adding a polyacrylonitrile porous polymer and hydroxylamine hydrochloride into a methanol solvent, stirring uniformly, standing and swelling for 12-24h, adding sodium hydroxide to adjust the pH of the solution to 8-9, heating to 65-80 ℃, reacting for 10-20h, carrying out reduced pressure distillation, washing with distilled water, and extracting with ethanol to prepare an amidoximated polyacrylonitrile porous polymer; (4) adding the nano CoS prepared in the step (1) into polyvinylpyrrolidone2Adding the amidoximated polyacrylonitrile porous polymer prepared in the step (3) after uniform ultrasonic dispersion, and heating to 50-Reacting for 12-24h at 70 ℃ to obtain the product containing nano CoS2Modifying a solution of a polyacrylonitrile porous polymer; (5) the nano CoS-containing material prepared in the step (4)2Using a solution for modifying polyacrylonitrile porous polymer as an electrostatic spinning solution, preparing a carbon nanofiber precursor through an electrostatic spinning process, placing the carbon nanofiber precursor in an atmosphere resistance furnace, heating the carbon nanofiber precursor to 300-350 ℃ at a heating rate of 5-10 ℃/min in the air atmosphere, carrying out thermal insulation pre-oxidation for 30-90min, heating the carbon nanofiber precursor to 900-1000 ℃ in the nitrogen atmosphere, carrying out thermal insulation calcination and thermal cracking for 1-2h, and preparing the hollow carbon nanofiber-CoS2The supercapacitor electrode material of (1).
2. The hollow carbon nanofiber-CoS as claimed in claim 12The electrode material of the super capacitor is characterized in that: the hydrothermal reaction device in the step (1) comprises a reaction chamber, a blast heater is arranged below the inner portion of the reaction chamber, a pulley block is fixedly connected to the inner wall of the reaction chamber, a guide wheel is movably connected to the pulley block, a guide rail is fixedly connected to the guide wheel, a carrying disc is fixedly connected to the guide rail, and a reaction kettle is arranged above the carrying disc.
3. The hollow carbon nanofiber-CoS as claimed in claim 22The electrode material of the super capacitor is characterized in that: in the step (2), the mass fraction of pore-forming agent cyclohexane is 20-25%, the mass fraction of emulsifier span 80 is 35-45%, and the mass fraction of calcium chloride is 0.05-0.5%.
4. The hollow carbon nanofiber-CoS as claimed in claim 22The electrode material of the super capacitor is characterized in that: the mass ratio of the acrylonitrile, the methyl acrylate, the itaconic acid and the azobisisobutyronitrile in the step (2) is 100:30-60:5-15: 2-8.
5. The hollow carbon nanofiber-CoS as claimed in claim 22The electrode material of the super capacitor is characterized in that: the polyacrylonitrile porous polymer in the step (2)The mass ratio of the hydroxylamine hydrochloride to the hydroxylamine hydrochloride is 10: 12-18.
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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20040083573A (en) * 2003-03-24 2004-10-06 김찬 Preparation of Carbon Nanotube Based Nanostructured Carbon Fiber by Electrospinning and Their Applications to Electric Double Layer Supercapacitor
CN102797111A (en) * 2012-08-16 2012-11-28 黑龙江大学 Method for preparing porous nitrogen-contained carbon fiber electrode material from melamine resin/polyvinyl alcohol aqueous solution through high-pressure static spinning technology
CN102881463A (en) * 2012-08-14 2013-01-16 北京大学 Fibrous supercapacitor and manufacturing method thereof
CN103098263A (en) * 2010-09-09 2013-05-08 加州理工学院 Electrochemical energy storage systems and methods
CN103474253A (en) * 2013-09-30 2013-12-25 武汉理工大学 Porous carbon microsphere electrode materials based on surface function functional group, preparing method of materials, super capacitor of materials, and preparing method of super capacitor
US9017653B2 (en) * 2012-06-14 2015-04-28 The Board Of Regents Of The University Of Texas System Nitric oxide-releasing compositions and methods
CN105858634A (en) * 2016-03-27 2016-08-17 华南理工大学 Emulsion gel based polyacrylonitrile/carbon porous material and preparation method thereof
CN107424847A (en) * 2017-07-21 2017-12-01 张娟 A kind of preparation method of nitrogen-doped carbon nano-fiber Supported Co acid nickel combination electrode material
CN109626435A (en) * 2018-12-28 2019-04-16 哈尔滨理工大学 A kind of preparation and its application of molybdenum disulfide nano sheet array/carbon nano-fiber
CN110713211A (en) * 2019-09-06 2020-01-21 扬州大学 Pearl necklace multilevel structure MoS2@ C-CNFs sodium ion battery negative electrode material and preparation method thereof

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI363361B (en) * 2007-12-31 2012-05-01 Taiwan Textile Res Inst Electrode of supercapacitor and the manufacturing method thereof
CN102838708A (en) * 2011-06-24 2012-12-26 苏州科技学院 Preparation method of acrylonitrile-itaconic acid bipolymer spinning solution
CN102587117B (en) * 2012-02-28 2014-07-16 中国科学院上海应用物理研究所 Amidoxime-based chelate polyacrylonitrile fiber and its preparation method and application
CN102943320B (en) * 2012-10-24 2014-07-09 长春理工大学 Erbium doped yttrium trifluoride upconversion luminescence hollow nanometer fiber preparation method
CN105513822B (en) * 2016-02-05 2017-09-29 扬州大学 The preparation method of the electrode material of manganese dioxide cladding hollow carbon fiber
EP3270392A1 (en) * 2016-07-13 2018-01-17 Rhodia Operations Pseudocapacitive materials for supercapacitor electrodes
CN106492879B (en) * 2016-10-17 2019-06-25 天津工业大学 Modified double scale polyacrylonitrile nanofiber iron complex catalyst of a kind of amidoxim and preparation method thereof

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20040083573A (en) * 2003-03-24 2004-10-06 김찬 Preparation of Carbon Nanotube Based Nanostructured Carbon Fiber by Electrospinning and Their Applications to Electric Double Layer Supercapacitor
CN103098263A (en) * 2010-09-09 2013-05-08 加州理工学院 Electrochemical energy storage systems and methods
US9017653B2 (en) * 2012-06-14 2015-04-28 The Board Of Regents Of The University Of Texas System Nitric oxide-releasing compositions and methods
CN102881463A (en) * 2012-08-14 2013-01-16 北京大学 Fibrous supercapacitor and manufacturing method thereof
CN102797111A (en) * 2012-08-16 2012-11-28 黑龙江大学 Method for preparing porous nitrogen-contained carbon fiber electrode material from melamine resin/polyvinyl alcohol aqueous solution through high-pressure static spinning technology
CN103474253A (en) * 2013-09-30 2013-12-25 武汉理工大学 Porous carbon microsphere electrode materials based on surface function functional group, preparing method of materials, super capacitor of materials, and preparing method of super capacitor
CN105858634A (en) * 2016-03-27 2016-08-17 华南理工大学 Emulsion gel based polyacrylonitrile/carbon porous material and preparation method thereof
CN107424847A (en) * 2017-07-21 2017-12-01 张娟 A kind of preparation method of nitrogen-doped carbon nano-fiber Supported Co acid nickel combination electrode material
CN109626435A (en) * 2018-12-28 2019-04-16 哈尔滨理工大学 A kind of preparation and its application of molybdenum disulfide nano sheet array/carbon nano-fiber
CN110713211A (en) * 2019-09-06 2020-01-21 扬州大学 Pearl necklace multilevel structure MoS2@ C-CNFs sodium ion battery negative electrode material and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
聚丙烯腈基碳纤维的研究进展;韦鑫;《成都纺织高等专科学校学报》;20170120;第1卷;全文 *
聚丙烯腈基碳纳米纤维在超级电容器电极材料中的应用研究进展;王赫;《材料导报》;20180315;第5卷;全文 *

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