CN109449001B - Hollow molybdenum disulfide-polyaniline sea urchin-shaped composite material and preparation method thereof - Google Patents
Hollow molybdenum disulfide-polyaniline sea urchin-shaped composite material and preparation method thereof Download PDFInfo
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- 229920000767 polyaniline Polymers 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 21
- 239000011733 molybdenum Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000004005 microsphere Substances 0.000 claims abstract description 45
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 42
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 40
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 32
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- 238000001354 calcination Methods 0.000 claims abstract description 14
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000015393 sodium molybdate Nutrition 0.000 claims abstract description 8
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 8
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 4
- 239000013078 crystal Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 26
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 238000001291 vacuum drying Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000005457 ice water Substances 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
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- 239000002244 precipitate Substances 0.000 claims description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229910052573 porcelain Inorganic materials 0.000 claims description 6
- 239000000523 sample Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000839 emulsion Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000012488 sample solution Substances 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 5
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- 239000004640 Melamine resin Substances 0.000 abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 4
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- 150000002500 ions Chemical class 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000003990 capacitor Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
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- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 229910052961 molybdenite Inorganic materials 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
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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
- H01G11/22—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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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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
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Abstract
The invention discloses a hollow molybdenum disulfide-polyaniline sea urchin-shaped composite material and a preparation method thereof, wherein the particle size of the hollow molybdenum disulfide-polyaniline microspheres is 1-3 mu m, and the specific surface area is 66m2And/g, mainly consisting of flaky molybdenum disulfide and rodlike polyaniline which expose {100} and {110} crystal faces. The preparation method comprises the steps of firstly, taking melamine resin as a template, taking sodium molybdate and thiourea as a molybdenum source and a sulfur source respectively, synthesizing molybdenum disulfide microspheres by a hydrothermal method, calcining for further treatment to obtain hollow microspheres consisting of a large amount of flaky molybdenum disulfide, uniformly mixing the prepared hollow molybdenum disulfide microspheres with an aniline solution, and carrying out oxidative polymerization on aniline to obtain the sea urchin-shaped molybdenum disulfide-polyaniline composite material. The hollow structure can increase the specific surface area of the composite material, improve the transmission rate of ions in the charge-discharge process, and ensure that the composite material can keep higher capacitance during charge-discharge under high current density.
Description
Technical Field
The invention belongs to the technical field of molybdenum disulfide-polyaniline electrode materials, and relates to preparation of a hollow molybdenum disulfide/polyaniline sea urchin-shaped microsphere composite material with a large specific surface area and a good appearance, which can be used as an electrode material of a super capacitor.
Background
Because of the increasing shortage of petroleum resources and the increasing pollution of the exhaust gas of internal combustion engines burning petroleum to the environment, the search for new safe and environment-friendly energy sources to replace fossil energy is a necessary trend in social development. More and more researchers are invested in researching novel energy devices for replacing internal combustion engines, and application research and development of hybrid power, fuel cells and chemical battery products are carried out, and certain effect is achieved. However, since the inherent critical weaknesses of short service life, poor temperature characteristics, environmental pollution caused by chemical batteries, complex system, high cost, etc. of these new energy devices have not been solved, the wide-range production and use of these new energy devices has not been realized. The super capacitor can be used for partially or completely replacing the traditional chemical battery for a traction power supply and a starting energy source of a vehicle, and has wider application range than the traditional chemical battery. Because of this, research and development of supercapacitors is being carried out without much effort in countries around the world, particularly in western developed countries. With the development of green electric automobiles, the research on the super capacitor also enters a brand new period.
There are many methods for improving the electrochemical performance of electrode materials, and performing material compounding and increasing the specific surface area of the material are undoubtedly the most common means. In 2015, Fan successfully prepared flower-like MoS by using simple hydrothermal method2a/C nanosphere. Flower-shaped MoS2The specific capacitance of the/C nanospheres reached 201.4F/g at a current density of 0.2A/g, indicating layered MoS2Has natural advantages in the application of the super capacitor. In 2015, Ren used three-dimensional (3D) tubular molybdenum disulfide (MoS)2) As an active material and framework in electrochemical reactions to provide more avenues for insertion and extraction of ions, by in situ oxidative polymerization of aniline monomers and 3D tubular MoS with varying amounts of PANI2the/PANI mixed material is prepared, and the PANI nanowire array with the diameter of 10-20nm can be controllably grown on the 3D tubular MoS2On the outer surface and on the inner surface. MoS obtained when the amount of PANI supported was 60%2the/PANI-60 hybrid electrode not only exhibited a high capacitance of 552F/g at a current density of 0.5A/g, but also had a capacity retention of 82% at current densities from 0.5 to 30A/g.
Disclosure of Invention
The invention aims to increase the specific surface area of a composite material so as to improve the electrochemical performance of the composite material, and provides a green, simple and convenient synthetic hollow-structure molybdenum disulfide microsphere on the surface of which polyaniline is generated by oxidative polymerization.
The technical purpose of the invention is realized by the following technical scheme:
the hollow molybdenum disulfide-polyaniline sea urchin-shaped composite material is characterized in that the composite material is hollow sea urchin-shaped microspheres and is micro-sizedThe particle diameter of the spheres is 1-3 mu m, and the specific surface area is 66m2And/g, mainly consisting of flaky molybdenum disulfide and rodlike polyaniline which expose {100} and {110} crystal faces.
The preparation method of the hollow molybdenum disulfide-polyaniline sea urchin-shaped composite material comprises the following steps:
(1) adding melamine and formaldehyde into water, performing ultrasound at room temperature for at least 1h, and stirring for at least 1h to form a solution A, wherein the molar ratio of the melamine to the formaldehyde is ensured to be 1: 12;
(2) adding sodium molybdate and thiourea into water, performing ultrasonic treatment for at least 1h at room temperature, and stirring for at least 1h to form a solution B, wherein the molar ratio of the sodium molybdate to the thiourea is ensured to be 1: 2;
(3) dropwise adding the solution B into the solution A under stirring at room temperature, and continuously stirring for 1-3 h after the dropwise adding is finished to obtain a white emulsion C;
(4) transferring the emulsion C into a 50ml reaction kettle, and heating at 180-200 ℃ for at least 24 h; cooling to room temperature, centrifuging, taking out the precipitate, washing the precipitate to be neutral by using ethanol and deionized water, and performing vacuum drying at the temperature of 60-80 ℃ to obtain a sample, namely molybdenum disulfide microspheres;
(5) dispersing the sample obtained in the step (4) into a porcelain boat, placing the porcelain boat into a tube furnace, calcining the porcelain boat for 5 hours at 800 ℃ under the protection of inert gas, wherein the heating rate is 5-10 ℃/min, and cooling to obtain hollow molybdenum disulfide microspheres;
(6) adding the hollow molybdenum disulfide microspheres obtained in the step (5) and ammonium persulfate into 0.5M H2SO4Performing ultrasonic treatment for at least 20min, and stirring for at least 30min to obtain a solution D; taking a proper amount of aniline solution, dropwise adding the aniline solution into the solution D under the stirring of an ice water bath, and stirring for 12 hours in the ice water bath to ensure that the molar ratio of ammonium persulfate to aniline is 1: 1; ensuring that the mass ratio of the hollow molybdenum disulfide microspheres to the aniline is 1: 1-4;
(7) centrifuging the sample solution obtained in the step (6), taking out a precipitate, washing the precipitate to be neutral by using ethanol and deionized water, and carrying out vacuum drying at the temperature of 60-80 ℃; the obtained sample is hollow molybdenum disulfide-polyaniline microspheres.
Further, in the step (5), the inert gas is one of nitrogen and argon, so that the spherical structure is maintained during the calcination.
The hollow molybdenum disulfide-polyaniline microsphere composite material prepared by the invention has the advantages of simple preparation, large specific surface area, excellent electrochemical cycle performance and the like. The melamine resin generation temperature is the same as the molybdenum disulfide generation temperature, so that the problem caused by different reaction temperatures can be avoided by using the melamine resin as a template, the melamine resin can be removed through calcination to obtain hollow molybdenum disulfide microspheres consisting of flaky molybdenum disulfide with stable structures, and the hollow molybdenum disulfide-polyaniline microsphere composite material can be prepared through oxidative polymerization of aniline at room temperature. The hollow spherical structure can provide more ways for the transmission of ions, and the molybdenum disulfide and polyaniline are compounded to fully play the synergistic effect of the molybdenum disulfide and the polyaniline, so that the electrochemical performance of the composite material is greatly improved.
Drawings
FIG. 1 is a scanning electron micrograph of a product of example 2 of the present invention; (a, d), (b, e) and (c, f) respectively correspond to the molybdenum disulfide microspheres before calcination, the molybdenum disulfide microspheres after calcination and the molybdenum disulfide-polyaniline microspheres.
FIG. 2 is a transmission electron micrograph of the product of example 2 of the present invention, wherein (a), (b), and (c) to (f) correspond to the calcined molybdenum disulfide microspheres and molybdenum disulfide-polyaniline microspheres, respectively.
FIG. 3 is a graph of IR spectrum measurements of the product of example 2 of the present invention.
FIG. 4 is an X-ray diffraction pattern of the product of example 2 of the present invention.
FIG. 5 is an X-ray photoelectron spectrum of the product of example 2 of the present invention.
FIG. 6 is a graph of the electrochemical performance of the product of example 2 of the present invention.
Detailed Description
The present invention is further illustrated by the following specific examples and figures, it should be noted that the following description is intended to illustrate the invention and not to limit the content thereof.
Example 1
(1) 0.6821g of melamine and 1.95g of formaldehyde (about 2.4ml), 0.58g of sodium molybdate and 0.36g of thiourea were dissolved in 20ml of deionized water respectively and subjected to ultrasonic treatment for 1 hour and stirred for 1 hour to form a solution A, B.
(2) Dropwise adding the solution B into the solution A under stirring at room temperature, continuing stirring for 3h after the dropwise addition is finished, transferring into a 50ml reaction kettle, and heating for 24h at 180 ℃. Cooling to room temperature, respectively washing with ethanol and deionized water by centrifugation, vacuum drying at 60 ℃, calcining for 5h at 800 ℃ in a tubular furnace under the protection of nitrogen, and heating at the rate of 5 ℃/min to obtain the hollow molybdenum disulfide microspheres.
(3) 0.05g of hollow molybdenum disulfide microspheres and 0.1225g of ammonium persulfate were added to 40ml of 0.5M H2SO4And (3) performing ultrasonic treatment for 20min, dropwise adding 0.05g of aniline solution under the stirring of an ice water bath, continuously stirring the mixture for 12h in the ice water bath, centrifuging, washing the mixture by using ethanol and deionized water respectively, and performing vacuum drying at the temperature of 60 ℃ to obtain the hollow molybdenum disulfide-polyaniline microsphere composite material.
(4) Mixing 8mg of the prepared composite material, 1mg of conductive carbon black and 1mg of PVDF uniformly in a mortar, coating the mixture on the treated foamed nickel, performing vacuum drying at 60 ℃, tabletting to prepare an electrode, and using 1M H2SO4The electrochemical performance of the prepared electrode is measured by taking the Ag/AgCl electrode as a reference electrode and the Pt electrode as a contrast electrode. The maximum capacitance of the electrode prepared by the composite material is 283F/g when the sweep speed is 5mV/s through cyclic voltammetry.
Example 2
(1) 0.6821g of melamine, 1.95g of formaldehyde (about 2.4ml), 0.58g of sodium molybdate and 0.36g of thiourea are respectively dissolved in 20ml of deionized water and are subjected to ultrasonic treatment for 1 hour and stirred for 1 hour to form a solution A, B.
(2) Dropwise adding the solution B into the solution A under stirring at room temperature, continuing stirring for 3h after the dropwise addition is finished, transferring into a 50ml reaction kettle, and heating for 24h at 180 ℃. Cooling to room temperature, respectively washing with ethanol and deionized water by centrifugation, vacuum drying at 60 ℃, calcining for 5h at 800 ℃ in a tubular furnace under the protection of nitrogen, and heating at the rate of 5 ℃/min to obtain the hollow molybdenum disulfide microspheres. The morphology of the molybdenum disulfide microspheres before and after calcination is shown in FIGS. 1(a, d) and (b, e), and the internal structure thereof is shown in FIGS. 2(a, b). As can be seen from the figure, the product after the hydrothermal reaction is microspherical molybdenum disulfide, and is converted into hollow molybdenum disulfide microspheres after calcination, the particle size of the microspheres is about 2 μm, the lattice spacing is 0.496nm, and the microspheres have good crystallinity.
(3) 0.05g of hollow molybdenum disulfide microspheres and 0.245g of ammonium persulfate were added to 40ml of 0.5M H2SO4And (3) performing ultrasonic treatment for 20min, dropwise adding 0.1g of aniline solution under the stirring of an ice water bath, continuously stirring the mixture for 12h in the ice water bath, centrifuging, washing the mixture by using ethanol and deionized water respectively, and performing vacuum drying at the temperature of 60 ℃ to obtain the hollow molybdenum disulfide-polyaniline microsphere composite material. The morphology and internal structure are shown in FIGS. 1(c, f) and 2 (c-f), respectively. The hollow molybdenum disulfide is subjected to the oxidative polymerization of aniline to successfully synthesize the hollow molybdenum disulfide-polyaniline sea urchin-shaped microsphere composite material. FIG. 3 is an infrared spectrum test chart of the obtained product, and it can be known that polyaniline is successfully loaded on molybdenum disulfide microspheres. Fig. 4 is an X-ray diffraction pattern of the product obtained in this example, which shows that the product after hydrothermal reaction and calcination treatment is molybdenum disulfide, and polyaniline is successfully supported on molybdenum disulfide microspheres. Fig. 5 is an X-ray photoelectron spectrum of the product obtained in this example, which shows that polyaniline exists on the molybdenum disulfide microspheres, and further confirms the successful preparation of the hollow molybdenum disulfide-polyaniline microsphere composite material.
(4) Mixing 8mg of the prepared composite material, 1mg of conductive carbon black and 1mg of PVDF uniformly in a mortar, coating the mixture on the treated foamed nickel, performing vacuum drying at 60 ℃, tabletting to prepare an electrode, and using 1M H2SO4The electrochemical performance of the prepared electrode is measured by taking the Ag/AgCl electrode as a reference electrode and the Pt electrode as a contrast electrode. FIG. 6 is a graph of electrochemical properties of the product obtained in this example, wherein a shows that the redox peak gradually increases with the sweep rate increased from 5mV/s to 100mV/s, indicating that the composite material has good rate capability, and b shows that the charge-discharge time gradually decreases with the current density increased from 0.8A/g to 20A/g. The maximum capacitance of the capacitor is 364F/g at a sweep rate of 5mV/s by cyclic voltammetry test. The retention rate of the cyclic capacitance of the material is up to 85 percent after 8000 cycles of charging and discharging, and the material shows good electrochemical performance.
Example 3
(1) 0.6821g of melamine, 1.95g of formaldehyde (about 2.4ml), 0.58g of sodium molybdate and 0.36g of thiourea are respectively dissolved in 20ml of deionized water and are subjected to ultrasonic treatment for 1 hour and stirred for 1 hour to form a solution A, B.
(2) Dropwise adding the solution B into the solution A under stirring at room temperature, continuing stirring for 3h after the dropwise addition is finished, transferring into a 50ml reaction kettle, and heating for 24h at 180 ℃. Cooling to room temperature, respectively washing with ethanol and deionized water by centrifugation, vacuum drying at 60 ℃, calcining for 5h at 800 ℃ in a tubular furnace under the protection of nitrogen, and heating at the rate of 5 ℃/min to obtain the hollow molybdenum disulfide microspheres.
(3) 0.05g of hollow molybdenum disulfide microspheres and 0.49g of ammonium persulfate were added to 40ml of 0.5M H2SO4And (3) performing ultrasonic treatment for 20min, dropwise adding 0.2g of aniline solution under the stirring of an ice water bath, continuously stirring the mixture for 12h in the ice water bath, centrifuging, washing the mixture by using ethanol and deionized water respectively, and performing vacuum drying at the temperature of 60 ℃ to obtain the hollow molybdenum disulfide-polyaniline microsphere composite material.
(4) Mixing 8mg of the prepared composite material, 1mg of conductive carbon black and 1mg of PVDF uniformly in a mortar, coating the mixture on the treated foamed nickel, performing vacuum drying at 60 ℃, tabletting to prepare an electrode, and using 1M H2SO4The electrochemical performance of the prepared electrode is measured by taking the Ag/AgCl electrode as a reference electrode and the Pt electrode as a contrast electrode. The maximum capacitance of the electrode prepared by the composite material is 295F/g when the sweep speed is 5mV/s through cyclic voltammetry.
Claims (2)
1. The preparation method of the hollow molybdenum disulfide-polyaniline sea urchin-shaped composite material is characterized by comprising the following steps:
(1) adding melamine and formaldehyde into water, performing ultrasound at room temperature for at least 1h, and stirring for at least 1h to form a solution A, wherein the molar ratio of the melamine to the formaldehyde is ensured to be 1: 12;
(2) adding sodium molybdate and thiourea into water, performing ultrasonic treatment for at least 1h at room temperature, and stirring for at least 1h to form a solution B, wherein the molar ratio of the sodium molybdate to the thiourea is ensured to be 1: 2;
(3) dropwise adding the solution B into the solution A under stirring at room temperature, and continuously stirring for 1-3 h after the dropwise adding is finished to obtain a white emulsion C;
(4) transferring the emulsion C into a 50ml reaction kettle, and heating at 180-200 ℃ for at least 24 h; cooling to room temperature, centrifuging, taking out the precipitate, washing the precipitate to be neutral by using ethanol and deionized water, and performing vacuum drying at the temperature of 60-80 ℃ to obtain a sample, namely molybdenum disulfide microspheres;
(5) dispersing the sample obtained in the step (4) into a porcelain boat, placing the porcelain boat into a tube furnace, calcining the porcelain boat for 5 hours at 800 ℃ under the protection of inert gas, wherein the heating rate is 5-10 ℃/min, and cooling to obtain hollow molybdenum disulfide microspheres;
(6) adding the hollow molybdenum disulfide microspheres obtained in the step (5) and ammonium persulfate into 0.5M H2SO4Performing ultrasonic treatment for at least 20min, and stirring for at least 30min to obtain a solution D; taking a proper amount of aniline solution, dropwise adding the aniline solution into the solution D under the stirring of an ice water bath, and stirring for 12 hours in the ice water bath to ensure that the molar ratio of ammonium persulfate to aniline is 1: 1; ensuring that the mass ratio of the hollow molybdenum disulfide microspheres to the aniline is 1: 1-4;
(7) centrifuging the sample solution obtained in the step (6), taking out a precipitate, washing the precipitate to be neutral by using ethanol and deionized water, and carrying out vacuum drying at the temperature of 60-80 ℃; the obtained sample is hollow molybdenum disulfide-polyaniline microspheres; the composite material is a hollow sea urchin-shaped microsphere, the particle size of the microsphere is 1-3 mu m, and the specific surface area is 66m2And/g, mainly consisting of flaky molybdenum disulfide and rodlike polyaniline which expose {100} and {110} crystal faces.
2. The method of claim 1, wherein in the step (5), the inert gas is one of nitrogen or argon so that the spherical structure is maintained during the calcination.
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