CN113178341B - Super capacitor based on MOFs material - Google Patents
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- CN113178341B CN113178341B CN202110479673.XA CN202110479673A CN113178341B CN 113178341 B CN113178341 B CN 113178341B CN 202110479673 A CN202110479673 A CN 202110479673A CN 113178341 B CN113178341 B CN 113178341B
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 60
- 239000000463 material Substances 0.000 title claims abstract description 26
- 239000003990 capacitor Substances 0.000 title claims abstract description 20
- 239000004793 Polystyrene Substances 0.000 claims abstract description 46
- 239000004005 microsphere Substances 0.000 claims abstract description 46
- 229920002223 polystyrene Polymers 0.000 claims abstract description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000005507 spraying Methods 0.000 claims abstract description 28
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 15
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 238000004140 cleaning Methods 0.000 claims abstract description 4
- 239000008367 deionised water Substances 0.000 claims abstract description 4
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 238000002791 soaking Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 51
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 11
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 10
- 238000004528 spin coating Methods 0.000 claims description 10
- 239000012466 permeate Substances 0.000 claims description 9
- 229920001220 nitrocellulos Polymers 0.000 claims description 8
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 6
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- UUZYBYIOAZTMGC-UHFFFAOYSA-M benzyl(trimethyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)CC1=CC=CC=C1 UUZYBYIOAZTMGC-UHFFFAOYSA-M 0.000 claims description 3
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000009501 film coating Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
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- 238000000034 method Methods 0.000 description 11
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- 239000011248 coating agent Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000013260 porous coordination network Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- VQBIYCQGHAHVPN-UHFFFAOYSA-N 1,7-dichloronaphthalene Chemical compound C1=CC=C(Cl)C2=CC(Cl)=CC=C21 VQBIYCQGHAHVPN-UHFFFAOYSA-N 0.000 description 1
- ADRYPAGQXFMVFP-UHFFFAOYSA-N 1,8-dichloronaphthalene Chemical compound C1=CC(Cl)=C2C(Cl)=CC=CC2=C1 ADRYPAGQXFMVFP-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- 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
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention relates to the technical field of super capacitors, in particular to a super capacitor based on MOFs materials, wherein an electrode is a self-supporting MOFs electrode; the preparation method of the self-supporting MOFs electrode comprises the following steps: compressing a polytetrafluoroethylene mask plate on the flexible PE film to obtain a film A; spraying 1-2 ml of the solution A to the film A by adopting a spraying method to obtain a film B; spraying 1-2 ml of the solution B to the film B by adopting a spraying method to obtain a film C; placing the film C in an air draft cabinet for heating; placing the film C in vacuum and keeping the temperature at 60 ℃ for 24h to obtain an interdigital electrode A; soaking the interdigital electrode A in deionized water and ethanol, cleaning for 2-3 times, and removing the ethanol; and (3) placing the interdigital electrode A in a dichloromethane solution, and dissolving the polystyrene microspheres and the PE film to obtain the self-supporting MOFs electrode. The invention can not increase the resistance of the electrode and can not obstruct the transmission of electrons, thereby improving the performance of the MOFs electrode and solving the technical problem of low performance of the existing super capacitor.
Description
Technical Field
The invention relates to the technical field of electrode preparation, in particular to a super capacitor based on MOFs materials.
Background
The super capacitor is a novel energy storage device, has the advantages of high specific power, long cycle life and high charging and discharging speed compared with a battery, and is increasingly widely applied. The metal organic framework compounds (MOFs) are crystalline porous materials with periodic network structures formed by connecting inorganic metal centers (metal ions or metal clusters) and bridged organic ligands through self-assembly, and the MOFs have the characteristics of both the rigidity of inorganic materials and the flexibility of organic materials. The material has the characteristics of large specific surface area, large pore volume and adjustable pores, and is an ideal material for preparing the super capacitor.
For example, chinese patent CN110767464A discloses a super capacitor containing MOFs material, which includes a battery cell, a gas storage sheet and a housing; the battery cell comprises a pole piece and an isolation film, wherein the pole piece comprises a current collector, a first MOFs coating arranged on the surface of the current collector, and a pole piece active coating arranged on the surface of the first MOFs coating; the gas storage sheet is arranged in the inner cavity of the shell and comprises a conductive carrier and a second MOFs coating arranged on the surface of the conductive carrier; the first MOFs coating is a PCNs coating, and the second MOFs coating is a ZIFs coating; the PCNs coating is formed by one or the combination of PCN-7, PCN-8, PCN-9, PCN-11, PCN-13 or PCN-14 through a physical vapor deposition method, an electroplating method, a transfer coating method, an in-situ surface growth method or a gravure printing method.
Because the MOFs material has a stable structure and poor compatibility when being directly compounded with a titanium electrode, the MOFs material is easy to fall off from the surface of the electrode in the using process, and can be mixed with an adhesive, so that the MOFs material is fixed on the surface of the electrode. However, both the MOFs material and the adhesive are not conductive, which easily increases the resistance of the electrode, so that the performance of the super capacitor is low.
Disclosure of Invention
The invention provides a super capacitor based on MOFs materials, which solves the technical problem of low performance of the conventional super capacitor.
Based on this, the invention aims to provide a super capacitor based on MOFs materials.
The basic scheme provided by the invention is as follows: a super capacitor based on MOFs material, wherein an electrode is a self-supporting MOFs electrode; the preparation method of the self-supporting MOFs electrode comprises the following steps:
s1, pressing a polytetrafluoroethylene mask plate on the flexible PE film, and spin-coating a polystyrene microsphere aqueous solution for 2-5 times; drying at the temperature of 60 ℃ for 0.5-2 h to obtain a polystyrene microsphere film with an interdigital structure, and marking as a film A; the thickness of the film A is determined according to the spin coating times and the concentration of the polystyrene microsphere aqueous solution;
s2, dissolving 0.001-0.01 mol of cobalt nitrate hexahydrate in a mixed solution of 40ml of methanol and 40ml of ethanol, and reacting for more than 30min to obtain a solution A; spraying 1-2 ml of solution A to the film A by adopting a spraying method, so that the solution A is uniformly covered and permeated into pores of the polystyrene microsphere, and obtaining the polystyrene microsphere/cobalt nitrate film with an interdigital structure after being uniformly covered by the solution A by permeation, and marking as a film B;
s3, dissolving 0.004-0.04 mol of methylimidazole and 0.0003-0.003 mol of benzyltrimethylammonium bromide in a mixed solution of 40ml of methanol and 40ml of ethanol, and stirring for more than 30min to obtain a solution B; spraying 1-2 ml of solution B to the film B by a spraying method, so that the solution B uniformly covers and permeates the polystyrene microsphere/cobalt nitrate film, and obtaining a polystyrene microsphere/cobalt nitrate/methylimidazole film with an interdigital structure after the solution B uniformly permeates and covers, and marking as a film C;
s4, placing the film C in an air draft cabinet, placing the film C for 1-2 hours at the temperature of 25 ℃, and then placing the film C for 0.5-1 hour at the temperature of 40 ℃; then placing the film C in vacuum, heating from 40 ℃ to 100 ℃, and keeping the constant temperature at 100 ℃ for 0.5-1 h;
s5, repeating the steps S2-S4 for 3-5 times, and removing the mask plate;
s6, placing the film C in vacuum, and keeping the film C at the temperature of 60 ℃ for 24 hours to obtain a polystyrene microsphere/MOFs interdigital electrode, which is marked as an interdigital electrode A;
s7, soaking the interdigital electrode A in deionized water and ethanol, and cleaning for 2-3 times; placing the interdigital electrode A in vacuum, keeping the interdigital electrode A at the temperature of 60 ℃ for 0.5-1 h, and removing ethanol;
s8, placing the interdigital electrode A, namely the polystyrene microsphere/MOFs interdigital electrode, in a dichloromethane solution, performing ultrasonic treatment for 2-10 min, and dissolving the polystyrene microsphere and the PE film to obtain the porous, uniform and compact MOFs self-supporting film, namely the self-supporting MOFs electrode.
The working principle and the advantages of the invention are as follows:
(1) placing the interdigital electrode A in a dichloromethane solution, and carrying out ultrasonic treatment for 2-10 min to dissolve the polystyrene microspheres and the PE film, so as to obtain a self-supporting MOFs electrode; by adopting the mode, compared with the mode of mixing the MOFs material and the adhesive, the adhesive is not used, the resistance of the electrode cannot be increased, the transmission of electrons cannot be hindered, and the performance of the super capacitor can be improved;
(2) placing the film C at the temperature of 25 ℃ for 1-2 h, and at the temperature of 40 ℃ for 0.5-1 h; placing the film B in vacuum, heating the film B from 40 ℃ to 100 ℃, and keeping the temperature for 0.5-1 h; the temperature is gradually increased in such a way, MOFs materials are generated through reaction, and meanwhile, the volatilization speed is slowed down, the reaction time is prolonged, and cracking can be prevented; the film C is placed in vacuum and kept at the temperature of 60 ℃ for 24 hours, which is beneficial to full reaction;
(3) spraying 1-2 ml of the solution A to the film A by adopting a spraying method, so that the solution A can uniformly cover and permeate into pores of the polystyrene microspheres as much as possible, and the uniformity of the solution A in the pores of the polystyrene microspheres is improved; spraying 1-2 ml of the solution B to the film B by adopting a spraying method, so that the solution B can uniformly cover and permeate the polystyrene microsphere/cobalt nitrate film as much as possible, and the uniformity of the solution B in the film C is improved;
(4) the polytetrafluoroethylene mask plate is tightly pressed on the flexible PE film, the polystyrene microsphere aqueous solution is spin-coated, the interdigital thickness can be conveniently increased through the spin-coating times, the spin-coating times and the concentration of the polystyrene microsphere aqueous solution jointly determine the thickness of the polystyrene microsphere film with the interdigital structure, and the operation is easy and the realization is convenient.
The invention does not adopt an adhesive, does not increase the resistance of the electrode, does not hinder the transmission of electrons, improves the performance of the MOFs electrode, and solves the technical problem of low performance of the existing super capacitor.
Further, in S1, the particle size of the polystyrene microsphere aqueous solution is 500 nm-2 um, and the molar concentration is 1-2.5%.
Further, in S1, the thickness of the film A is 10 to 100 μm.
Further, in S2, the pressure source is nitrogen, and 1-2 ml of the solution A is sprayed on the film A by adopting nitrogen; in S3, the pressure source is nitrogen, and 1-2 ml of the solution B is sprayed on the film B by adopting nitrogen.
Further, immediately after the spraying of the solution A, the solution B was sprayed.
Drawings
Fig. 1 is a microstructure diagram of an interdigital electrode a of an embodiment of the super capacitor based on MOFs materials of the present invention.
FIG. 2 is a microstructure diagram of a supported MOFs electrode according to an embodiment of the present invention based on a super capacitor made of MOFs materials.
Detailed Description
The following is further detailed by the specific embodiments:
example 1
The invention prepares the self-supporting MOFs electrode, and the specific implementation process is as follows:
s1, pressing a polytetrafluoroethylene mask plate on the flexible PE film, and spin-coating a polystyrene microsphere aqueous solution for 2-5 times; drying at the temperature of 60 ℃ for 0.5-2 h to obtain a polystyrene microsphere film with an interdigital structure, and marking as a film A; the thickness of the film A is determined by the spin coating times and the concentration of the polystyrene microsphere aqueous solution. In this embodiment, the particle size of the polystyrene microsphere aqueous solution is 500 nm-2 um, the molar concentration is 1-2.5%, and the thickness of the film A is 10-100 μm.
The interdigital thickness can be conveniently increased through the number of times of spin coating, the thickness of the polystyrene microsphere film with the interdigital structure is determined by the number of times of spin coating and the concentration of the polystyrene microsphere aqueous solution, and the method is easy to operate and convenient to realize.
S2, dissolving 0.001-0.01 mol of cobalt nitrate hexahydrate in a mixed solution of 40ml of methanol and 40ml of ethanol, and reacting for more than 30min to obtain a solution A; spraying 1-2 ml of the solution A to the film A by adopting a spraying method, wherein the pressure source is nitrogen, and spraying 1-2 ml of the solution A to the film A by adopting nitrogen; and enabling the solution A to uniformly cover and permeate into pores of the polystyrene microspheres to obtain the polystyrene microsphere/cobalt nitrate film with the interdigital structure after the solution A is uniformly penetrated and covered, and marking as a film B. And (3) spraying 1-2 ml of the solution A to the film A by adopting a spraying method, so that the solution A can be uniformly covered and permeated into the pores of the polystyrene microspheres as much as possible, and the uniformity of the solution A in the pores of the polystyrene microspheres is improved.
S3, dissolving 0.004-0.04 mol of methylimidazole and 0.0003-0.003 mol of benzyltrimethylammonium bromide in a mixed solution of 40ml of methanol and 40ml of ethanol, and stirring for more than 30min to obtain a solution B; spraying 1-2 ml of the solution B to the film B by adopting a spraying method, wherein the pressure source is nitrogen, spraying 1-2 ml of the solution B to the film B by adopting nitrogen, and immediately spraying the solution A to the film B; and enabling the solution B to uniformly cover and permeate the polystyrene microsphere/cobalt nitrate film to obtain the polystyrene microsphere/cobalt nitrate/methylimidazole film with the interdigital structure after the solution B is uniformly covered and permeated, and recording the film as a film C. And spraying 1-2 ml of the solution B to the film B by adopting a spraying method, so that the solution B can uniformly cover and permeate the polystyrene microsphere/cobalt nitrate film as far as possible, and the uniformity of the solution B in the film C is improved.
S4, placing the film C in an air draft cabinet, placing the film C for 1-2 hours at the temperature of 25 ℃, and then placing the film C for 0.5-1 hour at the temperature of 40 ℃; and then placing the film C in vacuum, raising the temperature from 40 ℃ to 100 ℃, and keeping the constant temperature at the temperature of 100 ℃ for 0.5-1 h. In such a way, the temperature is gradually increased, the MOFs material is generated through reaction, and meanwhile, the volatilization speed is slowed down, the reaction time is prolonged, and the cracking can be prevented; the film C was placed in vacuum and kept at 60 ℃ for 24h to facilitate a full reaction.
And S5, repeating the steps S2-S4 for 3-5 times, and removing the mask plate.
S6, placing the film C in vacuum and keeping the temperature at 60 ℃ for 24h to obtain the polystyrene microsphere/MOFs interdigital electrode, which is marked as interdigital electrode A, as shown in the attached figure 1.
S7, soaking the interdigital electrode A in deionized water and ethanol, and cleaning for 2-3 times; and placing the interdigital electrode A in vacuum, keeping the interdigital electrode A at the temperature of 60 ℃ for 0.5-1 h, and removing the ethanol.
S8, placing the interdigital electrode A, namely the polystyrene microsphere/MOFs interdigital electrode, in a dichloromethane solution, performing ultrasonic treatment for 2-10 min, dissolving the polystyrene microsphere and the PE film, and obtaining the porous, uniform and compact MOFs self-supporting thin film, namely the self-supporting MOFs electrode, as shown in the attached figure 2. In this way, compared with the mixing of the MOFs material and the adhesive, the adhesive is not used, the resistance of the electrode is not increased, and the transmission of electrons is not hindered, so that the performance of the MOFs electrode can be improved.
Example 2
The difference from example 1 is only that the prepared self-supporting MOFs electrodes were used for supercapacitors. Because the self-supporting MOFs electrode does not adopt an adhesive in the preparation process, compared with the method of mixing the MOFs material and the adhesive, the resistance of the electrode is small, the transfer process of electrons is smooth, and the performance of the MOFs electrode is high, so that the performance of the super capacitor is good.
The foregoing is merely an example of the present invention, and common general knowledge in the field of known specific structures and characteristics is not described herein in any greater extent than that known in the art at the filing date or prior to the priority date of the application, so that those skilled in the art can now appreciate that all of the above-described techniques in this field and have the ability to apply routine experimentation before this date can be combined with one or more of the present teachings to complete and implement the present invention, and that certain typical known structures or known methods do not pose any impediments to the implementation of the present invention by those skilled in the art. It should be noted that, for those skilled in the art, without departing from the structure of the present invention, several changes and modifications can be made, which should also be regarded as the protection scope of the present invention, and these will not affect the effect of the implementation of the present invention and the practicability of the patent. The scope of the claims of the present application shall be determined by the contents of the claims, and the description of the embodiments and the like in the specification shall be used to explain the contents of the claims.
Claims (5)
1. A super capacitor based on MOFs materials is characterized in that electrodes are self-supporting MOFs electrodes; the preparation method of the self-supporting MOFs electrode comprises the following steps:
s1, pressing a polytetrafluoroethylene mask plate on the flexible PE film, and spin-coating a polystyrene microsphere aqueous solution for 2-5 times; drying at the temperature of 60 ℃ for 0.5-2 h to obtain a polystyrene microsphere film with an interdigital structure, and marking as a film A; the thickness of the film A is determined according to the spin coating times and the concentration of the polystyrene microsphere aqueous solution;
s2, dissolving 0.001-0.01 mol of cobalt nitrate hexahydrate in a mixed solution of 40ml of methanol and 40ml of ethanol, and reacting for more than 30min to obtain a solution A; spraying 1-2 ml of solution A to the film A by adopting a spraying method, so that the solution A is uniformly covered and permeated into pores of the polystyrene microsphere, and obtaining the polystyrene microsphere/cobalt nitrate film with an interdigital structure after being uniformly covered by the solution A by permeation, and marking as a film B;
s3, dissolving 0.004-0.04 mol of methylimidazole and 0.0003-0.003 mol of benzyltrimethylammonium bromide in a mixed solution of 40ml of methanol and 40ml of ethanol, and stirring for more than 30min to obtain a solution B; spraying 1-2 ml of solution B to the film B by a spraying method, so that the solution B uniformly covers and permeates the polystyrene microsphere/cobalt nitrate film, and obtaining a polystyrene microsphere/cobalt nitrate/methylimidazole film with an interdigital structure after the solution B uniformly permeates and covers, and marking as a film C;
s4, placing the film C in an air draft cabinet, placing the film C for 1-2 hours at the temperature of 25 ℃, and then placing the film C for 0.5-1 hour at the temperature of 40 ℃; then placing the film C in vacuum, heating from 40 ℃ to 100 ℃, and keeping the constant temperature at 100 ℃ for 0.5-1 h;
s5, repeating the steps S2-S4 for 3-5 times, and removing the mask plate;
s6, placing the film C in vacuum, and keeping the film C at the temperature of 60 ℃ for 24 hours to obtain a polystyrene microsphere/MOFs interdigital electrode, which is marked as an interdigital electrode A;
s7, soaking the interdigital electrode A in deionized water and ethanol, and cleaning for 2-3 times; placing the interdigital electrode A in vacuum, keeping the interdigital electrode A at the temperature of 60 ℃ for 0.5-1 h, and removing ethanol;
s8, placing the interdigital electrode A, namely the polystyrene microsphere/MOFs interdigital electrode, in a dichloromethane solution, performing ultrasonic treatment for 2-10 min, and dissolving the polystyrene microsphere and the PE film to obtain the porous, uniform and compact MOFs self-supporting film, namely the self-supporting MOFs electrode.
2. The MOFs material-based supercapacitor according to claim 1, wherein in S1, the particle size of the polystyrene microsphere aqueous solution is 500 nm-2 um, and the molar concentration is 1-2.5%.
3. The MOFs material based supercapacitor according to claim 2, wherein in S1, the thickness of film A is 10 to 100 μm.
4. The MOFs material based supercapacitor according to claim 3, wherein in S2, the pressure source is nitrogen, and 1-2 ml of solution A is sprayed on the film A by using nitrogen; in S3, the pressure source is nitrogen, and 1-2 ml of the solution B is sprayed on the film B by adopting nitrogen.
5. The MOFs material based supercapacitor according to claim 4, wherein solution A is sprayed immediately after solution B is sprayed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110479673.XA CN113178341B (en) | 2021-04-30 | 2021-04-30 | Super capacitor based on MOFs material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110479673.XA CN113178341B (en) | 2021-04-30 | 2021-04-30 | Super capacitor based on MOFs material |
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| Publication Number | Publication Date |
|---|---|
| CN113178341A CN113178341A (en) | 2021-07-27 |
| CN113178341B true CN113178341B (en) | 2022-03-25 |
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