CN115064391B - Preparation method of electrode material applied to asymmetric supercapacitor - Google Patents
Preparation method of electrode material applied to asymmetric supercapacitor Download PDFInfo
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- 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 abstract description 9
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- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims abstract description 5
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- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 7
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- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 4
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- 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)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention provides a preparation method of an electrode material applied to an asymmetric supercapacitor, which is characterized in that the electrode material is compounded with a sulfide material to form a core-shell structure on the basis of a chemically etched MOF derivative material, and the specific capacity of the electrode material is greatly improved by constructing a composite structure of the MOF derivative substrate and the sulfide material on the basis of improving the electrochemical performance of the MOF derivative substrate. The invention discloses a preparation method of an electrode material applied to an asymmetric supercapacitor, which comprises the following steps: 1) Dissolving zinc nitrate hexahydrate and cobalt nitrate hexahydrate in water, and uniformly stirring and mixing to obtain a mixed solution A; 2) Taking the mixed solution as an electrostatic spinning solution, and adopting an electrostatic spinning method to obtain a polymer diaphragm matrix; 3) And (3) dropwise adding the mixed solution A obtained in the step (1) into the solution B obtained in the step (2), fully stirring and uniformly mixing, standing for 24 hours, carrying out suction filtration and separation, and washing with water and ethanol to obtain a precipitate MOF.
Description
Technical Field
The invention relates to the technical field of supercapacitors, in particular to a preparation method of an electrode material applied to an asymmetric supercapacitor.
Background
Fossil energy resources represented by petroleum resources are increasingly under tension, environmental pollution is becoming serious, and these problems force each country to strive for new energy sources with sustainable development and more advanced energy storage technologies. However, various novel clean energy sources such as wind power generation, photovoltaic power generation and the like have randomness and uncontrollability, and obvious output peaks and valleys often exist in practical application, and although considerable progress is made in recent years, the novel clean energy sources still cannot completely replace fossil energy systems. For peak clipping and valley filling, flexible access of clean energy to a power grid is realized, and stable energy supply by means of an energy storage facility is the best current solution.
Super-capacitors are a new type of energy storage device between electrolytic capacitors and batteries. Compared with the traditional capacitor, the super capacitor has larger specific capacity and higher energy density; supercapacitors have higher power densities and longer cycle lives than rechargeable batteries. The advantages of the super capacitor lead the super capacitor to have wide application prospect, such as the module group formed by the single super capacitor with large capacity is applied to cold start assistance of a heavy truck engine, a power battery hybrid assembly of a large electric vehicle, an energy heat exchanger of rail transit and the like.
Although supercapacitors are not long-lived in terms of energy density, developing high-capacity electrode materials suitable for supercapacitors is still significant in increasing the capacity of the supercapacitors in their operating states. The concept of an asymmetric supercapacitor is therefore proposed, which is characterized by the replacement of one side electrode with an electrode material having similar properties to a battery (called pseudocapacitance) compared to a conventional double layer electrochemical supercapacitor. Currently commonly used pseudocapacitive materials include systems of transition metal compounds, alloys, conductive polymers, etc., of which the transition metal compounds, particularly the mono-or poly-oxides and sulfides of metals such as Mn, co, ni, zn, are of greatest interest. One method of preparing transition metal compound materials with excellent properties is to obtain composite derivative materials of carbon skeleton and oxide by high temperature pyrolysis, starting from a MOF material template with a specific structure. There have been many studies on MOF derivative materials at present, but the capacity achieved is still far below the theoretical capacity, so there is still a need to further enhance the electrochemical properties of the materials by appropriate means.
Disclosure of Invention
The invention aims at providing a preparation method of an electrode material applied to an asymmetric supercapacitor aiming at the defects in the background technology. The electrode material disclosed by the invention adopts a composite structure of the MOF-based metal oxide material and the metal sulfide material, and the oxide material serving as a matrix also exerts the potential of sulfide on the basis of improving the performance of the electrode material through chemical etching.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the electrode material applied to the asymmetric supercapacitor comprises the following steps:
step 1, dissolving zinc nitrate hexahydrate and cobalt nitrate hexahydrate in water, and uniformly stirring and mixing to obtain a mixed solution A;
step 2, dissolving 2-methylimidazole in water, and stirring and mixing uniformly to obtain a solution B;
step 3, dropwise adding the mixed solution A obtained in the step 1 into the solution B obtained in the step 2, fully stirring and uniformly mixing, standing for 24 hours, carrying out suction filtration and separation, and washing with water and ethanol to obtain a precipitate MOF;
step 4, mixing the MOF obtained in the step 3 with a tannic acid solution, standing for a period of time, separating by a differential centrifugation method, and cleaning a solid by using water and ethanol to obtain a precursor;
step 5, calcining the precursor obtained in the step 4 in argon atmosphere, and then annealing in air to obtain a transition metal oxide material;
and 6, dispersing the transition metal oxide material obtained in the step 5, nickel nitrate hexahydrate, cobalt nitrate hexahydrate, thioacetamide and polyvinylpyrrolidone K40 (PVP K40) in a solution of water and glycol, mixing, performing hydrothermal reaction, and obtaining a solid phase product by suction filtration, namely a final product.
Compared with the prior art, the invention has the following beneficial effects:
the electrode material applied to the asymmetric supercapacitor provided by the invention has the advantages that the selected component materials are simple and easy to obtain, the price is low, and the preparation method is simple;
the electrode material applied to the asymmetric supercapacitor provided by the invention has the advantages that the discharge specific capacity under the test of three electrodes is effectively improved by the composite material structure constructed after basic modification.
Drawings
FIG. 1 is a graph showing charge and discharge test curves of three electrodes of the electrodes prepared in comparative examples 1 to 2 and examples 1 to 4;
FIG. 2 is a graph showing the specific capacity of the electrodes prepared in comparative examples 1 to 2 and examples 1 to 4;
fig. 3 is an SEM photograph of the electrode material prepared in example 4.
Detailed Description
The preparation process of the test pole piece adopted by the embodiment and the comparative example comprises the following steps: the electrode material of the embodiment or the comparative example, the conductive carbon black and the PVDF are fully and uniformly mixed, and then the N-methyl pyrrolidone is added and uniformly stirred to obtain electrode slurry; and then, uniformly coating the obtained slurry on foam nickel, drying, rolling and cutting to obtain the test pole piece.
The electrode plates prepared in the embodiment and the comparative example are tested by adopting a three-electrode method, a working electrode adopts a stainless steel electrode clamp to clamp the test electrode plate, a counter electrode adopts a platinum electrode, a reference electrode adopts an HgO electrode, an electrolyte adopts 100mL of 3mol/L potassium hydroxide aqueous solution, and electrochemical test is carried out in a glass sealed electrolytic cell.
The achievement of the object of the present invention is further described in detail below with reference to the accompanying drawings and specific examples.
Step 1, dissolving zinc nitrate hexahydrate with the concentration of 0.1mol/L and cobalt nitrate hexahydrate with the concentration of 0.2mol/L in water, and stirring and mixing uniformly to obtain 30mL of mixed solution A;
step 2, dissolving 2-methylimidazole with the concentration of 0.4g/ml in water, and uniformly stirring and mixing to obtain 30ml of solution B;
pumping the mixed solution A obtained in the step 1 into the solution B obtained in the step 2 by using a peristaltic pump at the speed of 1.5rpm, fully stirring and uniformly mixing, standing for 24 hours, carrying out suction filtration and separation, and washing with water and ethanol to obtain a precipitate MOF;
step 4, mixing the MOF obtained in the step 3 with 30mL of tannic acid solution with the concentration of 10g/L, standing for a period of time, separating by a differential centrifugation method, washing a solid by using water and ethanol to obtain a precursor, adding the mass of the MOF to be 0.1g, and standing for 0<t-30 minutes; the rotational speed used for separation by the differential centrifugation method is 12000rpm, and the time is 5 minutes;
step 5, calcining the precursor obtained in the step 4 in argon atmosphere, and then annealing in air to obtain a transition metal oxide material, wherein the calcining temperature in the argon atmosphere is 600 ℃, the heat preservation time is 2 hours, the heating rate is 3 ℃/min, and the gas flow rate is 60mL/min; annealing in air at 300 deg.c for 2 hr at 2 deg.c/min;
step 6, dispersing the transition metal oxide material obtained in the step 5, 50mg of nickel nitrate hexahydrate, 100mg of cobalt nitrate hexahydrate, 50mg of thioacetamide and 5mg of polyvinylpyrrolidone K40 (PVP K40) in a solution of water and ethylene glycol, mixing, performing hydrothermal reaction, and obtaining a solid phase product therein through suction filtration, wherein the dosage of the transition metal oxide material is 50mg, and the dosage of the transition metal oxide material is 3:1 total 60mL of mixed solution; the temperature of the hydrothermal reaction is 150 ℃ and the heat preservation time is 5 hours.
According to the specific implementation method of step 4 and step 6, the prepared samples are distinguished as shown in table 1:
| sample of | Standing time in step 4 | Whether or not to implement step 6 |
| Example 1 | 10 | Is that |
| Example 2 | 20 | Is that |
| Comparative example 1 | 0 (skip step 4) | Whether or not |
| Comparative example 2 | 10 | Whether or not |
| Comparative example 3 | 20 | Whether or not |
| Comparative example 4 | 0 (skip step 4) | Is that |
Table 1 differentiation of examples from comparative examples
Specific capacities of the test electrodes prepared in comparative examples 1 to 4 and examples 1 to 2 were measured as follows:
after the configuration of the test electrode and the relevant elements of the electrolytic cell is completed, the test electrode and the relevant elements of the electrolytic cell are connected into a CHI660E electrochemical workstation, a timing current method is adopted for testing, the test voltage range is 0-0.55V, and the test current density gradient is 1A/g, 2A/g, 3A/g, 5A/g, 8A/g and 10A/g, and the result is shown in figure 1.
The results of fig. 1 are further consolidated to provide fig. 2. It can be seen that comparative example 2, which was subjected to etching treatment according to step 4, had a considerable improvement in capacity as compared with comparative example 3, which demonstrates that the electrochemical performance of the MOF derivative can be effectively improved by the tannic acid etching treatment. And NiCo made in step 6 2 S 4 The composite work further strengthens the performance of the material, which is thatExample 1, example 2 and comparative example 4 are all embodied in which etching was performed for 20 minutes and with NiCo 2 S 4 Composite example 2 shows the highest specific capacity. The specific data obtained from the electrochemical test are shown in table 2.
Table 2 capacities of examples and comparative examples, in units of F/g
Fig. 3 is an SEM photograph of example 2. It can be seen that NiCo grows on MOF derivatives 2 S 4 Clusters, corroborating the conclusion
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered by the scope of the claims of the present invention.
Claims (7)
1. The preparation method of the electrode material applied to the asymmetric supercapacitor is characterized by comprising the following steps of: the method comprises the following steps:
step 1, dissolving zinc nitrate hexahydrate and cobalt nitrate hexahydrate in water, and uniformly stirring and mixing to obtain a mixed solution A;
step 2, dissolving 2-methylimidazole in water, and stirring and mixing uniformly to obtain a solution B;
step 3, dropwise adding the mixed solution A obtained in the step 1 into the solution B obtained in the step 2, fully stirring and uniformly mixing, standing for 24 hours, carrying out suction filtration and separation, and washing with water and ethanol to obtain a precipitate MOF;
step 4, mixing the MOF obtained in the step 3 with a tannic acid solution, standing for a period of time, separating by a differential centrifugation method, and cleaning a solid by using water and ethanol to obtain a precursor;
step 5, calcining the precursor obtained in the step 4 in argon atmosphere, naturally cooling the precursor, and then annealing the precursor in air, and cooling the precursor to obtain a transition metal oxide material;
and 6, dispersing the transition metal oxide material obtained in the step 5, nickel nitrate hexahydrate, cobalt nitrate hexahydrate, thioacetamide and polyvinylpyrrolidone K40 (PVP K40) in a solution of water and glycol, mixing, performing hydrothermal reaction, cooling after the reaction is finished, and obtaining a solid phase product therein through suction filtration, namely a final product.
2. The method for preparing the electrode material applied to the asymmetric supercapacitor according to claim 1, wherein the method comprises the following steps: in the step 1, the concentration of the zinc nitrate hexahydrate in the aqueous solution is 0.1mol/L, and the concentration of the cobalt nitrate hexahydrate in the aqueous solution is 0.2mol/L.
3. The method for preparing the electrode material applied to the asymmetric supercapacitor according to claim 2, wherein the method comprises the following steps: in step 2, the concentration of the 2-methylimidazole in the aqueous solution was 0.4g/ml.
4. A method for preparing an electrode material for an asymmetric supercapacitor according to claim 3, wherein: in step 3, the mixed solution A was added to the solution B using a peristaltic pump at a pumping rate of 1mL/s, wherein the ratio of the total added mixed solution A to the solution B was 1:1 by volume.
5. The method for preparing the electrode material applied to the asymmetric supercapacitor according to claim 2, wherein the method comprises the following steps: in the step 4, the concentration of the tannic acid solution is 10g/L, the MOF prepared in the step 3 is added into the tannic acid solution, the MOF is added into each 30mL of tannic acid aqueous solution, and the standing time is 0<t-30 minutes; the differential centrifugation method uses a rotational speed of 12000rpm for 5-10 minutes.
6. A method for preparing an electrode material for an asymmetric supercapacitor according to claim 3, wherein: in the step 5, the condition of argon atmosphere calcination is that the temperature is heated to 500-700 ℃ from room temperature at a heating rate of 3 ℃/min, then the heat preservation time is 2-5h, and the flow rate of argon is 60mL/min in the heating and heat preservation process; the annealing in air is carried out at a temperature rising rate of 2 ℃/min from room temperature to 250-350 ℃ and a heat preservation time of 2-5h.
7. The method for preparing the electrode material applied to the asymmetric supercapacitor according to claim 4, wherein the method comprises the following steps: in the step 6, the transition metal oxide material, the nickel nitrate hexahydrate, the cobalt nitrate hexahydrate, the thioacetamide and the PVP K40 are dissolved in a solution obtained by mixing water and ethylene glycol according to a volume ratio of 3:1, wherein the mass ratio of the thioacetamide to the PVP K40 is 10:10:20:10:1; the hydrothermal reaction is carried out at 140-160 ℃ and the heat preservation time is 5-12h.
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