CN114220667A - Hollow nickel hydroxide needle-punched microsphere electrode material and preparation method and application thereof - Google Patents
Hollow nickel hydroxide needle-punched microsphere electrode material and preparation method and application thereof Download PDFInfo
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- 239000004005 microsphere Substances 0.000 title claims abstract description 74
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000007772 electrode material Substances 0.000 title claims abstract description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229920005989 resin Polymers 0.000 claims abstract description 30
- 239000011347 resin Substances 0.000 claims abstract description 30
- HANVTCGOAROXMV-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine;urea Chemical compound O=C.NC(N)=O.NC1=NC(N)=NC(N)=N1 HANVTCGOAROXMV-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 20
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004202 carbamide Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 17
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 12
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 11
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 9
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000006230 acetylene black Substances 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 239000000839 emulsion Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 235000011837 pasties Nutrition 0.000 claims 2
- 239000003990 capacitor Substances 0.000 claims 1
- 238000007664 blowing Methods 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 11
- 231100000956 nontoxicity Toxicity 0.000 abstract description 3
- 238000005303 weighing Methods 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/42—Powders or particles, e.g. composition thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08G12/34—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds and acyclic or carbocyclic compounds
- C08G12/36—Ureas; Thioureas
- C08G12/38—Ureas; Thioureas and melamines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
Abstract
The invention discloses a hollow nickel hydroxide needle-punched microsphere electrode material and a preparation method thereof, melamine, paraformaldehyde and urea are dispersed in water to be polymerized to obtain white melamine formaldehyde urea copolycondensation resin microspheres, the white melamine formaldehyde urea copolycondensation resin microspheres are dispersed in a hydroalcoholic solution, nickel nitrate hexahydrate and urea are added to be fully dispersed, then the white melamine formaldehyde urea copolycondensation resin microspheres are transferred into a hydrothermal reaction kettle to react for 10 hours at 160 ℃, and then the white melamine formaldehyde urea copolycondensation resin microspheres are reacted for 2 hours at 100 ℃ and naturally cooled to obtain the hollow nickel hydroxide needle-punched microspheres. And uniformly mixing the prepared hollow nickel hydroxide needle punched microspheres, acetylene black and polytetrafluoroethylene emulsion according to the mass ratio of 80:10:10, blowing the mixture into paste, coating the paste material on foamed nickel by using the foamed nickel as a current collector, and drying the mixture in vacuum for 24 hours to finally obtain the required electrode. The hollow nickel hydroxide needle-punched microsphere electrode prepared by the method has the advantages of greenness, no toxicity, low density and excellent electrochemical performance, and can be widely applied to portable and flexible electrode materials.
Description
Technical Field
The invention belongs to the field of preparation of electrode materials, and particularly relates to a hollow nickel hydroxide needle-punched microsphere electrode material as well as a preparation method and application thereof.
Background
Hollow colloidal particles with well-defined structure and composition are of interest because of their unique structure-dependent properties, such as light weight, abundant active surface, considerable loading capacity and excellent surface permeability, and their widespread use in the following fields. Energy storage, biomedicine, catalysis, and environmental remediation. Recently, great efforts have been made in the design of the structure and composition of the colloidal shells to impart their desired morphology and properties, which are crucial for their interesting functional distribution and practical application. To date, despite the success of synthesizing colloidal shells using a wide variety of strategies, the sacrificial templating method is widely considered to be the most representative and straightforward of these strategies, by virtue of its size, shape and hollow structure of the cavity, which can be easily adjusted by selecting an appropriate template.
Disclosure of Invention
The invention aims to provide a hollow nickel hydroxide needle-punched microsphere electrode material and a preparation method and application thereof, aiming at the defects of the prior art. The hollow nickel hydroxide needle-punched microsphere electrode material prepared by the invention has the advantages of large specific surface area, no toxicity, excellent electrochemical performance and extremely wide application in portable and flexible electrode materials.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing a hollow nickel hydroxide needle-punched microsphere electrode material by taking melamine formaldehyde urea copolycondensation resin microspheres as a template specifically comprises the following steps:
(1) preparation of melamine formaldehyde urea copolycondensation resin microsphere
Dispersing melamine, paraformaldehyde and urea in 30ml of water, performing ultrasonic treatment for 30min, pouring into a three-neck flask, heating in a 60 ℃ oil bath, stirring for 30min, fully dispersing, and performing prepolymerization. Then 200ml of deionized water and 60 mu L of sulfuric acid are added into a three-neck flask, the mixture is fully stirred for 30min, heated at 110 ℃ for 60min and taken out to be cooled to room temperature. Centrifugally washing for 3 times, and drying for 24 hours at 80 ℃ to obtain the white melamine formaldehyde urea copolycondensation resin microspheres.
(2) Preparation of hollow nickel hydroxide needle-punched microspheres
100mg of melamine formaldehyde urea copolycondensation resin microspheres are dispersed in 80ml of hydroalcoholic solution, magnetic stirring is carried out at 400rpm for 30min, the mixture is fully dispersed, and then 870mg of nickel nitrate hexahydrate and 720mg of urea are added and fully stirred for 2 h. Transferring the obtained solution into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting at 160 ℃ for 10h, then reacting at 100 ℃ for 2h, naturally cooling, centrifugally washing for 3 times, and then blowing and drying at 80 ℃ to obtain the hollow nickel hydroxide needle-punched microspheres.
(3) Preparation of hollow nickel hydroxide needle-punched microsphere electrode material
Adding the hollow nickel hydroxide needle punched microspheres prepared in the step (2), acetylene black and polytetrafluoroethylene emulsion into the same weighing bottle according to the mass ratio of 80:10:10, stirring and mixing uniformly, blowing the sample into paste by using a hair drier, coating the paste material on the foamed nickel by using the foamed nickel as a current collector, and drying in vacuum at 80 ℃ for 24 hours to finally prepare the required electrode material.
Further, the weight ratio of melamine, paraformaldehyde and urea is 1:2: 1.
Further, the mass ratio of the melamine formaldehyde urea copolycondensation resin microspheres to the nickel nitrate hexahydrate to the urea in the step (2) is 1: 6-10: 5-10.
The invention has the beneficial effects that:
(1) the melamine formaldehyde urea copolycondensation resin microspheres provide support in the reaction, and the resin microspheres are gradually dissolved while crystal lattices are formed on the surface, so that the hollow nickel hydroxide needle-punched microspheres with large specific surface area are obtained. The nickel precursor may react with water, forming crystals only on the surface of the template and releasing H+Ions. H+The release of ions results in a decrease in pH, resulting in a weakly acidic mediator. This weakly acidic medium allows the template to dissolve slowly, and the process can be accelerated significantly by the introduction of a polar solvent (e.g., water) that is easily ionized. At lower temperatures and pressures, acidic conditions favor rapid crosslinking of the molecules, and at high temperatures and pressures, acidic conditions favor hydrolysis. Water as an inert solvent only at high temperature and high pressureIt is effective under critical conditions. In addition, the concentration of the prepolymer is particularly high in the crosslinking process, the crosslinking speed is far higher than the decomposition speed, and the concentration of the microspheres is very low in the hydroxide synthesis process so as to mainly decompose. Typical resins do not have substantial water as a solvent, which affects the synthesis of the hydroxide, while heating can convert insoluble melamine molecules into their hydroxymethyl derivatives, which are soluble in water, which gives melamine formaldehyde urea resins its unique advantages.
(2) The residual micromolecules have negative potential, and the morphology of the nickel hydroxide can be changed, so that the specific surface area of the material is increased, and the electrochemical performance is improved.
(3) The conductivity of the nickel hydroxide is poor, the microspheres are added, the residual micromolecules are combined with the nickel under the hydrothermal reaction to form a new conductive channel, the conductivity of the whole system can be improved, and the carbon quantum dots exposed on the surface layer can provide more active sites. The microsphere comprises Ni, O, H and C. Including decomposed melamine and urea derivatives, which contribute to hydroxide formation and bond with Ni to form conductive pathways and improve conductivity. Since the decomposed small molecules are gradually decomposed to promote crystallization on the surface of the existing crystal, the carbon-containing small molecules exposed on the surface layer can provide more active sites.
(4) The hollow nickel hydroxide needle-punched microsphere electrode prepared by the invention has the advantages of large specific surface area, no toxicity, excellent electrochemical performance and extremely wide application in portable and flexible electrode materials.
Drawings
FIG. 1 is an SEM image of hollow nickel hydroxide needle-punched microspheres prepared in example 1.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples.
Comparative example 1
(1) Preparation of melamine formaldehyde urea copolycondensation resin microsphere
Dispersing 130mg of melamine, 360mg of paraformaldehyde and 130mg of urea in 30ml of water, performing ultrasonic treatment for 30min, pouring into a three-neck flask, heating in an oil bath at 60 ℃, stirring for 30min, fully dispersing and performing prepolymerization. Then 200ml of deionized water and 60 mu L of sulfuric acid are added into a three-neck flask, the mixture is fully stirred for 30min, heated at 110 ℃ for 60min and taken out to be cooled to room temperature. Centrifugally washing for 3 times, and drying for 24 hours at 80 ℃ to obtain the white melamine formaldehyde urea copolycondensation resin microspheres.
(2) Preparation of hollow nickel hydroxide needle-punched microspheres
200mg of melamine formaldehyde urea copolycondensation resin microspheres are dispersed in 80ml of hydroalcoholic solution, are magnetically stirred at 400rpm for 30min and are fully dispersed, and then 870mg of nickel nitrate hexahydrate and 720mg of urea are added and are fully stirred for 2 h. Transferring the obtained solution into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting at 160 ℃ for 10h, then reacting at 100 ℃ for 2h, naturally cooling, centrifugally washing for 3 times, and then blowing and drying at 80 ℃ to obtain the hollow nickel hydroxide needle-punched microspheres.
(3) Preparation of hollow nickel hydroxide needle-punched microsphere electrode material
Adding the hollow nickel hydroxide needle punched microspheres prepared in the step (2), acetylene black and polytetrafluoroethylene emulsion into the same weighing bottle according to the mass ratio of 80:10:10, stirring and mixing uniformly, blowing the sample into paste by using a hair drier, coating the paste material on the foamed nickel by using the foamed nickel as a current collector, and drying in vacuum for 24 hours at 80 ℃ to finally prepare the required electrode.
Example 1
(1) Preparation of melamine formaldehyde urea copolycondensation resin microsphere
Dispersing 130mg of melamine, 360mg of paraformaldehyde and 130mg of urea in 30ml of water, performing ultrasonic treatment for 30min, pouring into a three-neck flask, heating in an oil bath at 60 ℃, stirring for 30min, fully dispersing and performing prepolymerization. Then 200ml of deionized water and 60 mu L of sulfuric acid are added into a three-neck flask, the mixture is fully stirred for 30min, heated at 110 ℃ for 60min and taken out to be cooled to room temperature. Centrifugally washing for 3 times, and drying for 24 hours at 80 ℃ to obtain the white melamine formaldehyde urea copolycondensation resin microspheres.
(2) Preparation of hollow nickel hydroxide needle-punched microspheres
100mg of melamine formaldehyde urea copolycondensation resin microspheres are dispersed in 80ml of hydroalcoholic solution, magnetic stirring is carried out at 400rpm for 30min, the mixture is fully dispersed, and then 870mg of nickel nitrate hexahydrate and 720mg of urea are added and fully stirred for 2 h. Transferring the obtained solution into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting at 160 ℃ for 10h, then reacting at 100 ℃ for 2h, naturally cooling, centrifugally washing for 3 times, and then blowing and drying at 80 ℃ to obtain the hollow nickel hydroxide needle-punched microspheres.
(3) Preparation of hollow nickel hydroxide needle-punched microsphere electrode material
Adding the hollow nickel hydroxide needle punched microspheres prepared in the step (2), acetylene black and polytetrafluoroethylene emulsion into the same weighing bottle according to the mass ratio of 80:10:10, stirring and mixing uniformly, blowing the sample into paste by using a hair drier, coating the paste material on the foamed nickel by using the foamed nickel as a current collector, and drying in vacuum for 24 hours at 80 ℃ to finally prepare the required electrode.
Example 2
(1) Preparation of melamine formaldehyde urea copolycondensation resin microsphere
Dispersing 130mg of melamine, 360mg of paraformaldehyde and 130mg of urea in 30ml of water, performing ultrasonic treatment for 30min, pouring into a three-neck flask, heating in an oil bath at 60 ℃, stirring for 30min, fully dispersing and performing prepolymerization. Then 200ml of deionized water and 60 mu L of sulfuric acid are added into a three-neck flask, the mixture is fully stirred for 30min, heated at 110 ℃ for 60min and taken out to be cooled to room temperature. Centrifugally washing for 3 times, and drying for 24 hours at 80 ℃ to obtain the white melamine formaldehyde urea copolycondensation resin microspheres.
(2) Preparation of hollow nickel hydroxide needle-punched microspheres
Dispersing 120mg of melamine formaldehyde urea copolycondensation resin microspheres in 80ml of hydroalcoholic solution, magnetically stirring at 400rpm for 30min, fully dispersing, then adding 870mg of nickel nitrate hexahydrate and 720mg of urea, and fully stirring for 2 h. Transferring the obtained solution into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting at 160 ℃ for 10h, then reacting at 100 ℃ for 2h, naturally cooling, centrifugally washing for 3 times, and then blowing and drying at 80 ℃ to obtain the hollow nickel hydroxide needle-punched microspheres.
(3) Preparation of hollow nickel hydroxide needle-punched microsphere electrode material
Adding the hollow nickel hydroxide needle punched microspheres prepared in the step (2), acetylene black and polytetrafluoroethylene emulsion into the same weighing bottle according to the mass ratio of 80:10:10, stirring and mixing uniformly, blowing the sample into paste by using a hair drier, coating the paste material on the foamed nickel by using the foamed nickel as a current collector, and drying in vacuum for 24 hours at 80 ℃ to finally prepare the required electrode.
Example 3
(1) Preparation of melamine formaldehyde urea copolycondensation resin microsphere
Dispersing 130mg of melamine, 360mg of paraformaldehyde and 130mg of urea in 30ml of water, performing ultrasonic treatment for 30min, pouring into a three-neck flask, heating in an oil bath at 60 ℃, stirring for 30min, fully dispersing and performing prepolymerization. Then 200ml of deionized water and 60 mu L of sulfuric acid are added into a three-neck flask, the mixture is fully stirred for 30min, heated at 110 ℃ for 60min and taken out to be cooled to room temperature. Centrifugally washing for 3 times, and drying for 24 hours at 80 ℃ to obtain the white melamine formaldehyde urea copolycondensation resin microspheres.
(2) Preparation of hollow nickel hydroxide needle-punched microspheres
Dispersing 140mg of melamine formaldehyde urea copolycondensation resin microspheres in 80ml of hydroalcoholic solution, magnetically stirring at 400rpm for 30min, fully dispersing, then adding 870mg of nickel nitrate hexahydrate and 720mg of urea, and fully stirring for 2 h. Transferring the obtained solution into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting at 160 ℃ for 10h, then reacting at 100 ℃ for 2h, naturally cooling, centrifugally washing for 3 times, and then blowing and drying at 80 ℃ to obtain the hollow nickel hydroxide needle-punched microspheres.
(3) Preparation of hollow nickel hydroxide needle-punched microsphere electrode material
Adding the hollow nickel hydroxide needle punched microspheres prepared in the step (2), acetylene black and polytetrafluoroethylene emulsion into the same weighing bottle according to the mass ratio of 80:10:10, stirring and mixing uniformly, blowing the sample into paste by using a hair drier, coating the paste material on the foamed nickel by using the foamed nickel as a current collector, and drying in vacuum for 24 hours at 80 ℃ to finally prepare the required electrode. The obtained electrode was subjected to density, specific surface area and electrochemical performance tests, and the results are shown in table 1.
TABLE 1 parameters of needled hollow nickel hydroxide materials
TABLE 2 parameters of the needled hollow nickel hydroxide electrode
In the embodiment, the mass of the added resin microspheres is in a proper range, the microspheres can be completely eliminated under the hydrothermal reaction, the specific surface area of the hollow nickel hydroxide can be effectively increased, and the effect of enhancing the specific capacitance is achieved, and the embodiment 3 has the most proper addition mass, so that the optimal result is obtained. The mass ratio of the added comparative example is out of the proper range, so that the specific surface area is greatly influenced, and the specific capacitance result is influenced.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (5)
1. A method for preparing a hollow nickel hydroxide needle-punched microsphere electrode material by taking melamine formaldehyde urea copolycondensation resin microspheres as a template is characterized by comprising the following steps: the method specifically comprises the following steps:
(1) preparation of melamine formaldehyde urea copolycondensation resin microsphere
Dispersing melamine, paraformaldehyde and urea in water, performing ultrasonic treatment for 30min, heating and stirring in an oil bath at 60 ℃ for 30min to fully disperse, performing prepolymerization, adding deionized water and sulfuric acid, fully stirring for 30min, heating at 110 ℃ for 60min, taking out, cooling to room temperature, centrifuging, washing and drying to obtain white melamine-formaldehyde-urea copolycondensation resin microspheres;
(2) preparation of hollow nickel hydroxide needle-punched microspheres
Dispersing melamine formaldehyde urea copolycondensation resin microspheres in a water-alcohol solution, magnetically stirring at 400rpm for 30min, fully dispersing, then adding nickel nitrate hexahydrate and urea, fully stirring for 2h, transferring the obtained solution into a hydrothermal reaction kettle, reacting at 160 ℃ for 10h, then reacting at 100 ℃ for 2h, naturally cooling, centrifugally washing for 3 times, and then carrying out air blast drying at 80 ℃ to obtain hollow nickel hydroxide needle-punched microspheres;
(3) preparation of hollow nickel hydroxide needle-punched microsphere electrode material
And (3) uniformly stirring and mixing the hollow nickel hydroxide needle punched microspheres prepared in the step (2), acetylene black and polytetrafluoroethylene emulsion according to the mass ratio of 80:10:10, drying to be pasty, coating the pasty material on foamed nickel by using the foamed nickel as a current collector, and drying in vacuum at 80 ℃ for 24 hours to finally prepare the hollow nickel hydroxide needle punched microsphere electrode material.
2. The method of claim 1, wherein: in the step (1), the mass ratio of melamine to paraformaldehyde to urea is 1:2: 1.
3. The method of claim 1, wherein: in the step (2), the mass ratio of the melamine formaldehyde urea copolycondensation resin microspheres to the nickel nitrate hexahydrate to the urea is 1: 6-10: 5-10.
4. A hollow nickel hydroxide needle punched microsphere electrode material prepared by the method of any one of claims 1 to 3.
5. Use of a hollow nickel hydroxide needle punched microsphere electrode material according to claim 4 in capacitor electrodes.
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