CN111554516A - ZnCo2O4-graphene hollow microsphere supercapacitor electrode material and preparation method thereof - Google Patents
ZnCo2O4-graphene hollow microsphere supercapacitor electrode material and preparation method thereof Download PDFInfo
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- 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
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- 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
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- 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
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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Abstract
The invention relates to the technical field of super capacitors and discloses ZnCo2O4The graphene hollow microsphere supercapacitor electrode material comprises the following formula raw materials and components: CoCl2、ZnCl2、NiCl2Reducing agent, NH4F. Urea in the mass ratio of 0.08-0.15:1.8-2:1:0.03-0.05:1.4-1.8:0.3-0.5: 2-3. The ZnCo2O4The porous nanometer Ni-doped ZnCo electrode material is prepared by taking hollow spherical graphene with huge surface area as a growth site2O4Uniformly loaded on the surface of graphene microspheresIs beneficial to doping ZnCo into nano Ni2O4Ni is doped in ZnCo2O4Form lattice defect to generate great amount of pore structure and increase ZnCo2O4The specific surface area and the abundant pore structure promote the wettability of the electrode material and the electrolyte, a large number of electrochemical active sites are exposed, and the graphene microspheres and the nano Ni are doped with ZnCo2O4A three-dimensional conductive network is formed between the two electrodes, so that the conductivity of the electrode material is enhanced, and the electrode material has excellent actual specific capacitance and good electrochemical cycle stability.
Description
Technical Field
The invention relates to the technical field of super capacitors, in particular to ZnCo2O4-graphene hollow microsphere supercapacitor electrode materials and a preparation method thereof.
Background
A super capacitor is called electrochemical capacitor and electric double-layer capacitor, it is a new energy storage device, it has advantages of high specific power, long cycle life and wide working temperature range, it has wide application prospect in mobile communication, electric automobile, aerospace and national defense science, the super capacitor includes electrode material, diaphragm and electrolyte, the electrode material and diaphragm are all set in the electrolyte solution, the electrode includes current collector and electrode material set on the current collector, usually, after fully grinding the electrode material, adding binder and conductive agent, then pressing on the current collector such as foam nickel, graphite flake or copper flake by pressing method such as compression molding method, cold isostatic pressing method, hot isostatic pressing method, etc. to make the working electrode material.
The current electrode materials of the super capacitor mainly comprise carbon material electrode materials, such as carbon nanofibers, graphene and carbon nanotubes; conductive polymer electrode materials such as polyaniline, polypyrrole, and the like; metal oxide and hydrate materials, e.g. RuO2、MnO2And SnO2Etc., wherein the multi-component metal oxide is ZnCo2O4Has the advantages of excellent physical and chemical properties, high theoretical specific volume, environmental protection and the like, and ZnCo with different morphologies2O4Such as nano-sheet, nano-wire, micro-sphere, etc., has larger specific surface area and better permeability, and can obviously improve ZnCo2O4Electrochemical performance of (2), however, ZnCo2O4The conductivity of the electrode material is low, so that the conductivity of the electrode material is poor, and the common ZnCo2O4Has a small specific surface area and insufficient exposure of electrochemically active sites, resulting in a low actual specific capacitance of the electrode material.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides ZnCo2O4An electrode material of a supercapacitor made of graphene hollow microspheres and a preparation method thereof, solving the problem of ZnCo2O4The poor conductivity of the electrode material solves the problem of ZnCo2O4The specific surface area of (2) is small.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: ZnCo2O4The graphene hollow microsphere supercapacitor electrode material comprises the following formula raw materials and components: graphene hollow microspheres, CoCl2、ZnCl2、NiCl2Reducing agent, NH4F. Urea in the mass ratio of 0.08-0.15:1.8-2:1:0.03-0.05:1.4-1.8:0.3-0.5: 2-3.
Preferably, the reducing agent is ascorbic acid.
Preferably, the preparation of the graphene hollow microsphere comprises the following steps:
(1) adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 2-4:1, and adding nano SiO2Placing the mixture in a constant-temperature ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 1-3h, adding ammonia water to adjust the pH value of the solution to 8-9, adding resorcinol and formaldehyde aqueous solution and cetyl trimethyl ammonium bromide, continuing the ultrasonic dispersion treatment for 20-40min, heating to 15-35 ℃, stirring at constant speed for reaction for 5-10h, filtering the solution to remove the solvent, washing the solid product with distilled water, fully drying, placing the solid product in an atmosphere furnace, heating to 140 ℃ for 180 ℃, performing heat preservation treatment for 30-90min, heating to 550 ℃ for 600 ℃, performing heat preservation and calcination for 1-2h, continuing heating to 820 ℃ for 850 ℃, performing heat preservation and calcination for 1-2h, and preparing the graphene-coated nano SiO2。
(2) Coating nano SiO with graphene2Placing the graphene hollow microspheres in a hydrofluoric acid solution with the mass fraction of 8-15%, placing the solution in a constant-temperature ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 1-2 hours, then stirring at a constant speed for reaction for 10-15 hours, filtering the solution to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the graphene hollow microspheres.
Preferably, the constant temperature ultrasonic treatment instrument includes instrument main part, the inside top fixedly connected with supersound appearance of instrument main part, supersound appearance below fixedly connected with ultrasonic probe, the below fixedly connected with base of instrument main part, the base top is provided with the water bath, the outer and heat preservation fixed connection of water bath, fixedly connected with fixed block on the inside of water bath, the inside draw-in groove that is provided with of fixed block, draw-in groove and fixture block swing joint, fixture block fixedly connected with bracing piece, bracing piece and objective table fixed connection, the objective table top is provided with the reaction bottle.
Preferably, the nano SiO2Has an average particle diameter of 10 to 20nm and a mass ratio of resorcinol, formaldehyde and cetyltrimethylammonium bromide of 1:0.2 to 0.6:0.1 to 0.25:1.5 to 4.
Preferably, the ZnCo2O4The preparation method of the graphene hollow microsphere supercapacitor electrode material comprises the following steps:
(1) adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 1-2:1, placing the hollow graphene microspheres into a constant-temperature ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 1-2h, and adding CoCl2、ZnCl2、NiCl2Reducing agent, NH4F and urea are uniformly stirred at a constant speed, the solution is transferred into a polytetrafluoroethylene reaction kettle and is placed in an oven to be heated to 140-180 ℃, the reaction lasts for 4-8h, the solution is filtered to remove the solvent, distilled water and ethanol are used for washing the solid product, the solid product is fully dried, the solid product is placed in an atmosphere furnace, the heating rate is 1-5 ℃/min, the temperature is raised to 420-480 ℃, the heat preservation treatment lasts for 2-4h, and the prepared porous Ni-doped ZnCo is doped2O4Loading graphene hollow microspheres, namely ZnCo2O4-graphene hollow microsphere supercapacitor electrode materials.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the ZnCo2O4-graphene hollow microsphere supercapacitor electrode material with nano SiO2Preparing the graphene-coated nano SiO by an in-situ polymerization method and a high-temperature thermal cracking method as a template2Then obtaining hollow spherical graphene with huge specific surface area by hydrofluoric acid etching, taking the hollow spherical graphene as a growth site, and generating porous nano Ni-doped ZnCo on the hollow micro-surface of the graphene by a hot solvent method2O4The nano Ni is uniformly loaded on the surface of the graphene microsphere, thereby being beneficial to doping ZnCo into nano Ni2O4Dispersion, reduction ofAgglomeration phenomenon, Ni doping in ZnCo2O4Form lattice defect to generate great amount of pore structure in crystal and increase ZnCo2O4The specific surface area of the graphene microsphere and the nano Ni-doped ZnCo are large, and the rich pore structure promotes the wettability of the electrode material and the electrolyte, so that a large number of electrochemical active sites can be exposed, and the graphene microsphere and the nano Ni-doped ZnCo2O4A three-dimensional conductive network is formed between the two layers, so that the conductivity of the electrode material is enhanced, and the ZnCo is enhanced under the synergistic action2O4The conductivity and actual specific capacitance of the electrode material.
Drawings
FIG. 1 is a schematic front view of an instrument body;
FIG. 2 is an enlarged schematic view of the stage;
fig. 3 is a schematic view of stage adjustment.
1. An instrument body; 2. an ultrasonic instrument; 3. an ultrasonic probe; 4. a base; 5. a water bath kettle; 6. a heat-insulating layer; 7. a fixed block; 8. a card slot; 9. a clamping block; 10. a support bar; 11. objective table, 12, reaction bottle.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: ZnCo2O4The graphene hollow microsphere supercapacitor electrode material comprises the following formula raw materials and components: graphene hollow microspheres, CoCl2、ZnCl2、NiCl2Reducing agents ascorbic acid, NH4F. Urea in the weight ratio of 0.08-0.15 to 1.8-2 to 1 to 0.03-0.05 to 1.4-1.8 to 0.3-0.5 to 2-3
The preparation method of the graphene hollow microspheres comprises the following steps:
(1) adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 2-4:1, and adding nano SiO with the average particle size of 10-20nm2Arranged in a constant temperature ultrasonic treatment instrument, the constant temperature ultrasonic treatment instrument comprises an instrument main body, an ultrasonic instrument fixedly connected with the upper part inside the instrument main body, an ultrasonic probe fixedly connected with the lower part of the ultrasonic instrument, a base fixedly connected with the lower part of the instrument main body, a water bath arranged above the base, a water bath outer layer and a water bath water tank arranged above the baseFixedly connected with the heat preservation layer, fixedly connected with the fixed block on the inside of the water bath kettle, the fixed block is internally provided with a clamping groove, the clamping groove is movably connected with the clamping block, the clamping block is fixedly connected with a supporting rod, the supporting rod is fixedly connected with an objective table, a reaction bottle is arranged above the objective table, ultrasonic dispersion treatment is carried out for 1-3h, then ammonia water is added to adjust the pH value of the solution to 8-9, resorcinol, formaldehyde water solution and hexadecyl trimethyl ammonium bromide are added, wherein nano SiO is2The mass ratio of the resorcinol to the formaldehyde to the hexadecyl trimethyl ammonium bromide is 1:0.2-0.6:0.1-0.25:1.5-4, the ultrasonic dispersion treatment is continued for 20-40min, the mixture is heated to 15-35 ℃, the mixture is stirred at a constant speed for reaction for 5-10h, the solution is filtered to remove the solvent, the solid product is washed by distilled water and is fully dried, the solid product is placed in an atmosphere furnace, the heating rate is 2-8 ℃/min, the temperature is increased to 140 ℃ and 180 ℃, the heat preservation treatment is carried out for 30-90min, the temperature is increased to 550 ℃ and 600 ℃, the heat preservation calcination is carried out for 1-2h, the temperature is continuously increased to 820 ℃ and 850 ℃, the heat preservation calcination is carried out for 1-2h, and the graphene-2。
(2) Coating nano SiO with graphene2Placing the graphene hollow microspheres in a hydrofluoric acid solution with the mass fraction of 8-15%, placing the solution in a constant-temperature ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 1-2 hours, then stirring at a constant speed for reaction for 10-15 hours, filtering the solution to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the graphene hollow microspheres.
ZnCo2O4The preparation method of the graphene hollow microsphere supercapacitor electrode material comprises the following steps:
(1) adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 1-2:1, placing the hollow graphene microspheres into a constant-temperature ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 1-2h, and adding CoCl2、ZnCl2、NiCl2Reducing agent, NH4F and urea are uniformly stirred at a constant speed, the solution is transferred into a polytetrafluoroethylene reaction kettle and is placed in an oven to be heated to 140-180 ℃, the reaction lasts for 4-8h, the solution is filtered to remove the solvent, distilled water and ethanol are used for washing the solid product, the solid product is fully dried, the solid product is placed in an atmosphere furnace, the heating rate is 1-5 ℃/min, the temperature is raised to 420-480 ℃, the heat preservation treatment lasts for 2-4h, and the prepared solid product isPorous Ni-doped ZnCo2O4Loading graphene hollow microspheres, namely ZnCo2O4-graphene hollow microsphere supercapacitor electrode materials.
ZnCo addition to N-methylpyrrolidone solvent2O4And uniformly dispersing the graphene hollow microsphere supercapacitor electrode material, the conductive agent carbon black and the adhesive polyvinylidene fluoride, uniformly coating the slurry on the surface of the copper foil, and fully drying to prepare the supercapacitor working electrode material.
Example 1
(1) Preparation of graphene-coated nano SiO2Component 1: adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 2:1, and adding nano SiO with the average particle size of 10nm2In the constant temperature ultrasonic processor, the constant temperature ultrasonic processor includes the instrument main part, the inside top fixedly connected with ultrasonic appearance of instrument main part, ultrasonic appearance below fixedly connected with ultrasonic probe, the below fixedly connected with base of instrument main part, the base top is provided with the water bath, water bath outer and heat preservation fixed connection, fixedly connected with fixed block on the inside of water bath, the inside draw-in groove that is provided with of fixed block, draw-in groove and fixture block swing joint, fixture block fixedly connected with bracing piece, bracing piece and objective table fixed connection, the objective table top is provided with the reaction bottle, ultrasonic dispersion handles 1h, add aqueous ammonia and adjust solution pH to 8, add resorcinol, the aqueous solution and the hexadecyl trimethyl ammonium bromide of formaldehyde, wherein nanometer SiO2Carrying out ultrasonic dispersion treatment for 20min continuously, heating to 15 ℃, stirring at a constant speed for 5h, filtering the solution to remove the solvent, washing the solid product with distilled water, fully drying, placing the solid product in an atmosphere furnace, heating to 140 ℃ at a heating rate of 2 ℃/min, carrying out heat preservation treatment for 30min, heating to 550 ℃, carrying out heat preservation calcination for 1h, continuing heating to 820 ℃, carrying out heat preservation calcination for 1h, and preparing the graphene-coated nano SiO2And (3) component 1.
(2) Preparing a graphene hollow microsphere component 1: coating nano SiO with graphene2Placing the component 1 in 8 percent of hydrofluoric acidAnd (3) placing the solution in a constant-temperature ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 1h, then stirring at a constant speed for reaction for 10h, filtering the solution to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to prepare the graphene hollow microsphere component 1.
(3) Preparation of ZnCo2O4Graphene hollow microsphere supercapacitor electrode material 1: adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the mixed solvent is 1:1, placing the graphene hollow microsphere component 1 into a constant-temperature ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 1 hour, and adding CoCl2、ZnCl2、NiCl2Reducing agent, NH4F and urea, wherein the mass ratio of seven substances is 0.08:1.8:1:0.03:1.4:0.3:2, the solution is transferred into a polytetrafluoroethylene reaction kettle after uniform stirring, the polytetrafluoroethylene reaction kettle is placed in an oven to be heated to 140 ℃, the reaction lasts for 4 hours, the solution is filtered to remove the solvent, distilled water and ethanol are used for washing a solid product, the solid product is fully dried, the solid product is placed in an atmosphere furnace, the heating rate is 1 ℃/min, the solid product is heated to 420 ℃, the heat preservation treatment lasts for 2 hours, and the prepared porous Ni-doped ZnCo is doped with Ni2O4Loading graphene hollow microspheres, namely ZnCo2O4Graphene hollow microsphere supercapacitor electrode material 1.
(4) Preparing a working electrode material 1 of the super capacitor: ZnCo addition to N-methylpyrrolidone solvent2O4The method comprises the steps of uniformly dispersing graphene hollow microsphere supercapacitor electrode material 1, conductive agent carbon black and adhesive polyvinylidene fluoride, uniformly coating slurry on the surface of copper foil, and fully drying to obtain the supercapacitor working electrode material 1.
Example 2
(1) Preparation of graphene-coated nano SiO2And (2) component: adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 2:1, and adding nano SiO with the average particle size of 20nm2The ultrasonic constant-temperature ultrasonic treatment instrument is arranged in the ultrasonic constant-temperature treatment instrument, and comprises an instrument main body, an ultrasonic instrument fixedly connected with the upper part inside the instrument main body, an ultrasonic probe fixedly connected with the lower part of the ultrasonic instrument, a base fixedly connected with the lower part of the instrument main body, a water bath kettle arranged above the base, a water tank arranged below the water bath kettle, a water tank arranged below,The outer fixed connection with the heat preservation of water bath, fixedly connected with fixed block on the inside of water bath, the inside draw-in groove that is provided with of fixed block, draw-in groove and fixture block swing joint, fixture block fixedly connected with bracing piece, bracing piece and objective table fixed connection, the objective table top is provided with the reaction bulb, ultrasonic dispersion handles 1h, add aqueous ammonia and adjust solution pH to 8 again, add the aqueous solution and the hexadecyl trimethyl ammonium bromide of resorcinol, formaldehyde, wherein nanometer SiO2Carrying out ultrasonic dispersion treatment for 40min continuously, heating to 15 ℃, uniformly stirring for reaction for 10h, filtering the solution to remove the solvent, washing the solid product with distilled water, fully drying, placing the solid product in an atmosphere furnace, heating to 140 ℃ at the rate of 2 ℃/min, carrying out heat preservation treatment for 90min, heating to 550 ℃, carrying out heat preservation calcination for 1h, continuously heating to 850 ℃, carrying out heat preservation calcination for 1h, and preparing the graphene-coated nano SiO2And (3) component 2.
(2) Preparing a graphene hollow microsphere component 2: coating nano SiO with graphene2And (3) placing the component 2 into a hydrofluoric acid solution with the mass fraction of 12%, placing the hydrofluoric acid solution into a constant-temperature ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 2 hours, then stirring at a constant speed for reaction for 15 hours, filtering the solution to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to prepare the graphene hollow microsphere component 2.
(3) Preparation of ZnCo2O4Graphene hollow microsphere supercapacitor electrode material 2: adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the mixed solvent is 1:1, placing a graphene hollow microsphere component 2 into a constant-temperature ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 2 hours, and adding CoCl2、ZnCl2、NiCl2Reducing agent, NH4F and urea, wherein the mass ratio of seven substances is 0.1:1.85:1:0.035:1.5:0.35:2.2, the solution is transferred into a polytetrafluoroethylene reaction kettle after uniform stirring, the polytetrafluoroethylene reaction kettle is placed in an oven to be heated to 140 ℃, the reaction lasts 8h, the solution is filtered to remove the solvent, the solid product is washed by distilled water and ethanol and is fully dried, the solid product is placed in an atmosphere furnace, the temperature rise rate is 5 ℃/min, the temperature rise is 480 ℃, the heat preservation treatment lasts 2h,prepared porous Ni-doped ZnCo2O4Loading graphene hollow microspheres, namely ZnCo2O4Graphene hollow microsphere supercapacitor electrode material 2.
(4) Preparing a working electrode material 2 of the super capacitor: ZnCo addition to N-methylpyrrolidone solvent2O4And uniformly dispersing the graphene hollow microsphere supercapacitor electrode material 2, the conductive agent carbon black and the adhesive polyvinylidene fluoride, uniformly coating the slurry on the surface of the copper foil, and fully drying to prepare the supercapacitor working electrode material 2.
Example 3
(1) Preparation of graphene-coated nano SiO2And (3) component: adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 3:1, and adding nano SiO with the average particle size of 20nm2In the constant temperature ultrasonic processor, the constant temperature ultrasonic processor includes the instrument main part, the inside top fixedly connected with ultrasonic appearance of instrument main part, ultrasonic appearance below fixedly connected with ultrasonic probe, the below fixedly connected with base of instrument main part, the base top is provided with the water bath, water bath outer and heat preservation fixed connection, fixedly connected with fixed block on the inside of water bath, the inside draw-in groove that is provided with of fixed block, draw-in groove and fixture block swing joint, fixture block fixedly connected with bracing piece, bracing piece and objective table fixed connection, the objective table top is provided with the reaction bottle, ultrasonic dispersion handles 2h, add aqueous ammonia and adjust solution pH to 9, add resorcinol, the aqueous solution and the hexadecyl trimethyl ammonium bromide of formaldehyde, wherein nanometer SiO2Continuously performing ultrasonic dispersion treatment for 30min, heating to 25 ℃, uniformly stirring for reaction for 8h, filtering the solution to remove the solvent, washing the solid product with distilled water, fully drying, placing the solid product in an atmosphere furnace, heating at the rate of 5 ℃/min to 160 ℃, performing heat preservation treatment for 60min, heating to 580 ℃, performing heat preservation calcination for 1.5h, continuously heating to 840 ℃, and performing heat preservation calcination for 1.5h to prepare the graphene-coated nano SiO by using the graphene-coated nano SiO2And (3) component.
(2) Preparing a graphene hollow microsphere component 3: mixing grapheneCoated nano SiO2And placing the component 3 in a hydrofluoric acid solution with the mass fraction of 10%, placing in a constant-temperature ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 1.5h, then stirring at a constant speed for reaction for 12h, filtering the solution to remove the solvent, washing the solid product with distilled water and ethanol, and sufficiently drying to prepare the graphene hollow microsphere component 3.
(3) Preparation of ZnCo2O4-graphene hollow microsphere supercapacitor electrode material 3: adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 1.5:1, placing the graphene hollow microsphere component 3 into a constant-temperature ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 1.5h, and adding CoCl2、ZnCl2、NiCl2Reducing agent, NH4F and urea, wherein the mass ratio of seven substances is 0.11:1.9:1:0.04:1.6:0.4:2.5, the solution is transferred into a polytetrafluoroethylene reaction kettle after uniform stirring, the polytetrafluoroethylene reaction kettle is placed in an oven to be heated to 160 ℃, the reaction lasts for 6 hours, the solution is filtered to remove the solvent, the solid product is washed by distilled water and ethanol and is fully dried, the solid product is placed in an atmosphere furnace, the heating rate is 2 ℃/min, the temperature is increased to 450 ℃, the heat preservation treatment lasts for 3 hours, and the prepared porous Ni-doped ZnCo is doped with Ni2O4Loading graphene hollow microspheres, namely ZnCo2O4-graphene hollow microsphere supercapacitor electrode material 3.
(4) Preparing a working electrode material 3 of the super capacitor: ZnCo addition to N-methylpyrrolidone solvent2O4And uniformly dispersing the graphene hollow microsphere supercapacitor electrode material 3, the conductive agent carbon black and the adhesive polyvinylidene fluoride, uniformly coating the slurry on the surface of the copper foil, and fully drying to prepare the supercapacitor working electrode material 3.
Example 4
(1) Preparation of graphene-coated nano SiO2And (4) component: adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 4:1, and adding nano SiO with the average particle size of 10nm2The ultrasonic constant-temperature ultrasonic treatment instrument is arranged in the ultrasonic constant-temperature treatment instrument, and the ultrasonic constant-temperature ultrasonic treatment instrument comprises an instrument main body, an ultrasonic instrument fixedly connected to the upper part in the instrument main body, an ultrasonic probe fixedly connected to the lower part of the ultrasonic instrument,Below fixedly connected with base of instrument main part, the base top is provided with the water bath, water bath is outer and heat preservation fixed connection, fixedly connected with fixed block on the inside of water bath, the inside draw-in groove that is provided with of fixed block, draw-in groove and fixture block swing joint, fixture block fixedly connected with bracing piece, bracing piece and objective table fixed connection, the objective table top is provided with the reaction flask, ultrasonic dispersion handles 2h, add aqueous ammonia and adjust solution pH to 8 again, add resorcinol, the aqueous solution and the hexadecyl trimethyl ammonium bromide of formaldehyde, wherein nanometer SiO2Carrying out ultrasonic dispersion treatment for 30min, heating to 35 ℃, uniformly stirring for reaction for 8h, filtering the solution to remove the solvent, washing the solid product with distilled water, fully drying, placing the solid product in an atmosphere furnace, heating to 150 ℃ at the heating rate of 8 ℃/min, carrying out heat preservation treatment for 60min, heating to 600 ℃, carrying out heat preservation calcination for 2h, continuously heating to 830 ℃, carrying out heat preservation calcination for 2h, and preparing the graphene-coated nano SiO2And (4) component.
(2) Preparing a graphene hollow microsphere component 4: coating nano SiO with graphene2And (3) placing the component 4 into a hydrofluoric acid solution with the mass fraction of 15%, placing the hydrofluoric acid solution into a constant-temperature ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 2 hours, then stirring at a constant speed for reaction for 15 hours, filtering the solution to remove the solvent, washing the solid product by using distilled water and ethanol, and sufficiently drying to prepare the graphene hollow microsphere component 4.
(3) Preparation of ZnCo2O4-graphene hollow microsphere supercapacitor electrode material 4: adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 2:1, placing a graphene hollow microsphere component 4 into a constant-temperature ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 1.5h, and adding CoCl2、ZnCl2、NiCl2Reducing agent, NH4F and urea, wherein the mass ratio of seven substances is 0.14:1.95:1:0.035:1.7:0.35:2.7, the solution is transferred into a polytetrafluoroethylene reaction kettle after uniform stirring, the polytetrafluoroethylene reaction kettle is placed in an oven to be heated to 180 ℃, the reaction is carried out for 6 hours, the solution is filtered to remove the solvent, the solid product is washed by distilled water and ethanol and is fully dried, and the solid product is placed in a placeHeating to 480 ℃ in an atmosphere furnace at the heating rate of 2 ℃/min, and carrying out heat preservation treatment for 2h to obtain the porous Ni-doped ZnCo2O4Loading graphene hollow microspheres, namely ZnCo2O4-graphene hollow microsphere supercapacitor electrode material 4.
(4) Preparing a working electrode material 4 of the super capacitor: ZnCo addition to N-methylpyrrolidone solvent2O4And uniformly dispersing the graphene hollow microsphere supercapacitor electrode material 4, the conductive agent carbon black and the adhesive polyvinylidene fluoride, uniformly coating the slurry on the surface of the copper foil, and fully drying to prepare the supercapacitor working electrode material 4.
Example 5
(1) Preparation of graphene-coated nano SiO2And (5) component: adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 4:1, and adding nano SiO with the average particle size of 20nm2In the constant temperature ultrasonic processor, the constant temperature ultrasonic processor includes the instrument main part, the inside top fixedly connected with ultrasonic appearance of instrument main part, ultrasonic appearance below fixedly connected with ultrasonic probe, the below fixedly connected with base of instrument main part, the base top is provided with the water bath, water bath outer and heat preservation fixed connection, fixedly connected with fixed block on the inside of water bath, the inside draw-in groove that is provided with of fixed block, draw-in groove and fixture block swing joint, fixture block fixedly connected with bracing piece, bracing piece and objective table fixed connection, the objective table top is provided with the reaction bottle, ultrasonic dispersion handles 3h, add aqueous ammonia and adjust solution pH to 9, add resorcinol, the aqueous solution and the hexadecyl trimethyl ammonium bromide of formaldehyde, wherein nanometer SiO2Continuously performing ultrasonic dispersion treatment for 40min, heating to 35 ℃, uniformly stirring for reaction for 10h, filtering the solution to remove the solvent, washing the solid product with distilled water, fully drying, placing the solid product in an atmosphere furnace, heating at the rate of 8 ℃/min to 180 ℃, performing heat preservation treatment for 90min, heating to 600 ℃, performing heat preservation calcination for 2h, continuously heating to 850 ℃, performing heat preservation calcination for 2h, and preparing the graphene-coated nano SiO by using the solution to obtain the graphene-coated nano SiO2And (5) component.
(2) Preparing a graphene hollow microsphere component 5: coating nano SiO with graphene2And (3) placing the component 5 into a hydrofluoric acid solution with the mass fraction of 15%, placing the hydrofluoric acid solution into a constant-temperature ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 2 hours, then stirring at a constant speed for reaction for 15 hours, filtering the solution to remove the solvent, washing the solid product by using distilled water and ethanol, and sufficiently drying to prepare the graphene hollow microsphere component 5.
(3) Preparation of ZnCo2O4-graphene hollow microsphere supercapacitor electrode material 5: adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 2:1, placing the graphene hollow microsphere component 5 into a constant-temperature ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 2 hours, and adding CoCl2、ZnCl2、NiCl2Reducing agent, NH4F and urea, wherein the mass ratio of seven substances is 0.15:2:1:0.05:1.8:0.5:3, the solution is transferred into a polytetrafluoroethylene reaction kettle after uniform stirring, the polytetrafluoroethylene reaction kettle is placed in a drying oven to be heated to 180 ℃, the reaction lasts 8 hours, the solution is filtered to remove the solvent, the solid product is washed by distilled water and ethanol and is fully dried, the solid product is placed in an atmosphere furnace, the heating rate is 5 ℃/min, the temperature is increased to 480 ℃, the heat preservation treatment lasts 4 hours, and the prepared porous Ni-doped ZnCo is prepared2O4Loading graphene hollow microspheres, namely ZnCo2O4-graphene hollow microsphere supercapacitor electrode material 5.
(4) Preparing a working electrode material 5 of the super capacitor: ZnCo addition to N-methylpyrrolidone solvent2O4And uniformly dispersing the graphene hollow microsphere supercapacitor electrode material 5, the conductive agent carbon black and the adhesive polyvinylidene fluoride, uniformly coating the slurry on the surface of the foamed nickel, and fully drying to prepare the supercapacitor working electrode material 5.
A working electrode material of a super capacitor is used as a working electrode, a saturated calomel electrode is used as a reference electrode, a platinum sheet electrode is used as a counter electrode, 1mol/L potassium hydroxide solution is used as electrolyte, and a 1470E electrochemical workstation is used for carrying out electrochemical performance test by a cyclic voltammetry method and a constant current charge-discharge method through a three-electrode system.
In summary, the ZnCo2O4-graphene hollow microsphere supercapacitor electrode material with nano SiO2Preparing the graphene-coated nano SiO by an in-situ polymerization method and a high-temperature thermal cracking method as a template2Then obtaining hollow spherical graphene with huge specific surface area by hydrofluoric acid etching, taking the hollow spherical graphene as a growth site, and generating porous nano Ni-doped ZnCo on the hollow micro-surface of the graphene by a hot solvent method2O4The nano Ni is uniformly loaded on the surface of the graphene microsphere, thereby being beneficial to doping ZnCo into nano Ni2O4Dispersing, reducing agglomeration, doping Ni in ZnCo2O4Form lattice defect to generate great amount of pore structure in crystal and increase ZnCo2O4The specific surface area of the graphene microsphere and the nano Ni-doped ZnCo are large, and the rich pore structure promotes the wettability of the electrode material and the electrolyte, so that a large number of electrochemical active sites can be exposed, and the graphene microsphere and the nano Ni-doped ZnCo2O4A three-dimensional conductive network is formed between the two layers, so that the conductivity of the electrode material is enhanced, and the ZnCo is enhanced under the synergistic action2O4The conductivity, actual specific capacitance and current density of the electrode material are 10mA/cm2When the specific capacitance reaches 1775.4-1826.4F/g, the capacitance retention rate of the electrode material after 1000 cycles can reach 89.0-90.1%, and the electrode material shows excellent actual specific capacitance and good electrochemical cycle stability.
Claims (6)
1. ZnCo2O4The graphene hollow microsphere supercapacitor electrode material comprises the following formula raw materials and components, and is characterized in that: graphene hollow microspheres, CoCl2、ZnCl2、NiCl2Reducing agent, NH4F. Urea in the mass ratio of 0.08-0.15:1.8-2:1:0.03-0.05:1.4-1.8:0.3-0.5: 2-3.
2. ZnCo as claimed in claim 12O4-graphene hollow microsphere supercapacitor electrode material characterized in that: the reducing agent is ascorbic acid.
3. ZnCo as claimed in claim 12O4-graphene hollow microsphere supercapacitor electrode material characterized in that: the preparation method of the graphene hollow microsphere comprises the following steps:
(1) adding nano SiO into a mixed solvent of distilled water and ethanol with the volume ratio of 2-4:12Placing the mixture in a constant-temperature ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 1-3h, adding ammonia water to adjust the pH value of the solution to 8-9, adding resorcinol and formaldehyde aqueous solution and cetyl trimethyl ammonium bromide, continuing the ultrasonic dispersion treatment for 20-40min, heating to 15-35 ℃ for reaction for 5-10h, filtering, washing and drying, placing the solid product in an atmosphere furnace, raising the temperature at the rate of 2-8 ℃/min to 140-180 ℃, performing heat preservation treatment for 30-90min, raising the temperature to 550-600 ℃, performing heat preservation calcination for 1-2h, continuing to raise the temperature to 820-850 ℃, performing heat preservation calcination for 1-2h, and preparing the graphene-coated nano SiO2；
(2) Coating nano SiO with graphene2Placing the hollow microspheres in 8-15% hydrofluoric acid solution, placing the hollow microspheres in a constant-temperature ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 1-2h, stirring the mixture for reaction for 10-15h, filtering, washing and drying the reaction product to prepare the graphene hollow microspheres.
4. ZnCo as claimed in claim 32O4-graphene hollow microsphere supercapacitor electrode material characterized in that: constant temperature ultrasonic treatment appearance includes instrument main part, the inside top fixedly connected with supersound appearance of instrument main part, supersound appearance below fixedly connected with ultrasonic probe, the below fixedly connected with base of instrument main part, the base top is provided with the water bath, the outer and heat preservation fixed connection of water bath, fixedly connected with fixed block on the inside of water bath, the inside draw-in groove, draw-in groove and fixture block swing joint, fixture block fixedly connected with bracing piece, bracing piece and objective table fixed connection that is provided with of fixed block, the objective table top is provided with the reaction bottle.
5. ZnCo as claimed in claim 32O4-graphene hollow microsphere supercapacitor electrode material characterized in that: the nano SiO2Has an average particle diameter of 10 to 20nm and a mass ratio of resorcinol, formaldehyde and cetyltrimethylammonium bromide of 1:0.2 to 0.6:0.1 to 0.25:1.5 to 4.
6. ZnCo as claimed in claim 12O4-graphene hollow microsphere supercapacitor electrode material characterized in that: the ZnCo2O4The preparation method of the graphene hollow microsphere supercapacitor electrode material comprises the following steps:
(1) adding graphene hollow microspheres into a mixed solvent of distilled water and ethanol with a volume ratio of 1-2:1, placing the mixture into a constant-temperature ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 1-2h, and adding CoCl2、ZnCl2、NiCl2Reducing agent, NH4F and urea, transferring the solution into a reaction kettle, heating to 140-180 ℃, reacting for 4-8h, filtering, washing and drying, placing the solid product into an atmosphere furnace, heating to 420-480 ℃ at the heating rate of 1-5 ℃/min, and carrying out heat preservation treatment for 2-4h to obtain the porous Ni-doped ZnCo2O4Loading graphene hollow microspheres, namely ZnCo2O4-graphene hollow microsphere supercapacitor electrode materials.
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