CN111508719A - Carbon-coated Co with shell-core structure3O4Super capacitor electrode material and preparation method thereof - Google Patents

Carbon-coated Co with shell-core structure3O4Super capacitor electrode material and preparation method thereof Download PDF

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CN111508719A
CN111508719A CN202010333397.1A CN202010333397A CN111508719A CN 111508719 A CN111508719 A CN 111508719A CN 202010333397 A CN202010333397 A CN 202010333397A CN 111508719 A CN111508719 A CN 111508719A
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陈志林
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • H01G11/32Carbon-based
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/24Electrodes 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • H01G11/32Carbon-based
    • H01G11/34Carbon-based characterised by carbonisation or activation of carbon
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • H01G11/46Metal oxides
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13Energy storage using capacitors

Abstract

The invention relates to the technical field of electrode materials of supercapacitors and discloses carbon-coated Co with a shell-core structure3O4The super capacitor electrode material comprises the following formula raw materials and components: aniline, 1, 3-phenylenediamine, initiator, phytic acid and Co (CH)3COOH)2. The carbon-coated Co with shell-core structure3O4The phytic acid-doped polyaniline copolymer hydrogel has a three-dimensional network structure and high porosity, and the phytic acid and Co are used as electrode materials of the super capacitor2+Has strong complexation effect and has the advantages of strong complexation effect,mixing Co (CH)3COOH)2Uniformly adsorbing the carbon material into hydrogel, carbonizing the three-dimensional network hydrogel into an N, P codoped porous carbon material, improving the wettability of the carbon material by phosphorus doping, enhancing the conductivity and capacitance of the carbon material by nitrogen doping, and obtaining Co (CH)3COOH)2Cracking at high temperature to Co3O4Uniformly dispersed in the porous carbon material to expose more electrochemical active sites, thereby improving the actual specific capacitance of the electrode material, and inhibiting Co by coating the carbon layer3O4The volume is expanded, and the cycling stability of the electrode material is improved.

Description

Carbon-coated Co with shell-core structure3O4Super capacitor electrode material and preparation method thereof
Technical Field
The invention relates to the technical field of electrode materials of supercapacitors, in particular to carbon-coated Co with a shell-core structure3O4An electrode material of a super capacitor and a preparation method thereof.
Background
Along with the increasing severity of energy crisis and environmental pollution problems, the development of novel efficient energy devices and energy systems is urgent, and supercapacitors are novel energy storage devices between traditional capacitors and rechargeable batteries, have the advantages of rapid charging and discharging of the capacitors and the energy storage characteristic of the batteries, and compared with capacitor storage batteries and traditional physical capacitors, supercapacitors have the advantages of high power density, long cycle life, wide working temperature limit, environmental protection and the like.
The performance of the super capacitor mainly depends on electrode materials, and the electrode materials of the super capacitor mainly comprise carbon material electrode materials, such as carbon nanofibers, carbon aerogel, carbon nanotubes and the like, and have large specific surface area and smaller internal resistance; metal oxide electrode materials such as ruthenium oxide, manganese oxide, tin oxide and the like have high theoretical specific capacitance; the conductive polymer such as polyaniline, polypyrrole, etc. has network three-dimensional structure, and electrons and ions in the electrode material can be transferred by exchange with ions in the electrolyte, wherein Co is3O4The material has low cost, less pollution and high theoretical specific capacity, is a super capacitor electrode material with great development potential, but Co3O4Low intrinsic conductivity, Co3O4The electrode material has poor conductivity, inhibits the transmission and migration of electrons and ions in electrode reaction, reduces the actual specific capacity of the electrode material, and is Co3O4When the electrode material generates pseudo-capacitance reaction, Co is caused3O4The volume of the electrode material is shrunk and expanded, so that the matrix of the electrode material is lost and even decomposed, and the electrochemical cycling stability of the electrode material is reduced.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides carbon-coated Co with a shell-core structure3O4The electrode material of super capacitor and its preparation process solve the problem of Co3O4The problem of poor conductivity of the electrode material is solved, and Co in pseudo-capacitance reaction is solved3O4The problem of volume expansion.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: carbon-coated Co with shell-core structure3O4The supercapacitor electrode material comprises the following formula raw materials and components in parts by weight, and is characterized in that: 30-35 parts of aniline, 4-6 parts of 1, 3-phenylenediamine, 18-22 parts of initiator, 10-14 parts of phytic acid, 23-38 parts of Co (CH3COOH)2, wherein the initiator is potassium persulfate.
Preferably, the carbon-coated Co of the core-shell structure3O4The preparation method of the electrode material of the super capacitor comprises the following steps:
(1) adding distilled water, 30-35 parts of aniline, 4-6 parts of 1, 3-phenylenediamine and 10-14 parts of phytic acid into a reaction bottle, uniformly stirring, adding 18-22 parts of initiator potassium persulfate, placing the reaction bottle into a low-temperature thermostat, uniformly stirring and reacting for 10-15 hours at 10-20 ℃, vacuum-drying the solution to remove the solvent, washing the solid product by using distilled water and ether, and fully drying to prepare the phosphoric acid doped polyaniline hydrogel.
(2) Adding distilled water, phosphoric acid doped polyaniline hydrogel and 23-38 parts of Co (CH3COOH)2 into a reaction bottle, placing the reaction bottle in a constant-temperature water bath, heating to 60-80 ℃, uniformly stirring for 6-10h, vacuum drying the solution to remove the solvent, placing the solid mixture in an atmosphere furnace, heating at the rate of 5-10 ℃/min to 450-3O4And (3) a supercapacitor electrode material.
Preferably, the cryostat includes the cryoscope, the inside insulating layer that is provided with of cryoscope, the insulating layer top is provided with the draw-in groove, draw-in groove and safety cover swing joint, the inner wall fixedly connected with slide rail of insulating layer, swing joint has the gyro wheel on the slide rail, gyro wheel and carriage release lever swing joint, the one end swing joint of carriage release lever has the regulator, the regulator is connected with the stationary phase is fixed, the inside below fixedly connected with agitating unit of cryoscope, agitating unit's top and stirring fan piece swing joint, the inside below fixedly connected with base of cryoscope, the inside of base is provided with rotary device, rotary device's top swing joint has the rotation axis, the fixed surface of rotation axis is connected with the magnet fan piece.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the carbon-coated Co with shell-core structure3O4The phytic acid is used as a gelling agent, aniline and 1, 3-phenylenediamine are used as monomers to prepare the phytic acid-doped polyaniline copolymer hydrogel, the polyaniline copolymer hydrogel has a three-dimensional network structure and high porosity, and the polyaniline copolymer hydrogel is mixed with Co (CH)3COOH)2Complexing, phosphate groups in phytic acid with Co2+Has strong complexation effect and can be used for complexing Co (CH)3COOH)2The polyaniline copolymer hydrogel is uniformly adsorbed into the polyaniline copolymer hydrogel and is uniformly distributed.
The carbon-coated Co with shell-core structure3O4The phytic acid doped polyaniline copolymer hydrogel contains rich nitrogen and phosphorus elements, the aniline copolymer three-dimensional network hydrogel with high porosity is carbonized into an N and P codoped porous carbon material through high-temperature carbonization and thermal cracking, the N and P codoped porous carbon material has rich mesopores and pore structures and large specific surface area, the phosphorus doping can enhance the wettability of the carbon material, so that electrolyte is fully soaked into the pore structures of the carbon material and is fully contacted with electrochemical active sites, and the nitrogen doping is favorable for enhancing the conductivity and capacitance of the carbon material.
The carbon-coated Co with shell-core structure3O4Electrode material of super capacitor, using phytic acid to mix Co (CH)3COOH)2Uniformly adsorbed into the three-dimensional network of polyaniline copolymer hydrogel, Co (CH)3COOH)2Pyrolysis at high temperature to form CoC2O4Further decomposed into Co3O4By regulating and controlling Co (CH)3COOH)2And polyaniline copolymer to control Co3O4The porous carbon material is uniformly dispersed in the porous carbon material in an optimal ratio to avoid Co3O4Agglomerate and pack, thereby making Co3O4More electrochemical active sites are exposed and fully contacted with the electrolyte, the actual specific capacitance of the electrode material is improved, and the rich pore structure of the porous carbon material is Co3O4Providing growth sites, forming a core-shell structure, the coating of the carbon layer suppressing Co3O4The volume expansion in the pseudo-capacitance reaction process effectively improves the electrochemical circulation stability of the electrode material.
Drawings
FIG. 1 is a schematic front view of a cryostat;
FIG. 2 is a schematic front view of the travel bar;
fig. 3 is a schematic view of the travel bar adjustment.
1. A cryogenic instrument; 2. a thermal insulation layer; 3. a card slot; 4. a protective cover; 5. a slide rail; 6. a roller; 7. a travel bar; 8. a regulator; 9. a fixing clip; 10. a stirring device; 11. stirring fan blades; 12. a base rod; 13. a rotating device; 14. a rotating shaft; 15. magnet fan blade.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: preferably, the carbon-coated Co of the core-shell structure3O4The preparation method of the electrode material of the super capacitor comprises the following steps:
(1) adding distilled water, 30-35 parts of aniline, 4-6 parts of 1, 3-phenylenediamine and 10-14 parts of phytic acid into a reaction bottle, uniformly stirring, adding 18-22 parts of initiator potassium persulfate, placing the reaction bottle into a cryostat, wherein the cryostat comprises a low-temperature instrument, a heat insulation layer is arranged in the low-temperature instrument, a clamping groove is arranged above the heat insulation layer, the clamping groove is movably connected with a protective cover, a sliding rail is fixedly connected with the inner wall of the heat insulation layer, a roller is movably connected on the sliding rail, the roller is movably connected with a movable rod, one end of the movable rod is movably connected with an adjuster, the adjuster is fixedly connected with a fixed clamp, a stirring device is fixedly connected below the interior of the low-temperature instrument, the upper part of the stirring device is movably connected with a stirring fan sheet, a base is fixedly connected below the interior of the low-temperature instrument, and, and (3) movably connecting a rotating shaft above the rotating device, fixedly connecting a magnet fan on the surface of the rotating shaft, stirring at a constant speed at 10-20 ℃ for reaction for 10-15h, carrying out vacuum drying on the solution to remove the solvent, washing the solid product by using distilled water and diethyl ether, and fully drying to prepare the phosphoric acid-doped polyaniline hydrogel.
(2) Adding distilled water, phosphoric acid doped polyaniline hydrogel and 23-38 parts of Co (CH) into a reaction bottle3COOH)2Placing a reaction bottle in a constant-temperature water bath kettle, heating to 60-80 ℃, uniformly stirring for 6-10h, vacuum drying the solution to remove the solvent, placing the solid mixture in an atmosphere furnace, heating to 450 ℃, (heating to 500 ℃) at the heating rate of 5-10 ℃/min, carrying out heat preservation treatment for 1-2h, heating to 720-3O4A supercapacitor electrode.
(3) Coating carbon of core-shell structure with Co3O4Uniformly dispersing the electrode material of the super capacitor, acetylene black serving as a conductive agent and polyvinylidene fluoride serving as a bonding agent in an N-methyl pyrrolidone solvent, uniformly coating the solution on a nickel sheet, and fully drying to prepare the working electrode of the super capacitor.
Example 1
(1) Preparing a phosphoric acid-doped polyaniline hydrogel component 1: adding distilled water, 30 parts of aniline, 4 parts of 1, 3-phenylenediamine and 10 parts of phytic acid into a reaction bottle, uniformly stirring, adding 18 parts of initiator potassium persulfate, placing the reaction bottle into a cryostat, wherein the cryostat comprises a cryo-instrument, a thermal insulation layer is arranged in the cryo-instrument, a clamping groove is arranged above the thermal insulation layer, the clamping groove is movably connected with a protective cover, the inner wall of the thermal insulation layer is fixedly connected with a sliding rail, a roller is movably connected on the sliding rail, the roller is movably connected with a moving rod, one end of the moving rod is movably connected with an adjuster, the adjuster is fixedly connected with a fixed clamp, a stirring device is fixedly connected below the interior of the cryo-instrument, the upper part of the stirring device is movably connected with a stirring fan, a base is fixedly connected below the interior of the cryo-instrument, a rotating device is arranged in the base, a rotating shaft is movably connected above the rotating device, stirring at constant speed at 10 ℃ for reaction for 10h, drying the solution in vacuum to remove the solvent, washing the solid product with distilled water and ether, and fully drying to prepare the phosphoric acid-doped polyaniline hydrogel component 1.
(2) Preparation of carbon-coated Co of core-shell structure3O4Supercapacitor electrode material 1: adding distilled water and phosphoric acid doped polyaniline hydrogel component 1 and 38 parts of Co (CH3COOH)2 into a reaction bottle, placing the reaction bottle into a constant-temperature water bath kettle, heating to 60 ℃, uniformly stirring for 6 hours, vacuum-drying the solution to remove the solvent, placing the solid mixture into an atmosphere furnace, heating at a rate of 5 ℃/min to 450 ℃, carrying out heat preservation treatment for 1 hour, heating to 720 ℃, carrying out heat preservation calcination for 1 hour, washing the solid product with distilled water and ethanol, fully drying, grinding into fine powder, and preparing to obtain the carbon-coated Co with the shell-core structure3O4Supercapacitor electrode material 1.
(3) Preparing a working electrode 1 of the super capacitor: coating carbon of core-shell structure with Co3O4Uniformly dispersing the electrode material 1 of the super capacitor, acetylene black serving as a conductive agent and polyvinylidene fluoride serving as a bonding agent in an N-methyl pyrrolidone solvent, uniformly coating the solution on a nickel sheet, and fully drying to prepare the working electrode 1 of the super capacitor.
Example 2
(1) Preparing a phosphoric acid-doped polyaniline hydrogel component 2: adding distilled water, 31.5 parts of aniline, 4.5 parts of 1, 3-phenylenediamine and 11 parts of phytic acid into a reaction bottle, uniformly stirring, adding 19 parts of initiator potassium persulfate, placing the reaction bottle into a cryostat, wherein the cryostat comprises a cryo-instrument, a thermal insulation layer is arranged in the cryo-instrument, a clamping groove is arranged above the thermal insulation layer, the clamping groove is movably connected with a protective cover, a slide rail is fixedly connected with the inner wall of the thermal insulation layer, a roller is movably connected on the slide rail and movably connected with a movable rod, one end of the movable rod is movably connected with an adjuster, the adjuster is fixedly connected with a fixed clamp, a stirring device is fixedly connected below the interior of the cryo-instrument, the upper part of the stirring device is movably connected with a stirring fan, a base is fixedly connected below the interior of the cryo-instrument, a rotating device is arranged in the base, a rotating shaft is movably connected above the rotating device, and a, stirring at a constant speed at 20 ℃ for reaction for 10h, drying the solution in vacuum to remove the solvent, washing the solid product with distilled water and diethyl ether, and fully drying to prepare the phosphoric acid-doped polyaniline hydrogel component 2.
(2) Preparation of carbon-coated Co of core-shell structure3O4Supercapacitor electrode material 2: adding distilled water, a phosphoric acid-doped polyaniline hydrogel component 2 and 34 parts of Co (CH3COOH)2 into a reaction bottle, placing the reaction bottle into a constant-temperature water bath kettle, heating to 60 ℃, uniformly stirring for 10 hours, carrying out vacuum drying on the solution to remove a solvent, placing a solid mixture into an atmosphere furnace, heating at a rate of 10 ℃/min to 500 ℃, carrying out heat preservation treatment for 1 hour, heating to 720 ℃, carrying out heat preservation calcination for 1 hour, washing a solid product with distilled water and ethanol, fully drying, grinding into fine powder, and preparing to obtain the carbon-coated Co with the shell-core structure3O4Supercapacitor electrode material 2.
(3) Preparing a working electrode 2 of the super capacitor: coating carbon of core-shell structure with Co3O4The supercapacitor electrode material 2, the conductive agent acetylene black and the adhesive polyvinylidene fluoride are uniformly dispersed in an N-methyl pyrrolidone solvent, the solution is uniformly coated on a nickel sheet and is fully dried, and the supercapacitor working electrode 2 is prepared.
Example 3
(1) Preparing a phosphoric acid-doped polyaniline hydrogel component 3: adding distilled water, 33.5 parts of aniline, 5 parts of 1, 3-phenylenediamine and 13 parts of phytic acid into a reaction bottle, uniformly stirring, adding 20.5 parts of initiator potassium persulfate, placing the reaction bottle into a cryostat, wherein the cryostat comprises a cryo-instrument, a thermal insulation layer is arranged in the cryo-instrument, a clamping groove is arranged above the thermal insulation layer, the clamping groove is movably connected with a protective cover, a slide rail is fixedly connected with the inner wall of the thermal insulation layer, a roller is movably connected on the slide rail, the roller is movably connected with a movable rod, one end of the movable rod is movably connected with an adjuster, the adjuster is fixedly connected with a fixed clamp, a stirring device is fixedly connected below the interior of the cryo-instrument, the upper part of the stirring device is movably connected with a stirring fan, a base is fixedly connected below the interior of the cryo-instrument, a rotating device is arranged in the base, a rotating shaft is movably connected above the rotating device, stirring at a constant speed at 15 ℃ for reaction for 12h, carrying out vacuum drying on the solution to remove the solvent, washing the solid product by using distilled water and diethyl ether, and fully drying to prepare the phosphoric acid-doped polyaniline hydrogel component 3.
(2) Preparation of carbon-coated Co of core-shell structure3O4Supercapacitor electrode material 3: adding distilled water, a phosphoric acid-doped polyaniline hydrogel component 3 and 28 parts of Co (CH3COOH)2 into a reaction bottle, placing the reaction bottle into a constant-temperature water bath kettle, heating to 70 ℃, uniformly stirring for 8 hours, carrying out vacuum drying on the solution to remove the solvent, placing the solid mixture into an atmosphere furnace, heating at a rate of 8 ℃/min to 470 ℃, carrying out heat preservation treatment for 1.5 hours, heating to 740 ℃, carrying out heat preservation calcination for 1.5 hours, washing the solid product with distilled water and ethanol, fully drying, grinding into fine powder, and preparing to obtain the carbon-coated Co with the shell-core structure3O4 Supercapacitor electrode material 3.
(3) Preparing a working electrode 3 of the super capacitor: coating carbon of core-shell structure with Co3O4The electrode material 3 of the super capacitor, acetylene black as a conductive agent and polyvinylidene fluoride as a bonding agent are uniformly dispersed in an N-methyl pyrrolidone solvent, and the solution is uniformly coated on a nickel sheet and fully dried to prepare the working electrode 3 of the super capacitor.
Example 4
(1) Preparing a phosphoric acid-doped polyaniline hydrogel component 4: adding distilled water, 35 parts of aniline, 6 parts of 1, 3-phenylenediamine and 14 parts of phytic acid into a reaction bottle, uniformly stirring, adding 22 parts of initiator potassium persulfate, placing the reaction bottle into a cryostat, wherein the cryostat comprises a cryo-instrument, a thermal insulation layer is arranged in the cryo-instrument, a clamping groove is arranged above the thermal insulation layer, the clamping groove is movably connected with a protective cover, the inner wall of the thermal insulation layer is fixedly connected with a sliding rail, a roller is movably connected on the sliding rail, the roller is movably connected with a moving rod, one end of the moving rod is movably connected with an adjuster, the adjuster is fixedly connected with a fixed clamp, a stirring device is fixedly connected below the interior of the cryo-instrument, the upper part of the stirring device is movably connected with a stirring fan, a base is fixedly connected below the interior of the cryo-instrument, a rotating device is arranged in the base, a rotating shaft is movably connected above the rotating device, stirring at a constant speed at 20 ℃ for reaction for 15h, carrying out vacuum drying on the solution to remove the solvent, washing the solid product by using distilled water and diethyl ether, and fully drying to prepare the phosphoric acid-doped polyaniline hydrogel component 4.
(2) Preparation of carbon-coated Co of core-shell structure3O4Supercapacitor electrode material 4: adding distilled water, a phosphoric acid-doped polyaniline hydrogel component 4 and 23 parts of Co (CH3COOH)2 into a reaction bottle, placing the reaction bottle into a constant-temperature water bath kettle, heating to 80 ℃, uniformly stirring for 10 hours, vacuum-drying the solution to remove the solvent, placing the solid mixture into an atmosphere furnace, heating at a rate of 10 ℃/min, heating to 500 ℃, carrying out heat preservation treatment for 2 hours, heating to 760 ℃, carrying out heat preservation calcination for 2 hours, washing the solid product with distilled water and ethanol, fully drying, grinding into fine powder, and preparing to obtain the carbon-coated Co with the shell-core structure3O4 Supercapacitor electrode material 4.
(3) Preparing a working electrode 4 of the super capacitor: coating carbon of core-shell structure with Co3O4The supercapacitor electrode material 4, the conductive agent acetylene black and the adhesive polyvinylidene fluoride are uniformly dispersed in an N-methyl pyrrolidone solvent, the solution is uniformly coated on a nickel sheet and is fully dried, and the supercapacitor working electrode 4 is prepared.
Comparative example 1
(1) Preparation of phosphoric acid-doped polyaniline hydrogel comparative component 1: adding distilled water, 29 parts of aniline, 3 parts of 1, 3-phenylenediamine and 9 parts of phytic acid into a reaction bottle, uniformly stirring, adding 16 parts of initiator potassium persulfate, placing the reaction bottle into a cryostat, wherein the cryostat comprises a cryo-instrument, a thermal insulation layer is arranged in the cryo-instrument, a clamping groove is arranged above the thermal insulation layer and movably connected with a protective cover, a sliding rail is fixedly connected with the inner wall of the thermal insulation layer, a roller is movably connected on the sliding rail and movably connected with a moving rod, one end of the moving rod is movably connected with an adjuster, the adjuster is fixedly connected with a fixed clamp, a stirring device is fixedly connected below the interior of the cryo-instrument, the upper part of the stirring device is movably connected with a stirring fan, a base is fixedly connected below the interior of the cryo-instrument, a rotating device is arranged in the base, a rotating shaft is movably connected above the rotating device, and a magnet fan is fixedly, and (3) uniformly stirring and reacting for 10 hours at 20 ℃, carrying out vacuum drying on the solution to remove the solvent, washing the solid product by using distilled water and diethyl ether, and fully drying to prepare the phosphoric acid-doped polyaniline hydrogel comparison component 1.
(2) Preparation of carbon-coated Co of core-shell structure3O4Comparative supercapacitor electrode material 1: adding distilled water and phosphoric acid doped polyaniline hydrogel into a reaction bottle to compare the component 1 with 43 parts of Co (CH3COOH)2, placing the reaction bottle into a constant-temperature water bath, heating to 80 ℃, uniformly stirring for 10 hours, vacuum-drying the solution to remove the solvent, placing the solid mixture into an atmosphere furnace, heating at the rate of 2 ℃/min, heating to 430 ℃, carrying out heat preservation treatment for 2 hours, heating to 700 ℃, carrying out heat preservation calcination for 1 hour, washing the solid product with distilled water and ethanol, fully drying, grinding into fine powder, and preparing to obtain the carbon-coated Co with the shell-core structure3O4Supercapacitor comparative electrode material 1.
(3) Preparation of comparative working electrode 1 of supercapacitor: coating carbon of core-shell structure with Co3O4Uniformly dispersing the comparative electrode material 1 of the super capacitor, acetylene black serving as a conductive agent and polyvinylidene fluoride serving as a bonding agent in an N-methyl pyrrolidone solvent, uniformly coating the solution on a nickel sheet, and fully drying to prepare the comparative working electrode 1 of the super capacitor.
Comparative example 2
(1) Preparing a phosphoric acid-doped polyaniline hydrogel comparison component 2: adding distilled water, 36 parts of aniline, 5 parts of 1, 3-phenylenediamine and 15 parts of phytic acid into a reaction bottle, uniformly stirring, adding 23 parts of initiator potassium persulfate, placing the reaction bottle into a cryostat, wherein the cryostat comprises a cryo-instrument, a thermal insulation layer is arranged in the cryo-instrument, a clamping groove is arranged above the thermal insulation layer, the clamping groove is movably connected with a protective cover, the inner wall of the thermal insulation layer is fixedly connected with a sliding rail, a roller is movably connected on the sliding rail, the roller is movably connected with a moving rod, one end of the moving rod is movably connected with an adjuster, the adjuster is fixedly connected with a fixed clamp, a stirring device is fixedly connected below the interior of the cryo-instrument, the upper part of the stirring device is movably connected with a stirring fan, a base is fixedly connected below the interior of the cryo-instrument, a rotating device is arranged in the base, a rotating shaft is movably connected above the rotating device, and (3) uniformly stirring and reacting for 10-h at 20 ℃, carrying out vacuum drying on the solution to remove the solvent, washing the solid product by using distilled water and diethyl ether, and fully drying to prepare the phosphoric acid-doped polyaniline hydrogel comparison component 2.
(2) Preparation of carbon-coated Co of core-shell structure3O4Comparative supercapacitor electrode material 2: adding distilled water and phosphoric acid doped polyaniline hydrogel contrast component 2 and 19 parts of Co (CH3COOH)2 into a reaction bottle, placing the reaction bottle in a constant-temperature water bath kettle, heating to 85 ℃, uniformly stirring for 12 hours, vacuum-drying the solution to remove the solvent, placing the solid mixture in an atmosphere furnace, heating at the rate of 15 ℃/min to 520 ℃, carrying out heat preservation treatment for 2 hours, heating to 780 ℃, carrying out heat preservation calcination for 2 hours, washing the solid product with distilled water and ethanol, fully drying, grinding into fine powder, and preparing to obtain the carbon-coated Co with the shell-core structure3O4Supercapacitor comparative electrode material 2.
(3) Preparation of comparative working electrode 2 of supercapacitor: coating carbon of core-shell structure with Co3O4Uniformly dispersing the comparative electrode material 2 of the super capacitor, acetylene black serving as a conductive agent and polyvinylidene fluoride serving as a bonding agent in an N-methyl pyrrolidone solvent, uniformly coating the solution on a nickel sheet, and fully drying to prepare the comparative working electrode 2 of the super capacitor.
A platinum sheet is used as an auxiliary electrode, an Hg/HgO electrode is used as a reference electrode, 6 mol/L potassium hydroxide solution is used as electrolyte, electrochemical performances of a working electrode 1-4 of a super capacitor and a comparative working electrode 1-2 of the super capacitor are tested in a CHI660E electrochemical workstation, and the test standard is GB/T34870.1-2017.
Figure BDA0002465762330000101
In summary, the shell-core structureCarbon coated Co3O4The phytic acid is used as a gelling agent, aniline and 1, 3-phenylenediamine are used as monomers to prepare the phytic acid-doped polyaniline copolymer hydrogel, the polyaniline copolymer hydrogel has a three-dimensional network structure and high porosity, and the polyaniline copolymer hydrogel is mixed with Co (CH)3COOH)2Complexing, phosphate groups in phytic acid with Co2+Has strong complexation effect and can be used for complexing Co (CH)3COOH)2The polyaniline copolymer hydrogel is uniformly adsorbed into the polyaniline copolymer hydrogel and is uniformly distributed.
The phytic acid doped polyaniline copolymer hydrogel contains rich nitrogen and phosphorus elements, the aniline copolymer three-dimensional network hydrogel with high porosity is carbonized into an N and P co-doped porous carbon material through high-temperature carbonization and thermal cracking, the carbon material has rich mesopore and pore structures and large specific surface area, the wettability of the carbon material can be enhanced through phosphorus doping, electrolyte is fully soaked into the pore structures of the carbon material and fully contacts with electrochemical active sites, and the nitrogen doping is favorable for enhancing the conductivity and the capacitance of the carbon material.
Phytic acid reacting Co (CH)3COOH)2Uniformly adsorbed into the three-dimensional network of polyaniline copolymer hydrogel, Co (CH)3COOH)2Pyrolysis at high temperature to form CoC2O4Further decomposed into Co3O4By regulating and controlling Co (CH)3COOH)2And polyaniline copolymer to control Co3O4The porous carbon material is uniformly dispersed in the porous carbon material in an optimal ratio to avoid Co3O4Agglomerate and pack, thereby making Co3O4More electrochemical active sites are exposed and fully contacted with the electrolyte, the actual specific capacitance of the electrode material is improved, and the rich pore structure of the porous carbon material is Co3O4Providing growth sites, forming a core-shell structure, the coating of the carbon layer suppressing Co3O4The volume expansion in the pseudo-capacitance reaction process effectively improves the electrochemical circulation stability of the electrode material.

Claims (4)

1. Carbon-coated Co with shell-core structure3O4The supercapacitor electrode material comprises the following formula raw materials and components in parts by weight, and is characterized in that: 30-35 parts of aniline, 4-6 parts of 1, 3-phenylenediamine, 18-22 parts of initiator, 10-14 parts of phytic acid and 23-38 parts of Co (CH)3COOH)2
2. The shell-core structure carbon-coated Co as claimed in claim 13O4The electrode material of the super capacitor is characterized in that: the initiator is potassium persulfate.
3. The shell-core structure carbon-coated Co as claimed in claim 13O4The electrode material of the super capacitor is characterized in that: carbon-coated Co of the core-shell structure3O4The preparation method of the electrode material of the super capacitor comprises the following steps:
(1) adding distilled water, 30-35 parts of aniline, 4-6 parts of 1, 3-phenylenediamine and 10-14 parts of phytic acid into a reaction bottle, uniformly stirring, adding 18-22 parts of initiator potassium persulfate, placing the reaction bottle into a low-temperature thermostat, uniformly stirring and reacting for 10-15 hours at a constant speed at 10-20 ℃, vacuum-drying the solution to remove the solvent, washing the solid product by using distilled water and ether, and fully drying to prepare the phosphoric acid doped polyaniline hydrogel;
(2) adding distilled water, phosphoric acid doped polyaniline hydrogel and 23-38 parts of Co (CH) into a reaction bottle3COOH)2Placing a reaction bottle in a constant-temperature water bath kettle, heating to 60-80 ℃, uniformly stirring for 6-10h, vacuum drying the solution to remove the solvent, placing the solid mixture in an atmosphere furnace, heating to 450 ℃, (heating to 500 ℃) at the heating rate of 5-10 ℃/min, carrying out heat preservation treatment for 1-2h, heating to 720-3O4And (3) a supercapacitor electrode material.
4. The carbon-coated Co with shell-core structure of claim 33O4The electrode material of the super capacitor is characterized in that:the cryostat includes the cryoscope, the inside insulating layer that is provided with of cryoscope, the insulating layer top is provided with the draw-in groove, draw-in groove and safety cover swing joint, the inner wall fixedly connected with slide rail of insulating layer, swing joint has the gyro wheel on the slide rail, gyro wheel and carriage release lever swing joint, the one end swing joint of carriage release lever has the regulator, the regulator is connected with the stationary phase is fixed, the inside below fixedly connected with agitating unit of cryoscope, agitating unit's top and stirring fan piece swing joint, the inside below fixedly connected with base of cryoscope, the inside of base is provided with rotary device, rotary device's top swing joint has the rotation axis, the fixed surface of rotation axis is connected with the magnet fan piece.
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