CN112435862A - Preparation method of novel asymmetric fibrous flexible supercapacitor - Google Patents
Preparation method of novel asymmetric fibrous flexible supercapacitor Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 17
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 17
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 17
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 14
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 13
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 11
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 9
- 238000011065 in-situ storage Methods 0.000 claims abstract description 5
- 238000005530 etching Methods 0.000 claims abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- 239000000047 product Substances 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 15
- 238000002791 soaking Methods 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 7
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000012159 carrier gas Substances 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical group [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 239000002071 nanotube Substances 0.000 claims 1
- 239000007784 solid electrolyte Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 2
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 abstract description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract 1
- 238000005470 impregnation Methods 0.000 abstract 1
- 229910052748 manganese Inorganic materials 0.000 abstract 1
- 239000011572 manganese Substances 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 239000003990 capacitor Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 9
- 230000007547 defect Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- 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
-
- 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
- H01G11/66—Current collectors
- H01G11/68—Current collectors characterised by their material
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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
- H01G11/66—Current collectors
- H01G11/70—Current collectors characterised by their structure
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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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- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
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Abstract
A preparation method of a novel asymmetric fibrous flexible supercapacitor is characterized in that the method utilizes a carbon nanotube layer grown in situ as an external electrode, and utilizes a one-step method to remove hard template silicon dioxide and fill electrolyte solution, and mainly comprises the following steps: firstly, taking potassium permanganate as a manganese source, and depositing and growing manganese dioxide on a conductive wire by using a hydrothermal method; secondly, coating silicon dioxide outside manganese dioxide by using a hydrothermal method, attaching a metal catalyst to the surface of the manganese dioxide by using an impregnation method, preparing a carbon nanotube layer by using a chemical vapor deposition method, transferring the carbon nanotube layer and a polyvinyl alcohol/potassium hydroxide electrolyte solution into a reaction kettle together, and preserving heat for a certain time at a certain temperature to obtain the novel asymmetric fibrous flexible supercapacitor. The invention has the advantage that the carbon nano tube layer with in-situ growth has good mutual contact with the outer electrode. When the electrolyte solution is filled, the silicon dioxide layer is removed by etching, so that the process flow is simplified.
Description
Technical Field
The invention belongs to the technical field of new energy storage, and relates to a preparation method of a novel asymmetric fibrous flexible supercapacitor.
Technical Field
With the increasing demand of people for fossil energy, environmental pollution is also becoming more serious and affects the normal life and production of human beings, and at the moment, the development and research of novel energy utilization and storage modes are promoted by people. The super capacitor is a novel high-efficiency energy storage device between a traditional capacitor and a rechargeable battery, and has the characteristics of quick charge and discharge of the capacitor and the energy storage characteristic of the battery. With the development of miniaturization of electronic devices, flexible supercapacitors have received more and more extensive attention, wherein fibrous flexible supercapacitors are considered to be an electrochemical energy storage device with great potential by virtue of their small size, excellent mechanical stability and high electrochemical performance. According to the difference of the relative positions of two electrodes of the capacitor, the fibrous flexible super capacitor can be generally divided into a fibrous super capacitor with a parallel structure, a fibrous super capacitor with a winding structure, a fibrous super capacitor with a coaxial structure and the like. The coaxial structure can also ensure that the two electrodes can not be peeled off when the supercapacitor is bent or kinked, thereby prolonging the service life of the device. On the other hand, due to the coaxial structure characteristics of the inner electrode and the outer electrode of the capacitor, the device is difficult to manufacture and complex in process. The current common methods are dipping-pulling method and two-dimensional sheet-shaped outer electrode coating method. In the dip-draw method, a substrate is first immersed in a solution containing an active material or a colloidal electrolyte solution, held for a certain period of time, and then taken out and dried to attach the electrode active material or the electrolyte solution to the surface of the one-dimensional substrate. This method has disadvantages in that the uniformity of the distance between the two electrodes and the good contact of the electrode active material with the electrolyte solution cannot be ensured, resulting in the degradation of the device performance. In the two-dimensional sheet-shaped outer electrode coating method, the outer electrode soaked by the electrolyte solution is coated on the inner electrode by the action of external force, and the method has the defects of high interface resistance and complex process in the device. In order to solve the problems, the patent provides a method for realizing the removal of a hard template silicon dioxide layer and the filling of an electrolyte solution by in-situ growth of active substances of inner and outer electrodes and a one-step method.
The conductive wire is used as a current collector of an inner electrode of a fibrous flexible super capacitor, and the excellent conductivity and mechanical property of the conductive wire are beneficial to the application of the conductive wire in the super capacitor. The good conductivity of the conductive wire effectively solves the defect of poor conductivity of pseudocapacitance materials such as manganese dioxide; the excellent mechanical property of the conductive wire can ensure that the super capacitor has longer service life.
The invention relates to a preparation method of a novel asymmetric fibrous flexible supercapacitor, which comprises the steps of firstly depositing and growing a manganese dioxide pseudocapacitance material on the surface of a conductive wire by using a hydrothermal method, then coating a hard template silicon dioxide layer, uniformly dispersing a cobalt-based catalyst on the surface of the hard template silicon dioxide layer, preparing a carbon nanotube layer by using a chemical vapor deposition method, then etching and removing the hard template silicon dioxide layer by using polyvinyl alcohol/potassium hydroxide under the hydrothermal condition, and simultaneously completing electrolyte solution filling, thus obtaining the novel asymmetric fibrous flexible supercapacitor. The method overcomes the defects of the existing production process, and has the advantages of simple process, wide application range, important research value and application prospect.
Disclosure of Invention
The invention relates to a preparation method of a novel asymmetric fibrous flexible supercapacitor, wherein in the preparation process, an outer electrode of the supercapacitor is prepared by adopting a carbon nanotube layer in-situ growth mode, then a hard template silicon dioxide layer is removed by utilizing polyvinyl alcohol/potassium hydroxide etching, and the filling of an electrolyte solution is completed, so that the novel asymmetric fibrous flexible supercapacitor is obtained, and the preparation process mainly comprises the following steps:
(1) sequentially soaking and cleaning the conductive wire by using acetone and dilute hydrochloric acid solution, and then washing the conductive wire to be neutral by using deionized water; transferring the treated conductive wire and a potassium permanganate solution with a certain concentration into a reaction kettle, and placing the reaction kettle into a drying oven with the reaction temperature raised for heat preservation for a certain time;
(2) placing the product in a mixed solution of ammonia water, tetraethyl orthosilicate, ethanol and deionized water, keeping the reaction at a reaction temperature for a certain reaction time, taking out and washing the product to be neutral, then soaking the product in a cobalt-based soluble salt solution with a certain concentration for a certain time, taking out and drying the product;
(3) placing the product in a tubular furnace, introducing acetylene into the tubular furnace to atmospheric pressure under a certain reaction temperature condition by taking argon-hydrogen mixed gas as carrier gas and acetylene as carbon source gas, keeping the reaction temperature for a certain time, naturally cooling the reaction product after the reaction is finished, and taking out the product;
(4) and transferring the product and a polyvinyl alcohol/potassium hydroxide solution with a certain concentration into a reaction kettle, preserving the heat at a certain temperature for a certain time, taking out, and drying at room temperature to obtain the novel asymmetric fibrous flexible supercapacitor.
2. The method for preparing the novel asymmetric fibrous flexible supercapacitor according to claim 1, wherein the conductive wires in the step (1) can be carbon fibers, copper wires, nickel wires, stainless steel wires; the concentration of the potassium permanganate solution is 0.003-0.006 mol/L, the reaction temperature is 80-150 ℃, and the reaction time is 8-24 h.
3. The method for preparing the novel asymmetric fibrous flexible supercapacitor according to claim 1, wherein the reaction temperature in the step (2) is 50 ℃ to 80 ℃. The reaction time is 8-12 h, the cobalt-based soluble salt is cobalt chloride, cobalt sulfate or cobalt nitrate, and the soaking time is 15-20 min.
4. The preparation method of the fibrous coaxial asymmetric flexible supercapacitor according to claim 1, wherein the reaction temperature of the tubular furnace in the step (3) is 700-900 ℃ and the reaction time is 5-10 min.
5. The preparation method of the fibrous coaxial asymmetric flexible supercapacitor according to claim 1, wherein the reaction temperature in the step (4) is 70-90 ℃ and the reaction time is 4-12 h.
Drawings
Fig. 1 is a schematic structural diagram of a novel asymmetric fibrous coaxial asymmetric flexible supercapacitor:
1-polyvinyl alcohol; a 2-carbon nanotube layer; 3-polyvinyl alcohol-potassium hydroxide; 4-manganese dioxide; 5-conductive filaments.
Fig. 2 is a scanning electron micrograph of a copper wire @ manganese dioxide inner electrode.
FIG. 3 is a scanning electron micrograph of the copper wire @ manganese dioxide @ silicon dioxide @ carbon nanotube layer structure.
FIG. 4 is a CV curve of the novel asymmetric fibrous coaxial asymmetric flexible supercapacitor under different sweep speeds.
Fig. 5 is a constant current charge and discharge curve of the novel asymmetric fibrous coaxial asymmetric flexible supercapacitor.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The technical solution of the invention is described in more detail with the following specific examples, but the examples are not to be construed as limiting the invention.
Detailed description of the preferred embodiment 1
(1) And (3) respectively soaking the copper wire in acetone and dilute hydrochloric acid solution for 10min and 30s, washing the copper wire to be neutral by using deionized water after each soaking, and drying the copper wire.
(2) Weighing 0.0316g potassium permanganate and dissolving in 50mL deionized water, stirring at room temperature for 10min, transferring the potassium permanganate and the copper wire to a reaction kettle, keeping the temperature at 150 ℃ for 8h, cooling, and washing and drying the product with deionized water.
(3) Measuring 10mL of ammonia water, adding the ammonia water into 30mL of deionized water, adding 20mL of ethanol after stirring for 20min, continuing stirring for 20min, then adding 9mL of tetraethyl orthosilicate, carrying out ultrasonic oscillation on the mixed solution for 10s, transferring the mixed solution and the product obtained in the step (2) into a reaction kettle, carrying out heat preservation at 60 ℃ for 12h, washing the product to be neutral, soaking the product in a saturated cobalt nitrate solution for 20min, and then drying the product at 60 ℃.
(4) And placing the product in the middle of a tubular furnace, heating to 700 ℃ in argon-hydrogen mixed atmosphere, preserving heat for 10min, introducing acetylene gas to atmospheric pressure, keeping the atmospheric pressure for 5min, vacuumizing the reaction tube, and naturally cooling to room temperature to obtain the carbon nanotube layer.
(5) 4g of polyvinyl alcohol and 5.941g of potassium hydroxide are respectively weighed, added into 45mL of deionized water and stirred at the temperature of 85 ℃ until the solution is clear, and the solution is the polyvinyl alcohol/potassium hydroxide electrolyte solution.
(6) And (3) transferring the product obtained in the step (4) and a polyvinyl alcohol/potassium hydroxide electrolyte solution into a reaction kettle together, keeping the temperature for 4 hours at 85 ℃, and naturally airing the product to finally obtain the novel asymmetric fibrous flexible supercapacitor.
Specific example 2
(1) And (3) respectively soaking the copper wire in acetone and dilute hydrochloric acid solution for 10min and 30s, washing the copper wire to be neutral by using deionized water after each soaking, and drying the copper wire.
(2) Weighing 0.0316g potassium permanganate and dissolving in 50mL deionized water, stirring at room temperature for 10min, transferring the potassium permanganate and the copper wire to a reaction kettle, keeping the temperature at 150 ℃ for 8h, cooling, and washing and drying the product with deionized water.
(3) Measuring 10mL of ammonia water, adding the ammonia water into 30mL of deionized water, adding 20mL of ethanol after stirring for 20min, continuing stirring for 20min, then adding 9mL of tetraethyl orthosilicate, carrying out ultrasonic oscillation on the mixed solution for 10s, transferring the mixed solution and the product obtained in the step (2) into a reaction kettle, carrying out heat preservation at 60 ℃ for 12h, washing the product to be neutral, soaking the product in a saturated cobalt nitrate solution for 20min, and then drying the product at 60 ℃.
(4) And placing the product in the middle of a tubular furnace, heating to 650 ℃ in argon-hydrogen mixed atmosphere, preserving heat for 10min, introducing acetylene gas to atmospheric pressure, keeping the atmospheric pressure for 5min, vacuumizing the reaction tube, and naturally cooling to room temperature to obtain the carbon nanotube layer.
(5) 4g of polyvinyl alcohol and 5.941g of potassium hydroxide are respectively weighed, added into 45mL of deionized water and stirred at the temperature of 85 ℃ until the solution is clear, and the solution is the polyvinyl alcohol/potassium hydroxide electrolyte solution.
(6) And (3) transferring the product obtained in the step (4) and a polyvinyl alcohol/potassium hydroxide electrolyte solution into a reaction kettle together, keeping the reaction kettle at the temperature of 80 ℃ for 4 hours, and naturally airing the product to finally obtain the novel asymmetric fibrous flexible supercapacitor.
Specific example 3
(1) And (3) respectively soaking the copper wire in acetone and dilute hydrochloric acid solution for 10min and 30s, washing the copper wire to be neutral by using deionized water after each soaking, and drying the copper wire.
(2) Weighing 0.0316g potassium permanganate and dissolving in 50mL deionized water, stirring at room temperature for 10min, transferring the potassium permanganate and the copper wire to a reaction kettle, keeping the temperature at 150 ℃ for 8h, cooling, and washing and drying the product with deionized water.
(3) Measuring 10mL of ammonia water, adding the ammonia water into 30mL of deionized water, adding 20mL of ethanol after stirring for 20min, continuing stirring for 20min, then adding 9mL of tetraethyl orthosilicate, carrying out ultrasonic oscillation on the mixed solution for 10s, transferring the mixed solution and the product obtained in the step (2) into a reaction kettle, carrying out heat preservation at 60 ℃ for 12h, washing the product to be neutral, soaking the product in a saturated cobalt nitrate solution for 20min, and then drying the product at 60 ℃.
(4) And placing the product in the middle of a tubular furnace, heating to 650 ℃ in argon-hydrogen mixed atmosphere, preserving heat for 10min, introducing acetylene gas to atmospheric pressure, keeping the atmospheric pressure for 5min, vacuumizing the reaction tube, and naturally cooling to room temperature to obtain the carbon nanotube layer.
(5) 4g of polyvinyl alcohol and 5.941g of potassium hydroxide are respectively weighed, added into 45mL of deionized water and stirred at the temperature of 85 ℃ until the solution is clear, and the solution is the polyvinyl alcohol/potassium hydroxide electrolyte solution.
(6) And (3) transferring the product obtained in the step (4) and a polyvinyl alcohol/potassium hydroxide electrolyte solution into a reaction kettle together, keeping the reaction kettle at the temperature of 90 ℃ for 4 hours, and naturally airing the product to finally obtain the novel asymmetric fibrous flexible supercapacitor.
The foregoing has described the basic principles, principal features, and advantages of the present experiment. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (5)
1. A novel preparation method of an asymmetric fibrous flexible supercapacitor comprises a manganese dioxide nano tube inner electrode taking a conductive wire as a substrate, a carbon nano tube layer outer electrode and a polyvinyl alcohol/potassium hydroxide solid electrolyte solution between the two electrodes, and is characterized in that the preparation process of the supercapacitor adopts a method for growing the carbon nano tube layer in situ, so that the carbon nano tube layer is well contacted with each other, the utilization rate of the electrodes is effectively improved, and a hydrothermal method is utilized, so that the etching removal of a hard template silicon dioxide layer and the filling of the polyvinyl alcohol/potassium hydroxide electrolyte solution are completed simultaneously, the process is simplified, and the preparation method of the novel asymmetric fibrous flexible supercapacitor comprises the following steps:
(1) sequentially soaking and cleaning the conductive wire by using acetone and dilute hydrochloric acid solution, and then washing the conductive wire to be neutral by using deionized water; transferring the treated conductive wire and a potassium permanganate solution with a certain concentration into a reaction kettle, and placing the reaction kettle into a drying oven with the reaction temperature raised for heat preservation for a certain time;
(2) placing the product in a mixed solution of ammonia water, tetraethyl orthosilicate, ethanol and deionized water, keeping the reaction at a reaction temperature for a certain reaction time, taking out and washing the product to be neutral, then soaking the product in a cobalt-based soluble salt solution with a certain concentration for a certain time, taking out and drying the product;
(3) placing the product in a tubular furnace, introducing acetylene into the tubular furnace to atmospheric pressure under a certain reaction temperature condition by taking argon-hydrogen mixed gas as carrier gas and acetylene as carbon source gas, keeping the reaction temperature for a certain time, naturally cooling the reaction product after the reaction is finished, and taking out the product;
(4) and transferring the product and a polyvinyl alcohol/potassium hydroxide solution with a certain concentration into a reaction kettle, preserving the heat at a certain temperature for a certain time, taking out, and drying at room temperature to obtain the novel asymmetric fibrous flexible supercapacitor.
2. The method for preparing the novel asymmetric fibrous flexible supercapacitor according to claim 1, wherein the conductive wires in the step (1) can be carbon fibers, copper wires, nickel wires, stainless steel wires; the concentration of the potassium permanganate solution is 0.003-0.006 mol/L, the reaction temperature is 80-150 ℃, and the reaction time is 8-24 h.
3. The method for preparing the novel asymmetric fibrous flexible supercapacitor according to claim 1, wherein the reaction temperature in the step (2) is 50 ℃ to 80 ℃. The reaction time is 8-12 h, the cobalt-based soluble salt is cobalt chloride, cobalt sulfate or cobalt nitrate, and the soaking time is 15-20 min.
4. The preparation method of the fibrous coaxial asymmetric flexible supercapacitor according to claim 1, wherein the reaction temperature of the tubular furnace in the step (3) is 600-900 ℃, and the reaction time is 5-10 min.
5. The preparation method of the fibrous coaxial asymmetric flexible supercapacitor according to claim 1, wherein the reaction temperature in the step (4) is 70-90 ℃ and the reaction time is 4-12 h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202011280273.8A CN112435862B (en) | 2020-11-16 | 2020-11-16 | Preparation method of novel asymmetric fibrous flexible supercapacitor |
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| CN114597514A (en) * | 2022-03-15 | 2022-06-07 | 江南大学 | Fibrous humidity battery |
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