CN111554519A - α -Bi2O3Carbon material-loaded supercapacitor electrode material and preparation method thereof - Google Patents
α -Bi2O3Carbon material-loaded supercapacitor electrode material and preparation method thereof Download PDFInfo
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- 239000007772 electrode material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims description 37
- 239000000463 material Substances 0.000 title description 6
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 102
- 239000002121 nanofiber Substances 0.000 claims abstract description 96
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 48
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 41
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 41
- 239000003990 capacitor Substances 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 79
- 238000010041 electrostatic spinning Methods 0.000 claims description 60
- 239000000243 solution Substances 0.000 claims description 50
- 239000007788 liquid Substances 0.000 claims description 39
- 239000002904 solvent Substances 0.000 claims description 39
- 238000001354 calcination Methods 0.000 claims description 29
- 238000004321 preservation Methods 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 26
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- -1 4-dibenzooxazinyl diphenyl disulfide Chemical compound 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- GUUVPOWQJOLRAS-UHFFFAOYSA-N diphenyl disulphide Natural products C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 17
- 238000003860 storage Methods 0.000 claims description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 16
- 239000012362 glacial acetic acid Substances 0.000 claims description 16
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 16
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 16
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 15
- 238000002347 injection Methods 0.000 claims description 15
- 239000007924 injection Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- MERLDGDYUMSLAY-UHFFFAOYSA-N 4-[(4-aminophenyl)disulfanyl]aniline Chemical compound C1=CC(N)=CC=C1SSC1=CC=C(N)C=C1 MERLDGDYUMSLAY-UHFFFAOYSA-N 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 8
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- 238000011068 loading method Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 abstract description 8
- 230000005540 biological transmission Effects 0.000 abstract description 6
- 239000003792 electrolyte Substances 0.000 abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 5
- 239000011593 sulfur Substances 0.000 abstract description 5
- 238000009825 accumulation Methods 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 45
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000002002 slurry Substances 0.000 description 12
- 238000001914 filtration Methods 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 238000009210 therapy by ultrasound Methods 0.000 description 7
- 229920000557 Nafion® Polymers 0.000 description 6
- 239000006230 acetylene black Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
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- 238000001291 vacuum drying Methods 0.000 description 5
- 238000004227 thermal cracking Methods 0.000 description 4
- 238000003411 electrode reaction Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000004966 Carbon aerogel Substances 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 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
- H01G11/46—Metal oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- H01G11/24—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- 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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Abstract
The invention relates to the technical field of super capacitor electrode materials, and discloses α -Bi2O3The carbon material loaded supercapacitor electrode material comprises the following formula raw materials and components of α -Bi2O3Nanofiber, 4' -diaminodiphenyl disulfide, formaldehyde, phenol and carbon nanotube, and the α -Bi2O3Carbon material-loaded supercapacitor electrode material, monoclinic phase α -Bi2O3The electrochemical performance of the catalyst is more excellent, the catalyst has good nano-morphology and huge specific surface areaLarge, α -Bi2O3The nano-fiber is uniformly dispersed on the surface of the carbon nano-tube to reduce α -Bi2O3The agglomeration and accumulation of the nano-fibers expose more electrochemical active sites, the actual specific capacity of the electrode material is improved, and the N, S double-doped porous carbon material is used as α -Bi2O3The N is doped to enhance the electronic conductivity of the electrode material, and the sulfur is doped into the carbon layer structure to enlarge the carbon layer spacing, so that the carbon material forms rich pore channel structures and mesoporous structures, provides transmission channels for ions and electrons, and is fully wetted with electrolyte.
Description
Technical Field
The invention relates to the technical field of super capacitor electrode materials, in particular to α -Bi2O3A super capacitor electrode material loaded with a carbon material and a preparation method thereof.
Background
Along with the energy crisis that the diminishing of fossil energy reserves brought increasingly, and the environmental pollution problem that the transitional utilization fossil fuel brought is more serious day by day, it is urgent to develop novel efficient green energy device and system, ultracapacitor system is a novel energy memory between traditional condenser and the rechargeable battery, not only has the characteristic of condenser quick charge-discharge, has the energy storage characteristic of battery simultaneously, ultracapacitor system has power density height, long cycle life, operating temperature clothes wide range, advantages such as green, be a novel energy device of green efficient.
The electrode material of the super capacitor is the most important component of the super capacitor, and the current electrode material of the super capacitor mainly comprises carbon materials such as carbon nano tubes, graphene, carbon aerogel and the like; transition metal oxide electrode materials such as ruthenium oxide, manganese oxide, and cobalt oxide; conductive polymer electrode materials such as polyaniline and polythiophene, etc., wherein Bi2O3Has higher theoretical specific capacity, is a super capacitor electrode material with very potential, but currently Bi2O3The electrode material has poor electron conductivity, inhibits the transmission and migration of electrons in electrode reaction, and Bi2O3Easily agglomerate in the electrode material, so that the electrochemical active sites are covered, and the actual specific capacitance of the electrode material is greatly reduced.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides α -Bi2O3The super capacitor electrode material of the load carbon material and the preparation method thereof solve the problem of Bi2O3The problem of poor electronic conductivity of the electrode material is solved, and the Bi is also solved2O3Easily agglomerated in the electrode material, resulting in a problem of coverage of electrochemically active sites.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme that the α -Bi2O3The supercapacitor electrode material loaded with the carbon material comprises the following formula raw materials in parts by weight andthe component (by weight portion) is 35-56 portions of α -Bi2O3The nano-fiber, 17-24 parts of 4,4' -diaminodiphenyl disulfide, 9-12 parts of formaldehyde, 14-19 parts of phenol and 4-8 parts of carbon nano-tube.
Preferably, the α -Bi2O3The preparation method of the nanofiber comprises the following steps:
(1) adding N, N-dimethylformamide solvent and polyvinylpyrrolidone into a reaction bottle, and adding glacial acetic acid and Bi (NO)3)3Placing a reaction bottle in a constant-temperature water bath kettle, heating to 40-60 ℃, uniformly stirring for 2-4h to obtain electrostatic spinning solution, pouring the electrostatic spinning solution into a liquid storage tank, wherein the voltage of an electrostatic spinning machine is 18-21kV, the flow rate of the electrostatic spinning solution is 0.4-0.8mL/h, the receiving distance between an injector needle and a receiver is 16-20cm, and carrying out an electrostatic spinning process to prepare a nanofiber precursor;
(2) placing the nanofiber precursor in a resistance furnace, heating to 520-540 ℃ at the heating rate of 2-4 ℃/min, carrying out heat preservation and calcination for 2-4h, grinding the calcination product into fine powder, and preparing the monoclinic α -Bi2O3And (3) nano fibers.
Preferably, the electrostatic spinning machine is a multi-nozzle electrostatic spinning machine and comprises a piston shaft, a cover plate is fixedly connected above the piston shaft, a liquid storage tank is fixedly connected above the cover plate, a piston is fixedly connected below the right side of the cover plate, a liquid guide pipe is fixedly connected below the cover plate, a switch valve is movably connected with the liquid guide pipe, an injection tube is arranged below the piston shaft, a micro-injector is arranged below the injection tube, and a receiver is arranged below the micro-injector.
Preferably, the polyvinylpyrrolidone and CH in glacial acetic acid3COOH and Bi (NO)3)3The mass ratio of (A) to (B) is 1:2-3: 1.2-1.5.
Preferably, the α -Bi2O3The preparation method of the carbon material loaded supercapacitor electrode material comprises the following steps:
(1) adding distilled water solvent into a reaction bottle, adding 35-56 parts of α -Bi2O3Mixing the nano-fiber and 4-8 parts of carbon nano-tube, placing the reaction bottle in an ultrasonic treatment instrument after uniformly stirring, addingHeating to 50-80 deg.C, performing ultrasonic dispersion treatment at ultrasonic frequency of 25-35KHz for 30-60min, filtering the solution to remove solvent, and preparing to obtain α -Bi2O3The nanofibers support carbon nanotubes.
(2) Adding toluene solvent α -Bi into a reaction bottle2O3Loading a carbon nano tube on a nano fiber, 9-12 parts of aqueous solution containing formaldehyde and 17-24 parts of 4,4' -diaminodiphenyl disulfide, placing a reaction bottle in an oil bath pot, heating to 40-50 ℃, uniformly stirring for 20-40min, adding 14-19 parts of phenol, heating to 100-125 ℃, uniformly stirring, refluxing and reacting for 6-8h, vacuum drying the solution to remove the solvent, washing the solid product by using diethyl ether and 10-20 mass percent sodium hydroxide solution, and fully drying to prepare the 4, 4-dibenzooxazinyl diphenyl disulfide loaded α -Bi2O3And (3) nano fibers.
(3) α -Bi is loaded on 4, 4-dibenzooxazinyl diphenyl disulfide2O3Placing the nano-fiber in an atmosphere resistance furnace and introducing nitrogen, wherein the heating rate is 1-2 ℃/min, heating to 250-plus-280 ℃, carrying out heat preservation treatment for 1-1.5h, the heating rate is adjusted to 3-8 ℃/min, heating to 420-plus-460 ℃, carrying out heat preservation calcination for 2-3h, heating to 720-plus-780 ℃, carrying out heat preservation calcination for 5-8h, and preparing to obtain α -Bi2O3A supercapacitor electrode material loaded with a carbon material.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the α -Bi2O3The carbon material-loaded supercapacitor electrode material is prepared into α -Bi with monoclinic crystal structure by an electrostatic spinning method and a thermal cracking method2O3Nanofibers, compared to ordinary Bi2O3Monoclinic phase α -Bi2O3The electrochemical performance of the material is more excellent, the material has good nano-morphology and large specific surface area, and the carbon nano tube is used as a carrier to ensure that α -Bi is used2O3The nano-fiber is uniformly dispersed on the surface of the carbon nano-tube, and α -Bi can be effectively reduced2O3The agglomeration and accumulation of the nano-fibers can expose more electrochemical active sitesAnd the carbon nano tube has excellent conductivity, can improve the conductivity of the electrode material of the super capacitor, and promotes the transmission and migration of electrons, thereby improving the actual specific capacity of the electrode material.
The α -Bi2O3Carbon material-loaded supercapacitor electrode material is prepared by taking 4, 4-dibenzooxazinyl diphenyl disulfide as precursor and preparing N, S double-doped porous carbon material serving as α -Bi through thermal cracking2O3And α -Bi2O3The nanofiber-loaded carbon nanotube composite electrode material has the advantages that the electronegativity of nitrogen is larger than that of carbon, the electropositivity of the carbon material can be enhanced, so that the electronic conductivity of the electrode material is enhanced, the atomic radius of sulfur is much larger than that of carbon atoms, sulfur is doped into the carbon layer structure, the carbon layer spacing can be enlarged, the carbon material forms rich pore channel structures and mesoporous structures, a transmission channel can be provided for ions and electrons in electrode reaction, electrolyte is fully wetted, and α -Bi is mixed with the electrolyte2O3The porous carbon material is fully contacted, and the specific surface area of the porous carbon material is large, so that abundant electrochemical active sites can be provided, and the electrochemical performance of the electrode material is integrally improved.
Drawings
FIG. 1 is a schematic front view of an electrospinning machine of the present invention;
figure 2 is a schematic top view of a catheter according to the invention;
FIG. 3 is a schematic top view of the switching valve adjustment of the present invention;
1. a piston shaft; 2. a cover plate; 3. a liquid storage tank; 4. a catheter; 5. an on-off valve; 6. a piston; 7. an injection tube; 8. micro injector, 9, receiver.
Detailed Description
To achieve the above object, the present invention provides specific embodiments and examples of α -Bi2O3The carbon material loaded supercapacitor electrode material comprises the following formula raw materials in parts by weight of 35-56 parts of α -Bi2O3The nano-fiber, 17-24 parts of 4,4' -diaminodiphenyl disulfide, 9-12 parts of formaldehyde, 14-19 parts of phenol and 4-8 parts of carbon nano-tube.
α-Bi2O3The preparation method of the nanofiber comprises the following steps:
(1) adding N, N-dimethylformamide solvent and polyvinylpyrrolidone into a reaction bottle, and adding glacial acetic acid and Bi (NO)3)3Wherein the CH in polyvinylpyrrolidone and glacial acetic acid3COOH and Bi (NO)3)3The mass ratio of the components is 1:2-3:1.2-1.5, the reaction bottle is placed in a constant temperature water bath, the temperature is raised to 40-60 ℃, the uniform stirring is carried out for 2-4h, the electrostatic spinning solution is obtained, the electrostatic spinning machine is a multi-nozzle electrostatic spinning machine and comprises a piston shaft, a cover plate is fixedly connected above the piston shaft, a liquid storage tank is fixedly connected above the cover plate, a piston is fixedly connected below the right side of the cover plate, a liquid guide pipe is fixedly connected below the cover plate, a switch valve is movably connected with the liquid guide pipe, an injection pipe is arranged below the piston shaft, a micro injector is arranged below the injection pipe, a multi-nozzle receiver is arranged below the micro injector, the efficiency of electrostatic spinning is greatly improved, the electrostatic spinning solution is poured into the liquid storage tank, the voltage of the electrostatic spinning machine is 18-21kV, the flow rate of the electrostatic spinning solution is 0.4-0.8mL, carrying out electrostatic spinning process to prepare a nanofiber precursor;
(2) placing the nanofiber precursor in a resistance furnace, heating to 520-540 ℃ at the heating rate of 2-4 ℃/min, carrying out heat preservation and calcination for 2-4h, grinding the calcination product into fine powder, and preparing the monoclinic α -Bi2O3And (3) nano fibers.
α-Bi2O3The preparation method of the carbon material loaded supercapacitor electrode material comprises the following steps:
(1) adding distilled water solvent into a reaction bottle, adding 35-56 parts of α -Bi2O3Uniformly stirring nanofiber and 4-8 parts of carbon nanotube, placing the reaction flask in an ultrasonic treatment instrument, heating to 50-80 ℃, performing ultrasonic dispersion treatment for 30-60min at the ultrasonic frequency of 25-35KHz, filtering the solution to remove the solvent, and preparing to obtain α -Bi2O3The nanofibers support carbon nanotubes.
(2) Adding toluene solvent α -Bi into a reaction bottle2O3Loading a carbon nano tube on a nano fiber, 9-12 parts of aqueous solution containing formaldehyde and 17-24 parts of 4,4' -diaminodiphenyl disulfide, placing a reaction bottle in an oil bath pot, heating to 40-50 ℃, uniformly stirring for 20-40min, adding 14-19 parts of phenol, heating to 100-125 ℃, uniformly stirring, refluxing and reacting for 6-8h, vacuum drying the solution to remove the solvent, washing the solid product by using diethyl ether and 10-20 mass percent sodium hydroxide solution, and fully drying to prepare the 4, 4-dibenzooxazinyl diphenyl disulfide loaded α -Bi2O3And (3) nano fibers.
(3) α -Bi is loaded on 4, 4-dibenzooxazinyl diphenyl disulfide2O3Placing the nano-fiber in an atmosphere resistance furnace and introducing nitrogen, wherein the heating rate is 1-2 ℃/min, heating to 250-plus-280 ℃, carrying out heat preservation treatment for 1-1.5h, the heating rate is adjusted to 3-8 ℃/min, heating to 420-plus-460 ℃, carrying out heat preservation calcination for 2-3h, heating to 720-plus-780 ℃, carrying out heat preservation calcination for 5-8h, and preparing to obtain α -Bi2O3A supercapacitor electrode material loaded with a carbon material.
Taking α -Bi2O3And (3) placing the supercapacitor electrode material loaded with the carbon material, the conductive agent acetylene black and a Nafion solution in an ethanol solvent, uniformly dispersing to form slurry, coating the slurry on a glassy carbon electrode, and fully drying to prepare the supercapacitor working electrode.
Example 1
(1) Preparation of nanofiber precursor component 1: adding N, N-dimethylformamide solvent and polyvinylpyrrolidone into a reaction bottle, and adding glacial acetic acid and Bi (NO)3)3Wherein the CH in polyvinylpyrrolidone and glacial acetic acid3COOH and Bi (NO)3)3The mass ratio of the components is 1:2:1.2, the reaction bottle is placed in a constant-temperature water bath kettle, the temperature is raised to 40 ℃, the mixture is stirred at a constant speed for 2 hours, and electrostatic spinning liquid is obtained, the electrostatic spinning machine is a multi-nozzle electrostatic spinning machine and comprises a piston shaft, a cover plate is fixedly connected above the piston shaft, a liquid storage tank is fixedly connected above the cover plate, a piston is fixedly connected below the right side of the cover plate, a liquid guide pipe is fixedly connected below the cover plate, the liquid guide pipe is movably connected with a switch valve, an injection tube is arranged below the piston shaft, a micro-injector is arrangedA multi-nozzle receiver is arranged below the type injector, so that the electrostatic spinning efficiency is greatly improved, the electrostatic spinning solution is poured into a liquid storage tank, the voltage of an electrostatic spinning machine is 18kV, the flow rate of the electrostatic spinning solution is 0.4mL/h, the receiving distance between the injector needle and the receiver is 16cm, the electrostatic spinning process is carried out, and the nanofiber precursor component 1 is prepared.
(2) Preparation of α -Bi2O3The nano-fiber component 1 is prepared by placing the nano-fiber precursor component 1 in a resistance furnace, heating to 520 ℃ at a heating rate of 2 ℃/min, carrying out heat preservation calcination for 2h, grinding the calcination product into fine powder, and preparing the monoclinic α -Bi2O3Nanofiber component 1.
(3) Preparation of α -Bi2O3The component 1 of the nanofiber-loaded carbon nanotube is prepared by adding 56 parts of α -Bi into a reaction bottle with distilled water solvent2O3Uniformly stirring 1 part of nanofiber component and 4 parts of carbon nanotube, placing a reaction bottle in an ultrasonic treatment instrument, heating to 50 ℃, performing ultrasonic dispersion treatment for 30min at the ultrasonic frequency of 25KHz, filtering the solution to remove the solvent, and preparing to obtain α -Bi2O3The nanofibers support carbon nanotube component 1.
(4) Preparation of 4, 4-Dibenzoxazinyl Diphenyl disulfide Supported α -Bi2O3The nanofiber component 1 is prepared by adding toluene solvent and α -Bi into a reaction bottle2O3Placing a reaction bottle in an oil bath pot, heating to 40 ℃, uniformly stirring for 20min, adding 14 parts of phenol, heating to 100 ℃, uniformly stirring and refluxing for 6h, carrying out vacuum drying on the solution to remove the solvent, washing a solid product by using diethyl ether and a sodium hydroxide solution with the mass fraction of 10%, and fully drying to prepare the 4, 4-dibenzooxazinyl diphenyl ether loaded with α -Bi2O3Nanofiber component 1.
(5) Preparation of α -Bi2O3Carbon material-loaded supercapacitor electrode material 1, 4-dibenzooxazinyl diphenyl disulfide is loaded with α -Bi2O3The nanofiber component 1 was placed in an atmospheric resistance furnace and nitrogen was passed throughHeating to 250 deg.C at a heating rate of 1 deg.C/min for 1 hr, heating to 420 deg.C at a heating rate of 3 deg.C/min for 2 hr, heating to 720 deg.C for 5 hr, and calcining to obtain α -Bi2O3A supercapacitor electrode material 1 supporting a carbon material.
(6) Taking α -Bi2O3And (2) placing the supercapacitor electrode material 1 loaded with the carbon material, acetylene black serving as a conductive agent and a Nafion solution in an ethanol solvent, uniformly dispersing to form slurry, coating the slurry on a glassy carbon electrode, and fully drying to prepare the supercapacitor working electrode 1.
Example 2
(1) Preparation of nanofiber precursor component 2: adding N, N-dimethylformamide solvent and polyvinylpyrrolidone into a reaction bottle, and adding glacial acetic acid and Bi (NO)3)3Wherein the CH in polyvinylpyrrolidone and glacial acetic acid3COOH and Bi (NO)3)3The mass ratio of the components is 1:2:1.2, a reaction bottle is placed in a constant-temperature water bath kettle, the temperature is raised to 60 ℃, the mixture is stirred at a constant speed for 2 hours, and electrostatic spinning liquid is obtained, wherein the electrostatic spinning machine is a multi-nozzle electrostatic spinning machine and comprises a piston shaft, a cover plate is fixedly connected above the piston shaft, a liquid storage tank is fixedly connected above the cover plate, a piston is fixedly connected below the right side of the cover plate, a liquid guide pipe is fixedly connected below the cover plate, the liquid guide pipe is movably connected with a switch valve, an injection tube is arranged below the piston shaft, a micro injector is arranged below the injection tube, and a multi-nozzle receiver is arranged below the micro injector, so that the electrostatic spinning efficiency is greatly improved, the electrostatic spinning liquid is poured into the liquid storage tank, the voltage of the electrostatic spinning machine is 18kV, the flow rate of the electrostatic spinning solution is 0.8 mL/h.
(2) Preparation of α -Bi2O3The nanofiber component 2 is prepared by placing the nanofiber precursor component 2 in a resistance furnace, heating to 540 ℃ at a heating rate of 2 ℃/min, keeping the temperature, calcining for 2h, grinding the calcined product into fine powder, and preparing the monoclinic α -Bi2O3Nanofiber component 2.
(3) Preparation of α -Bi2O3The component 2 of the nanofiber-loaded carbon nanotube is prepared by adding distilled water solvent into a reaction bottle, and adding 52 parts of α -Bi2O3Uniformly stirring 2 parts of nanofiber component and 5 parts of carbon nanotube, placing a reaction bottle in an ultrasonic treatment instrument, heating to 50 ℃, performing ultrasonic dispersion treatment for 60min at the ultrasonic frequency of 35KHz, filtering the solution to remove the solvent, and preparing to obtain α -Bi2O3The nanofibers carry carbon nanotube component 2.
(4) Preparation of 4, 4-Dibenzoxazinyl Diphenyl disulfide Supported α -Bi2O3The nanofiber component 2 is prepared by adding a toluene solvent, α -Bi into a reaction flask2O3Loading a carbon nano tube component 2 on nano fibers, 9.5 parts of aqueous solution containing formaldehyde and 18.5 parts of 4,4' -diaminodiphenyl disulfide into a reaction bottle, placing the reaction bottle in an oil bath pot, heating to 50 ℃, uniformly stirring for 20min, adding 15 parts of phenol, heating to 125 ℃, uniformly stirring, refluxing and reacting for 6h, drying the solution in vacuum to remove the solvent, washing a solid product by using diethyl ether and a sodium hydroxide solution with the mass fraction of 10%, and fully drying to prepare the 4, 4-dibenzooxazinyl diphenyl disulfide loaded with α -Bi2O3Nanofiber component 2.
(5) Preparation of α -Bi2O3Carbon material loaded supercapacitor electrode material 2, 4-dibenzooxazinyl diphenyl disulfide is loaded with α -Bi2O3Placing the nanofiber component 2 in an atmosphere resistance furnace, introducing nitrogen, heating to 250 ℃ at the heating rate of 1 ℃/min, carrying out heat preservation treatment for 1.5h, adjusting the heating rate to 3 ℃/min, heating to 420 ℃, carrying out heat preservation calcination for 3h, heating to 780 ℃, carrying out heat preservation calcination for 8h, and preparing to obtain α -Bi2O3And (3) a supercapacitor electrode material 2 loaded with a carbon material.
(6) Taking α -Bi2O3And (3) placing the supercapacitor electrode material 2 loaded with the carbon material, the conductive agent acetylene black and a Nafion solution in an ethanol solvent, uniformly dispersing to form slurry, coating the slurry on a glassy carbon electrode, and fully drying to prepare the supercapacitor working electrode 2.
Example 3
(1) Preparation of nanofiber precursorAnd (3) component: adding N, N-dimethylformamide solvent and polyvinylpyrrolidone into a reaction bottle, and adding glacial acetic acid and Bi (NO)3)3Wherein the CH in polyvinylpyrrolidone and glacial acetic acid3COOH and Bi (NO)3)3The mass ratio of the components is 1:2.5:1.4, the reaction bottle is placed in a constant-temperature water bath, the temperature is raised to 50 ℃, the mixture is stirred at a constant speed for 3 hours, and electrostatic spinning solution is obtained, wherein the electrostatic spinning machine is a multi-nozzle electrostatic spinning machine and comprises a piston shaft, a cover plate is fixedly connected above the piston shaft, a liquid storage tank is fixedly connected above the cover plate, a piston is fixedly connected below the right side of the cover plate, a liquid guide pipe is fixedly connected below the cover plate, the liquid guide pipe is movably connected with a switch valve, an injection tube is arranged below the piston shaft, a micro injector is arranged below the injection tube, and a multi-nozzle receiver is arranged below the micro injector, so that the electrostatic spinning efficiency is greatly improved, the electrostatic spinning solution is poured into the liquid storage tank, the voltage of the electrostatic spinning machine is 20kV, the flow rate of the electrostatic spinning solution is 0.6mL/h, and the.
(2) Preparation of α -Bi2O3The nanofiber component 3 is prepared by placing the nanofiber precursor component 3 in a resistance furnace, heating to 530 ℃ at a heating rate of 3 ℃/min, carrying out heat preservation and calcination for 3h, grinding the calcination product into fine powder, and preparing the monoclinic α -Bi2O3 A nanofiber component 3.
(3) Preparation of α -Bi2O3The component 3 of the nanofiber-loaded carbon nanotube is prepared by adding 47 parts of α -Bi into a reaction bottle with distilled water solvent2O3Uniformly stirring 3 parts of nanofiber component and 6 parts of carbon nanotube, placing the reaction flask in an ultrasonic treatment instrument, heating to 65 ℃, performing ultrasonic dispersion treatment for 45min at the ultrasonic frequency of 30KHz, filtering the solution to remove the solvent, and preparing to obtain α -Bi2O3The nanofibers carry carbon nanotube component 3.
(4) Preparation of 4, 4-Dibenzoxazinyl Diphenyl disulfide Supported α -Bi2O3The nanofiber component 3 is prepared by adding a toluene solvent, α -Bi into a reaction flask2O3A component 3 of a nanofiber-supported carbon nanotube containingPlacing a reaction bottle in an oil bath pot, heating to 45 ℃, uniformly stirring for 30min, adding 16.5 parts of phenol, heating to 100 ℃, uniformly stirring, refluxing for reaction for 7h, carrying out vacuum drying on the solution to remove the solvent, washing a solid product by using diethyl ether and a sodium hydroxide solution with the mass fraction of 15%, and fully drying to prepare the 4, 4-dibenzooxazinyl diphenyl disulfide supported α -Bi2O3 A nanofiber component 3.
(5) Preparation of α -Bi2O3Carbon material loaded supercapacitor electrode material 3, 4-dibenzooxazinyl diphenyl disulfide is loaded with α -Bi2O3Placing the nanofiber component 3 in an atmosphere resistance furnace, introducing nitrogen, heating to 270 ℃ at the heating rate of 1 ℃/min, carrying out heat preservation treatment for 1h, adjusting the heating rate to 5 ℃/min, heating to 440 ℃, carrying out heat preservation calcination for 2.5h, heating to 760 ℃, carrying out heat preservation calcination for 6h, and preparing to obtain α -Bi2O3A supercapacitor electrode material 3 supporting a carbon material.
(6) Taking α -Bi2O3And (3) placing the supercapacitor electrode material 3 loaded with the carbon material, the conductive agent acetylene black and a Nafion solution in an ethanol solvent, uniformly dispersing to form slurry, coating the slurry on a glassy carbon electrode, and fully drying to prepare the supercapacitor working electrode 3.
Example 4
(1) Preparation of nanofiber precursor component 4: adding N, N-dimethylformamide solvent and polyvinylpyrrolidone into a reaction bottle, and adding glacial acetic acid and Bi (NO)3)3Wherein the CH in polyvinylpyrrolidone and glacial acetic acid3COOH and Bi (NO)3)3The mass ratio of the components is 1:2:1.2, the reaction bottle is placed in a constant-temperature water bath kettle, the temperature is raised to 60 ℃, the mixture is stirred at a constant speed for 2 hours, and electrostatic spinning liquid is obtained, the electrostatic spinning machine is a multi-nozzle electrostatic spinning machine and comprises a piston shaft, a cover plate is fixedly connected above the piston shaft, a liquid storage tank is fixedly connected above the cover plate, a piston is fixedly connected below the right side of the cover plate, a liquid guide pipe is fixedly connected below the cover plate, the liquid guide pipe is movably connected with a switch valve, an injection tube is arranged below the piston shaft, and anThe preparation method comprises the steps of pouring the electrostatic spinning solution into a liquid storage tank, wherein the voltage of an electrostatic spinning machine is 21kV, the flow rate of the electrostatic spinning solution is 0.8mL/h, the receiving distance between a syringe needle and the receiver is 16cm, carrying out the electrostatic spinning process, and preparing the nanofiber precursor component 4.
(2) Preparation of α -Bi2O3The nanofiber component 4 is prepared by placing the nanofiber precursor component 4 in a resistance furnace, heating to 540 ℃ at a heating rate of 2 ℃/min, carrying out heat preservation and calcination for 2h, grinding the calcination product into fine powder, and preparing the monoclinic α -Bi2O3 A nanofiber component 4.
(3) Preparation of α -Bi2O3The component 4 of the nanofiber-loaded carbon nanotube is prepared by adding 40 parts of α -Bi into a reaction bottle with distilled water solvent2O3Uniformly stirring 4 parts of nanofiber component and 7 parts of carbon nanotube, placing a reaction bottle in an ultrasonic treatment instrument, heating to 50 ℃, performing ultrasonic dispersion treatment for 60min at the ultrasonic frequency of 35KHz, filtering the solution to remove the solvent, and preparing to obtain α -Bi2O3The nanofibers carry carbon nanotube component 4.
(4) Preparation of 4, 4-Dibenzoxazinyl Diphenyl disulfide Supported α -Bi2O3The nanofiber component 4 is prepared by adding a toluene solvent, α -Bi into a reaction flask2O3Loading a carbon nano tube component 4 on nano fibers, 10.5 parts of aqueous solution containing formaldehyde and 23 parts of 4,4' -diaminodiphenyl disulfide on the nano fibers, placing a reaction bottle in an oil bath pot, heating to 50 ℃, uniformly stirring for 20min, adding 17.5 parts of phenol, heating to 125 ℃, uniformly stirring, refluxing and reacting for 8h, drying the solution in vacuum to remove a solvent, washing a solid product by using diethyl ether and a sodium hydroxide solution with the mass fraction of 20%, and fully drying to prepare the 4, 4-dibenzooxazinyl diphenyl disulfide loaded α -Bi2O3 A nanofiber component 4.
(5) Preparation of α -Bi2O3Carbon material-loaded supercapacitor electrode material 4. 4, 4-dibenzooxazinyl diphenyl disulfide is loaded with α -Bi2O3The nanofiber component 4 is arranged inIntroducing nitrogen into an atmosphere resistance furnace, heating to 250 ℃ at the heating rate of 2 ℃/min, carrying out heat preservation treatment for 1h, adjusting the heating rate to 3 ℃/min, heating to 420 ℃, carrying out heat preservation calcination for 3h, heating to 720 ℃, carrying out heat preservation calcination for 8h, and preparing to obtain α -Bi2O3And a supercapacitor electrode material 4 supporting a carbon material.
(6) Taking α -Bi2O3And (3) placing the supercapacitor electrode material 4 loaded with the carbon material, the conductive agent acetylene black and a Nafion solution in an ethanol solvent, uniformly dispersing to form slurry, coating the slurry on a glassy carbon electrode, and fully drying to prepare the supercapacitor working electrode 4.
Example 5
(1) Preparation of nanofiber precursor component 5: adding N, N-dimethylformamide solvent and polyvinylpyrrolidone into a reaction bottle, and adding glacial acetic acid and Bi (NO)3)3Wherein the CH in polyvinylpyrrolidone and glacial acetic acid3COOH and Bi (NO)3)3The mass ratio of the components is 1:3:1.5, the reaction bottle is placed in a constant-temperature water bath kettle, the temperature is raised to 60 ℃, the mixture is stirred at a constant speed for 4 hours, and electrostatic spinning liquid is obtained, the electrostatic spinning machine is a multi-nozzle electrostatic spinning machine and comprises a piston shaft, a cover plate is fixedly connected above the piston shaft, a liquid storage tank is fixedly connected above the cover plate, a piston is fixedly connected below the right side of the cover plate, a liquid guide pipe is fixedly connected below the cover plate, the liquid guide pipe is movably connected with a switch valve, an injection tube is arranged below the piston shaft, a micro injector is arranged below the injection tube, a multi-nozzle receiver is arranged below the micro injector, the electrostatic spinning efficiency is greatly improved, the electrostatic spinning liquid is poured into the liquid storage tank, the voltage of the electrostatic spinning machine is 21kV, the flow rate of the electrostatic spinning solution is 0.8mL/h, the receiving distance between the.
(2) Preparation of α -Bi2O3The nanofiber component 5 is prepared by placing the nanofiber precursor component 5 in a resistance furnace, heating to 540 ℃ at a heating rate of 4 ℃/min, keeping the temperature, calcining for 4h, grinding the calcined product into fine powder, and preparing the monoclinic α -Bi2O3 A nanofiber component 5.
(3) Preparation of α -Bi2O3The component 5 of the nanofiber-loaded carbon nanotube is prepared by adding distilled water solvent into a reaction bottle, and adding 35 parts of α -Bi2O3Uniformly stirring 5 parts of nanofiber component and 8 parts of carbon nanotube, placing a reaction bottle in an ultrasonic treatment instrument, heating to 80 ℃, performing ultrasonic dispersion treatment for 60min at the ultrasonic frequency of 35KHz, filtering the solution to remove the solvent, and preparing to obtain α -Bi2O3The nanofibers carry the carbon nanotube component 5.
(4) Preparation of 4, 4-Dibenzoxazinyl Diphenyl disulfide Supported α -Bi2O3The nanofiber component 5 is prepared by adding a toluene solvent and α -Bi into a reaction bottle2O3Placing a reaction bottle in an oil bath pot, heating to 50 ℃, uniformly stirring for 40min, adding 19 parts of phenol, heating to 125 ℃, uniformly stirring, refluxing for reaction for 8h, vacuum-drying the solution to remove the solvent, washing a solid product by using diethyl ether and a sodium hydroxide solution with the mass fraction of 20%, and fully drying to prepare the 4, 4-dibenzooxazinyl diphenyl disulfide supported α -Bi2O3 A nanofiber component 5.
(5) Preparation of α -Bi2O3Super capacitor electrode material 5 loaded with carbon material, 4-dibenzooxazinyl diphenyl disulfide is loaded with α -Bi2O3Placing the nanofiber component 5 in an atmosphere resistance furnace, introducing nitrogen, heating to 280 ℃ at the heating rate of 2 ℃/min, carrying out heat preservation treatment for 1.5h, adjusting the heating rate to 8 ℃/min, heating to 460 ℃, carrying out heat preservation calcination for 3h, heating to 780 ℃, carrying out heat preservation calcination for 8h, and preparing to obtain α -Bi2O3A supercapacitor electrode material 5 supporting a carbon material.
(6) Taking α -Bi2O3And (3) placing the supercapacitor electrode material 5 loaded with the carbon material, the conductive agent acetylene black and a Nafion solution in an ethanol solvent, uniformly dispersing to form slurry, coating the slurry on a glassy carbon electrode, and fully drying to prepare the supercapacitor working electrode 5.
The electrochemical performance of the working electrode of the supercapacitor in examples 1-5 was tested in the CHI660D electrochemical workstation with a platinum electrode as an auxiliary electrode, a saturated calomel electrode as a reference electrode, and a 6mol/L potassium hydroxide solution as an electrolyte, and the test standard was GB/T34870.1-2017.
In summary, the α -Bi2O3The carbon material-loaded supercapacitor electrode material is prepared into α -Bi with monoclinic crystal structure by an electrostatic spinning method and a thermal cracking method2O3Nanofibers, compared to ordinary Bi2O3Monoclinic phase α -Bi2O3The electrochemical performance of the material is more excellent, the material has good nano-morphology and large specific surface area, and the carbon nano tube is used as a carrier to ensure that α -Bi is used2O3The nano-fiber is uniformly dispersed on the surface of the carbon nano-tube, and α -Bi can be effectively reduced2O3The agglomeration and accumulation of the nano-fibers can expose more electrochemical active sites, and the carbon nano-tubes have excellent conductivity, can improve the conductivity of the electrode material of the super capacitor, and promote the transmission and migration of electrons, thereby improving the actual specific capacity of the electrode material.
The method is characterized in that 4, 4-dibenzooxazinyl diphenyl disulfide is used as a precursor, and an N, S double-doped porous carbon material is prepared by thermal cracking and used as α -Bi2O3And α -Bi2O3The nanofiber-loaded carbon nanotube composite electrode material has the advantages that the electronegativity of nitrogen is larger than that of carbon, the electropositivity of the carbon material can be enhanced, so that the electronic conductivity of the electrode material is enhanced, the atomic radius of sulfur is much larger than that of carbon atoms, sulfur is doped into the carbon layer structure, the carbon layer spacing can be enlarged, the carbon material forms rich pore channel structures and mesoporous structures, a transmission channel can be provided for ions and electrons in electrode reaction, electrolyte is fully wetted, and α -Bi is mixed with the electrolyte2O3The porous carbon material has large specific surface area, can provide abundant electrochemical active sites, and improves the electrochemistry of the electrode material on the wholeAnd (4) performance.
Claims (5)
1.α -Bi2O3The carbon material loaded supercapacitor electrode material comprises the following formula raw materials and components in parts by weight, and is characterized in that 35-56 parts of α -Bi2O3The nano-fiber, 17-24 parts of 4,4' -diaminodiphenyl disulfide, 9-12 parts of formaldehyde, 14-19 parts of phenol and 4-8 parts of carbon nano-tube.
2.α -Bi according to claim 12O3The super capacitor electrode material of the loaded carbon material is characterized in that the α -Bi2O3The preparation method of the nanofiber comprises the following steps:
(1) adding polyvinylpyrrolidone, glacial acetic acid and Bi (NO) into N, N-dimethylformamide solvent3)3Heating the solution to 40-60 ℃, uniformly stirring for 2-4h to obtain electrostatic spinning solution, pouring the electrostatic spinning solution into a liquid storage tank, controlling the voltage of an electrostatic spinning machine to be 18-21kV, controlling the flow rate of the electrostatic spinning solution to be 0.4-0.8mL/h, controlling the receiving distance between an injector needle and a receiver to be 16-20cm, and carrying out electrostatic spinning process to prepare a nanofiber precursor;
(2) placing the nanofiber precursor in a resistance furnace, heating to 520-540 ℃ at the heating rate of 2-4 ℃/min, carrying out heat preservation and calcination for 2-4h, grinding the calcination product into fine powder, and preparing the monoclinic α -Bi2O3And (3) nano fibers.
3.α -Bi according to claim 22O3The super capacitor electrode material loaded with the carbon material is characterized in that: the electrostatic spinning machine is a multi-nozzle electrostatic spinning machine and comprises a piston shaft, a cover plate is fixedly connected above the piston shaft, a liquid storage tank is fixedly connected above the cover plate, a piston is fixedly connected below the right side of the cover plate, a liquid guide pipe is fixedly connected below the cover plate, a switch valve is movably connected with the liquid guide pipe, an injection tube is arranged below the piston shaft, a micro injector is arranged below the injection tube, and a receiver is arranged below the micro injector.
4.α -Bi according to claim 22O3The super capacitor electrode material loaded with the carbon material is characterized in that: CH in the polyvinylpyrrolidone and the glacial acetic acid3COOH and Bi (NO)3)3The mass ratio of (A) to (B) is 1:2-3: 1.2-1.5.
5.α -Bi according to claim 12O3The super capacitor electrode material of the loaded carbon material is characterized in that the α -Bi2O3The preparation method of the carbon material loaded supercapacitor electrode material comprises the following steps:
(1) adding 35-56 parts of α -Bi into distilled water solvent2O3Uniformly stirring the nano-fiber and 4-8 parts of carbon nano-tube, performing ultrasonic dispersion treatment on the solution at 50-80 ℃ for 30-60min at the ultrasonic frequency of 25-35KHz, removing the solvent from the solution, drying, and preparing to obtain α -Bi2O3The carbon nano tube is loaded on the nano fiber;
(2) α -Bi is added into toluene solvent2O3The preparation method comprises the steps of loading a carbon nano tube on nano fibers, 9-12 parts of aqueous solution containing formaldehyde and 17-24 parts of 4,4' -diaminodiphenyl disulfide, heating the solution to 40-50 ℃, uniformly stirring for 20-40min, adding 14-19 parts of phenol, heating to 100 ℃ and 125 ℃, reacting for 6-8h, removing the solvent from the solution, washing a solid product and drying to prepare 4, 4-dibenzooxazinyl diphenyl disulfide loaded α -Bi2O3A nanofiber;
(3) α -Bi is loaded on 4, 4-dibenzooxazinyl diphenyl disulfide2O3Placing the nano-fiber in an atmosphere resistance furnace and introducing nitrogen, wherein the heating rate is 1-2 ℃/min, heating to 250-plus-280 ℃, carrying out heat preservation treatment for 1-1.5h, the heating rate is adjusted to 3-8 ℃/min, heating to 420-plus-460 ℃, carrying out heat preservation calcination for 2-3h, heating to 720-plus-780 ℃, carrying out heat preservation calcination for 5-8h, and preparing to obtain α -Bi2O3A supercapacitor electrode material loaded with a carbon material.
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Application publication date: 20200818 |