CN111899981A - Cobalt molybdate nanosheet array electrode material taking three-dimensional graphene foam as substrate, and preparation method and application thereof - Google Patents
Cobalt molybdate nanosheet array electrode material taking three-dimensional graphene foam as substrate, and preparation method and application thereof Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 82
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000006260 foam Substances 0.000 title claims abstract description 52
- 239000002135 nanosheet Substances 0.000 title claims abstract description 37
- 239000007772 electrode material Substances 0.000 title claims abstract description 22
- 239000000758 substrate Substances 0.000 title claims abstract description 17
- KYYSIVCCYWZZLR-UHFFFAOYSA-N cobalt(2+);dioxido(dioxo)molybdenum Chemical compound [Co+2].[O-][Mo]([O-])(=O)=O KYYSIVCCYWZZLR-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910018864 CoMoO4 Inorganic materials 0.000 claims abstract description 33
- 239000002131 composite material Substances 0.000 claims abstract description 23
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 5
- 229910001868 water Inorganic materials 0.000 claims abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 3
- 235000015393 sodium molybdate Nutrition 0.000 claims abstract description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 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 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000010453 quartz Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 238000000137 annealing Methods 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000005530 etching Methods 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 239000012634 fragment Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 238000010301 surface-oxidation reaction Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 6
- 230000001351 cycling effect Effects 0.000 abstract description 5
- 239000011230 binding agent Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 7
- 239000003990 capacitor Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000006479 redox reaction Methods 0.000 description 5
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910018916 CoOOH Inorganic materials 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- 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
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Abstract
The invention belongs to the technical field of preparation of electrode materials of supercapacitors, and provides a cobalt molybdate nanosheet array electrode material taking three-dimensional graphene foam as a substrate, and a preparation method and application thereof, wherein foamed nickel and methane are respectively taken as a substrate and a carbon source, graphene is loaded on the surface of the foamed nickel by a chemical vapor deposition method, and nickel is etched by hydrochloric acid to obtain graphene foam; preparing a precursor solution by using graphene foam as a substrate, cobalt nitrate, sodium molybdate and water, and mixing the graphene foam and the precursor solution for hydrothermal reaction to obtain 3D-graphene @ CoMoO4A nanosheet array composite. The preparation method is simple and low in cost; CoMoO4The nano-sheets directly grow on the graphene foam substrate through hydrothermal, so that the use of a binder is effectively avoided; controlling the shape of the material by controlling the concentration of the precursor solution; the prepared composite electrode material has high specific capacitance and good cycling stability.
Description
Technical Field
The invention belongs to the technical field of preparation of electrode materials of supercapacitors, and particularly relates to a cobalt molybdate nanosheet array electrode material taking three-dimensional graphene foam as a substrate, and a preparation method and application thereof.
Background
With the development of scientific technology and the improvement of human living standard, the demand of energy is getting bigger and bigger, the global energy consumption is rapidly increased, various climate change problems are accompanied, and the development of sustainable and renewable energy is urgent.
In recent years researchers have developed a large number of energy storage devices based on electrochemical storage, such as electrochemical supercapacitors and electrochemical cells. Supercapacitors are receiving attention from a wide range of researchers because of their advantages such as fast charge and discharge rates, high power density, and long cycle life.
However, the lower energy density limits the practical application of the supercapacitor, and thus, extensive researchers have attempted to improve the energy density of the supercapacitor by developing new electrode materials. The pseudocapacitor can generate a rapid and reversible oxidation-reduction reaction, so that higher specific capacitance and higher energy density can be provided, but the cycle life of the pseudocapacitor is not as long as that of an electric double layer capacitor.
In recent years, transition metal oxides and composite transition metal oxides having excellent capacitance characteristics have been widely studied as electrode materials for pseudo capacitors. In addition, in order to enhance the cycle life of the pseudocapacitor, researchers have compounded transition metal oxides with carbon materials such as graphene and reduced graphene oxide.
Disclosure of Invention
The invention aims to provide a cobalt molybdate nanosheet array supercapacitor electrode material taking three-dimensional graphene foam as a substrate, and a preparation method and application thereof, wherein the material is three-dimensional stoneGraphene foam @ cobalt molybdate (i.e., 3D-graphene @ CoMoO)4) A nanosheet array composite. The preparation method is simple and low in cost, and the prepared 3D-graphene @ CoMoO4The nano-sheet array composite material has high specific capacitance and good cycling stability, can be applied to super capacitor electrode materials, and has good application prospect.
In order to achieve the purpose, the invention is realized by the following technical scheme: a cobalt molybdate nanosheet array supercapacitor electrode material taking three-dimensional graphene foam as a substrate is prepared by loading graphene on the surface of nickel foam through a chemical vapor deposition method by taking nickel foam and methane as the substrate and a carbon source respectively, and etching nickel through hydrochloric acid to obtain graphene foam; preparing a precursor solution by using graphene foam as a substrate, cobalt nitrate, sodium molybdate and water, and mixing the graphene foam and the precursor solution for hydrothermal reaction to obtain 3D-graphene @ CoMoO4A nanosheet array composite.
The method for preparing the cobalt molybdate nanosheet array supercapacitor electrode material taking the three-dimensional graphene foam as the substrate comprises the following specific steps:
(1) preparing three-dimensional graphene foam: synthesizing three-dimensional graphene foam by chemical vapor deposition by using nickel foam as a three-dimensional support template and a catalyst: placing foamed nickel in a horizontal quartz tube, and placing in Ar and H2Heating to 800-1200 ℃ within 18-22 min, then annealing for 4-6 min, cleaning the foam surface and eliminating a surface oxidation layer; then, CH is reacted at the temperature of 800-1200 DEG C4Introducing the graphene into a quartz tube for 4-6 min to synthesize graphene; after growth, rapidly cooling the quartz tube to room temperature at a cooling rate of 5-10 ℃/min; soaking the sample in hydrochloric acid to remove the nickel template, taking out and drying to obtain three-dimensional graphene foam;
(2) preparing a precursor solution: dissolving cobalt nitrate hexahydrate and sodium molybdate dihydrate into deionized water under constant magnetic stirring to obtain a precursor solution;
(3) preparation of 3D-graphene @ CoMoO4Nanosheet array composite: immersing the three-dimensional graphene foam prepared in the step (1) into a precursor solutionSealing and heating the autoclave to 160-200 ℃ and preserving heat for 6-10 h; after the reaction is finished and the temperature is cooled to room temperature, taking out the light purple graphene foam from the high-pressure kettle, washing for a plurality of times, removing residual nano-particle fragments, drying the product, and calcining in nitrogen to obtain the 3D-graphene @ CoMoO4。
The flow rate ratio of Ar to H2 in step (1) was 2.5: 1, CH41/50 for Ar; the concentration of hydrochloric acid is 2-5M, and the soaking time is 12-24 h; the drying method is vacuum drying at 60-80 ℃.
In the step (2), the molar ratio of the cobalt nitrate hexahydrate to the sodium molybdate dihydrate is 1: 1; the dosage ratio of the cobalt nitrate hexahydrate to the deionized water is 0.1-1.5 mmol: 60 mL.
And (4) filling the precursor solution in the inner container of the reaction kettle in the step (3) in an amount of 65-85% of the volume of the reaction kettle.
The specific method for calcining in the step (3) comprises the following steps: calcining for 1-3 h at 350-500 ℃.
And the washing step in the step (3) is to sequentially wash the mixture for 3 to 5 times by using ethanol and deionized water respectively.
The argon, the hydrogen and the nitrogen are pure gases.
As can be seen from FIG. 4, the pure nickel foam has a negligible effect on the electrode capacitance, 3D-graphene @ CoMoO4The CV area of the electrode is much larger than that of CoMoO4The CV areas of the electrode and graphene electrode, indicating a higher specific capacitance of the composite electrode, are all due to CoMoO4And the synergistic effect of graphene and the strong redox reaction occurring inside the composite electrode. CoMoO4Electrode and 3D-graphene @ CoMoO4The electrodes were each composed of a pair of strong redox peaks, indicating that the capacitive properties are mainly controlled by faradaic redox reactions.
The redox peaks corresponding to the faradaic reaction are as follows:
3[Co(OH)3]-↔Co3O4+4H2O+OH-+2e-；
Co3O4+H2O+OH-↔3CoOOH+e-；
CoOOH+OH-↔CoO2+H2O+e-。
compared with the prior art, the preparation method is simple and low in cost; CoMoO4The nano-sheets directly grow on the graphene foam substrate through hydrothermal, so that the use of a binder is effectively avoided; controlling the shape of the material by controlling the concentration of the precursor solution; the prepared composite electrode material has high specific capacitance and good cycling stability.
Drawings
FIG. 1 shows the 3D-graphene @ CoMoO obtained in example 1 of the present invention4Scanning electron microscope images of the nanosheet arrays;
FIG. 2 shows the 3D-graphene @ CoMoO obtained in example 1 of the present invention4An X-ray diffraction pattern of the nanosheet array;
FIG. 3 shows the 3D-graphene @ CoMoO obtained in example 1 of the present invention4X-ray photoelectron spectrum of the nanosheet array;
FIG. 4 shows the graphene foam and 3D-graphene @ CoMoO obtained in example 1 of the present invention4Electrode and CoMoO obtained in comparative example 1 of the invention4Cyclic voltammogram at a scan rate of 50 mV/s;
FIG. 5 shows the 3D-graphene @ CoMoO obtained in example 1 of the present invention4A charge-discharge curve diagram of the electrode under different current densities;
FIG. 6 is a CoMoO obtained in comparative example 1 of the present invention4A charge-discharge curve diagram of the electrode under different current densities;
FIG. 7 shows the graphene foam and 3D-graphene @ CoMoO obtained in example 1 of the present invention4Electrode and CoMoO obtained in comparative example 1 of the invention4A specific capacitance relation graph of the electrode under different current densities;
FIG. 8 shows the graphene foam and 3D-graphene @ CoMoO obtained in example 1 of the present invention4Electrode and CoMoO obtained in comparative example 1 of the invention4Electrode cycling stability profiles.
Detailed Description
In order to further explain the technical solution of the present invention, the present invention is explained in detail by the following specific examples.
Example 1: 3D-graphene @ CoMoO4The preparation method of the nanosheet array composite material comprises the following steps:
step 1, putting the cleaned foamed nickel into a horizontal quartz tube, and putting the cleaned foamed nickel into Ar and H2Heating to 1000 deg.C for 20 min, annealing for 5 min to clean foam surface and eliminate thin surface oxide layer, and removing CH at 1000 deg.C4Introducing into a quartz tube for 5 min, and cooling to room temperature to obtain a reaction product A;
and 2, adding 1 mmol of cobalt nitrate hexahydrate, 1 mmol of sodium molybdate dihydrate and 80 mL of deionized water into a 100 mL high-pressure kettle at room temperature, and uniformly stirring and dissolving to obtain a mixed aqueous solution B. Changing the amount of cobalt nitrate hexahydrate and sodium molybdate dihydrate in the reaction step so as to change the morphology of the reaction product cobalt molybdate nanosheet;
step 3, immersing the reaction product A into the mixed aqueous solution B, sealing and heating the high-pressure kettle to 160 ℃ for hydrothermal reaction, preserving heat for 10 hours, and cooling to room temperature to obtain a reaction product C;
step 4, washing the reaction product C with deionized water and ethanol for several times in sequence, and drying the reaction product C for 12 hours in vacuum at the temperature of 80 ℃ to obtain CoMoO growing on the graphene foam4A nanosheet array;
and 5, putting the product obtained in the step 4 into a tubular furnace, and calcining for 2 hours at 350 ℃ in a nitrogen atmosphere.
To prove 3D-graphene @ CoMoO4The structural characteristics of the nanosheet array composite material are shown in fig. 1 through a scanning electron microscope test: the material has a nanosheet structure, and CoMoO with the thickness of 0.6 mu m and optimal electrochemical performance is prepared by adjusting the concentration of reactants4Nanosheets; the X-ray diffraction test results are shown in fig. 2, with no diffraction peaks for nickel indicating that the nickel foam is completely dissolved; the X-ray photoelectron spectrum is shown in FIG. 3, which proves the successful synthesis of CoMoO4。
3D-graphene@CoMoO4The electrochemical performance test method of the nanosheet array composite material comprises the following steps: subjecting 3D-graphene@CoMoO4The electrode was directly immersed in 6M KOH solution, and the Hg/HgO electrode and the platinum electrode were used as a reference electrode and a counter electrode, respectively, and the electrochemical performance was tested in a three-electrode system.
The test results are shown in FIG. 5, and the discharge is performed in the range of-0.1 to 0.4V when the current density is 1 mA/cm23D-graphene @ CoMoO4The specific capacitance of the nano-sheet array composite material is up to 2737 mF/cm2. When the current density is increased to 10mA/cm23D-graphene @ CoMoO4The specific capacitance of the nano-sheet array composite material can still be maintained at high specific capacitance (2256 mF/cm)2) As shown in FIG. 7, the material has good rate capability.
As can be seen from FIG. 4, the pure nickel foam has a negligible effect on the electrode capacitance, 3D-graphene @ CoMoO4The CV area of the electrode is much larger than that of CoMoO4The CV areas of the electrode and graphene electrode, indicating a higher specific capacitance of the composite electrode, are all due to CoMoO4And the synergistic effect of graphene and the strong redox reaction occurring inside the composite electrode. CoMoO4Electrode and 3D-graphene @ CoMoO4The electrodes were each composed of a pair of strong redox peaks, indicating that the capacitive properties are mainly controlled by faradaic redox reactions.
At a current density of 1 mA/cm2Under the conditions, the charge-discharge cycle stability performance test of the composite electrode is carried out, the test result is shown in figure 8, after 4000 cycles, the capacitor can still keep about 81.76%, which shows that the composite electrode has good cycle stability, and the results show that the 3D-graphene @ CoMoO4The composite electrode is expected to be used as a high-quality electrode of a super capacitor, and provides a wide prospect for developing a unique nano-structure metal molybdate for the application of a hybrid super capacitor.
To demonstrate that graphene foam can be used not only as a substrate to prepare an integrated electrode, but also as a CoMoO4Providing good conductivity and thus improving the electrochemical performance, especially the cycling performance, of the material, comparative example 1 is provided.
Comparative example 1: prepare CoMoO4Electrodes, details of the steps not being particularly specifiedThe clear procedure was as described in example 1 for 3D-graphene @ CoMoO4The preparation method of the nano-sheet array composite material is the same, and the difference is that: in the step 3, the reaction product A is replaced by nickel foam.
For CoMoO4The electrode was electrochemically tested in the same manner as in example 1. When the current density is 1 mA/cm2Then, as shown in FIG. 6, CoMoO4The specific capacitance of the electrode is 2181.8 mF/cm2. As shown in FIG. 7, when the current density was increased to 10mA/cm2When the specific capacitance is 1706 mF/cm2. In FIG. 8, the current density was 1 mA/cm2The capacity retention ratio was 63.44% after 4000 cycles under the conditions of (1).
Claims (8)
1. A cobalt molybdate nanosheet array supercapacitor electrode material taking three-dimensional graphene foam as a substrate is characterized in that: respectively taking foamed nickel and methane as a substrate and a carbon source, loading graphene on the surface of the foamed nickel by a chemical vapor deposition method, and etching nickel by hydrochloric acid to obtain graphene foam; preparing a precursor solution by using graphene foam as a substrate, cobalt nitrate, sodium molybdate and water, and mixing the graphene foam and the precursor solution for hydrothermal reaction to obtain 3D-graphene @ CoMoO4A nanosheet array composite.
2. The method for preparing the cobalt molybdate nanosheet array supercapacitor electrode material based on the three-dimensional graphene foam as claimed in claim 1, wherein the method comprises the following steps: the method comprises the following specific steps:
(1) preparing three-dimensional graphene foam: synthesizing three-dimensional graphene foam by chemical vapor deposition by using nickel foam as a three-dimensional support template and a catalyst: placing foamed nickel in a horizontal quartz tube, and placing in Ar and H2Heating to 800-1200 ℃ within 18-22 min, then annealing for 4-6 min, cleaning the foam surface and eliminating a surface oxidation layer; then, CH is reacted at the temperature of 800-1200 DEG C4Introducing the graphene into a quartz tube for 4-6 min to synthesize graphene; after growth, rapidly cooling the quartz tube to room temperature at a cooling rate of 5-10 ℃/min; soaking the sample in hydrochloric acid to remove the nickel template, and takingDrying after the discharge to obtain three-dimensional graphene foam;
(2) preparing a precursor solution: dissolving cobalt nitrate hexahydrate and sodium molybdate dihydrate into deionized water under constant magnetic stirring to obtain a precursor solution;
(3) preparation of 3D-graphene @ CoMoO4Nanosheet array composite: immersing the three-dimensional graphene foam prepared in the step (1) into an autoclave containing a precursor solution, sealing and heating to 160-200 ℃, and keeping the temperature for 6-10 hours; after the reaction is finished and the temperature is cooled to room temperature, taking out the light purple graphene foam from the high-pressure kettle, washing for a plurality of times, removing residual nano-particle fragments, drying the product, and calcining in nitrogen to obtain the 3D-graphene @ CoMoO4。
3. The method for preparing the cobalt molybdate nanosheet array supercapacitor electrode material based on the three-dimensional graphene foam as claimed in claim 2, wherein: the flow rate ratio of Ar to H2 in step (1) was 2.5: 1, CH41/50 for Ar; the concentration of hydrochloric acid is 2-5M, and the soaking time is 12-24 h; the drying method is vacuum drying at 60-80 ℃.
4. The method for preparing the cobalt molybdate nanosheet array supercapacitor electrode material based on the three-dimensional graphene foam as claimed in claim 2, wherein: in the step (2), the molar ratio of the cobalt nitrate hexahydrate to the sodium molybdate dihydrate is 1: 1; the dosage ratio of the cobalt nitrate hexahydrate to the deionized water is 0.1-1.5 mmol: 60 mL.
5. The method for preparing the cobalt molybdate nanosheet array supercapacitor electrode material based on the three-dimensional graphene foam as claimed in claim 2, wherein: and (4) filling the precursor solution in the inner container of the reaction kettle in the step (3) in an amount of 65-85% of the volume of the reaction kettle.
6. The method for preparing the cobalt molybdate nanosheet array supercapacitor electrode material based on the three-dimensional graphene foam as claimed in claim 2, wherein: the specific method for calcining in the step (3) comprises the following steps: calcining for 1-3 h at 350-500 ℃.
7. The method for preparing the cobalt molybdate nanosheet array supercapacitor electrode material based on the three-dimensional graphene foam as claimed in claim 2, wherein: and the washing step in the step (3) is to sequentially wash the mixture for 3 to 5 times by using ethanol and deionized water respectively.
8. The method for preparing the cobalt molybdate nanosheet array supercapacitor electrode material based on the three-dimensional graphene foam as claimed in claim 2, wherein: the argon, the hydrogen and the nitrogen are pure gases.
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