CN114551906A - Three-dimensional nitrogen-doped graphene/molybdenum disulfide zinc-air battery material with long cycle life and preparation method thereof - Google Patents

Three-dimensional nitrogen-doped graphene/molybdenum disulfide zinc-air battery material with long cycle life and preparation method thereof Download PDF

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CN114551906A
CN114551906A CN202111668383.6A CN202111668383A CN114551906A CN 114551906 A CN114551906 A CN 114551906A CN 202111668383 A CN202111668383 A CN 202111668383A CN 114551906 A CN114551906 A CN 114551906A
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gas
nitrogen
room temperature
molybdenum disulfide
solution
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杨观华
欧阳林辉
李翼宏
王旭
***
王红强
李庆余
蔡业政
郑锋华
潘齐常
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Guangxi Normal University
Guangxi University of Science and Technology
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Guangxi Normal University
Guangxi University of Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention discloses a three-dimensional nitrogen-doped graphene/molybdenum disulfide zinc-air battery material with long cycle life and a preparation method thereof. In the composite material, graphene oxide is firstly prepared, then the graphene/molybdenum disulfide composite material is generated through hydrothermal reaction, and finally nitrogen doping is carried out at high temperature in the atmosphere of ammonia gas to form the three-dimensional nitrogen-doped graphene/molybdenum disulfide composite material. The flaky molybdenum disulfide and the flaky graphene in the composite material are mutually crossed and interleaved to form a three-dimensional network structure. The composite material has wide application prospect in the field of zinc-air batteries as a novel energy material.

Description

Three-dimensional nitrogen-doped graphene/molybdenum disulfide zinc-air battery material with long cycle life and preparation method thereof
[ technical field ] A
The invention relates to the technical field of metal-air batteries, in particular to a three-dimensional nitrogen-doped graphene/molybdenum disulfide zinc-air battery air catalytic material with long cycle life and a preparation method thereof.
[ background of the invention ]
In the current society, under the background of dual crisis of environmental pollution and traditional energy exhaustion, governments of various countries increase the investment in developing new energy in various forms. In order to make better use of new energy, the technology has been rapidly developed as a battery for energy conversion equipment. The zinc-air battery has the advantages of high energy density, environmental friendliness, high safety, low cost and the like, and is taken as a novel environment-friendly energy source and is favored by researchers. Although the zinc-air battery has many advantages, it has many obstacles in practical use, such as the zinc-air battery generating a high overpotential due to slow chemical kinetics during the discharge process. In order to reduce overpotential, researchers often use noble metals to raise the oxidation-reduction potential, such as Pt-based materials to raise the reduction potential, and Ru, Ir substrates to raise the oxygen evolution potential, however, these noble metals are scarce and not economically feasible, and are difficult to be applied in large-scale commercial applications. To overcome this obstacle, researchers have made great efforts to find new non-noble metal catalysts with high catalytic activity, aiming at achieving the green energy landscape as soon as possible.
The graphene has high specific surface area and high conductivity, and has wide application prospects in the fields of energy and catalysis. In addition, molybdenum disulfide is a typical transition metal sulfide, and has a two-dimensional structure similar to graphene, a high specific surface area, unique physical and chemical stability and an electronic structure.
[ summary of the invention ]
The invention aims to: in order to solve the problems, the three-dimensional nitrogen-doped graphene/molybdenum disulfide composite material is prepared by carrying out hydrothermal method and nitrogen doping treatment on graphene and sodium molybdate or ammonium molybdate, the embedding of the bent molybdenum disulfide in the composite material promotes the adsorption or activation of the graphene oxide nanosheets on oxygen molecules, and provides mechanical strength for the formation of the layered structure of the graphene oxide nanosheets, so that the electron or mass transmission is accelerated, and the electrocatalysis process is facilitated.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a three-dimensional nitrogen-doped graphene/molybdenum disulfide zinc-air battery material with long cycle life comprises the following steps:
1) measuring a certain amount of graphene oxide solution, adding the graphene oxide solution into certain distilled water, ethanol or a mixed solution of water and ethanol, and stirring or carrying out ultrasonic treatment at room temperature for a certain time to obtain a graphene oxide dispersion solution;
2) adding a certain amount of Cetyl Trimethyl Ammonium Bromide (CTAB) or Tetradecyl Trimethyl Ammonium Bromide (TTAB) or octadecyl trimethyl ammonium bromide (STAB) into the graphene oxide dispersion solution, and magnetically stirring or mechanically stirring at room temperature for a certain time to obtain a mixed solution I;
3) adding a certain amount of sodium molybdate or ammonium molybdate and L-cysteine or thiourea into the mixed solution I, and magnetically stirring or mechanically stirring for a certain time at room temperature to obtain a mixed solution II;
4) transferring the mixed solution II into a hydrothermal reaction kettle, and reacting for a certain time at a certain temperature;
5) after the reaction is finished, filtering the mixture for 3 to 10 times or centrifugally washing the mixture for 3 to 10 times by using ethanol, acetone, water or a mixed solution of two or three of the ethanol, the acetone and the water until the mixture is clean, and drying the mixture to obtain powder;
6) placing the dried powder in a tubular furnace, carrying out heat treatment in the atmosphere of nitrogen or argon or a first mixed gas of nitrogen and argon at a certain gas flow rate, and then cooling to room temperature in a programmed cooling mode to obtain a primary product;
7) placing the primary product in a second mixed gas, carrying out nitrogen doping on the composite material under certain gas flow, temperature and doping time, taking the furnace tube out of the tubular furnace, naturally cooling to room temperature, and collecting the obtained calcined product to obtain the three-dimensional nitrogen-doped graphene/molybdenum disulfide composite material;
the second mixed gas is a mixed gas of ammonia gas and hydrogen gas, or a mixed gas of ammonia gas and nitrogen gas, or a mixed gas of ammonia gas and argon gas.
Further, the volume of the graphene oxide solution is 1-20 mL, and the mass concentration is 5-20 mg/mL; the dosage of the distilled water, the ethanol or the mixed solution of the water and the ethanol is 30-100 mL, and the stirring or the ultrasonic treatment is carried out for a certain time of 10-120 min at room temperature.
Further, in step 2), the amount of Cetyl Trimethyl Ammonium Bromide (CTAB), Tetradecyl Trimethyl Ammonium Bromide (TTAB), or octadecyl trimethyl ammonium bromide (STAB) is 0.1 to 5g, and the time for magnetic stirring or mechanical stirring at room temperature is 6 to 48 hours.
Further, in the step 3), the amount of the sodium molybdate or the ammonium molybdate is 0.1 to 2.5g, the amount of the L-cysteine or the thiourea is 0.25 to 7.5g, and the magnetic stirring or mechanical stirring time at room temperature is 0.5 to 6 hours.
Further explaining, in the step 4), carrying out a hydrothermal reaction process in a hydrothermal reaction kettle, and reacting for 6-48 h at the temperature of 120-240 ℃.
Further explaining, in the step 6), the gas flow of the nitrogen or the argon or the mixed gas of the nitrogen and the argon is 50-400 mL/min; the argon in the mixed gas of the argon and the nitrogen accounts for 1 to 50 percent of the total volume; the heat treatment is as follows: heating from room temperature to 800-1050 ℃ at the heating rate of 1-20 ℃/min, and then carrying out heat preservation and calcination for 0.5-5 h; the procedure cooling process is that the temperature is reduced from 800-1050 ℃ to 25 ℃ at a cooling rate of 1-20 ℃/min.
Further, in step 7), ammonia gas accounts for 1% -30% of the total volume of the mixed gas of ammonia gas and hydrogen gas; ammonia gas in the mixed gas of ammonia gas and nitrogen gas accounts for 1-30% of the total volume; ammonia gas in the mixed gas of ammonia gas and argon gas accounts for 1% -30% of the total volume; the gas flow is 50-200 mL/min, the temperature of nitrogen doping is increased from room temperature to 750-1050 ℃ at the temperature increasing rate of 1-30 ℃/min, and the time of nitrogen doping is 5-90 min.
The invention also provides a three-dimensional nitrogen-doped graphene/molybdenum disulfide long-cycle-life zinc-air battery material which is prepared by adopting the preparation method of the three-dimensional nitrogen-doped graphene/molybdenum disulfide long-cycle-life zinc-air battery material as claimed in any one of claims 1-7.
Further, the zinc-air battery material has 150mW cm-2And the cell remained stable after 100 hours of charge-discharge cycling.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
according to the invention, graphene and molybdenum disulfide are subjected to a hydrothermal method and nitrogen doping treatment to prepare the three-dimensional nitrogen-doped graphene/molybdenum disulfide composite material, molybdenum disulfide and graphene in the composite material are subjected to interpenetrating and staggered to form a three-dimensional network structure, and the embedding of the bent molybdenum disulfide promotes the adsorption or activation of the graphene oxide nanosheets on oxygen molecules and provides mechanical strength for the formation of the layered structure of the graphene oxide nanosheets, so that the electron or mass transmission is accelerated, and the electrocatalysis process is facilitated. The composite material has wide application prospect in the field of zinc-air batteries as a novel energy material.
[ description of the drawings ]
Fig. 1 is a structural representation of a three-dimensional nitrogen-doped graphene/molybdenum disulfide composite material. FIG. A is an XRD (X-ray diffraction) diagram of a three-dimensional nitrogen-doped graphene/molybdenum disulfide composite material prepared by different mass ratios of sodium molybdate and graphene oxide; FIG. B is an XPS plot of three-dimensional nitrogen-doped graphene/molybdenum disulfide composites prepared with different mass ratios of sodium molybdate to graphene oxide; figure C is a raman plot of three-dimensional nitrogen-doped graphene/molybdenum disulfide composites prepared with different mass ratios of sodium molybdate to graphene oxide; fig. D, E and F are respectively peak-partial fitting graphs of molybdenum element, sulfur element, and nitrogen element in the three-dimensional nitrogen-doped graphene/molybdenum disulfide composite material (10: 1).
Fig. 2 is an SEM photograph of the three-dimensional nitrogen-doped graphene/molybdenum disulfide composite material of the present invention. The mass ratio of the sodium molybdate to the graphene oxide is as follows: FIG. A (7.5:1), FIG. B (10:1), FIG. C (12.5:1) and FIG. D (15: 1).
Fig. 3 is a cyclic voltammetry curve of the three-dimensional nitrogen-doped graphene/molybdenum disulfide composite material under nitrogen and oxygen. The mass ratio of the sodium molybdate to the graphene oxide is as follows: FIG. A (7.5:1), FIG. B (10:1), FIG. C (12.5:1) and FIG. D (15: 1).
Fig. 4 shows the electrochemical performance of the three-dimensional nitrogen-doped graphene/molybdenum disulfide composite material of the present invention. FIG. A: linear scanning voltammetry curves of the three-dimensional nitrogen-doped graphene/molybdenum disulfide composite material; and B: hydrogen peroxide content and electron transfer number of the three-dimensional nitrogen-doped graphene/molybdenum disulfide composite material; and (C) figure: the discharge curve and the power density of the three-dimensional nitrogen-doped graphene/molybdenum disulfide composite material; FIG. D: a charge-discharge curve of the three-dimensional nitrogen-doped graphene/molybdenum disulfide composite material (10: 1); FIG. E: linear sweep voltammetry curves of three-dimensional nitrogen-doped graphene/molybdenum disulfide composite materials (10:1) prepared at different heat treatment temperatures.
[ detailed description ] embodiments
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, embodiments accompanying figures are described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather should be construed as broadly as the present invention is capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Example 1:
3mL of 20mg/mL graphene oxide solution is weighed and placed in a beaker with the volume of 100mL, distilled water is added to the beaker to reach the volume of 80mL, and the volume is ultrasonically treated for 10 min. 0.87g of cetyltrimethylammonium bromide was weighed out and added to the above graphene oxide solution, and stirred at room temperature for 12 hours. Then 0.6g of sodium molybdate and 1.5g L-cysteine were added to the solution and stirring was continued at room temperature for 2 h. Then the solution is transferred to a hydrothermal reaction kettle and reacted for 24 hours at 200 ℃. After the reaction was complete, it was cooled to room temperature, washed repeatedly with distilled water and the black solid was filtered to neutrality. The black solid was dried at a temperature of 80 ℃ in a vacuum environment. The dried black solid was then placed in a quartz tube furnace. Introducing argon as a protective gas, wherein the gas flow is 100mL/min, heating from room temperature to 800 ℃ at the heating rate of 10 ℃/min, preserving heat for 2h, and then cooling from 800 ℃ to 25 ℃ at the cooling rate of 10 ℃/min to obtain a primary product. Weighing 100mg of initial product, carrying out nitrogen doping in a mixed gas of ammonia gas and argon gas (the ammonia gas accounts for 10% of the total volume), wherein the flow rate of the mixed gas is 50mL/min, heating the temperature of the tubular furnace from room temperature to 800 ℃ at the heating rate of 10 ℃/min, pushing the initial product to the central position of the furnace, keeping the temperature at 800 ℃ for 20min, taking the furnace tube out of the tubular furnace, naturally cooling to room temperature, and collecting the obtained calcined product for later use.
Example 2:
3mL of 20mg/mL graphene oxide solution is weighed and placed in a beaker with the volume of 100mL, distilled water is added to the beaker to reach the constant volume of 80mL, and the mixture is subjected to ultrasonic treatment for 10 min. 0.87g of cetyltrimethylammonium bromide was weighed out and added to the above graphene oxide solution, and stirred at room temperature for 12 hours. Then 0.45g of sodium molybdate and 1.5g L-cysteine were added to the solution and stirring was continued at room temperature for 2 h. Then the solution is transferred to a hydrothermal reaction kettle and reacted for 24 hours at 200 ℃. After the reaction was complete, it was cooled to room temperature, washed repeatedly with distilled water and the black solid was filtered to neutrality. The black solid was dried at a temperature of 80 ℃ in a vacuum environment. The dried black solid was then placed in a quartz tube furnace. Introducing argon as a protective gas, wherein the gas flow is 100mL/min, heating from room temperature to 800 ℃ at the heating rate of 20 ℃/min, preserving heat for 2h, and then cooling from 800 ℃ to 25 ℃ at the cooling rate of 20 ℃/min to obtain a primary product. Weighing 100mg of primary product, carrying out nitrogen doping in a mixed gas of ammonia gas and argon gas (the ammonia gas accounts for 20% of the total volume), wherein the flow rate of the mixed gas is 50mL/min, raising the temperature of the tubular furnace from room temperature to 800 ℃ at a heating rate of 10 ℃/min, pushing the primary product to the central position of the furnace, keeping the temperature at 800 ℃ for 20min, taking the furnace tube out of the tubular furnace, naturally cooling to room temperature, and collecting the obtained calcined product for later use.
Example 3:
3mL of 20mg/mL graphene oxide solution is weighed and placed in a beaker with the volume of 100mL, distilled water is added to the beaker to reach the constant volume of 80mL, and the mixture is subjected to ultrasonic treatment for 10 min. 0.87g of cetyltrimethylammonium bromide was weighed out and added to the above graphene oxide solution, and stirred at room temperature for 12 hours. Then 0.75g of sodium molybdate and 1.5g L-cysteine were added to the solution and stirring was continued at room temperature for 2 h. Then the solution is transferred to a hydrothermal reaction kettle and reacted for 24 hours at 200 ℃. After the reaction was complete, it was cooled to room temperature, washed repeatedly with distilled water and the black solid was filtered to neutrality. The black solid was dried at a temperature of 80 ℃ in a vacuum environment. The dried black solid was then placed in a quartz tube furnace. Introducing argon as a protective gas, wherein the gas flow is 100mL/min, heating from room temperature to 800 ℃ at the heating rate of 20 ℃/min, preserving heat for 2h, and then cooling from 800 ℃ to 25 ℃ at the cooling rate of 20 ℃/min to obtain a primary product. Weighing 100mg of initial product, carrying out nitrogen doping in a mixed gas of ammonia gas and argon gas (the ammonia gas accounts for 30% of the total volume), wherein the flow rate of the mixed gas is 100mL/min, raising the temperature of the tubular furnace from room temperature to 800 ℃ at the temperature raising rate of 5 ℃/min, pushing the initial product to the central position of the furnace, keeping the temperature at 800 ℃ for 20min, taking the furnace tube out of the tubular furnace, naturally cooling to the room temperature, and collecting the obtained calcined product for later use.
Example 4
3mL of 20mg/mL graphene oxide solution is weighed and placed in a beaker with the volume of 100mL, distilled water is added to the beaker to reach the constant volume of 80mL, and the mixture is subjected to ultrasonic treatment for 10 min. 0.87g of cetyltrimethylammonium bromide was weighed out and added to the above graphene oxide solution, and stirred at room temperature for 12 hours. Then 0.6g of sodium molybdate and 1.5g L-cysteine were added to the solution and stirring was continued at room temperature for 2 h. Then the solution is transferred to a hydrothermal reaction kettle and reacted for 24 hours at 200 ℃. After the reaction was complete, it was cooled to room temperature, washed repeatedly with distilled water and the black solid was filtered to neutrality. The black solid was dried at a temperature of 80 ℃ in a vacuum environment. The dried black solid was then placed in a quartz tube furnace. Introducing argon as a protective gas, wherein the gas flow is 100mL/min, heating from room temperature to 800 ℃ at the heating rate of 20 ℃/min, preserving heat for 2h, and then cooling from 800 ℃ to 25 ℃ at the cooling rate of 20 ℃/min to obtain a primary product. Weighing 100mg of initial product, carrying out nitrogen doping in a mixed gas of ammonia gas and nitrogen gas (the ammonia gas accounts for 15% of the total volume), wherein the flow rate of the mixed gas is 100mL/min, raising the temperature of the tubular furnace from room temperature to 950 ℃ at the temperature raising rate of 1 ℃/min, pushing the initial product to the central position of the furnace, keeping the temperature at 950 ℃ for 20min, taking the furnace tube out of the tubular furnace, naturally cooling to the room temperature, and collecting the obtained calcined product for later use.
Example 5:
3mL of 20mg/mL graphene oxide solution is weighed and placed in a beaker with the volume of 100mL, distilled water is added to the beaker to reach the constant volume of 80mL, and the mixture is subjected to ultrasonic treatment for 10 min. 0.87g of cetyltrimethylammonium bromide was weighed out and added to the above graphene oxide solution, and stirred at room temperature for 12 hours. Then 0.6g of sodium molybdate and 1.5g L-cysteine were added to the solution and stirring was continued at room temperature for 2 h. Then the solution is transferred to a hydrothermal reaction kettle and reacted for 24 hours at 200 ℃. After the reaction was complete, it was cooled to room temperature, washed repeatedly with distilled water and the black solid was filtered to neutrality. The black solid was dried at a temperature of 80 ℃ in a vacuum environment. The dried black solid was then placed in a quartz tube furnace. Introducing argon as a protective gas, wherein the gas flow is 100mL/min, heating from room temperature to 800 ℃ at the heating rate of 20 ℃/min, preserving heat for 2h, and then cooling from 800 ℃ to 25 ℃ at the cooling rate of 20 ℃/min to obtain a primary product. Weighing 100mg of the initial product, carrying out nitrogen doping in a mixed gas of ammonia gas and nitrogen gas (the ammonia gas accounts for 30% of the total volume), wherein the flow rate of the mixed gas is 200mL/min, raising the temperature of the tubular furnace from room temperature to 1000 ℃ at a heating rate of 10 ℃/min, pushing the initial product to the central position of the furnace, keeping the temperature at 1000 ℃ for 20min, taking the furnace tube out of the tubular furnace, naturally cooling to room temperature, and collecting the obtained calcined product for later use.
Example 6:
3mL of 20mg/mL graphene oxide solution is weighed and placed in a beaker with the volume of 100mL, distilled water is added to the beaker to reach the constant volume of 80mL, and the mixture is subjected to ultrasonic treatment for 10 min. 0.87g of cetyltrimethylammonium bromide was weighed out and added to the above graphene oxide solution, and stirred at room temperature for 12 hours. Then 0.6g of sodium molybdate and 1.5g L-cysteine were added to the solution and stirring was continued at room temperature for 2 h. Then the solution is transferred to a hydrothermal reaction kettle and reacted for 24 hours at 200 ℃. After the reaction was complete, cool to room temperature, repeatedly wash with distilled water and filter the black solid to neutral. The black solid was dried at a temperature of 80 ℃ in a vacuum environment. The dried black solid was then placed in a quartz tube furnace. Introducing argon as a protective gas, wherein the gas flow is 100mL/min, heating from room temperature to 800 ℃ at the heating rate of 20 ℃/min, preserving heat for 2h, and then cooling from 800 ℃ to 25 ℃ at the cooling rate of 20 ℃/min to obtain a primary product. Weighing 100mg of the initial product, carrying out nitrogen doping in a mixed gas of ammonia gas and nitrogen gas (the ammonia gas accounts for 5% of the total volume), wherein the flow rate of the mixed gas is 200mL/min, raising the temperature of the tubular furnace from room temperature to 1000 ℃ at a heating rate of 10 ℃/min, pushing the initial product to the central position of the furnace, keeping the temperature at 1000 ℃ for 20min, taking the furnace tube out of the tubular furnace, naturally cooling to room temperature, and collecting the obtained calcined product for later use.
Example 7:
weighing 1mL of 10mg/mL graphene oxide solution, placing the graphene oxide solution in a beaker with the volume of 100mL, adding ethanol to fix the volume to 90mL, and carrying out ultrasonic treatment for 100 min. 0.1g of cetyltrimethylammonium bromide was weighed into the above graphene oxide solution, and stirred at room temperature for 6 hours. Then 0.15g ammonium molybdate and 0.25g thiourea were added to the solution and stirring was continued at room temperature for 0.5 h. Then the solution is transferred to a hydrothermal reaction kettle and reacted for 6h at 120 ℃. After the reaction was complete, it was cooled to room temperature, washed repeatedly with distilled water and the black solid was filtered to neutrality. The black solid was dried at a temperature of 80 ℃ in a vacuum environment. The dried black solid was then placed in a quartz tube furnace. Introducing a mixed gas of nitrogen and argon (argon accounts for 30% of the total volume) as a protective gas, wherein the gas flow is 50mL/min, heating from room temperature to 1050 ℃ at the heating rate of 10 ℃/min, preserving heat for 0.5h, and then cooling from 800 ℃ to 25 ℃ at the cooling rate of 10 ℃/min to obtain a primary product. Weighing 100mg of initial product, carrying out nitrogen doping in a mixed gas of ammonia gas and hydrogen gas (the ammonia gas accounts for 20% of the total volume), wherein the flow rate of the mixed gas is 200mL/min, raising the temperature of the tubular furnace from room temperature to 1050 ℃ at the temperature raising rate of 30 ℃/min, pushing the initial product to the central position of the furnace, keeping the temperature at 1050 ℃ for 5min, taking the furnace tube out of the tubular furnace, naturally cooling to room temperature, and collecting the obtained calcined product for later use.
Example 8:
2mL of 5mg/mL graphene oxide solution is weighed and placed in a beaker with the volume of 100mL, the mixed solution of water and ethanol is added to the beaker to reach the constant volume of 90mL, and the mixture is stirred at room temperature for 120 min. 5g of hexadecyltrimethylammonium bromide was weighed, added to the graphene oxide solution, and magnetically stirred at room temperature for 6 hours. Then 1.25g ammonium molybdate and 7.5g thiourea were added to the solution and magnetic stirring was continued at room temperature for 6 h. The solution was then transferred to a hydrothermal reaction kettle and reacted at 240 ℃ for 48 h. After the reaction was complete, it was cooled to room temperature, washed repeatedly with distilled water and the black solid was filtered to neutrality. The black solid was dried at a temperature of 80 ℃ in a vacuum environment. The dried black solid was then placed in a quartz tube furnace. Introducing nitrogen as a protective gas, wherein the gas flow is 400mL/min, heating from room temperature to 1000 ℃ at the heating rate of 1 ℃/min, preserving heat for 5h, and then naturally cooling to room temperature to obtain a primary product. Weighing 100mg of the initial product, carrying out nitrogen doping in a mixed gas of ammonia gas and hydrogen gas (the ammonia gas accounts for 30% of the total volume), wherein the flow rate of the mixed gas is 200mL/min, raising the temperature of the tubular furnace from room temperature to 750 ℃ at the temperature raising rate of 30 ℃/min, pushing the initial product to the central position of the furnace, keeping the temperature at 750 ℃ for 90min, taking the furnace tube out of the tubular furnace, naturally cooling to the room temperature, and collecting the obtained calcined product for later use.
In experiments, the applicant has made studies: as shown in fig. 1: as can be derived from the structural characterization in fig. 1, the high temperature ammonia heat treatment enables doping with nitrogen elements, and the contained element content of each sample is shown in table 1.
TABLE 1
Figure BDA0003452253260000071
Table 1 shows the mass percentages of the elements of the three-dimensional nitrogen-doped graphene/molybdenum disulfide composite material prepared by using different mass ratios of sodium molybdate and graphene oxide. The result shows that the high-temperature heat treatment can effectively dope nitrogen elements on the graphene/molybdenum disulfide composite material.
As can be seen from fig. 2, the three-dimensional nitrogen-doped graphene/molybdenum disulfide composite material has a three-dimensional network structure and has a "corrugated" structure similar to graphene.
As can be seen from fig. 3, the mass ratio of sodium molybdate to graphene oxide is 10:1 composite material, which has a higher oxygen reduction potential of about 0.72V, compared to other composite materials.
As seen in fig. 4, diagram a: linear scanning voltammetry curves of the three-dimensional nitrogen-doped graphene/molybdenum disulfide composite material; and B: hydrogen peroxide content and electron transfer number of the three-dimensional nitrogen-doped graphene/molybdenum disulfide composite material; and (C) in a drawing: the discharge curve and the power density of the three-dimensional nitrogen-doped graphene/molybdenum disulfide composite material; FIG. D: a charge-discharge curve of the three-dimensional nitrogen-doped graphene/molybdenum disulfide composite material (10: 1); FIG. E: linear sweep voltammetry curves of three-dimensional nitrogen-doped graphene/molybdenum disulfide composite materials (10:1) prepared at different heat treatment temperatures. The result shows that the composite material with the mass ratio of sodium molybdate to graphene oxide being 10:1 shows higher power density and better cycle stability. Most preferably, the composite material with the mass ratio of sodium molybdate to graphene oxide of 10:1 is used for the zinc-air battery and has the performance of 150mWcm-2And the cell remained stable over 100 hours of charge-discharge cycling.
The above examples merely represent some embodiments of the present invention and are described in more detail and detail but are not to be construed as limiting the scope of the invention. It should be noted that it is possible for a person skilled in the art to make several variations and modifications without departing from the inventive concept, which fall within the scope of protection of the invention. Therefore, the protection scope of the present invention should be subject to the appended claims.

Claims (9)

1. A preparation method of a three-dimensional nitrogen-doped graphene/molybdenum disulfide zinc-air battery material with long cycle life is characterized by comprising the following steps: the method comprises the following steps:
1) measuring a certain amount of graphene oxide solution, adding the graphene oxide solution into certain distilled water, ethanol or a mixed solution of water and ethanol, and stirring or carrying out ultrasonic treatment at room temperature for a certain time to obtain a graphene oxide dispersion solution;
2) adding a certain amount of Cetyl Trimethyl Ammonium Bromide (CTAB) or Tetradecyl Trimethyl Ammonium Bromide (TTAB) or octadecyl trimethyl ammonium bromide (STAB) into the graphene oxide dispersion solution, and magnetically stirring or mechanically stirring at room temperature for a certain time to obtain a mixed solution I;
3) adding a certain amount of sodium molybdate or ammonium molybdate and L-cysteine or thiourea into the mixed solution I, and magnetically stirring or mechanically stirring for a certain time at room temperature to obtain a mixed solution II;
4) transferring the mixed solution II into a hydrothermal reaction kettle, and reacting for a certain time at a certain temperature;
5) after the reaction is finished, repeatedly filtering for 3-10 times or centrifugally washing for 3-10 times by using ethanol, acetone, water or a mixed solution of two or three of the ethanol, the acetone and the water until the solution is clean, and drying to obtain powder;
6) placing the dried powder in a tubular furnace, carrying out heat treatment in the atmosphere of nitrogen or argon or a first mixed gas of nitrogen and argon at a certain gas flow rate, and then cooling to room temperature in a programmed cooling mode to obtain a primary product;
wherein, the first mixed gas is a mixed gas of argon and nitrogen, and the argon accounts for 1-50% of the total volume.
7) Placing the primary product in a second mixed gas, carrying out nitrogen doping on the composite material under certain gas flow, temperature and doping time, taking the furnace tube out of the tubular furnace, naturally cooling to room temperature, and collecting the obtained calcined product to obtain the three-dimensional nitrogen-doped graphene/molybdenum disulfide composite material;
the second mixed gas is a mixed gas of ammonia gas and hydrogen gas, or a mixed gas of ammonia gas and nitrogen gas, or a mixed gas of ammonia gas and argon gas.
2. The method of claim 1, wherein: in the step 1), the volume of the graphene oxide solution is 1-20 mL, and the mass concentration is 5-20 mg/mL; the dosage of the distilled water, the ethanol or the mixed solution of the water and the ethanol is 30-100 mL, and the stirring or the ultrasonic treatment is carried out for a certain time of 10-120 min at room temperature.
3. The production method according to claim 1, characterized in that: in step 2), the amount of Cetyl Trimethyl Ammonium Bromide (CTAB), Tetradecyl Trimethyl Ammonium Bromide (TTAB) or octadecyl trimethyl ammonium bromide (STAB) is 0.1-5 g, and the time of magnetic stirring or mechanical stirring at room temperature is 6-48 h.
4. The method of claim 1, wherein: in the step 3), the amount of the sodium molybdate or the ammonium molybdate is 0.1-2.5 g, the amount of the L-cysteine or the thiourea is 0.25-7.5 g, and the magnetic stirring or mechanical stirring time at room temperature is 0.5-6 h.
5. The production method according to claim 1, characterized in that: and 4) carrying out a hydrothermal reaction process in the hydrothermal reaction kettle, and reacting for 6-48 h at the temperature of 120-240 ℃.
6. The method of claim 1, wherein: in the step 6), the gas flow of nitrogen or argon or the mixed gas of nitrogen and argon is 50-400 mL/min; the heat treatment is as follows: heating from room temperature to 800-1050 ℃ at a heating rate of 1-20 ℃/min, and then carrying out heat preservation and calcination for 0.5-5 h; the procedure cooling mode is characterized in that the temperature is reduced from 800-1050 ℃ to 25 ℃ at a cooling rate of 1-20 ℃/min.
7. The method of claim 1, wherein: in step 7), ammonia gas accounts for 1% -30% of the total volume of the mixed gas of ammonia gas and hydrogen gas; ammonia gas in the mixed gas of ammonia gas and nitrogen gas accounts for 1-30% of the total volume; ammonia gas in the mixed gas of ammonia gas and argon gas accounts for 1% -30% of the total volume; the gas flow is 50-200 mL/min, the temperature of nitrogen doping is increased from room temperature to 750-1050 ℃ at the temperature increasing rate of 1-30 ℃/min, and the time of nitrogen doping is 5-90 min.
8. A three-dimensional nitrogen-doped graphene/molybdenum disulfide long-cycle-life zinc-air battery material is characterized by being prepared by the preparation method of the three-dimensional nitrogen-doped graphene/molybdenum disulfide long-cycle-life zinc-air battery material according to any one of claims 1 to 7.
9. The zinc air cell material of claim 8, wherein the zinc air cell material has 150mW cm-2And the cell remained stable after 100 hours of charge-discharge cycling.
CN202111668383.6A 2021-12-31 2021-12-31 Three-dimensional nitrogen-doped graphene/molybdenum disulfide zinc-air battery material with long cycle life and preparation method thereof Pending CN114551906A (en)

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