CN111554941A - Bifunctional catalyst, preparation method thereof and metal-air battery - Google Patents
Bifunctional catalyst, preparation method thereof and metal-air battery Download PDFInfo
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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
- H01M4/90—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
-
- 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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
-
- 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
-
- 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
- H01M4/9041—Metals or alloys
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inert Electrodes (AREA)
- Catalysts (AREA)
- Hybrid Cells (AREA)
Abstract
The invention belongs to the technical field of catalysts, and particularly relates to a bifunctional catalyst, a preparation method thereof and a metal-air battery. In the bifunctional catalyst, the transition metal oxide and the transition metal single atom have higher stability under the synergistic action of the carbon nano tube, and the transition metal oxide and the transition metal single atom can be prevented from agglomerating; in addition, nitrogen doping brings a large number of crystal defects, provides more active sites for the catalyst in catalytic reaction, and is beneficial to promoting the generation of oxygen reduction reaction and oxygen precipitation reaction. The bifunctional catalyst can promote the generation of oxygen reduction reaction and oxygen precipitation reaction, and has the advantages of good stability and low cost while improving the catalytic efficiency. The bifunctional catalyst is applied to the metal-air battery, can improve the electrochemical performance of the obtained metal-air battery, promotes the large-scale production of the metal-air battery, and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a bifunctional catalyst, a preparation method thereof and a metal-air battery.
Background
After the second industrial revolution, the increase of the technological and medical level has promoted the increase of the population of the world, and the demand of the improvement of the living standard for energy also reaches the highest point of history. However, the conventional fossil energy has a limited reserve and the mining and using processes thereof easily cause environmental pollution, so that the development of new green energy is urgently needed. Lithium batteries and metal air batteries have the advantages of light pollution, low cost, high energy density and the like, and are considered as the leading force of new energy development in the future. Compared with a lithium battery, the zinc-air battery has higher energy density; compared with a fuel cell, the fuel cell has higher safety and practicability. At present, zinc-air batteries have been studied for application to electric vehicles. For example, 500 zinc-air battery electric vehicles were produced by eastern wind special vapor (ten weir) passenger vehicles limited in 2016 + 2017, the zinc-air battery electric vehicles carried by the battery vehicles are 50% of the weight of the lithium batteries, the driving range is 200% of the weight of the lithium batteries, and the initial cost is only 40%. The battery mass of the latest Model S of Tesla exceeds 500 kg, and the endurance mileage is less than 600 km, so that the metal-air battery has a huge prospect in the field of battery automobiles.
The main reasons impeding the large-scale application of metal-air batteries are the high cost of platinum-based catalysts, the low activity and poor stability of non-platinum-based catalysts, and therefore the development of high-activity non-platinum catalysts is the first line to promote the operation of metal-air batteries. Both transition metal oxides and metal monatomic catalysts have high catalytic activity for oxygen reduction, but the stability of these catalysts cannot meet the requirements of metal-air batteries. Therefore, the preparation of high performance, high stability and low cost catalysts by an efficient process is a current research hotspot.
Disclosure of Invention
The invention aims to provide a bifunctional catalyst, a preparation method thereof and a metal-air battery, and aims to solve the technical problems of high cost of a platinum-based catalyst, low activity of a non-platinum-based catalyst and poor stability of the conventional metal-air battery.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
one aspect of the present invention provides a method for preparing a bifunctional catalyst, comprising the steps of:
providing an organometallic framework, a transition metal compound;
mixing the organic metal framework and the transition metal compound to enable the transition metal compound to be adsorbed on the organic metal framework, so as to obtain the organic metal framework adsorbed with the transition metal compound;
and introducing a carbon source, and treating the organic metal framework adsorbed with the transition metal compound by a chemical vapor deposition method to simultaneously load transition metal oxide and transition metal single atoms on the nitrogen-doped carbon nanotube to obtain the bifunctional catalyst.
In a preferred embodiment of the present invention, in the step of mixing the organometallic framework and the transition metal compound, the mass ratio of the organometallic framework to the transition metal compound is (0.1-2): (0.1-1.5).
In a preferred embodiment of the present invention, in the step of treating the organic metal framework adsorbed with the transition metal compound by chemical vapor deposition, the temperature of the chemical vapor deposition treatment is 650 to 1100 ℃.
In a preferred embodiment of the present invention, before the step of treating the organometallic framework adsorbed with the transition metal compound by chemical vapor deposition, the method further comprises: and carrying out ultraviolet ozone irradiation treatment on the organic metal framework adsorbed with the transition metal compound.
As a further preferable technical scheme of the invention, the time of the ultraviolet ozone irradiation treatment is 1min-30 min.
As a preferable technical scheme of the invention, the organic metal framework is selected from at least one of Prussian blue, MIF-47, MIL-53(Fe), MIF-101(Cr), MIL-88(Fe), MOF-5, HKUST-1, CMK-3, Ni-Me4bpz, IRMOF-3, Mn-BTC, Al-MOFs, ZIF-8 and ZIF-67.
In a preferred embodiment of the present invention, in the step of mixing the organometallic framework and the transition metal compound, the mixing is performed by a solvent method or a deposition method.
In a more preferred embodiment of the present invention, the solvent method is a method of mixing the organometallic framework, the transition metal compound and a solvent, wherein the mass ratio of the organometallic framework, the transition metal compound and the solvent is (0.1-2): (0.1-1.5): (0.3-10).
In another aspect, the present invention provides a bifunctional catalyst comprising a nitrogen-doped carbon nanotube, and a transition metal oxide and a transition metal monoatomic atom supported on the nitrogen-doped carbon nanotube.
In yet another aspect, the present invention provides a metal-air battery comprising the above bifunctional catalyst.
The preparation method of the bifunctional catalyst utilizes the structural characteristics of porosity, high specific surface area and modifiability of the organic metal framework, and treats the organic metal framework adsorbed with the transition metal compound by a chemical vapor deposition method; the nitrogen-doped carbon nanotube has a hollow structure, so that the generated transition metal oxide is loaded on the inner wall and the outer wall of the nitrogen-doped Carbon Nanotube (CNT), and the generated transition metal monoatomic is anchored in the tube wall of the nitrogen-doped carbon nanotube, thereby obtaining the nitrogen-doped carbon nanotube simultaneously loaded with the transition metal oxide and the transition metal monoatomic. The preparation method of the bifunctional catalyst has the advantages of simple steps and easily controlled reaction process.
The bifunctional catalyst is a nitrogen-doped carbon nanotube simultaneously loaded with transition metal oxide and transition metal single atoms, wherein the transition metal oxide and the transition metal single atoms have higher stability under the synergistic action of the carbon nanotube, and can avoid the agglomeration of the transition metal oxide and the transition metal single atoms; in addition, nitrogen doping brings a large number of crystal defects, provides more active sites for the bifunctional catalyst in catalytic reaction, and is beneficial to promoting the generation of oxygen reduction reaction and oxygen precipitation reaction. In addition, compared with the traditional platinum-based catalyst, the bifunctional catalyst has the advantages of obviously reduced cost and higher stability.
The metal-air battery of the invention promotes the oxygen reduction reaction and the oxygen precipitation reaction due to the bifunctional catalyst with high catalytic efficiency, so that the metal-air battery of the invention has the advantages of high reaction efficiency, good stability, lower cost, contribution to realizing the industrialized development and good application prospect.
Drawings
FIG. 1 is a scanning electron microscope image of the bifunctional catalyst obtained in example 1 of the present invention;
FIG. 2 shows the current density of 5mA/cm of the metal-air battery obtained in example 1 of the present invention2The test result chart of alternating charging and discharging for 20 min;
FIG. 3 is a scanning electron microscope image of the bifunctional catalyst obtained in example 2 of the present invention;
FIG. 4 is a scanning electron microscope image of the bifunctional catalyst obtained in example 3 of the present invention;
FIG. 5 is a scanning electron microscope image of the bifunctional catalyst obtained in example 4 of the present invention;
FIG. 6 is a scanning electron microscope image of the bifunctional catalyst obtained in example 5 of the present invention.
Detailed Description
In order to make the objects, technical solutions and technical effects of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described, and the embodiments described below are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive step in connection with the embodiments of the present invention shall fall within the scope of protection of the present invention. Those whose specific conditions are not specified in the examples are carried out according to conventional conditions or conditions recommended by the manufacturer; the reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In the description of the invention, it is to be understood that unless the context clearly dictates otherwise, expressions of the singular form of a word are to be understood as encompassing the plural form of the word. The terms "comprises" or "comprising" are intended to specify the presence of stated features, components, quantities, steps, operations, elements, portions, or combinations thereof, but are not intended to preclude the presence or addition of one or more other features, components, quantities, steps, operations, elements, portions, or combinations thereof.
In addition, the weight of the related components mentioned in the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, it is within the scope of the disclosure that the content of the related components is scaled up or down according to the embodiments of the present invention. Specifically, the weight described in the embodiments of the present invention may be a unit of mass known in the chemical field such as μ g, mg, g, kg, etc.
The embodiment of the invention provides a preparation method of a bifunctional catalyst, which comprises the following steps:
s1, providing an organic metal framework and a transition metal compound;
s2, mixing the organic metal framework and the transition metal compound to make the transition metal compound adsorbed on the organic metal framework to obtain the organic metal framework adsorbed with the transition metal compound;
and S3, introducing a carbon source and a nitrogen source, treating the organic metal framework adsorbed with the transition metal compound by a chemical vapor deposition method, and simultaneously loading transition metal oxide and transition metal single atoms on the nitrogen-doped carbon nanotube to obtain the bifunctional catalyst.
The preparation method of the bifunctional catalyst utilizes the structural characteristics of porosity, high specific surface area and modifiability of the organic metal framework, and treats the organic metal framework adsorbed with the transition metal compound by a chemical vapor deposition method; the nitrogen-doped carbon nanotube has a hollow structure, so that the generated transition metal oxide is loaded on the inner wall and the outer wall of the nitrogen-doped carbon nanotube, and the generated transition metal monoatomic is anchored in the tube wall of the nitrogen-doped carbon nanotube, thereby obtaining the nitrogen-doped carbon nanotube simultaneously loaded with the transition metal oxide and the transition metal monoatomic. The preparation method of the bifunctional catalyst has the advantages of simple steps and easily controlled reaction process.
Specifically, in S1, the organic metal frameworks (MOFs) are a new class of porous crystalline materials, and are hybrid materials formed by organic ligands and transition metal ions through coordination bonds. The porosity of the organometallic framework enables it to have a high specific surface area, and the specific structural features of the organometallic framework enable it to have switchable ligands and metal centers, which are modifiable. In addition, the organic metal framework also has the advantages of low cost and good thermal stability. The Oxygen Evolution Reaction (OER) is a four-electron transfer process and has slow reaction kinetics, so that a transition metal monoatomic atom with high catalytic activity of the oxygen evolution reaction can be generated by taking an organic metal framework as a reaction raw material through pyrolysis, and the transition metal monoatomic atom is used for improving the rate of the oxygen evolution reaction.
In some embodiments, the organometallic framework is selected from at least one of Prussian blue, MIF-47, MIL-53(Fe), MIF-101(Cr), MIL-88(Fe), MOF-5, HKUST-1, CMK-3, Ni-Me4bpz, IRMOF-3, Mn-BTC, Al-MOFs, ZIF-8, ZIF-67.
The Oxygen Reduction Reaction (ORR) is a cathode reaction in a metal air battery. As a catalyst for oxygen reduction reactions, transition metal oxides have very good physical and electrochemical properties, are generally low in cost, can accelerate the occurrence and efficiency of oxygen reduction reactions, and are used to provide metal oxides during the preparation of bifunctional catalysts.
In S2, the organometallic framework and the transition metal compound may be mixed by various methods to adsorb the transition metal compound on the organometallic framework. In some embodiments, the adsorption of the transition metal compound onto the organometallic framework is performed using a solvent method. Specifically, the organometallic framework may be dispersed in a solvent, and then a transition metal compound may be added thereto and mixed to adsorb the transition metal compound on the organometallic framework, and then the solvent may be removed. Wherein, the solvent can be a conventional polar or non-polar solvent, for example, at least one selected from water, ethanol, methanol, diethyl ether, isopropanol, dichloromethane, benzene, carbon tetrachloride, hexane, DMSO, DMF, and acetone.
In some embodiments, the adsorption of the transition metal compound by the organometallic framework is performed using a deposition method. Optionally, the deposition method is an atomic layer deposition method and/or a pulsed laser deposition method to improve deposition efficiency.
By optimizing the addition amount of the organometallic framework and the transition metal compound, the transition metal compound is favorably and uniformly dispersed in the organometallic framework, so that the mass ratio of the organometallic framework to the transition metal compound is controlled to be (0.1-2): (0.1-1.5) in some embodiments. When the transition metal compound is adsorbed on the organometallic framework by a solvent method, the mass ratio of the organometallic framework to the transition metal compound and the solvent is preferably controlled to (0.1 to 2): (0.1 to 1.5): 0.3 to 10.
In some embodiments, after the organic metal framework adsorbed with the transition metal compound is obtained, the organic metal framework is further subjected to ozone irradiation treatment, so that the surface group of the organic metal framework is modified and the surface binding energy of the organic metal framework is improved, so as to further improve the binding effect of the subsequent transition metal compound and the nitrogen-doped carbon nanotube. Specifically, the irradiation can be performed by using an ultraviolet ozone cleaning machine, and the irradiation time is preferably 1min to 30 min. Specifically, typical, but not limiting, irradiation times are 1min, 5min, 10min, 15min, 20min, 25min, 30 min.
In S3, when the organic metal framework adsorbed with the transition metal compound is treated by the chemical vapor deposition method, the organic metal framework is pyrolyzed to generate transition metal oxide and metal monoatomic atoms due to the reaction temperature during the chemical vapor deposition treatment; meanwhile, the chemical vapor deposition method can also enable the transition metal compound to react to generate transition metal oxide, and in the process, the introduced carbon source and nitrogen source grow into the nitrogen-doped carbon nano tube, so that the nitrogen-doped carbon nano tube simultaneously loaded with the transition metal oxide and the transition metal monoatomic atom is obtained.
In some embodiments, the chemical vapor deposition treatment of the organometallic framework adsorbed with the transition metal compound with the introduction of a carbon source may be performed in a plasma enhanced chemical vapor deposition apparatus.
In some embodiments, inexpensive methane is preferred as a carbon source for growing carbon nanotubes.
Furthermore, the flow rate of the carbon source is 5sccm-200 sccm. The introduction of a proper amount of carbon source can avoid the problems of more impurities and the like caused by excessive carbon source on the premise of ensuring the growth of the carbon nano tube. Specifically, typical but non-limiting carbon source flow rates are 5sccm, 10sccm, 50sccm, 100sccm, 150sccm, 200 sccm.
In some embodiments, hydrogen gas may also be introduced during the growth of the carbon nanotubes. The hydrogen can control the cracking reaction speed of the carbon source, avoid that a large amount of cracked carbon atoms are not regularly arranged due to accelerated decomposition of the carbon source at high temperature and only deposit as amorphous carbon or carbon particles, and generate less carbon nano tubes.
Furthermore, the flow rate of the introduced hydrogen is 5sccm-200 sccm. The proper amount of hydrogen can control the cracking reaction speed of the carbon source, and simultaneously, the cost increase caused by excessive introduction is avoided. Specifically, typical but non-limiting nitrogen flow rates are 5sccm, 10sccm, 50sccm, 100sccm, 150sccm, 200 sccm.
In some embodiments, nitrogen is introduced at a flow rate of 0sccm to 300 sccm. It is understood that although the organic metal framework contains a certain amount of nitrogen which can be used as a nitrogen source for nitrogen-doped carbon nanotubes, the nitrogen-doped content of the obtained bifunctional catalyst can be moderate by introducing a proper amount of nitrogen, which is beneficial to providing enough positions for metal oxides and metal single atoms. Specifically, typical, but not limiting, nitrogen flow rates are 0sccm, 5sccm, 10sccm, 50sccm, 100sccm, 150sccm, 200sccm, 250sccm, 300 sccm.
The plasma radio frequency power, the ventilation time and the heating time can be adjusted according to actual conditions, such as: the radio frequency power of the plasma is 10W-300W; the aeration time is 1h-24 h; the heating temperature is 350-1100 ℃.
The embodiment of the invention also provides a bifunctional catalyst which comprises the nitrogen-doped carbon nanotube, and transition metal oxide and transition metal single atoms which are loaded on the nitrogen-doped carbon nanotube.
The bifunctional catalyst is a nitrogen-doped carbon nanotube simultaneously loaded with transition metal oxide and transition metal single atoms, wherein the transition metal oxide and the transition metal single atoms have higher stability under the synergistic action of the carbon nanotube, and can avoid the agglomeration of the transition metal oxide and the transition metal single atoms; in addition, nitrogen doping brings a large number of crystal defects, provides more active sites for the bifunctional catalyst in catalytic reaction, and is beneficial to promoting the generation of oxygen reduction reaction and oxygen precipitation reaction. In addition, compared with the traditional platinum-based catalyst, the bifunctional catalyst has the advantages of obviously reduced cost and higher stability.
The embodiment of the invention also provides a metal-air battery which comprises the bifunctional catalyst.
The metal-air battery is a battery which takes metal such as magnesium, aluminum, zinc, mercury, iron and the like as a negative electrode and takes oxygen or pure oxygen in the air as a positive electrode. The reactions at the oxygen end of the metal-air battery comprise an oxygen reduction reaction and an oxygen evolution reaction, and because the electrochemical processes of the oxygen reduction reaction and the oxygen evolution reaction are multi-step electron transfer reactions with slow kinetics, the electrochemical polarization is reduced and the oxygen electrochemical reaction rate is accelerated by adopting a catalyst. The invention replaces platinum-based catalyst with the bifunctional catalyst of the nitrogen-doped carbon nanotube which simultaneously loads transition metal oxide and transition metal single atom as the catalyst in the metal-air battery, and has the advantages of high reaction efficiency, good stability and low cost.
In some embodiments, the bifunctional catalyst of the present invention is mixed with a binder, a conductive agent, and a current collector in a mass ratio of (6-10) to (0.2-3) to (0-3) for use in assembling a metal-air battery.
Preferably, the binder is selected from Polytetrafluoroethylene (PTFE) and/or polyvinylidene fluoride (PVDF).
Preferably, the conductive agent is at least one selected from conductive carbon black, carbon nanotubes and graphene.
Preferably, the current collector is selected from carbon paper, carbon cloth, nickel foam. At least one of nickel sheet, stainless steel sheet, aluminum foil and titanium sheet.
In order to make the details and operation of the above-mentioned implementation of the present invention clearly understood by those skilled in the art and to make the advanced performance of the bifunctional catalyst, the preparation method thereof and the metal-air battery of the present invention obviously manifest, the above-mentioned technical solutions are exemplified by the following examples.
Example 1
(1) Taking 2g of MIF-53(Fe) to be ultrasonically treated in 100mL of ethanol solution, adding 50mg of cobaltosic oxide particles, stirring for 30min, and heating and drying in the air to obtain powder;
(2) irradiating the obtained powder in an ultraviolet ozone cleaning machine for 10 min;
(3) introducing 5sccm hydrogen, 10sccm methane and 0sccm nitrogen into the irradiated powder in a plasma enhanced chemical vapor deposition device, wherein the plasma radio frequency power is 50W, the introducing time is 4h, and the heating temperature of a tubular furnace is 800 ℃ to obtain Co3O4@Fe@CNT；
(4)Co3O4The mass ratio of @ Fe @ CNT to PTFE to super-P is 9:0.7:0.3, the zinc-air battery is assembled by pressing the sheet on a foamed nickel current collector at 5mA/cm2The charge and discharge test under constant current.
Co obtained in step (3)3O4The scanning electron micrograph of @ Fe @ CNT is shown in FIG. 1, and the charge and discharge test result of step (4) is shown in FIG. 2.
Example 2
(1) Taking 2g of ZIF-8, performing ultrasonic treatment in 300mL of methanol solution, adding 50mg of nickel chloride particles, stirring for 30min, and performing rotary vacuum drying to obtain powder;
(2) irradiating the obtained powder in an ultraviolet ozone cleaning machine for 20 min;
(3) introducing 30sccm hydrogen, 20sccm methane and 20sccm nitrogen into the irradiated powder in a plasma enhanced chemical vapor deposition device, wherein the plasma radio frequency power is 100W, the introducing time is 8h, and the heating temperature of a tubular furnace is 1100 ℃, so as to obtain NiO @ Ni @ CNT;
(4) the mass ratio of NiO @ Ni @ CNT to PVDF to graphene is 8.5:1.2:0.3, the NiO @ Ni @ CNT and PVDF are coated on a stainless steel current collector, and a zinc-air battery is assembled at the temperature of 30mA/cm2The charge and discharge test under constant current.
The scanning electron microscope image of the NiO @ Ni @ CNT obtained in the step (3) is shown in FIG. 3.
Example 3
(1) Taking 5g of ZIF-67, performing ultrasonic treatment on the ZIF-67 in 100mL of aqueous solution, adding 100mg of ferric nitrate particles, stirring for 30min, and performing rotary vacuum drying to obtain powder;
(2) irradiating the obtained powder in an ultraviolet ozone cleaning machine for 20 min;
(3) introducing 30sccm hydrogen, 20sccm methane and 20sccm nitrogen into the irradiated powder in a plasma enhanced chemical vapor deposition device, wherein the plasma radio frequency power is 100W, the introducing time is 8h, and the heating temperature of a tubular furnace is 1100 ℃, so as to obtain Fe2O3@Co@CNT；
(4)Fe2O3@ Co @ CNT, PTFE, super-P ═ 6:3:1, pressed on carbon paper current collector, assembled zinc-air battery, at 20mA/cm2The charge and discharge test under constant current.
Fe obtained in step (3)2O3FIG. 4 shows a scanning electron micrograph of @ Co @ CNT.
Example 4
(1) Taking 10g of MIF-101(Cr) to deposit an iron-based catalyst through ALD to obtain powder;
(2) irradiating the obtained powder in an ultraviolet ozone cleaning machine for 30 min;
(3) introducing 100sccm hydrogen, 200sccm methane and 5sccm nitrogen into the irradiated powder in a plasma enhanced chemical vapor deposition device, wherein the plasma radio frequency power is 300W, the introducing time is 24h, and the heating temperature of a tubular furnace is 900 ℃ to obtain Fe3O4@Cr@CNT；
(4)Fe3O4The mass ratio of @ Cr @ CNT to PTFE is 9.8:0.2, the zinc-air battery is assembled by pressing the sheet on a carbon cloth current collector at 10mA/cm2The charge and discharge test under constant current.
Fe obtained in step (3)3O4FIG. 5 shows a SEM image of @ Cr @ CNT.
Example 5
(1) Taking 10g of HKUST-1, and sequentially depositing a cobalt-based catalyst by ALD and PLD to obtain powder;
(2) irradiating the obtained powder in an ultraviolet ozone cleaning machine for 15 min;
(3) introducing 7sccm hydrogen, 30sccm methane and 50sccm nitrogen into the irradiated powder in a plasma enhanced chemical vapor deposition device, wherein the plasma radio frequency power is 10W, the introducing time is 9h, and the heating temperature of a tubular furnace is 650 ℃ to obtain Co3O4@Cu@CNT；
(4)Co3O4The mass ratio of @ Cu @ CNT to PTFE to CNT is 8.6:1.1:0.3, the sheet is pressed on a carbon cloth current collector, and a zinc-air battery is assembled at the temperature of 3mA/cm2The charge and discharge test under constant current.
Co obtained in step (3)3O4FIG. 6 shows a scanning electron micrograph of @ Cu @ CNT.
Comparative example 1
Pt/C @ IrO is traditionally adopted2Catalyst at 10mA/cm2The potential difference between charge and discharge was 0.79 mV.
Mixing Pt @ C, IrO2PTFE and super-P are mixed and ground for 30 minutes according to the mass ratio of 9:9:0.5:0.5, then the mixture is pressed on a carbon cloth current collector, and a zinc-air battery is assembled, wherein the concentration of the zinc-air battery is 5mA/cm respectively2And 10mA/cm2The charge and discharge test under constant current.
Comparative example 2
Ultrasonically dispersing 1.10mg of graphene in 100ml of alcohol solution;
2. adding 15mg of cobalt acetate, 2ml of 30 percent ammonia water and 5ml of water into the dispersion, stirring for 5 minutes, putting the mixture into a hydrothermal kettle, reacting for 10 hours at the temperature of 150 ℃, and centrifuging to obtain Co3O4@ N-graphene catalyst.
3.Co3O4The mass ratio of @ N-graphene to PTFE to CNT is 8.5:1.3:0.2, the mixture is pressed on foamed nickel, and a zinc-air battery is assembled at 5mA/cm2The charge and discharge test under constant current.
The results of the charge/discharge test potential differences of the air batteries obtained in examples 1 to 5 of the present invention and comparative examples 1 to 2 are shown in table 1.
TABLE 1 potential differences of Zinc-air batteries obtained in examples 1 to 5 and comparative examples 1 to 2
As can be seen from table 1, the zinc-air battery assembled with the dual-function catalyst obtained in the embodiment of the present invention is chargeable and dischargeable, and therefore, the dual-function catalyst obtained in the embodiment of the present invention has catalytic functions of oxygen reduction and oxygen precipitation. The smaller the potential difference value is at the same current density, the better the electrochemical performance of the zinc-air battery is, so the zinc-air batteries obtained in the examples 1 and 5 of the invention have better electrochemical performance than other examples.
Fig. 1 and fig. 3 to 6 show scanning electron microscope images of the bifunctional catalyst obtained in embodiments 1 to 5 of the present invention, and it can be seen that the main structure of the bifunctional catalyst obtained in embodiments 1 to 5 of the present invention is a carbon nanotube structure, wherein the particulate bright spots are transition metal oxides, which are loaded on the inner wall and the outer wall of the carbon nanotube; the transition metal is monatomic in the walls of the carbon nanotubes. Therefore, the bifunctional catalyst of the present invention is a nitrogen-doped carbon nanotube simultaneously supporting a transition metal oxide and a transition metal single atom.
The above examples are merely representative of individual embodiments of the present invention, and the description thereof is more specific and detailed, but not to be construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of a bifunctional catalyst is characterized by comprising the following steps:
providing an organometallic framework, a transition metal compound;
mixing the organic metal framework and the transition metal compound to enable the transition metal compound to be adsorbed on the organic metal framework, so as to obtain the organic metal framework adsorbed with the transition metal compound;
and introducing a carbon source, and treating the organic metal framework adsorbed with the transition metal compound by a chemical vapor deposition method to simultaneously load transition metal oxide and transition metal single atoms on the nitrogen-doped carbon nanotube to obtain the bifunctional catalyst.
2. The method for preparing a bifunctional catalyst as claimed in claim 1, wherein in the step of subjecting the organometallic framework and the transition metal compound to mixing treatment, the mass ratio of the organometallic framework to the transition metal compound is (0.1-2): 0.1-1.5.
3. The method for preparing a bifunctional catalyst according to claim 1, wherein in the step of treating the organometallic framework adsorbed with the transition metal compound by chemical vapor deposition, the temperature of the chemical vapor deposition treatment is 650 ℃ to 1100 ℃.
4. The method for preparing a bifunctional catalyst according to claim 1, wherein the step of treating the organometallic framework adsorbed with the transition metal compound by chemical vapor deposition further comprises: and carrying out ultraviolet ozone irradiation treatment on the organic metal framework adsorbed with the transition metal compound.
5. The method for preparing the bifunctional catalyst according to claim 4, wherein the time of the ultraviolet ozone irradiation treatment is 1min to 30 min.
6. The method for preparing the bifunctional catalyst according to any one of claims 1-5, wherein the organometallic framework is selected from at least one of Prussian blue, MIF-47, MIL-53(Fe), MIF-101(Cr), MIL-88(Fe), MOF-5, HKUST-1, CMK-3, Ni-Me4bpz, IRMOF-3, Mn-BTC, Al-MOFs, ZIF-8, ZIF-67.
7. The method for preparing a bifunctional catalyst as claimed in any one of claims 1 to 5, wherein the step of mixing the organometallic framework and the transition metal compound is a solvent method or a deposition method.
8. The method for preparing a bifunctional catalyst as defined in claim 7, wherein the solvent method comprises mixing the organometallic framework, the transition metal compound and a solvent, and the mass ratio of the organometallic framework, the transition metal compound and the solvent is (0.1-2): (0.1-1.5): (0.3-10).
9. A bifunctional catalyst comprising nitrogen-doped carbon nanotubes, and transition metal oxides and transition metal monatomics supported on the nitrogen-doped carbon nanotubes.
10. A metal-air battery comprising the bifunctional catalyst prepared by the method for preparing a bifunctional catalyst according to any one of claims 1 to 8, or the bifunctional catalyst according to claim 9.
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