CN114436242B - Three-dimensional heteroatom doped porous carbon material, and preparation method and application thereof - Google Patents
Three-dimensional heteroatom doped porous carbon material, and preparation method and application thereof Download PDFInfo
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 89
- 125000005842 heteroatom Chemical group 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
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- 239000000463 material Substances 0.000 claims abstract description 31
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 13
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 12
- 239000007772 electrode material Substances 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 11
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- 238000000034 method Methods 0.000 claims description 35
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- GPAPPPVRLPGFEQ-UHFFFAOYSA-N 4,4'-dichlorodiphenyl sulfone Chemical group C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1 GPAPPPVRLPGFEQ-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical group C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical group C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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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
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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
- H01G11/84—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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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention aims to solve the problems of the conventional COFs material and porous carbon material preparation technology and provides a three-dimensional heteroatom doped porous carbon material, and a preparation method and application thereof. The three-dimensional heteroatom doped porous carbon material is prepared by cross coupling reaction of a dihalogen aromatic heterocyclic organic monomer, a hydroxyl-containing aromatic conjugated organic monomer and anhydrous potassium carbonate, and then is prepared by taking a three-dimensional heteroatom-containing covalent organic framework as a precursor and roasting; the mass percentage of the hetero atom contained in the porous carbon material is 10-30%. The porous carbon material prepared by the invention is used as an electrode material of a supercapacitor and has excellent electrochemical performance.
Description
Technical Field
The invention belongs to the technical field of carbon materials, and particularly relates to a three-dimensional porous carbon material with a heteroatom-containing covalent organic framework structure, a preparation method thereof and application thereof in a supercapacitor electrode.
Background
With the advent of non-renewable, increasingly exhausted fossil fuels, and the like, the development of efficient energy storage devices has become a hotspot for scientific research. Supercapacitors, also known as electrochemical capacitors, are new energy storage devices that have received attention for their unique advantages of high power density, excellent cycling stability, rapid charge and discharge rates, and low maintenance costs. Among them, a device in which an electric double layer capacitor is provided in the form of accumulating charges at an electrode/electrolyte interface using a carbon material as an electrode material is called an electric double layer capacitor. Pseudocapacitors are pseudocapacitors that transfer electricity through faradic redox reactions, typically by assembling various compounds and conductive polymers.
The porous carbon material has become a research hot spot in the fields of chemistry, biology, materials and the like due to the advantages of high specific surface area, abundant pore structure, high chemical stability, good conductivity and the like, and is widely applied to the aspects of catalysis, drug loading, slow release, electrochemistry and the like. Porous carbon materials have been attracting attention as electrode materials for electric double layer supercapacitors because of their good electrical conductivity. However, the specific capacitance of the carbon material is low, so that the practical application value is greatly limited. It has been reported in the literature that heteroatom doped porous carbon is easily accessible by electrolyte ions, resulting in rapid diffusion of electrolyte ions to promote electron transfer and increase the specific capacitance of the electrode material.
Porous organic polymeric materials (POPs) have been rapidly developed as a new generation of porous materials, and are widely used in the fields of adsorbents, catalysts, gas storage and separation, energy storage, electronic devices, and the like. According to different structural characteristics, the polymer is mainly divided into a super cross-linked polymer material, a self-contained microporous polymer material, a conjugated microporous polymer material and a covalent organic framework material (COFs). COFs are novel porous materials formed by mutually connecting light elements such as C, H, O, N through covalent bonds, and have the characteristics of high specific surface area, good thermal stability, high porosity, low skeleton density, excellent physicochemical stability, multiple synthetic routes, easy modification, ordered structure, controllable functions and the like. COFs have a high specific surface area, excellent stability, and a good microporous structure, and can increase contact of an electrode electrolyte by ion transport in ordered pore channels, compared to conventional carbon materials. In addition, the extended pi-conjugated backbone can serve as an effective transport medium, which is beneficial to improving electrochemical performance. However, due to its limitations in the attachment method, COFs are more difficult to synthesize than other materials.
COFs materials were synthesized by the Cote topic group in 2005 using a topology design method; the Yaghi research group utilizes the dehydration condensation reaction of 1, 4-p-diphenyl boric acid on the Yaghi research group to synthesize the COFs material; however, the above methods have certain drawbacks to some extent; the various synthesis methods must use Pd, ni and other heavy metal catalysts for catalysis, thus not only increasing the cost, but also being incapable of industrial production, and the reaction steps are numerous, and some of the synthesis methods also need an autoclave for hydrothermal reaction, so that the synthesis methods have a certain danger.
Disclosure of Invention
The invention aims to solve the problems of the conventional COFs material and porous carbon material preparation technology and provides a three-dimensional heteroatom doped porous carbon material, and a preparation method and application thereof. The invention prepares a three-dimensional heteroatom-containing covalent organic framework material through cross coupling reaction of a dihalogen aromatic heterocyclic organic monomer, a hydroxyl-containing aromatic conjugated organic monomer and anhydrous potassium carbonate, and directly carries out high-temperature carbonization by taking the three-dimensional heteroatom-containing covalent organic framework material as a precursor to obtain the porous carbon material. The prepared porous carbon material is used as an electrode material of a supercapacitor and has excellent electrochemical performance.
According to one of the technical schemes, the three-dimensional heteroatom doped porous carbon material is obtained by taking a three-dimensional heteroatom-containing covalent organic framework HCOF-T as a precursor and roasting;
the mass percentage of the hetero atoms of the porous carbon material is 10-30%.
Further, the three-dimensional heteroatom doped porous carbon material has a specific surface area of 2000-3000m 2 And/g, the average pore diameter is 1.8-5.5nm.
Further, the three-dimensional heteroatom doped porous carbon material is characterized in that the heteroatom is an oxygen atom, a sulfur atom or an oxygen atom and a sulfur atom;
when the hetero atoms are oxygen atoms and sulfur atoms, the oxygen mass percent is 10-22% of the total mass of the porous carbon material, and the sulfur mass percent is 1.5-6% of the total mass of the porous carbon material.
The second technical scheme of the invention is that the preparation method of the three-dimensional heteroatom doped porous carbon material comprises the following steps:
1) Preparation of a three-dimensional heteroatom-containing covalent organic framework: uniformly mixing a dihalogen aromatic heterocyclic organic monomer, a hydroxyl-containing aromatic conjugated organic monomer and alkali in an inert gas atmosphere, adding a solvent, reacting for 4-5 hours at 150-170 ℃, washing the obtained product by a washing solvent, and drying to obtain a three-dimensional heteroatom-containing covalent organic framework material HCOF-T;
2) Preparation of porous carbon material: the preparation method comprises the steps of taking a three-dimensional heteroatom-containing covalent organic framework HCOF-T as a precursor, mixing with an activating agent, heating to 700-900 ℃ in a heating furnace at a speed of 3-5 ℃/min under an inert gas atmosphere, and preserving heat for 45-60 min at the temperature to obtain the porous carbon material.
Further, in the preparation method, the dihalogen aromatic heterocyclic organic monomer is an aromatic heterocyclic organic monomer containing two halogen atom structures.
Further, the preparation method comprises the steps of: 4,4 '-difluorodiphenyl sulfone, 2, 5-dichlorofuran, 4' -dichlorodiphenyl sulfone, 2, 5-dichloropyridine, 2, 5-dichlorothiophene.
Further, in the above preparation method, the hydroxyl-containing aromatic conjugated organic monomer is an aromatic conjugated organic monomer containing a hydroxyl structural unit.
Further, in the above preparation method, the hydroxyl-containing aromatic conjugated organic monomer is: tetra- (4-hydroxy-styrene), 4 '-dihydroxybenzophenone, 4' -dihydroxydiphenyl sulfone, 2, 7-dihydroxynaphthalene, 4 '-dihydroxydiphenyl ether, 3,5,3',5 '-tetramethyl-4, 4' -dihydroxybiphenyl.
Further, in the preparation method, the alkali is anhydrous alkali metal or anhydrous alkaline earth metal carbonate; for example, anhydrous sodium hydroxide, anhydrous potassium hydroxide, anhydrous sodium carbonate, and anhydrous potassium carbonate; preferably, the base is anhydrous potassium carbonate.
Further, in the preparation method, the solvent is anhydrous and anaerobic N, N-dimethylacetamide.
Further, in the preparation method, the solvent is added in a dropwise manner.
Further, in the preparation method, the ratio of the amount of the dihalogen aromatic heterocyclic organic monomer to the amount of the substance containing hydroxy aromatic conjugated organic monomer is 1:1.
Further, in the above preparation method, the ratio of the amount of the (dihalogen aromatic heterocyclic organic monomer+hydroxy-containing aromatic conjugated organic monomer) to the amount of the anhydrous potassium carbonate is 1:1 to 1:3.
Further, in the above preparation method, the ratio of the amount of the (dihalogen aromatic heterocyclic organic monomer+hydroxy-containing aromatic conjugated organic monomer) to the amount of the solvent substance is 1:10 to 1:150.
Further, in the above preparation method, the washing solvent is selected from two or three of N, N-dimethylacetamide, deionized water, acetone and dichloromethane.
Further, according to the preparation method, the mass ratio of the three-dimensional covalent organic framework structure HCOF-T to the activator is 0.25:1-4:1.
Further, in the preparation method, the activator is potassium hydroxide, potassium carbonate or zinc chloride.
The third technical scheme of the invention is that the application of the three-dimensional heteroatom doped porous carbon material is that the three-dimensional heteroatom doped porous carbon material is used as an electrode material of a supercapacitor.
Further, in the application, the porous carbon material is mixed with carbon black, polytetrafluoroethylene (PTFE) aqueous solution and absolute ethyl alcohol are added, after uniform grinding, the mixture is coated on foam nickel, and the mixture is pressed into tablets, and then the electrode is soaked in KOH solution for 10-12 hours, so that the working electrode is obtained.
The beneficial effects of the invention are as follows:
1. the method obtains the precursor containing the hetero atoms through cross coupling reaction, and then obtains the porous carbon material through high-temperature calcination. The method has the advantages of easily available raw materials, simple and reliable preparation process and higher yield, and can meet the actual production requirements.
2. The porous carbon material provided by the invention has a heteroatom-containing structure and a high specific surface area, can provide a large number of contact sites, has a specific capacitance as high as 430F/g, and overcomes the defect of poor electrochemical performance caused by large ion transmission resistance, long diffusion distance and small specific surface area of the traditional carbon material. Can be directly used as an electrode material of the super capacitor, has excellent electrochemical performance and has good application prospect in the energy storage field.
3. The porous carbon material provided by the invention is used as a supercapacitor electrode, and after 1000 times of cycle tests under the current density of 1A/g, the capacitance retention rate is 99.21%, so that the material has excellent cycle stability, and has good application prospect in the energy storage field as a supercapacitor electrode material.
4. The specific surface area of the porous carbon material provided by the invention is more than 2000m 2 And/g, the heteroatom-containing structure and the high specific surface area enable the material to be fully contacted with the electrolyte, and the specific capacitance is increased by providing a large number of ion storage active sites, so that the electrochemical performance of the material is improved.
Drawings
FIG. 1 is an infrared spectrum of the monomer used in example 1 and HCOF-T1 prepared;
wherein a is 4,4' -difluorodiphenyl sulfone, b is tetra- (4-hydroxystyrene) ethylene, and c is the prepared HCOF-T1.
FIG. 2 is a scanning electron microscope image of the precursor three-dimensional heteroatom-containing covalent organic framework material HCOF-T1 prepared in example 1.
FIG. 3 is a scanning electron microscope image of HCOF-T1-800 of the porous carbon material prepared in example 1.
FIG. 4 is XRD data for HCOF-T1-800 of the porous carbon material prepared in example 1.
FIG. 5 is a nitrogen adsorption-desorption isotherm of HCOF-T1-800 of the porous carbon material prepared in example 1.
FIG. 6 is a Raman curve of HCOF-T1-800 of the porous carbon material prepared in example 1.
FIG. 7 is a cyclic voltammogram of HCOF-T1-800 of the porous carbon material prepared in example 1;
(a) The speed is 5-100mv/s; (b) a speed of 100-500mv/s.
FIG. 8 is a constant current charge-discharge curve of HCOF-T1-800 of the porous carbon material prepared in example 1.
FIG. 9 is a graph showing the cycle performance of HCOF-T1-800 at 10A/g for the porous carbon material prepared in example 1.
Detailed Description
Example 1
The preparation method of the three-dimensional heteroatom doped porous carbon material HCOF-T1-800 comprises the following steps:
1. synthesis of three-dimensional heteroatom-containing covalent organic framework material HCOF-T1
250mg (1 mmol) of 4,4' -difluorodiphenyl sulfone, 200mg (0.5 mmol) of tetra- (4-hydroxystyrene) and 310mg (2.25 mmol) of anhydrous potassium carbonate are added into a round bottom flask under nitrogen atmosphere, then vacuum is pumped, nitrogen is introduced again, the circulation is repeated three times, and 10mL of anhydrous anaerobic N, N-dimethylacetamide is added into the reaction system by a dropwise adding method. Finally, the reaction system was heated to 165℃and reacted at reflux for 4.5 hours.
After the reaction is finished, the reactants are filtered by suction to leave solid insoluble matters, and the solid insoluble matters are respectively washed by N, N-dimethylacetamide and deionized water for removing unreacted monomers or residual catalysts which may exist. Drying for 12 hours at 180 ℃ in a vacuum drying oven, and then freeze-drying for 24 hours at-50 ℃ in vacuum, wherein the obtained powder is the three-dimensional oxygen-containing sulfur covalent organic framework material, the three-dimensional oxygen-containing sulfur covalent organic framework material is marked as HCOF-T1, the yield is 73.0%, the basic structural formula is shown as a structural formula I, and hetero atoms in the HCOF-T1 are oxygen and sulfur, so that the three-dimensional oxygen-containing sulfur covalent organic framework material is obtained.
The prepared covalent organic framework HCOF-T1 is characterized as a polymer, the molecular weight ranges from 1000 to 2000, and the results are shown in figures 1 to 3. FIG. 1 is an infrared spectrum of the monomer used in this example and HCOF-T1 obtained. FIG. 1 (b) is an infrared spectrum of tetra- (4-hydroxystyrene). From FIG. 1 (c), it can be seen that after the COFs material was synthesized, the stretching vibration peak of the hydroxyl group disappeared, and a stretching vibration peak of the Ar-O-Ar ether bond was obtained, indicating that a new ether bond was formed in the skeleton. FIG. 2 is a scanning electron microscope image of the prepared precursor three-dimensional heteroatom-containing covalent organic framework material HCOF-T1, and the three-dimensional structure of the HCOF-T1 can be observed.
2. Preparation of porous carbon Material HCOF-T1-800
The three-dimensional heteroatom-containing covalent organic framework material HCOF-T1 prepared in the step 1 is used as a precursor, and the precursor and potassium hydroxide are mixed according to the mass ratio of 1:2 is placed in a porcelain boat, then is horizontally placed in a tube furnace, is heated to 800 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, is kept at the temperature for 1 hour, is cooled to room temperature, and is obtained as the three-dimensional heteroatom doped porous carbon material based on the three-dimensional heteroatom-containing covalent organic framework material, and is marked as HCOF-T1-800.
FIG. 3 is a scanning electron microscope image of HCOF-T1-800 of the porous carbon material prepared in this example, and compared with FIG. 2, the morphology of the material is greatly changed and the pores are obviously increased before and after carbonization. FIG. 4 shows XRD data of HCOF-T1-800 of the porous carbon material prepared in this example. FIG. 5 is a nitrogen adsorption-desorption isotherm of HCOF-T1-800 of the porous carbon material prepared in this example. FIG. 6 is a Raman curve of HCOF-T1-800 of the porous carbon material prepared in this example.
Example 2
A preparation method of a three-dimensional heteroatom doped porous carbon material HCOF-T1-700 comprises the following steps: the procedure and method were substantially the same as in example 1, except that in step 2, the mixture was heated to 700℃at a heating rate of 5℃per minute and kept for 1 hour.
Example 3
A preparation method of a three-dimensional heteroatom doped porous carbon material HCOF-T1-900 comprises the following steps: the procedure and method were substantially the same as in example 1, except that in step 2, the mixture was heated to 900℃at a heating rate of 5℃per minute and kept for 1 hour.
Example 4
Preparing a three-dimensional heteroatom doped porous carbon material: the procedure and method were substantially the same as in example 1, except that the tetrakis- (4-hydroxystyrene) ethylene in step 1 was changed to 4,4' -dihydroxybenzophenone, and the resulting three-dimensional heteroatom-containing covalent organic framework was obtained in a yield of 75.2%.
Example 5
Preparing a three-dimensional heteroatom doped porous carbon material: the procedure and method were essentially the same as in example 1, except that the tetrakis- (4-hydroxystyrene) ethylene in step 1 was replaced with 4,4' -dihydroxydiphenyl sulfone, and the resulting covalent organic framework characterization was similar to example 1, with a yield of 78.5% for the resulting three-dimensional heteroatom-containing covalent organic framework.
Example 6
Preparing a three-dimensional heteroatom doped porous carbon material: the procedure and method were essentially the same as in example 1, except that the tetrakis- (4-hydroxystyrene) ethylene in step 1 was replaced with 2, 7-dihydroxynaphthalene, and the resulting covalent organic framework characterization was similar to example 1, with a yield of 80.5% for the three-dimensional heteroatom-containing covalent organic framework.
Example 7
Preparing a three-dimensional heteroatom doped porous carbon material: the procedure and method were essentially the same as in example 1 except that the tetrakis- (4-hydroxystyrene) ethylene in step 1 was replaced with 4,4' -dihydroxydiphenyl ether to give a covalent organic framework characterization result similar to example 1, and the yield of the resulting three-dimensional heteroatom-containing covalent organic framework was 75.5%.
Example 8
Preparing a three-dimensional heteroatom doped porous carbon material: the procedure and method were essentially the same as in example 1, except that the tetrakis- (4-hydroxystyrene) ethylene in step 1 was replaced with 3,5,3',5' -tetramethyl-4, 4' -dihydroxybiphenyl, and the resulting covalent organic framework characterization was similar to example 1, with a yield of 74.8% for the resulting three-dimensional heteroatom-containing covalent organic framework.
Example 9
Preparing a three-dimensional heteroatom doped porous carbon material: the procedure and method are essentially the same as in example 1, except that the 4,4' -difluorodiphenyl sulfone in step 1 is replaced with 2, 5-dichlorofuran to produce a covalent organic framework characterization result similar to example 1.
Example 10
Preparing a three-dimensional heteroatom doped porous carbon material: the procedure and method are essentially the same as in example 1, except that the 4,4 '-difluorodiphenyl sulfone in step 1 is replaced with 4,4' -dichlorodiphenyl sulfone to produce a covalent organic framework characterization result similar to example 1.
Example 11
Preparing a three-dimensional heteroatom doped porous carbon material: the procedure and method are essentially the same as in example 1, except that the 4,4' -difluorodiphenyl sulfone in step 1 is replaced with 2, 5-dichloropyridine to produce a covalent organic framework characterization result similar to example 1.
Example 12
Preparing a three-dimensional heteroatom doped porous carbon material: the procedure and method are essentially the same as in example 1, except that the 4,4' -difluorodiphenyl sulfone in step 1 is replaced with 2, 5-dichlorothiophene to produce a covalent organic framework characterization result similar to example 1.
Example 13
Application of porous carbon Material of example 1
1. The method comprises the following steps:
4mg of porous carbon material HCOF-T1-800,0.5mg of carbon black was added with 1 drop of Polytetrafluoroethylene (PTFE) aqueous solution (PTFE: deionized water=1:9) and 1 drop of absolute ethyl alcohol, ground into a black paste in a mortar, and applied to 1m 2 Pressing the foam nickel into a sheet by using 10MPa pressure, and soaking the pressed electrode in 6M KOH solution for 12 hours to obtain the working electrode.
The working electrode adopts porous carbon material HCOF-T1-800 supported foam nickel, the counter electrode adopts a platinum net, the reference electrode adopts Hg/HgO electrode, a three-electrode system is formed together, and a 6M KOH aqueous solution is used as an electrolyte solution.
2. Detection of
FIG. 7 is a cyclic voltammogram of HCOF-T1-800 of the porous carbon material prepared in example 1. As can be seen from fig. 7, the cyclic voltammogram of the HCOF-T1-800 porous carbon material shows a quasi-rectangular shape, which indicates that the material has good electrochemical reversibility and shows ideal electric double layer capacitor characteristics.
FIG. 8 is a constant current charge-discharge curve of HCOF-T1-800 of the porous carbon material prepared in example 1. As can be seen from FIG. 8, the HCOF-T1-800 porous carbon material curve presents a quasi-triangle shape, which shows that the HCOF-T1-800 porous carbon material has certain electrochemical behavior and is mild and good with the cyclic voltammogram, the specific capacitance is as high as 430F/g, and the electrochemical performance is far higher than that of other similar materials.
FIG. 9 is a graph showing the cycle performance of HCOF-T1-800 at 10A/g for the porous carbon material prepared in this example 1. From fig. 9, after 10000 times of circulation, the capacitor retention rate is 82.2%, and the coulomb efficiency is 92.3%, which indicates that the material has excellent circulation stability, and the material has good application prospect in the energy storage field as the super capacitor electrode material.
Claims (10)
1. The three-dimensional heteroatom doped porous carbon material is characterized in that a three-dimensional heteroatom doped porous carbon material is obtained by taking a three-dimensional heteroatom-containing covalent organic framework HCOF-T as a precursor and roasting;
the mass percentage of the hetero atoms of the porous carbon material is 10-30%;
the preparation method of the HCOF-T comprises the following steps: and in an inert gas atmosphere, uniformly mixing the dihalogen aromatic heterocyclic organic monomer, the hydroxyl-containing aromatic conjugated organic monomer and the alkali, adding a solvent, reacting for 4-5 hours at 150-170 ℃, washing the obtained product by using a washing solvent, and drying to obtain the three-dimensional heteroatom-containing covalent organic framework material HCOF-T.
2. The three-dimensional, heteroatom-doped porous carbon material of claim 1, characterized in that the porous carbon material has a specific surface area of 2000-3000m 2 /g, average pore size of 1.8-5.5. 5.5nm.
3. The three-dimensional, heteroatom-doped porous carbon material according to claim 1 or 2, characterized in that the heteroatoms are oxygen atoms, sulfur atoms, or oxygen and sulfur atoms;
when the hetero atoms are oxygen atoms and sulfur atoms, the oxygen mass percent is 10-22% of the total mass of the porous carbon material, and the sulfur mass percent is 1.5-6% of the total mass of the porous carbon material.
4. The method for preparing the three-dimensional heteroatom doped porous carbon material as claimed in claim 1, comprising the steps of:
1) Preparation of a three-dimensional heteroatom-containing covalent organic framework: uniformly mixing a dihalogen aromatic heterocyclic organic monomer, a hydroxyl-containing aromatic conjugated organic monomer and alkali in an inert gas atmosphere, adding a solvent, reacting for 4-5 hours at 150-170 ℃, washing the obtained product by a washing solvent, and drying to obtain a three-dimensional heteroatom-containing covalent organic framework material HCOF-T;
2) Preparation of porous carbon material: and (3) taking a three-dimensional heteroatom-containing covalent organic framework HCOF-T as a precursor, mixing with an activating agent, heating to 700-900 ℃ in a heating furnace at a speed of 3-5 ℃/min under an inert gas atmosphere, and preserving heat for 45-60 min at the temperature to obtain the porous carbon material.
5. The method for preparing a three-dimensional heteroatom doped porous carbon material according to claim 4, wherein the dihalogen aromatic heterocyclic organic monomer is an aromatic heterocyclic organic monomer containing two halogen atom structures;
the hydroxyl-containing aromatic conjugated organic monomer is an aromatic conjugated organic monomer containing a hydroxyl structural unit.
6. The method for preparing a three-dimensional heteroatom doped porous carbon material according to claim 4, wherein the solvent is anhydrous and oxygen-free N, N-dimethylacetamide.
7. The method for preparing a three-dimensional heteroatom doped porous carbon material according to claim 4, wherein the washing solvent is selected from two or three of N, N-dimethylacetamide, deionized water, acetone and methylene chloride.
8. The method for preparing a three-dimensional heteroatom doped porous carbon material according to claim 4, wherein the activator is potassium hydroxide, potassium carbonate, or zinc chloride.
9. Use of a three-dimensional heteroatom doped porous carbon material according to claim 1, characterized in that the three-dimensional heteroatom doped porous carbon material is used as electrode material for supercapacitors.
10. The use of a three-dimensional heteroatom doped porous carbon material according to claim 9, characterized in that the three-dimensional heteroatom doped porous carbon material is used as electrode material of a supercapacitor by the following method:
mixing a porous carbon material with carbon black, adding polytetrafluoroethylene aqueous solution and absolute ethyl alcohol, grinding uniformly, coating the mixture on foam nickel, tabletting, and soaking in KOH solution for 10-12 hours to obtain the working electrode.
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