CN114388822A - Cathode C @ Ni @ MnO of aluminum-air battery2Catalytic material and preparation method thereof - Google Patents
Cathode C @ Ni @ MnO of aluminum-air battery2Catalytic material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 75
- 230000003197 catalytic effect Effects 0.000 claims abstract description 64
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 47
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000013078 crystal Substances 0.000 claims abstract description 42
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 32
- 230000009466 transformation Effects 0.000 claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- 238000000498 ball milling Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 10
- 238000007599 discharging Methods 0.000 claims description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 24
- 229910052782 aluminium Inorganic materials 0.000 claims description 24
- 238000007873 sieving Methods 0.000 claims description 19
- 239000011812 mixed powder Substances 0.000 claims description 16
- 239000011324 bead Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 150000003624 transition metals Chemical class 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 239000003273 ketjen black Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 3
- 229910000914 Mn alloy Inorganic materials 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 14
- 239000001301 oxygen Substances 0.000 abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000009467 reduction Effects 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 5
- 230000005540 biological transmission Effects 0.000 abstract description 3
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- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 208000028659 discharge Diseases 0.000 abstract 2
- 239000003054 catalyst Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
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- 239000007789 gas Substances 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 150000002815 nickel Chemical group 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- 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
-
- 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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8689—Positive electrodes
-
- 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 provides a cathode C @ Ni @ MnO of an aluminum-air battery2The preparation method comprises the steps of carrying out microwave discharge treatment on manganese dioxide after crystal transformation, a nickel source and a carbon source by using a high-temperature crystal transformation technology, and then carrying out ball milling to obtain the cathode catalytic material. The invention adds metal nickel source, generates nickel atoms attached to the surfaces of manganese dioxide and carbon source through microwave plasma discharge, and then coats a good conductive carbon network and tightly combined nickel atoms on the surface of the cathode catalytic material prepared through high-energy mechanical ball milling, thereby increasing the active sites and the conductivity of the cathode catalytic material, generating more limited-area catalytic reaction active sites at the contact positions of the metal nickel atoms, the conductive carbon and the manganese dioxide during the oxygen reduction catalytic reaction, increasing the oxygen adsorption rate, increasing the electron transmission path, and rapidly transferring electrons, thereby reducing polarization, and the prepared catalytic material has high catalytic activity and high performanceStable, low production cost and simple process, and is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to the technical field of aluminum-air batteries, in particular to an aluminum-air battery cathode C @ Ni @ MnO2Catalytic materials and methods of making the same.
Background
The aluminum-air battery has the advantages of high specific energy (the theoretical specific energy reaches 8100Wh/kg), safety, environmental protection, rich aluminum resources, low price, convenient transportation, convenient maintenance and the like, and is widely concerned by researchers. The aluminum-air battery mainly comprises an aluminum anode, an air cathode and electrolyte, wherein the air cathode is used as an important component of the aluminum-air battery and consists of a catalyst layer, a current collector and a waterproof layer. The cathode material of the catalyst layer is used as an important medium for catalyzing the oxygen reduction reaction, and has very important influence on the comprehensive output performance of the aluminum-air battery, so that the research on the cathode material for catalyzing the aluminum-air battery is particularly important.
The catalytic cathode material of the aluminum air battery is mainly divided into noble metal (such as Pt) and alloy catalyst thereof, non-noble metal catalyst, carbonaceous nano material and the like. The noble metal catalyst has excellent performance, but is expensive and difficult to be widely applied; in addition, other catalysts reported in many researches have poor catalytic performance, poor circulation stability and complex manufacturing process, and are difficult to realize large-scale industrial production, thereby hindering the commercial application of the aluminum-air battery. Therefore, how to innovatively develop a cathode catalyst which has excellent performance and low price and is convenient for large-scale production and use becomes a problem to be solved at present.
Disclosure of Invention
Aiming at the technical problems that the aluminum-air battery cathode catalyst prepared by the prior art is poor in catalytic performance, poor in circulation stability, complex in manufacturing process, high in production cost and difficult to realize large-scale industrial production, the invention provides an aluminum-air battery cathode C @ Ni @ MnO2A method for preparing a catalytic material.
In order to solve the technical problems, the invention adopts the following technical scheme:
cathode C @ Ni @ MnO of aluminum-air battery2The preparation method of the catalytic material comprises the following steps:
s1, adding MnO2The material is placed in a muffle furnace for high-temperature crystal transformation treatment to obtain the MnO subjected to crystal transformation2The temperature of crystal transformation treatment is 200-500 ℃, and the time of crystal transformation treatment is 1-10 h;
s2 MnO after crystal transformation2Mixing the powder with a nickel source and a carbon source material, then placing the mixture into microwave equipment for discharging, wherein the microwave discharging time is 1-10 min, cooling the mixture to room temperature after discharging, and sieving the mixture to obtain mixed powder;
s3, ball-milling the mixed powder in a ball mill for 3-15 h, and sieving to obtain a cathode C @ Ni @ MnO2A catalytic material.
Further, in the step S1, the temperature rise rate of the muffle furnace is 2-10 ℃/min.
Further, in step S2, the nickel source is at least one of nickel powder, nickel flakes, nickel wires, and nickel mesh.
Further, in the step S2, the nickel source is a transition metal source or a metal alloy, the transition metal source is iron, copper or zinc, and the metal alloy is a nickel-iron alloy or a copper-manganese alloy.
Further, in the step S2, the discharging condition of the microwave device is in a vacuum environment or under the condition of introducing inert shielding gas, and the material is continuously stirred in the discharging process.
Further, in the step S2, the carbon source is at least one of graphene, graphite powder, ketjen black, acetylene black, vermicular graphite, conductive carbon fiber, conductive carbon quantum dots, and conductive carbon nanotubes.
Further, MnO is crystallized in said step S22The mass ratio of the nickel source to the carbon source material is 1-5: 0.5-4: 0.5 to 3.5.
Further, the amount of the ball milling beads in the ball mill in the step S3 is 50 to 200 g.
Further, the size of the mesh of the screen used in the steps S2 and S3 is 80 mesh.
The invention also provides an aluminum air battery cathode C @ Ni @ MnO2Catalytic material according to the aforementioned aluminum air cell cathode C @ Ni @ MnO2The catalytic material is prepared by a preparation method.
Compared with the prior art, the cathode C @ Ni @ MnO of the aluminum-air battery provided by the invention2The catalytic material is prepared by adding metal nickel source, discharging by microwave plasma to generate nickel atom attached to MnO2And the surface of a carbon source, and then a good conductive carbon network and nickel atoms which are tightly combined are coated on the surface of the cathode catalytic material prepared by high-energy mechanical ball milling, so that the active sites and the conductivity of the cathode catalytic material are increased; in the presence of oxygen reduction catalyst O2+2H2O+4e-＝4OH-Metal nickel atoms with conductive carbon and MnO2More limited catalytic reaction active sites are generated at the contact position, the oxygen adsorption rate is increased, the electron transmission path is increased, and electrons are rapidly transferred, so that the polarization is reduced, and the prepared catalytic material has high catalytic activity and stable performance. From this, it can be seen that MnO is used in the present application2And cheap raw materials such as carbon materials, and the like, so the preparation method has low production cost and simple preparation process, and is suitable for large-scale industrial production of cathode catalytic materials.
Drawings
FIG. 1 is an aluminum air cell cathode C @ Ni @ MnO provided by the present invention2The flow chart of the preparation method of the catalytic material is shown schematically.
FIG. 2 is an aluminum air cell cathode C @ Ni @ MnO provided by the present invention2The mechanism of the catalytic material is schematically shown.
FIG. 3 is an aluminum air provided by the present inventionBattery cathode C @ Ni @ MnO2A physical diagram of the catalytic material.
FIG. 4 is an aluminum air cell cathode C @ Ni @ MnO provided by the present invention2A picture of a cathode plate made of catalytic material.
FIG. 5 is an aluminum air cell cathode C @ Ni @ MnO provided by the present invention2Catalytic materials are schematic diagrams of a limited-area catalytic reaction when an oxygen reduction reaction occurs.
FIG. 6 is an aluminum air cell cathode C @ Ni @ MnO provided by the present invention2A schematic comparison of the catalytic material to the oxygen reduction linear voltammogram (ORR-LSV) of a commercial precious metal catalyst 20 wt.% Pt/C tested by a rotating disk device and electrochemical workstation.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further explained below by combining the specific drawings.
Referring to FIGS. 1 to 5, the present invention provides an aluminum air cell cathode C @ Ni @ MnO2The preparation method of the catalytic material comprises the following steps:
s1, adding MnO2(manganese dioxide) material is placed in a muffle furnace for high-temperature crystal transformation treatment to obtain MnO subjected to crystal transformation2The temperature of crystal transformation treatment is 200-500 ℃, and the time of crystal transformation treatment is 1-10 h;
s2 MnO after crystal transformation2Mixing the powder with a nickel source and a carbon source material, then placing the mixture into microwave equipment for discharging, wherein the microwave discharging time is 1-10 min, cooling the mixture to room temperature after discharging, and sieving the mixture to obtain mixed powder;
s3, ball-milling the mixed powder in a ball mill for 3-15 h, and sieving to obtain a cathode C @ Ni @ MnO2A catalytic material.
As a specific embodiment, the temperature rise rate of the muffle furnace in the step S1 is 2-10 ℃/min, so that a proper temperature rise rate can be matched according to the processing temperature, the micro crystal form of the slowly-heated material cannot be mutated, and the heating equipment is not damaged.
As a specific example, in step S2, the nickel source is at least one of nickel powder, nickel flakes, nickel wires, and nickel nets, that is, any one or a mixture of two or more of nickel powder, nickel flakes, nickel wires, and nickel nets.
As another specific example, in step S2, the nickel source is a transition metal source or a metal alloy, the transition metal source is iron, copper, or zinc, and the metal alloy is a nickel-iron alloy or a copper-manganese alloy.
As a specific embodiment, in the step S2, the discharging condition of the microwave device is in a vacuum environment or under the condition of introducing inert shielding gas, and the material is continuously stirred during the discharging process, so that the material is prevented from being oxidized by air when high temperature is generated by discharging, and the material can be sufficiently and uniformly treated by stirring the material.
As a specific embodiment, in step S2, the carbon source is at least one of graphene, graphite powder, ketjen black, acetylene black, vermicular graphite, conductive carbon fiber, conductive carbon quantum dot, and conductive carbon nanotube, that is, any one or a mixture of two or more of graphene, graphite powder, ketjen black, acetylene black, vermicular graphite, conductive carbon fiber, conductive carbon quantum dot, and conductive carbon nanotube.
As a specific example, MnO is crystallized in the step S22The mass ratio of the nickel source to the carbon source material is 1-5: 0.5-4: 0.5-3.5, so that the catalytic material with the best oxygen reduction performance can be prepared according to the change of the nickel source and the carbon source.
As a specific example, in the step S3, the amount of the ball milling beads in the ball mill is 50-200 g, so that the amount of the ball milling beads can be changed along with the change of the total weight of the material ratio, and the catalytic material with stable and consistent performance can be prepared.
As a specific example, the sieve used for sieving in steps S2 and S3 has a mesh size of 80 mesh, so that the catalytic material powder having a desired particle size can be obtained by direct sieving, and the catalytic material powder can be easily dispersed during the post-production of the electrode slurry.
The invention also provides an aluminum air battery cathode C @ Ni @ MnO2Catalytic material according to the aforementioned aluminum air cell cathode C @ Ni @ MnO2The catalytic material is prepared by a preparation method.
Compared with the prior art, the invention providesAluminum air cell cathode C @ Ni @ MnO2The catalytic material is prepared by adding metal nickel source, discharging by microwave plasma to generate nickel atom attached to MnO2And the surface of a carbon source, and then a good conductive carbon network and nickel atoms which are tightly combined are coated on the surface of the cathode catalytic material prepared by high-energy mechanical ball milling, so that the active sites and the conductivity of the cathode catalytic material are increased; in the presence of oxygen reduction catalyst O2+2H2O+4e-＝4OH-Metal nickel atoms with conductive carbon and MnO2More limited catalytic reaction active sites are generated at the contact position, the oxygen adsorption rate is increased, the electron transmission path is increased, and electrons are rapidly transferred, so that the polarization is reduced, and the prepared catalytic material has high catalytic activity and stable performance. From this, it can be seen that MnO is used in the present application2And cheap raw materials such as carbon materials, and the like, so the preparation method has low production cost and simple preparation process, and is suitable for large-scale industrial production of cathode catalytic materials.
To better understand the cathode C @ Ni @ MnO of the aluminum air battery provided by the invention2The method for preparing the catalytic material will be described in further detail with reference to specific examples.
Example 1:
cathode C @ Ni @ MnO of aluminum-air battery2The preparation method of the catalytic material comprises the following steps:
s1, adding MnO2The material is placed in a muffle furnace for high-temperature crystal transformation treatment to obtain the MnO subjected to crystal transformation2The temperature of crystal transformation treatment is 200 ℃, the heating rate is 2 ℃/min, and the time of crystal transformation treatment is 6 h;
s2 MnO after crystal transformation2The mass ratio of the nickel powder to the worm graphite is 2: 0.5: 1, discharging in microwave equipment after mixing, wherein the microwave discharge time is 2min, introducing nitrogen for protection and continuously stirring materials in the discharge process, cooling to room temperature after discharge, and sieving with a 80-mesh sieve to obtain mixed powder;
s3, ball-milling the mixed powder in a ball mill for 5 hours, wherein the using amount of ball-milled beads is 100g, and sieving the ball-milled beads with a 80-mesh sieve to obtain the cathode C @ Ni @ MnO2A catalytic material.
Example 2:
cathode C @ Ni @ MnO of aluminum-air battery2The preparation method of the catalytic material comprises the following steps:
s1, adding MnO2The material is placed in a muffle furnace for high-temperature crystal transformation treatment to obtain the MnO subjected to crystal transformation2The temperature of crystal transformation treatment is 300 ℃, the heating rate is 2 ℃/min, and the time of crystal transformation treatment is 4 h;
s2 MnO after crystal transformation2Mixing the nickel wire with ketjen black according to the mass ratio of 1: 1.5: 2, discharging in microwave equipment after mixing, wherein the microwave discharge time is 3min, introducing nitrogen for protection and continuously stirring the materials in the discharge process, cooling to room temperature after discharge, and sieving with a 80-mesh sieve to obtain mixed powder;
s3, ball-milling the mixed powder in a ball mill for 5 hours, wherein the using amount of ball-milled beads is 100g, and sieving the ball-milled beads with a 80-mesh sieve to obtain the cathode C @ Ni @ MnO2A catalytic material.
Example 3:
cathode C @ Ni @ MnO of aluminum-air battery2The preparation method of the catalytic material comprises the following steps:
s1, adding MnO2The material is placed in a muffle furnace for high-temperature crystal transformation treatment to obtain the MnO subjected to crystal transformation2The temperature of crystal transformation treatment is 350 ℃, the heating rate is 2 ℃/min, and the time of crystal transformation treatment is 2 h;
s2 MnO after crystal transformation2The mass ratio of the graphite powder to the nickel net is 2.5: 0.5: 1.5 discharging in microwave equipment after mixing, wherein the microwave discharge time is 4min, introducing nitrogen for protection and continuously stirring the materials in the discharge process, cooling to room temperature after discharge, and sieving with a 80-mesh sieve to obtain mixed powder;
s3, ball-milling the mixed powder in a ball mill for 6 hours, wherein the using amount of ball-milled beads is 120g, and sieving the ball-milled beads by using a 80-mesh sieve to obtain the cathode C @ Ni @ MnO2A catalytic material.
Example 4:
cathode C @ Ni @ MnO of aluminum-air battery2The preparation method of the catalytic material comprises the following steps:
s1, adding MnO2The material is placed in a muffle furnace for high-temperature crystal transformation treatment to obtain the MnO subjected to crystal transformation2The temperature of crystal transformation treatment is 420 ℃, the heating rate is 2 ℃/min, and the time of crystal transformation treatment is 6 h;
s2 MnO after crystal transformation2Mixing the nickel powder and the graphite powder according to the mass ratio of 2: 2: 1.5 discharging in microwave equipment after mixing, wherein the microwave discharge time is 2min, introducing nitrogen for protection and continuously stirring the materials in the discharge process, cooling to room temperature after discharge, and sieving with a 80-mesh sieve to obtain mixed powder;
s3, ball-milling the mixed powder in a ball mill for 8 hours, wherein the using amount of ball-milled beads is 100g, and sieving the ball-milled beads with a 80-mesh sieve to obtain the cathode C @ Ni @ MnO2A catalytic material.
Example 5:
cathode C @ Ni @ MnO of aluminum-air battery2The preparation method of the catalytic material comprises the following steps:
s1, adding MnO2The material is placed in a muffle furnace for high-temperature crystal transformation treatment to obtain the MnO subjected to crystal transformation2The temperature of crystal transformation treatment is 500 ℃, the heating rate is 2 ℃/min, and the time of crystal transformation treatment is 8 h;
s2 MnO after crystal transformation2The mass ratio of the nickel powder to the graphite powder to the graphene is 3.5: 2.5: 3 (wherein the mass ratio of the graphite powder to the graphene is 1: 1), mixing, placing in microwave equipment for discharging, wherein the microwave discharging time is 6min, introducing nitrogen for protection in the discharging process, continuously stirring the materials, cooling to room temperature after discharging, and sieving by using a 80-mesh sieve to obtain mixed powder;
s3, ball-milling the mixed powder in a ball mill for 10 hours, wherein the using amount of ball-milled beads is 150g, and sieving the ball-milled beads with a 80-mesh sieve to obtain the cathode C @ Ni @ MnO2A catalytic material.
Effect verification test: the C @ Ni @ MnO prepared in example 1 was taken separately2Dispersing 20 wt.% Pt/C of catalytic material and commercial noble metal catalyst in 500 microliters of deionized water, 490 microliters of isopropanol and 10 microliters of Nafion solution, after uniform ultrasonic dispersion, taking 10 microliters of sample solution to coat on a rotating disc electrode, drying, and testing an oxygen reduction line on an electrochemical workstationVoltammogram (ORR-LSV). A saturated Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, an electrolyte is 0.1M KOH solution, the test sweep rate is 10mV/s, oxygen is introduced in the test process to ensure that oxygen in the electrolyte reaches a saturated state, and an ORR-LSV curve obtained by the test is shown in figure 6. The results show that: c @ Ni @ MnO prepared by the invention2The catalytic material shows excellent oxygen reduction performance, and the limiting current density can reach 5.12mA/cm2And exhibits an excellent current plateau, indicating that the C @ Ni @ MnO prepared by the present invention is in this potential range2The catalytic material is in a state of complete mass transfer. C @ Ni @ MnO prepared in example 1 of the present invention2The half-wave potential in the ORR-LSV curve of the catalytic material was 0.80V, which was only 60mV deviation from 0.86V for the 20 wt.% Pt/C catalyst, very close to the catalytic activity of the platinum carbon catalyst. Thus, the C @ Ni @ MnO prepared by the preparation method of the present invention2The catalytic material has great development potential when being applied to the aluminum air battery.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (10)
1. Cathode C @ Ni @ MnO of aluminum-air battery2The preparation method of the catalytic material is characterized by comprising the following steps:
s1, adding MnO2The material is placed in a muffle furnace for high-temperature crystal transformation treatment to obtain the MnO subjected to crystal transformation2The temperature of crystal transformation treatment is 200-500 ℃, and the time of crystal transformation treatment is 1-10 h;
s2 MnO after crystal transformation2Mixing the powder with a nickel source and a carbon source material, then placing the mixture into microwave equipment for discharging, wherein the microwave discharging time is 1-10 min, cooling the mixture to room temperature after discharging, and sieving the mixture to obtain mixed powder;
s3, ball-milling the mixed powder in a ball mill for 3-15 h, and sieving to obtain the productCathode C @ Ni @ MnO2A catalytic material.
2. The aluminum air cell cathode of claim 1, C @ Ni @ MnO2The preparation method of the catalytic material is characterized in that in the step S1, the temperature rise rate of the muffle furnace is 2-10 ℃/min.
3. The aluminum air cell cathode of claim 1, C @ Ni @ MnO2The preparation method of the catalytic material is characterized in that the nickel source in the step S2 is at least one of nickel powder, nickel sheets, nickel wires and nickel nets.
4. The aluminum air cell cathode of claim 1, C @ Ni @ MnO2The preparation method of the catalytic material is characterized in that the nickel source in the step S2 is a transition metal source or a metal alloy, the transition metal source is iron, copper or zinc, and the metal alloy is a nickel-iron alloy or a copper-manganese alloy.
5. The aluminum air cell cathode of claim 1, C @ Ni @ MnO2The preparation method of the catalytic material is characterized in that the microwave equipment in the step S2 discharges under the vacuum environment or inert shielding gas, and the material is continuously stirred in the discharging process.
6. The aluminum air cell cathode of claim 1, C @ Ni @ MnO2The preparation method of the catalytic material is characterized in that the carbon source in the step S2 is at least one of graphene, graphite powder, Ketjen black, acetylene black, vermicular graphite, conductive carbon fiber, conductive carbon quantum dots and conductive carbon nanotubes.
7. The aluminum air cell cathode of claim 1, C @ Ni @ MnO2The preparation method of the catalytic material is characterized in that MnO is crystallized in the step S22The mass ratio of the nickel source to the carbon source material is 1-5: 0.5-4: 0.5 to 3.5.
8. According to the claimsSolving 1, namely cathode C @ Ni @ MnO of aluminum-air battery2The preparation method of the catalytic material is characterized in that the using amount of ball milling beads in the ball mill in the step S3 is 50-200 g.
9. The aluminum air cell cathode of claim 1, C @ Ni @ MnO2The method for preparing the catalytic material is characterized in that the sieve size of the sieve used for sieving in the steps S2 and S3 is 80 meshes.
10. Cathode C @ Ni @ MnO of aluminum-air battery2Catalytic material, characterized in that it is an aluminium air cell cathode C @ Ni @ MnO according to any of claims 1 to 92The catalytic material is prepared by a preparation method.
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