CN111342063A - Manganese dioxide-loaded nitrogen-sulfur double-doped graphene catalyst for oxygen reduction reaction, and preparation method and application thereof - Google Patents
Manganese dioxide-loaded nitrogen-sulfur double-doped graphene catalyst for oxygen reduction reaction, and preparation method and application thereof Download PDFInfo
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- H01M4/00—Electrodes
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- 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
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
Abstract
The invention discloses a manganese dioxide loaded nitrogen-sulfur double-doped graphene catalyst for oxygen reduction reaction, a preparation method and application thereof; the general formula of the catalyst is Mn-C-N/S, wherein hetero atoms N and S are doped to increase graphene defects and disorder degree; loading of various valence state manganese compounds to increase the electrocatalytic activity of the catalyst; when the mass ratio of the N/S co-doped reduced graphene oxide to the manganese chloride tetrahydrate to the potassium permanganate is 1:7.5:5, a clear oxygen reduction reaction peak is observed in-0.52V of the catalyst, and the peak current density is 5.72mA cm‑2Has the best oxygen reduction activity; preparing graphene oxide by adopting a Hummers modification method, and preparing a manganese dioxide-loaded nitrogen-sulfur double-doped graphene catalyst by adopting a two-step hydrothermal method; the reaction conditions of the invention are mildAnd the process flow is simple and convenient, the reaction process is easy to control, and a highly feasible way is provided for reducing the cost of the fuel cell and realizing commercialization.
Description
Technical Field
The invention relates to the technical field of fuel cell catalysis, in particular to a manganese dioxide loaded nitrogen-sulfur double-doped graphene catalyst for Oxygen Reduction Reaction (ORR), a preparation method and application.
Background
Fuel cells are one of new energy technologies, and are devices for converting chemical energy into electrical energy through chemical reactions. The method is not limited by Carnot cycle, chemical energy can be directly converted into electric energy through the reaction of catalytic fuel and oxygen, the energy efficiency is up to 70%, and most of products are water, so that the environmental damage is extremely low.
The fuel cell shows excellent cell performance and green environmental protection in application, but has many problems in terms of service life, stability and the like, and higher cost is always one of the bottlenecks in commercialization of the fuel cell. The cost of the fuel cell mainly comes from the noble metal catalyst, when the scale production is carried out, the cost of other parts can be greatly reduced, and the price of the platinum catalyst is improved due to the resource limitation. The fuel cell anode catalyst is used at about 10% and the cathode catalyst is used up to 70%. In addition, under the working environment of the fuel cell, the catalyst is very easy to be poisoned and deactivated or surface carbon deposition occurs, which not only shortens the service life of the fuel cell but also increases the cost of the cell. Therefore, it is a hot research issue to reduce the amount of noble metals such as Pt or to design new non-Pt based catalysts, to reduce the cost of fuel cells, and to improve the lifetime and stability.
For fuel cells, electrocatalysts in the fuel cathode play an important role in ensuring electrode performance and energy density. But the reaction kinetics of its oxygen reduction are slow and need to occur at very high overpotentials. Therefore, the key to improving ORR efficiency and reducing overpotential is the search for suitable electrocatalysts. A variety of electrocatalytic materials have been used as cathode catalysts, including noble metal catalysts and alloys thereof, transition metal oxide catalysts, metal macrocycle catalysts, and carbonaceous materials.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention aims to provide a manganese dioxide loaded nitrogen-sulfur double-doped graphene catalyst for Oxygen Reduction Reaction (ORR), a preparation method and application thereof, the catalyst has high activity, a hydrothermal synthesis method which is simple and easy to operate is adopted to prepare the high-activity manganese dioxide loaded nitrogen-sulfur double-doped graphene catalyst, the reaction condition is mild, the process flow is simple and convenient, and the reaction process is easy to control; the prepared manganese dioxide loaded nitrogen-sulfur double-doped graphene catalyst is easy to realize large-scale batch production. The method has great practical value in solving the problem of slow kinetics of the oxygen reduction reaction of the fuel cell and reducing the cost of the fuel cell.
In order to achieve the purpose, the invention adopts the following technical scheme:
a manganese dioxide-loaded nitrogen-sulfur double-doped graphene catalyst for oxygen reduction reaction is prepared by a two-step hydrothermal synthesis method, and has a general formula of Mn-C-N/S, wherein hetero atoms N and S are doped to increase graphene defects and disorder degree; loading of various valence state manganese compounds to increase the electrocatalytic activity of the catalyst; when the mass ratio of the N/S co-doped reduced graphene oxide to the manganese chloride tetrahydrate to the potassium permanganate is 1:7.5:5, a clear oxygen reduction reaction peak is observed in-0.52V of the catalyst, and the peak current density is 5.72mA cm-2And has the best oxygen reduction activity.
The preparation method of the catalyst comprises the following steps:
1) preparing a graphite oxide stock solution by a Hummers modification method; centrifuging, washing and stripping the obtained graphite oxide stock solution by using a centrifuge, taking the upper-layer centrifugate as graphene oxide after the centrifuging, washing and stripping are finished, and calibrating the concentration of the graphene oxide to be 4.4 mg/mL;
2) weighing graphene oxide, pouring clear water on the upper layer of a centrifugate after centrifugation, pouring graphene oxide on the lower part into a beaker, and adding an organic solvent, wherein the mass ratio of the graphene oxide to the organic solvent is 1: 10-20; then slowly adding a reducing agent with the mass 2-10 times that of the graphene oxide into the mixed solution of the graphene oxide and the organic solvent, and continuing ultrasonic treatment to form a uniform graphene oxide mixed solution; then transferring the graphene oxide mixed solution into a hydrothermal reaction kettle, sealing and completing a doping reduction process in a vacuum drying oven; taking out the reaction product after the reduction is finished, cooling, washing and filtering, and recording as N/S codoped reduced graphene oxide;
3) mixing N/S co-doped reduced graphene oxide, manganese chloride tetrahydrate and potassium permanganate according to the ratio of 1: 7.5-10: 5-20 under the condition of continuous stirring, then carrying out ultrasonic treatment on the suspension, pouring the suspension into a hydrothermal reaction kettle, and completing a hydrothermal synthesis reaction in a vacuum drying oven; taking out the reaction kettle after the reaction, naturally cooling to room temperature, and cleaning and filtering the obtained suspension by using ultrapure water; and after finishing, putting the obtained product into a freeze dryer for drying to obtain fluffy manganese dioxide loaded nitrogen-sulfur double-doped graphene catalyst powder.
The centrifugal washing and stripping step in the step 1) comprises the following steps: washing with 20% dilute hydrochloric acid solution to remove residual potassium permanganate in the stock solution; then, repeatedly cleaning with ultrapure water to remove graphite powder which does not participate in the reaction; centrifuging for 10 min/time; the centrifugal rotating speeds are 2000r/min, 6000r/min, 8000r/min, 10000r/min and 4000r/min in sequence.
The mass concentration of the graphene oxide measured in the step 2) is 4.4 mg/mL; centrifuging the graphene oxide for 10-30 min; the organic solvent in the step 2) is N-methylpyrrolidone, N-dimethylformamide or ethylene glycol; the reducing agent in the step 2) is thiourea or dopamine and cysteine;
the ultrasonic treatment time in the step 2) is 1-2 h;
the reaction temperature in the doping reduction process in the step 2) is 80-100 ℃; the reaction time is 12-24 h.
Continuously stirring and mixing the N/S co-doped reduced graphene oxide, the manganese chloride tetrahydrate and the potassium permanganate in the step 3), wherein the stirring time is 0.5-2 h;
the ultrasonic treatment time of the suspension in the step 3) is 1-2 h;
the hydrothermal synthesis reaction time in the step 3) is 2-5 h; the reaction temperature is 120-150 ℃;
the drying temperature in the freeze dryer in the step 3) is-65 ℃; the drying time is 24-48 h.
According to the characterization method of the manganese dioxide loaded nitrogen-sulfur double-doped graphene catalyst for the oxygen reduction reaction, the used material characterization means is SEM, XRD or BET; the performance evaluation method of the used catalyst is a rotating disc test system, a constant current discharge test or a polarization test.
An aluminum air fuel cell, wherein the anode is pure aluminum, the cathode is a manganese dioxide loaded nitrogen-sulfur double-doped graphene air electrode, and the electrolyte is a sodium hydroxide solution added with a corrosion inhibitor; the manganese dioxide-loaded nitrogen-sulfur double-doped graphene air electrode is prepared by mixing and coating a manganese dioxide-loaded nitrogen-sulfur double-doped graphene catalyst, conductive carbon black, a polytetrafluoroethylene binder and N-methylpyrrolidone on the surface of a nickel screen and pressing the mixture by using a hot press.
Adding a manganese dioxide-loaded nitrogen-sulfur double-doped graphene catalyst, conductive carbon black and a polytetrafluoroethylene binder with the mass concentration of 60% in a mass ratio of 3:3.5: 3.5; the amount of the added N-methyl pyrrolidone is 2-5 times of the total mass of the manganese dioxide loaded nitrogen-sulfur double-doped graphene, the conductive carbon black and the polytetrafluoroethylene.
Pressing by using a hot press, wherein the hot pressing temperature is 200-300 ℃; the hot pressing time is 10-30 min.
The concentration of the sodium hydroxide solution is 4 mol/L; the corrosion inhibitor is a composite corrosion inhibitor composed of sodium stannate and casein, wherein the concentration of the sodium stannate is 0.05mol/L, and the concentration of the casein is 0.6 g/L.
Compared with the prior art, the invention has the following advantages:
(1) according to the invention, the manganese dioxide-loaded nitrogen-sulfur double-doped graphene catalyst with ultrahigh activity is synthesized by a two-step hydrothermal method, the material synthesis method is simple, the environment is friendly, and the industrial production is easy to realize.
(2) The manganese dioxide loaded nitrogen-sulfur double-doped graphene catalyst prepared by the invention is proved to have excellent catalytic activity through a series of characterization means and catalyst performance evaluation, and is a high-performance and low-cost catalyst which is very suitable for fuel cells.
(3) The manganese dioxide-loaded nitrogen-sulfur double-doped graphene catalyst material prepared by the invention can be used as a substitute of a noble metal catalyst in the current market, greatly reduces the production and manufacturing cost of a fuel cell, and provides a solution with high feasibility for commercialization of the fuel cell.
Drawings
FIG. 1 is a SEM image of Mn-C-N/S-I prepared in example 1 of the present invention.
FIG. 2 is a SEM image of Mn-C-N/S-II prepared in example 2 of the present invention.
FIG. 3 is an X-ray powder diffraction pattern of Mn-C-N/S-I, Mn-C-N/S-II catalysts prepared in examples 1 and 2 of the present invention.
FIG. 4 is a graph of cyclic voltammograms of Mn-C-N/S-I, Mn-C-N/S-II prepared in examples 1 and 2 of the present invention.
Fig. 5 is a U-Capacity diagram corresponding to different current densities of the aluminum-air battery prepared in example 1 of the present invention.
Detailed Description
The present invention will be described in detail below with reference to the drawings and specific examples, but the present invention is not limited to the following examples.
Example 1
The preparation method of the manganese dioxide loaded nitrogen-sulfur double-doped graphene catalyst comprises the following steps:
the existing Hummers modification method in the prior art is adopted to prepare the graphite oxide stock solution, and the graphene oxide with the mass concentration of 4.4mg/mL is obtained through ultrapure water centrifugal stripping. Weighing 48mL of graphene oxide, centrifuging for 10min by using a centrifuge, pouring clear water on the upper layer of the centrifugate, pouring the graphene oxide on the lower part into a measuring cylinder, adding 50mL of organic solvent N-methylpyrrolidone, weighing 2g of thiourea, uniformly mixing the thiourea with the graphene oxide and the organic solvent, putting the mixture into a hydrothermal reaction kettle, carrying out nitrogen-doped reduction for 24h in a vacuum drying oven at 80 ℃, taking the graphene out of the reaction kettle after the reduction is finished, cooling and washing the graphene, mixing and stirring the N/S co-doped reduced graphene oxide suspension, manganese chloride tetrahydrate and potassium permanganate according to the mass ratio of 1:7.5:5, and continuously stirring for 30min, wherein the corresponding product is marked as Mn-C-N/S-I. Subsequently, the suspension was sonicated for 1h and reacted in a hydrothermal reaction kettle at 140 ℃ for 2 h. And naturally cooling the reaction kettle to room temperature, repeatedly centrifuging and washing the obtained suspension, and drying the obtained product in a freeze dryer for 36 hours to obtain fluffy manganese dioxide loaded nitrogen-sulfur double-doped graphene catalyst powder.
The method for preparing the manganese dioxide loaded nitrogen-sulfur double-doped graphene air electrode comprises the following steps:
weighing 1.5g of Mn-C-N/S catalyst, 1.75g of conductive carbon black and 1.75g of 60% polytetrafluoroethylene, mixing all the substances, adding 10mL of N-methylpyrrolidone to adjust the consistency of the mixture, uniformly mixing the substances, and pressing for 30min at 200 ℃ by using a hot press to prepare the manganese dioxide loaded nitrogen-sulfur double-doped graphene fuel cathode.
The method for preparing the aluminum-air fuel cell comprises the following steps:
the method comprises the steps of adopting a pure aluminum anode, a manganese dioxide loaded nitrogen-sulfur double-doped graphene air electrode as a cathode, adding 0.05mol/L sodium stannate and 0.6g/L casein into an electrolyte, and assembling the electrolyte into the aluminum-air battery.
Example 2
The preparation method of the manganese dioxide loaded nitrogen-sulfur double-doped graphene catalyst comprises the following steps:
the existing Hummers modification method in the prior art is adopted to prepare a graphite oxide precursor, and the graphene oxide with the mass concentration of 4.4mg/mL is obtained through ultrapure water centrifugal stripping. Weighing 48mL of graphene oxide, centrifuging for 10min by using a centrifuge, pouring clear water on the upper layer of the centrifugate, pouring the graphene oxide on the lower part into a measuring cylinder, adding 50mL of organic solvent N-methylpyrrolidone, weighing 2g of thiourea, uniformly mixing the thiourea with the graphene oxide and the organic solvent, putting the mixture into a hydrothermal reaction kettle, carrying out nitrogen-doped reduction for 24h in a vacuum drying oven at 80 ℃, taking the graphene out of the reaction kettle after the reduction is finished, cooling and washing the graphene, mixing and stirring the N/S co-doped reduced graphene oxide suspension, manganese chloride tetrahydrate and potassium permanganate according to the mass ratio of 1:10:20, and continuously stirring for 30min, wherein the corresponding product is marked as Mn-C-N/S-II. Subsequently, the suspension was sonicated for 1h and reacted in a hydrothermal reaction kettle at 140 ℃ for 2 h. And naturally cooling the reaction kettle to room temperature, repeatedly centrifuging and washing the obtained suspension, and drying the obtained product in a freeze dryer for 36 hours to obtain fluffy manganese dioxide loaded nitrogen-sulfur double-doped graphene catalyst powder.
The method for preparing the manganese dioxide loaded nitrogen-sulfur double-doped graphene air electrode comprises the following steps:
weighing 1.5g of Mn-C-N/S catalyst, 1.75g of conductive carbon black and 60% of polytetrafluoroethylene (with the density of 1.75 g), mixing all the substances, adding 20mL of N-methylpyrrolidone to adjust the consistency of the mixture, uniformly mixing the substances, and pressing for 20 min at 250 ℃ by using a hot press to prepare the manganese dioxide-loaded nitrogen-sulfur double-doped graphene fuel cathode.
The method for preparing the aluminum-air fuel cell comprises the following steps:
the method comprises the steps of adopting a pure aluminum anode, a manganese dioxide loaded nitrogen-sulfur double-doped graphene air electrode as a cathode, adding 0.05mol/L sodium stannate and 0.6g/L casein into an electrolyte, and assembling the electrolyte into the aluminum-air battery.
Example 3
The preparation method of the manganese dioxide loaded nitrogen-sulfur double-doped graphene catalyst comprises the following steps:
the existing Hummers modification method in the prior art is adopted to prepare a graphite oxide precursor, and the graphene oxide with the mass concentration of 4.4mg/mL is obtained through ultrapure water centrifugal stripping. Measuring 60mL of graphene oxide, centrifuging for 30min by using a centrifuge, pouring clear water on the upper layer of a centrifugate, pouring the graphene oxide on the lower part into a measuring cylinder, adding 30mL of organic solvent N, N-dimethylformamide, measuring 5mL of dopamine and 5mL of cysteine, uniformly mixing the graphene oxide and the organic solvent, putting the mixture into a hydrothermal reaction kettle, carrying out nitrogen-doped reduction for 12 hours in a vacuum drying oven at 100 ℃, taking the graphene out of the reaction kettle after the reduction is finished, cooling and washing the graphene, mixing and stirring the N/S co-doped reduced graphene oxide suspension, the manganese chloride tetrahydrate and the potassium permanganate according to the mass ratio of 1:7.5:5, and continuously stirring for 1 hour, wherein the corresponding product is marked as Mn-C-N/S-III. Subsequently, the suspension was sonicated for 1h and reacted in a hydrothermal reaction kettle at 120 ℃ for 5 h. And naturally cooling the reaction kettle to room temperature, repeatedly centrifuging and washing the obtained suspension, and drying the obtained product in a freeze dryer for 48 hours to obtain fluffy manganese dioxide loaded nitrogen-sulfur double-doped graphene catalyst powder.
Weighing 1.5g of Mn-C-N/S catalyst, 1.75g of conductive carbon black and 1.75g of 60% polytetrafluoroethylene, mixing all the substances, adding 30mL of N-methylpyrrolidone to adjust the consistency of the mixture, uniformly mixing the substances, pressing for 10min at 300 ℃ by using a hot press, and preparing the manganese dioxide loaded nitrogen-sulfur double-doped graphene air electrode.
The method for preparing the aluminum-air fuel cell comprises the following steps:
the method comprises the steps of adopting a pure aluminum anode, a manganese dioxide loaded nitrogen-sulfur double-doped graphene air electrode as a cathode, adding 0.05mol/L sodium stannate and 0.6g/L casein into an electrolyte, and assembling the electrolyte into the aluminum-air battery.
1. The microstructure of the Mn-C-N/S-I catalyst is measured by a field emission scanning electron microscope:
the manganese dioxide-supported nitrogen-sulfur double-doped graphene catalyst prepared in example 1 was subjected to determination of Mn-C-N/S-I microstructure by field emission scanning electron microscopy (FESEM (Carl Zeiss) SIGMA 500). The test results are shown in fig. 1:
as can be seen from fig. 1, when the N/S co-doped reduced graphene oxide suspension, the manganese chloride tetrahydrate and the potassium permanganate are mixed in a mass ratio of 1:7.5:5, the manganese oxide compound in the composite material Mn-C-N/S-I is uniformly and densely attached to the surface of the graphene sheet having the thin-layer wrinkled structure in a nano-bulk manner.
2. The microstructure of Mn-C-N/S-II is measured by field emission scanning electron microscopy:
the manganese dioxide-supported nitrogen-sulfur double-doped graphene catalyst prepared in example 2 was subjected to determination of Mn-C-N/S-II microstructure by a field emission scanning electron microscope (FESEM (Carl Zeiss) SIGMA 500). The test results are shown in fig. 2:
as can be seen from fig. 2, when the N/S co-doped reduced graphene oxide suspension, the manganese chloride tetrahydrate and the potassium permanganate are mixed in a mass ratio of 1:10:20, the manganese oxide compound in the composite material Mn-C-N/S-II is uniformly and densely attached to the surface of the graphene sheet having the thin-layer wrinkled structure in a nano-bulk manner.
X-ray diffraction test of crystalline phase structure:
x-ray diffraction tests on manganese dioxide supported nitrogen sulfur double doped graphene catalysts Mn-C-N/S-I, Mn-C-N/S-II catalysts prepared in examples 1 and 2 were performed on a temperature-variable X-ray diffractometer SmartLAB SE of japan chef. The X-ray diffraction test results are shown in fig. 3:
from fig. 3, it can be seen that the X-ray diffraction pattern of N/S co-doped reduced graphene oxide, Mn-C-N/S-I, Mn-C-N/S-II, the low and broad (002) diffraction peak detected between 20 ° and 30 ° in the X-ray diffraction pattern of Mn-C-N/S-II confirms the edge disordered stacking of graphene sheets, and the other two peaks at 2 θ ═ 37 ° (211) and 65.7 ° (002) indicate the α -MnO generated on the graphene surface2(JCPDS No. 15-0604); the mixed peak of the Mn-C-N/S-I diffraction pattern at 2 θ ═ 26.0 ° corresponds to the (002) plane of graphite. Peaks at 37 ° and 44.7 ° at 2 θ are clearly shown, confirming the crystal structure of Mn-C-N/S-I, with all diffraction peaks observed being expressed as γ -MnO2(JCPDS No. 02-1070).
4. Rotating disk electrode system test for redox activity:
the manganese dioxide supported nitrogen-sulfur double doped graphene catalysts prepared in examples 1 and 2 were tested in 0.1M KOH at room temperature using a rotating disk test system (PINE) of physchemi corporation, usa, to obtain cyclic voltammetry curves of the catalysts, and the redox activities of the catalysts were obtained, and the cyclic voltammetry curves are shown in fig. 4.
The effect of the ink formulation of the catalyst samples on the electrochemical performance was evaluated by Cyclic Voltammetry (CV). Researches on N/S co-doped reduced graphene oxide and single MnO2Mn-C-N/S-I, Mn-C-N/S-II in O2CV curve in saturated 0.1M KOH to reflect its electrocatalytic activity, as shown in figure 4. As shown in FIG. 4, a clear oxygen reduction reaction peak of the Mn-C-N/S-I catalytic material, reduced graphene oxide co-doped with N/S and pure MnO were observed in-0.52V2Compared with the catalyst, the initial potential and the current density are excellent, and the reduction reaction of Mn-C-N/S to oxygen is provedThe (ORR) should have excellent electrocatalytic activity.
5. Constant current discharge test for aluminum air fuel cell
The constant current discharge curve of the aluminum air fuel cell is measured on a RST 5000F electrochemical workstation by using manganese dioxide supported nitrogen-sulfur double-doped graphene catalyst Mn-C-N/S-I, Mn-C-N/S-II prepared in example 1 and example 2. The test results are shown in fig. 5:
all measurements in this section were performed in ambient air. The electrochemical performance of the aluminum air fuel cell was investigated by recording a constant current discharge curve. The discharge performance of the battery passes 0.1mA cm-2To 5mA cm-2Is characterized by the constant current discharge test of (1). The voltage starts to stabilize at about 1.4V and drops sharply at the end. When the discharge current density is less than 5mAcm-2Very limited specific capacitance, 5mA cm-2The specific capacity is maximum during discharge, and is as high as 1203.2mAh g-1The energy density was 1630.1 mWh g-1The method shows that the aluminum has higher utilization rate and has important significance in practical application.
Claims (10)
1. A manganese dioxide loaded nitrogen-sulfur double-doped graphene catalyst for oxygen reduction reaction is characterized in that: the catalyst is prepared by a two-step hydrothermal synthesis method, the general formula of the catalyst is Mn-C-N/S, and heteroatom N and S are doped to increase graphene defects and disorder degree; loading of various valence state manganese compounds to increase the electrocatalytic activity of the catalyst; when the mass ratio of the N/S co-doped reduced graphene oxide to the manganese chloride tetrahydrate to the potassium permanganate is 1:7.5:5, a clear oxygen reduction reaction peak is observed in-0.52V of the catalyst, and the peak current density is 5.72mA cm-2And has the best oxygen reduction activity.
2. A method for preparing the catalyst of claim 1, wherein: the method comprises the following steps:
1) preparing a graphite oxide stock solution by a Hummers modification method; centrifuging, washing and stripping the obtained graphite oxide stock solution by using a centrifuge, taking the upper-layer centrifugate as graphene oxide after the centrifuging, washing and stripping are finished, and calibrating the concentration of the graphene oxide to be 4.4 mg/mL;
2) weighing graphene oxide, pouring clear water on the upper layer of a centrifugate after centrifugation, pouring graphene oxide on the lower part into a beaker, and adding an organic solvent, wherein the mass ratio of the graphene oxide to the organic solvent is 1: 10-20; then slowly adding a reducing agent with the mass 2-10 times that of the graphene oxide into the mixed solution of the graphene oxide and the organic solvent, and continuing ultrasonic treatment to form a uniform graphene oxide mixed solution; then transferring the graphene oxide mixed solution into a hydrothermal reaction kettle, sealing and completing a doping reduction process in a vacuum drying oven; taking out the reaction product after the reduction is finished, cooling, washing and filtering, and recording as N/S codoped reduced graphene oxide;
3) mixing N/S co-doped reduced graphene oxide, manganese chloride tetrahydrate and potassium permanganate according to the ratio of 1: 7.5-10: 5-20 under the condition of continuous stirring, then carrying out ultrasonic treatment on the suspension, pouring the suspension into a hydrothermal reaction kettle, and completing a hydrothermal synthesis reaction in a vacuum drying oven; taking out the reaction kettle after the reaction, naturally cooling to room temperature, and cleaning and filtering the obtained suspension by using ultrapure water; and after finishing, putting the obtained product into a freeze dryer for drying to obtain fluffy manganese dioxide loaded nitrogen-sulfur double-doped graphene catalyst powder.
3. The method of claim 2, wherein: the centrifugal washing and stripping step in the step 1) comprises the following steps: washing with 20% dilute hydrochloric acid solution to remove residual potassium permanganate in the stock solution; then, repeatedly cleaning with ultrapure water to remove graphite powder which does not participate in the reaction; centrifuging for 10 min/time; the centrifugal rotating speeds are 2000r/min, 6000r/min, 8000r/min, 10000r/min and 4000r/min in sequence.
4. The method of claim 2, wherein: the mass concentration of the graphene oxide measured in the step 2) is 4.4 mg/mL; centrifuging the graphene oxide for 10-30 min; the organic solvent in the step 2) is N-methylpyrrolidone, N-dimethylformamide or ethylene glycol; the reducing agent in the step 2) is thiourea or dopamine and cysteine;
the ultrasonic treatment time in the step 2) is 1-2 h;
the reaction temperature in the doping reduction process in the step 2) is 80-100 ℃; the reaction time is 12-24 h.
5. The method of claim 2, wherein: continuously stirring and mixing the N/S co-doped reduced graphene oxide, the manganese chloride tetrahydrate and the potassium permanganate in the step 3), wherein the stirring time is 0.5-2 h;
the ultrasonic treatment time of the suspension in the step 3) is 1-2 h;
the hydrothermal synthesis reaction time in the step 3) is 2-5 h; the reaction temperature is 120-150 ℃;
the drying temperature in the freeze dryer in the step 3) is-65 ℃; the drying time is 24-48 h.
6. The characterization method of manganese dioxide supported nitrogen-sulfur double doped graphene catalyst for oxygen reduction reaction of claim 1, wherein the material characterization means used is SEM, XRD or BET; the performance evaluation method of the used catalyst is a rotating disc test system, a constant current discharge test or a polarization test.
7. An aluminum-air fuel cell, characterized by: the anode is pure aluminum, the cathode is a manganese dioxide loaded nitrogen-sulfur double-doped graphene air electrode, and the electrolyte is a sodium hydroxide solution added with a corrosion inhibitor; the manganese dioxide-loaded nitrogen-sulfur double-doped graphene air electrode is prepared by mixing and coating a manganese dioxide-loaded nitrogen-sulfur double-doped graphene catalyst, conductive carbon black, a polytetrafluoroethylene binder and N-methylpyrrolidone on the surface of a nickel screen and pressing the mixture by using a hot press.
8. An aluminum air fuel cell according to claim 7, characterized in that: adding a manganese dioxide-loaded nitrogen-sulfur double-doped graphene catalyst, conductive carbon black and a polytetrafluoroethylene binder with the mass concentration of 60% in a mass ratio of 3:3.5: 3.5; the amount of the added N-methyl pyrrolidone is 2-5 times of the total mass of the manganese dioxide loaded nitrogen-sulfur double-doped graphene, the conductive carbon black and the polytetrafluoroethylene.
9. An aluminum air fuel cell according to claim 7, characterized in that: pressing by using a hot press, wherein the hot pressing temperature is 200-300 ℃; the hot pressing time is 10-30 min.
10. The aluminum air fuel cell according to claim 7, characterized in that: the concentration of the sodium hydroxide solution is 4 mol/L; the corrosion inhibitor is a composite corrosion inhibitor composed of sodium stannate and casein, wherein the concentration of the sodium stannate is 0.05mol/L, and the concentration of the casein is 0.6 g/L.
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