CN115020112B - Configuration-controllable nitrogen-oxygen-fluorine co-doped carbon electrode material and preparation method thereof - Google Patents
Configuration-controllable nitrogen-oxygen-fluorine co-doped carbon electrode material and preparation method thereof Download PDFInfo
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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Abstract
The invention discloses a configuration-controllable nitrogen-oxygen-fluorine co-doped carbon electrode material and a preparation method thereof, belonging to the technical field of carbon materials, wherein the preparation method comprises the following steps: the preparation method comprises the steps of (1) hydrothermal synthesis of 2-amino-4-fluorophenol-formaldehyde copolymer resin, (2) carbonization of the copolymer resin, and (3) activation of carbonized products of the copolymer resin, wherein pyrrole nitrogen, hydroquinone hydroxyl/quinone carbonyl and semi-ion fluorocarbon bond co-doped carbon materials are obtained, low-temperature partial defluorination and carbonization are beneficial to forming a conjugated structure by adjacent benzene rings, and partial semi-ion fluorocarbon bond-induced charge redistribution is reserved, so that the nitrogen-oxygen fluorine co-doped carbon electrode material shows good conductivity and shows high rate performance when used as an electrode material of a supercapacitor; meanwhile, more pyrrole nitrogen and hydroquinone hydroxyl/quinone carbonyl are reserved as pseudocapacitance active sites by low-temperature carbonization and low-temperature activation treatment, and the pseudocapacitance characteristic and high specific capacity are shown when the active sites are used as the electrode material of the supercapacitor.
Description
Technical Field
The invention relates to a configuration-controllable nitrogen-oxygen-fluorine co-doped carbon electrode material and a preparation method thereof, and belongs to the technical field of carbon materials.
Background
In this worldwide age of intercommunications and electrification, there is a great desire for energy storage technologies that are suitable for both high energy density and high power density applications, and supercapacitors are becoming the primary choice in high power transmission or rapid energy harvesting applications, such as grid stabilization systems, aerospace devices, and the like. However, due to the charge storage mechanism limitations of the supercapacitor surface (or near-surface), they are limited in their popularization to large-scale commercial applications. As a core component of the supercapacitor, the electrodes have a crucial role in the performance of the supercapacitor. Therefore, it is important to develop an electrode material having both high capacity and high rate performance. The carbon material has the advantages of high specific surface area, controllable pore size distribution and the like, can store charges on the surface of the carbon material by reversibly adsorbing/desorbing electrolyte ions when the carbon material is used as an electrode material of a supercapacitor, and has the advantages of environment friendliness, good stability, high charge-discharge rate, long cycle life and the like.
However, the activated carbon electrode has been applied to commercial supercapacitors with high power density, but its specific capacity still needs to be improved because it stores energy mainly through an electric double layer mechanism. Therefore, the synthesis of carbon electrode materials with high specific capacities is critical to the development of high performance supercapacitors. The multi-element doping can utilize the capacity of hetero atoms to regulate and control the charge distribution of the carbon material, the synergistic effect generated among different elements and the increase of the number of active sites of oxidation-reduction reaction to improve the electrochemical performance. Considering that nitrogen-oxygen heteroatoms can show good pseudocapacitance characteristics, the capacity characteristics of the carbon electrode material are expected to be improved, and fluorine atoms with strongest electronegativity can maximally adjust the charge distribution of the carbon material so as to improve the multiplying power performance of the heteroatom-doped carbon material, so that the development of the multi-element doped carbon material becomes an important research direction at present. Nitrogen-oxygen co-doped carbon materials (Journal of Power Sources,2017,341,309-317.) and nitrogen-fluorine co-doped carbon materials (Journal of Energy Storage,2021, 38:1-6), etc. have been developed to exhibit good electrochemical performance, but it is currently difficult to control the nitrogen-oxygen-fluorine co-doping configuration, which hinders further development of high-performance nitrogen-oxygen-fluorine co-doped carbon materials.
Disclosure of Invention
In order to provide the nitrogen-oxygen-fluorine co-doped carbon electrode material and enable the nitrogen-oxygen-fluorine co-doped carbon electrode material to have high rate performance and pseudocapacitance characteristics when being used as a supercapacitor electrode material, the technical scheme of the invention provides the configuration-controllable nitrogen-oxygen-fluorine co-doped carbon electrode material and a preparation method thereof. The technical proposal is as follows:
the invention provides a configuration-controllable nitrogen-oxygen-fluorine co-doped carbon electrode material, which is prepared by mixing 2-amino-4-fluorophenol and hexamethylenetetramine, preparing copolymer resin by a hydrothermal method, performing heat treatment and activating.
The invention also provides a preparation method of the nitrogen-oxygen-fluorine co-doped carbon electrode material, which comprises the following steps:
(1) Adding 2-amino-4-fluorophenol and hexamethylenetetramine into water to dissolve to form a uniform solution, adding the uniform solution into a reaction kettle to carry out hydrothermal reaction to obtain a first product, washing the first product with water, and drying to obtain a copolymer resin sample;
(2) Placing the copolymer resin sample into a tube furnace, heating up and heat treating in nitrogen atmosphere, cooling and collecting a second product;
(3) And mixing and fully grinding the product II with potassium hydroxide, putting the mixture into a tube furnace, heating the mixture in a nitrogen atmosphere for activation reaction, cooling the mixture, collecting the product III, washing the product three-purpose hydrochloric acid solution and water to be neutral in sequence, and then drying the product in vacuum to obtain the nitrogen-oxygen-fluorine co-doped carbon electrode material.
Preferably, the molar ratio of 2-amino-4-fluorophenol to hexamethylenetetramine in step (1) is from 5:2 to 7:2, and the concentration of 2-amino-4-fluorophenol monomer is 0.025mol/L.
Preferably, the temperature of the hydrothermal reaction in the step (1) is 170-190 ℃, the time of the hydrothermal reaction is 23-25 h, the drying temperature is 50-70 ℃, and the drying time is 22-26 h.
Preferably, the temperature of the hydrothermal reaction in the step (1) is 180 ℃, the time of the hydrothermal reaction is 24 hours, the drying temperature is 60 ℃, and the drying time is 24 hours.
Preferably, the heat treatment temperature in the step (2) is 500-550 ℃, and the heat treatment time is 3-5 h.
Preferably, the heat treatment temperature in the step (2) is 500 ℃, and the heat treatment time is 4 hours.
Preferably, the mass ratio of the second product to the potassium hydroxide in the step (3) is 1:5-1:7, the activation reaction temperature is 500-550 ℃, the activation time is 7-9 h, the concentration of the hydrochloric acid solution is 0.4-0.6 mol/L, the vacuum drying temperature is 110-130 ℃, and the vacuum drying time is 11-13 h.
Preferably, in the step (3), the mass ratio of the second product to potassium hydroxide is 1:6, the activation reaction temperature is 500 ℃, the activation time is 8 hours, the concentration of the hydrochloric acid solution is 0.5mol/L, the vacuum drying temperature is 120 ℃, and the vacuum drying time is 12 hours.
The invention also provides application of the nitrogen-oxygen-fluorine co-doped carbon electrode material prepared by the preparation method in the electrode material of the super capacitor.
Compared with the prior art, the invention has the advantages that:
1) The 2-amino-4-fluorophenol-formaldehyde copolymer resin is subjected to partial defluorination and alkali activation pyrolysis to obtain a configuration-controllable nitrogen-oxygen-fluorine co-doped carbon electrode material (pyrrole nitrogen, hydroquinone hydroxyl/quinone carbonyl and semi-ion fluorocarbon bond co-doped carbon material), so that a great amount of heteroatoms are prevented from losing in the high-temperature heat treatment process, and meanwhile, the fine control of the heteroatom configuration of the nitrogen-oxygen-fluorine co-doped carbon electrode material is realized, and the nitrogen-oxygen-fluorine co-doped carbon electrode material prepared by the method shows good capacitance performance, excellent multiplying power performance and long cycle life when being used as a supercapacitor electrode material;
2) In the polymerization process of 2-amino-4-fluorophenol and hexamethylenetetramine, a fluoroaminophenol resin is generated, and HF and H are passed through in the low-temperature partial defluorination and carbonization 2 The removal of small molecules such as O and the like is connected into a large plane conjugated structure, and the partial retention of fluorine atoms increases the conductivity caused by electron polarization, so that the material has high rate capability when used as an electrode material of a supercapacitor; the low-temperature alkali activation treatment converts nitrogen configuration from pyridine nitrogen to pyrrole nitrogen, and the lower carbonization and activation temperature ensures that the configuration-controllable nitrogen-oxygen-fluorine co-doped carbon electrode material reserves more pyrrole nitrogen and hydroquinone hydroxyl/quinone carbonyl as pseudocapacitance active sites and shows pseudocapacitance characteristics and high specific capacity when used as a supercapacitor electrode material.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention, wherein:
FIG. 1a is a scanning electron micrograph of a configuration-controllable nitrogen-oxygen-fluorine co-doped carbon electrode material prepared in example 1 of the present invention;
FIG. 1b is a transmission electron micrograph of a configuration-controllable nitrogen-oxygen-fluorine co-doped carbon electrode material prepared in example 1 of the present invention;
FIG. 2 is a Raman spectrum of the configuration-controllable nitrogen-oxygen-fluorine co-doped carbon electrode material prepared in example 1 of the present invention;
FIGS. 3 a-3 d are X-ray photoelectron spectra of configuration-controllable nitrogen-oxygen-fluorine co-doped carbon electrode materials prepared in example 1 of the present invention;
FIG. 4 is a cyclic voltammogram of the configuration-controllable nitrogen-oxygen-fluorine co-doped carbon electrode material prepared in example 1 of the present invention as a supercapacitor electrode at different sweep rates in a 1mol/L sulfuric acid solution of a three-electrode system;
FIG. 5 shows specific capacitances of the configuration-controllable nitrogen-oxygen-fluorine co-doped carbon electrode material prepared in example 1 of the present invention as a supercapacitor electrode at different sweep rates in a three-electrode system 1mol/L sulfuric acid solution;
FIG. 6 is a constant current charging and discharging line with different current densities in a three-electrode system 1mol/L sulfuric acid solution, wherein the configuration-controllable nitrogen-oxygen-fluorine co-doped carbon electrode material prepared in the embodiment 1 of the invention is used as a supercapacitor electrode;
FIG. 7 is a graph showing the specific capacitance of the configuration-controllable nitrogen-oxygen-fluorine co-doped carbon electrode material prepared in example 1 of the present invention as a supercapacitor electrode at different current densities in a sulfuric acid solution of 1mol/L of a three-electrode system;
FIG. 8 is cycle life data of the configuration-controllable nitrogen-oxygen-fluorine co-doped carbon electrode material prepared in example 1 of the present invention as a supercapacitor electrode under the condition of 10A/g current density in a 1mol/L sulfuric acid solution of a three-electrode system.
Detailed Description
The following disclosure provides many different embodiments, or examples, for implementing different features of the invention. In order to simplify the present disclosure, components and arrangements of specific examples are described below. They are, of course, merely examples and are not intended to limit the invention. Furthermore, the present invention may repeat reference numerals and/or letters in the various examples, which are for the purpose of brevity and clarity, and which do not themselves indicate the relationship between the various embodiments and/or arrangements discussed.
The invention provides a configuration-controllable nitrogen-oxygen-fluorine co-doped carbon electrode material and a preparation method thereof, wherein 2-amino-4-fluorophenol and hexamethylenetetramine are prepared into 2-amino-4-fluorophenol-formaldehyde copolymer resin by a hydrothermal method, and then the 2-amino-4-fluorophenol-formaldehyde copolymer resin is subjected to low-temperature partial defluorination and alkali activation processes to obtain the configuration-controllable nitrogen-oxygen-fluorine co-doped carbon electrode material.
The preparation method comprises the following steps:
(1) Adding 2-amino-4-fluorophenol monomer and hexamethylenetetramine into 80mL of distilled water (or ultrapure water) according to a molar ratio of 5:2-7:2 (preferably 6:2) to be completely dissolved to form a uniform solution, adding the uniform solution into a 100mL reaction kettle to carry out hydrothermal reaction to obtain a product I, wherein the hydrothermal reaction temperature is 170-190 ℃ (preferably 180 ℃) and the reaction time is 23-25 hours (preferably 24 hours), washing the product with distilled water, and drying the product for 22-26 hours (preferably 24 hours) at 50-70 ℃ (preferably 60 ℃) to obtain a 2-amino-4-fluorophenol-formaldehyde copolymer resin sample;
(2) Placing the 2-amino-4-fluorophenol-formaldehyde copolymer resin sample prepared in the step (1) into a tube furnace, heating to 500-550 ℃ (preferably 500 ℃) in nitrogen atmosphere, performing heat treatment for 3-5 hours (preferably 4 hours), naturally cooling to room temperature, and collecting a second product;
(3) Mixing and grinding the product II prepared in the step (2) and potassium hydroxide according to the mass ratio of 1:5-1:7 (preferably 1:6), placing the mixture into a tubular furnace, heating the mixture to 500-550 ℃ (preferably 500 ℃) in a nitrogen atmosphere, activating the mixture for 7-9 h (preferably 8 h), naturally cooling the mixture to the room temperature, collecting the product III, sequentially washing the product III with 0.4-0.6 mol/L (preferably 0.5 mol/L) hydrochloric acid solution and distilled water (or ultrapure water) to pH=7, and then vacuum drying the mixture for 11-13 h (preferably 12 h) at 110-130 ℃ (preferably 120 ℃) to obtain the configuration-controllable nitrogen-oxygen-fluorine co-doped carbon electrode material.
Example 1
The preparation method of the configuration-controllable nitrogen-oxygen-fluorine co-doped carbon electrode material comprises the following steps of:
(1) Adding 2-amino-4-fluorophenol monomer and hexamethylenetetramine into 80mL of distilled water according to a molar ratio of 6:2 to be completely dissolved to form a uniform solution, wherein the concentration of the 2-amino-4-fluorophenol monomer is 0.025mol/L, adding the uniform solution into a 100mL reaction kettle, carrying out hydrothermal reaction at 180 ℃ for 24 hours to obtain a first product, washing the first product with distilled water, and drying at 60 ℃ for 24 hours to obtain a 2-amino-4-fluorophenol-formaldehyde copolymer resin sample;
(2) Placing the 2-amino-4-fluorophenol-formaldehyde copolymer resin sample prepared in the step (1) into a tube furnace, heating to 500 ℃ from room temperature in nitrogen atmosphere, performing heat treatment for 4 hours, naturally cooling to room temperature, and collecting a second product;
(3) Weighing and grinding the product II prepared in the step (2) and potassium hydroxide according to the mass ratio of 1:6, fully mixing, putting into a tube furnace, heating to 500 ℃ from room temperature in nitrogen atmosphere, activating for 8 hours, naturally cooling to room temperature, and collecting the product III. And (3) washing the collected product to pH=7 by using a three-purpose 0.5mol/L hydrochloric acid solution and distilled water in sequence, and then carrying out vacuum drying at 120 ℃ for 12 hours to obtain the configuration-controllable nitrogen-oxygen-fluorine co-doped carbon electrode material.
Fig. 1a is a scanning electron microscope photograph of the configuration-controllable nitrogen-oxygen-fluorine co-doped carbon electrode material prepared in this example 1, and fig. 1b is a transmission electron microscope photograph of the configuration-controllable nitrogen-oxygen-fluorine co-doped carbon electrode material prepared in this example 1, in which it can be seen that the nitrogen-oxygen-fluorine co-doped carbon electrode material prepared in the invention has a lamellar porous structure and coexists with a spherical morphology.
Fig. 2 is a raman spectrum of the configuration-controllable nitrogen-oxygen-fluorine co-doped carbon electrode material prepared in example 1 of the present invention, and it can be seen that the nitrogen-oxygen-fluorine co-doped carbon electrode material prepared in the present invention has obvious D-band and G-band characteristics, and has a high defect degree.
Fig. 3a to 3d are X-ray photoelectron spectra of the configuration-controllable nitrogen-oxygen-fluorine co-doped carbon electrode material prepared in this example 1, and it can be seen that the heteroatom configuration is a pyrrole nitrogen-dominant nitrogen configuration, a hydroquinone hydroxyl/quinone carbonyl coexisting oxygen configuration, and a semi-ionic fluorocarbon bond.
FIG. 4 is a cyclic voltammogram of the configuration-controllable nitrogen-oxygen-fluorine co-doped carbon electrode material prepared in the embodiment as a supercapacitor electrode at different sweep rates in a 1mol/L sulfuric acid solution of a three-electrode system, wherein symmetrical redox peaks show pseudocapacitance characteristics and electrochemical reversibility.
FIG. 5 shows that the configuration-controllable nitrogen-oxygen-fluorine co-doped carbon electrode material prepared in the embodiment has the specific capacity of the supercapacitor electrode at different sweeping speeds in a sulfuric acid solution with the concentration of 1mol/L in a three-electrode system, the sweeping speed is 1-50 mV/s, the corresponding specific capacity is 308-224F/g, the higher capacity is shown, the specific capacity retention rate is 73% after calculation, and the good multiplying power performance is shown.
FIG. 6 is a graph showing that the configuration-controllable nitrogen-oxygen-fluorine co-doped carbon electrode material prepared in the embodiment 1 is used as a constant current charging and discharging wire with different current densities in a sulfuric acid solution of a three-electrode system 1mol/L, and symmetrical redox peaks show pseudocapacitance characteristics and electrochemical reversibility.
FIG. 7 shows the specific capacitance of the configuration-controllable nitrogen-oxygen-fluorine co-doped carbon electrode material prepared in the embodiment 1 as a super capacitor electrode under different current densities in a sulfuric acid solution of a three-electrode system 1mol/L, wherein the current density is 1-20A/g, the corresponding specific capacitance is 324-247F/g, and the specific capacity retention rate is 76% by calculation, so that the super capacitor electrode has higher capacity and better multiplying power performance.
FIG. 8 is the cycle life data of the configuration-controllable nitrogen-oxygen-fluorine co-doped carbon electrode material prepared in the embodiment 1 as a supercapacitor electrode under the condition of 10A/g current density in a sulfuric acid solution of 1mol/L of a three-electrode system, wherein the specific capacity after 10000 circles is 247F/g, the capacity retention rate is close to 93%, and the supercapacitor electrode material has good cycle stability.
Example 2
The preparation method of the configuration-controllable nitrogen-oxygen-fluorine co-doped carbon electrode material comprises the following steps of:
(1) Adding 2-amino-4-fluorophenol monomer and hexamethylenetetramine into 80mL of distilled water according to a molar ratio of 5:2 to be completely dissolved to form a uniform solution, wherein the concentration of the 2-amino-4-fluorophenol monomer is 0.025mol/L, adding the uniform solution into a 100mL reaction kettle, carrying out hydrothermal reaction at 170 ℃ for 25h to obtain a first product, washing the first product with distilled water, and drying at 70 ℃ for 26h to obtain a 2-amino-4-fluorophenol-formaldehyde copolymer resin sample;
(2) Placing the 2-amino-4-fluorophenol-formaldehyde copolymer resin sample prepared in the step (1) into a tube furnace, heating to 525 ℃ from room temperature in nitrogen atmosphere, performing heat treatment for 5h, naturally cooling to room temperature, and collecting a second product;
(3) Weighing and grinding the product II prepared in the step (2) and potassium hydroxide according to the mass ratio of 1:7, fully mixing, putting into a tube furnace, heating to 525 ℃ from room temperature in nitrogen atmosphere, activating for 9 hours, naturally cooling to room temperature, and collecting the product III. And (3) washing the collected product to pH=7 by using a three-purpose 0.6mol/L hydrochloric acid solution and distilled water in sequence, and then vacuum drying at 130 ℃ for 11 hours to obtain the configuration-controllable nitrogen-oxygen-fluorine co-doped carbon electrode material.
Example 3
The preparation method of the configuration-controllable nitrogen-oxygen-fluorine co-doped carbon electrode material comprises the following steps of:
(1) Adding 2-amino-4-fluorophenol monomer and hexamethylenetetramine into 80mL of distilled water according to a molar ratio of 7:2 to be completely dissolved to form a uniform solution, wherein the concentration of the 2-amino-4-fluorophenol monomer is 0.025mol/L, then adding the uniform solution into a 100mL reaction kettle, carrying out hydrothermal reaction at 190 ℃ for 23h to obtain a first product, washing the first product with distilled water, and drying at 50 ℃ for 22h to obtain a 2-amino-4-fluorophenol-formaldehyde copolymer resin sample;
(2) Placing the 2-amino-4-fluorophenol-formaldehyde copolymer resin sample prepared in the step (1) into a tube furnace, heating to 550 ℃ from room temperature in nitrogen atmosphere, performing heat treatment for 3 hours, naturally cooling to room temperature, and collecting a second product;
(3) Weighing and grinding the product II prepared in the step (2) and potassium hydroxide according to the mass ratio of 1:5, fully mixing, putting into a tube furnace, heating to 550 ℃ from room temperature in nitrogen atmosphere, activating for 7 hours, naturally cooling to room temperature, and collecting the product III. And (3) washing the collected product to pH=7 by using a three-purpose 0.4mol/L hydrochloric acid solution and distilled water in sequence, and then vacuum drying at 110 ℃ for 13 hours to obtain the configuration-controllable nitrogen-oxygen-fluorine co-doped carbon electrode material.
Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention herein. This invention is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.
It is to be understood that the invention is not limited to the precise arrangements and instrumentalities shown in the drawings, which have been described above, and that various modifications and changes may be effected without departing from the scope thereof. The scope of the invention is limited only by the appended claims.
Claims (6)
1. The preparation method of the configuration-controllable nitrogen-oxygen-fluorine co-doped carbon electrode material is characterized by comprising the following steps of:
(1) Adding 2-amino-4-fluorophenol and hexamethylenetetramine into water to dissolve to form a uniform solution, adding the uniform solution into a reaction kettle to carry out hydrothermal reaction to obtain a product I, washing the product I with water, and drying to obtain a copolymer resin sample; the molar ratio of the 2-amino-4-fluorophenol to the hexamethylenetetramine is 5:2-7:2, and the concentration of the 2-amino-4-fluorophenol monomer is 0.025mol/L; the temperature of the hydrothermal reaction is 170-190 ℃, the time of the hydrothermal reaction is 23-25 h, the drying temperature is 50-70 ℃, and the drying time is 22-26 h;
(2) Placing the copolymer resin sample into a tube furnace, heating up and heat treating in nitrogen atmosphere, cooling and collecting a second product; the heat treatment temperature is 500-550 ℃, and the heat treatment time is 3-5 h;
(3) Mixing and fully grinding the product II with potassium hydroxide, putting the mixture into a tube furnace, heating the mixture in a nitrogen atmosphere for an activation reaction, cooling the mixture, collecting a product III, washing the product three-purpose hydrochloric acid solution and water to be neutral in sequence, and then drying the product in vacuum to obtain the nitrogen-oxygen-fluorine co-doped carbon electrode material; the mass ratio of the product II to the potassium hydroxide is 1:5-1:7, the temperature of the activation reaction is 500-550 ℃, the activation time is 7-9 h, the concentration of the hydrochloric acid solution is 0.4-0.6 mol/L, the vacuum drying temperature is 110-130 ℃, and the vacuum drying time is 11-13 h.
2. The method for preparing the configuration-controllable nitrogen-oxygen-fluorine co-doped carbon electrode material according to claim 1, wherein the temperature of the hydrothermal reaction in the step (1) is 180 ℃, the time of the hydrothermal reaction is 24 hours, the drying temperature is 60 ℃, and the drying time is 24 hours.
3. The method for preparing a configuration-controllable nitrogen-oxygen-fluorine co-doped carbon electrode material according to claim 1, wherein the heat treatment temperature in the step (2) is 500 ℃, and the heat treatment time is 4h.
4. The method for preparing a configuration-controllable nitrogen-oxygen-fluorine co-doped carbon electrode material according to claim 1, wherein in the step (3), the mass ratio of the product II to the potassium hydroxide is 1:6, the temperature of the activation reaction is 500 ℃, the activation time is 8h, the concentration of the hydrochloric acid solution is 0.5mol/L, the vacuum drying temperature is 120 ℃, and the vacuum drying time is 12h.
5. The configuration-controllable nitrogen-oxygen-fluorine co-doped carbon electrode material prepared by the preparation method according to any one of claims 1 to 4, wherein the nitrogen-oxygen-fluorine co-doped carbon electrode material is prepared by mixing 2-amino-4-fluorophenol with hexamethylenetetramine, preparing copolymer resin by a hydrothermal method, performing heat treatment and activating, and the nitrogen-oxygen-fluorine co-doped carbon electrode material is a pyrrole nitrogen, hydroquinone hydroxyl/quinone carbonyl and semi-ionic fluorocarbon bond co-doped carbon electrode material with pseudocapacitance activity.
6. The application of the configuration-controllable nitrogen-oxygen-fluorine co-doped carbon electrode material prepared by the preparation method according to any one of claims 1-4 in a supercapacitor.
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