CN110767463B - Biomass-based carbon material coated CoAl-LDH supercapacitor material and preparation method thereof - Google Patents
Biomass-based carbon material coated CoAl-LDH supercapacitor material and preparation method thereof Download PDFInfo
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- 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
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- 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
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- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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Abstract
The invention relates to the technical field of super capacitors, and discloses a biomass-based carbon material coated CoAl-LDH super capacitor material and a preparation method thereof, wherein the biomass-based carbon material coated CoAl-LDH super capacitor material comprises the following formula raw materials: N/P-doped chitosan-based porous carbon and Al2O3Hollow microspheres, CoCl2Urea, cetyl trimethyl ammonium bromide. The biomass-based carbon material coated CoAl-LDH supercapacitor material and the preparation method thereof, Al2O3The hollow microspheres have large specific surface area, provide a large number of redox reaction active sites for electrode reaction, have small particle diameter of the Co-Al double-metal hydroxide, shorten the diffusion distance of ions, and form a large number of radial pore canals in porous carbon formed by N/P doping, so that the Co-Al double-metal hydroxide is uniformly loaded on the porous carbon material, the aggregation of the double-metal hydroxide into macromolecules is avoided, a conductive interface is formed between the N/P doped porous carbon and the Co-Al double-metal hydroxide, and the diffusion and migration rates of ions and charges between the inner pores of the porous carbon material and electrolyte are improved.
Description
Technical Field
The invention relates to the technical field of super capacitors, in particular to a biomass-based carbon material coated CoAl-LDH super capacitor material and a preparation method thereof.
Background
The super capacitor is a novel energy storage device between a traditional capacitor and a rechargeable battery, not only has the characteristic of rapid charge and discharge of the capacitor, but also has the energy storage characteristic of the rechargeable battery, the super capacitor can be divided into a metal oxide electrode super capacitor, an organic polymer electrode super capacitor and a carbon electrode double-layer super capacitor according to the difference of electrode materials, and compared with a storage battery and a traditional physical capacitor, the super capacitor has the advantages of high power density, long cycle life, wide working temperature limit, less pollution and the like.
At present, the material of the super capacitor mainly comprises an active carbon material, a carbon nano tube, an active carbon fiber, graphene, a metal oxide material and the like, layered double hydroxides can be used as an electrode material to be applied to the super capacitor, the specific capacitance is good, but the conductivity and the electrochemical stability of the double hydroxides are poor, the energy density and the electrochemical cycle stability of the super capacitor are reduced, the particles of the double hydroxides are low, the specific surface area is not high, the double hydroxides are easy to agglomerate in an electrolyte, the diffusion and migration processes of ions in the electrode material and the electrolyte are inhibited, and the specific capacitance and the rate capability of the electrode material are reduced.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a biomass-based carbon material coated CoAl-LDH supercapacitor material and a preparation method thereof, solves the problems of poor conductivity and electrochemical stability of the existing double-metal hydroxide supercapacitor material, and simultaneously solves the problems that the double-metal hydroxide is easy to agglomerate in electrolyte, the diffusion and migration of ions in an electrode material and the electrolyte are inhibited, and the specific capacitance and the rate capability of the electrode material are reduced.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a biomass-based carbon material coated CoAl-LDH supercapacitor material and a preparation method thereof comprise the following formula raw materials in parts by weight: 48-70 parts of N/P-doped chitosan-based porous carbon and 2-4 parts of Al2O3Hollow microsphere, 10-20 parts of CoCl212-18 parts of urea and 6-10 parts of hexadecyl trimethyl ammonium bromide.
Preferably, the preparation method of the N/P-doped chitosan-based porous carbon comprises the following steps:
(1) adding a proper amount of distilled water and absolute ethyl alcohol into a reaction bottle, wherein the volume ratio of the distilled water to the absolute ethyl alcohol is 2-2.5:1, sequentially adding L-alanine and chitosan, slowly adding an esterification catalyst concentrated sulfuric acid while stirring at a constant speed, transferring the solution into a hydrothermal automatic reaction kettle, heating to 130-140 ℃, uniformly stirring for reaction for 10-12 hours, adding a sodium hydroxide solution while stirring after the reaction is finished, adjusting the pH to be neutral, performing vacuum filtration on the solution to remove the solvent, sequentially washing a solid product by using a proper amount of distilled water and absolute ethyl alcohol, and fully drying to obtain the esterified chitosan.
(2) Adding a proper amount of distilled water into a reaction bottle, slowly adding dilute hydrochloric acid to adjust the pH value to 3-4, then adding esterified chitosan, stirring at a constant speed, then adding a proper amount of absolute ethyl alcohol, a condensing agent of diisopropylcarbodiimide, guanidine phosphate and creatine phosphate sodium, wherein the volume ratio of the distilled water to the absolute ethyl alcohol is 1:3-4, transferring the solution into a hydrothermal automatic reaction kettle, heating to 130 ℃ and 140 ℃, stirring at a constant speed for self-polymerization reaction for 25-30 hours, cooling the solution to room temperature, slowly adding a sodium hydroxide solution, adjusting the pH value to be neutral, carrying out vacuum filtration on the solution, removing the solvent, and then washing the solid product by sequentially using a proper amount of distilled water and the absolute ethyl alcohol to obtain the amidated phosphate chitosan.
(3) Weighing a certain amount of amido phosphate chitosan, placing the mixture in an atmosphere resistance furnace, and introducing high-purity N2Calcining at the heating rate of 10 ℃/min for 3-5h at the temperature of 920-.
Preferably, the mass ratio of the L-alanine to the chitosan to the concentrated sulfuric acid is 10-15:1: 0.05-0.1.
Preferably, the mass ratio of the esterified chitosan to the guanidine phosphate to the creatine phosphate sodium and the diisopropylcarbodiimide is 1:8-10:6-8: 2-3.
Preferably, the preparation method of the biomass-based carbon material coated CoAl-LDH supercapacitor material comprises the following steps:
(1) adding distilled water, absolute ethyl alcohol, polyoxyethylene and propylene oxide solution into a reaction bottle, wherein the mass ratio of the distilled water to the absolute ethyl alcohol to the polyoxyethylene to the propylene oxide solution is 50-55:60-70:1:65-70, stirring at a constant speed for 1-3h, and adding a proper amount of AlCl3Stirring at constant speed for reaction for 2-5h, removing the solvent from the solution by vacuum filtration, placing the solid product in a resistance furnace at a heating rate of 5-10 ℃/min, and calcining at 650-670 ℃ for 2-4h to obtain Al2O3Hollow microspheres.
(2) Adding a proper amount of distilled water into a reaction bottle, and then adding 2-4 parts of Al2O3Hollow microsphere, 10-20 parts of CoCl2And 6-10 parts of hexadecyl trimethyl ammonium bromide, placing a reaction bottle in an ultrasonic dispersion instrument, heating to 50-60 ℃, performing ultrasonic dispersion treatment for 1-2 hours, adding 12-18 parts of urea, transferring the solution into a hydrothermal automatic reaction kettle after uniform stirring, heating to 210-220 ℃, performing uniform stirring reaction for 4-5 hours, cooling the solution to room temperature, performing vacuum filtration to remove the solvent, washing the solid product by using a proper amount of distilled water and absolute ethyl alcohol, and fully drying to prepare the Co-Al double metal hydroxide.
(3) And (3) adding a proper amount of distilled water into a reaction bottle, sequentially adding 48-70 parts of N/P-doped chitosan-based porous carbon and the Co-Al double metal hydroxide prepared in the step (2), placing the reaction bottle in an ultrasonic disperser, heating to 50-60 ℃, carrying out ultrasonic dispersion treatment for 4-5 hours at the ultrasonic frequency of 20-25KHz, removing the solvent from the solution through vacuum filtration, and completely drying to obtain the biomass-based carbon material coated CoAl-LDH supercapacitor material.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the biomass-based carbon material coated CoAl-LDH supercapacitor material and the preparation method thereof use Co-Al double metal hydroxide as the matrix component of the electrode material of the supercapacitor, and Al2O3The hollow microspheres have large specific surface area, provide a large number of oxidation-reduction reaction active sites for electrode reaction, increase charge storage, and further enhance the specific capacitance of the supercapacitor, and the Co-Al double metal hydroxide particles hydrothermally synthesized by the urea hydrolysis method have small pore diameter of only 2-4um, and a large number of pore channel structures are formed among the particles, so that a transmission channel is provided for ions in an electrode material, and the diffusion distance is shortened, thereby improving the rate capability of the electrode material.
The biomass-based carbon material-coated CoAl-LDH supercapacitor material and the preparation method thereof are characterized in that N/P-doped chitosan-based porous carbon is used for coating Co-Al bimetallic hydroxide, L-alanine, guanidine phosphate, creatine phosphate sodium and chitosan are polymerized into macromolecules with a branched three-dimensional structure through esterification reaction and amidation reaction, a large number of pore canal structures are formed among the macromolecules, the porous carbon material formed by calcination has a huge specific surface and a rich pore structure, and the porous carbon formed by N/P doping forms a complex mesoporous structure on the surface and a large number of radial pore canals inside, so that the Co-Al bimetallic hydroxide is uniformly loaded into the internal pores of the porous carbon material, the aggregation of the bimetallic hydroxide into macromolecules is avoided, and more active sites of redox reaction are exposed, the specific capacitance of the super capacitor is enhanced, the conductivity of the N/P doped porous carbon is better, a conductive interface is formed between Co-Al double metal hydroxides, the diffusion and migration rates of ions and charges between the internal pores of the porous carbon material and the electrolyte are improved, and the power density of the super capacitor and the rate capability of the electrode material are enhanced.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a biomass-based carbon material coated CoAl-LDH supercapacitor material and a preparation method thereof comprise the following formula raw materials in parts by weight: 48-70 parts of N/P-doped chitosan-based porous carbon and 2-4 parts of Al2O3Hollow microsphere, 10-20 parts of CoCl212-18 parts of urea and 6-10 parts of hexadecyl trimethyl ammonium bromide.
The preparation method of the N/P-doped chitosan-based porous carbon comprises the following steps:
(1) adding a proper amount of distilled water and absolute ethyl alcohol into a reaction bottle, wherein the volume ratio of the distilled water to the absolute ethyl alcohol is 2-2.5:1, sequentially adding L-alanine and chitosan, slowly adding an esterification catalyst concentrated sulfuric acid while stirring at a constant speed, wherein the mass ratio of the L-alanine to the chitosan to the concentrated sulfuric acid is 10-15:1:0.05-0.1, transferring the solution into a hydrothermal automatic reaction kettle, heating to 140 ℃, stirring at a constant speed for reaction for 10-12h, adding a sodium hydroxide solution while stirring after the reaction is finished, adjusting the pH value to be neutral, performing vacuum filtration on the solution to remove the solvent, sequentially using a proper amount of distilled water and absolute ethyl alcohol to wash a solid product, and fully drying to obtain the esterified chitosan.
(2) Adding a proper amount of distilled water into a reaction bottle, slowly adding dilute hydrochloric acid to adjust the pH value to 3-4, then adding esterified chitosan, stirring at a constant speed, adding a proper amount of absolute ethyl alcohol, a condensing agent of diisopropylcarbodiimide, guanidine phosphate and sodium creatine phosphate, wherein the mass ratio of the esterified chitosan to the guanidine phosphate to the sodium creatine phosphate to the diisopropylcarbodiimide is 1:8-10:6-8:2-3, the volume ratio of the distilled water to the absolute ethyl alcohol is 1:3-4, transferring the solution into a hydrothermal automatic reaction kettle, heating to 130 ℃. 140 ℃, stirring at a constant speed to carry out self-polymerization reaction for 25-30h, cooling the solution to room temperature, slowly adding a sodium hydroxide solution, adjusting the pH value to be neutral, carrying out vacuum filtration on the solution to remove a solvent, and then sequentially using a proper amount of distilled water and the absolute ethyl alcohol to wash a solid product, obtaining the amido phosphate ester chitosan.
(3) Weighing a certain amount of amido phosphate chitosan, placing the mixture in an atmosphere resistance furnace, and introducing high-purity N2Calcining at the heating rate of 10 ℃/min for 3-5h at the temperature of 920-.
The preparation method of the biomass-based carbon material coated CoAl-LDH supercapacitor material comprises the following steps:
(1) adding distilled water, absolute ethyl alcohol, polyoxyethylene and propylene oxide solution into a reaction bottle, wherein the mass ratio of the distilled water to the absolute ethyl alcohol to the polyoxyethylene to the propylene oxide solution is 50-55:60-70:1:65-70, stirring at a constant speed for 1-3h, and adding a proper amount of AlCl3Stirring at constant speed for reaction for 2-5h, removing the solvent from the solution by vacuum filtration, placing the solid product in a resistance furnace at a heating rate of 5-10 ℃/min, and calcining at 650-670 ℃ for 2-4h to obtain Al2O3Hollow microspheres.
(2) Adding a proper amount of distilled water into a reaction bottle, and then adding 2-4 parts of Al2O3Hollow microsphere, 10-20 parts of CoCl2And 6-10 parts of hexadecyl trimethyl ammonium bromide, placing a reaction bottle in an ultrasonic dispersion instrument, heating to 50-60 ℃, performing ultrasonic dispersion treatment for 1-2 hours, adding 12-18 parts of urea, transferring the solution into a hydrothermal automatic reaction kettle after uniform stirring, heating to 210-220 ℃, performing uniform stirring reaction for 4-5 hours, cooling the solution to room temperature, performing vacuum filtration to remove the solvent, washing the solid product by using a proper amount of distilled water and absolute ethyl alcohol, and fully drying to prepare the Co-Al double metal hydroxide.
(3) And (3) adding a proper amount of distilled water into a reaction bottle, sequentially adding 48-70 parts of N/P-doped chitosan-based porous carbon and the Co-Al double metal hydroxide prepared in the step (2), placing the reaction bottle in an ultrasonic disperser, heating to 50-60 ℃, carrying out ultrasonic dispersion treatment for 4-5 hours at the ultrasonic frequency of 20-25KHz, removing the solvent from the solution through vacuum filtration, and completely drying to obtain the biomass-based carbon material coated CoAl-LDH supercapacitor material.
Example 1:
(1) preparation of esterified Shell Polymer 1: adding an appropriate amount of distilled water and absolute ethyl alcohol into a reaction bottle, wherein the volume ratio of the distilled water to the absolute ethyl alcohol is 2:1, sequentially adding L-alanine and chitosan, slowly adding esterification catalyst concentrated sulfuric acid while stirring at a constant speed, the mass ratio of the L-alanine to the chitosan to the concentrated sulfuric acid is 10:1:0.05, transferring the solution into a hydrothermal automatic reaction kettle, heating to 130 ℃, reacting for 10 hours while stirring at a constant speed, adding a sodium hydroxide solution while stirring after the reaction is finished, adjusting the pH to be neutral, carrying out vacuum filtration on the solution, removing the solvent, sequentially washing a solid product by using an appropriate amount of distilled water and absolute ethyl alcohol, and fully drying to obtain an esterified chitosan compound 1.
(2) Preparation of an amidated phosphate ester chitosan compound 1: adding a proper amount of distilled water into a reaction bottle, slowly adding diluted hydrochloric acid to adjust the pH value to 4, then adding an esterified chitosan compound 1, uniformly stirring, adding a proper amount of absolute ethyl alcohol, a condensing agent of diisopropyl carbodiimide, guanidine phosphate and sodium creatine phosphate, wherein the mass ratio of the esterified chitosan compound 1 to the guanidine phosphate to the sodium creatine phosphate to the diisopropyl carbodiimide is 1:8:6:2, the volume ratio of the distilled water to the absolute ethyl alcohol is 1:3, transferring the solution into a hydrothermal automatic reaction kettle, heating to 130 ℃, uniformly stirring to carry out self-polymerization reaction for 25 hours, cooling the solution to room temperature, slowly adding a sodium hydroxide solution, adjusting the pH value to neutrality, carrying out vacuum filtration on the solution, removing the solvent, and sequentially washing the solid product by using a proper amount of distilled water and the absolute ethyl alcohol to obtain the amidated phosphate ester chitosan compound 1.
(3) Preparing an N/P-doped chitosan-based porous component 1: weighing a certain amount of the amidated phosphate chitosan compound 1, placing the amidated phosphate chitosan compound in an atmosphere resistance furnace, and introducing high-purity N2Calcining at the heating rate of 10 ℃/min for 3h at 920 ℃, and annealing at 920 ℃ for 2h to obtain the N/P-doped chitosan-based porous component 1.
(4) Preparation of Al2O3Hollow microspheres 1: adding distilled water, absolute ethyl alcohol, polyoxyethylene and propylene oxide solution into a reaction bottle, wherein the mass ratio of the distilled water to the absolute ethyl alcohol to the polyoxyethylene to the propylene oxide solution is 50:60:1:65, stirring at a constant speed for 1 hour, and adding a proper amount of AlCl3Stirring at constant speed for reaction for 2h, removing the solvent from the solution by vacuum filtration, placing the solid product in a resistance furnace at the heating rate of 5 ℃/min, and calcining at 650 ℃ for 2h to prepare Al2O3Hollow microspheres 1.
(5) Preparation of Co-Al double hydroxide 1: adding a proper amount of distilled water into a reaction bottle, and then adding 2 parts of Al2O3Hollow microsphere 1, 10 parts CoCl2And 6 parts of hexadecyl trimethyl ammonium bromide, placing a reaction bottle in an ultrasonic disperser, heating to 50 ℃, performing ultrasonic dispersion treatment for 1h, adding 12 parts of urea, stirring at a constant speed, transferring the solution into a hydrothermal automatic reaction kettle, heating to 210 ℃, stirring at a constant speed for reaction for 4h, cooling the solution to room temperature, performing vacuum filtration to remove the solvent, washing the solid product by using a proper amount of distilled water and absolute ethyl alcohol, and fully drying to prepare the Co-Al double metal hydroxide 1.
(6) Preparing a biomass-based carbon material coated CoAl-LDH supercapacitor material 1: adding a proper amount of distilled water into a reaction bottle, sequentially adding 70 parts of N/P-doped chitosan-based porous carbon component 1 and the Co-Al double metal hydroxide 1 prepared in the step (2), placing the reaction bottle in an ultrasonic disperser, heating to 50 ℃, carrying out ultrasonic dispersing treatment for 4 hours at the ultrasonic frequency of 20KHz, removing the solvent from the solution through vacuum filtration, and completely drying to obtain the biomass-based carbon material coated CoAl-LDH super capacitor material 1.
Example 2:
(1) preparation of esterified Shell Polymer 2: adding an appropriate amount of distilled water and absolute ethyl alcohol into a reaction bottle, wherein the volume ratio of the distilled water to the absolute ethyl alcohol is 2:1, sequentially adding L-alanine and chitosan, slowly adding esterification catalyst concentrated sulfuric acid while stirring at a constant speed, the mass ratio of the L-alanine to the chitosan to the concentrated sulfuric acid is 15:1:0.05, transferring the solution into a hydrothermal automatic reaction kettle, heating to 130 ℃, reacting for 10 hours while stirring at a constant speed, adding a sodium hydroxide solution while stirring after the reaction is finished, adjusting the pH to be neutral, carrying out vacuum filtration on the solution, removing the solvent, sequentially washing a solid product by using an appropriate amount of distilled water and absolute ethyl alcohol, and fully drying to obtain an esterified chitosan compound 2.
(2) Preparation of an amidated phosphate ester chitosan compound 2: adding a proper amount of distilled water into a reaction bottle, slowly adding diluted hydrochloric acid to adjust the pH value to 3, then adding an esterified chitosan compound 2, uniformly stirring, adding a proper amount of absolute ethyl alcohol, a condensing agent of diisopropyl carbodiimide, guanidine phosphate and sodium creatine phosphate, wherein the mass ratio of the esterified chitosan compound 2 to the guanidine phosphate to the sodium creatine phosphate to the diisopropyl carbodiimide is 1:8:8:2, the volume ratio of the distilled water to the absolute ethyl alcohol is 1:3, transferring the solution into a hydrothermal automatic reaction kettle, heating to 130 ℃, uniformly stirring to perform self-polymerization reaction for 30 hours, cooling the solution to room temperature, slowly adding a sodium hydroxide solution, adjusting the pH value to neutrality, performing vacuum filtration on the solution, removing the solvent, and sequentially washing the solid product by using a proper amount of distilled water and the absolute ethyl alcohol to obtain the amidated phosphate ester chitosan compound 2.
(3) Preparing an N/P-doped chitosan-based porous component 2: weighing a certain amount of the amidated phosphate chitosan compound 2, placing the amidated phosphate chitosan compound in an atmosphere resistance furnace, and introducing high-purity N2Calcining at the heating rate of 10 ℃/min for 5h at 920 ℃, and annealing at 920 ℃ for 2h to obtain the N/P-doped chitosan-based porous component 2.
(4) Preparation of Al2O3Hollow microspheres 2: adding distilled water, absolute ethyl alcohol, polyoxyethylene and propylene oxide solution into a reaction bottle, wherein the mass ratio of the distilled water to the absolute ethyl alcohol to the polyoxyethylene to the propylene oxide solution is 50:70:1:65, stirring at a constant speed for 3 hours, and adding a proper amount of AlCl3Stirring at constant speed for reaction for 2h, removing the solvent from the solution by vacuum filtration, placing the solid product in a resistance furnace at a heating rate of 10 ℃/min, and calcining at 670 ℃ for 2h to prepare Al2O3Hollow microspheres 2.
(5) Preparation of Co-Al double hydroxide 2: adding a proper amount of distilled water into a reaction bottle, and then adding 2.5 parts of Al2O3Hollow microsphere 2, 13.5 parts CoCl2And 7 parts of hexadecyl trimethyl ammonium bromide, placing a reaction bottle in an ultrasonic disperser, heating to 50 ℃, performing ultrasonic dispersion treatment for 2 hours, adding 14 parts of urea, stirring at constant speed, transferring the solution into a hydrothermal automatic reaction kettle, heating to 210 ℃, stirring at constant speed, reacting for 5 hours, and mixingAnd cooling the solution to room temperature, carrying out vacuum filtration to remove the solvent, washing the solid product by using a proper amount of distilled water and absolute ethyl alcohol, and fully drying to prepare the Co-Al double metal hydroxide 2.
(6) Preparing a biomass-based carbon material coated CoAl-LDH supercapacitor material 2: adding a proper amount of distilled water into a reaction bottle, sequentially adding 63 parts of N/P-doped chitosan-based porous carbon component 2 and the Co-Al double metal hydroxide 2 prepared in the step (2), placing the reaction bottle in an ultrasonic disperser, heating to 50 ℃, performing ultrasonic dispersion treatment for 4 hours at the ultrasonic frequency of 20KHz, removing the solvent from the solution through vacuum filtration, and completely drying to obtain the biomass-based carbon material coated CoAl-LDH supercapacitor material 2.
Example 3:
(1) preparation of esterified Shell Polymer 3: adding an appropriate amount of distilled water and absolute ethyl alcohol into a reaction bottle, wherein the volume ratio of the distilled water to the absolute ethyl alcohol is 2.5:1, sequentially adding L-alanine and chitosan, slowly adding an esterification catalyst concentrated sulfuric acid while stirring at a constant speed, wherein the mass ratio of the L-alanine to the chitosan to the concentrated sulfuric acid is 15:1:0.05, transferring the solution into a hydrothermal automatic reaction kettle, heating to 130 ℃, reacting for 12 hours while stirring at a constant speed, adding a sodium hydroxide solution while stirring the solution after the reaction is finished, adjusting the pH to be neutral, carrying out vacuum filtration on the solution, removing the solvent, sequentially washing the solid product with an appropriate amount of distilled water and absolute ethyl alcohol, and fully drying to obtain an esterified chitosan compound 3.
(2) Preparation of an amidated phosphate ester chitosan compound 3: adding a proper amount of distilled water into a reaction bottle, slowly adding diluted hydrochloric acid to adjust the pH value to 3, then adding an esterified chitosan compound 3, uniformly stirring, adding a proper amount of absolute ethyl alcohol, a condensing agent of diisopropylcarbodiimide, guanidine phosphate and sodium creatine phosphate, wherein the mass ratio of the esterified chitosan compound 3 to the guanidine phosphate to the sodium creatine phosphate to the diisopropylcarbodiimide is 1:10:6:3, the volume ratio of the distilled water to the absolute ethyl alcohol is 1:4, transferring the solution into a hydrothermal automatic reaction kettle, heating to 140 ℃, uniformly stirring to perform self-polymerization reaction for 30 hours, cooling the solution to room temperature, slowly adding a sodium hydroxide solution, adjusting the pH value to neutrality, performing vacuum filtration on the solution, removing the solvent, and sequentially washing the solid product by using a proper amount of distilled water and the absolute ethyl alcohol to obtain the amidated phosphate ester chitosan compound 3.
(3) Preparing an N/P-doped chitosan-based porous component 3: weighing a certain amount of the amidated phosphate chitosan compound 3, placing the amidated phosphate chitosan compound in an atmosphere resistance furnace, and introducing high-purity N2Calcining at the heating rate of 10 ℃/min for 3h at 920 ℃, and annealing at 920 ℃ for 2h to obtain the N/P-doped chitosan-based porous component 3.
(4) Preparation of Al2O3Hollow microspheres 3: adding distilled water, absolute ethyl alcohol, polyoxyethylene and propylene oxide solution into a reaction bottle, wherein the mass ratio of the distilled water to the absolute ethyl alcohol to the polyoxyethylene to the propylene oxide solution is 55:60:1:70, stirring at a constant speed for 3 hours, and adding a proper amount of AlCl3Stirring at constant speed for 5h, vacuum filtering to remove solvent, placing the solid product in a resistance furnace at a heating rate of 10 ℃/min, and calcining at 670 ℃ for 2h to obtain Al2O3Hollow microspheres 3.
(5) Preparation of Co-Al double hydroxide 3: adding a proper amount of distilled water into a reaction bottle, and then adding 3 parts of Al2O3Hollow microsphere 3, 15 parts CoCl2And 8 parts of hexadecyl trimethyl ammonium bromide, placing a reaction bottle in an ultrasonic disperser, heating to 60 ℃, performing ultrasonic dispersion treatment for 2 hours, adding 15 parts of urea, stirring at a constant speed, transferring the solution into a hydrothermal automatic reaction kettle, heating to 220 ℃, stirring at a constant speed, reacting for 4 hours, cooling the solution to room temperature, performing vacuum filtration to remove the solvent, washing the solid product by using a proper amount of distilled water and absolute ethyl alcohol, and fully drying to prepare the Co-Al double metal hydroxide 3.
(6) Preparing a biomass-based carbon material coated CoAl-LDH supercapacitor material 3: adding a proper amount of distilled water into a reaction bottle, sequentially adding 59 parts of the N/P-doped chitosan-based porous carbon component 3 and the Co-Al double metal hydroxide 3 prepared in the step (2), placing the reaction bottle in an ultrasonic disperser, heating to 60 ℃, carrying out ultrasonic dispersing treatment for 5 hours at the ultrasonic frequency of 20KHz, removing the solvent from the solution through vacuum filtration, and completely drying to obtain the biomass-based carbon material coated CoAl-LDH super capacitor material 3.
Example 4:
(1) preparation of esterified Shell Polymer 4: adding an appropriate amount of distilled water and absolute ethyl alcohol into a reaction bottle, wherein the volume ratio of the distilled water to the absolute ethyl alcohol is 2.5:1, sequentially adding L-alanine and chitosan, slowly adding an esterification catalyst concentrated sulfuric acid while stirring at a constant speed, wherein the mass ratio of the L-alanine to the chitosan to the concentrated sulfuric acid is 12:1:0.08, transferring the solution into a hydrothermal automatic reaction kettle, heating to 135 ℃, reacting for 12 hours while stirring at a constant speed, adding a sodium hydroxide solution while stirring the solution after the reaction is finished, adjusting the pH value to be neutral, carrying out vacuum filtration on the solution, removing the solvent, sequentially washing the solid product with an appropriate amount of distilled water and absolute ethyl alcohol, and fully drying to obtain an esterified chitosan compound 4.
(2) Preparation of an amidated phosphate ester chitosan compound 4: adding a proper amount of distilled water into a reaction bottle, slowly adding diluted hydrochloric acid to adjust the pH value to 4, then adding an esterified chitosan compound 4, uniformly stirring, adding a proper amount of absolute ethyl alcohol, a condensing agent of diisopropyl carbodiimide, guanidine phosphate and creatine phosphate sodium, wherein the mass ratio of the esterified chitosan compound 4 to the guanidine phosphate to the creatine phosphate sodium to the diisopropyl carbodiimide is 1:9:7:3, the volume ratio of the distilled water to the absolute ethyl alcohol is 1:3, transferring the solution into a hydrothermal automatic reaction kettle, heating to 135 ℃, uniformly stirring to carry out self-polymerization reaction for 28h, cooling the solution to room temperature, slowly adding a sodium hydroxide solution, adjusting the pH value to neutrality, carrying out vacuum filtration on the solution, removing the solvent, and sequentially washing the solid product by using a proper amount of distilled water and the absolute ethyl alcohol to obtain the amidated phosphate chitosan compound 4.
(3) Preparing an N/P-doped chitosan-based porous component 4: weighing a certain amount of the amidated phosphate chitosan compound 4, placing the amidated phosphate chitosan compound in an atmosphere resistance furnace, and introducing high-purity N2Calcining at the heating rate of 10 ℃/min for 4h at 930 ℃, and annealing at 930 ℃ for 3h to obtain the N/P-doped chitosan-based porous component 4.
(4) Preparation of Al2O3Hollow microspheres 4: adding distilled water, absolute ethyl alcohol, polyoxyethylene and propylene oxide solution into a reaction bottle, wherein the mass ratio of the distilled water to the absolute ethyl alcohol to the polyoxyethylene to the propylene oxide solution is 55:65:1:68,stirring at constant speed for 2h, and adding appropriate amount of AlCl3Stirring at constant speed for reaction for 4h, removing the solvent from the solution by vacuum filtration, placing the solid product in a resistance furnace at the heating rate of 8 ℃/min, and calcining at 660 ℃ for 3h to prepare Al2O3Hollow microspheres 4.
(5) Preparation of Co-Al double hydroxide 4: adding a proper amount of distilled water into a reaction bottle, and then adding 3.5 parts of Al2O3Hollow microsphere 4, 17 parts CoCl2And 8.5 parts of hexadecyl trimethyl ammonium bromide, placing a reaction bottle in an ultrasonic disperser, heating to 55 ℃, performing ultrasonic dispersion treatment for 2 hours, adding 16 parts of urea, stirring at a constant speed, transferring the solution into a hydrothermal automatic reaction kettle, heating to 215 ℃, stirring at a constant speed, reacting for 5 hours, cooling the solution to room temperature, performing vacuum filtration to remove the solvent, washing the solid product by using a proper amount of distilled water and absolute ethyl alcohol, and fully drying to prepare the Co-Al double metal hydroxide 4.
(6) Preparing a biomass-based carbon material coated CoAl-LDH supercapacitor material 4: adding a proper amount of distilled water into a reaction bottle, sequentially adding 55 parts of N/P-doped chitosan-based porous carbon component 4 and the Co-Al double metal hydroxide 4 prepared in the step (2), placing the reaction bottle in an ultrasonic disperser, heating to 55 ℃, carrying out ultrasonic dispersion treatment for 4 hours at the ultrasonic frequency of 25KHz, removing the solvent from the solution through vacuum filtration, and completely drying to obtain the biomass-based carbon material coated CoAl-LDH super capacitor material 4.
Example 5:
(1) preparation of esterified Shell Polymer 5: adding an appropriate amount of distilled water and absolute ethyl alcohol into a reaction bottle, wherein the volume ratio of the distilled water to the absolute ethyl alcohol is 2.5:1, sequentially adding L-alanine and chitosan, slowly adding an esterification catalyst concentrated sulfuric acid while stirring at a constant speed, wherein the mass ratio of the L-alanine to the chitosan to the concentrated sulfuric acid is 15:1:0.1, transferring the solution into a hydrothermal automatic reaction kettle, heating to 140 ℃, reacting for 12 hours while stirring at a constant speed, adding a sodium hydroxide solution while stirring the solution after the reaction is finished, adjusting the pH value to be neutral, carrying out vacuum filtration on the solution, removing the solvent, sequentially washing the solid product with an appropriate amount of distilled water and absolute ethyl alcohol, and fully drying to obtain an esterified chitosan compound 5.
(2) Preparation of an amidated phosphate ester chitosan compound 5: adding a proper amount of distilled water into a reaction bottle, slowly adding diluted hydrochloric acid to adjust the pH value to 4, then adding an esterified chitosan compound 5, uniformly stirring, then adding a proper amount of absolute ethyl alcohol, a condensing agent of diisopropylcarbodiimide, guanidine phosphate and sodium creatine phosphate, wherein the mass ratio of the esterified chitosan, the guanidine phosphate, the sodium creatine phosphate and the diisopropylcarbodiimide is 1:10:8:3, the volume ratio of the distilled water to the absolute ethyl alcohol is 1:4, transferring the solution into a hydrothermal automatic reaction kettle, heating to 130 ℃, uniformly stirring to carry out self-polymerization reaction for 30 hours, cooling the solution to room temperature, slowly adding a sodium hydroxide solution, adjusting the pH value to neutrality, carrying out vacuum filtration on the solution, removing the solvent, and then sequentially using a proper amount of distilled water and the absolute ethyl alcohol to wash the solid product to obtain the amidated phosphate ester chitosan compound 5.
(3) Preparing an N/P-doped chitosan-based porous component 5: weighing a certain amount of the amidated phosphate chitosan compound 5, placing the amidated phosphate chitosan compound in an atmosphere resistance furnace, and introducing high-purity N2Calcining at the heating rate of 10 ℃/min for 5h at 940 ℃, and annealing at 940 ℃ for 3h to obtain the N/P-doped chitosan-based porous component 5.
(4) Preparation of Al2O3Hollow microspheres 5: adding distilled water, absolute ethyl alcohol, polyoxyethylene and propylene oxide solution into a reaction bottle, wherein the mass ratio of the distilled water to the absolute ethyl alcohol to the polyoxyethylene to the propylene oxide solution is 55:70:1:70, stirring at a constant speed for 3 hours, and adding a proper amount of AlCl3Stirring at constant speed for reaction for 4h, removing the solvent from the solution by vacuum filtration, placing the solid product in a resistance furnace at a heating rate of 10 ℃/min, and calcining at 670 ℃ for 4h to prepare Al2O3Hollow microspheres 5.
(5) Preparation of Co-Al double hydroxide 5: adding a proper amount of distilled water into a reaction bottle, and then adding 4 parts of Al2O3Hollow microsphere 5, 20 parts of CoCl2And 10 parts of hexadecyl trimethyl ammonium bromide, placing the reaction bottle in an ultrasonic disperser, heating to 60 ℃, performing ultrasonic dispersion treatment for 2 hours, adding 18 parts of urea, stirring at a constant speed, transferring the solution into a hydrothermal automatic reaction kettle,heating to 220 ℃, stirring at a constant speed for reaction for 5 hours, cooling the solution to room temperature, carrying out vacuum filtration to remove the solvent, washing the solid product by using a proper amount of distilled water and absolute ethyl alcohol, and fully drying to prepare the Co-Al double metal hydroxide 5.
(6) Preparing a biomass-based carbon material coated CoAl-LDH supercapacitor material 5: adding a proper amount of distilled water into a reaction bottle, sequentially adding 48 parts of N/P-doped chitosan-based porous carbon component 5 and the Co-Al double metal hydroxide 5 prepared in the step (2), placing the reaction bottle in an ultrasonic disperser, heating to 60 ℃, carrying out ultrasonic dispersion treatment for 5 hours at the ultrasonic frequency of 25KHz, removing the solvent from the solution through vacuum filtration, and completely drying to obtain the biomass-based carbon material coated CoAl-LDH super capacitor material 5.
In summary, the CoAl-LDH super capacitor material coated by the biomass-based carbon material and the preparation method thereof use Co-Al double metal hydroxide as the matrix component of the super capacitor electrode material, and Al2O3The hollow microspheres have large specific surface area, provide a large number of oxidation-reduction reaction active sites for electrode reaction, increase charge storage, and further enhance the specific capacitance of the supercapacitor, and the Co-Al double metal hydroxide particles hydrothermally synthesized by the urea hydrolysis method have small pore diameter of only 2-4um, and a large number of pore channel structures are formed among the particles, so that a transmission channel is provided for ions in an electrode material, and the diffusion distance is shortened, thereby improving the rate capability of the electrode material.
N/P-doped chitosan-based porous carbon is used for coating Co-Al double metal hydroxide, macromolecules with a branched three-dimensional structure are polymerized through esterification reaction and amidation reaction between L-alanine, guanidine phosphate, creatine phosphate sodium and chitosan, a large number of pore canal structures are formed among the polymer macromolecules, the porous carbon material formed by calcination has a huge specific surface and rich pore structures, a complex mesoporous structure is formed on the surface through the porous carbon formed by N/P doping, a large number of radial pore canals are formed inside, the Co-Al double metal hydroxide is uniformly loaded into the inner pores of the porous carbon material, the double metal hydroxide is prevented from being agglomerated into macromolecules, so that more active sites of redox reaction are exposed, and the specific capacitance of the super capacitor is enhanced, and the N/P doped porous carbon has better conductivity, a conductive interface is formed between the Co-Al double metal hydroxides, the diffusion and migration rates of ions and charges between the internal pores of the porous carbon material and the electrolyte are improved, and the power density of the super capacitor and the rate capability of the electrode material are enhanced.
Claims (4)
1. A preparation method of a biomass-based carbon material coated CoAl-LDH supercapacitor material comprises the following formula raw materials in parts by weight, and is characterized in that: 48-70 parts of N/P-doped chitosan-based porous carbon and 2-4 parts of Al2O3Hollow microsphere, 10-20 parts of CoCl212-18 parts of urea and 6-10 parts of hexadecyl trimethyl ammonium bromide; the preparation method of the N/P-doped chitosan-based porous carbon comprises the following steps:
(1) adding distilled water and absolute ethyl alcohol into a reaction bottle, wherein the volume ratio of the distilled water to the absolute ethyl alcohol is 2-2.5:1, sequentially adding L-alanine, chitosan and an esterification catalyst concentrated sulfuric acid, transferring the solution into a hydrothermal automatic reaction kettle, heating to 130 ℃ and 140 ℃, uniformly stirring for reaction for 10-12h, adding a sodium hydroxide solution into the solution while stirring, adjusting the pH value to be neutral, performing vacuum filtration on the solution to remove the solvent, and sequentially washing a solid product by using distilled water and absolute ethyl alcohol to obtain esterified chitosan;
(2) adding distilled water into a reaction bottle, adding dilute hydrochloric acid to adjust the pH value to 3-4, adding esterified chitosan, adding absolute ethyl alcohol, condensing agent diisopropylcarbodiimide, guanidine phosphate and creatine phosphate sodium, wherein the volume ratio of the distilled water to the absolute ethyl alcohol is 1:3-4, transferring the solution into a hydrothermal automatic reaction kettle, heating to 130-;
(3) weighing amido phosphate chitosan, placing in an atmosphere resistance furnace, introducing high-purity N2Calcining at the heating rate of 10 ℃/min for 3-5h at the temperature of 920-;
the preparation method of the biomass-based carbon material coated CoAl-LDH supercapacitor material comprises the following steps:
(1) adding distilled water, absolute ethyl alcohol, polyoxyethylene and propylene oxide solution into a reaction bottle, stirring at constant speed for 1-3h, and adding AlCl3Stirring at constant speed for reaction for 2-5h, removing the solvent from the solution by vacuum filtration, placing the solid product in a resistance furnace at a heating rate of 5-10 ℃/min, and calcining at 650-670 ℃ for 2-4h to obtain Al2O3Hollow microspheres;
(2) adding distilled water into a reaction bottle, and then adding 2-4 parts of Al2O3Hollow microsphere, 10-20 parts of CoCl2And 6-10 parts of hexadecyl trimethyl ammonium bromide, placing a reaction bottle in an ultrasonic dispersion instrument, heating to 50-60 ℃, carrying out ultrasonic treatment for 1-2h, adding 12-18 parts of urea, transferring the solution into a hydrothermal automatic reaction kettle after uniform stirring, heating to 210 ℃ and 220 ℃, carrying out uniform stirring reaction for 4-5h, cooling the solution to room temperature, carrying out vacuum filtration to remove the solvent, washing the solid product by using a proper amount of distilled water and absolute ethyl alcohol, and fully drying to prepare Co-Al double metal hydroxide;
(3) and (3) adding a proper amount of distilled water into a reaction bottle, sequentially adding 48-70 parts of N/P-doped chitosan-based porous carbon and the Co-Al double metal hydroxide prepared in the step (2), placing the reaction bottle in an ultrasonic disperser, heating to 50-60 ℃, carrying out ultrasonic dispersion treatment for 4-5 hours at the ultrasonic frequency of 20-25KHz, removing the solvent from the solution through vacuum filtration, and completely drying to obtain the biomass-based carbon material coated CoAl-LDH supercapacitor material.
2. The method for preparing the biomass-based carbon material coated CoAl-LDH supercapacitor material according to claim 1, wherein the method comprises the following steps: the mass ratio of the L-alanine, the chitosan and the concentrated sulfuric acid in the step (1) is 10-15:1: 0.05-0.1.
3. The method for preparing the biomass-based carbon material coated CoAl-LDH supercapacitor material according to claim 2, wherein the method comprises the following steps: the mass ratio of the esterified chitosan, the guanidine phosphate, the creatine phosphate sodium and the diisopropylcarbodiimide in the step (2) is 1:8-10:6-8: 2-3.
4. The method for preparing the biomass-based carbon material coated CoAl-LDH supercapacitor material according to claim 3, wherein the method comprises the following steps: the mass ratio of the distilled water, the absolute ethyl alcohol, the polyoxyethylene and the propylene oxide solution in the step (1) is 50-55:60-70:1: 65-70.
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Application publication date: 20200207 Assignee: JIANGXI YUANSHI TECHNOLOGY CO.,LTD. Assignor: Jiangxi Gaoxin Frontier Technology Co.,Ltd. Contract record no.: X2022980021516 Denomination of invention: CoAl LDH supercapacitor material coated with biomass based carbon material and its preparation method Granted publication date: 20211203 License type: Common License Record date: 20221121 |