CN114388822B - Aluminum air battery cathode C@Ni@MnO 2 Catalytic material and preparation method thereof - Google Patents
Aluminum air battery cathode C@Ni@MnO 2 Catalytic material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 84
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 69
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 39
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 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 74
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000013078 crystal Substances 0.000 claims abstract description 37
- 238000000498 ball milling Methods 0.000 claims abstract description 31
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 10
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229910021389 graphene Inorganic materials 0.000 claims description 6
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- 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
- 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
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- 238000012546 transfer Methods 0.000 claims description 2
- 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
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
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- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 208000028659 discharge Diseases 0.000 abstract 2
- 238000009776 industrial production Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- 238000010586 diagram Methods 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910001092 metal group alloy Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910000914 Mn alloy Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052742 iron Inorganic materials 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
- 238000001075 voltammogram Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 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
- 239000011267 electrode slurry Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011261 inert gas Substances 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
- 238000012986 modification Methods 0.000 description 1
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- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000012257 stirred material Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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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 an aluminum air battery cathode C@Ni@MnO 2 The preparation method uses high Wen Zhuai crystal technology to convert manganese dioxide crystal, and then carries out microwave discharge treatment on the manganese dioxide crystal, a nickel source and a carbon source, and then carries out ball milling to prepare the cathode catalytic material. According to the invention, a metal nickel source is added, nickel atoms are generated through microwave plasma discharge and are attached to the surfaces of manganese dioxide and a carbon source, and then the surface of the prepared cathode catalytic material is coated with a good conductive carbon network and tightly combined nickel atoms through high-energy mechanical ball milling, so that the active site and the conductivity of the cathode catalytic material are increased, more limited catalytic reaction active sites are generated at the contact position of the metal nickel atoms, the conductive carbon and the manganese dioxide during the oxygen reduction catalytic reaction, the oxygen adsorption rate is increased, the electron transmission path is increased, electrons are rapidly transferred, and thus polarization is reduced, and the prepared catalytic material has the advantages of high catalytic activity, stable performance, low production cost and simple process and is suitable for mass 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@MnO 2 Catalytic materials and methods of making the same.
Background
The aluminum-air battery is widely paid attention to by researchers because of the advantages of high specific energy (theoretical specific energy of 8100 Wh/kg), safety, environmental protection, abundant aluminum resources, low price, convenient transportation, convenient maintenance and the like. 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 comprises a catalytic layer, a current collector and a waterproof layer. The cathode material of the catalytic layer is used as an important medium for catalyzing oxygen reduction reaction, has very important influence on the comprehensive output performance of the aluminum air battery, and is particularly important to research on the catalytic cathode material of the aluminum air battery.
The catalytic cathode material of the aluminum-air battery is mainly divided into noble metal (such as Pt) and alloy catalyst, non-noble metal catalyst, carbon nano material and the like. Among them, noble metal catalysts are expensive and difficult to be widely used, although they are excellent in performance; in addition, other catalysts reported by many researches have poor catalytic performance, poor circulation stability and complex manufacturing process, and are difficult to realize mass industrialized production, so that the commercial application of the aluminum air battery is hindered. Therefore, how to innovatively develop a cathode catalyst which is excellent in performance and low in cost and is convenient for large-scale production and use is a problem to be solved at present.
Disclosure of Invention
Aiming at the technical problems that the cathode catalyst of the aluminum air battery prepared by the prior art has poor catalytic performance, poor circulation stability, complex manufacturing process and high production cost, and is difficult to realize mass industrialized production, the invention provides the cathode C@Ni@MnO of the aluminum air battery 2 A method for preparing a catalytic material.
In order to solve the technical problems, the invention adopts the following technical scheme:
aluminum air battery cathode C@Ni@MnO 2 The preparation method of the catalytic material comprises the following steps:
s1, mnO is added 2 Placing the material in a muffle furnace for high-temperature crystal transformation treatment to obtain transformed MnO 2 The temperature of the crystal transformation treatment is 200-500 ℃, and the time of the crystal transformation treatment is 1-10 h;
s2, mnO after crystal transformation treatment 2 Mixing with nickel source and carbon source material, discharging in microwave equipment for 1-10 min, cooling to room temperature after discharging, and sieving to obtain mixed powder;
s3, ball milling the mixed powder in a ball mill for 3-15 h, and sieving to obtain the cathode C@Ni@MnO 2 Catalytic material.
Further, the temperature rising rate of the muffle furnace in the step S1 is 2-10 ℃/min.
Further, in the 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 apparatus is a vacuum environment or an inert shielding gas introducing condition, and the materials are 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 dot, and conductive carbon nanotube.
Further, the MnO is transformed in the step S2 2 The mass ratio of the nickel source to the carbon source material is 1-5: 0.5 to 4:0.5 to 3.5.
Further, the ball-milling beads in the ball mill in the step S3 are used in an amount of 50-200 g.
Further, the mesh size of the screen for sieving in the steps S2 and S3 is 80 mesh.
The invention also provides an aluminum air battery cathode C@Ni@MnO 2 Catalytic material according to the foregoing aluminum air cell cathode C@Ni@MnO 2 The preparation method of the catalytic material is provided.
Compared with the prior art, the cathode C@Ni@MnO of the aluminum air battery provided by the invention 2 Catalytic material and preparation method thereof, wherein nickel atoms are generated to be attached to MnO through microwave plasma discharge by adding metallic nickel source in preparation process 2 And the surface of the carbon source is coated with a good conductive carbon network and tightly combined nickel atoms on the surface of the cathode catalytic material prepared by high-energy mechanical ball milling, so that the active site and the conductive performance of the cathode catalytic material are improved; in the presence of oxygen reduction catalytic reaction O 2 +2H 2 O+4e - ＝4OH - Metal nickel atoms and conductive carbon and MnO 2 The contact position generates more limited catalytic reaction active sites, the oxygen adsorption rate is increased, the electron transmission path is increased, electrons are rapidly transferred, so that polarization is reduced, and the prepared catalytic material has high catalytic activity and stable performance. As can be seen from this, mnO is used in the present application 2 And carbon materials and other cheap raw materials, so that the production cost is low, the preparation process is simple, and the preparation method is suitable for mass industrialized production of cathode catalytic materials.
Drawings
FIG. 1 is a schematic diagram of an aluminum air cell cathode C@Ni@M provided by the inventionnO 2 The flow chart of the preparation method of the catalytic material is shown in the schematic diagram.
FIG. 2 is a schematic diagram of an aluminum air cell cathode C@Ni@MnO according to the present invention 2 Schematic of the mechanism of the catalytic material.
FIG. 3 is a schematic diagram of an aluminum air cell cathode C@Ni@MnO according to the present invention 2 Catalytic material physical diagram.
FIG. 4 is a schematic diagram of an aluminum air cell cathode C@Ni@MnO according to the present invention 2 A cathode pole piece physical diagram made of catalytic materials.
FIG. 5 is a schematic diagram of an aluminum air cell cathode C@Ni@MnO according to the present invention 2 The catalytic material limits the domain catalytic reaction schematic when the oxygen reduction reaction occurs.
FIG. 6 is a schematic diagram of an aluminum air cell cathode C@Ni@MnO according to the present invention 2 Catalytic materials versus commercial noble metal catalysts 20wt.% Pt/C oxygen reduction linear voltammograms (ORR-LSV) tested by a rotating disk device and electrochemical workstation.
Detailed Description
The invention is further described with reference to the following detailed drawings in order to make the technical means, the creation characteristics, the achievement of the purpose and the effect of the implementation of the invention easy to understand.
Referring to fig. 1 to 5, the invention provides an aluminum air battery cathode C@Ni@MnO 2 The preparation method of the catalytic material comprises the following steps:
s1, mnO is added 2 Placing (manganese dioxide) material into a muffle furnace for high-temperature crystal transformation treatment to obtain transformed MnO 2 The temperature of the crystal transformation treatment is 200-500 ℃, and the time of the crystal transformation treatment is 1-10 h;
s2, mnO after crystal transformation treatment 2 Mixing with nickel source and carbon source material, discharging in microwave equipment for 1-10 min, cooling to room temperature after discharging, and sieving to obtain mixed powder;
s3, ball milling the mixed powder in a ball mill for 3-15 h, and sieving to obtain the cathode C@Ni@MnO 2 Catalytic material.
As a specific example, the temperature rising rate of the muffle furnace in the step S1 is 2-10 ℃/min, so that the proper temperature rising rate can be matched according to the processing temperature, the microscopic crystal form of the slowly heated material can not be suddenly changed, and the heating equipment is not damaged.
As a specific embodiment, the nickel source in step S2 is at least one of nickel powder, nickel flakes, nickel wires, and nickel mesh, that is, any one or a mixture of two or more of nickel powder, nickel flakes, nickel wires, and nickel mesh.
As another specific embodiment, the nickel source in the step S2 is a transition metal source or a metal alloy, the transition metal source is iron, copper, zinc or the like, and the metal alloy is nickel-iron alloy or copper-manganese alloy or the like.
As a specific embodiment, the discharging condition of the microwave apparatus in step S2 is a vacuum environment or an inert gas protection condition, and the material is continuously stirred during the discharging process, so that the material is prevented from being oxidized by air when the discharging generates high temperature, and the stirred material can be sufficiently and uniformly processed.
As a specific embodiment, the carbon source in step S2 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 transformed in the step S2 2 The mass ratio of the nickel source to the carbon source material is 1-5: 0.5 to 4:0.5 to 3.5, thereby preparing the catalytic material with optimal oxygen reduction performance according to the change of a nickel source and a carbon source.
As a specific example, the ball-milling beads in the ball mill in the step S3 are used in an amount of 50-200 g, so that the ball-milling beads can be used in an amount which is changed along with the total weight change of the material proportion, and the catalytic material with stable and consistent performance is prepared.
As a specific example, the mesh size of the sieving screen in the steps S2 and S3 is 80 mesh, so that the catalytic material powder with the required particle size can be directly obtained by sieving, and the catalytic material powder is easy to disperse when the electrode slurry is manufactured in a later period.
The invention also provides an aluminum air battery cathode C@Ni@MnO 2 Catalytic material according to the foregoing aluminum air cell cathode C@Ni@MnO 2 The preparation method of the catalytic material is provided.
Compared with the prior art, the cathode C@Ni@MnO of the aluminum air battery provided by the invention 2 Catalytic material and preparation method thereof, wherein nickel atoms are generated to be attached to MnO through microwave plasma discharge by adding metallic nickel source in preparation process 2 And the surface of the carbon source is coated with a good conductive carbon network and tightly combined nickel atoms on the surface of the cathode catalytic material prepared by high-energy mechanical ball milling, so that the active site and the conductive performance of the cathode catalytic material are improved; in the presence of oxygen reduction catalytic reaction O 2 +2H 2 O+4e - ＝4OH - Metal nickel atoms and conductive carbon and MnO 2 The contact position generates more limited catalytic reaction active sites, the oxygen adsorption rate is increased, the electron transmission path is increased, electrons are rapidly transferred, so that polarization is reduced, and the prepared catalytic material has high catalytic activity and stable performance. As can be seen from this, mnO is used in the present application 2 And carbon materials and other cheap raw materials, so that the production cost is low, the preparation process is simple, and the preparation method is suitable for mass industrialized production of cathode catalytic materials.
In order to better understand the cathode C@Ni@MnO of the aluminum air battery provided by the invention 2 The method for preparing the catalytic material will be described in further detail with reference to specific examples.
Example 1:
aluminum air battery cathode C@Ni@MnO 2 The preparation method of the catalytic material comprises the following steps:
s1, mnO is added 2 Placing the material in a muffle furnace for high-temperature crystal transformation treatment to obtain transformed MnO 2 The temperature of the crystal transformation treatment is 200 ℃, the temperature rising rate is 2 ℃/min, and the time of the crystal transformation treatment is 6h;
s2, mnO after crystal transformation treatment 2 The mass ratio of the powder to the nickel powder and the vermicular graphite is 2:0.5:1, mixing, placing into microwave equipment for discharging for 2min, and dischargingIntroducing nitrogen for protection, continuously stirring the materials, cooling to room temperature after discharging, 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 ball milling amount of the ball milling beads is 100g, and sieving the ball milling beads by a 80-mesh sieve to obtain a cathode C@Ni@MnO 2 Catalytic material.
Example 2:
aluminum air battery cathode C@Ni@MnO 2 The preparation method of the catalytic material comprises the following steps:
s1, mnO is added 2 Placing the material in a muffle furnace for high-temperature crystal transformation treatment to obtain transformed MnO 2 The temperature of the crystal transformation treatment is 300 ℃, the heating rate is 2 ℃/min, and the time of the crystal transformation treatment is 4 hours;
s2, mnO after crystal transformation treatment 2 The mass ratio of the nickel wire to the ketjen black is 1:1.5:2, mixing and then placing the mixture into microwave equipment for discharging, wherein the microwave discharging time is 3min, 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 5 hours, wherein the ball milling amount of the ball milling beads is 100g, and sieving the ball milling beads by a 80-mesh sieve to obtain a cathode C@Ni@MnO 2 Catalytic material.
Example 3:
aluminum air battery cathode C@Ni@MnO 2 The preparation method of the catalytic material comprises the following steps:
s1, mnO is added 2 Placing the material in a muffle furnace for high-temperature crystal transformation treatment to obtain transformed MnO 2 The temperature of the crystal transformation treatment is 350 ℃, the heating rate is 2 ℃/min, and the time of the crystal transformation treatment is 2h;
s2, mnO after crystal transformation treatment 2 The mass ratio of the nickel powder to the nickel screen to the graphite powder is 2.5:0.5:1.5, mixing, placing into microwave equipment for discharging for 4min, introducing nitrogen for protection during discharging, continuously stirring materials, cooling to room temperature after discharging, 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 ball milling amount of the ball milling beads is 120g, and the ball milling beads are 80 meshesSieving to obtain cathode C@Ni@MnO 2 Catalytic material.
Example 4:
aluminum air battery cathode C@Ni@MnO 2 The preparation method of the catalytic material comprises the following steps:
s1, mnO is added 2 Placing the material in a muffle furnace for high-temperature crystal transformation treatment to obtain transformed MnO 2 The temperature of the crystal transformation treatment is 420 ℃, the temperature rising rate is 2 ℃/min, and the time of the crystal transformation treatment is 6h;
s2, mnO after crystal transformation treatment 2 The mass ratio of the nickel powder to the graphite powder is 2:2:1.5, mixing, placing into microwave equipment for discharging for 2min, introducing nitrogen for protection during discharging, continuously stirring materials, cooling to room temperature after discharging, 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 ball milling amount of the ball milling beads is 100g, and sieving the ball milling beads by a 80-mesh sieve to obtain a cathode C@Ni@MnO 2 Catalytic material.
Example 5:
aluminum air battery cathode C@Ni@MnO 2 The preparation method of the catalytic material comprises the following steps:
s1, mnO is added 2 Placing the material in a muffle furnace for high-temperature crystal transformation treatment to obtain transformed MnO 2 The temperature of the crystal transformation treatment is 500 ℃, the heating rate is 2 ℃/min, and the time of the crystal transformation treatment is 8h;
s2, mnO after crystal transformation treatment 2 The 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, then placing into microwave equipment for discharging, wherein the microwave discharging time is 6min, introducing nitrogen for protection in the discharging process, continuously stirring 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 ball milling amount of the ball milling beads is 150g, and sieving the ball milling beads with a 80-mesh sieve to obtain a cathode C@Ni@MnO 2 Catalytic material.
And (3) effect verification test: the C@Ni@MnO prepared in example 1 was taken separately 2 Catalytic material and commercial noble metal catalyst 20wt.% Pt/C were dispersed in 500 μl deionized water, 490 μl isopropanol, and 10 μl Nafion solution, and after ultrasonic dispersion was uniform, 10 μl of the sample was applied to a rotating disk electrode, dried, and tested on an electrochemical workstation for oxygen reduction linear voltammograms (ORR-LSV). The saturated Ag/AgCl electrode is used as a reference electrode, the Pt electrode is used as a counter electrode, the electrolyte is 0.1M KOH solution, the test sweeping speed is 10mV/s, oxygen is introduced during the test to ensure that the oxygen in the electrolyte reaches a saturated state, and the ORR-LSV curve obtained by the test is shown in figure 6. The results show that: the C@Ni@MnO prepared by the method 2 The catalytic material shows excellent oxygen reduction performance, and the limiting current density can reach 5.12mA/cm 2 And shows an excellent current platform, which shows that the C@Ni@MnO prepared by the invention is in the range of the potential 2 The catalytic material is in a state of complete mass transfer. C@Ni@MnO prepared in example 1 of the present invention 2 The half-wave potential in the ORR-LSV curve of the catalytic material is 0.80V, which has a deviation of only 60mV compared with 0.86V of 20wt.% Pt/C catalyst, which is very close to the catalytic activity of the Pt-C catalyst. Thus, the C@Ni@MnO prepared by the preparation method of the invention 2 Catalytic materials have great potential for use in aluminum air cells.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and 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 and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered by the scope of the claims of the present invention.
Claims (5)
1. Aluminum air battery cathode C@Ni@MnO 2 The preparation method of the catalytic material is characterized by comprising the following steps:
s1, mnO is added 2 Placing the material in a muffle furnace for high-temperature crystal transformation treatment to obtain transformed MnO 2 The temperature of the crystal transformation treatment is 200-500 ℃, and the time of the crystal transformation treatment is 1-10 h;
s2, carrying out crystal transformation treatmentMnO 2 Mixing with nickel source and carbon source material, discharging in microwave equipment for 1-10 min, cooling to room temperature after discharging, and sieving to obtain mixed powder;
s3, ball milling the mixed powder in a ball mill for 3-15 h, and sieving to obtain the cathode C@Ni@MnO 2 A catalytic material;
the nickel source in the step S2 is at least one of nickel powder, nickel flakes, nickel wires and nickel screens;
the discharging condition of the microwave equipment in the step S2 is a vacuum environment or an inert shielding gas introducing condition, and materials are continuously stirred in the discharging process;
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 dot and conductive carbon nanotube;
the step S2 is to transfer crystal MnO 2 The mass ratio of the nickel source to the carbon source material is 1-5: 0.5 to 4:0.5 to 3.5.
2. The aluminum air cell cathode c@ni@mno of claim 1 2 The preparation method of the catalytic material is characterized in that the temperature rising rate of the muffle furnace in the step S1 is 2-10 ℃/min.
3. The aluminum air cell cathode c@ni@mno of claim 1 2 The preparation method of the catalytic material is characterized in that the ball milling beads in the ball mill in the step S3 are used in an amount of 50-200 g.
4. The aluminum air cell cathode c@ni@mno of claim 1 2 The preparation method of the catalytic material is characterized in that the mesh size of the sieving screen in the steps S2 and S3 is 80 meshes.
5. Aluminum air battery cathode C@Ni@MnO 2 Catalytic material, characterized in that it is according to any one of claims 1 to 4, an aluminium air cell cathode c@ni@mno 2 The preparation method of the catalytic material is provided.
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