CN113178338A - Carbazolyl porous carbon/polyaniline composite electrode material and preparation method thereof - Google Patents
Carbazolyl porous carbon/polyaniline composite electrode material and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 77
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 title claims abstract description 54
- 239000007772 electrode material Substances 0.000 title claims abstract description 40
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims abstract description 51
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 36
- 238000000197 pyrolysis Methods 0.000 claims abstract description 24
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 40
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 32
- 239000000047 product Substances 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 29
- 238000005406 washing Methods 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000013315 hypercross-linked polymer Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 10
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 239000011363 dried mixture Substances 0.000 claims description 2
- 239000003990 capacitor Substances 0.000 abstract description 12
- 229920001088 polycarbazole Polymers 0.000 abstract description 9
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011148 porous material Substances 0.000 abstract description 5
- 239000002243 precursor Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 238000011068 loading method Methods 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 239000012776 electronic material Substances 0.000 abstract description 2
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- 239000000463 material Substances 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000008247 solid mixture Substances 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
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- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
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- 239000004744 fabric Substances 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 239000002245 particle Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
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- H—ELECTRICITY
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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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- H01G11/32—Carbon-based
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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
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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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
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Abstract
The invention belongs to the field of electronic materials, and particularly relates to a carbazolyl porous carbon/polyaniline composite electrode material and a preparation method thereof. The preparation process comprises the following steps: preparing hypercrosslinked polycarbazole by using carbazole as a monomer and dimethoxymethane as external crosslink, mixing the hypercrosslinked polycarbazole serving as a precursor of porous carbon with potassium hydroxide, carrying out high-temperature pyrolysis in a nitrogen atmosphere to obtain nitrogen-containing hierarchical porous carbon, and finally carrying polyaniline by a chemical oxidative polymerization method to prepare the carbazolyl porous carbon/polyaniline composite electrode material. The invention utilizes the nitrogen-containing functional group of carbazole and hypercrosslinking polymerizationThe pore structure of the substance, the specific surface area of the prepared nitrogen-doped porous carbon reaches 1576 m.g‑1The specific capacitance of the composite electrode material obtained after loading polyaniline reaches 462F g‑1And can be used for preparing a super capacitor.
Description
Technical Field
The invention belongs to the field of electronic materials, and particularly relates to a carbazolyl porous carbon/polyaniline composite electrode material and a preparation method thereof.
Background
The super capacitor is a new green energy storage device and generally comprises electrodes, a current collector, electrolyte and a diaphragm, wherein electrode materials are key factors influencing the performance of the super capacitor, the electrode materials directly determine performance parameters of the super capacitor, such as specific capacitance, circulation stability, energy density and power density, and the cost of the electrode materials and the large-scale production of the electrode materials determine whether the super capacitor can be put to the market.
Super capacitors can be classified into two main types, electric double layer capacitors and pseudo capacitors, according to the mechanism of electric energy storage. The electric double layer capacitor material is mainly a carbon material, and the pseudocapacitor material is mainly metal oxide and conductive polymer. The carbon material has low internal resistance, and the prepared electric double layer capacitor has high cycle stability and power density, but low specific capacitance and energy density. The pseudocapacitor has higher theoretical capacitance and energy density than the electric double layer capacitor, but the pseudocapacitor material has poor conductivity, so that the cycle stability and the rate capability of the pseudocapacitor material are poor, and the power density of the pseudocapacitor material is also inferior to that of the electric double layer capacitor. Therefore, organic compounding of carbon materials and pseudocapacitance materials is an important research point of current electrode materials, and a method for realizing synergy among different energy storage mechanism components is tried to obtain a composite material with excellent performance.
Disclosure of Invention
The invention aims to provide a carbazolyl porous carbon/polyaniline composite electrode material and a preparation method thereof, aiming at the defects of the prior art. In order to prepare a porous carbon/polyaniline composite electrode material with high electrochemical performance and improve the specific capacitance and the cycling stability of the material, carbazole is firstly subjected to hypercrosslinking by adopting an external cross-linking agent, the prepared hypercrosslinked polymer is used as a porous carbon precursor, meanwhile, nitrogen-containing porous carbon with a multi-stage pore structure is prepared by pyrolysis under the etching action of potassium hydroxide, and then polyaniline is loaded on the porous carbon by a chemical oxidative polymerization method to prepare the carbazolyl porous carbon/polyaniline composite electrode material.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a carbazolyl porous carbon/polyaniline composite electrode material comprises the following steps:
(1) and (3) carbazole monomer hypercrosslinking: dissolving a carbazole monomer in 1, 2-dichloroethane, adding dimethoxymethane, fully stirring, adding anhydrous ferric trichloride, heating to 80 ℃ while stirring, reacting at 80 ℃ for 24 hours, filtering a product, ultrasonically cleaning by using methanol, carrying out suction filtration until the filtrate is nearly colorless, and drying in vacuum at 80 ℃ to obtain a carbazolyl hypercrosslinked polymer; wherein the molar ratio of (carbazole + dimethoxymethane)/anhydrous ferric trichloride is 3:1-1:2, and the molar ratio of dimethoxymethane/carbazole is 3:1-1: 2.
(2) Preparing porous carbon by pyrolysis: dispersing the carbazolyl hypercrosslinked polymer prepared in the step (1) and potassium hydroxide in absolute ethyl alcohol according to the mass ratio of 1:2-1:6, stirring at 60 ℃ until the solvent is evaporated to dryness, then placing the dried mixture in a tubular furnace, heating to 600 ℃ and 900 ℃ at the speed of 5 ℃/min in the nitrogen atmosphere, then maintaining the temperature for pyrolysis for 1-3 hours at high temperature, and obtaining the carbazolyl porous carbon after acid washing, water washing and drying the pyrolysis product.
(3) Porous carbon-loaded polyaniline: dispersing carbazolyl porous carbon into 1M hydrochloric acid, adding aniline (the final concentration of aniline is 0.05M-0.2M, and the mass ratio of aniline to porous carbon is 2:1-1: 2) in a certain proportion, and stirring for 1 hour at 0-5 ℃ for later use; and dissolving a certain amount of ammonium persulfate in equivalent 1M hydrochloric acid (the molar ratio of aniline to ammonium persulfate is 5:1-1: 2), preserving at 0-5 ℃ for 0.5 hour, adding into the mixed solution, reacting at 0-5 ℃ for 12 hours, washing and drying the product to obtain the carbazolyl porous carbon/polyaniline composite electrode material.
According to the technical scheme, carbazole is used as a monomer of a super-crosslinked polymer, dimethoxymethane is used as an external crosslinking agent to prepare super-crosslinked polycarbazole, the super-crosslinked polycarbazole is used as a precursor of porous carbon and is mixed with potassium hydroxide, the nitrogen-containing hierarchical porous carbon is obtained through a high-temperature pyrolysis method, and finally polyaniline is loaded through a chemical oxidative polymerization method to prepare the carbazolyl porous carbon/polyaniline composite electrode material.
Compared with the prior art, the invention has the following advantages:
1. according to the preparation method, hypercrosslinked polycarbazole is used as a precursor of porous carbon, and a nitrogen-containing functional group of carbazole and a microporous structure of hypercrosslinked polymer are used to prepare the hypercrosslinked polycarbazole with the specific surface area of 1576 m g-1And nitrogen-doped porous carbon with the average pore diameter of 22.0A, and the specific capacitance of 462F g can be obtained after the nitrogen-doped porous carbon is loaded with polyaniline-1The composite electrode material of (1).
2. The hypercrosslinked polymer prepared by taking carbazole as a monomer has a rigid main chain and a conjugated electron-rich system, is favorable for forming a permanent porous structure, cannot be easily denatured, and porous carbon prepared by taking the hypercrosslinked polymer as a precursor can fully reserve the microporous structure and the rigid skeleton of hypercrosslinked polycarbazole, thereby being favorable for loading polyaniline and being favorable for diffusion and contact of electrolyte.
3. According to the invention, nitrogen-doped porous carbon is prepared by utilizing a nitrogen-containing functional group of carbazole through pyrolysis of hypercrosslinked polycarbazole, and the nitrogen doping can enhance the surface wettability of the material, provide richer active sites, provide pseudo capacitance for a carbon material, and improve the conductivity and charge storage capacity of the composite material after the porous carbon is loaded with polyaniline.
4. The carbazolyl porous carbon/polyaniline composite electrode material prepared by the invention is black powder, has excellent electrochemical performance and provides a new idea for preparation of the composite electrode material.
Drawings
FIG. 1 is a constant current charge-discharge curve of the porous carbon/polyaniline composite electrode material of example 1;
FIG. 2 is a scanning electron microscope photograph of the porous carbon/polyaniline composite electrode material of example 1;
FIG. 3 is a nitrogen adsorption and desorption curve of the carbazolyl porous carbon of example 1;
fig. 4 is a pore size distribution diagram of the carbazolyl porous carbon of example 1.
Detailed Description
In order to make the present invention easier to understand, the following examples will further illustrate the present invention, but the scope of the present invention is not limited to these examples.
Example 1
(1) Dissolving 30 mmol of carbazole monomer in 120mL of 1, 2-dichloroethane, adding 60 mmol of dimethoxymethane, fully stirring, adding 45 mmol of anhydrous ferric chloride, heating to 80 ℃ while stirring, reacting at 80 ℃ for 24 hours, filtering the product, ultrasonically cleaning by using methanol, performing suction filtration until the filtrate is nearly colorless, and drying in vacuum at 80 ℃ to obtain the carbazolyl hypercrosslinked polymer;
(2) dispersing 1g and 4g of potassium hydroxide of the product prepared in the step (1) in 300mL of absolute ethyl alcohol, heating to 60 ℃, stirring until the solvent is evaporated to dryness, placing the solid mixture in a tubular furnace, heating to 700 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, maintaining the high temperature of 700 ℃ for pyrolysis for 1.5 hours, cooling to room temperature, and carrying out acid washing, water washing and drying on the pyrolysis product to obtain the carbazolyl porous carbon;
(3) dispersing dried porous carbon 0.1396g and 0.0931g (1 mmol) aniline in 15mL 1M hydrochloric acid, and stirring at 0 ℃ for 1 hour for later use; dissolving 1 mmol of ammonium persulfate in 1M hydrochloric acid with the same amount, storing at 0 deg.C for 0.5 hr, adding into the mixed solution of aniline and carbon, reacting at 0 deg.C for 12 hr, washing with water, and drying to obtain carbazolyl porous carbon/polyaniline composite electrode material with specific capacitance of 462F g-1。
Example 2
(1) Dissolving 30 mmol of carbazole monomer in 120mL of 1, 2-dichloroethane, adding 60 mmol of dimethoxymethane, fully stirring, adding 60 mmol of anhydrous ferric trichloride, heating to 80 ℃ while stirring, reacting at 80 ℃ for 24 hours, filtering the product, ultrasonically cleaning by using methanol, performing suction filtration until the filtrate is nearly colorless, and drying in vacuum at 80 ℃ to obtain the carbazolyl hypercrosslinked polymer;
(2) and (2) dispersing 1g and 4g of potassium hydroxide of the product prepared in the step (1) in 300mL of absolute ethyl alcohol, heating to 60 ℃, stirring until the solvent is evaporated to dryness, placing the solid mixture in a tubular furnace, heating to 700 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, maintaining the high temperature of 700 ℃ for pyrolysis for 1.5 hours, cooling to room temperature, and carrying out acid washing, water washing and drying on the pyrolysis product to obtain the carbazolyl porous carbon.
(3) Dispersing dried porous carbon 0.1396g and 0.0931g (1 mmol) aniline in 15mL 1M hydrochloric acid, and stirring at 0 ℃ for 1 hour for later use; dissolving 1 mmol of ammonium persulfate in 1M hydrochloric acid with the same amount, preserving at 0 ℃ for 0.5 h, adding into the mixed solution of aniline and carbon, reacting at 0 ℃ for 12 h, washing the product with water, and drying to obtain the carbazolyl porous carbon/polyaniline composite electrode material.
Example 3
(1) Dissolving 22.5 mmol of carbazole monomer in 120mL of 1, 2-dichloroethane, adding 67.5 mmol of dimethoxymethane, fully stirring, adding 45 mmol of anhydrous ferric trichloride, heating to 80 ℃ while stirring, reacting at 80 ℃ for 24 hours, filtering the product, ultrasonically cleaning by using methanol, carrying out suction filtration until the filtrate is nearly colorless, and drying in vacuum at 80 ℃ to obtain the carbazolyl hypercrosslinked polymer;
(2) and (2) dispersing 1g and 4g of potassium hydroxide of the product prepared in the step (1) in 300mL of absolute ethyl alcohol, heating to 60 ℃, stirring until the solvent is evaporated to dryness, placing the solid mixture in a tubular furnace, heating to 700 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, maintaining the high temperature of 700 ℃ for pyrolysis for 1.5 hours, cooling to room temperature, and carrying out acid washing, water washing and drying on the pyrolysis product to obtain the carbazolyl porous carbon.
(3) Dispersing dried porous carbon 0.1396g and 0.0931g (1 mmol) aniline in 15mL 1M hydrochloric acid, and stirring at 0 ℃ for 1 hour for later use; dissolving 1 mmol of ammonium persulfate in 1M hydrochloric acid with the same amount, preserving at 0 ℃ for 0.5 h, adding into the mixed solution of aniline and carbon, reacting at 0 ℃ for 12 h, washing the product with water, and drying to obtain the carbazolyl porous carbon/polyaniline composite electrode material.
Example 4
(1) Dissolving 30 mmol of carbazole monomer in 120mL of 1, 2-dichloroethane, adding 60 mmol of dimethoxymethane, fully stirring, adding 45 mmol of anhydrous ferric chloride, stirring while heating to 80 ℃, reacting at 80 ℃ for 24 hours, filtering the product, ultrasonically cleaning by using methanol, carrying out suction filtration until the filtrate is nearly colorless, and drying in vacuum at 80 ℃ to obtain the carbazolyl hypercrosslinked polymer;
(2) and (2) dispersing 1g and 3g of potassium hydroxide of the product prepared in the step (1) in 300mL of absolute ethyl alcohol, heating to 60 ℃, stirring until the solvent is evaporated to dryness, placing the solid mixture in a tubular furnace, heating to 700 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, maintaining the high temperature of 700 ℃ for pyrolysis for 1.5 hours, cooling to room temperature, and carrying out acid washing, water washing and drying on the pyrolysis product to obtain the carbazolyl porous carbon.
(3) Dispersing dried porous carbon 0.1396g and 0.0931g (1 mmol) aniline in 15mL 1M hydrochloric acid, and stirring at 0 ℃ for 1 hour for later use; dissolving 1 mmol of ammonium persulfate in 1M hydrochloric acid with the same amount, preserving at 0 ℃ for 0.5 h, adding into the mixed solution of aniline and carbon, reacting at 0 ℃ for 12 h, washing the product with water, and drying to obtain the carbazolyl porous carbon/polyaniline composite electrode material.
Example 5
(1) Dissolving 30 mmol of carbazole monomer in 120mL of 1, 2-dichloroethane, adding 60 mmol of dimethoxymethane, fully stirring, adding 45 mmol of anhydrous ferric trichloride, stirring, heating to 80 ℃, reacting at 80 ℃ for 24 hours, filtering the product, ultrasonically cleaning by using methanol, carrying out suction filtration until the filtrate is nearly colorless, and drying in vacuum at 80 ℃ to obtain the carbazolyl hypercrosslinked polymer;
(2) and (2) dispersing 1g and 4g of potassium hydroxide of the product prepared in the step (1) in 300mL of absolute ethyl alcohol, heating to 60 ℃, stirring until the solvent is evaporated to dryness, placing the solid mixture in a tubular furnace, heating to 700 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, maintaining the high temperature of 700 ℃ for pyrolysis for 1.5 hours, cooling to room temperature, and carrying out acid washing, water washing and drying on the pyrolysis product to obtain the carbazolyl porous carbon.
(3) Dispersing dried porous carbon 0.0931g and 0.0931g (1 mmol) aniline in 15mL 1M hydrochloric acid, and stirring at 0 ℃ for 1 hour for later use; dissolving 1 mmol of ammonium persulfate in 1M hydrochloric acid with the same amount, preserving at 0 ℃ for 0.5 hour, adding into the mixed solution of aniline and carbon, reacting at 0 ℃ for 12 hours, washing the product with water, and drying to obtain the carbazolyl porous carbon/polyaniline composite electrode material.
Example 6
(1) Dissolving 30 mmol of carbazole monomer in 120mL of 1, 2-dichloroethane, adding 60 mmol of dimethoxymethane, fully stirring, adding 45 mmol of anhydrous ferric chloride, heating to 80 ℃ while stirring, reacting at 80 ℃ for 24 hours, filtering the product, ultrasonically cleaning by using methanol, performing suction filtration until the filtrate is nearly colorless, and drying in vacuum at 80 ℃ to obtain the carbazolyl hypercrosslinked polymer;
(2) and (2) dispersing 1g and 4g of potassium hydroxide of the product prepared in the step (1) in 300mL of absolute ethyl alcohol, heating to 60 ℃, stirring until the solvent is evaporated to dryness, placing the solid mixture in a tubular furnace, heating to 700 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, maintaining the high temperature of 700 ℃ for pyrolysis for 1.5 hours, cooling to room temperature, and carrying out acid washing, water washing and drying on the pyrolysis product to obtain the carbazolyl porous carbon.
(3) Dispersing dried porous carbon 0.1396g and 0.0931g (1 mmol) aniline in 15mL 1M hydrochloric acid, and stirring at 0 ℃ for 1 hour for later use; dissolving 1.5 mmol of ammonium persulfate in equivalent 1M hydrochloric acid, preserving at 0 ℃ for 0.5 h, adding into the mixed solution of aniline and carbon, reacting at 0 ℃ for 12 h, washing the product with water, and drying to obtain the carbazolyl porous carbon/polyaniline composite electrode material.
Application example
The invention determines the mass specific capacitance of the prepared carbazolyl porous carbon/polyaniline composite electrode material through an electrochemical workstation, and the specific measurement method comprises the following steps:
mixing the composite material prepared in the example 1 with polytetrafluoroethylene and acetylene black according to the mass ratio of 8:1:1, adding a few drops of ethanol to help dispersion, performing ultrasonic treatment for 5min, uniformly coating the mixture on hydrophilic carbon cloth treated by acetone, pressing the mixture into an electrode plate under the pressure of 10MPa, performing vacuum drying at 70 ℃, testing a constant current charge-discharge curve of the electrode by using an electrochemical workstation, and calculating the mass specific capacitance by using the following formula:
in the formula, CmIs specific capacitance by mass, F.g-1(ii) a I is a discharge current, A; Δ t is the discharge time, s; m is the mass of the active material of the working electrode, g; Δ V is the voltage drop, V.
FIG. 1 is a constant current charge/discharge curve of the composite electrode material in a three-electrode system at a current density of 1A/g, from which the specific capacitance of 462F/g can be calculated. Fig. 2 shows that the composite electrode material has a loose porous structure, which illustrates that the porous skeleton structure of the hypercrosslinked polycarbazole is better maintained after high-temperature carbonization, and meanwhile, the loading of polyaniline is proved by the rough surface of the particles. The nitrogen adsorption and desorption curve of fig. 3 shows that the synthesized carbazolyl porous carbon is basically microporous, and the existence of the hysteresis loop indicates that a certain mesopore exists. FIG. 4 is a pore size distribution diagram of the carbazolyl porous carbon, which shows that micropores below 2nm are mainly followed by mesopores of 2-50nm, indicating that the carbazolyl porous carbon is of a hierarchical pore structure.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (8)
1. A preparation method of a carbazolyl porous carbon/polyaniline composite electrode material is characterized by comprising the following steps: which comprises the following steps:
(1) and (3) carbazole monomer hypercrosslinking: dissolving a carbazole monomer in 1, 2-dichloroethane, adding dimethoxymethane, fully stirring, adding anhydrous ferric trichloride, heating to 80 ℃ while stirring, reacting at 80 ℃ for 24 hours, filtering a product, washing with alcohol, and drying to obtain a carbazolyl hypercrosslinked polymer;
(2) preparing porous carbon by pyrolysis: dispersing the carbazolyl hypercrosslinked polymer prepared in the step (1) and potassium hydroxide in absolute ethyl alcohol, stirring at 60 ℃ until the solvent is evaporated to dryness, then placing the dried mixture in a tubular furnace, heating to a specific temperature in a nitrogen atmosphere for high-temperature pyrolysis, and carrying out acid washing, water washing and drying on the pyrolysis product to obtain the carbazolyl porous carbon;
(3) porous carbon-loaded polyaniline: dispersing carbazolyl porous carbon in 1M hydrochloric acid, adding aniline, and stirring at 0-5 ℃ for 1 hour to obtain a mixed solution for later use; and dissolving ammonium persulfate in equivalent 1M hydrochloric acid, preserving at 0-5 ℃ for 0.5 hour, adding into the mixed solution, reacting at 0-5 ℃ for 12 hours, washing and drying the product to obtain the carbazolyl porous carbon/polyaniline composite electrode material.
2. The method for preparing the carbazolyl porous carbon/polyaniline composite electrode material according to claim 1, wherein: in the step (1), the molar ratio of (carbazole + dimethoxymethane)/anhydrous ferric chloride is 3:1-1:2, and the molar ratio of dimethoxymethane/carbazole is 3:1-1: 2.
3. The preparation method of the carbazolyl porous carbon/polyaniline composite electrode material according to claim 1, characterized in that: in the step (1), the alcohol washing and drying method comprises the following steps: the product was washed ultrasonically in methanol until the filtrate was nearly colorless, and then dried under vacuum at 80 ℃.
4. The preparation method of the carbazolyl porous carbon/polyaniline composite electrode material according to claim 1, characterized in that: in the step (2), the carbazolyl hypercrosslinked polymer and the potassium hydroxide are dispersed in the absolute ethyl alcohol according to the mass ratio of 1:2-1: 6.
5. The preparation method of the carbazolyl porous carbon/polyaniline composite electrode material according to claim 1, characterized in that: in the step (2), the high-temperature pyrolysis specifically comprises the following operations: raising the temperature to 600-900 ℃ at the heating rate of 5 ℃/min under the nitrogen atmosphere, and then maintaining the temperature for pyrolysis for 1-3 hours.
6. The preparation method of the carbazolyl porous carbon/polyaniline composite electrode material according to claim 1, characterized in that: in the step (3), the aniline concentration in the mixed solution is 0.05M-0.2M, the mass ratio of aniline/carbazolyl porous carbon is 2:1-1:2, and the molar ratio of aniline/ammonium persulfate is 5:1-1: 2.
7. A carbazolyl porous carbon/polyaniline composite electrode material obtained by the preparation method according to any one of claims 1 to 6.
8. The application of the carbazolyl porous carbon/polyaniline composite electrode material as defined in claim 7 to an electrode of a supercapacitor.
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111303412A (en) * | 2020-03-05 | 2020-06-19 | 西华师范大学 | Novel nitrogen-containing organic super-crosslinked polymer and preparation method and application thereof |
CN114602426A (en) * | 2022-02-18 | 2022-06-10 | 上海鎏明科技有限公司 | VOCs gas treatment method combining plasma with ozone |
CN114604905A (en) * | 2022-02-18 | 2022-06-10 | 上海鎏明科技有限公司 | Method for recycling ternary battery anode material by combining plasma with sulfate |
CN114709085A (en) * | 2022-04-22 | 2022-07-05 | 福州大学 | Nitrogen-doped sulfonated porous carbon/polyaniline composite electrode material and preparation method thereof |
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Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000024709A2 (en) * | 1998-10-26 | 2000-05-04 | E.I. Du Pont De Nemours And Company | Monomers, ionomers and polymers for electrochemical uses |
CN106158430A (en) * | 2016-09-06 | 2016-11-23 | 上海电力学院 | A kind of preparation method of the electrode material for ultracapacitor |
CN106378109A (en) * | 2016-10-10 | 2017-02-08 | 湘潭大学 | Multihole polycarbazole polymer and preparation method and application thereof |
US20180050328A1 (en) * | 2015-04-15 | 2018-02-22 | Agency For Science, Technology And Research | Modified porous hypercrosslinked polymers for co2 capture and conversion |
CN107875801A (en) * | 2016-09-30 | 2018-04-06 | 中国科学院大连化学物理研究所 | One kind prepares nitrogen-doped carbon material and its application by precursor of porous polymer with nitrogen |
CN108010750A (en) * | 2017-12-29 | 2018-05-08 | 福州大学 | A kind of preparation method of ultra-thin-wall multistage porous charcoal/carbon/polyaniline super capacitor electrode material |
CN108767275A (en) * | 2018-05-16 | 2018-11-06 | 湘潭大学 | A kind of nitrogen-doped carbon oxygen reduction catalyst and its preparation method and application based on tetrazine ring polycarbazole |
CN108948412A (en) * | 2018-05-17 | 2018-12-07 | 齐鲁工业大学 | A kind of siliceous poromeric preparation method for supercapacitor |
CN110491676A (en) * | 2019-07-29 | 2019-11-22 | 桂林理工大学 | A method of high pressure resistant electrode material is prepared using porous carbon polyaniline |
CN111627725A (en) * | 2020-06-09 | 2020-09-04 | 刘庆信 | N, S co-doped porous carbon electrode material with adjustable pore space and preparation method thereof |
CN111681883A (en) * | 2020-07-08 | 2020-09-18 | 刘栋 | N, S co-doped porous carbon supercapacitor electrode material and preparation method thereof |
-
2021
- 2021-04-20 CN CN202110425105.1A patent/CN113178338B/en active Active
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000024709A2 (en) * | 1998-10-26 | 2000-05-04 | E.I. Du Pont De Nemours And Company | Monomers, ionomers and polymers for electrochemical uses |
US20180050328A1 (en) * | 2015-04-15 | 2018-02-22 | Agency For Science, Technology And Research | Modified porous hypercrosslinked polymers for co2 capture and conversion |
CN106158430A (en) * | 2016-09-06 | 2016-11-23 | 上海电力学院 | A kind of preparation method of the electrode material for ultracapacitor |
CN107875801A (en) * | 2016-09-30 | 2018-04-06 | 中国科学院大连化学物理研究所 | One kind prepares nitrogen-doped carbon material and its application by precursor of porous polymer with nitrogen |
CN106378109A (en) * | 2016-10-10 | 2017-02-08 | 湘潭大学 | Multihole polycarbazole polymer and preparation method and application thereof |
CN108010750A (en) * | 2017-12-29 | 2018-05-08 | 福州大学 | A kind of preparation method of ultra-thin-wall multistage porous charcoal/carbon/polyaniline super capacitor electrode material |
CN108767275A (en) * | 2018-05-16 | 2018-11-06 | 湘潭大学 | A kind of nitrogen-doped carbon oxygen reduction catalyst and its preparation method and application based on tetrazine ring polycarbazole |
CN108948412A (en) * | 2018-05-17 | 2018-12-07 | 齐鲁工业大学 | A kind of siliceous poromeric preparation method for supercapacitor |
CN110491676A (en) * | 2019-07-29 | 2019-11-22 | 桂林理工大学 | A method of high pressure resistant electrode material is prepared using porous carbon polyaniline |
CN111627725A (en) * | 2020-06-09 | 2020-09-04 | 刘庆信 | N, S co-doped porous carbon electrode material with adjustable pore space and preparation method thereof |
CN111681883A (en) * | 2020-07-08 | 2020-09-18 | 刘栋 | N, S co-doped porous carbon supercapacitor electrode material and preparation method thereof |
Non-Patent Citations (3)
Title |
---|
常晴等: "超交联多孔碳的制备及其对甲苯吸附性能研究", 《广西大学学报(自然科学版)》 * |
杨娟等: "编织超交联微孔聚合物的研究进展", 《高分子通报》 * |
马加力: "氧化镁模板催化碳化反应制备多孔碳材料", 《中国优秀硕士学位论文全文数据库 (工程科技Ⅰ辑)》 * |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111303412A (en) * | 2020-03-05 | 2020-06-19 | 西华师范大学 | Novel nitrogen-containing organic super-crosslinked polymer and preparation method and application thereof |
CN111303412B (en) * | 2020-03-05 | 2023-05-05 | 西华师范大学 | Nitrogen-containing organic super-crosslinked polymer and preparation method and application thereof |
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CN114604905A (en) * | 2022-02-18 | 2022-06-10 | 上海鎏明科技有限公司 | Method for recycling ternary battery anode material by combining plasma with sulfate |
CN114709085A (en) * | 2022-04-22 | 2022-07-05 | 福州大学 | Nitrogen-doped sulfonated porous carbon/polyaniline composite electrode material and preparation method thereof |
CN114709085B (en) * | 2022-04-22 | 2023-01-10 | 福州大学 | Nitrogen-doped sulfonated porous carbon/polyaniline composite electrode material and preparation method thereof |
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CN115240987B (en) * | 2022-05-17 | 2023-10-20 | 中国计量大学 | Woven mesh composite structure carbon and preparation method and application thereof |
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