CN111564320B - Nano MnO 2 Supercapacitor electrode material of modified carbon cloth and preparation method thereof - Google Patents
Nano MnO 2 Supercapacitor electrode material of modified carbon cloth and preparation method thereof Download PDFInfo
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- 239000004744 fabric Substances 0.000 title claims abstract description 75
- 239000007772 electrode material Substances 0.000 title claims abstract description 51
- 150000001721 carbon Chemical class 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 95
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 75
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 75
- 239000004005 microsphere Substances 0.000 claims abstract description 58
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000004793 Polystyrene Substances 0.000 claims abstract description 28
- 229920002223 polystyrene Polymers 0.000 claims abstract description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 21
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 19
- 239000004917 carbon fiber Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- 239000012153 distilled water Substances 0.000 claims description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 35
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 26
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 24
- 239000012265 solid product Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 16
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 15
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 13
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 13
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 12
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 12
- 239000000467 phytic acid Substances 0.000 claims description 12
- 229940068041 phytic acid Drugs 0.000 claims description 12
- 235000002949 phytic acid Nutrition 0.000 claims description 12
- 239000002033 PVDF binder Substances 0.000 claims description 11
- 239000000853 adhesive Substances 0.000 claims description 11
- 230000001070 adhesive effect Effects 0.000 claims description 11
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 10
- 239000002270 dispersing agent Substances 0.000 claims description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 239000003125 aqueous solvent Substances 0.000 claims 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims 2
- 239000003990 capacitor Substances 0.000 abstract description 14
- 239000003792 electrolyte Substances 0.000 abstract description 6
- 229920000128 polypyrrole Polymers 0.000 abstract description 4
- 238000006479 redox reaction Methods 0.000 abstract description 4
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 238000004227 thermal cracking Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 58
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 238000001291 vacuum drying Methods 0.000 description 11
- 238000009210 therapy by ultrasound Methods 0.000 description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005530 etching Methods 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
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000004966 Carbon aerogel Substances 0.000 description 1
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical group [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 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
- 238000011161 development Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 238000000197 pyrolysis Methods 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
- 230000001629 suppression Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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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
-
- 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
-
- 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
-
- 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
-
- 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)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention relates to the technical field of super capacitors and discloses nano MnO 2 The supercapacitor electrode material of the modified carbon cloth comprises the following formula raw materials and components: n, P codoped carbon cloth, carbon nanotube hollow microsphere, KMnO 4 、MnSO 4 . The nanometer MnO 2-modified carbon cloth super capacitor electrode material takes the polystyrene nanometer microsphere as a template, and the obtained carbon nanometer tube hollow microsphere has a huge specific surface area and nanometer MnO 2 Coating carbon nano tube hollow microspheres to effectively inhibit nano MnO 2 The agglomeration phenomenon can expose more active sites of redox reaction, the carbon nano tube enhances the conductivity of the electrode material, the phosphorylated polypyrrole loaded carbon fiber cloth is subjected to high-temperature thermal cracking to obtain the N and P co-doped modified carbon cloth, the conductivity of the carbon fiber cloth is improved, and the nano MnO is added 2 The loaded carbon nanotube is coated on the modified carbon cloth, and has good wettability with electrolyte, so that the electrode material has higher actual specific capacitance and electrochemical performance.
Description
Technical Field
The invention relates to the technical field of super capacitors, in particular to nano MnO 2 -modified carbon cloth electrode material for super capacitor and its preparation method.
Background
The super capacitor is a novel energy storage device, is the novel components and parts of the interface bilayer that forms between electrode and the electrolyte storage energy, and super capacitor not only has the characteristic of condenser fast charge-discharge, has the energy storage characteristic of battery simultaneously, compares with battery and traditional physical capacitor, and super capacitor has power density height, long cycle life, work temperature limit is wide, non-maintaining, advantages such as green, can regard as auxiliary energy, have important application in electric automobile and smart power grids's storage system.
The current electrode material of the super capacitor mainly comprises carbon material electrode materials, such as carbon nanofibers, carbon aerogel, carbon nanotubes and the like; metal oxide electrode materials such as cobalt oxide, ruthenium oxide, manganese oxide, and the like; conductive polymer electrode materials such as polythiophene, polyaniline, and the like; wherein MnO is 2 The material has high theoretical specific capacitance, rich reserves and low price, is a super capacitor electrode material with great development potential, but MnO 2 Has low conductivity and suppresses electrons in the redox reaction of the electrode materialMigration and transmission greatly reduce the actual specific capacitance of the electrode material.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides nano MnO 2 The super capacitor electrode material of the modified carbon cloth and the preparation method thereof solve the problem of MnO 2 The conductivity of the electrode material is poor.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: nano MnO 2 The supercapacitor electrode material of the modified carbon cloth comprises the following formula raw materials and components in parts by weight: n, P co-doped carbon cloth, 44-62 parts of carbon nano tube hollow microspheres and 15-20 parts of KMnO 4 23-36 parts of MnSO 4 。
Preferably, the preparation method of the N, P co-doped carbon cloth comprises the following steps:
(1) Adding distilled water, carbon fiber cloth, phytic acid and pyrrole into a reaction bottle, adding an initiator potassium persulfate after uniformly stirring, placing the reaction bottle in an ice water bath, uniformly stirring and reacting for 5-8h at 0-5 ℃, vacuum drying the solution to remove a solvent, washing a solid product by using ethanol, fully drying, placing a carbon cloth mixture in an atmosphere resistance furnace, introducing argon, raising the temperature at the rate of 5-10 ℃, raising the temperature to 760-780, and calcining for 3-5h to obtain a calcined product, namely N, P co-doped carbon cloth.
Preferably, the mass ratio of the carbon fiber cloth to the phytic acid to the pyrrole to the potassium persulfate is 25-40.
Preferably, the preparation method of the carbon nanotube hollow microsphere comprises the following steps:
(1) Introducing nitrogen into a reaction bottle to discharge air, adding a mixed solvent of ethanol and distilled water, adding dispersing agents of sodium dodecyl benzene sulfonate and styrene, placing the reaction bottle into an ultrasonic treatment instrument, heating to 40-60 ℃, performing ultrasonic dispersion treatment for 1-2 hours, wherein the ultrasonic frequency is 25-35KHz, adding an initiator of ammonium persulfate, placing the reaction bottle into a constant-temperature water bath kettle, heating to 60-80 ℃, stirring at a constant speed for reaction for 12-18 hours, performing vacuum drying on the solution to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to prepare the polystyrene nano microspheres.
(2) Adding distilled water, polystyrene nano-microspheres and carbon nano-tubes into a reaction bottle, carrying out ultrasonic dispersion treatment on the solution at 45-75 ℃ for 1-3h with the ultrasonic frequency of 25-40KHz, placing the reaction bottle in an oil bath pot, heating to 90-110 ℃, stirring at constant speed until distilled water solvent is evaporated, placing a solid product in a tetrahydrofuran solvent, heating to 50-70 ℃, stirring at constant speed for 10-15h to remove the polystyrene microspheres, carrying out reduced pressure concentration on the solution to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the carbon nano-tube hollow microspheres.
Preferably, the mass ratio of the sodium dodecyl benzene sulfonate to the styrene to the ammonium persulfate is 1-35.
Preferably, the mass ratio of the polystyrene microspheres to the carbon nanotubes is 1.
Preferably, the nano MnO 2 The preparation method of the supercapacitor electrode material of the modified carbon cloth comprises the following steps:
(1) Adding distilled water solvent, 44-62 parts of carbon nano tube hollow microspheres and 15-20 parts of KMnO into a reaction bottle 4 23-36 parts of MnSO 4 Placing a reaction bottle in an ultrasonic treatment instrument, heating to 40-70 ℃, performing ultrasonic dispersion treatment for 40-60min at the ultrasonic frequency of 20-30KHz, transferring the solution into a high-pressure hydrothermal reaction kettle, placing the high-pressure hydrothermal reaction kettle in a reaction kettle heating box, heating to 160-200 ℃, reacting for 12-20h, performing vacuum drying on the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to prepare the nano MnO 2 And loading the carbon nano tube.
(2) MnO of nanometer 2 The preparation method comprises the steps of loading the carbon nano tube, the conductive carbon black and the adhesive polyvinylidene fluoride, uniformly dispersing the carbon nano tube, the conductive carbon black and the adhesive polyvinylidene fluoride in an N-methyl pyrrolidone solution according to a mass ratio of 8 2 -modified carbon cloth as electrode material for super capacitor.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the nanometer MnO 2-modified carbon cloth super capacitor electrode material is characterized in that polystyrene nanometer microspheres are used as templates to form pi-pi bonds with carbon nanotubes, the carbon nanotubes are adsorbed to the surfaces of the polystyrene nanometer microspheres, the polystyrene nanometer microspheres are removed through tetrahydrofuran etching, the obtained carbon nanotube hollow microspheres have large specific surface areas, and the nano MnO 2-modified carbon cloth super capacitor electrode material is prepared by using the carbon nanotube hollow microspheres as templates through a hydrothermal in-situ synthesis method 2 Coating carbon nano tube hollow microspheres to effectively inhibit nano MnO 2 Agglomeration phenomenon, and nano-sized MnO 2 The specific surface area is high, more redox reaction active sites can be exposed, and the carbon nano tube has high conductivity, so that the conductivity of the electrode material is greatly enhanced, the migration and diffusion of electrons in the oxidation reaction are promoted, and the pseudocapacitance and the electrochemical performance of the electrode material are improved.
The nanometer MnO 2 The supercapacitor electrode material of the modified carbon cloth takes the carbon fiber cloth as a substrate, phytic acid as a phosphorus source and pyrrole as a nitrogen source, the carbon fiber cloth is loaded with phosphorylated polypyrrole through polymerization reaction to form the phosphorylated polypyrrole, and the N and P co-doped modified carbon cloth is prepared through high-temperature thermal cracking 2 The loaded carbon nanotube is coated on the modified carbon cloth, and the obtained electrode material has good wettability with electrolyte, so that the electrode material has higher actual specific capacitance and electrochemical performance.
Detailed Description
To achieve the above objects, the present invention provides the following embodiments and examples: nano MnO 2 The supercapacitor electrode material of the modified carbon cloth comprises the following formula raw materials and components in parts by weight: n, P co-doped carbon cloth, 44-62 parts of carbon nanotube hollow microspheres and 15-20 parts of KMnO 4 23-36 parts of MnSO 4 。
The preparation method of the N and P co-doped carbon cloth comprises the following steps:
(1) Adding a distilled water solvent, carbon fiber cloth, phytic acid and pyrrole into a reaction bottle, uniformly stirring, adding an initiator potassium persulfate, wherein the mass ratio of the four components is (25-40).
The preparation method of the carbon nano tube hollow microsphere comprises the following steps:
(1) Introducing nitrogen into a reaction bottle to discharge air, adding a mixed solvent of ethanol and distilled water, wherein the volume ratio of the two solvents is 1:2.5-3.5, adding dispersing agents of sodium dodecyl benzene sulfonate and styrene, the mass ratio is 1.
(2) Adding distilled water, polystyrene nano microspheres and carbon nano tubes into a reaction bottle according to the mass ratio of 1.
Nano MnO 2 The preparation method of the supercapacitor electrode material of the modified carbon cloth comprises the following steps:
(1) Adding distilled water solvent, 44-62 parts of carbon nano tube hollow microspheres and 15-20 parts of KMnO into a reaction bottle 4 23-36 parts of MnSO 4 Placing a reaction bottle in an ultrasonic treatment instrument, heating to 40-70 ℃, performing ultrasonic dispersion treatment for 40-60min at the ultrasonic frequency of 20-30KHz, transferring the solution into a high-pressure hydrothermal reaction kettle, placing the high-pressure hydrothermal reaction kettle in a reaction kettle heating box, heating to 160-200 ℃, reacting for 12-20h, performing vacuum drying on the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to prepare the nano MnO 2 And carrying the carbon nano-tube.
(2) Adding nano MnO 2 The preparation method comprises the steps of loading the carbon nano tube, the conductive carbon black and the adhesive polyvinylidene fluoride, uniformly dispersing the carbon nano tube, the conductive carbon black and the adhesive polyvinylidene fluoride in an N-methyl pyrrolidone solution according to a mass ratio of 8 2 -modified carbon cloth supercapacitor electrode materials.
Example 1
(1) Preparing a component 1 of N, P co-doped carbon cloth: adding a distilled water solvent, carbon fiber cloth, phytic acid and pyrrole into a reaction bottle, uniformly stirring, adding an initiator potassium persulfate, wherein the mass ratio of the four is 25.5.
(2) Preparing a polystyrene nano microsphere component 1: introducing nitrogen into a reaction bottle to discharge air, adding a mixed solvent of ethanol and distilled water, wherein the volume ratio of the two solvents is 1:2.5, adding dispersing agents of sodium dodecyl benzene sulfonate and styrene, the mass ratio is 1.
(3) Preparing a carbon nano tube hollow microsphere component 1: adding distilled water, a polystyrene nano microsphere component 1 and a carbon nano tube into a reaction bottle according to the mass ratio of 1 to 2, carrying out ultrasonic dispersion treatment on the solution at 45 ℃ for 1h, wherein the ultrasonic frequency is 25KHz, placing the reaction bottle into an oil bath pot, heating to 90 ℃, uniformly stirring until a distilled water solvent is evaporated, placing a solid product into a tetrahydrofuran solvent, heating to 50 ℃, uniformly stirring for 10h to remove the polystyrene microspheres, carrying out reduced pressure concentration on the solution to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the carbon nano tube hollow microsphere component 1.
(4) Preparing to obtain nano MnO 2 Loading carbon nanotube component 1: distilled water solvent and 62 parts of carbon nano tube hollow microsphere component 1, 15 parts of KMnO are added into a reaction bottle 4 23 parts of MnSO 4 Placing a reaction bottle in an ultrasonic treatment instrument, heating to 40 ℃, performing ultrasonic dispersion treatment for 40min at the ultrasonic frequency of 20KHz, transferring the solution into a high-pressure hydrothermal reaction kettle, placing the reaction kettle in a reaction kettle heating box, heating to 160 ℃, reacting for 12h, performing vacuum drying on the solution to remove a solvent, washing a solid product by using distilled water and ethanol, and fully drying to prepare the nano MnO 2 Carrying a carbon nanotube component 1.
(5) Preparation of Nano MnO 2 Supercapacitor electrode material of modified carbon cloth 1: adding nano MnO 2 The loaded carbon nanotube component 1, the conductive carbon black and the adhesive polyvinylidene fluoride are uniformly dispersed in an N methyl pyrrolidone solution to form slurry according to the mass ratio of 8 2 -a supercapacitor electrode material of modified carbon cloth 1.
Example 2
(1) Preparing an N, P co-doped carbon cloth component 2: adding a distilled water solvent, carbon fiber cloth, phytic acid and pyrrole into a reaction bottle, uniformly stirring, adding an initiator potassium persulfate, wherein the mass ratio of the four is 40.5.
(2) Preparing a polystyrene nano microsphere component 2: introducing nitrogen into a reaction bottle to discharge air, adding a mixed solvent of ethanol and distilled water, adding dispersing agents of sodium dodecyl benzene sulfonate and styrene according to the volume ratio of 1 to 2.5, wherein the mass ratio of the dispersing agents of sodium dodecyl benzene sulfonate to styrene is 1.
(3) Preparing a carbon nano tube hollow microsphere component 2: adding distilled water, a polystyrene nano microsphere component 2 and a carbon nano tube into a reaction bottle according to the mass ratio of 1.
(4) Preparing to obtain nano MnO 2 Loading carbon nanotube component 2: distilled water solvent and 58 parts of carbon nano tube hollow microsphere component 2, 16 parts of KMnO are added into a reaction bottle 4 26 parts of MnSO 4 Placing the reaction flask in an ultrasonic treatment instrument, heating to 70 deg.C, performing ultrasonic dispersion treatment for 40min at ultrasonic frequency of 20KHz, transferring the solution into a high-pressure hydrothermal reaction kettle, placing in a heating tank of the reaction kettle, heating to 160 deg.C, reacting for 12h, vacuum drying the solution to remove solventWashing the solid product with distilled water and ethanol, and drying to obtain nanometer MnO 2 Supporting carbon nanotube component 2.
(5) Preparation of Nano MnO 2 Supercapacitor electrode material of modified carbon cloth 2: adding nano MnO 2 The loaded carbon nanotube component 2, the conductive carbon black and the adhesive polyvinylidene fluoride are uniformly dispersed in an N-methyl pyrrolidone solution to form slurry according to the mass ratio of 8 2 Supercapacitor electrode materials 2 of modified carbon cloth.
Example 3
(1) Preparing a N, P co-doped carbon cloth component 3: adding a distilled water solvent, carbon fiber cloth, phytic acid and pyrrole into a reaction bottle, uniformly stirring, adding an initiator potassium persulfate, wherein the mass ratio of the four is 32.5.
(2) Preparing a polystyrene nano microsphere component 3: introducing nitrogen into a reaction bottle to discharge air, adding a mixed solvent of ethanol and distilled water, adding dispersing agents of sodium dodecyl benzene sulfonate and styrene according to a volume ratio of 1.
(3) Preparing a carbon nano tube hollow microsphere component 3: adding distilled water, a polystyrene nano microsphere component 3 and a carbon nano tube into a reaction bottle according to the mass ratio of 1.
(4) Preparing to obtain nano MnO 2 Supporting a carbon nanotube component 3: distilled water solvent and 54 parts of carbon nano tube hollow microsphere component 3, 17 parts of KMnO are added into a reaction bottle 4 29 parts of MnSO 4 Placing a reaction bottle in an ultrasonic treatment instrument, heating to 60 ℃, performing ultrasonic dispersion treatment for 50min at the ultrasonic frequency of 25KHz, transferring the solution into a high-pressure hydrothermal reaction kettle, placing the reaction kettle in a reaction kettle heating box, heating to 180 ℃, reacting for 16h, performing vacuum drying on the solution to remove a solvent, washing a solid product by using distilled water and ethanol, and fully drying to prepare the nano MnO 2 Supporting carbon nanotube component 3.
(5) Preparation of Nano MnO 2 Supercapacitor electrode material of modified carbon cloth 3: mnO of nanometer 2 The loaded carbon nanotube component 3, the conductive carbon black and the adhesive polyvinylidene fluoride are uniformly dispersed in an N-methyl pyrrolidone solution to form slurry according to the mass ratio of 8 2 -a supercapacitor electrode material of modified carbon cloth 3.
Example 4
(1) Preparing a N, P co-doped carbon cloth component 4: adding a distilled water solvent, carbon fiber cloth, phytic acid and pyrrole into a reaction bottle, uniformly stirring, adding an initiator potassium persulfate, wherein the mass ratio of the four is 40.5.
(2) Preparing a polystyrene nano microsphere component 4: introducing nitrogen into a reaction bottle to discharge air, adding a mixed solvent of ethanol and distilled water, adding dispersing agents of sodium dodecyl benzene sulfonate and styrene, wherein the volume ratio of the sodium dodecyl benzene sulfonate to the styrene is 1:2.5, placing the reaction bottle into an ultrasonic treatment instrument, heating to 40 ℃, performing ultrasonic dispersion treatment for 2 hours, wherein the ultrasonic frequency is 25KHz, adding an initiator of ammonium persulfate, placing the reaction bottle into a constant-temperature water bath kettle, heating to 60 ℃, uniformly stirring for reaction for 18 hours, performing vacuum drying on the solution to remove the solvent, washing the solid product by using distilled water and ethanol, and sufficiently drying to prepare the polystyrene nano microsphere component 4.
(3) Preparing a carbon nano tube hollow microsphere component 4: adding distilled water, a polystyrene nano microsphere component 4 and a carbon nano tube into a reaction bottle, wherein the mass ratio is 1.
(4) Preparing to obtain nano MnO 2 Loading carbon nanotube component 4: distilled water solvent and 50 parts of carbon nano tube hollow microsphere component 4, 18 parts of KMnO are added into a reaction bottle 4 32 parts of MnSO 4 Placing a reaction bottle in an ultrasonic treatment instrument, heating to 40 ℃, performing ultrasonic dispersion treatment for 60min at the ultrasonic frequency of 20KHz, transferring the solution into a high-pressure hydrothermal reaction kettle, placing the reaction kettle in a reaction kettle heating box, heating to 160 ℃, reacting for 20h, performing vacuum drying on the solution to remove a solvent, washing a solid product by using distilled water and ethanol, and fully drying to prepare the nano MnO 2 Supporting the carbon nanotube component 4.
(5) Preparation of Nano MnO 2 Supercapacitor electrode material of modified carbon cloth 4: adding nano MnO 2 The loaded carbon nanotube component 4, the conductive carbon black and the adhesive polyvinylidene fluoride are uniformly dispersed in an N-methyl pyrrolidone solution to form slurry according to the mass ratio of 8 2 Supercapacitor electrode materials 4 of modified carbon cloth.
Example 5
(1) Preparing a component 5 of the N and P co-doped carbon cloth: adding a distilled water solvent, carbon fiber cloth, phytic acid and pyrrole into a reaction bottle, uniformly stirring, adding an initiator potassium persulfate, wherein the mass ratio of the four is 40.5.
(2) Preparing a polystyrene nano microsphere component 5: introducing nitrogen into a reaction bottle to discharge air, adding a mixed solvent of ethanol and distilled water, adding dispersing agents of sodium dodecyl benzene sulfonate and styrene, wherein the volume ratio of the sodium dodecyl benzene sulfonate to the styrene is 1:3, placing the reaction bottle into an ultrasonic treatment instrument, heating to 60 ℃, performing ultrasonic dispersion treatment for 2 hours, wherein the ultrasonic frequency is 35KHz, adding an initiator of ammonium persulfate, placing the reaction bottle into a constant-temperature water bath kettle, heating to 80 ℃, stirring at a constant speed for reaction for 18 hours, performing vacuum drying on the solution to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to prepare the polystyrene nano microsphere component 5.
(3) Preparing a carbon nano tube hollow microsphere component 5: adding distilled water, a polystyrene nano microsphere component 5 and a carbon nano tube into a reaction bottle according to the mass ratio of 1.
(4) Preparing to obtain nano MnO 2 Component 5 of the supported carbon nanotube: distilled water solvent, 44 parts of carbon nano tube hollow microsphere component 5 and 20 parts of KMnO are added into a reaction bottle 4 36 parts of MnSO 4 Placing a reaction bottle in an ultrasonic treatment instrument, heating to 70 ℃, performing ultrasonic dispersion treatment for 60min at the ultrasonic frequency of 30KHz, transferring the solution into a high-pressure hydrothermal reaction kettle, placing the reaction kettle in a reaction kettle heating box, heating to 200 ℃, reacting for 20h, performing vacuum drying on the solution to remove a solvent, washing a solid product by using distilled water and ethanol, and fully drying to prepare the nano MnO 2 Supporting the carbon nanotube component 5.
(5) Preparation of Nano MnO 2 Supercapacitor electrode material of modified carbon cloth 5: adding nano MnO 2 The loaded carbon nanotube component 5, the conductive carbon black and the adhesive polyvinylidene fluoride are uniformly dispersed in an N-methyl pyrrolidone solution to form slurry according to the mass ratio of 8 2 -a supercapacitor electrode material of modified carbon cloth 5.
With the nano MnO in examples 1-5 2 -modified carbon cloth as working electrode, pt sheet as counter electrode, hg/Hg 2 Cl 2 And as a reference electrode, taking a 0.5mol/L sulfuric acid solution as an electrolyte, and carrying out electrochemical performance test on a CHI760D electrochemical workstation, wherein the test standard is GB/T34870.1-2017.
In summary, the supercapacitor electrode material of the nano MnO 2-modified carbon cloth forms pi-pi bonds with the carbon nano-tubes by taking the polystyrene nano-microspheres as the template, the carbon nano-tubes are adsorbed on the surfaces of the polystyrene nano-microspheres, the polystyrene nano-microspheres are removed by tetrahydrofuran etching, the obtained carbon nano-tube hollow microspheres have huge specific surface areas, and the nano MnO is prepared by taking the carbon nano-tube hollow microspheres as the template through a hydrothermal in-situ synthesis method 2 Coated carbon nanotube hollow microspheresSphere, effective suppression of nano MnO 2 Agglomeration phenomenon, and nano-sized MnO 2 The specific surface area is high, more redox reaction active sites can be exposed, and the carbon nano tube has high conductivity, so that the conductivity of the electrode material is greatly enhanced, the migration and diffusion of electrons in the oxidation reaction are promoted, and the pseudocapacitance and the electrochemical performance of the electrode material are improved.
The preparation method comprises the steps of taking carbon fiber cloth as a substrate, phytic acid as a phosphorus source and pyrrole as a nitrogen source, forming phosphorylated polypyrrole loaded carbon fiber cloth through a polymerization reaction, and then performing high-temperature pyrolysis to prepare N and P co-doped modified carbon cloth, wherein the electronegativity of nitrogen is greater than that of carbon, so that carbon atom electrons are transferred to nitrogen atoms, and the positive charges of the carbon atoms are increased, so that the multi-carbon fiber cloth shows more excellent electropositive conductivity, phosphorus is used as an electron donor, a phosphorus-oxygen functional group formed by doping and adding a carbon layer has good hydrophilicity, and phosphorus is doped into a carbon layer framework to generate a large number of frontal structure defects, so that a large number of mesoporous structures are formed on the surface of the carbon fiber cloth, the contact area of an electrode material and an electrolyte is increased, the hydrophilicity of the carbon fiber cloth is improved under the synergistic effect, and nano MnO is used 2 The loaded carbon nanotube is coated on the modified carbon cloth, and the obtained electrode material has good wettability with electrolyte, so that the electrode material has higher actual specific capacitance and electrochemical performance.
Claims (5)
1. Nano MnO 2 The supercapacitor electrode material of the modified carbon cloth comprises the following formula raw materials and components in parts by weight, and is characterized in that: n, P co-doped carbon cloth, 44-62 parts of carbon nano tube hollow microspheres and 15-20 parts of KMnO 4 23-36 parts of MnSO 4 (ii) a The preparation method of the N, P co-doped carbon cloth comprises the following steps:
(1) Adding carbon fiber cloth, phytic acid, pyrrole and an initiator potassium persulfate into a distilled water solvent, reacting the solution at 0-5 ℃ for 5-8h, removing the solvent from the solution, washing a solid product and drying, placing a carbon cloth mixture into an atmosphere resistance furnace, introducing argon, raising the temperature at the rate of 5-10 ℃ to 760-780, and calcining for 3-5h to obtain a calcined product, namely N, P co-doped carbon cloth; the preparation method of the carbon nano tube hollow microsphere comprises the following steps:
(1) Adding dispersing agent sodium dodecyl benzene sulfonate and styrene into a mixed solvent of ethanol and distilled water with the volume ratio of 1:2.5-3.5, heating the solution to 40-60 ℃ in a nitrogen atmosphere, carrying out ultrasonic dispersion treatment for 1-2h, wherein the ultrasonic frequency is 25-35KHz, adding initiator ammonium persulfate, heating the solution to 60-80 ℃ in the nitrogen atmosphere, reacting for 12-18h, removing the solvent from the solution, washing a solid product, and drying to prepare the polystyrene nano-microsphere;
(2) Adding polystyrene nano microspheres and carbon nano tubes into a distilled aqueous solvent, carrying out ultrasonic dispersion treatment on the solution at 45-75 ℃ for 1-3h with the ultrasonic frequency of 25-40KHz, heating the solution to 90-110 ℃, stirring at constant speed until the distilled aqueous solvent is evaporated, placing a solid product into a tetrahydrofuran solvent, heating to 50-70 ℃, stirring at constant speed for 10-15h, removing the solvent from the solution, washing the solid product and drying to prepare the carbon nano tube hollow microspheres.
2. The nano MnO of claim 1 2 -a supercapacitor electrode material of modified carbon cloth, characterized in that: the mass ratio of the carbon fiber cloth to the phytic acid to the pyrrole to the potassium persulfate is (25-40).
3. The nano MnO of claim 1 2 -a supercapacitor electrode material of modified carbon cloth, characterized in that: the mass ratio of the sodium dodecyl benzene sulfonate to the styrene to the ammonium persulfate is (1).
4. The nano MnO of claim 1 2 -a supercapacitor electrode material of modified carbon cloth, characterized in that: the mass ratio of the polystyrene microspheres to the carbon nanotubes is 1.
5. The nano MnO of claim 1 2 -modified carbon cloth supercapacitor electrode material, characterized in thatIn the following steps: the nano MnO 2 The preparation method of the supercapacitor electrode material of the modified carbon cloth comprises the following steps:
(1) Adding 44-62 parts of carbon nano tube hollow microspheres and 15-20 parts of KMnO into distilled water solvent 4 23-36 parts of MnSO 4 Performing ultrasonic dispersion treatment on the solution at 40-70 ℃ for 40-60min at the ultrasonic frequency of 20-30KHz, transferring the solution into a hydrothermal reaction kettle, heating to 160-200 ℃, reacting for 12-20h, removing the solvent from the solution, washing a solid product, and drying to obtain the nano MnO 2 Loading carbon nanotubes;
(2) MnO of nanometer 2 The preparation method comprises the following steps of loading the carbon nanotube, conductive carbon black and adhesive polyvinylidene fluoride, uniformly dispersing the carbon nanotube, the conductive carbon black and the adhesive polyvinylidene fluoride in an N-methyl pyrrolidone solution to form slurry according to the mass ratio of 8 2 -modified carbon cloth supercapacitor electrode materials.
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