CN111777055A - Preparation method of heteroatom-doped porous carbon electrode material - Google Patents
Preparation method of heteroatom-doped porous carbon electrode material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 49
- 239000007772 electrode material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000499 gel Substances 0.000 claims abstract description 20
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000017 hydrogel Substances 0.000 claims abstract description 17
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 14
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 14
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 14
- 239000000661 sodium alginate Substances 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 239000003999 initiator Substances 0.000 claims abstract description 12
- 238000003763 carbonization Methods 0.000 claims abstract description 11
- 238000010000 carbonizing Methods 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000004108 freeze drying Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- 230000000977 initiatory effect Effects 0.000 claims description 7
- 230000033116 oxidation-reduction process Effects 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulphite Substances [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- QWMJEUJXWVZSAG-UHFFFAOYSA-N (4-ethenylphenyl)boronic acid Chemical compound OB(O)C1=CC=C(C=C)C=C1 QWMJEUJXWVZSAG-UHFFFAOYSA-N 0.000 claims description 3
- KKMZQOIASVGJQE-UHFFFAOYSA-N 3-thiophen-2-ylprop-2-enoic acid Chemical compound OC(=O)C=CC1=CC=CS1 KKMZQOIASVGJQE-UHFFFAOYSA-N 0.000 claims description 3
- HUTNXAYRNHOZHL-UHFFFAOYSA-N 4-methyl-3h-1,3-oxazol-2-one Chemical compound CC1=COC(=O)N1 HUTNXAYRNHOZHL-UHFFFAOYSA-N 0.000 claims description 3
- 229930029653 phosphoenolpyruvate Natural products 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- -1 phosphoenolpyruvate cyclohexylammonium salt Chemical class 0.000 claims description 2
- 239000003431 cross linking reagent Substances 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 239000003575 carbonaceous material Substances 0.000 description 14
- 238000011065 in-situ storage Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- AGPGZWSWDHDTSD-UHFFFAOYSA-N cyclohexanamine;2-oxopropanoic acid Chemical compound CC(=O)C([O-])=O.[NH3+]C1CCCCC1 AGPGZWSWDHDTSD-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- DTBNBXWJWCWCIK-UHFFFAOYSA-N phosphoenolpyruvic acid Chemical compound OC(=O)C(=C)OP(O)(O)=O DTBNBXWJWCWCIK-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- 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
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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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Abstract
The invention relates to a preparation method of a heteroatom-doped porous carbon electrode material, which comprises the following steps: uniformly mixing acrylamide, N' -methylene bisacrylamide, sodium alginate, a comonomer containing a heteroatom and water in a mass ratio of 0.02-0.1: 0.002-0.015: 0-0.02: 0-0.1: 1 to obtain a mixed solution, introducing nitrogen to remove oxygen, and adding an initiator to react to obtain hydrogel; and (3) freeze-drying the hydrogel to obtain dry gel, carbonizing the dry gel, and washing and drying to obtain the heteroatom-doped porous carbon electrode material. According to the preparation method, acrylamide and a comonomer containing heteroatoms are used as reactants, N, N' -methylene bisacrylamide is used as a cross-linking agent, sodium alginate is used as a viscosity regulator of a reaction system, the preparation method is simple, carbonization and heteroatom doping are completed in one step, and the prepared porous carbon electrode material is controllable in heteroatom type and content and has excellent capacitance performance.
Description
Technical Field
The invention relates to the technical field of electrode materials of supercapacitors, in particular to a preparation method of a heteroatom-doped porous carbon electrode material for a supercapacitor.
Background
With the gradual depletion of global fossil energy and the increasing severity of environmental problems, the development and utilization of new energy has attracted high attention from countries in the world. Efficient energy storage and conversion devices are the key to new energy utilization, so that novel electrochemical energy devices such as super capacitors, fuel cells and lithium batteries become the current research hotspots. In these electrochemical energy devices, the electrode material is a key factor affecting the performance.
Porous carbon materials are considered to be the most potential electrode materials due to their large specific surface area, tunable pore structure, good electrical conductivity, and more electrochemically active sites for many redox reactions. At present, the development of porous carbon materials focuses on two aspects of regulation and control of pore structures and heteroatom doping, which are also fundamental factors influencing the application performance of the porous carbon materials. Heteroatom doping is an effective method for improving the performance of the porous carbon electrode material. For example, the porous carbon is doped with a proper amount of heteroatoms such as N, B, P, S, the specific capacitance of the porous carbon material can be improved by utilizing the pseudocapacitance formed by the redox reaction of the heteroatoms, and the doping of the heteroatoms can also improve the conductivity, improve the wettability of the surface of the carbon material and further improve the capacitance performance of the carbon material. In electrocatalysis, non-metallic heteroatoms with different electronegativities are doped into a carbon electrode material, so that the electrical neutrality of a carbon sp2 hybridization orbital can be destroyed, electrons of surrounding carbon are redistributed, and the electrocatalysis performance is improved.
At present, research on heteroatom doped porous carbon is active, and the heteroatom doping mainly comprises two methods, namely in-situ doping and post-treatment doping. In-situ doping refers to directly carbonizing a carbon precursor rich in heteroatoms at high temperature to obtain heteroatom-doped porous carbon in one step; the post-treatment doping is to perform impregnation and oxidation treatment on the porous carbon, or to place the porous carbon in gas containing heteroatoms, such as ammonia gas, and react at high temperature to obtain the heteroatom-doped porous carbon. In-situ doping facilitates uniform incorporation of heteroatoms into porous carbon, but currently there are fewer precursors suitable for preparing in-situ doped porous carbon, while there are fewer precursors containing 2 different heteroatoms. The post-treatment doping process is generally tedious and time-consuming, and usually only functionalizes the porous carbon surface without changing the bulk structure. Therefore, the development of a new method for preparing heteroatom-doped porous carbon with simple and controllable process is still a challenging subject.
Disclosure of Invention
The invention aims to solve the defects and provides a preparation method of a heteroatom-doped porous carbon electrode material.
A preparation method of a heteroatom-doped porous carbon electrode material comprises the following steps:
(1) uniformly mixing acrylamide, N' -methylene bisacrylamide, sodium alginate, a comonomer containing heteroatoms and water to obtain a mixed solution, introducing nitrogen to remove oxygen, and adding an initiator to initiate a polymerization reaction to obtain hydrogel;
(2) and (3) freeze-drying the hydrogel to obtain dry gel, carbonizing the dry gel, and washing and drying to obtain the heteroatom-doped porous carbon electrode material.
In the step (1), the mass ratio of the acrylamide to the N, N' -methylene bisacrylamide to the sodium alginate to the heteroatom-containing comonomer to the water is 0.02-0.1: 0.002-0.015: 0-0.02: 0-0.1: 1, and more preferably 0.03-0.06: 0.002-0.008: 0.008-0.012: 0.03-0.06: 1.
Further, in the step (1), the comonomer containing the heteroatom is selected from any one or a mixture of more than two of 3- (4-pyridyl) acrylic acid, 3- (2-thienyl) acrylic acid, 4-vinyl phenylboronic acid or phosphoenolpyruvate cyclohexylammonium salt in any proportion.
Further, in the step (1), the amount of the initiator is 1-6% of the total mass of the acrylamide and the comonomer containing the heteroatom.
Further, in the step (1), the initiator is one of potassium persulfate, ammonium persulfate or a water-soluble oxidation-reduction initiation system, and the water-soluble oxidation-reduction initiation system is selected from any one of potassium persulfate-sodium sulfite, potassium persulfate-sodium bisulfite, ammonium persulfate-sodium sulfite or ammonium persulfate-sodium bisulfite water-soluble oxidation-reduction initiation system.
Further, in the step (1), when the initiator is potassium persulfate or ammonium persulfate, the reaction temperature is 65-75 ℃, and the reaction time is 2-5 hours; when the initiator is a water-soluble oxidation-reduction initiation system, the reaction temperature is 20-30 ℃, and the reaction time is 2-5 h.
Further, in the step (2), the carbonization is carried out in the atmosphere of nitrogen, the carbonization temperature is 700-1000 ℃, and the time is 2-4 h.
The preparation principle of the heteroatom-doped porous carbon is as follows: according to the invention, acrylamide and comonomer containing heteroatom are used as reactants, N, N '-methylene bisacrylamide is used as a cross-linking agent, sodium alginate is used as a viscosity regulator of a reaction system, acrylamide, comonomer containing heteroatom, N, N' -methylene bisacrylamide and sodium alginate are mixed with water to form a uniform solution before polymerization, and an initiator is added to initiate free radical polymerization. As the polymerization proceeds, a hydrogel gradually forms. Because the copolymer gel contains the heteroatoms, the heteroatoms are doped in the porous carbon in the high-temperature carbonization process.
The invention has the following beneficial effects:
(1) the gel is formed by copolymerizing the monomer containing the heteroatom and acrylamide, so that the heteroatom is uniformly distributed in the copolymer gel, and the uniform doping of the carbonized heteroatom in the porous carbon is ensured.
(2) The content of the heteroatoms in the porous carbon can be conveniently regulated and controlled by changing the amount of the added comonomer containing the heteroatoms.
(3) Monomers containing different heteroatoms are copolymerized, so that various heteroatom-codoped porous carbons can be prepared.
(4) The prepared porous carbon has good specific capacitance, and the mass specific capacitance can reach 260F/g when the current density is 0.5A/g.
Detailed Description
In order that the objects and advantages of the invention will be more clearly understood, the following description is given in conjunction with the accompanying examples. It is to be understood that the following text is merely illustrative of one or more specific embodiments of the invention and does not strictly limit the scope of the invention as specifically claimed.
Example 1
A preparation method of a heteroatom-doped porous carbon electrode material comprises the following steps:
(1) uniformly mixing 0.36g of acrylamide, 0.04g N, N' -methylene bisacrylamide, 0.10g of sodium alginate and 9.0g of water to obtain a mixed solution, introducing nitrogen into the mixed solution to remove oxygen for half an hour, adding 10mg of potassium persulfate (dissolved in 1mL of water), and reacting in a water bath at 70 ℃ for 2 hours to obtain hydrogel;
(2) and (3) freeze-drying the hydrogel to obtain dry gel, carbonizing the dry gel for 2 hours at 800 ℃ in a nitrogen atmosphere, and washing and drying to obtain the porous carbon electrode material.
The porous carbon material prepared by the method has the N content of 6.8 atm%, and when the charge-discharge current density is 0.5A/g, the specific capacitance is 208.2F/g.
Example 2
A preparation method of a heteroatom-doped porous carbon electrode material comprises the following steps:
(1) uniformly mixing 0.24g of acrylamide, 0.04g N, N' -methylene bisacrylamide, 0.10g of sodium alginate, 0.12g of 3- (4-pyridyl) acrylic acid and 9.0g of water to obtain a mixed solution, introducing nitrogen into the mixed solution to remove oxygen for half an hour, adding 10mg of ammonium persulfate (dissolved in 1mL of water), and reacting in a water bath at 70 ℃ for 4 hours to obtain hydrogel;
(2) and (3) freeze-drying the hydrogel to obtain dry gel, carbonizing the dry gel for 2 hours at 800 ℃ in a nitrogen atmosphere, and washing and drying to obtain the porous carbon electrode material.
The porous carbon material prepared by the method has the N content of 8.2 atm%, and when the charge-discharge current density is 0.5A/g, the specific capacitance is 229.6F/g.
Example 3
A preparation method of a heteroatom-doped porous carbon electrode material comprises the following steps:
(1) uniformly mixing 0.24g of acrylamide, 0.04g N, N' -methylene bisacrylamide, 0.10g of sodium alginate, 0.12g of 3- (2-thienyl) acrylic acid and 9.0g of water to obtain a mixed solution, introducing nitrogen into the mixed solution to remove oxygen for half an hour, adding 10mg of ammonium persulfate (dissolved in 1mL of water), and reacting in a water bath at 70 ℃ for 4 hours to obtain hydrogel;
(2) and (3) freeze-drying the hydrogel to obtain dry gel, carbonizing the dry gel for 2 hours at 800 ℃ in a nitrogen atmosphere, and washing and drying to obtain the porous carbon electrode material.
The porous carbon material prepared by the method is simultaneously doped with N and S, the N content is 4.8 atm%, the S content is 3.2 atm%, and when the charge-discharge current density is 0.5A/g, the specific capacitance is 216.9F/g.
Example 4
A preparation method of a heteroatom-doped porous carbon electrode material comprises the following steps:
(1) uniformly mixing 0.24g of acrylamide, 0.04g N, N' -methylene bisacrylamide, 0.10g of sodium alginate, 0.12g of 4-vinyl phenylboronic acid and 9.0g of water to obtain a mixed solution, introducing nitrogen into the mixed solution to remove oxygen for half an hour, adding 10mg of ammonium persulfate (dissolved in 1mL of water), and reacting in a water bath at 70 ℃ for 4 hours to obtain hydrogel;
(2) and (3) freeze-drying the hydrogel to obtain dry gel, carbonizing the dry gel for 2 hours at 800 ℃ in a nitrogen atmosphere, and washing and drying to obtain the porous carbon electrode material.
The porous carbon material prepared by the method is simultaneously doped with N and B, the N content is 6.0 atm%, the B content is 4.9 atm%, and when the charge-discharge current density is 0.5A/g, the specific capacitance is 260.0F/g.
Example 5
A preparation method of a heteroatom-doped porous carbon electrode material comprises the following steps:
(1) uniformly mixing 0.24g of acrylamide, 0.04g N, N' -methylene bisacrylamide, 0.10g of sodium alginate, 0.12g of phosphoenolpyruvate cyclohexylammonium pyruvate salt and 9.0g of water to obtain a mixed solution, introducing nitrogen into the mixed solution to remove oxygen for half an hour, adding 10mg of ammonium persulfate (dissolved in 1mL of water), and reacting in a water bath at 70 ℃ for 4 hours to obtain hydrogel;
(2) and (3) freeze-drying the hydrogel to obtain dry gel, carbonizing the dry gel for 2 hours at 800 ℃ in a nitrogen atmosphere, and washing and drying to obtain the porous carbon electrode material.
The porous carbon material prepared by the method is simultaneously doped with N and P, the N content is 6.2 atm%, the P content is 4.2 atm%, and when the charge-discharge current density is 0.5A/g, the specific capacitance is 241.8F/g.
Example 6
The preparation process was the same as in example 1 except that the carbonization temperature was 700 ℃.
The prepared porous carbon material has the N content of 10.1 atm%, and the specific capacitance of 220.8F/g when the charge-discharge current density is 0.5A/g.
Example 7
The preparation process was the same as in example 1 except that the carbonization temperature was 900 ℃.
The prepared porous carbon material has the N content of 3.9 atm%, and the specific capacitance of 186.4F/g when the charge-discharge current density is 0.5A/g.
Example 8
The preparation process was the same as in example 1 except that the carbonization temperature was 1000 ℃.
The prepared porous carbon material has the N content of 2.6 atm%, and the specific capacitance of 173.1F/g when the charge-discharge current density is 0.5A/g.
Example 1 is different from examples 6 to 8 only in the carbonization temperature, and as can be seen from the results of the measurement of the heteroatom content and the capacitance performance, the carbonization temperature is an important factor affecting the heteroatom content, and the higher the carbonization temperature is, the lower the heteroatom content gradually decreases.
In summary, the invention discloses a preparation method of heteroatom-doped porous carbon, and gel formed by copolymerization of acrylamide and a heteroatom-containing monomer is used as a carbon source in the method, so that uniform and controllable doping of heteroatoms in the porous carbon can be conveniently realized.
The above embodiments are only used to illustrate the present invention and do not limit the technical solutions described in the present invention; thus, while the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted; all such modifications and variations are intended to be included herein within the scope of this disclosure and the present invention and protected by the following claims.
Claims (7)
1. A preparation method of a heteroatom-doped porous carbon electrode material is characterized by comprising the following steps:
(1) uniformly mixing acrylamide, N' -methylene bisacrylamide, sodium alginate, a comonomer containing heteroatoms and water to obtain a mixed solution, introducing nitrogen to remove oxygen, and adding an initiator to initiate a polymerization reaction to obtain hydrogel;
(2) freeze-drying the hydrogel to obtain dry gel, carbonizing the dry gel, and washing and drying to obtain the heteroatom-doped porous carbon electrode material;
in the step (1), the mass ratio of acrylamide, N' -methylene bisacrylamide, sodium alginate, the heteroatom-containing comonomer and water is 0.02-0.1: 0.002-0.015: 0-0.02: 0-0.1: 1.
2. The preparation method of the heteroatom-doped porous carbon electrode material as claimed in claim 1, wherein in the step (1), the mass ratio of the acrylamide, the N, N' -methylenebisacrylamide, the sodium alginate, the heteroatom-containing comonomer and the water is 0.03-0.06: 0.002-0.008: 0.008-0.012: 0.03-0.06: 1.
3. The method for preparing the heteroatom-doped porous carbon electrode material as claimed in claim 1, wherein in the step (1), the heteroatom-containing comonomer is selected from any one or a mixture of more than two of 3- (4-pyridyl) acrylic acid, 3- (2-thienyl) acrylic acid, 4-vinylphenylboronic acid or phosphoenolpyruvate cyclohexylammonium salt in any proportion.
4. The method for preparing the heteroatom-doped porous carbon electrode material as claimed in claim 1, wherein in the step (1), the amount of the initiator is 1 to 6 percent of the total mass of the acrylamide and the heteroatom-containing comonomer.
5. The method for preparing a heteroatom-doped porous carbon electrode material as claimed in claim 1, wherein in step (1), the initiator is one of potassium persulfate, ammonium persulfate or a water-soluble oxidation-reduction initiation system selected from any one of potassium persulfate-sodium sulfite, potassium persulfate-sodium bisulfite, ammonium persulfate-sodium sulfite or ammonium persulfate-sodium bisulfite water-soluble oxidation-reduction initiation system.
6. The preparation method of the heteroatom-doped porous carbon electrode material as claimed in claim 5, wherein in the step (1), when the initiator is potassium persulfate or ammonium persulfate, the reaction temperature is 65-75 ℃, and the reaction time is 2-5 h; when the initiator is a water-soluble oxidation-reduction initiation system, the reaction temperature is 20-30 ℃, and the reaction time is 2-5 h.
7. The method for preparing a heteroatom-doped porous carbon electrode material as claimed in any one of claims 1 to 6, wherein in step (2), the carbonization is carried out in a nitrogen atmosphere at a temperature of 700 to 1000 ℃ for 2 to 4 hours.
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