CN109378224B - Preparation and application of thiourea aldehyde/polypyrrole composite material-based carbon electrode material - Google Patents
Preparation and application of thiourea aldehyde/polypyrrole composite material-based carbon electrode material Download PDFInfo
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- CN109378224B CN109378224B CN201811197468.9A CN201811197468A CN109378224B CN 109378224 B CN109378224 B CN 109378224B CN 201811197468 A CN201811197468 A CN 201811197468A CN 109378224 B CN109378224 B CN 109378224B
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- 229920000128 polypyrrole Polymers 0.000 title claims abstract description 66
- UMGDCJDMYOKAJW-UHFFFAOYSA-N aminothiocarboxamide Natural products NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims abstract description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000007772 electrode material Substances 0.000 title claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 38
- -1 thiourea aldehyde Chemical class 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 36
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000243 solution Substances 0.000 claims abstract description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 18
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- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 16
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- 238000005406 washing Methods 0.000 claims abstract description 11
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- 238000010000 carbonizing Methods 0.000 claims abstract description 9
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- 239000006185 dispersion Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 8
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000967 suction filtration Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 10
- 238000003763 carbonization Methods 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- 239000002077 nanosphere Substances 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
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- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 238000010277 constant-current charging Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- ZNNYSTVISUQHIF-UHFFFAOYSA-N formaldehyde;thiourea Chemical compound O=C.NC(N)=S ZNNYSTVISUQHIF-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
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- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a preparation method and application of a thiourea aldehyde/polypyrrole composite material-based carbon electrode material. The preparation method comprises the following steps: taking a certain amount of polypyrrole to disperse in deionized water, and carrying out ultrasonic treatment for 2 hours; adding a certain amount of thiourea and formaldehyde aqueous solution into the polypyrrole dispersion liquid, carrying out ultrasonic treatment for 5min, and mechanically stirring the reaction liquid; heating the reaction liquid to 40-65 ℃, adding a certain amount of concentrated hydrochloric acid solution, reacting for 2-5 hours, carrying out suction filtration on the product, washing the product with deionized water and absolute ethyl alcohol, and drying in an oven to obtain a powdered thiourea/polypyrrole composite material; and carbonizing the obtained composite material in an argon atmosphere to obtain the urea-formaldehyde sulfide/polypyrrole composite material-based carbon electrode material. The thiourea aldehyde/polypyrrole composite material-based carbon electrode material prepared by the invention has the advantages of stable structure, excellent electrochemical performance, good cycle performance and the like, and is very suitable for being applied to the field of supercapacitors as an electrode material.
Description
Technical Field
The invention belongs to the technical field of new energy electronic materials, and relates to a preparation method and application of a thiourea aldehyde/polypyrrole composite carbon electrode material.
Background
Nowadays, society faces serious energy crisis, and diversified researches are conducted in various countries to solve energy problems. These studies can be generally categorized as open source throttling. On one hand, novel energy sources such as solar energy, wind energy, hydroenergy, geothermal heat and the like are searched, and the energy sources are green sustainable energy sources; on the other hand, new energy storage devices, such as new lithium (sodium, potassium) ion batteries, super capacitors, etc., are developed, and these devices generally have higher energy density or power density and higher working efficiency than the conventional energy storage devices. The carbon material is a traditional material with low price and various existing forms, and has very important application value in various fields. Among them, carbon materials are being favored by a large number of researchers in the field of application of electrode materials. Generally, carbon materials exist in various forms, such as activated carbon, template carbon, carbon nanotubes, polymer-based carbon, and the like, which have their respective advantages and are successfully applied to various fields.
Generally, the microscopic morphology of the polymer material can be greatly preserved through carbonization, and if no special morphology design is adopted, the specific surface area of the polymer-based carbon material is relatively small, and the affinity of the carbon material with an aqueous solution is poor, so that the effective specific surface area of the electric double layer capacitance can be further reduced.
Song et al compounds melamine resin-based carbon material activated by KOH with polypyrrole nano-fiber to obtain a composite electrode material, and tests show that the specific capacitance value reaches 336.8F/g in 6 mol/L KOH electrolyte at a current density of 1A/g, and the capacitance retention rate is 94.3% after 3000 cycles of charging and discharging (Song L, Zou Y, Zhang H, et al. High performance super capacitor base on polypyrole/melamine used for modified carbon fiber material [ J ] International Journal of scientific, 2017, 20112: 1014.).
Chinese patent document CN108394888A discloses a method for preparing nitrogen-doped mesoporous hollow carbon nanospheres, which comprises the following steps: step 1: and (3) preparing a PMMA-PBMA-PMAA latex template. Weighing 0.32g of Methyl Methacrylate (MMA), 0.015 g of methyl acrylate (MAA), 0.285 g of Butyl Acrylate (BA), 0.003 g of Sodium Dodecyl Sulfate (SDS), 0.5 g of Ammonium Persulfate (APS) and 60 g of deionized water, stirring and mixing uniformly, then heating to 70-80 ℃ in a nitrogen atmosphere to react for 45min, then dropwise adding a mixed solution of 7.9 g of MMA, 5g of MAA, 7 g of BA, 0.125 g of Ethylene Glycol Dimethacrylate (EGDMA), 0.15g of APS and 10 g of deionized water into the reaction system, and continuing the whole process for 240 gKeeping the temperature at 70-80 ℃ for reaction for 60 minutes after dripping, and obtaining a polymethacrylate copolymer (PMMA-PBMA-PMAA) latex template; step 2: and (3) preparing polypyrrole with a core-shell structure. Adding 10 g of the latex template prepared in the step 1 into 100ml of mixed solution of deionized water and absolute ethyl alcohol (the ratio of the deionized water to the absolute ethyl alcohol is 4: 1), uniformly mixing, adding 0.5-2 ml of pyrrole monomer and 1 ml of concentrated hydrochloric acid (the mass concentration is 36-38%), then dropwise adding a mixed solution of 3.29 g of APS and 20 ml of deionized water into the reaction system under the condition of ice-water bath, wherein the dropwise adding process is about 30 minutes, and keeping the ice-water bath condition for reacting for 8 hours after the dropwise adding is finished; after the reaction is finished, centrifugally separating, washing with ethanol and deionized water, and then drying at 60 ℃ for 12 hours to obtain polypyrrole powder with a core-shell structure; and step 3: and (3) preparing the nitrogen-doped mesoporous hollow carbon nanospheres. And (3) putting 0.4-0.6 g of polypyrrole powder with the core-shell structure prepared in the step (2) into a tube furnace, heating to 500-900 ℃ in a nitrogen atmosphere, and carbonizing for 2 hours to obtain the nitrogen-doped mesoporous hollow carbon nanospheres. In step 3, the temperature rise rate of the tube furnace is 5 ℃/min. In step 3, the carbonization temperature is preferably 700 ℃. The nitrogen-doped mesoporous hollow carbon nanospheres with different carbonization temperatures are subjected to electrochemical characterization, and the specific discharge capacitance is up to 275.7F g under the carbonization condition of 700 DEG C-1. However, the method has complex process and complicated steps, and the used raw materials have high cost and are difficult to be applied in a large range.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method and application of a thiourea-formaldehyde/polypyrrole composite material-based carbon electrode material with simple and convenient synthesis process and good cycle performance.
The technical scheme of the invention is as follows:
according to the invention, the preparation method of the thiourea aldehyde/polypyrrole composite material based carbon electrode material comprises the following steps:
(1) 0.05g to 0.15g of polypyrrole is dispersed in 100ml of deionized water, and ultrasonic treatment is carried out for 2 hours;
(2) adding a certain amount of thiourea and formaldehyde aqueous solution into the polypyrrole dispersion liquid in the step (1), performing ultrasonic treatment for 5min, and mechanically stirring the reaction liquid, wherein the ratio of thiourea to formaldehyde is 1-3: 1;
(3) heating the reaction liquid obtained in the step (2) to 40-65 ℃, adding a certain amount of concentrated hydrochloric acid solution, reacting for 2-5 hours, carrying out suction filtration on a product, washing the product by using deionized water and absolute ethyl alcohol, and drying in a drying oven at 40 ℃ to obtain a powdered thiourea/polypyrrole composite material;
(4) carbonizing the composite material obtained in the step (3) at 600-850 ℃ for 1-4 h in an argon atmosphere at a heating rate of 2 ℃/min to obtain the urea-formaldehyde/polypyrrole composite material based carbon electrode material.
In one embodiment, the polypyrrole is prepared by the following steps:
0.2g of FeCl was taken2Dissolving in 88ml deionized water, adding 2ml pyrrole monomer, ultrasonic treating for 0.5h to make pyrrole in FeCl2The solution is uniformly dispersed; adding 10ml of 30% hydrogen peroxide solution into the reaction solution at room temperature, and reacting for 6 h; and (3) centrifuging the product, washing the product by using deionized water and absolute ethyl alcohol, and finally freezing and drying to obtain the polypyrrole.
According to the invention, the polypyrrole is preferably used in step (1) in an amount of 0.12 g.
According to the present invention, it is preferred that the ratio of thiourea to formaldehyde in step (2) is 3: 1.
According to the present invention, it is preferred that the reaction temperature in the step (3) is 55 ℃.
According to the present invention, it is preferred that the amount of concentrated hydrochloric acid used in step (3) is 0.4 ml.
According to the present invention, it is preferred that the reaction time in step (3) is 3 hours.
According to the present invention, it is preferable that the carbonization temperature in the step (4) is 750 ℃.
According to the present invention, it is preferable that the carbonization time in the step (4) is 3 hours.
An application of thiourea aldehyde/polypyrrole composite material based carbon electrode material is used for electrode material of super capacitor.
The technical advantages of the invention are as follows:
(1) the preparation method has the advantages of simple preparation process, easy operation and high repeatability.
(2) The thiourea aldehyde/polypyrrole composite material-based carbon electrode material prepared by the invention has the advantages of stable structure, excellent electrochemical performance, good cycle performance and the like, and is very suitable for being applied to the field of supercapacitors as an electrode material.
Drawings
FIG. 1 is a scanning electron microscope image of a thiourea aldehyde/polypyrrole composite carbon-based electrode material prepared in example 1 of the present invention.
Fig. 2 is a constant current charging and discharging curve diagram of the thiourea aldehyde/polypyrrole composite material-based carbon electrode material prepared in example 1 of the present invention.
FIG. 3 is a graph showing the cyclic charge and discharge curves of the thiourea aldehyde/polypyrrole composite carbon-based electrode material prepared in example 1 of the present invention at a current density of 10A/g.
Detailed Description
The present invention will be further described with reference to the following embodiments and drawings, but is not limited thereto.
Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1:
0.12g of polypyrrole is dispersed in 100ml of deionized water, and ultrasonic treatment is carried out for 2 hours; adding 17.52 g of thiourea and 6 ml of formaldehyde aqueous solution into the polypyrrole dispersion liquid, carrying out ultrasonic treatment for 5min, and mechanically stirring the reaction liquid; heating the reaction solution to 55 ℃, adding 0.4ml of concentrated hydrochloric acid solution into the reaction solution, reacting for 3 hours, carrying out suction filtration on a product, washing the product by using deionized water and absolute ethyl alcohol, and drying in a drying oven at 40 ℃ to obtain a powdered thiourea/polypyrrole composite material; carbonizing the obtained composite material at 750 ℃ for 3h in an argon atmosphere at the heating rate of 2 ℃/min to obtain the urea-formaldehyde sulfide/polypyrrole composite material based carbon electrode material.
A three-electrode system is adopted, a 2 mol/L sulfuric acid solution is used as an electrolyte, the specific capacitance measured by 1A/g is 226.8F/g, and the stability is good.
The scanning electron microscope image of the thiourea aldehyde/polypyrrole composite material-based carbon electrode material prepared in this example is shown in fig. 1, and it can be seen from fig. 1 that the electrode material is a randomly distributed block structure.
As shown in FIG. 2, the constant current charging and discharging of the thiourea aldehyde/polypyrrole composite material-based carbon electrode material prepared in the embodiment is shown in FIG. 2, and it can be seen from FIG. 2 that the specific capacitance measured at 1A/g is 226.8F/g, the specific capacitance measured at 0.5A/g is 240.4F/g, the specific capacitance measured at 2A/g is 201.8F/g, the specific capacitance measured at 10A/g is 152F/g, and the capacitance retention rate is 67%, which indicates that the material rate capability is good.
The cyclic charge-discharge curve of the thiourea aldehyde/polypyrrole composite material-based carbon electrode material prepared in the embodiment at a current density of 10A/g is shown in FIG. 3, and as can be seen from FIG. 3, the capacitance retention rate of the material after 10000 cycles of cyclic charge-discharge at a high current density is 121%, which indicates that the electrode material has a stable structure and excellent cycle performance.
Example 2:
0.05g of polypyrrole is dispersed in 100ml of deionized water, and ultrasonic treatment is carried out for 2 hours; adding 5.84 g of thiourea and 6 ml of formaldehyde aqueous solution into the polypyrrole dispersion liquid, carrying out ultrasonic treatment for 5min, and mechanically stirring the reaction liquid; heating the reaction solution to 40 ℃, adding 0.4ml of concentrated hydrochloric acid solution into the reaction solution, reacting for 5 hours, carrying out suction filtration on a product, washing the product by using deionized water and absolute ethyl alcohol, and drying in a drying oven at 40 ℃ to obtain a powdered thiourea/polypyrrole composite material; carbonizing the obtained composite material at 650 ℃ for 2h in an argon atmosphere at the heating rate of 2 ℃/min to obtain the urea-formaldehyde sulfide/polypyrrole composite material based carbon electrode material.
The specific capacitance of the three-electrode system was 171.8F/g measured at 1A/g using a 2 mol/L sulfuric acid solution as the electrolyte.
Example 3:
0.10 g of polypyrrole is dispersed in 100ml of deionized water, and ultrasonic treatment is carried out for 2 hours; adding 11.68 g of thiourea and 6 ml of formaldehyde aqueous solution into the polypyrrole dispersion liquid, carrying out ultrasonic treatment for 5min, and mechanically stirring the reaction liquid; heating the reaction solution to 65 ℃, adding 0.4ml of concentrated hydrochloric acid solution, reacting for 2 hours, carrying out suction filtration on the product, washing the product by using deionized water and absolute ethyl alcohol, and drying in a drying oven at 40 ℃ to obtain a powdered thiourea/polypyrrole composite material; carbonizing the obtained composite material for 1 h at 850 ℃ in an argon atmosphere at the heating rate of 2 ℃/min to obtain the urea-formaldehyde sulfide/polypyrrole composite material based carbon electrode material.
A three-electrode system is adopted, a 2 mol/L sulfuric acid solution is taken as an electrolyte, and the specific capacitance measured by 1A/g is 154.3F/g.
Example 4:
0.15g of polypyrrole is dispersed in 100ml of deionized water, and ultrasonic treatment is carried out for 2 hours; adding 17.52 g of thiourea and 6 ml of formaldehyde aqueous solution into the polypyrrole dispersion liquid, carrying out ultrasonic treatment for 5min, and mechanically stirring the reaction liquid; heating the reaction solution to 60 ℃, adding 0.4ml of concentrated hydrochloric acid solution, reacting for 4 hours, carrying out suction filtration on the product, washing the product by using deionized water and absolute ethyl alcohol, and drying in a drying oven at 40 ℃ to obtain a powdered thiourea/polypyrrole composite material; carbonizing the obtained composite material at 600 ℃ for 2h in an argon atmosphere at the heating rate of 2 ℃/min to obtain the urea-formaldehyde sulfide/polypyrrole composite material based carbon electrode material.
A three-electrode system is adopted, a 2 mol/L sulfuric acid solution is taken as an electrolyte, and the specific capacitance measured by 1A/g is 201.8F/g.
Example 5:
0.08 g of polypyrrole is dispersed in 100ml of deionized water, and ultrasonic treatment is carried out for 2 hours; adding 5.84 g of thiourea and 6 ml of formaldehyde aqueous solution into the polypyrrole dispersion liquid, carrying out ultrasonic treatment for 5min, and mechanically stirring the reaction liquid; heating the reaction solution to 45 ℃, adding 0.4ml of concentrated hydrochloric acid solution, reacting for 3 hours, carrying out suction filtration on the product, washing the product by using deionized water and absolute ethyl alcohol, and drying in a drying oven at 40 ℃ to obtain a powdered thiourea/polypyrrole composite material; carbonizing the obtained composite material at 700 ℃ for 3h in an argon atmosphere at the heating rate of 2 ℃/min to obtain the urea-formaldehyde sulfide/polypyrrole composite material based carbon electrode material.
The specific capacitance of the three-electrode system is 188.4F/g measured by 1A/g and using a 2 mol/L sulfuric acid solution as an electrolyte.
Claims (9)
1. A preparation method of thiourea aldehyde/polypyrrole composite material based carbon electrode material comprises the following steps:
(1) 0.05g to 0.15g of polypyrrole is dispersed in 100ml of deionized water, and ultrasonic treatment is carried out for 2 hours;
(2) adding a certain amount of thiourea and formaldehyde aqueous solution into the polypyrrole dispersion liquid in the step (1), performing ultrasonic treatment for 5min, and mechanically stirring the reaction liquid, wherein the ratio of thiourea to formaldehyde is 1-3: 1;
(3) heating the reaction liquid obtained in the step (2) to 40-65 ℃, adding a certain amount of concentrated hydrochloric acid solution, reacting for 2-5 hours, carrying out suction filtration on a product, washing the product by using deionized water and absolute ethyl alcohol, and drying in a drying oven at 40 ℃ to obtain a powdered thiourea/polypyrrole composite material;
(4) carbonizing the composite material obtained in the step (3) at 600-850 ℃ for 1-4 h in an argon atmosphere at a heating rate of 2 ℃/min to obtain the urea-formaldehyde/polypyrrole composite material based carbon electrode material.
2. The method for preparing the thiourea aldehyde/polypyrrole composite material based carbon electrode material according to claim 1, wherein the amount of polypyrrole used in the step (1) is 0.12 g.
3. The method for preparing the thiourea aldehyde/polypyrrole composite material based carbon electrode material according to claim 1, wherein the ratio of thiourea to formaldehyde in the step (2) is 3: 1.
4. The method for preparing the thiourea aldehyde/polypyrrole composite carbon-based electrode material according to claim 1, wherein the reaction temperature in the step (3) is 55 ℃.
5. The method for preparing the thiourea aldehyde/polypyrrole composite material based carbon electrode material according to claim 1, wherein the amount of the concentrated hydrochloric acid used in the step (3) is 0.4 ml.
6. The method for preparing the thiourea aldehyde/polypyrrole composite based carbon electrode material according to claim 1, wherein the reaction time in the step (3) is 3 hours.
7. The method for preparing the thiourea aldehyde/polypyrrole composite material based carbon electrode material according to claim 1, wherein the carbonization temperature in the step (4) is 750 ℃.
8. The method for preparing the thiourea aldehyde/polypyrrole composite based carbon electrode material according to claim 1, wherein the carbonization time in the step (4) is 3 h.
9. The preparation method of the thiourea aldehyde/polypyrrole composite carbon-based electrode material according to claim 1, wherein the polypyrrole is prepared by the following steps:
0.2g of FeCl was taken2Dissolving in 88ml deionized water, adding 2ml pyrrole monomer, ultrasonic treating for 0.5h to make pyrrole in FeCl2The solution is uniformly dispersed; adding 10ml of 30% hydrogen peroxide solution into the reaction solution at room temperature, and reacting for 6 h; and (3) centrifuging the product, washing the product by using deionized water and absolute ethyl alcohol, and finally freezing and drying to obtain the polypyrrole.
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