CN114436242A - 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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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. According to the three-dimensional heteroatom-doped porous carbon material, a cross coupling reaction is carried out on a double-halogen aromatic heterocyclic organic monomer, a hydroxyl-containing aromatic conjugated organic monomer and anhydrous potassium carbonate to prepare a three-dimensional heteroatom-containing covalent organic framework material, and then a three-dimensional heteroatom-containing covalent organic framework is used as a precursor and is roasted to obtain the three-dimensional heteroatom-doped porous carbon material; the mass percentage of the heteroatom in the porous carbon material is 10-30%. The porous carbon material prepared by the invention is used as a supercapacitor electrode material and shows excellent electrochemical performance.
Description
Technical Field
The invention belongs to the technical field of carbon materials, and particularly relates to a porous carbon material with a three-dimensional heteroatom-containing covalent organic framework structure, a preparation method of the porous carbon material and application of the porous carbon material in a super capacitor electrode.
Background
With the problems of non-renewable and gradually exhausted fossil fuels, the development of efficient energy storage devices has become a hot spot of scientific research. A supercapacitor, also called an electrochemical capacitor, is a new energy storage device, and has attracted attention due to its unique advantages of high power density, excellent cycle stability, fast charge and discharge rate, and low maintenance cost. Among them, a device that provides electric double layer capacitance by accumulating charges at an electrode/electrolyte interface using a carbon material as an electrode material is called an electric double layer capacitor. Pseudocapacitors are devices that transfer pseudocapacitance through faradaic redox reactions, typically various compounds and conducting polymers assembled together.
The porous carbon material has become a research hotspot in the fields of chemistry, biology, materials and the like due to the advantages of high specific surface area, rich 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 attracted attention as electrode materials for electric double layer supercapacitors because of their good electrical conductivity. However, the carbon material has a low specific capacitance, which greatly limits the practical application value. The document reports that heteroatom doped porous carbon is easy to be approached by electrolyte ions, so that the electrolyte ions can be rapidly diffused to promote electron transfer and improve the specific capacitance of an electrode material.
Porous organic polymer materials (POPs) have rapidly developed as a new generation of porous materials and are widely used in the fields of adsorbents, catalysts, storage and separation of gases, energy storage, electronic devices, and the like. According to different structural characteristics, the polymer material is mainly divided into a hypercrosslinked polymer material, a self-contained microporous polymer material, a conjugated microporous polymer material and a covalent organic framework material (COFs). The COFs are novel porous materials formed by connecting light elements such as C, H, O, N and the like through covalent bonds, and have the characteristics of high specific surface area, good thermal stability, high porosity, low skeleton density, excellent physical and chemical stability, various synthetic routes, easiness in modification, ordered structure, controllable functions and the like. Compared with the traditional carbon material, the COFs have high specific surface area, excellent stability and good micropore structure, and can increase the contact of electrode electrolyte through ion transmission in ordered pore channels. In addition, the expanded pi conjugated skeleton can serve as an effective transmission medium, and is favorable for improving the electrochemical performance. However, because of its limitations in the connection method, the synthesis of COFs is more difficult than other materials.
The Cote subject group synthesizes COFs materials by using a topological design method in 2005; the Yaghi research group synthesizes COFs materials by utilizing the dehydration condensation reaction of 1, 4-p-diphenylboronic acid on the COFs; however, the above methods all have certain drawbacks to some extent; in many synthesis methods, heavy metal catalysts such as Pd and Ni are used for catalysis, so that the cost is increased, industrial production cannot be performed, the reaction steps are various, and some methods also need a high-pressure kettle for hydrothermal reaction and have certain dangerousness.
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. According to the invention, a cross coupling reaction is carried out on a double-halogen aromatic heterocyclic organic monomer, a hydroxyl-containing aromatic conjugated organic monomer and anhydrous potassium carbonate to prepare a three-dimensional heteroatom-containing covalent organic framework material, and the three-dimensional heteroatom-containing covalent organic framework material is directly subjected to high-temperature carbonization as a precursor to obtain the porous carbon material. The prepared porous carbon material is used as a super capacitor electrode material and shows excellent electrochemical performance.
One of the technical schemes of the invention is that a three-dimensional heteroatom-doped porous carbon material is prepared by roasting a three-dimensional heteroatom-containing covalent organic framework HCOF-T serving as a precursor;
the mass percentage of the heteroatom of the porous carbon material is 10-30%.
Further, the specific surface area of the three-dimensional heteroatom-doped porous carbon material is 2000-3000m2(ii)/g, the average pore diameter is 1.8-5.5 nm.
Further, the above three-dimensional heteroatom is doped with a porous carbon material, and the heteroatom is an oxygen atom, a sulfur atom, or an oxygen atom and a sulfur atom;
when the heteroatoms are oxygen atoms and sulfur atoms, the mass percent of the oxygen is 10-22% of the total mass of the porous carbon material, and the mass percent of the sulfur 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 three-dimensional heteroatom-containing covalent organic frameworks: uniformly mixing a double-halogen aromatic heterocyclic organic monomer, a hydroxyl-containing aromatic conjugated organic monomer and alkali in an inert gas atmosphere, adding a solvent, reacting at the temperature of 150 ℃ and 170 ℃ for 4-5 hours, washing the obtained product with 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 the precursor with an activating agent, heating to 700-900 ℃ in a heating furnace at the speed of 3-5 ℃/min in the atmosphere of inert gas, and then preserving heat for 45-60 min at the temperature to obtain the porous carbon material.
Further, in the above preparation method, the double-halogen aromatic heterocyclic organic monomer is an aromatic heterocyclic organic monomer containing two halogen atom structures.
Further, in the above preparation method, the contained double-halogen aromatic heterocyclic organic monomer comprises: 4,4 '-difluoro diphenyl sulfone, 2, 5-dichloro furan, 4' -dichloro diphenyl sulfone, 2, 5-dichloropyridine and 2, 5-dichloro thiophene.
Further, in the above preparation method, the hydroxyl group-containing aromatic conjugated organic monomer is an aromatic conjugated organic monomer containing a hydroxyl group structural unit.
Further, in the above preparation method, the hydroxyl-containing aromatic conjugated organic monomer is: tetrakis- (4-hydroxystyrene), 4,4 '-dihydroxybenzophenone, 4,4' -dihydroxybenzenesulfone, 2, 7-dihydroxynaphthalene, 4,4 '-dihydroxydiphenyl ether, 3,5,3',5 '-tetramethyl-4, 4' -dihydroxybiphenyl.
Further, in the above production method, the base is an anhydrous alkali metal or an anhydrous alkaline earth metal carbonate; for example, anhydrous sodium hydroxide, anhydrous potassium hydroxide, anhydrous sodium carbonate, anhydrous potassium carbonate; preferably, the base is anhydrous potassium carbonate.
Further, in the above preparation method, the solvent is anhydrous and oxygen-free N, N-dimethylacetamide.
Further, in the above preparation method, the solvent is added dropwise.
Further, in the above production method, the ratio of the amounts of the substance of the dihalogen aromatic heterocyclic organic monomer to the substance of the hydroxyl-containing aromatic conjugated organic monomer is 1: 1.
Further, in the above preparation method, the ratio of the amounts of the (dihalogen aromatic heterocyclic organic monomer + hydroxyl-containing aromatic conjugated organic monomer) and the anhydrous potassium carbonate is 1:1 to 1: 3.
Further, in the above production method, the ratio of the amounts of the substance (the dihalogen heteroaromatic organic monomer + the hydroxyl-containing aromatic conjugated organic monomer) and the solvent is from 1:10 to 1: 150.
Further, in the above preparation method, the washing solvent is two or three selected from N, N-dimethylacetamide, deionized water, acetone and dichloromethane.
Further, in the above preparation method, the mass ratio of the three-dimensional covalent organic framework structure HCOF-T to the activator is 0.25:1 to 4: 1.
Further, in the above preparation method, the activating agent 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 and the carbon black are mixed, Polytetrafluoroethylene (PTFE) aqueous solution and absolute ethyl alcohol are added, the mixture is uniformly ground, coated on foamed nickel, pressed into sheets, and then the electrode is soaked in KOH solution for 10-12 hours, so that the working electrode is obtained.
The invention has the beneficial effects that:
1. the invention obtains the precursor containing the heteroatom 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 high 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 a super capacitor electrode material, shows excellent electrochemical performance and has good application prospect in the field of energy storage.
3. The porous carbon material provided by the invention is used as a super capacitor electrode, and the capacitance retention rate is 99.21% after 1000 times of cycle tests under the current density of 1A/g, which shows that the material has excellent cycle stability and has good application prospect in the field of energy storage as a super capacitor electrode material.
4. The specific surface area of the porous carbon material provided by the invention is more than 2000m2The material is fully contacted with an electrolyte by virtue of a heteroatom-containing structure and high specific surface area, and 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 a chart of the infrared spectrum of the monomer used in example 1 and HCOF-T1 obtained;
wherein a is 4,4' -difluorodiphenyl sulfone, b is tetrakis- (4-hydroxystyrene) ethylene, and c is the resulting HCOF-T1.
FIG. 2 is a scanning electron microscope image of a precursor three-dimensional heteroatom-containing covalent organic framework material HCOF-T1 prepared in example 1.
FIG. 3 is a scanning electron micrograph of HCOF-T1-800 of the porous carbon material prepared in example 1.
FIG. 4 is XRD data of 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 5-100 mv/s; (b) the speed is 100-500 mv/s.
FIG. 8 is a constant current charge and discharge curve of HCOF-T1-800 of the porous carbon material prepared in example 1.
FIG. 9 is a graph of the cycle performance at 10A/g of HCOF-T1-800 of the porous carbon material prepared in example 1.
Detailed Description
Example 1
A preparation method of a 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 (1mmol) of 4,4' -difluorodiphenyl sulfone, 200mg (0.5mmol) of tetrakis- (4-hydroxystyrene) ethylene and 310mg (2.25mmol) of anhydrous potassium carbonate were charged into a round-bottom flask under a nitrogen atmosphere, followed by vacuum evacuation and nitrogen re-introduction, and the cycle was repeated three times, and then 10mL of anhydrous oxygen-free N, N-dimethylacetamide was added dropwise to the reaction system. Finally, the reaction was heated to 165 ℃ and refluxed for 4.5 hours.
After the reaction is finished, carrying out suction filtration on the reactant to leave solid insoluble substances, and respectively washing the solid insoluble substances for multiple times by using N, N-dimethylacetamide and deionized water for removing unreacted monomers or residual catalysts which may exist. Drying in a vacuum drying oven at 180 ℃ for 12 hours, and then carrying out vacuum freeze drying at-50 ℃ for 24 hours to obtain powder, namely the three-dimensional covalent organic framework material containing the heteroatoms, wherein the powder is marked as HCOF-T1, the yield is 73.0%, the basic structural formula is shown as a structural formula I, and the heteroatoms in HCOF-T1 are oxygen and sulfur, namely the three-dimensional covalent organic framework material containing the oxygen and the sulfur.
The prepared covalent organic framework HCOF-T1 was characterized as a polymer with a molecular weight range of 1000-2000, and the results are shown in FIGS. 1-3. FIG. 1 shows an infrared spectrum of a monomer used in this example and HCOF-T1 obtained therefrom. FIG. 1(b) is an infrared spectrum of tetrakis- (4-hydroxystyrene) ethylene. As can be seen from FIG. 1(c), the hydroxyl stretching vibration peak disappears after the synthesis of the COFs material, and the stretching vibration peak of Ar-O-Ar ether bond is obtained, indicating that a new ether bond is formed in the skeleton. FIG. 2 is a scanning electron microscope image of the precursor three-dimensional heteroatom-containing covalent organic framework material HCOF-T1, and a three-dimensional structure of HCOF-T1 can be observed.
2. Preparation of porous carbon material HCOF-T1-800
Taking the three-dimensional heteroatom-containing covalent organic framework material HCOF-T1 prepared in the step 1 as a precursor, and mixing the precursor with potassium hydroxide according to the mass ratio of 1: 2, placing the mixture in a porcelain boat, horizontally placing the porcelain boat in a tube furnace, heating the mixture to 800 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, preserving the heat for 1 hour, cooling the mixture to room temperature, and obtaining the three-dimensional heteroatom-doped porous carbon material based on the three-dimensional heteroatom-containing covalent organic framework material, wherein the mark is HCOF-T1-800.
FIG. 3 is a scanning electron microscope image of HCOF-T1-800 of the porous carbon material prepared in this example, comparing with FIG. 2, before and after carbonization, the morphology of the material changes greatly, and the pores increase significantly. FIG. 4 is 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 ℃/min and held 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 temperature was raised to 900 ℃ at a rate of 5 ℃/min and maintained for 1 hour.
Example 4
Preparation of a three-dimensional heteroatom-doped porous carbon material: the procedure and method were substantially the same as in example 1, except that tetrakis- (4-hydroxybenzene) ethene was replaced with 4,4' -dihydroxybenzophenone in step 1, and the yield of the resulting three-dimensional heteroatom-containing covalent organic framework was 75.2%.
Example 5
Preparation of 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 was replaced with 4,4' -dihydroxydiphenylsulfone in step 1, and the resulting covalent organic skeleton was characterized similarly to example 1, and the yield of the resulting three-dimensional heteroatom-containing covalent organic skeleton was 78.5%.
Example 6
Preparation of 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 was replaced with 2, 7-dihydroxynaphthalene in step 1, and the resulting covalent organic skeleton was characterized similarly to example 1, and the yield of the resulting three-dimensional heteroatom-containing covalent organic skeleton was 80.5%.
Example 7
Preparation of a three-dimensional heteroatom-doped porous carbon material: the procedure and method were substantially the same as in example 1, except that tetrakis- (4-hydroxystyrene) ethylene was replaced with 4,4' -dihydroxydiphenyl ether in step 1, and the characterization result of the obtained covalent organic skeleton was similar to that in example 1, and the yield of the obtained three-dimensional heteroatom-containing covalent organic skeleton was 75.5%.
Example 8
Preparation of a three-dimensional heteroatom-doped porous carbon material: the procedure and method were substantially the same as in example 1, except that the covalent organic skeleton obtained in step 1 was characterized by replacing tetrakis- (4-hydroxystyrene) ethylene with 3,5,3',5' -tetramethyl-4, 4' -dihydroxybiphenyl, and the yield of the three-dimensional heteroatom-containing covalent organic skeleton was 74.8%, similarly to example 1.
Example 9
Preparation of a three-dimensional heteroatom-doped porous carbon material: the procedure and method were substantially the same as in example 1 except that 4,4' -difluorodiphenyl sulfone was changed to 2, 5-dichlorofuran in step 1, and the characterization results of the resulting covalent organic framework were similar to those in example 1.
Example 10
Preparation of a three-dimensional heteroatom-doped porous carbon material: the procedure and method were substantially the same as in example 1 except that 4,4 '-difluorodiphenyl sulfone was changed to 4,4' -dichlorodiphenyl sulfone in step 1, and the characterization results of the resulting covalent organic skeleton were similar to those in example 1.
Example 11
Preparation of a three-dimensional heteroatom-doped porous carbon material: the procedure and method were substantially the same as in example 1 except that 4,4' -difluorodiphenyl sulfone was replaced with 2, 5-dichloropyridine in step 1, and the characterization results of the resulting covalent organic framework were similar to those in example 1.
Example 12
Preparation of a three-dimensional heteroatom-doped porous carbon material: the procedure and method were substantially the same as in example 1 except that 4,4' -difluorodiphenyl sulfone was changed to 2, 5-dichlorothiophene in step 1, and the characterization results of the resulting covalent organic framework were similar to those in example 1.
Example 13
Application of the porous carbon Material of example 1
1. The method comprises the following steps:
grinding 4mg of porous carbon material HCOF-T1-800, 0.5mg of carbon black, 1 drop of aqueous solution of Polytetrafluoroethylene (PTFE) (PTFE: deionized water: 1:9) and 1 drop of absolute ethyl alcohol in a mortar into black paste, and coating the black paste onto 1m2Pressing the nickel foam into a sheet under the pressure of 10MPa, and soaking the pressed electrode in 6M KOH solution for 12 hours to obtain the working electrode.
The working electrode adopts foam nickel loaded with porous carbon material HCOF-T1-800, the counter electrode adopts platinum mesh, the reference electrode adopts Hg/HgO electrode, and a three-electrode system is formed together, and 6M KOH aqueous solution is used as 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 voltammetry curves of the HCOF-T1-800 porous carbon material show quasi-rectangular shapes, which indicates that the material has good electrochemical reversibility and shows ideal characteristics of an electric double layer capacitor.
FIG. 8 is a constant current charge and discharge curve of HCOF-T1-800 of the porous carbon material prepared in example 1. As can be seen from FIG. 8, the curve of the HCOF-T1-800 porous carbon material shows a quasi-triangular shape, which indicates that it has a certain electrochemical behavior and is mild and good with cyclic voltammetry curve, its specific capacitance is as high as 430F/g, and its electrochemical performance is much higher than that of other similar materials.
FIG. 9 is a graph showing the cycle characteristics at 10A/g of HCOF-T1-800 in the porous carbon material prepared in example 1. As can be seen from FIG. 9, after 10000 times of circulation, the capacitance retention rate is 82.2%, and the coulombic efficiency is 92.3%, which shows that the material has excellent circulation stability, and has good application prospect in the field of energy storage as a super capacitor electrode material.
Claims (10)
1. A three-dimensional heteroatom-doped porous carbon material is characterized in that a three-dimensional heteroatom-containing covalent organic framework HCOF-T is used as a precursor, and the precursor is roasted to obtain the three-dimensional heteroatom-doped porous carbon material;
the mass percentage of the heteroatom of the porous carbon material is 10-30%.
2. The three-dimensional heteroatom-doped porous carbon material as claimed in claim 1, wherein the specific surface area of the porous carbon material is 2000-3000m2(ii)/g, the average pore diameter is 1.8-5.5 nm.
3. The three-dimensional heteroatom-doped porous carbon material of claim 1 or 2, wherein the heteroatom is an oxygen atom, a sulfur atom, or an oxygen atom and a sulfur atom;
when the heteroatoms are oxygen atoms and sulfur atoms, the mass percent of the oxygen is 10-22% of the total mass of the porous carbon material, and the mass percent of the sulfur 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 according to claim 1, comprising the steps of:
1) preparation of three-dimensional heteroatom-containing covalent organic frameworks: uniformly mixing a double-halogen aromatic heterocyclic organic monomer, a hydroxyl-containing aromatic conjugated organic monomer and alkali in an inert gas atmosphere, adding a solvent, reacting at the temperature of 150 ℃ and 170 ℃ for 4-5 hours, washing the obtained product with 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 the precursor with an activating agent, heating to 700-900 ℃ in a heating furnace at the speed of 3-5 ℃/min in the atmosphere of inert gas, and then preserving heat for 45-60 min at the temperature to obtain the porous carbon material.
5. The method for preparing the three-dimensional heteroatom-doped porous carbon material as claimed in claim 4, wherein the double-halogen 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 the three-dimensional heteroatom-doped porous carbon material as claimed in 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 as claimed in claim 4, wherein the washing solvent is two or three selected from N, N-dimethylacetamide, deionized water, acetone and dichloromethane.
8. The method for preparing the three-dimensional heteroatom-doped porous carbon material according to claim 4, wherein the activator is potassium hydroxide, potassium carbonate or zinc chloride.
9. The application of the three-dimensional heteroatom-doped porous carbon material is characterized in that the three-dimensional heteroatom-doped porous carbon material is used as an electrode material of a supercapacitor.
10. The use of the three-dimensional heteroatom-doped porous carbon material as claimed in claim 9, wherein the method for using the three-dimensional heteroatom-doped porous carbon material as an electrode material of a supercapacitor is as follows:
mixing a porous carbon material with carbon black, adding a polytetrafluoroethylene aqueous solution and absolute ethyl alcohol, grinding uniformly, coating on foamed nickel, tabletting, and soaking in a KOH solution for 10-12 hours to obtain the working electrode.
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