CN112233909A - Zinc oxide-nano vanadium dioxide doped porous carbon composite electrode material and preparation method thereof - Google Patents
Zinc oxide-nano vanadium dioxide doped porous carbon composite electrode material and preparation method thereof Download PDFInfo
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- CN112233909A CN112233909A CN202011111051.3A CN202011111051A CN112233909A CN 112233909 A CN112233909 A CN 112233909A CN 202011111051 A CN202011111051 A CN 202011111051A CN 112233909 A CN112233909 A CN 112233909A
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- vanadium dioxide
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- nano vanadium
- composite electrode
- zinc oxide
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- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 title claims abstract description 66
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000007772 electrode material Substances 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 42
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 38
- 239000011701 zinc Substances 0.000 title claims abstract description 38
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 55
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 41
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000004246 zinc acetate Substances 0.000 claims abstract description 29
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 27
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000005187 foaming Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 239000004088 foaming agent Substances 0.000 claims abstract description 12
- 239000011261 inert gas Substances 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 238000005087 graphitization Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- -1 azo compound Chemical class 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 8
- 239000011787 zinc oxide Substances 0.000 abstract description 4
- 239000003990 capacitor Substances 0.000 description 11
- 238000004146 energy storage Methods 0.000 description 7
- 229910044991 metal oxide Inorganic materials 0.000 description 7
- 150000004706 metal oxides Chemical class 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium superoxide Chemical compound [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- ICGLPKIVTVWCFT-UHFFFAOYSA-N 4-methylbenzenesulfonohydrazide Chemical compound CC1=CC=C(S(=O)(=O)NN)C=C1 ICGLPKIVTVWCFT-UHFFFAOYSA-N 0.000 description 1
- 239000004156 Azodicarbonamide Substances 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910003266 NiCo Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 1
- 235000019399 azodicarbonamide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
- C08F220/48—Acrylonitrile with nitrogen-containing monomers
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
- C08J9/0071—Nanosized fillers, i.e. having at least one dimension below 100 nanometers
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
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- C08J9/104—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
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- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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Abstract
The invention belongs to the field of battery materials, and particularly relates to a porous carbon composite electrode material doped with zinc oxide and nano vanadium dioxide and a preparation method thereof. The invention aims to solve the technical problem of providing a preparation method of a porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide, which comprises the following steps: A. adding acrylonitrile, acrylamide, azodiisobutyronitrile, zinc acetate and nano vanadium dioxide into a solvent, uniformly mixing, adding an initiator, and reacting at 55-75 ℃ under inert gas to obtain functional polyacrylonitrile; B. uniformly mixing functional polyacrylonitrile, a polyacrylonitrile solution and a foaming agent, pouring the mixture into a mold for foaming at 160-190 ℃, cooling to room temperature after foaming is finished, and standing to obtain porous polyacrylonitrile; C. and carrying out graphitization reaction on the porous polyacrylonitrile to obtain the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide. The method can prepare the composite electrode material with excellent performance.
Description
Technical Field
The invention belongs to the field of battery materials, and particularly relates to a porous carbon composite electrode material doped with zinc oxide and nano vanadium dioxide and a preparation method thereof. The electrode material can be used for preparing super capacitor electrodes.
Background
The supercapacitor is an energy storage device with high efficiency, practicality and environmental protection, and has the advantages of high power density, convenient control, high conversion efficiency, wide working temperature range, no pollution and the like. Along with the improvement of the technology, the production cost is gradually reduced, and the energy storage battery is more and more applied to the field of energy storage, so that the energy storage battery can be replaced by the energy storage battery on many occasions in the future. But the super capacitor is expensive at present and cannot be used for large-scale power energy storage. Therefore, reducing the production cost is an essential step for the further development of super capacitors and the replacement of storage batteries in the future.
The super capacitor is composed of an electrode material, an electrolyte, a diaphragm, a collector and the like, each part has great influence on the super capacitor, and the electrode material plays a decisive role in the performance of the super capacitor. Common electrode materials of the super capacitor include carbon materials, metal oxide materials, conductive polymer materials and composite materials. Carbon materials are widely used as electrode materials for supercapacitors because of their low cost and various existing forms, but since they store energy only by means of an electric double layer, there is a limit in performance, and thus electrode development and research of metal oxide materials have been emerging. The metal oxide material is different from a carbon material electrode in an electric double layer capacitor for storing energy, and when the capacitor is charged and discharged, reversible oxidation-reduction reaction occurs at the interface of the metal oxide and a solution, so that higher specific capacity is obtained. The material electrode has larger specific capacity, but is expensive, and is not beneficial to the development of the super capacitor. The composite material is a composite material which is prepared by performing a nano-composite technology by using a carbon material as a matrix and a metal oxide as an active substance to improve the charge utilization rate in order to further increase the energy storage of the supercapacitor and enable the supercapacitor to have capacitance performance and electric double layer characteristics, and is a main direction for developing and researching the electrode material of the supercapacitor in the future.
The macroporous-mesoporous-microporous three-dimensional hierarchical porous carbon is prepared in the composite electrode by a template method and is used as an electrode material of the supercapacitor, so that the electrode material has smaller resistance and shorter diffusion path to promote ion transmission, the main dynamic limitation of the electrochemical process in the porous electrode is overcome, and the rapid diffusion of electrolyte ions at high rate is facilitated.
Pen\2253131of the institute of Material science and engineering of Tianjin university of Industrial science and the like, carbon black and nickel cobaltate nanowires are simultaneously loaded on the carbon nanofibers by a hydrothermal method by taking the carbon nanofibers as a substrate, and NiCo is prepared by further heat treatment2O4The carbon black @ nano carbon fiber self-supporting composite electrode has excellent cycling stability. However, the method is complicated in process due to the use of a hydrothermal method, and cannot be used for large-scale production.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide. The preparation method comprises the following steps:
A. adding acrylonitrile, acrylamide, azodiisobutyronitrile, zinc acetate and nano vanadium dioxide into a solvent, uniformly mixing, adding an initiator, and reacting at 55-75 ℃ under inert gas to obtain functional polyacrylonitrile;
B. uniformly mixing functional polyacrylonitrile, a polyacrylonitrile solution and a foaming agent, pouring the mixture into a mold for foaming at 160-190 ℃, cooling to room temperature after foaming is finished, and standing to obtain porous polyacrylonitrile;
C. and carrying out graphitization reaction on the porous polyacrylonitrile to obtain the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide.
In the step A of the preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide, the purity of the nano vanadium dioxide is more than 99%.
In the preparation method step A of the zinc oxide-nano vanadium dioxide doped porous carbon composite electrode material, the mass ratio of acrylonitrile to acrylamide to azobisisobutyronitrile is 85 to 14 to 1 to 98 to 1.
In the preparation method step A of the porous carbon composite electrode material doped with zinc oxide and nano vanadium dioxide, the mass ratio of the zinc acetate to the nano vanadium dioxide is 1: 1-3: 1.
In the step A of the preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide, the mass concentration of the total amount of acrylonitrile, acrylamide and azobisisobutyronitrile in the solution is 40-60%.
In the step A of the preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide, the total mass of zinc acetate and nano vanadium dioxide is 10-30% of the total mass of acrylonitrile, acrylamide and azobisisobutyronitrile.
In the step A of the preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide, the initiator is a persulfate. Potassium persulfate is preferred.
Further, in the step A of the preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide, the addition amount of the initiator is 0.3-1.5% of the total mass of acrylonitrile, acrylamide and azobisisobutyronitrile.
In the step A of the preparation method of the zinc oxide-nano vanadium dioxide porous carbon-doped composite electrode material, the solvent is any one of dimethyl sulfoxide, ethanol, acetone or petroleum ether.
In the step A of the preparation method of the zinc oxide-nano vanadium dioxide porous carbon-doped composite electrode material, the inert gas is nitrogen.
In the step A of the preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide, the reaction time is 20-30 hours.
In the step A of the preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide, uniformly mixing the materials for 10-20 minutes at a rotating speed of 300-500 rpm, and then performing ultrasonic treatment at a frequency of 5-20 KHZ for 5-15 minutes.
In the preparation method step B of the porous carbon composite electrode material doped with zinc oxide and nano vanadium dioxide, the mass ratio of the functional polyacrylonitrile to the polyacrylonitrile solution is 3: 7-5: 5.
Further, in the step B of the preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide, the mass concentration of the polyacrylonitrile solution is 70-90%.
In the step B of the preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide, the foaming agent is an azo compound or a sulfonyl hydrazine compound. Further, the azo compound is azodicarbonamide, azobisisobutyronitrile or difluorine diisoheptanonitrile. The sulfonyl hydrazide compound is p-toluenesulfonyl hydrazide or 4, 4-oxo-bis-benzenesulfonyl hydrazide.
In the step B of the preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide, the addition amount of the foaming agent is 1-5% of the total mass of the functional polyacrylonitrile and the polyacrylonitrile solution.
In the step B of the preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide, the foaming time is 15-30 minutes.
In the step B of the preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide, the standing time is 24-36 hours.
In the step C of the preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide, the graphitization reaction comprises the following steps: pre-oxidizing at 170-280 ℃ for 100-140 minutes, introducing inert gas, reacting at 600 +/-5 ℃, 650 +/-5 ℃, 700 +/-5 ℃, 750 +/-5 ℃ and 800 +/-5 ℃ for 20-40 minutes respectively, and cooling to room temperature under the protection of the inert gas.
Further, in the step C of the preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide, the inert gas is high-purity N2。
The invention also provides the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide prepared by the preparation method.
The method takes polyacrylonitrile as a base material, carries out foaming on the polyacrylonitrile to prepare communicated large pores and small pores, prepares micropores by decomposing zinc acetate, and finally prepares the large pores and small pores and microporous three-dimensional hierarchical porous carbon composite electrode material. The metal oxide generated in the decomposition process of the pore-forming agent selected by the method can be partially left in the ring formation process of polyacrylonitrile, so that the reaction active points are increased, and the performance of the capacitor is improved; meanwhile, the added metal oxide can generate chemical bonds when cyclizing with polyacrylonitrile, and is not easy to fall off in long-term use. The method has simple process and low cost, and can be used for industrial large-scale production; and the obtained material has excellent performance.
Detailed Description
The preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide comprises the following steps:
A. preparing functional polyacrylonitrile doped with zinc acetate-nano vanadium dioxide:
adding acrylonitrile, acrylamide, azodiisobutyronitrile, zinc acetate and nano vanadium dioxide into a solvent, stirring for 10-20 minutes at a rotating speed of 300-500 rpm by using a stirrer, performing ultrasonic treatment at a frequency of 5-20 KHZ for 5-15 minutes by using ultrasonic waves, adding an initiator, stirring, and heating to 55-75 ℃ under the protection of nitrogen to react for 20-30 hours to obtain functional polypropylene; the content of the monomer (the monomer is a mixture of acrylonitrile, acrylamide and azodiisobutyronitrile) in the solution is 40% -60%, the mass ratio of acrylonitrile to acrylamide to azodiisobutyronitrile is 85: 14: 1-98: 1, the mass ratio of zinc acetate to nano vanadium dioxide is 1: 1-3: 1, the mass ratio of zinc acetate to nano vanadium dioxide is 10% -30% of the total mass of the monomer, and the initiator is 0.3% -1.5% of the total mass of the monomer;
B. foaming polyacrylonitrile:
mixing the functional polyacrylonitrile prepared in the step A with a commercially available polyacrylonitrile solution according to a mass ratio of 3: 7-5: 5, adding a foaming agent (a commercially available azo compound or sulfonyl hydrazide compound foaming agent), uniformly mixing, placing into a mold with a required electrode size and thickness, foaming at 160-190 ℃ for 15-30 minutes, cooling to room temperature, standing at normal temperature for 24-36 hours, and taking out to obtain porous polyacrylonitrile; wherein the addition amount of the foaming agent is 1-5% of the mixed polypropylene solution;
C. preparing a porous carbon composite electrode material:
placing the porous polyacrylonitrile prepared in the step B in a carbonization furnace, pre-oxidizing for 100-140 minutes at the temperature of 170-280 ℃, and then introducing high-purity N2Respectively reacting at 600 +/-5 ℃, 650 +/-5 ℃, 700 +/-5 ℃, 750 +/-5 ℃ and 800 +/-5 ℃ for 20-40 minutes, and then cooling to room temperature under the protection of high-purity nitrogen.
In the step A of the method, if the zinc acetate and the nano vanadium dioxide are directly mixed by adopting the finished polyacrylonitrile, the zinc acetate and the nano vanadium dioxide are inorganic substances, have different polarities from the polyacrylonitrile and cannot be well mixed, and meanwhile, the zinc acetate and the nano vanadium dioxide have small particle size, are easy to agglomerate and are easy to be mixed unevenly, so that the performance of the final material is influenced. In the step A, acrylonitrile, acrylamide and azodiisobutyronitrile are used as raw materials, the acrylonitrile, the acrylamide, the azodiisobutyronitrile, zinc acetate and nano vanadium dioxide are uniformly mixed under ultrasonic waves, then an initiator is added, and the produced polyacrylonitrile wraps the zinc acetate and the nano vanadium dioxide, so that the zinc acetate and the nano vanadium dioxide are uniformly doped in the prepared polyacrylonitrile.
In the step A of the method, because zinc acetate is decomposed to form micropores, if the addition amount of the zinc acetate is too low, the generated micropores are less, and the effect cannot be achieved; if the addition amount of the zinc acetate is too high, too many micropores are generated, and the network structure formed by the polyacrylonitrile can be damaged. Therefore, the mass ratio of the zinc acetate to the nano vanadium dioxide is controlled to be 1: 1-3: 1, the mass ratio of the acrylonitrile to the acrylamide to the azobisisobutyronitrile is controlled to be 85: 14: 1-98: 1, and the total mass of the zinc acetate and the nano vanadium dioxide is 10-30% of the total mass of the acrylonitrile, the acrylamide and the azobisisobutyronitrile.
In step B of the method of the present invention, all the polyacrylonitrile raw materials adopted in the present invention can be prepared by using acrylonitrile, acrylamide, azobisisobutyronitrile as raw materials, but such operation is not economical and increases the operation cost, so that a part of polyacrylonitrile of the present invention is prepared by using acrylonitrile, acrylamide, azobisisobutyronitrile as raw materials, the main purpose is to uniformly dope zinc acetate and nano vanadium dioxide, and another part can be directly prepared by using a commercially available polyacrylonitrile solution. The mass concentration of the polyacrylonitrile solution is 70-90%. The solvent is dimethylformamide or dimethyl sulfoxide.
In the step B of the method, the foaming is not uniform, large holes and small holes can be formed, the large holes and the small holes are influenced by the foaming, and the micropores are influenced by the decomposition of zinc acetate which is a pore-forming agent at the foaming temperature. Therefore, the large and small holes can be controlled by controlling foaming conditions such as the addition amount of the foaming agent, the foaming temperature, the foaming time and the like, for example, the large amount of the foaming agent, the high temperature and the large holes generated in a long time are relatively large; the micropores can be controlled by the amount of zinc acetate added. The corresponding parameters can be controlled by those skilled in the art according to the requirements.
In the step C of the method, the porous polyacrylonitrile obtained in the step B cannot conduct electricity, and the material is used as an electrode material, so that the porous polyacrylonitrile obtained in the step B needs to be subjected to graphitization reaction so as to conduct electricity. The graphitization reaction may be carried out by a conventional method. Preferably, the graphitization reaction of the present invention comprises the steps of: pre-oxidizing at 170-280 ℃ for 100-140 minutes, introducing inert gas, reacting at 600 +/-5 ℃, 650 +/-5 ℃, 700 +/-5 ℃, 750 +/-5 ℃ and 800 +/-5 ℃ for 20-40 minutes, and cooling to room temperature under the protection of the inert gas.
The invention also provides the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide prepared by the method.
Example 1
Uniformly mixing the raw materials in a solvent dimethyl sulfoxide according to the following ratio of 20% of the total mass of acrylonitrile, acrylamide and azodiisobutyronitrile, 55% of the total mass of the acrylonitrile, the acrylamide and the azodiisobutyronitrile, 3: 1 of the zinc acetate and the nano vanadium dioxide, 0.3% of potassium peroxide, and reacting at 65 ℃ for 30 hours to obtain the functional polyacrylonitrile;
uniformly mixing the prepared functional polyacrylonitrile and 75% polyacrylonitrile solution according to the mass ratio of 3: 7 and the foaming amount of 2%, foaming at 160 ℃ for 25 minutes, cooling to room temperature, standing at normal temperature for 24 hours, placing in a carbonization furnace, pre-oxidizing at 170 ℃ for 140 minutes, and introducing high-purity N2Reacting at 600 deg.C, 650 deg.C, 700 deg.C, 750 deg.C and 800 deg.C for 40 min, cooling to room temperature to obtain electrode with specific capacitance of 0.189F-cm-2At a current density of 15mA cm-2Then, the specific capacitance after 2000 cycles was 89.12% of the initial value.
Example 2
Uniformly mixing the raw materials in a solvent dimethyl sulfoxide according to the following ratio of 15% of the total mass of acrylonitrile, acrylamide and azodiisobutyronitrile, 45% of the total mass of the acrylonitrile, the acrylamide and the azodiisobutyronitrile, 2: 1 of the zinc acetate and the nano vanadium dioxide, and 0.5% of potassium peroxide, and reacting at 65 ℃ for 25 hours to obtain the functional polyacrylonitrile;
uniformly mixing the prepared functional polyacrylonitrile and 80 mass percent polyacrylonitrile solution according to the mass ratio of 4: 6 and the foaming dose of 5 percent, foaming at 170 ℃ for 20 minutes, cooling to room temperature, standing at normal temperature for 30 hours, placing in a carbonization furnace, pre-oxidizing at 240 ℃ for 120 minutes, introducing high-purity N2Reacting at 600 deg.C, 650 deg.C, 700 deg.C, 750 deg.C and 800 deg.C for 30 min, cooling to room temperature to obtain electrode with specific capacitance of 0.191F cm-2At a current density of 10mA cm-2Then, the specific capacitance was 89.91% of the initial value after 2000 cycles of charge and discharge.
Example 3
Uniformly mixing the raw materials in a solvent dimethyl sulfoxide according to the following ratio of 25% of the total mass of acrylonitrile, acrylamide and azodiisobutyronitrile, 50% of the total mass of the acrylonitrile, the acrylamide and the azodiisobutyronitrile, 2: 1 of the zinc acetate and the nano vanadium dioxide, and reacting at 65 ℃ for 20 hours to obtain the functional polyacrylonitrile, wherein the mass ratio of the acrylonitrile to the acrylamide to the azodiisobutyronitrile is 95: 4: 1, and the mass ratio of the zinc acetate to the nano vanadium dioxide is 2: 1;
uniformly mixing the prepared functional polyacrylonitrile and a polyacrylonitrile solution with the mass concentration of 85% according to the mass ratio of 5: 5 and the foaming dose of 4%, foaming at 190 ℃ for 15 minutes, cooling to room temperature, standing at normal temperature for 36 hours, placing in a carbonization furnace, pre-oxidizing at 280 ℃ for 100 minutes, introducing high-purity N2Reacting at 600 deg.C, 650 deg.C, 700 deg.C, 750 deg.C and 800 deg.C for 20 min, cooling to room temperature to obtain electrode with specific capacitance of 0.194F cm-2At a current density of 5mA cm-2Then, the specific capacitance was 90.04% of the initial value after 2000 cycles of charge and discharge.
Claims (10)
1. The preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide is characterized by comprising the following steps of: the method comprises the following steps:
A. adding acrylonitrile, acrylamide, azodiisobutyronitrile, zinc acetate and nano vanadium dioxide into a solvent, uniformly mixing, adding an initiator, and reacting at 55-75 ℃ under inert gas to obtain functional polyacrylonitrile;
B. uniformly mixing functional polyacrylonitrile, a polyacrylonitrile solution and a foaming agent, pouring the mixture into a mold for foaming at 160-190 ℃, cooling to room temperature after foaming is finished, and standing to obtain porous polyacrylonitrile;
C. and carrying out graphitization reaction on the porous polyacrylonitrile to obtain the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide.
2. The preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide according to claim 1, characterized in that: in the step A, the mass ratio of the acrylonitrile to the acrylamide to the azobisisobutyronitrile is 85: 14: 1-98: 1; furthermore, the mass concentration of the total amount of acrylonitrile, acrylamide and azobisisobutyronitrile in the solution is 40-60%.
3. The preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide according to claim 1 or 2, characterized in that: in the step A, the mass ratio of the zinc acetate to the nano vanadium dioxide is 1: 1-3: 1; furthermore, the total mass of the zinc acetate and the nano vanadium dioxide is 10-30% of the total mass of the acrylonitrile, the acrylamide and the azobisisobutyronitrile.
4. The preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide according to any one of claims 1 to 3, characterized by comprising the following steps: in the step A, the initiator is a persulfate; further, the initiator is potassium persulfate; furthermore, the addition amount of the initiator is 0.3-1.5% of the total mass of acrylonitrile, acrylamide and azobisisobutyronitrile.
5. The preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide according to any one of claims 1 to 4, characterized by comprising the following steps: in the step A, the solvent is any one of dimethyl sulfoxide, ethanol, acetone or petroleum ether.
6. The preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide according to any one of claims 1 to 5, characterized by comprising the following steps: in the step B, the mass ratio of the functional polyacrylonitrile to the polyacrylonitrile solution is 3: 7-5: 5; further, the mass concentration of the polyacrylonitrile solution is 70-90%.
7. The preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide according to any one of claims 1 to 6, characterized by comprising the following steps: in the step B, the foaming agent is an azo compound or a sulfonyl hydrazine compound; furthermore, the addition amount of the foaming agent is 1-5% of the total mass of the functional polyacrylonitrile and the polyacrylonitrile solution.
8. The preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide according to any one of claims 1 to 7, characterized by comprising the following steps: in the step A, the reaction time is 20-30 hours; in the step B, the foaming time is 15-30 minutes; the standing time is 24-36 hours.
9. The preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide according to any one of claims 1 to 8, characterized by comprising the following steps: in step C, the graphitization reaction includes the following steps: pre-oxidizing at 170-280 ℃ for 100-140 minutes, introducing inert gas, reacting at 600 +/-5 ℃, 650 +/-5 ℃, 700 +/-5 ℃, 750 +/-5 ℃ and 800 +/-5 ℃ for 20-40 minutes respectively, and cooling to room temperature under the protection of the inert gas.
10. The porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide prepared by the preparation method of any one of claims 1 to 9.
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| CN104167303A (en) * | 2014-07-29 | 2014-11-26 | 上海应用技术学院 | Mesopore vanadium oxide/carbon composite nano material and preparation method thereof |
| CN105810955A (en) * | 2016-05-05 | 2016-07-27 | 攀钢集团研究院有限公司 | Preparation method for electrode of vanadium cell |
| CN110473715A (en) * | 2018-05-10 | 2019-11-19 | 北京化工大学 | A kind of VO2(B) nanobelt/graphene complex thin-film material and its synthetic method and all-solid-state supercapacitor |
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