CN110697794B - Cobalt sulfide/g-C with two-dimensional hollow nanosheet structure3N4Composite electrode material and preparation method thereof - Google Patents

Cobalt sulfide/g-C with two-dimensional hollow nanosheet structure3N4Composite electrode material and preparation method thereof Download PDF

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CN110697794B
CN110697794B CN201911110962.1A CN201911110962A CN110697794B CN 110697794 B CN110697794 B CN 110697794B CN 201911110962 A CN201911110962 A CN 201911110962A CN 110697794 B CN110697794 B CN 110697794B
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cobalt sulfide
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CN110697794A (en
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陶凯
李伟伟
韩磊
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Ningbo University
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    • C01G51/00—Compounds of cobalt
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    • C01B21/0605—Binary compounds of nitrogen with carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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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    • 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 OR LIGHT-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 provides cobalt sulfide/g-C with a two-dimensional hollow nanosheet structure3N4A composite electrode material and a preparation method thereof. The invention provides cobalt sulfide/g-C with a two-dimensional hollow nanosheet structure3N4The preparation method of (1). In particular to the formula g-C3N4Adding into a mixture containing cobalt salt and C4H6N2And a solvent by reacting cobalt ions with C4H6N2Reaction at g-C3N4Growing in situ to form a two-dimensional nanosheet precursor, adding a sulfur source, and performing hydrothermal reaction to obtain cobalt sulfide/g-C with a two-dimensional hollow nanosheet structure3N4A composite electrode material. The material of the invention has simple preparation process, low cost and no pollution. The composite electrode material can increase the contact area between the electrolyte solution and the electrode material, shorten the ion transmission path, accelerate the ion transmission rate and increase the conductivity. As an electrode material of a super capacitor, the material has excellent specific capacitance and cycling stability.

Description

Cobalt sulfide/g-C with two-dimensional hollow nanosheet structure3N4Composite electrode material and preparation method thereof
Technical Field
The invention relates to the technical field of supercapacitors and nanomaterials, in particular to cobalt sulfide/g-C with a two-dimensional hollow nanosheet structure3N4A composite electrode material and a preparation method thereof.
Background
Electrochemical supercapacitors are a source of electrical energy between conventional capacitors and batteries. The energy storage mechanism is divided into two types, namely an electric double layer capacitor and a Faraday pseudocapacitor. The charging device has the excellent characteristics of short charging time, high power density, good cycle stability, long service life, environmental friendliness, no pollution and the like, and is widely applied to the fields of communication, electronic products, new energy automobiles and the like. The super capacitor is an energy storage device, is a green technology combining energy and environmental protection, can provide sustainable energy when in application, and can also play the effect of environmental protection, so that the super capacitor is widely concerned in recent years.
Cobalt sulfide as an electrode material of a super capacitor, belonging to the field ofThe Faraday pseudo capacitor electrode material has the characteristics of multiple valence states, high theoretical capacity and the like. But its application is limited by the disadvantages of slow electrochemical reaction rate, poor conductivity and poor cycling stability. The invention relates to cobalt sulfide/g-C with a two-dimensional hollow nanosheet structure3N4The composite electrode material has the following advantages: firstly, introducing g-C with good conductivity3N4The resistance can be greatly reduced, and the conductivity of the electrode material is enhanced; the hollow nanosheet structure can avoid agglomeration of electrode materials, increase the contact area of the electrode materials and an electrolyte solution, shorten an ion transmission path, improve the electron transfer rate and further improve the specific capacitance. III, cobalt sulfide hollow nanosheet and g-C3N4And the cycling stability of the electrode material can be greatly improved through interaction.
Disclosure of Invention
The invention aims to provide cobalt sulfide/g-C with a two-dimensional hollow nanosheet structure3N4A composite electrode material and a preparation method thereof. The preparation method provided by the invention is simple, and the prepared electrode material has excellent electrochemical performance, stable performance and high repeatability.
The invention provides cobalt sulfide/g-C with a two-dimensional hollow nanosheet structure3N4The preparation method of the composite electrode material is implemented by the following technical scheme:
(1) putting a certain amount of one or more of melamine, thiourea and urea into a tube furnace, and calcining in a nitrogen atmosphere to obtain g-C3N4；
(2) g-C obtained by calcination3N4Mixing with solvent, ultrasonic dispersing, and adding C4H6N2Continuing to perform ultrasonic treatment to obtain a uniform solution;
(3) adding a proper amount of solvent into a certain amount of cobalt salt to form a uniform solution;
(4) mixing the two uniform solutions obtained in the steps (2) and (3), stirring, standing for a period of time, centrifuging, washing and drying to obtain cobalt sulfide/g-C with a two-dimensional hollow nanosheet structure3N4A precursor of the composite electrode material;
(5) putting the composite electrode material precursor obtained in the step (4) into a solution containing a sulfur source, and carrying out hydrothermal reaction to obtain cobalt sulfide/g-C with a two-dimensional hollow nanosheet structure3N4A composite electrode material.
Preferably, the cobalt salt and C in the step (4)4H6N2The mass ratio of the solvent is 1 to (0.5-7.5) to (40-510).
Preferably, the cobalt salt in step (3) comprises one or more of cobalt acetate, cobalt chloride, cobalt nitrate and cobalt sulfate.
Preferably, the stirring speed in the step (4) is 200-500 rpm, and the stirring time is 0.5-2 h; the standing time is 1-24 h.
Preferably, the sulfur source in step (5) comprises one or more of thioacetamide, sodium sulfide and thiourea.
Preferably, the concentration of the sulfur source in the step (5) is 2-10 g/L.
Preferably, the temperature of the hydrothermal reaction in the step (5) is 90-180 ℃, and the time of the hydrothermal reaction is 2-12 h.
Preferably, the centrifugal speed in the step (5) is 5000-9000 rpm, and the centrifugal time is 5-15 min; the drying temperature is 60-100 ℃, and the drying time is 8-24 h
Preferably, g-C in the composite electrode material3N4The mass ratio of the cobalt sulfide to the cobalt sulfide is 1: 15-45.
Preferably, the cobalt sulfide is in a two-dimensional hollow nanosheet structure, and the thickness of the cobalt sulfide is 250-300 nm.
The two-dimensional hollow cobalt sulfide nanosheet prepared by the preparation scheme provided by the invention is prepared from cobalt ions and C4H6N2The formed metal organic framework material is used as a template, and the metal organic framework material and a sulfur source are reacted to form the cobalt sulfide two-dimensional hollow nanosheet with good electrochemical performance.
The invention provides cobalt sulfide/g-C for preparing a two-dimensional hollow nanosheet structure3N4The preparation method of the composite electrode material is simple and needs raw materialsThe cost of the material is low. The whole preparation process comprises the preparation and conversion of the precursor, the time consumption is short, the structure of the obtained material is complete, the obtained material has strong stability and large surface area, and therefore, the material is suitable for being used as an electrode material of a super capacitor. Compared with a pure cobalt sulfide nanosheet, the composite electrode material has more excellent electrochemical performance, higher specific capacitance and circulation stability, and good application prospect.
The electrode material of the super capacitor provided by the invention shows good Faraday pseudo-capacitance performance in a 3M KOH electrolyte solution, the hollow sheet structure increases the contact area between the electrolyte solution and the electrode material, the ion transmission path is shortened, the ion transmission rate is accelerated, and the capacitance performance is improved; introduction of g-C with good conductivity3N4The resistance can be obviously reduced, and the conductivity can be improved; cobalt sulfide hollow nanosheet and g-C3N4And the cycling stability of the electrode material can be greatly improved through interaction. Electrochemical performance tests show that the cobalt sulfide/g-C with the two-dimensional hollow nanosheet structure3N4The composite material used as a super capacitor electrode material shows a good oxidation reduction peak, and has a high-efficiency charge and discharge process, excellent specific capacitance performance and good cycle stability. Wherein the specific capacity is up to 921.8Fg-1And the specific capacity retention rate after 5000 times of circulation is about 82.6 percent.
Drawings
FIG. 1a shows cobalt sulfide/g-C with a two-dimensional hollow nanosheet structure prepared in example 1 of the present invention3N4Scanning electron microscope images of the composite electrode material precursor; FIG. 1b shows cobalt sulfide/g-C with a two-dimensional hollow nanosheet structure prepared in example 1 of the present invention3N4Scanning electron microscope images of the composite electrode material;
FIG. 2 shows cobalt sulfide/g-C with a two-dimensional hollow nanosheet structure prepared in example 1 of the present invention3N4FIG. 2a is a plot of cyclic voltammograms at different sweep rates, FIG. 2b is a plot of chronoamperometry at different current densities, FIG. 2c is a plot of specific capacitance performance, and FIG. 2d is a plot of cyclic voltammograms at different current densities, and FIG. 2d is a plot of specific capacitance performanceAn impedance plot;
FIG. 3a is a scanning electron microscope image of a cobalt sulfide hollow nanosheet electrode material precursor prepared in a comparative example; FIG. 3b is a scanning electron microscope image of a cobalt sulfide hollow nanosheet electrode material prepared in a comparative example;
Detailed Description
The preparation process according to the invention is further illustrated below with reference to specific examples:
the invention provides cobalt sulfide/g-C with a two-dimensional hollow nanosheet structure3N4The preparation method of the composite electrode material comprises the following steps:
(1) calcining one or more of melamine, thiourea and urea in a tube furnace under the nitrogen atmosphere to obtain g-C3N4；
(2) G to C3N4Mixing with solvent, ultrasonic dispersing, and adding C4H6N2Continuing to perform ultrasonic dispersion to obtain a uniform solution;
(3) mixing cobalt salt with a solvent to obtain a uniform solution;
(4) mixing the two uniform solutions obtained in the steps (2) and (3), stirring, standing for a period of time, centrifuging, washing and drying to obtain cobalt sulfide/g-C with a two-dimensional hollow nanosheet structure3N4A precursor of the composite electrode material;
(5) putting the precursor obtained in the step (4) into a solution containing a sulfur source, carrying out hydrothermal reaction, automatically cooling to room temperature after the reaction, centrifuging, washing and drying the product to obtain cobalt sulfide/g-C with a two-dimensional hollow nanosheet structure3N4A composite electrode material.
The invention mixes cobalt salt and C4H6N2And mixing with a solvent to obtain a reaction solution. In the present invention, the cobalt salt, C4H6N2The mass ratio of the solvent is preferably 1: 0.5-7.5: 40-510. More preferably 1: 1.5-4.5: 50-375, most preferably 1: 2.3-3.7: 75-275.
In the present invention, the cobalt salt preferably includes one or more of cobalt acetate, cobalt chloride, cobalt nitrate, and cobalt sulfate. The solvent preferably comprises one or more of deionized water, ethanol, methanol and DMF.
In the invention, the stirring speed is preferably 200-500 rpm; the stirring time is preferably 0.5-2 h; the standing time is preferably 1-24 h; more preferably 2 to 12 hours. Most preferably 4-10 h.
Centrifuging, washing and drying to obtain cobalt sulfide/g-C with a two-dimensional hollow nanosheet structure3N4After the precursor of the electrode material is compounded, the precursor is put into a solution containing a sulfur source for hydrothermal reaction, the temperature is automatically reduced to room temperature after the reaction, and the product is centrifuged, washed and dried to obtain cobalt sulfide/g-C with a two-dimensional hollow nanosheet structure3N4A composite electrode material. In the invention, the sulfur source is preferably one or more of thioacetamide, sodium sulfide and thiourea; the concentration of the sulfur source is preferably 2-10 g/L, and more preferably 4.5-8 g/L; the hydrothermal reaction temperature is preferably 90-180 ℃, and more preferably 100-150 ℃; the time of the hydrothermal reaction is preferably 2-12 h, and more preferably 4-8 h.
The invention also provides cobalt sulfide/g-C with a two-dimensional hollow nanosheet structure, which is prepared by the preparation method in the technical scheme3N4A composite electrode material comprising g-C3N4And cobalt sulfide, g-C3N4The mass ratio of the cobalt sulfide to the cobalt sulfide is preferably 1: 15-45, and more preferably 1: 20-30; the cobalt sulfide is of a two-dimensional hollow nanosheet structure, and the thickness of the cobalt sulfide is preferably 250-300 nm.
The cobalt sulfide/g-C with the two-dimensional hollow nanosheet structure prepared by the preparation method provided by the invention3N4The composite electrode material has excellent specific capacitance performance and good cycle stability when being used as a super capacitor electrode material. Wherein the specific capacity is up to 921.8Fg-1And the specific capacity retention rate after 5000 times of circulation is about 82.6 percent.
To further illustrate the present invention, the following examples are given to illustrate cobalt sulfide/g-C of two-dimensional hollow nanosheet structure provided by the present invention3N4Composite electrode material and composite electrode materialThe preparation methods are described in detail, but they should not be construed as limiting the scope of the present invention.
Example 1:
7g of melamine were placed in a tube furnace under nitrogen atmosphere at 10 ℃ min-1The temperature rising rate is increased to 600 ℃ and calcined for 2 hours to obtain g-C3N4. Taking 10mg g-C3N4Sonicating in 40ml water for 1h, adding 1.31g C4H6N2Continuing the ultrasonic treatment for 1h, and taking 0.58g of Co (NO)3)2·6H2Dissolving O in 40ml of water; mixing the above two solutions, wherein cobalt salt and C4H6N2The mass ratio of water is as follows: 1: 2.26: 138. Stirring for 5min at the stirring speed of 450rpm, standing for 4h at 25 ℃, then centrifuging for 4min at the rotation speed of 7000rpm, respectively centrifuging and washing with deionized water and absolute ethyl alcohol for three times, drying the obtained product in a drying oven at 60 ℃ for 24h, and obtaining a precursor of the composite electrode material, wherein a scanning electron microscope picture of the precursor is shown in figure 1 a.
Adding the precursor obtained in the step into an ethanol solution containing 3g/L thioacetamide, adding the reaction solution into a polytetrafluoroethylene reaction kettle lining, reacting for 4h in a 120 ℃ drying oven, centrifuging for 4min at the rotating speed of 7000rpm, washing with water and ethanol for three times respectively, and then drying for 12h in a 65 ℃ vacuum drying oven to obtain cobalt sulfide/g-C with a two-dimensional hollow nanosheet structure3N4A composite electrode material.
The scanning electron microscope image of the composite material prepared by the embodiment is shown in FIG. 1b, and the two-dimensional hollow nano cobalt sulfide nanosheet grows in g-C closely3N4The above. The composite electrode material prepared in this example was subjected to electrochemical performance testing. The electrochemical performance is tested in a 3M KOH electrolyte solution, and a three-electrode system is formed by taking saturated calomel as a reference electrode, a Pt wire as a counter electrode and a composite electrode material as a working electrode. FIG. 2a shows the cyclic voltammogram of the material under different scanning speeds, and the closed cyclic voltammogram has a distinct redox peak, which indicates that the material belongs to a pseudocapacitive electrode material. FIG. 2b shows the charge and discharge of the material at different current densitiesThe specific capacitance value at different current densities was calculated from the specific capacitance calculation formula C ═ I Δ t)/(m Δ V by combining the charge-discharge curve graphs, as shown in fig. 2C, at 0.5Ag-1The specific capacitance value is as high as 921.8Fg-1Left and right. After 5000 cycles, the specific capacitance retention rate was 82.6%. Fig. 2d shows the ac impedance spectrum of the electrode material, from which it can be seen that the composite material has a lower charge transfer resistance.
Example 2:
7g of melamine were placed in a tube furnace under nitrogen atmosphere at 10 ℃ min-1The temperature rising rate is increased to 500 ℃ and calcined for 4 hours to obtain g-C3N4. 20mg of g-C are taken3N4Ultrasonically dispersing in 40mL of methanol for 0.5h, and taking 1.31g C4H6N2Adding into the above solution, continuing to perform ultrasonic treatment for 1h, and dissolving 0.35g of cobalt acetate in 40mL of methanol; mixing the above two solutions, wherein cobalt salt and C4H6N2The mass ratio of the solvent is as follows: 1: 3.7: 180.6. Stirring for 30min at the stirring speed of 250rpm, standing for 24h at 25 ℃, centrifuging for 5min at 8000rpm, washing with deionized water and methanol for three times respectively, and drying the obtained product in a drying oven at 60 ℃ for 24h to obtain the precursor of the composite electrode material.
Adding the precursor obtained in the step into an ethanol solution containing 4g/L sodium sulfide, adding the reaction solution into a polytetrafluoroethylene reaction kettle lining, placing the polytetrafluoroethylene reaction kettle lining in a drying oven at 100 ℃ for reaction for 5h, centrifuging at 8000rpm for 5min, washing with water and ethanol for three times respectively, and then placing the polytetrafluoroethylene reaction kettle lining in a vacuum drying oven at 70 ℃ for drying for 12h to obtain cobalt sulfide/g-C with a two-dimensional hollow nanosheet structure3N4A composite electrode material.
The test conditions of the composite electrode material prepared in this example are the same as those of example 1, and the experimental result shows that the current density is 0.5Ag-1The specific capacitance value is 781.5Fg-1After 5000 cycles, the specific capacity retention rate was 79.8%.
Example 3:
7g of thiourea was taken out at 10 ℃ for min under a nitrogen atmosphere-1The temperature rising rate is increased to 550 ℃ and calcined for 4 hours to obtainTo g-C3N4. 20mg of g-C are taken3N4Ultrasonically dispersing in 40mL deionized water for 0.5h, and taking 0.66g C4H6N2Dissolving in the above solution, and continuing to perform ultrasonic treatment for 0.5 h. Dissolving 0.26g of cobalt chloride in 40mL of deionized water; mixing the above two solutions, wherein cobalt salt and C4H6N2The mass ratio of the solvent is as follows: 1: 2.5: 308. Stirring for 5min at the stirring speed of 280rpm, standing for 4h at room temperature, centrifuging for 8min at 7000rpm, washing with water and absolute ethanol for three times, drying the obtained product in a drying oven at 60 ℃ for 24h to obtain cobalt sulfide/g-C with a two-dimensional hollow nanosheet structure3N4A precursor of the composite electrode material.
Putting the precursor prepared in the step into an aqueous solution containing 8g/L thiourea, adding the solution into a liner of a polytetrafluoroethylene reaction kettle, reacting for 6h in a drying oven at 120 ℃, centrifuging at 8000rpm, respectively centrifuging and washing with water and ethanol for three times, and then putting the solution into a vacuum drying oven at 65 ℃ for drying for 24h to obtain cobalt sulfide/g-C with a two-dimensional hollow nanosheet structure3N4A composite electrode material.
The test conditions of the composite electrode material prepared in this example are the same as those of example 1, and the experimental result shows that the current density is 0.5Ag-1The specific capacitance value is 842.2Fg-1After 5000 cycles, the specific capacity retention rate was 81.3%.
Example 4:
7g of melamine are taken and placed in a tube furnace at 10 ℃ for min under the nitrogen atmosphere-1The temperature rising rate is increased to 550 ℃ and calcination is carried out for 2 hours to obtain g-C3N4. Taking 10mg g-C3N4Ultrasonically dispersing in 35mL of methanol for 1h, and taking 0.47g C4H6N2Dissolving in the above solution, and continuing ultrasonic dispersion for 1 h. Another 0.12g CoCl was taken2·6H2Dissolving O in 35mL of methanol, and mixing the two solutions, wherein the cobalt salt and C4H6N2The mass ratio of the solvent is as follows: 1: 3.9: 461. Stirring at 350rpm for 0.5h, standing at room temperature for 24h, centrifuging at 7000rpm, washing with deionized water and ethanol three timesThen placing the mixture in a vacuum drying oven at 65 ℃ for drying for 12h to obtain cobalt sulfide/g-C with a two-dimensional hollow nanosheet structure3N4A precursor of the composite electrode material.
Putting the precursor prepared in the above step into a container containing 3g/L Na2Adding the solution into an ethanol solution of S, reacting in an oven at 120 ℃ for 8h, centrifuging at 7500rpm, washing with water and ethanol for three times, and drying in a vacuum drying oven at 80 ℃ for 24h to obtain cobalt sulfide/g-C with a two-dimensional hollow nanosheet structure3N4A composite electrode material.
The test conditions of the composite electrode material prepared in this example are the same as those of example 1, and the experimental result shows that the current density is 0.5Ag-1Specific capacitance value of 798.3Fg-1On the other hand, after 5000 cycles, the specific capacitance retention rate was 76.3%.
Example 5:
7g of melamine were placed in a tube furnace at 5 ℃ for min under nitrogen atmosphere-1The temperature rising rate is increased to 550 ℃ and calcination is carried out for 2 hours to obtain g-C3N4. Taking 30mg g-C3N4Ultrasonically dispersing in 30mL ethanol for 1h, and taking 1.31g C4H6N2Dissolving in the above solution. 0.79g of cobalt sulfate was dissolved in 30mL of ethanol. Mixing the above two solutions, wherein cobalt salt and C4H6N2The mass ratio of the solvent is as follows: 1: 1.7: 60. Stirring for 10min at the stirring speed of 260rpm, standing for 10h at room temperature, centrifuging, washing with deionized water and ethanol for three times, and drying in a vacuum drying oven at 60 ℃ for 20h to obtain cobalt sulfide/g-C with a two-dimensional hollow nanosheet structure3N4A precursor of the composite electrode material.
Putting the precursor prepared in the step into a water solution containing 3.55g/L thioacetamide, adding the solution into a lining of a polytetrafluoroethylene reaction kettle, reacting for 8 hours in a drying oven at 120 ℃, centrifuging, washing with ethanol for three times, and then drying for 20 hours in a vacuum drying oven at 60 ℃ to obtain cobalt sulfide/g-C with a two-dimensional hollow nanosheet structure3N4A composite electrode material.
The test conditions of the composite electrode material prepared in this example are the same as those of example 1, and the experimental result shows that the current density is 0.5Ag-1Specific capacitance value of 883.4Fg-1After 5000 cycles, the specific capacity retention rate was 78.2%.
Comparative example:
0.58g of Co (NO) was taken3)2·6H2O was dissolved in 40mL of water to obtain 1.3g C4H6N2Dissolving in 40mL of water; mixing the above two solutions, wherein cobalt salt and C4H6N2The mass ratio of water is as follows: 1: 2.3: 138. Stirring for 30min at the stirring speed of 300rpm, standing for 4h at 25 ℃ to obtain a precipitate, and centrifuging and washing the precipitate for 3 times by using water to obtain a precursor of the cobalt sulfide hollow nanosheet.
And adding the precursor obtained in the step into an ethanol solution containing 3g/L thioacetamide, adding the reaction solution into a polytetrafluoroethylene reaction kettle lining, reacting for 4 hours in a drying oven at 120 ℃, respectively carrying out centrifugal washing on the obtained precipitate with water and ethanol for three times, and then placing the precipitate in a vacuum drying oven at 65 ℃ for drying for 12 hours to obtain the cobalt sulfide hollow nanosheet.
The scanning electron microscope image of the precursor of the hollow cobalt sulfide nanosheet prepared in the comparative example is shown in fig. 3a, and it can be seen that the precursor is in a scattered nanosheet structure. An electron microscope picture of the vulcanized cobalt sulfide hollow nanosheet is shown in fig. 3b, and a part of the nanosheet is damaged and has an agglomeration phenomenon. Comparison with example 1 shows the results in g-C3N4Is a substrate, and has great benefit on the shape maintenance of materials. In addition, in g-C3N4The substrate can not only keep the appearance, but also be beneficial to improving the conductivity of the material when being used as an electrode material.
The test conditions of the cobalt sulfide hollow nanosheet prepared in the comparative example are the same as those of example 1, and the experimental result shows that the current density is 0.5Ag-1At a specific capacitance of 388.7Fg-1After 5000 cycles, the specific capacity retention rate was 43.2%.

Claims (3)

1. Cobalt sulfide with two-dimensional hollow nanosheet structure/g-C3N4The preparation method of the composite electrode material is characterized by comprising the following steps of:
7g of melamine were placed in a tube furnace under nitrogen atmosphere at 10 ℃ min-1The temperature rising rate is increased to 600 ℃ and calcined for 2 hours to obtain g-C3N4(ii) a Taking 10mg g-C3N4Sonicating in 40ml water for 1h, adding 1.31g C4H6N2Continuing the ultrasonic treatment for 1h, and taking 0.58g of Co (NO)3)2·6H2Dissolving O in 40ml of water; mixing the two solutions, stirring for 5min at the stirring speed of 450rpm, standing for 4h at 25 ℃, then centrifuging for 4min at the rotating speed of 7000rpm, respectively centrifuging and washing for three times by deionized water and absolute ethyl alcohol, and drying the obtained product in a drying oven at 60 ℃ for 24h to obtain a precursor of the composite electrode material;
adding the precursor obtained in the step into an ethanol solution containing 3g/L thioacetamide, adding the reaction solution into a polytetrafluoroethylene reaction kettle lining, reacting for 4h in a 120 ℃ drying oven, centrifuging for 4min at the rotating speed of 7000rpm, washing with water and ethanol for three times respectively, and then drying for 12h in a 65 ℃ vacuum drying oven to obtain cobalt sulfide/g-C with a two-dimensional hollow nanosheet structure3N4A composite electrode material.
2. Cobalt sulfide/g-C with two-dimensional hollow nanosheet structure prepared according to the preparation method of claim 13N4A composite electrode material.
3. Two-dimensional hollow nanosheet structure cobalt sulfide/g-C of claim 23N4Use of a composite electrode material, characterized in that it is applied as a composite electrode material in a supercapacitor.
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