CN111508722A - Polypyrrole coated MnO2-NiCo2S4Super capacitor electrode material and preparation method thereof - Google Patents
Polypyrrole coated MnO2-NiCo2S4Super capacitor 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
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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 electrode materials of super capacitors and discloses polypyrrole coated MnO2‑NiCo2S4The super capacitor electrode material comprises the following formula raw materials and components: pyrrole, ammonium persulfate and nano-porous NiCo2S4Graphene and KMnO loaded4Hexadecyl trimethyl ammonium bromide. The polypyrrole covers MnO2‑NiCo2S4Electrode material of super capacitor, oxalic acid, ammonia water and Ni2+、Co2+Forming nickel cobalt oxalate amine salt, and thermally cracking at high temperature to form nano NiCo2O4Loaded graphene, carbon dioxide and ammonia gas from thermal cracking of nickel cobalt oxalate amine salt from NiCo2O4Escape from the interior, generate a large amount of pore structure, and react with Na2S reaction to obtain nano porous NiCo2S4The loaded graphene is more beneficial to the transmission and diffusion of ions, and the linear nano MnO2NiCo can be avoided2O4The polypyrrole enhances the conductivity of the electrode material, provides a pseudocapacitor to enhance the actual capacitance of the electrode material, and is NiCo2O4The volume expansion of (a) is buffered by elasticity.
Description
Technical Field
The invention relates to the technical field of electrode materials of supercapacitors, in particular to polypyrrole coated MnO2-NiCo2S4Super capacitor electrode materialAnd a method for producing the same.
Background
The energy crisis and environmental pollution problem that overuse fossil fuel brought are growing serious day by day, it is the effective method to solve the problem to develop novel efficient energy device and system, ultracapacitor system is a novel green energy memory between traditional condenser and rechargeable battery, have the quick charge-discharge characteristic of condenser and the energy storage characteristic of battery simultaneously, the interface bilayer that forms between electrode and the electrolyte among the ultracapacitor system, store energy with this, when electrode and electrolyte contact, under the effect of coulomb power and intermolecular force, solid-liquid interface can produce the double-deck electric charge of stable and opposite sign, the negative plate attracts positive ion, the positive plate attracts the anion, thereby form the double electric layer capacitor on the surface of two electrodes.
The double-layer capacitor can be divided into a carbon electrode double-layer supercapacitor, a metal oxide electrode supercapacitor and an organic polymer electrode supercapacitor, and the electrode material of the carbon electrode double-layer supercapacitor mainly comprises carbon-based materials such as activated carbon, carbon nanofibers and carbon nanotubes; metal oxide electrode materials such as ruthenium oxide, manganese oxide, and cobalt oxide; a super capacitor made of conducting polymers such as polyaniline and polythiophene, wherein a ternary transition metal sulfide NiCo2S4The cobalt ions and the nickel ions in the nickel-cobalt composite electrode have various oxidation-reduction forms, and rich oxidation-reduction reactions can occur simultaneously, so that the cobalt-nickel composite electrode has high theoretical specific capacitance and good electrochemical storage performance, is a super capacitor electrode active material with great potential, but NiCo2S4The electrode material has low ion conductivity, is not beneficial to the transmission and migration of ions in the electrode reaction process, and NiCo2S4The volume expansion and contraction of the matrix can occur in the charge and discharge process, so that the material matrix is lost and even decomposed, and the rate capability and the electrochemical cycle stability of the electrode material are reduced.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides polypyrrole coated MnO2-NiCo2S4Super capacitorThe electrode material and the preparation method thereof solve the problem of NiCo2S4The ionic conductivity of the electrode material is low and problems of volume expansion and contraction easily occur.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: polypyrrole coated MnO2-NiCo2S4The super capacitor electrode material comprises the following formula raw materials in parts by weight: 14-20 parts of pyrrole, 12-15 parts of ammonium persulfate and 33-58 parts of nano porous NiCo2S4Loaded graphene and 16-20 parts of KMnO48-12 parts of hexadecyl trimethyl ammonium bromide.
Preferably, the nanoporous NiCo2S4The preparation method of the loaded graphene 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, adding carboxylated graphene, performing ultrasonic dispersion uniformly, and adding NiCl2、CoCl2Transferring the solution into an automatic reaction kettle after uniformly stirring, heating to 90-110 ℃, reacting for 15-25h, reducing the temperature to 65-85 ℃, adding polyvinylpyrrolidone and oxalic acid, adding ammonia water after uniformly stirring to adjust the pH value of the solution to 6-7, continuously reacting for 6-10h, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with distilled water and ethanol, drying, placing in a muffle furnace, and performing heat preservation and calcination at the temperature of 300-2O4And loading graphene.
(2) Adding distilled water and nano porous NiCo into a reaction bottle2O4Graphene and Na supported2S, after uniform ultrasonic dispersion, transferring the solution into an automatic reaction kettle, heating to 180-class 200 ℃, uniformly stirring for reaction for 15-20h, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the nano porous NiCo2S4And loading graphene.
Preferably, the carboxylated graphene and NiCl are2、CoCl2And the mass ratio of the polyvinylpyrrolidone to the oxalic acid is 1:2.5-3.5:5-7:9-12:14-18。
preferably, the nanoporous NiCo2O4Graphene and Na supported2The mass ratio of S is 1: 3-6.
Preferably, the polypyrrole covers MnO2-NiCo2S4The preparation method of the electrode material of the super capacitor comprises the following steps:
(1) adding 2-4% of polyethylene glycol aqueous solution and 33-58 parts of nano porous NiCo into a reaction bottle2S4Loaded graphene, 8-12 parts of hexadecyl trimethyl ammonium bromide and 16-20 parts of KMnO4After the ultrasonic dispersion is uniform, transferring the solution into an automatic reaction kettle, heating to 130-150 ℃, stirring at constant speed for reaction for 6-10h, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the linear nano MnO2Modified NiCo2O4And loading graphene.
(2) 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 1-1.5:1, and adding linear nano MnO2Modified NiCo2O4Loading graphene, 14-20 parts of pyrrole and 12-15 parts of ammonium persulfate, uniformly stirring and reacting at 0-5 ℃ for 30-40h, filtering the solution to remove the solvent, washing the solid product with distilled water, and fully drying to prepare polypyrrole coated MnO2-NiCo2S4And (3) a supercapacitor electrode material.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the polypyrrole covers MnO2-NiCo2S4The super capacitor electrode material takes carboxylated graphene as a carrier, and carboxyl and Ni2+And Co2+Performing a complex reaction of Ni2+And Co2+Uniformly adsorbing the graphene to the huge specific surface and lamellar structure of the graphene, adding oxalic acid as a precipitator, adding ammonia water for regulation, and mixing with Ni2+And Co2+Forming nickel cobalt oxalate amine salt, and forming nano NiCo through high-temperature thermal cracking2O4Loaded with graphene, and simultaneously carbon dioxide and ammonia gas generated by thermal cracking of nickel cobalt oxalate amine salt are separated from nano NiCo2O4The particles escape from the interior to generate a large amount of pore structures to form porous nano NiCo2O4Loading graphene, then reacting with Na2S is prepared into the nano porous NiCo through a hydrothermal synthesis method and an ion exchange method2S4The loaded graphene has a porous structure, so that the ion transmission and diffusion in the electrode reaction process are facilitated, the graphene has excellent conductivity, and the ion conductivity and the electronic conductivity of the electrode material are enhanced under the synergistic effect.
The polypyrrole covers MnO2-NiCo2S4Supercapacitor electrode material, porous nano NiCo2O4Manganese ions are absorbed into a pore channel structure, polyethylene glycol is used as a surfactant, and hexadecyl trimethyl ammonium bromide with long carbon chains is used as a template sacrificial agent to prepare linear nano MnO2Modified NiCo2O4Graphene-loaded, linear nano MnO2For NiCo2O4The structural stability of the matrix has good supporting effect, and NiCo can be avoided2O4The volume shrinkage during the redox reaction leads to the collapse of pores and channel structures.
The polypyrrole covers MnO2-NiCo2S4Electrode material of super capacitor, in-situ polymerization method, in-line nano MnO2Modified NiCo2O4A layer of conductive polypyrrole is generated on the surface of the loaded graphene, the conductivity of the electrode material can be further enhanced by the polypyrrole, the actual capacitance of the electrode material can be enhanced by providing a pseudo capacitor, and meanwhile, the flexible polypyrrole can be NiCo2O4The volume expansion of the alloy is buffered by elasticity, so that the mechanical stress is reduced, and NiCo is avoided2O4The excessive expansion of the matrix enhances the rate capability and the electrochemical cycle stability of the electrode material.
Detailed Description
To achieve the above object, the present invention provides the following embodimentsAnd examples: polypyrrole coated MnO2-NiCo2S4The super capacitor electrode material comprises the following formula raw materials in parts by weight: 14-20 parts of pyrrole, 12-15 parts of ammonium persulfate and 33-58 parts of nano porous NiCo2S4Loaded graphene and 16-20 parts of KMnO48-12 parts of hexadecyl trimethyl ammonium bromide.
Nanoporous NiCo2S4The preparation method of the loaded graphene 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, adding carboxylated graphene, performing ultrasonic dispersion uniformly, and adding NiCl2、CoCl2Transferring the solution into an automatic reaction kettle after uniformly stirring, heating to 90-110 ℃, reacting for 15-25h, reducing the temperature to 65-85 ℃, and adding polyvinylpyrrolidone and oxalic acid, wherein the carboxylated graphene and NiCl2、CoCl2The mass ratio of polyvinylpyrrolidone to oxalic acid is 1:2.5-3.5:5-7:9-12:14-18, ammonia water is added after the mixture is uniformly stirred to adjust the pH value of the solution to 6-7, the reaction is continued for 6-10h, the solution is cooled to room temperature, the solvent is removed by filtration, distilled water and ethanol are used for washing a solid product, the dried solid product is placed in a muffle furnace, and the heat preservation and calcination are carried out for 2-3h at the temperature of 330 ℃ under 300-2O4And loading graphene.
(2) Adding distilled water and nano porous NiCo into a reaction bottle2O4Graphene and Na supported2S, after the two components are uniformly dispersed by ultrasonic with the mass ratio of 1:3-6, transferring the solution into an automatic reaction kettle, heating to 180 ℃ and 200 ℃, uniformly stirring and reacting for 15-20h, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to prepare the nano porous NiCo2S4And loading graphene.
MnO coated with polypyrrole2-NiCo2S4The preparation method of the electrode material of the super capacitor comprises the following steps:
(1) adding 2-4% of polyethylene glycol aqueous solution and 33-58 parts of nano porous NiCo into a reaction bottle2S4Loaded graphene, 8-12 parts of hexadecyl trimethyl ammonium bromide and 16-20 parts of KMnO4After the ultrasonic dispersion is uniform, transferring the solution into an automatic reaction kettle, heating to 130-150 ℃, stirring at constant speed for reaction for 6-10h, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the linear nano MnO2Modified NiCo2O4And loading graphene.
(2) 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 1-1.5:1, and adding linear nano MnO2Modified NiCo2O4Loading graphene, 14-20 parts of pyrrole and 12-15 parts of ammonium persulfate, uniformly stirring and reacting at 0-5 ℃ for 30-40h, filtering the solution to remove the solvent, washing the solid product with distilled water, and fully drying to prepare polypyrrole coated MnO2-NiCo2S4And (3) a supercapacitor electrode material.
Coating polypyrrole with MnO2-NiCo2S4The electrode material 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 are uniformly coated on a foamed nickel substrate to prepare the working electrode material of the super capacitor.
Example 1
(1) Preparation of nanoporous NiCo2O4Graphene-loaded component 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, adding carboxylated graphene, performing ultrasonic dispersion uniformly, and adding NiCl2、CoCl2After uniformly stirring, transferring the solution into an automatic reaction kettle, heating to 90 ℃, reacting for 15h, reducing the temperature to 65 ℃, and adding polyvinylpyrrolidone and oxalic acid, wherein the carboxylated graphene and NiCl2、CoCl2Uniformly stirring, adding ammonia water to adjust the pH value of the solution to 6, continuously reacting for 6 hours, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product by using distilled water and ethanol, drying, placing in a muffle furnace, preserving heat at 300 ℃ for 2 hours, and calcining for 2 hours to obtain the nano porous NiCo2O4And carrying a graphene component 1.
(2) Preparation of nanoporous NiCo2S4Graphene-loaded component 1: adding distilled water and nano porous NiCo into a reaction bottle2O4Graphene-loaded component 1 and Na2S, after the two components are uniformly dispersed by ultrasonic with the mass ratio of 1:3, transferring the solution into an automatic reaction kettle, heating to 180 ℃, uniformly stirring for reaction for 15 hours, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product by using distilled water and ethanol, fully drying, and preparing the nano porous NiCo2S4And carrying a graphene component 1.
(3) Preparation of linear nano MnO2Modified NiCo2O4Graphene-loaded component 1: adding a 2 mass percent aqueous solution of polyethylene glycol and 58 parts of nano-porous NiCo into a reaction flask2S4Graphene-loaded component 1, 8 parts of hexadecyl trimethyl ammonium bromide and 16 parts of KMnO4After the ultrasonic dispersion is uniform, transferring the solution into an automatic reaction kettle, heating to 130 ℃, stirring at a constant speed for reaction for 6 hours, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the linear nano MnO2Modified NiCo2O4And carrying a graphene component 1.
(4) Preparation of polypyrrole coated MnO2-NiCo2S4Supercapacitor 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 ethanol is 1:1, and adding linear nano MnO2Modified NiCo2O4Loading graphene component 1, 14 parts of pyrrole and 12 parts of ammonium persulfate, stirring at a constant speed at 5 ℃ for reaction for 30 hours, filtering the solution to remove the solvent, washing the solid product with distilled water, and fully drying to prepare polypyrrole coated MnO2-NiCo2S4Supercapacitor electrode material 1.
(5) Coating polypyrrole with MnO2-NiCo2S4The electrode material 1 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 are uniformly coated on a foamed nickel substrateAnd finally, preparing the working electrode material 1 of the supercapacitor.
Example 2
(1) Preparation of nanoporous NiCo2O4And a graphene-loaded component 2: 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, adding carboxylated graphene, performing ultrasonic dispersion uniformly, and adding NiCl2、CoCl2After uniformly stirring, transferring the solution into an automatic reaction kettle, heating to 90 ℃, reacting for 25 hours, reducing the temperature to 85 ℃, and adding polyvinylpyrrolidone and oxalic acid, wherein the carboxylated graphene and NiCl2、CoCl2Uniformly stirring, adding ammonia water to adjust the pH value of the solution to 6, continuously reacting for 10 hours, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product by using distilled water and ethanol, drying, placing in a muffle furnace, preserving heat at 300 ℃ for 3 hours, and calcining for 3 hours to obtain the nano porous NiCo2O4And loading a graphene component 2.
(2) Preparation of nanoporous NiCo2S4And a graphene-loaded component 2: adding distilled water and nano porous NiCo into a reaction bottle2O4Loaded graphene component 2 and Na2S, after the two components are uniformly dispersed by ultrasonic with the mass ratio of 1:3, transferring the solution into an automatic reaction kettle, heating to 200 ℃, uniformly stirring for reaction for 20 hours, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product by using distilled water and ethanol, fully drying, and preparing the nano porous NiCo2S4And loading a graphene component 2.
(3) Preparation of linear nano MnO2Modified NiCo2O4And a graphene-loaded component 2: adding a 4 mass percent aqueous solution of polyethylene glycol and 47 parts of nano-porous NiCo into a reaction flask2S4Graphene-loaded component 2, 8.5 parts of hexadecyl trimethyl ammonium bromide and 17 parts of KMnO4After the ultrasonic dispersion is uniform, transferring the solution into an automatic reaction kettle, heating to 150 ℃, uniformly stirring for reaction for 10 hours, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product by using distilled water and ethanol, fully drying, and preparing the productPreparing to obtain linear nano MnO2Modified NiCo2O4And loading a graphene component 2.
(4) Preparation of polypyrrole coated MnO2-NiCo2S4Supercapacitor 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 ethanol is 1:1, and adding linear nano MnO2Modified NiCo2O4Loading graphene component 2, 15 parts of pyrrole and 12.5 parts of ammonium persulfate, uniformly stirring and reacting at 5 ℃ for 30 hours, filtering the solution to remove the solvent, washing the solid product with distilled water, and fully drying to prepare polypyrrole coated MnO2-NiCo2S4Supercapacitor electrode material 2.
(5) Coating polypyrrole with MnO2-NiCo2S4The supercapacitor electrode material 2, the conductive agent acetylene black and the adhesive polyvinylidene fluoride are uniformly dispersed in an N-methyl pyrrolidone solvent and uniformly coated on a foamed nickel substrate to prepare the supercapacitor working electrode material 2.
Example 3
(1) Preparation of nanoporous NiCo2O4The loaded graphene component 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 3:1, adding carboxylated graphene, performing ultrasonic dispersion uniformly, and adding NiCl2、CoCl2After uniformly stirring, transferring the solution into an automatic reaction kettle, heating to 110 ℃, reacting for 25 hours, reducing the temperature to 65 ℃, and adding polyvinylpyrrolidone and oxalic acid, wherein the carboxylated graphene and NiCl2、CoCl2Uniformly stirring, adding ammonia water to adjust the pH value of the solution to 7, continuously reacting for 8 hours, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product by using distilled water and ethanol, drying, placing in a muffle furnace, preserving heat at 315 ℃ and calcining for 2.5 hours to prepare the nano porous NiCo2O4And carrying a graphene component 3.
(2) Preparation of nanoporous NiCo2S4The loaded graphene component 3: adding distilled water and nano porous NiCo into a reaction bottle2O4Graphene-loaded component 1 and Na2S, after the two components are uniformly dispersed by ultrasonic with the mass ratio of 1:4.5, transferring the solution into an automatic reaction kettle, heating to 190 ℃, uniformly stirring for reaction for 18 hours, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product by using distilled water and ethanol, fully drying, and preparing the nano porous NiCo2S4And carrying a graphene component 3.
(3) Preparation of linear nano MnO2Modified NiCo2O4The loaded graphene component 3: adding a 3 mass percent aqueous solution of polyethylene glycol and 41 parts of nano-porous NiCo into a reaction flask2S4Graphene-loaded component 3, 10 parts of hexadecyl trimethyl ammonium bromide and 18 parts of KMnO4After the ultrasonic dispersion is uniform, transferring the solution into an automatic reaction kettle, heating to 140 ℃, stirring at a constant speed for reaction for 8 hours, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the linear nano MnO2Modified NiCo2O4And carrying a graphene component 3.
(4) Preparation of polypyrrole coated MnO2-NiCo2S4Supercapacitor 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 1.2:1, and adding linear nano MnO2Modified NiCo2O4Loading 3 parts of graphene component, 17.5 parts of pyrrole and 13.5 parts of ammonium persulfate, stirring at a constant speed at 2 ℃ for reaction for 35 hours, filtering the solution to remove the solvent, washing the solid product with distilled water, and fully drying to prepare polypyrrole coated MnO2-NiCo2S4Supercapacitor electrode material 3.
(5) Coating polypyrrole with MnO2-NiCo2S4The supercapacitor electrode material 3, the conductive agent acetylene black and the adhesive polyvinylidene fluoride are uniformly dispersed in an N-methyl pyrrolidone solvent and uniformly coated on a foamed nickel substrate to prepare the supercapacitor working electrode material 3.
Example 4
(1) Preparation of nanoporous NiCo2O4Loaded graphiteAlkene component 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 3:1, adding carboxylated graphene, performing ultrasonic dispersion uniformly, and adding NiCl2、CoCl2After uniformly stirring, transferring the solution into an automatic reaction kettle, heating to 110 ℃, reacting for 20 hours, reducing the temperature to 65 ℃, and adding polyvinylpyrrolidone and oxalic acid, wherein the carboxylated graphene and NiCl2、CoCl2Uniformly stirring, adding ammonia water to adjust the pH value of the solution to 7, continuously reacting for 10 hours, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product by using distilled water and ethanol, drying, placing in a muffle furnace, preserving heat at 300 ℃ for 3 hours, and calcining for 3 hours to obtain the nano porous NiCo2O4And carrying a graphene component 4.
(2) Preparation of nanoporous NiCo2S4The loaded graphene component 4: adding distilled water and nano porous NiCo into a reaction bottle2O4Loaded graphene component 4 and Na2S, after the two components are uniformly dispersed by ultrasonic with the mass ratio of 1:3, transferring the solution into an automatic reaction kettle, heating to 200 ℃, uniformly stirring for reaction for 20 hours, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product by using distilled water and ethanol, fully drying, and preparing the nano porous NiCo2S4And carrying a graphene component 4.
(3) Preparation of linear nano MnO2Modified NiCo2O4The loaded graphene component 4: adding a 4 mass percent aqueous solution of polyethylene glycol and 37 parts of nano-porous NiCo into a reaction flask2S4Graphene-loaded component 4, 11 parts of hexadecyl trimethyl ammonium bromide and 19 parts of KMnO4After the ultrasonic dispersion is uniform, transferring the solution into an automatic reaction kettle, heating to 150 ℃, uniformly stirring for reaction for 10 hours, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to prepare the linear nano MnO2Modified NiCo2O4And carrying a graphene component 4.
(4) Preparation of polypyrrole coated MnO2-NiCo2S4Supercapacitor 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 1.5:1, and adding linear nano MnO2Modified NiCo2O4Loading 4 parts of graphene component, 18.8 parts of pyrrole and 14.2 parts of ammonium persulfate, stirring at a constant speed at 5 ℃ for reaction for 40 hours, filtering the solution to remove the solvent, washing the solid product with distilled water, and fully drying to prepare polypyrrole coated MnO2-NiCo2S4Supercapacitor electrode material 4.
(5) Coating polypyrrole with MnO2-NiCo2S4The supercapacitor electrode material 4, the conductive agent acetylene black and the adhesive polyvinylidene fluoride are uniformly dispersed in an N-methyl pyrrolidone solvent and uniformly coated on a foamed nickel substrate to prepare the supercapacitor working electrode material 4.
Example 5
(1) Preparation of nanoporous NiCo2O4The loaded graphene component 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 4:1, adding carboxylated graphene, performing ultrasonic dispersion uniformly, and adding NiCl2、CoCl2After uniformly stirring, transferring the solution into an automatic reaction kettle, heating to 110 ℃, reacting for 25 hours, reducing the temperature to 85 ℃, and adding polyvinylpyrrolidone and oxalic acid, wherein the carboxylated graphene and NiCl2、CoCl2Uniformly stirring, adding ammonia water to adjust the pH value of the solution to 7, continuously reacting for 10 hours, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product by using distilled water and ethanol, drying, placing in a muffle furnace, preserving heat at 330 ℃ for 3 hours, and calcining for 3 hours to obtain the nano porous NiCo2O4And carrying a graphene component 5.
(2) Preparation of nanoporous NiCo2S4The loaded graphene component 5: adding distilled water and nano porous NiCo into a reaction bottle2O4Loaded graphene component 5 and Na2S, after the two are uniformly dispersed by ultrasonic with the mass ratio of 1:6, transferring the solution into an automatic reaction kettle, heating to 200 ℃, uniformly stirring for reaction for 20 hours, and cooling the solutionCooling to room temperature, filtering to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the nano-porous NiCo2S4And carrying a graphene component 5.
(3) Preparation of linear nano MnO2Modified NiCo2O4The loaded graphene component 5: adding a 4 mass percent aqueous solution of polyethylene glycol and 33 parts of nano-porous NiCo into a reaction bottle2S4Graphene-loaded component 5, 12 parts of hexadecyl trimethyl ammonium bromide and 20 parts of KMnO4After the ultrasonic dispersion is uniform, transferring the solution into an automatic reaction kettle, heating to 150 ℃, uniformly stirring for reaction for 10 hours, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to prepare the linear nano MnO2Modified NiCo2O4And carrying a graphene component 5.
(4) Preparation of polypyrrole coated MnO2-NiCo2S4Supercapacitor 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 1.5:1, and adding linear nano MnO2Modified NiCo2O4Loading 5 parts of graphene component, 20 parts of pyrrole and 15 parts of ammonium persulfate, uniformly stirring and reacting for 40 hours at 0 ℃, filtering the solution to remove the solvent, washing the solid product with distilled water, and fully drying to prepare polypyrrole coated MnO2-NiCo2S4Supercapacitor electrode material 5.
(5) Coating polypyrrole with MnO2-NiCo2S4The supercapacitor electrode material 5, the conductive agent acetylene black and the adhesive polyvinylidene fluoride are uniformly dispersed in an N-methyl pyrrolidone solvent and uniformly coated on a foamed nickel substrate to prepare the supercapacitor working electrode material 5.
In summary, the polypyrrole covers MnO2-NiCo2S4The super capacitor electrode material takes carboxylated graphene as a carrier, and carboxyl and Ni2+And Co2+Performing a complex reaction of Ni2+And Co2+Uniformly adsorbed to the huge specific surface and lamellar structure of graphene,then adding oxalic acid as precipitant, adding ammonia water for regulation, mixing with Ni2+And Co2+Forming nickel cobalt oxalate amine salt, and forming nano NiCo through high-temperature thermal cracking2O4Loaded with graphene, and simultaneously carbon dioxide and ammonia gas generated by thermal cracking of nickel cobalt oxalate amine salt are separated from nano NiCo2O4The particles escape from the interior to generate a large amount of pore structures to form porous nano NiCo2O4Loading graphene, then reacting with Na2S is prepared into the nano porous NiCo through a hydrothermal synthesis method and an ion exchange method2S4The loaded graphene has a porous structure, so that the ion transmission and diffusion in the electrode reaction process are facilitated, the graphene has excellent conductivity, and the ion conductivity and the electronic conductivity of the electrode material are enhanced under the synergistic effect.
Porous nano NiCo2O4Manganese ions are absorbed into a pore channel structure, polyethylene glycol is used as a surfactant, and hexadecyl trimethyl ammonium bromide with long carbon chains is used as a template sacrificial agent to prepare linear nano MnO2Modified NiCo2O4Graphene-loaded, linear nano MnO2For NiCo2O4The structural stability of the matrix has good supporting effect, and NiCo can be avoided2O4The volume shrinkage during the redox reaction leads to the collapse of pores and channel structures.
In-situ polymerization of in-line nano-MnO2Modified NiCo2O4A layer of conductive polypyrrole is generated on the surface of the loaded graphene, the conductivity of the electrode material can be further enhanced by the polypyrrole, the actual capacitance of the electrode material can be enhanced by providing a pseudo capacitor, and meanwhile, the flexible polypyrrole can be NiCo2O4The volume expansion of the alloy is buffered by elasticity, so that the mechanical stress is reduced, and NiCo is avoided2O4The excessive expansion of the matrix enhances the rate capability and the electrochemical cycle stability of the electrode material.
Claims (5)
1. Polypyrrole coated MnO2-NiCo2S4Super capacitor electrodeThe material comprises the following formula raw materials and components in parts by weight, and is characterized in that: 14-20 parts of pyrrole, 12-15 parts of ammonium persulfate and 33-58 parts of nano porous NiCo2S4Loaded graphene and 16-20 parts of KMnO48-12 parts of hexadecyl trimethyl ammonium bromide.
2. The polypyrrole coated MnO of claim 12-NiCo2S4The electrode material of the super capacitor is characterized in that: the nano porous NiCo2S4The preparation method of the loaded graphene comprises the following steps:
(1) adding carboxylated graphene into a mixed solvent of distilled water and ethanol with the volume ratio of 2-4:1, carrying out ultrasonic dispersion uniformly, and adding NiCl2、CoCl2Transferring the solution into an automatic reaction kettle after uniformly stirring, heating to 90-110 ℃, reacting for 15-25h, reducing the temperature to 65-85 ℃, adding polyvinylpyrrolidone and oxalic acid, adding ammonia water to adjust the pH value of the solution to 6-7, reacting for 6-10h, filtering, washing and drying the solution, placing the solid product into a muffle furnace, and performing heat preservation and calcination for 2-3h at the temperature of 300-2O4Loading graphene;
(2) adding nanoporous NiCo to distilled water2O4Graphene and Na supported2S, after the ultrasonic dispersion is uniform, transferring the solution into an automatic reaction kettle, heating to 180-200 ℃, reacting for 15-20h, filtering, washing and drying the solution to prepare the nano porous NiCo2S4And loading graphene.
3. The polypyrrole coated MnO of claim 12-NiCo2S4The electrode material of the super capacitor is characterized in that: the carboxylated graphene and NiCl2、CoCl2The mass ratio of the polyvinylpyrrolidone to the oxalic acid is 1:2.5-3.5:5-7:9-12: 14-18.
4. The polypyrrole coated MnO of claim 12-NiCo2S4Super capacitorAn electrode material, characterized in that: the nano porous NiCo2O4Graphene and Na supported2The mass ratio of S is 1: 3-6.
5. The polypyrrole coated MnO of claim 12-NiCo2S4The electrode material of the super capacitor is characterized in that: the polypyrrole covers MnO2-NiCo2S4The preparation method of the electrode material of the super capacitor comprises the following steps:
(1) adding 33-58 parts of nano porous NiCo into a water solution of polyethylene glycol with the mass fraction of 2-4%2S4Loaded graphene, 8-12 parts of hexadecyl trimethyl ammonium bromide and 16-20 parts of KMnO4After the ultrasonic dispersion is uniform, transferring the solution into an automatic reaction kettle, heating to 130-150 ℃, reacting for 6-10h, filtering, washing and drying the solution to prepare the linear nano MnO2Modified NiCo2O4Loading graphene;
(2) adding linear nano MnO into a mixed solvent of distilled water and ethanol with the volume ratio of 1-1.5:12Modified NiCo2O4Carrying graphene, 14-20 parts of pyrrole and 12-15 parts of ammonium persulfate, reacting for 30-40h at 0-5 ℃, filtering, washing and drying the solution to prepare polypyrrole coated MnO2-NiCo2S4And (3) a supercapacitor electrode material.
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