CN111508730B - Nickel-aluminum double metal hydroxide supercapacitor electrode material and preparation method thereof - Google Patents
Nickel-aluminum double metal hydroxide 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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- 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 a nickel-aluminum double metal hydroxide super capacitor electrode material which comprises the following formula raw materials and components: aniline, potassium persulfate, pyrrole, yttrium doped nickel aluminium double hydroxide. The nickel-aluminum double metal hydroxide supercapacitor electrode material is made of porous Al2O3The hollow microspheres are used as templates to prepare the layered yttrium-doped nickel-aluminum double hydroxide with the hollow structure, the specific surface area is large, the pore structure is rich, the layered yttrium-doped nickel-aluminum double hydroxide can be fully wetted and contacted with electrolyte, more electrochemical active sites are exposed, the yttrium doping reduces the impedance of the nickel-aluminum double hydroxide and promotes the transmission and migration of ions and charges, the surface of the yttrium-doped nickel-aluminum double hydroxide is modified with a layer of aniline-pyrrole copolymer with a shell-core structure, the electrode material is endowed with excellent conductivity, and the electrochemical window is widened.
Description
Technical Field
The invention relates to the technical field of electrode materials of a super capacitor, in particular to a nickel-aluminum double metal hydroxide super capacitor electrode material and a preparation method thereof.
Background
The super capacitor not only has the characteristic of rapid charge and discharge of the capacitor, but also has the energy storage characteristic of the battery, and is a novel energy storage device between the traditional capacitor and the rechargeable battery, compared with the storage battery and the traditional physical capacitor, the super capacitor has the advantages of high power density, long cycle life, wide working temperature limit, no maintenance, green environmental protection and the like, the super capacitor is divided into a double electric layer capacitor and a Faraday quasi capacitor, and the double electric layer capacitor generates stored energy by absorbing pure electrostatic charges on the surface of an electrode; the Faraday quasi-capacitor is mainly characterized in that reversible redox reaction is carried out on the surface and the vicinity of the surface through a Faraday quasi-capacitor active electrode material to generate the Faraday quasi-capacitor, so that the storage and the conversion of energy are realized.
The prior electrode material of the super capacitor mainly comprises carbon material electrode materials, and has the advantages of large specific surface area, abundant pore structures and small internal resistance, such as carbon nanofibers, glassy carbon, carbon nanotubes and the like; the metal oxide and hydroxide electrode materials can rapidly generate reversible electrode reaction, the electrode reaction can penetrate into the electrode, the electric double layer capacitance is large, and the energy density is high, such as ruthenium oxide, cobalt-based and nickel-based hydroxides and the like; the conductive polymer electrode material can form a network type three-dimensional structure, the migration of electrons and ions in the electrode can be completed through the exchange with ions in electrolyte, such as polyaniline, polythiophene and the like, wherein the nickel-aluminum double-metal hydroxide has a two-dimensional layered structure, the specific surface area is large, the double-electric-layer capacitance can be provided, and the nickel-aluminum can be used as an active site of electrochemical reaction through the pseudocapacitance effect, but hydrogen bonds exist among the lamellar structures of the nickel-aluminum double-metal hydroxide, so that the particles are agglomerated and aggregated due to the attraction of the hydrogen bonds, the electrochemical active site is covered, the conductivity of the nickel-aluminum double-metal hydroxide is poor, the electrochemical window is narrow, the reversible proceeding of the electrode reaction is influenced, and the electrochemical energy storage property of the electrode material is influenced.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a nickel-aluminum double metal hydroxide supercapacitor electrode material and a preparation method thereof, which solve the problems of easy agglomeration and aggregation of nickel-aluminum double metal hydroxide and poor conductivity and electrochemical window of nickel-aluminum double metal hydroxide
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: the nickel-aluminum double metal hydroxide supercapacitor electrode material comprises the following formula raw materials in parts by weight: 8-15 parts of aniline, 12-20 parts of potassium persulfate, 6-10 parts of pyrrole and 55-74 parts of yttrium-doped nickel-aluminum double hydroxide.
Preferably, the nickel-cobalt double metal hydroxide is prepared by the following method:
(1) adding distilled water, potassium aluminum sulfate and urea into a reaction bottle, uniformly stirring, heating the solution to 170-plus-one temperature of 200 ℃ in a microwave hydrothermal synthesizer, carrying out microwave hydrothermal reaction for 30-60min, centrifugally washing the solution by using distilled water, drying a solid product, placing the dried solid product in a muffle furnace, heating the solid product at the rate of 2-8 ℃/min to 550-plus-one temperature of 580 ℃, and carrying out heat preservation and calcination for 2-4h to obtain a porous Al-containing calcined product2O3A hollow ball.
(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 1:1-1.5, and adding porous Al2O3Hollow ball, adding Ni (NO) after stirring uniformly3)2、Y(NO3)3And uniformly stirring the solution, urea and hexamethylenetetramine, heating the solution to the temperature of 150 ℃ in a microwave hydrothermal synthesizer, carrying out microwave hydrothermal reaction for 2-6h, respectively carrying out centrifugal washing on the solution by using distilled water and ethanol, and drying a solid product to prepare the yttrium-doped nickel-cobalt double hydroxide.
Preferably, the mass ratio of the potassium aluminum sulfate to the urea in the step (1) is 1: 1.5-3.5.
Preferably, the porous Al in the step (1)2O3Hollow ball, adding Ni (NO) after stirring uniformly3)2、Y(NO3)3The mass ratio of the urea to the hexamethylenetetramine is 1:6.5-8.5:0.21-0.85:7-9: 20-25.
Preferably, microwave hydrothermal synthesis appearance includes instrument main part, the inside fixedly connected with heat preservation of instrument main part, the top fixedly connected with microwave generator of heat preservation, the inside both sides fixedly connected with heating rod of heat preservation, the bottom and the rotary device fixed connection of instrument main part, the inside bearing that is provided with of rotary device, bearing and rotary rod swing joint, the top and the objective table fixed connection of rotary rod, reation kettle has been held to the top of objective table, the surface of objective table is provided with the jack, jack and bolt swing joint, bolt fixedly connected with baffle.
Preferably, the preparation method of the electrode material of the nickel-aluminum double metal hydroxide supercapacitor is as follows:
(1) adding hydrochloric acid solution with the substance amount concentration of 0.8-1.2mol/L into a reaction bottle, adding 8-15 parts of aniline at 0-5 ℃, stirring to dissolve, adding 7-15 parts of potassium persulfate, stirring at a constant speed to react for 4-6h, adding 6-10 parts of pyrrole, stirring at a constant speed to react for 6-10h, drying the solution in vacuum to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to obtain the aniline-pyrrole copolymer with the shell-core structure.
(2) Adding distilled water and aniline-pyrrole copolymer into a reaction bottle, uniformly dispersing by ultrasonic, adding the rest 5 parts of potassium persulfate and 55-74 parts of yttrium-doped nickel-aluminum double hydroxide at 0-5 ℃, stirring at a constant speed for reaction for 5-10h, drying the solution in vacuum to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to prepare the nickel-aluminum double hydroxide supercapacitor electrode material.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the nickel-aluminum double metal hydroxide supercapacitor electrode material is prepared into porous Al through microwave hydrothermal preparation2O3The hollow microspheres are used as templates to prepare the layered yttrium-doped nickel-aluminum double metal hydroxide with the hollow structure, the specific surface area is large, the pore structure is rich, the layered yttrium-doped nickel-aluminum double metal hydroxide can be fully wetted and contacted with electrolyte, more electrochemical active sites are exposed, the impedance of the nickel-aluminum double metal hydroxide is reduced by doping the rare earth element yttrium, the transmission and migration of electrolyte ions and charges in the electrode are promoted, the conductivity of the electrode material is enhanced, and the Faraday redox reaction is promoted to store the charges and electric energy under the synergistic effect.
According to the nickel-aluminum double metal hydroxide supercapacitor electrode material, a layer of aniline-pyrrole copolymer with a shell-core structure is modified on the surface of yttrium-doped nickel-aluminum double metal hydroxide through an in-situ polymerization method, the shell-core aniline-pyrrole copolymer is more favorable for transmission and diffusion of ions and charges, compared with single polyaniline and polypyrrole, the shell-core aniline-pyrrole copolymer is more excellent in conductivity, the nickel-aluminum double metal hydroxide can be completely coated, the shell-core aniline-pyrrole copolymer and the single polyaniline are tightly combined, the electrode material is endowed with excellent conductivity, an electrochemical window is widened, the aniline-pyrrole copolymer can be used for improving the high Faraday pseudocapacitance of the electrode material, and the actual specific capacity of the electrode material is enhanced.
Drawings
FIG. 1 is a schematic front view of an instrument body of a microwave hydrothermal synthesizer;
FIG. 2 is an enlarged schematic view of the stage;
fig. 3 is a schematic view of damper adjustment.
1. An instrument body; 2. a heat-insulating layer; 3. a microwave generator; 4. a heating rod; 5. a rotating device; 6. a bearing; 7. rotating the rod; 8. an object stage; 9. a reaction kettle; 10. a jack; 11. a bolt; 12. and a baffle plate.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: the nickel-aluminum double metal hydroxide supercapacitor electrode material comprises the following formula raw materials in parts by weight: 8-15 parts of aniline, 12-20 parts of potassium persulfate, 6-10 parts of pyrrole and 55-74 parts of yttrium-doped nickel-aluminum double hydroxide.
The preparation method of the nickel-cobalt double metal hydroxide comprises the following steps:
(1) adding distilled water, potassium aluminum sulfate and urea into a reaction bottle, wherein the mass ratio of the two substances is 1:1.5-3.5, uniformly stirring, and then placing the solution into a microwave hydrothermal synthesizer, wherein the microwave hydrothermal synthesizer comprises an instrument main body, a heat preservation layer is fixedly connected inside the instrument main body, a microwave generator is fixedly connected above the heat preservation layer, heating rods are fixedly connected on two sides inside the heat preservation layer, the bottom of the instrument main body is fixedly connected with a rotating device, a bearing is arranged inside the rotating device and movably connected with a rotating rod, the upper part of the rotating rod is fixedly connected with an objective table, a reaction kettle is arranged above the objective table, jacks are arranged on the surface of the objective table and movably connected with bolts, a baffle is fixedly connected with the bolts and heated to 170-, drying the solid product, placing the dried solid product in a muffle furnace, heating to 550-580 ℃ at the heating rate of 2-8 ℃/min, and carrying out heat preservation and calcination for 2-4h to obtain a porous Al product2O3A hollow ball.
(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 1:1-1.5, and adding porous Al2O3Hollow ball, adding Ni (NO) after stirring uniformly3)2、Y(NO3)3Urea and hexamethylenetetramine in a mass ratio of 1:6.5-8.5:0.21-0.85:7-9:20-25, uniformly stirring, heating the solution to 180 ℃ in a microwave hydrothermal synthesizer, carrying out microwave hydrothermal reaction for 2-6h, and respectively using distilled water and ethylene glycol to carry out microwave hydrothermal reaction on the solutionAnd carrying out centrifugal washing on the alcohol, and drying the solid product to prepare the yttrium-doped nickel-cobalt double hydroxide.
The preparation method of the nickel-aluminum double metal hydroxide supercapacitor electrode material comprises the following steps:
(1) adding hydrochloric acid solution with the substance amount concentration of 0.8-1.2mol/L into a reaction bottle, adding 8-15 parts of aniline at 0-5 ℃, stirring to dissolve, adding 7-15 parts of potassium persulfate, stirring at a constant speed to react for 4-6h, adding 6-10 parts of pyrrole, stirring at a constant speed to react for 6-10h, drying the solution in vacuum to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to obtain the aniline-pyrrole copolymer with the shell-core structure.
(2) Adding distilled water and aniline-pyrrole copolymer into a reaction bottle, uniformly dispersing by ultrasonic, adding the rest 5 parts of potassium persulfate and 55-74 parts of yttrium-doped nickel-aluminum double hydroxide at 0-5 ℃, stirring at a constant speed for reaction for 5-10h, drying the solution in vacuum to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to prepare the nickel-aluminum double hydroxide supercapacitor electrode material.
Adding a nickel-aluminum double-metal hydroxide supercapacitor electrode material, a conductive agent acetylene black and a binder polyvinylidene fluoride into an N-methyl pyrrolidone solvent, uniformly stirring, uniformly coating slurry on a foamed nickel current collector, fully drying, preparing a supercapacitor working positive electrode, taking Ag/AgCl as a reference electrode and a platinum sheet as a working electrode, performing cyclic voltammetry test, wherein the scanning speed range is 10-150mV/s and a constant current charging and discharging method is adopted, the current density is 1-20A/g, the electrochemical performance of the supercapacitor working positive electrode is tested, and the cyclic stability performance test is carried out for 10000 cycles under 10-20A/g.
Example 1
(1) Preparation of porous Al2O3Hollow sphere component 1: adding distilled water, potassium aluminum sulfate and urea into a reaction bottle in a mass ratio of 1:1.5, uniformly stirring, and putting the solution into a microwave hydrothermal synthesizer, wherein the microwave hydrothermal synthesizer comprises an instrument main body, a heat-insulating layer fixedly connected in the instrument main body, a microwave generator fixedly connected above the heat-insulating layer, a microwave generator fixedly connected above the microwave generator, a microwave generator and a water tank fixedly connected above the microwave generator, wherein the microwave generator is arranged above the microwave generator, and the microwave generator is connected with the microwave generator and the water tank and is used for generating a microwave energy-saving water-saving agent,The inside both sides fixedly connected with heating rod of heat preservation, the bottom and the rotary device fixed connection of instrument main part, the inside bearing that is provided with of rotary device, bearing and rotary rod swing joint, the top and the objective table fixed connection of rotary rod, reation kettle has been held to the top of objective table, the surface of objective table is provided with the jack, jack and bolt swing joint, bolt fixedly connected with baffle, heat to 170 ℃, carry out microwave hydrothermal reaction 30min, use distilled water to carry out centrifugal washing with solution, place in the muffle furnace after the solid product is dry, the rate of rise of temperature is 2 ℃/min, the rate of rise of temperature to 550 ℃, the heat preservation is calcined for 2h, the calcination product is porous Al promptly2O3Hollow sphere component 1.
(2) Preparing yttrium-doped nickel-cobalt double metal hydroxide 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 1:1, and adding porous Al2O3The hollow ball component 1 is added with Ni (NO) after being evenly stirred3)2、Y(NO3)3The mass ratio of urea to hexamethylenetetramine is 1:6.5:0.21:7:20, the solution is heated to 150 ℃ in a microwave hydrothermal synthesizer after being uniformly stirred, microwave hydrothermal reaction is carried out for 2 hours, the solution is centrifugally washed by distilled water and ethanol respectively, and a solid product is dried to prepare the yttrium-doped nickel-cobalt double hydroxide component 1.
(3) Preparation of aniline-pyrrole copolymer of core-shell structure component 1: adding hydrochloric acid solution with the substance amount concentration of 0.8mol/L into a reaction bottle, adding 8 parts of aniline at 5 ℃, stirring to dissolve, adding 7 parts of potassium persulfate, stirring at a constant speed to react for 4 hours, adding 6 parts of pyrrole, stirring at a constant speed to react for 6 hours, drying the solution in vacuum to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the aniline-pyrrole copolymer component 1 with the shell-core structure.
(4) Preparing a nickel-aluminum double metal hydroxide supercapacitor electrode material 1: adding distilled water and the aniline-pyrrole copolymer component 1 into a reaction bottle, uniformly dispersing by ultrasonic, adding the remaining 5 parts of potassium persulfate and 74 parts of yttrium-doped nickel-aluminum double hydroxide component 1 at 5 ℃, stirring at a constant speed for reaction for 5 hours, drying the solution in vacuum to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to prepare the nickel-aluminum double hydroxide supercapacitor electrode material 1.
(5) Adding a nickel-aluminum double-metal hydroxide supercapacitor electrode material 1, a conductive agent acetylene black and a binder polyvinylidene fluoride into an N-methylpyrrolidone solvent, uniformly stirring, uniformly coating slurry on a foamed nickel current collector, fully drying, preparing to obtain a supercapacitor working positive electrode material 1, taking Ag/AgCl as a reference electrode and a platinum sheet as a working electrode, performing cyclic voltammetry test, testing the electrochemical performance of the supercapacitor working positive electrode by using a specific capacitance of 1636F/g when the current density is 1A/g, testing the cyclic stability performance by using 10000 cycles under 20A/g, and keeping the capacitance at 92.65%.
Example 2
(1) Preparation of porous Al2O3Hollow sphere component 2: adding distilled water, potassium aluminum sulfate and urea into a reaction bottle, wherein the mass ratio of the two substances is 1:1.5, uniformly stirring, and then placing the solution into a microwave hydrothermal synthesizer, wherein the microwave hydrothermal synthesizer comprises an instrument main body, a heat preservation layer is fixedly connected inside the instrument main body, a microwave generator is fixedly connected above the heat preservation layer, heating rods are fixedly connected on two sides inside the heat preservation layer, the bottom of the instrument main body is fixedly connected with a rotating device, a bearing is arranged inside the rotating device and movably connected with a rotating rod, the upper part of the rotating rod is fixedly connected with a carrying platform, a reaction kettle is placed above the carrying platform, a jack is arranged on the surface of the carrying platform and movably connected with a bolt, a baffle is fixedly connected with the bolt, heating is carried out to 170 ℃, carrying out microwave hydrothermal reaction for 60min, centrifugally washing the solution by using distilled water, drying a solid product, and then placing the dried solution into a muffle furnace, the heating rate is 2 ℃/min, the temperature is increased to 580 ℃, the heat preservation and the calcination are carried out for 4h, and the calcination product is porous Al2O3Hollow sphere component 2.
(2) Preparing yttrium-doped nickel-cobalt double metal hydroxide 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 1:1.5, and adding porous Al2O3The hollow ball component 2 is added with Ni (NO) after being evenly stirred3)2、Y(NO3)3The mass ratio of urea to hexamethylenetetramine is 1:6.5:0.45:9:20, the solution is heated to 180 ℃ in a microwave hydrothermal synthesizer after being uniformly stirred, microwave hydrothermal reaction is carried out for 6h, the solution is centrifugally washed by distilled water and ethanol respectively, and a solid product is dried to prepare the yttrium-doped nickel-cobalt double hydroxide component 2.
(3) Preparation of aniline-pyrrole copolymer of core-shell structure component 2: adding hydrochloric acid solution with the substance amount concentration of 1.2mol/L into a reaction bottle, adding 9.5 parts of aniline at 5 ℃, stirring to dissolve, adding 8.5 parts of potassium persulfate, stirring at a constant speed to react for 4 hours, adding 7 parts of pyrrole, stirring at a constant speed to react for 10 hours, drying the solution in vacuum to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the aniline-pyrrole copolymer component 2 with the shell-core structure.
(4) Preparing a nickel-aluminum double metal hydroxide supercapacitor electrode material 2: adding distilled water and the aniline-pyrrole copolymer component 2 into a reaction bottle, uniformly dispersing by ultrasonic, adding the rest 5 parts of potassium persulfate and 70 parts of yttrium-doped nickel-aluminum double hydroxide component 2 at 0 ℃, stirring at a constant speed for reaction for 10 hours, drying the solution in vacuum to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to prepare the nickel-aluminum double hydroxide supercapacitor electrode material 2.
(5) Adding a nickel-aluminum double-metal hydroxide supercapacitor electrode material 2, a conductive agent acetylene black and a binder polyvinylidene fluoride into an N-methylpyrrolidone solvent, uniformly stirring, uniformly coating slurry on a foamed nickel current collector, fully drying, preparing and obtaining a supercapacitor working positive electrode material 2, taking Ag/AgCl as a reference electrode and a platinum sheet as a working electrode, performing cyclic voltammetry test, testing the electrochemical performance of the supercapacitor working positive electrode by using a specific capacitance of 1627F/g when the current density is 1A/g, testing the cyclic stability performance of 10000 cycles under 20A/g, and keeping the capacitance at 94.09%.
Example 3
(1) Preparation of porous Al2O3Hollow sphere component 3: adding distilled water into the reaction bottleThe solution is put in a microwave hydrothermal synthesizer after being uniformly stirred, the microwave hydrothermal synthesizer comprises an instrument main body, a heat preservation layer is fixedly connected inside the instrument main body, a microwave generator is fixedly connected above the heat preservation layer, heating rods are fixedly connected on two sides inside the heat preservation layer, the bottom of the instrument main body is fixedly connected with a rotating device, a bearing is arranged inside the rotating device and movably connected with a rotating rod, the upper part of the rotating rod is fixedly connected with a carrying platform, a reaction kettle is arranged above the carrying platform, a jack is arranged on the surface of the carrying platform and movably connected with a bolt, the bolt is fixedly connected with a baffle plate and is heated to 185 ℃ for carrying out microwave hydrothermal reaction for 45min, the solution is centrifugally washed by using distilled water, a solid product is dried and then put in a muffle furnace, the heating rate is 5 ℃/min, heating to 570 ℃, and carrying out heat preservation and calcination for 3 hours to obtain a calcination product, namely porous Al2O3Hollow sphere fraction 3.
(2) Preparing yttrium-doped nickel-cobalt double metal hydroxide 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 1:1.2, and adding porous Al2O3The hollow ball component 3 is added with Ni (NO) after being evenly stirred3)2、Y(NO3)3The mass ratio of urea to hexamethylenetetramine is 1:7.5:0.65:8:22, the solution is heated to 160 ℃ in a microwave hydrothermal synthesizer after being uniformly stirred, microwave hydrothermal reaction is carried out for 4 hours, the solution is centrifugally washed by distilled water and ethanol respectively, and a solid product is dried to prepare the yttrium-doped nickel-cobalt double hydroxide component 3.
(3) Preparation of aniline-pyrrole copolymer of core-shell structure component 3: adding a hydrochloric acid solution with the substance amount concentration of 1mol/L into a reaction bottle, adding 11 parts of aniline at 2 ℃, stirring to dissolve, adding 11 parts of potassium persulfate, stirring at a constant speed to react for 5 hours, adding 8 parts of pyrrole, stirring at a constant speed to react for 8 hours, drying the solution in vacuum to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the aniline-pyrrole copolymer component 3 with the shell-core structure.
(4) Preparing a nickel-aluminum double metal hydroxide supercapacitor electrode material 3: adding distilled water and the aniline-pyrrole copolymer component 3 into a reaction bottle, uniformly dispersing by ultrasonic, adding the remaining 5 parts of potassium persulfate and 65 parts of yttrium-doped nickel-aluminum double hydroxide component 3 at 2 ℃, stirring at a constant speed for reaction for 8 hours, drying the solution in vacuum to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to prepare the nickel-aluminum double hydroxide supercapacitor electrode material 3.
(5) Adding a nickel-aluminum double-metal hydroxide supercapacitor electrode material 3, a conductive agent acetylene black and a binder polyvinylidene fluoride into an N-methylpyrrolidone solvent, uniformly stirring, uniformly coating slurry on a foamed nickel current collector, fully drying, preparing and obtaining a supercapacitor working positive electrode material 3, taking Ag/AgCl as a reference electrode and a platinum sheet as a working electrode, performing cyclic voltammetry test, testing the electrochemical performance of the supercapacitor working positive electrode by using a specific capacitance of 1591F/g when the current density is 1A/g, testing the cyclic stability performance by using 10000 cycles under 20A/g, and keeping the capacitance at 91.68%.
Example 4
(1) Preparation of porous Al2O3Hollow sphere component 4: adding distilled water, potassium aluminum sulfate and urea into a reaction bottle, wherein the mass ratio of the two substances is 1:3.5, uniformly stirring, and then placing the solution into a microwave hydrothermal synthesizer, wherein the microwave hydrothermal synthesizer comprises an instrument main body, a heat preservation layer is fixedly connected inside the instrument main body, a microwave generator is fixedly connected above the heat preservation layer, heating rods are fixedly connected on two sides inside the heat preservation layer, the bottom of the instrument main body is fixedly connected with a rotating device, a bearing is arranged inside the rotating device and movably connected with a rotating rod, the upper part of the rotating rod is fixedly connected with a carrying platform, a reaction kettle is placed above the carrying platform, a jack is arranged on the surface of the carrying platform and movably connected with a bolt, a baffle is fixedly connected with the bolt, heating is carried out to 170 ℃, carrying out microwave hydrothermal reaction for 60min, centrifugally washing the solution by using distilled water, drying a solid product, and then placing the dried solution into a muffle furnace, the heating rate is 8 ℃/min, the temperature is increased to 550 ℃, the heat preservation and the calcination are carried out for 3h, and the calcination product is porous Al2O3Hollow sphere fraction 4.
(2) Preparation of yttrium-doped nickel cobalt double metal hydroxide 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 1:1, and adding porous Al2O3The hollow ball component 4 is added with Ni (NO) after being evenly stirred3)2、Y(NO3)3The mass ratio of urea to hexamethylenetetramine is 1:6.5:0.7:9:20, the solution is heated to 150 ℃ in a microwave hydrothermal synthesizer after being uniformly stirred, microwave hydrothermal reaction is carried out for 6h, the solution is centrifugally washed by distilled water and ethanol respectively, and a solid product is dried to prepare the yttrium-doped nickel-cobalt double hydroxide component 4.
(3) Preparation of aniline-pyrrole copolymer of core-shell structure component 4: adding hydrochloric acid solution with the substance amount concentration of 1.2mol/L into a reaction bottle, adding 13.5 parts of aniline at 5 ℃, stirring to dissolve, adding 12 parts of potassium persulfate, stirring at a constant speed to react for 4 hours, adding 9 parts of pyrrole, stirring at a constant speed to react for 10 hours, drying the solution in vacuum to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the aniline-pyrrole copolymer component 4 with the shell-core structure.
(4) Preparing a nickel-aluminum double metal hydroxide supercapacitor electrode material 4: adding distilled water and the aniline-pyrrole copolymer component 4 into a reaction bottle, after uniform ultrasonic dispersion, adding the remaining 5 parts of potassium persulfate and 60.5 parts of yttrium-doped nickel-aluminum double hydroxide component 4 at 5 ℃, stirring at a constant speed for reaction for 5 hours, drying the solution in vacuum to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to prepare the nickel-aluminum double hydroxide supercapacitor electrode material 4.
(5) Adding a nickel-aluminum double-metal hydroxide supercapacitor electrode material 4, a conductive agent acetylene black and a binder polyvinylidene fluoride into an N-methylpyrrolidone solvent, uniformly stirring, uniformly coating slurry on a foamed nickel current collector, fully drying, preparing and obtaining a supercapacitor working positive electrode material 4, taking Ag/AgCl as a reference electrode and a platinum sheet as a working electrode, performing cyclic voltammetry test, testing the electrochemical performance of the supercapacitor working positive electrode by using a specific capacitance of 1603F/g when the current density is 4A/g, testing the cyclic stability performance by using 10000 cycles under 20A/g, and keeping the capacitance at 93.58%.
Example 5
(1) Preparation of porous Al2O3Hollow sphere component 5: adding distilled water, potassium aluminum sulfate and urea into a reaction bottle, wherein the mass ratio of the two substances is 1:3.5, uniformly stirring, and then placing the solution into a microwave hydrothermal synthesizer, wherein the microwave hydrothermal synthesizer comprises an instrument main body, a heat preservation layer is fixedly connected inside the instrument main body, a microwave generator is fixedly connected above the heat preservation layer, heating rods are fixedly connected on two sides inside the heat preservation layer, the bottom of the instrument main body is fixedly connected with a rotating device, a bearing is arranged inside the rotating device and movably connected with a rotating rod, the upper part of the rotating rod is fixedly connected with a carrying platform, a reaction kettle is placed above the carrying platform, a jack is arranged on the surface of the carrying platform and movably connected with a bolt, a baffle is fixedly connected with the bolt, heating is carried out to 200 ℃, carrying out microwave hydrothermal reaction for 60min, centrifugally washing the solution by using distilled water, drying a solid product, and then placing the dried solution into a muffle furnace, the heating rate is 8 ℃/min, the temperature is increased to 580 ℃, the heat preservation and the calcination are carried out for 4h, and the calcination product is porous Al2O3Hollow sphere fraction 5.
(2) Preparing yttrium-doped nickel-cobalt double metal hydroxide 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 1:1.5, and adding porous Al2O3The hollow ball component 5 is added with Ni (NO) after being evenly stirred3)2、Y(NO3)3The mass ratio of urea to hexamethylenetetramine is 1:8.5:0.85:9:25, the solution is heated to 180 ℃ in a microwave hydrothermal synthesizer after being uniformly stirred, microwave hydrothermal reaction is carried out for 6 hours, the solution is centrifugally washed by distilled water and ethanol respectively, and a solid product is dried to prepare the yttrium-doped nickel-cobalt double hydroxide component 5.
(3) Preparation of aniline-pyrrole copolymer of core-shell structure component 5: adding hydrochloric acid solution with the substance amount concentration of 1.2mol/L into a reaction bottle, adding 15 parts of aniline at 0 ℃, stirring to dissolve, adding 15 parts of potassium persulfate, stirring at a constant speed to react for 6 hours, adding 10 parts of pyrrole, stirring at a constant speed to react for 10 hours, drying the solution in vacuum to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the aniline-pyrrole copolymer component 5 with the shell-core structure.
(4) Preparing a nickel-aluminum double metal hydroxide supercapacitor electrode material 5: adding distilled water and the aniline-pyrrole copolymer component 5 into a reaction bottle, uniformly dispersing by ultrasonic, adding the rest 5 parts of potassium persulfate and 55 parts of yttrium-doped nickel-aluminum double hydroxide component 5 at 0 ℃, stirring at a constant speed for reaction for 10 hours, drying the solution in vacuum to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to prepare the nickel-aluminum double hydroxide supercapacitor electrode material 5.
(5) Adding a nickel-aluminum double-metal hydroxide supercapacitor electrode material 5, a conductive agent acetylene black and a binder polyvinylidene fluoride into an N-methylpyrrolidone solvent, uniformly stirring, uniformly coating slurry on a foamed nickel current collector, fully drying, and preparing to obtain a supercapacitor working positive electrode material 5, wherein Ag/AgCl is a reference electrode, a platinum sheet is a working electrode, performing cyclic voltammetry test, the specific capacitance is 1594F/g when the current density is 1A/g, the electrochemical performance of the supercapacitor working positive electrode is tested, the cyclic stability performance test is performed for 10000 cycles under 20A/g, and the capacitance retention rate is 92.96%.
In summary, the nickel-aluminum double metal hydroxide supercapacitor electrode material is prepared into porous Al through microwave hydrothermal preparation2O3The hollow microspheres are used as templates to prepare the layered yttrium-doped nickel-aluminum double metal hydroxide with the hollow structure, the specific surface area is large, the pore structure is rich, the layered yttrium-doped nickel-aluminum double metal hydroxide can be fully wetted and contacted with electrolyte, more electrochemical active sites are exposed, the impedance of the nickel-aluminum double metal hydroxide is reduced by doping the rare earth element yttrium, the transmission and migration of electrolyte ions and charges in the electrode are promoted, the conductivity of the electrode material is enhanced, and the Faraday redox reaction is promoted to store the charges and electric energy under the synergistic effect.
The surface of yttrium-doped nickel-aluminum double metal hydroxide is modified with a layer of aniline-pyrrole copolymer with a shell-core structure through an in-situ polymerization method, the shell-core aniline-pyrrole copolymer is more favorable for transmission and diffusion of ions and charges, compared with single polyaniline and polypyrrole, the shell-core aniline-pyrrole copolymer is more excellent in conductivity, the nickel-aluminum double metal hydroxide can be completely coated, the shell-core aniline-pyrrole copolymer and the single polyaniline are tightly combined, the electrode material is endowed with excellent conductivity, an electrochemical window is widened, and the aniline-pyrrole copolymer can improve higher faradaic pseudo capacitance for the electrode material and enhance the actual specific capacity of the electrode material.
Claims (4)
1. The nickel-aluminum double metal hydroxide supercapacitor electrode material comprises the following formula raw materials and components in parts by weight, and is characterized in that: 8-15 parts of aniline, 12-20 parts of potassium persulfate, 6-10 parts of pyrrole and 55-74 parts of yttrium-doped nickel-aluminum double hydroxide;
the preparation method of the yttrium-doped nickel-aluminum double metal hydroxide comprises the following steps: (1) adding aluminum potassium sulfate and urea into a distilled water solvent, uniformly stirring, heating the solution to 170-200 ℃ in a microwave hydrothermal synthesizer, carrying out microwave hydrothermal reaction for 30-60min, centrifugally washing and drying, placing a solid product in a muffle furnace at the temperature rise rate of 2-8 ℃/min, heating to 550-580 ℃, carrying out heat preservation and calcination for 2-4h, wherein the calcined product is porous Al2O3A hollow ball; (2) adding porous Al into a mixed solvent of distilled water and ethanol with the volume ratio of 1:1-1.52O3Hollow sphere, Ni (NO)3)2、Y(NO3)3Uniformly stirring urea and hexamethylenetetramine, heating the solution to 150-180 ℃ in a microwave hydrothermal synthesizer, carrying out microwave hydrothermal reaction for 2-6h, centrifugally washing and drying to prepare the yttrium-doped nickel-aluminum double metal hydroxide;
the preparation method of the nickel-aluminum double metal hydroxide supercapacitor electrode material comprises the following steps: (1) adding 8-15 parts of aniline and 7-15 parts of potassium persulfate into hydrochloric acid solution with the mass concentration of 0.8-1.2mol/L at 0-5 ℃, reacting for 4-6h, then adding 6-10 parts of pyrrole, reacting for 6-10h, removing the solvent, washing and drying to prepare the aniline-pyrrole copolymer with the shell-core structure; (2) adding aniline-pyrrole copolymer into a distilled water solvent, uniformly dispersing by ultrasonic, adding the remaining 5 parts of potassium persulfate and 55-74 parts of yttrium-doped nickel-aluminum double metal hydroxide at 0-5 ℃, reacting for 5-10h, removing the solvent, washing and drying to prepare the nickel-aluminum double metal hydroxide supercapacitor electrode material.
2. The nickel-aluminum double metal hydroxide supercapacitor electrode material according to claim 1, characterized in that: wherein the mass ratio of the aluminum potassium sulfate to the urea is 1: 1.5-3.5.
3. The nickel-aluminum double metal hydroxide supercapacitor electrode material according to claim 1, characterized in that: wherein the porous Al2O3Hollow sphere, Ni (NO)3)2、Y(NO3)3The mass ratio of the urea to the hexamethylenetetramine is 1:6.5-8.5:0.21-0.85:7-9: 20-25.
4. The nickel-aluminum double metal hydroxide supercapacitor electrode material according to claim 1, characterized in that: microwave hydrothermal synthesis appearance includes instrument main part, the inside fixedly connected with heat preservation of instrument main part, the top fixedly connected with microwave generator of heat preservation, the inside both sides fixedly connected with heating rod of heat preservation, the bottom and the rotary device fixed connection of instrument main part, the inside bearing that is provided with of rotary device, bearing and rotary rod swing joint, the top and the objective table fixed connection of rotary rod, reation kettle has been held to the top of objective table, the surface of objective table is provided with the jack, jack and bolt swing joint, bolt fixedly connected with baffle.
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