CN112382766A - Catalyst, method for preparing the same, and secondary battery comprising the same - Google Patents
Catalyst, method for preparing the same, and secondary battery comprising the same Download PDFInfo
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- CN112382766A CN112382766A CN202010870706.9A CN202010870706A CN112382766A CN 112382766 A CN112382766 A CN 112382766A CN 202010870706 A CN202010870706 A CN 202010870706A CN 112382766 A CN112382766 A CN 112382766A
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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
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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
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
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- H—ELECTRICITY
- 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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- 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
- H01M4/905—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC
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- 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
- Y02E60/10—Energy storage using batteries
Abstract
Disclosed are a secondary battery, a catalyst for the secondary battery, and a method for preparing the catalyst, the method comprising the steps of: s1: preparing an aluminum-based alloy by using Al, Fe, Co, Mn and X under a high-temperature condition, wherein X is a transition metal element different from Fe, Co and Mn; s2: placing the aluminum-based alloy in an alkaline solution to produce a powder alloy having a nanoporous structure, wherein Al chemically reacts with the alkaline solution, while Fe, Co, Mn, and X do not chemically react with the alkaline solution; s3: calcining the powder alloy in an oxygen-containing atmosphere to obtain a nano-porous structure (FeCoX)3O4/Mn3O4The spinel oxide composite material of (1).
Description
Technical Field
The invention relates to the technical field of batteries, in particular to but not limited to a rechargeable metal-air secondary battery, a bifunctional catalyst for the rechargeable metal-air secondary battery and a preparation method of the bifunctional catalyst.
Background
Rechargeable metal-air secondary batteries, such as zinc-air secondary batteries, typically include two electrochemical reactions: oxygen Evolution Reaction (OER) during charging and discharge processOxygen Reduction Reaction (ORR). In the prior art, commercial Pt/C catalysts and other noble metal catalysts (e.g., IrO) are commonly used2) Together, are used to facilitate the charging and discharging processes of the rechargeable metal-air secondary battery. However, the catalyst has high cost and poor durability, which hinders the practical industrial production application. Therefore, how to develop a low-cost, high-catalytic-activity and high-stability catalyst is crucial to the technical development of rechargeable metal-air batteries.
Disclosure of Invention
In view of the above, the present invention aims to provide a catalyst, a method for preparing the same, and a secondary battery containing the same, which can solve or at least reduce the above problems.
In one aspect, the present invention provides a method for preparing a catalyst, which is a bifunctional catalyst for a rechargeable metal-air secondary battery, the method comprising the steps of: s1: preparing an aluminum-based alloy by using Al, Fe, Co, Mn and X under a high-temperature condition, wherein X is a transition metal element different from Fe, Co and Mn; s2: placing the aluminum-based alloy in an alkaline solution to produce a powder alloy having a nanoporous structure, wherein Al chemically reacts with the alkaline solution, while Fe, Co, Mn, and X do not chemically react with the alkaline solution; s3: calcining the powder alloy in an oxygen-containing atmosphere to obtain a nano-porous structure (FeCoX)3O4/Mn3O4The spinel oxide composite material of (1).
In some embodiments, the X is selected from the group consisting of: ni, Cr, V, Nb, or any combination thereof.
In some embodiments, the aluminum-based alloy is in the form of a strip and/or a ribbon.
In some embodiments, the atomic number ratio of Al, Fe, Co, Mn, and X is 92:2:2:2: 2.
In some embodiments, the alkaline solution is a 2mol/L sodium hydroxide solution, and the Al chemically reacts with the alkaline solution for 12 hours.
In some embodiments, the step S1 includes the steps of: and smelting Al, Fe, Co, Mn and X for multiple times under the conditions of high temperature and inert gas to prepare an aluminum-based alloy precursor which is uniformly mixed, and then placing the aluminum-based alloy precursor into a vacuum melt-spinning furnace to perform secondary smelting under the condition of high temperature and rapidly cooling to prepare the aluminum-based alloy used in the step S2.
In another aspect, the present invention also provides a catalyst which is a bifunctional catalyst for a rechargeable metal-air secondary battery, the catalyst comprising a (FeCoX) having a nanoporous structure3O4/Mn3O4Wherein X is a transition metal element other than Fe, Co, Mn.
In some embodiments, the X is selected from the group consisting of: ni, Cr, V, Nb, or any combination thereof.
In some embodiments, the (FeCoX)3O4Is a spherical structure, an ellipsoidal structure, and/or a skeletal structure, and/or the Mn3O4Is in a sheet structure.
In still another aspect, the present invention also provides a secondary battery, including a positive electrode, a negative electrode, and an electrolyte, where the positive electrode includes the foregoing catalyst.
Compared with the prior art, the preparation method of the invention provides the following technical advantages: 1. the invention adopts cheap and easily available non-noble metal as raw material, has low cost and simple process, and has higher scale production value; 2. in the calcining process, excessive temperature and special gas protection atmosphere are not needed, so that the manufacturing cost is greatly reduced; 3. the catalyst prepared by the invention is a spinel oxide composite material with rich nano-pore structure, and more catalytic active sites are exposed, so that the catalyst has high reversible dual-function electrocatalytic activity of oxygen reduction and oxygen precipitation, and simultaneously, due to the addition of X, the material has strong stability; 4. with commercial Pt/C-IrO2Catalyst comparison, inventive (FeCoX)3O4/Mn3O4The catalyst has higher open-circuit voltage, smaller charge-discharge voltage gap and longer battery service lifeIts life is long.
Drawings
Further features of the present invention will become more apparent from the following description of preferred embodiments thereof, which are provided by way of example only, with reference to the accompanying drawings, in which:
FIG. 1 is a (FeCoX) solution prepared according to the first embodiment of the present invention3O4/Mn3O4Scanning transmission electron microscope images of the composite;
FIG. 2 is a (FeCoX) solution prepared according to the first embodiment of the present invention3O4/Mn3O4High resolution transmission electron microscope images of the composite;
FIG. 3 is a view showing (FeCoX) prepared in the first embodiment of the present invention3O4/Mn3O4A scanning transmission electron microscope-energy spectrometer map of the composite material;
FIG. 4 is a (FeCoX) solution prepared according to example two of the present invention3O4/Mn3O4A scanning transmission electron microscope-energy spectrometer map of the composite material;
FIG. 5 is (FeCo) prepared in comparative example one3O4/Mn3O4A scanning transmission electron microscope-energy spectrometer map of the composite material;
FIG. 6 is a graph comparing the X-ray diffraction patterns of composites prepared according to examples of the present invention and comparative example one;
FIG. 7 is a graph comparing oxygen reduction polarization curves for composites prepared according to various examples of the present invention and comparative example one, and a commercial Pt/C catalyst;
FIG. 8 shows a composite material prepared according to each example of the present invention and comparative example one and commercial IrO2A comparative plot of the oxygen evolution polarization profile of the catalyst;
FIG. 9 shows a composite material prepared according to examples of the present invention and comparative example one and commercial Pt/C-IrO2A graph comparing the bifunctional catalytic activities of the catalysts;
fig. 10 is a schematic view of an assembled zinc-air secondary battery of the present invention; and
FIG. 11 shows a schematic diagram of an embodiment of the present inventionPrepared (FeCoX)3O4/Mn3O4Graph of charge/discharge test of zinc-air battery of composite material.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below by way of examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example one
The first embodiment of the present invention provides a catalyst which is a bifunctional catalyst for a rechargeable metal-air secondary battery, particularly preferably for a zinc-air secondary battery. In other words, the catalyst of the present embodiment can effectively catalyze both an Oxygen Reduction Reaction (ORR) and an Oxygen Evolution Reaction (OER) of the secondary battery. Specifically, the catalyst of the present embodiment includes a catalyst having a nanoporous structure (FeCoX)3O4/Mn3O4Wherein X is a transition metal element other than Fe, Co, Mn, such as Ni, Cr, V, Nb, or any combination thereof. In this example, X is Ni. Said (FeCoX)3O4A spherical structure, an ellipsoidal structure, and/or a skeletal structure. As shown in FIG. 1, in the present embodiment (FeCoNi)3O4A generally spherical structure. The Mn is3O4Is in a sheet structure. Of the catalysts of the present example (FeCoNi)3O4Can effectively catalyze the Oxygen Evolution Reaction (OER), Mn of the secondary battery3O4The catalytic Oxygen Reduction Reaction (ORR) of the secondary battery can be effectively performed.
In this embodiment, the preparation method of the catalyst includes the following steps: s1: preparing an aluminum-based alloy by using Al, Fe, Co, Mn and Ni under a high-temperature condition; s2: removing aluminum in the aluminum-based alloy by using a dealloying method, specifically, putting the aluminum-based alloy into an alkaline solution to prepare a powder alloy with a nano porous structure, wherein Al and the alkaline solution are subjected to chemical reaction, and Fe, Co, Mn and NiDoes not chemically react with the alkaline solution; s3: calcining the powder alloy in an oxygen-containing atmosphere to obtain a nano-porous structure (FeCoX)3O4/Mn3O4The spinel oxide composite material of (1).
Preferably, the step S1 includes the steps of: firstly, Al, Fe, Co, Mn and Ni with high mass purity, preferably with the mass purity of more than 99.9 percent are selected as raw materials, wherein the atomic number ratio of the Al, the Fe, the Co, the Mn and the Ni is preferably 92:2:2: 2; then, putting the raw materials into a vacuum furnace, and smelting at high temperature (preferably 1300 ℃) under the protection of inert gas such as argon to prepare a uniformly mixed aluminum-based alloy precursor; preferably, the high-temperature smelting is performed for multiple times, for example, five times, so as to further improve the mixing uniformity of each metal in the aluminum-based alloy precursor; specifically, the aluminum-based alloy precursor is preferably heated by an electric arc for about 2 minutes until it is melted and then cooled for about 1 minute, reheated, and then cooled, and the cycle is repeated five times; finally, placing the aluminum-based alloy precursor in a vacuum melt-spinning furnace for secondary smelting under the high-temperature condition and rapidly cooling to prepare a strip-shaped and/or strip-shaped aluminum-based alloy; preferably, the current of an induction heating coil of the melt-spun furnace is selected to be 280A, and the tangential speed of a roller of the melt-spun furnace is 70 m/s; the resulting ribbon and/or strip of aluminum-based alloy has a thickness of about 50 μm and a width of about 5 mm.
Preferably, the alkaline solution in the step S2 is a 2mol/L sodium hydroxide solution. When the aforementioned aluminum-based alloy is placed in a 2mol/L sodium hydroxide solution, Al chemically reacts with the sodium hydroxide solution to be corroded, while Fe, Co, Mn, and Ni do not chemically react with the sodium hydroxide solution, and particularly, the aluminum-based alloy obtained in the aforementioned step S1 has a main component of aluminum, and the remaining metals are present only in a small amount. It will be appreciated by those skilled in the art that in still other embodiments, other concentrations of sodium hydroxide solution may be used, and even other alkaline solutions may be used. In this embodiment, the time for the Al to chemically react with the sodium hydroxide solution is preferably 12 hours. In this way, Al can be made to react more sufficiently with the sodium hydroxide solution so as to produce a black powder alloy having a more nanoporous structure. In addition, the aluminum-based alloy in the aforementioned step S1 is preferably manufactured in a band and/or a bar, which also further increases the reaction rate of Al in the aluminum-based alloy with the sodium hydroxide solution.
Preferably, the calcination process in step S3 is performed in a tube furnace. The calcination process should be sufficient to ensure that the air supply is sufficient to allow the metals to react with the oxygen. More preferably, the calcining temperature is 300 ℃, the calcining time is 2 hours, and the heating rate is 5 ℃/min.
FIG. 1 shows (FeCoNi) produced in this example3O4/Mn3O4Scanning transmission electron microscopy images (STEM) of the catalyst. As can be seen from the figure, the catalyst comprises two types of particles: one is nanospheres about 50nm in diameter and the other is nanoflakes about 15nm in thickness. Both particles contain a plurality of nanopores with a pore size of less than 10nm, as can also be confirmed from the High Resolution Transmission Electron Microscope (HRTEM) image of fig. 2. Fig. 3 is a scanning transmission electron microscope-energy spectrometer (STEM-EDS) map of the catalyst prepared in this example. It can be seen from the figure that the nanospheres are mainly oxides of FeCoNi, while the nanosheets are mainly oxides of Mn, and both are doped with Al.
Example two
The second embodiment of the present invention provides a catalyst which is a bifunctional catalyst for a rechargeable metal-air secondary battery (particularly preferably for a zinc-air secondary battery). In other words, the catalyst of the present embodiment can effectively catalyze both an Oxygen Reduction Reaction (ORR) and an Oxygen Evolution Reaction (OER) of the secondary battery. Specifically, the catalyst of the present embodiment includes a catalyst having a nanoporous structure (FeCoX)3O4/Mn3O4Wherein X is a transition metal element other than Fe, Co, Mn, such as Ni, Cr, V, Nb, or any combination thereof. In this example, X is V. Said (FeCoX)3O4A spherical structure, an ellipsoidal structure, and/or a skeletal structure. Such asFIG. 4 shows (FeCoV) in this embodiment3O4Generally a skeletal structure. The Mn is3O4Is in a sheet structure. Of the catalysts of the present example (FeCoV)3O4Can effectively catalyze the Oxygen Evolution Reaction (OER), Mn of the secondary battery3O4The catalytic Oxygen Reduction Reaction (ORR) of the secondary battery can be effectively performed.
In this embodiment, the preparation method of the catalyst includes the following steps: s1: preparing an aluminum-based alloy by using Al, Fe, Co, Mn and V under a high-temperature condition; s2: removing aluminum in the aluminum-based alloy by adopting a dealloying method, specifically, putting the aluminum-based alloy into an alkaline solution to prepare a powder alloy with a nano porous structure, wherein Al and the alkaline solution are subjected to chemical reaction, and Fe, Co, Mn and V are not subjected to chemical reaction; s3: calcining the powder alloy in an oxygen-containing atmosphere to obtain a nano-porous structure (FeCoX)3O4/Mn3O4The spinel oxide composite material of (1).
Preferably, the step S1 includes the steps of: firstly, selecting Al, Fe, Co, Mn and V with high mass purity, preferably with the mass purity of more than 99.9 percent as raw materials, wherein the atomic number ratio of the Al, the Fe, the Co, the Mn and the V is preferably 92:2:2: 2; then, putting the raw materials into a vacuum furnace, and carrying out high-temperature smelting under the protection of inert gas such as argon to prepare a uniformly mixed aluminum-based alloy precursor; preferably, the high-temperature smelting is performed for multiple times, for example, five times, so as to further improve the mixing uniformity of each metal in the aluminum-based alloy precursor; finally, placing the aluminum-based alloy precursor in a vacuum melt-spinning furnace for secondary smelting under the high-temperature condition and rapidly cooling to prepare a strip-shaped and/or strip-shaped aluminum-based alloy; preferably, the current of an induction heating coil of the melt-spun furnace is selected to be 280A, and the tangential speed of a roller of the melt-spun furnace is 70 m/s; the resulting ribbon and/or strip of aluminum-based alloy has a thickness of about 50 μm and a width of about 5 mm.
Preferably, the alkaline solution in the step S2 is a 2mol/L sodium hydroxide solution. When the aforementioned aluminum-based alloy is placed in a 2mol/L sodium hydroxide solution, Al reacts chemically with the sodium hydroxide solution to be corroded, while Fe, Co, Mn, and V do not react chemically with the sodium hydroxide solution, and particularly, the aluminum-based alloy obtained in the aforementioned step S1 has a main component of aluminum, and the remaining metals are present only in a small amount. It will be appreciated by those skilled in the art that in still other embodiments, other concentrations of sodium hydroxide solution may be used, and even other alkaline solutions may be used. In this embodiment, the time for the Al to chemically react with the sodium hydroxide solution is preferably 12 hours. In this way, Al can be made to react more sufficiently with the sodium hydroxide solution so as to produce a black powder alloy having a more nanoporous structure. In addition, the aluminum-based alloy in the aforementioned step S1 is preferably manufactured in a band and/or a bar, which also further increases the reaction rate of Al in the aluminum-based alloy with the sodium hydroxide solution.
Preferably, the calcination process in step S3 is performed in a tube furnace. More preferably, the calcining temperature is 300 ℃, the calcining time is 2 hours, and the heating rate is 5 ℃/min.
FIG. 4 is a (FeCoV) solution prepared according to example two of the present invention3O4/Mn3O4Scanning transmission electron microscope-energy spectrometer (STEM-EDS) map of the catalyst. Similarly to the examples, the dealloyed (Al) (FeCoV) prepared in example two3O4/Mn3O4The catalyst also exhibits similar nanocomposite structures, both nanoporous framework structures (mainly oxides of Fe, Co, V) and nanoflakes (mainly oxides of Mn).
EXAMPLE III
The third embodiment of the present invention provides a catalyst which is a bifunctional catalyst for a rechargeable metal-air secondary battery (particularly preferably for a zinc-air secondary battery). In other words, the catalyst of the present embodiment can effectively catalyze both an Oxygen Reduction Reaction (ORR) and an Oxygen Evolution Reaction (OER) of the secondary battery. Specifically, the catalyst of the present embodiment includes a catalyst having a nanoporous structure (FeCoX)3O4/Mn3O4Wherein X is a transition metal element other than Fe, Co, Mn, such as Ni, Cr, V, Nb, or any combination thereof. In this example, X is Cr. Said (FeCoCr)3O4A spherical structure, an ellipsoidal structure, and/or a skeletal structure. The Mn is3O4Is in a sheet structure. In the catalyst of this example (FeCoCr)3O4Can effectively catalyze the Oxygen Evolution Reaction (OER), Mn of the secondary battery3O4The catalytic Oxygen Reduction Reaction (ORR) of the secondary battery can be effectively performed.
In this embodiment, the preparation method of the catalyst includes the following steps: s1: preparing aluminum-based alloy by using Al, Fe, Co, Mn and Cr under a high-temperature condition; s2: removing aluminum in the aluminum-based alloy by adopting a dealloying method, specifically, putting the aluminum-based alloy into an alkaline solution to prepare a powder alloy with a nano porous structure, wherein Al and the alkaline solution are subjected to chemical reaction, and Fe, Co, Mn and Cr are not subjected to chemical reaction; s3: calcining the powder alloy in an oxygen-containing atmosphere to obtain (FeCoCr) alloy with a nano-porous structure3O4/Mn3O4The spinel oxide composite material of (1).
Preferably, the step S1 includes the steps of: firstly, Al, Fe, Co, Mn and Cr with high mass purity, preferably with the mass purity of more than 99.9 percent are selected as raw materials, wherein the atomic number ratio of the Al, the Fe, the Co, the Mn and the Cr is preferably 92:2:2: 2; then, putting the raw materials into a vacuum furnace, and carrying out high-temperature smelting under the protection of inert gas such as argon to prepare a uniformly mixed aluminum-based alloy precursor; preferably, the high-temperature smelting is performed for multiple times, for example, five times, so as to further improve the mixing uniformity of each metal in the aluminum-based alloy precursor; finally, placing the aluminum-based alloy precursor in a vacuum melt-spinning furnace for secondary smelting under the high-temperature condition and rapidly cooling to prepare a strip-shaped and/or strip-shaped aluminum-based alloy; preferably, the current of an induction heating coil of the melt-spun furnace is selected to be 280A, and the tangential speed of a roller of the melt-spun furnace is 70 m/s; the resulting ribbon and/or strip of aluminum-based alloy has a thickness of about 50 μm and a width of about 5 mm.
Preferably, the alkaline solution in the step S2 is a 2mol/L sodium hydroxide solution. When the aforementioned aluminum-based alloy is placed in a 2mol/L sodium hydroxide solution, Al chemically reacts with the sodium hydroxide solution to be corroded, and Fe, Co, Mn, and Cr do not chemically react with the sodium hydroxide solution, particularly, the aluminum-based alloy obtained in the aforementioned step S1 has a main component of aluminum, and the remaining metals are present only in a small amount. It will be appreciated by those skilled in the art that in still other embodiments, other concentrations of sodium hydroxide solution may be used, and even other alkaline solutions may be used. In this embodiment, the time for the Al to chemically react with the sodium hydroxide solution is preferably 12 hours. In this way, Al can be made to react more sufficiently with the sodium hydroxide solution so as to produce a black powder alloy having a more nanoporous structure. In addition, the aluminum-based alloy in the aforementioned step S1 is preferably manufactured in a band and/or a bar, which also further increases the reaction rate of Al in the aluminum-based alloy with the sodium hydroxide solution.
Preferably, the calcination process in step S3 is performed in a tube furnace. More preferably, the calcining temperature is 300 ℃, the calcining time is 2 hours, and the heating rate is 5 ℃/min.
Comparative example 1
Comparative example one provides a catalyst (FeCo) without X3O4/Mn3O4The preparation method comprises the following steps: s1: firstly, placing Al, Fe, Co and Mn with the mass purity of more than 99.9% into a vacuum melting furnace, repeatedly melting for five times under the protection of high temperature and argon gas to obtain a uniformly mixed aluminum-based alloy precursor, wherein the atomic number ratio of Al, Fe, Co and Mn is 94:2: 2; secondly, placing the obtained aluminum-based alloy precursor in a vacuum melt-spinning furnace for secondary smelting under the high-temperature condition and rapidly cooling to prepare a strip-shaped and/or strip-shaped aluminum-based alloy, wherein the current of an induction heating coil of the melt-spinning furnace is selected to be 280A, and the tangential speed of a roller of the melt-spinning furnace is 70 m/s; the obtained aluminum-based alloy in the form of strip and/or bar has a thickness of about 50 μm and a widthAbout 5 mm; s2: removing aluminum in the aluminum-based alloy by adopting a dealloying method, specifically, placing the obtained aluminum-based alloy in a 2mol/L sodium hydroxide solution for reacting for 12 hours to prepare a powder alloy with a nano porous structure; s3: calcining the powder alloy in a tube furnace at 300 deg.C for 2 hr at a rate of 5 deg.C/min to obtain (FeCo) with nano-porous structure3O4/Mn3O4The spinel oxide composite material of (1).
FIG. 5 is a graph of (FeCo) prepared in comparative example one3O4/Mn3O4Scanning transmission electron microscope-energy spectrometer (STEM-EDS) map of (a). As can be seen from the figure, even though there is no X in the raw material of comparative example one, (FeCo) was prepared by the dealloying preparation method of the present invention3O4/Mn3O4And also exhibit similar nanocomposite structures, i.e., both nanoporous skeletal structures and nanoflakes. This is also confirmed from fig. 6, which is a graph comparing X-ray diffraction (XRD) patterns of the composite materials prepared in the previous examples and comparative example one. As can be seen from fig. 6, each composite material has distinct diffraction peaks in the characteristic crystal planes of the spinel structures (311), (400) and (440), which proves that the material with the spinel oxide structure can be stably prepared by the dealloying preparation method of the present invention.
FIGS. 7 to 9 show the respective catalysts prepared in the first three examples and comparative example and commercial Pt/C-IrO2The results of electrochemical performance tests of the catalysts are compared. Preferably, electrochemical performance testing is performed using a three-electrode system. Specifically, the three electrodes comprise a working electrode, a counter electrode and a reference electrode, wherein the working electrode adopts a glassy carbon rotating disk electrode coated with a corresponding catalyst, the counter electrode adopts a platinum sheet electrode, and the reference electrode adopts an Ag/AgCl electrode. The working electrode is preferably prepared by the following method: mixing 4mg of corresponding catalyst, 3mg of carbon nano tube, 300 mu L of ethanol and 100 mu L of Nafion solution (0.5 wt.%), ultrasonically dispersing the mixed solution for 30min to obtain uniformly dispersed suspension, and dripping 5 mu L of uniformly dispersed suspension into a smooth glassy carbon rotating disc by using a 10 mu L liquid transfer gunAnd (4) drying the catalyst layer on the electrode by infrared to obtain a catalyst thin layer for testing. During testing, the rotating speed of the rotating disc is 1600 r/min. When ORR is tested, the electrolyte is 1M KOH aqueous solution saturated with oxygen. For testing OER, the electrolyte was 1M KOH in water saturated with nitrogen.
FIG. 7 is a graph comparing the ORR curves of the catalysts measured in an oxygen-saturated 1M KOH solution. As can be seen from FIG. 7, the catalyst (FeCoNi)3O4/Mn3O4The ORR performance of the catalyst is optimal, the half-wave potential is 0.79V, and the performance is equivalent to that of a commercial Pt/C catalyst (the half-wave potential is 0.80V). However, of this example (FeCoNi)3O4/Mn3O4Compared with a commercial Pt/C catalyst, the catalyst is prepared from a non-noble metal material, has lower preparation cost and is more suitable for large-scale production and application.
FIG. 8 is a graph comparing the OER curves of the catalysts measured in a 1M KOH solution saturated with nitrogen. As can be seen from FIG. 8, the catalyst (FeCoCr)3O4/Mn3O4The OER performance is optimal, and the current density is 10mA/cm2The voltage is only 1.48V and far exceeds the commercial IrO2The performance of the catalyst (voltage 1.54V at a current density of 10mA/cm 2).
Further, FIG. 9 shows each catalyst prepared in the foregoing three examples and comparative example one, and commercial Pt/C-IrO2Comparative graph of bifunctional catalytic activity of catalysts. As can be seen from fig. 9: (FeCoNi)3O4/Mn3O4With a very small voltage difference (0.69V) between OER and ORR, and (FeCoCr)3O4/Mn3O4、(FeCoV)3O4/Mn3O4Has a voltage difference between OER and ORR of 0.74V and 0.75V in this order, which is similar to that of commercial Pt/C-IrO2The catalysts (0.74V) were comparable, which demonstrates the high reversibility of the X-containing catalysts of the invention for oxygen electrocatalysis.
Referring to fig. 10, the present invention also provides a zinc-air secondary battery containing the catalyst of the present invention. In some embodiments, the zinc-air secondary battery is prepared by: catalyst to be uniformly dispersed (e.g., the foregoing embodiment)Example one catalyst (FeCoNi)3O4/Mn3O4) The suspension (the preparation method of the suspension can refer to the preparation method of the suspension in the preparation method of the working electrode) is coated on carbon cloth, and the carbon cloth and the zinc sheet with the oxide layer removed are assembled into the zinc-air secondary battery after infrared drying, and the electrolyte preferably adopts a mixed solution of 6M potassium hydroxide and 0.2M zinc acetate. After the zinc-air secondary battery is assembled, the zinc-air secondary battery stands for 20 minutes, and then the charging and discharging tests can be carried out.
Fig. 11 is a charge/discharge test curve on the above-described zinc-air battery. The results show that: compared with commercial Pt/C-IrO2Catalyst (FeCoNi)3O4/Mn3O4The catalyst has smaller potential difference in the early stage of charge/discharge, can stably charge and discharge for 400 hours, and has very high application prospect.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-listed embodiments, and any simple changes or equivalent substitutions of technical solutions that can be obviously obtained by those skilled in the art within the technical scope of the present invention are within the protection scope of the present invention.
Claims (10)
1. A method for preparing a catalyst, which is a bifunctional catalyst for a rechargeable metal-air secondary battery, comprising the steps of:
s1: preparing an aluminum-based alloy by using Al, Fe, Co, Mn and X under a high-temperature condition, wherein X is a transition metal element different from Fe, Co and Mn;
s2: placing the aluminum-based alloy in an alkaline solution to produce a powder alloy having a nanoporous structure, wherein Al chemically reacts with the alkaline solution, while Fe, Co, Mn, and X do not chemically react with the alkaline solution;
s3: calcining the powder alloy in an oxygen-containing atmosphere to obtain a nano-porous structure (FeCoX)3O4/Mn3O4The spinel oxide composite material of (1).
2. The method for preparing a catalyst according to claim 1, wherein X is selected from the group consisting of: ni, Cr, V, Nb, or any combination thereof.
3. The method for preparing a catalyst according to claim 1, wherein the aluminum-based alloy is in the form of a strip and/or a ribbon.
4. The method of preparing a catalyst according to claim 1, wherein the atomic number ratio of Al, Fe, Co, Mn, and X is 92:2:2:2: 2.
5. The method for preparing the catalyst according to claim 1, wherein the alkaline solution is a 2mol/L sodium hydroxide solution, and the time for the Al to chemically react with the alkaline solution is 12 hours.
6. The method for preparing a catalyst according to claim 1, wherein the step S1 includes the steps of: and smelting Al, Fe, Co, Mn and X for multiple times under the conditions of high temperature and inert gas to prepare an aluminum-based alloy precursor which is uniformly mixed, and then placing the aluminum-based alloy precursor into a vacuum melt-spinning furnace to perform secondary smelting under the condition of high temperature and rapidly cooling to prepare the aluminum-based alloy used in the step S2.
7. A catalyst, which is a bifunctional catalyst for a rechargeable metal-air secondary battery, characterized in that the catalyst comprises (FeCoX) having a nanoporous structure3O4/Mn3O4Wherein X is a transition metal element other than Fe, Co, Mn.
8. The catalyst according to claim 7, wherein X is selected from the group consisting of: ni, Cr, V, Nb, or any combination thereof.
9. The catalyst of claim 7, wherein the (FeCoX)3O4Is a spherical structure, an ellipsoidal structure, and/or a skeletal structure, and/or the Mn3O4Is in a sheet structure.
10. A secondary battery comprising a positive electrode, a negative electrode, and an electrolytic solution, characterized in that the positive electrode comprises the catalyst according to any one of claims 7 to 9.
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