CN112216528A - Method for preparing electrode plate of high-voltage water-system supercapacitor by hydrothermal method - Google Patents
Method for preparing electrode plate of high-voltage water-system supercapacitor by hydrothermal method Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000001027 hydrothermal synthesis Methods 0.000 title claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 42
- 239000004744 fabric Substances 0.000 claims abstract description 42
- 239000002131 composite material Substances 0.000 claims abstract description 35
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 33
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011258 core-shell material Substances 0.000 claims abstract description 27
- 239000003990 capacitor Substances 0.000 claims abstract description 24
- 239000002135 nanosheet Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 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 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
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- 238000002360 preparation method Methods 0.000 abstract description 4
- 238000002848 electrochemical method Methods 0.000 abstract description 3
- 231100000956 nontoxicity Toxicity 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 239000006258 conductive agent Substances 0.000 abstract 1
- 239000010413 mother solution Substances 0.000 abstract 1
- 239000011824 nuclear material Substances 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- -1 nitrate ions Chemical class 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
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- 238000001514 detection method Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000010792 warming 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
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
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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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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
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- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses a simple method for preparing a high-voltage water system super capacitor by using a hydrothermal method. According to the method, a potassium permanganate solution is used as a mother solution, cobaltosic oxide nanosheets loaded on carbon cloth fibers are used as a nuclear material, and a hydrothermal method is utilized to pyrolyze potassium permanganate in a high-temperature environment to grow a uniform manganese dioxide nanometer flake on the cobaltosic oxide nanosheets. The composite material with the core-shell structure can be directly used as an electrode plate of a super capacitor without a conductive agent and an additive. Electrochemical characterization shows that the composite material has an ultrahigh window voltage of 1.2V and the specific capacitance reaches the maximum under a three-electrode system; has the advantages of simple preparation steps, high repetition rate, low cost, no toxicity and the like.
Description
Technical Field
The invention belongs to the field of super capacitors, and particularly relates to a preparation method of a super capacitor electrode plate.
Background
Due to the large combustion and use of fossil energy such as coal, petroleum and natural gas, human beings discharge excessive carbon dioxide into the atmosphere, so that a series of environmental problems such as seawater acidification, global warming and the like are caused. Therefore, the method has urgent need of exploring a new energy source which is practical and feasible to replace fossil energy and relieve ecological pressure. The rapid development of new electronic devices has led to the need to develop portable energy storage devices with smaller size and higher energy density. The super capacitor has the advantages of high power density, long cycle life, low production cost and the like. Compared with a traditional capacitor, the super capacitor has larger specific capacitance; compared with a novel lithium battery, the super capacitor has higher charging and discharging speeds. However, the energy density of the initially manufactured super capacitor is still low compared to that of the conventional battery, and the development and application of the super capacitor are severely restricted. In the last decade, researchers have improved and optimized active materials of supercapacitors by various methods, and the electrochemical performance of the supercapacitors has been greatly improved, but until now, the window voltage of the supercapacitors is always lower for water-based supercapacitors, and there is a fresh report on achieving 1.2V window voltage. For supercapacitors, in order to achieve greater power density, the output voltage of the supercapacitor must be increased.
The nano material with the core-shell structure has good synergistic effect. Various core-shell structures with different morphologies can be prepared by a displacement method, a hydrothermal method, a solvothermal method and an electrodeposition method. Various reports show that the structure has good electrochemical performance and is a very valuable electrode material of a super capacitor. Hydrothermal methods are receiving increasing attention due to their advantages of inexpensive instrumentation and easy handling requirements.
In the prior art, a chinese granted patent CN110136993A provides a method for preparing a supercapacitor electrode plate by using a hydrothermal method, in which powdery particles of cobaltosic oxide are first put into a potassium permanganate solution, reaction time and temperature are controlled, manganese dioxide nanosheets pyrolyzed by potassium permanganate are self-assembled on a shell of the cobaltosic oxide in a high-temperature and high-pressure environment to form an intermediate composite material with a core-shell structure, the reacted powder is washed with deionized water, and dried at a constant temperature to obtain the intermediate composite material, and then the intermediate composite material is prepared into the supercapacitor electrode plate by a coating method. However, although the intermediate composite material has a window voltage of 1.2V, the specific capacitance is still relatively low, and the intermediate composite material needs to be coated on the nickel foam and pressed into a sheet to form a final electrode plate, which is complicated to process and easy to significantly affect the electrochemical performance of the electrode plate due to improper processing.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a brand-new method for preparing the electrode plate of the high-voltage water system super capacitor. Specifically, the following technique is used.
A method for preparing a high-voltage water system super capacitor electrode plate by using a hydrothermal method comprises the following steps:
s1, taking 0.04-0.08mol/L cobalt nitrate hexahydrate aqueous solution and 0.4-0.8mol/L dimethyl imidazole aqueous solution, and stirring and mixing the mixture uniformly according to the volume ratio of 1: 0.5-2;
s2, placing the mixed solution into a container with the area of 2 x 5cm2Standing the carbon cloth for reaction for 2-6 h;
s3, taking out the carbon cloth after reaction, and drying the carbon cloth for more than 8 hours in vacuum at the temperature of 60-80 ℃; heating to 350 ℃ at the heating rate of 1-3 ℃/min, calcining for 2h, and naturally cooling to room temperature to obtain the carbon cloth loaded with cobaltosic oxide nanosheets;
s4, pouring 50ml of deionized water into the carbon cloth obtained in the step S3 and 0.6-0.9mM of potassium permanganate, reacting at the constant temperature of 80-110 ℃ for 7-15h, naturally cooling to room temperature, and taking out the nanosheets; drying at 70 ℃ for 6h to obtain the intermediate of the cobaltosic oxide-manganese dioxide composite material with the core-shell structure. The composite material intermediate can be directly used as an electrode plate of a super capacitor.
In the preparation method, the step S1 and the step S2 adopt a solvothermal method, and the nitric acid solution has a corrosion effect on the carbon cloth fiber at high temperature and high pressure, so that the surface roughness of the carbon cloth fiber can be increased; the nitrate ions can form an amino functional pattern on the surface of the carbon cloth fiber. The growth of ZIF-67 on the carbon cloth surface was facilitated by the increase of surface roughness and functional groups. The calcination in step S3 is generally performed in a common muffle furnace, and the product obtained by the preparation is a carbon cloth with a porous metal oxide cobaltosic oxide nanosheet loaded on the surface. And S4, selecting a reaction kettle as a reaction container, drying at constant temperature by using a constant-temperature drying box, and finally obtaining the finished product of the electrode plate, namely, the cobaltosic oxide nanosheet loaded on the carbon cloth, wherein a layer of uniform manganese dioxide nanometer flake grows on the cobaltosic oxide nanosheet, so that the core-shell structure composite material which can be directly used as the electrode plate of the supercapacitor is formed. The ZIF-67 nanosheets with the best morphological structure can be obtained only when the reaction temperature of the step S4 is 70-110 ℃.
The electrode slice prepared by the method has simple steps, low cost and no toxicity, has an ultrahigh window voltage of 1.2V, and has a specific capacitance of 616.7F/g; the specific capacitance retention rate is up to 83.1 percent after being cycled 10000 times under the current density of 20A/g, and the stability is good. According to the composite material with the core-shell structure, the cobaltosic oxide nanosheet can only stably grow on the carbon cloth substrate, and cannot stably grow on other substrates such as foamed nickel and the like.
Preferably, in step S1, the concentration of the cobalt nitrate hexahydrate aqueous solution is 0.05mol/L, the concentration of the dimethylimidazole aqueous solution is 0.4mol/L, and the volume ratio is 1: 1.
Preferably, in step S2, the standing reaction time is 4 h.
Preferably, in step S3, the temperature for vacuum drying is 70 ℃, and the drying time is 12 h.
Preferably, in step S4, the potassium permanganate is used in an amount of 0.7 mM.
Preferably, in step S4, the isothermal reaction temperature is 90 ℃ and the reaction time is 12 h.
Compared with the prior art, the invention has the advantages that:
1. the electrochemical performance of the electrode slice prepared from the prepared composite material is remarkably improved, and the electrode slice has the ultrahigh window voltage of 1.2V and the maximum 616.7Fg in an electrochemical three-electrode system-1High specific capacitance of (2);
2. the raw materials of the invention are low in price, the core-shell structure composite material is directly grown on the carbon cloth by a hydrothermal method, and the core-shell structure composite material can be directly used as an electrode slice, and the invention has the advantages of few experimental steps, easy operation, easy repetition and low cost.
Drawings
Fig. 1 is a scanning microscope (SEM) image of a cobaltosic oxide-manganese dioxide core-shell structure composite supported on carbon cloth prepared in example 1;
FIG. 2 is a scanning microscope (SEM) image of ZIF-67 supported on a carbon cloth prepared in example 2;
fig. 3 is a scanning microscope (SEM) image of cobaltosic oxide nanosheets supported on carbon cloth prepared in example 2;
fig. 4 is a scanning microscope (SEM) image of the tricobalt tetraoxide-manganese dioxide core-shell structure composite supported on the carbon cloth prepared in example 2;
fig. 5 is an XRD pattern of the cobaltosic oxide-manganese dioxide core-shell structure composite supported on carbon cloth prepared in example 2;
FIG. 6 is an XPS survey of a Cobaltosic oxide-manganese dioxide core-shell structure composite supported on carbon cloth prepared in example 2;
fig. 7 is an Mn2p energy spectrum of the tricobalt tetraoxide-manganese dioxide core-shell structure composite supported on carbon cloth prepared in example 2;
fig. 8 is a Co2p energy spectrum of the tricobalt tetraoxide-manganese dioxide core-shell structure composite supported on carbon cloth prepared in example 2;
fig. 9 is a K2 p energy spectrum of the tricobalt tetraoxide-manganese dioxide core-shell structure composite supported on carbon cloth prepared in example 2;
fig. 10 is a discharge schematic diagram of a voltammogram of the supercapacitor electrode sheet prepared in example 2.
Fig. 11 is a schematic diagram of cross-current charging and discharging of the electrode plates of the supercapacitor prepared in example 2.
Fig. 12 is a schematic view of the cycle performance of the supercapacitor electrode sheet prepared in example 2.
Fig. 13 is a scanning microscope (SEM) image of the tricobalt tetraoxide-manganese dioxide core-shell structure composite supported on the carbon cloth prepared in example 3.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
In the embodiment, the electrode plate of the high-voltage water system super capacitor is prepared by the following method:
s1, rapidly stirring and uniformly mixing 0.05mol/L cobalt nitrate hexahydrate aqueous solution and 0.5mol/L dimethyl imidazole aqueous solution according to the volume ratio of 1:1 to obtain a mixed solution;
s2, placing the mixed solution into a container with the area of 2 x 5cm2Standing and reacting the carbon cloth for 4 hours;
s3, taking out the carbon cloth after reaction, and drying for 12h in vacuum at 7 ℃; heating to 350 ℃ at the heating rate of 1 ℃/min, calcining for 2h, and naturally cooling to room temperature to obtain the carbon cloth loaded with the cobaltosic oxide nanosheets;
s4, putting the carbon cloth obtained in the step S3 and 0.7mM potassium permanganate into a beaker, pouring 50ml of deionized water, pouring the mixed system into a polytetrafluoroethylene liner with the volume of 90ml, and putting the polytetrafluoroethylene liner into a reaction kettle; the reaction kettle is put in a constant-temperature drying oven to react for 12 hours at the constant temperature of 80 ℃, and the nanosheets are taken out after being naturally cooled to the room temperature; drying at 70 deg.C for 6h to obtain the intermediate of the core-shell structure cobaltosic oxide-manganese dioxide composite material which can be directly used as an electrode plate.
Example 2
The method for preparing the electrode plate of the high-voltage water system super capacitor adopted in the embodiment is only different from the method in the embodiment 1 in that: in step S4, when the reaction kettle is in the constant temperature drying oven, the reaction temperature is 90 ℃ and the reaction time is 12 h.
Example 3
The method for preparing the electrode plate of the high-voltage water system super capacitor adopted in the embodiment is only different from the method in the embodiment 1 in that: in step S4, when the reaction kettle is in the constant temperature drying oven, the reaction temperature is 110 ℃, and the reaction time is 12 h.
Comparative example 1
The method for preparing the electrode plate of the high-voltage water system super capacitor adopted by the comparative example is only different from the method adopted in example 1 in that the carbon cloth is not adopted, and the foamed nickel is adopted.
Comparative example 2
The only difference between the method for preparing the electrode sheet of the high-voltage water system supercapacitor adopted in the comparative example and the method for preparing the electrode sheet of the high-voltage water system supercapacitor adopted in the example 1 is that the carbon cloth is not adopted, but the copper foil is adopted.
Fig. 1 is a scanning microscope (SEM) image of the cobaltosic oxide-manganese dioxide core-shell structure composite supported on the carbon cloth of example 1; it can be seen from the figure that the composite nanosheet has a few fractures.
FIG. 2 is a scanning microscope (SEM) image of ZIF-67 supported on a carbon cloth of example 2, and it can be seen from FIG. 2 that ZIF-67 was uniformly grown on the carbon cloth.
Fig. 3 is a scanning microscope (SEM) image of the cobaltosic oxide nanosheets supported on the carbon cloth of example 2, and fig. 3 illustrates that after calcination at 350 ℃, ZIF-67 was oxidized to cobaltosic oxide nanosheets, with no collapse of the framework, and still being tightly supported on the carbon cloth.
Fig. 4 is a scanning microscope (SEM) image of the tricobalt tetraoxide-manganese dioxide core-shell structure composite supported on the carbon cloth of example 2. It can be seen from fig. 4 that the manganese dioxide nanosheets uniformly grow on the surface of the cobaltosic oxide nanosheets, and the manganese dioxide nanosheets are not stacked with each other and have spatial stereoscopy, so that not only is a larger contact area provided, but also the electrolyte can better permeate into the nanosheets.
Fig. 5 is an XRD pattern of the core-shell structure composite of example 2. The figure shows only the diffraction peak of cobaltosic oxide, which is matched with the peak of JCPDS no:42-1467 of standard card library, and no diffraction peak of manganese dioxide appears, which indicates that amorphous manganese dioxide is loaded on the surface of cobaltosic oxide.
FIG. 6 is an XPS survey of the core-shell composite of example 2 showing Mn, Co, O and K elements in the composite.
Fig. 7 is an Mn2p energy spectrum of the core-shell structure composite material of example 2, and it can be seen that the binding energies of the two orbitals of Mn2p are 642.04EV and 653.75EV, respectively.
Fig. 8 is a Co2p energy spectrum of the core-shell structure composite material of example 2, and it can be seen that the binding energies of two orbitals of Co2p are 780.3EV and 795.2EV, respectively.
Fig. 9 shows a K2 p energy spectrum of the core-shell structure composite material of example 2, and it can be seen that the binding energies of the two orbitals of K2 p are 292.3EV and 295.27EV, respectively.
Fig. 10 is a schematic voltammogram discharge diagram (CV diagram) of the supercapacitor electrode sheet of example 2, showing reversible redox peaks, illustrating that the material has good rate capability.
FIG. 11 is a schematic diagram (GCD diagram) illustrating the cross-current charging and discharging of the electrode plate of the super capacitor in example 2, wherein the electrode plate has a window voltage of 1.2V and a specific capacitance of 4A g-1Current density of up to 590.7F g-1。
FIG. 12 is a schematic view of the cycle performance of the electrode sheet of the supercapacitor according to example 2, the electrode sheet being at 20A g-1The specific capacitance retention rate of the capacitor is up to 83.1% after 10000 times of circulation under the current density, which shows that the capacitor has very stable electrochemical performance.
Electrochemical characterization of the supercapacitor electrode sheets prepared in the above examples and comparative examples
The electrochemical characterization method comprises the following steps: (1) inserting the prepared super capacitor electrode slice into a 1M sodium sulfate solution by taking the prepared super capacitor electrode slice as a working electrode, silver/silver chloride as a reference electrode and a platinum sheet as a counter electrode; (2) and directly representing the window voltage, specific capacitance and other electrochemical properties of the intermediate composite material by using an electrochemical workstation by adopting cyclic voltammetry and constant current charge-discharge testing technology.
The detection result shows that the electrode plate of the supercapacitor prepared from the cobaltosic oxide-manganese dioxide intermediate composite material with the core-shell structure prepared in the example 2 has an ultrahigh voltage window of 1.2V in a three-electrode system, and the specific capacitance is at the current density4A g-1In the case of (2) up to 590.7F g-1. The specific capacitance of the embodiment 1 and the embodiment 3 respectively reaches 341.3F g under the same current density-1、475.3F g-1. Whereas the ZIF-67 supported on carbon cloth prepared in comparative examples 1 and 2 had no stability, was very easy to drop, and did not grow much.
Claims (6)
1. A method for preparing a high-voltage water system super capacitor electrode plate by using a hydrothermal method is characterized by comprising the following steps:
s1, taking 0.04-0.08mol/L cobalt nitrate hexahydrate aqueous solution and 0.4-0.8mol/L dimethyl imidazole aqueous solution, and stirring and mixing the mixture uniformly according to the volume ratio of 1: 0.5-2;
s2, placing the mixed solution into a container with the area of 2 x 5cm2Standing the carbon cloth for reaction for 2-6 h;
s3, taking out the carbon cloth after reaction, and drying the carbon cloth for more than 8 hours in vacuum at the temperature of 60-80 ℃; heating to 350 ℃ at the heating rate of 1-3 ℃/min, calcining for 2h, and naturally cooling to room temperature to obtain the carbon cloth loaded with cobaltosic oxide nanosheets;
s4, pouring 50ml of deionized water into the carbon cloth obtained in the step S3 and 0.6-0.9mM of potassium permanganate, reacting at the constant temperature of 80-110 ℃ for 7-15h, naturally cooling to room temperature, and taking out the nanosheets; drying at 70 ℃ for 6h to obtain the intermediate of the cobaltosic oxide-manganese dioxide composite material with the core-shell structure.
2. The method for preparing a high-voltage aqueous supercapacitor electrode sheet according to claim 1, wherein in step S1, the concentration of the aqueous solution of cobalt nitrate hexahydrate is 0.05mol/L, the concentration of the aqueous solution of dimethylimidazole is 0.5mol/L, and the volume ratio is 1: 1.
3. The method for preparing the high-voltage water-based supercapacitor electrode sheet by the hydrothermal method according to claim 1, wherein the standing reaction time in step S2 is 4 hours.
4. The method for preparing the high-voltage water-based supercapacitor electrode sheet according to claim 1, wherein the vacuum drying temperature is 70 ℃ and the drying time is 12 hours in step S3.
5. The method for preparing the electrode sheet of the high-voltage water-based supercapacitor by the hydrothermal method according to claim 1, wherein in step S4, the amount of potassium permanganate is 0.7 mM.
6. The method for preparing the electrode sheet of the high-voltage water-based supercapacitor by using the hydrothermal method according to claim 1, wherein the isothermal reaction temperature is 90 ℃ and the reaction time is 12 hours in step S4.
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